CN108502855A - A kind of preparation method of trivalent thulium doped aluminum nitride taper nanostructure - Google Patents

A kind of preparation method of trivalent thulium doped aluminum nitride taper nanostructure Download PDF

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CN108502855A
CN108502855A CN201810352170.4A CN201810352170A CN108502855A CN 108502855 A CN108502855 A CN 108502855A CN 201810352170 A CN201810352170 A CN 201810352170A CN 108502855 A CN108502855 A CN 108502855A
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aluminum nitride
aln
preparation
nanostructure
doped aluminum
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CN108502855B (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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

Abstract

Trivalent thulium (the Tm of the present invention3+) doped aluminum nitride (AlN) taper nanostructure preparation method belong to nano material prepare and luminescent material technical field.By Al powder and TmO2Powder presses 100：0.5~1 molar ratio is uniformly mixed, and is pressed into briquetting；Briquetting is placed in graphite pot, is put into the reative cell of horizontal DC arc discharge device；Nitrogen is filled with after reative cell is evacuated, nitrogen pressure is 40~50kPa, and copper pot is passed through recirculated cooling water；In discharge process, rotary speed that cathode is counterclockwise is 2 π/min, and holding voltage is 20~30V, and electric current is 100~120A, is reacted 5~15 minutes；It is passivated 5~7 hours in nitrogen environment again, the lint sprills that grey is collected in condenser wall and in graphite pot are Tm3+Adulterate AlN taper nanostructures.The present invention has many advantages, such as that method is simple, rapid reaction, low cost, pollution-free, yield is big, sample purity is high, favorable repeatability, without adding catalyst.

Description

A kind of preparation method of trivalent thulium doped aluminum nitride taper nanostructure
Technical field
The invention belongs to technical fields prepared by nano material and luminescent material, more particularly to a kind of simple to prepare three Valence thulium (Tm3+) doped aluminum nitride (AlN) taper nanostructure method.
Background technology
Rare earth-doped semiconductor has broad application prospects because of its unique characteristics of luminescence in optoelectronic areas.It is rear-earth-doped III group-III nitride semiconductor, because it has important potential application in electroluminescent device, fiber optic communication and other photoelectric fields It is worth and receives more and more attention.In III group-III nitride, GaN has been widely studied, and is had been observed that in GaN each The VISIBLE LIGHT EMISSION that kind rare earth element (Er, Tm, Eu, Dy, Pr and Tb) emits at room temperature.The reason of GaN is taken seriously is in addition to it Outside with excellent chemical stability, also having benefited from the broad stopband of GaN makes it suitable for the basis material as rare earth ion, because This will allow luminescent material that can send out broader spectrum.It is relatively fewer to the research report of AlN compared with GaN.In fact, Compared with GaN, AlN has outstanding physical characteristic, for example, it is high rigidity, highly thermally conductive property, corrosion-resistant, there is conjunction with Si and GaAs The temperature suitability of reason；In addition, the ultra-wide forbidden band (Eg=6.2eV) of AlN also shows that it is more suitable for the matrix of rare earth ion Material is not only because rear-earth-doped aluminium nitride by the light emitting region with bigger, also because rare earth ion is in AlN matrixes There to be smaller temperature quenching effect (energy gap of basis material is wider, and quenching effect is smaller).Therefore, use AlN as The basis material of rare earth ion, theoretically should be more more advantageous than GaN.
So far, rare earth Tm3+It is relatively fewer to adulterate AlN reports, is focused only in AlN films, mainly uses molecule Beam epitaxy (Materials Science and Engineering B105 (2003) 91-96) and magnetron sputtering (Chinese Physics 15 (2006) 2445-05) method.And nano-powder Tm3+Adulterating AlN, there is presently no method preparations.
Invention content
The technical problem to be solved by the present invention is to, overcome large radius element doping difficult, and preparation process moderate purity it is not high, The shortcomings of reaction process is complicated, low output, discloses the trivalent thulium (Tm that a kind of preparation process is simple, yield is high, sample purity is high3+) The method of doped aluminum nitride (AlN) taper nanostructure.
Trivalent thulium (the Tm of the present invention3+) doped aluminum nitride (AlN) taper nanostructure method, be to be put using direct-current arc Electric installation.Specific technical solution is as follows.
A kind of preparation method of trivalent thulium doped aluminum nitride taper nanostructure, which is characterized in that include the following steps：It will Al powder and TmO2Powder presses 100：0.5~1 molar ratio is uniformly mixed, and is pressed into briquetting；Briquetting is placed in graphite pot, is put into In the indoor copper pot anode of reaction of horizontal DC arc discharge device, tungsten bar cathode is placed with copper pot anode relative level；It will Reative cell is filled with nitrogen after being evacuated, nitrogen pressure is 40~50kPa, and copper pot is passed through recirculated cooling water；In discharge process, Rotary speed that cathode is counterclockwise is 2 π/min, and holding voltage is 20~30V, and electric current is 100~120A, is reacted 5~15 minutes；Again It is passivated 5~7 hours in nitrogen environment, the lint sprills that grey is collected in condenser wall and in graphite pot are Tm3+Adulterate AlN Taper nanostructure.
Further, the Al and TmO2The molar ratio of powder is 100：0.5~1.
Further, the taper nanostructure is tapered.
Further, the nitrogen optimum response air pressure is 40kPa.
Further, the reaction condition of the DC arc discharge device is：Voltage is 20V, electric current 100A.
The present invention using the preparation of DC arc discharge device mix thulium aluminum nitride nanometer piece with method simple, rapid reaction, It is inexpensive, pollution-free, yield is big, sample purity is high, favorable repeatability, excellent without adding any catalyst, template, substrate etc. Point.The product of preparation has application potential in photoemitter, the fields such as fluorescent powder, scintillator detector.
Description of the drawings
The horizontal DC arc discharge structure drawing of device of Fig. 1 present invention.
Fig. 2 is Tm made from embodiment 23+Adulterate the SEM figures of AlN nanocones.
Fig. 3 is Tm made from embodiment 23+Adulterate the EDS figures of AlN nanocones.
Fig. 4 is Tm made from embodiment 23+Adulterate the XRD spectra of AlN nanocones.
Fig. 5 is Tm made from embodiment 23+Adulterate the PL spectrograms of AlN nanocones.
Fig. 6 is Tm made from embodiment 33+Adulterate the SEM figures of AlN nanocones.
Fig. 7 is Tm made from embodiment 33+Adulterate the EDS figures of AlN nanocones.
Fig. 8 is Tm made from embodiment 33+Adulterate the XRD spectra of AlN nanocones.
Fig. 9 is Tm made from embodiment 33+Adulterate the PL spectrograms of AlN nanocones.
Figure 10 is Tm made from embodiment 43+Adulterate the SEM figures of AlN nanocones.
Figure 11 is Tm made from embodiment 43+Adulterate the XRD diagram of AlN nanocones.
Figure 12 is AlN sample Ps L collection of illustrative plates made from embodiment 5.
Specific implementation mode
1 DC arc discharge apparatus structure of embodiment
It is illustrated with reference to Fig. 1 the present invention and prepares Tm3+Adulterate the horizontal direct current electric arc device structure of AlN nanocones.In Fig. 1,1 is Reative cell, 2 be condenser wall, and 3 be the cathode being made of tungsten bar, 4 sample collection areas, 5Al and TmO2Mixed-powder block, 6 water coolings are followed Ring is anode, and 7 water inlets, it is gas outlet that 8 water outlets 9, which are air inlet 10,.
The plasma under hot environment in direct-current arc, is to prepare Tm3+Adulterate the key point of AlN nanocones.Directly Arc process is flowed in the dynamic extreme environment of high temperature, high ionization and high quenching, passes through high temperature evaporation, distillation and electronics and ion beam Detonation, easily forming nanometer and sub-nanometer scale has the reactant cluster of high reaction activity.These clusters are in appropriate nucleating condition Under be conducive to the Tm of large radius3+In ion doping to AlN matrix.Graphite pot constitute anode can effective high temperature resistance, and During the reaction, graphite crucible can effectively restore TmO2In oxygen, keep sample adulteration uniform, purity is high.The moon that tungsten bar is constituted Pole can effective high temperature resistance, cathode prolongs uniform rotation counterclockwise, can be the reaction of anode in preparation process in horizontal type structure The reaction of raw material evenly.
Embodiment 2 prepares Tm3+Adulterate the overall process of AlN nanocones.
By Al and Tm2O3Powder presses 100：0.5 molar ratio is put into batch mixer and is uniformly mixed.The mixed powder of 5g is taken out, Using tablet press machine briquetting, it is pressed into a diameter of 1.8cm, the cylinder of a height of 2cm.The mixed block being pressed into is put into graphite pot, then is put In the reative cell Anodic for entering DC arc discharge device.The anode of arc discharge device is that copper pot (is placed with common in copper pot Electrode graphite pot as anode), cathode is tungsten electrode, and tungsten bar cathode is placed with copper pot anode relative level.By direct-current arc The reative cell of electric discharge device is evacuated and (is less than 5pa), then fills 40kPa nitrogen.Copper pot is passed through recirculated cooling water, starts to put Electricity.In discharge process, rotary speed that cathode is counterclockwise is 2 π/min, and holding voltage is 20V, electric current 100A, reacts 5 points Clock.It is passivated in nitrogen compression ring border again 7 hours, then collects the villous Tm of grey in condenser wall3+Adulterate AlN nanocones.
Fig. 2 provides the Tm of above-mentioned condition preparation3+Adulterate the SEM figures of AlN nanocones, it can be seen that sample is pyramid type shape Looks, length are 50nm~2 μm, and top is pointed, a diameter of 20~50nm.Fig. 3 provides the EDS of the nanocone of above-mentioned condition preparation Figure, it can be deduced that sample is to be made of tri- kinds of elements of Al, N and Tm, and the content of Tm is about 0.9%.Fig. 4 provides above-mentioned condition The Tm of preparation3+Adulterate the XRD spectra of AlN nanocone structures, it was demonstrated that sample AlN occurs without impurity peaks.But with pure AlN The XRD spectra of sample compares, and all XRD diffraction maximums are moved to low-angle, it was demonstrated that and the Tm of big ionic radius is doped in AlN, Its lattice is set to become larger.Fig. 5 is Tm prepared by above-mentioned condition3+The PL spectrograms for adulterating AlN nanocones have a weak in 473nm to 500nm Glow peak correspond to Tm3+4f-4f is converted1D2-3F4With1G4-3H6.Correspond to there are one narrow very strong glow peak in 800nm3H4-3H6Conversion, correspond near infrared region.
Embodiment 3 prepares Tm3+Adulterate the overall process of AlN nanocones.
By Al and Tm2O3Powder presses 100：1 molar ratio is put into batch mixer and is uniformly mixed.The mixed powder for taking out 3g, makes With tablet press machine briquetting, it is pressed into a diameter of 1.8cm, the cylinder of a height of 1cm.The mixed block being pressed into is put into graphite pot, is placed into In the reative cell Anodic of DC arc discharge device.The anode of arc discharge device is that copper pot (is placed with common work in copper pot For the electrode graphite pot of anode), cathode is tungsten bar electrode, tungsten bar cathode is placed with copper pot anode relative level.By direct-current arc The reative cell of electric discharge device is evacuated and (is less than 5pa), then fills 50kPa nitrogen.Copper pot is passed through recirculated cooling water, starts to put Electricity.In discharge process, rotary speed that cathode is counterclockwise is 2 π/min, and holding voltage is 30V, electric current 120A, reacts 15 points Zhong Hou, then be passivated 6 hours in nitrogen environment, the Tm of grey is collected in condenser wall3+Adulterate AlN samples.Fig. 7 provides above-mentioned item Tm prepared by part3+The SEM figures for adulterating AlN confirm that it is tapered structure that sample, which is made,.Fig. 8 provides the Tm of above-mentioned condition preparation3+It mixes The EDS of miscellaneous AlN schemes, it can be deduced that sample is to be made of tri- kinds of elements of Al, N and Tm, and the content of Tm is 1.8%.Fig. 8 is provided Tm prepared by above-mentioned condition3+Adulterate the XRD spectra of AlN classification nanostructures, it was demonstrated that sample AlN, but have a small amount of thulium nitride (TmN) impurity peaks.Fig. 9 is Tm prepared by above-mentioned condition3+The PL spectrograms for adulterating AlN nanocones have a weak glow peak in 519nm It is to be generated by N and O defects, in 800nm, there are one narrow very strong glow peaks to correspond to Tm3+'s3H4-3H6Conversion, corresponds to Near infrared region.
Embodiment 4 prepares Tm3+Adulterate the overall process of AlN nanocones.
By AlN and Tm2O3Powder presses 100：2 ratio is put into batch mixer and is uniformly mixed.The mixed powder of 5g is taken out, is used Tablet press machine briquetting is pressed into a diameter of 3cm, the cylinder of a height of 3cm.The mixed block being pressed into is put into graphite pot, places into direct current In the reative cell Anodic of arc discharge device.The anode of arc discharge device is that copper pot (is placed in copper pot collectively as sun The electrode graphite pot of pole), cathode is tungsten bar electrode.The reative cell of DC arc discharge device is evacuated and (is less than 5pa), so After fill 5kPa nitrogen.Copper pot is passed through recirculated cooling water, starts to discharge, and in discharge process, holding voltage is 20V, and electric current is 80A.Reaction after five minutes, then is passivated 6 hours in ar gas environment, and grey lint shape sample is collected in condenser wall.Figure 10 is provided The SEM of sample prepared by above-mentioned condition schemes, the block structure for being made from confirmation.Figure 11 provides the sample of above-mentioned condition preparation XRD spectrum confirms that sample obtained is AlN, but also contains a large amount of Al impurity.
Embodiment 5 prepares the overall process of AlN.
The Al powder for taking out 5g is pressed into a diameter of 1.8cm, the cylinder of a height of 3cm using tablet press machine briquetting.By what is be pressed into Mixed block is put into graphite pot, places into the reative cell Anodic of DC arc discharge device.The anode of arc discharge device is Copper pot (is placed with the electrode graphite pot collectively as anode) in copper pot, cathode is tungsten electrode.By DC arc discharge device Reative cell is evacuated and (is less than 5pa), then fills 40kPa nitrogen.Copper pot is passed through recirculated cooling water, starts to discharge.It was discharging It is 30V, electric current 120A that voltage is kept in journey, is reacted 8 minutes.It is passivated in nitrogen environment 5 hours, is then received in condenser wall again Collect the AlN nanometer rods of white fluffy.Figure 12 is the PL spectrograms of pure AlN prepared by above-mentioned condition, and only there are one very weak wide Glow peak in 592nm, is generated by the defect of AlN itself.

Claims (5)

1. a kind of preparation method of trivalent thulium doped aluminum nitride taper nanostructure, which is characterized in that include the following steps：
By Al powder and TmO2Powder presses 100：0.5~1 molar ratio is uniformly mixed, and is pressed into briquetting；
Briquetting is placed in graphite pot, is put into the indoor copper pot anode of reaction of horizontal DC arc discharge device, tungsten bar is cloudy It is placed with copper pot anode relative level pole；
Nitrogen is filled with after reative cell is evacuated, nitrogen pressure is 40~50kPa, and copper pot is passed through recirculated cooling water；
In discharge process, rotary speed that cathode is counterclockwise is 2 π/min, and holdings voltage is 20~30V, electric current for 100~ 120A reacts 5~15 minutes；
It is passivated 5~7 hours in nitrogen environment again, the lint sprills that grey is collected in condenser wall and in graphite pot are trivalent The symmetrical nanostructure of six side of thulium doped aluminum nitride.
2. the preparation method of trivalent thulium doped aluminum nitride taper nanostructure according to claim 1, which is characterized in that institute State Al and TmO2The molar ratio of powder is 100：0.5~1.
3. the preparation method of trivalent thulium doped aluminum nitride taper nanostructure according to claim 1, which is characterized in that institute It is tapered to state the symmetrical nanostructure of six sides.
4. the preparation method of trivalent thulium doped aluminum nitride taper nanostructure according to claim 1, which is characterized in that institute It is 40kPa to state nitrogen optimum response air pressure.
5. the preparation method of trivalent thulium doped aluminum nitride taper nanostructure according to claim 1, which is characterized in that institute The reaction condition for the DC arc discharge device stated is：Voltage is 20V, electric current 100A.
CN201810352170.4A 2018-04-19 2018-04-19 Preparation method of trivalent thulium-doped aluminum nitride conical nanostructure Active CN108502855B (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102910598A (en) * 2012-10-31 2013-02-06 吉林大学 Yttrium-doped aluminum nitride diluted magnetic semiconductor quasi-array microtube and fabrication method of microtube

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102910598A (en) * 2012-10-31 2013-02-06 吉林大学 Yttrium-doped aluminum nitride diluted magnetic semiconductor quasi-array microtube and fabrication method of microtube

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
QIUSHI WANG等: "Synthesis, photoluminescence and ferromagnetic properties of pencil-like Y doped AlN microrods", 《CERAMICS INTERNATIONAL》 *

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