CN103086394A - Preparation method of high-quantum-efficiency blue-light-emitting BCNO phosphor - Google Patents
Preparation method of high-quantum-efficiency blue-light-emitting BCNO phosphor Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title abstract description 8
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 44
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 44
- 238000005245 sintering Methods 0.000 claims abstract description 36
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000004327 boric acid Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 71
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000005352 clarification Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 8
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 7
- 150000002910 rare earth metals Chemical class 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 229920000877 Melamine resin Polymers 0.000 abstract 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 abstract 1
- 229960004011 methenamine Drugs 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 description 18
- 238000006862 quantum yield reaction Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 238000009766 low-temperature sintering Methods 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 4
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- UHVIINMHYMRQHX-UHFFFAOYSA-N [O].[N].[C].[B] Chemical compound [O].[N].[C].[B] UHVIINMHYMRQHX-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005415 bioluminescence Methods 0.000 description 1
- 230000029918 bioluminescence Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000001427 incoherent neutron scattering Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
The invention relates to a preparation method of a high-quantum-efficiency blue-light-emitting BCNO phosphor. The method which selects raw materials comprising boric acid, melamine and hexamethylene tetramine comprises a step of obtaining a BCNO precursor in a water phase and a step of sintering the precursor in a muffle furnace without a protection atmosphere at a low temperature to prepare the BCNO phosphor. The quantum efficiency of the non-rare-earth doped blue-light-emitting BCNO phosphor prepared in the invention at an emitting peak of 456nm reaches 95%, and is greater than the highest quantum efficiency (79%) of blue-light-emitting BCNO phosphors reported at present; and compared with present rare-earth doped blue-light-emitting phosphors, the high-quantum-efficiency blue-light-emitting BCNO phosphor in the invention has a same efficiency, can avoid the use of rare earth elements having the disadvantages of high price and environmental pollution, can substitute present commercial blue-light-emitting phosphors, and has a wide application prospect.
Description
Technical field
The invention belongs to technical field of function materials, more particularly, relate to the preparation method of a kind of high-quantum efficiency blue emission BCNO (boron carbon nitrogen oxygen) fluorescent material.
Background technology
Present phosphor material powder is mostly with rare earth element (Eu
2+, Ce
3+Deng) as activator and luminous, not only expensive, and contaminate environment.BCNO is a kind of non-rear-earth-doped luminous fluorescent material, has not caused people's extensive concern as activator because it does not need rare earth element.BCNO fluorescent material has preparation temperature lower (700 ~ 900 ℃), the atmosphere sintering that do not need protection (namely realizing sintering in air), energy-conserving and environment-protective, excitation spectrum wide ranges (from the ultraviolet to the blue light), emmission spectrum is adjustable (visible-range), and fluorescence lifetime the many merits such as can regulate in nanosecond to a millisecond magnitude.Have broad application prospects in fields such as illumination and demonstration, white light LEDs, fluorescein, bioluminescence imaging, DNA marker and medical science.The emission wavelength of BCNO fluorescent material can be regulated by changing processing condition and parameter, and the emission wavelength of BCNO can be from being adjusted near nearly red spectral band (emission peak is 570nm) near blue wave band (emission peak is 470nm) at present.The quantum yield of BCNO fluorescent material reduces along with the red shift of emission wavelength, and the sub-efficient of maximum amount of the blue emission BCNO fluorescent material of report is 79% at present, and its emission peak is in 470nm left and right (blue emission), and commercial blue-emitting phosphor is BaMgAl
10O
17: Eu
2+, its quantum yield is 95%.In addition, people generally adopt urea combustion to prepare BCNO fluorescent material, although the method preparation is simple, but the poor controllability of the method, sintering time has a significant impact emmission spectrum, sintering time differs the deviation that several minutes can cause emmission spectrum tens nanometers, simultaneously can produce ammonia during Urea, thereby can cause environmental pollution.Therefore, urea combustion is unfavorable for the needs of batch production and the environmental protection of BCNO fluorescent material.The present invention adopts Liquid preparation methods to go out presoma, adopts the low-temperature sintering presoma to prepare the BCNO fluorescent material of high-quantum efficiency, and the quantum yield of its blue emission can reach 95%, can substitute present commercial blue light fluorescent powder.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of high-quantum efficiency blue emission BCNO fluorescent material is provided, raw materials used is boric acid, trimeric cyanamide and hexamethylenetetramine, utilize the carbon-nitrogen bond in hexamethylenetetramine, carbon-the nitrogen bond of suitable concn is incorporated in the reaction of boric acid and trimeric cyanamide, prepares the BCNO fluorescent material of high-quantum efficiency.At first the present invention obtains the precursor of BCNO at aqueous phase; retort furnace low temperature sintering presoma in unprotect atmosphere prepares BCNO fluorescent material at last, and the method has good controllability, and environmental protection; nontoxic pollution-free meets the needs that green industry develops.
Technical purpose of the present invention is achieved by following technical proposals:
A kind of preparation method of high-quantum efficiency blue emission BCNO fluorescent material comprises the following steps:
1) add deionized water in reactor, and be heated to 70 ~ 90 ℃ and remain this temperature range; Add again boric acid and trimeric cyanamide, stir and clarified to solution in 1 hour; Material proportion is: every 0.01mol trimeric cyanamide adds 70 ~ 100mL deionized water; Mol ratio boric acid: trimeric cyanamide=1:1;
2) add hexamethylenetetramine in the solution that upwards step obtains, stirred solution is to clarification; Solution temperature remains between 70 ~ 90 ℃, and stirred solution changed solution in another reactor after 6 hours, then is heated to 100 ℃, stirs simultaneously, until with the water evaporate to dryness, obtain the precursor of BCNO; Material proportion is: mol ratio boric acid: hexamethylenetetramine=1:0.1 ~ 0.5;
3) take out the precursor of BCNO, put into retort furnace, carry out sintering the scopes of 600 ~ 700 ℃, sintering time is 12 hours;
4) sintering is closed the retort furnace naturally cooling after finishing, and takes out product after muffle furnace is down to room temperature, and fully grinding namely obtains BCNO fluorescent material in agate mortar.
Described step 2) in, material proportion is preferably mol ratio boric acid: hexamethylenetetramine=1:0.1.
Described step 3) it is 625 ℃ that the sintering temperature in is preferably.
Beneficial effect of the present invention is: equipment used is general retort furnace, raw material is boric acid, trimeric cyanamide and hexamethylenetetramine, simply, cheaply, method is simple, nontoxic pollution-free, emmission spectrum is adjustable in the blue wave band scope, and is insensitive to sintering time, good reproducibility is easy to batch production.Quantum yield when the non-rear-earth-doped blue emission BCNO fluorescent material emission peak of preparation is 456nm can reach 95%, greater than the sub-efficient of maximum amount (79%) of the blue emission BCNO fluorescent material of reporting at present; Compare with the fluorescent material that has commercial rear-earth-doped blue emission now, efficient is identical, but can avoid using rare earth element expensive, contaminate environment, can substitute the blue-emitting phosphor of present commercialization, has broad application prospects.
Description of drawings
Fig. 1 be when boric acid be 0.01mol, when trimeric cyanamide is 0.01mol, adopt the X-ray diffractogram of BCNO fluorescent material of the hexamethylenetetramine preparation (being embodiment 1-5) of different mole numbers.Testing tool is X-ray diffractometer (Rigaku UltimaIV), and sweep limit is 10 – 70 degree, scanning speed be 2 degree/minute, scanning step is 0.02 degree.Dotted line is standard spectral line corresponding to boron trioxide (PDF#06-0297).
Fig. 2 be when boric acid be 0.01mol, when trimeric cyanamide is 0.01mol, the scanning electron microscope (SEM) photograph of BCNO fluorescent material of (embodiment 1) preparation when hexamethylenetetramine is 0.001mol.Testing tool is scanning electron microscope (PHENOM G2).
Fig. 3 be when boric acid be 0.01mol, when trimeric cyanamide was 0.01mol, when hexamethylenetetramine is 0.001mol, the x-ray photoelectron of the BCNO fluorescent material of (embodiment 1) preparation can spectrogram.Testing tool is x-ray photoelectron spectroscopy (PHI1600EXCA).
Fig. 4 be when boric acid be 0.01mol, when trimeric cyanamide is 0.01mol, adopt the infrared spectrogram of BCNO fluorescent material of the hexamethylenetetramine preparation (being embodiment 1-5) of different mole numbers.Testing tool is Fourier transform infrared spectroscopy (Bruker, WQF-410), and test specification is 400 to 4000 wave numbers.
Fig. 5 be when boric acid be 0.01mol, when trimeric cyanamide is 0.01mol, adopt the utilizing emitted light spectrogram of BCNO fluorescent material of the hexamethylenetetramine preparation (being embodiment 1-5) of different mole numbers.Testing tool is fluorescence spectrophotometer (Horiba, FL-3-22).Exciting light is the monochromatic ray of 370nm, and the emmission spectrum test specification is 390-720nm.
Fig. 6 be when boric acid be 0.01mol, when trimeric cyanamide is 0.01mol, the X-ray diffractogram of the BCNO fluorescent material of sintering (embodiment 6,7,9) under differing temps when hexamethylenetetramine is 0.001mol.Testing tool is X-ray diffractometer (Rigaku Ultima IV), and sweep limit is the 10-70 degree, scanning speed be 2 the degree/minute, scanning step be 0.02 the degree.Dotted line is standard spectral line corresponding to boron trioxide (PDF#06-0297).
Fig. 7 be when boric acid be 0.01mol, when trimeric cyanamide is 0.01mol, when hexamethylenetetramine is 0.001mol under differing temps sintering (embodiment 1, the utilizing emitted light spectrogram of BCNO fluorescent material 6-9).Testing tool is fluorescence spectrophotometer (Horiba, FL-3-22).Exciting light is the monochromatic ray of 370nm, and the emmission spectrum test specification is 390-720nm.
Embodiment
Further illustrate technical scheme of the present invention below in conjunction with specific embodiment.
The quality of the main material that the present invention is used is boric acid (molecular weight: 61.83,99.5%), trimeric cyanamide (molecular weight: 126.12 purity:, 99.5%) and hexamethylenetetramine (molecular weight: 140.19 purity:, purity: 99.5%), but it is not as limitation of the present invention.
Adopt the hexamethylenetetramine of different moles to prepare BCNO fluorescent material.
Embodiment 1:
1, add the deionized water of 80mL in flask, and be heated to 85 ℃;
When 2, solution temperature is 85 ℃ in flask, add the boric acid of 0.01mol and the trimeric cyanamide of 0.01mol, do not stop to be stirred to the solution clarification, solution temperature remains on 85 ℃;
3, the hexamethylenetetramine that adds 0.001mol in solution does not stop stirred solution to clarification, and solution temperature remains on 85 ℃, stir and pour solution into beaker after 6 hours, solution is heated to 100 ℃ and stirring simultaneously, until with the water evaporate to dryness, obtain the precursor of BCNO;
4, take out the precursor of BCNO, put into retort furnace and carry out low-temperature sintering, sintering temperature is 625 ℃, and sintering time is 12 hours; Sintering is closed the retort furnace naturally cooling after finishing, and takes out sample after muffle furnace is down to room temperature, and fully ground sample namely obtained BCNO fluorescent material in 1 hour in agate mortar.
Other steps are with embodiment 1, and difference is that the hexamethylenetetramine mole number in step 2 changes 0.002mol into by 0.001mol.
Other steps are with embodiment 1, and difference is that the hexamethylenetetramine mole number in step 2 changes 0.003mol into by 0.001mol.
Other steps are with embodiment 1, and difference is that the hexamethylenetetramine mole number in step 2 changes 0.004mol into by 0.001mol.
Other steps are with embodiment 1, and difference is that the hexamethylenetetramine mole number in step 2 changes 0.005mol into by 0.001mol.
Test result: adopt the hexamethylenetetramine of different moles to prepare BCNO fluorescent material by low-temperature sintering method, fluorescent material has been carried out the measurement of X-ray diffraction, scanning electron microscope, x-ray photoelectron power spectrum, infrared spectra, emmission spectrum and quantum yield..Test result is respectively as shown in Fig. 1, Fig. 2, Fig. 3, Fig. 4, Fig. 5 and table 1.Fig. 1 be when boric acid be 0.01mol, trimeric cyanamide is 0.01mol, adopts the X-ray diffractogram of BCNO fluorescent material of the hexamethylenetetramine preparation of different moles, in figure, the diffraction peak at dotted line place shows the B that contains cubic structure in sample
2O
3(unreacted is the boric acid degradation production completely, can remove by hot water wash), the broad peak proof sample of 23 degree and 43 degree left and right appearance is staggered floor BN structure, and not crystallization fully; Fig. 2 be when boric acid be 0.01mol, trimeric cyanamide is 0.01mol, the scanning electron microscope (SEM) photograph of the BCNO fluorescent material that hexamethylenetetramine prepares when being 0.001mol.The scanning electron microscope result shows that the pattern of sample is irregular, rough, particle size is several microns, and (fluorescent material that studies show that at present micron-scale has higher quantum yield, and the fluorescent material quantum yield of nano-scale is lower, in addition, pattern is irregular and rough more is conducive to absorb exciting light, reduces reflection).Fig. 3 be when boric acid be 0.01mol, trimeric cyanamide is 0.01mol, the x-ray photoelectron of the BCNO fluorescent material that hexamethylenetetramine prepares when being 0.001mol can spectrogram, as shown in Figure 3, contains B, C, N, O element in sample.Fig. 4 provides be when boric acid be 0.01mol, when trimeric cyanamide is 0.01mol, the infrared spectrogram of the BCNO fluorescent material of the hexamethylenetetramine preparation of different moles, as can be seen from Figure 4, contain the chemical bonds such as B-N, B-N-B, B-O, B-C and C-N in BCNO fluorescent material, also proof is BCNO fluorescent material really.Fig. 5 be when boric acid be 0.01mol, when trimeric cyanamide is 0.01mol, the utilizing emitted light spectrogram of BCNO fluorescent material under 370nm excites for preparing when adopting the hexamethylenetetramine of different moles.When hexamethylenetetramine was 0.001mol, the emmission spectrum of fluorescent material was at the 400-520nm wave band, and emission peak is in the 460nm left and right; When hexamethylenetetramine was 0.003mol, the emmission spectrum of fluorescent material was at the 420-540nm wave band, and emission peak is in the 480nm left and right; When hexamethylenetetramine was 0.005mol, the emmission spectrum of fluorescent material was at the 450-570nm wave band, and emission peak is in the 500nm left and right; As shown in Figure 4, along with the increase of hexamethylenetetramine consumption, the emission peak of BCNO emission red shift, the emmission spectrum of BCNO fluorescent material also can be regulated at visible-range, and red shift occurs along with the increase of hexamethylenetetramine mole number in emission peak positions.Table 1 be when boric acid be 0.01mol, when trimeric cyanamide is 0.01mol, adopt emission peak and the quantum yield of BCNO fluorescent material of the hexamethylenetetramine preparation of different mole numbers.As seen from table, when hexamethylenetetramine was 0.001mol, the emission peak of BCNO was 456nm, and quantum yield is 95%.Along with the increase of hexamethylenetetramine molar weight, the emission peak red shift of BCNO, quantum yield reduces.When hexamethylenetetramine was 0.005mol, the emission peak of BCNO was 503nm, and quantum yield is 21%.
Table 1 be when boric acid be 0.01mol, when trimeric cyanamide is 0.01mol, adopt emission peak and the quantum yield of BCNO fluorescent material of the hexamethylenetetramine preparation of different mole numbers.Quantum yield testing tool used is fluorescence spectrophotometer (Horiba, FL-3-22), and exciting light is the monochromatic ray of 370nm.
Table 1
Embodiment 6,
Other steps are with embodiment 1, and difference is that the sintering temperature in step 4 changes 600 ℃ into by 625 ℃.
Embodiment 7,
Other steps are with embodiment 1, and difference is that the sintering temperature in step 4 changes 650 ℃ into by 625 ℃.
Embodiment 8,
Other steps are with embodiment 1, and difference is that the sintering temperature in step 4 changes 675 ℃ into by 625 ℃.
Embodiment 9,
Other steps are with embodiment 1, and difference is that the sintering temperature in step 4 changes 700 ℃ into by 625 ℃.
Test result: prepared BCNO fluorescent material by low-temperature sintering method under different sintering temperatures, fluorescent material has been carried out X-ray diffraction, scanning electron microscope, infrared spectra and emission spectroscopy measurements.Fig. 6 be when boric acid be 0.01mol, trimeric cyanamide is 0.01mol, the X-ray diffractogram of the BCNO fluorescent material of differing temps sintering preparation when hexamethylenetetramine is 0.001mol, as seen from the figure, the diffraction peak of BCNO fluorescent material is offset to high angle along with the increase of sintering temperature, the halfwidth of diffraction peak reduces, and the crystallinity of interpret sample improves along with the increase of sintering temperature.Fig. 7 be when boric acid be 0.01mol, trimeric cyanamide is 0.01mol, the utilizing emitted light spectrogram of the BCNO fluorescent material of sintering under differing temps when hexamethylenetetramine is 0.001mol.When sintering temperature is 600 when spending, the emmission spectrum of fluorescent material is at the 420-520nm wave band, and emission peak is in the 460nm left and right; When sintering temperature is 650 when spending, the emmission spectrum of fluorescent material is at the 400-510nm wave band, and emission peak is in the 450nm left and right; When sintering temperature is 700 when spending, the emmission spectrum of fluorescent material is at the 400-500nm wave band, and emission peak is in the 436nm left and right; As shown in Figure 7, the emmission spectrum of this BCNO fluorescent material is along with sintering temperature increases to 700 ℃ from 600 ℃ of C, emission peak positions generation blue shift.
According to above result, can find out that the method for preparing high-quantum efficiency blue emission BCNO fluorescent material that the present invention proposes does not need to use urea, sintering temperature is low, insensitive to sintering time, the preparation method is simple, good reproducibility, be easy to produce in batches, nontoxic pollution-free, meet the needs of current green industry development.In addition, all can regulate the emmission spectrum of BCNO fluorescent material by the consumption that changes hexamethylenetetramine.When mol ratio boric acid: trimeric cyanamide: during hexamethylenetetramine=0.01:0.01:0.001, sintering temperature is between 600 ~ 700 ℃, the emmission spectrum of BCNO fluorescent material is at blue wave band, and the quantum yield of fluorescent material reduces along with temperature raises first to increase afterwards, when sintering temperature is 625 ℃, BCNO fluorescent material emission blue light, and has the sub-efficient 95% of maximum amount, can substitute the blue emission rare earth doping fluorescent powder of present commercialization, greatly reduce production costs, have broad application prospects in association areas such as semiconductor lightings.
Above the present invention has been done exemplary description; should be noted that; in the situation that do not break away from core of the present invention, the replacement that is equal to that any simple distortion, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (3)
1. the preparation method of a high-quantum efficiency blue emission BCNO fluorescent material is characterized by and comprises the following steps:
1) add deionized water in reactor, and be heated to 70 ~ 90 ℃ and remain this temperature range; Add again boric acid and trimeric cyanamide, stir and clarified to solution in 1 hour; Material proportion is: every 0.01mol trimeric cyanamide adds 70 ~ 100mL deionized water; Mol ratio boric acid: trimeric cyanamide=1:1;
2) add hexamethylenetetramine in the solution that upwards step obtains, stirred solution is to clarification; Solution temperature remains between 70 ~ 90 ℃, and stirred solution changed solution in another reactor after 6 hours, then is heated to 100 ℃, stirs simultaneously, until with the water evaporate to dryness, obtain the precursor of BCNO; Material proportion is: mol ratio boric acid: hexamethylenetetramine=1:0.1 ~ 0.5;
3) take out the precursor of BCNO, put into retort furnace, carry out sintering the scopes of 600 ~ 700 ℃, sintering time is 12 hours;
4) sintering is closed the retort furnace naturally cooling after finishing, and takes out product after muffle furnace is down to room temperature, and fully grinding namely obtains BCNO fluorescent material in agate mortar.
2. the preparation method of high-quantum efficiency blue emission BCNO fluorescent material as claimed in claim 1, is characterized by described step 2) in, material proportion is mol ratio boric acid: hexamethylenetetramine=1:0.1.
3. the preparation method of high-quantum efficiency blue emission BCNO fluorescent material as claimed in claim 1, is characterized by described step 3) in sintering temperature be 625 ℃.
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| CN104531146A (en) * | 2014-12-02 | 2015-04-22 | 河北工业大学 | Preparation method of orange-red light emission adjustable BCNO fluorescent powder |
| CN105505388A (en) * | 2015-12-25 | 2016-04-20 | 河北工业大学 | Method for preparing BCNO light-emitting nanosheet |
| CN106590643A (en) * | 2016-12-12 | 2017-04-26 | 河北工业大学 | Preparation method and application of blue light emitting BCNO quantum dots |
| CN107057686A (en) * | 2017-05-12 | 2017-08-18 | 临沂大学 | A kind of New Solid yellow fluorescent powder |
| CN108704659A (en) * | 2018-06-05 | 2018-10-26 | 河北工业大学 | A kind of visible light-responded TiO2The preparation method of/BCNO nanometer sheet composite catalysts |
| CN109133942A (en) * | 2018-09-17 | 2019-01-04 | 河北工业大学 | A kind of preparation method of the active nitride boron fibre of high-specific surface area |
| CN116333733A (en) * | 2023-03-28 | 2023-06-27 | 安阳工学院 | Method for preparing high quantum efficiency ultraviolet emission melem fluorescent powder in ammonia atmosphere |
| US11959002B2 (en) | 2020-11-19 | 2024-04-16 | University Of Houston System | Blue-emitting phosphors and methods of use thereof |
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| CN104531146A (en) * | 2014-12-02 | 2015-04-22 | 河北工业大学 | Preparation method of orange-red light emission adjustable BCNO fluorescent powder |
| CN105505388A (en) * | 2015-12-25 | 2016-04-20 | 河北工业大学 | Method for preparing BCNO light-emitting nanosheet |
| CN105505388B (en) * | 2015-12-25 | 2017-08-29 | 河北工业大学 | A kind of preparation method of BCNO Illuminant nanometers piece |
| CN106590643A (en) * | 2016-12-12 | 2017-04-26 | 河北工业大学 | Preparation method and application of blue light emitting BCNO quantum dots |
| CN106590643B (en) * | 2016-12-12 | 2018-10-26 | 河北工业大学 | A kind of preparation method and applications of blue emission BCNO quantum dots |
| CN107057686A (en) * | 2017-05-12 | 2017-08-18 | 临沂大学 | A kind of New Solid yellow fluorescent powder |
| CN108704659A (en) * | 2018-06-05 | 2018-10-26 | 河北工业大学 | A kind of visible light-responded TiO2The preparation method of/BCNO nanometer sheet composite catalysts |
| CN108704659B (en) * | 2018-06-05 | 2021-02-19 | 河北工业大学 | Visible light response TiO2Preparation method of/BCNO nanosheet composite catalyst |
| CN109133942A (en) * | 2018-09-17 | 2019-01-04 | 河北工业大学 | A kind of preparation method of the active nitride boron fibre of high-specific surface area |
| US11959002B2 (en) | 2020-11-19 | 2024-04-16 | University Of Houston System | Blue-emitting phosphors and methods of use thereof |
| CN116333733A (en) * | 2023-03-28 | 2023-06-27 | 安阳工学院 | Method for preparing high quantum efficiency ultraviolet emission melem fluorescent powder in ammonia atmosphere |
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