CN114895536A - Preparation method of patterned Zn-MOF film based on laser direct writing - Google Patents

Preparation method of patterned Zn-MOF film based on laser direct writing Download PDF

Info

Publication number
CN114895536A
CN114895536A CN202210823416.8A CN202210823416A CN114895536A CN 114895536 A CN114895536 A CN 114895536A CN 202210823416 A CN202210823416 A CN 202210823416A CN 114895536 A CN114895536 A CN 114895536A
Authority
CN
China
Prior art keywords
patterned
laser direct
film
photoresist
zinc
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.)
Granted
Application number
CN202210823416.8A
Other languages
Chinese (zh)
Other versions
CN114895536B (en
Inventor
关玲玲
曹春
夏贤梦
邱毅伟
沈小明
匡翠方
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Lab
Original Assignee
Zhejiang Lab
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Zhejiang Lab filed Critical Zhejiang Lab
Priority to CN202210823416.8A priority Critical patent/CN114895536B/en
Publication of CN114895536A publication Critical patent/CN114895536A/en
Application granted granted Critical
Publication of CN114895536B publication Critical patent/CN114895536B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2051—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
    • G03F7/2053—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a laser
    • 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
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/70383—Direct write, i.e. pattern is written directly without the use of a mask by one or multiple beams
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a preparation method of a patterned Zn-MOF film based on laser direct writing, belonging to the technical field of patterned materials, and the preparation method comprises the following steps: (1) performing patterned photoetching on the zinc-based photoresist by using a femtosecond laser direct writing technology, and developing to obtain a polymerized photoetching pattern; (2) carrying out high-temperature annealing on the obtained photoetching pattern to obtain a patterned ZnO film; (3) the method has the advantages that the patterned Zn-MOF film can be rapidly prepared by utilizing a laser direct writing method, the operation is simple, and the pattern of the MOF film can be controlled in a micron size.

Description

Preparation method of patterned Zn-MOF film based on laser direct writing
Technical Field
The invention belongs to the field of patterning materials, and particularly relates to a method for preparing a patterned Zn-MOF film by using a laser direct writing technology.
Background
The femtosecond laser direct writing technology is to directly generate a two-dimensional or three-dimensional structure by using femtosecond laser beams to write on a substrate coated with photoresist, and is an ideal means of mask-free micro-nano processing.
Metal-organic frameworks (MOFs) are crystalline materials formed by self-assembly of Metal ions or Metal clusters with organic ligands. The metal organic framework material is widely applied to the fields of gas adsorption, catalysis, biological medicine carrying, luminescence and the like due to the advantages of large specific surface area, high porosity, modifiability, adjustable structure and performance and the like. However, for the fields of micro-nano electronic devices, batteries, super capacitors, sensing and the like, the MOFs as solid powder cannot meet the requirements of practical devices. Therefore, research and development of MOFs films have been receiving wide attention, and mainly focused on the fields of methods for preparing MOFs films, preparation of patterned MOFs films, preparation of mixed matrix MOFs films, and the like.
Aiming at the growth of uniform MOF films with large areas, the methods mainly adopted at present comprise an in-situ growth method, a layer-by-layer growth method, a seed crystal growth method and a chemical vapor deposition method. However, for some specific applications, such as microfluidics, chips, etc., it is desirable to integrate MOFs into a fixed location in a small device. At this time, growing only MOF films of large area cannot meet the demand, and therefore, the development of new methods for preparing patterned MOF films of microscopic size is urgent.
Disclosure of Invention
The present invention is directed to addressing the limitations of the prior art by providing a simple method of making micron-sized patterned MOF films using femtosecond laser direct writing techniques.
The invention adopts the following technical scheme:
a preparation method of a patterned Zn-MOF film based on laser direct writing comprises the following steps:
s1: preparing a zinc-based photoresist:
weighing a monomer, a solvent and a photoinitiator according to a proportion, adding the monomer, the solvent and the photoinitiator into a brown bottle, ultrasonically dissolving, and filtering for a plurality of times by using a 0.22 mu m needle head type filter to obtain a zinc-based photoresist;
s2: laser direct writing:
dropwise adding the zinc-based photoresist on common glass, spin-coating on a photoresist homogenizer to prepare a photoresist film, and developing after exposing the photoresist film by using femtosecond laser to obtain a photoresist pattern;
s3: high-temperature oxidation:
placing the photoresist pattern obtained after exposure and development in a muffle furnace, and annealing for 1-3 h at 600-800 ℃ in an air atmosphere to obtain a patterned ZnO film;
s4: preparation of Zn-MOF film:
dissolving dimethyl imidazole in N, N-Dimethylformamide (DMF) and H 2 And (2) ultrasonically dissolving the O in the mixed solution, transferring the solution into a reaction kettle, placing the prepared patterned ZnO film into the solution, reacting at 70-100 ℃, washing the reacted film for a plurality of times by using methanol, and drying at 60 ℃ to obtain the patterned ZIF-8 film.
Preferably, the monomer in step S1 is zinc acrylate or zinc methacrylate.
Preferably, the solvent in step S1 is propylene glycol monomethyl ether, ethylene glycol monomethyl ether or a mixture of the two.
Preferably, the photoinitiator in step S1 is 7-diethylamino-3-thenoyl coumarin.
Preferably, in the step S1, the mass of the monomer in the zinc-based photoresist accounts for 5-10% of the mass of the solvent, and the mass of the initiator accounts for 0.5-2.5% of the mass of the monomer.
Preferably, in step S3, the temperature increase rate and the temperature decrease rate during annealing are set to 20 ℃/min and 5 ℃/min, respectively.
Preferably, in the step S4, dimethyl imidazole, N-Dimethylformamide (DMF) and H 2 The mass ratio of O is 1: 114: 30-50.
Preferably, in step S1, the ultrasonic dissolution is 30 min.
Preferably, in the step S4, the reaction time of the patterned ZnO film in the solution is 24-36 h.
Preferably, in step S4, the film after reaction is washed and then dried at 60 ℃ for 1 hour.
The invention has the beneficial effects that:
(1) the preparation method realizes the preparation of the patterned Zn-MOF film by a laser direct writing method, has simple preparation method, and can realize the preparation of the MOF film with any pattern.
(2) According to the invention, the zinc-based photoresist is used for photoetching and then is oxidized at high temperature to generate the patterned ZnO film which is used as a metal source for MOF growth, so that the problem of adhesion between the MOF film and the substrate is solved, and the substrate is not required to be pretreated.
(3) The femtosecond laser direct writing technology can control the pattern in the micron size, so that the position and the size of the MOF pattern can be accurately controlled, and the application of the MOF film in an actual device is very facilitated.
Drawings
FIG. 1 is a rectangular pattern after photolithographic development of a zinc-based photoresist in example 1;
FIG. 2 is a zinc oxide pattern obtained by high temperature annealing of a zinc-based photoresist pattern of example 1;
FIG. 3 is a patterned ZIF-8 film obtained in example 1 by placing a zinc oxide pattern after high temperature annealing in a ligand solution and subjecting it to hydrothermal reaction;
FIG. 4 is a powder diffraction XRD pattern of ZIF-8 obtained in example 1.
Detailed Description
The present invention will be further illustrated with reference to the following examples, which are not intended to limit the scope of the present invention, and various modifications and variations can be made by those skilled in the art without inventive changes based on the technical solution of the present invention.
The invention relates to a preparation method of a patterned Zn-MOF film based on laser direct writing, which comprises the following steps:
s1: preparing a zinc-based photoresist:
weighing a monomer, a solvent and a photoinitiator according to a proportion, adding the monomer, the solvent and the photoinitiator into a brown bottle, ultrasonically dissolving, and filtering for a plurality of times by using a 0.22 mu m needle head type filter to obtain a zinc-based photoresist;
s2: laser direct writing:
dropwise adding the zinc-based photoresist on common glass, spin-coating on a photoresist homogenizer to prepare a photoresist film, and developing after exposing the photoresist film by using femtosecond laser to obtain a photoresist pattern;
s3: high-temperature oxidation:
placing the photoresist pattern obtained after exposure and development in a muffle furnace, and annealing for 1-3 h at 600-800 ℃ in an air atmosphere to obtain a patterned ZnO film;
s4: preparation of Zn-MOF film:
dissolving dimethyl imidazole in a mixed solution of N, N-dimethylformamide and water, ultrasonically dissolving, transferring to a reaction kettle, placing the prepared patterned ZnO film in the solution, reacting at 70-100 ℃, washing the reacted film for several times by using methanol, and drying at 60 ℃ to obtain the patterned ZIF-8 film.
Wherein, the monomer in the step S1 is zinc acrylate or zinc methacrylate.
Wherein, the solvent in the step S1 is propylene glycol monomethyl ether, ethylene glycol monomethyl ether or a mixture of the two.
Wherein the photoinitiator in the step S1 is 7-diethylamino-3-thenoyl coumarin.
In the step S1, the mass of the monomer in the zinc-based photoresist accounts for 5-10% of the mass of the solvent, and the mass of the initiator accounts for 0.5-2.5% of the mass of the monomer.
Wherein, in the step S1, ultrasonic dissolution is 30 min.
In step S3, the temperature increase rate during annealing is 20 ℃/min, and the temperature decrease rate is 5 ℃/min.
In the step S4, the mass ratio of the dimethyl imidazole to the N, N-dimethylformamide to the water is 1: 114: 30-50.
In the step S4, the reaction time of the patterned ZnO film in the solution is 24-36 h.
In step S4, the film after reaction is dried at 60 ℃ for 1 hour after being washed.
Example 1:
(1) weighing zinc methacrylate (10 g), propylene glycol monomethyl ether (100 g) and 7-diethylamino-3-thiophene formyl coumarin (100 mg), placing in a brown glass bottle, ultrasonically dissolving for 30min, and filtering for 2 times by using a 0.22 mu m needle head type filter to obtain a zinc-based photoresist;
(2) and dropping the synthesized zinc-based photoresist on a glass substrate, spin-coating at 500 rpm for 10s, and spin-coating at 1000 rpm for 60 s to obtain the zinc-based photoresist film. And then 780 nm femtosecond laser is used for writing, and the monomer at a specific position is polymerized through focus scanning to realize patterning writing. After the writing is finished, developing in propylene glycol methyl ether acetate for 30 s, then placing in isopropanol for developing for 30 s, and drying at room temperature to obtain a writing pattern, as shown in figure 1;
(3) and placing the obtained photoresist pattern in a muffle furnace, and annealing for 1h in an air atmosphere at the annealing temperature of 600 ℃, the heating rate of 20 ℃/min and the cooling rate of 5 ℃/min. Obtaining a patterned zinc oxide film after annealing, as shown in figure 2;
(4) 100 mg of dimethylimidazole was weighed out and dissolved in 12 mL (11.4 g) of DMF and 4 mL (4 g) of H 2 In the O solution, the solution was dissolved by sonication and transferred to a 25 mL reaction vessel. And then the prepared patterned zinc oxide film is placed in the solution to react for 30 hours at the temperature of 80 ℃. And (3) washing the reacted film for 3 times by using methanol, and drying the film at 60 ℃ for 1h to obtain a patterned ZIF-8 film, wherein an electron microscope photo shows that a uniform and compact micron-sized patterned ZIF-8 film is obtained as shown in FIG. 3.
As shown in FIG. 4, the powder diffraction XRD pattern of ZIF-8 prepared in example 1, the synthesized ZIF-8 corresponded very well to the diffraction peak obtained by computational simulation, indicating good crystallinity of MOF.
Example 2:
(1) weighing zinc acrylate (8 g), ethylene glycol monomethyl ether (100 g) and 7-diethylamino-3-thenoyl coumarin (40 mg) and placing in a brown glass bottle, dissolving for 30min by ultrasonic, and filtering for 2 times by using a 0.22 mu m needle filter to obtain the zinc-based photoresist.
(2) And dropping the synthesized zinc-based photoresist on a glass substrate, spin-coating at 500 rpm for 10s, and spin-coating at 1000 rpm for 60 s to obtain the zinc-based photoresist film. And then 780 nm femtosecond laser is used for writing, and the monomers at specific positions are polymerized through focus scanning to realize patterned writing. After the writing is finished, developing in propylene glycol methyl ether acetate for 30 s, then placing in isopropanol for developing for 30 s, and drying at room temperature to obtain the writing pattern.
(3) And placing the obtained photoresist pattern in a muffle furnace, and annealing for 2 h in an air atmosphere at the annealing temperature of 700 ℃, the heating rate of 20 ℃/min and the cooling rate of 5 ℃/min. And annealing to obtain the patterned zinc oxide film.
(4) 100 mg of dimethylimidazole was weighed out and dissolved in 12 mL (11.4 g) of DMF and 3 mL (3 g) of H 2 In the O solution, the solution was dissolved by sonication and transferred to a 25 mL reaction vessel. And then the prepared patterned ZnO film is placed in the solution to react for 36 hours at 70 ℃. And washing the reacted film for 5 times by using methanol, and drying the film for 1h at the temperature of 60 ℃ to obtain the patterned ZIF-8 film.
Example 3:
(1) weighing zinc methacrylate (5 g), ethylene glycol monomethyl ether (50 g), propylene glycol monomethyl ether (50 g) and 7-diethylamino-3-thiophene formyl coumarin (125 mg) in a brown glass bottle, dissolving for 30min by ultrasonic wave, and filtering for 2 times by using a 0.22 mu m needle filter to obtain the zinc-based photoresist.
(2) And dropping the synthesized zinc-based photoresist on a glass substrate, spin-coating at 500 rpm for 10s, and spin-coating at 1000 rpm for 60 s to obtain the zinc-based photoresist film. And then 780 nm femtosecond laser is used for writing, and the monomers at specific positions are polymerized through focus scanning to realize patterned writing. After the writing is finished, developing in propylene glycol methyl ether acetate for 30 s, then placing in isopropanol for developing for 30 s, and drying at room temperature to obtain the writing pattern.
(3) And placing the obtained photoresist pattern in a muffle furnace, and annealing for 3 h in an air atmosphere at the annealing temperature of 800 ℃, the heating rate of 20 ℃/min and the cooling rate of 5 ℃/min. And annealing to obtain the patterned zinc oxide film.
(4) 100 mg of dimethylimidazole was weighed out and dissolved in 12 mL (11)4 g) DMF and 5 mL (5 g) H 2 In the O solution, the solution was dissolved by sonication and transferred to a 25 mL reaction vessel. And then the prepared patterned ZnO film is placed in the solution to react for 24 hours at the temperature of 100 ℃. And washing the reacted film for 4 times by using methanol, and drying the film for 1h at the temperature of 60 ℃ to obtain the patterned ZIF-8 film.

Claims (10)

1. A preparation method of a patterned Zn-MOF film based on laser direct writing is characterized by comprising the following steps:
s1: preparing a zinc-based photoresist:
weighing a monomer, a solvent and a photoinitiator according to a proportion, adding the monomer, the solvent and the photoinitiator into a brown bottle, ultrasonically dissolving, and filtering for a plurality of times by using a 0.22 mu m needle head type filter to obtain a zinc-based photoresist;
s2: laser direct writing:
dropwise adding the zinc-based photoresist on common glass, spin-coating on a photoresist homogenizer to prepare a photoresist film, and developing after exposing the photoresist film by using femtosecond laser to obtain a photoresist pattern;
s3: high-temperature oxidation:
placing the photoresist pattern obtained after exposure and development in a muffle furnace, and annealing for 1-3 h at 600-800 ℃ in an air atmosphere to obtain a patterned ZnO film;
s4: preparation of Zn-MOF film:
dissolving dimethyl imidazole in a mixed solution of N, N-dimethylformamide and water, ultrasonically dissolving, transferring to a reaction kettle, placing the prepared patterned ZnO film in the solution, reacting at 70-100 ℃, washing the reacted film for several times by using methanol, and drying at 60 ℃ to obtain the patterned ZIF-8 film.
2. The method of making a laser direct write based patterned Zn-MOF film according to claim 1, wherein: in the step S1, the monomer is zinc acrylate or zinc methacrylate.
3. The method of making a laser direct write based patterned Zn-MOF film according to claim 1, wherein: in the step S1, the solvent is propylene glycol monomethyl ether, ethylene glycol monomethyl ether or a mixture of the two.
4. The method for preparing the laser direct writing based patterned Zn-MOF film according to claim 1, wherein: the photoinitiator in the step S1 is 7-diethylamino-3-thenoyl coumarin.
5. The method of making a laser direct write based patterned Zn-MOF film according to claim 1, wherein: in the step S1, the mass of the monomer in the zinc-based photoresist accounts for 5-10% of the mass of the solvent, and the mass of the initiator accounts for 0.5-2.5% of the mass of the monomer.
6. The method of making a laser direct write based patterned Zn-MOF film according to claim 1, wherein: in the step S3, the temperature rise rate during annealing is 20 ℃/min, and the temperature drop rate is 5 ℃/min.
7. The method of making a laser direct write based patterned Zn-MOF film according to claim 1, wherein: in the step S4, the mass ratio of the dimethyl imidazole to the N, N-dimethylformamide to the water is 1: 114: 30-50.
8. The method of making a laser direct write based patterned Zn-MOF film according to claim 1, wherein: in step S1, ultrasonic dissolution is performed for 30 min.
9. The method of making a laser direct write based patterned Zn-MOF film according to claim 1, wherein: in the step S4, the reaction time of the patterned ZnO film in the solution is 24-36 h.
10. The method of making a laser direct write based patterned Zn-MOF film according to claim 1, wherein: in step S4, the film after reaction is dried at 60 ℃ for 1 hour after being washed.
CN202210823416.8A 2022-07-14 2022-07-14 Preparation method of patterned Zn-MOF film based on laser direct writing Active CN114895536B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210823416.8A CN114895536B (en) 2022-07-14 2022-07-14 Preparation method of patterned Zn-MOF film based on laser direct writing

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210823416.8A CN114895536B (en) 2022-07-14 2022-07-14 Preparation method of patterned Zn-MOF film based on laser direct writing

Publications (2)

Publication Number Publication Date
CN114895536A true CN114895536A (en) 2022-08-12
CN114895536B CN114895536B (en) 2022-11-11

Family

ID=82729675

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210823416.8A Active CN114895536B (en) 2022-07-14 2022-07-14 Preparation method of patterned Zn-MOF film based on laser direct writing

Country Status (1)

Country Link
CN (1) CN114895536B (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170198393A1 (en) * 2014-04-30 2017-07-13 Imec Vzw Method of Producing a Thin Metal-Organic Framework Film Using Vapor Phase Precursors
CN109195700A (en) * 2016-05-31 2019-01-11 Eth苏黎世公司 self-supporting MOF film
CN109360862A (en) * 2018-10-26 2019-02-19 中国石油大学(华东) One kind driving photodetector and preparation method thereof based on ZnO nanorod/Si hetero-junctions certainly
CN109675607A (en) * 2019-01-17 2019-04-26 上海大学 Fe3O4The preparation method of@ZnO@N-C composite photocatalyst material
US20200197901A1 (en) * 2018-10-25 2020-06-25 Uti Limited Partnership Metal organic framework (mof) composite materials, methods, and uses thereof
US20210162388A1 (en) * 2019-12-02 2021-06-03 Center for Innovative Materials and Architectures METAL ORGANIC FRAMEWORKS (MOFs) AND METHODS OF SYNTHESIZING AND USING THE SAME
CN114326295A (en) * 2022-03-15 2022-04-12 之江实验室 Femtosecond laser direct writing method for zinc oxide micro-nano pattern

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170198393A1 (en) * 2014-04-30 2017-07-13 Imec Vzw Method of Producing a Thin Metal-Organic Framework Film Using Vapor Phase Precursors
CN109195700A (en) * 2016-05-31 2019-01-11 Eth苏黎世公司 self-supporting MOF film
US20200197901A1 (en) * 2018-10-25 2020-06-25 Uti Limited Partnership Metal organic framework (mof) composite materials, methods, and uses thereof
CN109360862A (en) * 2018-10-26 2019-02-19 中国石油大学(华东) One kind driving photodetector and preparation method thereof based on ZnO nanorod/Si hetero-junctions certainly
CN109675607A (en) * 2019-01-17 2019-04-26 上海大学 Fe3O4The preparation method of@ZnO@N-C composite photocatalyst material
US20210162388A1 (en) * 2019-12-02 2021-06-03 Center for Innovative Materials and Architectures METAL ORGANIC FRAMEWORKS (MOFs) AND METHODS OF SYNTHESIZING AND USING THE SAME
CN114326295A (en) * 2022-03-15 2022-04-12 之江实验室 Femtosecond laser direct writing method for zinc oxide micro-nano pattern

Also Published As

Publication number Publication date
CN114895536B (en) 2022-11-11

Similar Documents

Publication Publication Date Title
CN102338986B (en) Organic-inorganic composite laser thermal-etching film and micro-nano graph preparation method
CN105694051B (en) Metal organic frame cross linking membrane based on click chemistry and preparation method and application
CN112947002A (en) Photoresist material for micro-nano processing, preparation and application thereof
CN110452403B (en) Flexible nano composite holographic storage film, preparation method and application thereof
CN101412533B (en) Method for preparing uniform zinc oxide nano tube in water solution
CN111215032B (en) Rapid preparation method of MOF material
CN105238349A (en) Fe3O4-ZnO nano composite material and preparation method thereof
CN114895536B (en) Preparation method of patterned Zn-MOF film based on laser direct writing
CN110256706A (en) A kind of synthetic method of metal-organic framework materials high molecular polymer film
CN113717397A (en) Preparation method of metal cluster-based crystalline porous material
CN101759374B (en) Preparation method of visible light frequency band left-hand metamaterial based on three-dimensional nano silver tree dendritic structures
CN109877342A (en) A kind of amorphous noble metal nano-plate and preparation method thereof
CN114015102A (en) Method for modifying surface of membrane by inverse miniemulsion
CN110092591B (en) VO with three-dimensional ordered porous network structure2Film, preparation method and application thereof
CN109521649A (en) A kind of integral system pinpointing transfer and alignment photoetching for two-dimensional material
CN102424356B (en) Device and method for preparing metal nanoparticle microarray chip
CN102990077B (en) Method for growing bismuth nanoparticles on oxide substrate in situ
CN106589394B (en) A kind of cobalt coordination polymer and preparation method thereof
CN102268001A (en) Preparation method of one-dimensional metal phthalocyanine compound nano-crystals
CN111607387A (en) Photocatalytic microsphere motor based on carbon dots and preparation method and application thereof
CN1600674A (en) Nano composite inorganic semiconductor hollow ball and preparation method
CN115160372B (en) Composite high polymer film material based on tungsten/copper/sulfur cluster compound, preparation method thereof and application of three-order nonlinear optics
Duan et al. Visible‐Light‐Responsive Crystalline Solids by Equipping Covalent Organic Frameworks with Donor‐Acceptor Stenhouse Adducts
CN115196585A (en) Magnetic control micro-nano robot and manufacturing method and application thereof
CN101240164A (en) Method for synthesizing sensitive photochromic WO3 nano powder by formaldehyde inducement

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