CN112899647A - Preparation method of one-dimensional cadmium sulfoselenide semiconductor nanowire, nanowire and device - Google Patents

Preparation method of one-dimensional cadmium sulfoselenide semiconductor nanowire, nanowire and device Download PDF

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CN112899647A
CN112899647A CN202110054151.5A CN202110054151A CN112899647A CN 112899647 A CN112899647 A CN 112899647A CN 202110054151 A CN202110054151 A CN 202110054151A CN 112899647 A CN112899647 A CN 112899647A
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cadmium
dimensional
nanowire
semiconductor nanowire
sulfide
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戴放
沈吉
刘彬
常维静
徐叔喜
王仕鑫
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China North Industries Group Corp No 214 Research Institute Suzhou R&D Center
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China North Industries Group Corp No 214 Research Institute Suzhou R&D Center
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Abstract

The invention discloses a preparation method of a one-dimensional cadmium selenide semiconductor nanowire, which comprises the following steps: depositing a metal catalyst film on a substrate; uniformly mixing cadmium sulfide and cadmium selenide in the presence of protective gas; heating the substrate on which the catalyst film is deposited and the mixed cadmium sulfide and cadmium selenide, and obtaining the nanowire by a chemical vapor deposition method. The chemical vapor deposition method can realize large-area batch growth, effectively control the growth direction and length of the semiconductor nanowire and obviously improve the carrier mobility. The prepared photoelectric detector has excellent performance.

Description

Preparation method of one-dimensional cadmium sulfoselenide semiconductor nanowire, nanowire and device
Technical Field
The invention relates to the technical field of nano material synthesis, in particular to a preparation method of a one-dimensional cadmium sulfoselenide semiconductor nanowire, the one-dimensional cadmium sulfoselenide semiconductor nanowire and a device comprising the one-dimensional cadmium sulfoselenide semiconductor nanowire.
Background
Semiconductor nanowires/ribbons play an important role in electronic, optoelectronic and nanoelectromechanical devices, while they can also be used as additives in other materials, as wiring in integrated circuits, as field emission devices and as nanosensors. The II-VI semiconductor nanowire has unique photoelectric characteristics and is very expected to become a next-generation high-performance photoelectric material. In a plurality of research fields of photoelectric devices, the photoelectric characteristics of the semiconductor nanowire can be greatly improved by changing the carrier mobility of the semiconductor nanowire through doping. The mobility of semiconductor nanowires is related to a number of factors, such as the growth direction, doping, crystalline quality, and surface state of the nanowires.
The current generation of uniformly doped mixed semiconductor nanowires remains a challenge. At present, the growth modes of the nanowire are mainly two, namely a gas-liquid-solid growth mode and a gas-solid growth mode. In a gas-liquid-solid growth mode, the melting point of a catalyst for growing the nanowire is lower than the growth temperature of the nanowire, the growth process is completed in a liquid phase, and each crystal face grows uniformly and generally has no good controllability. In a gas-solid growth mode, the high-melting-point metal catalyst exists as a solid crystal all the time, and the lowest energy crystal face of the high-melting-point metal catalyst can be regulated and controlled to selectively extend the nanowire so as to control the growth of the nanowire. The invention is achieved accordingly.
Disclosure of Invention
In view of the above technical problems, the present invention aims to: the preparation method of the one-dimensional cadmium sulfoselenide semiconductor nanowire is provided, the large-area batch growth can be realized by adopting a chemical vapor deposition method, the growth direction and the length of the semiconductor nanowire can be effectively controlled, and the carrier mobility is obviously improved. The prepared photoelectric detector has excellent performance.
The technical scheme of the invention is as follows:
a preparation method of a one-dimensional cadmium sulfoselenide semiconductor nanowire comprises the following steps:
s01: depositing a metal catalyst film on a substrate;
s02: uniformly mixing cadmium sulfide and cadmium selenide in the presence of protective gas;
s03: and (4) heating the substrate obtained in the step (S01) and the mixed cadmium sulfide and cadmium selenide, and obtaining the one-dimensional nanowire by a chemical vapor deposition method.
In a preferred technical solution, in the step S01, the metal catalyst thin film is Ni, Cr, or Pt, and the thickness of the metal catalyst thin film is 5nm to 10 nm.
In a preferred technical solution, the shielding gas in the step S02 is N2And Ar2Mixed gas with the mixing ratio of N2：Ar2=6：4。
In a preferred technical solution, the heating method in the step S03 includes heating to 690-.
In a preferred technical scheme, in the step S02, the mixing ratio of cadmium sulfide and cadmium selenide is CdS: CdSe = 3.7: 6.3.
the invention also discloses a one-dimensional cadmium sulfoselenide semiconductor nanowire obtained by adopting the preparation method of the one-dimensional cadmium sulfoselenide semiconductor nanowire.
The invention also discloses a device, which comprises the one-dimensional cadmium sulfoselenide semiconductor nanowire prepared by the method.
The invention also discloses a photoelectric detector, which sequentially comprises the following components from bottom to top: the cadmium selenide sulfide nanowire array comprises a silicon dioxide substrate, metal electrodes on two sides and a one-dimensional cadmium selenide sulfide semiconductor nanowire, wherein the one-dimensional cadmium selenide sulfide semiconductor nanowire is the one-dimensional cadmium selenide sulfide semiconductor nanowire.
The invention also discloses a preparation method of the photoelectric detector, which comprises the following steps:
s11: depositing a metal catalyst film on a substrate;
s12: uniformly mixing cadmium sulfide and cadmium selenide in the presence of protective gas;
s13: heating the substrate in the step S11 and the mixed cadmium sulfide and cadmium selenide, obtaining the nanowire by a chemical vapor deposition method, and rapidly cooling to room temperature under protective gas flow;
s14: mechanically stripping the substrate of the one-dimensional cadmium selenide sulfide semiconductor nanowire to transfer the one-dimensional cadmium selenide sulfide semiconductor nanowire to SiO2A substrate;
s15: and preparing electrode films at two ends of the nanowire by a photoetching process.
In a preferred technical scheme, the electrode film is gold, and the thickness of the electrode film is 250nm-300 nm.
Compared with the prior art, the invention has the advantages that:
the invention discloses a method for growing a CdSSe semiconductor nanowire/ribbon by using a gas-solid method, which is used for obtaining a one-dimensional CdSSe semiconductor nanowire with very thin thickness. The prepared photoelectric detector has excellent performance.
Drawings
The invention is further described with reference to the following figures and examples:
FIG. 1 is a flow chart of a method for preparing a one-dimensional cadmium sulfoselenide semiconductor nanowire according to the present invention;
FIG. 2 is an electron microscope image of a one-dimensional cadmium sulfoselenide semiconductor nanowire/ribbon prepared by the method of the present invention;
FIG. 3 is an electron microscope image of the cadmium sulfoselenide semiconductor nanoribbon Au electrode of the invention;
FIG. 4 is a schematic diagram of the change of current with bias voltage of the photodetector prepared by the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings in conjunction with the following detailed description. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
As shown in figure 1, the preparation method of the one-dimensional cadmium sulfoselenide semiconductor nanowire of the invention has a nanowire growth mechanism of a gas-solid growth mechanism, and comprises the following steps:
s01: depositing a metal catalyst film on a substrate;
s02: uniformly mixing cadmium sulfide and cadmium selenide in the presence of protective gas;
s03: and (4) heating the substrate obtained in the step (S01) and the mixed cadmium sulfide and cadmium selenide, and obtaining the one-dimensional nanowire by a chemical vapor deposition method.
One-dimensional nanowires are referred to herein as nanowires that are obtained with very thin thickness, very close to one-dimensional.
In step S01, the substrate is a single crystal Si substrate, the metal catalyst thin film is Ni, Cr, or Pt, and the thickness of the metal catalyst thin film is 5nm to 10 nm.
The protective gas in step S02 is an inert gas.
In a preferred embodiment, N is2And Ar2The purity of the mixed gas and the purity of the two gases are both 99.999 percent, and the mixing proportion is N2：Ar2=6：4。
In step S02, the cadmium sulfide and cadmium selenide are preferably in powder form, with a purity of 99.999% and a particle size of less than 100 mesh.
In a preferred embodiment, the mixing ratio of cadmium sulfide and cadmium selenide is CdS: CdSe = 3.7: 6.3.
the heating method in step S03 includes heating to 690-850 deg.C, maintaining for a certain period of time, and controlling the temperature at 500-620 deg.C.
The invention controls the growth of the semiconductor nanowire by realizing a gas-solid growth mode. The cadmium sulfoselenide semiconductor nano-belt obtained by the method is a single crystal material. As shown in fig. 2, the obtained nanowire/ribbon has the advantages of thin thickness, long length, controllable width, high crystal quality and high carrier mobility.
In a preferred embodiment, Au electrodes are prepared at two ends of the cadmium selenide sulfide semiconductor nanobelt through a photoetching process, and the thickness of an Au electrode film is 250nm-300 nm. As shown in fig. 3.
The semiconductor nano-wire plays an important role in electronic, photoelectronic and nano-electronic mechanical instruments, and can be used as an additive in other materials, a connecting wire in an integrated circuit, a field emission device and a nano sensor.
In another embodiment, a device comprises the one-dimensional cadmium sulfoselenide semiconductor nanowire prepared by the method.
In another embodiment, a photodetector includes, in order from bottom to top: the cadmium selenide sulfide nanowire array comprises a silicon dioxide substrate, metal electrodes on two sides and a one-dimensional cadmium selenide sulfide semiconductor nanowire, wherein the one-dimensional cadmium selenide sulfide semiconductor nanowire is the one-dimensional cadmium selenide sulfide semiconductor nanowire. The current of the photodetector varies with the bias voltage as shown in fig. 4. Has excellent performance.
In another embodiment, a method of fabricating a photodetector includes:
s11: depositing a metal catalyst film on a substrate;
s12: uniformly mixing cadmium sulfide and cadmium selenide in the presence of protective gas;
s13: heating the substrate in the step S11 and the mixed cadmium sulfide and cadmium selenide, obtaining the nanowire by a chemical vapor deposition method, and rapidly cooling to room temperature under protective gas flow;
s14: mechanically stripping the substrate of the one-dimensional cadmium selenide sulfide semiconductor nanowire to transfer the one-dimensional cadmium selenide sulfide semiconductor nanowire to SiO2A substrate;
s15: and preparing electrode films at two ends of the nanowire by a photoetching process.
In a preferred embodiment, the electrode thin film is gold, and the thickness of the electrode thin film is 250nm-300 nm.
The following is a detailed description of a specific example:
a method of fabricating a photodetector, comprising:
(1) depositing a 5nmPt film on a single crystal Si substrate through thermal evaporation, placing the prepared substrate in the middle of a downstream area of a tube furnace, and then placing a crucible containing semiconductor powder source materials in an upstream area of the tube furnace at a distance of 12cm from the substrate;
(2) vacuumizing the quartz tube until the air pressure is less than 2 x 10-3Torr, and introducing N2、Ar2Mixing protective gas for 0.5 hour with the mixing ratio of N2：Ar2= 6: 4, discharging residual air;
(3) keeping the flow rate of the protective gas unchanged, heating the CdS and CdSe mixed powder and the substrate to 690-850 ℃ evaporation source material, and then controlling the temperature range to 500-620 ℃ for continuous growth for 10-40 minutes; the mixing ratio of cadmium sulfide and cadmium selenide is CdS: CdSe = 3.7: 6.3;
(4) after the growth is finished, stopping heating, and rapidly cooling to room temperature under the protective air flow.
(5) Mechanically stripping the grown substrate, and transferring the nanoribbon to SiO2Preparing Au electrode on the substrate by photolithography, and forming a device structure comprising SiO2Substrate, CdSSe semiconductor nanowires/ribbons, gold electrodes.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explaining the principles of the invention and are not to be construed as limiting the invention. Therefore, any modification, equivalent replacement, improvement and the like made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. Further, it is intended that the appended claims cover all such variations and modifications as fall within the scope and boundaries of the appended claims or the equivalents of such scope and boundaries.

Claims (10)

1. A preparation method of a one-dimensional cadmium sulfoselenide semiconductor nanowire is characterized by comprising the following steps:
s01: depositing a metal catalyst film on a substrate;
s02: uniformly mixing cadmium sulfide and cadmium selenide in the presence of protective gas;
s03: and (4) heating the substrate obtained in the step (S01) and the mixed cadmium sulfide and cadmium selenide, and obtaining the one-dimensional nanowire by a chemical vapor deposition method.
2. The method for preparing one-dimensional cadmium sulfoselenide semiconductor nanowires of claim 1, wherein the metal catalyst thin film in step S01 is Ni, Cr, or Pt, and the thickness of the metal catalyst thin film is 5nm to 10 nm.
3. The method for preparing one-dimensional cadmium sulfoselenide semiconductor nanowires of claim 1, wherein the shielding gas of step S02 is N2And Ar2Mixed gas with the mixing ratio of N2：Ar2=6：4。
4. The method as claimed in claim 1, wherein the heating step in step S03 includes heating to 690-850 ℃ for a certain period of time, and controlling the temperature at 500-620 ℃.
5. The method for preparing a one-dimensional cadmium sulfoselenide semiconductor nanowire according to claim 1, wherein the mixing ratio of cadmium sulfide and cadmium selenide in the step S02 is CdS: CdSe = 3.7: 6.3.
6. a one-dimensional cadmium sulfoselenide semiconductor nanowire, characterized in that the one-dimensional cadmium sulfoselenide semiconductor nanowire is obtained by the preparation method of the one-dimensional cadmium sulfoselenide semiconductor nanowire according to any one of claims 1 to 5.
7. A device comprising the one-dimensional cadmium sulfoselenide semiconductor nanowire of claim 6.
8. A photoelectric detector is characterized by sequentially comprising from bottom to top: a silicon dioxide substrate, metal electrodes on two sides and a one-dimensional cadmium selenide sulfide semiconductor nanowire, wherein the one-dimensional cadmium selenide sulfide semiconductor nanowire is the one-dimensional cadmium selenide sulfide semiconductor nanowire of claim 6.
9. A method of fabricating a photodetector, comprising:
s11: depositing a metal catalyst film on a substrate;
s12: uniformly mixing cadmium sulfide and cadmium selenide in the presence of protective gas;
s13: heating the substrate in the step S11 and the mixed cadmium sulfide and cadmium selenide, obtaining the nanowire by a chemical vapor deposition method, and rapidly cooling to room temperature under protective gas flow;
s14: mechanically stripping the substrate of the one-dimensional cadmium selenide sulfide semiconductor nanowire to transfer the one-dimensional cadmium selenide sulfide semiconductor nanowire to SiO2A substrate;
s15: and preparing electrodes at two ends of the nanowire by a photoetching process.
10. The method of claim 9, wherein the electrode is gold, and the thickness of the electrode thin film is 250nm to 300 nm.
CN202110054151.5A 2021-01-15 2021-01-15 Preparation method of one-dimensional cadmium sulfoselenide semiconductor nanowire, nanowire and device Pending CN112899647A (en)

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