CN104418387B - A kind of molybdenum disulfide nano thin slice and preparation method thereof - Google Patents
A kind of molybdenum disulfide nano thin slice and preparation method thereof Download PDFInfo
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- CN104418387B CN104418387B CN201310367292.8A CN201310367292A CN104418387B CN 104418387 B CN104418387 B CN 104418387B CN 201310367292 A CN201310367292 A CN 201310367292A CN 104418387 B CN104418387 B CN 104418387B
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- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 58
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 63
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 39
- 239000011733 molybdenum Substances 0.000 claims abstract description 39
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000005864 Sulphur Substances 0.000 claims abstract description 20
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- 239000012159 carrier gas Substances 0.000 claims description 20
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 9
- 239000011593 sulfur Substances 0.000 abstract description 9
- 239000012071 phase Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 239000002360 explosive Substances 0.000 abstract description 4
- 241000446313 Lamella Species 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000007790 solid phase Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 12
- 239000010453 quartz Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000003708 ampul Substances 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- 239000002060 nanoflake Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 2
- 230000018199 S phase Effects 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical group C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004630 atomic force microscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/22—Particle morphology extending in two dimensions, e.g. plate-like with a polygonal circumferential shape
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The present invention relates to a kind of molybdenum disulfide nano thin slice and preparation method thereof. In inert atmosphere, Yu Mu source, sulphur source steam is contacted and carry out chemical vapour deposition (CVD), to form the molybdenum disulfide nano thin slice of erectting on substrate; The reaction condition of described chemical vapour deposition (CVD) is: reaction temperature is 690～750 DEG C, and the reaction time is 5～60min. The pattern of described molybdenum disulfide nano thin slice is special, size uniform, and the overwhelming majority is individual layer, and can realize Large-Area-Uniform growth; Its size is at 0.3～2 μ m, thickness <1nm. The present invention is compared with the traditional method of preparing molybdenum bisuphide lamella, and technique is simple, easy to operate, is easy to realize large-scale production, requires lower to experimental situation; Adopt carbon disulfide to replace traditional solid phase or gas phase sulfur source, can not only overcome solid-state sulphur source and can not accurately control that sulphur source passes into and the defect of the time point that ends, can avoid using the potential safety hazard in inflammable, explosive gaseous sulfur source simultaneously.
Description
Technical field
The invention belongs to field of nano material preparation, specifically, relate to a kind of molybdenum disulfide nano thin slice andIts preparation method.
Background technology
In field of nanometer technology, developing rapidly of Graphene makes stratified material again become people in recent yearsThe focus of research. Stratified material is to be formed by faint Interaction between layers is stacking by two-dimentional molecular layer, withThe reduction of dimension, the electronics structure of stratified material has been compared obviously different from bulk.
Molybdenum bisuphide is same with its unique structure and electronics property as typical class Graphene stratiform materialAttract people to note. Individual layer molybdenum bisuphide is by tri-layers of former molecular sandwich of layers (see figure 1) of S-Mo-S,Thickness only hasAnd have the direct band gap of about 1.78eV, these characteristics are being made individual layer molybdenum bisuphideFor example, during for the raw material of semiconductor electronics device (field-effect transistor FET), there is greater advantage. SeparatelyOutward, a large amount of dangling bonds of molybdenum bisuphide marginal existence, these hang bond energy becomes good catalytic active center.
Existing conventional method lithium ion graft process, mechanical stripping method, the biography of preparing molybdenum disulfide nano thin sliceSystem chemical vapour deposition technique etc. But there are more following problems in these preparation methods:
1) the required experiment condition harshness of lithium ion graft process, experiment must be carried out in the environment of anhydrous and oxygen-free,And experimental period is long, generally need one to two day time. The molybdenum disulfide nano of preparing by lithium ion intercalationThin slice crystalline quality is poor, fault of construction is many, and the electronics device performance of preparing with this is difficult to reach application and wantsAsk;
2) although mechanical stripping method can obtain high-quality individual layer molybdenum bisuphide thin slice, the amount of mechanical stripping is non-Normal few, can not large-scale application;
3) the molybdenum disulfide nano thin slice that traditional chemical vapour deposition technique synthesizes is in early days one in productFraction, majority is fullerene structure, part is tube, and the MoS that thin slice comprises2Number of molecule layers alsoMore. Recently, part Study person obtains thinner molybdenum disulfide nano thin slice, evaporation on substrate in advanceThe nano level metal molybdenum of one deck, this process has not only increased the complexity of technique, and consume more multipotency withAnd the time. In addition, the sulphur source overwhelming majority who uses in traditional chemical vapour deposition process for solid (as sulphur powder,Thiocarbamide etc.), part is gas (as hydrogen sulfide). Solid-state sulphur source is unfavorable for accurately controlling sulphur source and passes into and endTime point, although and gaseous sulfur source can meet the condition of above-mentioned accurate control, gaseous sulfur source is inflammable,Explosive characteristic is that preparation process is brought potential safety hazard.
CN102849798A discloses a kind of molybdenum disulfide nano sheet thin-film material and preparation method thereof. This is thinMembrane material is MoS2Nanometer sheet is erect and is grown in an orderly manner in conductive substrates, MoS2The diameter of nanometer sheet is0.05-2 μ m, the thickness of nanometer sheet is 2-30nm. Its preparation method has two kinds, one be with copper sheet, silver strip,Titanium sheet, tungsten sheet, molybdenum sheet and carbon are substrate, by substrate be placed in molybdate sulfur-containing compound (comprise thiocarbamide,Thioacetamide, Cys) carry out hydro-thermal reaction in solution, in substrate growth fine and close, evenly haveThe MoS of order2Nano-sheet film. Another kind method be by molybdenum sheet directly insert sulfur-containing compound (comprise thiocarbamide,Thioacetamide, Cys) in solution, under hydrothermal condition, there is vulcanization reaction, in molybdenum substrateForm fine and close MoS uniformly2Nanometer sheet order thin film. It is orderly that this patent utilizes Liquid preparation methods to erectMoS2Nanometer sheet. As everyone knows, the nano material of the high crystalline quality of preparing with vapor phase method is compared, liquidThe standby nano material crystallinity of phase legal system is poor, in product, can have a large amount of crystal structure defects. Fault of constructionCan for example, the application aspect high-quality electronics device (field-effect transistor) of restriction product. In addition, shouldThe molybdenum disulfide nano sheet thickness that patent system obtains is at 2～30nm, the number of plies all more than three layers, and curingMolybdenum only just has the direct forbidden band of 1.78eV in the time of individual layer. Therefore compared to the molybdenum bisuphide of individual layer, thisMolybdenum bisuphide thin slice thicker in bright does not still have competitive advantage in high-end electronics device.
Therefore, explore one simple to operate, safe ready, can prepare the super of a large amount of high crystalline qualities simultaneouslyThe method of thin molybdenum disulfide nano thin slice has important scientific value and practical significance.
Summary of the invention
The object of the invention is to the deficiency for existing issue, provide a kind of molybdenum disulfide nano thin slice andPreparation method.
For reaching this object, the present invention by the following technical solutions:
A kind of molybdenum disulfide nano preparation of sections method, in inert atmosphere, connects Yu Mu source, sulphur source steamTouch and carry out chemical vapour deposition (CVD), to form the molybdenum disulfide nano thin slice of erectting on substrate; Described chemistryThe reaction condition of vapour deposition is: reaction temperature is 690～750 DEG C, and the reaction time is 5～60min.
In the present invention, at 690～750 DEG C, after heating certain hour, top, molybdenum source forms the higher molybdenum of concentrationSource vapour pressure, react with the molybdenum source steam of generation in the sulphur source passing into, and the molybdenum bisuphide steam of generation can sinkAmass around molybdenum source and be adsorbed on substrate surface, forming the molybdenum bisuphide lamella of erectting.
In the present invention, the consumption in He Liu source, described molybdenum source can be selected in relative broad range, as long as obtainThe size of molybdenum disulfide nano thin slice can meet the demand of semi-conducting material. In the present invention, makeThe size of molybdenum disulfide nano thin slice (is the maximum length and width value of irregular thin slice, can shows by scanning electronMicro mirror characterizes and obtains) be 0.3～2 μ m, thickness < 1nm(characterizes known according to Atomic Mechanics microscope). And rootAccording to the demand of different semi-conducting materials, those skilled in the art can carry out easily He Liu source, molybdenum source and useThe selection of amount, thus make the size that makes molybdenum disulfide nano thin slice at 0.3～2 μ m, thickness < 1nm,This repeats no more.
In the present invention, as long as the temperature and time of controlling the steam contact of Yu Mu source, sulphur source is in described scopeRealize object of the present invention. Those skilled in the art can understand, and the present invention can be real in quartz ampouleThe contact in Yu Liu source, existing molybdenum source, and heat by tube furnace, described quartz ampoule and tube furnace all can lead toCross commercially available. A preferred embodiment of the invention, described molybdenum disulfide nano preparation of sectionsMethod comprises molybdenum source is placed in quartz ampoule, then quartz ampoule put into tube furnace and heat, and treats molybdenum source instituteThe temperature of position, place reaches after 690～750 DEG C, has the carrier gas of carbon disulfide, 5～60min toward passing into load in quartz ampouleAfter, can obtain molybdenum disulfide nano thin slice of the present invention.
In the present invention, the inert gas that inert atmosphere is provided can be the conventional indifferent gas using in various this areasBody, for example argon gas, nitrogen or both gaseous mixtures.
In the present invention, described molybdenum source can be any this area conventional use for the preparation of molybdenum disulfide nanoThe material of thin slice, is preferably molybdenum trioxide.
In the time adopting molybdenum trioxide to do molybdenum source, without post processing, can directly indifferent gas be put into in the molybdenum source of buyingIn atmosphere, heat, with the molybdenum trioxide that utilizes steam-like at high temperature with sulphur source haptoreaction, obtain two of gas phaseMolybdenum sulfide Direct precipitation or be adsorbed in substrate surface.
It is to utilize its easily characteristic of distillation as molybdenum source that the present invention adopts molybdenum trioxide. Erect for obtaining large areaMolybdenum disulfide nano thin slice must have sufficient molybdenum bisuphide steam. But the fusing point of molybdenum bisuphide own is highBe difficult for distillation; Molybdate can decompose after uniform temperature simultaneously, and before distillation, reaction is converted into solid-state two sulphurChange molybdenum. Therefore the molybdenum trioxide that, itself is easily converted into gaseous state is more conducive to produce large after High Temperature Gas phase reactionAmount molybdenum bisuphide steam is for vapour deposition.
The present invention utilizes carbon disulfide for sulphur source. In the time using carbon disulfide as sulphur source, Yu Mu source, sulphur source connectsTactile amount is easier to control. In addition, although hydrogen sulfide has phase with carbon disulfide at gas usage controlling party maskSame effect, prepare molybdenum disulfide nano thin slice and have following defect but react with molybdenum trioxide with hydrogen sulfide:
1) utilize hydrogen sulfide to do sulphur source and need higher reaction temperature (840～950 DEG C), be unfavorable for saving the energy.Excess Temperature also can cause the own free energy of nano flake that generates too high and easily curl into tubulose or class richnessStrangle alkene structure, be unfavorable for synthetic a large amount of, uniform molybdenum disulfide nano thin slice;
2) hydrogen sulfide itself is inflammable, explosive, in use has potential safety hazard.
In the present invention, utilize carbon disulfide as sulphur source to temperature require low, can obtain lot of pure,Molybdenum disulfide nano thin slice has been avoided the potential safety hazard that may exist simultaneously uniformly.
In order to obtain the molybdenum disulfide nano thin slice that pattern and performance are more excellent, described sulphur source preferably by withThe mode that carrier gas imports adds, thereby contacts and carry out chemical vapour deposition (CVD) with molybdenum source steam. Now described carrier gasNot only can, for the reaction in He Liu source, molybdenum source provides inert atmosphere, can also promote the reaction in Yu Liu source, molybdenum source to enterOK. Described carrier gas can be the conventional inert gas using in any this area, for example argon gas, nitrogen or bothGaseous mixture.
Wherein, the present invention is not particularly limited the flow rate of described carrier gas, the flow rate of described carrier gasCan be 20～250sccm, for example, can select 20.2～248.9sccm, 29～233sccm, 38.5～217.8sccm,50～204sccm，58.7～190.3sccm，65～180sccm，82～148.7sccm，93.2～123sccm，100～118sccm, 107sccm etc., are preferably 50～200sccm. Sccm is volume flow unit, meansMark condition milliliter per minute.
The carbon disulfide that the present invention preferably uses is colourless liquid, and therefore, in practical operation, carbon disulfide canDirectly to import with carrier gas, pass in carbon disulfide by carrier gas, the carrier gas that makes to be loaded with carbon disulfide steam withMolybdenum source contacts. Amount to the carbon disulfide adding with carrier gas has no particular limits.
In chemical vapour deposition reaction condition of the present invention, its reaction temperature can be selected 690.2～749.6 DEG C,697.4～740 DEG C, 708.6～734.8 DEG C, 715～729 DEG C, 721.4 DEG C etc., described reaction temperature is preferably 720 DEG C.
In chemical vapour deposition reaction condition of the present invention, its reaction time can be selected 5.02～59.6min,7.6～52.1min, 10～48.6min, 13.7～42min, 19～34.7min, 25～30min, 28.7min etc.,The described reaction time is preferably 30min.
Substrate of the present invention can select this area conventional adopt can withstand high temperatures (at least 450 DEG C)Inert substrate, such as silicon chip or graphite foil etc. While selecting silicon chip as substrate, need carry out surface treatment to it.Concrete grammar is: first, the silicon chip having cut is put into respectively to ethanol and deionized water for ultrasonic 15min; ItsInferior, the silicon chip after drying is put into sulfuric acid/hydrogen peroxide mixed solution heating water bath 15min; Finally use ethanolWith twice oven dry of washed with de-ionized water. Surface-treated object is mainly the pollutant in order to remove silicon chip surface,To avoid these pollutants to have a negative impact in molybdenum bisuphide growth course. Because of graphite foil itself frangibleCharacteristic, select graphite foil during as substrate without it is further processed.
The present invention also provides a kind of molybdenum disulfide nano thin slice that is made setting by said method, described two sulphurThe pattern of changing molybdenum nano flake is special, size uniform, and the overwhelming majority is individual layer, and it is equal to realize large areaEven growth; Its size is at 0.3～2 μ m, thickness < 1nm. Described " size " is greatly enhancing most of irregular thin sliceWide value, can be characterized and be obtained by SEM; Described " thickness " is micro-according to Atomic MechanicsMirror characterizes and obtains.
The characteristic of molybdenum disulfide nano thin slice of the present invention is given by above-mentioned preparation method.
Compared with prior art scheme, the present invention has following beneficial effect:
The present invention is compared with the traditional method of preparing molybdenum bisuphide lamella, and technique is simple, easy to operate, easilyIn realizing large-scale production, require lower to experimental situation; Adopt carbon disulfide replace traditional solid phase (asSulphur powder) or gas phase sulfur source (for example hydrogen sulfide), can not only overcome solid-state sulphur source and can not accurately control sulphur source and pass intoAnd the defect of the time point of cut-off, the while can avoid using the potential safety hazard in inflammable, explosive gaseous sulfur source.
The molybdenum disulfide nano thin slice pattern of setting prepared by the inventive method is special, size uniform, absolutely large portionBe divided into individual layer, and can realize Large-Area-Uniform growth; Molybdenum disulfide nano lamina dimensions size approximately 0.3～2 μ m,Thickness < 1nm, mostly is six side's phase molybdenum disulfide nano flake structures.
Brief description of the drawings
Fig. 1 is molybdenum bisuphide monolayer structural representation;
Fig. 2 is the molybdenum disulfide nano thin slice chemical vapor deposition unit schematic diagram used that preparation is erect;
Wherein: 1-flowmeter; 2-triple valve; 3-is equipped with the bubbler of carbon disulfide; 4-substrate; 5-tri-is oxidizedMolybdenum powder.
Fig. 3 is the SEM (SEM) of the molybdenum disulfide nano thin slice prepared of the embodiment of the present invention 1Photo;
Fig. 4 is the transmission electron microscope (TEM) of the molybdenum disulfide nano thin slice prepared of the embodiment of the present invention 1Photo; Wherein, (a) being low power transmission electron microscope photo, is (b) high-resolution-ration transmission electric-lens photo and quickFourier transformation figure;
Fig. 5 is that the AFM of the molybdenum disulfide nano thin slice of the setting that makes of the embodiment of the present invention 1 shinesSheet;
Fig. 6 is the molybdenum disulfide nano thin slice that makes of the embodiment of the present invention 1 and the molybdenum disulfide powder buiedRaman spectrogram;
Fig. 7 is the SEM (SEM) of the molybdenum disulfide nano thin slice that makes of the embodiment of the present invention 2Photo;
Fig. 8 is the SEM (SEM) of the molybdenum disulfide nano thin slice that makes of the embodiment of the present invention 3Photo;
Fig. 9 is the SEM (SEM) of the molybdenum disulfide nano thin slice that makes of the embodiment of the present invention 4Photo.
The present invention is described in more detail below. But following example is only simple and easy example of the present invention,Do not represent or limit the scope of the present invention, protection scope of the present invention is as the criterion with claims.
Detailed description of the invention
For the present invention is described better, be convenient to understand technical scheme of the present invention, typical case of the present invention but non-limitThe embodiment of property processed is as follows:
In following examples, inert gas or the carrier gas of use are argon gas; Molybdenum trioxide is liked purchased from AlphaSha (Tianjin) Co., Ltd, purity is 99.5%; Liquid sulfur source is purchased from the fine chemistry industry research of Tianjin, Tianjin sectionInstitute, the pure carbon disulfide of analysis that purity is 99wt%; Tube furnace used is that the brilliant material technology of Hefei section is limitedThe GSL-1100X-S multistation tube type high-temperature furnace that company produces; Measurement gas flow be Zhejiang Yuyao City silverThe LZB-2 spinner flowmeter that circulation instrument Co., Ltd produces; That microstructure characterizes employing is HitachiS-4800 type SEM; It is the Tecnai producing in FEI Co. of the U.S. that transmission electron microscopy characterizesOn G2F20U-TWIN transmission electron microscope, complete; Raman spectrum utilizes Renishaw company to produceInViaplus type laser Raman spectrometer gathers; Lamellar spacing utilizes Vecco company to produceMultimode-N3-AM type Atomic Mechanics microscope is measured.
Embodiment 1
(1) utilize chemical vapor deposition unit as shown in Figure 2, by the molybdenum trioxide powder without any processingEnd 5 is positioned over the middle part of quartz boat as molybdenum source, quartz boat is put into quartz ampoule, makes molybdenum source be positioned at tubular typeThe central area of stove. Utilize vavuum pump to drain the air in quartz ampoule, then pass into inert gas, so followEncircle the oxygen of as far as possible discharging in quartz ampoule for 3 times. Then constantly to the indifferent gas that is blown into 250sccm in quartz ampouleBody 30min, to drain as far as possible oxygen. Start subsequently heating, in heating process, inert gas flow velocity remains on25sccm, controlling heating rate is 10 DEG C/min;
(2) in the time that tube furnace central area temperature reaches 720 DEG C, pass into load and have the carrier gas of carbon disulfide (Before passing into quartz ampoule, first carrier gas is passed in the bubbler 3 that carbon disulfide is housed, control by triple valve 2Inert gas or be loaded with passing into of carbon disulfide gas), carrier gas flux 100sccm; Described carrier gas flux passes throughFlowmeter 1 is monitored;
(3), after 30min, on substrate 4, form the molybdenum disulfide nano thin slice of erectting. Close tube furnace,Pass into the inert gas that 200sccm is loaded with carbon disulfide, until temperature drops to room temperature.
The product that the present embodiment obtains is as shown in the stereoscan photograph in Fig. 3. As can be seen from Figure 3,The nano flake size uniform arriving and size are at 0.3～2 μ m.
Its transmission electron microscope photo as shown in Figure 4, (a) is low power transmission electron microscope photo, is (b) highDifferentiate transmission electron microscope photo and Fast Fourier Transform (FFT) figure thereof. As can be seen from the figure this molybdenum disulfide nano is thinSheet is monocrystalline six side's phase structures.
Fig. 5 is the atomic force microscopy of prepared molybdenum disulfide nano thin slice. According to Fig. 5, recordRandom molybdenum disulfide nano sheet thickness is 0.631nm, is monolayer molybdenum bisuphide.
Fig. 6 is the Raman spectrogram of prepared molybdenum disulfide nano thin slice, itself and two of 99.5% purity of buyingMolybdenum sulfide powder Raman spectrogram is closely similar.
Embodiment 2
Prepare molybdenum disulfide nano thin slice according to the method in embodiment 1. Different, tube furnace centerWhen territory temperature reaches 750 DEG C, passing into load has the carrier gas of carbon disulfide steam, and its flow is 250sccm, anti-Answer after 5min, close tube furnace. The electron scanning micrograph of the product that the present embodiment obtains is as Fig. 7 instituteShow. This result is similar to embodiment 1 result, has grown equally uniform molybdenum disulfide nano thin slice.
Embodiment 3
Prepare molybdenum disulfide nano thin slice according to the method in embodiment 1. Different, tube furnace centerWhen territory temperature reaches 690 DEG C, passing into load has the carrier gas of carbon disulfide steam, and its flow is 20sccm, anti-Answer after 60min, close tube furnace. The electron scanning micrograph of the product that the present embodiment obtains is as Fig. 8Shown in. The present embodiment result is similar to embodiment 1,2 results, has grown equally uniform molybdenum disulfide nanoThin slice.
Embodiment 4
Prepare molybdenum disulfide nano thin slice according to the method in embodiment 1. Different, tube furnace centerWhen territory temperature reaches 690 DEG C, passing into load has the carrier gas of carbon disulfide steam, and its flow is 100sccm, anti-Answer after 60min, close tube furnace. The electron scanning micrograph of the product that the present embodiment obtains is as Fig. 9Shown in, the molybdenum disulfide nano thin slice growth making is evenly. Unique difference is to be mixed with and to receive in these thin slicesThe bar-shaped special appearance that rice thin slice is self-assembled into, and this does not affect the knot of synthetic molybdenum disulfide nano thin sliceCrystalloid amount and thickness.
Can find out from the result of embodiment, the present invention has grown uniform two by simple methodMolybdenum sulfide nano flake.
More than describe the preferred embodiment of the present invention in detail, still, the present invention is not limited to above-mentioned enforcementDetail in mode, within the scope of technical conceive of the present invention, can enter technical scheme of the present inventionThe multiple simple variant of row, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characterictic described in above-mentioned detailed description of the invention,In reconcilable situation, can combine by any suitable mode, for fear of unnecessary weightMultiple, the present invention is to the explanation no longer separately of various possible combinations.
In addition, between various embodiment of the present invention, also can be combined, as long as it is notRun counter to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (7)
1. a molybdenum disulfide nano preparation of sections method, is characterized in that, in inert atmosphere, by sulphurYu Mu source, source steam contacts and carries out chemical vapour deposition (CVD), to form the molybdenum disulfide nano of erectting on substrateThin slice; The reaction condition of described chemical vapour deposition (CVD) is: reaction temperature is 690～750 DEG C, and the reaction time is5～60min; Wherein, described molybdenum source is molybdenum trioxide, and described sulphur source is carbon disulfide; Described carbon disulfide is logicalCrossing the mode importing with carrier gas adds;
Described preparation method makes the molybdenum disulfide nano thin slice of setting, the shape of described molybdenum disulfide nano thin sliceLooks are special, size uniform, the overwhelming majority are individual layer, and can realize Large-Area-Uniform growth; Its size exists0.3～2 μ m, thickness < 1nm.
2. preparation method as claimed in claim 1, is characterized in that, described carrier gas is argon gas and/or nitrogen.
3. preparation method as claimed in claim 1, is characterized in that, the flow rate of described carrier gas is20～250sccm。
4. preparation method according to claim 1, is characterized in that, the flow rate of described carrier gas is50～200sccm。
5. preparation method as claimed in claim 1, is characterized in that, described reaction temperature is 720 DEG C.
6. preparation method as claimed in claim 1, is characterized in that, the described reaction time is 30min.
7. preparation method as claimed in claim 1, is characterized in that, described substrate is graphite foil or silicon chip.
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