CN105800566A - Method for growing single-layer and multi-layer transition metal sulfides through alternating injection of reactants - Google Patents

Method for growing single-layer and multi-layer transition metal sulfides through alternating injection of reactants Download PDF

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Publication number
CN105800566A
CN105800566A CN201610236670.2A CN201610236670A CN105800566A CN 105800566 A CN105800566 A CN 105800566A CN 201610236670 A CN201610236670 A CN 201610236670A CN 105800566 A CN105800566 A CN 105800566A
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multilamellar
transition metal
sulfide
diethyl
reactants
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张天宁
陈鑫
张克难
俞伟伟
孙艳
戴宁
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Shanghai Institute of Technical Physics of CAS
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Shanghai Institute of Technical Physics of CAS
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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
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/20—Methods for preparing sulfides or polysulfides, in general
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/007—Titanium sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/06—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

The invention discloses a method for growing single-layer and multi-layer transition metal sulfides through alternating injection of reactants. By the adoption of the method, deposition reaction of the reactants is achieved alternately, the number of layers and area of grown transition metal sulfides are controlled by controlling reaction temperature and time, and layered transition metal sulfides high in quality are obtained. The method has the advantages that growth condition is accurate and controllable, operation is easy and convenient, and large-area preparation of transition metal sulfides can be achieved. The method has broad application prospects in fields such as nano-electronical appliances, lubricating materials and photocatalysis.

Description

The method alternately injecting reactant growth monolayer and multilamellar transient metal sulfide
Technical field
The invention belongs to technical field of novel materials, relate to nano material preparation technology, refer specifically to the method by alternately injecting reactant growth monolayer and multilamellar transient metal sulfide.
Background technology
Since the two of Univ Manchester UK in 2004 scientists successfully separate Graphene, two-dimensional material enjoys people to favor with the electricity of its excellence, optics, mechanical property.Graphene is at lithium ion battery, and solaode, sensor aspect obtain application, show splendid performance.While it is true, the Graphene of intrinsic is absent from band gap, this severely limits its application in electronics and opto-electronic device.Transient metal sulfide from block materials become two-dimensional structure time, electronic band structure is become direct band gap from non-immediate band gap, has many similar characteristics even better than Graphene, therefore stores at energy, electronics, is used widely in the field such as photoelectricity.The basic chemical formula of transient metal sulfide is MX2, wherein M is VI race element or other transition metals (Mo, W, Ti), and X is chalcogen (S, Se, Te), wherein with MoS2And WS2For Typical Representative, with MOS2For example, macroscopic view MOS2Having layer structure, the structure of each layer is S-Mo-S (X-M-X), and sulphur atom and the one layer of molybdenum atom containing 2 layers of hexagonal arrangement, Van der Waals force combines between layers.The preparation method of two dimension transient metal sulfide is mainly by mechanical stripping method and chemical vapour deposition technique at present.Mechanical stripping method is the method for the most traditional preparation two-dimensional material, and preparation method is simple, it is thus achieved that sample defects few, but yield is relatively low, be not suitable for large area produce.Chemical vapour deposition technique mainly at high temperature by molybdenum source and sulfur vapor reaction, generates MoS on substrate2Thin film.The method is to prepare the highly crystalline mass M OS of large area2Most efficient method, has superiority at size, the number of plies and physical property controlling party mask, but preparation technology is also immature at present.The greatest problem of current restriction ultra-thin two-dimension stratified material practical application is the acquisition of high-quality wafer scale material.Obtain high-quality wafer scale molybdenum bisuphide material by the mode of control simple to operation to be significant, one of key challenge of its application especially.
Summary of the invention
The present invention provides a kind of technique controlled, simple to operate by alternately injecting reactant to reaction cavity, the method for growth monolayer and multilamellar transient metal sulfide.The method utilizes consumption and the response time by accurately controlling reactant pulses, makes reactant pulses alternately enter cavity and is deposited reaction, thus controlling the number of plies and the area of transient metal sulfide growth, obtains the nonwoven fabric from filaments of high-quality transient metal sulfide.
It is characterized in that deposition process method is as follows:
It is that the silicon of 1-100 square centimeter, sapphire sheet, piezoid, mica sheet or surface length have aluminium sesquioxide, titanium dioxide, silica membrane or surface to have the substrate of stereochemical structure to be placed in reaction cavity by clean area, controlling reaction pressure at 1-20 millibar, reaction temperature is 100-700 DEG C；One or more different transition metal reactants and one or more chalcogens are alternately injected by carrier gas, control carrier gas flux in 1-500 cubic centimetre/second, the interval time that different reactants injects is 1 second-10 minutes, alternately inject circulation 1-1000 time altogether, substrate obtains monolayer and multilamellar transient metal sulfide.
Described transition metal reactant refers to hexacarbonylmolybdenum, tungsten carbonyl, isopropanol molybdenum, isopropyl titanate.
Described chalcogen refers to diethyl sulfide, diethyl selenide, tellurium diethyl, hydrogen sulfide.
The invention have the advantage that growth conditions controllable precise, simple to operation, it may be achieved prepared by the large area of transient metal sulfide.Have broad application prospects in fields such as nano electron device, lubriation material, photocatalysis.
Accompanying drawing explanation
Fig. 1: alternately inject the schematic diagram of reactant, is alternately injected by two reactants of A and B, reaches the purpose of deposition monolayer and multilamellar transient metal sulfide.
Detailed description of the invention:
Embodiment 1
Being placed in deposition reaction cavity by the silicon substrate that 100 square centimeters clean, control reaction pressure at 5 millibars, reaction temperature is 700 DEG C；Arranging carrier gas flux is 100 cubic centimetres/second, injecting hexacarbonylmolybdenum and hydrogen sulfide by carrier gas to cavity cycle alternation, hexacarbonylmolybdenum and hydrogen sulfide interval time are 3 minutes, and hydrogen sulfide and hexacarbonylmolybdenum interval time are 1 minute, inject 10 circulations altogether, obtain monolayer molybdenum bisuphide at deposited on substrates.
Embodiment 2
The length that 1 square centimeter clean having the silicon chip of thin film silicon oxide silicon be placed in deposition reaction cavity, controls reaction pressure at 15 millibars, reaction temperature is 100 DEG C；Arranging carrier gas flux is 500 cubic centimetres/second, hexacarbonylmolybdenum and diethyl sulfide is injected to cavity cycle alternation by carrier gas, hexacarbonylmolybdenum and diethyl sulfide interval time are 10 minutes, diethyl sulfide and hexacarbonylmolybdenum interval time are 10 minutes, injecting 100 circulations altogether, deposition obtains multilamellar molybdenum bisuphide.
Embodiment 3
Being placed in deposition reaction cavity by stratiform Muscovitum 21.3 square centimeters clean, control reaction pressure at 20 millibars, reaction temperature is 300 DEG C；Arranging carrier gas flux is 400 cubic centimetres/second, injecting tungsten carbonyl and hydrogen sulfide by carrier gas to cavity cycle alternation, tungsten carbonyl and hydrogen sulfide interval time are 30 seconds, and hydrogen sulfide and tungsten carbonyl interval time are 20 seconds, injecting 1000 circulations altogether, deposition obtains multilamellar tungsten disulfide.
Embodiment 4
Being placed in deposition reaction cavity by stratiform Muscovitum 4 square centimeters clean, control reaction pressure at 2 millibars, reaction temperature is 250 DEG C；Arranging carrier gas flux is 10 cubic centimetres/second, isopropanol molybdenum and diethyl selenide is injected to cavity cycle alternation by carrier gas, isopropanol molybdenum and diethyl selenide interval time are 3 seconds, diethyl selenide and isopropanol molybdenum interval time are 8 minutes, injecting 1000 circulations altogether, deposition obtains monolayer and multilamellar two selenizing molybdenum.
Embodiment 5
By piezoid 4.5 square centimeters clean, silicon chip 36 square centimeters clean is placed in deposition reaction cavity, controls reaction pressure at 17 millibars, and reaction temperature is 220 DEG C；Arranging carrier gas flux is 100 cubic centimetres/second, isopropanol molybdenum, diethyl selenide, diethyl sulfide is injected to cavity cycle alternation by carrier gas, circular order is isopropanol molybdenum-diethyl selenide-isopropanol molybdenum-diethyl sulfide, isopropanol molybdenum and diethyl selenide interval time are 1 minute, diethyl selenide and isopropanol molybdenum are 50 seconds isopropanol molybdenums interval time and diethyl sulfide interval time is 40 seconds, the interval time of diethyl sulfide and isopropanol molybdenum is 23 seconds, injecting 1000 circulations altogether, deposition obtains multilamellar two selenizing molybdenum and molybendum disulfide complexes.
Embodiment 6
The spacing 10 microns by surface etch 50 square centimeters clean, high 2 microns, the silicon chip of the cuboid array of each 5 microns of length and width is placed in deposition reaction cavity, controls reaction pressure at 7.3 millibars, and reaction temperature is 620 DEG C；Arranging carrier gas flux is 33 cubic centimetres/second, isopropyl titanate and hydrogen sulfide is injected to cavity cycle alternation by carrier gas, isopropyl titanate and hydrogen sulfide interval time are 2.5 minutes, the interval time of hydrogen sulfide and isopropyl titanate is 3 seconds, inject 754 circulations, deposition acquisition monolayer and multilamellar and titanium disulfide and trisulfides titanium altogether.
Embodiment 7
The spacing 20 microns by surface etch 80 square centimeters clean, high 3 microns, the titanium dioxide silicon chip that radius is the cylindrical-array of 5 microns is placed in deposition reaction cavity, controls reaction pressure at 13 millibars, and reaction temperature is 360 DEG C；Arranging carrier gas flux is 150 cubic centimetres/second, isopropanol molybdenum, diethyl selenide, tungsten carbonyl, hydrogen sulfide is injected to cavity cycle alternation by carrier gas, isopropanol molybdenum and diethyl selenide interval time are 1.5 minutes, diethyl selenide and tungsten carbonyl interval time are 1 minute, the interval time of tungsten carbonyl and hydrogen sulfide is 10 seconds, the interval time of hydrogen sulfide and isopropanol molybdenum is 44 seconds, injecting 314 circulations altogether, deposition obtains monolayer and multilamellar molybdenum bisuphide, two selenizing molybdenums, two tungsten selenide, tungsten disulfide complex.
Embodiment 8
Having the silicon chip of 30nm titanium deoxid film to be placed in deposition reaction cavity surface length 44 square centimeters clean, control reaction pressure at 19.6 millibars, reaction temperature is 550 DEG C；Arranging carrier gas flux is 98 cubic centimetres/second, hexacarbonylmolybdenum and tellurium diethyl is injected to cavity cycle alternation by carrier gas, hexacarbonylmolybdenum and tellurium diethyl interval time are 5 minutes, tellurium diethyl and hexacarbonylmolybdenum interval time are 3.3 minutes, injecting 618 circulations altogether, deposition obtains monolayer and multilamellar two telluride molybdenum.
Embodiment 9
Surface length 11.2 square centimeters clean is had long 2 microns, radius 100 nano zine oxide nanometer stick array piezoid be placed in deposition reaction cavity, control reaction pressure at 7.9 millibars, reaction temperature is 138.1 DEG C；Arranging carrier gas flux is 167 cubic centimetres/second, hexacarbonylmolybdenum, hydrogen sulfide and diethyl sulfide is injected to cavity cycle alternation by carrier gas, circular order is hexacarbonylmolybdenum-hydrogen sulfide-hexacarbonylmolybdenum-diethyl sulfide, hexacarbonylmolybdenum and hydrogen sulfide interval time are 8 seconds, hydrogen sulfide and hexacarbonylmolybdenum interval time are 16 seconds, and hexacarbonylmolybdenum and diethyl sulfide interval time are 5 minutes, and diethyl sulfide and hexacarbonylmolybdenum interval time are 6 minutes, injecting 663 circulations altogether, deposition obtains monolayer and multilamellar molybdenum bisuphide.
Embodiment 10
Surface length 1.6 square centimeters clean is had long 4 microns, external diameter 350 nanometers, the Nano tube array of titanium dioxide that internal diameter is 250 nanometers titanium substrate be placed in deposition reaction cavity, control reaction pressure at 45.7 millibars, reaction temperature is 159.6 DEG C；Arranging carrier gas flux is 105 cubic centimetres/second, hexacarbonylmolybdenum, isopropyl titanate and hydrogen sulfide is injected to cavity cycle alternation by carrier gas, circular order is hexacarbonylmolybdenum-hydrogen sulfide-isopropyl titanate-hydrogen sulfide, hexacarbonylmolybdenum and hydrogen sulfide interval time are 66 seconds, hydrogen sulfide and isopropyl titanate interval time are 26 seconds, isopropyl titanate and hydrogen sulfide interval time are 6.8 minutes, diethyl sulfide and hexacarbonylmolybdenum interval time are 76 seconds, injecting 885 circulations altogether, deposition obtains monolayer and multilamellar molybdenum bisuphide and titanium disulfide or trisulfides titanium complex.

Claims (3)

1. the method alternately injecting reactant growth monolayer and multilamellar transient metal sulfide, it is characterised in that method is as follows:
It is that the silicon of 1-100 square centimeter, sapphire sheet, piezoid, mica sheet or surface length have aluminium sesquioxide, titanium dioxide, silica membrane or surface to have the substrate of stereochemical structure to be placed in reaction cavity by clean area, controlling reaction pressure at 1-20 millibar, reaction temperature is 100-700 DEG C；One or more different transition metal reactants and one or more chalcogens are alternately injected by carrier gas, control carrier gas flux in 1-500 cubic centimetre/second, the interval time that different reactants injects is 1 second-10 minutes, alternately inject circulation 1-1000 time altogether, substrate obtains monolayer and multilamellar transient metal sulfide.
2. a kind of method alternately injecting reactant growth monolayer and multilamellar transient metal sulfide according to claim 1, it is characterised in that: described transition metal reactant refers to hexacarbonylmolybdenum, tungsten carbonyl, isopropanol molybdenum, isopropyl titanate.
3. a kind of method alternately injecting reactant growth monolayer and multilamellar transient metal sulfide according to claim 1, it is characterised in that: described chalcogen refers to diethyl sulfide, diethyl selenide, tellurium diethyl, hydrogen sulfide.
CN201610236670.2A 2016-04-15 2016-04-15 Method for growing single-layer and multi-layer transition metal sulfides through alternating injection of reactants Pending CN105800566A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110300731A (en) * 2017-02-02 2019-10-01 纳米2D材料有限公司 The 2D stratified material that shines is synthesized using the precursor of amine-metal complex and slow release sulphur
CN110863189A (en) * 2019-11-11 2020-03-06 中国科学院上海技术物理研究所 Method for growing single-layer telluride doped structure by pulse type injection of reactant
CN110923663A (en) * 2019-11-11 2020-03-27 中国科学院上海技术物理研究所 Method for growing large-area single-layer or multi-layer molybdenum ditelluride structure through secondary reaction
CN111020526A (en) * 2019-11-11 2020-04-17 中国科学院上海技术物理研究所 Method for preparing single-layer and multi-layer vanadium diselenide materials through alternative reaction

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CN105408516A (en) * 2013-07-31 2016-03-16 建国大学校产学协力团 MoS2 thin film and method for manufacturing same
WO2015094549A2 (en) * 2013-12-18 2015-06-25 Asm Ip Holding B.V. Sulfur-containing thin films
CN104561937A (en) * 2015-01-05 2015-04-29 上海纳米技术及应用国家工程研究中心有限公司 Method for preparing WS2 film having solid lubrication function by means of atomic layer deposition

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110300731A (en) * 2017-02-02 2019-10-01 纳米2D材料有限公司 The 2D stratified material that shines is synthesized using the precursor of amine-metal complex and slow release sulphur
CN110300731B (en) * 2017-02-02 2021-11-30 纳米2D材料有限公司 Synthesis of luminescent 2D layered materials using amine-metal complexes and precursors with slow release of sulfur
CN110863189A (en) * 2019-11-11 2020-03-06 中国科学院上海技术物理研究所 Method for growing single-layer telluride doped structure by pulse type injection of reactant
CN110923663A (en) * 2019-11-11 2020-03-27 中国科学院上海技术物理研究所 Method for growing large-area single-layer or multi-layer molybdenum ditelluride structure through secondary reaction
CN111020526A (en) * 2019-11-11 2020-04-17 中国科学院上海技术物理研究所 Method for preparing single-layer and multi-layer vanadium diselenide materials through alternative reaction

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Application publication date: 20160727