CN114517091B - 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 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 the silicon nitride nanowire; (2) The prepared silicon nitride nanowire and the rare earth oxide are mixed to prepare the rare earth doped silicon nitride nanowire. The rare earth doped silicon nitride nanowire prepared by the method is uniform and high in purity, and can be used for realizing the successful doping of rare earth ions, so that infinite possibility is provided for devices in the light-emitting field of nanoscale materials.
Description
Technical Field
The invention relates to the technical field of nano luminescent materials, in particular to a preparation method of a rare earth doped silicon nitride nanowire.
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 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 oxidation resistance, wear resistance, thermal shock resistance and other comprehensive properties. In the semiconductor field, the wide band gap of silicon nitride makes it an excellent host material for high concentration doping, so that the silicon nitride nanowire semiconductor material is one of the most promising materials for storage and communication fields. In addition, the physical properties of the semiconductor are closely related to its bandgap structure, which can be tuned by doping, so that the luminescence properties of the semiconductor can be tuned by introducing appropriate doping. Silicon nitride is a semiconductor with a wide forbidden band (-5.0 eV), so that the silicon nitride has the potential of obtaining a high doping concentration and excellent host material, and can be widely applied to the fields of photoelectron information and nanotechnology.
In the prior art, the method for preparing the rare earth doping of the silicon nitride nanowire mainly comprises a nitration reaction, a low-temperature ball milling high-temperature calcination method, a liquid nitrogen freezing method for preparing nanocrystalline silicon powder, nitriding in ammonia gas and the like. The doped silicon nitride nanowire prepared by the method mostly has 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 the large-size rare earth ions into the silicon nitride so as to replace the silicon ions; the oxidation phenomenon is serious in the preparation process, the production efficiency and purity of the nanowire are 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 luminous performance of the silicon nitride cannot be effectively improved; the size of the silicon nitride nanowire is difficult to control, etc. For example Si (NH) 2 Thermally decomposing at 1000 ℃ for 4 hours to prepare amorphous silicon nitride powder, and then preparing rare earth doped silicon nitride powder by nitration reaction with rare earth ion powder; the method is characterized in that high-speed rotating silicon-doped nanocrystalline powder 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 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 luminescence performance, so that the application of the silicon nitride nanowire in the field of optoelectronic devices is limited. Therefore, a new method for preparing the silicon nitride nanowire with simple process, low cost, suitability for industrial production, high purity, high yield, uniform scale, controllable doping, short-wave luminescence property, good monochromaticity and high luminescence intensity is urgently needed to be found.
In order to solve the problems, the technology aims at preparing the silicon nitride nanowire by a plasma arc method and realizing the luminescence of materials doped with different rare earth ions through the prepared silicon nitride nanowire, and takes four valence rare earth ions as an example, the rare earth ions with different ion radiuses can be effectively doped, so that the simple material and the safe processing process of the silicon nitride nanowire are ensured, and the technical possibility is provided for realizing the luminescence performance of the same matrix material for adjusting the doping of different rare earths.
Disclosure of Invention
The invention aims to provide a preparation method for preparing a silicon nitride nanowire and a rare earth ion doped silicon nitride nanowire, which solves the technical problem that the rare earth ion doped silicon nitride nanowire is difficult to prepare in the prior art. The preferred technical solutions of the technical solutions provided by the present invention can produce a plurality of technical effects described below.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a rare earth ion doped silicon nitride nanowire, the rare earth ion comprising a divalent or trivalent rare earth ion.
Preferably, the nanowire diameter is 50-100nm.
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 nanowire uses silicon nitride nanowire and rare earth oxide as raw materials to prepare rare earth doped silicon nitride nanowire.
Preferably, the rare earth doped silicon nitride nanowires are prepared using a plasma arc process.
Preferably, the silicon nitride nanowire powder and the 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, then filling nitrogen, and filling circulating cooling liquid into the graphite pot and the condensation wall;
performing discharge treatment;
and collecting the products on the anode of the graphite pot and the cathode of the tungsten rod in the reaction chamber, namely the rare earth doped silicon nitride nanowire.
Preferably, the silicon nitride nanowires are prepared using a plasma arc process.
Preferably, the method comprises:
silicon powder is put into a graphite crucible anode in a reaction chamber of a direct current arc discharge device to be used as a reaction raw material;
vacuumizing the reaction chamber, then filling nitrogen, and filling circulating cooling liquid into the graphite pot and the condensation wall;
performing discharge treatment;
on the condensation wall in the reaction chamber, silicon nitride nanowires are collected.
Preferably, the silicon nitride nanowires consist essentially of alpha-Si 3 N 4 Nanowires.
Preferably, the rare earth oxide is Eu 2 O 3 、Tb 4 O 7 Or CeO 2 One or more of the following.
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 higher purity, and can realize the successful doping of rare earth ions by using the silicon nitride nanowire, thereby providing infinite possibility for devices in the light-emitting field of nanoscale materials.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic structural view of a reaction chamber used in the method of the present invention;
FIG. 2 is Si prepared according to the present invention 3 N 4 Scanning electron microscope image of nanowire example 1
FIG. 3 is Si prepared according to the present invention 3 N 4 XRD pattern of nanowire example 1;
FIG. 4 is Si prepared according to the present invention 3 N 4 Nanowire realityEDS Spectrum of example 1
FIG. 5 shows Eu according to the present invention 2+ Doped Si 3 N 4 Scanning electron microscope image of nanowire example 2;
FIG. 6 is Eu according to the present invention 2+ Doped Si 3 N 4 XRD pattern of nanowire example 2;
FIG. 7 shows Eu according to the present invention 2+ Doped Si 3 N 4 EDS Spectrum of nanowire example 2
FIG. 8 shows Eu according to the present invention 2+ Doped Si 3 N 4 PL spectrum of nanowire example 2;
FIG. 9 shows Eu according to the present invention 3+ Doped Si 3 N 4 Scanning electron microscope image of nanowire example 3;
FIG. 10 shows Eu according to the present invention 3+ Doped Si 3 N 4 XRD pattern of nanowire example 3;
FIG. 11 shows Eu according to the present invention 3+ Doped Si 3 N 4 EDS Spectrum of nanowire example 3
FIG. 12 shows Eu according to the present invention 3+ Doped Si 3 N 4 PL spectrum of nanowire example 3;
FIG. 13 is a Tb of the present invention 3+ Doped Si 3 N 4 Scanning electron microscope image of nanowire example 4;
FIG. 14 is a Tb of the present invention 3+ Doped Si 3 N 4 XRD pattern of nanowire example 4;
FIG. 15 is a Tb of the present invention 3+ Doped Si 3 N 4 EDS Spectrum of nanowire example 4
FIG. 16 is a Tb of the present invention 3+ Doped Si 3 N 4 PL spectrum of nanowire example 4;
FIG. 17 is a view of Ce of the present invention 3+ Doped Si 3 N 4 Scanning electron microscope image of nanowire example 5;
FIG. 18 is a view of Ce of the present invention 3+ Doped Si 3 N 4 XRD pattern of nanowire example 5;
FIG. 19 is a view of Ce of the present invention 3+ Doped Si 3 N 4 Nanowire example 5EDS energy spectrum
FIG. 20 is a view of Ce of the present invention 3+ Doped Si 3 N 4 PL spectrum of nanowire example 5;
in the figure: 1. a reaction chamber; 2. a condensation wall; 3. a tungsten cathode; 4. a reaction raw material; 5. a graphite crucible anode; 6. a cooling water port; 7. an air inlet; 8. a vent port; 9. a condensing 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 will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims.
In the description of the present invention, it should 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 the orientations or positional relationships shown in fig. 1 are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention.
The technical scheme of the invention is specifically described below with reference to the accompanying drawings.
Fig. 1 is a schematic diagram of a 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 the reaction chamber 1, wherein a reaction raw material 4 (which is formed by mixing the reaction raw materials and pressing the mixture 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 the reaction products, circulating cooling water is introduced into the graphite crucible anode 5 and the condensation wall 2, wherein a cooling water inlet and a cooling water outlet are arranged below the graphite crucible anode 5, namely a cooling water outlet 6 (the cooling water outlet 6 comprises a water inlet and a water outlet) in fig. 1, and two ends of the condensation wall 2 are respectively provided with a condensation wall water inlet 9 and a condensation wall water outlet 10. After the reaction is completed, collecting reaction products in the reaction chamber, wherein the collected products are the silicon nitride nanowires.
The reaction chamber 1 is internally provided with a condensation wall 2, and cooling water (which can be recycled) is required to be introduced into the positions of the graphite crucible anode 5 and the condensation wall 2 so as to reduce the temperature of the graphite crucible anode 5 and the condensation wall 2.
The invention provides a method for preparing a silicon nitride nanowire and a rare earth doped silicon nitride nanowire. The silicon nitride nanowire can be obtained in principle through various channels, and the rare earth doping preparation process is completed by adopting the self-prepared silicon nitride nanowire. Specifically, the method comprises the following steps:
(1) The reaction raw materials containing silicon powder or silicon nitride powder are put into a tabletting mould to be pressed into ingots 4, and the prepared ingots 4 are put into a graphite crucible anode 5 positioned in a reaction chamber 1 of a direct current arc discharge device (at the moment, the cathode material in the reaction chamber 1 is a tungsten rod with better high-temperature resistance effect, namely a tungsten cathode 3);
(2) Introducing a 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) Placing the reaction raw materials containing silicon nitride nanowire powder and rare earth oxide powder into a tabletting mold to be pressed into an ingot 4, and placing 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, the cathode material in the reaction chamber 1 is a tungsten rod with better high-temperature resistance effect, namely a tungsten cathode 3);
(5) Introducing a 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 reaction products in the reaction chamber, wherein the collected products are the rare earth doped silicon nitride nanowires.
In the process of discharge treatment, the structure of the reaction chamber 1 is shown in fig. 1, the inside of the reaction chamber is a high-temperature and high-energy environment, and plasma generated by a direct current arc in the high-temperature environment is a key point for preparing the rare earth doped silicon nitride nanowire. The specific working principle is as follows: under the dynamic extreme environment of high temperature, high ionization and high quenching, the direct current arc is easy to form reactant clusters with high reactivity in nanometer scale through high temperature evaporation, sublimation and electron and ion beam detonation. 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 rare earth-containing powder, so that the sample is uniformly doped and has high purity. The rare earth element has better luminous performance, so that the prepared product has better application prospect in the optical field, and provides infinite possibility for devices in the luminous field of nanoscale materials. Compared with other processing methods, the processing method is simple and convenient to operate, the reaction conditions are relatively mild, the subsequent recycling is relatively convenient, and the rare earth doped silicon nitride nanowire can be relatively simply prepared.
Note that, when introducing the shielding gas into the reaction chamber 1, it is necessary to achieve this through the gas inlet 7 and the gas outlet 8.
In order to secure the reaction effect, it is necessary to limit the specific reaction conditions.
The silicon nitride nanowire prepared by the method has a linear structure with the length of tens of micrometers and the diameter of 50-100nm. It should be noted that the final physical properties of the product are affected by the raw materials, and the luminescence characteristics thereof may also vary somewhat depending on whether the raw materials contain rare earth elements or not and the types of rare earth elements contained therein.
As an alternative embodiment, the reactionThe rare earth oxide powder in the raw material is Eu 2 O 3 、Tb 4 O 7 、CeO 2 One or more of the following.
It should be noted that the above-mentioned reactive materials containing rare earth elements may be rare earth simple substances and/or rare earth nitrides, 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:
Eu 2+ the doped silicon nitride nanowire emits light with orange light emitted by 608nm under the excitation of 400 nm; eu (Eu) 3+ The doped silicon nitride nanowire emits light with red light emitted by 610nm under the excitation of 280 nm; tb (Tb) 3+ The doped silicon nitride nanowire emits light with green light emitted by 542nm under excitation of 286 nm; ce (Ce) 3+ The doped silicon nitride nanowire emits light with blue light emitted at 490nm under excitation at 335 nm.
The specific reaction conditions and the products obtained will also vary somewhat depending on the starting materials.
Example 1:
the embodiment provides a method for preparing silicon nitride nanowires by using a direct current arc method, which comprises the following preparation processes:
silicon powder is placed in a graphite crucible anode 5 (the specific position of the silicon powder is shown in figure 1), and circulating cooling water is introduced into the anode 5 and a condensation wall 2; the reaction chamber 1 is first vacuumized, then filled with nitrogen gas and repeatedly scrubbed to remove oxygen and water in the reaction chamber 1. Nitrogen gas is introduced into the direct current arc plasma reaction chamber 1 through the pipeline, and when the air pressure is 40kPa, the gas charging pipeline is closed, and discharge is started. The voltage was kept at 20V and the current was kept at 100A during the discharge for 10min. And collecting the reaction product obtained after discharge on the condensation wall to obtain the silicon nitride nanowire.
From the transmission electron microscope image of fig. 2, it can be seen that the prepared nanowire has a linear structure with a length of tens of micrometers and a diameter of 50-100nm; as can be seen from the XRD diffraction peak pattern of FIG. 3, the prepared samples were a large amount of alpha-Si 3 N 4 With small amounts of beta-Si 3 N 4 The structure, at the same time, 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 nanowire has main 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 to 8, the present embodiment provides a method for preparing Eu by a direct current arc method based on the first step of preparing a silicon nitride nanowire 2+ The ion doped silicon nitride nanowire is prepared by the following steps:
silicon nitride nanowires and Eu 2 O 3 The powder is prepared from the following components in percentage by weight: 1, putting the mixture into a tabletting mould, and using a tabletting machine to press the mixture into ingots to obtain cylinders 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 a condensation wall 2; the reaction chamber 1 is first vacuumized, then filled with nitrogen gas and repeatedly scrubbed to remove oxygen and water in the reaction chamber 1. Nitrogen gas is introduced into the direct current arc plasma reaction chamber 1 through the pipeline, and when the air pressure is 40kPa, the gas charging pipeline is closed, and discharge is started. The voltage was kept at 15V and the current was 100A during the discharge for 2min. Eu on graphite pot 2+ Ion doped silicon nitride nanowires.
From the transmission electron microscope image of fig. 5, it can be seen that the length of the prepared nanowire is tens of micrometers, and the diameter is 50-100nm; as can be seen from the XRD diffraction peak pattern of FIG. 6, the prepared sample is alpha-Si 3 N 4 With beta-Si 3 N 4 The structure, at the same time, 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 main components of the nanowires are Si and N, in a ratio close to 1:1, further indicating the high purity of the sample, wherein Eu 2+ The doping concentration of the ions is 0.57%, indicating Eu 2+ Successful doping of ions; FIG. 8 shows a PL spectrum with a broad hump at 360nm from 200nm to 500nm, derived from Eu 2+ 4f of ions 7 -4f 6 5d transition, emission spectrum extending from 500nm to 750nm, peak at 610nm, due to Eu 2+ 4f of ions 6 5d-4f 7 Is able to see Eu 2+ Successful doping of the ions causes the silicon nitride nanowires to have orange light emission of 610nm under excitation of 400 nm.
Example 3:
this example provides Eu production by DC arc method 3+ The ion doped silicon nitride nanowire is prepared by the following steps:
the silicon nitride nanowire prepared in example 1 was reacted with Eu 2 O 3 The powder is prepared from the following components in percentage by weight: 1.5, and placing into a tabletting mold, and tabletting into ingots by using a tablet press to obtain cylinders 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 a condensation wall 2; the reaction chamber 1 is first vacuumized, then filled with nitrogen gas and repeatedly scrubbed to remove oxygen and water in the reaction chamber 1. Nitrogen enters the direct current arc plasma reaction chamber 1 through the pipeline, and when the air pressure is 50KPa, the gas charging pipeline is closed, and discharge is started. The voltage was kept at 25V and the current was 110A during the discharge for 5min. Collecting and grinding the reaction product obtained after discharge at the contact edge part of the tungsten rod, and observing the ground sample to obtain clear Eu 3+ Ion doped silicon nitride nanowires.
From the transmission electron microscope image of fig. 9, it can be seen that the length of the prepared nanowire is tens of micrometers, and the diameter is 50-100nm; as can be seen from the XRD diffraction peak pattern of FIG. 10, the prepared sample is alpha-Si 3 N 4 With beta-Si 3 N 4 The structure, at the same time, no diffraction peak of other impurities is found, which indicates that the purity of the sample is very high; EDS analysis of fig. 11 shows that the main components of the nanowires are Si and N, in a ratio close to 1:1, further indicating the high purity of the sample, wherein Eu 3+ The doping concentration of the ions is 0.14%, indicating Eu 3+ Successful doping of ions; FIG. 12 PL spectrum with a broad hump at 280nm from 200nm to 450nm, derived from Eu 3+ The transition of ion 4f-5d has four small peaks at 363nm, 382nm, 396nm and 414nm, and is derived from Eu 3+ Of ions 7 F 0 - 5 D 4 、 7 F 0 - 5 L 7 、 7 F 0 - 5 L 6 、 7 F 0 - 5 D 3 Is a transition of (2); the emission spectrum extends from 500nm to 750nm, with peaks at 591nm, 610nm, 660nm, 713nm, where the peak at 610nm is reached due to Eu 3+ Of ions 5 D 0 - 7 F 1 、 5 D 0 - 7 F 2 、 5 D 0 - 7 F 3 、 5 D 0 - 7 F 4 Is able to see Eu 3+ Successful doping of the ions causes the silicon nitride nanowires to have a red emission of 610nm under excitation of 280 nm.
Example 4:
this example provides a method of preparing a doped Tb using direct current arc 3+ The preparation process of the ionic silicon nitride nanowire is as follows:
combining silicon nitride nanowires with Tb 4 O 7 The powder is prepared from the following components in percentage by weight: 1, putting the mixture into a tabletting mould, and using a tabletting machine to press the mixture into ingots to obtain cylinders 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 a condensation wall 2; the reaction chamber 1 is first vacuumized, then filled with nitrogen gas and repeatedly scrubbed to remove oxygen and water in the reaction chamber 1. Nitrogen enters the direct current arc plasma reaction chamber 1 through the pipeline, and when the air pressure is 30KPa, the gas charging pipeline is closed, and discharge is started. The voltage was kept at 20V and the current at 90A during the discharge for 2min. Collecting and grinding the reaction product obtained after discharge in the inner part of the contact edge of the graphite crucible and the tungsten rod, and observing the ground sample to obtain clear Tb 3+ Ion doped silicon nitride nanowires.
From the transmission electron microscope image of FIG. 13, it can be seen that the prepared silicon nitride nanowire has a length of tens of micrometers and a diameter of 50-100nm; as can be seen from the XRD diffraction peak pattern of FIG. 14, the prepared sample is alpha-Si 3 N 4 With beta-Si 3 N 4 The structure, at the same time, no diffraction peak of other impurities is found, which indicates that the purity of the sample is very high; FIG. 15The EDS analysis of (2) shows that the main components of the nano-sheet are Si and N, and the ratio of the Si to the N is close to 1:1, further indicating the high purity of the sample, wherein Tb 3+ The doping concentration of the ions is 0.47%; the PL spectrum of FIG. 16 is centered at about 286nm with a strong band belonging to Tb 3+ 4f of ions 8 -4f 7 5d 1 The absorption transition of (2) is that the emission spectrum extends from 400nm to 750nm, and obvious peaks are arranged at 488nm, 542nm, 587nm and 620nm, which is due to Tb 3+ Of ions 5 D 4 - 7 F 6 、 5 D 4 - 7 F 5 、 5 D 4 - 7 F 4 、 5 D 4 - 7 F 3 Can be seen from the transition of Tb 3+ Successful doping of ions causes the silicon nitride nanowires to emit 542nm green light under excitation of 286 nm.
Example 5:
the embodiment provides the preparation of the Ce doped material by the direct current arc method 3+ The preparation process of the ionic silicon nitride nanowire is as follows:
silicon nitride nanowires and CeO 2 The powder is prepared from the following components in percentage by weight: 1, putting the mixture into a tabletting mould, and using a tabletting machine to press the mixture into ingots to obtain cylinders 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 a condensation wall 2; the reaction chamber 1 is first vacuumized, then filled with nitrogen gas and repeatedly scrubbed to remove oxygen and water in the reaction chamber 1. Nitrogen enters the direct current arc plasma reaction chamber 1 through the pipeline, and when the air pressure is 35KPa, the gas charging pipeline is closed, and discharge is started. The voltage was kept at 20V and the current was 100A during the discharge for 2min. Collecting and grinding the reaction product obtained after discharge in the inner part of the contact edge of the graphite crucible and the tungsten rod, and observing the ground sample to obtain clear Ce 3+ Ion doped silicon nitride nanowires.
From the transmission electron microscope image of FIG. 17, it can be seen that the prepared silicon nitride nanowire has a length of tens of micrometers and a diameter of 50-100nm; as can be seen from the XRD diffraction peak pattern of FIG. 18, the prepared sample is alpha-Si 3 N 4 With beta-Si 3 N 4 The structure, at the same time, 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 nanoplatelets have main components Si and N in a ratio approaching 1:1, further indicating the high purity of the sample, wherein Ce 3+ 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, derived from Ce 3+ The transition of ion 4f-5d, the emission spectrum extends from 400nm to 750nm, peaks at 490nm, due to Ce 3+ The transition of ion 5d-4f, ce can be seen 3 + The doped silicon nitride nanowire emits light with blue light emitted at 490nm under excitation at 335 nm.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (3)
1. A method of preparing a rare earth ion doped silicon nitride nanowire, the method comprising:
firstly, silicon powder is put into a graphite crucible anode in a reaction chamber of a direct current arc discharge device to be used as a reaction raw material; vacuumizing the reaction chamber, then filling nitrogen, and filling circulating cooling liquid into the graphite pot and the condensation wall; performing discharge treatment; collecting silicon nitride nanowires on the condensation wall in the reaction chamber;
secondly, 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, then filling nitrogen, and filling circulating cooling liquid into the graphite pot and the condensation wall; performing discharge treatment; and collecting the products on the anode of the graphite pot and the cathode of the tungsten rod in the reaction chamber, namely the rare earth doped silicon nitride nanowire.
2. The method of claim 1, wherein the silicon nitride nanowires areMainly composed of alpha-Si 3 N 4 The rare earth doped silicon nitride nanowire is composed of nanowires, and the diameter of the rare earth doped silicon nitride nanowire is 50-100nm.
3. The method of claim 2, wherein the rare earth oxide is Eu 2 O 3 、Tb 4 O 7 Or CeO 2 One or more of the following.
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