CN1166725C - Method for ordered arrangement of nano particles on solid base surface - Google Patents
Method for ordered arrangement of nano particles on solid base surface Download PDFInfo
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- CN1166725C CN1166725C CNB021550190A CN02155019A CN1166725C CN 1166725 C CN1166725 C CN 1166725C CN B021550190 A CNB021550190 A CN B021550190A CN 02155019 A CN02155019 A CN 02155019A CN 1166725 C CN1166725 C CN 1166725C
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Abstract
The present invention relates to a method for orderly arranging nanometer particles on the surface of a solid base, and the present invention belongs to the technical field of nanometers. The method of the present invention comprises the following specific steps: a chain-shaped organic molecule with a hydrophilic base group and a hydrophobic base group is dissolved in a volatile nonaqueous solvent; nanometer particles combined with the chain-shaped organic molecule with a hydrophilic base group and a hydrophobic base group are dispersed in a solution; pure water is used as a base solution, and the nonaqueous solution which contains the nanometer particles is spread in a Langmuir groove; film pressure of a monomolecular film of the nanometer particles on the water surface is controlled; the film is transferred onto the surface of the processed solid base by a vertical pulling method, which forms a Y-type LB film; the prepared nanometer particle film is processed in an annealing mode at high temperature or is irradiated with high-energy light rays; some organic molecules are dissociated and evaporated from a substrate; the nanometer particles are reserved on the base. The provided method has the characteristics of simple and easy operation, high transferring efficiency, ordered particle arrangement on the surface of the film, convenient adjustment of dimension and thickness, etc., the prepared film has few defects, and the method also has the advantages of wide application range and convenient generalization and application.
Description
Technical field
What the present invention relates to is a kind of method of the nano particle of arranging, and the method for particularly a kind of solid substrate surface ordered arrangement nano particle belongs to field of nanometer technology.
Background technology
The focus that nano material becomes current research owing to the special property that shows at aspects such as electronics, magnetics, optics and catalysis and considerable application prospect.Nano-particle material can be prepared by high-quality by several different methods at present, as sol-gel method, optical radiation oxidation reduction process, electrochemical redox method and sputtering method etc.Yet, along with the development of nano electron device, on the increasing solid substrate surface that requires quantitatively to arrange nano particle different in an orderly manner.The LB technology because have that thin film deposition thickness is quantitatively controlled, zero defect, characteristics such as simple to operate and shown remarkable advantages in this field.In recent years, adopt the LB unimolecular film as matrix, successfully prepared semiconductor nano material films such as metal nanoparticle such as Ag, Au and CdS, ZnS, PbS, CdSe, PbSe by inducing organic and method inorganic nano-particle of nucleating growth thereon.By literature search, find relevant Chinese invention patent, its patent No. is 98103527.2, Granted publication number is CN 1075842C's, name is called " forming the method less than 10 nano metal clusters and sequential 2 D dot-matrix of metallic atoms on unimolecular film ", its readme is " a kind of method that forms on unimolecular film less than 10 nano metal clusters and sequential 2 D dot-matrix of metallic atoms; it is characterized in that; the two-dimentional structure of single channel process system atoms metal: in standard unimolecular film groove; with the pure water is end liquid; will be dissolved in the amphiphilic polymer among the chloroform or the unimolecular film of straight chain fatty acid or aliphatic amide and spread in the groove; then unimolecular film is depressed into constant pressure, after the balance, amphiphilic polymer need be used the UV-irradiation polymerization, or directly spreads the good film of polymerization.In end liquid, inject 5 * 10 then
-6M to 5 * 10
-4The aqueous solution of M metal-salt or metal salt complex, the concentration that makes the metal ion in the end liquid is 5 * 10
-6M to 5 * 10
-4M; With horizontal crystal pulling method or vertical crystal pulling method polymeric film is transferred on the hydrophobic slide glass, slide glass is immersed fully rinsing in the pure water, and then immerse 10
-6M to 10
-4Reduce in the reductive agent aqueous solution of M, at last slide glass is cleaned, nitrogen dries up, and forms the sequential 2 D dot-matrix less than 10 nano metal atoms on unimolecular film.", it discloses a kind of method that forms less than 10 nano metals bunch and sequential 2 D dot-matrix of metallic atoms on unimolecular film.This method mainly adopts organic LB unimolecular film to induce parfacies solution metal ion or metal complex ion, and need in film process metal ion or metal complex ion be reduced to metallics when preparation metal nanoparticle film.This class methods raw material consumption amount is big, and the particulate size is difficult for regulating in the prepared film, and operation is comparatively complicated, is difficult for large-scale film forming and application.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, the method of a kind of solid substrate surface ordered arrangement nano particle is provided, the present invention realizes the method for ordered arrangement nano particle on the solid substrate surface with simple, practical method, and the gained nanometer particle film is stable, orderly.Can be implemented in the operation of individual layer and the orderly film of multi-layer nano grade particles on the different solid substrate.
The present invention is achieved by the following technical solutions, and concrete steps of the present invention are as follows:
A. will have hydrophilic and chain organics molecule hydrophobic grouping is dissolved in the non-aqueous volatile solvent.Will with the chain organics molecule bonded nanoparticulate dispersed that has hydrophilic and hydrophobic grouping in above-mentioned solution.
B. solid substrate is carried out hydrophilic or hydrophobic treatment.
C. in the Langmuir groove, be end liquid, the above-mentioned non-aqueous solution that contains nano particle is spread in the groove, the mould of control water surface nano particle monomolecular film with the pure water.Transfer to the solid substrate surface of handling with film via vertical pulling and form Y-type LB film.
D. prepared nanometer particle film is carried out high temperature annealing or high energy irradiate light, some organic molecules dissociate, and evaporate from substrate, and nano particle is retained in the substrate.
In step a, organic molecule used in the present invention is a kind of hydrophilic and chain organics molecule hydrophobic grouping of having, and its hydrophilic radical can be groups such as amino, carboxyl, sulfydryl, carbonatoms 14～22.The kind and the concentration of control organic molecule in non-aqueous solvent that change organic molecule can change nano particle in the distribution density of film surface and the degree of order of arranging.Organic molecule optimum concentration range in the ordered arrangement process is 1 * 10
-5～6 * 10
-4Between the M, the concentration of nano particle in non-aqueous solvent is between 1～10mg/ml.Preferably use the mixing solutions of two organic molecular species that contain amino and carboxylic group respectively when arranging the Nanoalloy particle, the ratio of two organic molecular species blended amount of substances is controlled between 0.1: 1～10: 1 relatively good.Non-aqueous volatile solvent used in the present invention is hexane, chloroform, toluene.The nano particle that the present invention arranged is of a size of 1～30 nanometer, and the nano particle of being arranged comprises metallic particles, alloying pellet and metal oxide particle.Metal can be elements such as transition metal iron, cobalt, nickel, platinum, and the alloying pellet of being arranged mainly is iron platinum, cobalt platinum, cobalt-nickel alloy, and metal oxide particle mainly is cobalt oxide, nickel oxide, titanium oxide, ferric oxide, stannic oxide, zinc oxide.
In step b, solid state substrate used in the present invention mainly is the silicon chip of sheet glass, silicon chip and surface oxidation.
In step c, mould is controlled between 15～30mN/m.With the non-aqueous solution of nano particle sprawl after the water surface need static more than 30 minutes so that non-aqueous solvent fully volatilizees, push away film behind the required pressure under constant pressure balance 0.5～2 hour, membrane speed remains 1～10mm/min.
In steps d, the present invention stably is arranged in the solid substrate surface for making nano particle, after the film forming film has been taked the processing of high temperature annealing and high energy light photograph.Wherein metal and alloying pellet film adopt the method for high temperature annealing in inert gas environment, the annealing temperature of film is controlled at 500～650 ℃, and under this temperature, kept 1～60 minute, the nano-metal-oxide particle film adopts in air or oxygen atmosphere high temperature annealing or adopts the method for high energy irradiate light.According to the nano-metal-oxide particle of being arranged and the difference of employed organic molecule, the time of annealing and illumination is also different.The temperature that annealing comparatively is fit to is 300～650 ℃, and temperature kept 1～60 minute, and high energy light irradiation time kept 1～40 minute.
The present invention has substantive distinguishing features and marked improvement.The present invention utilizes the Langmuir-Blodgett technology to prepare the nanometer particle film of thickness homogeneous and controllable, and in unitary film, nano particle can realize that sequential 2 D arranges.Since in film process with the nano particle for preparing as raw material, therefore enlarged the kind of the nano particle that can arrange, and made the particle size of film surface convenient adjustable, be easy to control.Be dispersed in the chain length of organic molecule in the non-aqueous solvent and the ordered arrangement that concentration can realize nano particle easily by adjusting simultaneously.The order thin film of being arranged can keep advantages of higher stability after annealing or photo-irradiation treatment, steady time was above 72 hours.In addition since with nanoparticulate dispersed in non-aqueous solvent and sprawl on the water surface, thereby saved raw material greatly.Characteristics such as method provided by the present invention has simple, and transfer efficiency height, the particle size of film surface and thickness are conveniently adjustable, prepared film defects is few, and this method is applied widely, is easy to be extended and applied.
Embodiment
Provide following examples in conjunction with content of the present invention:
Arranging of embodiment 1 nanometer Fe-Pt alloy particle film
Through step a of the present invention, will contain 4 nanometer iron-platinum alloy particles concentration is 2.5mg/ml, and the organic molecule total concn is 2 * 10
-4The hexane solution of the 450 μ l of M spreads on the water surface, and balance is after 30 minutes, and to constant pressure 20mN/m, balance adopted film via vertical pulling to transfer on the sheet glass after 30 minutes with mould, and membrane speed remains 2mm/min, cleans oven dry.Repeat the multilayer film that the process of lifting can obtain controllable thickness.The gained film adds 600 ℃ of annealing of thermic 10 minutes under nitrogen protection, obtain the nanometer Fe-Pt alloy particle single thin film of cubic ordered arrangement.
Arranging of embodiment 2 iron nano-particle films
To contain 10 nanometer iron nano-particle concentration is 8mg/ml, and organic molecule concentration is 1 * 10
-4The chloroformic solution of the 350 μ l of M spreads on the water surface, and balance is after 30 minutes, and to constant pressure 28mN/m, balance adopted film via vertical pulling to transfer on the sheet glass after 30 minutes with mould, and membrane speed remains 8mm/min, cleans oven dry.Repeat the multilayer film that the process of lifting can obtain controllable thickness.The gained film is heated to 500 ℃ of annealing 20 minutes under nitrogen protection, obtain the iron nano-particle single thin film of six side's ordered arrangements.
Arranging of embodiment 3 TiOx nano particle films
With 30 nano-titanium oxide concentrations of nanoparticles is 5mg/ml, and organic molecule concentration is 4 * 10
-4The toluene solution of the 400 μ l of M spreads on the water surface, and balance is after 30 minutes, and to constant pressure 15mN/m, balance adopted film via vertical pulling to transfer on the sheet glass after 60 minutes with mould, and membrane speed remains 5mm/min, cleans oven dry.Repeat the multilayer film that the process of lifting can obtain controllable thickness.Resulting film according to 5 minutes, can obtain TiOx nano particle individual layer and multilayer order film through high energy light.
Claims (10)
1. the method for a solid substrate surface ordered arrangement nano particle is characterized in that, the present invention includes following steps:
A. will have hydrophilic and chain organics molecule hydrophobic grouping and be dissolved in the non-aqueous volatile solvent, will with the chain organics molecule bonded nanoparticulate dispersed that has hydrophilic and hydrophobic grouping in above-mentioned solution,
B. solid substrate is carried out hydrophilic or hydrophobic treatment,
C. in the Langmuir groove, with the pure water is end liquid, the above-mentioned non-aqueous solution that contains nano particle is spread in the groove mould of control water surface nano particle monomolecular film, transfer to the solid substrate surface of handling with film via vertical pulling and form Y-type LB film
D. prepared nanometer particle film is carried out high temperature annealing or high energy irradiate light, some organic molecules dissociate, and evaporate from substrate, and nano particle is retained in the substrate.
2. the method for this solid substrate according to claim 1 surface ordered arrangement nano particle, it is characterized in that, employed organic molecule is a kind of hydrophilic and chain organics molecule hydrophobic grouping of having in step a, its hydrophilic radical is amino, carboxyl, mercapto groups, carbonatoms 14～22.
3. the method for this solid substrate according to claim 2 surface ordered arrangement nano particle is characterized in that the organic molecule concentration range is 1 * 10
-5～6 * 10
-4Between the M, the concentration in non-aqueous solvent of nano particle is between 1～10mg/ml.
4. the method for this solid substrate according to claim 3 surface ordered arrangement nano particle, it is characterized in that, use the mixing solutions of two organic molecular species that contain amino and carboxylic group respectively when arranging the Nanoalloy particle, the ratio of blended amount of substance is between 0.1: 1～10: 1.
5. the method for this solid substrate according to claim 3 surface ordered arrangement nano particle is characterized in that non-aqueous solvent is imitative, the toluene of hexane, oxygen.
6. the method for this solid substrate according to claim 1 surface ordered arrangement nano particle, it is characterized in that, the nano particle of being arranged in step a is of a size of 1～30 nanometer, the nano particle of being arranged comprises metallic particles, alloying pellet and metal oxide particle, metal is transition metal iron, cobalt, nickel, platinum element, the alloying pellet of being arranged is iron platinum, cobalt platinum, cobalt-nickel alloy, and metal oxide particle is cobalt oxide, nickel oxide, titanium oxide, ferric oxide, stannic oxide, zinc oxide.
7. the method for this solid substrate according to claim 1 surface ordered arrangement nano particle is characterized in that the solid substrate in step b is the silicon chip of sheet glass, silicon chip and surface oxidation.
8. the method for this solid substrate according to claim 1 surface ordered arrangement nano particle, it is characterized in that, mould is controlled between 15～30mN/m among the step c, the non-aqueous solution of nano particle is sprawled need be static more than 30 minutes after the water surface, so that non-aqueous solvent fully volatilizees, push away film behind the required pressure under constant pressure balance 0.5～2 hour, membrane speed remains 1～10mm/min.
9. the method for this solid substrate according to claim 1 surface ordered arrangement nano particle, it is characterized in that, when high temperature annealing of in the steps d film being taked and high energy photo-irradiation treatment, wherein metal and alloying pellet film adopt the method for high temperature annealing in inert gas environment, the annealing temperature of film is controlled at 500～650 ℃, and keeps under this temperature 1～60 minute.
10. the method for this solid substrate according to claim 9 surface ordered arrangement nano particle, it is characterized in that, the nano-metal-oxide particle film adopts in air or oxygen atmosphere high temperature annealing or adopts the method for high energy irradiate light, annealing temperature is 300～650 ℃, temperature kept 1～60 minute, and high energy light irradiation time kept 1～40 minute.
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| CNB021550190A CN1166725C (en) | 2002-12-19 | 2002-12-19 | Method for ordered arrangement of nano particles on solid base surface |
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| CNB021550190A CN1166725C (en) | 2002-12-19 | 2002-12-19 | Method for ordered arrangement of nano particles on solid base surface |
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| CN1166725C true CN1166725C (en) | 2004-09-15 |
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| EP2257989A2 (en) * | 2008-03-25 | 2010-12-08 | Corning Incorporated | Substrates for photovoltaics |
| CN105067601B (en) * | 2015-07-16 | 2017-07-07 | 重庆大学 | A kind of functionalization test paper film based on nm of gold and the method for detecting iron ion |
| CN104990918B (en) * | 2015-07-16 | 2017-06-27 | 重庆大学 | A kind of test paper film based on nm of gold and its method for detecting lead ion |
| WO2017100758A1 (en) * | 2015-12-10 | 2017-06-15 | Cornell University | Organized nanoparticulate and microparticulate coatings and methods of making and using same |
| CN106784186B (en) * | 2016-12-23 | 2020-07-21 | Tcl科技集团股份有限公司 | L B quantum dot film, light-emitting diode and preparation method |
| CN110098427A (en) * | 2019-05-27 | 2019-08-06 | 苏州氢极能源科技有限公司 | Proton exchange membrane of fuel cell and preparation method thereof |
| CN111044511A (en) * | 2019-12-27 | 2020-04-21 | 华南理工大学 | Color-changing nano material-based colorimetric test paper sheet and preparation method and application thereof |
| CN111455466B (en) * | 2020-04-14 | 2021-07-13 | 西安交通大学 | Preparation method of colloidal crystal based on LB membrane method |
| CN115561846B (en) * | 2022-09-27 | 2024-10-18 | 华中科技大学 | Surface plasmon-based response pattern, preparation method and application thereof |
| CN115897227B (en) * | 2022-12-21 | 2024-09-03 | 江苏工程职业技术学院 | Preparation method of polyester with ordered micro-nano structure and hydrophobic property |
| CN117239030A (en) * | 2023-11-13 | 2023-12-15 | 江西兆驰半导体有限公司 | Electrode surface hydrophobic LED chip and preparation method thereof |
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