CN104174860B - Preparation method for alloy nano-particles adopting core-shell structures - Google Patents
Preparation method for alloy nano-particles adopting core-shell structures Download PDFInfo
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- CN104174860B CN104174860B CN201410400714.1A CN201410400714A CN104174860B CN 104174860 B CN104174860 B CN 104174860B CN 201410400714 A CN201410400714 A CN 201410400714A CN 104174860 B CN104174860 B CN 104174860B
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Abstract
The invention discloses a preparation method for core-shell type alloy nano-particles. The method comprises the steps as follows: firstly, a self-assembling monomolecular layer is grown on the surface of an oxide substrate by utilizing an organic silane coupling agent; secondly, a metal core is grown on the surface, where the self-assembling monomolecular layer is grown, of the substrate through atomic layer deposition; thirdly, a metal shell layer wrapping the core is grown on the metal core selectively through the atomic layer deposition. According to the method, the dimensions of the core and the thickness of the shell layer, as well as the alloying constituent ratio of the core and the shell can be controlled by adjusting growth circulating times of the atomic layer deposition. According to the substrate modification method adopted by the preparation method, the preparation of alloy nano-particles adopting core-shell structures is realized; as the atomic layer deposition technology is adopted, the grown alloy nano-particles adopting the core-shell structures are enabled to achieve nanoscale controllability; moreover, as the substrate modification-based method has lower requirements for the atomic layer deposition technology, the preparation method provided by the invention can be popularized for the construction of the core-shell structures of binary alloy nano-particles.
Description
Technical field
The invention belongs to composite nano materials preparation field, receive more particularly, to a kind of alloy with nucleocapsid structure
The preparation method based on gas phase ald of rice grain.
Background technology
Alloy nanoparticle comprises two or more composition, due to the synergism between Multiple components, compares
Metallic particles in single component generally has more excellent property.Can tie in nano-scale dimension precise control alloy nucleocapsid
The size of structure granule, component ratio and structure etc. are significant for improving its performance.Wherein controlledly synthesis has nucleocapsid
The alloy nanoparticle of structure is one, this field study hotspot.Due to the alloy nanoparticle of nucleocapsid structure have special double
Metal interface stress and electron transport property, the property of two kinds of metals of performance that can be bigger.In optics, it is catalyzed, biochemistry,
The numerous areas such as electronic product have a good application prospect.The size to alloying pellet for many surface chemical reactions, composition ratio
Example is very sensitive, and this also proposes stern challenge to its preparation method.
The method preparing alloy nanoparticle at present is based on liquid phase process, and the small-size effect due to nano-particle,
High surface free energy property makes the nano-particle of liquid phase synthesis easily produce reunion.And the purification of the nano-particle synthesizing and receipts
Collection there is also certain difficulty.Therefore a kind of can precise control alloy nanoparticle size, the method for component ratio still have
Greatly demand.
Technique for atomic layer deposition is emerging film deposition techniques.One circulation of ald is divided into two and half
Reaction, this half-reaction is that the chemisorbed based on surface saturation is carried out, between by noble gases purge separate.This saturation
Chemisorptive properties become from restricted it is ensured that a deposition cycle is carried out with monoatomic layer.Therefore, it is possible in deposition
During by grow cycle-index film thickness is carried out with the control of Subnano-class.And the thin film depositing has guarantor's type
Property good, uniformly, thickness Subnano-class is controlled for thickness, the advantages of deposited material is extensive.
There are some researchs by atomic layer deposition applications in the controllable growth aspect of nano-particle at present, using atomic layer
Deposition growing from restricted, can deposit and control the mean diameter of granule and there is narrower grain by growing cycle-index
Footpath is distributed.Also there is document (Chemistry of materials, 2012,24,2973-2977) to report and can utilize atomic layer
Deposition growing has the pallas nano-particle of nucleocapsid structure.Specific embodiment is to deposit the substrate of the core having palladium
On, by controlling partial pressure of oxygen during deposition platinum shell, realize the core surfaces that platinum is optionally grown in palladium, thus obtaining nucleocapsid
Structure.This method requires very strictly for the control of the partial pressure of oxygen in deposition, because partial pressure of oxygen has for the migration of platinum
Very big impact, can form in the superficial growth of metallic core such as palladium if will not grow in substrate when partial pressure of oxygen is less
Nucleocapsid structure.And partial pressure of oxygen larger when, platinum is unrestricted in the growth of substrate surface.
But can there is following defect in actual applications in above technology：Due to accurately controlling in necessary for growth
The partial pressure of presoma processed, also results in depositing device and more complicates.Growth simultaneously for the ald of some metals
Partial pressure (concentration) for another kind of presoma and insensitive when, then this growth will not have selectivity, hence for life
Long nucleocapsid structure causes difficulty.
Content of the invention
For the defect of prior art, it is an object of the invention to proposing a kind of method system modified by oxide base
Get everything ready the method for the alloy nanoparticle having nucleocapsid structure.The method comprises the steps：
Go out self assembled monolayer using organo silane coupling agent in oxide base superficial growth, this self-composed monomolecular
Layer has the avtive spot not covered by organosilan；
Using ald on the avtive spot of described self assembled monolayer deposited metal core；
The shell of growth metal is coated using ald on described metallic core.
Further, described oxide-base bottom material is silicon oxide or aluminium oxide.
Further, described organosilan is octadecyl trichlorosilane alkane, n-octyl silane or octadecyl
Silane.
Further, the range of reaction temperature of described ald is 150 DEG C -300 DEG C.
Further, the diameter dimension of described metallic core and described metal shell layer is determined by the number of times that atomic deposition circulates
Fixed.
According to the method for the alloy nanoparticle preparing nucleocapsid structure of the present invention, advantage be achieved that：
(1) because ald is by carrying out from the chemical absorption of surface reaction limiting, in depositing each time only
One monoatomic layer of growth, is the Technology of a size being capable of precise control deposited material；
(2) self-limiting characteristics based on ald itself, for the synthesis of nano-particle, can be deposited by control
Cycle-index realize the particle diameter distribution of nano-particle of growth is regulated and controled, the particle diameter of the nano-particle of growth and deposition
The substantially linear relation of cycle-index.Cycle-index ratio by adjusting two kinds of metal growth courses realizes nano-particle simultaneously
The alloying component ratio of core and shell.This is the big advantage preparing nano-particle using technique for atomic layer deposition, and this is for granule
The highstrung catalytic reaction of size, alloying component is highly important.
(3) present invention is using based on the nano-particle preparation under gas phase vacuum environment, the nano-particle direct growth of deposition
In substrate surface, therefore there is not the agglomeration that liquid phase method prepares nano-particle appearance, there is not purification yet and collect target
The difficulty of product.
Brief description
Fig. 1 is the flow chart preparing core shell nanoparticles structure according to the present invention；
Fig. 2 is the palladium according to preparation in embodiments of the invention 1 is core, and platinum is that the bianry alloy nucleocapsid structure of shell is received
The transmission electron microscope photo of rice grain；
Fig. 3 is the palladium according to preparation in embodiments of the invention 1 is core, and platinum is that the bianry alloy nucleocapsid structure of shell is received
Energy dispersion X-ray spectrum (Energy Dispersive X-Ray Spectroscopy) the line scanning figure of rice grain；
Fig. 4 is to be core according to the palladium in the present invention, and platinum is the heavy of the mean diameter of alloy nanoparticle and the platinum of shell
The linear relationship chart of long-pending cycle-index.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, below in conjunction with drawings and Examples, right
The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only in order to explain the present invention, and
It is not used in the restriction present invention.
Wherein, as shown in figure 1, according to the present invention the flow chart preparing core shell nanoparticles structure, wherein by using
The organic coupling agents such as octadecyl trichlorosilane alkane, n-octyl silane, octadecyl trimethoxysilane are in oxide-base basal surface
Grow self assembled monolayer, thus being modified to substrate surface.Self assembled monolayer due to growth has
Defect, these fault locations become the avtive spot of ald growth.These defect points are that oxide base is not had
Some sites that machine silane covers, these sites can allow ald grow at this position, and other is covered by organosilan
The place of lid hinders the growth of ald, and such a metal precursor passes through ald by the work in fault location
Property site grows metallic core.
When continuing another kind of metal of deposition, this metal precursor can only optionally coat and be grown in former metal core
Heart surface, and other passive area not Absorption Growth in substrate.Because the position that other positions are still covered by organosilan
The ald of another kind of metal will be stopped, so shell can only optionally be grown on the metallic core prepared
Structure, thus obtain the metal nanoparticle with nucleocapsid structure.
The present invention uses and oxide base is modified obtaining organic self assembled monolayer.Due to organosilan, energy
Enough in hydroxylated superficial growth, and oxide surface is respectively provided with equally distributed hydroxyl, and therefore this method of modifying can be fitted
Should have the nano-particle of nucleocapsid structure in the surface modification of oxide base and using ald growth, wherein aoxidize
The material of thing substrate can be silicon oxide or aluminium oxide etc..
Embodiment 1
1) by silicon chip in deionized water, ammonia, dioxygen water volume ratio is 5:1:20min is boiled, subsequently in 1 mixed solution
Dry up silicon chip using high pure nitrogen standby.With dry toluene as solvent, take octadecyl trichlorosilane alkane coupling agent in dry toluene
In be configured to the solution of 10mmol/L, mix homogeneously.Cleaning silicon wafer is rested in the solution of above-mentioned octadecyl trichlorosilane alkane,
Time of repose is 2 hours, obtains the self assembly organic monolayer in silicon chip surface octadecyl trichlorosilane alkane.Whole octadecane
The preparation process of base trichlorosilane self assembled monolayer is carried out in the environment of exclusion of water and oxygen.
2) by 1) in the length silicon chip that has octadecyl trichlorosilane alkane self-assembled monolayer of preparation put into atomic layer deposition apparatus
In, the palladium nano-particles of 300 circulations are deposited in silicon chip surface.The palladium source using is 1,1,1,5,5,5- hexafluoroacetylacetone palladium
(II), another kind of presoma is 37% formalin.The reaction temperature of ald is 200 DEG C, and carrier gas is nitrogen, forerunner
The body burst length is 2s, and nitrogen scavenging period is 5s.Finally obtain in the silicon chip surface modified through octadecyl trichlorosilane alkane
The palladium nanoparticle core that is evenly distributed.
3) by 2) sample continue its surface deposit platinum, number of deposition cycles be 25 times.The platinum source using is trimethyl
(methyl cyclopentadienyl) platinum (IV), another kind of presoma is oxygen.The range of reaction temperature of ald is 300 DEG C, carries
Gas is nitrogen, and the presoma burst length is 2s, and nitrogen scavenging period is 5s.It is transmission electricity under low amplification as shown in Figure 2
Palladium captured by sub- microscope/platinum alloy Core-shell Structure Nanoparticles.Fig. 3 show with transmission electron microscope to wherein one
The structural characterization that nano-particle is carried out, enters row element using the energy dispersion X-ray spectrogrph of transmission electron microscope to single granule and divides
The line scanning of cloth.It can be seen that the scanning carrying out with scanning direction, the signal of platinum element first occurs, about 1 nanometer it
Afterwards, start the signal that palladium occurs.Result shows that platinum is distributed on top layer, and palladium is internally distributed.In whole line scanning spectra, the letter of platinum
Number in outside, the signal of palladium is in kernel.Prove that the nano-particle prepared is nucleocapsid structure, and shell is uniformly and symmetrically distributed.Palladium
About 4 nanometers of kernel size, about 1 nanometer of the shell thickness of platinum.
Embodiment 2
1) by silicon chip in deionized water, ammonia, dioxygen water volume ratio is 5:1:20min is boiled, subsequently in 1 mixed solution
Dry up silicon chip using high pure nitrogen standby.With dry toluene as solvent, octadecyl trichlorosilane alkane is taken to configure in dry toluene
Become the solution of 10mmol/L, mix homogeneously.Cleaning silicon wafer is rested in the solution of above-mentioned octadecyl trichlorosilane alkane, during standing
Between be 2 hours.Obtain the self assembly organic monolayer in silicon chip surface octadecyl trichlorosilane alkane.Whole octadecyl trichlorine
The preparation process of silane self assembled monolayer is carried out in the environment of exclusion of water and oxygen.
2) by 1) in the length silicon chip that has octadecyl trichlorosilane alkane self-assembled monolayer of preparation put into atomic layer deposition apparatus
In, the Pt nanoparticle of 100 circulations is deposited in silicon chip surface.The platinum source using is trimethyl (methyl cyclopentadienyl) platinum
(IV), another kind of presoma is oxygen.The reaction temperature of ald is 300 DEG C, and carrier gas is nitrogen, the presoma burst length
For 2s, nitrogen scavenging period is 5s.
3) by 2) in prepare the shell that sample surfaces continue depositing Pd, the atomic layer deposition cycles number of times of use is 150 times.
The palladium source using is 1,1,1,5,5,5- hexafluoroacetylacetone palladium (II), and another kind of presoma is 37% formalin.Atom
The reaction temperature of layer deposition is 200 DEG C, and carrier gas is nitrogen, and the presoma burst length is 2s, and nitrogen scavenging period is 5s.Deposition is followed
Ring number of times is 2 times.Obtain platinum/palldium alloy Core-shell Structure Nanoparticles, and characterized with transmission electron microscope.
In the present invention, through overtesting, it is possible to obtain in the life of the Core-shell Structure Nanoparticles of palladium (core)/platinum (shell)
In growth process, fixation is used the palladium of about 5 nanometers of mean diameter as core growth Core-shell Structure Nanoparticles.Wherein using platinum shell
The cycle-index of layer preparation and the relation of mean particle size are as shown in figure 4, be wherein approximately linear relation.Can pass through
The particle diameter distribution and two to adjust Core-shell Structure Nanoparticles for the atomic layer deposition cycles number of times of palladium and platinum in control growth course
The element ratio of first alloy.Demonstrate effectiveness of the invention, feasibility and controllability.
As it will be easily appreciated by one skilled in the art that the foregoing is only presently preferred embodiments of the present invention, not in order to
Limit the present invention, all any modification, equivalent and improvement made within the spirit and principles in the present invention etc., all should comprise
Within protection scope of the present invention.
Claims (5)
1. a kind of preparation method of nucleocapsid structure alloy nanoparticle, the method comprises the steps：
Go out self assembled monolayer using organo silane coupling agent in oxide base superficial growth, this self assembled monolayer has
There is the avtive spot not covered by organosilan；
Using ald on the avtive spot of described self assembled monolayer deposited metal core, obtain and be evenly distributed
Metallic core；
The shell of growth metal is coated using ald on described metallic core；
In described ald, carrier gas is nitrogen.
2. the preparation method of nucleocapsid structure alloy nanoparticle as claimed in claim 1 is it is characterised in that described oxide-base
Bottom material is silicon oxide or aluminium oxide.
3. the preparation method of nucleocapsid structure alloy nanoparticle as claimed in claim 1 or 2 is it is characterised in that described organic
Silane is octadecyl trichlorosilane alkane, n-octyl silane or octadecyl trimethoxysilane.
4. the preparation method of nucleocapsid structure alloy nanoparticle as claimed in claim 3 is it is characterised in that described atomic layer deposition
Long-pending range of reaction temperature is 150 DEG C -300 DEG C.
5. the preparation method of nucleocapsid structure alloy nanoparticle as claimed in claim 4 is it is characterised in that described metallic core
With the size of described metal shell layer, and the element ratio of core and shell determines by the number of times that atomic deposition circulates.
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| CN105170147B (en) * | 2015-06-17 | 2017-08-29 | 中国科学技术大学 | A kind of hydrogenation catalyst and preparation method thereof |
| CN105290394B (en) * | 2015-11-03 | 2017-04-26 | 宁波大学 | Silver-mesoporous silica-silver sandwich core shell nanometer material and preparation and application thereof |
| CN105750541B (en) * | 2016-04-13 | 2018-10-12 | 西安近代化学研究所 | A method of reducing zirconium powder electric spark sensitivity using atomic layer deposition clad |
| CN111471979A (en) * | 2020-04-10 | 2020-07-31 | 上海大学 | PbS/PbSe core-shell structure nano film and integrated tapered optical fiber amplifier |
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| JP2010185135A (en) * | 2009-01-14 | 2010-08-26 | Kyushu Univ | Method for producing core shell type metal nanoparticle |
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| CN102184848A (en) * | 2011-05-11 | 2011-09-14 | 复旦大学 | Metal nanocrystalline storage capacitor and preparation method thereof |
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| CN1324412A (en) * | 1998-10-02 | 2001-11-28 | Nkt研究中心有限公司 | Method for metallizing surface of a solid polymer substrate and the product obtd. |
| JP2010185135A (en) * | 2009-01-14 | 2010-08-26 | Kyushu Univ | Method for producing core shell type metal nanoparticle |
| CN101996928A (en) * | 2009-08-14 | 2011-03-30 | 中芯国际集成电路制造(上海)有限公司 | Method for forming semiconductor device |
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