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WO2013037951A1 - Dépôt de catalyseur pour l'élaboration de nanotubes de carbone - Google Patents

Dépôt de catalyseur pour l'élaboration de nanotubes de carbone Download PDF

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Publication number
WO2013037951A1
WO2013037951A1 PCT/EP2012/068086 EP2012068086W WO2013037951A1 WO 2013037951 A1 WO2013037951 A1 WO 2013037951A1 EP 2012068086 W EP2012068086 W EP 2012068086W WO 2013037951 A1 WO2013037951 A1 WO 2013037951A1
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Prior art keywords
catalyst
diffusion barrier
patterned surface
nano patterned
protrusions
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English (en)
Inventor
Rafal Dominik WIERZBICKI
Kristian MØLHAVE
Peter Boggild
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Danmarks Tekniske Universitet
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Danmarks Tekniske Universitet
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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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/347—Ionic or cathodic spraying; Electric discharge
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by catalysts
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/04—Coating on selected surface areas, e.g. using masks
    • C23C14/046—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/08—Aligned nanotubes

Definitions

  • the present invention relates to a method for nano-scale deposition of catalyst and to devices for use as templates for nano-scale deposition of catalysts. Additionally, the present invention relates to methods of growing carbon nanotubes. Background
  • nano-scale deposition of catalyst material is of great importance.
  • examples of such applications are for the creation of various optical devices and/or as a starting point for various chemical processes e.g. growth of carbon nanotubes (CNT).
  • CNT carbon nanotubes
  • Carbon nanotubes due to their unique physicochemical properties are a subject of extensive studies in many application fields including electronics, electrochemistry, or biotechnology, to mention the few.
  • PECVD Plasma enhanced chemical vapour deposition
  • Metal catalysts nickel, iron, or other are used in the process, where each single particle nucleates one nanotube, and defines its diameter and structure.
  • the catalyst pattern defines distribution of carbon nanotubes in the forest [Meyyappan, M., A review of plasma enhanced chemical vapour deposition of carbon nanotubes. Journal of Physics D- Applied Physics, 2009. 42(21 ).].
  • Several approaches of patterning the catalyst are available, offering different level of control and feature size. The simplest involves annealing of a thin (few to tens of nm) film of the catalyst, where islands of catalyst agglomerates into nanoparticles with a random nonuniform distribution of droplet size [Meyyappan, M., A review of plasma enhanced chemical vapour deposition of carbon nanotubes. Journal of Physics D-Applied Physics, 2009. 42(21 ).].
  • Photolithography is a well established patterning method for achieving a more uniformly deposition of catalyst material, but unfortunately, it is limited to submicron resolutions. E-beam writing offers ultimate resolution, however, it is too expensive and very time consuming for mass production since each island of catalyst material needs to printed individually.
  • Shadow masking has been used for catalyst patterning [Wei, H., et al., Patterned forest-assembly of singlewall carbon nanotubes on gold using a non-thiol functionalization technique. Journal of Materials Chemistry, 2007. 17(43): p. 4577-4585.]; yet it suffers proximity errors.
  • Self assembly also offers a good alternative and can provide nanometric patterning [Lee, S.H., et al., Tailored Assembly of Carbon Nanotubes and Graphene.
  • the invention relates to a method of depositing islands of catalyst with a predetermined density.
  • the method may comprise the step of
  • the method may further comprise the step of
  • the diffusion barrier covered nano patterned surface may thus be configured to ensure that no more than a single island of catalyst is formed on each plateau.
  • a sub sequent growth of carbon nanotubes from the deposited islands may result in that no more than a single carbon nanotube is grown from each plateau.
  • An island of catalyst may be a connected amount of catalyst material.
  • the catalyst islands may have any shape e.g. round, triangular or rectangular. In some embodiments the catalyst islands is approximately round. The catalyst islands may have a widest width between 10 nm to 1000 nm.
  • the catalyst material may be any material suitable for use as a catalyst. In some embodiments the catalyst material is a metal catalyst material e.g. Nickel (Ni), iron (Fe) or copper (Cu). In some embodiments the catalyst material is a catalyst material suitable for use for subsequent growth of carbon nanotubes.
  • the diffusion barrier may be made of any material suitable for preventing the catalyst from substantially diffusing into the nano patterned surface. The diffusion barrier may be made of a metal material e.g.
  • the diffusion barrier may form an outer layer covering the nano patterned surface.
  • the diffusion barrier layer may have an approximately equal thickness, and may have a uniform thickness across the nano patterned surface.
  • the nano patterned surface may be made of a any material suitable to form the base material for e.g.
  • the carbon nantotubes such as a polymer material, a semi conductor material, such as a group IV material, such as a silicon material, such as a germanium material, etc, such as a group lll-V material, such as a gallium arsenide, a silicon dioxide, a glass, etc.
  • the nano patterned surface may comprise a plurality of features having a scale below a micrometer e.g. the height and/or width of the features may be below a micrometer.
  • Each plateau may comprise a plateau surface that may be planar or convex. The plateau surface may face substantially away from the nano patterned surface.
  • a plateau may be elevated compared to at least a part of the nano patterned surface immediately surrounding the plateau.
  • the catalyst may be deposited using a method securing an even distribution of catalyst material over the diffusion barrier covered nano patterned surface.
  • the catalyst may be deposited by using any thin film deposition method, e.g. e-beam deposition, thermal evaporation, sputtering, etc.
  • the step of obtaining a diffusion barrier covered nano patterned surface comprising a plurality of plateaus, having a density of plateaus dependent on the predetermined density of islands may comprise obtaining a diffusion barrier covered nano patterned surface comprising a plurality of plateaus, having a density of plateaus substantially equal to the predetermined density of islands of catalyst.
  • the diffusion barrier covered nano patterned surface may be configured to ensure that a single island of catalyst is formed on each plateau by having the plateaus formed on nano scale features having a shape preventing catalyst material from diffusing/travelling from one plateau to another.
  • the diffusion barrier covered nano patterned surface may be heated to a temperature within the range of 300 degrees to 1000 degrees, for a period of time within the range of 10 seconds to 5000 seconds.
  • the density of catalyst islands on a surface e.g. the diffusion barrier covered nano patterned surface, is defined as the average number of catalyst island pr surface area.
  • the density of plateaus is defined as the average number of plateaus per surface area.
  • surface area is defined as the surface area of a 2 dimensional reference plane positioned so that the average distance between the plateaus / islands and the reference plane is minimized.
  • the density of plateaus is between 10 and 1000 plateaus pr square micrometer.
  • the method further comprises depositing islands of catalyst having a predetermined average size, wherein the step of obtaining a diffusion barrier covered nano patterned surface comprises: obtaining a diffusion barrier covered nano patterned surface having plateaus with an average size dependent on the predetermined average size of the catalyst islands. Consequently, a surface having a predetermined density of catalyst islands and a predetermined average size of the catalyst islands may be formed.
  • obtaining a diffusion barrier covered nano patterned surface having large plateaus large islands of catalyst material may be created and
  • the average width of the plateaus is between 10 nanometre and 500 nanometre.
  • the average width of the plateaus is between 100 nanometre and 500 nanometre.
  • the diffusion barrier covered nano patterned surface comprises gaps between adjacent plateaus.
  • the average depth of the gaps is between 5 nanometre and 5000 nanometre.
  • the average depth of the gaps is between 100 nanometre and 1000 nanometre.
  • gaps with an average depth within the above specified range may secure that the diffusion barrier covered nano patterned surface is especially effective at ensuring that a single island of catalyst is formed on each plateau. Deeper gaps may make the diffusion barrier covered nano patterned surface more difficult to manufacture, and more shallow gaps may increase the chance that catalyst material travels / diffuse from one plateau to the next.
  • the average width of the gaps is between 1 nanometre and 1000 nanometre.
  • the average width of the gaps is between 100 nanometre and 500 nanometre. It is possible to control the nanograss properties with reactive ion etching
  • RIE reactive ion etching
  • the step of obtaining a diffusion barrier covered nano patterned surface comprises:
  • the nano patterned surface may be covered with a diffusion barrier by thin film deposition methods, e.g. PVD or CVD evaporation, sputtering, electroplating, etc.
  • thin film deposition methods e.g. PVD or CVD evaporation, sputtering, electroplating, etc.
  • the step of obtaining a nano patterned surface comprises: obtaining a nano patterned surface, comprising a plurality of protrusions protruding from a surface, having a density of protrusions dependent on the predetermined density of catalyst islands, wherein a plateau is formed at the top of each protrusion after the nano patterned surface has been covered with said diffusion barrier.
  • the protrusions may be randomly distributed over the surface.
  • the nano patterned surface may be created by using a reactive ion etch process anisotropic wet etching, laser or microwave irradiation, shadow masking or lithography (UV, e-beam).
  • the density of protrusions is between 1 and 1000 protrusions pr square micrometer, such as between 10 and 700, such as between 50 and 500, such as below 1000, such as below 700 protrusion pr square micrometer.
  • the density of protrusions is between 10 and 1000 protrusions pr square micrometer.
  • the density of protrusions is defined as the average number of protrusions pr surface area, where surface area is defined as the surface area of a 2 dimensional reference plane positioned so that the average distance between the top of the protrusions and the reference plane is minimized.
  • the average height of the protrusions is between 5 nanometre and 5000 nanometre. In some embodiments, the average height of the protrusions is between 100 nanometre and 1000 nanometre.
  • the average thickness of the diffusion barrier is between 0.1 nanometre and 1000 nanometre. In some embodiments, the average thickness of the diffusion barrier is between 1 nanometre and 500 nanometre, such as below 500 nm.
  • the ratio between the average thickness of the diffusion barrier and the average distance between protrusions is between 0.25 and 0.5.
  • ration is defined as the average thickness of the diffusion barrier divided with the average distance between protrusions both measured in nanometres.
  • a value V specifying the relationship between the average thickness of the diffusion barrier and the density of protrusions is between 0.25 and 0.5, where V is defined as
  • V (VD) ⁇ T
  • D is defined as the density of protrusions pr square micrometer
  • T is defined as the average thickness of the diffusion barrier
  • a catalyst layer is deposited on the diffusion barrier covered nano patterned surface having an average thickness between 1 nanometre and 20 nanometre.
  • the step of obtaining a nano patterned surface comprises:
  • process parameters of the reactive ion etching process is chosen to create a density of protrusions dependent on the predetermined density of catalyst islands.
  • the invention relates to a method of growing carbon nanotubes, comprising the steps of:
  • the invention relates to a product obtainable by a method as described previously.
  • the product is directly obtained by a method as described above.
  • the invention relates to a device for use as a template for growing carbon nanotubes, wherein said device comprises a diffusion barrier covered nano patterned surface comprising a plurality of plateaus; wherein said diffusion barrier covered nano patterned surface is configured to ensure, after deposition and annealing of a catalyst, that no more than a single island of catalyst is formed on each plateau, so that a sub sequent growth of carbon nanotubes from the deposited islands result in growth of no more than a single carbon nanotube from each plateau.
  • the device further comprises a catalyst deposited on said diffusion barrier covered nano patterned surface.
  • the density of plateaus is between 1 and 1000 plateau(s) pr square micrometer.
  • the density of plateaus is between 10 and 1000 plateau(s) pr square micrometer.
  • the density of plateaus is defined as the average number of plateaus per surface area, where surface area is defined as the surface area of a 2 dimensional reference plane positioned so that the average distance between the plateaus and the reference plane is minimized.
  • the average width of the plateaus is between 10 nanometres and 500 nanometres.
  • the average width of the plateaus is between 100 nanometres and 500 nanometres. In some embodiments, the diffusion barrier covered nano patterned surface comprises gaps between adjacent plateaus. In some embodiments, the average depth of the gaps is between 5 nanometres and 5000 nanometres.
  • the average depth of the gaps is between 100 nanometres and 1000 nanometres.
  • the average width of the gaps is between 100 nanometres and 500 nanometres. In some embodiments, the average width of the gaps is between 1 nanometre and 1000 nanometres.
  • the diffusion barrier covered nano patterned surface comprises:
  • the nano patterned surface comprises a plurality of protrusions, and wherein a plateau is formed, at the top of the protrusions, by the diffusion barrier.
  • the nano patterned surface is obtainable by a reactive ion etching process. In some embodiments, the nano patterned surface comprises silicon nano grass.
  • the density of protrusions is betweenl and 1000 protrusions pr square micrometer. In some embodiments, the density of protrusions is betweenI O and 1000 protrusions pr square micrometer.
  • the density of protrusions is defined as the average number of protrusions pr surface area, where surface area is defined as the surface area of a 2 dimensional reference plane positioned so that the average distance between the top of the protrusions and the reference plane is minimized.
  • the average height of the protrusions is between 5 nanometres and 5000 nanometres.
  • the average height of the protrusions is between 100 nanometres and 1000 nanometres. In some embodiments, the average thickness of the diffusion barrier is between 1 nanometre and 1000 nanometres.
  • the average thickness of the diffusion barrier is between 1 nanometre and 500 nanometres.
  • the ratio between the average thickness of the diffusion barrier and the average distance between protrusions is between 0.25 and 0.5. Where the ratio is defined as the average thickness of the diffusion barrier divided with the average distance between protrusions both measured in nanometres.
  • a value V specifying the relationship between the average thickness of the diffusion barrier and the density of protrusions is between 0.25 and 0.5, where V is defined as
  • V (VD) ⁇ T
  • the device further comprises a catalyst layer deposited on the diffusion barrier covered nano patterned surface having an average thickness between 1 nanometre and 20 nanometre.
  • the device further comprises islands of catalyst, wherein a single island of catalyst is positioned on top of each plateaus.
  • the invention relates to a carbon nanotube device comprising a device as describe previously, wherein a carbon nanotube is positioned on top of each plateau.
  • the invention relates to use of a device as described above as a template for depositing catalyst material.
  • the different aspects of the present invention can be implemented in different ways including the methods for depositing islands of catalyst, and to device for use as a template for depositing catalyst described above and in the following, each yielding one or more of the benefits and advantages described in connection with at least one of the aspects described above, and each having one or more preferred embodiments corresponding to the preferred embodiments described in connection with at least one of the aspects described above and/or disclosed in the dependant claims.
  • Fig. 1 a-b show a diffusion barrier covered nano patterned surface according to an embodiment of the present invention.
  • Fig. 2 illustrates the principle of a diffusion barrier.
  • Fig. 3a-d show different type of diffusion barrier covered nano patterned surfaces according to some embodiments of the present invention.
  • Fig. 4a-d show a method of depositing catalyst and further growing carbon nanotubes according to an embodiments of the present invention.
  • Fig. 5a shows an electron microscope image of a nano patterned surface according to an embodiment of the present invention.
  • Fig. 5b shows an electron microscope image of a diffusion barrier covered nano patterned surface according to an embodiment of the present invention.
  • Fig. 6a-b show electron microscope images of a carbon nano tube device according to an embodiment of the present invention.
  • Fig. 7a shows an electron microscope image of a plurality of carbon nano tubes grown from a template for growing carbon nano tubes according to an embodiment of the present invention.
  • Fig. 7b shows an electron microscope image of a plurality of carbon nano tubes grown without the use of a template according to the invention.
  • Figure 8 shows SEM top views of the investigated nanograss samples.
  • Figure 9 shows radial uniformity of two silicon nanograss recipes.
  • Figure 10 shows nanograss NND control with RIE chamber pressure and processing time.
  • Figure 1 1 shows SEM images of the fabricated CNT samples.
  • Figure 12 shows diameter distributions of the CNT forests.
  • Fig. 1 a-b show a schematic drawing of a diffusion barrier covered nano patterned surface according to an embodiment of the present invention.
  • Fig. 1 a shows a top view of the diffusion barrier covered nano patterned surface
  • Fig 1 b shows a cross-section of the diffusion barrier covered nano patterned surface taken along the stippled line 106.
  • the diffusion barrier covered nano patterned surface comprises a plurality of plateaus 102.
  • the plateaus 102 are in this embodiment positioned at the top of the protrusions. In this embodiment gaps are present between adjacent plateaus 102.
  • the diffusion barrier covered nano patterned surface is configured to ensure that no more than a single island of catalyst material is formed on each plateau 102, after catalyst material has been deposited and annealed.
  • the diffusion barrier covered nano patterned surface comprises a nano patterned surface 101 and a diffusion barrier 104.
  • the nano pattern of the nano patterned surface 101 is created by a plurality of protrusions 103.
  • the protrusions 103 are in this embodiment positioned in a non-regular fashion e.g. not in a regular grid.
  • the nano patterned surface may comprise protrusions positioned in a regular grid.
  • the density of plateaus 102 is defined as the number of plateaus pr surface area, where surface area is defined as the surface area of a reference plane 105, positioned so that the average distance between the plateaus 102 and the reference plane is minimized e.g. the density is defined as the number of plateaus on/above/below the reference plane 105 divided with the 2 dimensional surface area of the reference plane 105.
  • the surface area of the reference plane 105 may correspond to the surface area of the nano patterned surface before it has been nano patterned e.g. the surface area of the silicon surface before it is patterned using the reactive ion etch process.
  • the density of protrusions 103 is defined as the number of protrusions 103 pr surface area, where surface area is defined as the surface area of a reference plane 107, positioned so that the average distance between the protrusions 103 and the reference plane 107 is minimized e.g. the density is defined as the number of protrusions on/above/below the reference plane 107 divided with the 2 dimensional surface area of the reference plane 107.
  • the surface area of the reference plane 107 may correspond to the surface area of the nano patterned surface before it has been nano patterned e.g. the surface area of the silicon surface before it is patterned using the reactive ion etch process.
  • Fig. 2 illustrates the principle of a diffusion barrier. Shown is a nano patterned surface 201 covered with a diffusion barrier 202.
  • the diffusion barrier 202 prevents a substrate 203, e.g. a catalyst, from vertically diffusing into the underlying surface 201 .
  • Fig. 3a-d shows cross-sections of different type of diffusion barrier covered nano patterned surfaces according to some embodiments of the present invention.
  • Fig. 3a shows a diffusion barrier covered nano patterned surface, where the nano pattern of the nano patterned surface is created by a plurality of pyramid shaped or conical shaped protrusions 302.
  • Fig. 3b shows a diffusion barrier covered nano patterned surface, where the nano pattern of the nano patterned surface is created by a plurality of box shaped protrusions 303.
  • Fig. 3c shows a diffusion barrier covered nano patterned surface, where the nano pattern of the nano patterned surface is created by a plurality of needle shaped or conical shaped protrusions.
  • Fig. 3d shows a diffusion barrier covered nano patterned surface, where the nano pattern of the nano patterned surface is created by a plurality of hemispherical protrusions 302.
  • Figs.4a-d illustrate schematically a method of depositing catalyst and further growing carbon nanotubes according to an embodiments of the present invention.
  • Fig. 4a shows a cross-section of a nano patterned surface 401 comprising a plurality of protrusions 402. The protrusions have a height 403 and a distance between them of 404.
  • Fig. 4b shows the nano patterned surface after being covered with a diffusion barrier 405.
  • the diffusion barrier 405 may be applied using the principles described above.
  • the diffusion barrier 405 may have a substantially uniform thickness over the nano patterned surface 401 .
  • the diffusion barrier 405 creates a plurality of plateaus 409 positioned above the plurality of protrusions 402.
  • Fig 4c shows the diffusion barrier covered nano patterned surface after a catalyst 406 has been deposited.
  • the catalyst 406 may be deposited using the techniques described above.
  • the catalyst 406 may be distributed in small droplets over the diffusion barrier 405.
  • Fig 4d shows the diffusion barrier covered nano patterned surface after the catalyst has been annealed by heating the diffusion barrier covered nano patterned surface.
  • the catalyst material has aggregated into islands of catalyst material 407 having a high uniformity in size, where no more than on island is formed on each plateau. This may be ensured by having plateaus with a desired height, shape, size, and/or distribution.
  • Fig 4e shows the diffusion barrier covered nano patterned surface after growth of carbon nanotubes 410.
  • the carbon nanotubes 410 may be grown using the plasma enhanced vapour deposition method see "A review of plasma enhanced vapour deposition of carbon nanotubes, Meyyappan, M., Journal of Physics D-Applied Physics, 2009.42(21 )".
  • a single carbon nano tube is grown from each island of catalyst material.
  • a forest of carbon nanotubes with a high uniformity can be grown.
  • a nano patterned surface may be created using the reactive ion etching (RIE) process.
  • RIE reactive ion etching
  • a plurality of protrusions may be formed having a desired density of protrusions pr square micro meter. This may be used to deposit islands of catalyst with a predetermined desired density e.g. as plateaus may be formed on top of the protrusions after deposition of a diffusion barrier.
  • the RIE process in a commercial ASE (Advanced Silicon Etcher) system may be controlled by the following parameters: etch gas flows, etch time, platen power, coil power, chamber pressure and wafer chuck temperature. To etch silicon a mixture of sulfur hexafluoride (SF6) and oxygen (02) may be used.
  • SF6 sulfur hexafluoride
  • oxygen 02
  • Height of the structures may be controlled by the processing time; the higher the processing time, the higher obtained structures.
  • the structure protrusions
  • the structure may keep constant aspect ratio (ratio between height and width), so with higher processing time, the structures may become wider, and more sparsely distributed.
  • the density of the nanograss may be inversely proportional to the processing time. Processing time may be varied in a range from single seconds to half an hour.
  • the chamber pressure may be changed.
  • the chamber pressure may also influence the density, which may be inversely proportional to the pressure.
  • the pressure may be changed from 1 to 100 mTorr.
  • all the process parameters may be cross-coupled. That is, a change of one parameters may change all the features of the nanograss. If only one feature needs to be controlled (i.e. density), all the parameters may need to be tuned accordingly.
  • the chamber pressure may be used to control the density of protrusions. See also "Towards easily reproducible nano-structured SERS substrates, Sensors, 2009 IEEE, On pages: 1763 - 1767".
  • Fig. 5a shows an electron microscope image of a nano patterned surface according to an embodiment of the present invention.
  • the nano patterned surface comprises a plurality of protrusions 501 .
  • the nano patterned surface is Silicon nanograss.
  • the silicon nanograss was fabricated at a 4" low-doped silicon wafer, using RIE processing in an Advanced Silicon Etching (ASE) system.
  • ASE Advanced Silicon Etching
  • Fig. 5b shows an electron microscope image of the nano patterned surface shown in Fig. 5a after a diffusion barrier has been applied according to an embodiment of the present invention.
  • the diffusion barrier forms a plurality of slightly convex plateaus 502 on top of the protrusions.
  • the nanograss was coated in a Wordentec system with 150nm of titanium tungsten diffusion barrier, and 8nm of nickel catalyst by magnetron sputtering, and e-beam evaporation, respectively.
  • Fig. 6a-b show electron microscope images of a carbon nano tube device, according to an embodiment of the present invention.
  • the carbon nano tubes have been grown using the plasma enhanced chemical vapour deposition method.
  • the diffusion barrier covered nano patterned surface shown in 5b has been used a template for depositing catalyst material.
  • the catalyst material has been deposited and subsequently annealed whereby no more than a single island of catalyst material is formed on the plateaus.
  • Carbon nanotubes were grown in Aixtron's 6" Black Magic system, using PECVD recipe. The sample was annealed at 600C for 60s in pure ammonia
  • Fig. 7a shows an electron microscope image of a plurality of carbon nano tubes 701 702 grown from a template for growing carbon nano tubes according to an embodiment of the present invention.
  • Fig. 7b shows an electron microscope image of a plurality of carbon nano tubes 703 704 grown without the use of a template according to the invention. It can be seen by comparing the two images that a higher uniformity in distribution, height and diameter may be achieved by using a template for growing carbon nano tubes and/or a method according to the present invention.
  • the density, aspect ratio and height of the nanograss are controlled solely with the parameters of the reactive ion etching (RIE) of the plane silicon wafer [Jansen, H., et al., The black silicon method - a universal method for determining the parameter setting of fluorine-based reactive ion etcher in deep silicon trench etching with profile control. Journal of Micromechanics and Microengineering, 1995. 5(2): p. 1 15-120.].
  • RIE reactive ion etching
  • the RIE method offers maskless fabrication of black silicon nanograss.
  • the masking effect is obtained with the native silicon oxide residing on the wafers and the etched protrusion profiles and densities are controlled with a balance between chemical and physical etching processes present within the RIE.
  • This offers a rich variety of morphologies, densities, aspect ratios and heights [Jansen, H., et al.,
  • the black silicon method - a universal method for determining the parameter setting of fluorine-based reactive ion etcher in deep silicon trench etching with profile control. Journal of Micromechanics and Microengineering, 1995. 5(2): p. 1 15-120.].
  • the nanograss protrusions shall be straight or slightly undercut pillars, so the gaps that remain after the diffusion barrier coating are of a minimal size.
  • the aspect ratio of the protrusions shall not be too high, as the coated protrusions are supposed to mechanically support the nanotubes.
  • the density of the protrusions per surface area should be batch repeatable and uniform across the wafers.
  • the protrusions shall not cluster but be distributed uniformly. Otherwise, large gaps between the protrusions would allow the catalyst to collect and form nanoparticles of uncontrollable sizing.
  • the images were subjected to Gaussian filter (2 pix), and binary threshold was applied. The threshold value was set for each image manually preserving the least bright peaks. Particles were counted with the particle analysis standard ImageJ function, and the mean and variance of the distances between nearest neighbors (NND) were measured with a Delaunay-Voronoi triangulation algorithm plug-in [Schindelin, J. and L. Paul Chew, http://fiji.se/wiki/index.php/Delaunay_Voronoi.].
  • each wafer was sputtercoated with TiW, and e- beam evaporated with Ni (Table 1 ). The wafers were subsequently
  • Figure 1 1 shows the SEM images of the fabricated CNT samples.: a) flat control sample with 8 nm of catalyst (Control_a), b) flat control sample with 10 nm of the catalyst (Control_b), c) silicon nanograss coated with 8 nm of catalyst (RIE 1 ), d) silicon nanograss coated with 10 nm of catalyst (RIE_1 b). Scale bar: 2 ⁇ for all images. The diameters and the CNT number density were measured manually. Histograms were used to evaluate the diameter distributions ( Figure 12).
  • a visual inspection as well as histograms indicates a significant difference in CNT formation between the two flat control samples ( Figure 1 1 a and Figure 1 1 c).
  • the CNT forest on the sample Control_a with 8 nm of the catalyst is relatively uniform, while the forest grown on sample Control_b from 10 nm of catalyst exhibits high non-uniformities with several CNTs of high diameter present.
  • Investigation of the CNTs grown on nanograss shows a considerable improvement of the diameter distributions for both RIE_1 a and RIE_1 b samples, correlated with the fact that most of the nanotubes grow from single nanograss protrusions ( Figure 1 1 ).
  • the narrow end of the histograms can be attributed to CNTs growing from in- between the CNTs, while the thick diameter CNTs seem to be growing from merged protrusion tops ( Figure 6a) (growth of the CNTs from large gaps caused by clustering should not be considered, as the nanograss recipe RIE 1 exhibits negligible clustering). Both histograms are fairly symmetrical and that indicates lack of dominance of either of the effects.
  • the diameter distribution is narrower for the sample covered with less catalyst (RIE_1 a). This can be explained with lower probability of peak-to-peak particle merging, as well as lower amount deposited into the narrow gaps between the protrusions, and thus lower probability of CNT growth.
  • nanograss properties It is possible to control the nanograss properties with RIE processing parameters and obtain nearest neighbor distance between the protrusions in the range of 150 to 700 nm.
  • the growth is wafer-to-wafer repeatable and yields ca. 40% of each wafer surface. Growth of the carbon nanotubes on the nanograss highly improves their diameter distribution and NND, and the mean diameter is controllable with the amount of deposited catalyst.

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Abstract

La présente invention concerne un procédé permettant le dépôt d'îlots de catalyseurs en respectant une densité prédéterminée. Ce procédé comporte plusieurs étapes. Une première étape consiste à réaliser une surface nanostructurée couverte d'une barrière de diffusion comprenant une pluralité de plateaux, la densité des plateaux dépendant de la densité prédéterminée des îlots de catalyseur. Une deuxième étape consiste ensuite à déposer le catalyseur sur ladite surface nanostructurée couverte de la barrière de diffusion. Une troisième étape consiste enfin à chauffer la surface nanostructurée couverte de la barrière de diffusion après que le catalyseur ait été déposé, de façon à réaliser un recuit du catalyseur, ce qui aboutit à la formation des îlots de catalyseur. Selon l'invention, la surface nanostructurée couverte de la barrière de diffusion est configurée de façon à garantir qu'il n'y aura réalisation que d'un seul îlot de catalyseur sur chaque plateau, et que la croissance des nanotubes de carbone, intervenant à partir des îlots déposés, ne donne lieu à la croissance que d'un seul nanotube de carbone à partir de chacun des plateaux.
PCT/EP2012/068086 2011-09-16 2012-09-14 Dépôt de catalyseur pour l'élaboration de nanotubes de carbone Ceased WO2013037951A1 (fr)

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RU2609788C1 (ru) * 2015-11-24 2017-02-03 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский университет "Московский институт электронной техники" (МИЭТ) Способ изготовления катализатора из нанопроволоки
CN109321900A (zh) * 2018-10-21 2019-02-12 浙江海洋大学 一种金属氧化物纳米草的制备方法
US11101082B2 (en) 2017-03-07 2021-08-24 University Of South-Eastern Norway On-chip supercapacitor with silicon nanostructure
RU2787291C1 (ru) * 2022-05-05 2023-01-09 Федеральное государственное учреждение "Федеральный научно-исследовательский центр "Кристаллография и фотоника" Российской академии наук" Способ получения катализатора для окисления СО на основе медных нанопроволок
US12033796B2 (en) * 2017-03-07 2024-07-09 University Of South-Eastern Norway Deposited carbon film on etched silicon for on-chip supercapacitor

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015051380A (ja) * 2013-09-05 2015-03-19 大日本印刷株式会社 金属粒子担持触媒、及びその製造方法
RU2609788C1 (ru) * 2015-11-24 2017-02-03 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский университет "Московский институт электронной техники" (МИЭТ) Способ изготовления катализатора из нанопроволоки
US11101082B2 (en) 2017-03-07 2021-08-24 University Of South-Eastern Norway On-chip supercapacitor with silicon nanostructure
US12033796B2 (en) * 2017-03-07 2024-07-09 University Of South-Eastern Norway Deposited carbon film on etched silicon for on-chip supercapacitor
CN109321900A (zh) * 2018-10-21 2019-02-12 浙江海洋大学 一种金属氧化物纳米草的制备方法
CN109321900B (zh) * 2018-10-21 2020-06-16 浙江海洋大学 一种金属氧化物纳米草的制备方法
RU2787291C1 (ru) * 2022-05-05 2023-01-09 Федеральное государственное учреждение "Федеральный научно-исследовательский центр "Кристаллография и фотоника" Российской академии наук" Способ получения катализатора для окисления СО на основе медных нанопроволок

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