CN101205629A - 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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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 invention relates to a luminescent material, in particular to a silicon nitride-based nanowire and a preparation method thereof.
Background
The one-dimensional materials including nanowires, nanotubes, nanorods and the like have a microscopic one-dimensional structure and a large specific surface area, so that the one-dimensional materials have wide application prospects in the fields of catalysis, environmental protection and assembly of other functional materials, and become one of main research hotspots in recent years. On the other hand, silicon nitride ceramics have been gaining wide attention over the last thirty years. In recent years, one hotspot of research has been silicon nitride nanowires. The silicon nitride nanowire has many advantages of silicon nitride ceramics, and has good elasticity and bending performance. Silicon nitride nanowires are excellent semiconductors, are excellent candidates for the fabrication of microelectronic and optical devices, and can serve as both working elements and connecting wires in the devices. Silicon nitride nanowires are required to have good optical properties in the design and assembly of miniature electronic and optical devices, particularly solar cells and photodiodes. The preparation and luminescence properties of pure silicon nitride nanowires have been intensively studied by technologists. In 2005, CN1699639A disclosed an alpha-Si3N4The solvothermal reaction process of preparing monocrystal nanometer line includes mixing SiCl in the molar ratio of 1 to 1.5-154And Mg3N2Mixing, sealing and reacting at 550-700 ℃ for more than 5 hours; the product is washed by acid and water, centrifugally separated and dried to obtain the silicon nitride nanowire powder. Research results show that the obtained silicon nitride nanowire can emit weak visible light under the excitation of deep ultraviolet light. The light emission mechanism is due to surface defects of the nanowires, which determines that the light emission is weak and uncontrollable.
Reports on silicon nitride-based nanowires with strong luminescence properties have not been found so far.
Disclosure of Invention
The invention aims to provide a silicon nitride-based nanowire with strong fluorescence luminescence property and a preparation method thereof aiming at the defects in the prior art.
The object of the present invention is achieved as follows.
The fluorescent silicon nitride-based nanowire provided by the invention has the silicon nitride-based alpha-Si3N4The nano-wire has the radius of 10-500nm and the length of 200nm-1mm, and is characterized in that rare earth metal ions are contained in the crystal cell gap of the nano-wire silicon nitride base to form the nano-wire taking metal ion solid solution as the luminescence center; or, covering the surface of the nanowire with a Boron Nitride (BN) protective layer. The rare earth metal ions are any one or two or more than two of Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and the thickness of the boron nitride protective layer is 1-20 nm.
The preparation method of the fluorescent silicon nitride-based nanowire comprises the step of preparing alpha-Si by the prior art3N4The nano-wire powder is characterized in that the preparation process comprises the following steps:
(1) dissolving rare earth oxide with nitric acid to obtain a rare earth nitrate solution, wherein the molar ratio of rare earth ions to nitrate ions is 1: 4, and then filtering and evaporating to dryness to obtain rare earth nitrate powder.
(2) alpha-Si to be prepared by the prior art3N4Mixing the nano-wire powder with the rare earth nitrate powder, and dissolvingDissolving in alcohol water solution, dispersing for 5-30 min to obtain mixed slurry, wherein alpha-Si3N4The mol ratio of the nano wire to the rare earth nitrate is 1: 0.0002-0.02; the alcohol is methanol or ethanol; the volume solid content of the prepared slurry is 1-25 percent; the alpha-Si3N4The radius of the nano-wire is 10-500nm, and the length of the nano-wire is 200nm-1 mm.
(3) And drying the mixed slurry at 40-80 ℃ for 20-60 minutes until the liquid phase is completely removed to obtain dry powder.
(4) And (3) placing the dried powder in a flowing nitrogen and/or ammonia environment, heating to 1400 ℃ plus 1800 ℃ at the speed of 1-10 ℃/min, and preserving the heat for 2-6 hours to obtain the fluorescent silicon nitride-based nanowire containing the rare earth metal ions in the crystal cell gap. Or,
(5) adding boron oxide or boric acid or simple substance boron powder into the dried powder, wherein the content of the boron oxide or boric acid or simple substance boron accounts for 0.1-3 wt% of the total weight; then heating to 1400 ℃ plus 1800 ℃ at the speed of 1-10 ℃/min in a flowing nitrogen and/or ammonia environment, and keeping the temperature for 2-6h to obtain the fluorescent silicon nitride-based nanowire with the surface covered with a boron nitride protective layer with the thickness of 1-20nm and rare earth metal ions contained in the crystal cell gap.
In the prior art, it is generally believed that silicon nitride nanowires can emit weak visible light under the excitation of deep ultraviolet light, but the application of the silicon nitride nanowires is greatly limited due to weak and uncontrollable light. According to the invention based on alpha-Si3N4Features of microstructure, i.e. alpha-Si3N4The nano-wire is arranged by Si-N chains in an ABCD mode, each unit cell has two large gaps, rare earth metal ions with optical activity enter the crystal lattice by utilizing the crystal lattice distortion of the surface of the nano-wire to form a solid solution of the metal ions, and therefore the nano-wire can emit bright fluorescence. The maximum luminescence wavelength of the fluorescence spectrum is 420-680nm, and the maximum excitation wavelength of the excitation spectrum is 250-450 nm. In addition, the fluorescence silicon nitride-based nanowire has the BN layer which is extremely stable in protection, so that the fluorescence quenching temperature is high, the luminous intensity is high, the material degradation and the luminance reduction are small when an excitation source excites, and the improvement is realizedThe service life is prolonged, so that the LED lamp is expected to be widely applied to the fields of microelectronics, optics, illumination and the like. Compared with the prior art, the preparation method provided by the invention also has the following advantages: the equipment is simple, the cost is low, and large-scale industrial production is facilitated; the synthesis process is simple, the controllability is strong, and the nanowire phosphors with different sizes and different optical properties can be obtained by controlling some key process parameters in the synthesis process, so that the application range of the nanowire phosphors can be further expanded.
Further explanation is made below by means of the drawings and examples.
Drawings
FIG. 1 is a scanning electron micrograph of fluorescent silicon nitride-based nanowires of the present invention (sample of example 1).
Fig. 2 is a transmission electron micrograph (2.1) and a high resolution electron micrograph (2.2) of the fluorescent silicon nitride-based nanowires of the present invention (sample of example 1). In fig. 2.2, 1 is a silicon nitride-based nanowire, and 2 is a boron nitride thin film protective layer.
FIG. 3 is EDS spectra of the inside (3.1) and the surface (3.2) of the nanowire in the high resolution electron microscope of FIG. 2;
FIG. 4 is an XRD diffraction pattern of fluorescent silicon nitride-based nanowires of the present invention (sample of example 1);
FIG. 5 is an excitation and emission spectra of fluorescent silicon nitride-based nanowires of the present invention (sample of example 1);
FIG. 6 is an excitation and emission spectra of starting silicon nitride nanowires used in the present invention (sample of example 1);
FIG. 7 is an excitation and emission spectra of fluorescent silicon nitride-based nanowires of the present invention (sample example 2);
FIG. 8 is a graph of the emission spectra of fluorescent silicon nitride-based nanowires of the present invention (sample example 4); .
Detailed Description
Example 1:
(1) preparation of alpha-Si by means of the prior art3N4Nanowire:
the preparation process is as described in the Journal of Material Chemistry of Synthesis and catalysis of silicon carbide and nitride catalysts nanocompress (Journal of Material Chemistry 2002, 12, 1606-1611), in which a mixture of silica gel and elemental silicon is heated to produce SiO in gas phase, and in flowing ammonia at 1350 deg.C, alpha-Si is obtained by gas-solid growth3N4The nano wire can control the length and the diameter of the nano wire by controlling airflow, temperature and the like, so that the diameter of the nano wire is about 100-200 nanometers, and the length of the nano wire is 100-300 micrometers;
(2) dissolving 0.5 millimole europium oxide in 10 ml nitric acid solution with concentration of 0.4 mol/L, heating to 60 ℃, after complete dissolution, evaporating to dryness at 100 ℃ to obtain rare earth nitrate Eu (NO)3)3；
(3) The prepared alpha-Si3N4Nanowire 0.01 mol (1.4 g) and 0.05 mmol (0.0169 g) of Eu (NO)3)3Mixing, dissolving in 20 ml ethanol/water (volume ratio 1: 1), and dispersing with ultrasound (power 400W, frequency 40KHZ) for 10 min to obtain mixed slurry with volume solid content of 2.5%;
(4) then transferring the mixed slurry into a rotary vacuum drier for drying, and drying for 30 minutes at 40 ℃ to obtain dry powder;
(5) the above dried powder was placed on the bottom and previously charged with about 0.014 g of B2O3In a BN crucible of powder, then in a flowing N2/NH3Ambient atmosphere (N)2/NH3The ratio is 5: 1, the flow rate is 0.2ml/min) is increased to 1500 ℃ at the heating rate of 5 ℃/min,
and preserving the heat for 4 hours to obtain the yellow fluorescent silicon nitride-based nanowire.
As shown in fig. 1, the fluorescent silicon nitride-based nanowire synthesized by the present embodiment has a smooth surface and uniform thickness in the radial direction. As can be seen from FIG. 2, the surface of the fluorescent silicon nitride-based nanowire is covered with a dense and uniform boron nitride film protective layer with the thickness of 3 nanometers. From the EDS spectra of the inner part (3.1) and the surface (3.2) of the nanowire in the high resolution electron microscope of FIG. 3, it can be proved that the inner part is Eu-doped Si3N4The surface is BN. XRD phase analysis of the fluorescent silicon nitride-based nanowires was performed, as shown in FIG. 4, which is consistent with standard α -Si3N4The powder diffraction card (No.83-0700) was satisfied, and it was confirmed that it was α -Si3N4. Fig. 5 is an emission and excitation spectrum of the fluorescent silicon nitride-based nanowire measured using a fluorescence spectrophotometer, from which it can be seen that it can be excited by light in a wide wavelength band region from ultraviolet to visible light to emit bright yellow light having a maximum luminescence wavelength of 590 nm. Compared to the emission and excitation spectra of the starting silicon nitride nanowires shown in fig. 6, it can be seen that both the excitation and emission wavelengths are fundamentally changed, increasing the brightness by more than 10 times.
Example 2:
(1) preparation of alpha-Si by means of the prior art3N4The nanowire is 0.01 mol (1.4 g) with a diameter of about 300-400 nm and a length of 500-800 μm, and the specific preparation process is the same as that of example 1.
(2) Dissolving dysprosium oxide of 0.5 mmol in nitric acid solution of 10 ml concentration of 0.4 mol/L, heating to 60 deg.C, completely dissolving, and evaporating to dryness at 100 deg.C to obtain rare earth nitrate Dy (NO)3)3：
(3) 0.01 mol (1.4 g) of alpha-Si is added3N4The nanowires were mixed with 0.1 mmol (0.0348 g) of Dy (NO)3)3Mixing, dissolving in 10 ml of methanol/water (volume ratio 1: 1), and dispersing for 20 minutes by ultrasonic (power 400W, frequency 40 KHZ);
(4) the mixed slurry was then transferred to a rotary vacuum drier for drying and dried at 60 ℃ for 20 minutes.
(5) After drying, the mixture was transferred to a BN crucible, and about 0.028 g of B was previously added to the bottom2O3And (3) powder. Raising the temperature to 1750 ℃ at the heating rate of 10 ℃/min, and preserving the heat for 6 hours. The atmosphere being N2And the flow rate is 0.4ml/min, and the white fluorescent silicon nitride-based nanowire can be prepared.
The nanowires prepared in this example emitted blue and yellow light (shown as emitting white light) with maximum emission wavelengths of 482nm and 578nm under excitation of ultraviolet light, as shown in fig. 7.
Example 3:
the preparation process is the same as example 2, but in step (5) B is not added2O3Powder to obtain a nano wire taking Dy metal ion solid solution as a luminescence center; the nanowire emits blue light and yellow light with the maximum light emission wavelengths of 482nm and 578nm (shown as emitting white light) under ultraviolet light, the excitation and emission spectra are similar to those of fig. 7, the intensity is reduced by 40% compared with the case of the boron nitride thin film protective layer of example 2, but the intensity is increased by more than 5 times compared with the nanowire without metal ion solid solution as the light emission center in the prior art.
Example 4:
(1) preparation of alpha-Si by means of the prior art3N4The nanowire is 0.01 mol (1.4 g) to have a diameter of about 30-40 nm and a length of 500-1000 nm, and the specific preparation process is the same as that of example 1.
(2) Dissolving ytterbium oxide 0.5 mmol in nitric acid solution 10 ml with concentration of 0.4 mol/L, heating to 60 deg.C, dissolving completely, and evaporating to dryness at 100 deg.C to obtain rare earth nitrate Yb (NO)3)3：
(3) 0.01 mol (1.4 g) of alpha-Si is added3N4Nanowires were mixed with 0.005 mmol (0.0018 g) of Yb (NO)3)3Mixing, dissolving in 5ml of ethanol/water (volume ratio 1: 1),ultrasonic dispersion is carried out for 30 minutes;
(4) the mixed slurry was then transferred to a rotary vacuum drier for drying and dried at 80 ℃ for 10 minutes.
(5) After drying, the mixture was transferred to a BN crucible, and about 0.028 g of H was previously added to the bottom3BO3And (3) powder. Heating to 1700 ℃ at the heating rate of 10 ℃/min, and preserving the heat for 2 hours. Atmosphere is NH3And the flow rate is 0.05ml/min, and the yellow-green fluorescent silicon nitride-based nanowire can be prepared.
The nanowire prepared in this embodiment emits yellow-green light with a maximum light emitting wavelength of 540nm under the excitation of ultraviolet and visible light, as shown in fig. 8.
Claims (4)
1. A silicon nitride-based nano-wire emitting fluorescence, wherein the silicon nitride-based nano-wire is alpha-Si3N4The nano-wire is characterized in that rare earth metal ions are accommodated in crystal cell gaps of the nano-wire silicon nitride base to form the nano-wire taking metal ion solid solution as a luminescence center, wherein the rare earth metal ions are one or two or more elements of Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
2. The fluorescent silicon nitride-based nanowire of claim 1, wherein the surface of the nanowire with the solid solution of metal ions as the luminescent center is covered with a boron nitride protective layer.
3. The fluorescent silicon nitride-based nanowires of claim 2, wherein the boron nitride protective layer has a thickness of 1-20 nm.
4. The method of making a fluorogenic silicon nitride-based nanowire as defined in claim 1 or 2 comprising making α -Si by prior art techniques3N4The nano-wire powder is characterized in that the preparation process comprises the following steps:
(1) dissolving rare earth oxide with nitric acid to obtain a rare earth nitrate solution, wherein the molar ratio of rare earth ions to nitrate ions is 1: 4, and then filtering and evaporating to dryness to obtain rare earth nitrate powder;
(2) alpha-Si to be prepared by the prior art3N4Mixing the nano-wire powder and the rare earth nitrate powder, dissolving the mixture in an alcohol-water solution, and dispersing the mixture for 5 to 30 minutes to obtain mixed slurry, wherein alpha-Si3N4The mol ratio of the nano wire to the rare earth nitrate is 1: 0.0002-0.02, and the alcohol is methanol or ethanol; the volume solid content of the prepared slurry is 1-25 percent; the alpha-Si3N4The radius of the nanowire is 10-500nm, and the length of the nanowire is 200nm-1 mm;
(3) drying the mixed slurry at 40-80 ℃ for 20-60 minutes until the liquid phase is completely removed to obtain dry powder;
(4) placing the dried powder in a flowing nitrogen and/or ammonia environment, heating to 1400 ℃ plus 1800 ℃ at the speed of 1-10 ℃/min, and preserving the heat for 2-6 hours to obtain the fluorescent silicon nitride-based nanowire containing rare earth metal ions in the crystal cell gap; or,
(5) adding boron oxide or boric acid or simple substance boron powder into the dried powder, wherein the content of the boron oxide or boric acid or simple substance boron accounts for 0.1-3 wt% of the total weight; then heating to 1400 ℃ plus 1800 ℃ at the speed of 1-10 ℃/min in a flowing nitrogen and/or ammonia environment, and keeping the temperature for 2-6h to obtain the fluorescent silicon nitride-based nanowire with the surface covered with a boron nitride protective layer with the thickness of 1-20nm and rare earth metal ions contained in the crystal cell gap.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101565279A CN101205629B (en) | 2006-12-21 | 2006-12-21 | Fluorescent silicon nitride based nano thread and preparation thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114517091A (en) * | 2022-03-09 | 2022-05-20 | 渤海大学 | Rare earth ion doped silicon nitride nanowire and preparation method thereof |
| CN115043409A (en) * | 2021-12-29 | 2022-09-13 | 渤海大学 | Tb 3+ Doped SiO 2 Nanowire and nanocrystal material and preparation method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115043409A (en) * | 2021-12-29 | 2022-09-13 | 渤海大学 | Tb 3+ Doped SiO 2 Nanowire and nanocrystal material and preparation method |
| CN115043409B (en) * | 2021-12-29 | 2023-06-27 | 渤海大学 | Tb (Tb) 3+ Doped SiO 2 Nanowire and nanocrystalline material and preparation method |
| CN114517091A (en) * | 2022-03-09 | 2022-05-20 | 渤海大学 | Rare earth ion doped silicon nitride nanowire and preparation method thereof |
| CN114517091B (en) * | 2022-03-09 | 2023-09-12 | 渤海大学 | Rare earth ion doped silicon nitride nanowire and preparation method thereof |
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