CN105838362B - A kind of red long afterglow luminous material and preparation method thereof - Google Patents
A kind of red long afterglow luminous material and preparation method thereof Download PDFInfo
- Publication number
- CN105838362B CN105838362B CN201610256393.1A CN201610256393A CN105838362B CN 105838362 B CN105838362 B CN 105838362B CN 201610256393 A CN201610256393 A CN 201610256393A CN 105838362 B CN105838362 B CN 105838362B
- Authority
- CN
- China
- Prior art keywords
- luminous material
- long afterglow
- red long
- pure
- afterglow luminous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/74—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing arsenic, antimony or bismuth
- C09K11/7485—Borates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/74—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing arsenic, antimony or bismuth
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/74—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing arsenic, antimony or bismuth
- C09K11/7442—Aluminates; Silicates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7729—Chalcogenides
- C09K11/773—Chalcogenides with zinc or cadmium
Abstract
The invention provides red long afterglow luminous material and preparation method thereof, the long after glow luminous material is [Zn(1‑x‑y‑z‑n)MgxMyLz]O:nBi；M is the one or more in B, Al, Ga, In, Zr, Si, Eu, Sc, Y, La, Nd, Gd, Dy and Lu, and L is the one or more in alkali metal atom；X is that 0~0.4, y is that 0.0001~0.12, z is that 0.0001~0.15, n is 0.0001~0.1.Compared with prior art, red long afterglow luminous material provided by the invention is using zinc oxide, magnesia as matrix, bismuth ion is the centre of luminescence, low price alkali metal ion and high valence ion are co-dopant ions, it effectively can be excited by the blue light ingredient in daylight particularly daylight, twilight sunset is bright and the time is longer；Red long afterglow luminous material preparation technology is simple simultaneously.
Description
Technical field
The invention belongs to embedded photoluminescent material technical field, more particularly to a kind of red long afterglow luminous material and its preparation
Method.
Background technology
Long after glow luminous material is a kind of new energy-conservation low light illuminant material, the material can effectively absorb it is ultraviolet or
Visible ray storage energy, and in the form of light discharge these energy, it is widely used in amblyopia illumination, building flaw detection, hair
The fields such as light instruction, AC LED, as it is other illumination and display industry, pursue multiple color long after glow luminous material with
It is the final goal of long after glow luminous material industry to realize all-colour luminous illumination.However, due to a variety of colors long lad phosphor
Decay it is different so that it is long-persistence luminous this target to be realized by red-green-blue, therefore, it is necessary to research and develop
The long-afterglow material of multiple color.
At present, blueness, the long lad phosphor of green have tended to be ripe, and have been used for actual production, and still, performance is excellent
Different red long lad phosphor is still very deficient.The red long afterglow material used at present is still traditional sulfide material,
Such material physical chemistry property is unstable, meets water and is extremely easy in decomposition, it is necessary to which can be only achieved round-the-clock stabilization by film-coating technique makes
Commercialization purpose, moreover, using sulfide strong as raw material, contaminative in the preparation process of such material.Research at present
Most red long afterglow materials of report also have rare earth oxysalt or nitride that either transition metal ions activates, but
These materials often can only could produce red twilight sunset under ultraviolet irradiation, and the afterglow performance under excited by visible light
It is poor, limit its application.
The content of the invention
In view of this, the technical problem to be solved in the present invention be to provide it is a kind of can be by the red long-afterglow of excited by visible light
Luminescent material and preparation method thereof.
The invention provides a kind of red long afterglow luminous material, as shown in formula (I)：
[Zn(1-x-y-z-n)MgxMyLz]O:nBi (I)；
Wherein, the one or more in M B, Al, Ga, In, Zr, Si, Eu, Sc, Y, La, Nd, Gd, Dy and Lu, L are alkali
One or more in metallic atom；
The x is that 0~0.4, y is that 0.0001~0.12, z is that 0.0001~0.15, n is 0.0001~0.1.
Preferably, the alkali metal atom is the one or more in Li, Na and K.
Preferably, the x is 0.05~0.2.
Preferably, the y is 0.02~0.06.
Preferably, the z is 0.02~0.08.
Preferably, the n is 0.01~0.05.
Present invention also offers a kind of preparation method of red long afterglow luminous material, including：
Zinc source compound, magnesium source compound, bismuth source compound, alkali metal source compound and M source compounds are mixed, roasting
Burn, obtain red long afterglow luminous material；
The M is that M is one or more in B, Al, Ga, In, Zr, Si, Eu, Sc, Y, La, Nd, Gd, Dy and Lu；
M atoms, alkali metal source in magnesium atom, M source compounds in zinc atom, magnesium source compound in the zinc source compound
The mol ratio of alkali metal atom and the bismuth atom of bismuth atom in bismuth source compound is (1-x-y-z-n) in compound：x：y：z：n；Institute
It is that 0~0.4, y is that 0.0001~0.12, z is that 0.0001~0.15, n is 0.0001~0.1 to state x.
Preferably, the zinc source compound be the oxide of zinc, the carbonate of zinc, the nitrate of zinc, zinc oxalates with
One or more in the acetate of zinc；
The magnesium source compound is the oxide of magnesium, the carbonate of magnesium, the nitrate of magnesium, the oxalates of magnesium and the acetic acid of magnesium
One or more in salt；
The bismuth source compound is the one or more in the oxide, the carbonate of bismuth and the nitrate of bismuth of bismuth；
The alkali metal source compound is in the oxide, the carbonate of alkali metal and the nitrate of alkali metal of alkali metal
It is one or more；
One or more in oxide, M carbonate and M nitrate that the M source compounds are M.
Preferably, the roasting is carried out in calcination atmosphere；The calcination atmosphere is in air, nitrogen, argon gas and oxygen
One or more.
Preferably, the temperature of the roasting is 700 DEG C~1300 DEG C；The time of the roasting is 0.5~20h.
The invention provides a kind of red long afterglow luminous material and preparation method thereof, the long after glow luminous material such as formula
(I) shown in：[Zn(1-x-y-z-n)MgxMyLz]O:nBi(I)；Wherein, M B, Al, Ga, In, Zr, Si, Eu, Sc, Y, La, Nd, Gd,
One or more in Dy and Lu, L are the one or more in alkali metal atom；The x be 0~0.4, y be 0.0001~
0.12, z is that 0.0001~0.15, n is 0.0001~0.1.Compared with prior art, red long-afterglow provided by the invention lights
For material using zinc oxide, magnesia as matrix, bismuth ion is the centre of luminescence, low price alkali metal ion and high valence ion be codope from
Son, it effectively can be excited by the blue light ingredient in daylight particularly daylight, twilight sunset is bright and the time is longer；The red is long simultaneously
Afterglow materials preparation technology is simple, low raw-material cost, and product chemical property is stable, fluffy, easy grinding, "dead",
Environment will not be damaged.
Brief description of the drawings
Fig. 1 is the excitation-emission spectrogram of the red long afterglow luminous material obtained in the embodiment of the present invention 1；
Fig. 2 is the afterglow spectrogram of the red long afterglow luminous material obtained in the embodiment of the present invention 1；
Fig. 3 is the decay of afterglow curve map of the red long afterglow luminous material obtained in the embodiment of the present invention 1.
Embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, all
Belong to the scope of protection of the invention.
The invention provides a kind of red long afterglow luminous material, as shown in formula (I)：
[Zn(1-x-y-z-n)MgxMyLz]O:nBi (I)；
Wherein, the one or more in M B, Al, Ga, In, Zr, Si, Eu, Sc, Y, La, Nd, Gd, Dy and Lu, it is preferably
B, the one or more in the one or more in Al, Ga, In and Eu, more preferably B, Al, Ga and In, most preferably B；At this
Invent in some embodiments provided, the M is preferably B；In some embodiments provided by the invention, the M is preferably Al；
In some embodiments provided by the invention, the M is preferably Ga；In some embodiments provided by the invention, the M is preferred
For In；In other embodiments provided by the invention, the M is preferably Eu；L is the one or more in alkali metal atom,
One or more preferably in Li, Na and K, more preferably Li or Na, it is further preferably Li；In some implementations provided by the invention
In example, the L is preferably Li；In other embodiments provided by the invention, the L is preferably Na；Provided by the invention
In other embodiments, the L is preferably K.In red long afterglow luminous material provided by the invention, component based on ZnO,
MgO is regulation matrix components, and Bi is light emitting ionic, and M and L is co-dopant ions.
The x is 0~0.4, preferably 0.05~0.2, more preferably 0.08~0.15；In some realities provided by the invention
Apply in example, the x is preferably 0.05；X is preferably 0.1 described in other embodiments provided by the invention；Carried in the present invention
X is preferably 0.2 described in other embodiments supplied；The y is 0.0001~0.12, preferably 0.001~0.12, more preferably
It is further preferably 0.02~0.06 for 0.01~0.12, most preferably 0.03~0.05；In some embodiments provided by the invention
In, the y is preferably 0.02；In some embodiments provided by the invention, the y is preferably 0.04；Provided by the invention
In other embodiments, the y is preferably 0.06；The z is 0.0001~0.15, preferably 0.001~0.15, more preferably
0.01~0.15, it is further preferably 0.02~0.08, most preferably 0.03~0.05；In some embodiments provided by the invention,
The z is preferably 0.02；In some embodiments provided by the invention, the z is preferably 0.04；Provided by the invention another
In a little embodiments, the z is preferably 0.08；The n be 0.0001~0.1, preferably 0.01~0.05, more preferably 0.02~
0.05；In some embodiments provided by the invention, the n is preferably 0.01；In some embodiments provided by the invention, institute
It is preferably 0.02 to state n；In other embodiments provided by the invention, the n is preferably 0.05.
In some embodiments provided by the invention, the red long afterglow luminous material is preferably Zn0.9B0.04Li0.04O:
0.02Bi；In some embodiments provided by the invention, the red long afterglow luminous material is preferably Zn0.9Al0.04Li0.04O:
0.02Bi；In some embodiments provided by the invention, the red long afterglow luminous material is preferably Zn0.9Ga0.04Li0.04O:
0.02Bi；In some embodiments provided by the invention, the red long afterglow luminous material is preferably Zn0.9In0.04Li0.04O:
0.02Bi；In some embodiments provided by the invention, the red long afterglow luminous material is preferably Zn0.9Eu0.04Li0.04O:
0.02Bi；In some embodiments provided by the invention, the red long afterglow luminous material is preferably Zn0.9B0.04Na0.04O:
0.02Bi；In some embodiments provided by the invention, the red long afterglow luminous material is preferably Zn0.9B0.04K0.04O:
0.02Bi；In some embodiments provided by the invention, the red long afterglow luminous material is preferably Zn0.91B0.04Li0.04O:
0.01Bi；In some embodiments provided by the invention, the red long afterglow luminous material is preferably Zn0.87B0.04Li0.04O:
0.05Bi；In some embodiments provided by the invention, the red long afterglow luminous material is preferably Zn0.92B0.02Li0.04O:
0.02Bi；In some embodiments provided by the invention, the red long afterglow luminous material is preferably Zn0.88B0.06Li0.04O:
0.02Bi；In some embodiments provided by the invention, the red long afterglow luminous material is preferably Zn0.92B0.04Li0.02O:
0.02Bi；In some embodiments provided by the invention, the red long afterglow luminous material is preferably Zn0.86B0.04Li0.08O:
0.02Bi；In some embodiments provided by the invention, the red long afterglow luminous material is preferably
Zn0.85Mg0.05B0.04Li0.04O:0.02Bi；In some embodiments provided by the invention, the red long afterglow luminous material
Preferably Zn0.80Mg0.10B0.04Li0.04O:0.02Bi；In other embodiments provided by the invention, the red long-afterglow
Luminescent material is preferably Zn0.70Mg0.20B0.04Li0.04O:0.02Bi。
For red long afterglow luminous material provided by the invention using zinc oxide, magnesia as matrix, bismuth ion is the centre of luminescence,
Low price alkali metal ion and high valence ion are co-dopant ions, it effectively can be swashed by the blue light ingredient in daylight particularly daylight
Hair, twilight sunset is bright and the time is longer.
Present invention also offers a kind of preparation method of above-mentioned red long afterglow luminous material, including：By zinc source compound,
Magnesium source compound, bismuth source compound, alkali metal source compound and the mixing of M source compounds, roasting, obtain the luminous material of red long-afterglow
Material；The M is that M is one or more in B, Al, Ga, In, Zr, Si, Eu, Sc, Y, La, Nd, Gd, Dy and Lu；The zinc source
Alkali metal atom in M atoms, alkali metal source compound in magnesium atom, M source compounds in zinc atom, magnesium source compound in compound
Mol ratio with the bismuth atom of bismuth atom in bismuth source compound is (1-x-y-z-n)：x：y：z：n；The x is that 0~0.4, y is
0.0001~0.12, z are that 0.0001~0.15, n is 0.0001~0.1.
Wherein, the M, L, x, y, z and n are same as above, will not be repeated here.
In the present invention, the zinc source compound is the compound well known to those skilled in the art containing zinc ion,
Special limitation is had no, is preferably the oxide of zinc, the carbonate of zinc, the nitrate of zinc, the oxalates and zinc of zinc in the present invention
Acetate in one or more, more preferably zinc oxide；In some embodiments provided by the invention, the zinc source
Compound is preferably ZnO.
The magnesium source compound is magnesium source compound well known to those skilled in the art, has no special limitation, this
Be preferably in invention the oxide of magnesium, the carbonate of magnesium, the nitrate of magnesium, the oxalates of magnesium and one kind in the acetate of magnesium or
It is a variety of, the more preferably oxide of magnesium；In some embodiments provided by the invention, the magnesium source compound is preferably MgO.
The bismuth source compound is bismuth source compound well known to those skilled in the art, has no special limitation, this
The preferably oxidation of the oxide of bismuth, the carbonate of bismuth and one or more, more preferably bismuth in the nitrate of bismuth in invention
Thing；In some embodiments provided by the invention, the bismuth source compound is preferably Bi2O3。
The alkali metal source compound is the compound well known to those skilled in the art for including alkali metal ion, and
Be preferably without special limitation, in the present invention alkali metal oxide, the carbonate of alkali metal and the nitrate of alkali metal in
The carbonate of one or more, more preferably alkali metal；In some embodiments provided by the invention, the alkali metal oxide
Thing is preferably Li2CO3。
The M source compounds are the compound well known to those skilled in the art for including M, have no special limitation,
It is preferably the one or more in M oxide, M carbonate and M nitrate, more preferably M oxide in the present invention；
In some embodiments provided by the invention, the M source compounds are preferably B2O3；In some embodiments provided by the invention,
The M source compounds are preferably In2O3；In some embodiments provided by the invention, the M source compounds are preferably Ga2O3；
In some embodiments provided by the invention, the M source compounds are preferably Eu2O3。
Zinc source compound, magnesium source compound, bismuth source compound, alkali metal source compound and M source compounds are mixed；This hair
The bright process to the mixing does not have special limitation, is by raw material mixing using mixed method well known to those skilled in the art
Can；
It is calcined after mixing, is carried out preferably in calcination atmosphere；The calcination atmosphere is roasting well known in the art
Atmosphere is burnt, has no special limitation, is preferably the one or more in air, nitrogen, argon gas and oxygen in the present invention, more
Preferably air；The present invention does not have special limitation to the device of the roasting, it is preferred to use well known to those skilled in the art
High temperature furnace；The temperature of the roasting is preferably 700 DEG C~1300 DEG C, and more preferably 800 DEG C~1100 DEG C, be further preferably 900 DEG C
~1100 DEG C, most preferably 1000 DEG C；The time of the roasting is preferably 0.5~20h, more preferably 5~20h, further preferably for
10~15h, most preferably 10h.
After the completion of roasting, room temperature is preferably naturally cooled to, obtains red long afterglow luminous material.
Red long afterglow luminous material preparation technology of the present invention is simple, low raw-material cost, and product chemical property is stable, fluffy
Pine, easy grinding is "dead", and environment will not be damaged
In order to further illustrate the present invention, with reference to embodiments to a kind of long after glow luminous material provided by the invention and
Its preparation method is described in detail.
Reagent used is commercially available in following examples.
Embodiment 1
Raw material is ZnO (analysis is pure), Bi2O3(spectroscopic pure), B2O3(analysis is pure) and Li2CO3(analysis pure), above-mentioned substance it
Between mol ratio be 0.90：0.01：0.02：0.02, raw material is weighed in above ratio, is placed into after mixing in corundum crucible, then
1100 DEG C of roasting 10h in air atmosphere are put into high temperature furnace, room temperature is naturally cooled to, obtains red afterglow materials.
The red long afterglow luminous material obtained in embodiment 1 be yellow powder, molecular formula Zn0.9B0.04Li0.04O:
0.02Bi。
The red long afterglow luminous material obtained in embodiment 1 is analyzed, obtains its excitation-emission spectrogram, is such as schemed
Shown in 1.As shown in Figure 1, its excitation emission spectra is broadband emission, in the case where near ultraviolet and blue light excite, is obtained in embodiment 1
The maximum emission wavelength of red long afterglow luminous material is located near 620nm, and glow color is red.
By the red long afterglow luminous material obtained in embodiment 1 with removing light source after 435nm blue light chronic exposures 5min,
Its twilight sunset luminescent spectrum figure is obtained, as shown in Figure 2；It is as shown in Figure 3 to obtain its twilight sunset attenuation curve figure.From Fig. 2 and Fig. 3.
The red long afterglow luminous material obtained in embodiment 1 can effectively be excited by the blue light components in daylight and produce red twilight sunset,
Persistence is up to more than 60min.
Embodiment 2
Raw material is ZnO (analysis is pure), Bi2O3(spectroscopic pure), B2O3(analysis is pure) and Li2CO3(analysis is pure), above-mentioned substance
Mol ratio is 0.90：0.01：0.02：0.02.Raw material is weighed in above ratio, is placed into corundum crucible, places into after mixing
In high temperature furnace in air atmosphere 1000 DEG C roasting 10h, naturally cool to room temperature, obtain red long afterglow luminous material.
The red long afterglow luminous material obtained in embodiment 2 be yellow powder, molecular formula Zn0.9B0.04Li0.04O:
0.02Bi, maximum emission wavelength are located near 620nm, and glow color is red.With being removed after 435nm blue light chronic exposures 5min
Light source, sustainable more than the 60min of twilight sunset of material.
Embodiment 3
Raw material is ZnO (analysis is pure), Bi2O3(spectroscopic pure), B2O3(analysis is pure) and Li2CO3(analysis pure), above-mentioned substance it
Between mol ratio be 0.90：0.01：0.02：0.02.Raw material is weighed in above ratio, is placed into after mixing in corundum crucible, then
900 DEG C of roasting 10h in air atmosphere are put into high temperature furnace, room temperature is naturally cooled to, obtains red long afterglow luminous material.
The red long afterglow luminous material obtained in embodiment 3 be yellow powder, molecular formula Zn0.9B0.04Li0.04O:
0.02Bi, maximum emission wavelength are located near 620nm, and glow color is red.With being removed after 435nm blue light chronic exposures 5min
Light source, sustainable more than the 50min of twilight sunset of material.
Embodiment 4
Raw material is ZnO (analysis is pure), Bi2O3(spectroscopic pure), B2O3(analysis is pure) and Li2CO3(analysis pure), above-mentioned substance it
Between mol ratio be 0.90：0.01：0.02：0.02.Raw material is weighed in above ratio, is placed into after mixing in corundum crucible, then
800 DEG C of roasting 10h in air atmosphere are put into high temperature furnace, room temperature is naturally cooled to, obtains red long afterglow luminous material.
The red long afterglow luminous material obtained in embodiment 4 be yellow powder, molecular formula Zn0.9B0.04Li0.04O:
0.02Bi, maximum emission wavelength are located near 620nm, and glow color is red.With being removed after 435nm blue light chronic exposures 5min
Light source, sustainable more than the 50min of twilight sunset of material.
Embodiment 5
Raw material is ZnO (analysis is pure), Bi2O3(spectroscopic pure), Al2O3(analysis is pure) and Li2CO3(analysis is pure), above-mentioned substance
Between mol ratio be 0.90：0.01：0.02：0.02, raw material is weighed in above ratio, is placed into after mixing in corundum crucible,
1000 DEG C of roasting 10h in air atmosphere are placed into high temperature furnace, naturally cool to room temperature, red long-afterglow is obtained and lights material
Material.
The red long afterglow luminous material obtained in embodiment 5 be yellow powder, molecular formula Zn0.9Al0.04Li0.04O:
0.02Bi, maximum emission wavelength are located near 620nm, and glow color is red.With being removed after 435nm blue light chronic exposures 5min
Light source, the twilight sunset of material can last about more than 40min.
Embodiment 6
Raw material is ZnO (analysis is pure), Bi2O3(spectroscopic pure), Ga2O3(analysis is pure) and Li2CO3(analysis is pure), above-mentioned substance
Between mol ratio be 0.90：0.01：0.02：0.02, raw material is weighed in above ratio, is placed into after mixing in corundum crucible,
1000 DEG C of roasting 10h in air atmosphere are placed into high temperature furnace, naturally cool to room temperature, red long-afterglow is obtained and lights material
Material.
The red long afterglow luminous material obtained in embodiment 6 be yellow powder, molecular formula Zn0.9Ga0.04Li0.04O:
0.02Bi, maximum emission wavelength are located near 620nm, and glow color is red.With being removed after 435nm blue light chronic exposures 5min
Light source, the twilight sunset of material can last about more than 50min.
Embodiment 7
Raw material is ZnO (analysis is pure), Bi2O3(spectroscopic pure), In2O3(analysis is pure) and Li2CO3(analysis is pure), above-mentioned substance
Between mol ratio be 0.90：0.01：0.02：0.02, raw material is weighed in above ratio, is placed into after mixing in corundum crucible,
1000 DEG C of roasting 10h in air atmosphere are placed into high temperature furnace, naturally cool to room temperature, red long-afterglow is obtained and lights material
Material.
The red long afterglow luminous material obtained in embodiment 7 be yellow powder, molecular formula Zn0.9In0.04Li0.04O:
0.02Bi, maximum emission wavelength are located near 620nm, and glow color is red.With being removed after 435nm blue light chronic exposures 5min
Light source, the twilight sunset of material can last about more than 40min.
Embodiment 8
Raw material is ZnO (analysis is pure), Bi2O3(spectroscopic pure), Eu2O3(analysis is pure) and Li2CO3(analysis pure), between them
Mol ratio be 0.90：0.01：0.02：0.02, raw material is weighed in above ratio, is placed into after mixing in corundum crucible, then put
Enter in high temperature furnace 1000 DEG C of roasting 10h in air atmosphere, naturally cool to room temperature, obtain red long afterglow luminous material.
The red long afterglow luminous material obtained in embodiment 8 be yellow powder, molecular formula Zn0.9Eu0.04Li0.04O:
0.02Bi, maximum emission wavelength are located near 620nm, and glow color is red.With being removed after 435nm blue light chronic exposures 5min
Light source, the twilight sunset of material can last about more than 30min.
Embodiment 9
Raw material is ZnO (analysis is pure), Bi2O3(spectroscopic pure), B2O3(analysis is pure) and Na2CO3(analysis pure), between them
Mol ratio is 0.90：0.01：0.02：0.02, raw material is weighed in above ratio, is placed into corundum crucible, places into after mixing
In high temperature furnace in air atmosphere 1000 DEG C roasting 10h, naturally cool to room temperature, obtain red long afterglow luminous material.
The red long afterglow luminous material obtained in embodiment 9 be yellow powder, molecular formula Zn0.9B0.04Na0.04O:
0.02Bi, maximum emission wavelength are located near 620nm, and glow color is red.With being removed after 435nm blue light chronic exposures 5min
Light source, the twilight sunset of material can last about more than 40min.
Embodiment 10
Raw material is ZnO (analysis is pure), Bi2O3(spectroscopic pure), B2O3(analysis is pure) and K2CO3(analysis pure), between them
Mol ratio is 0.90：0.01：0.02：0.02, raw material is weighed in above ratio, is placed into corundum crucible, places into after mixing
In high temperature furnace in air atmosphere 1000 DEG C roasting 10h, naturally cool to room temperature, obtain red long afterglow luminous material.
The red long afterglow luminous material obtained in embodiment 10 be yellow powder, molecular formula Zn0.9B0.04K0.04O:
0.02Bi, maximum emission wavelength are located near 620nm, and glow color is red.With being removed after 435nm blue light chronic exposures 5min
Light source, the twilight sunset of material can last about more than 30min.
Embodiment 11
Raw material is ZnO (analysis is pure), Bi2O3(spectroscopic pure), B2O3(analysis is pure) and Li2CO3(analysis pure), between them
Mol ratio is 0.91：0.005：0.02：0.02, raw material is weighed in above ratio, is placed into corundum crucible, places into after mixing
In high temperature furnace in air atmosphere 1000 DEG C roasting 10h, naturally cool to room temperature, obtain red long afterglow luminous material.
The red long afterglow luminous material obtained in embodiment 11 is the powder of yellow, and molecular formula is
Zn0.91B0.04Li0.04O:0.01Bi, maximum emission wavelength are located near 620nm, and glow color is red.Held with 435nm blue lights
Light source is removed after continuous irradiation 5min, the twilight sunset of material can last about more than 50min.
Embodiment 12
Raw material is ZnO (analysis is pure), Bi2O3(spectroscopic pure), B2O3(analysis is pure) and Li2CO3(analysis pure), between them
Mol ratio is 0.87：0.025：0.02：0.02, raw material is weighed in above ratio, is placed into corundum crucible, places into after mixing
In high temperature furnace in air atmosphere 1000 DEG C roasting 10h, naturally cool to room temperature, obtain red long afterglow luminous material.
The red long afterglow luminous material obtained in embodiment 12 is the powder of yellow, and molecular formula is
Zn0.87B0.04Li0.04O:0.05Bi, maximum emission wavelength are located near 620nm, and glow color is red.Held with 435nm blue lights
Light source is removed after continuous irradiation 5min, the twilight sunset of material can last about more than 40min.
Embodiment 13
Raw material is ZnO (analysis is pure), Bi2O3(spectroscopic pure), B2O3(analysis is pure) and Li2CO3(analysis pure), between them
Mol ratio is 0.92：0.01：0.01：0.02, raw material is weighed in above ratio, is placed into corundum crucible, places into after mixing
In high temperature furnace in air atmosphere 1000 DEG C roasting 10h, naturally cool to room temperature, obtain red long afterglow luminous material.
The red long afterglow luminous material obtained in embodiment 13 is the powder of yellow, and molecular formula is
Zn0.92B0.02Li0.04O:0.02Bi, maximum emission wavelength are located near 620nm, and glow color is red.Held with 435nm blue lights
Light source is removed after continuous irradiation 5min, the twilight sunset of material can last about more than 50min.
Embodiment 14
Raw material is ZnO (analysis is pure), Bi2O3(spectroscopic pure), B2O3(analysis is pure) and Li2CO3(analysis pure), between them
Mol ratio is 0.88：0.01：0.03：0.02, raw material is weighed in above ratio, is placed into corundum crucible, places into after mixing
In high temperature furnace in air atmosphere 1000 DEG C roasting 10h, naturally cool to room temperature, obtain red long afterglow luminous material.
The red long afterglow luminous material obtained in embodiment 14 is the powder of yellow, and molecular formula is
Zn0.88B0.06Li0.04O:0.02Bi, maximum emission wavelength are located near 620nm, and glow color is red.Held with 435nm blue lights
Light source is removed after continuous irradiation 5min, the twilight sunset of material can last about more than 50min.
Embodiment 15
Raw material is ZnO (analysis is pure), Bi2O3(spectroscopic pure), B2O3(analysis is pure) and Li2CO3(analysis pure), between them
Mol ratio is 0.92：0.01：0.02：0.01, raw material is weighed in above ratio, is placed into corundum crucible, places into after mixing
In high temperature furnace in air atmosphere 1000 DEG C roasting 10h, naturally cool to room temperature, obtain red long afterglow luminous material.
The red long afterglow luminous material obtained in embodiment 15 is the powder of yellow, and molecular formula is
Zn0.92B0.04Li0.02O:0.02Bi, maximum emission wavelength are located near 620nm, and glow color is red.Held with 435nm blue lights
Light source is removed after continuous irradiation 5min, the twilight sunset of material can last about more than 50min.
Embodiment 16
Raw material is ZnO (analysis is pure), Bi2O3(spectroscopic pure), B2O3(analysis is pure) and Li2CO3(analysis pure), between them
Mol ratio is 0.86：0.01：0.02：0.04, raw material is weighed in above ratio, is placed into corundum crucible, places into after mixing
In high temperature furnace in air atmosphere 1000 DEG C roasting 10h, naturally cool to room temperature, obtain red long afterglow luminous material.
The red long afterglow luminous material obtained in embodiment 16 is the powder of yellow, and molecular formula is
Zn0.86B0.04Li0.08O:0.02Bi, maximum emission wavelength are located near 620nm, and glow color is red.Held with 435nm blue lights
Light source is removed after continuous irradiation 5min, the twilight sunset of material can last about more than 50min.
Embodiment 17
Raw material is ZnO (analysis is pure), Bi2O3(spectroscopic pure), B2O3(analysis is pure) and Li2CO3(analysis pure), between them
Mol ratio is 0.90：0.01：0.02：0.02, raw material is weighed in above ratio, is placed into corundum crucible, places into after mixing
In high temperature furnace in air atmosphere 1000 DEG C roasting 5 hours, naturally cool to room temperature, obtain red long afterglow luminous material.
The red long afterglow luminous material obtained in embodiment 17 is the powder of yellow, and molecular formula is
Zn0.90B0.04Li0.04O:0.02Bi, maximum emission wavelength are located near 620nm, and glow color is red.Held with 435nm blue lights
Light source is removed after continuous irradiation 5min, the twilight sunset of material can last about more than 60min.
Embodiment 18
Raw material is ZnO (analysis is pure), Bi2O3(spectroscopic pure), B2O3(analysis is pure) and Li2CO3(analysis pure), between them
Mol ratio is 0.90：0.01：0.02：0.02, raw material is weighed in above ratio, is placed into corundum crucible, places into after mixing
In high temperature furnace in air atmosphere 1000 DEG C roasting 12h, naturally cool to room temperature, obtain red long afterglow luminous material.
The red long afterglow luminous material obtained in embodiment 18 is the powder of yellow, and molecular formula is
Zn0.90B0.04Li0.04O:0.02Bi, maximum emission wavelength are located near 620nm, and glow color is red.Held with 435nm blue lights
Light source is removed after continuous irradiation 5min, the twilight sunset of material can last about more than 60min.
Embodiment 19
Raw material is ZnO (analysis is pure), Bi2O3(spectroscopic pure), B2O3(analysis is pure) and Li2CO3(analysis pure), between them
Mol ratio is 0.90：0.01：0.02：0.02, raw material is weighed in above ratio, is placed into corundum crucible, places into after mixing
In high temperature furnace in nitrogen atmosphere 1000 DEG C roasting 10h, naturally cool to room temperature, obtain red long afterglow luminous material.
The red long afterglow luminous material obtained in embodiment 19 is the powder of yellow, and molecular formula is
Zn0.90B0.04Li0.04O:0.02Bi, maximum emission wavelength are located near 620nm, and glow color is red.Held with 435nm blue lights
Light source is removed after continuous irradiation 5min, the twilight sunset of material can last about more than 60min.
Embodiment 20
Raw material is ZnO (analysis is pure), Bi2O3(spectroscopic pure), B2O3(analysis is pure) and Li2CO3(analysis pure), between them
Mol ratio is 0.90：0.01：0.02：0.02, raw material is weighed in above ratio, is placed into corundum crucible, places into after mixing
In high temperature furnace in oxygen atmosphere 1000 DEG C roasting 10h, naturally cool to room temperature, obtain red long afterglow luminous material.
The red long afterglow luminous material obtained in embodiment 20 is the powder of yellow, and molecular formula is
Zn0.90B0.04Li0.04O:0.02Bi, maximum emission wavelength are located near 620nm, and glow color is red.Held with 435nm blue lights
Light source is removed after continuous irradiation 5min, the twilight sunset of material can last about more than 60min.
Embodiment 21
Raw material is ZnO (analysis is pure), MgO (analysis is pure), Bi2O3(spectroscopic pure), B2O3(analysis is pure) and Li2CO3(analysis
It is pure), the mol ratio between them is 0.85：0.05：0.01：0.02：0.02, raw material is weighed in above ratio, is placed after mixing
Enter in corundum crucible, place into high temperature furnace 1000 DEG C of roasting 10h in air atmosphere, naturally cool to room temperature, obtain red length
Afterglow materials.
The red long afterglow luminous material obtained in embodiment 21 is the powder of yellow, and molecular formula is
Zn0.85Mg0.05B0.04Li0.04O:0.02Bi, maximum emission wavelength are located near 620nm, and glow color is red.It is blue with 435nm
Light source, sustainable more than the 80min of twilight sunset are removed after light chronic exposure 5min.
Embodiment 22
Raw material is ZnO (analysis is pure), MgO (analysis is pure), Bi2O3(spectroscopic pure), B2O3(analysis is pure) and Li2CO3(analysis
It is pure), the mol ratio between them is 0.80：0.10：0.01：0.02：0.02, raw material is weighed in above ratio, is placed after mixing
Enter in corundum crucible, place into high temperature furnace 1000 DEG C of roasting 10h in air atmosphere, naturally cool to room temperature, obtain red
Long after glow luminous material.
The red long afterglow luminous material obtained in embodiment 22 is the powder of yellow, and molecular formula is
Zn0.80Mg0.10B0.04Li0.04O:0.02Bi, maximum emission wavelength are located near 620nm, and glow color is red.It is blue with 435nm
Light source, sustainable more than the 90min of twilight sunset are removed after light chronic exposure 5min.
Embodiment 23
Raw material is ZnO (analysis is pure), MgO (analysis is pure), Bi2O3(spectroscopic pure), B2O3(analysis is pure) and Li2CO3(analysis
It is pure), the mol ratio between them is 0.70：0.20：0.01：0.02：0.02, raw material is weighed in above ratio, is placed after mixing
Enter in corundum crucible, place into high temperature furnace and be calcined 10h in 1000 DEG C, naturally cool to room temperature, obtain red long-afterglow and light
Material.
The red long afterglow luminous material obtained in embodiment 23 is the powder of yellow, and molecular formula is
Zn0.70Mg0.20B0.04Li0.04O:0.02Bi, maximum emission wavelength are located near 620nm, and glow color is red.It is blue with 435nm
Light source, sustainable more than the 70min of twilight sunset are removed after light chronic exposure 5min.
Claims (9)
- A kind of 1. red long afterglow luminous material, as shown in formula (I)：[Zn(1-x-y-z-n)MgxMyLz]O:nBi (I)；Wherein, the one or more in M B, Al, Ga, In, Zr, Si, Eu, Sc, Y, La, Nd, Gd, Dy and Lu, L are alkali metal One or more in atom；The x is that 0~0.4, y is that 0.0001~0.12, z is that 0.0001~0.15, n is 0.0001~0.1.
- 2. red long afterglow luminous material according to claim 1, it is characterised in that the alkali metal atom is Li, Na With the one or more in K.
- 3. red long afterglow luminous material according to claim 1, it is characterised in that the x is 0.05~0.2.
- 4. red long afterglow luminous material according to claim 1, it is characterised in that the y is 0.02~0.06.
- 5. red long afterglow luminous material according to claim 1, it is characterised in that the z is 0.02~0.08.
- 6. red long afterglow luminous material according to claim 1, it is characterised in that the n is 0.01~0.05.
- A kind of 7. preparation method of the red long afterglow luminous material described in claim 1, it is characterised in that including：Zinc source compound, magnesium source compound, bismuth source compound, alkali metal source compound and M source compounds are mixed, roasting, obtained To red long afterglow luminous material；The M is the one or more in B, Al, Ga, In, Zr, Si, Eu, Sc, Y, La, Nd, Gd, Dy and Lu；M atoms, alkali metal source compound in magnesium atom, M source compounds in zinc atom, magnesium source compound in the zinc source compound The mol ratio of middle alkali metal atom and bismuth atom in bismuth source compound is (1-x-y-z-n)：x：y：z：n；The x is 0~0.4, y It is that 0.0001~0.15, n is 0.0001~0.1 for 0.0001~0.12, z；The temperature of the roasting is 700 DEG C~1300 DEG C；The time of the roasting is 0.5~20h.
- 8. preparation method according to claim 7, it is characterised in that the zinc source compound is the oxide of zinc, zinc Carbonate, the nitrate of zinc, the oxalates of zinc and zinc acetate in one or more；The magnesium source compound is in the oxide of magnesium, the carbonate of magnesium, the nitrate of magnesium, the oxalates of magnesium and the acetate of magnesium One or more；The bismuth source compound is the one or more in the oxide, the carbonate of bismuth and the nitrate of bismuth of bismuth；The alkali metal source compound is one kind in the oxide, the carbonate of alkali metal and the nitrate of alkali metal of alkali metal It is or a variety of；One or more in oxide, M carbonate and M nitrate that the M source compounds are M.
- 9. preparation method according to claim 7, it is characterised in that the roasting is carried out in calcination atmosphere；The roasting Burning atmosphere is the one or more in air, nitrogen, argon gas and oxygen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610256393.1A CN105838362B (en) | 2016-04-21 | 2016-04-21 | A kind of red long afterglow luminous material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610256393.1A CN105838362B (en) | 2016-04-21 | 2016-04-21 | A kind of red long afterglow luminous material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105838362A CN105838362A (en) | 2016-08-10 |
| CN105838362B true CN105838362B (en) | 2018-04-10 |
Family
ID=56590229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610256393.1A Active CN105838362B (en) | 2016-04-21 | 2016-04-21 | A kind of red long afterglow luminous material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105838362B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2594325B2 (en) * | 1988-06-27 | 1997-03-26 | 日亜化学工業株式会社 | Mixed-length afterglow red-emitting phosphor and phosphor film |
| US6419854B1 (en) * | 1998-06-16 | 2002-07-16 | Sarnoff Corporation | Long persistence red phosphors and method of making |
| CN103160278A (en) * | 2013-03-20 | 2013-06-19 | 广东工业大学 | Red long-lasting phosphor material and preparation method thereof |
| CN103627287A (en) * | 2013-11-08 | 2014-03-12 | 青岛益群漆业集团有限公司 | High-strength anti-fouling internal wall paint |
| CN103923653B (en) * | 2014-05-05 | 2015-12-30 | 青岛大学 | A kind of red long afterglow luminous material and preparation method thereof |
-
2016
- 2016-04-21 CN CN201610256393.1A patent/CN105838362B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105838362A (en) | 2016-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110257057B (en) | Yellow long-afterglow luminescent material and preparation method thereof | |
| CN104087292B (en) | A kind of Mn 4+the red illuminating material adulterated, preparation method and novel illumination light source | |
| Cai et al. | Luminescent properties of Sr2B2O5: Tm3+, Na+ blue phosphor | |
| CN107189776B (en) | Green silicate long-afterglow luminescent material and preparation method thereof | |
| CN111196925A (en) | Mn4+Doped red fluorescent material and preparation method thereof | |
| Shih et al. | The luminescent properties of Pr3+ ion-doped BaY2ZnO5 phosphor under blue light irradiation | |
| CN111234814B (en) | Mn (manganese)4+Doped nitrogen oxide red fluorescent powder and preparation method thereof | |
| CN105524614B (en) | A kind of germanate red long afterglow luminous material and preparation method thereof | |
| CN104774609B (en) | A kind of long after glow luminous material and preparation method thereof | |
| CN114686225A (en) | Near-infrared fluorescent powder and preparation method and application thereof | |
| CN114437724A (en) | Gallate-based multicolor long-afterglow luminescent material and preparation method thereof | |
| CN107418571B (en) | Mn (manganese)2+Doped yellow long-afterglow luminescent material and preparation method thereof | |
| CN113717722B (en) | Bismuth ion doped borate narrow-band blue fluorescent powder, preparation method thereof and luminescent device | |
| CN103146381B (en) | Aluminate red phosphor activated by manganese ion and preparation method thereof | |
| CN107502350A (en) | A kind of praseodymium doped laminated perovskite type red long afterglow luminous material, Its Preparation Method And Use | |
| CN106147759A (en) | A kind of white light LEDs borate substrate fluorescent powder and preparation method thereof | |
| CN112980444B (en) | Garnet-based long-afterglow luminescent material and preparation method thereof | |
| CN105778904B (en) | A kind of gallium aluminium hydrochlorate base fluorescent material and preparation method thereof | |
| CN108949173B (en) | Cyan silicate ultra-long afterglow luminescent material and preparation method thereof | |
| CN105838362B (en) | A kind of red long afterglow luminous material and preparation method thereof | |
| CN108728088B (en) | Europium ion excited silicate white light fluorescent powder and preparation method thereof | |
| CN108276998B (en) | Trivalent samarium ion doped barium gadolinium titanate red fluorescent powder and preparation method thereof | |
| CN102337127A (en) | Long after-glow phosphorescent material and preparation method thereof | |
| CN107474838B (en) | Blue-green long-afterglow luminescent material and preparation method thereof | |
| CN104194781B (en) | Long persistence luminescent material with single substrate and adjustable persistence colors and preparation method of long persistence luminescent material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |