WO2025085123A2 - Nitrure de bore hexagonal cristallin avec enrichissement en isotope d'azote -15 - Google Patents

Nitrure de bore hexagonal cristallin avec enrichissement en isotope d'azote -15 Download PDF

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Publication number
WO2025085123A2
WO2025085123A2 PCT/US2024/034488 US2024034488W WO2025085123A2 WO 2025085123 A2 WO2025085123 A2 WO 2025085123A2 US 2024034488 W US2024034488 W US 2024034488W WO 2025085123 A2 WO2025085123 A2 WO 2025085123A2
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boron
boron nitride
composition
mixture
hexagonal boron
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WO2025085123A3 (fr
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James H. Edgar
Eli. M. JANZEN
Hannah E. SCHUTTE
Thomas Poirier
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Kansas State University
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Kansas State University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
    • C01B21/0641—Preparation by direct nitridation of elemental boron

Definitions

  • Embodiments according to the present invention are directed toward crystalline hexagonal boron nitride (hBN) enriched with the nitrogen- 15 isotope and methods of making the same.
  • hBN hexagonal boron nitride
  • Hexagonal boron nitride is the second most important two- dimensional material after graphite and its monolayer derivative, graphene. Although hBN and graphite have similar crystal structures and lattice parameters, their properties are quite different. Graphite is electrically conductive; hBN is an electrical insulator. Graphite is opaque; hBN is optically transparent from deep ultraviolet through the infrared wavelengths. Graphite reacts with oxygen and air at low temperatures, while hBN is chemically inert. Thus, in many ways, the properties of hBN and graphite are complimentary.
  • crystalline hBN are advantageous for a wide range of nanophotonic, electronic, and quantum devices. Because its optical properties are hyperbolic, it can compress infrared light to extremely small volumes, through the use of hyperbolic phonon polaritons. This is useful in nanophotonics as it increases lightmatter interactions, and thereby chemical and biological sensing. It also enables much higher image resolutions, hyperlensing, than is possible using the source free-space light. hBN analogue switches with high power handling and switching speeds have shown promise for high frequency devices, while hBN-based memristors integrated into CMOS devices for computation had superior endurance compared to more mature technologies. hBN is appealing for quantum devices due to its ability to host bright, stable, single photon emitters, some of which are magnetically addressable.
  • Hexagonal boron nitride has been a commercial product for over 60 years as amorphous fine powders and very fine grain ( ⁇ 20 micron) solids.
  • new interest in crystalline (ideally single crystals) hBN for potential electronic, optoelectronic, nanophotonic and quantum devices has accelerated over the past twenty years. This is due in part to crystalline hBN’s unique optical properties. It has the potential to be an excellent sensor of specific organic molecules since its infrared frequency range matches those of the vibrational properties of specific organic ligands.
  • hBN is also appealing for quantum devices based on defects that emit at visible light frequencies that are sensitive to magnetic fields.
  • hBN crystalline flakes that are enriched in either the boron- 10 (h 10 BN) or boron- 11 (h n BN) isotope.
  • Most hBN has the natural distribution of boron isotopes, which is 20% 10 B and 80% n B.
  • isotropically pure boron-10 or boron-11 in the synthesis of hBN crystalline hBN flakes can be produced that have superior infrared optical properties, which render the flake preferred for use in nanophotonic devices.
  • a hexagonal boron nitride composition enriched in nitrogen-15 isotope comprising at least 50%, by weight of h 10 B 13 N, h n B 1;, N, or a mixture thereof.
  • a method of producing a hexagonal boron nitride composition enriched in nitrogen- 15 isotope comprises providing a source of boron and heating the source of boron to a temperature of 1550°C or greater under an N2/H2 atmosphere comprising 15 N2 gas and H2 gas to create a composition comprising boron nitride.
  • the composition comprising boron nitride is cooled and single crystals of the hexagonal boron nitride are precipitated. The single crystals of the hexagonal boron nitride are recovered from the composition.
  • the devices comprising the hexagonal boron nitride composition as described herein are provided.
  • the devices may include an optoelectronic device, a nanophotonic device, or a quantum device.
  • Figure 1 is an optical micrograph of a crystalline hBN flake produced by precipitation from a molten metal solution.
  • Fig. 2 is a temperature profile of a two-part process used to produce isotopically-controlled hBN crystals.
  • Fig. 3 is an image of the surface of an Ni-Cr-B ingot after precipitation of hB 15 N crystals on the surface of the ingot.
  • Fig. 4 is a micrograph of an h 10 B 15 N single crystal mechanically exfoliated from a solidified ingot.
  • hBN The properties of hBN can be varied by controlling its concentrations of boron isotopes.
  • boron isotopes There are two stable boron isotopes, which are naturally distributed as approximately 20% 10 B and 80% n B. These isotopes have distinctly different properties. Their nuclear spins are 3 and 3/2 for 10 B and n B respectively.
  • 10 B has one of the largest neutron capture cross section of any isotope of any element, approximately 3855 barns for neutrons with velocities of 2200 m/s. For the majority of element isotopes, the neutron capture cross section is on the order of one or less.
  • the boron isotope enrichment of hBN leads to certain characteristic distinctions. For instance, the energy band gap of hBN is slightly reduced (increased) when enriched in 10 B ( n B). Also, the E2 g peak position in the Raman spectra is shifted up from 1,366 cm' 1 for hBN with the natural distribution of boron isotopes to 1,383 cm' 1 for h 10 BN and down to 1,357 cm' 1 for h n BN. The FWHM of the E2 g peak at room temperature of the boron monoisotopic hBN is reduced to 3.0 cm' 1 from 7.5 cm' 1 for natural hBN. This reduced Raman peak width is due to less isotopic disorder.
  • the maximum peak width is predicted to occur with isotope concentrations of 65% n B and 35% 10 B.
  • the phonon lifetime for monoisotopic hBN is increased by a factor of 2.7 from h nat BN.
  • S-NOM scattering type near field optical microscopy
  • the phonon-polariton propagation length is significantly increased in monoisotopic hBN.
  • the maximum hyperbolic phonon polariton lifetimes measured is 4.2 ps with propagation lengths of 25 pm, and an eight-fold increased figure of phonon propagating merit in comparison to h nat BN.
  • the longer phonon lifetimes achieved by eliminating isotopic disorder also increases the thermal conductivity of hBN.
  • Monoisotopic hBN has also proven advantageous in several applications.
  • the longer hyperbolic phonon polariton propagation distance in isotopically enriched h 10 BN enables the production of an anomalous, concave wave front on a h 10 BN metasurface.
  • Demonstrating hyperlensing objects as small as 44 nm separated by distances of 25 nm can be resolved viaN-SOM with light with a free-space wavelength of 6.76 pm using h n BN.
  • Vibrational strong coupling between phonon polaritons in hBN and organic molecules has also been shown. This has the potential to reduce the size and enhance the sensitivity of on-chip spectroscopes.
  • the optical properties of h n BN can be changed by placing it in contact with VO2 which was changed from a dielectric to a metal by changing its temperature.
  • Further control over the properties of hBN can be achieved by changing the concentration of the nitrogen isotope in crystalline hBN.
  • Natural nitrogen is predominantly 14 N (99.6%) with a small amount of 15 N (0.4%).
  • changing the nitrogen isotopes as well as the boron isotopes offers the possibility of shifting its Reststrahlen band, to better match the infrared absorption of specific organic molecules, thus achieving sensors that are better (more sensitive at detecting specific organic compounds.
  • 14 N and 15 N have different nuclear spins, 1 and 1 respectively, which may prove important in quantum applications. Unlike 14 N, 15 N reacts with high energy protons to form carbon and an alpha particle.
  • hBN crystals can be prepared that are enriched in the nitrogen-15 isotope, both h , 0 B 15 N and h”B 15 N.
  • a hBN composition is provided in which h 10 B 13 N and/or h n B 15 N comprise the predominant hBN species.
  • the hBN composition comprises at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 98% by weight of h 10 B 13 N, h n B 1:, N, or a mixture thereof.
  • the hBN composition is depleted in h 10 B 14 N and/or h n B 14 N.
  • the hBN composition comprises hBN flakes of single-crystal hBN.
  • hB 15 N there are at least two potential advantages to this 15 N enriched material, hB 15 N.
  • hB 13 N Another application in which hB 13 N can be useful is micro nuclear magnetic resonance (NMR) spectroscopy.
  • NMR micro nuclear magnetic resonance
  • hB 15 N NMR with unprecedented high resolution can be possible.
  • hB 15 N is an alternative to the current leading contender for micro-NMR, which is diamond with the nitrogenvacancy (NV) center.
  • the present invention pertains to a static process for synthesis of hB 15 N, in which the furnace can be filled once with the 15 N enriched gas, and not changed over course of the synthesis process.
  • hB 15 N crystalline flakes are produced by precipitation from molten metal solutions.
  • a source of boron is provided and heated to a temperature sufficient to cause the boron to dissolve within one or more metal solvents.
  • the molten metal solution is prepared by heating the source of boron to at temperature of 1550°C or greater under a nitrogen/hydrogen atmosphere comprising 15 N2 gas and H2 gas to create a composition comprising boron nitride.
  • the N2/H2 atmosphere comprises isotopically pure 15 N2 gas (i.e., at least 95%, at least 98%, or at least 99% pure 15 N2).
  • the hydrogen concentration of the N2/H2 atmosphere is no greater than 10% so as to avoid surface etching of the hBN crystals.
  • the N2/H2 atmosphere a hydrogen to nitrogen molar ratio of from 0.7 to 1.2, or from 0.8 to 1.1, or from 0.9 to 1.
  • the N2/H2 atmosphere is charged to a furnace containing the source of boron and remains static (i.e., there is no continuous flow of N2) throughout the heating step.
  • the source of boron may be substantially monoisotopic. That is, the source of boron is enriched to nearly 100% 10 B or 100% n B (i.e., greater than 98%, or greater than 99%); however, this need not always be the case and a mixture of boron isotopes can be provided.
  • the source of boron can be formed by mixing a boron powder comprising isotopically pure 10 B or n B, or a mixture of 10 B and n B with nickel and chromium powders to form a boron-containing mixture.
  • iron can be substituted for the nickel in forming the molten metal solution.
  • the mass ratio of nickel or iron to boron, and chromium to boron is from 10: 1 to 50: 1, from 15: 1 to 40:1, 20: 1 to 30: 1, or about 24:1.
  • the mass ratio of nickel or iron to chromium is from 0.1 : 1 to 10:1, from 0.25: 1 to 4: 1, from 0.5: 1 to 2: 1, or about 1 : 1. Accordingly, a preferred mass ratio of nickel or iron to chromium to boron in the boron-containing mixture is about 12: 12: 1.
  • the boron-containing mixture is heated under an argon/hydrogen atmosphere to 1550°C or greater to form the metal solution.
  • the ratio of argon to hydrogen in the argon/hydrogen atmosphere is about 93 to 7.
  • the pressure of the atmosphere within the furnace containing the boron- containing mixture is 600 to 1200 torr, or 700 to 1 100 torr, 800 to 1000 torr, or about 850 torr.
  • the heating step can be carried out for a period of time of from 2 hr. to 4 days, to 6 hr. to 3 days, from 12 hr. to 2 days, or about 24 hr.
  • the boron-containing mixture is then cooled to form a homogeneous boron- metal ingot.
  • the boron-metal ingot comprises the source of boron from which the hB 15 N is synthesized.
  • the composition comprised of boron nitride and metals is cooled thereby precipitating single crystals of the hB 1:> N.
  • the cooling step comprises slowly cooling the composition comprising boron nitride at a rate of 1 -4°C/hr. to a temperature of 1500°C to precipitate the crystals of hB 15 N.
  • the precipitated crystals of hB 15 N are recovered from the composition.
  • the recovery step comprises recovering an ingot comprising the source of boron having a layer of the single crystals of the hexagonal boron nitride contained thereon.
  • the recovery step can further comprise mechanically exfoliating free-standing hexagonal boron nitride flakes from the ingot comprising the source of boron.
  • the hBN crystals made according to any embodiment of the present invention can be used in fabricating various electronic devices.
  • the electronic device comprises an optoelectronic device, a nanophotonic device, or a quantum device.
  • the electronic device may comprise an analogue switch or a memristor.
  • the device may comprise a sensor for detecting one or more organic molecules.
  • This step is to create a homogenous ingot and remove some of the impurities brought into the system by the source materials. Thus, no nitrogen is used because the formation of hBN interferes with thorough mixing of the components. Hydrogen, diluted with argon for safety, is included in this step to help remove oxygen impurities by reacting with residual oxygen to form water vapor and carry it out of the system.
  • the ingot produced in the first step is placed in the same furnace purged of air and backfilled with a mixture isotopically pure 15 N2 gas and hydrogen.
  • the gas mixture comprised between 8%-9% hydrogen and 91%-92% nitrogen. Due to the high cost of 15 N2 gas, it was not continuously flowed through the system and was instead sealed off once the pressure rose to atmospheric pressure. Then the furnace was heated to 1550°C, held there for 24 hours, and slowly cooled at l°C/hr. to 1500°C to carefully precipitate hBN single crystals as illustrated by the solid line in Fig. 2.
  • the alumina boat contains a solidified metal ingot with a layer of hBN crystals covering its top surface.
  • Fig. 3 is an image of the surface of the ingot surface comprising hB 15 N crystals. Mechanical exfoliation of the hBN from the ingot produces free-standing hBN flakes, which are shown in Fig. 4.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Luminescent Compositions (AREA)

Abstract

L'invention concerne une composition comprenant du nitrure de bore hexagonal cristallin (hBN) enrichi en isotope d'azote 15 et son procédé de préparation. Le hBN enrichi en 15N peut être utilisé dans la fabrication de dispositifs électroniques comprenant des capteurs quantiques de contrainte et de champs magnétiques, et des capteurs chimiques infrarouges.
PCT/US2024/034488 2023-06-20 2024-06-18 Nitrure de bore hexagonal cristallin avec enrichissement en isotope d'azote -15 Ceased WO2025085123A2 (fr)

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US20100218801A1 (en) * 2008-07-08 2010-09-02 Chien-Min Sung Graphene and Hexagonal Boron Nitride Planes and Associated Methods
DE102012104049A1 (de) * 2012-05-09 2013-11-28 Esk Ceramics Gmbh & Co. Kg Bornitrid-Agglomerate, Verfahren zu deren Herstellung und deren Verwendung
CN109791876B (zh) * 2016-05-12 2023-08-15 环球晶圆股份有限公司 在硅基电介质上直接形成六方氮化硼
GB201612419D0 (en) * 2016-07-18 2016-08-31 Cambridge Entpr Ltd A scalable quantum-confined device
WO2020155737A1 (fr) * 2019-01-29 2020-08-06 齐鲁工业大学 Poudre composite de nanofeuille de nitrure de bore hexagonal revêtue de nickel, sa préparation et matériau de coupe en céramique composite haute performance
EP3723122B1 (fr) * 2019-04-10 2023-02-15 AT & S Austria Technologie & Systemtechnik Aktiengesellschaft Support de composant comprenant une structure à double couche
US11624127B2 (en) * 2019-10-29 2023-04-11 Samsung Electronics Co., Ltd. Boron nitride layer, apparatus including the same, and method of fabricating the boron nitride layer

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