CN104449689A - Preparation method of rare-earth doped GaN material - Google Patents
Preparation method of rare-earth doped GaN material Download PDFInfo
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- CN104449689A CN104449689A CN201410809041.5A CN201410809041A CN104449689A CN 104449689 A CN104449689 A CN 104449689A CN 201410809041 A CN201410809041 A CN 201410809041A CN 104449689 A CN104449689 A CN 104449689A
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Abstract
The invention discloses a preparation method of a rare-earth (RE) doped GaN material, and relates to the technical field of RE doped GaN. The whole preparation process of the RE doped GaN material briefly comprises the following three steps: firstly, heating by adopting a magnetic stirring oil bath; secondly, performing high-temperature calcination to prepare a GaN doped Er<3+> precursor material; and finally, performing high-temperature ammoniation on the precursor material to prepare GaN:Er<3+> nano-particles. The RE doped GaN luminescent material prepared by the method disclosed by the invention has the advantages of high purity, high brightness, long service life, good monochromaticity, low temperature quenching effect and the like.
Description
Technical field
What the present invention relates to is rare earth (RE) Doped GaN technical field, is specifically related to a kind of preparation method of rear-earth-doped GaN material.
Background technology
In recent years, rare earth (RE) Doped GaN arouses great concern, and theoretical investigation shows, the band gap of semiconductor material is wider, and temperature quenching effect is lower, and from the viewpoint of this, GaN is suitable as rare earth luminous substrate material very much.Trivalent rare earth ions RE
3+occupy the position of Ga in GaN lattice, form displacement doping, can increase in 4f layer the circuitous probability that jumps, this is highly beneficial to raising luminous efficiency.Therefore, GaN becomes RE
3+one of desirable substrate material that doping is luminous.Rear-earth-doped GaN luminescent material has the advantages such as brightness is high, the life-span is long, monochromaticity is good, temperature quenching effect is low.Due to quantum confined effect, novel physicochemical property can be presented after material nano, particularly there is strong emission characteristic.GaN nano material is one of studied maximum material, as mixed rare earth, not only will can obtain the character of GaN semiconductor nanoparticle, system also will present the character of rare earth element, and rear-earth-doped GaN material overcome oxide-base rare earth luminescent material can not with the integrated feature of modern semiconductors industry.More existing study group report preparation and the light emission characteristic thereof of the rare earth doped material of GaN at present.As U.Hommerich group adopts MOMBE legal system to mix the GaN film of Er for original position, and successfully prepare the photodiode (LED) of 1550nm.Rare earth Tb has successfully prepared in study group of domestic Pan Xiao army
3+ion doping GaN material, due to rare earth Tb
3+the intrinsic of ion is luminous at about 550nm, consistent with the green standard of the international color council (CIE), therefore Tb
3+doped semiconductor materials also receives the concern of people.In the research of rear-earth-doped GaN, the Er of rare earth element er Er
3+the intrinsic of ion is luminous sends out light rosy at about 620nm, and this makes Er
3+ion is applied more in glass-doped, and Er is at the window of the corresponding silica fibre Minimal energy loss of the infraluminescence of 1540nm simultaneously, and it is persistently overheating that this makes Er be entrained in the research of opticfiber communication numerous areas.Owing to lacking suitable substrate, usually there is a large amount of defects in GaN film material, for overcoming the difficulty that luminescent properties brings further, realize the light emission of high efficient and reliable, particularly meet CIE standard, inexpensive and can remain a huge challenge for light-emitting material used in everyday in flexible substrate making devices.
The preparation method of existing nano GaN material and dopant material thereof mainly contains sol-gel method, chemical Vapor deposition process and inorganic hot melt process, and these methods are all comparatively complicated and consuming time.
Summary of the invention
For the deficiency that prior art exists, the present invention seeks to the preparation method being to provide a kind of rear-earth-doped GaN material, the rear-earth-doped GaN luminescent material prepared by the method has the advantages such as purity is high, brightness is high, the life-span is long, monochromaticity is good, temperature quenching effect is low.
To achieve these goals, the present invention realizes by the following technical solutions: a kind of rear-earth-doped GaN material, with Ga
2o
3and Er
2o
3for starting material, three step ammonia reduction methods are utilized to prepare GaN:Er
3+nano particle; Reaction starting material are as follows: according to target the atom number proportioning of product gallium element Er, rare earth element Ga is x: y mol ratio calculating preparation three groups of sample desired raw material amounts being respectively 2%, 4%, 6.25%; Ga
2o
3: purity is 99.99%; Er
2o
3: purity is 99.99%; HNO
3: purity is 99.99%.
A preparation method for rear-earth-doped GaN material, its preparation process is:
1, according to target the molar ratio computing of product calculates desired raw material amount: the atom number proportioning of gallium element Er, rare earth element Ga is x: y be respectively 2%, 4%, 6.25%, wherein 0.1%≤y≤8%.
2, clean: ultrasonic cleaning, 30-60min, washed with de-ionized water; Dry, about 60min, temperature 120 DEG C.
3, weigh: weigh and adopt highly sensitive electronic analytical balance, instrument zero before weighing, product of getting it filled are appropriate to the occasion few unsuitable many.
4, mix
(1) Ga
2o
3and Er
2o
3put into magnetic stirring apparatus oil bath after adding concentrated nitric acid mixing and be heated to 120 DEG C, keep 60min, magnetic agitation evaporate to dryness, obtains the nitrate containing crystal water.
(2) nitrate obtained is put in quartz tube furnace calcines, be heated to rapidly 70 DEG C from room temperature, used time 7min; 200 DEG C are warmed up to, used time 130min from 70 DEG C; From 200 DEG C of rapid temperature increases to 500 DEG C, used time 30min; After 500 DEG C of calcining 240min, be cooled to room temperature, most of nitrate transformation is persursor material before ammonification-containing the oxide compound of erbium, gallium.
Note: this process silica tube two ends blowing air.
(3) oxide compound obtained is put into agate mortar and grind 1h.
5, ammonification
Above-mentioned product is put into tubular quartz stove and carry out ammonification according to following process setting program.
To sum up, the preparation process of whole rear-earth-doped GaN material can be sketched as following three steps: first adopt magnetic agitation oil bath heating, and then GaN doping Er is prepared in high-temperature calcination
3+presoma material, GaN:Er prepared by final high temperature ammonification presoma material
3+nano particle.
1. beneficial effect of the present invention: the present invention uses the high purity Ga of specific proportioning
2o
3and Er
2o
3for starting material, be dissolved in concentrated nitric acid, ultrasonic agitation 30min makes it mix, at magnetic stirring apparatus oil bath 120 DEG C, stir 60min, and keeps temperature until obtain white powder---the nitrate containing crystal water.Again product nitrate is put in quartz tube furnace and calcines, obtain persursor material---containing the oxide compound of erbium, gallium.The presoma method of the rare earth doped material of such making nano GaN is compared with topmost traditional method sol-gel method, and safety simple to operate, saves time over half.
2. the major equipment that the present invention uses is quartz tube furnace, and main chemical reactions is the first the first step, Ga (NO
3)
3decompose under high temperature and produce Ga
2o
3and then by NH under high temperature
3decompose the H produced
2be reduced to Ga
2o and Ga etc., thereafter Ga
2o and Ga and NH
3reaction generates GaN.Visible it is simple to operate, and product purity is high.Under existing inorganic hot melt/hydrothermal condition, the condition of synthesis of nano GaN is very harsh, and reactor must can bear higher temperature and pressure, is difficult in laboratory conditions reach, and solvent is (as benzene, toluene, NaN
3deng) environmental pollution is very large.In contrast, more convenient, simple, the environmental protection of preparation method of the present invention.
3. the Er of the rare earth element er Er of the present invention's employing
3+the intrinsic of ion is luminous at about 620nm, sends out light rosy, consistent with the standard of the international color council (CIE).The rare earth element er simultaneously adopted is applied more in the doping of glasswork, and its doping performance is more stable.About rare earth Er
3+the volumetric molar concentration proportioning problem of ion doping GaN nano particle for improving luminescent properties further, realize the light emission of high efficient and reliable and particularly meet CIE standard, inexpensive and in flexible substrate making devices, and can have very major and immediate significance for light-emitting material used in everyday.
Embodiment
The technique means realized for making the present invention, creation characteristic, reaching object and effect is easy to understand, below in conjunction with embodiment, setting forth the present invention further.
This embodiment is by the following technical solutions: a kind of rear-earth-doped GaN material, with Ga
2o
3and Er
2o
3for starting material, three step ammonia reduction methods are utilized to prepare GaN:Er
3+nano particle; Reaction starting material are as follows: according to target the atom number proportioning of product gallium element Er, rare earth element Ga is x: y mol ratio calculating preparation three groups of sample desired raw material amounts being respectively 2%, 4%, 6.25%; Ga
2o
3: purity is 99.99%; Er
2o
3: purity is 99.99%; HNO
3: purity is 99.99%.
A preparation method for rear-earth-doped GaN material, its preparation process is:
1, according to target the molar ratio computing of product calculates desired raw material amount: the atom number proportioning of gallium element Er, rare earth element Ga is x: y be respectively 2%, 4%, 6.25%, wherein 0.1%≤y≤8%.
2, clean: ultrasonic cleaning, 30-60min, washed with de-ionized water; Dry, about 60min, temperature 120 DEG C.
3, weigh: weigh and adopt highly sensitive electronic analytical balance, instrument zero before weighing, product of getting it filled are appropriate to the occasion few unsuitable many.
4, mix
(1) Ga
2o
3and Er
2o
3put into magnetic stirring apparatus oil bath after adding concentrated nitric acid mixing and be heated to 120 DEG C, keep 60min, magnetic agitation evaporate to dryness, obtains the nitrate containing crystal water.
(2) nitrate obtained is put in quartz tube furnace calcines, be heated to rapidly 70 DEG C from room temperature, used time 7min; 200 DEG C are warmed up to, used time 130min from 70 DEG C; From 200 DEG C of rapid temperature increases to 500 DEG C, used time 30min; After 500 DEG C of calcining 240min, be cooled to room temperature, most of nitrate transformation is persursor material before ammonification-containing the oxide compound of erbium, gallium.
Note: this process silica tube two ends blowing air.
(3) oxide compound obtained is put into agate mortar and grind 1h.
5, ammonification
Above-mentioned product is put into tubular quartz stove and carry out ammonification according to following process setting program.
This embodiment uses the high purity Ga of specific proportioning
2o
3and Er
2o
3for starting material, be dissolved in concentrated nitric acid, ultrasonic agitation 30min makes it mix, at magnetic stirring apparatus oil bath 120 DEG C, stir 60min, and keeps temperature until obtain white powder---the nitrate containing crystal water.Again product nitrate is put in quartz tube furnace and calcines, obtain persursor material---containing the oxide compound of erbium, gallium.The presoma method of the rare earth doped material of such making nano GaN is compared with topmost traditional method sol-gel method, and safety simple to operate, saves time over half.
The major equipment that this embodiment uses is quartz tube furnace, and main chemical reactions is the first the first step, Ga (NO
3)
3decompose under high temperature and produce Ga
2o
3and then by NE under high temperature
3decompose the H produced
2be reduced to Ga
2o and Ga etc., thereafter Ga
2o and Ga and NH
3reaction generates GaN.Visible it is simple to operate, and product purity is high.Under existing inorganic hot melt/hydrothermal condition, the condition of synthesis of nano GaN is very harsh, and reactor must can bear higher temperature and pressure, is difficult in laboratory conditions reach, and solvent is (as benzene, toluene, NaN
3deng) environmental pollution is very large.In contrast, more convenient, simple, the environmental protection of preparation method of the present invention.
The Er of the rare earth element er Er that this embodiment adopts
3+the intrinsic of ion is luminous at about 620nm, sends out light rosy, consistent with the standard of the international color council (CIE).The rare earth element er simultaneously adopted is applied more in the doping of glasswork, and its doping performance is more stable.About rare earth Er
3+the volumetric molar concentration proportioning problem of ion doping GaN nano particle for improving luminescent properties further, realize the light emission of high efficient and reliable and particularly meet CIE standard, inexpensive and in flexible substrate making devices, and can have very major and immediate significance for light-emitting material used in everyday.
More than show and describe ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (4)
1. a rear-earth-doped GaN material, is characterized in that, a kind of rear-earth-doped GaN material, with Ga
2o
3and Er
2o
3for starting material, three step ammonia reduction methods are utilized to prepare GaN:Er
3+nano particle; Reaction starting material are as follows: according to target the atom number proportioning of product gallium element Er, rare earth element Ga is x: y mol ratio calculating preparation three groups of sample desired raw material amounts being respectively 2%, 4%, 6.25%; Ga
2o
3: purity is 99.99%; Er
2o
3: purity is 99.99%; HNO
3: purity is 99.99%.
2. the preparation method of a kind of rear-earth-doped GaN material according to claim 1, it is characterized in that, its preparation process is:
(1), according to target the molar ratio computing of product calculates desired raw material amount: the atom number proportioning of gallium element Er, rare earth element Ga is x: y be respectively 2%, 4%, 6.25%, wherein 0.1%≤y≤8%;
(2), clean: ultrasonic cleaning, 30-60min, washed with de-ionized water; Dry, about 60min, temperature 120 DEG C;
(3), weigh: weigh and adopt highly sensitive electronic analytical balance, instrument zero before weighing, product of getting it filled are appropriate to the occasion few unsuitable many;
(4), mix;
(5), ammonification.
3. the preparation method of a kind of rear-earth-doped GaN material according to claim 2, is characterized in that, the concrete steps of described step (4) are:
(1), Ga203 and Er203 put into magnetic stirring apparatus oil bath and be heated to 120 DEG C after adding concentrated nitric acid mixing, and keep 60min, magnetic agitation evaporate to dryness, obtains the nitrate containing crystal water;
(2), by the nitrate obtained be put in quartz tube furnace and calcine, be heated to rapidly 70 DEG C from room temperature, used time 7min; 200 DEG C are warmed up to, used time 130min from 70 DEG C; From 200 DEG C of rapid temperature increases to 500 DEG C, used time 30min; After 500 DEG C of calcining 240min, be cooled to room temperature, most of nitrate transformation is persursor material before ammonification-containing the oxide compound of erbium, gallium;
(3) oxide compound obtained is put into agate mortar and grind 1h.
4. the preparation method of a kind of rear-earth-doped GaN material according to claim 2, is characterized in that, described step (5) concrete steps are: above-mentioned product is put into tubular quartz stove and carry out ammonification according to following process setting program:
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107364838A (en) * | 2017-06-19 | 2017-11-21 | 南开大学 | The preparation method of the gallium nitride nano material of iron series element doping |
| CN113666410A (en) * | 2021-08-24 | 2021-11-19 | 安徽工业大学 | Method for directly preparing gallium oxide by using gallium nitride waste |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391872A (en) * | 2011-12-07 | 2012-03-28 | 苏州科技学院 | Er doped GaN fluorescent powder and preparation method thereof |
| CN103173221A (en) * | 2013-03-20 | 2013-06-26 | 中国科学院苏州纳米技术与纳米仿生研究所 | Upconversion fluorescent material and preparation method thereof |
-
2014
- 2014-12-14 CN CN201410809041.5A patent/CN104449689A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391872A (en) * | 2011-12-07 | 2012-03-28 | 苏州科技学院 | Er doped GaN fluorescent powder and preparation method thereof |
| CN103173221A (en) * | 2013-03-20 | 2013-06-26 | 中国科学院苏州纳米技术与纳米仿生研究所 | Upconversion fluorescent material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 高崴崴等: "Er:GaN微纳米晶发光性能研究", 《人工晶体学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107364838A (en) * | 2017-06-19 | 2017-11-21 | 南开大学 | The preparation method of the gallium nitride nano material of iron series element doping |
| CN107364838B (en) * | 2017-06-19 | 2019-12-03 | 南开大学 | The preparation method of the gallium nitride nano material of iron series element doping |
| CN113666410A (en) * | 2021-08-24 | 2021-11-19 | 安徽工业大学 | Method for directly preparing gallium oxide by using gallium nitride waste |
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Application publication date: 20150325 |
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