WO2024002578A1 - Matériau, procédé et appareil pour former une couche de matériau 2d à motifs - Google Patents

Matériau, procédé et appareil pour former une couche de matériau 2d à motifs Download PDF

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Publication number
WO2024002578A1
WO2024002578A1 PCT/EP2023/062853 EP2023062853W WO2024002578A1 WO 2024002578 A1 WO2024002578 A1 WO 2024002578A1 EP 2023062853 W EP2023062853 W EP 2023062853W WO 2024002578 A1 WO2024002578 A1 WO 2024002578A1
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Prior art keywords
forming
precursor material
constituents
crosslinks
transition metal
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PCT/EP2023/062853
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English (en)
Inventor
Syam Parayil VENUGOPALAN
Vina FARAMARZI
Shashank BALASUBRAMANYAM
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Asml Netherlands B.V.
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Publication of WO2024002578A1 publication Critical patent/WO2024002578A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/165—Monolayers, e.g. Langmuir-Blodgett
    • 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
    • C23C16/04—Coating on selected surface areas, e.g. using masks
    • C23C16/047—Coating on selected surface areas, e.g. using masks using irradiation by energy or particles
    • 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
    • C23C16/305—Sulfides, selenides, or tellurides
    • 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
    • C23C16/48—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 by irradiation, e.g. photolysis, radiolysis, particle radiation
    • C23C16/483—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 by irradiation, e.g. photolysis, radiolysis, particle radiation using coherent light, UV to IR, e.g. lasers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/167—Coating processes; Apparatus therefor from the gas phase, by plasma deposition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
    • H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/24—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only semiconductor materials not provided for in groups H01L29/16, H01L29/18, H01L29/20, H01L29/22
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/778—Field effect transistors with two-dimensional charge carrier gas channel, e.g. HEMT ; with two-dimensional charge-carrier layer formed at a heterojunction interface

Definitions

  • the present invention relates to materials, methods and apparatuses for forming a patterned layer of 2D material.
  • a lithographic apparatus is a machine constructed to apply a desired pattern onto a substrate.
  • a lithographic apparatus can be used, for example, in the manufacture of integrated circuits (ICs).
  • a lithographic apparatus may, for example, project a pattern at a patterning device (e.g., a mask) onto a layer of radiation-sensitive material (resist) provided on a substrate.
  • a patterning device e.g., a mask
  • resist radiation-sensitive material
  • a lithographic apparatus may use electromagnetic radiation.
  • the wavelength of this radiation determines the minimum size of features which can be formed on the substrate.
  • a lithographic apparatus which uses extreme ultraviolet (EUV) radiation, having a wavelength within the range 4-20 nm, for example 6.7 nm or 13.5 nm, may be used to form smaller features on a substrate than a lithographic apparatus which uses, for example, radiation with a wavelength of 193 nm.
  • EUV extreme ultraviolet
  • a material for depositing on a substrate comprising: an oxide of Tellurium, Transition metal telluride, and/or Transition metal dichalcogenide; and ligands for forming crosslinks in response to illumination by radiation.
  • a system for forming a pattern of 2D material on a surface comprising one or more apparatuses configured to: deposit a precursor material on a surface, wherein the precursor material comprises one or more constituents for forming a 2D material on the surface and one or more constituents for forming crosslinks in response to illumination by radiation; illuminate the deposited precursor material with patterned radiation such that crosslinks form in the illuminated precursor material; perform a development process for removing precursor material that does not comprise crosslinks; perform one or more processes for removing constituents of the precursor material such that substantially only the one or more constituents for forming the 2D material remain; and perform a crystallization process for forming the 2D material on the surface.
  • a method of forming a pattern of 2D material on a surface comprising: depositing a precursor material on a surface, wherein the precursor material comprises one or more constituents for forming a 2D material on the surface and one or more constituents for forming crosslinks in response to illumination by radiation; illuminating the deposited precursor material with patterned radiation such that crosslinks form in the illuminated precursor material; performing a development process for removing precursor material that does not comprise crosslinks; performing one or more processes for removing the constituents of the precursor material such that substantially only the one or more constituents for forming the 2D material remain; and performing a crystallization process for forming the 2D material on the surface.
  • a device comprising one or more layers of 2D material, wherein the device is manufactured according to the method of the third aspect.
  • a substrate at least partially coated with the material according to the first aspect.
  • a substrate with a 2D material formed thereon wherein the 2D material is formed according to the method of the third aspect.
  • a substrate with a 2D material formed thereon wherein the 2D material comprises Tellurium.
  • a substrate with a 2D material formed thereon wherein the 2D material comprises one or more of Tellurene or atoms of a transition metal, M, covalently bonded with atoms of a chalcogen, Q, in the MQ2 form, such as MoTe2, M0S2, PtTe 2 , WTe 2 , WS 2 , or WSe 2 .
  • M transition metal
  • Q chalcogen
  • FIG. 1 depicts a lithographic system comprising a lithographic apparatus and a radiation source
  • FIG. 2A schematically shows a metal oxide nanocluster
  • FIG. 2B schematically shows a metal oxide nanocluster during, or soon after, an EUV exposure process
  • FIG. 2C schematically shows a plurality of metal oxide nanoparticles and ligands after a plurality of exposed metal oxide nanoclusters have condensed
  • FIG. 3 schematically shows a MOSFET with the channel of the MOSFET made from a 2D material
  • FIG. 4A schematically shows a substrate, with a patterned arrangement of structures, that has been coated with a precursor material;
  • FIG. 4B schematically shows an EUV exposure process being performed;
  • FIG. 4C schematically shows remaining precursor material after a development process has been performed
  • FIG. 4E schematically shows constituents of 2D material after insertion and/or replacement processes have been performed
  • FIG. 5 schematically shows an exposure process arrangement for using a kinetic plasma to perform a crystallization process
  • FIG. 6A-6C schematically shows a number of different waveforms may be applied during the crystallization process.
  • Figure 1 shows a lithographic system comprising a radiation source SO and a lithographic apparatus LA.
  • the radiation source SO is configured to generate an EUV radiation beam B and to supply the EUV radiation beam B to the lithographic apparatus LA.
  • the lithographic apparatus LA comprises an illumination system IL, a support structure MT configured to support a patterning device MA (e.g., a mask), a projection system PS and a substrate table WT configured to support a substrate W.
  • a patterning device MA e.g., a mask
  • the illumination system IL is configured to condition the EUV radiation beam B before the EUV radiation beam B is incident upon the patterning device MA.
  • the illumination system IL may include a facetted field mirror device 10 and a facetted pupil mirror device 11.
  • the faceted field mirror device 10 and faceted pupil mirror device 11 together provide the EUV radiation beam B with a desired cross-sectional shape and a desired intensity distribution.
  • the illumination system IL may include other mirrors or devices in addition to, or instead of, the faceted field mirror device 10 and faceted pupil mirror device 11.
  • the EUV radiation beam B interacts with the patterning device MA. As a result of this interaction, a patterned EUV radiation beam B’ is generated.
  • the projection system PS is configured to project the patterned EUV radiation beam B’ onto the substrate W.
  • the projection system PS may comprise a plurality of mirrors 13,14 which are configured to project the patterned EUV radiation beam B’ onto the substrate W held by the substrate table WT.
  • the projection system PS may apply a reduction factor to the patterned EUV radiation beam B’, thus forming an image with features that are smaller than corresponding features on the patterning device MA. For example, a reduction factor of 4 or 8 may be applied.
  • the projection system PS may include a different number of mirrors (e.g., six or eight mirrors).
  • the substrate W may include previously formed patterns. Where this is the case, the lithographic apparatus LA aligns the image, formed by the patterned EUV radiation beam B’, with a pattern previously formed on the substrate W.
  • a relative vacuum i.e. a small amount of gas (e.g. hydrogen) at a pressure well below atmospheric pressure, may be provided in the radiation source SO, in the illumination system IL, and/or in the projection system PS.
  • gas e.g. hydrogen
  • the radiation source SO shown in Figure 1 is, for example, of a type which may be referred to as a laser produced plasma (LPP) source.
  • a laser system 1 which may, for example, include a CO2 laser, is arranged to deposit energy via a laser beam 2 into a fuel, such as tin (Sn) which is provided from, e.g., a fuel emitter 3.
  • tin is referred to in the following description, any suitable fuel may be used.
  • the fuel may, for example, be in liquid form, and may, for example, be a metal or alloy.
  • the fuel emitter 3 may comprise a nozzle configured to direct tin, e.g. in the form of droplets, along a trajectory towards a plasma formation region 4.
  • the laser beam 2 is incident upon the tin at the plasma formation region 4.
  • the deposition of laser energy into the tin creates a tin plasma 7 at the plasma formation region 4.
  • Radiation, including EUV radiation, is emitted from the plasma 7 during deexcitation and recombination of electrons with ions of the plasma.
  • Collector 5 comprises, for example, a near-normal incidence radiation collector 5 (sometimes referred to more generally as a normal-incidence radiation collector).
  • the collector 5 may have a multilayer mirror structure which is arranged to reflect EUV radiation (e.g., EUV radiation having a desired wavelength such as 13.5 nm).
  • EUV radiation e.g., EUV radiation having a desired wavelength such as 13.5 nm.
  • the collector 5 may have an ellipsoidal configuration, having two focal points. A first one of the focal points may be at the plasma formation region 4, and a second one of the focal points may be at an intermediate focus 6, as discussed below.
  • the laser system 1 may be spatially separated from the radiation source SO. Where this is the case, the laser beam 2 may be passed from the laser system 1 to the radiation source SO with the aid of a beam delivery system (not shown) comprising, for example, suitable directing mirrors and/or a beam expander, and/or other optics.
  • a beam delivery system (not shown) comprising, for example, suitable directing mirrors and/or a beam expander, and/or other optics.
  • the laser system 1, the radiation source SO and the beam delivery system may together be considered to be a radiation system.
  • Radiation that is reflected by the collector 5 forms the EUV radiation beam B.
  • the EUV radiation beam B is focused at intermediate focus 6 to form an image at the intermediate focus 6 of the plasma present at the plasma formation region 4.
  • the image at the intermediate focus 6 acts as a virtual radiation source for the illumination system IL.
  • the radiation source SO is arranged such that the intermediate focus 6 is located at or near to an opening 8 in an enclosing structure 9 of the radiation source SO.
  • Figure 1 depicts the radiation source SO as a laser produced plasma (LPP) source
  • any suitable source such as a discharge produced plasma (DPP) source or a free electron laser (FEL) may be used to generate EUV radiation.
  • the process of manufacturing semiconductors comprises coating a surface of the substrate with a resist. An exposure process may then be performed in which the surface coated by the resist is irradiated by the patterned EUV radiation beam. Photons in the patterned EUV radiation beam react with the resist to induce a change in the irradiated parts of the resist.
  • a development process may then be performed in which either only the changed parts of the resist, or only the unchanged parts of the resist, are removed so that the surface of the substrate is coated with resist with a pattern that is dependent on the pattern of the EUV radiation beam. Further processes may then be performed to manufacture semiconductors in dependence on the pattern of the resist on the surface of the substrate.
  • a known resist suitable for use with lithography is a chemically amplified resist (CAR) and may be based on polymers. Upon exposure to electromagnetic radiation, the polymers in the CAR absorb photons and secondary electrons may be generated. The generation of secondary electrons in the resist is how a high-energy photon loses most of its energy.
  • CAR chemically amplified resist
  • the secondary electrons in the resist diffuse and may generate further secondary electrons with lower energies until the energy of the secondary electrons is lower than that required to break bonds in the CAR.
  • the electrons generated excite photo-acid generators (PAGs) which subsequently decompose and can catalyse a de-blocking reaction that occurs on the polymer. This leads to a change in solubility of the CAR.
  • PAGs photo-acid generators
  • Alternative resists for use in lithography, in particular EUV lithography comprise metal oxide nanoclusters. These resists comprise metal oxide nanoparticles which are prevented from clustering together by each metal oxide nanoparticle having a ligand shell. Upon EUV exposure, photons are absorbed by the nanoparticles and secondary electrons are generated that cause the metal oxide nanoparticles to cluster together. This changes the solubility of the exposed parts of the resist. A development process may then remove only the unexposed parts of the resist, or only the exposed parts of the resist. A metal oxide nanoparticle has a higher EUV absorption cross-section than the carbon atoms in a CAR and there is therefore a greater likelihood of EUV photons being absorbed. Accordingly, metal oxide based resists require a less intense EUV beam and/or a shorter exposure time. Furthermore, the different conversion mechanism has potentially lower chemical noise than CAR resist system.
  • FIG. 2A schematically shows a metal oxide nanocluster.
  • the metal oxide cluster comprises a metal oxide nanoparticle 201 that is surrounded by ligands 202.
  • the ligands 202 form a shell around the metal oxide nanoparticle 201.
  • the metal oxide nanoparticle 201 may be, for example, tin oxide.
  • Each ligand may be a polymer structure.
  • Figure 2B schematically shows the metal oxide nanocluster 201 during, or soon after, an EUV exposure process.
  • a metal oxide nanoparticle 201 has absorbed an EUV photon and this has caused a photoelectron to be generated.
  • the photoelectron further collides with atoms and has caused secondary electrons to be generated.
  • the secondary electrons have caused the dissociation of at least one of the ligands 202 of a metal oxide nanoparticle 201 and an active site 203 has formed due to the dissociation.
  • Figure 2C schematically shows a plurality of metal oxide nanoparticles 201 and ligands 202 after a plurality of exposed metal oxide nanoclusters have condensed.
  • Oxygen bonds 204 may have formed between the active sites 203 so as to bond a plurality of metal oxide nanoclusters together.
  • the plurality of bonded together metal oxide nanoclusters shown in Figure 2C may have a different solubility to the unexposed metal nanoclusters as shown in in Figure 2A.
  • the plurality of bonded together metal oxide nanoclusters shown in Figure 2C may be insoluble in development fluid and therefore remain during a subsequently performed development process.
  • unexposed metal nanoclusters may be soluble in development fluid and therefore removed during the development process.
  • 2D materials may be used.
  • 2D materials are atomically thin flat layers and therefore have a very low height above the surface that they are formed on.
  • a monolayer of a 2D material typically has a sub-nanometer thickness.
  • a potential use of 2D materials is as the channel of a MOSFET.
  • a problem with the standard non-2D materials used for the channel of a MOSFET is that short channel effects, such as leakage due to tunneling, impose a limit to the minimum channel length.
  • Forming the MOSFET channel from 2D materials enables channel lengths smaller than the limits imposed by conventional semiconductors, such as silicon.
  • FIG. 3 schematically shows a MOSFET with the channel of the MOSFET made from a 2D material.
  • the MOSFET comprises a substrate 301, 302.
  • the substrate may comprise a layer of Silicon dioxide, SiO2, 302 on a layer of Silicon 301.
  • Formed on the substrate 301, 302 may be the source 303 and drain 306 of the MOSFET, both of which may be metal layers.
  • the channel 307 of the MOSFET is a layer of 2D material.
  • An oxide layer 304 may be formed on the channel 307.
  • the oxide layer 304 may be, for example, Hafnium dioxide, HfO2.
  • MOSFET Metal-Oxide-Semiconductor
  • the gate 305 of the MOSFET is typically poly-Si or any conducting material.
  • MOSFET may also use 2D materials.
  • di-electric may be provided on both sides of the channel and the die-electric may also be a 2D material, such as hBN.
  • the 2D material used for the channel of the MOSFET may be, for example, Molybdenum disulfide, M0S2.
  • a single layer of M0S2 is a crystalline structure with a single layer of Molybdenum atoms arranged between two single layers of sulfur atoms.
  • the height of the single layer of M0S2 may be about 0.65nm to Inm.
  • Such a 2D material has semiconductor properties, a low relative dielectric constant and other properties that make it suitable for use as the channel of the MOSFET.
  • the channel of the MOSFET is made from a 2D material, the channel may be shorter than if standard non- 2D materials are used. Many other 2D materials may be used for the channel due to their semiconductor bandgap.
  • the 2D material may be WS2, WSe2, MoTe2, or other 2D materials.
  • a problem with the use of 2D materials in structures such as that shown in Figure 3 is that it is difficult to correctly form a patterned layer of 2D material.
  • 2D materials are very sensitive and may be damaged by the standard patterning processes such as resist coating, lithography, etch and resist stripping.
  • WO2019166318A1 discloses resist-less direct patterned EUV deposition of 2D materials.
  • a problem with the techniques described therein is that a very high EUV dose is required.
  • the required EUV dose may be a lot larger than 100mJ/cm 2 .
  • CVD Chemical Vapor Deposition
  • W02020207759A1 discloses a technique of direct EUV induced deposition. However, a large EUV exposure dose is still required.
  • the EUV exposure dose may be at least 1.5 to 2 J/cm 2 to deposit a monolayer of 2D material.
  • Embodiments solve at least some of the above problems by providing a new approach to forming 2D materials on surfaces such as a substrate.
  • Embodiments comprise including one or more constituents of a 2D material in a solid precursor material.
  • the precursor material may be referred to as a resist matrix.
  • the precursor material is a resist-type material and it adsorbs EUV photons in its bulk.
  • the precursor material may be deposited, in a similar way to known techniques with a resist, on a surface, such as the surface of a substrate.
  • the precursor material may then be patterned with EUV radiation.
  • a development process may then be performed for removing the regions of the precursor material that were not illuminated by the EUV radiation. This leaves a patterned arrangement of remaining precursor material.
  • An etch process may then be performed for removing the constituents of the remaining precursor material other than the desired one or more constituents for forming the 2D material. Insertion and/or replacement processes may then be performed to provide all of the required constituents of the 2D material.
  • a process may then performed for crystallizing the constituents of the 2D material.
  • a pattern of 2D material is
  • the required EUV dose may be no more than that required for standard EUV resist patterning. That is to say, the required EUV dose may be similar to that needed to pattern a metal oxide based resist.
  • the required EUV dose may be less than or equal to about 100 mJ/cm 2 .
  • Figure 4 A schematically shows a substrate 401, W that has already had a patterned arrangement of structures 403 formed on it according to known techniques.
  • the structures 403, and unpatterned regions of the substrate 401, W have been coated with a precursor material 402a.
  • the precursor material 402a may have been deposited by, for example, chemical vapor deposition, CVD, AED, spin coating or other known techniques for depositing a resist.
  • the precursor material 402a may be a nanocluster with a similar, or the same, structure as the metal oxide nanocluster as described earlier with reference to Figures 2A to 2C. That is to say, the precursor material 402a may have a core 201, that may be a metal comprising core 201, that is surrounded by ligands 202. The ligands 202 form a shell around the core 201. Each ligand may be a polymer structure.
  • the core 201 may comprise, for example, one or more of an oxide of Tellurium (such as Tellurium oxide, Tellurium trioxide or, preferably, Tellurium dioxide), Transition metal telluride, or Transition metal dichalcogenide.
  • an oxide of Tellurium such as Tellurium oxide, Tellurium trioxide or, preferably, Tellurium dioxide
  • Transition metal telluride or Transition metal dichalcogenide.
  • the absorption of EUV photons by Tellurium is relatively high.
  • a further advantage of using Tellurium in the core 201 is that the Tellurium may form part of the 2D material that is eventually produced.
  • the 2D material may be, for example, MoTe2, WTe2, PtTe2 or Tellurene.
  • Figure 4B schematically shows an EUV exposure process being performed.
  • the precursor material 402a is illuminated by patterned EUV radiation 404.
  • the illuminated precursor material 402a absorbs EUV photons. This causes photoelectrons to be generated and the collision between photoelectrons and atoms causes secondary electrons to be generated.
  • the secondary electrons cause the dissociation of the ligands 202 so that active sites 203 are formed in a process that is similar to, or the same as, the process shown in Figure 2B.
  • a plurality of the nanoclusters may then condense to form condensed precursor material 402b.
  • the condensation process may be similar to, or the same as, the process shown in Figure 2C.
  • the condensation process may comprise bonds 204 forming between the active sites 203 so as to bond a plurality of nanoclusters together. Each bond may be, for example, an Oxygen bond or a Tellurium bond.
  • a development process may then be performed.
  • the condensed precursor material 402b may have a different solubility to the unexposed regions of precursor material 402a.
  • the condensed precursor material 402b may be insoluble in development fluid and therefore not removed by the development process.
  • the unexposed precursor material 402a may be soluble in development fluid and therefore removed during the development process.
  • Figure 4C schematically shows the remaining precursor material 402b after the development process has been performed.
  • the development process may be a wet development process.
  • an EUV induced deposition process may be used to form a pattern of the precursor material 402b.
  • the content of each core 201 and/or the elements that bond the nanoclusters together following the condensation process may be substantially the only differences between the provision of a patterned precursor material 402b according to embodiments and the resist patterning techniques as described with reference to Figures 2A to 2C.
  • a process may then be performed for stripping the precursor material 402c so that substantially only the constituents that are required by the further processes for forming the 2D material remain.
  • Figure 4D schematically shows the remaining constituents 402c after the precursor material 402b has been stripped.
  • the remaining constituents 402c may be transition metal precursors or transition metal dichalcogenide precursors.
  • the process for stripping the precursor material 402b may be an etching process and is preferably a selective dry etch process.
  • the etching process may be radical based and comprise only chemical etching. There may be no bias voltage applied during the etching process so that there is no ion based etching.
  • One or more processes may then be performed for providing all of the constituents that are required for forming the 2D material.
  • one or more processes may be performed for inserting a chalcogen.
  • Each process for inserting a chalcogen may be a CVD process.
  • the inserted chalcogen may be any of the elements in group 16 of the periodic table.
  • the inserted chalcogen may be Sulfur, Selenium or Tellurium.
  • the chalcogen insertion process may not be required if the desired chalcogen for the 2D material was a constituent of the precursor material 402a.
  • one or more processes may be performed for replacing a constituent of the remaining precursor material 402c.
  • Each process for replacing a constituent may be a CVD process.
  • the metal inserted by the replacement process may, for example, any of Molybdenum, Tungsten, Palladium, Platinum, Zirconium or Tin.
  • the remaining precursor material 402c comprises Tin, that may be in the form of Tin oxide, a process may be performed for replacing the Tin with Molybdenum.
  • Figure 4E schematically shows the constituents of the 2D material 402d after the above described insertion and/or replacement processes have been performed.
  • the constituents of the 2D material 402d may not currently be in a crystalline form.
  • a further process may therefore be performed for re-arranging the constituents of the 2D material 402d into a crystalline structure so as to form crystallized 2D material 402e as schematically shown in Figure 4F.
  • a number of different processes may be performed for forming the 2D material into a crystalline structure.
  • a temperature based crystallization process such as annealing, may be performed.
  • the crystallization process is performed by using a kinetic plasma with ion energy control provided by a tailored waveform.
  • Figure 5 schematically shows the configuration of an exposure process arrangement for using a kinetic plasma to perform the crystallization process.
  • the exposure process arrangement comprises a substrate W.
  • the substrate W comprises a substrate body 505.
  • the substrate body 505 may have on it a patterned layer 504 of the constituents of the 2D material 402d that are initially not in a crystallized form.
  • the substrate body 505 may be secured to a substrate table 507 by an electrostatic clamp 506.
  • the patterned layer 504 of the constituents of the 2D material 402d may be arranged so that at least part of it may be illuminated by EUV radiation.
  • the path of the EUV radiation may be orthogonal to the major surfaces of the substrate W.
  • An illumination region 502 may be defined between a grounded wall 501 and the exposed major surface of the substrate W. When the exposed major surface of the substrate W is illuminated, EUV radiation may pass through one or more openings in the grounded wall 501 and through the illumination region 502.
  • the exposure process arrangement may further comprise a matching box 508 and a power supply arrangement 514.
  • the power supply arrangement 514 may comprise a switch 509, a ground terminal 510, a sinusoidal waveform generator 511 and a flexible waveform generator 512.
  • the switch 509 may control the type of waveform that is output by the power supply arrangement 514.
  • the output of the power supply arrangement 514 may be an AC voltage.
  • An AC voltage output from the power supply arrangement 514 may generate an alternating electric field 513 in the patterned layer 504 of the constituents of 2D material 402d.
  • the direction of the alternating electric field 513 in the patterned layer 504 of the constituents of 2D material 402d may be substantially orthogonal to the major surfaces of the substrate W.
  • the direction of the alternating electric field 513 in the patterned layer 504 of the constituents of 2D material 402d may therefore be substantially in line with, or parallel to, the path of the EUV radiation that illuminates the exposed major surface of the substrate W.
  • the alternating electric field 313 in the patterned layer 504 of the constituents of 2D material 402d may cause the 2D material to crystallize into a layer of crystallized 2D material 402e.
  • FIG. 6A and 6B show sinusoidal waveforms with different frequencies that may be applied.
  • a tailored waveform such as that shown in Figure 6C is applied.
  • Such a tailored waveform may be configured to apply an appropriate energy for re-arranging atoms so as to appropriately form the crystallized 2D material 402e.
  • embodiments provide a new technique for forming a patterned layer of a 2D material on a surface, such as the surface of a substrate 401, W.
  • the required EUV dose may be substantially less than that required by known EUV based techniques for forming patterned 2D materials.
  • the formed 2D material may comprise atoms of a transition metal, M, and atoms of a chalcogen, Q.
  • M may be from any of groups IV, V or VI of the periodic table.
  • Q may be any chalcogen, such as Sulfur, Selenium and Tellurium.
  • the M and Q atoms may form a covalently bonded 2D layer of the MQ2 type with a hexagonal lattice.
  • Embodiments include a number of modifications and variations to the above-described techniques.
  • Embodiments include more than one apparatus, or tool, being used in the formation of the 2D material.
  • the process for crystallizing the constituents of the 2D material may be performed in a separate apparatus, or separate tool, from the apparatus, or tool, that illuminates the deposited precursor material with patterned radiation.
  • EUV radiation is used to illuminate the deposited precursor material.
  • Embodiments also include radiation with wavelengths other than EUV being used in the formation the 2D material.
  • embodiments include illuminating the precursor material with DUV radiation.
  • the type of precursor material that is used may be dependent on the wavelength of the radiation that illuminates it. Accordingly, the precursor material used with DUV radiation may be different from that used with EUV radiation, so that the bulk of the precursor material efficiently absorbs the DUV radiation.
  • different development and/or stripping processes may be performed that are appropriate for the used precursor material.
  • Embodiments also include using a different precursor material such that the regions of the precursor material that were illuminated are removed the development process, and the regions of the precursor material that were not illuminated are not removed by the development process.
  • Embodiments have described the formation of a single layer of 2D material. Embodiments also include the described techniques being used to form a multi-layer material and/or a plurality of overlapping layers of 2D material.
  • Embodiments are not restricted to forming a pattern with a specific type of 2D material, or for the patterned 2D material being for the specific purpose of providing the channel of a MOSFET.
  • Embodiments include the formation of a patterned arrangement of a number of different types of 2D material for any purpose.
  • embodiments include forming patterned arrangements of 2D materials for use as metal caps or diffusion barrier interconnectors.
  • Embodiments include forming a pattern of any type of 2D material as is required given the purpose of the 2D material in the manufactured device.
  • Figures 4A to 4F show the formation of a layer of 2D material on a substrate 401, W that already has a patterned arrangement of structures formed on it.
  • Embodiments also include forming a layer of 2D material on the surface of a substrate that does not already have structures formed on it.
  • Embodiments include the core 201 of the precursor material alternatively, or additionally, comprising one or more of Molybdenum, Tungsten, Palladium, Platinum, Zirconium, Tin or oxides thereof.
  • the core 201 may alternatively, or additionally, comprise other transition metals and/or oxides thereof.
  • Embodiments include the following numbered clauses:
  • a material for depositing on a substrate comprising: an oxide of Tellurium, Transition metal telluride, and/or Transition metal dichalcogenide; and ligands for forming crosslinks in response to illumination by radiation.
  • Transition metal telluride comprises one or more of Molybdenum telluride, Tungsten telluride or Platinum telluride.
  • a system for forming a pattern of 2D material on a surface comprising one or more apparatuses configured to: deposit a precursor material on a surface, wherein the precursor material comprises one or more constituents for forming a 2D material on the surface and one or more constituents for forming crosslinks in response to illumination by radiation; illuminate the deposited precursor material with patterned radiation such that crosslinks form in the illuminated precursor material; perform a development process for removing precursor material that does not comprise crosslinks; perform one or more processes for removing constituents of the precursor material such that substantially only the one or more constituents for forming the 2D material remain; and perform a crystallization process for forming the 2D material on the surface.
  • system comprises a chemical vapor deposition, CVD, apparatus configured to perform the insertion process.
  • an apparatus of the system is configured to further perform a replacement process for replacing one or more of the constituents for forming the 2D material.
  • system comprises a chemical vapor deposition, CVD, apparatus configured to perform the replacement process.
  • Transition metal telluride is Molybdenum telluride, Tungsten telluride or Platinum telluride.
  • a method of forming a pattern of 2D material on a surface comprising: depositing a precursor material on a surface, wherein the precursor material comprises one or more constituents for forming a 2D material on the surface and one or more constituents for forming crosslinks in response to illumination by radiation; illuminating the deposited precursor material with patterned radiation such that crosslinks form in the illuminated precursor material; performing a development process for removing precursor material that does not comprise crosslinks; performing one or more processes for removing the constituents of the precursor material such that substantially only the one or more constituents for forming the 2D material remain; and performing a crystallization process for forming the 2D material on the surface.
  • the method further comprises performing an insertion process for inserting a constituent of the 2D material to be formed on the surface.
  • the method further comprises performing a replacement process for replacing one or more of the constituents for forming the 2D material.
  • Transition metal telluride is Molybdenum telluride, Tungsten telluride or Platinum telluride.
  • a device comprising one or more layers of 2D material, wherein the device is manufactured according to the method of any of clauses 19 to 33.
  • the formed 2D material comprises one or more of Tellurene or atoms of a transition metal, M, covalently bonded with atoms of a chalcogen, Q, in the MQ2 form, such as MoTe2, M0S2, PtTe2, WTe2, WS2, or WSe2.

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Abstract

L'invention concerne un procédé permettant de former un motif de matériau 2D sur une surface (401), le procédé consistant à : déposer un matériau précurseur (402a) sur une surface, le matériau précurseur comprenant un ou plusieurs constituants servant à former un matériau 2D sur la surface et un ou plusieurs constituants servant à former des réticulations suite à un éclairage par rayonnement ; éclairer le matériau précurseur déposé avec un rayonnement à motifs de façon à ce que des réticulations se forment dans le matériau précurseur éclairé (402b) ; effectuer un processus de développement pour éliminer le matériau précurseur qui ne comprend pas de réticulations (402a) ; effectuer un ou plusieurs processus pour éliminer les constituants du matériau précurseur de façon à ce qu'il ne reste sensiblement que le ou les constituants servant à former le matériau 2D (402c, 402d) ; et effectuer un processus de cristallisation pour former le matériau 2D sur la surface (402e).
PCT/EP2023/062853 2022-06-27 2023-05-12 Matériau, procédé et appareil pour former une couche de matériau 2d à motifs WO2024002578A1 (fr)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190129301A1 (en) * 2016-05-19 2019-05-02 Asml Netherlands B.V. Resist compositions
WO2019166318A1 (fr) 2018-03-02 2019-09-06 Asml Netherlands B.V. Procédé et appareil de formation d'une couche de matériau à motifs
US20190383770A1 (en) * 2017-01-19 2019-12-19 Roswell Biotechnologies, Inc. Solid state sequencing devices comprising two dimensional layer materials
WO2020207759A1 (fr) 2019-04-12 2020-10-15 Asml Netherlands B.V. Procédé et appareil de formation de couche de matériau à motif
US11063164B1 (en) * 2020-09-17 2021-07-13 Allen Howard Engel Method and materials to manufacture heterojunctions, diodes, and solar cells
WO2021202146A1 (fr) * 2020-03-30 2021-10-07 Lam Research Corporation Structure et procédé permettant de réaliser un développement à sec de ton positif par une surcouche hermétique
WO2022016123A1 (fr) * 2020-07-17 2022-01-20 Lam Research Corporation Résines photosensibles à co-réactifs organiques déposées à sec
EP4001455A1 (fr) * 2020-11-18 2022-05-25 ASML Netherlands B.V. Procédé de formation d'une couche de matériau à motifs
WO2022106157A1 (fr) * 2020-11-18 2022-05-27 Asml Netherlands B.V. Procédé pour former une couche de matériau à motif
WO2022125388A1 (fr) * 2020-12-08 2022-06-16 Lam Research Corporation Développement de résine photosensible avec de la vapeur organique

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190129301A1 (en) * 2016-05-19 2019-05-02 Asml Netherlands B.V. Resist compositions
US20190383770A1 (en) * 2017-01-19 2019-12-19 Roswell Biotechnologies, Inc. Solid state sequencing devices comprising two dimensional layer materials
WO2019166318A1 (fr) 2018-03-02 2019-09-06 Asml Netherlands B.V. Procédé et appareil de formation d'une couche de matériau à motifs
WO2020207759A1 (fr) 2019-04-12 2020-10-15 Asml Netherlands B.V. Procédé et appareil de formation de couche de matériau à motif
WO2021202146A1 (fr) * 2020-03-30 2021-10-07 Lam Research Corporation Structure et procédé permettant de réaliser un développement à sec de ton positif par une surcouche hermétique
WO2022016123A1 (fr) * 2020-07-17 2022-01-20 Lam Research Corporation Résines photosensibles à co-réactifs organiques déposées à sec
US11063164B1 (en) * 2020-09-17 2021-07-13 Allen Howard Engel Method and materials to manufacture heterojunctions, diodes, and solar cells
EP4001455A1 (fr) * 2020-11-18 2022-05-25 ASML Netherlands B.V. Procédé de formation d'une couche de matériau à motifs
WO2022106157A1 (fr) * 2020-11-18 2022-05-27 Asml Netherlands B.V. Procédé pour former une couche de matériau à motif
WO2022125388A1 (fr) * 2020-12-08 2022-06-16 Lam Research Corporation Développement de résine photosensible avec de la vapeur organique

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