CN106773529B - Method for preparing titanium dioxide pattern without residual layer by using room temperature transfer imprinting technology - Google Patents
Method for preparing titanium dioxide pattern without residual layer by using room temperature transfer imprinting technology Download PDFInfo
- Publication number
- CN106773529B CN106773529B CN201611093131.4A CN201611093131A CN106773529B CN 106773529 B CN106773529 B CN 106773529B CN 201611093131 A CN201611093131 A CN 201611093131A CN 106773529 B CN106773529 B CN 106773529B
- Authority
- CN
- China
- Prior art keywords
- room temperature
- substrate
- titanium dioxide
- residual layer
- pattern
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
the invention relates to a method for preparing a titanium dioxide pattern without a residual layer by utilizing a room temperature transfer imprinting technology, which comprises the following steps of (1) mixing a thermoplastic polymer solution and a titanium dioxide sol or a titanium salt solution to prepare a precursor solution; (2) then spin-coating or spray-coating the step precursor solution on the surface of a soft template with a convex-concave structure on the surface to form a composite film; (3) then contacting the soft template obtained in the step (2) with a hydrophilic substrate at room temperature, and transferring the composite membrane to the surface of the substrate; (4) then calcining the sample obtained in the step (3), and cooling to room temperature; (5) and (5) finally, placing the sample obtained in the step (4) in a mixed solution of titanium salt, concentrated hydrochloric acid and water, and forming a titanium dioxide pattern without a residual layer on the surface of the substrate under a hydrothermal condition. The invention relates to the technical field of material micro-nano processing, and can prepare a titanium dioxide pattern without a residual layer on a plane and a curved substrate by utilizing a room temperature transfer imprinting technology.
Description
Technical Field
The invention relates to the technical field of material micro-nano processing, in particular to a method for preparing a residual-layer-free titanium dioxide pattern by utilizing a room-temperature back-printing technology.
Background
Titanium dioxide (TiO)2) Is an excellent semiconductor material, has many good characteristics, such as no toxicity, no harm, stable chemical properties, high photoelectric conversion efficiency, low preparation cost and the like, and can be patterned in sensors, solar cells and photocatalysisAnd has wide application in biology and other fields.
Currently, patterned TiO is prepared2The method comprises the following steps: lithography, electron beam lithography, self-assembly, scanning probe, nanoimprint, and the like. CN1785683 reports a method for preparing a patterned titanium dioxide microstructure by using a planar substrate as a base and titanium dioxide sol as a raw material; CN1880519 reports a method for preparing titanium dioxide inverse opal photonic crystals on quartz glass or monocrystalline silicon by using silica spheres as auxiliary templates; TiO successfully imprinted by Saman Safari Diachari in Advanced Functional Material (2013)23: 2201-2211 using ethylene glycol acetoacetate methacrylate as a stabilizer for metal alkoxides2and (4) nano-pattern. However, the general process of the patterning method is complex, and special instruments and equipment are needed, so that large-area preparation is difficult to realize; meanwhile, the TiO constructed by the method2The residual layer exists in the pattern, which limits the patterning of TiO2The use of (1).
Disclosure of Invention
the invention aims to solve the problem of preparing TiO2The problem of residual layer in the pattern provides a method for preparing a titanium dioxide pattern without residual layer by using a room temperature transfer imprinting technology, which is characterized by comprising the following steps:
(1) firstly, mixing a thermoplastic polymer solution and a titanium dioxide sol or a titanium salt solution by ultrasound and heating to prepare a precursor solution;
(2) Then spin-coating or spray-coating the precursor solution obtained in the step (1) on the surface of a soft template with a convex-concave structure on the surface to form a composite film;
(3) Then contacting the soft template with the composite film attached to the surface obtained in the step (2) with a hydrophilic substrate at room temperature, separating the soft template from the surface of the substrate after 5-600 s, and transferring the composite film on the surface of the soft template to the surface of the substrate;
(4) Then calcining the substrate with the composite film attached to the surface obtained in the step (3), and cooling to room temperature after calcining;
(5) finally, placing the sample obtained after calcination in the step (4) inIn a mixed solution of titanium salt, concentrated hydrochloric acid and water, TiO without a residual layer is formed on the surface of a substrate under hydrothermal conditions2And (4) patterning.
Further, the thermoplastic polymer in step (1) includes polymethyl methacrylate, polystyrene, polyurethane, polyethylene, polypropylene, polyvinyl chloride, polybutylene, polyvinyl alcohol, polystyrene-butadiene copolymer, poly-styrene-polyoxyethylene copolymer, ABS resin, polyacrylamide, polyethylene oxide.
Further, the soft template in the steps (2) and (3) comprises a polydimethylsiloxane template, an ethylene propylene diene monomer template, a perfluoropolyether template and a polyurethane acrylate template.
Further, the substrate in the steps (3) to (5) comprises a plane and curved silicon wafer, a silicon oxide wafer, a gallium arsenide wafer, a quartz wafer, a conductive glass wafer and a polymer wafer.
Further, the room temperature in the step (3) is 0-40 ℃, and the hydrophilic substrate is realized by treating the substrate with oxygen plasma, ultraviolet ozone or solution.
further, the hydrophilic method for solution treatment in the step (3) is to place the substrate in a mixed aqueous solution of ammonia water and hydrogen peroxide, or place the substrate in a mixed solution of concentrated sulfuric acid and hydrogen peroxide, and perform treatment under the heating condition of 50-90 ℃.
Further, the calcining temperature in the step (4) is 200-550 ℃, and the calcining time is 1-7 hours.
Further, the reaction temperature of the hydrothermal condition in the step (5) is 60-200 ℃, and the reaction time is 2-19 h.
the invention has the following advantages:
(1) Preparation of residue-free TiO by room-temperature embossing and hydrothermal Synthesis2A pattern;
(2) high-resolution TiO can be prepared by controlling the concentration in the precursor liquid2A pattern;
(3) different TiO can be prepared by using different templates2A pattern having a multiplicity;
(4) Preparation of TiO2Simple and convenient pattern method, mild and easily controlled conditions, rightthe requirement of reaction equipment is low, and the requirement of large-scale production is met.
Drawings
FIG. 1 is a diagram of the preparation of a residue-free TiO layer using a room temperature transfer imprinting technique2A process schematic of the pattern;
FIG. 2 is an atomic force image of the composite film obtained by the room temperature transfer imprinting technique in example 1;
FIG. 3 shows the TiO obtained by room temperature transfer imprinting in example 12Scanning electron microscope pictures of the strips.
Detailed Description
Example 1:
The method comprises the following steps: preparation of precursor solution
The polymethyl methacrylate (PMMA) solid is ultrasonically heated and dissolved in an acetone solution to prepare a PMMA solution with the mass concentration of 2.5%, and the PMMA solution is uniformly mixed with an equal volume of 0.5mol/L ethanol solution of tetrabutyl titanate to prepare a precursor solution.
step two: preparation of Soft formwork
Weighing a prepolymer of Polydimethylsiloxane (PDMS) and an initiator according to a mass ratio of 10: 1, stirring and mixing; then casting the mixture on a silicon template with the strip width of 3 mu m and the interval of 1 mu m, and curing the mixture in an environment of 60 ℃; and (3) after curing, separating the PDMS from the silicon template to obtain the PDMS soft template.
Step three: soft template surface spin coating precursor solution
Under the conditions that the rotating speed is 4000rpm and the rotating time is 30s, the precursor liquid is coated on the surface of the PDMS soft template in a spinning mode, and the PDMS soft template with the composite membrane attached to the surface is obtained
Step four: hydrophilic treatment of substrates
Carrying out hydrophilic treatment on a silicon substrate by adopting a solution method, specifically, putting the silicon wafer in a volume ratio of 7: 3, heating the mixed solution of concentrated sulfuric acid and hydrogen peroxide at 90 ℃ for 2 hours. Taking out, washing with distilled water, and blowing with nitrogen gas for later use.
Step five: transfer of the composite film to the surface of the substrate
And (3) at room temperature, contacting the PDMS soft template with the composite film attached to the surface obtained in the third step with the hydrophilic silicon wafer substrate obtained in the fourth step, separating the PDMS from the surface of the silicon wafer substrate after 60 seconds, and transferring the composite film on the surface of the PDMS to the surface of the silicon wafer substrate.
Step six: TiO 22Preparation of the Pattern
And D, placing the sample obtained in the fifth step in a 200 ℃ muffle furnace for calcining for 2h, and then cooling to room temperature. And then placing the calcined sample into a mixed solution of tetrabutyl titanate, concentrated hydrochloric acid and water, adding the calcined sample into the mixed solution at 90 ℃ for 8 hours under a hydrothermal condition, and then taking out the sample and drying the sample by using nitrogen.
Example 2:
The method comprises the following steps: preparation of precursor solution
The method comprises the following steps of ultrasonically heating and dissolving a polymethyl methacrylate (PMMA) solid into an acetone solution to prepare a PMMA solution with the mass concentration of 1%, and uniformly mixing the PMMA solution with an equal volume of 0.2mol/L ethanol solution of tetrabutyl titanate to prepare a precursor solution.
Step two: preparation of Soft formwork
Weighing a prepolymer of Polydimethylsiloxane (PDMS) and an initiator according to a mass ratio of 10: 1, stirring and mixing; then casting the silicon template on a silicon template with the square width of 1 mu m and the interval of 1 mu m, and curing the silicon template at the temperature of 80 ℃; and (3) after curing, separating the PDMS from the silicon template to obtain the PDMS soft template.
Step three: soft template surface spin coating precursor solution
Under the conditions that the rotating speed is 6000rpm and the rotating time is 30s, the precursor liquid is coated on the surface of the PDMS soft template in a spinning mode, and the PDMS soft template with the composite membrane attached to the surface is obtained
step four: hydrophilic treatment of substrates
carrying out hydrophilic treatment on a silicon substrate by adopting a solution method, specifically, putting the silicon wafer in a volume ratio of 7: 3, heating the mixed solution of concentrated sulfuric acid and hydrogen peroxide at 90 ℃ for 2 hours. Taking out, washing with distilled water, and blowing with nitrogen gas for later use.
Step five: transfer of the composite film to the surface of the substrate
And (3) at room temperature, contacting the PDMS soft template with the composite film attached to the surface obtained in the third step with the hydrophilic silicon wafer substrate obtained in the fourth step, separating the PDMS from the surface of the silicon wafer substrate after 120s, and transferring the composite film on the surface of the PDMS to the surface of the silicon wafer substrate.
Step six: TiO 22preparation of the Pattern
and D, placing the sample obtained in the fifth step in a 200 ℃ muffle furnace for calcining for 2h, and then cooling to room temperature. And then placing the calcined sample into a mixed solution of tetrabutyl titanate, concentrated hydrochloric acid and water, adding the calcined sample into the mixed solution at 90 ℃ for 8 hours under a hydrothermal condition, and then taking out the sample and drying the sample by using nitrogen.
Example 3:
the method comprises the following steps: preparation of precursor solution
The Polystyrene (PS) solid is ultrasonically heated and dissolved in an acetone solution to prepare a PS solution with the mass concentration of 1.5%, and the PS solution is uniformly mixed with an equal volume of 0.5mol/L ethanol solution of tetrabutyl titanate to prepare a precursor solution.
Step two: preparation of Soft formwork
Weighing a prepolymer of Polydimethylsiloxane (PDMS) and an initiator according to a mass ratio of 10: 1, stirring and mixing; then casting the silicon template on a silicon template with the square width of 1 mu m and the interval of 1 mu m, and curing the silicon template at the temperature of 60 ℃; and (3) after curing, separating the PDMS from the silicon template to obtain the PDMS soft template.
Step three: soft template surface spin coating precursor solution
Under the conditions that the rotating speed is 4000rpm and the rotating time is 30s, the precursor liquid is coated on the surface of the PDMS soft template in a spinning mode, and the PDMS soft template with the composite membrane attached to the surface is obtained
Step four: hydrophilic treatment of substrates
Carrying out hydrophilic treatment on the capillary by adopting a solution method, specifically putting the capillary at a volume ratio of 7: 3, heating the mixed solution of concentrated sulfuric acid and hydrogen peroxide at 90 ℃ for 2 hours. Taking out, washing with distilled water, and blowing with nitrogen gas for later use.
Step five: transfer of the composite film to the surface of the substrate
And (3) at room temperature, contacting the PDMS soft template with the composite film attached to the surface obtained in the third step with the outer wall of the hydrophilic capillary obtained in the fourth step, separating PDMS from the surface of the silicon wafer substrate after 60 seconds, and transferring the composite film on the surface of the PDMS to the surface of the outer wall of the capillary.
step six: TiO 22Preparation of the Pattern
And D, placing the sample obtained in the fifth step in a 200 ℃ muffle furnace for calcining for 2h, and then cooling to room temperature. And then placing the calcined sample into a mixed solution of tetrabutyl titanate, concentrated hydrochloric acid and water, adding the calcined sample into the mixed solution at 90 ℃ for 8 hours under a hydrothermal condition, and then taking out the sample and drying the sample by using nitrogen.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention relates, many simple deductions or substitutions may be made without departing from the spirit of the invention, which should be construed as falling within the scope of the invention.
Claims (7)
1. A method for preparing a titanium dioxide pattern without a residual layer by using a room temperature transfer imprinting technology is characterized by comprising the following steps of:
(1) Firstly, mixing a thermoplastic polymer solution and a titanium dioxide sol or a titanium salt solution by ultrasound and heating to prepare a precursor solution;
(2) Then spin-coating or spray-coating the precursor solution obtained in the step (1) on the surface of a soft template with a convex-concave structure on the surface to form a composite film;
(3) then contacting the soft template with the composite film attached to the surface obtained in the step (2) with a hydrophilic substrate at room temperature, separating the soft template from the surface of the substrate after 5-600 s, and transferring the composite film on the surface of the soft template to the surface of the substrate;
(4) Then calcining the substrate with the composite film attached to the surface obtained in the step (3), and cooling to room temperature after calcining;
(5) Finally, placing the sample obtained after calcination in the step (4) in a mixed solution of titanium salt, concentrated hydrochloric acid and water, and forming TiO without a residual layer on the surface of the substrate under the hydrothermal condition2A pattern;
The thermoplastic polymer in the step (1) comprises polymethyl methacrylate, polystyrene, polyurethane, polyethylene, polypropylene, polyvinyl chloride, polybutylene, polystyrene-butadiene copolymer, poly-p-styrene-polyoxyethylene copolymer, ABS resin, polyacrylamide and polyethylene oxide.
2. The method of claim 1, wherein the pattern of titanium dioxide is formed without a residual layer by a room temperature transfer imprinting technique, comprising: the soft templates in the steps (2) and (3) comprise a polydimethylsiloxane template, an ethylene propylene diene monomer template, a perfluoropolyether template and a polyurethane acrylate template.
3. The method of claim 1, wherein the pattern of titanium dioxide is formed without a residual layer by a room temperature transfer imprinting technique, comprising: the substrate in the steps (3) - (5) comprises a plane and curved silicon wafer, an oxidized silicon wafer, a gallium arsenide wafer, a quartz wafer, a conductive glass wafer and a polymer wafer.
4. The method of claim 1, wherein the pattern of titanium dioxide is formed without a residual layer by a room temperature transfer imprinting technique, comprising: the room temperature in the step (3) is 0-40 ℃, and the hydrophilic substrate is realized by treating the substrate with oxygen plasma, ultraviolet ozone or solution.
5. The method of claim 4, wherein the pattern of titanium dioxide is formed without a residual layer by a room temperature transfer imprinting technique, comprising: the solution treatment substrate is prepared by placing the substrate in a mixed aqueous solution of ammonia water and hydrogen peroxide, or placing the substrate in a mixed solution of concentrated sulfuric acid and hydrogen peroxide, and treating the substrate under the heating condition of 50-90 ℃.
6. the method of claim 1, wherein the pattern of titanium dioxide is formed without a residual layer by a room temperature transfer imprinting technique, comprising: the calcining temperature in the step (4) is 200-550 ℃, and the calcining time is 1-7 h.
7. The method of claim 1, wherein the pattern of titanium dioxide is formed without a residual layer by a room temperature transfer imprinting technique, comprising: the hydrothermal condition in the step (5) has a reaction temperature of 80-200 ℃ and a reaction time of 2-19 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611093131.4A CN106773529B (en) | 2016-12-02 | 2016-12-02 | Method for preparing titanium dioxide pattern without residual layer by using room temperature transfer imprinting technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611093131.4A CN106773529B (en) | 2016-12-02 | 2016-12-02 | Method for preparing titanium dioxide pattern without residual layer by using room temperature transfer imprinting technology |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106773529A CN106773529A (en) | 2017-05-31 |
| CN106773529B true CN106773529B (en) | 2019-12-13 |
Family
ID=58913662
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611093131.4A Active CN106773529B (en) | 2016-12-02 | 2016-12-02 | Method for preparing titanium dioxide pattern without residual layer by using room temperature transfer imprinting technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106773529B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108445717A (en) * | 2018-03-08 | 2018-08-24 | 常熟理工学院 | A kind of photocuring titaniferous nano impression glue, preparation method and its application in not anti-sticking template directly imprints |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105540654A (en) * | 2015-12-10 | 2016-05-04 | 西安电子科技大学 | Preparation method for multilayer TiO2 nanostructured array material |
-
2016
- 2016-12-02 CN CN201611093131.4A patent/CN106773529B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105540654A (en) * | 2015-12-10 | 2016-05-04 | 西安电子科技大学 | Preparation method for multilayer TiO2 nanostructured array material |
Non-Patent Citations (3)
| Title |
|---|
| Biomimetic fabrication and tunable wetting properties of three-dimensional hierarchical ZnO structures by combining soft lithography templated with lotus leaf and hydrothermal treatments;Shuxi Dai et al.;《CrystEngComm》;20130304;第5417-5421页 * |
| Sub-50 nm patterning of functional oxides by soft lithographic edge printing;Antony George et al.;《Journal of Materials Chemistry》;20120330;第9501-9503页 * |
| 图案化氧化锌纳米棒阵列的构筑;张电波;《中国优秀硕士学位论文全文数据库 工程科技 I辑》;20121015;正文第24-35页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106773529A (en) | 2017-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102795592A (en) | Selective etching reparation method and application of PDMS (polydimethylsiloxane) elastomer surface hard film layer | |
| CN102689870B (en) | Nano porous material capable of being perfomed direct photoetching imaging and preparation method thereof | |
| KR20090028246A (en) | Blockcopolymer nonostructures formed on a pattern whose shape is not coincide with that of the blockcopolymer nonostructures and method for preparing thereof | |
| Hamdana et al. | Towards fabrication of 3D isotopically modulated vertical silicon nanowires in selective areas by nanosphere lithography | |
| CN108671859B (en) | Method for preparing Janus particles based on lysozyme nano-film | |
| CN1286711C (en) | Method for constructing non-close packing colloid balls ordered arrangement using soft-graving technology | |
| CN110526588B (en) | Method for initiating growth of crystalline block copolymer micelle brush based on material surface | |
| Su et al. | A heatable and evaporation-free miniature reactor upon superhydrophobic pedestals | |
| Mir et al. | Conductive polymer-Ag honeycomb thin film: the factors affecting the complexity of the microstructure | |
| CN106773529B (en) | Method for preparing titanium dioxide pattern without residual layer by using room temperature transfer imprinting technology | |
| CN104851844A (en) | Water and oxygen resistant blocking layer and preparation method and application thereof | |
| Takei et al. | Eco-friendly, water-repellent, light-transparent film derived from psicose using nanoimprint lithography | |
| CN103157525B (en) | Preparation method of micro-fluid one-way valve device based on silicon nano-pillar array | |
| Wang et al. | Controllable domain morphology in coated poly (lactic acid) films for high-efficiency and high-precision transportation of water droplet arrays | |
| CN106750473B (en) | A method of high-resolution thermoplastic polymer pattern is prepared using the anti-stamping technique of room temperature | |
| CN104851846A (en) | Flexible water and oxygen resistant packaging structure and preparation method and application thereof | |
| CN106478976B (en) | A method of thermoplastic polymer is patterned using room temperature transfer stamping technique | |
| KR20130124702A (en) | Direct transfer methods of graphene | |
| CN102219557B (en) | Preparation method of patterned zinc oxide film | |
| CN114317005B (en) | Application of photonic crystal material in preparation of light-driven or temperature-driven device | |
| CN106527044B (en) | A method of utilizing the zinc oxide pattern of room temperature transfer stamping technique preparation noresidue layer | |
| Cheng et al. | Kinetic investigation of the electrochemical synthesis of vertically-aligned periodic arrays of silicon nanorods on (001) Si substrate | |
| CN109979876B (en) | Method for preparing organic semiconductor material annular array integrated photoelectric device by using soft lithography technology | |
| CN106750419B (en) | A method of thermoplastic polymer multilevel structure is prepared using the anti-stamping technique of room temperature | |
| CN105047818A (en) | Method for preparing organic functional material pattern by use of adhesive emulsion, and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |