CN101205629B - Fluorescent silicon nitride based nano thread and preparation thereof - Google Patents
Fluorescent silicon nitride based nano thread and preparation thereof Download PDFInfo
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- CN101205629B CN101205629B CN2006101565279A CN200610156527A CN101205629B CN 101205629 B CN101205629 B CN 101205629B CN 2006101565279 A CN2006101565279 A CN 2006101565279A CN 200610156527 A CN200610156527 A CN 200610156527A CN 101205629 B CN101205629 B CN 101205629B
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Abstract
The invention relates to a luminescent material, in particular to a silicon nitride based nano wire and preparing method thereof. The fluorescigenic silicone nitride based nano wire is of alpha- Si3N4 phase, rare earth metal ions are contained in silicon nitride based unit cell interstices of the nano wire, thereby forming the nano wire taking metal ions sosoloid as luminescent center, or the surface of the nano wire is covered with a kubonit protective layer. The rare earth metal ions are any one or two or more elements in Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. The maximum luminous wavelength of a fluorescence spectrum of the invention is 420-680nm, and the maximum excitation wavelength of an excitation spectrum is 250-450nm. Because of the protection of the kubonit, the invention not only has high fluorescent quenching temperature and high luminous intensity, but also the material deterioration and luminance is reduced smaller when an excitation source is excited, thereby improving the service life. The invention is hopeful to be widely applied in micro-electronics, optics, illumination and other fields.
Description
Technical field
The present invention relates to luminescent material, be specifically related to silicon nitride based nano thread and preparation method thereof.
Background technology
One-dimensional material comprises nano wire, nanotube, nanometer rod etc. owing to have the microcosmic one-dimentional structure, and big specific surface area makes it have wide practical use in catalysis, environmental protection and other functional materials assembling field, has become one of main research focus in recent years.On the other hand, silicon nitride ceramics also has been subjected to extensive attention in the last thirty years.In recent years, a focus of people's research was a beta-silicon nitride nanowire.Beta-silicon nitride nanowire possesses elasticity and bending property preferably simultaneously except the lot of advantages that possesses silicon nitride ceramics.Beta-silicon nitride nanowire is a kind of good semi-conductor, is the outstanding candidate material of preparation miniature electronic and optics, both can be used as the working cell in device, can become the connection lead again.In the design and assembling of miniature electronic and optics, particularly in solar cell and the photorectifier, need beta-silicon nitride nanowire to have the good optical performance.Scientific and technical personnel have carried out deep research to the preparation and the luminescent properties of purity nitrogen silicon nanowires.2005, CN1699639A disclosed a kind of α-Si
3N
4The method for solvent thermal reaction preparation of monocrystal nanowire, this method in molar ratio 1: 1.5-15 is with SiCl
4And Mg
3N
2Mix, be sealed in 550-700 ℃ of reaction more than 5 hours; Product can obtain the beta-silicon nitride nanowire powder through pickling and washing, centrifugation and drying.Result of study shows that the gained beta-silicon nitride nanowire can send faint visible light under the exciting of deep UV (ultraviolet light).Its luminescence mechanism is because the surface imperfection of nano wire, and this has determined it luminous is faint with uncontrollable.
So far still find no the report of the silicon nitride based nano thread that closes high luminous performance.
Summary of the invention
The objective of the invention is to,, provide a kind of silicon nitride based nano thread and preparation method thereof with hyperfluorescence luminescent properties at deficiency of the prior art.
Purpose of the present invention realizes in the following manner.
Fluorescent silicon nitride based nano thread of the present invention, nano wire wherein is nitride silicon based to be α-Si
3N
4Phase, nano wire radius are that 10-500nm, length are 200nm-1mm, it is characterized in that, accommodate rare earth ion in the nitride silicon based structure cell space of nano wire, form with the nano wire of metal ion sosoloid as luminescence center; Perhaps, be coated with boron nitride (BN) protective layer in this nanowire surface.Described rare earth ion is Ce, Pr, and Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, any among the Lu or two kinds or two or more elements, the thickness of described boron nitride protective layer is 1-20nm.
The preparation method of fluorescent silicon nitride based nano thread of the present invention comprises with prior art for preparing α-Si
3N
4The nano wire powder is characterized in that, its preparation process is:
(1) rare earth oxide is obtained rare earth nitrate solution with nitric acid dissolve, wherein the mol ratio of rare earth ion and nitrate ion is 1: 4, then it is filtered evaporate to dryness and obtains the rare earth nitrate powder.
(2) will utilize the α-Si of prior art for preparing
3N
4The nano wire powder mixes with the rare earth nitrate powder, is dissolved in then to disperse to obtain in 5-30 minute mixed slurry, wherein α-Si in the alcohol solution
3N
4The mol ratio of nano wire and rare earth nitrate is 1: 0.0002-0.02; Described alcohol is methyl alcohol or ethanol; It is 1%-25% that the slurry volume solid content is joined by institute; Described α-Si
3N
4The nano wire radius is that 10-500nm, length are 200nm-1mm.
(3) mixed slurry was removed to liquid phase fully at 40-80 ℃ time dry 20-60 minute, obtained dry powder.
(4) dry powder is placed flowing nitrogen and/or ammonia environment, be heated to 1400-1800 ℃, be incubated 2-6 hour, promptly obtain accommodating in the structure cell space fluorescent silicon nitride based nano thread of rare earth ion with 1-10 ℃/min speed.
Perhaps,
(5) add boron oxide or boric acid or pure boron powder in the powder after drying, wherein the content of boron oxide or boric acid or pure boron accounts for the 0.1-3wt% of gross weight; Then in flowing nitrogen and/or ammonia environment; be heated to 1400-1800 ℃ with 1-10 ℃/min speed; soaking time is 2-6h, and promptly obtaining surface coverage has the fluorescent silicon nitride based nano thread that accommodates rare earth ion in the thick boron nitride protective layer of 1-20nm, the structure cell space.
In the prior art, it is conventionally believed that beta-silicon nitride nanowire can send faint visible light under the exciting of deep UV (ultraviolet light), but because light is weak and uncontrollable, this is very limited its application.The present invention is according to α-Si
3N
4The characteristics of microstructure, i.e. α-Si
3N
4Be to arrange in the mode of ABCD by the Si-N chain, each structure cell all has two big spaces, utilizes the lattice distortion of nanowire surface, makes to have optically active rare earth ion and enter lattice, form the sosoloid of metal ion, thereby make nano wire can send bright fluorescence.The maximum emission wavelength of fluorescence spectrum is 420-680nm, and excitation spectrum maximum excitation wavelength is 250-450nm.In addition, because fluorescent silicon nitride based nano thread has the protection of BN layer extremely stable, not only fluorescent quenching temperature height; the luminous intensity height, and excitaton source when exciting material degradation and briliancy reduce for a short time, improved work-ing life; therefore, be expected in the acquisition widespread use of fields such as microelectronics, optics, illumination.Compared to existing technology, preparation method of the present invention also has the following advantages: equipment is simple, and is with low cost, helps large-scale industrial production; Synthesis technique is simple, and controllability is strong, and can obtain different size by some key process parameters in the control synthesis technique, and therefore the nano wire fluor of different optical performance can further enlarge its range of application.
Make below by drawings and Examples and to further specify.
Description of drawings
Fig. 1 is the stereoscan photograph of fluorescent silicon nitride based nano thread of the present invention (embodiment 1 sample).
Fig. 2 is the transmission electron microscope photo (2.1) and the high-resolution electron microscopy photo (2.2) of fluorescent silicon nitride based nano thread of the present invention (embodiment 1 sample).Among Fig. 2 .2,1 is silicon nitride based nano thread, and 2 is the boron nitride pellicle protective layer.
Fig. 3 be among Fig. 2 in the high-resolution electron microscopy nano wire inside (3.1) and the surface (3.2) the EDS spectrogram;
Fig. 4 is the XRD diffraction spectrogram of fluorescent silicon nitride based nano thread of the present invention (embodiment 1 sample);
Fig. 5 is exciting and emmission spectrum figure of fluorescent silicon nitride based nano thread of the present invention (embodiment 1 sample);
Fig. 6 is exciting and emmission spectrum figure of the used initial beta-silicon nitride nanowire of the present invention (embodiment 1 sample);
Fig. 7 is exciting and emmission spectrum figure of fluorescent silicon nitride based nano thread of the present invention (embodiment 2 samples);
Fig. 8 is the emmission spectrum figure of fluorescent silicon nitride based nano thread of the present invention (embodiment 4 samples);
Embodiment
Embodiment 1:
(1) utilizes prior art for preparing α-Si
3N
4Nano wire:
Concrete preparation process is as " materials chemistry " magazine " Synthesis and characterization of siliconcarbide; silicon oxynitride and silicon nitride nanowires " (Journal ofMaterial Chemistry 2002,12,1606-1611) described in the paper, promptly by heating the mixture of silica gel and elemental silicon, generate gas phase SiO, in 1350 ℃ of mobile ammonias, obtain α-Si by vapor-solid growth
3N
4Nano wire can make its diameter be about the 100-200 nanometer by control nanowire length and diameters such as control air-flow, temperature, and length is the 100-300 micron;
(2) europium sesquioxide with 0.5 mmole is dissolved in the salpeter solution that 10 ml concns are 0.4 mol, is heated to 60 degree, and after the dissolving, 100 degree evaporates to dryness obtain rare earth nitrate Eu (NO fully
3)
3
(3) with the α-Si that makes
3N
4Eu (the NO of nano wire 0.01 mole of (1.4 restrain) and 0.05 mmole (0.0169 gram)
3)
3Mix, and be dissolved in 20 milliliters ethanol/water (volume ratio 1: the 1) solution, and ultrasonic (power 400W, frequency 40KHZ) disperseed 10 minutes, make mixed slurry, institute joins the slurry volume solid content and is about 2.5%;
(4) then mixed slurry is changed over to the rotary vacuum drier drying, drying is 30 minutes under 40 ℃, obtains dry powder;
(5) above-mentioned dry powder is placed the bottom have an appointment in advance 0.014 the gram B
2O
3In the BN crucible of powder, then at mobile N
2/ NH
3Ambiance (N
2/ NH
3Ratio 5: 1, flow velocity are 0.2ml/min) in rise to 1500 ℃ with the temperature rise rate of 5 ℃/min,
Be incubated 4 hours, promptly obtain the xanchromatic fluorescent silicon nitride based nano thread.
As shown in Figure 1, the synthetic fluorescent silicon nitride based nano thread pattern smooth surface that obtains of present embodiment is in radial direction nano wire even thickness.As can be seen from Figure 2, this fluorescent silicon nitride based nano thread surface coverage has the fine and close boron nitride pellicle protective layer uniformly of one deck 3 nanometer thickness.The EDS spectrogram on nano wire inside (3.1) and surface (3.2) can prove that its inside is the adulterated Si of Eu from Fig. 3 high-resolution electron microscopy
3N
4, the surface is BN.This fluorescent silicon nitride based nano thread is done the XRD facies analysis, as shown in Figure 4, this and standard α-Si
3N
4Powdery diffractometry card (No.83-0700) meets, thereby can be confirmed to be α-Si
3N
4Fig. 5 is to use the emission and the excitation spectrum of this fluorescent silicon nitride based nano thread of fluorescent spectrophotometer assay, and therefrom as can be seen, it can be by the optical excitation in the very wide band zone from the ultraviolet to the visible light, and sending maximum emission wavelength is the bright gold-tinted of 590nm.Compare with excitation spectrum with the emission of initial silicon nitride silicon nanowires shown in Figure 6, as can be seen, the change of essence has all taken place in excitation wavelength and emission wavelength, and brightness has increased more than 10 times.
Embodiment 2:
(1) utilizes prior art for preparing α-Si
3N
40.01 mole of nano wire (1.4 gram) makes its diameter be about the 300-400 nanometer, and length is the 500-800 micron, and concrete preparation process is with embodiment 1.
(2) dysprosium oxide with 0.5 mmole is dissolved in the salpeter solution that 10 ml concns are 0.4 mol, is heated to 60 degree, and after the dissolving, 100 degree evaporates to dryness obtain rare earth nitrate Dy (NO fully
3)
3:
(3) with 0.01 mole of (1.4 gram) α-Si
3N
4Dy (the NO of nano wire and 0.1 mmole (0.0348 gram)
3)
3Mix, and be dissolved in 10 milliliters methanol (volume ratio 1: the 1) solution, ultrasonic (power 400W, frequency 40KHZ) disperseed 20 minutes;
(4) then mixed slurry is changed over to the rotary vacuum drier drying, drying is 20 minutes under 60 ℃.
(5) change the BN crucible after the drying over to, the bottom adds the B of about 0.028 gram in advance
2O
3Powder.Temperature rise rate with 10 ℃/min rises to 1750 ℃, is incubated 6 hours.Atmosphere is N
2, flow velocity is 0.4ml/min, can prepare the fluorescent silicon nitride based nano thread of white.
The nano wire that present embodiment makes sends blue light and the gold-tinted (be shown as and send white light) that maximum emission wavelength is 482nm and 578nm under the exciting of UV-light, as shown in Figure 7.
Embodiment 3:
Concrete preparation process is with embodiment 2, but do not add B in step (5)
2O
3Powder obtains with the nano wire of Dy metal ion sosoloid as luminescence center; This nano wire sends blue light and the gold-tinted (be shown as and send white light) that maximum emission wavelength is 482nm and 578nm equally under UV-light; excite similar to Fig. 7 to emmission spectrum; compare with the situation that the boron nitride pellicle protective layer is arranged of embodiment 2; its strength degradation 40%; but compare as the nano wire of luminescence center with non-metallic ion sosoloid in the prior art, its intensity has still increased more than 5 times.
Embodiment 4:
(1) utilizes prior art for preparing α-Si
3N
40.01 mole of nano wire (1.4 gram) makes its diameter be about the 30-40 nanometer, and length is the 500-1000 nanometer, and concrete preparation process is with embodiment 1.
(2) ytterbium oxide with 0.5 mmole is dissolved in the salpeter solution that 10 ml concns are 0.4 mol, is heated to 60 degree, and after the dissolving, 100 degree evaporates to dryness obtain rare earth nitrate Yb (NO fully
3)
3:
(3) with 0.01 mole of (1.4 gram) α-Si
3N
4Yb (the NO of nano wire and 0.005 mmole (0.0018 gram)
3)
3Mix, and be dissolved in 5 milliliters ethanol/water (volume ratio 1: the 1) solution ultra-sonic dispersion 30 minutes;
(4) then mixed slurry is changed over to the rotary vacuum drier drying, drying is 10 minutes under 80 ℃.
(5) change the BN crucible after the drying over to, the bottom adds the H of about 0.028 gram in advance
3BO
3Powder.Temperature rise rate with 10 ℃/min rises to 1700 ℃, is incubated 2 hours.Atmosphere is NH
3, flow velocity is 0.05ml/min, can prepare yellowish green fluorescent silicon nitride based nano thread.
The nano wire that present embodiment makes sends the yellow green light that maximum emission wavelength is 540nm under the exciting of ultraviolet-visible, as shown in Figure 8.
Claims (4)
1. fluorescigenic silicon nitride based nano thread, nano wire wherein is nitride silicon based to be α-Si
3N
4Phase, nano wire radius are that 10-500nm, length are 200nm-1mm, it is characterized in that, accommodate rare earth ion in the nitride silicon based structure cell space of nano wire, forming with metal ion sosoloid is the nano wire of luminescence center, and described rare earth ion is Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, any among the Lu or two or more elements.
2. fluorescigenic silicon nitride based nano thread as claimed in claim 1 is characterized in that, described is that the surface coverage of the nano wire of luminescence center has the boron nitride protective layer with metal ion sosoloid.
3. fluorescigenic silicon nitride based nano thread as claimed in claim 2 is characterized in that, the thickness of described boron nitride protective layer is 1-20nm.
4. the preparation method of the silicon nitride based nano thread that fluoresces as claimed in claim 1 or 2 comprises with prior art for preparing α-Si
3N
4The nano wire powder is characterized in that, its preparation process is:
(1) rare earth oxide is obtained rare earth nitrate solution with nitric acid dissolve, wherein the mol ratio of rare earth ion and nitrate ion is 1: 4, then it is filtered evaporate to dryness and obtains the rare earth nitrate powder;
(2) will utilize the α-Si of prior art for preparing
3N
4The nano wire powder mixes with the rare earth nitrate powder, is dissolved in then to disperse to obtain in 5-30 minute mixed slurry, wherein α-Si in the alcohol solution
3N
4The mol ratio of nano wire and rare earth nitrate is 1: 0.0002-0.02, described alcohol are methyl alcohol or ethanol; It is 1%-25% that the slurry volume solid content is joined by institute; Described α-Si
3N
4The nano wire radius is that 10-500nm, length are 200nm-1mm;
(3) mixed slurry was removed to liquid phase fully at 40-80 ℃ time dry 20-60 minute, obtained dry powder;
(4) dry powder is placed flowing nitrogen and/or ammonia environment, be heated to 1400-1800 ℃, be incubated 2-6 hour, promptly obtain accommodating in the structure cell space fluorescent silicon nitride based nano thread of rare earth ion with 1-10 ℃/min speed; Perhaps,
(5) add boron oxide or boric acid or pure boron powder in the powder after drying, wherein the content of boron oxide or boric acid or pure boron accounts for the 0.1-3wt% of gross weight; Then in flowing nitrogen and/or ammonia environment; be heated to 1400-1800 ℃ with 1-10 ℃/min speed; soaking time is 2-6h, and promptly obtaining surface coverage has the fluorescent silicon nitride based nano thread that accommodates rare earth ion in the thick boron nitride protective layer of 1-20nm, the structure cell space.
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