Metal monatomic deposition method and monatomic deposition equipment
By combining an electric field and a gas flow carrier in the deposition chamber, the problem of poor adhesion between metal single atoms and the substrate was solved, improving deposition efficiency and stability, and enhancing catalytic and energy performance.
Patent Information
- Application Number
- CN202511198106.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-25
- Publication Date
- 2025-11-21
AI Technical Summary
In existing technologies, the poor bonding force between metal single atoms and substrate materials leads to low deposition efficiency, poor stability, easy migration and aggregation to form nanoparticles, and loss of active sites.
By applying an electric field in the deposition chamber, metal single atoms are moved toward the substrate using a gas flow carrier, and deposition is accelerated under the action of the electric field, thereby improving the bonding force between the metal single atoms and the substrate.
It improves the collection rate and stability of metal single atoms on the substrate, suppresses migration and aggregation, and enhances performance in catalysis and energy fields.
Smart Images
Figure CN120989559A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of atomic deposition, in particular to a metal single atom deposition method and a single atom deposition device. BACKGROUND
[0002] Metal single atom deposition (SAD) is a technology for dispersing metal in the form of isolated single atoms on the surface of a substrate, such as a process for stably anchoring a single metal atom in the form of atomic dispersion on a specific substrate surface. In recent years, it has attracted much attention due to its unique performance in the fields of catalysis, energy storage, electronic devices, etc.
[0003] Metal single atom deposition can be achieved by atomic layer deposition, chemical vapor deposition, high-temperature pyrolysis, etc. Existing single atom deposition devices usually place the substrate in a deposition chamber, then prepare the raw material into a single atom form and introduce it into the deposition chamber, and the metal single atoms are deposited on the substrate through self-diffusion movement. However, the self-diffusion movement speed of metal single atoms is slow, the deposition efficiency is low, the atom movement has no directionality, resulting in low collection rate, and the kinetic energy is small, so the binding force between the metal single atoms and the substrate material is poor, which leads to the migration and aggregation of metal single atoms to form nanoparticles due to high surface energy, resulting in the loss of active sites and thus reducing the stability of single atom materials.
[0004] Therefore, how to effectively improve the binding force between metal single atoms and substrate materials is a technical problem to be solved by those skilled in the art. SUMMARY
[0005] Therefore, the present application provides a metal single atom deposition method and a single atom deposition device which can effectively improve the binding force between metal single atoms and substrate materials.
[0006] The present application provides a metal single atom deposition method, comprising:
[0007] S1: placing a substrate in a deposition cavity;
[0008] S2: introducing metal single atoms into the deposition cavity, wherein the metal single atoms move towards the substrate through a gas flow carrier; and
[0009] S3: applying an electric field in the deposition cavity, wherein the metal single atoms accelerate towards the substrate under the action of the electric field and are deposited on the substrate.
[0010] In an embodiment, the substrate is one or more of a powdered metal, an oxide, and a nitride.
[0011] In an embodiment, the electric field is applied around the substrate or on the substrate.
[0012] In one embodiment, the electric field is a negative pressure, a positive pressure, or a high pressure that attracts the metal single atoms.
[0013] In one embodiment, the voltage of the electric field is set to 1 to 1000V.
[0014] In one embodiment, the substrate undergoes a pretreatment process prior to step S1, the pretreatment process including:
[0015] P1: The nanopowder is ball-milled according to the type of metal and particle size.
[0016] P2: Cleaning treatment of the ball-milled nanopowder; and
[0017] P3: Vacuum ion beam bombardment of the cleaned nanopowder.
[0018] In one embodiment, step P2, cleaning the nanopowder, includes:
[0019] The nanopowder was ultrasonically cleaned with ethanol for 1–60 min.
[0020] The nanopowder is subjected to alkaline washing using a composite alkaline detergent. The composite alkaline detergent is mixed with water at a volume ratio of 1:100 and then ultrasonically cleaned for 1 to 20 minutes. The composite alkaline detergent is prepared by adding sodium alkylnaphthalene sulfonate at a temperature of 50 to 70 degrees Celsius to potassium pyrophosphate and sodium metasilicate at a content of 0.5 to 6%.
[0021] The nanopowder was ultrasonically cleaned with deionized water for 10–30 minutes, 2–5 times.
[0022] The nanoparticles were vacuum dried at 30–120 degrees Celsius and 0.05–0.2 MPa for 1–10 hours; and
[0023] The nanoparticles were plasma cleaned at a power of 30–1000 W for 10–1000 s.
[0024] In one embodiment, in step P3, before the vacuum ion beam bombardment, the initial vacuum level of the equipment cavity is adjusted to 10. -5 ~10 -3 Pa, time set to 10–3000 s, beam current density set to 0.5–5 mA / cm² 2 The ion beam energy was set to 500–5000 eV, and after adjustment, the nanoparticles were bombarded with vacuum ion beams according to the set parameters.
[0025] In one embodiment, the metal monatomic atoms include one or more of Pt, Pd, Ir, Ni, Co, Fe, Cu, Ag, Au, Mn, Ru, Rh, W, Mo, and Sn; and / or, the substrate includes one or more of Pt, Pd, Ir, Ni, Co, Fe, Cu, Ag, Au, Mn, Ru, Rh, W, Mo, Sn, Ti, Al, oxides, nitrides, and carbonitrides thereof.
[0026] The present application also provides a monatomic atom deposition apparatus for depositing metal monatomic atoms on a substrate according to the metal monatomic atom deposition method as described above.
[0027] In summary, the present application provides a metal monatomic atom deposition method and a monatomic atom deposition apparatus, the metal monatomic atom deposition method including: placing a substrate in a deposition chamber; introducing metal monatomic atoms into the deposition chamber, the metal monatomic atoms moving towards the substrate by means of a gas flow carrier; and applying an electric field in the deposition chamber, the metal monatomic atoms accelerating towards the substrate under the action of the electric field and depositing on the substrate. The present application achieves the acceleration and directional deposition of the metal monatomic atoms by means of the directional movement of the gas flow carrier and the electric field. The gas flow carrier can gather the metal monatomic atoms in a certain area and move them towards the substrate in a directional manner, thus having a certain acceleration effect, improving the collection rate of the metal monatomic atoms on the substrate, and further increasing the moving speed and kinetic energy of the metal monatomic atoms in the gas flow carrier when they encounter the accelerating electric field, thus increasing the energy of the metal monatomic atoms when they contact the surface of the substrate, and thus improving the binding force between the metal monatomic atoms and the substrate material and the stability of the monatomic material. BRIEF DESCRIPTION OF DRAWINGS
[0028] Figure 1 The figure is a process flow diagram of the metal monatomic atom deposition method in one embodiment of the present application.
[0029] Figure 2 The figure is a process flow diagram of the pre-treatment of the substrate before deposition in one embodiment of the present application. DETAILED DESCRIPTION
[0030] In order to facilitate the understanding of the present application, the present application will be described more fully below with reference to the accompanying drawings. The embodiments of the present application are shown in the accompanying drawings. However, the present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present application more thorough and comprehensive.
[0031] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs. The terminology used in the description of the present application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present application.
[0032] Reference is made to Figure 1 As shown in the drawings, the present application provides a metal monatomic deposition method, which can be applied in technical fields such as sensing, catalysis, energy storage, biological medicine and electronic devices, for example, for preparing metal monatomic catalysts, semiconductors, thin films generated by the reaction between metal monatomic and substrate materials, etc. Specifically, the metal monatomic deposition method comprises the following steps:
[0033] S1: placing a substrate in a deposition cavity;
[0034] S2: introducing metal monatomic into the deposition cavity, the metal monatomic moving towards the substrate by means of a gas flow carrier;
[0035] For example, when the monatomic enters the deposition cavity, a directional moving gas flow is generated by a gas flow generating device, which can be a high-speed moving inert gas carrying the monatomic into the deposition cavity, wherein the gas flow generating device can be an existing fan, a compression pump / compressor (for generating a compressed gas flow), etc.; and
[0036] S3: applying an electric field in the deposition cavity, the metal monatomic accelerating towards the substrate under the action of the electric field and depositing on the substrate;
[0037] For example, an electric field opposite to the charge type carried by the monatomic is applied on the substrate, the attraction of the applied electric field to the monatomic makes the monatomic accelerate towards the substrate; or a high voltage is applied on the substrate while changing the gas flow rate, so that the monatomic is accelerated to deposit on the substrate, wherein the electric field can be configured as a conventional coil, electrode or power supply, etc.
[0038] Optionally, an atomic deposition device can be provided, which can include a manufacturing unit for processing raw materials to prepare metal monatomic and a deposition unit, the deposition cavity described above can be a deposition cavity of the deposition unit, the prepared metal monatomic is introduced into the deposition cavity, the deposition unit is used to deposit the prepared metal monatomic on the substrate, the gas flow generating device can be arranged in the manufacturing unit, and the electric field can be arranged in the deposition unit. Alternatively, the atomic deposition device can only perform the deposition operation of the metal monatomic on the substrate, the preparation of the metal monatomic is completed by an external instrument or device, the prepared metal monatomic is introduced into the deposition cavity for deposition operation, the gas flow generating device can be arranged in the external instrument or device, and the electric field can be arranged in the atomic deposition device.
[0039] The metal monatomic atom can include, but is not limited to, one or more of Pt, Pd, Ir, Ni, Co, Fe, Cu, Ag, Au, Mn, Ru, Rh, W, Mo, Sn, etc., for example, the metal monatomic atom is preferably silver, copper or nickel. The substrate can be one or more of a combination of powdered metal, oxide and nitride nano-powder, for example, the substrate can include, but is not limited to, one or more of Pt, Pd, Ir, Ni, Co, Fe, Cu, Ag, Au, Mn, Ru, Rh, W, Mo, Sn, Ti, Al and oxides, nitrides and carbon nitrides thereof, for example, the substrate is preferably aluminum oxide, titanium oxide or carbon nitride.
[0040] In some embodiments, after the metal monatomic atom is deposited on the substrate, the charge redistribution between the substrate material and the metal monatomic atom can change its catalytic activity, or the substrate material can directly participate in the reaction and form a synergistic active site with the metal unit.
[0041] The gas flow carrier can be provided by a gas flow generating device provided in the equipment corresponding to the deposition cavity, and the gas flow carrier is controlled to flow continuously towards the direction where the substrate is located. The metal monatomic atom is immediately wrapped by the gas flow carrier and moves towards the substrate after being introduced into the deposition cavity. The gas flow carrier can have the effect of gathering the metal monatomic atom in a certain area and moving towards the substrate in a directional manner, and has a certain acceleration effect, thereby improving the collection rate of the metal monatomic atom on the substrate.
[0042] The electric field can be applied around the substrate or directly to the substrate. The electric field acceleration, for example, is a negative pressure or a positive pressure applied to the substrate to attract the metal monatomic atom, and the selection of the negative pressure or the positive pressure is determined by the type of the metal monatomic atom. The metal monatomic atom encounters an acceleration electric field in the gas flow carrier, which can further increase the moving speed of the metal monatomic atom, improve the kinetic energy of the metal monatomic atom, and make the metal monatomic atom have high energy when contacting the surface of the substrate, thereby improving the bonding force between the metal monatomic atom and the substrate material, anchoring the metal monatomic atom, inhibiting its migration, avoiding the loss of active sites caused by agglomeration, not only improving the stability of the monatomic material (anti-migration and anti-sintering), but also regulating the electronic structure and creating a synergistic active site, thereby optimizing its performance in the fields of catalysis, energy, etc. Future research needs to combine theoretical calculations (such as DFT) and in-situ characterization to accurately design the metal monatomic atom-substrate interaction.
[0043] Preferably, the voltage of the electric field is set to 1-1000V.
[0044] In some embodiments, the voltage of the electric field can also be set to 0, i.e. without accelerating the monatomic atom, which is suitable for substrates with requirements for monatomic atom deposition depth.
[0045] Please refer to Figure 2 As shown in FIG. 1, before step S1, a pretreatment process can be performed on the substrate, and the pretreatment process includes:
[0046] P1: Ball milling the nano-powder according to the metal type and particle size;
[0047] P2: Washing the nano-powder after ball milling; and
[0048] P3: Vacuum ion beam bombardment of the washed nano-powder.
[0049] The ball milling treatment can unify the size and size of the nano-powder, thereby unifying the particle size / roughness, and the unified size facilitates subsequent processing and improves the processing effect.
[0050] In step P2, the washing of the nano-powder can include alkaline washing, ultrasonic cleaning, plasma cleaning, etc. Specifically:
[0051] The nano-powder is ultrasonically cleaned with ethanol for 1-60 min. Ethanol ultrasonic cleaning can increase the dispersion degree of the nano-powder, and the nano-powder is less likely to agglomerate after ethanol ultrasonic cleaning.
[0052] The nano-powder is alkaline washed with a composite alkaline detergent. The composite alkaline detergent is mixed with water in a volume ratio of 1:100, and the nano-powder is ultrasonically cleaned for 1-20 min. The composite alkaline detergent is prepared by adding 0.5-6% potassium pyrophosphate and sodium metasilicate to sodium alkyl naphthalene sulfonate at 50-70°C. Alkaline washing can remove organic matter such as oil and grease on the surface of the nano-powder.
[0053] The nano-powder is ultrasonically cleaned with deionized water for 10-30 min, 2-5 times. The ultrasonic cleaning here is to remove the washing liquid residue in the alkaline washing.
[0054] The nano-powder is vacuum dried at 30-120°C, 0.05-0.2 MPa for 1-10 h. For example, the nano-powder is dried in an oven, so that the nano-powder is dried, facilitating subsequent operations.
[0055] The nano-powder is plasma cleaned at a power of 30-1000 W for 10-1000 s. The dried nano-powder is plasma cleaned to remove residual substances in the previous step, achieving further cleaning.
[0056] In step P3, before vacuum ion beam bombardment, the initial vacuum degree of the equipment cavity is adjusted to 10 -5 ~10 -3 Pa, the setting time is 10-3000 s, and the beam current density is 0.5-5 mA / cm 2, set the ion beam energy to 500-5000eV, and after adjustment, the nano powder is subjected to vacuum ion beam bombardment according to the set parameters. The vacuum ion beam bombardment of the cleaned nano powder can increase the active sites on the surface of the nano powder, activate the surface of the powdered substrate, and thus improve the bonding force between the metal monatomic and the powdered substrate.
[0057] Three specific embodiments of depositing metal monatomic on a substrate by using the metal monatomic deposition method of the present application are listed below.
[0058] Embodiment one
[0059] Depositing metal monatomic silver on an aluminum oxide substrate.
[0060] A certain amount of aluminum oxide nano powder is provided, the particle size of the aluminum oxide nano powder is measured, the ball milling process parameters of the aluminum oxide nano powder are determined according to the measurement results, and the aluminum oxide nano powder is subjected to ball milling treatment according to the ball milling process parameters.
[0061] The ball-milled aluminum oxide nano powder is subjected to ultrasonic cleaning with ethanol for 15min; then the aluminum oxide nano powder is subjected to ultrasonic cleaning with deionized water for 15min, 3 times; the cleaned aluminum oxide nano powder is vacuum dried at 60 degrees Celsius and 0.1MPa for 1h; then the dried aluminum oxide nano powder is subjected to plasma cleaning with argon plasma at a power of 50W for 5min.
[0062] Before vacuum ion beam bombardment, the initial vacuum degree of the equipment cavity is adjusted to 10 -4 Pa, the setting time is 10min, the beam current density is 1.5mA / cm 2 , the ion beam energy is 3keV, and after adjustment, the aluminum oxide nano powder is subjected to vacuum ion beam bombardment with argon ion beam according to the set parameters to obtain a powdered aluminum oxide substrate.
[0063] According to the above steps S1, S2 and S3, metal monatomic silver is deposited on the powdered aluminum oxide substrate, wherein the voltage of the electric field is controlled to be positive 200V.
[0064] Embodiment two
[0065] Depositing metal monatomic copper on titanium oxide powder.
[0066] A certain amount of titanium oxide nano powder is provided, the particle size of the titanium oxide nano powder is measured, the ball milling process parameters of the titanium oxide nano powder are determined according to the measurement results, and the titanium oxide nano powder is subjected to ball milling treatment according to the ball milling process parameters.
[0067] The milled titanium oxide nanopowder is ultrasonically cleaned with ethanol for 15 minutes; the titanium oxide nanopowder is then ultrasonically cleaned with deionized water for 15 minutes, twice; the cleaned titanium oxide nanopowder is vacuum dried at 60 degrees Celsius and 0.1 MPa for 1 hour; and the dried titanium oxide nanopowder is then plasma cleaned with hydrogen-argon mixed plasma at a power of 80 W for 5 minutes.
[0068] Before vacuum ion beam bombardment, the initial vacuum degree of the equipment cavity is adjusted to 10 -4 Pa, the setting time is 12 minutes, the beam current density is 0.5 mA / cm 2 , and the ion beam energy is 1.5 keV; after the adjustment is completed, the titanium oxide nanopowder is vacuum ion beam bombarded according to the set parameters to obtain a powdered titanium oxide substrate.
[0069] According to the above steps S1, S2 and S3, metal monatomic copper is deposited on the powdered titanium oxide substrate, wherein the voltage of the control electric field is positive 300 V.
[0070] Example Three
[0071] Metal monatomic nickel is deposited on the carbon nitride.
[0072] A certain amount of carbon nitride nanopowder is provided, the particle size of the carbon nitride nanopowder is measured, the ball milling process parameters of the carbon nitride nanopowder are determined according to the measurement results, and the carbon nitride nanopowder is ball milled according to the ball milling process parameters.
[0073] The milled carbon nitride nanopowder is ultrasonically cleaned with ethanol for 15 minutes; the carbon nitride nanopowder is then ultrasonically cleaned with deionized water for 15 minutes, twice; the cleaned carbon nitride nanopowder is vacuum dried at 60 degrees Celsius and 0.1 MPa for 1 hour; and the dried carbon nitride nanopowder is then plasma cleaned with argon plasma at a power of 100 W for 15 minutes.
[0074] Before vacuum ion beam bombardment, the initial vacuum degree of the equipment cavity is adjusted to 10 -4 Pa, the setting time is 2 minutes, the beam current density is 0.5 mA / cm 2 , and the ion beam energy is 1 keV; after the adjustment is completed, the carbon nitride nanopowder is vacuum ion beam bombarded according to the set parameters to obtain a powdered carbon nitride substrate.
[0075] According to the above steps S1, S2 and S3, metal monatomic nickel is deposited on the powdered carbon nitride substrate, wherein the voltage of the control electric field is positive 500 V.
[0076] Through the test results of the above three embodiments, it can be known that the metal monatomic deposition method provided in the application can effectively improve the binding force of the metal monatomic and the substrate material, and further improve the stability of the monatomic material.
[0077] The application also provides a monatomic deposition device, which performs deposition of metal monatomic on a substrate according to the metal monatomic deposition method as above. The monatomic deposition device is, for example, a monatomic cluster generator, which can generate atomic gas through a high-frequency pulse discharge (PEA) technology, apply a high-frequency pulse electric field between electrodes to generate pulse electric arc discharge, and thus generate an atomic gas phase beam and a cluster gas phase beam. Such a monatomic cluster generator does not need chemical precursors, reduces environmental pollution and health risks, can quickly generate monatomic and clusters, can flexibly control the average particle size and yield of the produced material, and uses a purely physical method without chemical pollution to obtain a pure gas phase material beam.
[0078] In summary, the application provides a metal monatomic deposition method and a monatomic deposition device. The metal monatomic deposition method comprises: placing a substrate in a deposition chamber; introducing metal monatomic into the deposition chamber, the metal monatomic moving towards the substrate through a gas flow carrier; and applying an electric field in the deposition chamber, the metal monatomic accelerating towards the substrate under the action of the electric field and depositing on the substrate. The application realizes the acceleration and directional deposition of the metal monatomic through the directional movement of the gas flow carrier and the electric field. The gas flow carrier can gather the metal monatomic in a certain area and move towards the substrate in a directional manner, has a certain acceleration effect, improves the collection rate of the metal monatomic on the substrate, and further increases the moving speed and kinetic energy of the metal monatomic in the gas flow carrier when the metal monatomic encounters the acceleration electric field, so that the energy of the metal monatomic is high when it contacts the substrate surface, thereby improving the binding force of the metal monatomic and the substrate material and improving the stability of the monatomic material.
[0079] In the description of the present specification, the description of the terms "some embodiments", "other embodiments", "ideal embodiments", and the like means that the specific features, structures, materials, or characteristics described in connection with the embodiments or examples are included in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example.
[0080] The technical features of the above embodiments can be combined in any manner. In order to make the description concise, all possible combinations of the technical features of the above embodiments are not described, but as long as the combinations of the technical features do not exist contradictions, they should be considered as the scope of the present application.
[0081] The above embodiments only express several implementation ways of the present application, and the description is relatively specific and detailed, but it should not be understood as a limitation to the patent scope of the application. It should be pointed out that for ordinary skilled persons in the art, several modifications and improvements can be made without departing from the concept of the present application, which all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application should be subject to the appended claims.
Claims
1. A method of metal monolayer deposition, characterized by, The method comprises: S1: placing a substrate in a deposition chamber; S2: introducing metal monomers into the deposition chamber, the metal monomers moving towards the substrate by means of a gas flow carrier; S3: applying an electric field in the deposition chamber, the metal monomers accelerating towards the substrate under the action of the electric field and depositing on the substrate. The substrate is one or more of a powdered metal, an oxide, and a nitride.
2. The metal monolayer deposition method of claim 1, wherein, The electric field is applied around or on the substrate.
3. The metal monolayer deposition method of claim 1, wherein, The electric field is a negative pressure, a positive pressure, or a high pressure that attracts the metal monomers.
4. The metal monolayer deposition method of claim 1, wherein, The voltage of the electric field is set to 1-1000 V.
5. The metal monolayer deposition method of claim 1, wherein, Before the step S1, a pretreatment process is performed on the substrate, the pretreatment process comprising:
6. The metal monolayer deposition method of claim 2, wherein, P1: ball milling the nano-powder according to the type of metal and the particle size; P2: cleaning the ball-milled nano-powder; and P3: vacuum ion beam bombardment of the cleaned nano-powder. In the step P2, the cleaning of the nano-powder comprises:
7. The metal monolayer deposition method of claim 6, wherein, ultrasonic cleaning of the nano-powder with ethanol for 1-60 min; alkali cleaning of the nano-powder with a composite alkaline detergent, the composite alkaline detergent being mixed with water at a volume ratio of 1:100 and then ultrasonically cleaned with the nano-powder for 1-20 min, wherein the composite alkaline detergent is configured by adding 0.5-6% potassium pyrophosphate and sodium metasilicate to sodium alkylnaphthalene sulfonate at 50-70°C; ultrasonic cleaning of the nano-powder with deionized water for 10-30 min for 2-5 times; vacuum drying of the nano-powder at 30-120°C and 0.05-0.2 MPa for 1-10 h; and plasma cleaning of the nano-powder at a power of 30-1000 W for 10-1000 s. The metal monomers comprise one or more of Pt, Pd, Ir, Ni, Co, Fe, Cu, Ag, Au, Mn, Ru, Rh, W, Mo, and Sn; and / or the substrate comprises one or more of Pt, Pd, Ir, Ni, Co, Fe, Cu, Ag, Au, Mn, Ru, Rh, W, Mo, Sn, Ti, Al, and oxides, nitrides, and carbon nitrides thereof.
8. The metal monolayer deposition method of claim 6, wherein, The initial vacuum degree of the equipment cavity is adjusted to 10 -5 ~ 10 -3 Pa before the vacuum ion beam bombardment in the step P3 2 , the setting time is 10~3000s, the setting beam current density is 0.5~5mA / cm 2 , and the setting ion beam energy is 500~5000eV, and after the adjustment is completed, the nano powder is subjected to vacuum ion beam bombardment according to the set parameters.
9. The metal monatomic deposition method of any one of claims 1-8, wherein, The monatomic deposition device deposits metal monomers on a substrate according to the metal monatomic deposition method of any one of claims 1-9.
10. A monatomic deposition apparatus, characterized by,