CN110028047B - Mono-oriented and compositionally tunable CdSxSe1-xAlloy nanowire array and preparation method thereof - Google Patents

Mono-oriented and compositionally tunable CdSxSe1-xAlloy nanowire array and preparation method thereof Download PDF

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CN110028047B
CN110028047B CN201810030033.9A CN201810030033A CN110028047B CN 110028047 B CN110028047 B CN 110028047B CN 201810030033 A CN201810030033 A CN 201810030033A CN 110028047 B CN110028047 B CN 110028047B
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CN110028047A (en
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孟祥敏
成华秋
夏静
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Technical Institute of Physics and Chemistry of CAS
University of Chinese Academy of Sciences
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    • 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
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G11/00—Compounds of cadmium
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    • 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
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX 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
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer

Abstract

The invention discloses single-orientation and component-adjustable CdSxSe1‑xThe preparation method of the alloy nanowire array comprises the following steps: heating the CdS single crystal wafer in situ by adopting a thermal evaporation method to obtain a CdS single crystal wafer with CdS nano-wire arrays uniformly distributed on the surface; the CdS single crystal wafer with CdS nano-wire arrays uniformly distributed on the surface is used as a substrate, CdSe powder is used as a raw material, protective gas is used as a carrier, and a physical vapor deposition method is adopted to prepare the CdS with single orientation and adjustable componentsxSe1‑xThe alloy nanowire array is characterized in that x is more than 0 and less than or equal to 1. The preparation method is simple, and the CdS with large area, good crystallinity, consistent crystal orientation and adjustable components is successfully preparedxSe1‑xAnd (3) alloy nanowire arrays.

Description

Mono-oriented and compositionally tunable CdSxSe1-xAlloy nanowire array and preparation method thereof
Technical Field
The invention relates to the technical field of nano semiconductors. More particularly, it relates to a single orientation and adjustable component CdSxSe1-xAn alloy nanowire array and a preparation method thereof.
Background
Since the discovery of Carbon Nanotubes (CNTs) by the professor s.iijima of japan scientists in 1991, efficient carrier transport and alignment control have been ensured due to the confinement effect of carriers and light transport of one-dimensional semiconductor nanomaterials in two dimensions, and thus one-dimensional nanostructure materials have attracted much attention. The one-dimensional nanowire array formed by regularly arranging a large number of vertically grown one-dimensional nanowires has unique electrical, optical, magnetic and other properties, so that the method has very important significance for the research of large-scale functional devices such as a photoelectric detector, a pressure sensor, a field effect transistor and the like.
With the continuous progress of the nanomaterial fabrication technology over the last decades, various methods for synthesizing one-dimensional semiconductor nanomaterials have been developed. However, the prepared one-dimensional nano materials such as nanowires, nanobelts and the like have disordered distribution and inconsistent growth orientation, or are intertwined with each other, are difficult to separate and have more defects, and the application and development of the one-dimensional nano materials in the aspects of device processing, assembly and the like are severely restricted.
Typically, a single component semiconductor material has a fixed bandgap and only responds optically to photon energies near its bandgap. Although in principle a fixed band gap value may vary with size, temperature etc., the range of variation is quite limited. This has influenced the development of semiconductor devices in the field of multifunctional and diversified tunable optoelectronic devices and broad spectral responses. Common semiconductor alloy materials have the characteristics of gradual change of components, adjustable band gap, high concentration of internal carriers and the like, and have outstanding advantages in the aspects of mechanics, piezoelectric property, photoelectric conversion property and the like. The one-dimensional semiconductor nano material of the IIB-VIA family compounds of cadmium sulfide (CdS) and cadmium selenide (CdSe) is a hotspot research material in the field of photoelectric detection because the nano structure of the one-dimensional semiconductor nano material has the characteristics of high gain, high reliability, long service life and the like and also shows good photoconductive effect. Thus based on CdSxSe1-xCharacteristic of conductivity change of alloy nanomaterial under illumination condition, CdSxSe1-xThe wide-spectrum photoelectric detector has the advantages of high photoresponse, high response speed, high external quantum efficiency and the like, and can better meet the requirements of the photoelectric detection field, thereby having wider application prospect.
With the continuous progress of material preparation technology, the preparation methods of one-dimensional semiconductor nano-structure materials include a gas-liquid-solid (VLS) method, a template method, molecular beam epitaxy, an electron beam lithography technology and the like, and the methods have advantages and inevitable defects. For example, the VLS growth method is used to grow a variety of one-dimensional semiconductor nanowires with controlled size, orientation, and composition, but the method requires support from an external metal and thus may introduce contamination. The molecular beam epitaxy method is favorable for controlling the composition and structure of the whole nanowire, and the nanowire with low defect concentration and good uniformity can be prepared, but the method has the defects of high cost, low yield, fine operation and the like.
Therefore, a novel and efficient preparation method is found, and the method has very important practical significance in preparing the one-dimensional semiconductor nanowire array with high quality, large area and controllable crystal structure.
Disclosure of Invention
The first purpose of the invention is to provide CdS with single orientation and adjustable componentsxSe1-xA method for preparing an alloy nanowire array. The preparation method is simple, and the CdS with large area, good crystallinity, consistent crystal orientation and adjustable components is successfully preparedxSe1-xAnd (3) alloy nanowire arrays.
The second purpose of the invention is to provide the CdS with single orientation and adjustable componentsxSe1-xAnd (3) alloy nanowire arrays.
In order to achieve the first purpose, the invention adopts the following technical scheme:
single-orientation and component-adjustable CdSxSe1-xThe preparation method of the alloy nanowire array comprises the following steps:
heating the CdS single crystal wafer in situ by adopting a thermal evaporation method to obtain a CdS single crystal wafer with CdS nano-wire arrays uniformly distributed on the surface;
the CdS single crystal wafer with CdS nano-wire arrays uniformly distributed on the surface is used as a substrate, CdSe powder is used as a raw material, protective gas is used as a carrier, and a physical vapor deposition method is adopted to prepare the CdS with single orientation and adjustable componentsxSe1-xThe alloy nanowire array is characterized in that x is more than 0 and less than or equal to 1.
Preferably, the structure of the CdS single crystal wafer is a hexagonal structure and is oriented in a [0001] direction.
Preferably, the method for heating the CdS single crystal wafer in situ by the thermal evaporation method comprises the following steps:
the single polishing surface of the CdS single crystal wafer is upward and is arranged in the heating center of a tube furnace;
vacuumizing the tube furnace, introducing protective gas, and controlling the pressure in the tube to be 50-500Pa in the inflation process;
heating the tubular furnace to 680-750 ℃ at a heating rate of 15-25 ℃/min, and reacting for 20-60min at the temperature, wherein the flow rate of the protective gas is 30-50 sccm;
and after the reaction is finished, naturally cooling the tubular furnace to room temperature to obtain the CdS single crystal wafer with the CdS nano-wire arrays uniformly distributed on the surface.
Preferably, the physical vapor deposition method specifically includes the steps of:
weighing CdSe powder in a ceramic boat, and placing the ceramic boat in a high-temperature zone heating center of a double-temperature zone tube furnace;
taking the CdS single crystal wafer with the CdS nano-wire arrays uniformly distributed on the surface as a substrate, and placing the substrate in a heating center of a low-temperature area of the double-temperature-area tubular furnace;
vacuumizing the tube furnace, introducing protective gas, and controlling the pressure in the tube to be 50-500Pa in the inflation process;
heating the high temperature region of the tubular furnace to 630-730 ℃ at a heating rate of 15-25 ℃/min, heating the low temperature region of the tubular furnace to 500-620 ℃ at the same heating rate, and reacting for 20-60min under the condition, wherein the flow rate of the protective gas is 30-50 sccm;
after the reaction is finished, the tubular furnace is naturally cooled to room temperature to obtain the CdS with single orientation and adjustable componentsxSe1-xAnd (3) alloy nanowire arrays.
Preferably, the protective gas is a mixed gas of hydrogen and an inert gas, wherein the inert gas is one or a mixture of nitrogen, helium, argon and neon.
Preferably, the volume content of the hydrogen and the inert gas in the mixed gas is as follows: 5-10% of hydrogen and 95-90% of inert gas.
Preferably, the first and second electrodes are formed of a metal,in the step of heating the low temperature region of the tube furnace to 500-620 ℃ at a heating rate of 15-25 ℃/min, the deposition temperature of CdSe steam on the substrate is adjusted within the temperature range of 500-620 ℃ to realize the CdS reactionxSe1-xAnd regulating and controlling components of the alloy nanowire array.
To achieve the second objective, the present invention provides a single-orientation and adjustable-component CdS prepared by the above preparation methodxSe1-xAn alloy nanowire array, wherein the single-orientation CdS is uniformly distributed on the surface of template size of CdS single crystal waferxSe1-xAnd (3) alloy nanowire arrays.
The invention has the following beneficial effects:
in the technical scheme of the preparation method, the CdS with single orientation and adjustable component content is prepared in a large areaxSe1-xAnd (3) alloy nanowire arrays. The method has the advantages of simple operation, no catalyst, short preparation time, no pollution, and suitability for mass production, and the prepared CdSxSe1-xThe alloy nanowire has uniform length, large length-diameter ratio and moderate density, and has very important application value in the fields of solar cells, photocatalysis and photoelectric detectors.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 shows an original CdS single crystal wafer (a), a CdS single crystal wafer (b) with CdS nano-wire arrays uniformly distributed on the surface, and a single-orientation CdS uniformly distributed on the template size of the CdS single crystal wafer in the preparation method of embodiment 1 of the inventionxSe1-xScanning electron microscope image of the alloy nanowire array (c).
FIG. 2 shows a reaction scheme in the production method of example 1 of the present invention.
FIG. 3 shows the single orientation CdS obtained in the preparation method of example 1xSe1-xAnd (3) a scanning electron microscope image of the alloy nanowire array, wherein a is a top view, b is a partial enlarged view of a, and c is a side view.
FIG. 4 shows the present invention separatelySingle CdS prepared as in example 1xSe1-xA Transmission Electron Microscope (TEM) bright field image (a) of the alloy nanowire; single CdSxSe1-xA local Transmission Electron Microscope (TEM) bright field image (b) of the alloy nanowire; single CdSxSe1-xHigh Resolution Transmission Electron Microscopy (HRTEM) photographs of the alloy nanowires and corresponding Selected Area Electron Diffraction (SAED) pictures (c); single CdSxSe1-xA scanning transmission electron microscope bright field image (STEM) (d) of the alloy nanowire; corresponding Cd, S and Se element distribution maps (e) and EDS maps (f).
FIG. 5 shows CdS obtained in example 1 of the present inventionxSe1-xRoom temperature PL plot of alloy nanowire arrays.
FIG. 6 shows CdS obtained in examples of the present invention and comparative examplesxSe1-xAnd when x in the alloy nanowire array is respectively 0, 0.13, 0.35, 0.56, 0.77 and 1, the PL graph of the alloy nanowire array at room temperature is shown.
FIG. 7 shows CdS obtained in an example of the present inventionxSe1-xAnd when x in the alloy nanowire array is 0.13, 0.35, 0.56 and 0.77 respectively, the EDS energy spectrum of the alloy nanowire array is shown.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
One embodiment of the invention provides single-orientation and adjustable-component CdSxSe1-xThe preparation method of the alloy nanowire array comprises the following steps:
heating the CdS single crystal wafer in situ by adopting a thermal evaporation method to obtain a CdS single crystal wafer with CdS nano-wire arrays uniformly distributed on the surface;
the CdS single crystal wafer with CdS nano-wire arrays uniformly distributed on the surface is used as a substrate, CdSe powder is used as a raw material, protective gas is used as a carrier, and the CdS single crystal wafer is prepared by a physical vapor deposition methodCds to mono-orientation and tunable in compositionxSe1-xThe alloy nanowire array is characterized in that x is more than 0 and less than or equal to 1.
In the embodiment, a CdS single crystal wafer is heated in situ by a thermal evaporation method, a CdS nanowire array with a stable structure is easily obtained, the obtained CdS single crystal wafer with the CdS nanowire array uniformly distributed on the surface is used as a substrate, and a physical vapor deposition method is adopted, so that CdS with good crystallinity, consistent crystal orientation and adjustable components is preparedxSe1-xAnd (3) alloy nanowire arrays. The preparation method is simple, environment-friendly and easy for mass production.
In a preferred example, the structure of the CdS single crystal wafer is a hexagonal structure and is oriented to [0001]]And (4) direction. In the embodiment of the invention, CdS is influenced on the crystal form and the orientation of a CdS single crystal waferxSe1-xPreparation of alloy nanowire array, only when the used CdS single crystal wafer is in a hexagonal structure and is oriented to [0001]]When the CdS nanowire array is oriented, the CdS nanowire array with the size of the template can be prepared on the CdS single crystal wafer, so that the large-area single-orientation CdS nanowire array is obtained on the surface of the CdS single crystal wafer, and the large-area single-orientation CdS nanowire array with adjustable components is further prepared on the CdS single crystal waferxSe1-xAnd (3) alloy nanowire arrays.
In this embodiment, x may be any value within the range of (0, 1), and it should be clear to those skilled in the art that the selection of x depends on the specific reaction conditions.
In a preferred example, the method for heating the CdS single crystal wafer in situ by the thermal evaporation method comprises the following steps:
the single polishing surface of the CdS single crystal wafer is upward and is arranged in the heating center of a tube furnace;
vacuumizing the tube furnace, introducing protective gas, and controlling the pressure in the tube to be 50-500Pa in the inflation process;
heating the tubular furnace to 680-750 ℃ at a heating rate of 15-25 ℃/min, and reacting for 20-60min at the temperature, wherein the flow rate of the protective gas is 30-50 sccm;
and after the reaction is finished, naturally cooling the tubular furnace to room temperature to obtain the CdS single crystal wafer with the CdS nano-wire arrays uniformly distributed on the surface.
In this example, the temperature of the tube furnace is controlled at 680-750 ℃, so that on one hand, the whole single crystal wafer can be prevented from being evaporated due to overhigh temperature, and on the other hand, the situation that the thermal evaporation of the single crystal wafer cannot be realized due to overlow temperature can be avoided, so that the CdS single crystal wafer with the CdS nanowire arrays uniformly distributed on the surface can not be prepared.
In the embodiment of the invention, the single polished surface of the CdS single crystal wafer refers to one surface of the CdS single crystal wafer. Further, when the tube furnace is evacuated and the tube furnace is placed under vacuum, the degree of vacuum of the tube furnace is preferably in the range of 0.1 to 10 Pa.
In yet another preferred example, the physical vapor deposition method specifically includes the steps of:
weighing CdSe powder in a ceramic boat, and placing the ceramic boat in a high-temperature zone heating center of a double-temperature zone tube furnace;
taking the CdS single crystal wafer with the CdS nano-wire arrays uniformly distributed on the surface as a substrate, and placing the substrate in a heating center of a low-temperature area of the double-temperature-area tubular furnace;
vacuumizing the tube furnace, introducing protective gas, and controlling the pressure in the tube to be 50-500Pa in the inflation process;
heating the high temperature region of the tubular furnace to 630-730 ℃ at a heating rate of 15-25 ℃/min, heating the low temperature region of the tubular furnace to 500-620 ℃ at the same heating rate, and reacting for 20-60min under the condition, wherein the flow rate of the protective gas is 30-50 sccm;
after the reaction is finished, the tubular furnace is naturally cooled to room temperature to obtain the CdS with single orientation and adjustable componentsxSe1-xAnd (3) alloy nanowire arrays.
In this example, when the tube furnace is evacuated and the tube furnace is placed under vacuum, the degree of vacuum of the tube furnace is preferably 0.1 to 10 Pa.
Wherein, the high temperature of the tube furnace is raised to 630-730 ℃ to facilitate the evaporation of the CdSe powder, and the low temperature is raised to 500-620 ℃ to facilitate the deposition of CdSe vapor on the substrate.
In the embodiment of the invention, the low-temperature zone of the tube furnace is controlled at 15-25 DEG CIn the step of heating up to 500-620 ℃ at the heating speed of/min, the deposition temperature of CdSe steam on the substrate is adjusted within the temperature range of 500-620 ℃ to realize CdS reactionxSe1-xAnd regulating and controlling components of the alloy nanowire array.
Further, it is understood that the protective gas in this embodiment is a gas that serves to protect the reaction from stably proceeding and does not participate in the reaction. In a preferred example, the protective gas is a mixture of hydrogen and an inert gas, wherein the inert gas is selected from one or more of nitrogen, helium, argon and neon. In the mixed gas, the volume contents of hydrogen and inert gas are as follows: 5-10% of hydrogen and 95-90% of inert gas. Under the condition, the prepared CdSxSe1-xThe crystallinity and the orientation unicity of the alloy nanowire array are better, and the distribution of the nanowire array is more uniform.
In another embodiment of the invention, the single-orientation and component-adjustable CdS prepared by the preparation method is also providedxSe1-xAlloy nanowire array with uniformly distributed single-orientation CdS on the surface of template size of CdS single crystal waferxSe1-xAnd (3) alloy nanowire arrays.
The technical solution of the present invention is described below with reference to some specific preferred embodiments:
example 1
Single-orientation and component-adjustable CdSxSe1-xThe preparation method of the alloy nanowire array comprises the following steps:
placing a CdS single crystal wafer with length, width and thickness of 5 x 3 x 0.5mm and hexagonal structure oriented to [0001] crystal orientation in a heating center of a horizontal tube furnace with a single polished surface facing upwards, wherein the scanning electron microscope image of the single crystal wafer is shown as a in FIG. 1;
opening a mechanical pump for vacuum pumping, and introducing argon-hydrogen mixed gas (volume ratio is 95%: 5%) as protective gas into the tubular furnace when the pressure in the furnace is reduced to 0.1 Pa;
heating to 700 ℃ at a heating speed of 20 ℃/min and keeping for 20 minutes, wherein the flow rate of argon-hydrogen mixed gas is controlled at 45sccm in the reaction process;
after the reaction is finished, naturally cooling the tube furnace to room temperature to obtain a CdS single crystal wafer with CdS nano-wire arrays uniformly distributed on the surface, wherein a scanning electron microscope image of the single crystal wafer is shown as b in figure 1;
weighing 0.5 g of CdSe powder, putting the CdSe powder into a ceramic boat, and then putting the ceramic boat into a high-temperature area heating center of a double-temperature area tube furnace;
as shown in fig. 2, a prepared CdS single crystal wafer with a CdS nanowire array uniformly distributed on the surface is used as a substrate and placed in a low-temperature region heating center of a dual-temperature region tube furnace;
vacuumizing the tube furnace, introducing argon-hydrogen mixed gas (volume ratio is 95%: 5%) into the furnace when the pressure in the furnace is reduced to 0.1Pa, and maintaining the pressure in the cavity at 500 Pa;
heating the high-temperature region heating center of the double-temperature region tubular furnace to 650 ℃ at a heating speed of 20 ℃/min, heating the low-temperature region heating center of the double-temperature region tubular furnace to 520 ℃ at the same heating rate, and keeping the temperature for 30 minutes, wherein the flow rate of argon-hydrogen mixed gas is controlled to be 40sccm in the reaction process;
after the reaction is finished, the temperature of the tube furnace is naturally reduced to the room temperature, the CdS single crystal wafer substrate is taken out, and the uniformly distributed single-oriented CdS on the whole surface (namely the size of the template) of the CdS single crystal wafer is obtainedxSe1-xAnd (3) an alloy nanowire array, wherein a scanning electron microscope image of the alloy nanowire array is shown as c in FIG. 1. FIG. 3 is the CdS obtainedxSe1-xAnd (3) a high-magnification SEM image of the alloy nanowire array, wherein a is a top view, b is a partial enlarged view of a, and c is a side view.
As can be seen from FIG. 1, the original CdS single crystal wafer has smooth and flat surface without any defects and impurities, the CdS single crystal wafer prepared by the in-situ thermal evaporation method has rough and uneven surface, and the CdS single crystal wafer prepared by the physical vapor deposition method is further adoptedxSe1-xThe alloy nanowire array is uniformly distributed on the surface of the CdS single wafer.
Further from FIG. 3, the resulting CdS is seenxSe1-xHigh-power SEM image of alloy nanowire array, and obtained CdS can be seen from the imagexSe1-xAlloy nanowire array growth methodThe length of the film is about 20 μm.
The single CdS are shown in FIG. 4xSe1-xTransmission Electron Microscope (TEM) bright field image (a), CdS of alloy nanowiresxSe1-xThe shape of the alloy nanowire is in a pointed cone shape with a thin head part and a thick root part; single CdSxSe1-xA local Transmission Electron Microscope (TEM) bright field image (b) of the alloy nanowire; single CdSxSe1-xA high-resolution transmission electron microscope (HRTEM) picture of the alloy nanowire and a corresponding Selected Area Electron Diffraction (SAED) picture (c) are obtained, diffraction points are periodically arranged, are bright and sharp, and are marked with interplanar spacings of 0.68nm and 0.36nm which respectively correspond to a (0001) crystal face and a (01-10) crystal face, so that the prepared CdS is shownxSe1-xThe alloy nanowire has good single crystal property and a hexagonal crystal structure; single CdSxSe1-xA scanning transmission electron microscope bright field image (STEM) (d) of the alloy nanowire; corresponding Cd, S and Se element distribution maps (e) and EDS maps (f). Cd. S, Se the three elements are evenly distributed on the nanowire, the difference of the light and shade contrast of the element surface distribution diagram of the nanowire at different positions is not seen, therefore, the nanowire is seen to be an alloy structure, and the proportion of the S element in the alloy is about 0.86 according to the content ratio of the three elements in the EDS energy spectrum, namely x is about 0.86, and the room temperature PL diagram of the component alloy nanowire array is shown in FIG. 5.
Example 2
Single-orientation and component-adjustable CdSxSe1-xThe preparation method of the alloy nanowire array comprises the following steps:
placing a CdS single crystal plate with a hexagonal structure, wherein the CdS single crystal plate is 5 x 3 x 0.5mm in length, width and thickness and oriented to [0001] crystal orientation in a heating center of a horizontal tube furnace in a single polishing surface upward mode;
opening a mechanical pump for vacuum pumping, and introducing argon-hydrogen mixed gas (volume ratio is 95%: 5%) as protective gas into the tubular furnace when the pressure in the furnace is reduced to 0.1 Pa;
heating to 680 ℃ at the heating rate of 15 ℃/min and keeping for 30 minutes, and controlling the flow rate of argon-hydrogen mixed gas at 40sccm in the reaction process;
after the reaction is finished, the temperature of the tube furnace is naturally reduced to room temperature, and a CdS single crystal wafer with CdS nano-wire arrays uniformly distributed on the surface is obtained;
weighing 0.5 g of CdSe powder, putting the CdSe powder into a ceramic boat, and then putting the ceramic boat into a high-temperature area heating center of a double-temperature area tube furnace;
as shown in FIG. 2, the prepared CdS single crystal wafer with CdS nano-wire arrays uniformly distributed on the surface is used as a substrate and is placed in a low-temperature region heating center of a double-temperature region spaced tube furnace.
Vacuumizing the tube furnace, introducing argon-hydrogen mixed gas (volume ratio is 95%: 5%) into the furnace when the pressure in the furnace is reduced to 0.1Pa, and maintaining the pressure in the cavity at 300 Pa;
heating the high-temperature region heating center of the double-temperature region tubular furnace to 660 ℃ at a heating speed of 15 ℃/min, heating the low-temperature region heating center of the double-temperature region tubular furnace to 570 ℃ at the same heating rate, keeping the temperature for 30 minutes, and controlling the flow rate of argon-hydrogen mixed gas to 35sccm in the reaction process;
after the reaction is finished, the temperature of the tube furnace is naturally reduced to the room temperature, the CdS single wafer substrate is taken out, and the single-oriented CdS uniformly distributed on the whole surface of the CdS single wafer is obtainedxSe1-xAnd (3) alloy nanowire arrays. Measuring CdS by means of characteristics such as TEM and PL spectraxSe1-xThe value of x in the alloy is about 0.56, and the morphology of the nanowire array is similar to that of the nanowire array obtained in example 1.
Example 3
Single-orientation and component-adjustable CdSxSe1-xThe preparation method of the alloy nanowire array comprises the following steps:
placing a CdS single crystal plate with a hexagonal structure, wherein the CdS single crystal plate is 5 x 3 x 0.5mm in length, width and thickness and oriented to [0001] crystal orientation in a heating center of a horizontal tube furnace in a single polishing surface upward mode;
opening a mechanical pump for vacuum pumping, and introducing argon-hydrogen mixed gas (volume ratio is 95%: 5%) as protective gas into the tubular furnace when the pressure in the furnace is reduced to 0.1 Pa;
heating to 700 ℃ at the heating rate of 18 ℃/min and keeping the temperature for 40 minutes, and controlling the flow rate of argon-hydrogen mixed gas to be 35sccm in the reaction process;
after the reaction is finished, the temperature of the tube furnace is naturally reduced to room temperature, and a CdS single crystal wafer with CdS nano-wire arrays uniformly distributed on the surface is obtained;
weighing 0.5 g of CdSe powder, putting the CdSe powder into a ceramic boat, and then putting the ceramic boat into a high-temperature area heating center of a double-temperature area tube furnace;
as shown in FIG. 2, the prepared CdS single crystal wafer with CdS nano-wire arrays uniformly distributed on the surface is used as a substrate and is placed in a low-temperature region heating center of a double-temperature region spaced tube furnace.
Vacuumizing the tube furnace, introducing argon-hydrogen mixed gas (volume ratio is 95%: 5%) into the furnace when the pressure in the furnace is reduced to 0.1Pa, and maintaining the pressure in the cavity at 300 Pa;
heating the high-temperature region heating center of the double-temperature region tubular furnace to 680 ℃ at a heating speed of 18 ℃/min, heating the low-temperature region heating center of the double-temperature region tubular furnace to 600 ℃ at the same heating rate, and keeping the temperature for 30 minutes, wherein the flow rate of argon-hydrogen mixed gas is controlled to be 40sccm in the reaction process;
after the reaction is finished, the temperature of the tube furnace is naturally reduced to the room temperature, the CdS single wafer substrate is taken out, and the single-oriented CdS uniformly distributed on the whole surface of the CdS single wafer is obtainedxSe1-xAnd (3) alloy nanowire arrays. Measuring CdS by means of characteristics such as TEM and PL spectraxSe1-xThe value of x in the alloy nanowire array is about 0.13, and the morphology of the nanowire array is similar to that of the nanowire array obtained in example 1.
In the preparation process of the alloy nanowire array, the temperature of the low-temperature region of the double-temperature-region tubular furnace is adjusted, and the deposition temperature of CdSe steam on the substrate is adjusted within the temperature range of 500-620 ℃, so that the prepared CdS nanowire arrayxSe1-xX in the alloy nanowire array is respectively 0.13 (product of example 3), 0.35, 0.56 (product of example 2), 0.77 and 1, and as comparison, the photoluminescence performance of the CdSe single crystal wafer is characterized, namely a PL spectrum when x is 0, and the room-temperature PL spectrums of different components are shown in FIG. 5. As can be seen from the figure, each component corresponds to a strong band edge emission, which illustrates the prepared CdSxSe1-xAlloy nanowire array toolHas high crystallinity and homogeneity. As the value of the S component x increases, the emission peak can be continuously adjusted in the range of 506nm to 708nm and obvious blue shift occurs.
In addition, CdS prepared by adopting the preparation methodxSe1-xThe EDS spectrum of the alloy nanowire array is shown in FIG. 6 when x is 0.13 (product of example 3), 0.35, 0.56 (product of example 2) and 0.77 respectively. As can be seen from the gray shaded area in the graph, the Se and S element composition dynamically changes corresponding to the S element ratio in fig. 5. As the S component increases, the Se component tends to decrease.
Comparative example 1
Example 1 is repeated with the difference that, if a hexagonal structure is chosen, the orientation is [10-10 ]]The CdS single crystal wafer is used as a raw material to prepare CdSxSe1-xAlloy nanowire arrays, unable to obtain CdS in large areas or uniformly distributed over the surface of template sizexSe1-xAnd (3) alloy nanowire arrays.
Comparative example 2
Example 1 is repeated, except that in the process of preparing the CdS single crystal wafer with the CdS nanowire arrays distributed on the surface, the temperature is increased from 700 ℃ to 800 ℃, the other conditions are not changed, and the CdS single crystal wafer with the CdS nanowire arrays distributed on the surface cannot be prepared.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims (8)

1. Single-orientation and component-adjustable CdSxSe1-xThe preparation method of the alloy nanowire array is characterized by comprising the following steps of:
heating the CdS single crystal wafer in situ by adopting a thermal evaporation method to obtain a CdS single crystal wafer with CdS nano-wire arrays uniformly distributed on the surface;
the CdS single crystal wafer with CdS nano-wire arrays uniformly distributed on the surface is used as a substrate, CdSe powder is used as a raw material, protective gas is used as a carrier, and a physical vapor deposition method is adopted to prepare the CdS with single orientation and adjustable componentsxSe1-xThe alloy nanowire array is characterized in that x is more than 0 and less than or equal to 1;
wherein the temperature of the CdS single crystal wafer in-situ heated by the thermal evaporation method is 680-750 ℃.
2. The method according to claim 1, wherein the structure of the CdS single crystal wafer is hexagonal structure and is oriented in [0001] direction.
3. The preparation method according to claim 1, wherein the method for heating the CdS single crystal wafer in situ by the thermal evaporation method comprises the following steps:
the single polishing surface of the CdS single crystal wafer is upward and is arranged in the heating center of a tube furnace;
vacuumizing the tube furnace, introducing protective gas, and controlling the pressure in the tube to be 50-500Pa in the inflation process;
heating the tubular furnace to 680-750 ℃ at a heating rate of 15-25 ℃/min, and reacting for 20-60min at the temperature, wherein the flow rate of the protective gas is 30-50 sccm;
and after the reaction is finished, naturally cooling the tubular furnace to room temperature to obtain the CdS single crystal wafer with the CdS nano-wire arrays uniformly distributed on the surface.
4. The method according to claim 1, wherein the physical vapor deposition method comprises the steps of:
weighing CdSe powder in a ceramic boat, and placing the ceramic boat in a high-temperature zone heating center of a double-temperature zone tube furnace;
taking the CdS single crystal wafer with the CdS nano-wire arrays uniformly distributed on the surface as a substrate, and placing the substrate in a heating center of a low-temperature area of the double-temperature-area tubular furnace;
vacuumizing the tube furnace, introducing protective gas, and controlling the pressure in the tube to be 50-500Pa in the inflation process;
heating the high temperature region of the tubular furnace to 630-730 ℃ at a heating rate of 15-25 ℃/min, heating the low temperature region of the tubular furnace to 500-620 ℃ at the same heating rate, and reacting for 20-60min under the condition, wherein the flow rate of the protective gas is 30-50 sccm;
after the reaction is finished, the tubular furnace is naturally cooled to room temperature to obtain the CdS with single orientation and adjustable componentsxSe1-xAnd (3) alloy nanowire arrays.
5. The method according to claim 1, 3 or 4, wherein the protective gas is a mixture of hydrogen and an inert gas, wherein the inert gas is selected from one or more of nitrogen, helium, argon and neon.
6. The preparation method according to claim 5, wherein the volume content of the hydrogen and the inert gas in the mixed gas is as follows: 5-10% of hydrogen and 95-90% of inert gas.
7. The method as claimed in claim 4, wherein the CdSe vapor deposition temperature in the substrate is adjusted within the temperature range of 500-620 ℃ in the step of raising the temperature of the low temperature region of the tube furnace to 500-620 ℃ at a heating rate of 15-25 ℃/min, so as to realize CdS dopingxSe1-xAnd regulating and controlling components of the alloy nanowire array.
8. Single-oriented and compositionally tunable CdS prepared according to any one of claims 1-7xSe1-xThe alloy nanowire array is characterized in that the single-orientation CdS is uniformly distributed on the surface of a template size of a CdS single crystal waferxSe1-xAnd (3) alloy nanowire arrays.
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