WO2019153699A1 - Nanofeuille de tellure bidimensionnelle, sa méthode de fabrication et son application - Google Patents

Nanofeuille de tellure bidimensionnelle, sa méthode de fabrication et son application Download PDF

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WO2019153699A1
WO2019153699A1 PCT/CN2018/100581 CN2018100581W WO2019153699A1 WO 2019153699 A1 WO2019153699 A1 WO 2019153699A1 CN 2018100581 W CN2018100581 W CN 2018100581W WO 2019153699 A1 WO2019153699 A1 WO 2019153699A1
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nanosheet
dimensional
tantalum
thickness
dimensional tantalum
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PCT/CN2018/100581
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English (en)
Chinese (zh)
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张晗
谢中建
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深圳大学
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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
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/02—Elemental selenium or tellurium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/0272—Selenium or tellurium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
    • H01L31/09—Devices sensitive to infrared, visible or ultraviolet radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites

Definitions

  • the invention relates to the field of nano materials, in particular to a two-dimensional bismuth nanosheet and a preparation method and application thereof.
  • Two-dimensional materials refer to materials that can move freely (planar motion) on two non-nanoscale dimensions, such as nanofilms, superlattices, and quantum wells.
  • the two-dimensional material was proposed along with the successful separation of the monoatomic graphite material graphene from the Geim team at the University of Manchester in 2004. Among them are boron nitride, molybdenum disulfide, silene, terpene, black phosphorus and the like called "white graphite”.
  • the two-dimensional materials described above are layered materials, that is, composed of strong chemical bonds in the layers and weak van der Waals forces between the layers. It is easily peeled off into a two-dimensional material by a mechanical peeling method and a liquid phase peeling method.
  • the types of these two-dimensional layered materials are limited, so this greatly limits the development of two-dimensional functional materials. The development of a wider variety of two-dimensional functional materials is imminent.
  • the present invention provides a two-dimensional tantalum nanosheet, which is a novel two-dimensional functional material with good photoelectric detection function.
  • a first aspect of the invention provides a two-dimensional tantalum nanosheet having a thickness of from 1 to 50 nm.
  • the two-dimensional tantalum nanosheet has a thickness of 1-5 nm.
  • the two-dimensional tantalum nanosheet has a thickness of 5-10 nm.
  • the two-dimensional tantalum nanosheet has a thickness of 10-50 nm.
  • the two-dimensional tantalum nanosheet has a thickness of 3-5 nm.
  • the two-dimensional tantalum nanosheet has a length to width dimension of 10-200 nm.
  • the two-dimensional tantalum nanosheet has a length to width dimension of 10-50 nm.
  • the two-dimensional tantalum nanosheet has a length to width dimension of 50-100 nm.
  • the two-dimensional tantalum nanosheet has a length to width dimension of 100-200 nm.
  • the two-dimensional tantalum nanosheet has a length to width dimension of 30-40 nm.
  • the two-dimensional tantalum nanosheet provided by the first aspect of the invention has a narrow band gap, a wide response spectrum, good stability, and excellent photoelectric detection performance.
  • a second aspect of the present invention provides a method for preparing a two-dimensional tantalum nanosheet, comprising the following steps:
  • the tantalum raw material is provided, and the tantalum raw material is peeled off by a liquid phase stripping method to obtain a two-dimensional tantalum nanosheet having a thickness of 1 to 50 nm.
  • liquid phase stripping method specifically comprises the following operations:
  • the bismuth raw material is added to the solvent, and the probe is ultrasonicated for 8-15 hours in an ice bath environment; after the ultrasonication of the probe is finished, the water bath ultrasonication is continued, and the ultrasonic bath time is 3-10 h, and the temperature of the water bath is maintained. 5-15 ° C; after ultrasonication, centrifugation and drying to obtain two-dimensional cerium nanosheets.
  • the ultrasonic power of the probe is 200-250W.
  • the probe ultrasound is non-continuous ultrasound, and the ultrasonic on/off time is selected to be 2/4 s.
  • the water bath ultrasonic power is 300-380W.
  • the centrifugation operation comprises: using a centrifugal force of 0.5-6 kg, centrifuging for 20-35 min, taking the supernatant, and then continuously centrifuging the supernatant with 10-15 kg for 25-35 min to obtain a precipitate; after the obtained precipitate is dried That is, the two-dimensional tantalum nanosheet is obtained.
  • the solvent comprises at least one of isopropyl alcohol, ethanol, acetone, water, and methylpyrrolidone (ie, N-methylpyrrolidone, NMP).
  • concentration of the ruthenium raw material in the solvent is 1-7 mg/mL.
  • the bismuth raw material comprises glutinous rice flour or glutinous rice.
  • the prior art generally employs a liquid phase lift-off method for stripping a two-dimensional layered material.
  • the present invention is the first to use a liquid phase stripping method to strip two-dimensional non-layered metal tantalum single material, and has achieved success.
  • a second aspect of the present invention provides a method for preparing a two-dimensional tantalum nanosheet, which is prepared by a liquid phase stripping method for a first time from a non-layered tantalum raw material to obtain a two-dimensional tantalum nanosheet, which has good peeling effect and can be mass-produced.
  • the two-dimensional bismuth nanosheet has lower cost and the preparation method is simple and easy to operate.
  • a third aspect of the invention provides the use of a two-dimensional germanium nanosheet as described above in a photodetector.
  • the two-dimensional germanium nanosheet of the present invention has good photodetection performance, it can be suitably used for a photodetector.
  • the two-dimensional tantalum nanosheet provided by the invention has excellent photoelectric detection performance
  • the preparation method of the two-dimensional tantalum nanosheet provided by the invention is the first method for preparing the two-dimensional tantalum nanosheet from the non-layered tantalum raw material by the liquid phase stripping method, and the stripping effect is good, and the large-scale preparation of the two-dimensional tantalum can be realized. Nanosheets, low cost, simple and easy to prepare method;
  • Example 1 is a transmission electron micrograph of a two-dimensional tantalum nanosheet prepared in Example 1;
  • Example 2 is an atomic force micrograph of a two-dimensional tantalum nanosheet prepared in Example 1;
  • Example 3 is an absorption spectrum diagram of a liquid phase stripping process of a two-dimensional tantalum nanosheet in Example 1;
  • Fig. 4 is an absorption spectrum diagram and a band gap diagram of two-dimensional bismuth nanosheet aqueous dispersions of different sizes.
  • two-dimensional tantalum nanosheet or " ⁇ " referred to in the present invention, unless otherwise specified, refers to elemental germanium.
  • a first aspect of the embodiments of the present invention provides a two-dimensional germanium nanosheet having a thickness of 1 to 50 nm.
  • the two-dimensional tantalum nanosheet has a thickness of 3-5 nm.
  • the two-dimensional tantalum nanosheet has a thickness of 1-5 nm.
  • the two-dimensional tantalum nanosheet has a thickness of 5-10 nm.
  • the two-dimensional tantalum nanosheet has a thickness of 10-50 nm.
  • the two-dimensional tantalum nanosheet has a thickness of 1 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm or 50 nm.
  • the two-dimensional tantalum nanosheet has a length to width dimension of 10 to 200 nm.
  • the two-dimensional germanium nanosheet has a length to width dimension of 10-50 nm.
  • the two-dimensional tantalum nanosheet has a length to width dimension of 50-100 nm.
  • the two-dimensional germanium nanosheet has a length to width dimension of 100-200 nm.
  • the two-dimensional tantalum nanosheet has a length to width dimension of 30-40 nm.
  • the two-dimensional tantalum nanosheet has a length to width dimension of 10-30 nm.
  • the two-dimensional ⁇ nanosheet has a length and width dimension of 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, 150 nm, 160 nm, 170 nm. , 180 nm, 190 nm or 200 nm.
  • the two-dimensional germanium nanosheet has a light response wavelength range of 500 nm or less.
  • the two-dimensional tantalum nanosheet has a narrow band gap, so that it can respond to the range from ultraviolet light to visible light; secondly, it has better time stability and stable photodetection cycle. Sex. Two-dimensional bismuth nanosheets can achieve better photometric stability within 2 weeks. In the 10h photodetection cycle test, the light probe signal showed only a slight attenuation. Therefore, the two-dimensional germanium nanosheet provided by the embodiment of the invention has a narrow band gap, a wide response spectrum, good stability, and excellent photoelectric detection performance.
  • a second aspect of the embodiments of the present invention provides a method for preparing a two-dimensional tantalum nanosheet, comprising the following steps:
  • the tantalum raw material is provided, and the tantalum raw material is peeled off by a liquid phase stripping method to obtain a two-dimensional tantalum nanosheet having a thickness of 1 to 50 nm.
  • the bismuth raw material is a two-dimensional non-layered metal ruthenium element, and may be a ruthenium powder or a ruthenium block, and the size and shape thereof are not particularly limited, and may be micron or millimeter. Block.
  • the bismuth raw material can be obtained by purchase.
  • the band gap of the tantalum raw material is about 0.3 eV, and the band gap of the two-dimensional tantalum nanosheet obtained after peeling is also narrow, and can be used for detecting light with a long wavelength.
  • the liquid phase stripping method specifically includes the following operations:
  • the bismuth raw material is added to the solvent, and the probe is ultrasonicated for 8-15 hours in an ice bath environment; after the ultrasonication of the probe is finished, the water bath ultrasonication is continued, and the ultrasonic bath time is 3-10 h, and the temperature of the water bath is maintained. 5-15 ° C; after ultrasonication, centrifugation and drying to obtain two-dimensional cerium nanosheets.
  • the solvent comprises at least one of isopropanol, ethanol, acetone, water, and methylpyrrolidone.
  • the concentration of the rhodium material in the solvent is from 1 to 7 mg/mL.
  • the probe has an ultrasonic power of 200-250W. Further optionally, the ultrasonic power of the probe is 240W.
  • the probe is sonicated for 10 hours.
  • the probe ultrasound is non-continuous ultrasound
  • the ultrasonic on/off time is selected to be 2/4 s, that is, ultrasonic for 2 s, then the ultrasonic probe is turned off for 4 s, the ultrasound is continued for 2 s, and so on.
  • the water bath has an ultrasonic power of 300-380 W. Further optionally, the water bath ultrasonic power is 360W.
  • the time of the water bath ultrasound is 8 h.
  • the water bath temperature is maintained at 10 °C.
  • the centrifuging operation comprises: firstly using a centrifugal force of 0.5-6 kg, centrifuging for 20-35 min, taking the supernatant; then, the supernatant is continuously centrifuged with a centrifugal force of 10-15 kg. At 25-35 min, a precipitate is obtained as a two-dimensional tantalum nanosheet.
  • the supernatant is taken; then the supernatant is centrifuged for 30 min with a centrifugal force of 12 kg to obtain a precipitate, and the obtained precipitate is dried to obtain a two-dimensional tantalum nanosheet.
  • the manner of drying is not limited, and may be, for example, vacuum drying.
  • the prior art generally employs a liquid phase lift-off method for stripping a two-dimensional layered material.
  • the present invention uses a liquid phase stripping method to strip two-dimensional non-layered elemental tantalum materials and succeeds.
  • a second aspect of the present invention provides a method for preparing a two-dimensional tantalum nanosheet, which is prepared by a liquid phase stripping method for a first time from a non-layered tantalum raw material to obtain a two-dimensional tantalum nanosheet, which has good peeling effect and can be mass-produced.
  • the two-dimensional bismuth nanosheet has lower cost and the preparation method is simple and easy to operate.
  • a third aspect of the invention provides the use of a two-dimensional germanium nanosheet as described above in a photodetector.
  • the two-dimensional germanium nanosheet of the present invention has good photodetection performance, it can be well used as a photodetector.
  • a method for preparing a two-dimensional tantalum nanosheet comprises the following steps:
  • the required two-dimensional bismuth nanosheets are obtained by centrifugation. First, the centrifugal force of 2000g was used and centrifuged for 30 minutes. The supernatant was taken, and then the supernatant was centrifuged for 30 min at 12000 g to obtain a precipitate, which was vacuum dried to obtain a two-dimensional tantalum nanosheet.
  • Fig. 1 it is an electron mirror topography of a two-dimensional metal elemental tantalum nanosheet. Its size is less than 100 nm.
  • Figure 2 shows an atomic force micrograph. As can be seen from the figure, the thickness of the two-dimensional tantalum nanosheet is about 4 nm. Therefore, by observation by transmission electron microscopy and atomic force microscopy, two-dimensional elemental germanium nanosheets can be peeled off by liquid phase stripping.
  • Figure 4a is an absorption spectrum of two-dimensional tantalum nanosheets of different sizes under different centrifugal forces (rotational speeds) during the first centrifugation.
  • Figure 4b shows different bandgap plots for tantalum nanosheets at different speeds.
  • the dimensions of the two-dimensional tantalum nanosheets corresponding to the rotational speeds of 0.5-1 kg, 1-3 kg, and 3-6 kg are about 200 nm, about 100 nm, and about 50 nm.
  • the absorption spectrum was measured using an ultraviolet-spectrophotometer. Different sizes of cerium nanosheet dispersions were placed in a quartz cuvette and placed in an ultraviolet spectrophotometer card slot to measure absorbance.
  • band gaps of the yttrium nanosheets corresponding to the rotational speeds of 0.5-1 kg, 1-3 kg and 3-6 kg were 1.63 eV, 1.72 eV and 1.90 eV, respectively.
  • Larger size two-dimensional germanium nanosheets have smaller band gaps and can achieve longer wavelength response. Smaller size two-dimensional germanium nanosheets can achieve higher photodetection signals due to their larger surface area.
  • a method for preparing a two-dimensional tantalum nanosheet comprises the following steps:
  • the required two-dimensional bismuth nanosheets are obtained by centrifugation. First, centrifugal force of 1800 g was used and centrifuged for 35 min. The supernatant was taken, and then the supernatant was centrifuged at 15000 g for 25 min to obtain a precipitate, which was vacuum dried to obtain a two-dimensional tantalum nanosheet.
  • a method for preparing a two-dimensional tantalum nanosheet comprises the following steps:
  • (1) 500 mg of a mash block was added to 100 ml of isopropyl alcohol. Then select the probe ultrasound 250W, ultrasound for 8h. The ultrasound on/off time was chosen to be 2/4 s and ultrasound was performed in an ice bath environment. After the probe is ultrasonicated, it is then ultrasonically probed in a water bath. The water bath ultrasonic power is 380W. The ultrasound time was 3 h. The bath temperature is maintained at 5 ° C;
  • the required two-dimensional bismuth nanosheets are obtained by centrifugation.
  • the centrifugal force of 2200 g was used and centrifuged for 20 min. The supernatant was taken, and then the supernatant was centrifuged for 35 min at 10000 g to obtain a precipitate, which was vacuum dried to obtain a two-dimensional tantalum nanosheet.

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Abstract

La présente invention concerne une nanofeuille de tellure bidimensionnelle. La feuille de tellure bidimensionnelle a une épaisseur de 1 à 50 nm. La nanofeuille de tellure bidimensionnelle selon la présente invention présente d'excellentes performances de détection photoélectrique. La présente invention concerne en outre une méthode de fabrication de la nanofeuille de tellure bidimensionnelle, comprenant les étapes suivantes consistant à : fournir une matière première de tellure, et exfolier la matière première de tellure au moyen d'une exfoliation en phase liquide pour obtenir une nanofeuille de tellure bidimensionnelle, la nanofeuille de tellure bidimensionnelle ayant une épaisseur de 1 à 50 nm. Selon la présente invention, une nanofeuille de tellure bidimensionnelle est fabriquée à partir d'une matière première de tellure non stratifiée au moyen d'une exfoliation en phase liquide pour la première fois, et l'effet d'exfoliation est bon ; de plus, la fabrication à grande échelle de nanofeuilles de tellure bidimensionnelles peut être mise en œuvre, les coûts sont faibles, et la méthode de fabrication est simple et facile à utiliser. La présente invention porte également sur une application de la nanofeuille de tellure bidimensionnelle dans un photodétecteur.
PCT/CN2018/100581 2018-02-09 2018-08-15 Nanofeuille de tellure bidimensionnelle, sa méthode de fabrication et son application WO2019153699A1 (fr)

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