CN111118450A - ZnO thin film structure and preparation method thereof - Google Patents
ZnO thin film structure and preparation method thereof Download PDFInfo
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- CN111118450A CN111118450A CN201911337264.5A CN201911337264A CN111118450A CN 111118450 A CN111118450 A CN 111118450A CN 201911337264 A CN201911337264 A CN 201911337264A CN 111118450 A CN111118450 A CN 111118450A
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- C—CHEMISTRY; METALLURGY
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- 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
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- 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
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- 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
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Abstract
The invention discloses a ZnO film structure which comprises a substrate, a nano forest arranged on the substrate and a ZnO layer deposited on the nano forest. The invention also discloses a preparation method of the ZnO film, which comprises the steps of firstly selecting the substrate, coating the polymer layer on the substrate, then forming the nano forest structure, and finally depositing the ZnO layer on the nano forest structure. Compared with the traditional ZnO film, the ZnO film structure provided by the invention has the characteristics of reduced raw materials and reduced cost, and simultaneously has the characteristics of high porosity and large specific surface area of the nano forest itself. The preparation method of the ZnO film structure combines the magnetron sputtering method with the nano forest preparation process, can adjust the thickness, the appearance, the growth direction and the density of the film in the ZnO film structure through parameter control, and has the advantages of simple process and convenient operation.
Description
Technical Field
The invention relates to the field of semiconductor material processing, in particular to a ZnO film structure and a preparation method thereof.
Background
ZnO thin films are widely used for applications such as surface acoustic wave devices, planar optical waveguides, transparent electrodes, ultraviolet light emitting devices, gas sensors, etc. because they have excellent properties such as transparent conductivity, piezoelectricity, photoelectricity, gas sensitivity, and pressure sensitivity.
In order to better apply the ZnO film, the preparation of a high-quality ZnO film structure is the key. The preparation methods of ZnO film structures with different shapes are different, and the excellent ZnO film preparation method is uniform in distribution, controllable in shape, simple in process and low in cost. The conventional ZnO film preparation methods include vapor deposition, pulsed laser deposition, spray pyrolysis, a sol-gel method, magnetron sputtering, a vacuum thermal evaporation method, an electron beam evaporation deposition method, molecular beam epitaxy and the like. The advantages and the disadvantages of different preparation methods are different, for example, the preparation process of the spray pyrolysis method is simple, the prepared structure is uniformly distributed, and the defects are that the prepared nano structure has larger grain diameter; the nano structure prepared by the sol-gel method has high purity, uniform distribution, small yield, long preparation period and easy environmental pollution; the nano structure prepared by a hydrothermal method has high crystallinity, good dispersibility and higher cost; the ZnO nano film prepared by the ultrasonic method has low preparation temperature, but metal zinc particles are used, so that pollution is easy to exist, short circuit is easy to cause particularly in the application of electrical elements, and the reliability is reduced; the vacuum thermal evaporation method has higher requirement on temperature, is difficult to prepare a film with good crystallinity, and has poor process repeatability; the electron beam evaporation deposition method can generate secondary electrons in the preparation process, and easily influences the quality and purity of the prepared ZnO film.
Therefore, there is a need for a method for preparing a ZnO film, which has uniform distribution and controllable morphology and can reduce the cost.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect that the cost control, the distribution uniformity and the appearance controllability in the existing ZnO film preparation technology cannot be achieved at the same time, thereby providing a ZnO film structure and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a ZnO film structure, which comprises,
a substrate, a first electrode and a second electrode,
a nano-forest structure disposed on the substrate,
wrapping a ZnO layer of a nano forest structure;
the height of the nano forest structure is 0.1-50 mu m, and the thickness of the ZnO layer is 50-500 nm.
Further, the nano forest structure is a one-dimensional ordered structure formed by one of a nanofiber structure, a nano column structure, a nano cone structure or a nanofiber-nano column structure and a nanofiber-nano cone structure.
Further, the material forming the nano-pillars or nano-cones is consistent with the substrate material;
the material forming the nanofibers is a polymer.
Preferably, the substrate material is silicon-based, glass, quartz, sapphire, Polymethylmethacrylate (PMMA), Polytetrafluoroethylene (PTFE), cross-linked Polystyrene (PS), and Polycarbonate (PC);
the polymer comprises one of positive photoresist, negative photoresist, polyimide, polydimethylsiloxane and other polymer materials which can be subjected to plasma bombardment.
Further, the diameter of the nano fiber is 50-150nm, and the height is 0.1-50 μm;
the diameter of the bottom of the nano column or the nano cone is 50-500nm, and the height of the nano column or the nano cone is 0.1-3 mu m;
and nano-scale gaps are formed among the nano-fibers, the nano-columns or the nano-cones.
The invention also discloses a preparation method of the ZnO film structure, which comprises the following steps:
s1: coating a polymer layer on a substrate;
s2: forming a nano forest structure;
s3: and depositing a ZnO layer on the nano forest structure.
Further, the step S2 is:
if the nano forest structure is a nano fiber, bombarding the polymer layer to form the nano forest structure; or the like, or, alternatively,
if the nano forest structure is a nano fiber-nano column or a nano fiber-nano cone, bombarding the polymer layer to form a nano fiber, and then taking the nano fiber as a mask layer to etch the substrate to form the substrate with the nano column or the nano cone; or the like, or, alternatively,
if the nano forest structure is a nano column or a nano cone, bombarding the polymer layer to form nano fibers, then taking the nano fibers as a mask layer, carrying out etching treatment on the substrate to form the substrate with the nano column or the nano cone, and finally removing the mask layer of the nano fibers.
Further, the bombardment is carried out for 1-2 times by plasma, the used plasma is one of argon plasma, oxygen plasma or nitrogen plasma which can cause ashing and dissociation to the polymer, the flow of a plasma gas source in each bombardment is 20-100sccm, the cavity pressure is 0.5-10Pa, the radio frequency power is 100-350W, and the processing time is 2-180 min.
The etching treatment is reactive ion etching, and the used gas is Cl2、Br2HBr and CF3One of Br, or Cl2/HBr、SF6/O2/CHF3、SF6/Cl2/HBr、Cl2/He/O2/HBr、SF6/O2And SF6/Cl2/O2The gas is mixed according to any proportion, the conditions of reactive ion etching are that the radio frequency power is 300-;
the nanofiber mask layer is removed by wet etching, specifically, HF and NH4F is prepared according to the proportion of 1:7 to mitigate the corrosion of the hydrofluoric acid solution for 50-90 s.
In addition, if the nano-forest structures are nano-fibers, the polymer layer may be patterned after forming the polymer layer between steps S1 and S2, that is, the polymer layer may be covered with a mask layer, and the polymer layer may be etched under the mask of the mask layer and removed to form patterning of the polymer layer. If the polymer layer is a photosensitive polymer material, such as a positive photoresist, a negative photoresist, etc., the patterning of the polymer layer can be directly performed by photolithography and development.
Preferably, in step S1, the coating is spin coating, the spin coating speed is 2000-4000rpm, and the spin coating time is 30-60S;
the baking temperature is 90-120 ℃, and the baking time is 8-15 min.
In the step S3, the deposition is sputtering deposition by using a magnetron sputtering device, wherein the sputtering temperature is 15-50 ℃, and the sputtering time is 0.1-5 h.
In addition, in step S3, metal ions of the ZnO thin film may be doped, the doped ions may be gold (Au) ions, silver (Ag) ions, cobalt (Co) ions, or nickel (Ni) ions, and the ion doping may improve the specific gas sensing capability of ZnO, thereby expanding the application of ZnO in specific gas sensors.
The technical scheme of the invention has the following advantages:
1. compared with the traditional ZnO film, the ZnO film structure provided by the invention has the advantages that ZnO is deposited on the nano forest, and the ZnO film structure utilizes the height of the nano forest to prepare the ZnO film with the same height, uses fewer ZnO raw materials, reduces the cost of the ZnO film, has the characteristics of high porosity and large surface area of the nano forest, and enhances the performance of the ZnO film. For example, in the application of gas sensor, the high porosity and large surface area increase the physical and chemical adsorption of the ZnO film, thereby improving the gas-sensitive performance of the ZnO film with the same film thickness.
2. According to the ZnO film structure provided by the invention, the nano forest can be in a structure of nano fiber, nano cone and nano column, and ZnO deposited on the nano forests with different structures can be applied to the aspects of biology, molecular detection, micro flow control, gas sensing, humidity sensing and the like according to different requirements.
3. The preparation method of the ZnO film structure combines the magnetron sputtering method with the nano forest preparation process, can adjust the thickness, the appearance, the growth direction and the density of the film in the ZnO film structure through parameter control, and has the advantages of simple process and convenient operation.
4. The preparation method of the ZnO film structure can be used for carrying out graphical treatment on the polymer layer before the nano forest is prepared, and can also be used for doping metal ions during deposition of the ZnO film, so that the application range of the ZnO film structure is expanded.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic structural diagram of a completed nanofiber prepared on a substrate in examples 1-7 of the present application;
FIG. 2 is a schematic structural diagram of a nanofiber substrate after depositing a ZnO layer thereon in example 1 of the present application;
FIG. 3 is a SEM image of ZnO layer deposited on the nanofiber in example 1 of the present application;
FIG. 4 is a schematic diagram of a nanofiber-nanocone structure after reactive ion etching in example 2 of the present application;
FIG. 5 is a scanning electron micrograph of a nanofiber-nanocone structure after reactive ion etching in example 2 of the present application;
FIG. 6 is a schematic structural diagram of a nanofiber-nanocone structure after a ZnO layer is deposited thereon in example 2 of the present application;
FIG. 7 is a scanning electron micrograph of a ZnO layer deposited on a nanofiber-nanocone structure in example 2 of the present application;
FIG. 8 is a schematic structural diagram of a nanocone after wet etching in example 3 of the present application;
FIG. 9 is a scanning electron micrograph of a nanocone after wet etching in example 3 of the present application;
FIG. 10 is a schematic structural diagram of a ZnO layer deposited on a nanocone structure in example 3 of the present application;
FIG. 11 is a schematic diagram of the structure of the nanofiber-nanorod after reactive ion etching in example 4 of the present application;
fig. 12 is a schematic structural view after a ZnO layer is deposited on the nanofiber-nanorod structure in example 4 of the present application;
FIG. 13 is a schematic structural diagram of a nano-pillar after wet etching in example 5 of the present application;
FIG. 14 is a schematic structural view after a ZnO layer is deposited on the nano-pillar structure in example 5 of the present application;
FIG. 15 is a schematic structural view after a ZnO layer is deposited on the nanofibers in example 6 of the present application;
FIG. 16 is a SEM image of ZnO layer deposited on the nanofibers in example 6 of the present application;
fig. 17 is a schematic structural view of a polymer layer subjected to patterning in example 7 of the present application.
Reference numerals:
1-a substrate; 2-nanofibers; 3-ZnO film; 4-nanocone; 5-nano-pillars, 6-patterned polymer layer.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Examples 1-7 of the present application used single crystal silicon as the substrate material, examples 1-6 used polyimide as the polymer material, and example 7 used SU-8 photoresist as the polymer material.
Example 1
The embodiment provides a preparation method of a ZnO thin film structure, which comprises the following steps:
(1) spin-coating a polyimide layer with the thickness of 4 microns on a monocrystalline silicon substrate, wherein the rotation speed is 2500rpm, the spin-coating time is 40s, the monocrystalline silicon substrate is placed on a hot plate for baking after the spin-coating, the baking temperature is 120 ℃, and the baking time is 10 min;
(2) performing a plasma bombardment process by using plasma cleaning equipment, wherein the used plasmas are oxygen plasma and argon plasma, the flow of an oxygen plasma gas source is 50sccm, the flow of an argon plasma gas source is 20sccm, the pressure of an oxygen cavity is 5Pa, the pressure of an argon cavity is 2Pa, the radio frequency power is 350W, the processing time of the oxygen plasma is 9min, the processing time of the argon plasma is 25min, and nanofibers are obtained on a substrate, as shown in FIG. 1, the diameter of the nanofibers is 50-100nm, the number of the nanofibers in each square micrometer area is 20-40, and the height of the nanofibers is 1.7 micrometers;
(3) and (3) carrying out sputtering deposition of a ZnO layer on the surface of the nanofiber by using magnetron sputtering equipment, wherein the sputtering temperature is 25 ℃, the sputtering time is 0.5h, and the thickness of the deposited ZnO layer is 100nm to obtain a nanofiber-ZnO film core-shell structure, as shown in figure 2, and a scanning electron microscope photo thereof is as shown in figure 3.
Example 2
The embodiment provides a preparation method of a ZnO thin film structure, which comprises the following steps:
(1) spin-coating a polyimide layer with the thickness of 3 microns on a monocrystalline silicon substrate, wherein the rotation speed is 3300rpm, the spin-coating time is 40s, the substrate is placed on a hot plate for baking after the spin-coating, the baking temperature is 120 ℃, and the baking time is 10 min;
(2) performing a plasma bombardment process by using plasma cleaning equipment, wherein the used plasma is oxygen plasma, the flow of an oxygen plasma gas source is 50sccm, the cavity pressure is 5Pa, the radio-frequency power is 350W, the oxygen plasma treatment time is 9min, and a nanofiber structure is obtained on the substrate, as shown in FIG. 1, the diameter of the nanofiber is 100-150nm, the number of nanofibers in each square micron area is 10-15, and the height of the nanofiber is 0.85 μm;
(3) performing reactive ion etching on the substrate by using the nano-fiber as a mask, wherein the etching gas is chlorine (Cl)2) And hydrogen bromide (HBr), the radio frequency power is 350W, the chamber pressure is 400mTorr, the etching time is 300s, more materials are etched on the upper part of the etched structure than on the lower part of the etched structure, and a nanofiber-nanocone structure is formed, as shown in FIG. 4, the diameter of the bottom of the nanocone is 150-500nm, the diameter of the tip is 5-25nm, the number of the nanocone structures in each square micron area is 3-40, the height of the nanocone is 0.8 μm, and a scanning electron microscope photo is shown in FIG. 5;
(4) and (3) carrying out sputtering deposition of a ZnO layer on the surface of the nanofiber-nanocone by using magnetron sputtering equipment, wherein the sputtering temperature is 25 ℃, and the sputtering time is 0.25h, so as to obtain a nanofiber-nanocone-ZnO film structure, as shown in figure 6, the thickness of the ZnO layer is 50nm, and a scanning electron microscope photo is as shown in figure 7.
Example 3
The difference between this embodiment and embodiment 2 is that each step has different parameters, and a wet etching process is added after step (3) to remove the nanofibers, so as to obtain a nanocone-ZnO thin film structure.
(1) Spin-coating a polyimide layer with the thickness of 5 microns on a monocrystalline silicon substrate, wherein the rotation speed is 2000rpm and the spin-coating time is 40s, placing the monocrystalline silicon substrate on a hot plate for baking after the spin-coating, and the baking temperature is 120 ℃ and the baking time is 10 min;
(2) performing a plasma bombardment process by using plasma cleaning equipment, wherein the used plasma is oxygen plasma, the flow of an oxygen plasma gas source is 50sccm, the cavity pressure is 5Pa, the radio-frequency power is 350W, the oxygen plasma treatment time is 9min, and a nanofiber structure is obtained on the substrate, as shown in FIG. 1, the diameter of the nanofiber is 100-150nm, and the number of nanofibers in each square micron area is 10-15;
(3) the nano-fiber is used as a mask,performing reactive ion etching on the substrate with chlorine (Cl) as etching gas2) And hydrogen bromide (HBr), the radio frequency power is 350W, the chamber pressure is 400mTorr, the etching time is 300s, more materials are etched on the upper part of the structure after etching compared with the lower part of the structure to form a nanofiber-nanocone structure, as shown in FIG. 4, the diameter of the bottom of the nanocone is 150-500nm, the diameter of the tip is 5-25nm, the number of the nanocone structures in each square micron area is 3-40, and the height of the nanocone is 1.2 μm;
(4) removing the nanofibers by wet etching, and adding HF and NH4F is prepared into a mild hydrofluoric acid solution according to the ratio of 1:7 for 60s, the nano-fibers are removed, and a nano-cone structure is left, as shown in figure 8, and a scanning electron micrograph is shown in figure 9;
(5) and (3) carrying out sputtering deposition of the ZnO layer on the surface of the nanocone by using magnetron sputtering equipment, wherein the sputtering temperature is 25 ℃, and the sputtering time is 0.5h, so as to obtain a nanocone-ZnO thin film structure, and the thickness of the ZnO layer is 100nm as shown in figure 10.
Example 4
The embodiment provides a preparation method of a ZnO thin film structure, which comprises the following steps:
(1) spin-coating a polyimide layer with the thickness of 4 microns on a monocrystalline silicon substrate, wherein the rotation speed is 2500rpm, the spin-coating time is 40s, the monocrystalline silicon substrate is placed on a hot plate for baking after the spin-coating, the baking temperature is 120 ℃, and the baking time is 10 min;
(2) performing a plasma bombardment process by using plasma cleaning equipment, wherein the used plasmas are oxygen plasma and argon plasma, the flow of an oxygen plasma gas source is 50sccm, the flow of an argon plasma gas source is 20sccm, the pressure of an oxygen cavity is 5Pa, the pressure of an argon cavity is 2Pa, the radio-frequency power is 350W, the processing time of the oxygen plasma is 9min, the processing time of the argon plasma is 25min, as shown in FIG. 1, the diameter of the nanofiber is 50-100nm, 20 nanofibers in each square micrometer area are, and the height of the nanofiber is 1.7 mu m;
(3) taking the nanofiber structure as a mask, and performing reactive ion etching on the substrate by using chlorine (Cl) as etching gas2) And hydrogen bromide (HBr), RF power of 350W, chamber pressure of400mTorr, the etching time is 240s, and a nanofiber-nanorod structure is formed after etching, as shown in FIG. 11, the diameter of the nanorod is 50-500nm, the number of the nanorod structures in each square micron area is 3-40, and the height of the nanorod is 1 μm;
(4) and (3) carrying out sputtering deposition of the ZnO film on the surface of the nanofiber-nanorod by using magnetron sputtering equipment, wherein the sputtering temperature is 25 ℃, and the sputtering time is 0.75h, so as to obtain a nanofiber-nanorod-ZnO film structure, as shown in figure 12, the thickness of the ZnO film is 150 nm.
Example 5
The difference between this embodiment and embodiment 4 is that the parameters of each step are different, and a wet etching process is added after step (3) to remove the nanofibers, so as to obtain the nanorod-ZnO thin film structure.
The embodiment provides a preparation method of a ZnO thin film structure, which comprises the following steps:
(1) spin-coating a polyimide layer with the thickness of 3.5 mu m on a monocrystalline silicon substrate, wherein the rotation speed is 3000rpm and the spin-coating time is 40s, the substrate is placed on a hot plate for baking after the spin-coating, the baking temperature is 120 ℃, and the baking time is 10 min;
(2) performing a plasma bombardment process by using plasma cleaning equipment, wherein the used plasmas are oxygen plasma and argon plasma, the flow of an oxygen plasma gas source is 50sccm, the flow of an argon plasma gas source is 20sccm, the pressure of an oxygen cavity is 5Pa, the pressure of an argon cavity is 2Pa, the radio-frequency power is 350W, the processing time of the oxygen plasma is 9min, the processing time of the argon plasma is 25min, as shown in FIG. 1, the diameter of the nanofiber is 50-100nm, 20 nanofibers in each square micrometer area are, and the height of the nanofiber is 1.5 mu m;
(3) taking the nanofiber structure as a mask, and performing reactive ion etching on the substrate by using chlorine (Cl) as etching gas2) And hydrogen bromide (HBr), the radio frequency power is 350W, the chamber pressure is 400mTorr, the etching time is 240s, and a nanofiber-nanocolumn structure is formed after etching, as shown in fig. 11, the diameter of the nanocolumn is 50-500nm, the number of the nanocolumn structures in each square micron area is 3-40, and the height of the nanocolumn is 1.5 μm;
(4) removing the nanofibers by wet etching, and adding HF and NH4F is prepared according to the ratio of 1:7 to relieve the corrosion of hydrofluoric acid solution for 60s, the nano-fibers are removed, and nano-columns are left, as shown in figure 13;
(5) sputtering deposition of a ZnO film is carried out on the surface of the nano-pillar by using magnetron sputtering equipment, wherein the sputtering temperature is 25 ℃, the sputtering time is 1h, and a nano-pillar-ZnO film structure is obtained, as shown in FIG. 14, and the thickness of the ZnO film is 200 nm.
Example 6
The difference between this example and example 1 is that the parameters of each step are different, and the thickness of the deposited ZnO layer is increased in the previous step (3) to obtain a nanofiber-ZnO film structure with a pore top seal in the middle.
The embodiment provides a preparation method of a ZnO thin film structure, which comprises the following steps:
(1) spin-coating a polyimide layer with the thickness of 5 microns on a monocrystalline silicon substrate, wherein the rotation speed is 2000rpm and the spin-coating time is 40s during the spin-coating, and then placing the substrate on a hot plate for baking, wherein the baking temperature is 120 ℃, and the baking time is 10 min;
(2) performing a plasma bombardment process by using plasma cleaning equipment, wherein the used plasmas are oxygen plasma and argon plasma, the flow of an oxygen plasma gas source is 50sccm, the flow of an argon plasma gas source is 20sccm, the pressure of an oxygen cavity is 5Pa, the pressure of an argon cavity is 2Pa, the radio frequency power is 350W, the processing time of the oxygen plasma is 9min, the processing time of the argon plasma is 25min, and nanofibers are obtained on the substrate, as shown in FIG. 1, the diameter of the nanofibers is 50-100nm, the number of the nanofibers in each square micrometer area is 20-40, and the height of the nanofibers is 2 micrometers;
(3) and (3) carrying out sputtering deposition of a ZnO layer on the surface of the nanofiber by using magnetron sputtering equipment, wherein the sputtering temperature is 25 ℃, and the sputtering time is 1.5h, so as to obtain the nanofiber-ZnO film core-shell structure with the top seal and the middle part provided with pores, as shown in fig. 15, the thickness of the ZnO film is 300nm, and the scanning electron microscope photo of the ZnO film is as shown in fig. 16.
Example 7
This embodiment is an embodiment in which the polymer layer is patterned after it is formed.
The embodiment provides a preparation method of a ZnO thin film structure, which comprises the following steps:
(1) spin-coating a 30-micrometer SU-8 photoresist layer on a monocrystalline silicon substrate at 2000rpm for 60s, baking on a hot plate at 100 deg.C for 7 min;
(2) and carrying out patterning treatment on the SU-8 photoresist layer. Designing a photoetching mask into a desired pattern, carrying out photoetching exposure on a sample on a photoetching machine, aligning the mask with a substrate, carrying out exposure operation, immersing the sample into a developing solution for developing operation after exposure is finished, and then cleaning the developing solution to finish patterning treatment, as shown in FIG. 17;
(3) carrying out a plasma bombardment process by using plasma cleaning equipment, wherein the used plasmas are oxygen plasma and argon plasma, the flow of an oxygen plasma gas source is 60sccm, the flow of an argon plasma gas source is 30sccm, the pressure of an oxygen cavity is 5Pa, the pressure of an argon cavity is 2Pa, the radio frequency power is 350W, the processing time of the oxygen plasma is 60min, the processing time of the argon plasma is 60min, a nanofiber structure is obtained on a substrate, the diameter of the nanofiber is 50-150nm, 20-40 nanofibers in each square micrometer area are formed, and the height of the nanofiber is 25 micrometers;
(4) and (3) carrying out sputtering deposition of the ZnO layer on the surface of the nanofiber structure by using magnetron sputtering equipment, wherein the sputtering temperature is 25 ℃, and the sputtering time is 0.5h, so that the nanofiber-ZnO layer structure is obtained, and the thickness of the ZnO film is 100 nm.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A ZnO thin film structure is characterized by comprising,
a substrate, a first electrode and a second electrode,
a nano-forest structure disposed on the substrate,
wrapping a ZnO layer of a nano forest structure;
the height of the nano forest structure is 0.1-50 mu m, and the thickness of the ZnO layer is 50-500 nm.
2. The ZnO thin film structure of claim 1, wherein the ZnO thin film structure,
the nano forest structure is a one-dimensional ordered structure formed by one of a nanofiber structure, a nano column structure, a nano cone structure or a nanofiber-nano column structure and a nanofiber-nano cone structure.
3. The ZnO thin film structure of claim 2, wherein the material forming the nano-pillars or nano-cones is identical to the substrate material;
the material forming the nanofibers is a polymer.
4. The ZnO thin film structure according to claim 2 or 3,
the diameter of the nano fiber is 50-150nm, and the height of the nano fiber is 0.1-50 mu m;
the diameter of the bottom of the nano column or the nano cone is 50-500nm, and the height of the nano column or the nano cone is 0.1-3 mu m;
and nano-scale gaps are formed among the nano-fibers, the nano-columns or the nano-cones.
5. A method for preparing the ZnO film structure of any one of claims 1 to 4, which is characterized by comprising the following steps:
s1: coating a polymer layer on a substrate;
s2: forming a nano forest structure;
s3: and depositing a ZnO layer on the nano forest structure.
6. The method for preparing the ZnO thin film structure of claim 5, wherein the step S2 is as follows:
if the nano forest structure is a nano fiber, bombarding the polymer layer to form the nano forest structure; or the like, or, alternatively,
if the nano forest structure is a nano fiber-nano column or a nano fiber-nano cone, bombarding the polymer layer to form a nano fiber, and then taking the nano fiber as a mask layer to etch the substrate to form the substrate with the nano column or the nano cone; or the like, or, alternatively,
if the nano forest structure is a nano column or a nano cone, bombarding the polymer layer to form nano fibers, then taking the nano fibers as a mask layer, carrying out etching treatment on the substrate to form the substrate with the nano column or the nano cone, and finally removing the mask layer of the nano fibers.
7. The method as claimed in claim 6, wherein the bombardment is performed by plasma for 1-2 times, the plasma used is one of argon plasma, oxygen plasma or nitrogen plasma, the flow rate of the plasma gas source is 20-100sccm, the chamber pressure is 0.5-10Pa, the RF power is 100-350W, and the treatment time is 2-180 min.
8. The method according to claim 6, wherein the etching process is reactive ion etching and the gas used is Cl2、Br2HBr and CF3One of Br, or Cl2/HBr、SF6/O2/CHF3、SF6/Cl2/HBr、Cl2/He/O2/HBr、SF6/O2And SF6/Cl2/O2The gas is mixed according to any proportion, the conditions of reactive ion etching are that the radio frequency power is 300-;
the nanofiber mask layer is removed by wet etching, specifically, HF and NH4F is prepared according to the proportion of 1:7 to mitigate the corrosion of the hydrofluoric acid solution for 50-90 s.
9. The production method according to claim 5,
in step S1, the coating is spin coating, the spin coating rotation speed is 2000-4000rpm, and the spin coating time is 30-60S;
the baking temperature is 90-120 ℃, and the baking time is 8-15 min.
10. The method according to claim 5, wherein in step S3, the deposition is sputtering deposition by using a magnetron sputtering device, the sputtering temperature is 15-50 ℃, and the sputtering time is 0.1-5 h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111896121A (en) * | 2020-07-13 | 2020-11-06 | 无锡物联网创新中心有限公司 | MEMS thermopile infrared detector |
| CN112520688A (en) * | 2020-11-13 | 2021-03-19 | 中国科学院微电子研究所 | Preparation method of nano forest structure |
| CN113005432A (en) * | 2021-02-18 | 2021-06-22 | 西安交通大学 | Method for depositing ZnO functional layer in patterned mode, strain sensor and preparation method of strain sensor |
| CN114113031A (en) * | 2021-10-26 | 2022-03-01 | 中国科学院微电子研究所 | Three-dimensional SERS substrate and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060197436A1 (en) * | 2005-03-01 | 2006-09-07 | Sharp Laboratories Of America, Inc. | ZnO nanotip electrode electroluminescence device on silicon substrate |
| CN102024637A (en) * | 2009-09-17 | 2011-04-20 | 深圳华映显示科技有限公司 | Method for preparing zinc oxide nano column array field emission component |
| US20110247548A1 (en) * | 2010-04-12 | 2011-10-13 | Gwangju Institute Of Science And Technology | Method For Fabricating Of ZnO Particle And Method For Fabricating Of ZnO Rod |
| CN104931480A (en) * | 2015-06-17 | 2015-09-23 | 中国科学院微电子研究所 | SERS substrate and manufacturing method thereof |
| CN105866187A (en) * | 2016-03-25 | 2016-08-17 | 中国科学院高能物理研究所 | Semiconductor gas-sensitive sensor and making method thereof |
| CN106206779A (en) * | 2016-08-01 | 2016-12-07 | 中国科学院高能物理研究所 | Heterojunction solar battery with silicon nano column array as substrate and preparation method thereof |
| CN107991768A (en) * | 2017-11-28 | 2018-05-04 | 中国科学院微电子研究所 | MEMS optics, light-absorption nano structure and preparation method thereof |
| CN109742242A (en) * | 2019-03-01 | 2019-05-10 | 常熟理工学院 | A kind of wide spectrum nano-array detector and preparation method thereof |
-
2019
- 2019-12-23 CN CN201911337264.5A patent/CN111118450A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060197436A1 (en) * | 2005-03-01 | 2006-09-07 | Sharp Laboratories Of America, Inc. | ZnO nanotip electrode electroluminescence device on silicon substrate |
| CN102024637A (en) * | 2009-09-17 | 2011-04-20 | 深圳华映显示科技有限公司 | Method for preparing zinc oxide nano column array field emission component |
| US20110247548A1 (en) * | 2010-04-12 | 2011-10-13 | Gwangju Institute Of Science And Technology | Method For Fabricating Of ZnO Particle And Method For Fabricating Of ZnO Rod |
| CN104931480A (en) * | 2015-06-17 | 2015-09-23 | 中国科学院微电子研究所 | SERS substrate and manufacturing method thereof |
| CN105866187A (en) * | 2016-03-25 | 2016-08-17 | 中国科学院高能物理研究所 | Semiconductor gas-sensitive sensor and making method thereof |
| CN106206779A (en) * | 2016-08-01 | 2016-12-07 | 中国科学院高能物理研究所 | Heterojunction solar battery with silicon nano column array as substrate and preparation method thereof |
| CN107991768A (en) * | 2017-11-28 | 2018-05-04 | 中国科学院微电子研究所 | MEMS optics, light-absorption nano structure and preparation method thereof |
| CN109742242A (en) * | 2019-03-01 | 2019-05-10 | 常熟理工学院 | A kind of wide spectrum nano-array detector and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111896121A (en) * | 2020-07-13 | 2020-11-06 | 无锡物联网创新中心有限公司 | MEMS thermopile infrared detector |
| CN112520688A (en) * | 2020-11-13 | 2021-03-19 | 中国科学院微电子研究所 | Preparation method of nano forest structure |
| CN113005432A (en) * | 2021-02-18 | 2021-06-22 | 西安交通大学 | Method for depositing ZnO functional layer in patterned mode, strain sensor and preparation method of strain sensor |
| CN113005432B (en) * | 2021-02-18 | 2022-05-20 | 西安交通大学 | Method for depositing ZnO functional layer in patterned mode, strain sensor and preparation method of strain sensor |
| CN114113031A (en) * | 2021-10-26 | 2022-03-01 | 中国科学院微电子研究所 | Three-dimensional SERS substrate and preparation method and application thereof |
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