Preparation method of bud-shaped nanostructure and bud-shaped nanostructure template

Abstract

The present application discloses a preparation method of a bud-shaped nanostructure and a bud-shaped nanostructure template, the method comprising: providing a substrate; forming a metal film layer on the surface of the substrate; forming a photoresist layer on the surface of the metal film layer, the photoresist layer having ring terraces; performing reactive ion beam etching on the metal film layer, the angle between the etching beam and the normal of the metal film layer being between 75° and 89°; removing the photoresist layer to obtain a bud-shaped nanostructure with periodic distribution. The bud-shaped nanostructure template comprises a substrate and a metal film layer arranged on the surface of the substrate, the metal film layer having a periodically arranged bud-shaped nanostructure. There is no need to use various chemicals to perform corrosion operations on the adhesive structure, which can avoid introducing other unnecessary defects, simplify the operation steps, and ensure the safety of the experimenters. At the same time, by controlling the ring terrace layout on the photoresist layer and combining the etching beam, a periodic bud-shaped nanostructure can be obtained simply and conveniently.

Description

Technical Field

[0001] The invention relates to the technical field of nanostructures, and in particular to a preparation method of a bud-shaped nanostructure and a bud-shaped nanostructure template. Background Art

[0002] Nanostructure is a new system constructed or created according to certain rules based on nanoscale material units. With the development of science and technology, the types of nanomaterials are becoming more and more abundant, such as nanotubes, nanofibers, nanorods, nanowires, nanoparticles, nanocones and nanosheets. Among these nanomaterials, the development and utilization of bud-shaped 3D nanostructures is a research hotspot in the field of micro-nano materials in recent years. Compared with spherical nanoparticles, these structures have a higher surface area to volume ratio, which is conducive to improving the efficiency of surface reactions. Its current main preparation methods are single-layer colloidal crystal template method, induced growth method, etc. The single-layer colloidal crystal template method uses a single-layer colloidal crystal formed by self-assembly as a template (such as commonly used colloidal particle monodisperse polystyrene microspheres), and deposits a precious metal film layer on the top layer or gap of the template microsphere through physical vapor deposition, chemical or electrochemical deposition and other technologies. After etching, the template is removed by dissolving with an organic solvent (such as chloroform, dichlorotoluene, etc.) or high-temperature treatment to obtain a flower-shaped or bud-shaped structure.

[0003] In the single-layer colloidal crystal template method, the periodicity of the polystyrene template cannot be guaranteed during the preparation process, and the polystyrene microspheres cannot be completely removed by dissolving them in organic solvents in actual operations, and polystyrene residues may also be left in the structure. Summary of the invention

[0004] The present invention aims at overcoming at least one of the above problems and provides a method for preparing a bud-shaped nanostructure and a bud-shaped nanostructure template.

[0005] The technical solution adopted by the present invention is as follows:

[0006] The present application provides a method for preparing a bud-shaped nanostructure, comprising the following steps:

[0007] Providing a substrate, wherein the substrate is a cleaned substrate free of impurities;

[0008] forming a metal film layer on the surface of the substrate;

[0009] forming a photoresist layer on the surface of the metal film layer, wherein the photoresist layer has a plurality of periodically arranged ring terraces;

[0010] Performing reactive ion beam etching on the metal film layer formed with the photoresist layer, wherein the angle between the etching beam and the normal line of the metal film layer is between 75° and 89°;

[0011] The photoresist layer is removed to obtain a flower-bud-shaped nanostructure with periodic distribution.

[0012] Compared with the traditional single-layer colloidal crystal template method and the main features of its process, the method provided by this application does not require the use of various chemicals to corrode the adhesive structure, which can not only avoid the introduction of other unnecessary defects, but also simplify the operation steps and ensure the safety of the experimenters. At the same time, by controlling the ring stage layout on the photoresist layer and combining the etching beam, a periodic bud-shaped nanostructure can be obtained simply and conveniently.

[0013] Furthermore, the specific steps of performing reactive ion beam etching on the metal film layer include:

[0014] Fixing the substrate formed with the metal film layer and the photoresist layer on the chamber tray of the ion beam etcher;

[0015] Set the argon flow rate of the ion beam etcher between 10sccm and 17sccm, the acceleration voltage between 120V and 160V, the beam current between 180mA and 202mA, and the pressure in the chamber between 6*10 -4 Pa~9*10 -4 Pa, and the etching time is between 180s and 420s.

[0016] In actual use, the tray holding the substrate rotates at a speed of 10rpm / min. As the tray rotates, the ion etching beam will perform small angle etching on all sides of the hole structure, and the etching beam changes slowly, which can produce a flower bud shape.

[0017] Furthermore, the angle between the etching beam of the ion beam etcher and the normal line of the metal film layer is between 75° and 82°.

[0018] In actual use, when the etching beam increases or the angle between the etching beam and the normal of the metal film layer is less than 75°, the flower-bud-shaped nanostructure cannot be formed; when the angle is between 82° and 89°, the outer diameter of the flower-bud-shaped nanostructure is slightly larger, and 75° to 82° is the optimal range for forming the flower-bud-shaped nanostructure.

[0019] Furthermore, the cleaning step of the substrate includes:

[0020] The target substrate is placed in a first cleaning solution for acid cleaning for 15 to 20 minutes, wherein the first cleaning solution is a mixture of concentrated sulfuric acid and hydrogen peroxide in a volume ratio of 7:3;

[0021] Use pure water for ultrasonic cleaning for 15min to 20min, and then use nitrogen to blow dry;

[0022] The substrate is neutralized and cleaned for 5 to 6 minutes using a second cleaning solution, wherein the second cleaning solution is a mixture of ammonia water, hydrogen peroxide and pure water in a volume ratio of 1:5:100;

[0023] The drying process is carried out at a temperature of 55°C to 65°C.

[0024] Furthermore, a metal film layer is sputtered on the surface of the substrate by magnetron sputtering;

[0025] The thickness of the metal film layer formed by sputtering is 300nm to 500nm;

[0026] The metal film layer is a silver film layer.

[0027] In actual use, the metal film layer may also be a gold film layer, a copper film layer, an aluminum film layer or a titanium film layer.

[0028] Furthermore, when the metal film layer is formed by sputtering by magnetron sputtering,

[0029] The vacuum degree of the sputtering equipment was set to 6.6×10 -6 Pa~6.4×10 -6 Pa;

[0030] The argon pressure inside the sputtering equipment is set to 1.2Pa~1.3Pa;

[0031] The sample stage speed is set to 5rpm~6rpm;

[0032] The sputtering power is set to 70W~73W;

[0033] The pre-sputtering time is 3600s~4000s;

[0034] The sputtering rate is 0.05 nm·s -1 ~0.055nm·s -1 .

[0035] Further, the photoresist layer is formed by photolithography, and the specific steps of the photolithography include:

[0036] Spin coating photoresist on the surface of the metal film layer;

[0037] After sequentially performing exposure operation, post-baking operation and development operation, a plurality of periodically arranged ring terraces are formed on the metal film layer, and the plurality of ring terraces are the photoresist layer;

[0038] The inner diameter of the ring stage is between 200nm and 300nm, the outer diameter of the ring stage is between 500nm and 600nm, and the interval between adjacent ring stages is between 608nm and 620nm.

[0039] Furthermore, the exposure time of the exposure operation is 30s to 40s;

[0040] During the post-baking operation, the post-baking temperature is 110°C to 200°C, and the post-baking time is 1min to 2min;

[0041] The developing time of the developing operation is 80s to 90s.

[0042] Further, the stripping operation of the etched photoresist layer includes:

[0043] Clean the etched substrate;

[0044] Set the oxygen flow rate of the plasma degumming machine to 200 sccm~220 sccm, the power to 500W~550W, the chamber pressure to 60Pa~62Pa, and the degumming time to 10min~15min;

[0045] The cleaned substrate is placed vertically into a plasma degumming machine for dry oxygen degumming to obtain a flower-bud-shaped nanostructure with periodic distribution.

[0046] The present application also provides a flower-bud-shaped nanostructure template, comprising a substrate and a metal film layer arranged on the surface of the substrate, the metal film layer having periodically arranged flower-bud-shaped nanostructures, and the center of the flower-bud-shaped nanostructure has a concave core;

[0047] The depth of the concave core is between 280nm and 350nm;

[0048] The outer diameter of the bud-shaped nanostructure is between 500nm and 600nm;

[0049] The spacing between adjacent bud-shaped nanostructures is between 608nm and 620nm;

[0050] The flower bud-shaped nanostructure is prepared by the above-mentioned method for preparing a flower bud-shaped nanostructure.

[0051] The flower-bud-shaped nanostructure template provided by the present application will not introduce any material residue and does not require the use of corrosive chemicals, while the periodicity of the flower-bud-shaped nanostructure can be guaranteed.

[0052] The beneficial effects of the present invention are:

[0053] The method provided by the present application does not require the use of various chemicals to corrode the adhesive structure, which can avoid introducing other unnecessary defects, simplify the operation steps, and ensure the safety of the experimenters. At the same time, by controlling the ring stage layout on the photoresist layer and combining the etching beam, a periodic bud-shaped nanostructure can be obtained simply and conveniently. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] Figure 1 This is a schematic diagram of the preparation process of the bud-shaped nanostructure according to an embodiment of the present invention;

[0055] Figure 2 is a schematic diagram of the top view of S3 in the method for preparing a bud-shaped nanostructure according to an embodiment of the present invention;

[0056] Figure 3 is a schematic diagram of the top view of S4 in the method for preparing a bud-shaped nanostructure in an embodiment of the present invention;

[0057] Figure 4 is a schematic diagram of the top view of S5 in the method for preparing a bud-shaped nanostructure according to an embodiment of the present invention;

[0058] Figure 5 It is a schematic diagram of a physical flower-bud-shaped nanostructure prepared by using the method for preparing a flower-bud-shaped nanostructure according to an embodiment of the present invention.

[0059] The reference numerals in the figures are:

[0060] 10. Substrate; 20. Metal film layer; 30. Photoresist layer; 310. Ring stage; 40. Etching beam; 50. Normal line of metal film layer; 100. Flower-bud-shaped nanostructure. DETAILED DESCRIPTION

[0061] The present invention is described in detail below in conjunction with the accompanying drawings.

[0062] like Figure 1 to Figure 4 As shown, the present application provides a method for preparing a bud-shaped nanostructure, comprising the following steps:

[0063] S1. Providing a substrate 10, the substrate 10 is a cleaned substrate free of impurities;

[0064] S2. Forming a metal film layer 20 on the surface of the substrate 10;

[0065] S3. A photoresist layer 30 is formed on the surface of the metal film layer 20, wherein the photoresist layer 30 has a plurality of periodically arranged ring stages 310;

[0066] S4. The metal film layer 20 formed with the photoresist layer 30 is subjected to reactive ion beam etching, wherein the angle between the etching beam 40 and the normal line 50 of the metal film layer is between 75° and 82°;

[0067] S5. The photoresist layer 30 is removed to obtain a flower-bud-shaped nanostructure 100 with periodic distribution.

[0068] Compared with the traditional single-layer colloidal crystal template method and the main features of its process, the method provided by the present application does not need to use various chemicals to corrode the adhesive structure, which can avoid introducing other unnecessary defects, simplify the operation steps, and ensure the safety of the experimenters. At the same time, by controlling the layout of the ring stage 310 on the photoresist layer 30 and combining the etching beam 40, a periodic bud-shaped nanostructure can be obtained simply and conveniently.

[0069] In this embodiment, the specific steps of performing reactive ion beam etching on the metal film layer 20 include:

[0070] The substrate 10 formed with the metal film layer 20 and the photoresist layer 30 is fixed on the chamber tray of the ion beam etcher;

[0071] Set the argon flow rate of the ion beam etcher to 15 sccm, the acceleration voltage to 120 V, the beam current to 200 mA, and the chamber pressure to 8*10 -4 Pa, etching time is 300s.

[0072] like Figure 3 As shown, in actual use, the tray holding the substrate 10 rotates at a speed of 10 rpm / min. As the tray rotates, the ion etching beam 40 etches the hole structure at a small angle all around, and the etching beam 40 changes slowly, which can produce a flower bud shape.

[0073] In this embodiment, the angle between the etching beam 40 of the ion beam etcher and the normal line 50 of the metal film layer is 78°.

[0074] In actual use, when the etching beam increases or the angle between the etching beam 40 and the normal 50 of the metal film layer is less than 75°, the flower-bud-shaped nanostructure 100 cannot be formed; when the angle is between 82° and 89°, the outer diameter of the flower-bud-shaped nanostructure 100 is slightly larger, and 75° to 82° is the optimal range for forming the flower-bud-shaped nanostructure 100.

[0075] In this embodiment, the cleaning step of the substrate 10 includes:

[0076] The target substrate 10 is placed in a first cleaning solution for acid cleaning for 15 minutes. The first cleaning solution is a mixture of concentrated sulfuric acid and hydrogen peroxide in a volume ratio of 7:3.

[0077] Use pure water for ultrasonic cleaning for 20 minutes, and then use nitrogen to blow dry;

[0078] The substrate 10 is neutralized and cleaned for 5 minutes using a second cleaning solution, wherein the second cleaning solution is a mixture of ammonia water, hydrogen peroxide and pure water in a volume ratio of 1:5:100;

[0079] The drying process was carried out at a temperature of 60°C.

[0080] In this embodiment, the metal film layer 20 is formed on the surface of the substrate 10 by sputtering using a magnetron sputtering method;

[0081] The thickness of the metal film layer 20 formed by sputtering is 400 nm;

[0082] The metal film layer 20 is a silver film layer.

[0083] In other embodiments, the metal film layer may also be a gold film layer, a copper film layer, an aluminum film layer or a titanium film layer.

[0084] In this embodiment, when the metal film layer 20 is formed by magnetron sputtering,

[0085] The vacuum degree of the sputtering equipment was set to 6.4×10 -6 Pa;

[0086] The argon pressure inside the sputtering equipment was set to 1.2 Pa;

[0087] The sample stage speed was set to 5 rpm;

[0088] The sputtering power was set to 70W;

[0089] The pre-sputtering time was 3700 s;

[0090] The sputtering rate is 0.055nm·s -1 .

[0091] In this embodiment, the photoresist layer 30 is formed by photolithography, and the specific steps of the photolithography include:

[0092] Spin-coat photoresist on the surface of the metal film layer 20;

[0093] After exposure operation, post-baking operation and development operation, a plurality of periodically arranged ring-shaped terraces 310 are formed on the metal film layer 20, and the plurality of ring-shaped terraces 310 form a photoresist layer 30;

[0094] The inner diameter of the ring stage 310 is between 200 nm and 300 nm, the outer diameter of the ring stage 310 is between 500 nm and 600 nm, and the interval between adjacent ring stages 310 is between 608 nm and 620 nm.

[0095] In this embodiment, the exposure time of the exposure operation is 35s;

[0096] During the post-baking operation, the post-baking temperature is 110°C and the post-baking time is 2 minutes;

[0097] The developing time of the developing operation is 80 seconds.

[0098] In this embodiment, the stripping operation of the etched photoresist layer 30 includes:

[0099] Cleaning the etched substrate 10;

[0100] Set the oxygen flow rate of the plasma degumming machine to 200sccm, the power to 500W, the chamber pressure to 60Pa, and the degumming time to 10min;

[0101] The cleaned substrate 10 is placed vertically into a plasma degumming machine for dry oxygen degumming to obtain a flower-bud-shaped nanostructure with periodic distribution.

[0102] like Figure 5 As shown, the bud-shaped nanostructures prepared by the method provided in the present application are distributed periodically and have a clear structure.

[0103] The present application also provides a flower-bud-shaped nanostructure template, comprising a substrate 10 and a metal film layer 20 disposed on the surface of the substrate 10, the metal film layer 20 having periodically disposed flower-bud-shaped nanostructures 100, and the center of the flower-bud-shaped nanostructure 100 having a concave core;

[0104] The depth of the concave core is 300nm;

[0105] The outer diameter of the bud-shaped nanostructure 100 is 582 nm;

[0106] The spacing distance between adjacent bud-shaped nanostructures 100 is 608 nm;

[0107] The flower bud-shaped nanostructure 100 is prepared by the above-mentioned method for preparing a flower bud-shaped nanostructure.

[0108] The flower-bud-shaped nanostructure template provided by the present application will not introduce any material residue and does not require the use of corrosive chemicals, while the periodicity of the flower-bud-shaped nanostructure 100 can be guaranteed.

[0109] The above description is only a preferred embodiment of the present invention, and does not limit the patent protection scope of the present invention. Any equivalent structural transformation made by using the contents of the present invention and the drawings, directly or indirectly used in other related technical fields, is also included in the protection scope of the present invention.

Claims

1. A method for preparing a bud-shaped nanostructure, characterized in that: The steps include: Providing a substrate, wherein the substrate is a cleaned substrate free of impurities; forming a metal film layer on the surface of the substrate; forming a photoresist layer on the surface of the metal film layer, wherein the photoresist layer has a plurality of periodically arranged ring terraces; Performing reactive ion beam etching on the metal film layer formed with the photoresist layer; The angle between the etching beam and the normal line of the metal film layer is between 75° and 89°; The photoresist layer is removed to obtain a flower-bud-shaped nanostructure with periodic distribution; The specific steps of performing reactive ion beam etching on the metal film layer include: Fixing the substrate formed with the metal film layer and the photoresist layer on the chamber tray of the ion beam etcher; Set the argon flow rate of the ion beam etcher to between 10 sccm and 17 sccm, the acceleration voltage to between 120 V and 160 V, the beam current to between 180 mA and 202 mA, and the pressure in the chamber to between 6*10 -4 Pa~9*10 -4 Pa, and the etching time is between 180s and 420s.

2. The method for preparing a bud-shaped nanostructure according to claim 1, characterized in that: The angle between the etching beam of the ion beam etcher and the normal line of the metal film layer is between 75° and 82°.

3. The method for preparing a bud-shaped nanostructure according to claim 1, characterized in that: The cleaning step of the substrate comprises: The target substrate is placed in a first cleaning solution for acid cleaning for 15 to 20 minutes, wherein the first cleaning solution is a mixture of concentrated sulfuric acid and hydrogen peroxide in a volume ratio of 7:3; Use pure water for ultrasonic cleaning for 15min~20min, and then use nitrogen to blow dry; The substrate is neutralized and cleaned for 5 to 6 minutes using a second cleaning solution, wherein the second cleaning solution is a mixture of ammonia water, hydrogen peroxide and pure water in a volume ratio of 1:5:100; The drying process is carried out at a temperature of 55°C to 65°C.

4. The method for preparing a bud-shaped nanostructure according to claim 1, characterized in that: sputtering to form a metal film layer on the surface of the substrate by magnetron sputtering; The thickness of the metal film layer formed by sputtering is 300nm~500nm; The metal film layer is a silver film layer.

5. The method for preparing a bud-shaped nanostructure according to claim 4, characterized in that: When a metal film is formed by sputtering by magnetron sputtering, The vacuum degree of the sputtering equipment was set to 6.6×10 -6 Pa~6.4×10 -6 Pa; The argon pressure inside the sputtering equipment was set to 1.2 Pa~1.3 Pa; The sample stage speed was set to 5 rpm~6 rpm; The sputtering power was set to 70 W~73 W; The pre-sputtering time is 3600 s~4000 s; The sputtering rate is 0.05 nm·s -1 ~0.055 nm·s -1 .

6. The method for preparing a bud-shaped nanostructure according to claim 1, characterized in that: The photoresist layer is formed by photolithography, and the specific steps of the photolithography operation include: Spin coating photoresist on the surface of the metal film layer; After sequentially performing exposure operation, post-baking operation and development operation, a plurality of periodically arranged ring terraces are formed on the metal film layer, and the plurality of ring terraces are the photoresist layer; The inner diameter of the ring stage is between 200nm and 300nm, the outer diameter of the ring stage is between 500nm and 600nm, and the interval between adjacent ring stages is between 608nm and 620nm.

7. The method for preparing a bud-shaped nanostructure according to claim 6, characterized in that: The exposure time of the exposure operation is 30s~40s; During the post-baking operation, the post-baking temperature is 110°C to 200°C, and the post-baking time is 1min to 2min; The developing time of the developing operation is 80s to 90s.

8. The method for preparing a bud-shaped nanostructure according to claim 1, characterized in that: The stripping operation of the etched photoresist layer includes: Clean the etched substrate; Set the oxygen flow rate of the plasma degumming machine to 200 sccm~220 sccm, the power to 500 W~550 W, the chamber pressure to 60 Pa~62 Pa, and the degumming time to 10 min~15 min; The cleaned substrate is placed vertically into a plasma degumming machine for dry oxygen degumming to obtain a flower-bud-shaped nanostructure with periodic distribution.

9. A bud-shaped nanostructure template, characterized in that: It comprises a substrate and a metal film layer arranged on the surface of the substrate, the metal film layer has a periodically arranged flower bud-shaped nanostructure, and the center of the flower bud-shaped nanostructure has a concave core; The depth of the concave core is between 280nm and 350nm; The outer diameter of the bud-shaped nanostructure is between 500nm and 600nm; The spacing between adjacent bud-shaped nanostructures is between 608nm and 620nm; The flower bud-shaped nanostructure is prepared by the method for preparing a flower bud-shaped nanostructure according to any one of claims 1 to 8.

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