阅读说明：本技术 一种氧化铜/铜钼氧化物纳米异质结构材料及其制备方法 (A kind of copper oxide/copper-molybdenum oxidate nano heterogeneous structure material and preparation method thereof ) 是由 刘仲武 唐春梅 余红雅 钟喜春 邱万奇 于 2019-08-23 设计创作，主要内容包括：本发明属于光电材料领域,公开了一种氧化铜/铜钼氧化物纳米异质结构材料及其制备方法。直接采用Cu片为基底或在非Cu材料基底上生长一层Cu膜,然后采用电场辅助热氧化法加热处理,在基底上得到CuO纳米棒；采用热蒸发法在CuO纳米棒表面制备铜钼氧化物纳米片层,得到所述氧化铜/铜钼氧化物纳米异质结构材料。本发明制备的CuO纳米棒为单晶,铜钼氧化物纳米片层为纳米晶或单晶；获得了以CuO纳米棒为树干,铜钼氧化物为枝的树枝状形貌；纳米异质结构的高比表面积以及大面积的异质界面等特性有望获得预期的增强或优异的物理化学性能。(The invention belongs to field of photovoltaic materials, a kind of copper oxide/copper-molybdenum oxidate nano heterogeneous structure material and preparation method thereof is disclosed.It directlys adopt Cu piece to be substrate or grow one layer of Cu film in non-Cu material substrate, is then heated using electric field-assisted thermal oxidation method, CuO nanometer rods are obtained in substrate；Copper-molybdenum oxidate nano lamella is prepared in CuO nanorod surfaces using thermal evaporation, obtains the copper oxide/copper-molybdenum oxidate nano heterogeneous structure material.CuO nanometer rods prepared by the present invention are monocrystalline, and copper-molybdenum oxidate nano lamella is nanocrystalline or monocrystalline；It obtains using CuO nanometer rods as trunk, copper-molybdenum oxide is the dendroid pattern of branch；The characteristics such as the high-specific surface area of nano-heterogeneous structure and the heterogeneous interface of large area are expected to obtain expected enhancing or excellent physical and chemical performance.)

1. a kind of copper oxide/copper-molybdenum oxidate nano heterogeneous structure material preparation method, it is characterised in that including preparing as follows Step:

(1) it directlys adopt Cu piece to be substrate or grow one layer of Cu film in non-Cu material substrate, then uses the hot oxygen of electric field-assisted The heat treatment of change method, obtains CuO nanometer rods in substrate；

(2) copper-molybdenum oxidate nano lamella is prepared in CuO nanorod surfaces using thermal evaporation, obtains the copper oxide/copper-molybdenum Oxidate nano heterogeneous structure material.

2. a kind of copper oxide according to claim 1/copper-molybdenum oxidate nano heterogeneous structure material preparation method, special Sign is: Cu piece substrate is in the oxidation for removing Cu piece surface using the preceding mode being cleaned by ultrasonic again through sand paper polishing in step (1) Layer and pollutant.

3. a kind of copper oxide according to claim 1/copper-molybdenum oxidate nano heterogeneous structure material preparation method, special Sign is: non-Cu material substrate refers to Si piece, glass, Al in step (1)₂O₃Substrate or nickel foam.

4. a kind of copper oxide according to claim 1/copper-molybdenum oxidate nano heterogeneous structure material preparation method, special Sign is: the non-Cu material substrate refers to Si piece.

5. a kind of copper oxide according to claim 1/copper-molybdenum oxidate nano heterogeneous structure material preparation method, special Sign is: one layer of Cu film grown described in step (1) in non-Cu material substrate and is prepared using sputter deposition, actual conditions Are as follows: using pure Cu as target, background vacuum: 2~4 × 10^-4Pa, argon atmosphere, sputtering pressure: 0.3~0.7Pa, room temperature deposition, Sputtering power: 100~200W；The Cu film with a thickness of 1~10 μm.

6. a kind of copper oxide according to claim 5/copper-molybdenum oxidate nano heterogeneous structure material preparation method, special Sign is: the non-Cu material substrate refers to Si piece substrate, before sputtering sedimentation Cu film, the one layer of Cr conduct of preparatory sputtering sedimentation Buffer layer.

7. a kind of copper oxide according to claim 1/copper-molybdenum oxidate nano heterogeneous structure material preparation method, special Sign is: the condition of the heat treatment of electric field-assisted thermal oxidation method described in step (1) are as follows: oxidate temperature: 300~450 DEG C, when Between: 4~for 24 hours, and air atmosphere, electric field strength: 0~16667V m^-1, direction of an electric field is upward.

8. a kind of copper oxide according to claim 1/copper-molybdenum oxidate nano heterogeneous structure material preparation method, special Sign is: detailed process of the thermal evaporation described in step (2) in CuO nanorod surfaces preparation copper-molybdenum oxidate nano lamella Are as follows: Mo piece is placed in heating plate through sand paper polishing, ultrasonic cleaning, drying, it is then that the substrate containing CuO nanometer rods is hanging It is inverted in 2~10mm above Mo piece, Mo piece temperature is heated in air atmosphere to 400~500 DEG C, carries out thermal evaporation deposition 0.5 Copper-molybdenum oxidate nano lamella is prepared in CuO nanorod surfaces in~32h.

9. a kind of copper oxide/copper-molybdenum oxidate nano heterogeneous structure material, it is characterised in that: pass through any one of claim 1~8 The method is prepared.

10. a kind of copper oxide according to claim 9/copper-molybdenum oxidate nano heterogeneous structure material, it is characterised in that: institute Stating copper oxide/copper-molybdenum oxidate nano heterogeneous structure material is using CuO nanometer rods as trunk, and copper-molybdenum oxidate nano lamella is branch Dendroid pattern；Wherein the diameter of CuO nanometer rods is 20~200nm, the crystallite dimension of copper-molybdenum oxidate nano lamella is 5~ 200nm。

Technical field

The invention belongs to field of photovoltaic materials, and in particular to a kind of copper oxide/copper-molybdenum oxidate nano heterogeneous structure material And preparation method thereof.

Background technique

Ingredient, pattern and the structure etc. of nano-heterogeneous structure all will affect the physics such as its electricity, optics and magnetics and chemistry Property, unique property and the application value in the function elements such as battery, sensor and capacitor receive researcher's Extensive concern.Especially one-dimensional heterogeneous nanometer rods/line, two dimension are limited between carrier, high-specific surface area and heterogeneous interface The characteristics such as high contact area make it possible to expected enhancing or excellent performance occur.But it is most of at present nano heterogeneous The problems such as structure is synthesized by chemical method, more, complex process that there are steps and environmental pollution.

Summary of the invention

In place of the above shortcoming and defect of the existing technology, the primary purpose of the present invention is that providing a kind of oxidation Copper/copper-molybdenum oxidate nano heterogeneous structure material preparation method.The present invention is by combining sputtering sedimentation, thermal oxide and thermal evaporation Method, success are prepared on different substrates based on one-dimensional copper oxide (CuO) nanometer rods, and are receiving for the second phase with copper-molybdenum oxide Rice heterogeneous structure material.

Another object of the present invention is to provide a kind of copper oxide being prepared by the above method/copper-molybdenum oxides to receive Rice heterogeneous structure material.

The object of the invention is achieved through the following technical solutions:

A kind of preparation method of copper oxide/copper-molybdenum oxidate nano heterogeneous structure material, including following preparation step:

(1) it directlys adopt Cu piece to be substrate or grow one layer of Cu film in non-Cu material substrate, then uses electric field-assisted Thermal oxidation method heat treatment, obtains CuO nanometer rods in substrate；

(2) using thermal evaporation CuO nanorod surfaces prepare copper-molybdenum oxidate nano lamella, obtain the copper oxide/ Copper-molybdenum oxidate nano heterogeneous structure material.

Further, Cu piece substrate is removing Cu piece using the preceding mode being cleaned by ultrasonic again through sand paper polishing in step (1) The oxide layer and pollutant on surface.

Further, non-Cu material substrate includes but is not limited to Si piece, glass, Al in step (1)₂O₃Substrate, nickel foam. More preferably Si piece.

Further, one layer of Cu film is grown described in step (1) in non-Cu material substrate and uses sputter deposition system It is standby, actual conditions are as follows: using pure Cu as target, background vacuum: 2~4 × 10^-4Pa, argon atmosphere, sputtering pressure: 0.3~ 0.7Pa, room temperature deposition, sputtering power: 100~200W；Cu film with a thickness of 1~10 μm.

Further, the non-Cu material substrate refers to Si piece substrate, before sputtering sedimentation Cu film, preparatory sputtering sedimentation One layer of Cr is as buffer layer.

Further, the condition of the heat treatment of electric field-assisted thermal oxidation method described in step (1) are as follows: oxidate temperature: 300 ~450 DEG C, the time: 4~for 24 hours, and air atmosphere, electric field strength: 0~16667V m^-1, direction of an electric field is upward.

Further, thermal evaporation described in step (2) is in CuO nanorod surfaces preparation copper-molybdenum oxidate nano lamella Detailed process are as follows: Mo piece is placed in heating plate through sand paper polishing, ultrasonic cleaning, drying, then will contain CuO nanometer rods Substrate is vacantly inverted in 2~10mm above Mo piece, heats Mo piece temperature in air atmosphere to 400~500 DEG C, carries out thermal evaporation 0.5~32h is deposited, copper-molybdenum oxidate nano lamella is prepared in CuO nanorod surfaces.

A kind of copper oxide/copper-molybdenum oxidate nano heterogeneous structure material, is prepared by the above method.

Further, the copper oxide/copper-molybdenum oxidate nano heterogeneous structure material is the copper using CuO nanometer rods as trunk Molybdenum oxide nanoscale twins are the dendroid pattern of branch；Wherein the diameter of CuO nanometer rods is 20~200nm, and copper-molybdenum oxide is received The crystallite dimension of rice lamella is 5~200nm.

Preparation method of the invention and obtained product have the following advantages that and the utility model has the advantages that

(1) present invention prepares oxide heterogeneous structure using non-chemicals such as sputtering sedimentation, thermal oxide and thermal evaporations The work of material there is presently no being reported, and this preparation method have simple process, it is at low cost, be not necessarily to catalyst, energy The advantages that a wide range of preparation and environment friendly.

(2) oxide heterogeneous structure can be directly assembled into the need for meeting different function device in different base by the present invention It asks, suitable for the different base that structure can be kept not to be destroyed at a temperature of lower 300~450 DEG C.

(3) CuO nanometer rods prepared by the present invention are monocrystalline, and copper-molybdenum oxidate nano lamella is nanocrystalline or monocrystalline；It obtains Using CuO nanometer rods as trunk, copper-molybdenum oxide is the dendroid pattern of branch；The high-specific surface area of nano-heterogeneous structure and big The characteristics such as the heterogeneous interface of area are expected to obtain expected enhancing or excellent physical and chemical performance.

Detailed description of the invention

Fig. 1 is copper oxide in the embodiment of the present invention/copper-molybdenum oxidate nano heterogeneous structure material preparation flow figure.

Fig. 2 is the scanning electron microscope (SEM) photograph of copper oxide copper-molybdenum oxidate nano heterogeneous structure material on Si base in embodiment 1.

Fig. 3 is dendroid copper oxide/copper-molybdenum oxidate nano heterogeneous structure material scanning electron microscope on Si base in embodiment 2 Figure.

Fig. 4 is dendroid copper oxide/copper-molybdenum oxidate nano heterogeneous structure material transmission electron microscope on Si base in embodiment 2 Figure.

Fig. 5 is dendroid copper oxide/copper-molybdenum oxidate nano heterogeneous structure material element power spectrum on Si base in embodiment 2 Surface scan figure.

Fig. 6 is different elements in dendroid copper oxide/copper-molybdenum oxidate nano heterogeneous structure material on Si base in embodiment 2 X-ray photoelectron spectroscopy figure.

Fig. 7 is the CuO nanometer rods of thermal oxide preparation on Si base, the α-MoO that on Si base prepared by thermal evaporation₃Micro-nano lamella with And copper oxide/copper-molybdenum oxidate nano heterogeneous structure material Raman spectrogram on Si base in embodiment 1 and embodiment 2.

Fig. 8 is Cu on piece copper oxide in embodiment 3/copper-molybdenum oxidate nano heterogeneous structure material scanning electron microscope (SEM) photograph.

Specific embodiment

Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited In this.