Method for vapor phase growth of atomic clusters through supersaturation technology and application

Abstract

The invention discloses a method for vapor-phase growth of atomic clusters through a supersaturation technology. The method comprises the following steps: carrying out surface treatment on a substrate; preparing a precursor, and adjusting the gas pressure and the precursor flow to control the carbon atom concentration of acetylene decomposition; through gradient temperature design, thermodynamics of a gas phase environment and parameters of precursor concentration are regulated and controlled, nucleation and continuous growth of atomic clusters are controlled, and nano-structure crystals, namely submicron atomic clusters, are finally formed through crystal nucleuses. According to the method for vapor phase growth of the atomic cluster through the supersaturation technology and the application, the size and the structure of the grown atomic cluster can be regulated and controlled, the high-purity atomic cluster is achieved, solvent pollution is avoided, and in-situ deposition and efficient nucleation can be achieved.

Description

Technical Field

[0001] The present invention relates to the technical field of nanomaterial preparation, and particularly to a method and application for vapor-growing atomic clusters by a supersaturation technique. Background Art

[0002] An atomic cluster is a microscopic aggregate composed of several to hundreds of atoms, and its size is between that of a single atom and macroscopic matter (typical size 0.1 - 300 nm). For example, carbon atom clusters can exhibit different colors under specific conditions, that is, the color can be regulated according to the size and distribution characteristics of the atomic clusters, namely structural color. Currently, methods for growing atomic clusters include laser ablation technology, magnetron sputtering method, cluster beam deposition, colloid chemistry method, and electrochemical deposition, etc. However, the equipment used in these methods is expensive and can only grow a certain specific type of atomic cluster. At the same time, the clusters grown by these methods have a wide size distribution, poor monodispersity, and are prone to adsorb impurities on the surface, making it difficult to achieve large-scale mass production and bringing great challenges to subsequent applications. Summary of the Invention

[0003] In view of the above-mentioned defects of the prior art, the technical problem to be solved by the present invention is that the equipment used in the existing atomic cluster growth methods is expensive and can only grow a certain specific type of atomic cluster, and the grown clusters have a wide size distribution, poor monodispersity, are prone to adsorb impurities on the surface, and it is difficult to achieve large-scale mass production. A method and application for vapor-growing atomic clusters by a supersaturation technique according to the present invention can regulate the size and structure of the grown atomic clusters, achieve high-purity atomic clusters without solvent pollution, and can be in-situ deposited and efficiently nucleated.

[0004] To achieve the above object, the present invention provides a method for vapor-growing atomic clusters by a supersaturation technique, comprising the following steps:

[0005] Perform surface treatment on the substrate;

[0006] Configure the precursor, and adjust the gas pressure and precursor flow rate to control the carbon atom concentration decomposed from acetylene;

[0007] By designing the gradient temperature, regulating the thermodynamic parameters of the gas phase environment and the precursor concentration, control the nucleation of atomic clusters and continuously grow them, and finally form a nanostructured crystal, namely sub-micron atomic clusters, through the crystal nuclei.

[0008] Further, performing surface treatment on the substrate specifically includes oxidation treatment, plasma treatment, and physical polishing treatment. The total treatment time of the substrate surface is 5 s to 180 s, and the surface roughness of the substrate is controlled below 5 nm.

[0009] Further, the substrate needs to undergo oxidation treatment, plasma treatment, and physical polishing treatment, specifically including: first, oxidation treatment is carried out using ozone irradiation, and the oxidation treatment time is 30 s to 100 s; then plasma treatment is carried out using hydrogen plasma, the treatment power is set to 200 watts, and the plasma treatment time is 5 s to 150 s; then physical polishing is carried out, and the surface of the substrate is mechanically polished using a polishing liquid containing alumina, cerium oxide, and silicon carbide, and the polishing time is 5 s to 180 s.

[0010] Further, the precursor is configured with a carbon-containing gas or an organic compound containing zinc and almost or containing titanium.

[0011] Further, the carbon-containing gas includes one or more of methane, acetylene, ethylene, alcohol, and acetone.

[0012] Further, the carbon atom concentration of acetylene decomposition is controlled by adjusting the gas pressure and the precursor flow rate. Specifically, the air pressure in the precursor decomposition chamber is adjusted to 20 T to 1300 T, N2 is used as the carrier gas, and the N2 carrier gas flow rate is controlled at 50 to 500 sccm.

[0013] Further, the gradient temperature design includes a high-temperature zone, a medium-temperature nucleation zone, and a low-temperature growth zone. Among them, the temperature of the high-temperature zone is 1200 °C, the temperature of the medium-temperature nucleation zone is 500 °C, and the temperature of the low-temperature growth zone is 100 °C.

[0014] Further, through the electric device, the substrate rotates automatically in the chamber to ensure the uniformity of the growth of atomic clusters. The growth process is observed through a transparent hanging window, the growth time is controlled within 10 seconds to 2 hours, and after the growth is completed, it cools down automatically under nitrogen protection.

[0015] In a preferred embodiment of the present invention, a submicron atomic cluster generated by a method of gas-phase growth of atomic clusters through supersaturation technology is provided, which is applied to structural color, hydrophilic and hydrophobic surface regulation, material surface modification, and electrocatalysis.

[0016] Technical effects

[0017] A method for gas-phase growth of atomic clusters through supersaturation technology provided by the present invention. Atoms or molecules in the supersaturated gas randomly collide to form tiny nuclei. By regulating parameters such as the thermodynamics of the gas phase environment and the precursor concentration, the nuclei grow continuously and finally form nanostructured crystals. The specific technical effects include the following:

[0018] 1. Size and structure regulation

[0019] The present invention adopts a supersaturated process gas phase technology. By adjusting the gas pressure, temperature, etc., the supersaturation is adjusted by controlling the concentration of the precursor to affect the kinetic energy and collision frequency of gas molecules (for example, increasing the concentration of the precursor, the supersaturation increases, the probability of atomic collision increases, and more atoms aggregate to form nuclei), enabling the precursor to participate in the growth process of atomic clusters in a gas phase state, thereby achieving the regulation of the nucleation rate, control of the number of atoms in the cluster, the size of atomic clusters, etc. At the same time, this gas phase technology is applicable to a variety of precursors, and can be extended to gases (carbon-containing gases C2H2, CH4), inorganic semiconductors (Si, Ge), oxides (ZrO2, TiO2), organic substances and metals (Au, Pt), etc., providing a basis for customized material design.

[0020] 2. High purity and solvent-free pollution

[0021] This supersaturated gas phase deposition technology does not require the participation of excessive solvents, catalysts, activators and other substances. The raw materials can independently participate in the reaction to form atomic clusters, avoiding impurity residues. At the same time, this supersaturated gas phase technology is suitable for various gas pressure conditions, and the gas pressure can be extended to 20T - 500T, facilitating the regulation of the atomic cluster size and avoiding interference from the external environment, especially suitable for fields with high purity requirements (such as quantum devices, biomedical probes, high-precision and advanced fields such as chips).

[0022] 3. In-situ deposition and efficient nucleation

[0023] Under the gas phase supersaturated state with a high atomic concentration, atoms quickly nucleate to form atomic clusters and can be directly deposited on the substrate surface. By regulating the gas pressure, precursor concentration during the growth process, and according to the type of precursor, the growth time can be widely regulated (from 5 seconds to 2 hours). For example, atomic clusters of carbon atoms can be grown within 5s - 240s, and atomic clusters of metal oxide TiO2 can be grown within 30min - 2h. By controlling the time, the formation kinetics of atomic clusters can be optimized, selectively growing atomic cluster islands, patterned thin films and porous coatings; it is applicable to the preparation of large-area devices (such as solar cell electrodes, sensors and multi-layer refractive index optical devices, etc.).

[0024] The following will further illustrate the concept, specific structure and technical effects of the present invention in conjunction with the accompanying drawings to fully understand the purpose, features and effects of the present invention. Brief description of the drawings

[0025] Figure 1 It is a diagram of an atomic cluster thin film of a preferred embodiment of the present invention;

[0026] Figure 2 It is a diagram of atomic cluster nanoparticles of a preferred embodiment of the present invention. Detailed implementation manners

[0027] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention more clear and understandable, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0028] The present invention provides a method for gas-phase growth of atomic clusters by supersaturation technology, comprising the following steps:

[0029] First, the surface of the substrate is treated; specifically, it includes oxidation treatment, plasma treatment and physical polishing treatment. The total treatment time of the substrate surface is 5 s to 180 s, and the surface roughness of the substrate is controlled below 5 nm; the substrate needs to undergo oxidation treatment, plasma treatment and physical polishing treatment, specifically including: first, oxidation treatment is carried out using ozone irradiation, and the oxidation treatment time is 30 s to 100 s; then plasma treatment is carried out using hydrogen plasma, the treatment power is set to 200 watts, and the plasma treatment time is 5 s to 150 s; then physical polishing is carried out, and the surface of the substrate is mechanically polished with a polishing liquid containing alumina, cerium oxide and silicon carbide, and the polishing time is 5 s to 180 s.

[0030] Secondly, a precursor is configured, and the carbon atom concentration of acetylene decomposition is controlled by adjusting the gas pressure and the precursor flow rate; the precursor is configured with a carbon-containing gas or an organic substance containing zinc and almost or containing titanium; the carbon-containing gas includes one or more of methane, acetylene, ethylene, alcohol, and acetone. Adjusting the gas pressure and the precursor flow rate to control the carbon atom concentration of acetylene decomposition specifically means adjusting the air pressure in the precursor decomposition chamber to 20 T to 1300 T, using N2 as the carrier gas, and controlling the N2 carrier gas flow rate at 50 to 500 sccm.

[0031] Finally, by designing the gradient temperature, controlling the thermodynamics of the gas phase environment and the parameters of the precursor concentration, the nucleation of atomic clusters is controlled and continuously grown, and finally a nanostructured crystal, that is, a submicron atomic cluster, is formed through the crystal nucleus; the gradient temperature design includes a high temperature zone, a medium temperature nucleation zone and a low temperature growth zone. Among them, the temperature of the high temperature zone is 1200 °C, the temperature of the medium temperature nucleation zone is 500 °C, and the temperature of the low temperature growth zone is 100 °C; through an electric device, the substrate is automatically rotated in the cavity to ensure the uniformity of atomic cluster growth, and the growth process is observed through a transparent suspension window. The growth time is controlled within 10 seconds to 2 hours. After the growth is completed, it is automatically cooled under nitrogen protection.

[0032] In a preferred embodiment of the present invention, a submicron atomic cluster generated by a method for gas-phase growth of atomic clusters by supersaturation technology is provided, which is applied to structural color, hydrophilic and hydrophobic surface regulation, material surface modification, and electrocatalysis.

[0033] Example 1:

[0034] The carbon film was treated with oxygen plasma for 20 s. Using acetylene (C2H2) as the precursor, the flow rate of C2H2 was 5 sccm, high-purity nitrogen (99.999%) was used as the carrier gas with a flow rate of 200 sccm, the hydrogen-argon mixed gas in the cavity (H2 / Ar = 5 / 95) had a flow rate of 100 sccm, the cavity pressure was 30 T, and the reaction cavity was a two-temperature-zone horizontal vacuum tube furnace (quartz tube diameter 60 mm, length 800 mm). The evaporation zone: high-frequency induction heating coil (temperature 800 °C), the atomic cluster nucleation zone, (temperature control range 300 - 800 - 1200 °C, accuracy ±3 °C), the substrate was a 2-inch diameter carbon film, and the growth time was 10 minutes. As shown in Attachment Figure 2 a, the atomic cluster size reached about 10 μm.

[0035] Example 2:

[0036] The carbon film was treated with oxygen plasma for 20 s. The precursor was acetylene (C2H2) with a flow rate of 20 sccm, high-purity nitrogen (99.999%) was used as the carrier gas with a flow rate of 200 sccm, the hydrogen-argon mixed gas in the cavity (H2 / Ar = 5 / 95) had a flow rate of 100 sccm, the cavity pressure was 30 T, and the reaction cavity was a two-temperature-zone horizontal vacuum tube furnace (quartz tube diameter 60 mm, length 800 mm). The evaporation zone: high-frequency induction heating coil (temperature 800 °C), the atomic cluster nucleation zone, (temperature control range 300 - 800 - 1200 °C, accuracy ±3 °C), the substrate was a 2-inch diameter carbon film, and the growth time was 10 minutes. As shown in Attachment Figure 2 b, the atomic cluster size reached about 12 μm.

[0037] Example 3:

[0038] The carbon film was treated with oxygen plasma for 20 s. The precursor was acetylene (C2H2) with a flow rate of 30 sccm, high-purity nitrogen (99.999%) was used as the carrier gas with a flow rate of 300 sccm, the hydrogen-argon mixed gas in the cavity (H2 / Ar = 5 / 95) had a flow rate of 100 sccm, the cavity pressure was 30 T, and the reaction cavity was a two-temperature-zone horizontal vacuum tube furnace (quartz tube diameter 60 mm, length 800 mm). The evaporation zone: high-frequency induction heating coil (temperature 800 °C), the atomic cluster nucleation zone, (temperature control range 300 - 800 - 1200 °C, accuracy ±3 °C), the substrate was a 2-inch diameter carbon film, and the growth time was 10 minutes. As shown in Attachment Figure 2 c, the atomic cluster size reached about 17 μm.

[0039] Example 4:

[0040] The carbon film was treated with oxygen plasma for 20 s. The precursor was acetylene (C2H2) with a flow rate of 30 sccm. High-purity nitrogen (99.999%) was used as the carrier gas with a flow rate of 300 sccm. The gas mixture in the cavity was a hydrogen-argon mixture (H2 / Ar = 5 / 95) with a flow rate of 100 sccm. The pressure in the cavity was 30 T. The reaction cavity was a horizontal tube furnace with a two-temperature zone (quartz tube diameter: 60 mm, length: 800 mm). The evaporation zone: high-frequency induction heating coil (temperature: 800 °C), atomic cluster nucleation zone (temperature control range: 200 - 900 - 1100 °C, accuracy: ±3 °C). The substrate was a 2-inch diameter carbon film. The growth time was 10 minutes. As shown in Figure 2 Figure d, the size of the atomic clusters reached about 11 μm.

[0041] The preferred specific embodiments of the present invention have been described in detail above. It should be understood that those of ordinary skill in the art can make many modifications and variations based on the concept of the present invention without creative efforts. Therefore, all technical solutions that can be obtained by those skilled in the art in the technical field of the present invention through logical analysis, reasoning, or limited experiments based on the concept of the present invention on the basis of the prior art should be within the protection scope determined by the claims.

Claims

1. A method for gas-phase growth of atomic clusters by supersaturation technology, characterized in that, Including the following steps: Perform surface treatment on the substrate; Configure the precursor, adjust the gas pressure and precursor flow rate to control the carbon atom concentration of acetylene decomposition; Through gradient temperature design, regulate the thermodynamic parameters of the gas phase environment and the precursor concentration, control the nucleation and continuous growth of atomic clusters, and finally form a nanostructured crystal, namely submicron atomic clusters, through crystal nuclei.

2. The method for vapor-phase growth of atomic clusters by supersaturation technology as claimed in claim 1, wherein, Perform surface treatment on the substrate, specifically including oxidation treatment, plasma treatment and physical polishing treatment. The surface treatment time of the substrate is 5s to 180s, and the surface roughness of the substrate is controlled below 5nm.

3. The method for growing atomic clusters by vapor phase using supersaturation technology as claimed in claim 1, characterized in that, The oxidation treatment, plasma treatment and physical polishing treatment specifically include: first, perform oxidation treatment using ozone irradiation, and the oxidation treatment time is 30s to 100s; then perform plasma treatment using hydrogen plasma, the treatment power is set to 200 watts, and the plasma treatment time is 5s to 150s; then perform physical polishing, and mechanically polish the surface of the substrate with a polishing liquid containing alumina, cerium oxide, and silicon carbide, and the polishing time is 5s to 180s.

4. The method for vapor-phase growth of atomic clusters by supersaturation technology according to claim 1, characterized in that, The precursor is configured with a carbon-containing gas or an organic compound containing zinc and almost or containing titanium.

5. The method for vapor-phase growth of atomic clusters by supersaturation technology as claimed in claim 4, wherein The carbon-containing gas includes one or more of methane, acetylene, ethylene and other carbon sources such as alcohol and acetone.

6. The method for growing atomic clusters by vapor phase through supersaturation technology as claimed in claim 1, wherein Adjust the gas pressure and precursor flow rate to control the carbon atom concentration of acetylene decomposition. Specifically, adjust the air pressure in the precursor decomposition cavity to 20T to 1300T, use N2 as the carrier gas, and control the carrier gas flow rate at 50 to 500 sccm.

7. A method for gas-phase growing atomic clusters by supersaturation technology according to claim 1, characterized in that, The gradient temperature design includes a high-temperature zone, a medium-temperature nucleation zone and a low-temperature growth zone. Among them, the temperature of the high-temperature zone is 1200°C, the temperature of the medium-temperature nucleation zone is 500°C, and the temperature of the low-temperature growth zone is 100°C.

8. The method for growing atomic clusters by vapor phase through supersaturation technology as claimed in claim 1, wherein, Through an electric device, the substrate rotates automatically in the cavity to ensure the uniformity of atomic cluster growth. Observe the growth process through a transparent suspension window. The growth time is controlled within 10 seconds to 2 hours. After the growth is completed, it cools down automatically under nitrogen protection.

9. A submicron atomic cluster generated by a method of growing atomic clusters by vapor phase through a supersaturation technique as described in any one of claims 1-8, characterized in that, Applied to structural color, hydrophilic and hydrophobic surface regulation, material surface modification, and electrocatalysis.

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