CN117888089A - Periodic net structure template and preparation method thereof - Google Patents
Periodic net structure template and preparation method thereof Download PDFInfo
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- CN117888089A CN117888089A CN202410072080.5A CN202410072080A CN117888089A CN 117888089 A CN117888089 A CN 117888089A CN 202410072080 A CN202410072080 A CN 202410072080A CN 117888089 A CN117888089 A CN 117888089A
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- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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Abstract
The invention relates to the technical field of nano materials, and provides a periodic reticular structure template and a preparation method thereof. According to the invention, a silicon dioxide film layer and a silver film layer are deposited on the surface of a substrate, then operations such as photoresist coating, exposure, development and the like are carried out on the silver film layer, a substrate with a netlike photoresist coating is obtained, and then the structure is etched and photoresist removed, so that a periodic netlike structure template can be obtained. The substrate with the periodic net structure is obtained by means of the semiconductor production process, the reaction time of the traditional process is greatly reduced, the operation is simple, and a large-area structure template with good periodicity can be obtained; the required reticular structure template is obtained by controlling the condition of the reactive ion beam etching, various chemicals such as modifiers harmful to the body are not needed, the safety of experimental operators can be ensured, the surface activity of the nano structure cannot be influenced, and the template is further applied.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a periodic reticular structure template and a preparation method thereof.
Background
The nanostructure composed of multiple dimensions, multiple components and multiple layers has rich aggregation property and synergistic effect, and the nanostructure with different performance characteristics is assembled into a new material complex, thus providing more possibility for the realization of nanomaterial devices. For example, the nano-network structure can more effectively carry out charge transmission and energy transmission due to the higher internal and external surface areas and stronger interaction among particles, so that the structure further shows stronger photoelectric properties. The excellent optical and electrical properties of the noble metal nano particles (silver and gold) enable the noble metal nano particles to have wide application value in the fields of photonics, sensing and the like, and the noble metal nano particles are prepared into a net structure, so that the coupling effect among the particles can be further enhanced.
At present, most of preparation methods of nano metal reticular structures regulate and control solvent environments where nano particles are located, for example, modifying agents such as toluene, chloroform, polyelectrolyte salt substances and the like are added in an interface self-assembly method to obtain the nano particle reticular membrane structure. The surface of the net-shaped structure film is covered with a layer of organic polymer, which can passivate the surface activity of the nano material, and is not beneficial to further application.
Disclosure of Invention
In view of the above, the present invention provides a periodic mesh structure template and a method for preparing the same. The preparation method provided by the invention does not need to use various chemicals such as modifiers harmful to the body, does not passivate the surface activity of the nano material, can ensure the safety of experimental operators, is simple to operate, and can obtain a large-area structure template with good periodicity.
In order to achieve the above object, the present invention provides the following technical solutions:
a method for preparing a periodic net-shaped structure template, comprising the following steps:
sequentially depositing a silicon dioxide film layer and a silver film layer on the surface of the substrate;
coating photoresist on the surface of the silver film layer, and then exposing and developing to obtain a netlike photoresist coating;
and etching the silver film layer and the silicon dioxide film layer in the exposed area on the substrate by adopting a reactive ion beam etching method, and removing the reticular photoresist coating to obtain the periodic reticular structure template.
Preferably, the thickness of the silicon dioxide film layer is 500+/-30 nm, and the surface roughness of the silicon dioxide film layer is less than or equal to 1.5nm.
Preferably, the method for depositing the silicon dioxide film layer comprises a plasma enhanced chemical vapor deposition method; the reaction gas adopted by the plasma enhanced chemical vapor deposition method is SiH 4 And N 2 O; the SiH is 4 And N 2 The flow ratio of O is 1: 13-15; the N is 2 The flow rate of O is 190-200 cm 3 A/min; the deposition time of the plasma enhanced chemical vapor deposition method is 6-8 min.
Preferably, the thickness of the silver film layer is 140+/-2 nm; and the surface roughness of the silver film layer is less than or equal to 1.5nm.
Preferably, the method for depositing the silver film layer comprises a magnetron sputtering method; the conditions of the magnetron sputtering method include: vacuum degree of 6.6X10 -6 ～6.4×10 -6 Pa, argon pressure of 1.2-1.3 Pa, sputtering power of 70-73W, sample stage rotation speed of 5-6 rpm, pre-sputtering time of 360-400 s, and sputtering rate of 0.050-0.055 nm.s -1 。
Preferably, the exposure time is 30-40 s; the development time is 80-90 s; the post-baking is carried out on the photoresist after exposure; the post-baking temperature is 110-200 ℃ and the time is 1-2 min.
Preferably, the conditions for etching the silver film layer and the silicon dioxide film layer by the reactive ion beam etching method independently include: the etching angle is 0-10 degrees, the argon flow is 5-10 sccm, and the pressure in the cavity is 8 multiplied by 10 -4 Pa; the total time for etching the silver film layer and the silicon dioxide film layer is 10-50 s.
Preferably, the method for removing the mesh photoresist layer is a dry oxygen photoresist removing method; the conditions of the dry oxygen photoresist stripping method comprise: the oxygen flow is 200-220 sccm, the power is 500-550W, the pressure in the cavity is 60-62 Pa, and the photoresist removing time is 10-15 min.
Preferably, the periodic reticular structure template comprises a substrate, a silicon dioxide porous structure layer arranged on the surface of the substrate, and a silver reticular structure layer arranged on the surface of the silicon dioxide porous structure layer; the holes in the silver mesh structure are conical holes with large upper part and small lower part, the aperture of the large-size surface of each conical hole is 400-455 nm, the hole depth of each conical hole is 120-130 nm, and the mesh width of the silver mesh structure is 140-190 nm; the holes in the silicon dioxide porous structure are cylindrical holes; the pore diameter of the silica pore-shaped structure is 140-180 nm, and the pore depth is 50-80 nm.
The invention also provides the periodic reticular structure template prepared by the preparation method.
The invention provides a preparation method of a periodic net-shaped structure template, which comprises the following steps: sequentially depositing a silicon dioxide film layer and a silver film layer on the surface of the substrate; coating photoresist on the surface of the silver film layer, and then exposing and developing to obtain a netlike photoresist coating; and etching the silver film layer and the silicon dioxide film layer in the exposed area on the substrate by adopting a reactive ion beam etching method, and removing the reticular photoresist coating to obtain the periodic reticular structure template. The substrate with the periodic structure is obtained by means of the semiconductor production process, the reaction time of the traditional process is greatly reduced, the operation is simple, large-area preparation can be realized, and the prepared periodic net structure is uniform in size and high in resolution; the invention obtains the required net-shaped structure template by controlling the condition of the reactive ion beam etching, does not need to use various chemicals such as modifiers harmful to the body, can ensure the safety of experiment operators, can not leave chemical reagents on the surface of the nano material, can not influence the surface activity of the nano material, and is beneficial to the further application of the template.
In addition, because the lattices between the silver and the glass wafer are not matched, the adhesive force between the silver and the glass substrate is lower, and the silicon dioxide structure layer plays a role in connecting the silver layer and the substrate, so that the combination between the silver reticular structure and the substrate is tighter through the combination of the silicon dioxide film layer and the silver film layer.
Furthermore, the invention obtains the silicon dioxide porous layer with smaller pore diameter and the silver reticular layer with larger pore diameter by controlling etching parameters, and the regular porous structure of the silicon dioxide can strengthen the integral property of the structure to a certain extent, and the invention is particularly mainly characterized in the following aspects: 1. the silicon dioxide has higher refractive index, when the structure is irradiated by light, the light has a refractive phenomenon in the silver mesh structure, and can be further refracted by the silicon dioxide porous layer, so that the refractive index of the whole structure can be enhanced to a certain extent; 2. the net structure is overlapped with the hole-shaped structure, so that the number of plasmonic hot spots of the whole structure can be increased, and the structure can have higher Raman response.
Drawings
FIG. 1 is a schematic illustration of a preparation flow of the present invention; wherein: 1-a substrate; 2-photoresist; 3-silver film layer; 4-a silicon dioxide film layer; 5-silver network; 6-a silica pore structure;
FIG. 2 is a front AFM top view of a template with periodic network structure prepared in example 1.
Detailed Description
The invention provides a preparation method of a periodic net-shaped structure template, which comprises the following steps:
sequentially depositing a silicon dioxide film layer and a silver film layer on the surface of the substrate;
coating photoresist on the surface of the silver film layer, and then exposing and developing to obtain a netlike photoresist coating;
and etching the silver film layer and the silicon dioxide film layer in the exposed area on the substrate by adopting a reactive ion beam etching method, and removing the reticular photoresist coating to obtain the periodic reticular structure template.
FIG. 1 is a schematic diagram of the preparation process of the present invention, and the preparation method of the present invention is described in detail below with reference to FIG. 1.
According to the invention, a silicon dioxide film layer and a silver film layer are sequentially deposited on the surface of a substrate. The invention has no special requirement on the substrate, and can be realized by adopting the method which is well known to the skilled in the art, such as silicon chip, quartz, high borosilicate glass and the like; preferably, the substrate is cleaned prior to the depositing; the cleaning preferably comprises ultrasonic cleaning by sequentially adopting acetone, ethanol and deionized water; the ultrasonic cleaning time of the acetone, the ethanol and the deionized water is preferably 30min, and the cleaning temperature is preferably room temperature; after cleaning, the substrate is preferably dried; the temperature of the drying is preferably 100 ℃; the drying is preferably carried out in an oven.
In the invention, the thickness of the silicon dioxide film layer is preferably 500+/-30 nm, and the surface roughness of the silicon dioxide film layer is preferably less than or equal to 1.5nm; the method for depositing the silicon dioxide film layer preferably comprises a plasma enhanced chemical vapor deposition method; the reaction gas used in the plasma enhanced chemical vapor deposition method is preferably SiH 4 And N 2 O; the SiH is 4 And N 2 The flow ratio of O is preferably 1:13 to 15, more preferably 1:14; the N is 2 The flow rate of O is preferably 190-200 cm 3 A/min; the deposition time of the plasma enhanced chemical vapor deposition method is preferably 6-8 min.
In the invention, the thickness of the silver film layer is preferably 140+/-2 nm; the surface roughness of the silver film layer is preferably less than or equal to 1.5nm; the method for depositing the silver film layer preferably comprises a magnetron sputtering method; the conditions of the magnetron sputtering method preferably include: vacuum degree of 6.6X10 -6 ～6.4×10 -6 Pa, argon pressure of 1.2-1.3 Pa, sputtering power of 70-73W, sample stage rotation speed of 5-6 rpm, pre-sputtering time of 360-400 s, and sputtering rate of 0.050-0.055 nm.s -1 The method comprises the steps of carrying out a first treatment on the surface of the The target material adopted by the magnetron sputtering is a silver target material.
After the silver film layer is deposited, the invention coats photoresist on the surface of the silver film layer, and then exposes and develops the photoresist to obtain the netlike photoresist coating. The invention has no special requirement on the type of the photoresist, and the photoresist is well known to the person skilled in the art; the exposure time is preferably 30 to 40 seconds; the post-baking is carried out on the photoresist after exposure; the post-baking temperature is preferably 110-200 ℃, and the time is preferably 1-2 min. The development time is preferably 80 to 90 seconds; preferably, the aqueous rinse is used for 1.5min after development. In the invention, the mesh aperture of the mesh photoresist coating is preferably 300-500 nm, and the thickness of the mesh photoresist layer is preferably 400-600 nm. After the preparation of the reticular photoresist layer is finished, the surface of the substrate is sequentially provided with a silicon dioxide film layer, a silver film layer and a reticular photoresist coating from bottom to top.
After the reticular photoresist coating is obtained, the silver film layer and the silicon dioxide film layer in the exposed area on the substrate are etched by adopting a reactive ion beam etching method. In the present invention, the conditions for etching the silver film layer by the reactive ion beam etching method preferably include: the etching angle is 0-10 degrees, preferably 8-10 degrees, the argon flow is preferably 5-10 sccm, more preferably 6-8 sccm, and the pressure in the cavity is preferably 8×10 -4 Pa. The conditions for etching the silicon dioxide film layer by adopting the reactive ion beam etching method preferably comprise: the etching angle is 0-10 degrees, preferably 0-3 degrees, the argon flow is preferably 5-10 sccm, more preferably 6-8 sccm, and the pressure in the cavity is preferably 8×10 -4 Pa; the total time for etching the silver film layer and the silicon dioxide film layer by adopting the reactive ion beam etching method is preferably 10-50 s, more preferably 20-50 s, and in the specific embodiment of the invention, the time for etching the silver film layer is preferably 30s, and the time for etching the silicon dioxide film layer is preferably 20s. In the specific embodiment of the invention, preferably, the conical holes with the upper size and the lower size are etched on the silver film layer by controlling the etching angle, and the cylindrical holes with the consistent pore size are obtained on the silicon dioxide film layer. During etching, the silver film layer is etched through, etching space is reserved at the bottom of the silicon dioxide film layer to protect the substrate, and the thickness of the residual silicon dioxide film layer is preferably 420-450 nm. In a specific embodiment of the present invention, it is preferable that the substrate provided with the mesh-shaped photoresist coating layer is placed on a chamber tray of a reactive ion beam etcher, and then an etching operation is performed according to set conditions.
After etching is completed, the invention removes the reticular photoresist coating to obtain the template with the periodical reticular structure. In the invention, the method for removing the reticular photoresist layer is preferably a dry oxygen photoresist removing method; the conditions of the dry oxygen stripping method preferably include: the oxygen flow is 200-220 sccm, the power is 500-550W, the pressure in the cavity is 60-62 Pa, and the photoresist removing time is 10-15 min. In the specific embodiment of the invention, the etched substrate is preferably cleaned and then vertically placed in a plasma photoresist remover, and dry oxygen photoresist removal is performed according to set program conditions. And after photoresist removal is finished, cleaning the substrate, and thus obtaining the template with the periodic net structure.
In the invention, the periodic reticular structure template comprises a substrate, a silicon dioxide porous structure layer arranged on the surface of the substrate and a silver reticular structure layer arranged on the surface of the silicon dioxide porous structure layer; the holes in the silicon dioxide porous structure layer are preferably cylindrical holes with consistent upper and lower dimensions, and the holes in the silver mesh structure layer are preferably conical holes with large upper part and small lower part; specifically, the pore diameter of the large-size surface of the conical pores in the silver mesh structure is preferably 400-455 nm, and the diameter of the small-pore surface of the conical pores is preferably the same as the diameter of the pores in the silica pore structure; the hole depth of the conical hole is preferably 120-130 nm, and when the silver film is etched at an inclined angle by adopting a reactive ion beam etching machine, a certain vertical component exists to etch the silver film downwards, so that the thickness of the silver film can be reduced, and the depth of the conical hole is slightly smaller than the initial thickness of the silver film; the mesh width of the silver mesh structure is preferably 140-190 nm; the pore diameter of the silica pore structure is preferably 140-180 nm, and the pore depth is preferably 50-80 nm. In the invention, the periodic network structure specifically refers to a silicon dioxide porous structure layer and small holes in a silver network structure layer which are arranged in an array to form a network.
The invention also provides the periodic reticular structure template prepared by the preparation method. The periodic net-shaped structure template prepared by the method has uniform size and high resolution, the silver film layer is more closely connected with the substrate, and the integral property of the structure is good.
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) Sequentially placing the substrate (quartz glass) into acetone, ethanol and deionized water for ultrasonic treatment at normal temperature for 30min, and drying in a 100 ℃ oven for standby.
(2) Plating a silicon dioxide film layer on the surface of the cleaned substrate by adopting a Plasma Enhanced Chemical Vapor Deposition (PECVD), wherein the thickness is controlled to be 500nm, and the surface roughness Ra is less than or equal to 1.5nm; siH is used in the plating process 4 And N 2 O is a reaction gas, siH 4 And N 2 The flow ratio of O is 1:14, N 2 The flow rate of O is set to 200cm 3 /min and kept constant for 8min.
(3) And (3) plating a silver film layer with the thickness of 140nm on the surface plated with the silicon dioxide film layer by magnetron sputtering. Vacuum degree of magnetron sputtering is 6.5X10 -6 Pa, argon pressure of 1.2Pa, sputtering power of 70W, sample stage rotation speed of 5rpm, pre-sputtering time of 400s, and sputtering rate of 0.050 nm.s -1 The target material adopted by sputtering is a silver target material.
(4) And after the silver film layer plating is completed, carrying out photoetching operation on the obtained structure. Firstly, photoresist is coated on a silver film layer in a spinning way, and then the photoresist coating with a periodic reticular structure is obtained through exposure, post-baking and development in sequence. Wherein the exposure time is 30s, the post-baking is performed by using a hot plate, the temperature is between 200 ℃, the time is 1min, the development time is 80s, and the water is used for washing 1.5min after the development. The structure obtained at this time is sequentially a substrate bottom, a silicon dioxide layer, a silver film layer and a photoresist pattern from bottom to top.
(5) And carrying out reactive ion etching on the substrate after the photoresist pattern is prepared. And fixing the substrate on a cavity tray of a reactive ion beam etching machine, and then performing etching operation according to set conditions. When etching the silver film layer, the etching angle is 10 degrees, and the argon flow is 10 degreessccm, 8X 10 intra-cavity pressure -4 Pa, etching time is 30s. After the silver film layer is etched through, continuing to etch the silicon dioxide film layer, wherein the etching angle is 0 DEG, the argon flow is 10sccm, and the pressure in the cavity is 8 multiplied by 10 when the silicon dioxide film layer is etched -4 Pa, etching time is 20s.
The dimensions of the composite structure obtained after etching: the pore diameter (large-size surface of the conical pores) of the silver reticular structure is 455nm, the pore depth is 122nm, and the network width is 188nm; the pore diameter of the lower silica pore structure was 157nm and the pore depth was 75nm.
(6) And photoresist removing operation is carried out on the etched substrate. And cleaning the etched substrate, vertically placing the cleaned substrate into a plasma photoresist remover, and performing dry oxygen photoresist removal according to set program conditions. The conditions at this time were controlled as follows: the oxygen flow is 200sccm, the power is 500W, the pressure in the cavity is 60Pa, and the photoresist removing time is 10min. And after photoresist removal is finished, cleaning the substrate, and thus obtaining the template with the periodic net structure.
Fig. 2 is a front AFM top view of a template with periodic network structure prepared in this example. As can be seen from fig. 2, the template with a periodic network structure prepared according to the present invention is uniform in size.
In summary, after the substrate plated with the silicon dioxide film layer is obtained through the semiconductor production process, the substrate with the reticular photoresist coating is obtained through performing operations such as photoetching, gluing, exposure, developing and the like on the silver film layer through magnetron sputtering. And then carrying out etching and dry oxidation photoresist removal operation on the structure to obtain the mesh structure with a good period. The substrate with the periodic structure is obtained by means of the semiconductor production process, the reaction time of the traditional process is greatly reduced, the operation is simple, and a large-area structure template with good periodicity can be obtained; and the required reticular structure template is obtained by controlling the condition of the reactive ion beam etching, and various chemicals such as modifiers harmful to the body are not needed, so that the safety of experimental operators can be ensured, and the surface activity of the nano structure is not influenced.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the periodic net-shaped structure template is characterized by comprising the following steps of:
sequentially depositing a silicon dioxide film layer and a silver film layer on the surface of the substrate;
coating photoresist on the surface of the silver film layer, and then exposing and developing to obtain a netlike photoresist coating;
and etching the silver film layer and the silicon dioxide film layer in the exposed area on the substrate by adopting a reactive ion beam etching method, and removing the reticular photoresist coating to obtain the periodic reticular structure template.
2. The method according to claim 1, wherein the thickness of the silica film layer is 500±30nm, and the surface roughness of the silica film layer is 1.5nm or less.
3. The method of claim 1 or 2, wherein the method of depositing the silicon dioxide film layer comprises a plasma enhanced chemical vapor deposition method; the reaction gas adopted by the plasma enhanced chemical vapor deposition method is SiH 4 And N 2 O; the SiH is 4 And N 2 The flow ratio of O is 1:13-15, and the ratio of N is as follows 2 The flow rate of O is 190-200 cm 3 A/min; the deposition time of the plasma enhanced chemical vapor deposition method is 6-8 min.
4. The method of claim 1, wherein the silver film layer has a thickness of 140 ± 2nm; and the surface roughness of the silver film layer is less than or equal to 1.5nm.
5. The method of claim 1 or 4, wherein the method of depositing the silver film layer comprises magnetron sputteringThe method comprises the steps of carrying out a first treatment on the surface of the The conditions of the magnetron sputtering method include: vacuum degree of 6.6X10 -6 ～6.4×10 -6 Pa, argon pressure of 1.2-1.3 Pa, sputtering power of 70-73W, sample stage rotation speed of 5-6 rpm, pre-sputtering time of 360-400 s, and sputtering rate of 0.050-0.055 nm.s -1 。
6. The method according to claim 1, wherein the exposure time is 30 to 40 seconds; the development time is 80-90 s; the post-baking is carried out on the photoresist after exposure; the post-baking temperature is 110-200 ℃ and the time is 1-2 min.
7. The method of claim 1, wherein the conditions for etching the silver film layer and the silicon dioxide film layer by the reactive ion beam etching method independently comprise: the etching angle is 0-10 degrees, the argon flow is 5-10 sccm, and the pressure in the cavity is 8 multiplied by 10 -4 Pa; the total time for etching the silver film layer and the silicon dioxide film layer is 10-50 s.
8. The method of claim 1, wherein the method of removing the mesh photoresist layer is a dry oxygen photoresist removal method; the conditions of the dry oxygen photoresist stripping method comprise: the oxygen flow is 200-220 sccm, the power is 500-550W, the pressure in the cavity is 60-62 Pa, and the photoresist removing time is 10-15 min.
9. The method of claim 1, wherein the periodic network template comprises a substrate, a silica pore structure layer disposed on a surface of the substrate, and a silver network layer disposed on a surface of the silica pore structure layer; the holes in the silver mesh structure are conical holes with large upper part and small lower part, the aperture of the large-size surface of each conical hole is 400-455 nm, the hole depth of each conical hole is 120-130 nm, and the mesh width of the silver mesh structure is 140-190 nm; the holes in the silicon dioxide porous structure are cylindrical holes; the pore diameter of the silica pore-shaped structure is 140-180 nm, and the pore depth is 50-80 nm.
10. A periodic network template prepared by the method of any one of claims 1 to 9.
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