CN104894530B - A kind of two-dimentional transition metal chalcogenide film and its preparation method and application - Google Patents
A kind of two-dimentional transition metal chalcogenide film and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of two-dimentional transition metal chalcogenide film and its preparation method and application, the two-dimentional transition metal chalcogenide refers to：ZrS2、ZrSe2、HfS2And HfSe2；It uses chemical vapour deposition technique to deposit the two-dimentional transition metal chalcogenide for forming individual layer or few layer on boron nitride-base bottom.Method provided by the present invention can controllably synthesize thickness in 1nm or so on boron nitride-base bottom, the two-dimentional transition metal chalcogenide film of hexagon or triangle more than 1 μm, realize two-dimentional ZrS2、ZrSe2、HfS2And HfSe2Large area continuous film and monodomain region controllable growth.
Description
Technical field
The present invention relates to technical field of semiconductor, and in particular to a kind of two-dimensional semiconductor nano thin-film and its preparation side
Method and application, more particularly to a kind of two-dimentional transition metal chalcogenide film with high high mobility potential quality and preparation method thereof
And application.
Background technology
The two-dimensional semiconductor nano thin-film of atomic level thickness, such as Transition-metal dichalcogenide, there is certain band gap,
On-off ratio is very high, has great application prospect in terms of nanometer electronic device.But practical application request has the two of high mobility
Wiener meter level thin film semiconductor material, to be satisfied with the use of nanometer electronic device under various environment.And the individual layer two of high mobility
Dimension atomic crystal all has critically important impetus to logical device, spectral detection, opto-electronic conversion field.
Transition-metal dichalcogenide, such as ZrS2、ZrSe2、HfS2、HfSe2Deng the structure with class graphene, by three layers
Atom is with D3d3Point group forms, the stratiform knot for the class block graphite to be formed that interacted between layers with weak Van der Waals force
Structure.The ZrS of individual layer2、ZrSe2、HfS2、HfSe2Structure is similar, be all by tri- layers of molecular sandwich structures of original of S-M-S, its
Thickness about 0.60nm, edge have very high electron mobility without dangling bonds in theory, have excellent optics, electricity,
Mechanical performance, aroused great concern in nanometer electronic device field, there is huge application prospect.
The research and utilization liquid phase synthesizing method such as Jung-tak Jang obtains thin slice ZrS at present2(bibliography：
Ultrathin Zirconium Disulfide Nanodiscs,Jung-tak Jang,et al,JACS,2011,133
(20):7636-7639), Ruoyu Yue etc. are investigated prepares thin layer HfSe with molecular beam epitaxy2(bibliography：HfSe2
Thin Films:2D Transition Metal Dichalcogenides Grown by Molecular Beam
Epitaxy,Ruoyu Yue,et al,ACS Nano 2015,9(1):474–480)。
Nath etc. thermally decomposes the IVth B metal trisulfide in reducing atmosphere, is successfully prepared for its disulphide
Nanotube；In Ar (95%)+H2(5%) HfS is thermally decomposed in 900 DEG C in mixed atmosphere3, obtained HfS2Nanotube；Similar
In atmosphere, about 900 DEG C of thermal decomposition ZrS3Also ZrS has been obtained2Nanotube；And in H2In+He atmosphere, 800 DEG C of thermal decomposition TiS3Equally
Also it is prepared for TiS2Nanotube, but it can not be stabilized (bibliography in tem analysis to electron beam sensitive：M Nath,
C N R Rao.Angew.Chem.Int.Ed.,2002,41:3451-3454).Chen etc. is reacted using solution chemistry, and chemistry turns
Change and the TiS of high-purity has been made in gas phase reaction respectively2Nanotube (bibliography：J Chen,Z L Tao,S L
Li.Angew.Chem.Soc.,2003,42:2147-2151)。
Wang Yuefeng etc. is with MoO3It is raw material with S powder, high-purity argon gas is carrier gas and reaction atmosphere, in quartz tube reactor,
Fullerene structure MoS is prepared with chemical vapour deposition technique2Nano-particle, the composition of product is measured with XRD, SEM observations
The overall microscopic appearance of product.As a result show, at 900 DEG C, lead to argon gas 1cm3/ min, 8h is incubated, average grain diameter is prepared for and exists
250nm or so high-purity fullerene structure MoS2Nano-particle (bibliography：Wang Yuefeng etc., chemical vapour deposition technique prepare rich
Alkene structure molybdenum disulfide nano particle is strangled, using chemical industry, the 12nd phase, on December 28th, 2008).
However, larger area individual layer ZrS is not yet prepared using cheap effectively continuous growing method at present2、ZrSe2、
HfS2、HfSe2Nano thin-film, therefore how to realize the continuous growth of larger area individual layer two dimension transition metal chalcogenide film
It is current urgent problem to be solved.
The content of the invention
For the technology for the continuous growth that can not realize larger area individual layer two-dimensional semiconductor nano thin-film in the prior art
Problem, the invention provides a kind of two-dimentional transition metal chalcogenide film and its preparation method and application.Methods described can
Realize larger area individual layer or few layer vulcanization zirconium (ZrS2), selenizing zirconium (ZrSe2), vulcanization hafnium (HfS2), selenizing hafnium (HfSe2)
Continuous growth.
To reach this goal of the invention, the present invention uses following technical scheme：
In a first aspect, the invention provides a kind of preparation method of two-dimentional transition metal chalcogenide film, its use
Learn vapour deposition process and continuous two-dimentional transition metal chalcogenide film is made, wherein, the transition metal chalcogenide is
ZrS2、ZrSe2、HfS2Or HfSe2In any one.
Although having been disclosed for preparing transition metal chalcogenide film using chemical vapour deposition technique in the prior art,
Such as molybdenum disulfide etc., however, (such as curing zirconium is 527 because curing zirconium and curing hafnium are easily oxidized or decomposed
DEG C (800K) is decomposed into non-laminar Zr3S4, 627 DEG C (900K) are oxidized to ZrO2, and sulphur and zirconium chloride need higher than
Reaction generation curing zirconium crystal at a temperature of 900 DEG C), so must react in the absence of oxygen, and with sulfur-rich condition
To prevent to vulcanize the decomposition of zirconium.Further, since vulcanization zirconium and vulcanization the hafnium nucleation rate in oxidation silicon base are too big, it is difficult to are formed
The film of large area, from the substrate grown of this atomically flating of boron nitride, the individual layer of larger area or few layer can be obtained
Film.
In the present invention, the preparation method of the two-dimentional transition metal chalcogenide film includes：In oxygen-free environment, load is passed through
Gas and protective gas, Zr/Hf sources and S/Se sources are heated respectively to volatilizing, in high-temperature region generation gas phase ZrS2、ZrSe2、HfS2Or
HfSe2In any one, and on the boron nitride-base bottom of low-temperature space chemical vapor deposition formed film.
Heretofore described Zr/Hf source-representation zirconium sources and/or hafnium source, "/" therein represent the implication of "and/or"；Institute
S/Se source-representations sulphur source and/or selenium source are stated, "/" therein represents the implication of "and/or", and the implication is applied to whole invention.
In the present invention, the heating-up temperature in zirconium (Zr) source is 160-180 DEG C, for example, can be 160 DEG C, 162 DEG C, 165
DEG C, 168 DEG C, 170 DEG C, 172 DEG C, 175 DEG C, preferably 178 DEG C, 180 DEG C, 180 DEG C.
In the present invention, the heating-up temperature in hafnium (Hf) source is 170-190 DEG C, for example, can be 170 DEG C, 172 DEG C, 175
℃、178℃、180℃、182℃、185℃、188℃、190℃。
In the present invention, the heating-up temperature in sulphur (S) source is 130-150 DEG C, for example, can be 130 DEG C, 132 DEG C, 135
℃、138℃、140℃、142℃、145℃、148℃、150℃。
In the present invention, the heating-up temperature in selenium (Se) source is 230-250 DEG C, for example, can be 230 DEG C, 232 DEG C, 235
℃、238℃、240℃、242℃、245℃、248℃、250℃。
In the present invention, central temperature >=900 DEG C of the high-temperature region, such as can be 900 DEG C, 910 DEG C, 920 DEG C, 930
DEG C, 940 DEG C, 950 DEG C, 960 DEG C, 970 DEG C, 980 DEG C, 990 DEG C, more than 1000 DEG C etc., do not itemize herein；In addition,
In the present invention, the temperature of the chemical vapor deposition is 700-900 DEG C, for example, can be 700 DEG C, 705 DEG C, 710 DEG C, 715 DEG C,
720℃、725℃、767℃、784℃、806℃、825℃、838℃、847℃、862℃、889℃、900℃。
In the present invention, the carrier gas is argon gas and/or hydrogen, preferably argon gas and hydrogen.
Preferably, the protective gas is argon gas and/or hydrogen；It is further preferred that hydrogen in the protective gas
The volumn concentration of gas is 10-100%, for example, can be 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%,
90%th, 100%；It is further preferred that it is 1 that the protective gas, which is volume ratio,:3 hydrogen and the mixture of argon gas.
In the present invention, the Zr sources are purity>99.9% powder ZrCl4；Preferably, the Hf sources are purity>
99.9% powder HfCl4。
Preferably, the S sources are purity>99.9% S powder；Preferably, the Se sources are purity>99.9% Se powder.
Preferably, the boron nitride-base bottom is to peel off mono-crystal nitride boron powder mechanical stripping method to arrive to pass through surface oxidation
Property processing silicon chip on；It is further preferred that the oxidated layer thickness of the silicon chip is 300nm.
Preferably, the boron nitride passes through the high temperature anneal；It is further preferred that the high temperature anneal temperature is 600
DEG C, annealing time 1h.
As currently preferred technical scheme, the described method comprises the following steps：
(1) Zr/Hf sources and S/Se sources and boron nitride-base bottom are respectively placed in quartz ampoule successively according to airflow direction；
(2) oxidizing gas in quartz ampoule is removed；
(3) carrier gas and protective gas are passed through with 20-45sccm flow velocity, while heat Zr/Hf sources and S/Se sources to waving
Hair, wherein, the heating-up temperature in the Zr sources is 160-180 DEG C, and the heating-up temperature in Hf sources is 170-190 DEG C, the heating-up temperature in S sources
For 130-150 DEG C, the heating-up temperature in Se sources is 230-250 DEG C；It is incubated 10-30min；Chemical reaction generation occurs in high-temperature region
ZrS2、ZrSe2、HfS2Or HfSe2In any one, when airflow downstream is cooled to 700-900 DEG C, be deposited on boron nitride-base bottom
On；
(4) room temperature is cooled to, obtains the two-dimentional ZrS on boron nitride2、ZrSe2、HfS2Or HfSe2In any one.
In the present invention, the flow velocity of the carrier gas and protective gas is 20-45sccm, for example, can be 20sccm,
22sccm, 25sccm, 28sccm, 30sccm, 32sccm, 35sccm, 40sccm, 42sccm, 45sccm, preferably 40sccm.
The time of the present invention for keeping volatilization temperature is 10-30min, for example, 10min, 11min, 12min, 13min,
14min, 15min, 18min, 20min, 22min, 25min, 30min etc., preferably 20min.
When prepare vulcanize zirconium when, the thermograde of the temperature of the chemical vapor deposition in the direction of the air flow is 20 DEG C/cm；
Hydrogen containing 10-50v%, preferably 25v% in the protective gas.
When preparing selenizing zirconium, the hydrogen containing 50-100v%, preferably 100v% in the protective gas.
The technical scheme further preferred as the present invention, the described method comprises the following steps：
(1) by one of S or Se, ZrCl4It is respectively placed in successively with boron nitride-base bottom in a diameter of 1 inch of quartz ampoule；
The position of the silicon base distance high-temperature district center is 2cm-30cm；The quality of the S or Se are 1g, the ZrCl4Quality
For 0.1-0.2g；
(2) 0.1-0.5Pa will be evacuated to inside quartz ampoule；
(3) carrier gas and protective gas are passed through with 40sccm flow velocity, while diamond heating is to 950 DEG C or more；
(4) S to 130-150 DEG C or Se to 230-250 DEG C, heating ZrCl are heated respectively4To 160-180 DEG C and be incubated 10~
30min；The S or Se and ZrCl of volatilization4In 950 DEG C of high-temperature region reaction generation ZrS2Or ZrSe2, and under the drive of air-flow extremely
During 700-900 DEG C of cooling area, it is deposited on boron nitride；In quartz ampoule, thermograde in the direction of the air flow is 20 DEG C/cm；
(5) heating ZrCl is stopped4And tube furnace, continue heat S or Se to high-temperature region central temperature at 700 DEG C stop plus
Heat；
(6) room temperature is cooled to, stopping is passed through protective gas, obtains two-dimentional ZrS2Or ZrSe2Film.
As another preferable technical scheme of the present invention, the described method comprises the following steps：
(1) by one of S or Se, HfCl4It is respectively placed in successively with boron nitride-base bottom in a diameter of 1 inch of quartz ampoule；
The position of the silicon base distance high-temperature district center is 2cm~30cm；The quality of the S or Se are 1.5g, the HfCl4Matter
Measure as 0.1-0.2g；
(2) 0.1-0.5Pa will be evacuated to inside quartz ampoule；
(3) carrier gas and protective gas are passed through with 40sccm flow velocity, while diamond heating is to 950 DEG C or more；
(4) S to 130-150 DEG C or Se to 230-250 DEG C, heating HfCl are heated respectively4To 170-190 DEG C and it is incubated 10-
30min；The S or Se and HfCl of volatilization4In 950 DEG C of high-temperature region reaction generation HfS2Or HfSe2, and under the drive of air-flow extremely
During 700-900 DEG C of cooling area, it is deposited on boron nitride；In quartz ampoule, thermograde in the direction of the air flow is 20 DEG C/cm；
(5) heating HfCl is stopped4And tube furnace, continue heating selenium to high-temperature region central temperature to stopping at 700 DEG C and heat；
(6) room temperature is cooled to, stopping is passed through protective gas, obtains two-dimentional HfS2Or HfSe2Film.
Second aspect, present invention also offers a kind of two-dimentional transition metal being prepared according to first aspect methods described
Chalkogenide film, the two-dimentional transition metal chalcogenide film are triangle or hexagon monodomain region or continuous film.
The length of side of heretofore described triangle or hexagon monodomain region is 1-3 μm, for example, can be 1 μm, 1.2 μm, 1.3
μm、1.5μm、1.8μm、2μm、2.5μm、2.8μm、3μm；Preferably, the size of the continuous film obtains nitrogen by mechanical stripping
The size for changing boron thin slice determines.
The third aspect, present invention also offers the two-dimentional transition metal chalcogenide film according to second aspect two
Application in wiener meter level thin film semiconductor material.
Compared with prior art, the present invention has the advantages that：
(1) preparation method of two-dimentional transition metal chalcogenide film provided by the present invention can obtain length and be more than 1 μ
More than m ZrS2、ZrSe2、HfS2、HfSe2Film, realize the company of large area individual layer or few layer two-dimensional semiconductor nano thin-film
Continuous growth；
(2) selection of the invention by volatilization temperature, growth time to protective gas, zirconium chloride and hafnium chloride, it is excellent
Change chemical gaseous phase depositing process, so as to obtain thickness in 1-3nm, two-dimentional transition metal sulfur family of the size more than 1 μm
Thing film；
(3) present invention realizes two-dimentional ZrS2、ZrSe2、HfS2、HfSe2Large area continuous film and monodomain region it is controllable
Growth.
Brief description of the drawings
Fig. 1 is the ZrS in table 12SEM SEM phenograms；
Fig. 2 is the ZrS in table 12Atomic force microscope phenogram；
Fig. 3 is the ZrS in table 12SEAD SARD phenogram；
Fig. 4 is the ZrS in table 12Characteristic Raman peak with thickness change Raman collection of illustrative plates；
Fig. 5 is the ZrS for the monodomain region that the zirconium chloride in table 1 obtains when heating-up temperature is 170 DEG C2AFM
Figure；
Fig. 6 is the ZrS for the continuous film that the zirconium chloride in table 1 obtains when heating-up temperature is 180 DEG C2Atomic force microscopy
Mirror figure；
Fig. 7 is the ZrS obtained under the differential responses time in table 22Atomic force microscopy diagram；
Fig. 8 is the ZrS obtained under the different deposition temperatures in table 32Surface coverage and thickness statistical chart；
Fig. 9 is the ZrSe obtained in embodiment 22Atomic force microscopy diagram.
Figure 10 is the HfSe obtained in embodiment 42Atomic force microscopy diagram.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in understanding the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1
It is a kind of that individual layer or few layer ZrS are prepared using chemical vapor deposition unit2、ZrSe2、HfS2Or HfSe2Method, institute
The device that chemical vapor deposition unit is known in the art is stated, the chemical vapor deposition unit that the present embodiment uses adds including tubular type
Hot stove, heating tape and quartz ampoule, wherein, quartzy pipe range 1.4m, 1 inch of diameter, and the both ends of quartz ampoule have vacuum valve, are used for
The inside of quartz ampoule is vacuumized and is sent into protective gas；Quartz ampoule will be longer than tubular heater, ensure a part of stone
It is external that English pipe is located at tube furnace, for preventing ZrCl4/HfCl4And S/Se, ensure ZrCl4/HfCl4With S/Se not by heating furnace
Temperature influences；The heating furnace is provided with an independent thermocouple in quartz ampoule, for the corresponding positions in heated quarty tube
Put；Heating tape by thermocouple, heating tape, temperature controller and source line group into.
Methods described comprises the following steps：
(1) take commercially available silicon chip (be purchased from the high P- silicon chips of crystal technique Co., Ltd of Hefei section, the Ω of resistance value 0.02~0.6,
0.5mm × 4 inch), obtained by oxidation processes covered with SiO thick 3000nm2Silicon chip, cutting obtain the small of 6 × 8mm
Piece；Boron nitride monocrystal is peeled off onto the silicon chip of well cutting with mechanical stripping method, by 600 DEG C, the high annealing of 1 hour, treated
With；
(2) 0.1g zirconium chlorides, 1.0g sulphur powders and 8 silicon bases are positioned over a diameter of 1 inch according to the direction of air-flow
Quartz ampoule in, wherein it is external to be located at tube furnace for zirconium chloride and sulphur；Heating tape is wound on quartz ampoule and corresponds to zirconium chloride and sulphur
The position of powder, the distance of every silicon base is 1cm；
(3) 0.1Pa will be evacuated to inside quartz ampoule, removes oxidizing gas；
(4) protective gas is continually fed into quartz ampoule with 40sccm flow velocity, while tube furnace is begun to warm up；
Tube furnace is warming up to 950 DEG C after 40min；Heating zirconium chloride and sulphur content are started simultaneously at not to 170 DEG C and 130 DEG C, in the work of air-flow
Under, the zirconium chloride and sulphur of volatilization diffuse to the heating zone of tube furnace, and chemical reaction generation vulcanization zirconium occurs in high-temperature region, due to
The temperature of silicon base lay down location is more and more lower with airflow direction, and the thermograde of reduction is about 20 DEG C/cm, silicon base lay down location
Temperature about between 700-900 DEG C, vulcanization zirconium deposit on a silicon substrate；The protective gas is that volume ratio is 1:3
Hydrogen and argon gas；
In order to better control over the trend of the temperature of silicon base lay down location and thermograde drop, those skilled in the art can be with
Warming plate or other insulation materials, the present invention is set to be not specifically limited.
(5) after reacting 20min, heating zirconium chloride and tube furnace are stopped, tube furnace stops heating when naturally cooling to 700 DEG C
Sulphur；
(6) room temperature is naturally cooled to, stopping is passed through protective gas, obtains two dimension vulcanization zirconium.
Embodiment 2
One kind prepares two-dimentional ZrSe using chemical vapor deposition unit2Method, the chemical vapor deposition unit and reality
Apply that example 1 is identical, the difference of methods described and embodiment 1 is：
Source described in step (2) is selenium and zirconium chloride, and heating volatilization temperature is 230 DEG C and 170 DEG C respectively, and zirconium chloride is placed
In the upstream of air-flow, selenium is placed on the downstream of zirconium chloride, and step (4) described protective gas is only hydrogen, and what is obtained is two dimension
Selenizing zirconium.
The ZrSe that the embodiment obtains2Atomic force microscopy diagram is as shown in Figure 9.
Embodiment 3
One kind prepares two-dimentional HfS using chemical vapor deposition unit2Method, the chemical vapor deposition unit with implement
Example 1 is identical, and the difference of methods described and embodiment 1 is：
Source described in step (2) is sulphur and hafnium chloride, and heating volatilization temperature is 130 DEG C and 170 DEG C respectively, and hafnium chloride is placed
In the upstream of air-flow, sulphur is placed on the downstream of zirconium chloride.
Embodiment 4
A kind of method that two-dimentional IV subgroup chalkogenide is prepared using chemical vapor deposition unit, the chemical vapor deposition
Product device is same as Example 2, and the difference of methods described and embodiment 2 is：
Source described in step (2) is selenium and hafnium chloride, and heating volatilization temperature is 230 DEG C and 170 DEG C respectively, and hafnium chloride is placed
In the upstream of air-flow, selenium is placed on the downstream of zirconium chloride.
The HfSe that the embodiment obtains2Atomic force microscopy diagram is as shown in Figure 10.
It is to be placed in zirconium chloride under different heating-up temperatures to carry out the resulting ZrS that volatilizees below2Growth result, specifically
As shown in table 1.
Table 1
| Sequence number | Heating-up temperature (DEG C) | Decrement (g) | Two-dimensional morphology |
| 1 | 150 | 0.003 | Almost do not deposit |
| 2 | 160 | 0.006 | It is very rare, about 1 μm of monodomain region |
| 3 | 170 | 0.012 | Monodomain region |
| 4 | 175 | 0.017 | Monodomain region |
| 5 | 180 | 0.023 | Continuous film in uniform thickness |
| 6 | 190 | 0.043 | The film of uneven thickness |
The resulting ZrS that volatilizees is carried out as it can be seen from table 1 zirconium chloride is placed under different heating-up temperatures2Growth
As a result difference.
Fig. 1 is the ZrS that table 1 provides2SEM SEM phenograms, be distributed as seen from Figure 1 on boron nitride
ZrS2Hexagon；Fig. 2 is the ZrS that table 1 provides2Atomic force microscope phenogram, from left to right three width figures can see
Go out 1.0nm, 1.6nm and pyramid shape different-thickness ZrS2；Fig. 3 is the ZrS that table 1 provides2SEAD SARD table
Sign figure, wherein the interplanar distance and ZrS that show2Interplanar distance it is consistent；Fig. 4 is the ZrS that table 1 provides2Characteristic Raman peak with thickness
The Raman collection of illustrative plates of change is spent, described characteristic peak is A1g vibration modes；Fig. 5 be table 1 provide when the heating-up temperature of zirconium chloride is
The ZrS of the monodomain region obtained at 170 DEG C2Atomic force microscopy diagram；Fig. 6 be table 1 provide when the heating-up temperature of zirconium chloride is
The ZrS of the continuous film obtained at 180 DEG C2Atomic force microscopy diagram.
It is by zirconium chloride ZrS resulting under the differential responses time below2Growth result, it is specific as shown in table 2.Figure
7 be the ZrS obtained under the differential responses time that table 2 provides2Atomic force microscopy diagram.
Table 2
| Sequence number | Reaction time (min) | Two-dimensional morphology |
| 1 | 5 | Very rare individual layer, 1.1nm or so |
| 2 | 10 | Rare individual layer, 1.1nm or so |
| 3 | 20 | Monodomain region, thickness is in 1.0-1.5nm |
| 4 | 30 | Uneven thick-layer, thickness about 3nm |
| 5 | 40 | Very uneven thick-layer, thickness about 3nm |
From table 2 it can be seen that by zirconium chloride under the differential responses time obtained by ZrS2Growth result difference.
It is by zirconium chloride ZrS resulting under different deposition temperatures below2Growth result, it is specific as shown in table 3.Figure
8 be the ZrS obtained under the different deposition temperatures that table 3 provides2Surface coverage and thickness statistical chart.
Table 3
| Sequence number | Heating-up temperature (DEG C) | Two-dimensional morphology |
| 1 | 900 | 1.2nm or so, coverage rate 10% |
| 2 | 860 | It is uneven, thickness 1.5-3nm, coverage rate 80% |
| 3 | 830 | 1.2-1.8nm coverage rate 70% |
| 4 | 800 | 1.2nm or so, coverage rate 50% |
| 5 | 750 | 1.2nm or so, coverage rate 15% |
| 6 | 700 | It is uneven, 1.0-1.5nm or so, coverage rate 10% |
It is by zirconium chloride ZrS resulting under different protective gas below2Growth result, it is specific as shown in table 4.
Table 4
| Sequence number | Gas flow | Two-dimensional morphology |
| 1 | 40sccm Ar | Thickness 2-3nm, it is deposited on edge, seldom more |
| 2 | 35sccm Ar+5sccm H2 | Thickness 1.8-2nm, the hexagon less than 1 μm |
| 3 | 30sccm Ar+10sccm H2 | Thickness 1.2-1.5nm, 1 μm or so hexagon |
| 4 | 25sccm Ar+15sccmH2 | Thickness 1.5-1.8nm, 1 μm or so hexagon |
| 5 | 20sccm Ar+20sccm H2 | Thickness 1.8-2nm, 1 μm or so hexagon |
| 6 | 10sccm Ar+30sccm H2 | Thickness 2nm or so, 1 μm or so hexagon |
Applicant states that the present invention illustrates the detailed process equipment of the present invention and technological process by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, the improvement of boron nitride-base bottom preparation method, specific side
Selection of formula etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (20)
1. a kind of preparation method of two-dimentional transition metal chalcogenide film, it is characterised in that it includes：In oxygen-free environment, lead to
Enter carrier gas and protective gas, Zr/Hf sources and S/Se sources are heated respectively to volatilizing, in high-temperature region generation gas phase ZrS2、ZrSe2、
HfS2Or HfSe2In any one, and on the boron nitride-base bottom of low-temperature space chemical vapor deposition formed film；
The heating-up temperature in the Zr sources is 175-180 DEG C；The heating-up temperature in the Hf sources is 185-190 DEG C；The heating in the S sources
Temperature is 135-150 DEG C；The heating-up temperature in the Se sources is 235-250 DEG C；Central temperature >=950 DEG C of the high-temperature region；Institute
The temperature for stating chemical vapor deposition is 700-862 DEG C；
The volumn concentration of hydrogen is 10-100% in the protective gas.
2. according to the method for claim 1, it is characterised in that the heating-up temperature in the Zr sources is 180 DEG C.
3. method according to claim 1 or 2, it is characterised in that the carrier gas is argon gas and/or hydrogen.
4. according to the method for claim 3, it is characterised in that the carrier gas is argon gas and hydrogen.
5. according to the method for claim 1, it is characterised in that the protective gas is that volume ratio is 1:3 hydrogen and
The mixture of argon gas.
6. according to the method for claim 1, it is characterised in that the Zr sources are purity>99.9% powder ZrCl4。
7. according to the method for claim 1, it is characterised in that the Hf sources are purity>99.9% powder HfCl4。
8. according to the method for claim 1, it is characterised in that the S sources are purity>99.9% S powder.
9. according to the method for claim 1, it is characterised in that the Se sources are purity>99.9% Se powder.
10. according to the method for claim 1, it is characterised in that the boron nitride-base bottom is to use mono-crystal nitride boron powder
Mechanical stripping method is peeled off onto the silicon chip by surface oxidation processing.
11. according to the method for claim 10, it is characterised in that the oxidated layer thickness of the silicon chip is 300nm.
12. according to the method for claim 10, it is characterised in that the boron nitride passes through the high temperature anneal.
13. according to the method for claim 12, it is characterised in that the high temperature anneal temperature is 600 DEG C, and annealing time is
1h。
14. according to the method for claim 1, it is characterised in that the described method comprises the following steps：
(1) Zr/Hf sources and S/Se sources and boron nitride-base bottom are respectively placed in quartz ampoule successively according to airflow direction；
(2) oxidizing gas in quartz ampoule is removed；
(3) carrier gas and protective gas are passed through with 20-45sccm flow velocity, while heat the extremely volatilization of Zr/Hf sources and S/Se sources, its
In, the heating-up temperature in the Zr sources is 175-180 DEG C；The heating-up temperature in the Hf sources is 185-190 DEG C；The heating in the S sources
Temperature is 135-150 DEG C；The heating-up temperature in the Se sources is 235-250 DEG C；It is incubated 10-30min；It is anti-that chemistry occurs in high-temperature region
ZrS should be generated2、ZrSe2、HfS2Or HfSe2In any one, when airflow downstream is cooled to 700-862 DEG C, be deposited on nitridation
On boryl bottom；
(4) room temperature is cooled to, obtains the two-dimentional ZrS on boron nitride2、ZrSe2、HfS2Or HfSe2In any one.
15. according to the method for claim 1, it is characterised in that the described method comprises the following steps：
(1) by one of S or Se, ZrCl4It is respectively placed in successively with boron nitride-base bottom in a diameter of 1 inch of quartz ampoule；The nitrogen
The position for changing boryl bottom distance high-temperature district center is 2cm-30cm；The quality of the S or Se are 1g, the ZrCl4Quality be
0.1-0.2g；
(2) 0.1-0.5Pa will be evacuated to inside quartz ampoule；
(3) carrier gas and protective gas are passed through with 40sccm flow velocity, while diamond heating is to 950 DEG C or more；
(4) S to 135-150 DEG C or Se to 235-250 DEG C, heating ZrCl are heated respectively4To 175-180 DEG C and it is incubated 10-30min；
The S or Se and ZrCl of volatilization4In 950 DEG C of high-temperature region reaction generation ZrS2Or ZrSe2, and to cooling area under the drive of air-flow
At 700-862 DEG C, it is deposited on boron nitride；In quartz ampoule, thermograde in the direction of the air flow is 20 DEG C/cm；
(5) heating ZrCl is stopped4And tube furnace, continue heat S or Se to high-temperature region central temperature at 700 DEG C stop heating；
(6) room temperature is cooled to, stopping is passed through protective gas, obtains two-dimentional ZrS2Or ZrSe2Film.
16. according to the method for claim 1, it is characterised in that the described method comprises the following steps：
(1) by one of S or Se, HfCl4It is respectively placed in successively with boron nitride-base bottom in a diameter of 1 inch of quartz ampoule；The nitrogen
The position for changing boryl bottom distance high-temperature district center is 2cm-30cm；The quality of the S or Se are 1.5g, the HfCl4Quality
For 0.1-0.2g；
(2) 0.1-0.5Pa will be evacuated to inside quartz ampoule；
(3) carrier gas and protective gas are passed through with 40sccm flow velocity, while diamond heating is to 950 DEG C or more；
(4) S to 135-150 DEG C or Se to 235-250 DEG C, heating HfCl are heated respectively4To 185-190 DEG C and it is incubated 10-30min；
The S or Se and HfCl of volatilization4In 950 DEG C of high-temperature region reaction generation HfS2Or HfSe2, and to cooling area under the drive of air-flow
At 700-862 DEG C, it is deposited on boron nitride；In quartz ampoule, thermograde in the direction of the air flow is 20 DEG C/cm；
(5) heating HfCl is stopped4And tube furnace, continue heating selenium to high-temperature region central temperature to stopping at 700 DEG C and heat；
(6) room temperature is cooled to, stopping is passed through protective gas, obtains two-dimentional HfS2Or HfSe2Film.
17. a kind of two-dimentional transition metal chalcogenide film being prepared according to any one of claim 1-16 methods described,
Characterized in that, the two-dimentional transition metal chalcogenide film is triangle or hexagon monodomain region or continuous film.
18. two-dimentional transition metal chalcogenide film according to claim 17, it is characterised in that the triangle or six
The length of side of side shape monodomain region is 1-3 μm.
19. two-dimentional transition metal chalcogenide film according to claim 17, it is characterised in that the continuous film
The size that size is obtained boron nitride flakes by mechanical stripping determines.
20. two-dimentional transition metal chalcogenide film according to claim 17 is in two-dimensional nanoscale thin film semiconductor material
In application.
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