CN107057691B - A kind of preparation method of the colloidal state silicon nanocrystal of surface modification - Google Patents
A kind of preparation method of the colloidal state silicon nanocrystal of surface modification Download PDFInfo
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- CN107057691B CN107057691B CN201710462264.2A CN201710462264A CN107057691B CN 107057691 B CN107057691 B CN 107057691B CN 201710462264 A CN201710462264 A CN 201710462264A CN 107057691 B CN107057691 B CN 107057691B
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C01B21/00—Nitrogen; Compounds thereof
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The present invention relates to a kind of preparation method of the colloidal state silicon nanocrystal of surface modification, the preparation method is the following steps are included: the 1) mixed liquor of nano silica fume and organic solvent, and laser burn is handled under stirring；2) by the mixed liquor separating treatment after laser burn, colloidal state silicon nanocrystal is obtained.The particle size distribution range of preparation method preparation gained colloidal state silicon nanocrystal is controllable, and good dispersion, soilless sticking occurs, and can avoid the generation of oxidation.
Description
Technical field
The present invention relates to colloidal crystal fields, and in particular to a kind of preparation method of the colloidal state silicon nanocrystal of surface modification.
Technical background
Si NCs (silicon nanocrystal) is widely used in because with spectral tunability and due to high photoluminescence efficiency by people
The fields such as optoelectronic device and biological fluorescent labelling.The silicon element one of most as nature content, it is non-toxic, relative to tradition
Semiconductor-quantum-point has wider Research Prospects.Its quantum structure has quantum limitation effect, in entire visible-range
It inside can get stable luminescence generated by light [Silicon quantum wire array fabrication by
electrochemical and chemical dissolution of wafers,Applied Physics Letters,
1990,57(10):1046-1048].Colloidal state Si NCs because having good dispersibility, stable physics and chemistry in the solution
State is not easy to be oxidized, good biocompatibility, becomes the hot spot that current scholars study.
The preparation method of colloidal state Si NCs is divided into: (1) method from top to bottom, (2) method, (3) reactant first decompose from bottom to top
Synthetic method again, wherein needing the subsequent processings such as thermal oxide [High-yield preparation of blue-emitting mostly
colloidal Si nanocrystals by selective laser ablation of porous silicon in
Liquid, Nanotechnology, 2014,25 (27): 275602], passivation step is various, has toxicity [Size using reagent
and structure control of si nanoparticles by laser ablation in different
liquid media and further centrifugation classification,Journal of Physical
Chemistry C,2009,113(44):19091-19095].And Si NCs size distribution obtained is extensively, causes luminescence band
Extensively, the problems such as fluorescence efficiency is low.
Laser liquid phase inustion, have many advantages, such as one-step synthesis, liquid phase medium it is nontoxic, without heating, utilize party's legal system
The application prospect of standby colloid Si NCs is good.How Si NCs size is accurately controlled by laser liquid phase inustion to be distributed, increase
Photoluminescence intensity need further to study.
Summary of the invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide the preparation sides of the colloid Si NCs of surface modification a kind of
Method.
To achieve the above object, the technical solution of the present invention is as follows: a kind of preparation side of the colloidal state silicon nanocrystal of surface modification
Method, comprising the following steps:
1) mixed liquor of nano silica fume and organic solvent, the laser burn under stirring；
2) by the mixed liquor separating treatment after laser burn, colloidal state silicon nanocrystal is obtained；
Wherein, organic solvent is ethyl alcohol, toluene, n-hexylene or 1- octadecylene；
Laser burn condition is titanium/sapphire laser parameter: power: 600~810mW, wavelength: 500~800nm,
Irradiation duration: 100fs, frequency: 80MHz；Burn 1~6h of duration.
The mixing ratio of nano silica fume and organic solvent is 1~5mg/1ml.The mixing ratio of nano silica fume and organic solvent is preferred
For 1~3mg/1ml.
The particle diameter distribution of colloidal state silicon nanocrystal is 2~13nm, and average particle size distribution is 3.5~7.5nm.
Preferably, organic solvent is n-hexylene, and the mixing ratio of nano silica fume and organic solvent is 1mg/ml.
Preferably, titanium/sapphire laser parameter are as follows: power: 810mW, wavelength: 800nm, irradiation duration:
100fs, frequency: 80MHz；Burn duration 3h.
In step 1), magnetic agitation mixed liquor.
In step 2), the mode of separating treatment is centrifuge separation.
Centrifuge separation condition is 8000~12000rpm of revolving speed, 15~45min of duration.Preferably, revolving speed 10000~
11000rpm, 15~25min of duration.
Nano silica fume is monocrystalline silicon piece or monocrystalline silicon powder, and nano silica fume partial size is 50~120nm.Preferably, nano silica fume
Partial size be 90~100nm.
Compared with prior art, the invention has the following advantages that
(1) preparation method of the invention, for the first time by organic solvent used in the present invention (toluene, n-hexylene or 1- octadecylene) and
Lasing condition (laser, laser parameter) combines, and step preparation has the colloidal state silicon nanocrystal of surface modification.It makes through the invention
Preparation Method such as changes solution concentration, can Effective Regulation colloidal state silicon nanocrystal particle size distribution range, improve colloidal state silicon nanocrystal
Photoluminescence intensity.
(2) organic solvent used in the present invention is toluene, n-hexylene or 1- octadecylene, belongs to low toxicity or innocuous agents, and environment is dirty
Contaminate small, injury of human is low, meets the green non-pollution of production technology to the maximum extent.
(3) preparation method of the invention, preparation process is simple, and process conditions are easily controllable, at low cost.
(4) preparation method of the invention burns technology using laser liquid phase, and a step prepares the colloidal state Si of surface passivation
NCs, without subsequent processing steps such as thermal oxide, passivation.
(5) utilize preparation method of the invention, the preparation gained particle size narrow distribution range of colloidal state silicon nanocrystal and it is equal
Even, crystal is in dispersity, soilless sticking phenomenon.
(6) preparation method of the invention is utilized, the surface of preparation gained colloidal state silicon nanocrystal is covered by chemical bonding
Organic matter effectively prevent aggregation and the surface oxidation of crystal grain, improves its stability in the solution.
(7) preparation method of the invention is utilized, the quantum yield of preparation gained colloidal state silicon nanocrystal is high, can be widely applied to
The fields such as photoelectric device LED, solar power generation and biological fluorescent labelling.
Detailed description of the invention
Fig. 1 is the transmission electron microscope figure and size distribution plot of the colloidal state Si NCs of Examples 1 to 3 preparation.
Fig. 2 be Examples 1 to 3 preparation colloidal state Si NCs under 360nm exciting light luminescence generated by light map.
Fig. 3 is the transmission electron microscope figure of colloidal state Si NCs prepared by embodiment 1.
Fig. 4 is the Fourier transform infrared spectrogram of colloidal state Si NCs prepared by embodiment 1.
Fig. 5 is the fluorescent emission map under colloidal state Si NCs difference excitation wavelength prepared by embodiment 1.
Specific embodiment
Further illustratively the present invention will be described in detail combined with specific embodiments below.It should be noted that for these
The explanation of embodiment is used to help understand the present invention, but and does not constitute a limitation of the invention.
Nano silica fume used in following embodiment is selected from monocrystalline silicon piece or monocrystalline silicon powder.
Embodiment 1
1) 100nm nano silica fume 5mg is weighed, is placed in sample bottle, adds 5ml n-hexylene, is put into magnetic stir bar, be placed in magnetic
On power blender.
2) by titanium/sapphire laser, (power: 810mW, wavelength: 800nm, irradiation continue while magnetic agitation
Time: 100fs, frequency: 80MHz) liquid phase ablation 3h.
3) sample after ablation is centrifuged under 11000rpm revolving speed 15min, obtains colloidal state Si NCs.
The transmission electron microscope figure of colloidal state Si NCs is as shown in Fig. 1 (a) and Fig. 3, the size point of colloidal state Si NCs
Shown in Butut such as Fig. 1 (b), luminescence generated by light map is as shown in Fig. 2, colloidal state Si NCs under colloidal state Si NCs 360nm exciting light
Fourier transform infrared spectrogram as shown in figure 4, fluorescent emission map such as Fig. 5 institute under colloidal state Si NCs difference exciting light
Show.
Embodiment 2
1) 100nm nano silica fume 10mg is weighed, is placed in sample bottle, adds 5ml toluene, is put into magnetic stir bar, be placed in magnetic
On power blender.
2) by titanium/sapphire laser, (power: 810mW, wavelength: 800nm, irradiation continue while magnetic agitation
Time: 100fs, frequency: 80MHz) liquid phase ablation 3h.
3) sample after ablation is centrifuged under 11000rpm revolving speed 15min, obtains colloidal state Si NCs.
Shown in transmission electron microscope figure such as Fig. 1 (c) of colloidal state Si NCs, the size distribution plot of colloidal state Si NCs is such as
Shown in Fig. 1 (d).
Embodiment 3
1) 100nm nano silica fume 15mg is weighed, is placed in sample bottle, adds 5ml 1- octadecylene, is put into magnetic stir bar, sets
In on magnetic stirring apparatus.
2) by titanium/sapphire laser, (power: 810mW, wavelength: 800nm, irradiation continue while magnetic agitation
Time: 100fs, frequency: 80MHz) liquid phase ablation 3h.
3) sample after ablation is centrifuged under 11000rpm revolving speed 15min, obtains colloidal state Si NCs.
Shown in transmission electron microscope figure such as Fig. 1 (e) of colloidal state Si NCs, the size distribution plot of colloidal state Si NCs is such as
Shown in Fig. 1 (f).
Effect explanation
Transmission electron microscope figure, the size distribution plot, exciting light of gained colloidal state Si NCs are prepared in conjunction with above-described embodiment
Lower luminescence generated by light map and infrared spectrogram illustrate the feasibility and effect of preparation method of the present invention.
(a) of Fig. 1, (c), (e) display, the crystalchecked of the preparation gained colloidal state silicon nanocrystal of embodiment 1,2,3, in dispersion
State, and soilless sticking phenomenon.
The particle size of (b) of Fig. 1, (d), (f) display, the preparation gained colloidal state silicon nanocrystal of embodiment 1,2,3 is distributed model
It encloses and corresponds to 2~5.5nm, 3~11nm, 3~13nm, average grain diameter corresponds to 3.61nm, 6.22nm, 7.54nm.From embodiment 1
To embodiment 3, the particle size distribution and average grain diameter of colloidal state silicon nanocrystal are in be gradually increased trend.Analyzing influence because
Element are as follows: the mixed proportion of monocrystalline silicon powder and organic solvent increases to 3mg/1ml, monocrystalline silicon in unit organic solvent from 1mg/1ml
The quality of powder increases, and the partial size of colloidal state silicon nanocrystal is caused to increase.Generally speaking, the preparation of colloidal state silicon nanocrystal of the present invention is utilized
The size range of method preparation gained colloidal state silicon nanocrystal is controllable, and particle size distribution range is narrower, and partial size is smaller, particle diameter distribution
It is more uniform.
Fig. 2 is shown, under the conditions of 360nm exciting light, Examples 1 to 3 preparation gained colloidal state silicon nanocrystal generates photic
Luminous intensity, and the photoluminescence intensity of the preparation gained colloidal state Si of embodiment 1 NCs is higher than embodiment 2 and embodiment 3.It is found that
The particle size distribution range of colloidal state silicon nanocrystal is narrower, and particle size is smaller, and photoluminescence intensity is bigger.Therefore, selection is implemented
Example 1 preferably, as its preparation obtained by colloidal state Si NCs infrared spectrogram and different exciting lights under fluorescent emission
The feasibility and effect of preparation method of the present invention is further illustrated in map.
The peak Si-C and other organo-functional group absorption peaks that Fig. 4 is shown show the preparation gained colloidal state silicon nanocrystal of embodiment 1
Surface mainly passes through Si-C key grafting organic matter and is modified, and stable structure.In addition, colloidal state silicon nanocrystal surface can also pass through
The chemical bonds such as Si-O key graft organic matter.
Fig. 5 shows that colloidal state silicon nanocrystal prepared by embodiment 1 can produce fluorescence under 340nm~360nm exciting light,
And fluorescence intensity is stablized by force, each lower Fluorescent peal generated of wavelength light excitation is without significant change.
In conclusion the colloidal state silicon nanocrystal of surface modification organic matter is prepared in laser liquid phase inustion of the present invention, and
The surface modification stable structure.By the Surface Modification Effect, prevents colloidal state silicon nanocrystal from reuniting, it is made to be uniformly dispersed；It avoids
The oxidation of colloidal state silicon nanocrystal, adjusts its biocompatibility；Colloidal state silicon nanocrystal partial size is adjusted, keeps its particle size distribution range narrow and equal
It is even.
Claims (9)
1. a kind of preparation method of the colloidal state silicon nanocrystal of surface modification, which comprises the following steps:
1) mixed liquor of nano silica fume and organic solvent, the laser burn under stirring；
2) by the mixed liquor separating treatment after laser burn, colloidal state silicon nanocrystal is obtained；
Wherein, organic solvent is ethyl alcohol, toluene, n-hexylene or 1- octadecylene；
Laser burn condition is titanium/sapphire laser parameter: power: 600~810mW, wavelength: 500~800nm, irradiation
Duration: 100fs, frequency: 80MHz；Burn 1~6h of duration.
2. preparation method according to claim 1, which is characterized in that the mixing ratio of nano silica fume and organic solvent be 1~
5mg/1ml。
3. preparation method according to claim 1, which is characterized in that the particle diameter distribution of colloidal state silicon nanocrystal is 2~13nm,
Average particle size distribution is 3.5~7.5nm.
4. preparation method according to claim 1, which is characterized in that organic solvent is n-hexylene, nano silica fume with it is organic
The mixing ratio of solvent is 1mg/ml.
5. preparation method according to claim 1, which is characterized in that titanium/sapphire laser parameter is power:
810mW, wavelength: 800nm, irradiation duration: 100fs, frequency: 80MHz；Burn duration 3h.
6. preparation method according to claim 1, which is characterized in that in step 1), magnetic agitation mixed liquor.
7. preparation method according to claim 1, which is characterized in that in step 2), separating treatment mode is centrifuge separation.
8. preparation method according to claim 7, which is characterized in that centrifuge separation condition is, revolving speed 8000~
12000rpm, 15~45min of duration.
9. preparation method according to claim 1, which is characterized in that nano silica fume partial size is 50~120nm.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1974883A (en) * | 2006-11-30 | 2007-06-06 | 复旦大学 | Prepn process of nanometer silicon crystal |
| CN102231420A (en) * | 2011-06-28 | 2011-11-02 | 复旦大学 | Method for introducing extra nucleation points to silicon nanocrystalline film |
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2017
- 2017-06-19 CN CN201710462264.2A patent/CN107057691B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1974883A (en) * | 2006-11-30 | 2007-06-06 | 复旦大学 | Prepn process of nanometer silicon crystal |
| CN102231420A (en) * | 2011-06-28 | 2011-11-02 | 复旦大学 | Method for introducing extra nucleation points to silicon nanocrystalline film |
Non-Patent Citations (3)
| Title |
|---|
| Laser Annealing of Silicon Nanocrystal Films Prepared by Pulsed-Laser Deposition;X.Y.Chen等;《Journal of Vacuum Science & Technology B》;20040831;第22卷(第4期);1731-1737 |
| Width of Nucleation Region of Si Nanocrystal Grains Prepared by Pulsed Laser Ablation with Different Laser Fluence;Zechao Deng等;《Journal of Nanoparticles》;20121231;ID105685，1-6 |
| 硅纳米晶的制备及其在太阳电池中的应用研究;刘超等;《化学进展》;20150905;第27卷(第9期);1302-1312 |
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