A two-dimensional Ga2S3 material, its preparation method and application

Abstract

The application discloses a two-dimensional Ga2S3 material and a preparation method and application thereof, and the preparation method comprises the following steps: performing sulfurization treatment on two-dimensional Ga2O3 in a plasma gas flow atmosphere to obtain the two-dimensional Ga2S3 material. The application provides a method for preparing two-dimensional Ga2S3, and wafer-level super-large-size two-dimensional Ga2S3 can be prepared by taking two-dimensional Ga2O3 prepared by magnetron sputtering as a template. Furthermore, the thickness of the two-dimensional Ga2S3 can be controlled by controlling the sputtering time, and the purity of the two-dimensional Ga2S3 can be improved by the plasma-enhanced sulfurization method, so that the controllable preparation of the two-dimensional Ga2S3 is finally realized.

Description

Technical Field

[0001] This invention relates to the field of semiconductor material preparation technology, and in particular to a two-dimensional Ga2S3 material, its preparation method, and its applications. Background Technology

[0002] Ultrathin two-dimensional materials have attracted widespread attention in the scientific community due to the excellent physical properties resulting from the quantum confinement effect induced by their unique two-dimensional structure, such as highly tunable band gaps, high carrier mobility, and the potential to overcome short-channel effects. They are important materials for realizing next-generation electronic and optoelectronic devices. Among them, two-dimensional Ga2S3 is a p-type semiconductor with a direct band gap. As a two-dimensional post-transition metal sulfide, it has atomically thin thickness and a tunable band gap that varies with thickness, showing great application potential in the development of topological insulators, transistors, and sensors. However, since Ga2S3 itself is not a layered crystal structure composed of van der Waals forces, it cannot be obtained through mechanical exfoliation. Current research on the growth of two-dimensional Ga2S3 mainly focuses on chemical vapor deposition, but the lateral dimensions of the prepared two-dimensional Ga2S3 are only on the micrometer scale, which severely limits its application development.

[0003] Currently, Ga2S3 materials are also prepared using sulfidation methods, but the degree of sulfidation is not high, and the purity of the resulting products is low, which limits their further application. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the purpose of this invention is to provide a two-dimensional Ga2S3 material, its preparation method, and its applications. The method of preparing two-dimensional Ga2S3 using two-dimensional Ga2O3 as a template can achieve controllable thickness, large size, and high purity of two-dimensional Ga2S3.

[0005] The first objective of this invention is to provide a two-dimensional Ga2S3 material.

[0006] The second objective of this invention is to provide a method for preparing the above-mentioned two-dimensional Ga2S3 material.

[0007] A third objective of this invention is to provide the application of the aforementioned two-dimensional Ga2S3 material in the fabrication of photodetectors.

[0008] The objective of this invention is achieved through the following technical solution:

[0009] A method for preparing two-dimensional Ga2S3 material includes the following steps:

[0010] Two-dimensional Ga2O3 was subjected to sulfidation treatment in a plasma gas flow atmosphere to obtain two-dimensional Ga2S3 material.

[0011] Furthermore, the two-dimensional Ga2S3 was prepared by magnetron sputtering.

[0012] Preferably, the two-dimensional Ga2S3 is grown on the surface of SiO2; more preferably, the SiO2 is a SiO2 / Si substrate; the SiO2 / Si substrate is cleaned before magnetron sputtering.

[0013] Preferably, the magnetron sputtering is performed under a protective atmosphere; more preferably, the pressure of the protective atmosphere is 0.6-1 Pa, and the protective atmosphere is an argon flow.

[0014] Preferably, the target material for magnetron sputtering is Ga2O3.

[0015] Preferably, the power of the magnetron sputtering is 30-70W;

[0016] Preferably, the magnetron sputtering time is 50-300s.

[0017] Preferably, a gas scrubbing treatment is performed before magnetron sputtering; that is, a vacuum is first drawn, and then an inert gas is introduced; the vacuum degree of the vacuum drawing is 5×10⁻⁶. -4 Pa.

[0018] Furthermore, the plasma gas flow atmosphere is an inert gas flow processed by plasma treatment;

[0019] Preferably, the plasma power of the plasma treatment is 80-100W, the flow rate of the inert gas stream is 30-70 sccm, and the inert gas is argon.

[0020] Furthermore, the sulfur source for the sulfidation treatment is sulfur powder;

[0021] Preferably, the mass ratio of the sulfur powder to the volume ratio of the two-dimensional Ga2O3 is 100-200 mg: (1.5-3.6) * 10. -4 mm 3 The sulfur powder is located upstream of the two-dimensional Ga2O3.

[0022] Furthermore, the vulcanization temperature is 550-650℃; the holding time for the vulcanization is 5-15 minutes.

[0023] Furthermore, the vulcanization treatment is followed by natural cooling.

[0024] Furthermore, a gas washing treatment is performed before the vulcanization process; that is, a vacuum is first drawn, and then an inert gas stream is introduced for washing; the vacuum degree of the vacuum drawing is 8×10⁻⁶. -3 Pa; the flow rate of the inert gas stream is 300 sccm; the washing time is 10 min.

[0025] The two-dimensional Ga2S3 material prepared by the above method.

[0026] The above-mentioned two-dimensional Ga2S3 material is used in the fabrication of photodetectors.

[0027] The present invention has the following advantages over the prior art:

[0028] (1) The present invention uses a template-based sulfurization method to prepare two-dimensional Ga2S3, which, compared with the traditional chemical vapor deposition method, can produce two-dimensional Ga2S3 with ultra-large lateral dimensions. The lateral dimensions of two-dimensional Ga2S3 prepared by traditional chemical vapor deposition are only at the micrometer level, while the template-based sulfurization method can obtain ultra-large two-dimensional Ga2S3 at the wafer level.

[0029] (2) The present invention selects two-dimensional Ga2O3 prepared by magnetron sputtering as a template for preparing two-dimensional Ga2S3. Compared with the two-dimensional Ga2O3 obtained by liquid metal printing, it has the following advantages: the thickness of two-dimensional Ga2O3 can be controlled by controlling the sputtering time, thereby controlling the thickness of two-dimensional Ga2S3.

[0030] (3) The present invention uses a plasma-enhanced method to sulfide two-dimensional Ga2O3, which is more thorough than the commonly used high-temperature sulfide method and produces two-dimensional Ga2S3 with higher purity. Attached Figure Description

[0031] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0032] Figure 1 The O1s spectrum of the two-dimensional Ga2S3 XPS characterization prepared in Example 1 of the present invention is shown.

[0033] Figure 2 The O1s spectrum of the two-dimensional Ga2S3 XPS characterization prepared in Example 2 of the present invention is shown.

[0034] Figure 3 This is an atomic force microscope image of two-dimensional Ga2S3 prepared in Example 2 of the present invention.

[0035] Figure 4 This is an atomic force microscope image of two-dimensional Ga2S3 prepared in Example 3 of the present invention.

[0036] Figure 5 The photoresponse curve of the two-dimensional Ga2S3-based photodetector prepared in Example 5 of the present invention. Detailed Implementation

[0037] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. It should be understood that the specific embodiments described are merely used to explain the present invention and are not intended to limit the present invention.

[0038] The method for preparing two-dimensional Ga2S3 material provided by this invention includes the following steps:

[0039] (1) Two-dimensional Ga2O3 was prepared by magnetron sputtering.

[0040] Furthermore, the two-dimensional Ga2O3 preparation method includes: cleaning the SiO2 / Si substrate; transferring the substrate into the cavity of a magnetron sputtering device and evacuating it to the required vacuum level; introducing Ar, adjusting the gas flow rate to control the gas pressure inside the cavity, adjusting the sputtering power, and sputtering with a Ga2O3 target; and obtaining two-dimensional Ga2O3 after sputtering for a certain period of time.

[0041] Furthermore, the required vacuum level is 5 × 10⁻⁶. -4 Pa.

[0042] Furthermore, the internal air pressure is 0.6-1 Pa, and the sputtering power is 30-70 W.

[0043] Furthermore, the sputtering time is 50-300s.

[0044] (2) Plasma-enhanced sulfidation of two-dimensional Ga2O3 was performed to obtain two-dimensional Ga2S3.

[0045] Furthermore, the plasma-enhanced sulfidation method includes: transferring a sheet with a two-dimensional Ga2O3 surface obtained by magnetron sputtering to a tube furnace for plasma-enhanced chemical vapor deposition, and placing a certain amount of sulfur powder as a sulfur source at its upstream position; evacuating to the required vacuum level, and then continuously introducing a large flow rate of Ar for a period of time to purge the remaining air in the tube furnace; heating to a set temperature, adjusting the plasma power and continuously introducing a certain flow rate of Ar as a carrier gas, holding at the temperature for a period of time; and naturally cooling to obtain two-dimensional Ga2S3.

[0046] Furthermore, the amount of sulfur powder used is 100-200 mg, and the required vacuum degree is 8 × 10⁻⁶. -3 Pa.

[0047] Furthermore, the flow rate of the Ar washing gas is 300 sccm, and the washing time is 10 min.

[0048] Furthermore, the temperature is set to 550-650℃, the plasma power to 80-100W, the Ar flow rate to 50sccm, and the holding time to 5-15min.

[0049] Example 1:

[0050] This embodiment provides a method for preparing two-dimensional Ga2S3, specifically including:

[0051] (1) Substrate pretreatment: SiO2 / Si substrate (size 1*1cm) was selected as the substrate for material growth, and the SiO2 surface of the substrate was cleaned for 5 min with O2 plasma with a power of 100W.

[0052] (2) Transfer the pretreated substrate into the magnetron sputtering equipment cavity, using the SiO2 side of the substrate as the growth surface, and evacuate to 5×10⁻⁶. -4 Pa;

[0053] (3) Introduce Ar, adjust the airflow to control the pressure inside the cavity to 0.6 Pa, adjust the sputtering power to 30 W, and sputter using Ga2O3 target material for 50 s;

[0054] (4) Transfer the substrate with two-dimensional Ga2O3 on the surface obtained by magnetron sputtering to a tube furnace, weigh 100mg of sulfur powder, load it in a quartz boat, and place it upstream of the substrate.

[0055] (5) Evacuate to 8×10 -3 Pa, then continuously introduce 300 sccm of Ar for 10 minutes;

[0056] (6) Set the program to heat the tube furnace to 550°C, introduce 50 sccm of Ar, continue for 5 minutes, and then let it cool down naturally.

[0057] Figure 1 The O1s spectrum of the two-dimensional Ga2S3 XPS characterization prepared in this embodiment is shown.

[0058] Example 2:

[0059] This embodiment provides a method for preparing two-dimensional Ga2S3, specifically including:

[0060] (1) Substrate pretreatment: SiO2 / Si substrate (size 1*1cm) was selected as the substrate for material growth, and the SiO2 surface of the substrate was cleaned for 5 min with O2 plasma with a power of 100W.

[0061] (2) Transfer the pretreated substrate into the magnetron sputtering equipment cavity, using the SiO2 side of the substrate as the growth surface, and evacuate to 5×10⁻⁶. -4 Pa;

[0062] (3) Introduce Ar, adjust the airflow to control the pressure inside the cavity to 0.6 Pa, adjust the sputtering power to 30 W, and sputter using Ga2O3 target material for 50 s;

[0063] (4) Transfer the substrate with two-dimensional Ga2O3 on the surface obtained by magnetron sputtering to a tube furnace, weigh 100mg of sulfur powder, load it in a quartz boat, and place it upstream of the substrate.

[0064] (5) Evacuate to 8×10 -3 Pa, then continuously introduce 300 sccm of Ar for 10 minutes;

[0065] (6) Set the program to heat the tube furnace to 550°C, adjust the plasma power to 80W, introduce 50 sccm of Ar, continue for 5 minutes, and then let it cool down naturally.

[0066] Figure 2 The XPS characterization O1s spectrum of the two-dimensional Ga2S3 prepared in this embodiment shows that the peak area ratio corresponding to the incompletely reacted Ga2O3 is significantly smaller than that obtained in Example 1, indicating that the plasma-enhanced sulfidation method can significantly improve the purity of the prepared two-dimensional Ga2S3.

[0067] Figure 3 The image shows an atomic force microscope image (top view of the surface) of two-dimensional Ga2S3 prepared for this embodiment. It can be seen from the image that the thickness of the two-dimensional Ga2S3 is 1.5 nm.

[0068] Example 3:

[0069] This embodiment provides a method for preparing two-dimensional Ga2S3, specifically including:

[0070] (1) Substrate pretreatment: SiO2 / Si substrate (size 1*1cm) was selected as the substrate for material growth, and the SiO2 surface of the substrate was cleaned for 5 min with O2 plasma with a power of 100W.

[0071] (2) Transfer the pretreated substrate into the magnetron sputtering equipment cavity, using the SiO2 side of the substrate as the growth surface, and evacuate to 5×10⁻⁶. -4 Pa;

[0072] (3) Introduce Ar, adjust the airflow to control the pressure inside the cavity to 0.8 Pa, adjust the sputtering power to 50 W, and sputter using Ga2O3 target material for 100 s;

[0073] (4) Transfer the substrate with two-dimensional Ga2O3 on the surface obtained by magnetron sputtering to a tube furnace, weigh 150 mg of sulfur powder, load it in a quartz boat, and place it upstream of the substrate.

[0074] (5) Evacuate to 8×10 -3 Pa, then continuously introduce 300 sccm of Ar for 10 minutes;

[0075] (6) Set the program to heat the tube furnace to 600°C, adjust the plasma power to 100W, introduce 50 sccm of Ar, continue for 10 minutes, and then let it cool down naturally.

[0076] Figure 4 The image shows an atomic force microscope image of two-dimensional Ga2S3 prepared for this embodiment. It can be seen from the image that the thickness of the two-dimensional Ga2S3 is 3.6 nm.

[0077] Example 4:

[0078] This embodiment provides a method for preparing two-dimensional Ga2S3, specifically including:

[0079] (1) Substrate pretreatment: SiO2 / Si substrate (size 1*1cm) was selected as the substrate for material growth, and the SiO2 surface of the substrate was cleaned for 5 min with O2 plasma with a power of 100W.

[0080] (2) Transfer the pretreated substrate into the magnetron sputtering equipment cavity, using the SiO2 side of the substrate as the growth surface, and evacuate to 5×10⁻⁶. -4 Pa;

[0081] (3) Introduce Ar, adjust the airflow to control the pressure inside the cavity to 1 Pa, adjust the sputtering power to 50 W, and sputter using Ga2O3 target material for 300 s.

[0082] (4) Transfer the substrate with two-dimensional Ga2O3 on the surface obtained by magnetron sputtering to a tube furnace, weigh 200mg of sulfur powder, load it in a quartz boat, and place it upstream of the substrate.

[0083] (5) Evacuate to 8×10 -3 Pa, then continuously introduce 300 sccm of Ar for 10 minutes;

[0084] (6) Set the program to heat the tube furnace to 650°C, adjust the plasma power to 100W, introduce 50 sccm of Ar, continue for 15 minutes, and then let it cool down naturally.

[0085] Example 5:

[0086] This embodiment provides a method for fabricating two-dimensional Ga2S3 and its photodetector, specifically including:

[0087] (1) Substrate pretreatment: SiO2 / Si substrate (size 1*1cm) was selected as the substrate for material growth, and the SiO2 surface of the substrate was cleaned for 5 min with O2 plasma with a power of 100W.

[0088] (2) Transfer the pretreated substrate into the magnetron sputtering equipment cavity, using the SiO2 side of the substrate as the growth surface, and evacuate to 5×10⁻⁶. -4 Pa;

[0089] (3) Introduce Ar, adjust the airflow to control the gas pressure in the cavity to 0.8 Pa, adjust the sputtering power to 50 W, and sputter using Ga2O3 target material for 200 s;

[0090] (4) Transfer the substrate with two-dimensional Ga2O3 on the surface obtained by magnetron sputtering to a tube furnace, weigh 180 mg of sulfur powder, load it in a quartz boat, and place it upstream of the substrate.

[0091] (5) Evacuate to 8×10 -3 Pa, then continuously introduce 300 sccm of Ar for 10 minutes;

[0092] (6) Set the program to heat the tube furnace to 650°C, adjust the plasma power to 100W, introduce 50sccm of Ar, continue for 12min, and then let it cool down naturally.

[0093] (7) The prepared two-dimensional Ga2S3 sample was cleaned to remove residual sulfur powder on its surface: it was ultrasonically cleaned in isopropanol, deionized water and anhydrous ethanol for 20 min in sequence. The cleaned sample was then transferred to a drying oven and dried at 90℃ for 30 min.

[0094] (8) Photolithography is performed on the cleaned sample to obtain the electrode pattern: An appropriate amount of photoresist (RZJ304) is dropped onto the sample surface and placed in a spin coater. The sample is first processed at a speed of 500 r / s for 5 s, and then processed at a speed of 2000 r / s for 30 s. The rectifier epitaxial wafer coated with photoresist is pre-baked at 95°C for 45 s, and then exposed to the rectifier epitaxial wafer for 2 s using a photolithography machine to obtain the electrode pattern. Finally, the rectifier epitaxial wafer is immersed in the developer for 60 s and then cleaned.

[0095] (9) Depositing electrodes on the sample surface: Transfer the sample with the electrode pattern to the electron beam evaporation equipment and evacuate to 3×10⁻⁶. -4 Pa, followed by sequentially evaporating 30 / 90nm thick Ti / Au as electrode metal;

[0096] (10) Remove residual photoresist from the sample: Immerse the sample after vapor deposition in the photoresist removal solution, then place it in acetone and ethanol for ultrasonic treatment for 10 min and transfer it to a drying oven. Set the temperature to 90℃ and dry for 30 min to obtain a two-dimensional Ga2S3-based photodetector.

[0097] Figure 5 The light response curve of the two-dimensional Ga2S3-based photodetector prepared in this embodiment shows that the device has the strongest response to 430nm light, and the photocurrent-to-dark-current ratio is greater than 10. 2 .

[0098] The above description is merely a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope disclosed in the present invention, based on the technical solution and inventive concept of the present invention, shall fall within the scope of protection of the present invention.

Claims

1. A method for preparing a two-dimensional Ga2S3 material, characterized in that, Includes the following steps: Two-dimensional Ga2O3 was subjected to sulfidation treatment in a plasma gas flow atmosphere to obtain two-dimensional Ga2S3 material; the two-dimensional Ga2O3 was prepared by magnetron sputtering; the two-dimensional Ga2O3 was grown on the surface of SiO2; the SiO2 was a SiO2 / Si substrate; the magnetron sputtering was performed under a protective atmosphere flow; the pressure of the protective atmosphere flow was 0.6-1 Pa, and the protective atmosphere flow was an argon flow. The target material for magnetron sputtering is a Ga2O3 target material; The power of the magnetron sputtering is 30-70 W; the time of the magnetron sputtering is 50-300 s; the plasma gas flow atmosphere is an inert gas flow of plasma treatment; the plasma power of the plasma treatment is 80-100 W, the flow rate of the inert gas flow is 30-70 sccm, and the inert gas is argon; the sulfur source of the sulfurization treatment is sulfur powder; the mass and volume ratio of the sulfur powder to two-dimensional Ga2O3 is 100-200 mg:(1.5-3.6)*10 -4 mm 3 ; the sulfur powder is upstream of the two-dimensional Ga2O3.

2. The method of claim 1, wherein the two-dimensional Ga2S3 material is prepared by a method comprising: The vulcanization temperature is 550-650℃; the holding time for the vulcanization is 5-15 min.

3. The method for preparing two-dimensional Ga2S3 material according to claim 1, characterized in that, The vulcanization process is followed by natural cooling.

4. The two-dimensional Ga2S3 material prepared by the preparation method according to any one of claims 1-3.

5. The application of the two-dimensional Ga2S3 material according to claim 4 in the fabrication of photodetectors.

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