WO2019200599A1 - Porous titanium nitride single crystal material, preparation method therefor and use thereof - Google Patents

Porous titanium nitride single crystal material, preparation method therefor and use thereof Download PDF

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WO2019200599A1
WO2019200599A1 PCT/CN2018/083869 CN2018083869W WO2019200599A1 WO 2019200599 A1 WO2019200599 A1 WO 2019200599A1 CN 2018083869 W CN2018083869 W CN 2018083869W WO 2019200599 A1 WO2019200599 A1 WO 2019200599A1
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single crystal
titanium nitride
nitride single
porous titanium
slm
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PCT/CN2018/083869
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French (fr)
Chinese (zh)
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谢奎
林国明
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中国科学院福建物质结构研究所
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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
    • C01B21/076—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 titanium or zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/18—Epitaxial-layer growth characterised by the substrate
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/38—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C30B29/64—Flat crystals, e.g. plates, strips or discs
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices

Definitions

  • the present application relates to a porous titanium nitride single crystal material, a preparation method and application thereof, and belongs to the field of inorganic materials.
  • Titanium nitride is an excellent and stable electronic conductor with high melting point and high hardness.
  • the Ti-N bond moiety contains the nature of a covalent bond, while the trivalent ion of titanium provides a free electron that acts as a carrier to exhibit the properties of the electron conductor.
  • the trivalent ions of titanium on the surface of titanium nitride are generally considered to be active atoms.
  • Titanium nitride nanoparticles which can serve as catalyst and catalyst support electrodes in the field of electrocatalysis and electrochemical energy storage systems.
  • the porous titanium nitride electrodes currently prepared are all based on amorphous or polycrystalline titanium nitride powders, with numerous grain boundaries and uncertain end atoms on the surface.
  • the main methods for preparing titanium nitride include chemical vapor deposition (CVD), physical vapor deposition (PVD), plasma chemical vapor deposition (PCVD), ion beam assisted deposition (IBAD), and hollow cathode ion plating (HCD). ), plasma immersion ion implantation (PIII), laser nitridation state (LN), and the like.
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • PCVD plasma chemical vapor deposition
  • IBAD ion beam assisted deposition
  • HCD hollow cathode ion plating
  • PIII plasma immersion ion implantation
  • LN laser nitridation state
  • the titanium nitride single crystal which can be produced has only a micron size or a single crystal thin film of a micron thickness. How to realize large-sized titanium nitride single crystal is still a scientific problem.
  • Metallic porous solid materials have important applications in photocatalytic and electrochemical energy storage.
  • the large porosity provides a large specific surface area for highly efficient reactions.
  • Existing methods for preparing nanoporous materials such as use of templates, bubbling, dealloying, Kirkendall effect, and resonant osmotic shock The method is complicated, and the maximum crystal size that can be prepared is only on the order of micrometers, and there is a lack of a method for preparing macroscopic scale nanoporous titanium nitride single crystal.
  • a porous titanium nitride single crystal material having a porous structure having a large size.
  • the present application provides a method for preparing a nano-sized porous titanium nitride single crystal film having a large size of 100 faces, 110 faces, and 111 faces, and a self-supporting nanoporous titanium nitride crystal, which relates to a method for preparing a large-sized nanoporous single crystal crystal.
  • a method in particular a method of nitriding growth, for preparing a large-sized nanoporous titanium nitride single crystal.
  • a method for preparing a nanoporous titanium nitride single crystal film a barium titanate single crystal or a titanium dioxide single crystal substrate is placed in a high temperature ammonia-containing atmosphere, and a surface of the barium titanate single crystal or the titanium dioxide single crystal substrate is nitrided to form a nanoporous Titanium nitride.
  • a method for preparing a self-supporting nanoporous titanium nitride single crystal placing a barium titanate single crystal or a titanium dioxide single crystal substrate in a high temperature ammonia-containing atmosphere, and first nitriding the surface of the barium titanate single crystal or the titanium dioxide single crystal substrate The nanoporous titanium nitride is grown, and as the nitridation time increases, the barium titanate single crystal or the titanium dioxide single crystal substrate is completely nitrided and transformed into a self-supporting nanoporous titanium nitride single crystal.
  • the purpose of the present application is to solve the problem that the existing method for preparing a nanoporous crystal material is complicated and limited to micron-scale crystal preparation, which is disadvantageous for large-scale production and application; on the other hand, it is a titanium nitride base.
  • the device provides a high-quality and inexpensive large-size 100-, 110-, and 111-sided nanoporous titanium nitride single crystal substrate, thereby greatly improving the performance of the titanium nitride-based device.
  • the invention has the advantages of simple, low-cost and large-scale production of the nanoporous titanium nitride single crystal film with large size of 100 faces and 111 faces and the self-supporting nanoporous titanium nitride crystal.
  • the porous titanium nitride single crystal material is characterized in that the porous titanium nitride single crystal material contains pores of 10 nm to 1000 nm.
  • the porous titanium nitride single crystal material contains pores of 10 nm to 500 nm.
  • the porous titanium nitride single crystal material is a porous titanium nitride single crystal film and/or a porous titanium nitride single crystal.
  • the porous titanium nitride single crystal crystal is a self-supporting nanoporous titanium nitride crystal.
  • the surface of the porous titanium nitride single crystal thin film is at least one of a (100) plane, a (110) plane, and a (111) plane of the porous titanium nitride single crystal.
  • the porous titanium nitride single crystal material is a porous titanium nitride single crystal
  • the largest surface of the crystal is in the (100) plane, the (110) plane, and the (111) plane of the porous titanium nitride single crystal. At least one side.
  • one dimension of the largest surface of the porous titanium nitride single crystal crystal is 0.1 cm to 30 cm.
  • one dimension of the largest surface of the porous titanium nitride single crystal crystal is from 1 cm to 5 cm.
  • the porous titanium nitride single crystal crystal has a size of 0.1 cm to 30 cm;
  • the porous titanium nitride single crystal thin film has a thickness of 10 nm to 100 ⁇ m.
  • the porous titanium nitride single crystal has a size of 1 cm to 5 cm.
  • the present invention provides a method for preparing a porous titanium nitride single crystal material according to any one of the preceding claims, characterized in that it comprises at least: contacting a titanium source with a raw material gas containing ammonia gas to obtain the Porous titanium nitride single crystal material;
  • the titanium source is at least one selected from the group consisting of barium titanate single crystal materials and titanium dioxide single crystal materials.
  • the barium titanate single crystal is (100) face barium titanate crystal, (111) face barium titanate crystal or (110) face barium titanate crystal, and the titanium dioxide single crystal is (001) face titanium dioxide, ( 110) Surface titanium dioxide or (100) surface titanium dioxide.
  • the barium titanate single crystal material is in contact with the raw material gas containing ammonia gas, and is at least one of a (110) plane, a (111) plane, and a (100) plane of the barium titanate single crystal.
  • the titanium dioxide single crystal material is in contact with the raw material gas containing ammonia gas, and is at least one of a (001) plane, a (110) plane, and a (100) plane of the titanium dioxide single crystal.
  • the barium titanate single crystal material is a barium titanate single wafer; the largest surface of the barium titanate single wafer is a single crystal (100) plane, a (111) plane or a (110) plane and contains ammonia gas. Raw material gas contact.
  • the titanium dioxide single crystal material is a titanium dioxide single wafer; the surface having the largest area of the titanium dioxide single wafer is a single crystal (001) plane, a (100) plane or a (110) plane in contact with the raw material gas containing ammonia gas.
  • the temperature of the reaction is from 1173K to 1873K;
  • the pressure of the reaction is from 0.1 Torr to 1000 Torr;
  • the reaction time is from 1 min to 500 h.
  • the temperature of the reaction is from 1373 K to 1873 K.
  • the temperature of the reaction is from 1373 K to 1573 K.
  • the temperature of the reaction is from 1173K to 1373K.
  • the pressure of the reaction is from 0.1 Torr to 700 Torr;
  • the pressure of the reaction is from 10 Torr to 400 Torr.
  • reaction time is from 30 min to 20 h.
  • reaction time is from 30 min to 100 h.
  • the upper temperature limit of the reaction is selected from the group consisting of 1223K, 1273K, 1373K, 1473K, 1573K, 1673K, 1773K or 1873K; the lower limit is selected from 1173K, 1223K, 1273K, 1373K, 1473K, 1573K, 1673K or 1773K.
  • the upper time limit of the reaction is selected from 2 min, 10 min, 20 min, 50 min, 1 h, 10 h, 20 h, 50 h, 100 h, 150 h, 200 h, 300 h, 400 h or 500 h; the lower limit is selected from 1 min, 10 min, 20 min, 50 min. , 1h, 10h, 20h, 50h, 100h, 150h, 200h, 300h or 400h.
  • the upper pressure limit of the reaction is selected from the group consisting of 0.2 Torr, 0.5 Torr, 10 Torr, 20 Torr, 50 Torr, 100 Torr, 200 Torr, 300 Torr, 400 Torr, 500 Torr, 600 Torr, 700 Torr, 700 Torr, 800 Torr, 900 Torr or 1000 Torr; Torr, 0.2 Torr, 0.5 Torr, 10 Torr, 20 Torr, 50 Torr, 100 Torr, 200 Torr, 300 Torr, 400 Torr, 500 Torr, 600 Torr, 700 Torr, 800 Torr, 900 Torr or 1000 Torr.
  • the contact time of the barium titanate single crystal/titanium dioxide single crystal material with the raw material gas containing ammonia gas ranges from 1 min to 20 h. .
  • the lower limit of the time range of the barium titanate single crystal/titanium dioxide single crystal material in contact with the raw material gas containing ammonia gas is selected from the group consisting of 10 min. 20 min, 30 min, 1 h, 2 h, 3 h, 4 h, 5 h, 10 h, 15 h or 18 h; the upper limit is selected from 20 min, 30 min, 1 h, 2 h, 3 h, 4 h, 5 h, 10 h, 15 h, 18 h or 20 h.
  • the contact reaction time should satisfy that all of the barium titanate/titanium dioxide single crystal material is converted into a porous titanium nitride single crystal material.
  • the porous titanium nitride single crystal material is a porous titanium nitride single crystal
  • the barium titanate single crystal/titanium dioxide single crystal material is reacted with the ammonia gas-containing raw material gas for a reaction time of 10 to 500 hours.
  • the upper limit of the time range of the titanium nitride single crystal material in contact with the raw material gas containing ammonia gas is selected from the group consisting of 15h, 20h, and 50h. , 100h, 150h, 200h, 250h, 300h, 350h, 400h, 450h or 500h; the lower limit is selected from 10h, 15h, 20h, 50h, 100h, 150h, 200h, 250h, 300h, 350h, 400h or 450h.
  • the crystal size of the obtained porous titanium nitride single crystal crystal is equal to the size of the barium titanate single crystal/titanium dioxide single crystal material used.
  • a person skilled in the art can obtain a desired porous titanium nitride single crystal by selecting an appropriately sized barium titanate single crystal/titanium dioxide material according to actual needs.
  • the ammonia-containing feed gas includes at least one of ammonia gas, nitrogen gas, argon gas, and hydrogen gas;
  • the flow rate of ammonia gas is recorded as a
  • the flow rate of nitrogen gas is recorded as b
  • the flow rate of argon gas is recorded as c
  • the flow rate of hydrogen gas is recorded as d, which satisfies:
  • the ammonia-containing feed gas includes at least one of ammonia gas, nitrogen gas, argon gas, and hydrogen gas;
  • the flow rate of ammonia gas is recorded as a
  • the flow rate of nitrogen gas is recorded as b
  • the flow rate of argon gas is recorded as c
  • the flow rate of hydrogen gas is recorded as d, which satisfies:
  • the upper limit of the flow rate of the ammonia gas is selected from the group consisting of 0.1 SLM, 0.3 SLM, 0.5 SLM, 1 SLM, 1.5 SLM, 2 SLM, 3 SLM, 4 SLM, 5 SLM, 6 SLM, 7 SLM, 8 SLM, 9 SLM, 10 SLM, 20 SLM, 30 SLM, 40SLM, 50SLM, 60SLM, 70SLM, 80SLM, 90SLM or 100SLM; lower limit selected from 0.05SLM, 0.1SLM, 0.3SLM, 0.5SLM, 1SLM, 1.5SLM, 2SLM, 3SLM, 4SLM, 5SLM, 6SLM, 7SLM, 8SLM, 9SLM, 10SLM, 20SLM, 30SLM, 40SLM, 50SLM, 60SLM, 70SLM, 80SLM or 90SLM.
  • the upper limit of the flow range of the nitrogen gas is selected from the group consisting of 0.01 SLM, 0.1 SLM, 0.2 SLM, 0.3 SLM, 0.5 SLM, 0.8 SLM, 1 SLM, 2 SLM, 5 SLM, 10 SLM, 20 SLM, 50 SLM, 80 SLM or 100 SLM; 0SLM, 0.01SLM, 0.1SLM, 0.2SLM, 0.3SLM, 0.5SLM, 0.8SLM, 1SLM, 2SLM, 5SLM, 10SLM, 20SLM, 50SLM or 80SLM.
  • the upper limit of the flow rate of the argon gas is selected from the group consisting of 0.01 SLM, 0.1 SLM, 0.2 SLM, 0.5 SLM, 0.8 SLM, 1 SLM, 2 SLM, 5 SLM, 10 SLM, 20 SLM, 50 SLM, 80 SLM or 100 SLM; 0.01 SLM, 0.1 SLM, 0.2 SLM, 0.5 SLM, 0.8 SLM, 1 SLM, 2 SLM, 5 SLM, 10 SLM, 20 SLM, 50 SLM or 80 SLM.
  • the upper limit of the flow range of the hydrogen gas is selected from the group consisting of 0.01 SLM, 0.1 SLM, 0.2 SLM, 0.5 SLM, 0.8 SLM, 1 SLM, 2 SLM, 5 SLM, 10 SLM, 20 SLM, 50 SLM, 80 SLM or 100 SLM; the lower limit is selected from 0 SLM, 0.01 SLM, 0.1SLM, 0.2SLM, 0.5SLM, 0.8SLM, 1SLM, 2SLM, 5SLM, 10SLM, 20SLM, 50SLM or 80SLM.
  • the method comprises at least: reacting at least one of a barium titanate single crystal and a titanium dioxide single crystal in an ammonia-containing atmosphere, and nitriding the surface of the barium titanate single crystal and/or the titanium dioxide single crystal to obtain a porous Titanium nitride single crystal film.
  • the method comprises at least: reacting at least one of barium titanate single crystal and titanium dioxide single crystal in an ammonia-containing atmosphere, and nitriding and growing the surface of the barium titanate single crystal and/or the titanium dioxide single crystal, thereby obtaining Porous titanium nitride single crystal.
  • the method for preparing a nanoporous titanium nitride single crystal film and a self-supporting nanoporous titanium nitride single crystal includes the following steps:
  • Step one using a barium titanate single wafer, a titanium dioxide single wafer as a substrate;
  • Step 2 placing a barium titanate single crystal and a titanium dioxide single wafer substrate in a vapor phase epitaxial growth reaction chamber, and nitriding the surface of the substrate to form a nanoporous titanium nitride single crystal film in a high temperature ammonia-containing atmosphere;
  • Step 3 As the nitridation time increases, further nitriding conversion growth is performed, and the barium titanate single crystal or the titanium dioxide single wafer substrate is completely nitrided and transformed into a self-supporting nanoporous titanium nitride single crystal.
  • the barium titanate single crystal substrate in the first step is one of (100) plane barium titanate crystal, titanium dioxide (100) crystal, titanium dioxide (110) crystal or titanium dioxide (001) crystal.
  • the scale of the barium titanate single crystal or the titanium dioxide single wafer substrate in the step 1 ranges from 0.1 cm to 30 cm.
  • the high temperature nitriding conversion growth temperature ranges from 1373 K to 1873 K.
  • the ammonia-containing atmosphere adopts a flow rate of ammonia gas + b flow rate of nitrogen gas + c flow rate of argon gas + d flow rate of hydrogen gas flow, wherein 0.05 SLM ⁇ a ⁇ 100 SLM, 0 SLM ⁇ b ⁇ 100 SLM, 0SLM ⁇ c ⁇ 100SLM, 0SLM ⁇ d ⁇ 100SLM.
  • the nitriding time range in the second step is from 1 minute to 500 hours.
  • the nitriding atmosphere pressure range in the second step is 0.1 Torr to 700 Torr.
  • the method for preparing a nanoporous titanium nitride single crystal film and a self-supporting nanoporous titanium nitride single crystal comprises the following steps:
  • the barium titanate single crystal substrate in (a1) is (100) face barium titanate.
  • the scale of the barium titanate single crystal substrate in (a1) ranges from 1 cm to 5 cm.
  • the high temperature nitriding conversion growth temperature range of the (b1) is 1373K to 1573K.
  • the ammonia-containing atmosphere in (b1) adopts a flow rate of ammonia gas + b flow rate of nitrogen gas + c flow rate of argon gas + d flow rate of hydrogen gas flow, wherein 0.05 SLM ⁇ a ⁇ 10 SLM, 0 SLM ⁇ b ⁇ 1 SLM, 0 SLM ⁇ c ⁇ 1 SLM, 0 SLM ⁇ d ⁇ 1 SLM.
  • the nitriding time range in the (b1) 30 minutes to 100 hours.
  • the nitriding atmosphere pressure range in the above (b1) is from 10 Torr to 400 Torr.
  • the nanoporous titanium nitride single crystal in (c1) is a large-sized 100-sided nanoporous titanium nitride single crystal.
  • the method for preparing a nanoporous titanium nitride single crystal film and a self-supporting nanoporous titanium nitride single crystal comprises the following steps:
  • the titanium dioxide single crystal substrate in the (a2) is a (001) plane titanium dioxide single crystal.
  • the scale of the titanium dioxide single crystal substrate in the (a2) range is from 1 cm to 5 cm.
  • the high temperature nitriding conversion growth temperature range of the (b2) is: 1173K to 1373K.
  • the ammonia-containing atmosphere in the (b2) uses a flow rate of ammonia gas + b flow rate of nitrogen + c flow rate of argon gas + d flow rate of hydrogen gas flow, wherein 0.05 SLM ⁇ a ⁇ 10 SLM, 0 SLM ⁇ b ⁇ 1 SLM, 0 SLM ⁇ c ⁇ 1SLM, 0SLM ⁇ d ⁇ 1SLM.
  • the nitriding time range in the (b2) is 30 minutes to 20 hours.
  • the nanoporous titanium nitride single crystal in the (c2) is a large-sized (110)-face nanoporous titanium nitride single crystal.
  • the method for preparing a nanoporous titanium nitride single crystal film and a self-supporting nanoporous titanium nitride single crystal comprises the following steps:
  • the titanium dioxide single crystal substrate in the (a3) is (100) plane titanium oxide.
  • the scale of the titanium dioxide single crystal substrate in the (a3) range is from 1 cm to 5 cm.
  • the high temperature nitriding conversion growth temperature range of the (b3) is: 1173K to 1373K.
  • the ammonia-containing atmosphere in (b3) adopts a flow rate of ammonia gas + b flow rate of nitrogen gas + c flow rate of argon gas + d flow rate of hydrogen gas flow, wherein 0.05 SLM ⁇ a ⁇ 10 SLM, 0 SLM ⁇ b ⁇ 1 SLM, 0 SLM ⁇ c ⁇ 1SLM, 0SLM ⁇ d ⁇ 1SLM.
  • the nitriding time range in the (b3) is 30 minutes to 20 hours.
  • the nanoporous titanium nitride single crystal in (c3) is a large-sized (111)-face nanoporous titanium nitride single crystal.
  • the invention develops a large-sized, low-cost 100-face nano-porous titanium nitride single crystal by converting a large-sized barium titanate single crystal or a titanium dioxide single crystal into a crystal of the same size nanoporous titanium nitride single crystal. , a 110-sided nanoporous titanium nitride single crystal and a 111-sided nanoporous titanium nitride single crystal.
  • the porous titanium nitride single crystal material according to any one of the above, the at least one of the porous titanium nitride single crystal materials prepared according to any one of the above methods is provided in the electrode material. Application in .
  • SLM is an abbreviation of Standard Litre Per Minute, indicating a flow rate of 1 L/min in a standard state.
  • the size of the crystal and the one-dimensional size in the largest surface of the crystal refer to the distance between the two nearest neighbors on the largest area of the crystal.
  • the barium titanate crystal or the titanium dioxide crystal is similar to the titanium nitride crystal structure, so that the barium titanate single crystal or the titanium dioxide single crystal substrate and the ammonia gas are transformed and grown by the outer and inner nitriding at high temperature. Titanium nitride crystal, the remaining products are completely volatilized;
  • the present application utilizes the characteristics that the content of titanium in the same volume of barium titanate or titanium dioxide crystal is less than the content of titanium in the titanium nitride crystal, so that the barium titanate or titanium dioxide single crystal substrate and the ammonia gas are at a high temperature and Nitriding to form a nanoporous titanium nitride single crystal;
  • the method for preparing nanoporous titanium nitride single crystal crystal of the present application is simple in operation, good in repeatability and low in price;
  • the material described in the present application has a self-supporting structure, and when it is a bulk single crystal, as a new material, it has potential applications in the fields of photoelectric conversion, catalysis, electrocatalysis, and electrochemical energy storage systems.
  • 3 is an SEM image of a sample 3 #large size (111) plane nanoporous titanium nitride single crystal
  • Fig. 4 is a graph showing the electrical properties of samples 1# to 3#.
  • barium titanate single crystal is based on the literature [Christo Guguschev, Zbigniew Galazka, Dirk J. Kok, Uta Juda, Albert Kwasniewski and Reinhard Uecker. Growth of SrTiO 3 bulk single crystals using edge-defined film-fed growth and the Czochralski methods The method in .Crystengcomm, 2015, 17(25): 4662-4668] is prepared.
  • the titanium dioxide single crystal is a method according to the literature [Experimental Study on Growth Conditions of Big-bulk Rutile Crystal. Bi Xiaoguo; Xiu Zhimeng; Sun Xudong; et al; Journal of Synthetic Crystals, 2004, 33(2): 244-249. Prepared.
  • a (100)-faced barium titanate single crystal substrate having a size of 1 cm was placed on a high-purity alumina boat, and then placed in an alumina tube reactor, and a raw material gas containing ammonia gas was introduced (the raw material gas was ammonia gas).
  • nitrogen composition ammonia 0.5SLM, nitrogen 0.5SLM) and the system is heated to 1523K, maintaining the system pressure is 300Torr, after 120 minutes of reaction, cooling to room temperature, the porous nitrogen grown on the surface of the barium titanate single wafer substrate
  • a titanium single crystal film sample having a film thickness of 500 nm was recorded as sample M1 # .
  • a (100)-faced barium titanate single crystal substrate having a size of 1 cm was placed on a high-purity alumina boat, and then placed in an alumina tube reactor, and a raw material gas containing ammonia gas was introduced (the raw material gas was ammonia gas).
  • hydrogen composition ammonia 0.5SLM, hydrogen 0.1SLM) and the system is heated to 1623K, maintaining the system pressure is 300Torr, after 100 hours of reaction, cooling to room temperature, to obtain a porous titanium nitride single crystal sample, recorded as sample 1 # , Sample 1 # has a crystal size of 1 cm.
  • a (001) surface titanium dioxide single crystal substrate having a size of 1 cm was placed on a high-purity alumina boat, and then placed in an alumina tube reactor, and a feed gas containing ammonia gas was introduced (the feed gas was made up of ammonia gas and nitrogen gas).
  • a film sample having a film thickness of about 500 nm is designated as sample M2 # .
  • the (001)-faced titanium dioxide single crystal substrate having a size of 1 cm is placed on a high-purity graphite heating body of a high-frequency induction furnace, and then placed in a quartz reactor, and a raw material gas containing ammonia gas is introduced (the raw material gas is ammonia).
  • Gas and hydrogen composition ammonia gas 0.3SLM, hydrogen 0.2SLM) and the system is heated to 1173K, the system pressure is maintained at 50 Torr, after 100 hours of reaction, cooling to room temperature, a porous titanium nitride single crystal sample is obtained, which is recorded as a sample. 2 # , sample 2 # crystal size is 1cm.
  • a (100)-face titanium dioxide single crystal substrate having a size of 1 cm was placed on a high-purity alumina boat, and then placed in an alumina tube reactor, and a feed gas containing ammonia gas was introduced (the feed gas was composed of ammonia gas and hydrogen gas).
  • a film sample having a film thickness of 1000 nm was designated as sample M3 # .
  • a (100)-face titanium dioxide single crystal substrate having a size of 1 cm was placed on a high-purity alumina boat, and then placed in an alumina tube reactor, and a feed gas containing ammonia gas was introduced (the feed gas was composed of ammonia gas and hydrogen gas).
  • the basic preparation steps of the sample M4 # to the sample M9 # were the same as those of the sample M1 # in Example 1, and the substrate and the reaction conditions were changed to obtain different samples.
  • the relationship between the sample number and the substrate and reaction conditions is shown in Table 1.
  • the thickness of the sample M4 # to the sample M9 # is in the range of 10 nm to 100 ⁇ m.
  • sample 1# to sample 9# was characterized by scanning electron microscopy. The results showed that samples 1# to 9# all had pores of 10 nm to 500 nm.
  • Sample # 4 Sample # 5 Sample morphology similar to # 1 to # 1 is a typical representative sample, which is (100) plane of titanium nitride nano-porous monocrystalline crystal SEM photograph shown in Figure 1, it may be made of FIG. It is seen that titanium nitride has a porous skeleton structure.
  • Samples # 6 and # 7 Sample morphology similar to the sample # 2 to # 2 as a typical representative sample, which is (110) plane of titanium nitride nano-porous monocrystalline crystal SEM photograph shown in Figure 2, may be made of FIG.
  • Sample 8 Sample # 9 and # morphology similar to the sample # 3 with that of sample # 3 is a typical representative of (111) plane of titanium nitride nano-porous monocrystalline crystal SEM photograph shown in Figure 3, it may be made of FIG. The porous structure of titanium nitride is seen.
  • sample M1 # to sample M9 # are similar to sample 1 # to sample 9 # , respectively, and the scanning electron micrograph of sample M1 # is similar to sample 1 # .
  • the pore range of the product is in the range of 10 nm to 1000 nm.
  • Sample # 1 to Sample # 9 crystal are titanium nitride single crystal
  • the samples Ml ⁇ # # M3 are samples of titanium nitride single crystal thin film.
  • FIG. Figure 4 shows the results of the electrical performance test of samples 1 # to 3 # of the sample. It can be seen from the figure that the porous titanium nitride single crystal has excellent electrical conductivity.

Abstract

Disclosed are a porous titanium nitride single crystal material, a preparation method therefor and the use thereof. The porous titanium nitride single crystal material contains pores of 10 nm-1000 nm. The porous titanium nitride single crystal, as a new material, has potential applications in the fields of photovoltaic conversion, catalysis and electrocatalysis, as well as in an electrochemical energy storage system. Furthermore, the method for the crystal material has a simple operation, a good repeatability and a low cost.

Description

一种多孔氮化钛单晶材料及其制备方法和应用Porous titanium nitride single crystal material and preparation method and application thereof 技术领域Technical field
本申请涉及一种多孔氮化钛单晶材料及其制备方法和应用，属于无机材料领域。The present application relates to a porous titanium nitride single crystal material, a preparation method and application thereof, and belongs to the field of inorganic materials.
背景技术Background technique
氮化钛是一种优良的、稳定的电子导体，熔点高，硬度高。在立方结构中，Ti-N键部分包含共价键的性质，而钛的三价离子提供了一个自由电子，作为载流子表现出电子导体的性质。在催化和电催化应用中，氮化钛表面的钛的三价离子通常被认为是活性原子。氮化钛纳米粒子，在电催化领域和电化学能源存储***中，可以作为催化剂和催化剂支撑电极。目前制备的多孔氮化钛电极，都是基于无定型或者多晶的氮化钛粉末，晶界众多，表面的终止原子不确定。Titanium nitride is an excellent and stable electronic conductor with high melting point and high hardness. In the cubic structure, the Ti-N bond moiety contains the nature of a covalent bond, while the trivalent ion of titanium provides a free electron that acts as a carrier to exhibit the properties of the electron conductor. In catalytic and electrocatalytic applications, the trivalent ions of titanium on the surface of titanium nitride are generally considered to be active atoms. Titanium nitride nanoparticles, which can serve as catalyst and catalyst support electrodes in the field of electrocatalysis and electrochemical energy storage systems. The porous titanium nitride electrodes currently prepared are all based on amorphous or polycrystalline titanium nitride powders, with numerous grain boundaries and uncertain end atoms on the surface.
由于氮化钛的高熔点和高温生长时高的氮离解压，所以难以用熔体制备其单晶材料，采用高温高压技术也很难得到衬底尺度的体单晶材料。目前制备氮化钛的主要方法有化学气相沉积法(CVD)、物理气相沉积法(PVD)、等离子体化学气相沉积法(PCVD)、离子束辅助沉积法(IBAD)、空心阴极离子镀(HCD)、等离子体浸没离子注入(PIII)、激光氮化州(LN)等。但是能够制备的氮化钛单晶只具有微米尺寸，或者是微米厚度的单晶薄膜。而如何实现大尺寸的氮化钛体单晶还是科学难题。Due to the high melting point of titanium nitride and the high nitrogen decompression pressure during high temperature growth, it is difficult to prepare a single crystal material from the melt, and it is difficult to obtain a bulk single crystal material of a substrate size by high temperature and high pressure technology. At present, the main methods for preparing titanium nitride include chemical vapor deposition (CVD), physical vapor deposition (PVD), plasma chemical vapor deposition (PCVD), ion beam assisted deposition (IBAD), and hollow cathode ion plating (HCD). ), plasma immersion ion implantation (PIII), laser nitridation state (LN), and the like. However, the titanium nitride single crystal which can be produced has only a micron size or a single crystal thin film of a micron thickness. How to realize large-sized titanium nitride single crystal is still a scientific problem.
金属性多孔固体材料在光催化和电化学能源存储方面具有重要的应用。大的孔隙率能够为高效率的反应提供大的比表面积。现有制备纳米多孔材料的方法如模板法(use of templates)、起泡法(bubbling)、脱合金成分腐蚀法(dealloying)、柯肯特尔效应法(Kirkendall effect)，共振渗透法(collective osmotic shock)等，其方法复杂，并且所能制备的最大晶体尺度仅在微米量级，欠缺一种可以制备宏观尺度纳米多孔氮化钛单晶晶体的方法。Metallic porous solid materials have important applications in photocatalytic and electrochemical energy storage. The large porosity provides a large specific surface area for highly efficient reactions. Existing methods for preparing nanoporous materials such as use of templates, bubbling, dealloying, Kirkendall effect, and resonant osmotic shock The method is complicated, and the maximum crystal size that can be prepared is only on the order of micrometers, and there is a lack of a method for preparing macroscopic scale nanoporous titanium nitride single crystal.
因此，有必要提供一种制备大尺寸纳米多孔氮化钛单晶晶体的方法，来为氮化钛基电极提供优质的大尺寸100面、110面和111面的纳米多孔 氮化钛单晶材料。Therefore, it is necessary to provide a method for preparing a large-sized nanoporous titanium nitride single crystal crystal to provide a high-quality large-size 100-, 110-, and 111-face nanoporous titanium nitride single crystal material for a titanium nitride-based electrode. .
发明内容Summary of the invention
根据本申请的一个方面，提供了一种多孔氮化钛单晶材料，该材料具有多孔结构，具有大尺寸。According to an aspect of the present application, there is provided a porous titanium nitride single crystal material having a porous structure having a large size.
本申请提供一种制备大尺寸100面、110面和111面的纳米多孔氮化钛单晶薄膜及自支撑纳米多孔氮化钛晶体的方法，它涉及一种制备大尺寸纳米多孔单晶晶体的方法，尤其是氮化生长制备大尺寸纳米多孔氮化钛单晶晶体的方法。制备纳米多孔氮化钛单晶薄膜的方法：将钛酸锶单晶或者二氧化钛单晶衬底置于高温含氨氛围中，钛酸锶单晶或者二氧化钛单晶衬底表面氮化生长出纳米多孔氮化钛。制备自支撑纳米多孔氮化钛单晶晶体的方法：将钛酸锶单晶或者二氧化钛单晶衬底置于高温含氨氛围中，钛酸锶单晶或者二氧化钛单晶衬底表面首先氮化转化生长出纳米多孔氮化钛，随着氮化时间的增加，钛酸锶单晶或者二氧化钛单晶衬底完全氮化转化生长成自支撑纳米多孔氮化钛单晶晶体。本申请的目的一方面是要解决现有制备纳米多孔晶体材料的方法复杂且仅限微米量级的晶体制备尺度，不利于规模化生产和应用的问题；另一方面是要为氮化钛基器件提供质优价廉的同质大尺寸100面、110面和111面的纳米多孔氮化钛单晶衬底，从而大幅提升氮化钛基器件性能。本发明制备大尺寸100面110面和111面的纳米多孔氮化钛单晶薄膜及自支撑纳米多孔氮化钛晶体的方法简单、价格低廉、可规模化生产。The present application provides a method for preparing a nano-sized porous titanium nitride single crystal film having a large size of 100 faces, 110 faces, and 111 faces, and a self-supporting nanoporous titanium nitride crystal, which relates to a method for preparing a large-sized nanoporous single crystal crystal. A method, in particular a method of nitriding growth, for preparing a large-sized nanoporous titanium nitride single crystal. A method for preparing a nanoporous titanium nitride single crystal film: a barium titanate single crystal or a titanium dioxide single crystal substrate is placed in a high temperature ammonia-containing atmosphere, and a surface of the barium titanate single crystal or the titanium dioxide single crystal substrate is nitrided to form a nanoporous Titanium nitride. A method for preparing a self-supporting nanoporous titanium nitride single crystal: placing a barium titanate single crystal or a titanium dioxide single crystal substrate in a high temperature ammonia-containing atmosphere, and first nitriding the surface of the barium titanate single crystal or the titanium dioxide single crystal substrate The nanoporous titanium nitride is grown, and as the nitridation time increases, the barium titanate single crystal or the titanium dioxide single crystal substrate is completely nitrided and transformed into a self-supporting nanoporous titanium nitride single crystal. The purpose of the present application is to solve the problem that the existing method for preparing a nanoporous crystal material is complicated and limited to micron-scale crystal preparation, which is disadvantageous for large-scale production and application; on the other hand, it is a titanium nitride base. The device provides a high-quality and inexpensive large-size 100-, 110-, and 111-sided nanoporous titanium nitride single crystal substrate, thereby greatly improving the performance of the titanium nitride-based device. The invention has the advantages of simple, low-cost and large-scale production of the nanoporous titanium nitride single crystal film with large size of 100 faces and 111 faces and the self-supporting nanoporous titanium nitride crystal.
所述多孔氮化钛单晶材料，其特征在于，所述多孔氮化钛单晶材料中含有10nm～1000nm的孔。The porous titanium nitride single crystal material is characterized in that the porous titanium nitride single crystal material contains pores of 10 nm to 1000 nm.
可选地，所述多孔氮化钛单晶材料中含有10nm～500nm的孔。Optionally, the porous titanium nitride single crystal material contains pores of 10 nm to 500 nm.
可选地，所述多孔氮化钛单晶材料为多孔氮化钛单晶薄膜和/或多孔氮化钛单晶晶体。Optionally, the porous titanium nitride single crystal material is a porous titanium nitride single crystal film and/or a porous titanium nitride single crystal.
可选地，所述多孔氮化钛单晶晶体为自支撑纳米多孔氮化钛晶体。Optionally, the porous titanium nitride single crystal crystal is a self-supporting nanoporous titanium nitride crystal.
可选地，所述多孔氮化钛单晶薄膜的表面为多孔氮化钛单晶的(100)面、(110)面、(111)面中的至少一面。Optionally, the surface of the porous titanium nitride single crystal thin film is at least one of a (100) plane, a (110) plane, and a (111) plane of the porous titanium nitride single crystal.
可选地，所述多孔氮化钛单晶材料是多孔氮化钛单晶晶体时，晶体的 最大表面为多孔氮化钛单晶的(100)面、(110)面、(111)面中的至少一面。Optionally, when the porous titanium nitride single crystal material is a porous titanium nitride single crystal, the largest surface of the crystal is in the (100) plane, the (110) plane, and the (111) plane of the porous titanium nitride single crystal. At least one side.
可选地，所述多孔氮化钛单晶晶体的最大表面中一维的尺寸为0.1cm～30cm。Optionally, one dimension of the largest surface of the porous titanium nitride single crystal crystal is 0.1 cm to 30 cm.
可选地，所述多孔氮化钛单晶晶体的最大表面中一维的尺寸为1cm～5cm。Optionally, one dimension of the largest surface of the porous titanium nitride single crystal crystal is from 1 cm to 5 cm.
可选地，所述多孔氮化钛单晶晶体的尺寸为0.1cm～30cm；Optionally, the porous titanium nitride single crystal crystal has a size of 0.1 cm to 30 cm;
所述多孔氮化钛单晶薄膜的厚度为10nm～100μm。The porous titanium nitride single crystal thin film has a thickness of 10 nm to 100 μm.
可选地，所述多孔氮化钛单晶晶体的尺寸为1cm～5cm。Optionally, the porous titanium nitride single crystal has a size of 1 cm to 5 cm.
本申请的另一方面，提供了上述任一项所述的多孔氮化钛单晶材料的制备方法，其特征在于，至少包括：将钛源与含有氨气的原料气接触反应，得到所述多孔氮化钛单晶材料；In another aspect, the present invention provides a method for preparing a porous titanium nitride single crystal material according to any one of the preceding claims, characterized in that it comprises at least: contacting a titanium source with a raw material gas containing ammonia gas to obtain the Porous titanium nitride single crystal material;
其中，所述钛源选自钛酸锶单晶材料、二氧化钛单晶材料中的至少一种。Wherein, the titanium source is at least one selected from the group consisting of barium titanate single crystal materials and titanium dioxide single crystal materials.
可选地，所述钛酸锶单晶为(100)面钛酸锶晶体，(111)面钛酸锶晶体或(110)面钛酸锶晶体，二氧化钛单晶为(001)面二氧化钛、(110)面二氧化钛或(100)面二氧化钛。Optionally, the barium titanate single crystal is (100) face barium titanate crystal, (111) face barium titanate crystal or (110) face barium titanate crystal, and the titanium dioxide single crystal is (001) face titanium dioxide, ( 110) Surface titanium dioxide or (100) surface titanium dioxide.
可选地，所述钛酸锶单晶材料与含有氨气的原料气接触的是钛酸锶单晶的(110)面、(111)面、(100)面中的至少一面。Optionally, the barium titanate single crystal material is in contact with the raw material gas containing ammonia gas, and is at least one of a (110) plane, a (111) plane, and a (100) plane of the barium titanate single crystal.
可选地，所述二氧化钛单晶材料与含有氨气的原料气接触的是二氧化钛单晶的(001)面、(110)面、(100)面中的至少一面。Optionally, the titanium dioxide single crystal material is in contact with the raw material gas containing ammonia gas, and is at least one of a (001) plane, a (110) plane, and a (100) plane of the titanium dioxide single crystal.
可选地，所述钛酸锶单晶材料是钛酸锶单晶片；钛酸锶单晶片面积最大的面是单晶的(100)面、(111)面或(110)面与含有氨气的原料气接触。Optionally, the barium titanate single crystal material is a barium titanate single wafer; the largest surface of the barium titanate single wafer is a single crystal (100) plane, a (111) plane or a (110) plane and contains ammonia gas. Raw material gas contact.
可选地，所述二氧化钛单晶材料是二氧化钛单晶片；二氧化钛单晶片面积最大的面是单晶的(001)面、(100)面或(110)面与含有氨气的原料气接触。Optionally, the titanium dioxide single crystal material is a titanium dioxide single wafer; the surface having the largest area of the titanium dioxide single wafer is a single crystal (001) plane, a (100) plane or a (110) plane in contact with the raw material gas containing ammonia gas.
可选地，所述反应的温度为1173K～1873K；Optionally, the temperature of the reaction is from 1173K to 1873K;
所述反应的压力为0.1Torr～1000Torr；The pressure of the reaction is from 0.1 Torr to 1000 Torr;
所述反应的时间为1min～500h。The reaction time is from 1 min to 500 h.
可选地，所述反应的温度为1373K～1873K。Alternatively, the temperature of the reaction is from 1373 K to 1873 K.
可选地，所述反应的温度为1373K～1573K。Alternatively, the temperature of the reaction is from 1373 K to 1573 K.
可选地，所述反应的温度为1173K～1373K。Alternatively, the temperature of the reaction is from 1173K to 1373K.
可选地，所述反应的压力为0.1Torr～700Torr；Optionally, the pressure of the reaction is from 0.1 Torr to 700 Torr;
可选地，所述反应的压力为10Torr～400Torr。Alternatively, the pressure of the reaction is from 10 Torr to 400 Torr.
可选地，所述反应的时间为30min～20h。Optionally, the reaction time is from 30 min to 20 h.
可选地，所述反应的时间为30min～100h。Optionally, the reaction time is from 30 min to 100 h.
可选地，所述反应的温度上限选自1223K、1273K、1373K、1473K、1573K、1673K、1773K或1873K；下限选自1173K、1223K、1273K、1373K、1473K、1573K、1673K或1773K。Optionally, the upper temperature limit of the reaction is selected from the group consisting of 1223K, 1273K, 1373K, 1473K, 1573K, 1673K, 1773K or 1873K; the lower limit is selected from 1173K, 1223K, 1273K, 1373K, 1473K, 1573K, 1673K or 1773K.
可选地，所述反应的时间上限选自2min、10min、20min、50min、1h、10h、20h、50h、100h、150h、200h、300h、400h或500h；下限选自1min、10min、20min、50min、1h、10h、20h、50h、100h、150h、200h、300h或400h。Optionally, the upper time limit of the reaction is selected from 2 min, 10 min, 20 min, 50 min, 1 h, 10 h, 20 h, 50 h, 100 h, 150 h, 200 h, 300 h, 400 h or 500 h; the lower limit is selected from 1 min, 10 min, 20 min, 50 min. , 1h, 10h, 20h, 50h, 100h, 150h, 200h, 300h or 400h.
可选地，所述反应的压力上限选自0.2Torr、0.5Torr、10Torr、20Torr、50Torr、100Torr、200Torr、300Torr、400Torr、500Torr、600Torr、700Torr、700Torr、800Torr、900Torr或1000Torr；下限选自0.1Torr、0.2Torr、0.5Torr、10Torr、20Torr、50Torr、100Torr、200Torr、300Torr、400Torr、500Torr、600Torr、700Torr、800Torr、900Torr或1000Torr。Optionally, the upper pressure limit of the reaction is selected from the group consisting of 0.2 Torr, 0.5 Torr, 10 Torr, 20 Torr, 50 Torr, 100 Torr, 200 Torr, 300 Torr, 400 Torr, 500 Torr, 600 Torr, 700 Torr, 700 Torr, 800 Torr, 900 Torr or 1000 Torr; Torr, 0.2 Torr, 0.5 Torr, 10 Torr, 20 Torr, 50 Torr, 100 Torr, 200 Torr, 300 Torr, 400 Torr, 500 Torr, 600 Torr, 700 Torr, 800 Torr, 900 Torr or 1000 Torr.
可选地，当多孔氮化钛单晶材料为多孔氮化钛单晶薄膜时，所述钛酸锶单晶/二氧化钛单晶材料与含有氨气的原料气接触反应的时间范围为1min～20h。Optionally, when the porous titanium nitride single crystal material is a porous titanium nitride single crystal film, the contact time of the barium titanate single crystal/titanium dioxide single crystal material with the raw material gas containing ammonia gas ranges from 1 min to 20 h. .
可选地，当多孔氮化钛单晶材料为多孔氮化钛单晶薄膜时，所述钛酸锶单晶/二氧化钛单晶材料与含有氨气的原料气接触反应的时间范围下限选自10min、20min、30min、1h、2h、3h、4h、5h、10h、15h或18h；上限选自20min、30min、1h、2h、3h、4h、5h、10h、15h、18h或20h。Optionally, when the porous titanium nitride single crystal material is a porous titanium nitride single crystal film, the lower limit of the time range of the barium titanate single crystal/titanium dioxide single crystal material in contact with the raw material gas containing ammonia gas is selected from the group consisting of 10 min. 20 min, 30 min, 1 h, 2 h, 3 h, 4 h, 5 h, 10 h, 15 h or 18 h; the upper limit is selected from 20 min, 30 min, 1 h, 2 h, 3 h, 4 h, 5 h, 10 h, 15 h, 18 h or 20 h.
当制备的多孔氮化钛单晶材料为多孔氮化钛单晶晶体时，接触反应时间应满足使钛酸锶/二氧化钛单晶材料全部转化为多孔氮化钛单晶材料。When the prepared porous titanium nitride single crystal material is a porous titanium nitride single crystal, the contact reaction time should satisfy that all of the barium titanate/titanium dioxide single crystal material is converted into a porous titanium nitride single crystal material.
可选地，当多孔氮化钛单晶材料为多孔氮化钛单晶晶体时，所述钛酸锶单晶/二氧化钛单晶材料与含有氨气的原料气接触反应的时间为 10h～500h。Alternatively, when the porous titanium nitride single crystal material is a porous titanium nitride single crystal, the barium titanate single crystal/titanium dioxide single crystal material is reacted with the ammonia gas-containing raw material gas for a reaction time of 10 to 500 hours.
本领域技术人员可根据实际需要和所采用的钛酸锶单晶/二氧化钛单晶材料的尺寸，确定合适的接触反应时间。Those skilled in the art can determine the appropriate contact reaction time according to actual needs and the size of the barium titanate single crystal/titanium dioxide single crystal material used.
可选地，当多孔氮化钛单晶材料为多孔氮化钛单晶晶体时，所述氮化钛单晶材料与含有氨气的原料气接触反应的时间范围上限选自15h、20h、50h、100h、150h、200h、250h、300h、350h、400h、450h或500h；下限选自10h、15h、20h、50h、100h、150h、200h、250h、300h、350h、400h或450h。Optionally, when the porous titanium nitride single crystal material is a porous titanium nitride single crystal, the upper limit of the time range of the titanium nitride single crystal material in contact with the raw material gas containing ammonia gas is selected from the group consisting of 15h, 20h, and 50h. , 100h, 150h, 200h, 250h, 300h, 350h, 400h, 450h or 500h; the lower limit is selected from 10h, 15h, 20h, 50h, 100h, 150h, 200h, 250h, 300h, 350h, 400h or 450h.
采用本申请所提供的方法，所得到的多孔氮化钛单晶晶体的晶体尺寸与所采用的钛酸锶单晶/二氧化钛单晶材料的尺寸相等。本领域技术人员可以根据实际需要，通过选择合适尺寸的钛酸锶单晶/二氧化钛材料，得到所需要的多孔氮化钛单晶晶体。Using the method provided herein, the crystal size of the obtained porous titanium nitride single crystal crystal is equal to the size of the barium titanate single crystal/titanium dioxide single crystal material used. A person skilled in the art can obtain a desired porous titanium nitride single crystal by selecting an appropriately sized barium titanate single crystal/titanium dioxide material according to actual needs.
可选地，所述含有氨气的原料气中包括氨气和氮气、氩气、氢气中的至少一种；Optionally, the ammonia-containing feed gas includes at least one of ammonia gas, nitrogen gas, argon gas, and hydrogen gas;
其中，氨气的流量记为a，氮气的流量记为b，氩气的流量记为c，氢气的流量记为d，满足：Among them, the flow rate of ammonia gas is recorded as a, the flow rate of nitrogen gas is recorded as b, the flow rate of argon gas is recorded as c, and the flow rate of hydrogen gas is recorded as d, which satisfies:
0.05SLM≤a≤100SLM；0.05SLM≤a≤100SLM;
0SLM≤b≤100SLM；0SLM≤b≤100SLM;
0SLM≤c≤100SLM；0SLM≤c≤100SLM;
0SLM≤d≤100SLM。0SLM≤d≤100SLM.
可选地，所述含有氨气的原料气中包括氨气和氮气、氩气、氢气中的至少一种；Optionally, the ammonia-containing feed gas includes at least one of ammonia gas, nitrogen gas, argon gas, and hydrogen gas;
其中，氨气的流量记为a，氮气的流量记为b，氩气的流量记为c，氢气的流量记为d，满足：Among them, the flow rate of ammonia gas is recorded as a, the flow rate of nitrogen gas is recorded as b, the flow rate of argon gas is recorded as c, and the flow rate of hydrogen gas is recorded as d, which satisfies:
0.05SLM≤a≤10SLM；0.05SLM≤a≤10SLM;
0SLM≤b≤1SLM；0SLM≤b≤1SLM;
0SLM≤c≤1SLM；0SLM≤c≤1SLM;
0SLM≤d≤1SLM。0SLM≤d≤1SLM.
可选地，所述氨气的流量范围上限选自0.1SLM、0.3SLM、0.5SLM、1SLM、1.5SLM、2SLM、3SLM、4SLM、5SLM、6SLM、7SLM、8SLM、 9SLM、10SLM、20SLM、30SLM、40SLM、50SLM、60SLM、70SLM、80SLM、90SLM或100SLM；下限选自0.05SLM、0.1SLM、0.3SLM、0.5SLM、1SLM、1.5SLM、2SLM、3SLM、4SLM、5SLM、6SLM、7SLM、8SLM、9SLM、10SLM、20SLM、30SLM、40SLM、50SLM、60SLM、70SLM、80SLM或90SLM。Optionally, the upper limit of the flow rate of the ammonia gas is selected from the group consisting of 0.1 SLM, 0.3 SLM, 0.5 SLM, 1 SLM, 1.5 SLM, 2 SLM, 3 SLM, 4 SLM, 5 SLM, 6 SLM, 7 SLM, 8 SLM, 9 SLM, 10 SLM, 20 SLM, 30 SLM, 40SLM, 50SLM, 60SLM, 70SLM, 80SLM, 90SLM or 100SLM; lower limit selected from 0.05SLM, 0.1SLM, 0.3SLM, 0.5SLM, 1SLM, 1.5SLM, 2SLM, 3SLM, 4SLM, 5SLM, 6SLM, 7SLM, 8SLM, 9SLM, 10SLM, 20SLM, 30SLM, 40SLM, 50SLM, 60SLM, 70SLM, 80SLM or 90SLM.
可选地，所述氮气的流量范围上限选自0.01SLM、0.1SLM、0.2SLM、0.3SLM、0.5SLM、0.8SLM、1SLM、2SLM、5SLM、10SLM、20SLM、50SLM、80SLM或100SLM；下限选自0SLM、0.01SLM、0.1SLM、0.2SLM、0.3SLM、0.5SLM、0.8SLM、1SLM、2SLM、5SLM、10SLM、20SLM、50SLM或80SLM。Optionally, the upper limit of the flow range of the nitrogen gas is selected from the group consisting of 0.01 SLM, 0.1 SLM, 0.2 SLM, 0.3 SLM, 0.5 SLM, 0.8 SLM, 1 SLM, 2 SLM, 5 SLM, 10 SLM, 20 SLM, 50 SLM, 80 SLM or 100 SLM; 0SLM, 0.01SLM, 0.1SLM, 0.2SLM, 0.3SLM, 0.5SLM, 0.8SLM, 1SLM, 2SLM, 5SLM, 10SLM, 20SLM, 50SLM or 80SLM.
可选地，所述氩气的流量范围上限选自0.01SLM、0.1SLM、0.2SLM、0.5SLM、0.8SLM、1SLM、2SLM、5SLM、10SLM、20SLM、50SLM、80SLM或100SLM；下限选自0SLM、0.01SLM、0.1SLM、0.2SLM、0.5SLM、0.8SLM、1SLM、2SLM、5SLM、10SLM、20SLM、50SLM或80SLM。Optionally, the upper limit of the flow rate of the argon gas is selected from the group consisting of 0.01 SLM, 0.1 SLM, 0.2 SLM, 0.5 SLM, 0.8 SLM, 1 SLM, 2 SLM, 5 SLM, 10 SLM, 20 SLM, 50 SLM, 80 SLM or 100 SLM; 0.01 SLM, 0.1 SLM, 0.2 SLM, 0.5 SLM, 0.8 SLM, 1 SLM, 2 SLM, 5 SLM, 10 SLM, 20 SLM, 50 SLM or 80 SLM.
可选地，所述氢气的流量范围上限选自0.01SLM、0.1SLM、0.2SLM、0.5SLM、0.8SLM、1SLM、2SLM、5SLM、10SLM、20SLM、50SLM、80SLM或100SLM；下限选自0SLM、0.01SLM、0.1SLM、0.2SLM、0.5SLM、0.8SLM、1SLM、2SLM、5SLM、10SLM、20SLM、50SLM或80SLM。Optionally, the upper limit of the flow range of the hydrogen gas is selected from the group consisting of 0.01 SLM, 0.1 SLM, 0.2 SLM, 0.5 SLM, 0.8 SLM, 1 SLM, 2 SLM, 5 SLM, 10 SLM, 20 SLM, 50 SLM, 80 SLM or 100 SLM; the lower limit is selected from 0 SLM, 0.01 SLM, 0.1SLM, 0.2SLM, 0.5SLM, 0.8SLM, 1SLM, 2SLM, 5SLM, 10SLM, 20SLM, 50SLM or 80SLM.
可选地，所述方法至少包括：将钛酸锶单晶、二氧化钛单晶中的至少一种在含氨氛围中反应，钛酸锶单晶和/或二氧化钛单晶表面氮化生长，得到多孔氮化钛单晶薄膜。Optionally, the method comprises at least: reacting at least one of a barium titanate single crystal and a titanium dioxide single crystal in an ammonia-containing atmosphere, and nitriding the surface of the barium titanate single crystal and/or the titanium dioxide single crystal to obtain a porous Titanium nitride single crystal film.
可选地，所述方法至少包括：将钛酸锶单晶、二氧化钛单晶中的至少一种在含氨氛围中反应，钛酸锶单晶和/或二氧化钛单晶表面氮化转化生长，得到多孔氮化钛单晶晶体。Optionally, the method comprises at least: reacting at least one of barium titanate single crystal and titanium dioxide single crystal in an ammonia-containing atmosphere, and nitriding and growing the surface of the barium titanate single crystal and/or the titanium dioxide single crystal, thereby obtaining Porous titanium nitride single crystal.
作为一种实施方式，所述制备纳米多孔氮化钛单晶薄膜及自支撑纳米多孔氮化钛单晶晶体的方法，包括以下步骤：As an embodiment, the method for preparing a nanoporous titanium nitride single crystal film and a self-supporting nanoporous titanium nitride single crystal includes the following steps:
步骤一、采用钛酸锶单晶片,二氧化钛单晶片为衬底；Step one, using a barium titanate single wafer, a titanium dioxide single wafer as a substrate;
步骤二、将钛酸锶单晶，二氧化钛单晶片衬底置于气相外延生长反应 室中，在高温含氨氛围中衬底表面氮化生长出纳米多孔氮化钛单晶薄膜；Step 2: placing a barium titanate single crystal and a titanium dioxide single wafer substrate in a vapor phase epitaxial growth reaction chamber, and nitriding the surface of the substrate to form a nanoporous titanium nitride single crystal film in a high temperature ammonia-containing atmosphere;
步骤三、随着氮化时间的增加，进一步进行氮化转化生长，将钛酸锶单晶或二氧化钛单晶片衬底完全氮化转化生长成自支撑纳米多孔氮化钛单晶晶体。Step 3: As the nitridation time increases, further nitriding conversion growth is performed, and the barium titanate single crystal or the titanium dioxide single wafer substrate is completely nitrided and transformed into a self-supporting nanoporous titanium nitride single crystal.
可选地，所述步骤一中的钛酸锶单晶衬底为(100)面钛酸锶晶体，二氧化钛(100)晶体，二氧化钛(110)晶体或二氧化钛(001)晶体中的一种。Optionally, the barium titanate single crystal substrate in the first step is one of (100) plane barium titanate crystal, titanium dioxide (100) crystal, titanium dioxide (110) crystal or titanium dioxide (001) crystal.
可选地，所述步骤一中的钛酸锶单晶或二氧化钛单晶片衬底的尺度范围：0.1cm～30cm。Optionally, the scale of the barium titanate single crystal or the titanium dioxide single wafer substrate in the step 1 ranges from 0.1 cm to 30 cm.
可选地，所述步骤二中高温氮化转化生长温度范围：1373K～1873K。Optionally, in the second step, the high temperature nitriding conversion growth temperature ranges from 1373 K to 1873 K.
可选地，所述步骤二中含氨氛围采用a流量的氨气+b流量的氮气+c流量的氩气+d流量的氢气气流，其中0.05SLM≤a≤100SLM、0SLM≤b≤100SLM、0SLM≤c≤100SLM、0SLM≤d≤100SLM。Optionally, in the second step, the ammonia-containing atmosphere adopts a flow rate of ammonia gas + b flow rate of nitrogen gas + c flow rate of argon gas + d flow rate of hydrogen gas flow, wherein 0.05 SLM ≤ a ≤ 100 SLM, 0 SLM ≤ b ≤ 100 SLM, 0SLM≤c≤100SLM, 0SLM≤d≤100SLM.
可选地，所述步骤二中氮化时间范围：1分钟～500小时。Optionally, the nitriding time range in the second step is from 1 minute to 500 hours.
可选地，所述步骤二中氮化氛围压力范围：0.1Torr～700Torr。Optionally, the nitriding atmosphere pressure range in the second step is 0.1 Torr to 700 Torr.
作为一种具体的实施方法，所述制备纳米多孔氮化钛单晶薄膜及自支撑纳米多孔氮化钛单晶晶体的方法，其制备方法包括以下步骤：As a specific implementation method, the method for preparing a nanoporous titanium nitride single crystal film and a self-supporting nanoporous titanium nitride single crystal, the preparation method comprises the following steps:
(a1)、采用钛酸锶单晶片为衬底；(a1) using a barium titanate single wafer as a substrate;
(b1)、将钛酸锶单晶衬底置于气相外延生长反应室中，在高温含氨氛围中衬底表面氮化转化生长出纳米多孔氮化钛单晶薄膜；(b1) placing a barium titanate single crystal substrate in a vapor phase epitaxial growth reaction chamber, and nitriding the surface of the substrate to form a nanoporous titanium nitride single crystal film in a high temperature ammonia-containing atmosphere;
(c1)、随着氮化时间的增加，进一步进行氮化转化生长，将钛酸锶单晶衬底完全氮化转化生长成自支撑纳米多孔氮化钛单晶晶体。(c1), as the nitridation time increases, further nitriding conversion growth is performed, and the barium titanate single crystal substrate is completely nitrided and transformed into a self-supporting nanoporous titanium nitride single crystal.
所述(a1)中的钛酸锶单晶衬底为(100)面钛酸锶。The barium titanate single crystal substrate in (a1) is (100) face barium titanate.
所述(a1)中的钛酸锶单晶衬底的尺度范围：1cm～5cm。The scale of the barium titanate single crystal substrate in (a1) ranges from 1 cm to 5 cm.
所述(b1)中高温氮化转化生长温度范围：1373K～1573K。The high temperature nitriding conversion growth temperature range of the (b1) is 1373K to 1573K.
所述(b1)中所述含氨氛围采用a流量的氨气+b流量的氮气+c流量的氩气+d流量的氢气气流，其中0.05SLM≤a≤10SLM、0SLM≤b≤1SLM、0SLM≤c≤1SLM、0SLM≤d≤1SLM。The ammonia-containing atmosphere in (b1) adopts a flow rate of ammonia gas + b flow rate of nitrogen gas + c flow rate of argon gas + d flow rate of hydrogen gas flow, wherein 0.05 SLM ≤ a ≤ 10 SLM, 0 SLM ≤ b ≤ 1 SLM, 0 SLM ≤ c ≤ 1 SLM, 0 SLM ≤ d ≤ 1 SLM.
所述(b1)中所述氮化时间范围：30分钟～100小时。The nitriding time range in the (b1): 30 minutes to 100 hours.
所述(b1)中所述氮化氛围压力范围：10Torr～400Torr。The nitriding atmosphere pressure range in the above (b1) is from 10 Torr to 400 Torr.
所述(c1)中纳米多孔氮化钛单晶晶体为大尺寸100面纳米多孔氮化钛单晶晶体。The nanoporous titanium nitride single crystal in (c1) is a large-sized 100-sided nanoporous titanium nitride single crystal.
作为一种具体的实施方法，所述制备纳米多孔氮化钛单晶薄膜及自支撑纳米多孔氮化钛单晶晶体的方法，其制备方法包括以下步骤：As a specific implementation method, the method for preparing a nanoporous titanium nitride single crystal film and a self-supporting nanoporous titanium nitride single crystal, the preparation method comprises the following steps:
(a2)、采用二氧化钛单晶片为衬底；(a2) using a titanium dioxide single wafer as a substrate;
(b2)、将二氧化钛单晶衬底置于气相外延生长反应室中，在高温含氨氛围中衬底表面氮化转化生长出纳米多孔氮化钛单晶薄膜；(b2) placing a titanium dioxide single crystal substrate in a vapor phase epitaxial growth reaction chamber, and nitriding the surface of the substrate to form a nanoporous titanium nitride single crystal film in a high temperature ammonia-containing atmosphere;
(c2)、随着氮化时间的增加，进一步进行氮化转化生长，将二氧化钛单晶衬底完全氮化转化生长成自支撑纳米多孔氮化钛单晶晶体。(c2), as the nitridation time increases, further nitriding conversion growth is performed, and the titanium dioxide single crystal substrate is completely nitrided and transformed into a self-supporting nanoporous titanium nitride single crystal.
所述(a2)中的二氧化钛单晶衬底为(001)面二氧化钛单晶。The titanium dioxide single crystal substrate in the (a2) is a (001) plane titanium dioxide single crystal.
所述(a2)中的二氧化钛单晶衬底的尺度范围：1cm～5cm。The scale of the titanium dioxide single crystal substrate in the (a2) range is from 1 cm to 5 cm.
所述(b2)中高温氮化转化生长温度范围：1173K～1373K。The high temperature nitriding conversion growth temperature range of the (b2) is: 1173K to 1373K.
所述(b2)中含氨氛围采用a流量的氨气+b流量的氮气+c流量的氩气+d流量的氢气气流，其中0.05SLM≤a≤10SLM、0SLM≤b≤1SLM、0SLM≤c≤1SLM、0SLM≤d≤1SLM。The ammonia-containing atmosphere in the (b2) uses a flow rate of ammonia gas + b flow rate of nitrogen + c flow rate of argon gas + d flow rate of hydrogen gas flow, wherein 0.05 SLM ≤ a ≤ 10 SLM, 0 SLM ≤ b ≤ 1 SLM, 0 SLM ≤ c ≤1SLM, 0SLM≤d≤1SLM.
所述(b2)中氮化时间范围：30分钟～20小时。The nitriding time range in the (b2) is 30 minutes to 20 hours.
所述(b2)中氮化氛围压力范围：10Torr～400Torr。The nitriding atmosphere pressure range in the (b2): 10 Torr to 400 Torr.
所述(c2)中纳米多孔氮化钛单晶晶体为大尺寸(110)面纳米多孔氮化钛单晶晶体。The nanoporous titanium nitride single crystal in the (c2) is a large-sized (110)-face nanoporous titanium nitride single crystal.
作为一种具体的实施方法，所述制备纳米多孔氮化钛单晶薄膜及自支撑纳米多孔氮化钛单晶晶体的方法，其制备方法包括以下步骤：As a specific implementation method, the method for preparing a nanoporous titanium nitride single crystal film and a self-supporting nanoporous titanium nitride single crystal, the preparation method comprises the following steps:
(a3)、采用二氧化钛单晶片为衬底；(a3) using a titanium dioxide single wafer as a substrate;
(b3)、将二氧化钛单晶衬底置于气相外延生长反应室中，在高温含氨氛围中衬底表面氮化转化生长出纳米多孔氮化钛单晶薄膜；(b3) placing a titanium dioxide single crystal substrate in a vapor phase epitaxial growth reaction chamber, and nitriding the surface of the substrate to form a nanoporous titanium nitride single crystal film in a high temperature ammonia-containing atmosphere;
(c3)、随着氮化时间的增加，进一步进行氮化转化生长，将二氧化钛单晶衬底完全氮化转化生长成自支撑纳米多孔氮化钛单晶晶体。(c3), as the nitridation time increases, further nitriding conversion growth is performed, and the titanium dioxide single crystal substrate is completely nitrided and transformed into a self-supporting nanoporous titanium nitride single crystal.
所述(a3)中的二氧化钛单晶衬底为(100)面二氧化钛。The titanium dioxide single crystal substrate in the (a3) is (100) plane titanium oxide.
所述(a3)中的二氧化钛单晶衬底的尺度范围：1cm～5cm。The scale of the titanium dioxide single crystal substrate in the (a3) range is from 1 cm to 5 cm.
所述(b3)中高温氮化转化生长温度范围：1173K～1373K。The high temperature nitriding conversion growth temperature range of the (b3) is: 1173K to 1373K.
所述(b3)中含氨氛围采用a流量的氨气+b流量的氮气+c流量的氩 气+d流量的氢气气流，其中0.05SLM≤a≤10SLM、0SLM≤b≤1SLM、0SLM≤c≤1SLM、0SLM≤d≤1SLM。The ammonia-containing atmosphere in (b3) adopts a flow rate of ammonia gas + b flow rate of nitrogen gas + c flow rate of argon gas + d flow rate of hydrogen gas flow, wherein 0.05 SLM ≤ a ≤ 10 SLM, 0 SLM ≤ b ≤ 1 SLM, 0 SLM ≤ c ≤1SLM, 0SLM≤d≤1SLM.
所述(b3)中氮化时间范围：30分钟～20小时。The nitriding time range in the (b3) is 30 minutes to 20 hours.
所述(b3)中氮化氛围压力范围：10Torr～400Torr。The nitriding atmosphere pressure range in the (b3): 10 Torr to 400 Torr.
所述(c3)中纳米多孔氮化钛单晶晶体为大尺寸(111)面纳米多孔氮化钛单晶晶体。The nanoporous titanium nitride single crystal in (c3) is a large-sized (111)-face nanoporous titanium nitride single crystal.
本发明通过将大尺寸钛酸锶单晶或二氧化钛单晶晶体氮化转化生长成同尺寸纳米多孔氮化钛单晶晶体，另辟蹊径开发出大尺寸、低成本100面纳米多孔氮化钛单晶晶体、110面纳米多孔氮化钛单晶晶体和111面的纳米多孔氮化钛单晶晶体。The invention develops a large-sized, low-cost 100-face nano-porous titanium nitride single crystal by converting a large-sized barium titanate single crystal or a titanium dioxide single crystal into a crystal of the same size nanoporous titanium nitride single crystal. , a 110-sided nanoporous titanium nitride single crystal and a 111-sided nanoporous titanium nitride single crystal.
本申请的有一方面，提供了上述任一项所述的多孔氮化钛单晶材料、根据上述任一项所述方法制备得到的多孔氮化钛单晶材料中的至少一种在电极材料中的应用。In one aspect, the porous titanium nitride single crystal material according to any one of the above, the at least one of the porous titanium nitride single crystal materials prepared according to any one of the above methods is provided in the electrode material. Application in .
本申请中，SLM是Standard Litre Per Minute的缩写，表示标准状态下1L/min的流量。In the present application, SLM is an abbreviation of Standard Litre Per Minute, indicating a flow rate of 1 L/min in a standard state.
本申请中，所述晶体的尺寸和晶体最大表面中一维的尺寸是指一块晶体上面积最大的面上相邻最远两点的距离。In the present application, the size of the crystal and the one-dimensional size in the largest surface of the crystal refer to the distance between the two nearest neighbors on the largest area of the crystal.
本申请能产生的有益效果包括：The beneficial effects that can be produced by this application include:
(1)本申请中利用钛酸锶晶体或二氧化钛晶体与氮化钛晶体结构相近的特点，使钛酸锶单晶或二氧化钛单晶衬底与氨气在高温下由外及里氮化转化生长氮化钛晶体，其余产物完全挥发；(1) In the present application, the barium titanate crystal or the titanium dioxide crystal is similar to the titanium nitride crystal structure, so that the barium titanate single crystal or the titanium dioxide single crystal substrate and the ammonia gas are transformed and grown by the outer and inner nitriding at high temperature. Titanium nitride crystal, the remaining products are completely volatilized;
(2)本申请利用同体积钛酸锶或二氧化钛晶体中的钛含量比氮化钛晶体中钛的含量少的特点，使得钛酸锶或二氧化钛单晶衬底与氨气在高温下由外及里氮化转化生成纳米多孔氮化钛单晶晶体；(2) The present application utilizes the characteristics that the content of titanium in the same volume of barium titanate or titanium dioxide crystal is less than the content of titanium in the titanium nitride crystal, so that the barium titanate or titanium dioxide single crystal substrate and the ammonia gas are at a high temperature and Nitriding to form a nanoporous titanium nitride single crystal;
(3)本申请首次报道了纳米多孔氮化钛单晶晶体、大尺寸(100)面纳米多孔氮化钛单晶晶体；(3) This application reports for the first time a nanoporous titanium nitride single crystal, a large-sized (100)-face nanoporous titanium nitride single crystal;
(4)本申请制备纳米多孔氮化钛单晶晶体的方法操作简单、重复性好、价格低廉；(4) The method for preparing nanoporous titanium nitride single crystal crystal of the present application is simple in operation, good in repeatability and low in price;
(5)本申请中所述材料具有自支撑结构，为块状单晶时，作为一种新材料，在光电转换，催化，电催化领域以及电化学能源存储***中都有潜在的应用。(5) The material described in the present application has a self-supporting structure, and when it is a bulk single crystal, as a new material, it has potential applications in the fields of photoelectric conversion, catalysis, electrocatalysis, and electrochemical energy storage systems.
附图说明DRAWINGS
图1为样品1 #大尺寸(100)面纳米多孔氮化钛单晶晶体的SEM图； 1 is an SEM image of a sample 1 #large size (100) plane nanoporous titanium nitride single crystal;
图2为样品2 #大尺寸(110)面纳米多孔氮化钛单晶晶体的SEM图； 2 is an SEM image of a sample 2 #large size (110) plane nanoporous titanium nitride single crystal;
图3为样品3 #大尺寸(111)面纳米多孔氮化钛单晶晶体的SEM图； 3 is an SEM image of a sample 3 #large size (111) plane nanoporous titanium nitride single crystal;
图4为样品1#～3#的电学性能测试图。Fig. 4 is a graph showing the electrical properties of samples 1# to 3#.
具体实施方式detailed description
下面结合实施例详述本申请，但本申请并不局限于这些实施例。The present application is described in detail below with reference to the embodiments, but the application is not limited to the embodiments.
如无特别说明，本申请的实施例中的原料均通过商业途径购买。The raw materials in the examples of the present application were all commercially purchased unless otherwise stated.
其中，钛酸锶单晶为根据文献【Christo Guguschev,Zbigniew Galazka,Dirk J.Kok,Uta Juda,Albert Kwasniewski and Reinhard Uecker.Growth of SrTiO 3 bulk single crystals using edge-defined film-fed growth and the Czochralski methods.Crystengcomm,2015,17(25):4662-4668】中的方法制备得到。 Among them, barium titanate single crystal is based on the literature [Christo Guguschev, Zbigniew Galazka, Dirk J. Kok, Uta Juda, Albert Kwasniewski and Reinhard Uecker. Growth of SrTiO 3 bulk single crystals using edge-defined film-fed growth and the Czochralski methods The method in .Crystengcomm, 2015, 17(25): 4662-4668] is prepared.
二氧化钛单晶为根据文献【Experimental Study on Growth Conditions of Big-bulk Rutile Crystal.Bi Xiaoguo；Xiu Zhimeng；Sun Xudong；etal；Journal of Synthetic Crystals,2004,33(2):244-249.】中的方法制备得到。The titanium dioxide single crystal is a method according to the literature [Experimental Study on Growth Conditions of Big-bulk Rutile Crystal. Bi Xiaoguo; Xiu Zhimeng; Sun Xudong; et al; Journal of Synthetic Crystals, 2004, 33(2): 244-249. Prepared.
本申请的实施例中分析方法如下：The analysis method in the embodiment of the present application is as follows:
利用JEOL JSM 6330F型扫描电镜分析。Scanning electron microscopy analysis using JEOL JSM 6330F.
利用PPMS-9T型电学性能分析。Use PPMS-9T type electrical performance analysis.
实施例1 样品M1 #和样品1 #的制备 Example 1 Preparation of Samples M1 # and Sample 1 #
将尺寸为1cm的(100)面钛酸锶单晶衬底，置于高纯氧化铝舟上，然后放入氧化铝管反应器中，通入含有氨气的原料气(原料气由氨气和氮气组成：氨气0.5SLM，氮气0.5SLM)并将体系加热至1523K，保持体系压力为300Torr，反应120分钟后，冷却至室温，即得生长在钛酸锶单晶 片衬底表面的多孔氮化钛单晶薄膜样品，薄膜厚度为500nm，记为样品M1 #。 A (100)-faced barium titanate single crystal substrate having a size of 1 cm was placed on a high-purity alumina boat, and then placed in an alumina tube reactor, and a raw material gas containing ammonia gas was introduced (the raw material gas was ammonia gas). And nitrogen composition: ammonia 0.5SLM, nitrogen 0.5SLM) and the system is heated to 1523K, maintaining the system pressure is 300Torr, after 120 minutes of reaction, cooling to room temperature, the porous nitrogen grown on the surface of the barium titanate single wafer substrate A titanium single crystal film sample having a film thickness of 500 nm was recorded as sample M1 # .
将尺寸为1cm的(100)面钛酸锶单晶衬底，置于高纯氧化铝舟上，然后放入氧化铝管反应器中，通入含有氨气的原料气(原料气由氨气和氢气组成：氨气0.5SLM，氢气0.1SLM)并将体系加热至1623K，保持体系压力为300Torr，反应100小时后，冷却至室温，即得多孔氮化钛单晶晶体样品，记为样品1 #，样品1 #的晶体尺寸为1cm。 A (100)-faced barium titanate single crystal substrate having a size of 1 cm was placed on a high-purity alumina boat, and then placed in an alumina tube reactor, and a raw material gas containing ammonia gas was introduced (the raw material gas was ammonia gas). And hydrogen composition: ammonia 0.5SLM, hydrogen 0.1SLM) and the system is heated to 1623K, maintaining the system pressure is 300Torr, after 100 hours of reaction, cooling to room temperature, to obtain a porous titanium nitride single crystal sample, recorded as sample 1 # , Sample 1 # has a crystal size of 1 cm.
实施例2 样品M2 #和样品2 #的制备 Example 2 Preparation of Samples M2 # and Sample 2 #
将尺寸为1cm的(001)面二氧化钛单晶衬底，置于高纯氧化铝舟上，然后放入氧化铝管反应器中，通入含有氨气的原料气(原料气由氨气和氮气组成：氨气0.3SLM，氮气0.3SLM)并将体系加热至1173K，保持体系压力为50Torr，反应120分钟后，冷却至室温，即得生长在二氧化钛单晶片衬底表面的多孔氮化钛单晶薄膜样品，薄膜厚度约为500nm，记为样品M2 #。 A (001) surface titanium dioxide single crystal substrate having a size of 1 cm was placed on a high-purity alumina boat, and then placed in an alumina tube reactor, and a feed gas containing ammonia gas was introduced (the feed gas was made up of ammonia gas and nitrogen gas). Composition: ammonia gas 0.3SLM, nitrogen 0.3SLM) and the system is heated to 1173K, the system pressure is maintained at 50 Torr, after 120 minutes of reaction, cooling to room temperature, the porous titanium nitride single crystal grown on the surface of the titanium dioxide single wafer substrate is obtained. A film sample having a film thickness of about 500 nm is designated as sample M2 # .
将尺寸为1cm的(001)面二氧化钛单晶衬底，置于高频感应炉的高纯石墨加热体上，然后放入石英反应器中，通入含有氨气的原料气(原料气由氨气和氢气组成：氨气0.3SLM，氢气0.2SLM)并将体系加热至1173K，保持体系压力为50Torr，反应100小时后，冷却至室温，即得多孔氮化钛单晶晶体样品，记为样品2 #，样品2 #的晶体尺寸为1cm。 The (001)-faced titanium dioxide single crystal substrate having a size of 1 cm is placed on a high-purity graphite heating body of a high-frequency induction furnace, and then placed in a quartz reactor, and a raw material gas containing ammonia gas is introduced (the raw material gas is ammonia). Gas and hydrogen composition: ammonia gas 0.3SLM, hydrogen 0.2SLM) and the system is heated to 1173K, the system pressure is maintained at 50 Torr, after 100 hours of reaction, cooling to room temperature, a porous titanium nitride single crystal sample is obtained, which is recorded as a sample. 2 # , sample 2 # crystal size is 1cm.
实施例3 样品M3 #和样品3 #的制备 Example 3 Preparation of Samples M3 # and Sample 3 #
将尺寸为1cm的(100)面二氧化钛单晶衬底，置于高纯氧化铝舟上，然后放入氧化铝管反应器中，通入含有氨气的原料气(原料气由氨气和氢气组成：氨气0.3SLM，氢气0.1SLM)并将体系加热至1173K，保持体系压力为50Torr，反应120分钟后，冷却至室温，即得生长在二氧化钛单晶片衬底表面的多孔氮化钛单晶薄膜样品，薄膜厚度为1000nm，记为样品M3 #。 A (100)-face titanium dioxide single crystal substrate having a size of 1 cm was placed on a high-purity alumina boat, and then placed in an alumina tube reactor, and a feed gas containing ammonia gas was introduced (the feed gas was composed of ammonia gas and hydrogen gas). Composition: ammonia gas 0.3SLM, hydrogen 0.1SLM) and the system is heated to 1173K, the system pressure is maintained at 50 Torr, after 120 minutes of reaction, cooling to room temperature, the porous titanium nitride single crystal grown on the surface of the titanium dioxide single wafer substrate is obtained. A film sample having a film thickness of 1000 nm was designated as sample M3 # .
将尺寸为1cm的(100)面二氧化钛单晶衬底，置于高纯氧化铝舟上，然后放入氧化铝管反应器中，通入含有氨气的原料气(原料气由氨气和氢 气组成：氨气0.3SLM，氢气0.1SLM)并将体系加热至1173K，保持体系压力为50Torr，反应120小时后，冷却至室温，即得多孔氮化钛单晶晶体样品，记为样品3 #，样品3 #的晶体尺寸为1cm。 A (100)-face titanium dioxide single crystal substrate having a size of 1 cm was placed on a high-purity alumina boat, and then placed in an alumina tube reactor, and a feed gas containing ammonia gas was introduced (the feed gas was composed of ammonia gas and hydrogen gas). composition: 0.3 slm ammonia, hydrogen 0.1 slm) and the system was heated to 1173K, keeping the internal pressure of 50 Torr is, 120 hours after the reaction was cooled to room temperature, i.e. much titanium nitride single crystal pore crystalline sample, referred to as sample # 3, The crystal size of sample 3 # was 1 cm.
实施例4 样品M4 #～样品M9 #的制备 Sample Preparation Example 4 M4 # ~ sample embodiment M9 #
样品M4 #～样品M9 #的基本制备步骤同实施例1中的样品M1 #，改变衬底和反应条件，得到不同的样品。样品编号与衬底和反应条件的关系如表1所示。 The basic preparation steps of the sample M4 # to the sample M9 # were the same as those of the sample M1 # in Example 1, and the substrate and the reaction conditions were changed to obtain different samples. The relationship between the sample number and the substrate and reaction conditions is shown in Table 1.
表1Table 1
Figure PCTCN2018083869-appb-000001
Figure PCTCN2018083869-appb-000001
其中，所述样品M4 #～样品M9 #的厚度为10nm～100μm范围内。 The thickness of the sample M4 # to the sample M9 # is in the range of 10 nm to 100 μm.
实施例5 样品4 #～样品9 #的制备 Example 5 Preparation of Sample 4 # ～样9 #
样品4 #～样品9 #的基本制备步骤同实施例1中的样品1 #，改变衬底和反应条件，得到不同的样品。样品编号与衬底和反应条件的关系如表2所示。 The basic preparation steps of Sample 4 # to Sample 9 # were the same as those of Sample 1 # in Example 1, and the substrate and reaction conditions were changed to obtain different samples. The relationship between the sample number and the substrate and reaction conditions is shown in Table 2.
表2Table 2
样品编号Sample serial number 衬底、原料气、反应温度、反应压力Substrate, feed gas, reaction temperature, reaction pressure 反应时间Reaction time
4 # 4 # 同M4 # Same as M4 # 100h100h
5 # 5 # 同M5 # Same as M5 # 100h100h
6 # 6 # 同M6 # Same as M6 # 100h100h
7 # 7 # 同M7 # Same as M7 # 100h100h
8 # 8 # 同M8 # Same as M8 # 100h100h
9 # 9 # 同M9 # Same as M9 # 100h100h
实施例6 样品M1 #～样品M9 #、样品1 #～样品9 #的形貌表征 Example 6 Morphological Characterization of Sample M1 # ～Sample M9 # , Sample 1 # ～样9 #
采用扫描电镜对样品1#～样品9#的形貌进行了表征，结果显示，样品1#～样品9#均具有10nm～500nm的孔。样品4 #和样品5 #的形貌与样品1 #类似，以样品1 #为典型代表，其(100)面纳米多孔氮化钛单晶晶体的扫描电镜照片如图1所示，由图可以看出氮化钛具有多孔的骨架结构。样品6 #和样品7 #的形貌与样品2 #类似，以样品2 #为典型代表，其(110)面纳米多孔氮化钛单晶晶体的扫描电镜照片如图2所示，由图可以看出氮化钛的多孔结构。样品8 #和样品9 #的形貌与样品3 #类似，以样品3 #为典型代表，其(111)面纳米多孔氮化钛单晶晶体的扫描电镜照片如图3所示，由图可以看出氮化钛的多孔结构。 The morphology of sample 1# to sample 9# was characterized by scanning electron microscopy. The results showed that samples 1# to 9# all had pores of 10 nm to 500 nm. And Sample # 4 Sample # 5 Sample morphology similar to # 1 to # 1 is a typical representative sample, which is (100) plane of titanium nitride nano-porous monocrystalline crystal SEM photograph shown in Figure 1, it may be made of FIG. It is seen that titanium nitride has a porous skeleton structure. Samples # 6 and # 7 Sample morphology similar to the sample # 2 to # 2 as a typical representative sample, which is (110) plane of titanium nitride nano-porous monocrystalline crystal SEM photograph shown in Figure 2, may be made of FIG. The porous structure of titanium nitride is seen. Sample 8 Sample # 9 and # morphology similar to the sample # 3 with that of sample # 3 is a typical representative of (111) plane of titanium nitride nano-porous monocrystalline crystal SEM photograph shown in Figure 3, it may be made of FIG. The porous structure of titanium nitride is seen.
样品M1 #～样品M9 #的扫描电镜照片分别与样品1 #～样品9 #类似，如样品M1 #的扫描电镜照片与样品1 #类似。其中，所述产品的孔范围均在10nm～1000nm范围内。 The scanning electron micrographs of sample M1 # to sample M9 # are similar to sample 1 # to sample 9 # , respectively, and the scanning electron micrograph of sample M1 # is similar to sample 1 # . Wherein, the pore range of the product is in the range of 10 nm to 1000 nm.
实施例7 样品1 #～样品9 #的结构/元素表征 Example 7 Structure/Element Characterization of Sample 1 # ～样9 #
采用X射线晶体衍射以及电子束刻蚀结合透射电镜的方法对样品M1 #～样品M3 #、样品1 #～样品9 #进行了原子结构表征，结果显示，这些样品都是多孔的氮化钛单晶。 The method employed in conjunction with transmission electron microscopy and X-ray diffraction of the electron beam lithography to Sample # Sample Ml M3 #, Sample # 1 to Sample # 9 were characterized atoms, the results show that these samples are of the porous titanium nitride single crystal.
由此可知，样品1 #～样品9 #均为氮化钛单晶晶体，样品M1 #～样品M3 #均为氮化钛单晶薄膜。 It can be seen, Sample # 1 to Sample # 9 crystal are titanium nitride single crystal, the samples Ml ~ # # M3 are samples of titanium nitride single crystal thin film.
实施例8 样品1 #～样品9 #的电学性能测试 Example 8 Electrical property test of sample 1 # ～sample 9 #
本实施例中对样品1 #～样品9 #的电学性能进行测试，测试结果典型的如图4所示。图4为样品的样品1 #～样品3 #的电学性能测试结果。从图中 可以看出多孔氮化钛单晶具有优良的导电性能。 In the present embodiment, the electrical properties of the samples 1 # to 9 # were tested, and the test results are typically shown in FIG. Figure 4 shows the results of the electrical performance test of samples 1 # to 3 # of the sample. It can be seen from the figure that the porous titanium nitride single crystal has excellent electrical conductivity.
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。The above description is only a few examples of the present application, and is not intended to limit the scope of the application. However, the present application is disclosed in the preferred embodiments, but is not intended to limit the application, any person skilled in the art, It is within the scope of the technical solution to make a slight change or modification with the technical content disclosed above, which is equivalent to the equivalent embodiment, without departing from the technical scope of the present application.

Claims (12)

  1. 一种多孔氮化钛单晶材料，其特征在于，所述多孔氮化钛单晶材料中含有10nm～1000nm的孔。A porous titanium nitride single crystal material, characterized in that the porous titanium nitride single crystal material contains pores of 10 nm to 1000 nm.
  2. 根据权利要求1所述的多孔氮化钛单晶材料，其特征在于，所述多孔氮化钛单晶材料为多孔氮化钛单晶薄膜和/或多孔氮化钛单晶晶体。The porous titanium nitride single crystal material according to claim 1, wherein the porous titanium nitride single crystal material is a porous titanium nitride single crystal film and/or a porous titanium nitride single crystal.
  3. 根据权利要求2所述的多孔氮化钛单晶材料，其特征在于，所述多孔氮化钛单晶薄膜的表面为多孔氮化钛单晶的(100)面、(110)面、(111)面中的至少一面。The porous titanium nitride single crystal material according to claim 2, wherein the surface of the porous titanium nitride single crystal thin film is a (100) plane, a (110) plane, and (111) of a porous titanium nitride single crystal. At least one side of the face.
  4. 根据权利要求2所述的多孔氮化钛单晶材料，其特征在于，所述多孔氮化钛单晶晶体的尺寸为0.1cm～30cm；The porous titanium nitride single crystal material according to claim 2, wherein the porous titanium nitride single crystal has a size of 0.1 cm to 30 cm;
    所述多孔氮化钛单晶薄膜的厚度为10nm～100μm。The porous titanium nitride single crystal thin film has a thickness of 10 nm to 100 μm.
  5. 根据权利要求2所述的多孔氮化钛单晶材料，其特征在于，所述多孔氮化钛单晶晶体的尺寸为1cm～5cm。The porous titanium nitride single crystal material according to claim 2, wherein the porous titanium nitride single crystal has a size of from 1 cm to 5 cm.
  6. 权利要求1至5任一项所述的多孔氮化钛单晶材料的制备方法，其特征在于，至少包括：将钛源与含有氨气的原料气接触反应，得到所述多孔氮化钛单晶材料；The method for preparing a porous titanium nitride single crystal material according to any one of claims 1 to 5, further comprising: contacting a titanium source with a raw material gas containing ammonia gas to obtain the porous titanium nitride single Crystal material
    其中，所述钛源选自钛酸锶单晶材料、二氧化钛单晶材料中的至少一种。Wherein, the titanium source is at least one selected from the group consisting of barium titanate single crystal materials and titanium dioxide single crystal materials.
  7. 根据权利要求6所述的方法，其特征在于，所述反应的温度为1173K～1873K；The method according to claim 6, wherein the temperature of the reaction is from 1173K to 1873K;
    所述反应的压力为0.1Torr～1000Torr；The pressure of the reaction is from 0.1 Torr to 1000 Torr;
    所述反应的时间为1min～500h；The reaction time is from 1 min to 500 h;
  8. 根据权利要求6所述的方法，其特征在于，所述反应的温度为1373K～1873K。The method of claim 6 wherein the temperature of the reaction is from 1373 K to 1873 K.
  9. 根据权利要求6所述的方法，其特征在于，所述含有氨气的原料 气中包括氨气和氮气、氩气、氢气中的至少一种；The method according to claim 6, wherein the ammonia-containing feed gas comprises at least one of ammonia gas and nitrogen gas, argon gas, and hydrogen gas;
    其中，氨气的流量记为a，氮气的流量记为b，氩气的流量记为c，氢气的流量记为d，满足：Among them, the flow rate of ammonia gas is recorded as a, the flow rate of nitrogen gas is recorded as b, the flow rate of argon gas is recorded as c, and the flow rate of hydrogen gas is recorded as d, which satisfies:
    0.05SLM≤a≤100SLM；0.05SLM≤a≤100SLM;
    0SLM≤b≤100SLM；0SLM≤b≤100SLM;
    0SLM≤c≤100SLM；0SLM≤c≤100SLM;
    0SLM≤d≤100SLM。0SLM≤d≤100SLM.
  10. 根据权利要求6所述的方法，其特征在于，所述方法至少包括：将钛酸锶单晶、二氧化钛单晶中的至少一种在含氨氛围中反应，钛酸锶单晶和/或二氧化钛单晶表面氮化生长，得到多孔氮化钛单晶薄膜。The method according to claim 6, wherein the method comprises at least: reacting at least one of barium titanate single crystal, titanium dioxide single crystal in an ammonia-containing atmosphere, barium titanate single crystal and/or titanium dioxide The surface of the single crystal is nitrided to form a porous titanium nitride single crystal film.
  11. 根据权利要求6所述的方法，其特征在于，所述方法至少包括：将钛酸锶单晶、二氧化钛单晶中的至少一种在含氨氛围中反应，钛酸锶单晶和/或二氧化钛单晶表面氮化生长，得到多孔氮化钛单晶晶体。The method according to claim 6, wherein the method comprises at least: reacting at least one of barium titanate single crystal, titanium dioxide single crystal in an ammonia-containing atmosphere, barium titanate single crystal and/or titanium dioxide The surface of the single crystal is nitrided to grow to obtain a porous titanium nitride single crystal.
  12. 权利要求1至5任一项所述的多孔氮化钛单晶材料、根据权利要求6至11任一项所述方法制备得到的多孔氮化钛单晶材料中的至少一种在电极材料中的应用。At least one of the porous titanium nitride single crystal material according to any one of claims 1 to 5, the porous titanium nitride single crystal material prepared by the method according to any one of claims 6 to 11, in the electrode material Applications.
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