A method for preparing a gold nanocylinder array

Abstract

The application provides a preparation method of gold nanocylinder array and belongs to the technical field of photoelectric materials. The preparation method comprises the following steps: preparing a polystyrene microsphere monolayer film on the upper surface of a substrate, reducing the diameter of the polystyrene microsphere by etching to obtain an etched substrate; plating an aluminum oxide film on the upper surface of the etched substrate in an atomic layer deposition mode, removing the second polystyrene microsphere and the aluminum oxide film on the surface of the second polystyrene microsphere, retaining the remaining aluminum oxide film on the upper surface of the etched substrate, and obtaining an aluminum oxide plating substrate; plating a gold film on the upper surface of the aluminum oxide plating substrate in a magnetron sputtering mode, removing the remaining aluminum oxide film and the gold film on the surface of the remaining aluminum oxide film, and obtaining a gold nanocylinder array on the upper surface of the substrate. The polystyrene microsphere monolayer film is used to replace the traditional photolithography technology to prepare the gold nanocylinder array, the preparation method is simple, the production cost is low, the preparation efficiency is high, and large-scale mass production of the gold nanocylinder array can be realized.

Description

Technical Field

[0001] This invention belongs to the field of optoelectronic materials technology, specifically relating to a method for preparing a gold nanocylinder array. Background Technology

[0002] Nanoarrays, as periodic surface structures, are widely used in various fields due to their unique optical properties. Nanoarrays made of various noble metals and with diverse morphologies have been extensively applied in optics, solar cells, energy storage, and biosensing. Currently, the main method for fabricating high-quality nanoarrays is photolithography, such as conventional photolithography, electron beam lithography, and nanoimprint lithography. While photolithography can produce high-precision and uniform nanoarrays, its complex process parameters and high production costs limit its application to small-scale production of nanopore arrays, hindering large-scale mass production. Summary of the Invention

[0003] The purpose of this invention is to provide a method for preparing gold nanocylinder arrays. This invention uses a polystyrene microsphere monolayer film instead of traditional photolithography to prepare gold nanocylinder arrays. The preparation method is simple, has low production cost, high preparation efficiency, and enables large-scale mass production of gold nanocylinder arrays.

[0004] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0005] This invention provides a method for fabricating gold nanocylinder arrays without photolithography, comprising the following steps:

[0006] A polystyrene microsphere monolayer film is prepared on the upper surface of a substrate, wherein the polystyrene microsphere monolayer film is formed by first polystyrene microspheres in contact with each other;

[0007] The first polystyrene microsphere in a substrate with a polystyrene microsphere monolayer film on the upper surface is etched into a second polystyrene microsphere to obtain an etched substrate. The diameter of the second polystyrene microsphere is smaller than the diameter of the first polystyrene microsphere.

[0008] An aluminum oxide film is deposited on the upper surface of the etched substrate by atomic layer deposition. The aluminum oxide film on the surface of the second polystyrene microspheres and the second polystyrene microspheres is removed, while the remaining aluminum oxide film on the upper surface of the etched substrate is retained, resulting in an aluminum oxide-coated substrate.

[0009] A gold film is deposited on the upper surface of the alumina-coated substrate by magnetron sputtering. The remaining alumina film and the gold film on the surface of the remaining alumina film are removed to obtain the gold nanocylinder array on the upper surface of the substrate.

[0010] Preferably, the substrate includes at least one of a glass substrate, a silicon substrate, a silicon carbide substrate, and a quartz substrate.

[0011] Preferably, the method for preparing a polystyrene microsphere monolayer film on the upper surface of the substrate includes: forming a polystyrene microsphere dispersion film on a water surface by gas-liquid self-assembly; adding sodium dodecyl sulfate solution to the edge of the polystyrene microsphere dispersion film to form a polystyrene microsphere monolayer film on the water surface; and transferring the polystyrene microsphere monolayer film from the water surface to the upper surface of the substrate.

[0012] Preferably, the diameter of the first polystyrene microsphere is 180–220 nm.

[0013] Preferably, the sodium dodecyl sulfate solution has a mass fraction of 1-3%.

[0014] Preferably, the diameter of the second polystyrene microsphere is 130–170 nm.

[0015] Preferably, the etching conditions are: stage angle 0–5°; oxygen flow rate 5–10 sccm; etching time 10–20 min; and intracavitary pressure 6 × 10⁻⁶. -4 ~8×10 -4 Pa; plate voltage 450-500V; accelerating voltage 100-120V; beam current 180-200mA.

[0016] Preferably, the thickness of the alumina film is 70-80 nm.

[0017] Preferably, the deposition rate of the alumina film is:

[0018] Preferably, the thickness of the gold film is 45–55 nm; the deposition rate of the gold film is…

[0019] This invention provides a method for fabricating a gold nanocylinder array without photolithography, comprising the following steps: preparing a polystyrene microsphere monolayer film on the upper surface of a substrate, wherein the polystyrene microsphere monolayer film is formed by first polystyrene microspheres in contact with each other; etching the first polystyrene microspheres in the substrate with the polystyrene microsphere monolayer film on the upper surface into second polystyrene microspheres to obtain an etched substrate, wherein the diameter of the second polystyrene microspheres is smaller than the diameter of the first polystyrene microspheres; depositing an alumina film on the upper surface of the etched substrate by atomic layer deposition, removing the second polystyrene microspheres and the alumina film on the surface of the second polystyrene microspheres, retaining the remaining alumina film on the upper surface of the etched substrate to obtain an alumina-plated substrate; depositing a gold film on the upper surface of the alumina-plated substrate by magnetron sputtering, removing the remaining alumina film and the gold film on the surface of the remaining alumina film, thereby obtaining the gold nanocylinder array on the upper surface of the substrate. In this invention, a polystyrene microsphere monolayer film is used as a template for preparing gold nanocylinder arrays. The polystyrene microspheres have mature synthesis conditions, stable physicochemical properties, and strong size reduction capabilities. At the same time, this invention uses a template method to prepare gold nanocylinder arrays, eliminating the traditional photolithography step, simplifying the preparation method of gold nanocylinder arrays, improving preparation efficiency, and enabling large-scale mass production of gold nanocylinder arrays. Attached Figure Description

[0020] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0021] Figure 1 This is a cross-sectional view of the fabrication process of gold nanocylinder arrays, where 1-glass substrate; 2-polystyrene microspheres; 3-alumina film; 4-gold film;

[0022] Figure 2 Top view of a polystyrene microsphere monolayer film;

[0023] Figure 3 Top view of the etched polystyrene microsphere substrate;

[0024] Figure 4 This is a top view of the glass substrate after it has been coated with alumina.

[0025] Figure 5 Top view of the glass substrate after the polystyrene microspheres have been removed;

[0026] Figure 6 A top view of the gold-plated glass substrate;

[0027] Figure 7 This is a top view of the glass substrate after the aluminum oxide has been removed. Detailed Implementation

[0028] This invention provides a method for fabricating gold nanocylinder arrays without photolithography, comprising the following steps:

[0029] A polystyrene microsphere monolayer film is prepared on the upper surface of a substrate, wherein the polystyrene microsphere monolayer film is formed by first polystyrene microspheres in contact with each other;

[0030] The first polystyrene microsphere in a substrate with a polystyrene microsphere monolayer film on the upper surface is etched into a second polystyrene microsphere to obtain an etched substrate. The diameter of the second polystyrene microsphere is smaller than the diameter of the first polystyrene microsphere.

[0031] An aluminum oxide film is deposited on the upper surface of the etched substrate by atomic layer deposition. The aluminum oxide film on the surface of the second polystyrene microspheres and the second polystyrene microspheres is removed, while the remaining aluminum oxide film on the upper surface of the etched substrate is retained, resulting in an aluminum oxide-coated substrate.

[0032] A gold film is deposited on the upper surface of the alumina-coated substrate by magnetron sputtering. The remaining alumina film and the gold film on the surface of the remaining alumina film are removed to obtain the gold nanocylinder array on the upper surface of the substrate.

[0033] In this invention, unless otherwise specified, all raw materials used are commercially available products well known to those skilled in the art or prepared using methods well known to those skilled in the art.

[0034] This invention prepares a polystyrene microsphere monolayer film on the upper surface of a substrate, wherein the polystyrene microsphere monolayer film is formed by first polystyrene microspheres in contact with each other. In this invention, the substrate preferably includes at least one of a glass substrate, a silicon substrate, a silicon carbide substrate, and a quartz substrate, more preferably a glass substrate or a silicon carbide substrate. Before preparing the polystyrene microsphere monolayer film on the upper surface of the substrate, this invention preferably washes the substrate; the washing reagents are preferably acetone, ethanol, and water in sequence. The washing in this invention is preferably performed under ultrasonic conditions; the washing time for each reagent is preferably 8–15 min, more preferably 10 min. This invention removes impurities from the substrate surface through washing. In this invention, the method for preparing the polystyrene microsphere monolayer film on the upper surface of the substrate preferably includes: forming a polystyrene microsphere dispersion film on a water surface using a gas-liquid self-assembly method; adding sodium dodecyl sulfate solution dropwise to the edge of the polystyrene microsphere dispersion film to form a polystyrene microsphere monolayer film on the water surface; and transferring the polystyrene microsphere monolayer film from the water surface to the upper surface of the substrate. In this invention, polystyrene microspheres and a dispersant are preferably mixed to obtain a diluted polystyrene microsphere solution. The diluted polystyrene microsphere solution is then added dropwise to water using a pipette, forming a polystyrene microsphere monolayer film on the water surface through gas-liquid self-assembly. The polystyrene microspheres and dispersant are preferably mixed under ultrasonic conditions; the ultrasonication time is preferably 3 minutes. In this invention, the dispersant preferably comprises ethanol and water, and the volume ratio of ethanol to water is preferably 1-2:1-3, more preferably 1:1. The mass fraction of polystyrene microspheres in the diluted polystyrene microsphere solution is preferably 1-5%, more preferably 1.5-5%. In this invention, the mass fraction of sodium dodecyl sulfate solution is preferably 1-5%, more preferably 2%. In this invention, sodium dodecyl sulfate solution is added dropwise to the edge of the polystyrene microsphere dispersion film, resulting in a denser arrangement of the polystyrene microsphere monolayer film. In this invention, a cleaned substrate is preferably submerged underwater, and the polystyrene microsphere monolayer film is slowly retrieved, allowing the polystyrene microsphere monolayer film to adhere to the substrate, thus completing the transfer of the polystyrene microsphere monolayer film from the water surface to the upper surface of the substrate. After the transfer of the polystyrene microsphere monolayer film, the substrate with the attached polystyrene microsphere monolayer film is preferably dried; the drying is preferably carried out in an oven; the drying temperature is preferably 50-80°C, more preferably 60°C; the drying time is preferably 30-60 minutes, more preferably 30 minutes. This invention achieves complete evaporation of moisture through drying, forming a densely packed polystyrene microsphere monolayer film on the substrate surface. The polystyrene microsphere monolayer film of this invention is formed by first polystyrene microspheres in contact with each other; the diameter of the first polystyrene microspheres is preferably 180-220 nm, more preferably 200 nm.

[0035] After obtaining a substrate with a polystyrene microsphere monolayer film on its upper surface, the present invention etches the first polystyrene microsphere in the substrate with the polystyrene microsphere monolayer film on its upper surface into a second polystyrene microsphere, obtaining an etched substrate, wherein the diameter of the second polystyrene microsphere is smaller than the diameter of the first polystyrene microsphere. In the present invention, the etching conditions are preferably as follows: the stage angle is preferably 0–5°, more preferably 0°; the oxygen flow rate is preferably 5–10 sccm, more preferably 10 sccm; the etching time is preferably 10–20 min, more preferably 10 min; and the cavity pressure is preferably 6 × 10⁻⁶. -4 ~8×10 -4 Pa, more preferably 8 × 10 Pa -4 Pa; the plate voltage is preferably 450-500V, more preferably 500V; the accelerating voltage is preferably 100-120V, more preferably 100V; the beam current is preferably 180-200mA, more preferably 200mA. The diameter of the second polystyrene microsphere in this invention is preferably 130-170nm, more preferably 150nm.

[0036] After obtaining the etched substrate, this invention deposits an alumina film on the upper surface of the etched substrate using atomic layer deposition (ALD). The alumina film on the surface of the second polystyrene microspheres and the second polystyrene microspheres is removed, leaving the remaining alumina film on the upper surface of the etched substrate, resulting in an alumina-coated substrate. This invention uses atomic layer deposition to deposit an alumina film on the upper surface of the etched substrate, obtaining a substrate loaded with an alumina-coated film. In this invention, the preferred deposition rate of the alumina film is... More preferably In this invention, the thickness of the alumina film is preferably 70-80 nm, more preferably 75 nm. After obtaining the substrate loaded with the alumina film, this invention preferably immerses the substrate loaded with the alumina film in chloroform and allows it to stand. After standing, it is ultrasonically treated in chloroform to remove the alumina film on the surface of the second polystyrene microspheres. After the treatment, the substrate with the alumina film removed from the surface of the second polystyrene microspheres is washed and dried sequentially to obtain the alumina-coated substrate. In this invention, the standing time is preferably 20-30 h, more preferably 24 h; the ultrasonic treatment time is preferably 10-30 min, more preferably 30 min. In this invention, the washing preferably includes sequential alcohol washing and water washing; the reagent used for alcohol washing is preferably ethanol, and the alcohol washing time is preferably 10-15 min, more preferably 10 min; the reagent used for water washing is preferably deionized water, and the water washing time is preferably 10-15 min, more preferably 10 min. In this invention, the drying is preferably carried out in an oven; the drying temperature is preferably 60–80°C, more preferably 80°C; and the drying time is preferably 30–40 min, more preferably 30 min. This invention removes chloroform from the substrate surface through drying.

[0037] After obtaining an alumina-coated substrate, this invention deposits a gold film on the upper surface of the alumina-coated substrate using magnetron sputtering. The remaining alumina film and the gold film on its surface are then removed, resulting in the gold nanocylinder array on the upper surface of the substrate. This invention uses magnetron sputtering to deposit a gold film on the upper surface of the alumina-coated substrate to obtain a glass substrate loaded with a gold film. In this invention, the preferred gold film deposition rate is... More preferably In this invention, the thickness of the gold film is preferably 45-55 nm, more preferably 50 nm. After obtaining the glass substrate loaded with the gold film, this invention preferably immerses the glass substrate loaded with the gold film in a phosphoric acid solution and allows it to stand to remove the remaining alumina film and the gold film on the surface of the remaining alumina film. In this invention, the mass fraction of the phosphoric acid solution is preferably 3-5%, more preferably 5%. In this invention, the standing temperature is preferably 50-70°C, more preferably 70°C; the standing time is preferably 3-6 min, more preferably 5 min.

[0038] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0039] The glass substrate used in this embodiment has a diameter of 4 inches;

[0040] The polystyrene microsphere dispersion used in the examples contained 5% polystyrene microspheres by mass, and the polystyrene microspheres had a particle size of 200 nm. They were purchased from Shanghai Huizhi Biotechnology Co., Ltd.

[0041] Figure 1 This is a cross-sectional view of the fabrication process of the gold nanocylinder array, where 1 is a glass substrate; 2 is a polystyrene microsphere; 3 is an alumina film; and 4 is a gold film.

[0042] Example 1

[0043] (1) The glass substrate was sequentially immersed in acetone, ethanol, and deionized water, and sonicated for 10 minutes in each solution to remove impurities from the surface of the glass substrate. 200 μL of polystyrene microsphere dispersion, 300 μL of ethanol, and 300 μL of deionized water were mixed in a small reagent bottle and sonicated for 3 minutes to form a uniformly dispersed diluent. The diluent was then added dropwise to a quartz container containing deionized water using a pipette, forming a polystyrene microsphere monolayer on the water surface through gas-liquid self-assembly. 0.2 mL of 2% sodium dodecyl sulfate solution was then added dropwise to the edge of the polystyrene microsphere monolayer to further densify the membrane. Finally, the clean glass substrate was submerged in the water, and the polystyrene microsphere monolayer was slowly lifted out, allowing the polystyrene microsphere monolayer to adhere to the glass substrate. Next, the glass substrate with the polystyrene microsphere monolayer film attached was placed in an oven and kept at 60°C for 30 minutes to allow the moisture to evaporate completely, thus forming a densely packed polystyrene microsphere monolayer film on the surface of the glass substrate. Figure 1 (a) and Figure 2 As shown.

[0044] (2) A glass substrate with a polystyrene microsphere monolayer film on its upper surface was placed in a reactive ion etching (RIE) machine for etching to reduce the size of the polystyrene microspheres. The etching conditions were as follows: stage angle 0°; oxygen flow rate 10 sccm; etching time 10 min; cavity pressure 8 × 10⁻⁶. -4 Pa; plate voltage is 500V; accelerating voltage is 100V; beam current is 200mA. After etching, an etched substrate is obtained. The polystyrene microspheres on the surface of the etched substrate have a diameter of 150nm, such as... Figure 1 (b) and Figure 3 As shown.

[0045] (3) The etched substrate is placed in an atomic layer deposition apparatus to deposit a layer of aluminum oxide with a thickness of 75 nm, at a deposition rate of [missing information]. A glass substrate loaded with an alumina film is obtained, such as... Figure 1 (c) and Figure 4 As shown. A glass substrate loaded with an alumina-coated film was immersed in chloroform for 24 hours. After standing, it was ultrasonically treated in chloroform for 30 minutes to remove the polystyrene microspheres and the alumina film on their surface. Afterward, the glass substrate with the alumina film removed was rinsed with ethanol and deionized water for 10 minutes each, and then heated in an oven at 80°C for 30 minutes to remove residual chloroform, resulting in an alumina-coated substrate, as shown. Figure 1 (d) and Figure 5 As shown.

[0046] (4) A 50 nm thick gold film is deposited on the alumina-plated substrate using magnetron sputtering at a deposition rate of [missing information]. A glass substrate loaded with a gold-plated film is obtained, such as... Figure 1 (e) and Figure 6 As shown, a glass substrate loaded with a gold-plated film is immersed in a 5% (w / w) phosphoric acid solution and left to stand at 70°C for 5 minutes. This removes the remaining alumina film and the gold film on its surface, resulting in a gold nanocylinder array on the glass substrate surface. Figure 1 (f) and Figure 7 As shown.

[0047] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A method for preparing a gold nanocylinder array, characterized in that, Without using photolithography, the following steps are included: A polystyrene microsphere monolayer film is prepared on the upper surface of a substrate. The polystyrene microsphere monolayer film is formed by first polystyrene microspheres in contact with each other, and the diameter of the first polystyrene microspheres is 180~220 nm. The first polystyrene microsphere in a substrate with a polystyrene microsphere monolayer film on the upper surface is etched into a second polystyrene microsphere to obtain an etched substrate. The diameter of the second polystyrene microsphere is 130~170nm. An aluminum oxide film with a thickness of 70-80 nm is deposited on the upper surface of the etched substrate by atomic layer deposition. The aluminum oxide film is then removed from the second polystyrene microspheres and the aluminum oxide film on the surface of the second polystyrene microspheres, while the remaining aluminum oxide film on the upper surface of the etched substrate is retained to obtain an aluminum oxide-coated substrate. A gold film with a thickness of 45-55 nm is deposited on the upper surface of the alumina substrate by magnetron sputtering. The remaining alumina film and the gold film on the surface of the remaining alumina film are removed to obtain the gold nanocylinder array on the upper surface of the substrate.

2. The preparation method according to claim 1, characterized in that, The substrate includes at least one of a glass substrate, a silicon substrate, a silicon carbide substrate, and a quartz substrate.

3. The preparation method according to claim 1, characterized in that, The method for preparing a polystyrene microsphere monolayer film on the upper surface of a substrate includes: forming a polystyrene microsphere dispersion film on a water surface by gas-liquid self-assembly; adding sodium dodecyl sulfate solution to the edge of the polystyrene microsphere dispersion film to form a polystyrene microsphere monolayer film on the water surface; and transferring the polystyrene microsphere monolayer film from the water surface to the upper surface of the substrate.

4. The preparation method according to claim 3, characterized in that, The sodium dodecyl sulfate solution has a mass fraction of 1-3%.

5. The preparation method according to claim 1, characterized in that, The etching conditions are as follows: stage angle 0~5°; oxygen flow rate 5~10 sccm; etching time 10~20 min; cavity pressure 6×10 -4 ~8×10 -4 Pa; plate voltage 450~500V; accelerating voltage 100~120V; beam current 180~200mA.

6. The preparation method according to claim 1, characterized in that, The deposition rate of the alumina film is 1~2 Ås. -1 .

7. The preparation method according to claim 1, characterized in that, The gold film has a deposition rate of 1~3 Ås. -1 .

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