阅读说明：本技术 一种基于化学气相沉积的半导体复合材料的制备方法 (A kind of preparation method of the semiconductor composite based on chemical vapor deposition ) 是由 吴亿 相倩 李凡 陈文龙 马艳玲 施枫磊 邬剑波 邓涛 陶鹏 宋成轶 尚文 于 2019-08-08 设计创作，主要内容包括：本发明涉及一种基于化学气相沉积的半导体复合材料的制备方法,在化学气相沉积反应室内,采用半导体合成原料以化学气相沉积法在基底上沉积半导体材料,得到半导体材料与基底之间具有耦合界面的目的产物。与现有技术相比,本发明利用化学气相沉积制备出具有特定耦合界面的金属半导体复合物,该材料既具备了基底金属材料的优异电导性能和表面结构性质,同时又因其特殊的耦合界面,使得材料的电催化性能进一步提高。(The present invention relates to a kind of preparation methods of semiconductor composite based on chemical vapor deposition, in chemical vapor deposition reaction chamber, use semiconductor synthesis material with chemical vapour deposition technique the deposited semiconductor material in substrate, obtain between semiconductor material and substrate with coupled interface purpose product.Compared with prior art, the present invention prepares the metal semiconductor compound with specific coupled interface using chemical vapor deposition, the material had both had the excellent conductivity and surface structure properties of base metal material, simultaneously again because of its special coupled interface, so that the electrocatalysis of material can be further improved.)

1. a kind of preparation method of the semiconductor composite based on chemical vapor deposition, which is characterized in that in chemical vapor deposition Product reaction chamber in, use semiconductor synthesis material with chemical vapour deposition technique the deposited semiconductor material in substrate, partly led With the purpose product of coupled interface between body material and substrate.

2. a kind of preparation method of semiconductor composite based on chemical vapor deposition according to claim 1, special Sign is that the semiconductor synthesis material includes chalcogen simple substance and transition metal oxide.

3. a kind of preparation method of semiconductor composite based on chemical vapor deposition according to claim 2, special Sign is that the semiconductor synthesis material is sulphur powder and molybdenum oxide, and corresponding semiconductor material is molybdenum disulfide.

4. a kind of preparation method of semiconductor composite based on chemical vapor deposition according to claim 2, special Sign is that the semiconductor synthesis material is selenium powder and molybdenum oxide, and corresponding semiconductor material is selenizing molybdenum.

5. a kind of preparation method of semiconductor composite based on chemical vapor deposition according to claim 2, special Sign is, in chemical vapor deposition processes, the mass ratio of chalcogen simple substance and transition metal oxide is 8000-12000:1.

6. a kind of preparation method of semiconductor composite based on chemical vapor deposition according to claim 2, special Sign is, in chemical vapor deposition processes, chalcogen simple substance is 20-40cm at a distance from transition metal oxide.

7. a kind of preparation method of semiconductor composite based on chemical vapor deposition according to claim 1, special Sign is that the substrate is the metal or silica of tabular, bulk, foam-like or film-form.

8. a kind of preparation method of semiconductor composite based on chemical vapor deposition according to claim 7, special Sign is that the metal is a kind of simple substance or several alloys in cobalt, nickel, copper, tungsten, titanium, aluminium or iron.

9. a kind of preparation method of semiconductor composite based on chemical vapor deposition according to claim 1, special Sign is that the deposition reaction temperature in substrate is 300-800 DEG C, and the deposition reaction time is 10-60min.

10. a kind of preparation method of semiconductor composite based on chemical vapor deposition according to claim 1, special Sign is, in chemical vapor deposition processes, the protection air-flow flow of introducing arrives the section 100sccm 10.

Technical field

The invention belongs to metal semiconductor field of material technology, are related to a kind of semiconductors coupling based on chemical vapor deposition The preparation method of material.

Background technique

This basic chemical reaction process of electrolysis water plays very in the fields such as the energy, catalyst, sea water desalination Important role.There are mainly two types of existing industrialization electrolytic hydrogen production methods: electrolyzed alkaline water hydrogen manufacturing, polymer dielectric electrolysis Water hydrogen manufacturing.Electrolyzed alkaline water hydrogen manufacturing is still in developing stage；Reason is that the prior art directly will lead to electrode corrosion with seawater It is reduced with efficiency, needs higher voltage to realize the preparation of hydrogen, be on the other hand that the price of high-efficient electrode material is relatively more high Expensive, the requirement to electrolyte is also higher.

Chinese patent 201910446436.6 discloses a kind of preparation of molybdenum disulfide composite material bifunctional electrocatalyst Method and application, preparation method be first be made presoma [email protected], then through be carbonized be made C-N/Co, then with four sulphur It is added in n,N-Dimethylformamide together for ammonium molybdate, hydrazine hydrate multiple by the tentatively obtained molybdenum disulfide of the method for solvent heat Condensation material, it is finally thermally treated to be stabilized to get molybdenum disulfide composite material C-N/Co is arrived₄S₃@MoS₂.The patent system is standby Although the composite material of electrolytic catalysis has preferable catalytic performance, liquid phase preparation, repetitive rate is lower, product structure It can often be not sufficiently stable.

Summary of the invention

It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind to be based on chemical gaseous phase The preparation method of the semiconductor composite of deposition.

The purpose of the present invention can be achieved through the following technical solutions:

A kind of preparation method of the semiconductor composite based on chemical vapor deposition, which is characterized in that in chemical gaseous phase In deposition reaction room, use semiconductor synthesis material with chemical vapour deposition technique the deposited semiconductor material in substrate, obtain half With the purpose product of coupled interface between conductor material and substrate.

Further, the semiconductor synthesis material includes chalcogen simple substance and transition metal oxide.Chemical gaseous phase During deposition reaction, chalcogen simple substance reacts first with transition metal oxide generates gas intermediate product, rear intermediate gas Body product further reacts generation molybdenum disulfide with sulfur vapor and deposits to substrate surface.

Further, the semiconductor synthesis material is sulphur powder and molybdenum oxide, and corresponding semiconductor material is two sulphur Change molybdenum.

Further, the semiconductor synthesis material is selenium powder and molybdenum oxide, and corresponding semiconductor material is selenizing Molybdenum.

Further, in chemical vapor deposition processes, the additive amount (matter of chalcogen simple substance and transition metal oxide Measure ratio) than being about 8000-12000:1 (preferably about 10000:1 or so).

Further, in chemical vapor deposition processes, chalcogen simple substance is 20- at a distance from transition metal oxide 40cm。

Further, the substrate is the metal or silica of tabular, bulk, foam-like or film-form.Substrate tool There is excellent electrical conductance, porosity is between 0%~100%.When substrate selects porous metal material (the i.e. gold of foam-like Belong to material) when, due to vapor deposition, semiconductor can be in porous metal material surface homoepitaxial；During the growth process, due to base Bottom surface is coarse, and forming core site is intensive, and semiconductor is more likely to vertical-growth, ultimately forms the semiconductor display of rock-steady structure； Electrolyte feed channel is provided while cellular solid is as support substrate, guarantees that electrolysis water processing efficient carries out.And Smooth silicon oxide surface, semiconductor material can tend to horizontal growth.That is, the semiconductor material grown in substrate There are much relations with the roughness of substrate surface.

Further, the semiconductor material of growth is in nano-chip arrays, nano particle or bulk.Preferably semiconductor material The nano-chip arrays shape of vertical-growth, such nano-sheet pattern make material have great specific surface area, are electrocatalytic reaction More active sites are provided, meanwhile, this semiconductor material is because its nanometer sheet edge is similar to platinum to the adsorption energy of hydrogen, again The hydrogen that electrolysis water process can be greatly facilitated generates reaction rate.

Further, the metal is a kind of simple substance or several alloys in cobalt, nickel, copper, tungsten, titanium, aluminium or iron.

Further, the deposition reaction temperature in substrate is 300-800 DEG C, and the deposition reaction time is 10-60min.

Further, in chemical vapor deposition processes, the protection air-flow flow of introducing arrives the section 100sccm 10.

In the present invention, semiconductor material will form sulfuric horizon during being grown in substrate between the two, this sulfuric horizon Oxygen can be effectively facilitated and generate reaction rate；Meanwhile a kind of coupled interface is formed between sulfide and semiconductor, the interface to It can be stabilized during electrocatalytic reaction, and the hydrogen generation efficiency in electrolysis water reaction process can be effectively facilitated and produce oxygen effect Rate.

Chemical vapor deposition method used in the present invention is controllable, by changing reaction condition, available difference product Composite material.For example, reaction temperature can change under 300 to 800 degrees Celsius, the protection air-flow flow of introducing can be arrived 10 The section 100sccm, the raw material amount of being put into can suitably change, the distance between reactant and the length in reaction time can be adjusted The whole metal semiconductor composite material for obtaining different-shape.Substrate vulcanizes first, and molybdenum sulfide deposits in substrate, when with reaction Between increase, the active site of molybdenum sulfide deposition vulcanizes molybdenum sheet with the gradually progress of reaction after these specific structures become Constantly growth, final nanometer sheet is increasing, more and more thinner.By changing base material, as on smooth silica, active sites Point is few, and molybdenum sulfide growth is not affected by interference between each other, therefore is in triangle sheet-like morphology, and in the shaggy material such as iron nickel On, deposition site is more, and molybdenum sulfide growth mutually restricts, and squeezes, ultimately forms the laminated structure of vertical-growth.

Metal semiconductor composite material prepared by the present invention had both had the excellent conductivity of metal material, had simultaneously The special attribute of semiconductor, and the hydrogen of electrolysis water is generated the intermediate coupled interface formed and oxygen generation reaction has catalysis Effect can generate hydrogen and oxygen under lower overpotential again.This material can be applied not only in electrolysis water reaction, right In photocatalytic water, light degradation and oxygen reduction reaction, also available effective use.

Firstly, as the temperature rises, the introducing of sulfur vapor, base material starts to vulcanize, and later, sulfur vapor and MoO₃Shape At gas intermediate product, further this product is reacted in substrate surface with sulfur vapor, due to the presence in Basal Activity site, sulphur Change molybdenum just to grow on these sites, is based on the substrate sulfide formed before, first coupling circle when just starting growth Face is formed, i.e., S the and Mo bonding at surface, internal then be substrate sulfide.Further after reaction, molybdenum sulfide is grown into, shape Slabbing structure.It can be seen that by the control reaction time, molybdenum sulfide state (the i.e. size of available difference growth time Thickness pattern).

Compared with prior art, the present invention utilizes the semiconductor composite of chemical vapor deposition growth, converts electrical energy into The material of different-shape, different characteristics can be synthesized by the selection to base material and semiconductor growing reaction raw materials for Hydrogen Energy Material, which not only has stable physical structure, during electrolysis water, is also able to maintain stable performance.Specifically, Have the following advantages that and the utility model has the advantages that

(1) present invention uses substrate of the metal or alloy as chemical vapour deposition technique, and the compound of generation can be improved The stability and electric conductivity of material.

(2) the metal semiconductor composite material that the present invention synthesizes, prepares simple, cheap, stable structure.

(3) present invention can change the pattern of material by the condition of regulation chemical vapor deposition.

(4) the Hydrogen Energy cleanliness without any pollution that the present invention generates, there is energy-saving and emission-reduction effect.

(5) semiconductor composite that the present invention synthesizes has excellent electrolysis water performance.

Detailed description of the invention

Fig. 1 is the composite optical photo that growing substrate is silica；

Fig. 2 is the composite material electron scanning micrograph that matrix is alloy；

Fig. 3 is that different growth time material electrolysis water hydrogen generate kinetic current density with the variation relation figure of voltage.

Fig. 4 is to grow MoS in different base₂Hydrogen to generate kinetic current density luxuriant and rich with fragrance with the variation relation figure and tower of voltage That curve graph；

Fig. 5 is to grow MoS in different base₂Oxygen to generate kinetic current density luxuriant and rich with fragrance with the variation relation figure and tower of voltage That curve graph；

Fig. 6 is Co-MoS prepared by embodiment 3₂The oxygen of material generates kinetic current density with the variation electrochemistry of voltage Performance map；

Fig. 7 is Cu-MoS prepared by embodiment 5₂The electron scanning micrograph of material；

Fig. 8 is Cu-MoS prepared by embodiment 5₂The hydrogen of material generates kinetic current density with the variation electrochemistry of voltage Performance map；

Fig. 9 is CuNi-MoS prepared by embodiment 6₂The electron scanning micrograph of material；

Figure 10 is CuNi-MoS prepared by embodiment 6₂The hydrogen of material generates kinetic current density with the variation electricity of voltage Chemical property figure；

Figure 11 is CoNi-MoS prepared by embodiment 7₂The electron scanning micrograph of material；

Figure 12 is CoNi-MoS prepared by embodiment 7₂The hydrogen of material generates kinetic current density with the variation electricity of voltage Chemical property figure.

Specific embodiment

The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.The present embodiment is with technical solution of the present invention Premised on implemented, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to Following embodiments.