A one-dimensional GaSe nanoribbon and its preparation method
By controlling the growth conditions of GaSe nanoribbons using a tube furnace method, the problem of efficiently preparing high-quality GaSe nanoribbons in existing technologies has been solved, achieving high crystallinity and uniform morphology, and expanding its application potential in the fields of optics and electronics.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- KUNMING UNIV OF SCI & TECH
- Filing Date
- 2024-12-03
- Publication Date
- 2026-04-17
AI Technical Summary
Existing technologies are difficult to efficiently prepare high-quality one-dimensional GaSe nanoribbons, and they also suffer from problems such as complex processes, high costs, long growth cycles, and poor purity and crystallinity, which affect their application in the fields of optics and electronics.
A tube furnace method was used to mix GaSe powder with Ga metal and place it in a specific temperature zone. By controlling the temperature zone temperature, gas flow rate and gas composition, GaSe nanoribbons were grown, avoiding the use of metal catalysts and using a protective gas as a carrier gas to control the growth density and length of the nanoribbons.
The growth of high-quality one-dimensional GaSe nanoribbons was achieved. The material has high crystallinity, uniform morphology, and smooth surface, and possesses excellent optical and electrical properties, making it suitable for fields such as field-effect transistors and photodetectors.
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Figure CN119528094B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of nanomaterial growth technology, specifically relating to a one-dimensional GaSe nanoribbon and its preparation method. Background Technology
[0002] GaSe, an important III-VI group semiconductor material, is valued for its high carrier mobility, suitable optical bandgap, nonlinear optical properties, and excellent photoresponse characteristics. In optics, gallium selenide exhibits high optical transmittance in the visible and near-infrared regions, making it suitable for fabricating optical windows, lenses, and other optical components. It also possesses strong second-order nonlinear optical effects, enabling its application in nonlinear optical devices such as laser frequency conversion and optical switches. In electrical engineering, as a semiconductor material, its moderate bandgap and high carrier mobility offer potential applications in field-effect transistors and photodetectors. Furthermore, gallium selenide shows promise in other fields such as flexible electronics and energy conversion.
[0003] However, existing preparation methods have several drawbacks. While the hydrothermal method is relatively simple, low-cost, and allows for control over the size and morphology of the nanoribbons, it requires high pressure and results in poor product purity and crystallinity. Molecular beam epitaxy (MBE), although capable of producing high-quality, ultrathin nanoribbons with precise control over thickness and composition, suffers from expensive equipment, complex operation, slow growth rate, and low yield. Mechanical exfoliation methods exhibit irregular morphology, low yield, and significant time consumption. The morphology of the nanoribbons has a crucial impact on their performance and applications. Existing synthesis methods struggle to achieve high-density one-dimensional gallium selenide nanomaterials and suffer from drawbacks such as complex processes, high costs, long growth cycles, low quality, and poor versatility. This poses a challenge to the need for integrating more transistors into chips to achieve complex functions. Therefore, obtaining large quantities of high-quality GaSe nanoribbons in a simple manner, especially considering the quantum confinement effect and unique physicochemical properties resulting from reduced material dimensionality, has become a key issue in current technological development. Summary of the Invention
[0004] To address the shortcomings of the prior art, this invention provides one-dimensional GaSe nanoribbons and their preparation method.
[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0006] The preparation method of one-dimensional GaSe nanoribbons includes the following steps:
[0007] (1) Mix GaSe powder with Ga metal and place it in the first temperature zone of a tube furnace. Place the substrate on a high-temperature plate to form a laminate and place the laminate in the second temperature zone of the tube furnace.
[0008] (2) After evacuating the tubular furnace to a pressure lower than 0.1 Pa, a protective gas is introduced to purge it, and then the pressure is maintained at 1 atm.
[0009] (3) Control the temperature of the first temperature zone and the second temperature zone to 900-960℃ and 600-750℃ respectively. Then, evacuate the tube furnace to a pressure lower than 0.1Pa and introduce protective gas to grow the material.
[0010] (4) After growth, turn off the heating power supply, keep the protective gas flow rate constant, and cool to room temperature to obtain one-dimensional GaSe nanoribbons.
[0011] As a preferred embodiment of the present invention, the mass ratio of GaSe powder to Ga metal is controlled to be (1.5-2):1. If it is not within this range, only particles can be grown on the substrate, and GaSe nanoribbons cannot be grown.
[0012] In a preferred embodiment of the present invention, in step (2), the protective gas is gas A at 500-1000 sccm and hydrogen at 40-100 sccm; gas A is argon or nitrogen.
[0013] In a preferred embodiment of the present invention, the purging time in step (2) is 10-30 minutes.
[0014] In a preferred embodiment of the present invention, in step (3), the protective gas is gas B at 50-100 sccm and hydrogen at 5-10 sccm; gas B is argon or nitrogen.
[0015] In a preferred embodiment of the present invention, the material growth time in step (2) is 2-30 min.
[0016] In a preferred embodiment of the present invention, the substrate is a SiO2 substrate, sapphire, fused silica or mica sheet; the high-temperature resistant plate is a quartz plate.
[0017] As a preferred embodiment of the present invention, the substrate is repeatedly rinsed with ethanol and then rinsed with a high-speed argon gas flow before use.
[0018] The present invention also claims protection for the one-dimensional GaSe nanoribbons prepared by the method described above.
[0019] Compared with the prior art, the beneficial effects of the present invention are as follows: The present invention places a metal source containing GaSe and Ga in a specific temperature zone of a tube furnace as a precursor. At high temperature, without the need to add a metal catalyst, the mixture volatilizes and diffuses to the substrate in the second temperature zone to obtain high-quality nanoribbons. Furthermore, the growth density and length of the nanoribbons can be controlled by adjusting the concentration of the metal source, the carrier gas flow rate, and the distance between the metal source and the substrate. Attached Figure Description
[0020] Figure 1 This is a schematic diagram of the GaSe nanoribbon growth process of the present invention.
[0021] Figure 2 This is a SEM image of the GaSe nanoribbons prepared in Example 1 of this invention.
[0022] Figure 3 This is a partial SEM image of the GaSe nanoribbons prepared in Example 1 of the present invention.
[0023] Figure 4 These are the Raman and fluorescence spectra of the GaSe nanoribbon sample from Example 1 of this invention; a is the Raman spectrum; b is the fluorescence spectrum.
[0024] Figure 5 These are SEM images of the GaSe nanoribbon sample from Example 2 of this invention and corresponding scan distribution diagrams of Ga and Se elements.
[0025] Figure 6 These are SEM morphology images and EDS spectra of the GaSe nanoribbons prepared in Example 3 of this invention; where a is the SEM morphology image and b is the EDS spectra.
[0026] Figure 7 This is a SEM image of the material on the SiO2 substrate prepared in Comparative Example 1 of this invention.
[0027] Figure 8 These are SEM images of the material on the SiO2 substrate prepared in Comparative Example 3 of this invention. a is a low-magnification SEM image of the material; b is a high-magnification SEM image of the material. Detailed Implementation
[0028] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.
[0029] Figure 1 This is a schematic diagram of the apparatus for preparing GaSe nanoribbons according to the present invention, as shown below. Figure 1 As shown, the device includes a high-temperature tube furnace, within which a first temperature zone and a second temperature zone with different heating temperatures are provided. In this invention, a protective gas is introduced into the tube furnace, and the first and second temperature zones are sequentially arranged along the gas flow direction. The first temperature zone has a temperature of 900–960°C, and the second temperature zone has a temperature of 600–750°C. The protective gas can also serve as a carrier gas, and the protective gas is either argon or a mixture of nitrogen and hydrogen.
[0030] Example 1
[0031] The preparation method of one-dimensional GaSe nanoribbons includes the following steps:
[0032] (1) 80 mg of Ga metal was dispersed into multiple spherical particles by passing it through a quartz "sieve" with a pore size of 0.5 mm and a pore spacing of 5 mm. These particles covered 120 mg of GaSe powder. The mixture of Ga metal and GaSe powder was placed in the first temperature zone of a tube furnace. A 1 × 1 cm SiO2 substrate was repeatedly cleaned with ethanol and then rinsed with high-speed argon gas. The substrate was then placed on a high-temperature resistant quartz plate to form a laminate. The laminate was placed in the second temperature zone of the tube furnace, with the substrate 12 cm away from the Ga and GaSe mixture.
[0033] (2) After evacuating the tube furnace to a pressure below 0.1 Pa, 500 sccm Ar + 40 sccm hydrogen gas was introduced and purged sequentially through the Ga and GaSe powder mixture and the laminate for 10 min. Then, the inlet and outlet valves were closed to maintain the pressure inside the tube at 1 atm. The heating rate was then controlled at 22 °C / min to raise the first temperature zone to 900 °C and the second temperature zone to 690 °C. Then, the vacuum pump was turned on until the pressure inside the tube furnace was below 0.1 Pa, and 50 sccm Ar + 5 sccm H2 gas was introduced and the growth was maintained at this temperature for 5 min.
[0034] (3) After growth, turn off the heating power supply, maintain the Ar gas flow rate constant, and cool to room temperature to obtain a GaSe nanoribbon sample on a clean SiO2 substrate. Figure 2 As shown, zigzag and linear GaSe nanoribbons were formed on the substrate in Example 1. Figure 3 As shown, scanning electron microscopy (SEM) images of single GaSe nanoribbons reveal that the GaSe nanoribbons have uniform width and smooth surface. Figure 4 As shown in Figure a, the Raman spectrum of a single GaSe nanoribbon at room temperature is shown at 129.6 cm⁻¹. -1 209.7cm -1 233.2cm -1 and 303.5cm -1 The four characteristic peaks correspond to the A peaks of GaSe nanoribbons. 1 1g E 1 2g E 2 1g and A 2 1g Vibration mode. E 1 2g and E 2 1g Corresponding vibration modes in the plane, two A 1gThe corresponding out-of-plane vibrational modes. Figure b shows the photoluminescence spectrum of a single GaSe nanoribbon at room temperature, with an emission peak at 619 nm (2 eV). The full width at half maximum (FWHM) of the emission peak is approximately 10 nm, which is relatively small. The grown GaSe nanoribbon exhibits excellent optical properties, and the material also has very good crystallinity.
[0035] Example 2
[0036] The preparation method of one-dimensional GaSe nanoribbons includes the following steps:
[0037] (1) 100 mg of Ga metal was dispersed into multiple spherical particles by passing it through a quartz "sieve" with a pore size of 0.5 mm and a pore spacing of 5 mm. These particles covered 170 mg of GaSe powder. The mixture of Ga metal and GaSe powder was placed in the first temperature zone of a tube furnace. A 1 × 1 cm SiO2 substrate was repeatedly cleaned with ethanol and then rinsed with high-speed argon gas. The substrate was then placed on a high-temperature resistant quartz plate to form a laminate. The laminate was placed in the second temperature zone of the tube furnace, with the substrate 12 cm away from the Ga and GaSe mixture.
[0038] (2) After evacuating the tubular furnace to a pressure below 0.1 Pa, 500 sccm Ar + 40 sccm hydrogen gas was introduced and purged sequentially through the Ga and GaSe powder mixture and the laminate for 10 min. Then, the inlet and outlet valves were closed to maintain the pressure inside the tube at 1 atm. The heating rate was then controlled at 20 °C / min to raise the first temperature zone to 930 °C and the second temperature zone to 710 °C. Then, the vacuum pump was turned on until the pressure inside the tubular furnace was below 0.1 Pa, and 50 sccm Ar + 5 sccm H2 gas was introduced and the furnace was kept at this temperature for 2 min.
[0039] (3) After growth, turn off the heating power supply, maintain the Ar gas flow rate constant, and cool to room temperature to obtain a GaSe nanoribbon sample on a clean SiO2 substrate. Figure 5 As shown, the Ga and Se elements are evenly distributed on the GaSe nanoribbons, which also indicates that the grown material has a very uniform structure.
[0040] Example 3
[0041] The preparation method of one-dimensional GaSe nanoribbons includes the following steps:
[0042] (1) 100 mg of Ga metal was dispersed into multiple spherical particles by passing it through a quartz "sieve" with a pore size of 0.5 mm and a pore spacing of 5 mm. These particles covered 200 mg of GaSe powder. The mixture of Ga metal and GaSe powder was placed in the first temperature zone of a tube furnace. A 1 × 1 cm SiO2 substrate was repeatedly cleaned with ethanol and then rinsed with high-speed argon gas. The substrate was then placed on a high-temperature resistant quartz plate to form a laminate. The laminate was placed in the second temperature zone of the tube furnace, with the substrate 12 cm away from the Ga and GaSe mixture.
[0043] (2) After evacuating the tubular furnace to a pressure below 0.1 Pa, 500 sccm Ar + 40 sccm hydrogen gas was introduced and purged sequentially through the Ga and GaSe powder mixture and the laminate for 10 min. Then, the inlet and outlet valves were closed to maintain the pressure inside the tube at 1 atm. The heating rate was then controlled at 20 °C / min to raise the first temperature zone to 960 °C and the second temperature zone to 750 °C. Then, the vacuum pump was turned on until the pressure inside the tubular furnace was below 0.1 Pa, and 50 sccm Ar + 5 sccm H2 gas was introduced. The furnace was then kept at this temperature for 30 min.
[0044] (3) After growth, turn off the heating power supply, maintain the Ar gas flow rate constant, and cool to room temperature to obtain a GaSe nanoribbon sample on a clean SiO2 substrate. Figure 6 As shown, the nanoribbons have a uniform width and a smooth surface. Furthermore, the EDS spectrum reveals that the nanoribbons contain only Ga and Se elements in a ratio close to 1:1, indicating that the synthesized nanoribbons have a stoichiometric ratio of 1:1, i.e., GaSe.
[0045] Comparative Example 1
[0046] A method for preparing GaSe material includes the following steps:
[0047] (1) 80 mg of Ga metal was dispersed into multiple spherical particles by passing it through a quartz "sieve" with a pore size of 0.5 mm and a pore spacing of 5 mm. These particles covered 120 mg of GaSe powder. The mixture of Ga metal and GaSe powder was placed in the first temperature zone of a tube furnace. A 1 × 1 cm SiO2 substrate was repeatedly cleaned with ethanol and then rinsed with high-speed argon gas. The substrate was then placed on a high-temperature resistant quartz plate to form a laminate. The laminate was placed in the second temperature zone of the tube furnace, with the substrate 12 cm away from the Ga and GaSe mixture.
[0048] (2) After evacuating the tubular furnace to a pressure below 0.1 Pa, 500 sccm Ar + 40 sccm hydrogen gas was introduced and passed sequentially through the Ga and GaSe mixture and the laminate for 10 min. Then, the inlet and outlet valves were closed to maintain the pressure inside the tube at 1 atm. The heating rate was then controlled at 22 °C / min to raise the first temperature zone to 850 °C and the second temperature zone to 660 °C. The vacuum pump was then turned on until the pressure inside the tubular furnace was below 0.1 Pa. 50 sccm Ar + 5 sccm H2 gas was then introduced and the furnace was kept at this temperature for 5 min.
[0049] (3) After growth, turn off the heating power supply, maintain the Ar gas flow rate constant, and cool to room temperature to obtain a GaSe nanoribbon sample on a clean SiO2 substrate. Figure 7 As shown, no GaSe nanoribbons were observed to form on the SiO2 substrate.
[0050] Comparative Example 2
[0051] A method for preparing GaSe material includes the following steps:
[0052] (1) Place 120 mg of GaSe powder in the first temperature zone of the tube furnace. Clean the 1×1 cm SiO2 substrate repeatedly with ethanol, then rinse with high-speed argon gas, and place it on a high-temperature resistant quartz plate to form a laminate. Place the laminate in the second temperature zone of the tube furnace, with the substrate 12 cm away from the GaSe powder.
[0053] (2) After evacuating the tube furnace to a pressure below 0.1 Pa, 500 sccm Ar + 40 sccm hydrogen gas was introduced and purged through the GaSe powder and laminate for 10 min. Then, the inlet and outlet valves were closed to maintain the pressure inside the tube at 1 atm. The heating rate was then controlled at 22℃ / min to raise the first temperature zone to 900℃ and the second temperature zone to 690℃. After turning on the vacuum pump until the pressure inside the tube furnace was below 0.1 Pa, 50 sccm Ar + 5 sccm H2 was introduced and the growth was maintained at this temperature for 5 min.
[0054] (3) After growth, the heating power was turned off, the Ar gas flow rate was kept constant, and the mixture was cooled to room temperature. Some small particles were generated on the SiO2 substrate of Comparative Example 2, but no nanoribbon morphology material was found.
[0055] Comparative Example 3
[0056] A method for preparing GaSe material includes the following steps:
[0057] (1) 80 mg of Ga metal was dispersed into multiple spherical particles through a quartz "sieve" with a pore size of 0.5 mm and a pore spacing of 5 mm. These particles covered 120 mg of Na2Se powder. The mixture of Ga metal and Na2Se powder was placed in the first temperature zone of a tube furnace. A 1 × 1 cm SiO2 substrate was repeatedly cleaned with ethanol, followed by rinsing with high-speed argon gas. The substrate was then placed on a high-temperature resistant quartz plate to form a laminate. The laminate was placed in the second temperature zone of the tube furnace, with the substrate 12 cm away from the Ga metal and Na2Se mixture.
[0058] (2) After evacuating the tubular furnace to a pressure below 0.1 Pa, 500 sccm Ar + 40 sccm hydrogen gas was introduced and purged sequentially through the Ga metal and Na2Se mixture and the laminate for 10 min. Then, the inlet and outlet valves were closed to maintain the pressure inside the tube at 1 atm. The heating rate was then controlled at 22 °C / min to raise the first temperature zone to 900 °C and the second temperature zone to 690 °C. Then, the vacuum pump was turned on until the pressure inside the tubular furnace was below 0.1 Pa, and 50 sccm Ar + 5 sccm H2 gas was introduced and the furnace was kept at this temperature for 5 min.
[0059] (3) After growth is complete, turn off the heating power, maintain the Ar gas flow rate at a constant level, and cool to room temperature. Figure 8 As shown, some small particles are aggregated on the SiO2 substrate, but no nanoribbon morphology material was found.
[0060] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.
Claims
1. A method for preparing one-dimensional GaSe nanoribbons, characterized in that, Includes the following steps: (1) The GaSe powder and Ga metal are mixed and placed in the first temperature zone of a tube furnace, the substrate is placed on a high-temperature plate to form a laminate, and the laminate is placed in the second temperature zone of the tube furnace; the mass ratio of the GaSe powder to the Ga metal is (1.5-2):1; (2) After evacuating the tubular furnace to a pressure lower than 0.1 Pa, a protective gas is introduced to purge it, and then the pressure is maintained at 1 atm. (3) Control the temperature of the first temperature zone and the second temperature zone to 900~960℃ and 600~750℃ respectively. Then, evacuate the tube furnace until the gas pressure is below 0.1Pa, and then introduce protective gas to grow the material. (4) After growth, turn off the heating power supply, keep the protective gas flow rate constant, and cool to room temperature to obtain one-dimensional GaSe nanoribbons.
2. The method for preparing one-dimensional GaSe nanoribbons as described in claim 1, characterized in that, In step (2), the protective gas is gas A at 500-1000 sccm and hydrogen at 40-100 sccm; gas A is argon or nitrogen.
3. The method for preparing one-dimensional GaSe nanoribbons as described in claim 1, characterized in that, In step (2), the purging time is 10-30 minutes.
4. The method for preparing one-dimensional GaSe nanoribbons as described in claim 1, characterized in that, In step (3), the protective gas is gas B at 50-100 sccm and hydrogen at 5-10 sccm; gas B is argon or nitrogen.
5. The method for preparing one-dimensional GaSe nanoribbons as described in claim 1, characterized in that, In step (3), the material growth time is 2-30 minutes.
6. The method for preparing one-dimensional GaSe nanoribbons as described in claim 1, characterized in that, The substrate is a SiO2 substrate, sapphire, fused silica, or mica sheet; the high-temperature resistant plate is a quartz plate.
7. The method for preparing one-dimensional GaSe nanoribbons as described in claim 1, characterized in that, The substrate was repeatedly rinsed with ethanol and then with a high-speed argon gas flow before use.
8. One-dimensional GaSe nanoribbons prepared by the method described in any one of claims 1-7.