CN106119804A - A kind of method based on short annealing metallic film self-assembled nanometer particle - Google Patents
A kind of method based on short annealing metallic film self-assembled nanometer particle Download PDFInfo
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- CN106119804A CN106119804A CN201610699894.7A CN201610699894A CN106119804A CN 106119804 A CN106119804 A CN 106119804A CN 201610699894 A CN201610699894 A CN 201610699894A CN 106119804 A CN106119804 A CN 106119804A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
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Abstract
The invention discloses a kind of method based on short annealing metallic film self assembly metal nanoparticle, it is characterised in that step is as follows: first, backing material deposits layer of metal thin film, forms the substrate being coated with metallic film；Then place the substrate in quick anneal oven; load cycle of annealing to make annealing treatment; by to initial temperature, heating rate, the time in temperature and in annealing the flow-control of protective gas carry out rapid thermal annealing, obtain being prepared for the substrate of layer of metal nanoparticle.The method uses and grows nano-particle on substrate, its low cost, simple, it is possible to be uniformly dispersed, particle diameter is consistent, the nano-particle of morphology controllable.
Description
Technical field
The invention belongs to nanoparticle preparing technical field, particularly relate to a kind of based on short annealing metallic film self assembly
The method of nanoparticle.
Background technology
Metal nanoparticle, due to skin effect and quantum size effect, shows many unique optics, electricity and magnetic
Learn character.Wherein, local surface plasma resonance characteristic (the Localized surface of metal nanoparticle
Plasmonresonance, LSPR) it is research and one of the focus of application.When lambda1-wavelength is much smaller than the metallic nanoparticle period of the day from 11 p.m. to 1 a.m
Local surface plasma resonance can be excited in surfaces of metal nanoparticles, selectivity photon can be strengthened in nanoparticle surface and inhale
Receive and produce local and strengthen electric field.These characteristics of metal nanoparticle are at bio-sensing, Surface-enhanced spectroscopic, plasma too
The fields such as sun energy battery, optical pickocff, catalysis are studied widely and are applied.
These special performances of metal nanoparticle are to be determined by the size of nanoparticle, shape, distribution, thus receive
The preparation of the size of rice corpuscles, morphology controllable becomes extremely important.Find or explore one and have that equipment is simple, operation and maintenance becomes
This is the lowest, growing method simple and fast, become that point mass is high, the metal nanoparticle preparation method that is prone to the advantages such as Industry Promotion is
Urgent need to solve the problem in this field.
The common method preparing metal nanoparticle at present on substrate is that colloidal metal nanoparticle is fixed on substrate
On.Metal in metal salt solution is restored by the method first with chemical reduction reaction, prepares nano metallic colloid
Solution, then transfer to this colloid solution be evaporated by liquid by thermal evaporation on substrate, on substrate, just prepare metal nano
Particle.But nano-particle skewness prepared by this method, easily there is agglomeration, and stability and repeatability
The highest.Other nanometer preparation method also has photoetching technique and nanolithography etc., and their preparation cost is high, technique is more multiple
Miscellaneous, can not large-scale promotion use.
Summary of the invention
It is contemplated that for the defect existing for above-mentioned prior art and deficiency, it is provided that a kind of based on short annealing metal
The method of thin-film self-assembling nanoparticle, the method uses and grows nano-particle on substrate, its low cost, simple, energy
Access Discrete Distribution, and be uniformly dispersed, the nano-particle of uniform particle diameter.
The present invention realizes by using following technical proposals:
A kind of method based on short annealing metallic film self-assembled nanometer particle, it is characterised in that step is as follows:
First, at deposition on substrate layer of metal thin film, then deposition having the substrate of film be placed in quick anneal oven, loading is moved back
Fire program makes annealing treatment, by initial temperature, heating rate, time in temperature and the stream of protective gas in annealing
Amount control carries out rapid thermal annealing, obtains being prepared for the substrate of one layer of nanoparticle.
Described " load cycle of annealing to make annealing treatment, by initial temperature, heating rate, the time in temperature and
In annealing, the flow-control of protective gas carries out rapid thermal annealing " specifically comprise the following steps that
Arranging initial temperature: set according to ambient temperature, the time is set to 5-15s, and protective gas speed is set to 8-12SLPM
(stard liter per minute, standard liters per minute flow value, lower same)；
Temperature rise period: annealing temperature is set to 300-800 DEG C, the heating-up time is 20-30s, and protective gas speed is 2-5SLPM；
In thermophase: temperature is maintained at 300-800 DEG C, the time is 20-40s, and protective gas speed is 2-5SLPM；
Temperature-fall period: temperature is set to room temperature, the time is 60-100s, and protective gas speed is 8-12SLPM；
When temperature-fall period terminates, when temperature is less than 100 DEG C, from quick anneal oven, take out the base being prepared for one layer of nanoparticle
Sheet.
The THICKNESS CONTROL of described deposit metal films is between 2-20nm.
The material of described metallic film is the alloy of gold, silver, platinum or gold, silver, platinum.
The material of described backing material is GaAs substrate, silicon chip, glass, ITO or thin-film solar cells.
Described deposition process is magnetron sputtering method, ion sputtering process, electron beam evaporation or thermal evaporation.
Described cooling uses water-cooled and the air-cooled mode combined, water-cooling system configuration to be set to 25 DEG C.Air cooling system
Employing protective gas is lowered the temperature.
Described protective gas is nitrogen or argon.
Compared with prior art, what the present invention was reached has the beneficial effect that:
1, this method applies solid dehumidification principle.The sedimentation state of solid film is typically meta or instability, when this
After metastable state is destroyed, the graininess that thin film is little by developing into thermal equilibrium state.This process is to be tended to minimum by surface to drive
Move.When thin film is the thinnest when, this process can be carried out at a temperature of far below film melting points.This process is just known as
Solid-state dehumidification.By depositing one layer of metastable thin film on substrate, carry out annealing the most at a certain temperature and force solid
The generation of dehumidification.The method can be used for the self assembly that nanoparticle arranges.The method causing solid dehumidification generally has electron beam
Bombardment, particle beam irradiation and thermal annealing.There is significant limitation in electron beam and particle beam, as the highest in use cost, be difficult to big
Scale use and high energy particle cause the defect of material and device.And short annealing processes and causes thin film solid state dehumidification phenomenon to produce
Life is a kind of method of simple economy.The metal nanoparticle density that meta-stable metal thin film dehumidification produces is made by short annealing
High, the agglomeration of the particle that is evenly distributed, avoids, possesses simple to operation, nanoparticle morphology controllable, and it is excellent that preparation efficiency is high etc.
Point.Rapid thermal annealing is to realize nanoparticle independently to fill the most quick and economic method.
2, this method uses one layer of thin metal film of deposition on substrate, is then processed by short annealing, is taken off by solid-state
Moor is managed, the graininess that thin film will develop under thermal equilibrium condition.Use each control parameter in step described in this method, in conjunction with
Embodiment and accompanying drawing, the metal nanoparticle density that this method produces is high, the agglomeration of the particle that is evenly distributed, avoids,
Possess simple to operation, nanoparticle morphology controllable, preparation efficiency advantages of higher.
Accompanying drawing explanation
Below in conjunction with specification drawings and specific embodiments, the present invention is described in further detail, wherein:
Fig. 1 be gallium arsenide substrate 8nm gold very thin film at 500 DEG C, annealing 30s annealing generate golden nanometer particle schematic diagram；
Fig. 2 is that silicon solar cell 10s steams gold thin film 400 DEG C, the golden nanometer particle schematic diagram that annealing 30s annealing generates；
Fig. 3 is that silicon solar cell 10s steams gold thin film 500 DEG C, the golden nanometer particle schematic diagram that annealing 30s annealing generates；
Fig. 4 is that silicon solar cell 10s steams gold thin film 600 DEG C, the golden nanometer particle schematic diagram that annealing 30s annealing generates.
Detailed description of the invention
Self-assembling of gold nanoparticles on embodiment 1:GaAs substrate.(seeing Fig. 1)
First GaAs substrate is cleaned up, dry up with nitrogen.Utilize compact particle sputter, substrate sputters layer of metal
Thin film, controls the thickness of sputtered film, after thin film sputtering completes, by the thickness of high-resolution XRD testing film by sputtering time
Degree (i.e. by XRR technical testing film thickness).The thin film of 12 seconds sputtering time thickness of test result is that 8nm is thick.
Start quick anneal oven, steaming has the substrate of metallic film be positioned on load plate.After closing cavity, main frame sets
Putting annealing conditions: initial temperature, temperature sets according to ambient temperature, is traditionally arranged to be 25 DEG C, and the time is set to about 10s, nitrogen
Gas speed is set to 10SLPM；Temperature rise period, annealing temperature is set to 500 DEG C, and the heating-up time is 25s, and nitrogen rate is 3SLPM；Stay
Thermophase, temperature is maintained at 500 DEG C, and the time is 30s, and nitrogen rate is 3SLPM；Temperature-fall period, temperature is set to room temperature, time
Between be 90s, nitrogen rate is 10SLPM.When temperature-fall period terminates, when temperature is less than 100 DEG C, slowly open chamber door, take out base
Sheet.One layer of golden nanometer particle it is prepared on substrate.
Embodiment 2: Self-assembling of gold nanoparticles on silicon solar cell.(seeing Fig. 2-4)
Monocrystal silicon n+-p type solaode commercially is removed front silver electrode and silicon nitride anti-reflection layer removes work
Substrate for sputtering.Method is that cell piece is immersed in HF:H2O be 1:3 volume ratio etchant solution in 30 minutes, can be fine
Remove surface anti-reflection layer, expose the pyramid texture of battery surface.After removing anti-reflection layer, more successively by solaode
Sheet puts into each ultrasonic cleaning 5 minutes in acetone soln, aqueous isopropanol, deionized water, with organics removal, impurity etc..By base
Originally after cleaning up, dry up with nitrogen stand-by.
Then on silicon solar cell substrate, sputter thin film with particle sputter, control thin film by sputtering time
Thickness.The steaming gold time is 10s
Start quick anneal oven, steaming has the substrate of metallic film be positioned on load plate.Being respectively provided with annealing temperature is 400 DEG C,
500 DEG C, 600 DEG C of annealing temperatures (seeing Fig. 2-4).Nanoparticle increases and particle diameter increase along with annealing temperature, by annealing
Temperature controls the size of nanoparticle.
Claims (8)
1. a method based on short annealing metallic film self-assembled nanometer particle, it is characterised in that step is as follows:
First, backing material deposits layer of metal thin film, forms the substrate being coated with metallic film；Then place the substrate in fast
In fast annealing stove, load cycle of annealing make annealing treatment, by initial temperature, heating rate, the time in temperature and annealing
In process, the flow-control of protective gas carries out rapid thermal annealing, obtains being prepared for the substrate of one layer of nanoparticle.
Method based on short annealing metallic film self-assembled nanometer particle the most according to claim 1, it is characterised in that:
Described " load cycle of annealing to make annealing treatment, by initial temperature, heating rate, time in temperature with making annealing treatment
The flow-control of middle protective gas carries out rapid thermal annealing " specifically comprise the following steps that
Arranging initial temperature: set according to ambient temperature, the time is set to 5-15s, and protective gas speed is set to 8-12SLPM；
Temperature rise period: annealing temperature is set to 300-800 DEG C, the heating-up time is 20-30s, and protective gas speed is 2-5SLPM；
In thermophase: temperature is maintained at 300-800 DEG C, the time is 20-40s, and protective gas speed is 2-5SLPM；
Temperature-fall period: temperature is set to room temperature, the time is 60-100s, and protective gas speed is 8-12SLPM；
When temperature-fall period terminates, when temperature is less than 100 DEG C, from quick anneal oven, take out the base being prepared for one layer of nanoparticle
Sheet.
Method based on short annealing metallic film self-assembled nanometer particle the most according to claim 1, it is characterised in that:
The THICKNESS CONTROL of described deposit metal films is between 2-20nm.
Method based on short annealing metallic film self-assembled nanometer particle the most according to claim 1, it is characterised in that:
The material of described metallic film is the alloy of gold, silver, platinum or gold, silver, platinum.
Method based on short annealing metallic film self-assembled nanometer particle the most according to claim 1, it is characterised in that:
The material of described backing material is GaAs substrate, silicon chip, glass, ITO or thin-film solar cells.
Method based on short annealing metallic film self-assembled nanometer particle the most according to claim 1, it is characterised in that:
Described deposition process is magnetron sputtering method, ion sputtering process, electron beam evaporation or thermal evaporation.
Method based on short annealing metallic film self-assembled nanometer particle the most according to claim 2, it is characterised in that:
Described cooling uses water-cooled and the air-cooled mode combined, water-cooling system configuration to be set to 25 DEG C, and air cooling system uses protection
Gas is lowered the temperature.
Method based on short annealing metallic film self-assembled nanometer particle the most according to claim 2, it is characterised in that:
Described protective gas is nitrogen or argon.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106949914A (en) * | 2017-03-23 | 2017-07-14 | 山东大学 | A kind of utilization local phasmon structure improves the method that photo-thermal excites micro-cantilever vibrational energy conversion efficiency |
| CN108004506A (en) * | 2017-12-07 | 2018-05-08 | 青岛大学 | A kind of noble metal nano particles based on In alloys and preparation method thereof |
| CN109270102A (en) * | 2018-09-18 | 2019-01-25 | 昆明理工大学 | A kind of preparation method of the gradient nano fine copper SEM sample for DIC analysis |
| CN110656306A (en) * | 2019-10-15 | 2020-01-07 | 北京理工大学 | Metal @ GST medium heterogeneous nano core-shell structure and preparation method thereof |
| CN110893461A (en) * | 2019-11-06 | 2020-03-20 | 肇庆市华师大光电产业研究院 | Preparation method of nanoparticles with three-level composite structure |
| CN110923628A (en) * | 2019-11-06 | 2020-03-27 | 南京理工大学 | Preparation method of novel surface cluster molecules |
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- 2016-08-22 CN CN201610699894.7A patent/CN106119804A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106949914A (en) * | 2017-03-23 | 2017-07-14 | 山东大学 | A kind of utilization local phasmon structure improves the method that photo-thermal excites micro-cantilever vibrational energy conversion efficiency |
| CN108004506A (en) * | 2017-12-07 | 2018-05-08 | 青岛大学 | A kind of noble metal nano particles based on In alloys and preparation method thereof |
| CN109270102A (en) * | 2018-09-18 | 2019-01-25 | 昆明理工大学 | A kind of preparation method of the gradient nano fine copper SEM sample for DIC analysis |
| CN109270102B (en) * | 2018-09-18 | 2021-07-16 | 昆明理工大学 | Preparation method of gradient nano pure copper SEM sample for DIC analysis |
| CN110656306A (en) * | 2019-10-15 | 2020-01-07 | 北京理工大学 | Metal @ GST medium heterogeneous nano core-shell structure and preparation method thereof |
| CN110893461A (en) * | 2019-11-06 | 2020-03-20 | 肇庆市华师大光电产业研究院 | Preparation method of nanoparticles with three-level composite structure |
| CN110923628A (en) * | 2019-11-06 | 2020-03-27 | 南京理工大学 | Preparation method of novel surface cluster molecules |
| CN110893461B (en) * | 2019-11-06 | 2021-08-24 | 肇庆市华师大光电产业研究院 | Preparation method of nanoparticles with three-level composite structure |
| CN110923628B (en) * | 2019-11-06 | 2021-11-26 | 南京理工大学 | Preparation method of novel surface cluster molecules |
| CN114107903A (en) * | 2021-11-12 | 2022-03-01 | 中国工程物理研究院电子工程研究所 | Optical PUF (physical unclonable function), and preparation method and application thereof |
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Application publication date: 20161116 |