CN108502855B - Preparation method of trivalent thulium-doped aluminum nitride conical nanostructure - Google Patents

Preparation method of trivalent thulium-doped aluminum nitride conical nanostructure Download PDF

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CN108502855B
CN108502855B CN201810352170.4A CN201810352170A CN108502855B CN 108502855 B CN108502855 B CN 108502855B CN 201810352170 A CN201810352170 A CN 201810352170A CN 108502855 B CN108502855 B CN 108502855B
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aluminum nitride
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CN108502855A (en
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王秋实
朱革
王闯
钟敏
辛双宇
张伟
张丽娜
史力斌
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Bohai University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/072—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with aluminium
    • C01B21/0722—Preparation by direct nitridation of aluminium
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Abstract

Third of the inventionThulium (Tm)3+) A preparation method of a doped aluminum nitride (AlN) conical nano structure belongs to the technical field of nano material preparation and luminescent materials. Mixing Al powder with TmO2The powder is prepared by mixing the following components in percentage by weight: uniformly mixing the components in a molar ratio of 0.5-1, and pressing into a briquette; putting the pressing block into a graphite pot, and putting the graphite pot into a reaction chamber of a horizontal direct current arc discharge device; vacuumizing the reaction chamber, filling nitrogen into the reaction chamber, wherein the pressure of the nitrogen is 40-50 kPa, and introducing circulating cooling water into a copper pot; in the discharging process, the counter-clockwise rotating speed of the cathode is 2 pi/min, the voltage is kept to be 20-30V, the current is 100-120A, and the reaction lasts for 5-15 minutes; passivating for 5-7 hours in a nitrogen environment, and collecting gray fluffy powder on a condensation wall and in a graphite pot to be Tm3+Doped AlN tapered nanostructures. The method has the advantages of simplicity, quick reaction, low cost, no pollution, high yield, high sample purity, good repeatability, no need of adding a catalyst and the like.

Description

Preparation method of trivalent thulium-doped aluminum nitride conical nanostructure
Technical Field
The invention belongs to the technical field of preparation of nano materials and luminescent materials, and particularly relates to simple preparation of trivalent thulium (Tm)3+) Methods of doping aluminum nitride (AlN) tapered nanostructures.
Background
The rare earth doped semiconductor has wide application prospect in the field of photoelectron because of the unique luminescence property. Rare earth doped group iii nitride semiconductors are receiving increasing attention because they have significant potential application values in electroluminescent devices, fiber optic communications, and other optoelectronic fields. Among group iii nitrides, GaN has been extensively studied, and visible light emission emitted at room temperature by various rare earth elements (Er, Tm, Eu, Dy, Pr, and Tb) has been observed in GaN. GaN is valued for the reason that, in addition to its excellent chemical stability, it also benefits from its wide bandgap making it suitable as a matrix material for rare earth ions, as this will allow the luminescent material to emit a wider spectrum of light. AlN studies have reported relatively little compared to GaN. In fact, AlN has superior physical properties compared to GaN, such as high hardness, high thermal conductivity, corrosion resistance, reasonable temperature compatibility with Si and GaAs; in addition, the ultra-wide band gap (Eg ═ 6.2eV) of AlN also suggests that it is more suitable as a matrix material for rare earth ions, not only because rare earth doped aluminum nitride will have a larger luminescence range, but also because rare earth ions will have a smaller temperature quenching effect in the AlN matrix (the wider the band gap of the matrix material, the smaller the quenching effect). Therefore, AlN as a matrix material for rare earth ions should theoretically have advantages over GaN.
To date, rare earth Tm3+Doped AlN has been reported relatively rarely, but concentrated in AlN films, mainly using methods of molecular beam epitaxy (Materials Science and Engineering B105(2003) 91-96) and magnetron sputtering (chinese physics 15(2006) 2445-05). And nano powder Tm3+Doped AlN has not been prepared by the methods at present.
Disclosure of Invention
The invention aims to overcome the defects of difficult doping of large-radius elements, low purity, complex reaction process, low yield and the like in the preparation process and discloses trivalent thulium (Tm) with simple preparation process, high yield and high sample purity3+) Methods of doping aluminum nitride (AlN) tapered nanostructures.
Trivalent thulium (Tm) of the present invention3+) The method of doping conical nanometer structure of aluminum nitride (AlN) is to use DC arc discharge device. The specific technical scheme is as follows.
A preparation method of a trivalent thulium doped aluminum nitride conical nano structure is characterized by comprising the following steps: mixing Al powder with TmO2The powder is prepared by mixing the following components in percentage by weight: uniformly mixing the components in a molar ratio of 0.5-1, and pressing into a briquette; putting the pressed block into a graphite pot, and putting the pressed block into the graphite potIn a copper pot anode in a reaction chamber of the horizontal direct current arc discharge device, a tungsten rod cathode and the copper pot anode are relatively and horizontally arranged; vacuumizing the reaction chamber, filling nitrogen into the reaction chamber, wherein the pressure of the nitrogen is 40-50 kPa, and introducing circulating cooling water into a copper pot; in the discharging process, the counter-clockwise rotating speed of the cathode is 2 pi/min, the voltage is kept to be 20-30V, the current is 100-120A, and the reaction lasts for 5-15 minutes; passivating for 5-7 hours in a nitrogen environment, and collecting gray fluffy powder on a condensation wall and in a graphite pot to be Tm3+Doped AlN tapered nanostructures.
Further, the Al is mixed with TmO2The molar ratio of the powder is 100: 0.5 to 1.
Further, the tapered nanostructure is tapered.
Further, the optimum reaction pressure of nitrogen gas was 40 kPa.
Further, the reaction conditions of the direct current arc discharge device are as follows: the voltage was 20V and the current was 100A.
The thulium-doped aluminum nitride nanosheet prepared by using the direct-current arc discharge device has the advantages of simple method, quick reaction, low cost, no pollution, high yield, high sample purity, good repeatability, no need of adding any catalyst, template, substrate and the like. The prepared product has application potential in the fields of photoelectric emitters, fluorescent powder, scintillator detectors and the like.
Drawings
FIG. 1 is a structural diagram of a horizontal DC arc discharge device according to the present invention.
FIG. 2 is Tm obtained in example 23+SEM images of doped AlN nanocones.
FIG. 3 is Tm obtained in example 23+EDS plot of doped AlN nanocones.
FIG. 4 is Tm obtained in example 23+XRD spectrum of doped AlN nanocone.
FIG. 5 is Tm obtained in example 23+PL spectrum of doped AlN nanocones.
FIG. 6 is Tm obtained in example 33+SEM images of doped AlN nanocones.
FIG. 7 is Tm obtained in example 33+Doped AlN nanoparticlesEDS picture of cone.
FIG. 8 is Tm obtained in example 33+XRD spectrum of doped AlN nanocone.
FIG. 9 is Tm obtained in example 33+PL spectrum of doped AlN nanocones.
FIG. 10 is Tm obtained in example 43+SEM images of doped AlN nanocones.
FIG. 11 is Tm obtained in example 43+XRD pattern of doped AlN nanocones.
FIG. 12 is a PL map of the AlN sample obtained in example 5.
Detailed Description
EXAMPLE 1 DC arc discharge device Structure
The preparation of Tm in accordance with the present invention is illustrated with reference to FIG. 13+A horizontal direct current arc device structure doped with AlN nanocones. In FIG. 1, 1 is a reaction chamber, 2 is a condensation wall, 3 is a cathode composed of a tungsten rod, 4 is a sample collection area, 5Al and TmO2Mixing the powder blocks, using 6 water cooling circulation as an anode, 7 water inlets, 8 water outlets, 9 air inlets and 10 air outlets.
Plasma in a high temperature environment in a direct current arc is used for preparing Tm3+The key point of the doped AlN nanocone is. The direct current arc method is easy to form reactant clusters with high reactivity in nanometer and sub-nanometer scales 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 favor the Tm of large radii under appropriate nucleation conditions3+Ions are doped into the AlN matrix. The anode formed by the graphite pot can effectively resist high temperature, and the graphite pot can effectively reduce TmO in the reaction process2The medium oxygen ensures that the sample is uniformly doped and has high purity. The cathode formed by the tungsten rod can effectively resist high temperature, and the cathode in the horizontal structure rotates anticlockwise at a constant speed in the preparation process, so that the reaction raw materials of the anode can react more uniformly.
Example 2 preparation of Tm3+And doping the AlN nanocones.
Mixing Al with Tm2O3The powder is prepared by mixing the following components in percentage by weight: 0.5 mol ratio is put into a mixer to be mixed evenly. 5g of the mixed powder was taken outAnd pressing into a cylinder with the diameter of 1.8cm and the height of 2cm by using a tablet press. And putting the pressed mixed block into a graphite pot, and then putting the mixed block into an anode in a reaction chamber of a direct current arc discharge device. The anode of the arc discharge device is a copper pot (an electrode graphite pot which is used as the anode together is arranged in the copper pot), the cathode is a tungsten electrode, and the cathode of the tungsten rod and the anode of the copper pot are oppositely and horizontally arranged. The reaction chamber of the dc arc discharge apparatus was evacuated (less than 5pa) and then charged with 40kPa nitrogen. Circulating cooling water is introduced into the copper pot, and discharging is started. In the discharging process, the counter-clockwise rotation speed of the cathode is 2 pi/min, the holding voltage is 20V, the current is 100A, and the reaction lasts for 5 minutes. Passivating for 7 hours in nitrogen atmosphere, and collecting Tm in gray villus form on condensation wall3+And doping AlN nanocones.
FIG. 2 shows Tm prepared under the above conditions3+The SEM image of the AlN-doped nanocone shows that the sample is conical, the length is 50 nm-2 mu m, the top is pointed, and the diameter is 20-50 nm. FIG. 3 shows an EDS diagram of the nanocones prepared under the above-described conditions, and it can be understood that the sample is composed of three elements of Al, N and Tm, and the Tm content is about 0.9%. FIG. 4 shows Tm prepared under the above conditions3+An XRD spectrogram of the AlN-doped nanocone structure proves that the sample is AlN and no impurity peak appears. However, compared with the XRD spectrum of a pure AlN sample, all XRD diffraction peaks move to a small angle, and the Tm with a large ionic radius is proved to be doped into AlN, so that the crystal lattice of the AlN becomes large. FIG. 5 is Tm prepared under the above conditions3+PL spectrum of doped AlN nanopyramid with weak light emitting peak corresponding to Tm at 473nm to 500nm3+4f-4f conversion1D2-3F4And1G4-3H6. A narrow and strong luminescence peak at 800nm corresponds to3H4-3H6Corresponds to the near infrared region.
Example 3 preparation of Tm3+And doping the AlN nanocones.
Mixing Al with Tm2O3The powder is prepared by mixing the following components in percentage by weight: 1 is put into a mixer to be mixed evenly. Taking out 3g of the mixed powder, briquetting with a tablet press to obtain a cylinder with a diameter of 1.8cm and a height of 1cm. And putting the pressed mixed block into a graphite pot, and then putting the mixed block into an anode in a reaction chamber of a direct current arc discharge device. The anode of the arc discharge device is a copper pot (an electrode graphite pot which is used as the anode together is arranged in the copper pot), the cathode is a tungsten rod electrode, and the tungsten rod cathode and the copper pot anode are oppositely and horizontally arranged. The reaction chamber of the dc arc discharge apparatus was evacuated (less than 5pa) and then charged with 50kPa nitrogen. Circulating cooling water is introduced into the copper pot, and discharging is started. During the discharge, the cathode was rotated at a counter-clockwise speed of 2 π/min, held at a voltage of 30V, and at a current of 120A, reacted for 15 minutes, then passivated in a nitrogen atmosphere for 6 hours, and the gray Tm was collected on the condensation wall3+The AlN sample was doped. FIG. 7 shows Tm prepared under the above conditions3+The SEM image of the doped AlN confirms that the prepared sample has a cone-shaped structure. FIG. 8 shows Tm prepared under the above conditions3+EDS (enhanced Desorption) graph of doped AlN shows that the sample consists of three elements of Al, N and Tm, and the Tm content is 1.8%. FIG. 8 shows Tm prepared under the above conditions3+The XRD spectrum of the doped AlN graded nanostructure proves that the sample is AlN, but has a small amount of thulium nitride (TmN) impurity peak. FIG. 9 is Tm prepared under the above conditions3+The PL spectrum of the AlN-doped nanocone has a weak luminescence peak at 519nm caused by N and O defects, and a narrow and strong luminescence peak at 800nm corresponding to Tm3+Is/are as follows3H4-3H6The transitions correspond to the near infrared region.
Example 4 preparation of Tm3+And doping the AlN nanocones.
Mixing AlN with Tm2O3The powder is prepared by mixing the following components in percentage by weight: 2 is put into a mixer to be mixed evenly. 5g of the mixed powder was taken out, and pressed into a cylinder having a diameter of 3cm and a height of 3cm by briquetting using a tablet press. And putting the pressed mixed block into a graphite pot, and then putting the mixed block into an anode in a reaction chamber of a direct current arc discharge device. The anode of the arc discharge device is a copper pot (an electrode graphite pot which is used as the anode together is arranged in the copper pot), and the cathode of the arc discharge device is a tungsten rod electrode. The reaction chamber of the dc arc discharge apparatus was evacuated (less than 5pa) and then charged with 5kPa nitrogen. And (3) introducing circulating cooling water into the copper pot, starting discharging, and keeping the voltage at 20V and the current at 80A in the discharging process. After 5 minutes of reactionThen, after passivation for 6 hours under argon atmosphere, a grey wool-like sample was collected on the condensation wall. Fig. 10 shows an SEM image of the sample prepared under the above conditions, confirming that the bulk structure is obtained. Fig. 11 shows an XRD pattern of the sample prepared under the above conditions, confirming that the obtained sample is AlN, but also contains a large amount of Al impurities.
Example 5 the overall procedure for the preparation of AlN.
5g of Al powder was taken out, and pressed into a cylinder having a diameter of 1.8cm and a height of 3cm by briquetting using a tablet press. And putting the pressed mixed block into a graphite pot, and then putting the mixed block into an anode in a reaction chamber of a direct current arc discharge device. The anode of the arc discharge device is a copper pot (an electrode graphite pot which is used as the anode together is arranged in the copper pot), and the cathode of the arc discharge device is a tungsten electrode. The reaction chamber of the dc arc discharge apparatus was evacuated (less than 5pa) and then charged with 40kPa nitrogen. Circulating cooling water is introduced into the copper pot, and discharging is started. During the discharge, the voltage was kept at 30V and the current at 120A, and the reaction was carried out for 8 minutes. Then passivating for 5 hours in a nitrogen environment, and collecting white villiform AlN nanorods on a condensation wall. FIG. 12 is a PL spectrum of pure AlN prepared under the above conditions, with only a very weak broad peak at 592nm, due to AlN defects.

Claims (1)

1. A preparation method of a trivalent thulium doped aluminum nitride hexagonal symmetrical nano structure is characterized by comprising the following steps:
mixing Al powder with Tm2O3The powder is prepared by mixing the following components in percentage by weight: uniformly mixing the components in a molar ratio of 0.5-1, and pressing into a briquette;
placing the pressing block in a graphite pot, placing the pressing block in a copper pot anode in a reaction chamber of a horizontal direct current arc discharge device, and horizontally placing a tungsten rod cathode and the copper pot anode relatively;
vacuumizing the reaction chamber, filling nitrogen gas with the pressure of 40kPa, and filling circulating cooling water into the copper pot;
in the discharging process, the counter-clockwise rotating speed of the cathode is 2 pi/min, the voltage is kept to be 20V, the current is 100A, and the reaction lasts for 5-15 minutes;
passivating for 5-7 hours in a nitrogen environment, and collecting gray fluffy powder on a condensation wall and in a graphite pot, wherein the fluffy powder is a conical trivalent thulium-doped aluminum nitride hexagonal symmetrical nano structure with the length of 50 nm-2 mu m, the top of the conical trivalent thulium-doped aluminum nitride hexagonal symmetrical nano structure is pointed and the diameter of the conical trivalent thulium-doped aluminum nitride hexagonal symmetrical nano structure is 20-50 nm.
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Synthesis, photoluminescence and ferromagnetic properties of pencil-like Y doped AlN microrods;Qiushi Wang等;《Ceramics International》;20171231;第43卷;第3319-3320页 *

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