CN107188220B - A kind of two-dimensional nano Ga2In4S9The preparation method and product of crystalline material - Google Patents
A kind of two-dimensional nano Ga2In4S9The preparation method and product of crystalline material Download PDFInfo
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- CN107188220B CN107188220B CN201710469672.0A CN201710469672A CN107188220B CN 107188220 B CN107188220 B CN 107188220B CN 201710469672 A CN201710469672 A CN 201710469672A CN 107188220 B CN107188220 B CN 107188220B
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- C01G15/00—Compounds of gallium, indium or thallium
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Abstract
The invention discloses a kind of two-dimensional nano Ga2In4S9The preparation method of crystalline material uses chemical vapour deposition technique elemental sulfur and liquid gallium indium eutectic alloy for source substance, deposits the Ga of required thickness on substrate2In4S9Crystal；Conversion zone has upstream warm area, center warm area and downstream warm area, and elemental sulfur is placed in upstream warm area, and liquid gallium indium eutectic alloy is placed on center warm area, substrate is placed in downstream warm area since its evaporation required temperature is higher；Using the temperature difference of different warm areas, elemental sulfur steam and gallium-indium alloy steam react in center warm area and generate Ga2In4S9, and downstream warm area is brought by carrier gas, deposition becomes two-dimensional nano Ga on substrate2In4S9Crystalline material.Using the method for the present invention, the consistent two-dimensional nano Ga of thickness uniform form has been prepared2In4S9Crystalline material has bright prospects in the application of opto-electronic device.
Description
Technical field
The invention belongs to nano semiconductor material fields, more particularly, to a kind of two-dimensional nano Ga2In4S9Crystalline material
Preparation method and product.
Background technique
The discovery of graphene has greatly pushed the research of two-dimensional material, and only the material of several atomic thickness, can have non-
The fundamental characteristics (Science 2004,306,666-669) of Chang Butong.Many researchers develop being permitted for the substance immediately
More application characteristics, from flexible screen is made to energy storage.Unfortunately, graphene band gap is zero, is made of graphene
At transistor can not turn off, this limits its application in opto-electronic device and digital electron device to a certain extent
(Nature Photonics 2013,7,888-891), and for this field, ideal material is semiconductor.Although
Have much makes its band gap become to regulate and control about to the method that graphene is modified, but all encounters complex process, at
The problem of this valuableness is not suitable for being applied to universal semiconductor microactuator nano parts field, however obtained in terms of graphene preparation
Successful experience motivated researcher explore alternative semiconductor two-dimensional material (Advanced Materials 2014,26,
2648–2653；ACS Nano.2015,9,2740-2748).
It is of interest by numerous scholars that there are also the two-dimensional materials of many class graphenes, especially transient metal sulfide
(ACS Nano 2012,6,74-78) and III-VI A race two-dimensional material such as GaSe (ACS gradually to come into the picture now
Nano 2014,8,1485-1490), InSe (Advanced Materials 2014,26,6587-6593), GaS
(Nanoscale 2014,6,2582-2587) etc..Compared with these two-dimentional binary materials, two-dimentional gallium base shape chalcogenide
Crystalline material is due to significant anisotropy, excellent photoluminescence performance, the excellent performance such as high optical responsivity, because
This has more positive application value in micro-nano device field.
Wherein, Ga2In4S9As a kind of important ternary gallium base shape chalcogenide material, since it is to environment and life
Object harm is small, and has excellent photoelectric properties, and the application potential in micro-nano electronics and micro-nano photoelectronics is huge.But
It is to utilize Ga now2In4S9The opto-electronic device of two-dimensional layer crystalline material production is rarely reported, and is largely determined by high quality
Ga2In4S9The synthetic technology problem of two-dimensional layer crystalline material.
How to manufacture cheaply uniformly, flawless thin layer have become all two-dimensional material functionizations to be solved one
A major issue." adhesive tape method " can be perfectly suitable for transient metal sulfide, but expend the time.And how to obtain list
Crystal block shape Ga2In4S9Method it is still immature, lead to this method higher cost.Chemical peeling can produce several grams of sub-micro
The multilayer substance of meter great little, but the crystal structure of product obtained and electronic structure are all changed.Using from bottom to top
Synthetic method, such as hydrothermal synthesis can obtain molybdenum disulfide two-dimensional structure, but same because liquid environment will lead to product
Size is small and performance changes, it is difficult to meet the requirements.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of two-dimensional nano Ga2In4S9Crystal
The preparation method and product of material, its object is to the optimizations of selection and reaction condition by material, obtain large scale, pattern
The uniform two dimension Ga of regular, Elemental redistribution2In4S9Crystalline material.
To achieve the above object, according to one aspect of the present invention, a kind of two-dimensional nano Ga is provided2In4S9Crystalline material
Preparation method, which is characterized in that conversion zone is divided into upstream warm area, center warm area and downstream warm area in the horizontal direction；It is logical
The temperature for crossing control centre's warm area makes the temperature of center warm area be respectively higher than upstream warm area and downstream warm area, and utilizes center
The temperature difference of warm area and upstream warm area, downstream warm area, makes sulphur source steam be formed in upstream warm area, liquid eutectic gallium indium source steam is formed
In center warm area, and center warm area into is brought sulphur source steam by carrier gas and reacts generation Ga with liquid eutectic gallium indium source2In4S9, then
The Ga that reaction is generated2In4S9It brings downstream warm area into, makes Ga2In4S9Deposition is received as two dimension on the substrate for being set to downstream warm area
Rice Ga2In4S9Crystalline material；
The sulphur source and gallium indium source are respectively elemental sulfur and liquid gallium indium eutectic alloy, and the two is independently placed in upstream
Warm area and center warm area.
Preferably, the elemental sulfur is sulphur powder.
Preferably, the temperature of the center warm area is 800 DEG C~950 DEG C, the Ga2In4S9Depositing temperature on substrate
It is 500 DEG C~650 DEG C.
Preferably, the pressure in the conversion zone is equal to an atmospheric pressure.
Preferably, the carrier gas is made of the Ar gas that purity is 99.999%.
Preferably, the flow of carrier gas described in reaction process is 25sccm~100sccm.
Preferably, the substrate is mica or the insulating silicon for being coated with silica oxide layer.
Preferably, it is then charged with Ar gas first by conversion zone forvacuum before reaction and carries out gas washing repeatedly until emptying empty
Gas.
Preferably, with a thickness of 1~6 Ga2In4S9Structure single layer.
It is another aspect of this invention to provide that additionally providing a kind of two-dimensional nano Ga prepared in this way2In4S9Crystal material
Material, which is characterized in that pattern is triangle, 1~3 Ga of thickness2In4S9Structure sheaf.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, have below beneficial to effect
Fruit:
1) it selects sulphur simple substance and liquid gallium indium eutectic alloy respectively as sulphur source and gallium indium source, reduces reaction temperature, subtract
Small energy consumption, realizes the controllable of preparation process；
2) substrate center warm area keeps certain distance, avoids substrate and is destroyed；
3) by the two-dimensional nano Ga of the method for the present invention preparation2In4S9Crystalline material surfacing, S, Ga and In distribution are equal
Even, pattern is triangle, has bright prospects in the application of electronic device.
Detailed description of the invention
Fig. 1 is that two-dimensional nano Ga is prepared in embodiment 12In4S9The schematic device of crystalline material；
Fig. 2 a~Fig. 2 g is the crystalline material pattern top view of embodiment 1-7 preparation respectively；
Fig. 3 is the measurement figure of crystalline material thickness prepared by embodiment 1；
Fig. 4 a~Fig. 4 c is the elemental composition analysis chart of crystalline material prepared by embodiment 1；
Fig. 5 a, Fig. 5 b are the Crystal Structure figures of crystalline material prepared by embodiment 1.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
Embodiment 1
Fig. 1 is according to the invention a kind of to prepare two-dimensional nano Ga2In4S9The methods experiment device cross-sectional view of crystalline material.
Depositing device uses horizontal pipe furnace 1, pipe range 80cm, center warm area range 10cm, and temperature setting is 950 DEG C, heating rate 30
DEG C/min.Sulphur source 2 is used as using sulphur powder (S) (>=99.99%), is placed on upstream warm area, the distance of distance center warm area is
18cm selects liquid gallium indium eutectic alloy 3 (Ga:In=3:1, >=99.99%) to be used as gallium source and indium source, is centrally disposed warm area
Place.Using the silicon-on-insulator of the commercially available silica oxide layer for being coated with 300nm thickness as substrate 4, it is placed on downstream distance
Product is received at 13cm, depositing temperature is 500 DEG C.Forvacuum is first carried out before the reaction to 20Pa or so, is then charged with flow
For 630sccm Ar gas to an atmospheric pressure, and gas washing at least 3 times repeatedly, to exclude remnant oxygen.Stream is passed through in reaction process
Measuring the Ar gas for being 100sccm and keeping pressure is an atmospheric pressure.Reaction time is 15 minutes, and carrier gas is kept after reaction
Constant, product cools to room temperature with the furnace, and the silicon-on-insulator substrate 4 for being coated with silica oxide layer collects product Ga2In4S9, obtain
Two-dimensional nano Ga2In4S9Crystalline material.
Embodiment 2
Embodiment 1 is repeated with the same steps, difference is, the Ar that flow is 50sccm is passed through in reaction process
Gas.
Embodiment 3
Embodiment 1 is repeated with the same steps, difference is, the temperature setting of center warm area is 850 DEG C,
Ga2In4S9Depositing temperature on substrate is 580 DEG C.
Embodiment 4
Embodiment 1 is repeated with the same steps, difference is, the temperature setting of center warm area is 900 DEG C.
Embodiment 5
Embodiment 1 is repeated with the same steps, difference is, receives substrate 4 and selects commercially available mica sheet.
Embodiment 6
Embodiment 1 is repeated with the same steps, difference is, the reaction time is 10 minutes, Ga2In4S9In substrate
On depositing temperature be 650 DEG C.
Embodiment 7
Embodiment 1 is repeated with the same steps, difference is, the reaction time is set as 30 minutes, in reaction process
It is passed through the Ar gas that flow is 25sccm.
Analysis of experimental results
With optical microscopy to the two-dimensional nano Ga prepared in embodiment 1-72In4S9Crystalline material carries out surface topography table
Sign, is as a result shown in Fig. 2.Wherein Fig. 2 a- Fig. 2 g respectively indicates the two-dimensional nano Ga prepared in embodiment 1-72In4S9Crystalline material
Surface topography map.
It can be seen that the shape of the material is consistent from Fig. 2 a, 2b, 2f, and have a generally triangular shape.It can be seen that from Fig. 2 c
When central temperature is 850 DEG C, material has no regular morphology；It can be seen that from Fig. 2 d when central temperature is 900 DEG C, crystal
Material morphology is simultaneously irregular, a small amount of triangle only occurs；It can be seen that from Fig. 2 e when the commercially available mica sheet of selection is as reception lining
When bottom 4, it is unable to get the product of regular triangular shape, the pattern of material presents round；And it can be seen that 30 points of reaction from Fig. 2 g
The shape of Zhong Shi, the crystalline material of preparation are thicker.
With the method on atomic force microscope probe scanned sample surface to the two-dimensional nano prepared in embodiment 1-7
Ga2In4S9Crystalline material carries out thickness measure, and the single-sheet thickness for measuring the material of the preparation of embodiment 1 is 2.4nm, is equivalent to 2
Ga2In4S9Structure single layer (thickness of 10 layers of atomic layer)；Embodiment 2 is 2~3 Ga2In4S9Structure single layer, embodiment 3 are 3
~5 Ga2In4S9Structure single layer, irregular shape prepared by embodiment 4 is at product with a thickness of 2~3 Ga2In4S9Structure list
Thickness degree (thickness of 10~15 layers of atom)；Embodiment 5 prepare material with a thickness of 3 Ga2In4S9Structure thickness in monolayer (15
The thickness of layer atom)；Embodiment 6 is 4~6 Ga2In4S9Structure single layer, the material prepared in embodiment 7 with a thickness of 5~6
A Ga2In4S9Structure thickness in monolayer (more than 30 atomic layer level thickness), wherein the measurement result of the material of embodiment 1 is shown in Fig. 3.
With energy dispersion X-ray spectrum to the two-dimensional nano Ga prepared in embodiment 12In4S9Crystalline material carries out ingredient point
Analysis, is as a result shown in Fig. 4 a Fig. 4 b, it was demonstrated that sulphur, gallium and three kinds of Elemental redistributions of indium are uniform in product.
With transmission electron microscope to the two-dimensional nano Ga prepared in embodiment 12In4S9Crystalline material carries out crystal structure
Characterization, wherein Fig. 5 a be high-resolution lattice image, Fig. 5 b be corresponding electron diffraction pattern, in conjunction with Fig. 4 susceptible of proof product be two
Wiener rice Ga2In4S9Crystalline material.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (5)
1. a kind of two-dimensional nano Ga2In4S9The preparation method of crystalline material, which is characterized in that conversion zone is divided into the horizontal direction
Sulphur source and liquid gallium indium eutectic alloy are independently placed in upstream warm area by upstream warm area, center warm area and downstream warm area
And center warm area；The temperature of control centre's warm area is 950 DEG C, and the temperature of center warm area is made to be respectively higher than upstream warm area and downstream
Warm area makes sulphur source steam be formed in upstream warm area, liquid eutectic using the temperature difference of center warm area and upstream warm area, downstream warm area
Gallium indium source steam is formed in center warm area, and brings sulphur source steam into center warm area by carrier gas and react with liquid eutectic gallium indium source
Generate Ga2In4S9, forvacuum is first carried out before the reaction to 20Pa, is then charged with Ar gas that flow is 630sccm to one big
Air pressure, and gas washing at least 3 times repeatedly are passed through the Ar gas that flow is 100sccm and protect to exclude remnant oxygen in reaction process
Holding pressure is an atmospheric pressure, and the reaction time is 15 minutes, and carrier gas remains unchanged after reaction；Reaction is generated by carrier gas
Ga2In4S9It brings downstream warm area into, makes Ga2In4S9It is deposited on the substrate of downstream warm area, obtains under 500 DEG C of depositing temperatures
Obtain the uniform two-dimentional ternary nano Ga triangular in shape of regular appearance, Elemental redistribution2In4S9Crystalline material.
2. preparation method according to claim 1, which is characterized in that the sulphur source is sulphur powder.
3. preparation method according to claim 1, which is characterized in that the Ar gas group that the carrier gas is 99.999% by purity
At.
4. preparation method according to claim 1, which is characterized in that the substrate is mica or is coated with silica oxidation
The insulating silicon of layer.
5. the two-dimentional ternary nano Ga prepared with any one of claim 1-4 the method2In4S9Crystalline material, feature
It is, with a thickness of 1~6 Ga2In4S9Structure single layer.
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| CN110364419B (en) * | 2019-06-29 | 2021-09-21 | 华南理工大学 | Two-dimensional InGaSe nano material growing on Si substrate and preparation method thereof |
| CN110364418B (en) * | 2019-06-29 | 2021-11-23 | 华南理工大学 | Grown on SiO2Two-dimensional InGaS nano material on substrate and preparation method thereof |
| CN110284191B (en) * | 2019-07-26 | 2020-08-18 | 华中科技大学 | Two-dimensional inorganic molecular crystal material and preparation method thereof |
| CN110846719B (en) * | 2019-11-28 | 2021-02-09 | 华中科技大学 | Two-dimensional non-layered In2SnS4Crystalline material and method for producing same |
| CN112520716B (en) * | 2020-11-27 | 2022-11-01 | 国家纳米科学中心 | Two-dimensional layered CuInP2S6 semiconductor material and preparation method thereof |
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| CN105463580A (en) * | 2016-01-07 | 2016-04-06 | 中国科学院理化技术研究所 | Preparation method of cadmium selenide or cadmium sulfide two-dimensional monocrystal nanosheet |
| CN105839072A (en) * | 2016-04-19 | 2016-08-10 | 陕西师范大学 | Method for preparing rhenium disulfide thin film through chemical vapor deposition |
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| CN105463580A (en) * | 2016-01-07 | 2016-04-06 | 中国科学院理化技术研究所 | Preparation method of cadmium selenide or cadmium sulfide two-dimensional monocrystal nanosheet |
| CN105839072A (en) * | 2016-04-19 | 2016-08-10 | 陕西师范大学 | Method for preparing rhenium disulfide thin film through chemical vapor deposition |
Non-Patent Citations (1)
| Title |
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| Optical Absorption and Photoelectric Properties of Ga2In4S9 Single Crystals;N. A. MOLDOVYAVN et al.;《Cryst. Res. Technol.》;19901231;第25卷(第7期);第847-853页 |
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