CN114517091A - Rare earth ion doped silicon nitride nanowire and preparation method thereof - Google Patents
Rare earth ion doped silicon nitride nanowire and preparation method thereof Download PDFInfo
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Abstract
The invention provides a rare earth ion doped silicon nitride nanowire and a preparation method thereof, relates to the technical field of new nano luminescent materials, and mainly aims to realize the preparation of the rare earth ion doped silicon nitride nanowire. The preparation method comprises the following steps: (1) silicon powder and nitrogen are used as raw materials, and a direct current arc method is adopted to prepare silicon nitride nanowires; (2) the prepared silicon nitride nanowire is mixed with rare earth oxide to prepare the rare earth doped silicon nitride nanowire. The rare earth doped silicon nitride nanowire prepared by the method is uniform and has high purity, the successful doping of rare earth ions can be realized by the silicon nitride nanowire, and infinite possibility is provided for devices in the field of light emission of nano-scale materials.
Description
Technical Field
The invention relates to the technical field of nano luminescent materials, in particular to a preparation method of rare earth doped silicon nitride nanowires.
Background
With the rapid development of the optoelectronic information technology industry in China, people put more stringent and urgent demands on semiconductor materials, which are key materials for storage and communication. Nitride nanowire semiconductor material: aluminum nitride, gallium nitride, silicon nitride nanowires are the third generation of semiconductor materials following silicon and gallium arsenide. Silicon nitride is a structural material with low density, high specific strength, high specific modulus, good thermal shock and excellent comprehensive performances such as oxidation resistance, abrasion resistance, thermal shock resistance and the like. In the semiconductor field, the wide band gap of silicon nitride makes it an excellent host material for high concentration doping, and thus, the silicon nitride nanowire semiconductor material is one of the most promising materials in the fields of storage and communication. In addition, the physical properties of a semiconductor are closely related to the bandgap structure thereof, which can be adjusted by doping, and thus the emission properties of the semiconductor can be adjusted by introducing appropriate doping. Silicon nitride is a wide bandgap (5.0 eV) semiconductor, so that a high doping concentration can be obtained, and the silicon nitride has the potential of an excellent host material and can be widely applied to the fields of photoelectron information and nanotechnology.
In the prior art, the rare earth doping method for preparing the silicon nitride nanowire mainly comprises the steps of nitration reaction, low-temperature ball milling and high-temperature calcination, liquid nitrogen freezing to prepare nanocrystalline silicon powder, nitriding in ammonia gas and the like. The doped silicon nitride nanowires prepared by the method mostly have the following defects or defects: the radius of the rare earth ions is larger than that of the silicon ions, and the conventional method is difficult to dope large-size rare earth ions into silicon nitride to replace the silicon ions; the oxidation phenomenon is serious in the preparation process, the production efficiency of the nanowire is low, the purity is low, and more lattice defects exist; the cost is high, the process is complex, and the method is not suitable for industrial production; the doping controllability is poor, and the luminescent performance of the silicon nitride cannot be effectively improved; the size of the silicon nitride nanowire is difficult to control, and the like. For example, with Si (NH)2Thermally decomposing at 1000 deg.c for 4 hr to prepare amorphous silicon nitride powder, and nitrifying with RE ion powder to prepare RE doped silicon nitride powder; the method is characterized in that silicon-doped nanocrystalline powder rotating at a high speed is synthesized by adopting a low-temperature processing method, Si powder and rare earth ion-containing powder are mixed and placed in liquid nitrogen for ball milling, and then the mixture is placed in a high-temperature furnace for calcination. The doping control of the silicon nitride nanowire is difficult to realize through the prior art, and the prepared silicon nitride nanowire has weak and unstable luminous performance, so that the silicon nitride nanowire is applied to the field of optoelectronic devices The application is limited. Therefore, a new method which is simple in process, low in cost, suitable for industrial production, high in purity, high in yield, uniform in size, controllable in doping, good in monochromaticity and high in luminous intensity and capable of preparing the silicon nitride nanowires with short-wave luminous performance is urgently needed.
In order to solve the above problems, the present patent technology is directed to a plasma arc method for preparing silicon nitride nanowires and realizing the luminescence of materials doped with different rare earth ions through the prepared silicon nitride nanowires, taking four valence state rare earth ions as an example, the rare earth ions with different ionic radii can be effectively doped, on one hand, the simple material and safe processing process in the preparation and processing process of the silicon nitride nanowires are ensured, and on the other hand, the technical possibility is provided for realizing the adjustment of the luminescence property of different rare earth doping by using the same substrate material.
Disclosure of Invention
The invention aims to provide a method for preparing a silicon nitride nanowire and a rare earth ion doped silicon nitride nanowire, and solves the technical problem that the rare earth ion doped silicon nitride nanowire prepared in the prior art is difficult to prepare. The technical effects that can be produced by the preferred technical scheme of the technical schemes provided by the invention are described in detail in the following.
In order to realize the purpose, the invention provides the following technical scheme:
a rare earth ion doped silicon nitride nanowire, the rare earth ion comprising a divalent or trivalent rare earth ion.
Preferably, the nanowires have a diameter of 50-100 nm.
The invention also provides a preparation method of the rare earth doped silicon nitride nanowire, which comprises the following steps:
a method for preparing rare earth doped silicon nitride nanowires is used for preparing the rare earth doped silicon nitride nanowires by using the silicon nitride nanowires and rare earth oxides as raw materials.
Preferably, the rare earth doped silicon nitride nanowire is prepared by a plasma arc method.
Preferably, silicon nitride nanowire powder and rare earth oxide powder are mixed and placed in a graphite crucible anode positioned in a reaction chamber of the direct current arc discharge device;
vacuumizing the reaction chamber, filling nitrogen, and introducing circulating cooling liquid into the graphite pot and the condensation wall;
performing discharge treatment;
and collecting products, namely the rare earth doped silicon nitride nanowire, on the graphite pot anode and the tungsten rod cathode in the reaction chamber.
Preferably, the silicon nitride nanowires are prepared using a plasma arc method.
Preferably, the method comprises:
putting silicon powder into a graphite crucible anode in a reaction chamber of a direct current arc discharge device to serve as a reaction raw material;
Vacuumizing the reaction chamber, filling nitrogen, and introducing circulating cooling liquid into the graphite pot and the condensation wall;
performing discharge treatment;
and collecting the silicon nitride nanowires on the condensation wall in the reaction chamber.
Preferably, the silicon nitride nanowires consist essentially of α -Si3N4And (4) forming the nano wire.
Preferably, the rare earth oxide is Eu2O3、Tb4O7Or CeO2One or more of.
Compared with the prior art, the preparation method of the rare earth doped silicon nitride nanowire provided by the preferred embodiment of the invention has the advantages of simple conditions, easiness in operation, high efficiency, energy conservation, environmental friendliness and no generation of any harmful gas in the process. The rare earth doped silicon nitride nanowire prepared by the method is uniform and has high purity, the successful doping of rare earth ions can be realized by the silicon nitride nanowire, and infinite possibility is provided for devices in the field of light emission of nano-scale materials.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic view of the structure of a reaction chamber used in the method of the present invention;
FIG. 2 shows Si prepared by the present invention3N4Scanning Electron microscopy of nanowire example 1
FIG. 3 is Si prepared by the present invention3N4XRD pattern of nanowire example 1;
FIG. 4 shows Si prepared by the present invention3N4EDS spectra for nanowire example 1
FIG. 5 shows Eu according to the present invention2+Doping of Si3N4Scanning electron microscopy of nanowire example 2;
FIG. 6 shows Eu according to the present invention2+Doping of Si3N4XRD pattern of nanowire example 2;
FIG. 7 shows Eu according to the present invention2+Doping of Si3N4EDS spectra for nanowire example 2
FIG. 8 shows Eu according to the present invention2+Doping of Si3N4PL spectrum of nanowire example 2;
FIG. 9 shows Eu according to the present invention3+Doping of Si3N4Scanning electron microscopy of nanowire example 3;
FIG. 10 shows Eu according to the present invention3+Doping of Si3N4XRD pattern of nanowire example 3;
FIG. 11 shows Eu according to the present invention3+Doping of Si3N4EDS energy Spectrum for nanowire example 3
FIG. 12 shows Eu according to the present invention3+Doping of Si3N4PL spectrum of nanowire example 3;
FIG. 13 is a Tb of the invention3+Doping of Si3N4Scanning electron micrographs of nanowire example 4;
FIG. 14 is Tb according to the invention3+Doping of Si3N4XRD pattern of nanowire example 4;
FIG. 15 is a Tb of the invention3+Doping of Si3N4EDS spectra for nanowire example 4
FIG. 16 is Tb according to the invention3+Doping of Si3N4PL spectrum of nanowire example 4;
FIG. 17 is Ce of the present invention3+Doping of Si3N4Scanning electron micrographs of nanowire example 5;
FIG. 18 is Ce of the present invention3+Doping of Si3N4XRD pattern of nanowire example 5;
FIG. 19 is Ce of the present invention3+Doping of Si3N4EDS spectra for nanowire example 5
FIG. 20 is Ce of the present invention3+Doping of Si3N4PL spectrum of nanowire example 5;
in the figure: 1. a reaction chamber; 2. a condensation wall; 3. a tungsten cathode; 4. reaction raw materials; 5. a graphite crucible anode; 6. a cooling water port; 7. an air inlet; 8. an air release port; 9. a condenser wall water inlet; 10. and a water outlet of the condensation wall.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", etc., indicate orientations or positional relationships based on those shown in fig. 1, and are only for convenience of description and simplicity of description, but do not indicate or imply that the referenced device or element must have a particular orientation, be constructed in a particular orientation, and be operated, and thus should not be considered as limiting the present invention.
The technical scheme of the invention is specifically explained in the following by combining the attached drawings.
FIG. 1 is a schematic diagram of the DC arc system used in the method of the present invention.
As shown in fig. 1, a condensation wall 2, a tungsten cathode 3 and a graphite crucible anode 5 are arranged in a reaction chamber 1, wherein a reaction raw material 4 (formed by mixing reaction raw materials and pressing the reaction raw materials by a tablet press) is filled on one side of the graphite crucible anode 5 facing the tungsten cathode 3, and the graphite crucible anode 5 and the tungsten cathode 3 are connected with a direct current power supply. In order to ensure the smooth condensation of reaction products, the graphite crucible anode 5 and the condensation wall 2 are both provided with circulating cooling water, wherein a cooling water inlet and a cooling water outlet are arranged below the graphite crucible anode 5, namely a cooling water inlet 6 (the cooling water inlet 6 comprises a water inlet and a water outlet) in fig. 1, and the two ends of the condensation wall 2 are respectively provided with a condensation wall water inlet 9 and a condensation wall water outlet 10. And after the reaction is finished, collecting a reaction product in the reaction chamber, wherein the collected product is the silicon nitride nanowire.
The condensation wall 2 is arranged in the reaction chamber 1, and cooling water (which can be recycled) needs to be introduced into the graphite crucible anode 5 and the condensation wall 2 to reduce the temperature of the graphite crucible anode 5 and the condensation wall 2.
The invention provides a method for preparing silicon nitride nanowires and rare earth doped silicon nitride nanowires, which is used for preparing the rare earth doped silicon nitride nanowires by taking the silicon nitride nanowires and rare earth oxides as raw materials. The silicon nitride nanowires can be obtained through various channels in principle, and the invention adopts the self-prepared silicon nitride nanowires to complete the rare earth doping preparation process. Specifically, the method comprises the following steps:
(1) putting a reaction raw material containing silicon powder or silicon nitride powder into a tabletting mold to be pressed into an ingot 4, and putting the prepared ingot 4 into a graphite crucible anode 5 positioned in a reaction chamber 1 of the direct current arc discharge device (at this time, a cathode material in the reaction chamber 1 is a tungsten rod with a good high-temperature resistance effect, namely a tungsten cathode 3);
(2) introducing protective atmosphere into the reaction chamber 1 to remove oxygen and water in the reaction chamber 1, and then performing discharge treatment;
(3) and collecting reaction products in the reaction chamber, wherein the collected products are the silicon nitride nanowires.
(4) Putting a reaction raw material containing silicon nitride nanowire powder and rare earth oxide powder into a tabletting mold to be pressed into an ingot 4, and putting the prepared ingot 4 into a graphite crucible anode 5 positioned in a reaction chamber 1 of a direct current arc discharge device (at the moment, a cathode material in the reaction chamber 1 is a tungsten rod with a good high-temperature resistance effect, namely a tungsten cathode 3);
(5) Introducing protective atmosphere into the reaction chamber 1 to remove oxygen and water in the reaction chamber 1, and then performing discharge treatment;
(6) and collecting a reaction product in the reaction chamber, wherein the collected product is the rare earth doped silicon nitride nanowire.
During the discharge treatment, the structure of the reaction chamber 1 is shown in fig. 1, the interior of the reaction chamber is a high-temperature and high-energy environment, and the plasma generated by the direct current arc in the high-temperature environment is the key point for preparing the rare earth doped silicon nitride nanowire. The specific working principle is as follows: the direct current electric arc is easy to form a reactant cluster with nanoscale and high reaction activity through high-temperature evaporation, sublimation and detonation of electrons and ion beams under the dynamic extreme environment of high temperature, high ionization and high quenching. These clusters facilitate the doping of large radius rare earth ions into the silicon nitride matrix under appropriate nucleation conditions. The anode formed by the graphite crucible can effectively resist high temperature, and in the reaction process, the graphite crucible can effectively reduce substances except rare earth ions in the rare earth-containing powder, so that the sample is uniformly doped and has high purity. Because the rare earth element has better luminous performance, the prepared product has better application prospect in the optical field, and infinite possibility is provided for devices in the luminous field of nano-grade materials. Compared with other processing methods, the processing method is simple and convenient to operate, relatively mild in reaction conditions, relatively convenient to subsequently recycle and capable of relatively simply preparing the rare earth doped silicon nitride nanowire.
It should be noted that when introducing the shielding gas into the reaction chamber 1, it is necessary to realize this by the gas inlet 7 and the gas outlet 8.
In order to ensure the reaction effect, the specific reaction conditions need to be limited.
The silicon nitride nanowire prepared by the method is of a linear structure with the length of dozens of microns and the diameter of 50-100 nm. It should be noted that the final physical properties of the product are affected by the raw materials, and the light emission characteristics of the product also vary depending on whether or not the raw materials contain rare earth elements and the types of rare earth elements.
As an alternative embodiment, the rare earth oxide powder in the reaction raw material is Eu2O3、Tb4O7、CeO2One or more of.
It should be noted that the above-mentioned reaction raw material containing rare earth element may also be a rare earth simple substance and/or a rare earth nitride, etc.
As an alternative embodiment, the molar ratio of silicon nitride nanowires to rare earth oxide powder is 100: 0.5 to 7. When the silicon nitride nanowire contains a certain amount of rare earth elements, the silicon nitride nanowire can emit visible light under corresponding light excitation. For example:
Eu2+the doped silicon nitride nanowire emits orange light with emission of 608nm under the excitation of 400 nm; eu (Eu) 3+The doped silicon nitride nanowire emits red light with emission of 610nm under the excitation of 280 nm; tb3+The doped silicon nitride nanowire emits light under the excitation of 286nm, and has green light emitted at 542 nm; ce3+The doped silicon nitride nanowires emit green light with 490nm emission under the excitation of 335 nm.
The specific reaction conditions and the obtained products also have certain differences according to the differences of the reaction raw materials.
Example 1:
the embodiment provides a method for preparing a silicon nitride nanowire by using a direct current arc method, which comprises the following steps:
silicon powder is placed in a graphite crucible anode 5 (the specific position is shown in figure 1), and circulating cooling water is introduced into the anode 5 and the condensation wall 2; the reaction chamber 1 is first evacuated and then purged with nitrogen gas repeatedly to remove oxygen and water in the reaction chamber 1. Nitrogen gas is fed into the direct current arc plasma reaction chamber 1 through a pipeline, and when the air pressure is 40kPa, the gas charging pipeline is closed, and discharging is started. The voltage is kept at 20V and the current is kept at 100A during the discharging process, and the reaction is carried out for 10 min. And collecting the reaction product obtained after discharging on the condensation wall to obtain the silicon nitride nanowire.
The transmission electron microscope image of FIG. 2 shows that the prepared nanowire has a linear structure with a length of tens of microns and a diameter of 50-100 nm; as can be seen from the XRD diffraction peak diagram of FIG. 3, the prepared sample contains a large amount of alpha-Si 3N4With small amounts of beta-Si3N4The structure, and no diffraction peak of other impurities is found, which indicates that the purity of the sample is very high; EDS analysis of fig. 4 shows that the nanowires have major components of Si and N, in a ratio close to 1: 1, further indicating the high purity of the sample.
Example 2:
as shown in FIGS. 5-8, this example provides a DC arc method for preparing Eu on the basis of preparing silicon nitride nanowires in the first step2+The ion-doped silicon nitride nanowire is prepared by the following steps:
silicon nitride nano-wire and Eu2O3The powder is prepared by mixing the following components in percentage by weight: 1, putting the mixture into a tabletting mold, and pressing the mixture into an ingot by using a tabletting machine to obtain a cylinder with the diameter of 1.8cm and the height of 2 cm. Placing the obtained ingot in a graphite crucible anode 5 (the specific position of the ingot is shown in figure 1), and introducing circulating cooling water into the anode 5 and the condensation wall 2; the reaction chamber 1 is first evacuated and then purged with nitrogen gas repeatedly to remove oxygen and water in the reaction chamber 1. Nitrogen gas is fed into the direct current arc plasma reaction chamber 1 through a pipeline, and when the air pressure is 40kPa, the gas charging pipeline is closed, and discharging is started. The voltage is kept at 15V and the current is kept at 100A during the discharging process, and the reaction is carried out for 2 min. Eu on graphite pot2+Ion-doped silicon nitride nanowires.
The transmission electron microscope image in FIG. 5 shows that the prepared nanowire has a length of tens of micrometers and a diameter of 50-100 nm; as can be seen from the XRD peak diagram of FIG. 6, the prepared sample is alpha-Si3N4With beta-Si3N4The structure, and no diffraction peak of other impurities is found, which indicates that the purity of the sample is very high; EDS analysis of fig. 7 shows that the nanowires have major components of Si and N, in a ratio close to 1: 1, further indicating the high purity of the sample, wherein Eu2+The doping concentration of the ion was 0.57%, indicating that Eu2+Successfully doping ions; the PL spectrum of FIG. 8 has a broad hump at 360nm from 200nm to 500nm, derived from Eu 2+4f of ion7-4f 65d transition, the emission spectrum extending from 500nm to 750nm peaking at 610nm due to Eu 2+4f of ion 65d-4f7Is shown, Eu is observed2+Successful doping of the ions resulted in 610nm orange emission of the silicon nitride nanowires under excitation at 400 nm.
Example 3:
this example provides the preparation of Eu by direct Current arc Process3+The ion-doped silicon nitride nanowire is prepared by the following steps:
the silicon nitride nanowires prepared in example 1 were mixed with Eu2O3The powder is prepared by mixing the following components in percentage by weight: 1.5, placing the mixture into a tabletting mold, and pressing the mixture into an ingot by using a tabletting machine to obtain a cylinder with the diameter of 1.8cm and the height of 2 cm. Placing the obtained ingot in a graphite crucible anode 5 (the specific position of the ingot is shown in figure 1), and introducing circulating cooling water into the anode 5 and the condensation wall 2; the reaction chamber 1 is first evacuated and then purged with nitrogen gas repeatedly to remove oxygen and water in the reaction chamber 1. Nitrogen enters the direct current arc plasma reaction chamber 1 through a pipeline, and when the air pressure is 50KPa, the gas charging pipeline is closed, and discharge is started. During the discharge process, the voltage is kept at 25V, the current is kept at 110A, and the reaction is carried out for 5 min. Collecting reaction products obtained after discharging at the contact edge part of the tungsten rod, grinding the reaction products, and observing the ground sample to obtain clear Eu 3+Ion-doped silicon nitride nanowires.
The transmission electron microscope image of FIG. 9 shows that the prepared nanowire has a length of tens of micrometers and a diameter of 50-100 nm; as can be seen from the XRD peak pattern of FIG. 10, the prepared sample is alpha-Si3N4With beta-Si3N4Structure while not finding itDiffraction peaks of other impurities, indicating that the purity of the sample is high; EDS analysis of fig. 11 shows that the nanowires have major components of Si and N, in a ratio close to 1: 1, further indicating the high purity of the sample, wherein Eu3+The doping concentration of the ion was 0.14%, indicating that Eu3+Successfully doping ions; the PL spectrum of FIG. 12 has a broad hump at 280nm from 200nm to 450nm, originating from Eu3+The 4f-5d transition of the ion has four small peaks at 363nm, 382nm, 396nm and 414nm, and is derived from Eu3+Of ions7F0-5D4、7F0-5L7、7F0-5L6、7F0-5D3A transition of (c); the emission spectrum extends from 500nm to 750nm, with peaks at 591nm, 610nm, 660nm, 713nm, wherein the peak is reached at 610nm due to Eu3+Of ions5D0-7F1、5D0-7F2、5D0-7F3、5D0-7F4Is shown, Eu is observed3+Successful doping of the ions resulted in 610nm red emission of the silicon nitride nanowires under 280nm excitation.
Example 4:
this example provides a Tb-doped alloy prepared by a direct current arc process3+The ionic silicon nitride nanowire is prepared by the following steps:
Mixing silicon nitride nano-wire with Tb4O7The powder is prepared by mixing the following components in parts by weight: 1, putting the mixture into a tabletting mold, and pressing the mixture into an ingot by using a tabletting machine to obtain a cylinder with the diameter of 1.8cm and the height of 2 cm. Placing the obtained ingot in a graphite crucible anode 5 (the specific position is shown in figure 1), and introducing circulating cooling water into the anode 5 and the condensation wall 2; firstly, the reaction chamber 1 is vacuumized, and then nitrogen is filled for repeatedly washing gas to remove oxygen and water in the reaction chamber 1. Nitrogen enters the direct current arc plasma reaction chamber 1 through a pipeline, and when the air pressure is 30KPa, the gas charging pipeline is closed, and discharge is started. The voltage is kept at 20V and the current is kept at 90A during the discharging process, and the reaction is carried out for 2 min. On stoneCollecting the reaction product obtained after discharging at the inner part of the contact edge of the ink crucible and the tungsten rod, grinding the reaction product, observing the ground sample, and observing clear Tb3+Ion-doped silicon nitride nanowires.
The transmission electron microscope image of FIG. 13 shows that the prepared silicon nitride nanowire has a length of tens of micrometers and a diameter of 50-100 nm; as can be seen from the XRD diffraction peak diagram of FIG. 14, the prepared sample is alpha-Si3N4With beta-Si3N4The structure is adopted, and meanwhile, no diffraction peak of other impurities is found, which indicates that the purity of the sample is very high; EDS analysis of fig. 15 shows that the major components of the nanoplatelets are Si and N, in a ratio close to 1: 1, further indicating high purity of the sample, wherein Tb 3+The doping concentration of the ions is 0.47%; the strong band of the PL spectrum of FIG. 16 centered around 286nm belongs to Tb 3+4f of ion8-4f 75d1The emission spectrum extends from 400nm to 750nm, and has obvious peaks at 488nm, 542nm, 587nm and 620nm due to Tb3+Of ions5D4-7F6、5D4-7F5、5D4-7F4、5D4-7F3Can see Tb3+Successful doping of the ions gave 542nm green emission of the silicon nitride nanowires under 286nm excitation.
Example 5:
this example provides the preparation of Ce-doped bodies using a direct current arc process3+The ionic silicon nitride nanowire is prepared by the following steps:
silicon nitride nano wire and CeO2The powder is prepared by mixing the following components in percentage by weight: 1, putting the mixture into a tabletting mold, and pressing the mixture into an ingot by using a tabletting machine to obtain a cylinder with the diameter of 1.8cm and the height of 2 cm. Placing the obtained ingot in a graphite crucible anode 5, and introducing circulating cooling water into the anode 5 and the condensation wall 2; the reaction chamber 1 is first evacuated and then purged with nitrogen gas repeatedly to remove oxygen and water in the reaction chamber 1. Nitrogen is led into the direct current arc plasma reaction chamber 1 through a pipeline, and when the air pressure is 35KPa, the air charging is closedThe tube, the discharge is started. The voltage is kept at 20V and the current is kept at 100A during the discharging process, and the reaction is carried out for 2 min. Collecting and grinding a reaction product obtained after discharging at the inner part of the contact edge of the graphite crucible and the tungsten rod, observing a ground sample, and observing clear Ce 3+Ion-doped silicon nitride nanowires.
The transmission electron microscope image in FIG. 17 shows that the prepared silicon nitride nanowire has a length of tens of micrometers and a diameter of 50-100 nm; as can be seen from the XRD peak pattern of FIG. 18, the prepared sample is alpha-Si3N4With beta-Si3N4The structure, and no diffraction peak of other impurities is found, which indicates that the purity of the sample is very high; EDS analysis of fig. 19 shows that the nanosheets are primarily Si and N, in a ratio close to 1: 1, further indicating the high purity of the sample, wherein Ce3+The doping concentration of the ions is 0.11%; in FIG. 20, the PL spectrum has a broad hump at 335nm from 200nm to 400nm, originating from Ce3+The 4f-5d transition of the ion, the emission spectrum extending from 400nm to 750nm, peaking at 490nm, is due to Ce3+Transition of 5d-4f of the ion, Ce can be seen3 +The doped silicon nitride nanowires emit green light with 490nm emission under the excitation of 335 nm.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (9)
1. A rare earth ion doped silicon nitride nanowire, wherein the rare earth ion comprises a divalent or trivalent rare earth ion.
2. The rare earth ion doped silicon nitride nanowire of claim 1, wherein the nanowire is 50-100nm in diameter.
3. A method for preparing rare earth ion doped silicon nitride nanowires is characterized in that the rare earth ion doped silicon nitride nanowires are prepared by taking the silicon nitride nanowires and rare earth oxides as raw materials.
4. The method of claim 3, wherein the rare earth doped silicon nitride nanowires are prepared using a plasma arc process.
5. The method according to claim 4, characterized in that it comprises: mixing silicon nitride nanowire powder and rare earth oxide powder and placing the mixture in a graphite crucible anode positioned in a reaction chamber of a direct current arc discharge device;
vacuumizing the reaction chamber, filling nitrogen, and introducing circulating cooling liquid into the graphite pot and the condensation wall; discharging treatment;
and collecting products, namely the rare earth doped silicon nitride nanowire, on the graphite pot anode and the tungsten rod cathode in the reaction chamber.
6. The method of claim 3, wherein the silicon nitride nanowires are prepared using a plasma arc process.
7. The method of claim 6, wherein the method comprises:
putting silicon powder into a graphite crucible anode in a reaction chamber of a direct current arc discharge device to serve as a reaction raw material;
vacuumizing the reaction chamber, filling nitrogen, and introducing circulating cooling liquid into the graphite pot and the condensation wall; discharging treatment;
and collecting the silicon nitride nanowires on the condensation wall in the reaction chamber.
8. The method of claim 7, wherein the silicon nitride nanowires consist essentially of α -Si3N4And (4) forming the nano wire.
9. According to claim 8The method is characterized in that the rare earth oxide is Eu2O3、Tb4O7Or CeO2One or more of.
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