AU2021102707A4 - A controllable preparation method of metal palladium nanoparticle array - Google Patents
A controllable preparation method of metal palladium nanoparticle array Download PDFInfo
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- AU2021102707A4 AU2021102707A4 AU2021102707A AU2021102707A AU2021102707A4 AU 2021102707 A4 AU2021102707 A4 AU 2021102707A4 AU 2021102707 A AU2021102707 A AU 2021102707A AU 2021102707 A AU2021102707 A AU 2021102707A AU 2021102707 A4 AU2021102707 A4 AU 2021102707A4
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 85
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 16
- 239000002184 metal Substances 0.000 title claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 78
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 54
- 238000004544 sputter deposition Methods 0.000 claims abstract description 43
- 238000000137 annealing Methods 0.000 claims abstract description 40
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 39
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 21
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 abstract description 17
- 239000001257 hydrogen Substances 0.000 description 27
- 229910052739 hydrogen Inorganic materials 0.000 description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 20
- 235000012431 wafers Nutrition 0.000 description 14
- 238000003825 pressing Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- 230000004044 response Effects 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- -1 surface waves Chemical class 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 239000013077 target material Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32018—Glow discharge
- H01J37/32027—DC powered
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
- H01J37/3402—Gas-filled discharge tubes operating with cathodic sputtering using supplementary magnetic fields
- H01J37/3405—Magnetron sputtering
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Analytical Chemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
A controllable preparation method of metal Palladium nanoparticle array. The method
includes the following steps of: placing the selected substrate for sputtering in the
vacuum magnetron sputtering equipment, controlling the vacuum of the sputtering
room at 10-4 Pa, filling the sputtering room with shielding gas, adjusting the flowmeter
until the flow of the shielding gas is displayed as 10-15 seem; when the vacuum of
the magnetron sputtering equipment is 1-5 Pa, turning on the general power supply
for direct-current sputtering to make the target gradually ignited; when the target is
ignited, adjusting the slide valve to make the vacuum of the magnetron sputtering
equipment displayed as 0.5-7 Pa, controlling the power as 30-80 W for sputtering,
sputtering for 1-5 s; heating the obtained palladium continuous substrate in the
vacuum of 0.1-1 Torr; obtaining palladium nanoparticle array after annealing.
-1/6
FIG. 1
FIG. 3
Description
-1/6
FIG. 1
FIG. 3
The present invention relates to the technical field of materials, in particular to the controllable preparation method of metal palladium nanoparticle array.
A low-dimensional nanomaterial has many excellent properties compared to traditional block materials, such as size effect, surface effect, quantum confinement effect, Coulomb blockade and macro quantum tunnel effect, which plays an outstanding role in application fields such as sound, light, electricity, heat, catalysis and sensor. With excellent sensing properties, the low-dimensional nanomaterial is favored by scientists and engineers. After the structure of nanomaterial is modified, it can meet the demands of some applications to a certain degree. For example, as the size of the nanoparticle is reduced, the collective oscillation of electrons in the conduction band changes the electrical, optical and magnetic properties of the material. This property can also be significantly applied in gas sensor technology. With proper modifications on the structure of nanomaterial, the performance of the sensor can be greatly optimized. At present, common hydrogen sensors are mainly based on metal oxides, surface waves, metals and semiconductor films. The development of hydrogen sensor at room temperature has become a main development trend. The palladium nanoparticle array, one of the low dimensional nanomaterials, constructs a hydrogen sensor with the use of palladium nanoparticle and nanowire, becoming popular in this field. In 1866, T. Graham found that metal palladium could adsorb hydrogen to form metal hydride which contains a certain number of hydrogen atoms in the crystal lattice of the face-centered cubic (FCC) structure
of palladium. The chemical formula is PdHx. At room temperature, PdHx has two phases,
a phase and P phase. Although the crystal lattice maintains a face-centered cubic (FCC)
structure during the entire reaction between hydrogen and palladium, the constant and resistance values of the crystal lattice of palladium undergo a huge change which is mainly
caused by the phase change of PdHx. From a low concentration to the highest concentration of a phase, the crystal lattice constant of palladium only slightly changed. When the hydride gradually forms phases, the crystal lattice expands acutely, and the appearance of hydrogen atoms causes the electron transport in the oxide under the influence of scattering to a certain extent. Therefore, with the adsorption of hydrogen, the resistance value of the palladium material continues to increase. The adsorption of hydrogen by palladium is a reversible physico-chemical process and hydrogen atoms can diffuse rapidly in the palladium crystal lattice. Although currently there are many literature reports on hydrogen sensors at room temperature, it is not suitable for practical applications and mass production due to their relatively long response time. Among the currently used gas sensor alarm devices, the response time is a key factor influencing their practical applications. Therefore, a gas sensor that can quickly respond to the detected gas is of great significance to production and living.
The present invention aims at addressing the above-mentioned defects in the prior techniques and provides a controllable preparation method of palladium nanoparticles array with excellent performance. A controllable preparation method of metal palladium nanoparticle array can be operated according to the following steps: step 1: selecting a substrate for sputtering; step 2: preparing a palladium continuous film substrate; placing the substrate in a vacuum magnetron sputtering equipment, and when the vacuum in the vacuum magnetron sputtering equipment is controlled to be 10- Pa, filling the vacuum magnetron sputtering equipment with shielding gas and adjusting the flowmeter until the flow of shielding gas is -15 seem; when the vacuum of the magnetron sputtering equipment is 1-5 Pa, turning on the general power supply for direct-current sputtering to make the target gradually ignited; when the target is ignited, adjusting the slide valve to make the passage for the exhausted gas smaller, and slowing the exhausted gas down in order to make the vacuum of the magnetron sputtering equipment is 0.5-7 Pa, controlling the power within 30-80 W for sputtering with the sputtering time of 1-5 s; obtaining a palladium continuous film substrate;
step 3: annealing the substrate; heating the palladium continuous film substrate obtained in step 2 under the condition of a vacuum of 0.1-1 Torr, and heating the palladium continuous film substrate at a rate of 4-10 °C/min; increasing the temperature to 200-800 °C and continuing heating for 30-90 min, then obtaining a palladium nanoparticle array after annealing Further, the controllable preparation method of metal palladium nanoparticle array characterized in that before the preparation of palladium nanoparticle array, the substrate need to be ultrasonically cleaned by acetone, ethanol and deionized water in turn for 10-30 min, and then baked in air at a temperature of 40-60 °C for 20-30 min. Further, the controllable preparation method of metal palladium nanoparticle array characterized in that the substrate is a silicon/ silicon dioxide polished oxide wafer Further, the controllable preparation method of metal palladium nanoparticle array characterized in that the shielding gas is argon gas. Further, the controllable preparation method of metal palladium nanoparticle array characterized in that in the step 3, heat the palladium nanoparticle array substrate obtained in step 2 under the condition of a vacuum of1 MPa, and heat the palladium continuous film substrate at a rate of 4-10 °C /min; increasing the temperature to 350 °C and continuing heating for 20 min, a palladium nanoparticle array can then be obtained after annealing. The present invention adopts a standard magnetron sputtering method to sputter the metal palladium nanoparticle array on the silicon/silicon dioxide substrate, which composes of a gas sensitive material compared with traditional block palladium or continuous palladium film substrate. The metal nanoparticle array has a higher specific surface area and can absorb hydrogen faster and respond quickly. A sensor based on the gas-sensitive material which has better sensitivity, faster response speed and greater recovery performance can be massively applied in production and living to detect hydrogen leakage and provide safety protection.
FIG. 1 is a SEM view of the palladium nanoparticle array in Embodiment 4; FIG. 2 is a SEM view of the palladium nanoparticle array in Embodiment 5; FIG. 3 is a SEM view of the palladium nanoparticle array in Embodiment 6; FIG. 4 is a SEM view of the palladium nanoparticle array in Embodiment 7; FIG. 5 is a SEM view of the palladium nanoparticle array in Embodiment 8;
FIG. 6 is a SEM view of the palladium nanoparticle array in Embodiment 9; FIG. 7 is a SEM view of the palladium nanoparticle array in Embodiment 10; FIG. 8 is a SEM view of the palladium nanoparticle array in Embodiment 11; FIG. 9 is a SEM view of the palladium nanoparticle array in Embodiment 12; FIG. 10 is a SEM view of the palladium continuous film substrate in Embodiment 13; FIG. 11 is a hydrogen sensitive response curve of the palladium continuous film substrate in Embodiment 4; FIG. 12 is a hydrogen sensitive response curve of the palladium nanoparticle array in Embodiment 13.
In order to clarify the purposes, technical solutions and advantages of the present invention, the technical solutions in the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of them. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present invention. Embodiment 1: 1. Selecting the substrate: the P100 silicon/silicon dioxide polished oxide wafer was used as a substrate for sputtering in the experiment with a diameter of 99.5 mm, a thickness of 0.17 mm and the thickness of silicon dioxide of 0.001 mm. The polished silicon oxide wafer is cut into several substrates with a specification of 20 mmx10 mm, which is convenient for subsequent testing and packaging. P100 polished silicon oxide wafers are currently on sale in the market, such as the P100 polished silicon oxide wafer produced by Hengyang Transistor Co., Ltd. The address of the company is No. 7 Yijiatang, Baishazhou, Yanfeng District, Hengyang. The P100 silicon/silicon dioxide polished oxide wafer has no response to hydrogen; only a sample with palladium nanoparticle array sputtered on the substrate is a fine gas-sensitive material. 2. Cleaning the substrate: the P100 polished silicon oxide wafer cut into the
specification of 20 mm x 10 mm in step 1 is ultrasonically cleaned by acetone, ethanol
and deionized water in turn for 30 min, and then baked in air at a temperature of 60 °C for 20 min to obtain a clean and dry silicon/silicon dioxide substrate.
The cleaning agent used to clean P100 polished silicon dioxide wafer is analytically pure acetone, analytically pure anhydrous ethanol and deionized water. The ultrasonic apparatus used in ultrasonic cleaning is currently on sale in the market, such as the KQ-25ODE numerical-controlled ultrasonic cleaner produced by Kunshan Ultrasonic Instrument Co., Ltd. with power usually at 40-100 W. 3.Preparing a palladium continuous film substrate by adopting a standard direct current magnetron sputtering technology (1) Placing the sample: first turning on the vacuum indicator to check whether the vacuum magnetron sputtering equipment is in a vacuum; if it is in a vacuum, opening the V2 valve to deflate to make sure the atmospheric pressure in the vacuum magnetron sputtering equipment and the outside atmospheric pressure are the same; turning on the light in the vacuum magnetron sputtering equipment, and making sure that the manipulator is placed under the target damper, the positioning lock is unplugged and the shielding cover is raised; pressing "up" on the control panel to raise the shielding cover slowly to a proper position; cleaning the vacuum magnetron sputtering equipment and target position with a gauze dipped in anhydrous ethanol, and then placing and fixing the target material in the center of the target position; then fixing
the clean P100 polished silicon oxide substrate with a specification of 20 mmx 10 mm
obtained from step 2 on the sample holder and fixing the sample holder on the spinning disk; pressing "down" on the control panel to lower the shielding cover down slowly. (2) Exhausting into vacuum: closing V2, turning on the mechanical pump and opening the Vi valve to exhaust the air in the vacuum magnetron sputtering equipment and sample chamber; when the vacuum displayed by the vacuum indicator is below 15 Pa, closing the Vi valve, opening the electromagnetic closing valve, starting the molecular pump, opening the slide valve G, and continuing to exhaust the vacuum magnetron sputtering equipment and sample chamber for 3 hours. (3) The sputtering process: when the vacuum in the vacuum magnetron sputtering equipment reaches 10-4 Pa, turning on the parameter-controlling computer to start sputtering; filling the vacuum magnetron sputtering equipment with argon gas, opening the main valve of gas cylinder, V5 and V3 in turn, turning on the flow indicator and the control gear of gas flow valve, and adjusting the flowmeter until the gas flow is displayed as 12 seem.; adjusting the slide valve until the vacuum indicator displays the vacuum as 3 Pa, which is conducive to ignition; then turning on the general power supply for direct-current sputtering, pressing the direct-current sputtering switch, adjusting the current-voltage knob, and observing the target ignited gradually; when the target is ignited, adjusting the slide valve until the vacuum indicator displays as 5 Pa, and adjusting the current-voltage knob until the power is 70 W; using the computer to control the position of the sample holder, and seeing the reaction time is 1 s. (4) The closing process: after the sputtering is completed according to "(3) The sputtering process", adjusting the power to zero and adjusting the current-voltage knob to zero; stopping sending argon gas to the vacuum magnetron sputtering equipment, and closing the control gear of gas flow valve, V3 valve, V5 valve and the main valve of gas cylinder in turn; continuing to close in turn the stepper motor, slide valve G, molecular pump, electromagnetic closing valve and mechanical pump; opening the V2 valve to deflate to make sure the atmospheric pressure in the vacuum magnetron sputtering equipment and the outside atmospheric pressure are the same; pressing "up" on the control panel to raise the shielding cover slowly to a proper position; taking out the sputtered sample of palladium continuous film substrate. 4. Annealing the substrate: placing the palladium continuous film substrate obtained from step 3 into the center of the heating zone of the tubular furnace, sealing the tubular furnace mouth, and starting the mechanical pump button; exhausting the inner side of tubular furnace to 0.1 Torr, and heating at a rate of 4 °C/min to 800 °C, while maintaining for 60 min; after annealing, obtaining a palladium nanoparticle array. Embodiment 2: 1. Selecting the substrate: the P100 silicon/silicon dioxide polished oxide wafer was used as a substrate for sputtering in the experiment with a diameter of 100 mm, a thickness of 0.16 mm and the thickness of silicon dioxide of 0.00095 mm. The polished silicon oxide wafer is cut into several substrates with a specification of 20 mmx10 mm. 2. Cleaning the substrate: the P100 polished silicon oxide wafer cut into the specification of 20 mm x 10 mm in step 1 is ultrasonically cleaned by acetone, ethanol and deionized water in turn for 20 min, and then baked in air at a temperature of 40 °C for 25 min to obtain a clean and dry silicon/silicon dioxide substrate.
3. Preparing a palladium continuous film substrate by adopting a standard direct current magnetron sputtering technology (1) Placing the sample: first turning on the vacuum indicator to check whether the vacuum magnetron sputtering equipment is in a vacuum; if it is in a vacuum, opening the V2 valve to deflate to make sure the atmospheric pressure in the vacuum magnetron sputtering equipment and the outside atmospheric pressure are the same; turning on the light in the vacuum magnetron sputtering equipment, and making sure that the manipulator is placed under the target damper, the positioning lock is unplugged and the shielding cover is raised; pressing "up" on the control panel to raise the shielding cover slowly to a proper position; cleaning the vacuum magnetron sputtering equipment and target position with a gauze dipped in anhydrous ethanol, and then placing and fixing the target material in the center of the target position; then fixing
the clean P100 polished silicon oxide substrate with a specification of 20 mmx 10 mm
obtained from step 2 on the sample holder and fixing the sample holder on the spinning disk; pressing "down" on the control panel to lower the shielding cover down slowly. (2) Exhausting into vacuum: closing V2, turn on the mechanical pump and open the Vi valve to exhaust the air in the vacuum magnetron sputtering equipment and sample chamber; when the vacuum displayed by the vacuum indicator is below 15 Pa, closing the Vi valve, opening the electromagnetic closing valve, starting the molecular pump, opening the slide valve G, and continuing to exhaust the vacuum magnetron sputtering equipment and sample chamber for 4 hours. (3) The sputtering process: when the vacuum in the vacuum magnetron sputtering equipment reaches 10-4 Pa, turning on the parameter-controlling computer to start sputtering; filling the vacuum magnetron sputtering equipment with argon gas, opening the main valve of gas cylinder, V5 and V3 in turn, turning on the flow indicator and the control gear of gas flow valve, and adjusting the flowmeter until the gas flow is displayed as 10 seem; adjusting the slide valve until the vacuum indicator displays the vacuum as 3 Pa, which is conducive to ignition; then turning on the general power supply for direct-current sputtering, pressing the direct-current sputtering switch, adjusting the current-voltage knob, and seeing the target ignited gradually; when the target is ignited, adjusting the slide valve until the vacuum indicator displays as 0.5 Pa, and adjusting the current-voltage knob until the power is 80 W; using the computer to control the position of the sample holder, and seeing the reaction time is 3 s. (4) The closing process: after the sputtering is completed according to "(3) The sputtering process", adjusting the power to zero and adjusting the current-voltage knob to zero; stopping sending argon gas to the vacuum magnetron sputtering equipment, and closing the control gear of gas flow valve, V3 valve, V5 valve and the main valve of gas cylinder in turn; continuing to close in turn the stepper motor, slide valve G, molecular pump, electromagnetic closing valve and mechanical pump; opening the V2 valve to deflate to make sure the atmospheric pressure in the vacuum magnetron sputtering equipment and the outside atmospheric pressure are the same; pressing "up" on the control panel to raise the shielding cover slowly to a proper position; taking out the sputtered sample of palladium continuous film substrate. 4. Annealing the substrate: placing the palladium continuous film substrate obtained from step 3 into the center of the heating zone of the tubular furnace, sealing the tubular furnace mouth, and starting the mechanical pump button; exhausting the inner side of tubular furnace to 0.5 Torr, and heating at a rate of 6 °C/min to 400 °C, while maintaining for 30 min; after annealing, obtaining a palladium nanoparticle array. Embodiment 3: 1. Selecting the substrate: the P100 silicon/silicon dioxide polished oxide wafer was used as a substrate for sputtering in the experiment with a diameter of 100.5 mm, a thickness of 0.18 mm and the thickness of silicon dioxide of 0.00105 mm. The polished silicon oxide wafer is cut into several substrates with a specification of 20 mmx10 mm. 2. Cleaning the substrate: the P100 polished silicon oxide wafer cut into the specification of 20 mm x 10 mm in step 1 is ultrasonically cleaned by acetone, ethanol and deionized water in turn for 10 min, and then baked in air at a temperature of 50 °C for 30 min to obtain a clean and dry silicon/silicon dioxide substrate. 3. Preparing a palladium continuous film substrate by adopting a standard direct current magnetron sputtering technology (1) Placing the sample: first turning on the vacuum indicator to check whether the vacuum magnetron sputtering equipment is in a vacuum; if it is in a vacuum, opening
Q the V2 valve to deflate to make sure the atmospheric pressure in the vacuum magnetron sputtering equipment and the outside atmospheric pressure are the same; turning on the light in the vacuum magnetron sputtering equipment, and making sure that the manipulator is placed under the target damper, the positioning lock is unplugged and the shielding cover is raised; pressing "up" on the control panel to raise the shielding cover slowly to a proper position; cleaning the vacuum magnetron sputtering equipment and target position with a gauze dipped in anhydrous ethanol, and then placing and fixing the target material in the center of the target position; then fixing the clean P100 polished silicon oxide substrate with a specification of 20 mmx 10 mm obtained from step 2 on the sample holder and fixing the sample holder on the spinning disk; pressing "down" on the control panel to lower the shielding cover down slowly. (2) Exhausting into vacuum: closing V2, turning on the mechanical pump and opening the Vi valve to exhaust the air in the vacuum magnetron sputtering equipment and sample chamber; when the vacuum displayed by the vacuum indicator is below 15 Pa, closing the Vi valve, opening the electromagnetic closing valve, starting the molecular pump, opening the slide valve G, and continuing to exhaust the vacuum magnetron sputtering equipment and sample chamber for 4 hours. (3) The sputtering process: when the vacuum in the vacuum magnetron sputtering equipment reaches 10-4 Pa, turning on the parameter-controlling computer to start sputtering; filling the vacuum magnetron sputtering equipment with argon gas, opening the main valve of gas cylinder, V5 and V3 in turn, turning on the flow indicator and the control gear of gas flow valve, and adjusting the flowmeter until the gas flow is displayed as 15 seem; adjusting the slide valve until the vacuum indicator displays the vacuum as 1 Pa, which is conducive to ignition; then turning on the general power supply for direct-current sputtering, pressing the direct-current sputtering switch, adjusting the current-voltage knob, and seeing the target ignited gradually; when the target is ignited, adjusting the slide valve until the vacuum indicator displays as 7 Pa, and adjusting the current-voltage knob until the power is 30 W; using the computer to control the position of the sample holder, and seeing the reaction time is 5 s. (4) The closing process: after the sputtering is completed according to "(3) The sputtering process", adjusting the power to zero and adjust the current-voltage knob to zero; stopping sending argon gas to the vacuum magnetron sputtering equipment, and closing the control gear of gas flow valve, V3 valve, V5 valve and the main valve of gas cylinder in turn; continuing to close in turn the stepper motor, slide valve G, molecular pump, electromagnetic closing valve and mechanical pump; opening the V2 valve to deflate to make sure the atmospheric pressure in the vacuum magnetron sputtering equipment and the outside atmospheric pressure are the same; pressing "up" on the control panel to raise the shielding cover slowly to a proper position; taking out the sputtered sample of palladium continuous film substrate. 4. Annealing the substrate: placing the palladium continuous film substrate obtained from step 3 into the center of the heating zone of the tubular furnace, sealing the tubular furnace mouth, and starting the mechanical pump button; exhausting the inner side of tubular furnace to 1 Torr, and heating at a rate of 10 °C/min to 200 °C, while maintaining for 90 min; after annealing, obtaining a palladium nanoparticle array. Embodiment 4: The steps in the present embodiment are the same as those in the Embodiment 1, except that the annealing temperature is 200 °C in the step of annealing the substrate. Embodiment 5: The steps in the present embodiment are the same as those in the Embodiment 1, except that the annealing temperature is 250 °C in the step of annealing the substrate. Embodiment 6: The steps in the present embodiment are the same as those in the Embodiment 1, except that the annealing temperature is 300 °C in the step of annealing the substrate. Embodiment 7: The steps in the present embodiment are the same as those in the Embodiment 1, except that the annealing temperature is 350 °C in the step of annealing the substrate. Embodiment 8: The steps in the present embodiment are the same as those in the Embodiment 1, except that the annealing temperature is 400 °C in the step of annealing the substrate. Embodiment 9: The steps in the present embodiment are the same as those in the Embodiment 1, except that the annealing temperature is 500 °C in the step of annealing the substrate. Embodiment 10: The steps in the present embodiment are the same as those in the Embodiment 1,
1(n except that the annealing temperature is 600 °C in the step of annealing the substrate. Embodiment 11: The steps in the present embodiment are the same as those in the Embodiment 1, except that the annealing temperature is 700 °C in the step of annealing the substrate. Embodiment 12: The steps in the present embodiment are the same as those in the Embodiment 1, except that the annealing temperature is 800 °C in the step of annealing the substrate Embodiment 13: The steps in the present embodiment are the same as those in the Embodiment 1, except that there is no annealing step in the embodiment. The magnetron sputtering principle refers to that under the influence of an electric field, an electron flies at an accelerating speed towards the substrate and then collides with argon atom, ionizing a large number of argon ions and electrons, the latter fly to the substrate. As the argon ions bombard the target at an accelerating speed under the influence of the electric field, they sputter a large number of atoms with neutral target atoms (or molecules) depositing on the substrate to form a film. Under the influence of the Lorentz Force of the magnetic field in the process of flying to the substrate at an accelerating speed, the secondary electrons are confined in the plasma region near the target area which has a high density of the plasma; Due to the influence of the magnetic field, the secondary electrons follow a circular motion around the target area; with a long motion path, the electrons continuously collide with argon atoms to ionize a large number of argon ions, bombarding the target during the motion; after multiple collisions, when the energy of the electrons gradually decreases, the electrons can get rid of the restraint of the magnetic force lines and move away from the target and finally deposit on the substrate. The magnetron sputtering changes the direction of motion of electrons by the confinement of the magnetic field and the extension of the motion path of electrons so as to improve the ionization rate of the working gas and make efficient use of the electron energy. The magnetron sputtering is characterized by a rapid film formation, a low temperature substrate, the good adhesiveness of the film and a possible large-area plating. The direct-current magnetron sputtering equipment used in the present invention is currently on sale in the market, such as the JGPH50 high vacuum magnetron sputtering equipment produced by Shenyang Scientific Instrument Development Center Co., Ltd., Chinese Academy of Sciences. The heating equipment used to heat the substrate is the tubular furnace on the market, such as the CVD (G)-06/50/2 high-temperature tubular furnace produced by Hefei Rixin High Temperature Technology Co., Ltd. Example 1:
As shown in Table 1, Embodiments 1', 2' and 3' are continuous films obtained by
sputtering according to the step 2 method; Comparative Embodiment 1 is a palladium continuous film obtained by direct-current magnetron sputtering with a sputtering power of 20 W, a sputtering pressure of 0.6-3 Pa, and a sputtering time of 10-60 s. Comparative Embodiment 2 is a palladium continuous film obtained by chemical vapor deposition; the preparation of the film is conducted in a high vacuum magnetron sputtering equipment with a magnetron, a cluster source of plasma gas. The output power during the deposition is 50 W, and the deposition pressure is 120 Pa. Detected array thicknesses and hydrogen responding times related to each thicknesses are shown in Table 1. Table 1 Film Thickness after the Hydrogen Responding sputtering Time
Embodiment 1' 10 nm 140-170s
Embodiment 2' ~34 nm 160-180 s
Embodiment 3' ~56 nm 170-210 s
Comparative Embodiment ~100 nm 190-220s
1'
Comparative Embodiment ~150 nm 200-230s
2'
As shown in Table 1, if the palladium continuous film substrate is prepared according to the sputtering method of the present invention, the hydrogen responding time is shorter.
Example 2 As the present example adds an annealing step based on Example 1, obtained array thicknesses and hydrogen responding times related to each thicknesses are shown in Table 2. Table 2
Film Thickness after the Hydrogen Responding
sputtering Time Embodiment -10nm 30-50s
Embodiment 2 ~34 nm 35-70s Embodiment -56nm 45-80s
Based on Example 1, the example adopts the method of the present invention, namely sputtering first, then after annealing, obtaining the thicknesses of palladium nanoparticle array and corresponding hydrogen responding time. According to FIG. 2, palladium nanoparticle array prepared through the present invention method has a shorter hydrogen responding time. Example 3: Please refer to FIG. 1-10, under the same conditions, if the annealing temperature is different,the pattern of palladium nanoparticle array is obviously different. When the
annealing temperature is 350 °C, the gaps among palladium nanoparticle array
become larger, resulting in better hydrogen absorption of the array in a hydrogen environment and lattice expansion of the palladium nanoparticle array; accordingly, the resistance of palladium nanoparticle array is rapidly changed and the array rapidly respond to hydrogen with a responding time of 30-45 s. When the annealing temperature is above 400 °C, the gaps among palladium nanoparticle array expand so that the responding time to hydrogen is longer. Please refer to FIG. 1-10, the response time to hydrogen of palladium continuous film substrate obtained without annealing is 140-210 s; when the annealing temperature is
200 °C, the response time to hydrogen of the obtained palladium nanoparticle array
is 30-80 s. It is clear that including the annealing step in the present invention method largely reduces the responding time to hydrogen.
1'2
Finally, the above embodiments are only used to explain technical solutions of the present invention and are not intended to limit the present invention; although the present invention has been described in detail with reference to the above embodiments, technicians of ordinary skill in the art should understand that it is still possible to modify the technical solutions recorded in the above embodiments, or equivalently replace some of the technical features; any modification or equivalent replacement shall be made to ensure the essence of the corresponding technical solutions are included within the spirit and scope of all technical solutions of embodiments in the present invention.
1 A
Claims (5)
- What is claimed is: 1. A controllable preparation method of metal palladium nanoparticle array, characterized by comprising the steps of: step 1: selecting a substrate for sputtering; step 2: preparing a palladium continuous film substrate; placing the substrate in a vacuum magnetron sputtering equipment, and when the vacuum in the vacuum magnetron sputtering equipment is controlled to be 10-4 Pa, filling the vacuum magnetron sputtering equipment with shielding gas and adjusting the flowmeter until the flow of shielding gas is -15 seem; when the vacuum of the magnetron sputtering equipment is 1-5 Pa, turning on the general power supply for direct-current sputtering to make the target gradually ignited; when the target is ignited, adjusting the slide valve to make the passage for the exhausted gas smaller, and slowing the exhausted gas down in order to make the vacuum of the magnetron sputtering equipment is 0.5-7 Pa, controlling power within 30-80 W for sputtering with the sputtering time of 1-5 s; obtaining a palladium continuous film substrate; step 3: annealing the substrate; heating the palladium continuous film substrate obtained in step 2 under the condition of a vacuum of 0.1-1 Torr, and heating the palladium continuous film substrate at a rate of 4-10 °C/min; increasing the temperature to 200-800 °C and continuing heating for 30-90 min, obtaining palladium nanoparticle array after annealing.
- 2. The controllable preparation method of metal palladium nanoparticle array of claim 1, characterized in that before the preparation of palladium nanoparticle array, ultrasonically cleaning the substrate by acetone, ethanol and deionized water in turn for 10-30 minu, and then baking the substrate in air at a temperature of 40-60 °C for 20-30 min.
- 3. The controllable preparation method of metal palladium nanoparticle array of claim 1, characterized in that the substrate is a silicon/ silicon dioxide polished oxide wafer.
- 4. The controllable preparation method of metal palladium nanoparticle array of claim 1, characterized in that the shielding gas is argon gas.
- 5. The controllable preparation method of metal palladium nanoparticle array of claim 1, characterized in that in step 3, heating the palladium continuous film substrate obtained from step 2 in a vacuum of 0.1 Torr, and heating the palladium continuous film substrate at a rate of 4 °C/min; increasing temperature to to 350 °C and continuing heating for 60 min, then obtaining a palladium nanoparticle array after annealing.-1/6- May 2021 2021102707FIG. 1FIG. 2FIG. 3FIG. 5 FIG. 4 -2/6-FIG. 7 FIG. 6 -3/6-FIG. 9 FIG. 8 -4/6--5/6-FIG. 11 FIG. 10-6/6-FIG. 12
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