WO2013130027A1 - Propriétés d'absorption et de filtrage de lumière de nanofils semi-conducteurs orientés verticalement - Google Patents

Propriétés d'absorption et de filtrage de lumière de nanofils semi-conducteurs orientés verticalement Download PDF

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WO2013130027A1
WO2013130027A1 PCT/US2011/047189 US2011047189W WO2013130027A1 WO 2013130027 A1 WO2013130027 A1 WO 2013130027A1 US 2011047189 W US2011047189 W US 2011047189W WO 2013130027 A1 WO2013130027 A1 WO 2013130027A1
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nanowires
nanowire
substrate
nanowire array
array
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PCT/US2011/047189
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English (en)
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Young-June Yu
Munib Wober
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Zena Technologies, Inc.
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    • H—ELECTRICITY
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    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
    • H01L31/035209—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures
    • H01L31/035227—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures the quantum structure being quantum wires, or nanorods
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    • H01L27/15—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components having potential barriers, specially adapted for light emission
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    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
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    • H01L27/1461—Pixel-elements with integrated switching, control, storage or amplification elements characterised by the photosensitive area
    • H—ELECTRICITY
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    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H01L27/14601—Structural or functional details thereof
    • H01L27/1462—Coatings
    • H01L27/14621—Colour filter arrangements
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    • H01L27/144—Devices controlled by radiation
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    • H01L27/14683—Processes or apparatus peculiar to the manufacture or treatment of these devices or parts thereof
    • H01L27/14692—Thin film technologies, e.g. amorphous, poly, micro- or nanocrystalline silicon
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    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
    • H01L31/035272—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions characterised by at least one potential jump barrier or surface barrier
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    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
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    • H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
    • H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by potential barriers, e.g. phototransistors
    • H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
    • H01L31/102—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier
    • H01L31/105—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier the potential barrier being of the PIN type
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/548—Amorphous silicon PV cells

Definitions

  • Nanostructures often exhibit spectacular physical properties not present in their bulk counterparts. Optical properties of nanostructures have been one of the recent research focuses. Tuning optical properties of nanostructures would facilitate their applications in the semiconductor, optics, and consumer electronics industry.
  • optical properties of nanostructures can be controlled by their chemical composition. Chemical doping can change electronic structures of the materials semiconductor nanostructures are composed of, which in turn changes their interaction with light.
  • arranging nanostructures into a regular lattice can yield optical properties individual nanostructures lack.
  • these conventional approaches often require complex chemical synthesis or post-synthesis manipulation, and thus are less robust against minute variations of conditions and cannot easily and accurately position nanostructures in a functional device.
  • the approach described herein overcomes these problems of the conventional approaches by harnessing small physical sizes of nanostructures and a top-down fabrication process (i.e., part of a piece of bulk material is removed until desired nanostructures are achieved).
  • a nanowire array comprising a substrate and a plurality of nanowires extending essentially perpendicularly from the substrate; wherein: a refractive index of the nanowires is at least two times of a refractive index of a
  • DOC cladding of the nanowires Preferably a number density of the nanowires is at most about 1.8/ ⁇ 2 .
  • the nanowire array can be fabricated using a method comprising: (a) coating the substrate with a resist layer; (b) generating a pattern of dots in the resist layer using a lithography technique; (c) developing the pattern in the resist layer; (d) depositing a mask layer; (e) lifting off the resist layer; (f) forming the nanowires by dry etching the substrate; (g) optionally removing the mask player; wherein shapes and sizes of the dots determine the cross-sectional shapes and sizes of the nanowires.
  • the nanowire array can be used as a photodetector, a submicron color filter, a static color display or a dynamic color display.
  • Fig. 1 A shows a perspective schematic of a nanowire array.
  • Fig. IB shows a cross sectional schematic of the nanowire array of Fig. 1A.
  • Figs. 2A-2D are SEM images of an exemplary nanowire array.
  • Fig. 3 A shows measured reflectance spectra of nanowire arrays with nanowires of a series of different radii.
  • Fig. 3B shows simulated reflectance spectra of the nanowire arrays of Fig. 3 A.
  • Fig. 3C shows dip positions in measured and simulated reflectance spectra of nanowire arrays, as functions of the radii of the nanowires thereon.
  • Fig. 4A-4C show a major transverse component of the Hij mode at different wavelengths, near a nanowire in an nanowire array.
  • Fig. 4D shows a schematic illustration of possible pathways of white light normally incident on the nanowire array.
  • Fig. 5A shows simulated effective refractive indexes (n eff ) of the Hij modes, as a function of wavelength, of three nanowire arrays with different nanowire radii.
  • Fig. 5B shows simulated absorption spectra of the nanowire arrays of Fig. 5 A.
  • FIG. 5C compares a simulated absorption spectrum of the substrate in a nanowire array, a simulated absorption spectrum of the nanowires (of 45 nm radius) in the nanowire array, and a simulated refiectance spectrum of the entire nanowire array.
  • Fig. 6 shows a schematic top view of four pixels of the dynamic color display comprising a nanowire array according to an embodiment.
  • Figs. 7A and 7B show schematics of two exemplary apparatuses for measuring reflectance spectra of the nanowire array.
  • a nanowire array comprising a substrate and a plurality of nanowires extending essentially perpendicularly from the substrate; wherein a refractive index of the nanowires is at least two times of a refractive index of a cladding of the nanowires.
  • a number density of the nanowires preferably is at most about 1.8/ ⁇ 2 .
  • a nanowire array comprises a substrate and a plurality of nanowires extending essentially perpendicularly from the substrate;
  • nanowire array is operable as a submicron color filter.
  • a "submicron color filter” as used herein means that an optical filter that allows light of certain wavelengths to pass through and optical elements in the filter are less than a micron at least in one dimension.
  • a nanowire array comprises a substrate and a plurality of nanowires extending essentially perpendicularly from the substrate;
  • the nanowires do not substantially couple.
  • substantially couple means the nanowires collectively interact with incident light such that spectral properties (e.g., reflectance spectrum) of the nanowire array are distinct from spectral properties of individual nanowire in the nanowire array.
  • the nanowires do not substantially couple means one nanowire does not affect the properties of a neighboring nanowire. For example, when the pitch of the nanowires is changed and there is no color change of the light absorbed or reflected by the nanowire, then the nanowires do not substantially couple.
  • a nanowire array comprises a substrate and a plurality of nanowires extending essentially perpendicularly from the substrate; the nanowire array does not appear black to naked eye.
  • naked eye means human visual perception that is unaided by enhancing equipment.
  • the nanowire array does not appear black to naked eye means that the reflected visible light from the nanowire is substantially zero, which could happen under certain conditions based on the nanowire length, radius and pitch, as well as the optical properties of the substrate.
  • a nanowire as used herein means a structure that has a size constrained to at most 1000 nm in two dimensions and unconstrained in the other dimension.
  • An array as used herein means a systematic arrangement of objects such as a grid.
  • the term "nanowires extending essentially perpendicularly from the substrate” as used herein means that angles between the nanowires and the substrate are from 85° to 90°.
  • Cladding as used herein means a substance surrounding the nanowires, which can be vacuum, air, water, etc.
  • a refractive index of the nanowires as used herein means a ratio of the speed of light in vacuum relative to that in the nanowires.
  • a number density of the nanowires as used herein means that an average number of nanowires per unit area of the substrate.
  • each of the nanowires in the nanowire array has an essentially uniform chemical composition from one end of the nanowire to an opposite end of the nanowire in a longitudinal direction of the nanowire.
  • chemical composition of the nanowires as used herein means the simplest whole number ratio of atoms of each element present in the nanowires.
  • the term "essentially uniform chemical composition” as used herein means that the ratio of atoms varies at most 3%, preferably at most 1%.
  • longitudinal direction of the nanowire as used herein means a direction pointing from one end of the nanowire farthest from the substrate to one end of the nanowire nearest to the substrate.
  • each of the nanowires in the nanowire array is single crystalline, multi-crystalline or amorphous. That the nanowire is single crystalline as used herein means that the crystal lattice of the entire nanowire is
  • nanowire continuous and unbroken throughout the entire nanowire, with no grain boundaries therein. That the nanowire is multi-crystalline as used herein means that the nanowire comprises grains of crystals separated by grain boundaries. That the nanowire is amorphous as used herein means that the nanowire has a disordered atomic structure.
  • the nanowires in the nanowire array are composed of a semiconductor or an electrically insulating material.
  • a conductor can be a material with essentially zero band gap.
  • the electrical conductivity of a conductor is generally above 10 3 S/cm.
  • a semiconductor can be a material with a finite band gap upto about 3 eV and general has an electrical conductivity in the range of 10 3 to 10 8 S/cm.
  • An electrically insulating material can be a material with a band gap greater than about 3 eV and generally has an electrical conductivity below 10 8 S/cm.
  • the nanowires in the nanowire array comprise one or more materials selected from the group consisting of Si, Ge, GaN, GaAs, Si0 2 ,
  • radii of the nanowires in the nanowire array are from 10 to 1000 nm; lengths of the nanowires are from 0.01 to 10 ⁇ .
  • the nanowires and the substrate in the nanowire array have substantially the same chemical composition.
  • standard chemical composition as used herein means that the substrate and the nanowires are identical materials.
  • substantially same here means the chemical composition differs by no more than 3%, preferably by no more than 1%.
  • the nanowires and the substrate in the nanowire array are single crystalline and the lattices of the nanowires and the lattice of the substrate are continuous at interfaces therebetween. Namely, there is no grain boundary at the interfaces between the nanowires and the substrate.
  • the nanowires in the nanowire array are arranged in a predetermined pattern such as a rectangular grid, a square grid, concentric circle, hexagonal grid.
  • a distance of a nanowire to a nearest neighbor of the nanowire along a direction parallel to the substrate is at least 800 nm, preferably at most 10000 nm.
  • a reflectance spectrum of the nanowire array has a dip; the dip position shifts to shorter wavelength with decreasing radii of the nanowires; and the dip position is independent from a distance of a nanowire to a nearest neighbor of the nanowire along a direction parallel to the substrate.
  • a reflectance spectrum as used herein means a ratio of the intensity of reflected light at a certain wavelength to the intensity of incident light at the same wavelength, as a function of wavelength.
  • a “dip” in a reflectance spectrum as used herein means that a region in the reflectance spectrum wherein the reflectance is smaller than the reflectance in surrounding regions of the reflectance spectrum.
  • the "dip position” as used herein means the wavelength in the dip at which the reflectance is a minimum.
  • a reflectance spectrum of the nanowire array is independent from incident angles of illumination.
  • an incident angle as used herein means the angle between a ray of light incident on the substrate and the line perpendicular to the substrate at the point of incidence.
  • a method of fabricating the nanowire array comprises: (a) coating the substrate with a resist layer; (b) generating a pattern of dots in the resist layer using a lithography technique; (c) developing the pattern in the resist layer; (d) depositing a mask layer; (e) lifting off the resist layer; (f) forming the nanowires by dry etching the substrate; (g) optionally removing the mask player; wherein shapes and sizes of the dots determine the cross-sectional shapes and sizes of the nanowires.
  • a resist layer as used herein means a thin layer used to transfer a pattern to the substrate which the resist layer is deposited upon.
  • a resist layer can be patterned via lithography to form a (sub)micrometer-scale, temporary mask that protects selected areas of the underlying substrate during subsequent processing steps.
  • the resist is generally proprietary mixtures of a polymer or its precursor and other small molecules (e.g. photoacid generators) that have been
  • a lithography technique can be photolithography, e-beam lithography, holographic lithography.
  • Photolithography is a process used in microfabrication to selectively remove parts of a thin film or the bulk of a substrate. It uses light to transfer a geometric pattern from a photo mask to a light-sensitive chemical photo resist, or simply "resist," on the substrate. A series of chemical treatments then engraves the exposure pattern into the material underneath the photo resist. In complex integrated circuits, for example a modern CMOS, a wafer will go through the photolithographic cycle up to 50 times.
  • E-beam lithography is the practice of scanning a beam of electrons in a patterned fashion across a surface covered with a film (called the resist), ("exposing" the resist) and of selectively removing either exposed or non-exposed regions of the resist (“developing”).
  • the purpose, as with photolithography, is to create very small structures in the resist that can subsequently be transferred to the substrate material, often by etching. It was developed for manufacturing integrated circuits, and is also used for creating nanotechnology artifacts.
  • Holographic lithography also known as Interference lithography
  • the basic principle is the same as in interferometry or holography.
  • An interference pattern between two or more coherent light waves is set up and recorded in a recording layer (photoresist).
  • This interference pattern consists of a periodic series of fringes representing intensity minima and maxima.
  • a photoresist pattern corresponding to the periodic intensity pattern emerges.
  • a mask layer as used herein means a layer that protects an underlying portion of the substrate from being etched.
  • “Dry etching” as used herein means an etching technique without using a liquid etchant.
  • a method using the nanowire array 1 as a photodetector comprises: shining light on the nanowire array; measuring photocurrent on the nanowires; measuring photocurrent on the substrate; comparing the
  • a photodetector as used herein means a sensor of light.
  • a method using the nanowire array as a static color display comprises: determining locations and radii of the nano wires from an image to be displayed; fabricating the nanowires with the determined radii at the determined locations on the substrate; shining white light on the nanowire array.
  • a dynamic color display comprises the nanowire array, an array of independently addressable white light sources on a side of the substrate opposite the nanowires, wherein each white light source corresponds to and is aligned in the substrate plane with one of the nanowires.
  • Independently addressable white light sources as used herein mean that each source can be controlled, adjusted, turned on or off, independently from other sources.
  • White light as used herein means a combination of visible light of different wavelengths in equal proportions.
  • the white light sources in the dynamic color display are white LEDs.
  • LEDs are also known as light-emitting diodes.
  • a first group of the nanowires have a first radius
  • a second group of the nanowires have a second radius
  • a third group of the nanowires have a third radius
  • the first group of the nanowires only allow red light to pass
  • the second group of the nanowires only allow green light to pass
  • the third group of the nanowires only allow blue light to pass.
  • a submicron color filter comprising the nanowire array, wherein each nanowire is placed on a photodetector, wherein only incident light with wavelengths in a dip of a reflectance spectrum of each nanowire is allowed reach the photodetector below.
  • a method using the submicron color filter comprises shining white light on the nanowire array, detecting transmitted light below the nanowires.
  • a ratio of a radius of the nanowires to a pitch of the nanowires is at most 0.5.
  • Figs. 1A and IB show schematics of a nanowire array 100, according to an embodiment.
  • the nanowire array 100 comprises a substrate 110 and a plurality of nanowires 120 extending essentially vertically from the substrate 110 (e.g. angles between the nanowires 120 and the substrate 110 are from 85° to 90°).
  • Each nanowire 120 preferably has uniform chemical composition along its entire length.
  • Each nanowire 120 is single crystalline, multi-crystalline or amorphous.
  • the nanowires 120 preferably are made of a suitable semiconductor or an electrically insulating materials, examples of which include Si, Ge, GaN, GaAs, Si02, Si 3 N 4 , etc.
  • a ratio of the refractive index (i.e., refractive index contrast) of the nanowires 120 and the refractive index of a cladding 130 (i.e., materials surround the nanowires 120) is preferably at least 2, more preferably at least 3.
  • Radii of the nanowires 120 preferably are from 10 to 1000 nm, more preferably from 20 to 80 nm, most preferably from 45 to 75 nm.
  • Lengths of the nanowires 120 are preferably from 0.01 to 10 ⁇ , more preferably 0.1 to 5 ⁇ .
  • the nanowires 120 and the substrate 110 preferably have substantially the same chemical composition. Crystal lattices of the nanowires 120 and the substrate 110, if both are single crystalline, are preferably continuous at interfaces therebetween.
  • the nanowires 120 can have the same or different shape and size.
  • the nanowires 120 can be arranged in any suitable pattern, examples of which include a rectangular grid, a square grid, a hexagonal grid, concentric rings, etc.
  • a distance between a nanowire 120 of the nanowire array 100 to a nearest neighbor nanowire of the nanowire array 100 along a direction parallel to the substrate is also known as "pitch" or "pitch distance".
  • a ratio of the radius of the nanowires 120 to the pitch should not be too high, i.e., preferably at most 0.5, more preferably at most 0.1.
  • the nanowires 120 substantially couple to each other (i.e., the nanowires 120 collectively interact with incident light such that spectral properties (e.g., reflectance spectrum) of the nanowire array 100 are distinct from spectral properties of individual nanowire 120 in the nanowire array 100) and the nanowire array 100 appears black to naked eyes and cannot function as color filters or displays.
  • the number density of the nanowires 120 average
  • the pitch of the nanowires 120 is at least 500 nm.
  • Figs. 2A-2D show exemplary scanning electron microscope (SEM) images of the nanowire array 100.
  • SEM scanning electron microscope
  • Fig. 3 A shows measured reflectance spectra of five nanowire arrays 100, each of which consists 10,000 nanowires 120 consisting of silicon arranged in a 100 ⁇ ⁇ 100 ⁇ square grid on the substrate 110 consisting of silicon, wherein the pitch of these nanowire arrays 100 and the length of the nanowires 120 are about 1 ⁇ .
  • These five nanowire arrays 100 are identical except that the nanowires 120 thereof have uniform radii of 45 nm, 50 nm, 55 nm, 60 nm, 65 nm and 70 nm, respectively.
  • these nanowire arrays 100 Under white light illumination, these nanowire arrays 100 appear to be different colors (e.g., red, green, blue, cyan, etc.) to naked eyes.
  • the reflectance spectrum of each of these nanowire arrays 100 shows one dip, i.e., incident light at wavelengths within the dip is reflected at a lesser proportion compared to incident light at wavelengths outside the dip .
  • Positions of the dip dictates the apparent colors of the nanowire arrays 100. For example, if the position of the dip is between 700 and 635 nm, the nanowire array 100 appears cyan; if the position of the dip is between 560 and 490 nm, the nanowire array 100 appears magenta; if the position of the dip is between 490 and 450 nm, the nanowire 100 appears yellow.
  • Position of the dip progressively shifts to shorter wavelength from about 770 nm in the nanowire array 100 with the largest nanowires 120 (70 nm in radius) to about 550 nm in the nanowire array 100 with the smallest nanowires 120 (45 nm in radius).
  • the positions of the dips in these five nanowire arrays 100 range across the entire visible spectrum.
  • the position of the dip is independent from the pitch of the nanowire array 100, which indicates that the dips are not due to diffractive or coupling effects. Although diffractive and coupling effects are not required, the nanowire array 100 can function when such effects are present.
  • the nanowire array 100 preferably has a pitch greater than 800 nm so that
  • Fig. 3A also illustrates that magnitudes of the dips increase with the positions of the dips in wavelength, due to strong material dispersion of the substrate material above its bandgap (i.e., the refractive index of the substrate 110 increases at wavelengths above the bandgap of the material thereof while the effective refractive index of a guided mode in the nanowires 120 remains close to the refractive index of air, which leads to higher refractive index contrast between the guided mode and the substrate 110 and thus stronger reflectance in the dip, i.e., smaller magnitude of the dip, at shorter wavelengths).
  • more than one dip may be present in its reflectance spectrum and the nanowire array may appear in a combination of colors.
  • the reflectance spectra can be measured with focused or collimated incident illumination.
  • reflected light is collected by the same objective lens 830 and partially refiected by a beam splitter 820 to a spectrometer 850.
  • An iris 840 is used at the image plane of the objective lens 830 to reject any light other than light reflected by the nanowire array 100.
  • incident white light from a light source 815 is collimated by a lens 835 and directed to the nanowire array 100 through a beam splitter 825; reflected light is collected by a 10 x objective lens 865 to a spectrometer 855.
  • An iris 845 is used at the image plane of the objective lens 865 to reject any light other than light reflected by the nanowire array 100.
  • a silver mirror can used to measure absolute intensity of reflected light, which is used to calculate (i.e., normalize) the reflectance spectra.
  • the reflectance spectra are found to be essentially independent from the incident angle, which indicates that the reflectance spectra are dominated by coupling dynamics between normal component of the incident light and the nanowire array 100.
  • Fig. 3B shows simulated reflectance spectra of the five nanowire arrays 100 in Fig. 3A using the finite difference time domain (FDTD) method.
  • the FDTD method is a method of numerically simulating propagation of light in a structure and can be used to predict detailed characteristics of the propagation.
  • Lumerical's (Lumerical Solutions, Inc.) FDTD and MODE solvers were used to perform the simulation. Two dimensional models were constructed in MODE solver by simply specifying nanowire radius, pitch and material properties. A periodic boundary condition is then imposed in the substrate plane. These modes were used to study the evolution of the fundamental mode of the nano wires 120 as a function of wavelength. Full three dimensional models were constructed in Lumerical's FDTD solver by specifying complete nanowire geometry along with pitch and material properties. Periodic boundary conditions in the substrate plane and absorbing boundary conditions along the z axis (normal direction of the substrate 110) were imposed. A plane wave pulse source of the appropriate bandwidth was launched along the z axis and monitors placed to compute the total absorbed, transmitted and reflected fluxes as a function of wavelength. The nano wires 120 and the substrate 110 were assumed to be silicon in the simulation.
  • Fig. 3C shows the positions of the dips as a function of radii of the nanowires 120 in both of the measured and simulated reflectance spectra, which shows an essentially linear dependence on the nanowire radii.
  • the essentially linear dependence indicates a strong correlation or agreement between the measured and simulated reflectance spectra.
  • Wavelength selective reflection of the nanowire array 100 as shown in Figs. 3A and 3B originates from strong wavelength dependence of field distribution of the fundamental guided mode (HEij mode) of each nanowire 120.
  • the fundamental guided mode as used herein means the guided mode with the lowest frequency.
  • the guided mode of a nanowire 120 as used herein means a mode whose field decays monotonically in the transverse direction (directions parallel to the substrate 110) everywhere external to the nanowire 120 and which does not lose power to radiation.
  • Symmetry prevents efficient interaction between the nanowire 120 and other guided mode, and the nanowire 120 is too small to support higher order HEi, m modes (guided
  • Figs. 4A-4C show a major transverse component (e.g. E y ) (a field component perpendicular to the direction of propagation of the mode) of the Hij mode at different wavelengths.
  • E y a major transverse component perpendicular to the direction of propagation of the mode
  • a transverse field that is partially contained in the nanowire 120 and partially extends into the cladding 130, as shown in Fig. 4A. Incident light at these wavelengths can efficiently excite the HEij mode and be guided by the nanowire 120 to the substrate 110 or be absorbed by the nanowire 120.
  • the large refractive index contrast between the nanowire 120 and the cladding leads to non-negligible longitudinal field component (E z ) (i.e., field component parallel to the direction of propagation of the mode) which has significant overlap with the nanowire 120; since the modal absorption is proportional to the spatial density of electromagnetic energy, which includes E z , incident light at these wavelengths can both efficiently couple to (i.e., a significant portion of the incident light propagates inside the nanowire 120) and be absorbed by the nanowire 120.
  • E z longitudinal field component
  • the field distribution of the HEij mode of each nanowire 120 is characterized by a transverse field essentially confined in the nanowire 120 due to large refractive index contrast between the nanowire 120 and the cladding, as shown in Fig. 4B. Incident light at these wavelengths cannot efficiently excite the HEij mode and thus cannot be efficiently guided or absorbed by the nanowire 120; incident light at these wavelengths is substantially reflected by an interface of the substrate 110 and the cladding 130. At wavelengths well above the dip of the reflectance spectrum, the field distribution of the HEi j mode of each nanowire 120 is
  • Fig. 4C a transverse field essentially expelled from the nanowire 120, as shown in Fig. 4C.
  • Incident light at these wavelengths can efficiently excite the HEij mode but the HEij mode at these wavelengths cannot be efficiently guided or absorbed by the nanowire 120; incident light at these wavelengths is substantially reflected by an interface of the substrate 110 and the cladding.
  • Fig. 4D shows schematic illustration of possible pathways of white light normally incident on the nanowire array 100. Light of wavelengths beyond the dip in the reflectance spectrum is reflected by the substrate 110; light of wavelengths in the dip is guided by the nanowire 120 to transmitted through the substrate 110 or absorbed by the nanowire 120.
  • Fig. 5A shows simulated effective refractive indexes (n eff ) of the Hij modes, as a function of wavelength, of three nanowire arrays 100 with different nanowire radii (45 nm, 55 nm and 70 nm in traces 501, 502 and 503, respectively), wherein n eff are obtained by the FDTD method over a 1 ⁇ by 1 ⁇ unit cell under periodic boundary conditions, the material of the nanowire arrays 100 is assumed to be silicon, the cladding is assumed to be air, and length of the nano wires 120 is assumed to be 1 ⁇ .
  • a periodic boundary condition is a set of boundary conditions that are often used to model a large system as an infinite periodic tile of a small unit cell.
  • n eff increases sharply and approaches ns; (refractive index of silicon) for wavelengths shorter than the corresponding dip position in Fig. 3 A.
  • the dip occurs where n eff asymptotes to n air (refractive index of air).
  • n eff as a function of wavelength also called a dispersion curve
  • Fig. 5B shows simulated absorption spectra (obtained by the FDTD method) of the nanowire arrays 100 of Fig. 5 A (traces 511, 512 and 513 corresponding to nanowire arrays with nano wires of 45 nm, 55 nm and 70 nm radii, respectively).
  • blue light ⁇ 500 nm
  • Fig. 5B shows simulated absorption spectra (obtained by the FDTD method) of the nanowire arrays 100 of Fig. 5 A (traces 511, 512 and 513 corresponding to nanowire arrays with nano wires of 45 nm, 55 nm and 70 nm radii, respectively).
  • blue light ⁇ 500 nm
  • the Hi j mode can be absorbed in a 1 ⁇ length of the nanowire.
  • 5C compares a simulated absorption spectrum 521 of the substrate 110 in the nanowire array 100 with nanowires 120 of 45 nm radius (corresponding to traces 501 and 511), a simulated absorption spectrum 523 of the nanowires 120 of 45 nm radius in this nanowire array 100, and a simulated reflectance spectrum 522 of this nanowire array 100.
  • the dip in the reflectance spectrum 522 is slightly redshifted relative to the peak in the absorption spectrum 523 of the nanowires 120, which indicates that the long wavelength edge of the dip arises more from coupling to the substrate 110. Nonetheless, this shows that the guided light is in fact absorbed in the nanowires 120, and so the shape of the reflectance spectrum 523 and the amount of light absorbed in the nanowires 120 can be controlled by altering the length thereof.
  • the light absorbed by the substrate 110 can be enhanced or diminished by the nano wires 120 relative to light absorption of a planar substrate, depending on whether the nanowires 120 absorb or merely couple to the substrate 110.
  • the fact that the filtering characteristics of the nanowire array 100 are related to absorption in different parts thereof can lead to useful applications in optoelectronic devices.
  • a method of fabricating the nanowire array 100 includes (a) coating the substrate 110 with a resist layer (e.g. e-beam resist, photo resist, etc.); (b) generating a pattern of dots in the resist layer using a lithography technique (e.g. photolithography, e-beam lithography, holographic lithography, etc.); (c) developing the pattern in the resist layer; (d) depositing a mask layer (e.g.
  • a resist layer e.g. e-beam resist, photo resist, etc.
  • a lithography technique e.g. photolithography, e-beam lithography, holographic lithography, etc.
  • the resist can be poly(methyl methacrylate) (available from MicroChem located in Newton, MA).
  • the mask layer can be aluminum deposited by a suitable technique such as e-beam evaporation, thermal evaporation, sputtering, etc. The mask layer can be about 40 nm thick.
  • the substrate 110 can be a single crystalline silicon wafer.
  • Dry etching can be conducted in an inductively coupled plasma-reactive ion etcher (such as those available from Surface Technology Systems, located at Redwood City, CA).
  • An exemplary dry etching process includes alternating etch and deposition steps at room temperature, wherein 60 seem of SF 6 and 160 seem of C 4 F 8 gases were used therein, respectively.
  • the mask layer can be removed using a suitable etchant (e.g. Type A aluminum etchant available from Transene Company Inc. located in Danvers, MA) or solvent (e.g. acid, base, or organic solvent).
  • SEM images can be taken in an SEM such as Zeiss Ultra55 available from Carl Zeiss NTS located at Peabody, MA.
  • a method using the nanowire array 100 as a photodetector comprises: shining light on the nanowire array 100; measuring photocurrent on the nanowires 120;
  • the nanowire array 100 can also be used as a submicron color filter.
  • each of the nanowires 120 in the nanowire array 100 can be placed on a photodetector. Only incident light with wavelengths in the dip of the reflectance
  • a method using the nanowire array 100 as a submicron color filter comprises shining white light on the nanowire array 100, detecting transmitted light below the nanowires 120.
  • a method using the nanowire array 100 as a static color display comprises: determining locations and radii of nanowires from an image to be displayed;
  • the nanowire array 100 can display a color image under white light illumination.
  • the nanowire array can also be used in a dynamic color display.
  • the word "dynamic” here means that the display can display different images at different times.
  • the dynamic color display according to one embodiment, comprises the nanowire array 100, an array of independently addressable white light sources on a side of the substrate 110 opposite the nanowires 120, wherein each white light source
  • Nanowires 715, 725, 735 and 745 respectively correspond to and are aligned with white light sources 710, 720, 730 and 740.
  • the white light sources can be white LEDs.
  • the nanowire 715 has a radius of about 45 nm and only allows red light to pass.
  • the nanowires 725 and 735 have a radius of about 60 nm and only allows green light to pass.
  • the nanowire 745 has a radius of about 70 nm and only allows blue light to pass.
  • the independently addressable white light sources can be replaced by a scanning white light beam.

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Abstract

La présente invention concerne un réseau de nanofils comprenant un substrat et une pluralité de nanofils s'étendant essentiellement verticalement à partir du substrat. Chacun des nanofils présente une composition chimique uniforme sur toute sa longueur ; un indice de réfraction des nanofils est au moins deux fois supérieur à celui d'un placage des nanofils. Le réseau de nanofils est utile en tant que photodétecteur, filtre coloré sous-micronique, afficheur couleur statique ou afficheur couleur dynamique.
PCT/US2011/047189 2011-05-20 2011-08-10 Propriétés d'absorption et de filtrage de lumière de nanofils semi-conducteurs orientés verticalement WO2013130027A1 (fr)

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