CN108998017A - One kind near-infrared long after glow luminous material of matrix containing silicon spinel and preparation method thereof - Google Patents
One kind near-infrared long after glow luminous material of matrix containing silicon spinel and preparation method thereof Download PDFInfo
- Publication number
- CN108998017A CN108998017A CN201810778552.3A CN201810778552A CN108998017A CN 108998017 A CN108998017 A CN 108998017A CN 201810778552 A CN201810778552 A CN 201810778552A CN 108998017 A CN108998017 A CN 108998017A
- Authority
- CN
- China
- Prior art keywords
- long
- glow luminous
- infrared
- luminous material
- containing silicon
- 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.)
- Pending
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
- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
- C09K11/68—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten
- C09K11/685—Aluminates; Silicates
Abstract
One kind near-infrared long after glow luminous material of matrix containing silicon spinel and preparation method thereof, belongs to long after glow luminous material technical field.The preparation method of the near-infrared long after glow luminous material of matrix containing silicon spinel, it using zinc compound, gallium-containing compound, silicon-containing compound, containing chromium compound as raw material, solid powder raw material is ground to obtain presoma, it puts into crucible high temperature furnace and is warming up to 1100 DEG C of -1400 DEG C of roasting temperatures 1-3 times, gained product of roasting is crushed, grinds to obtain the near-infrared long after glow luminous material of matrix containing silicon spinel.Low raw-material cost of the invention, simple possible, it is low for equipment requirements, it will not melten glass through 1400 DEG C of high temperature sinterings, there is long after glow luminous material of the present invention transmitting range to be located near infrared region, and the advantageous properties such as afterglow intensity is strong, persistence is long, and luminous efficiency is good, can effectively excite within the scope of 250nm-600nm, emission wavelength range is between 600-850nm.
Description
Technical field
The invention belongs to long after glow luminous material technical fields, are related to a kind of near-infrared long afterglow of matrix containing silicon spinel hair
Luminescent material and preparation method thereof may be used to indicate illumination and image checking field.
Background technique
Long after glow luminous material is that one kind can absorb-store extraneous optical radiation energy, and slowly release shining for light
Material.This characteristic is widely used in guidance lighting, such as emergency exit sign, passageway for fire apparatus, building decoration field, closely
Gradually to expand to the application fields such as bio-imaging, information storage again.The long-afterglow material of existing visible region is broadly divided into indigo plant
Light, green light and red light material, wherein the optical properties such as luminous intensity and persistence of blue and green luminescent material are
The requirement of practical application is reached.But red long afterglow material luminous intensity and persistence are relatively poor, constrain it and answer
With.
In recent years, near-infrared long-afterglow material receives significant attention in bio-imaging field, but near-infrared long afterglow material
Material will be lower than blue and green long afterglow fluorescent material either in fluorescence intensity or on persistence.Main cause
There are two aspects: one, few with near-infrared luminous luminescent center ion (mainly includes Cr3+、Mn2+、Mn4+Deng), make close red
The launch wavelength adjustability of outer long after glow luminous material is limited；Two: being suitble to the matrix of above-mentioned luminescent center ion doping few, cause
The property of optimization long-afterglow material is difficult.Therefore, the matrix for finding new long after glow luminous material is particularly important.Report at present
In the near-infrared long-afterglow material in road, most representative is Cr3+The spinelle matrix near-infrared long after glow luminous material of doping
ZnGa2O4:Cr3+.Because in spinelle ZnGa2O4In, rich in the antistructure defect exchanged due to Zn and Ga case.Just because of this
Kind of antistructure defect plays the role of the trap for storing carrier, and just making to change material has preferable afterglow intensity and time,
But still have with a distance from very big from practical application.This patent is based on non-equivalence replacement policy, proposes to construct a kind of siliceous spinelle
Matrix near-infrared long after glow luminous material.Point defect caused by richer non-equivalence is replaced can be obtained within this material, i.e., more
More trap for being used to store carrier, to realize better afterglow property.
Summary of the invention
The purpose of the present invention is to provide near-infrared long after glow luminous material of matrix containing silicon spinel and preparation method thereof,
The cost of material is low, simple process, luminous efficiency are good for this, can effectively excite within the scope of 250nm-600nm, emission wavelength model
It encloses between 600-850nm.
One kind near-infrared long after glow luminous material of matrix containing silicon spinel, it is characterised in that the luminescent material
Chemical expression are as follows:
Zn2+aGaa(2-x)SiO4+4a:xCr3+
In formula: 0 < a≤20,0.001≤x≤0.1.
One kind near-infrared long after glow luminous material of matrix containing silicon spinel, it is characterised in that 0.1≤a≤10,
0.002≤x≤0.03。
One kind near-infrared long after glow luminous material of matrix containing silicon spinel, it is characterised in that 2≤a≤7,0.003
≤x≤0.015；Preferably a=5 or 6,0.005≤x≤0.01.
The preparation method of the near-infrared long after glow luminous material of matrix containing silicon spinel, it is characterised in that contain zinc impregnation
It closes object, gallium-containing compound, silicon-containing compound, contain chromium compound for raw material, matrix containing silicon spinel is made using high temperature solid-state method
Near-infrared long after glow luminous material.
The method of the near-infrared long after glow luminous material of matrix containing silicon spinel, it is characterised in that including following step
It is rapid:
1) chemical expression Zn is pressed2+aGaa(2-x)SiO4+4a:xCr3+In stoichiometric ratio, weigh corrresponding quality respectively
Raw material zinc compound, silicon-containing compound, contains chromium compound at gallium-containing compound, and solid powder raw material is ground to obtain forerunner
Body；
2) presoma is put into crucible, under air or nitrogen atmosphere, 1100 DEG C -1400 DEG C is warming up in high temperature furnace
Roasting temperature 1-3 times, gained product of roasting are crushed, grind to obtain the near-infrared long after glow luminous material of matrix containing silicon spinel.
The method of the near-infrared long after glow luminous material of matrix containing silicon spinel, it is characterised in that grinding in agate or
It is carried out in corundum mortar, milling time 10-30min.
The method of the near-infrared long after glow luminous material of matrix containing silicon spinel, it is characterised in that raw material is each element
Oxide, preferably zinc oxide, gallium oxide, silica, chromium oxide.
The method of the near-infrared long after glow luminous material of matrix containing silicon spinel, it is characterised in that in step 2) every time
Calcining time is 3-24 hours, and heating rate is 5 DEG C/min~15 DEG C/min.
Compared with prior art, beneficial effects of the present invention are as follows:
The near-infrared long after glow luminous material of matrix containing silicon spinel obtained by the present invention, extends long-afterglow material to base
The alternative of matter improves the performance of the red afterglowing material of near-infrared.The present invention is prepared more than the near-infrared of matrix containing silicon spinel length
Low raw-material cost used in brightness luminescent material, simple possible, it is low for equipment requirements, it will not be melted through 1400 DEG C of high temperature sinterings
Melt vitrifying, there is long after glow luminous material of the present invention transmitting range to be located near infrared region, and afterglow intensity is strong, twilight sunset
The advantageous properties such as time length, and luminous efficiency is good, can effectively excite within the scope of 250nm-600nm, emission wavelength range
Between 600-850nm.
Detailed description of the invention
Fig. 1 is the excitation spectrum of the near-infrared long after glow luminous material of matrix containing silicon spinel made from the embodiment of the present invention 1
And launching light spectrogram, in figure, bold portion is exciting light spectrogram, and dotted portion is launching light spectrogram；
Fig. 2 is the X-ray diffraction of the near-infrared long after glow luminous material of matrix containing silicon spinel made from the embodiment of the present invention 1
Spectrogram；
Fig. 3 is the decay of afterglow of the near-infrared long after glow luminous material of matrix containing silicon spinel made from the embodiment of the present invention 1
Spectrogram.
Specific embodiment
In order to which the present invention is further explained, so that those skilled in the art can be further understood that the present invention, tie below
Embodiment is closed the preparation of the near-infrared long after glow luminous material of matrix containing silicon spinel is described in detail:
Embodiment 1: a kind of siliceous spinel structure near-infrared long-afterglow material, material be it is powdered, molecular formula is as follows:
Zn6Ga7.84SiO20:0.04Cr3+.It is 99.9% or more oxidation with purity the preparation method is as follows: measuring ratio according to molecular formula
Zinc, gallium oxide, silica, chromium oxide be raw material, specific quality be respectively 1.1233g, 1.6900g, 0.1382g,
0.0070g.In the agate mortar by above-mentioned raw materials mixture, grinding uniformly, is fitted into corundum crucible, in nitrogen inert atmosphere
In, 1350 DEG C are warming up to the heating rate of 10 DEG C/min, after keeping the temperature primary roasting 8 hours, room temperature is cooled to the furnace, through broken
It is broken, grind siliceous spinel structure near-infrared long-afterglow material, excitation spectrum and launching light spectrogram as shown in Figure 1, in figure,
Bold portion is exciting light spectrogram, and dotted portion is launching light spectrogram；X-ray diffraction spectrogram is as shown in Figure 2；Decay of afterglow spectrogram
As shown in figure 3, emission wavelength range is located at 600- as can be seen from Fig. 1 it can be seen that material is Spinel from chart sign
Between 850nm, the peak position of emission peak is located at 694nm or so, and twilight sunset can continue more than for 24 hours.
Embodiment 2:
A kind of siliceous spinel structure near-infrared long-afterglow material, material be it is powdered, molecular formula is as follows:
Zn3Ga1.99SiO8:0.01Cr3+.It is 99.9% or more oxidation with purity the preparation method is as follows: measuring ratio according to molecular formula
Zinc, gallium oxide, silica, chromium oxide be raw material, specific quality be respectively 1.4652g, 1.1191g, 0.3605g,
0.0046g.In the agate mortar by above-mentioned raw materials mixture, grinding uniformly, is fitted into corundum crucible, in air atmosphere, with
The heating rate of 10 DEG C/min is warming up to 900 DEG C, after keeping the temperature primary roasting 8 hours, cools to room temperature with the furnace.By the sample of pre-burning
Product take out regrinding, then are warming up to 1350 DEG C of calcinings with the heating rate of 10 DEG C/min, after keeping the temperature primary roasting 8 hours, with
Furnace is cooled to room temperature.Resulting materials are Spinel, and emission wavelength range is between 600-850nm, the peak position position of emission peak
In 695nm or so, twilight sunset can continue more than for 24 hours.
Embodiment 3:
A kind of siliceous spinel structure near-infrared long-afterglow material, material be it is powdered, molecular formula is as follows:
Zn4Ga3.96SnO12:0.02Cr3+.It is 99.9% or more oxidation with purity the preparation method is as follows: measuring ratio according to molecular formula
Zinc, gallium oxide, silica, chromium oxide be raw material, specific quality be respectively 1.2698g, 1.4475g, 0.2343g,
0.0059g.In the agate mortar by above-mentioned raw materials mixture, grinding uniformly, is fitted into corundum crucible, in air atmosphere, with
The heating rate of 15 DEG C/min is warming up to 1400 DEG C, after keeping the temperature primary roasting 12 hours, cools to room temperature with the furnace.Resulting materials are
Spinel, emission wavelength range is between 600-850nm, and the peak position of emission peak is located at 694nm or so, and twilight sunset can continue
More than for 24 hours.
Embodiment 4:
A kind of siliceous spinel structure near-infrared long-afterglow material, material be it is powdered, molecular formula is as follows:
Zn8Ga11.64SiO28:0.06Cr3+.It is 99.9% or more oxygen with purity the preparation method is as follows: measuring ratio according to molecular formula
Change zinc, gallium oxide, silica, chromium oxide be raw material, specific quality be respectively 1.0745g, 1.8001g, 0.0991g,
0.0075g.In the agate mortar by above-mentioned raw materials mixture, grinding uniformly, is fitted into corundum crucible, in nitrogen atmosphere, with
The heating rate of 10 DEG C/min is warming up to 1300 DEG C, after keeping the temperature primary roasting 12 hours, cools to room temperature with the furnace.Resulting materials are
Spinel, emission wavelength range is between 600-850nm, and the peak position of emission peak is located at 694nm or so, and twilight sunset can continue
More than for 24 hours.
Embodiment 5:
A kind of siliceous spinel structure near-infrared long-afterglow material, material be it is powdered, molecular formula is as follows:
Zn10Ga15.36SiO36:0.08Cr3+.It is 99.9% or more oxygen with purity the preparation method is as follows: measuring ratio according to molecular formula
Change zinc, gallium oxide, silica, chromium oxide be raw material, specific quality be respectively 1.0419g, 1.8427g, 0.0769g,
0.0078g.In the agate mortar by above-mentioned raw materials mixture, grinding uniformly, is fitted into corundum crucible, in nitrogen atmosphere, with
The heating rate of 10 DEG C/min is warming up to 600 DEG C, after keeping the temperature primary roasting 6 hours, cools to room temperature with the furnace.By the sample of pre-burning
Product take out regrinding, then are warming up to 900 DEG C of calcinings with the heating rate of 10 DEG C/min, after keeping the temperature primary roasting 6 hours, with furnace
It is cooled to room temperature.Sample is taken out again and is regrind, then 1350 DEG C of calcinings, heat preservation one are warming up to the heating rate of 10 DEG C/min
After secondary roasting 6 hours, room temperature is cooled to the furnace.Resulting materials are Spinel, emission wavelength range be located at 600-850nm it
Between, the peak position of emission peak is located at 694nm or so, and twilight sunset can continue more than for 24 hours.
Embodiment 6:
A kind of siliceous spinel structure near-infrared long-afterglow material, material be it is powdered, molecular formula is as follows:
Zn12Ga19SiO44:0.1Cr3+.It is 99.9% or more oxidation with purity the preparation method is as follows: measuring ratio according to molecular formula
Zinc, gallium oxide, silica, chromium oxide be raw material, specific quality be respectively 1.0256g, 1.8698g, 0.0631g,
0.0080g.In the agate mortar by above-mentioned raw materials mixture, grinding uniformly, is fitted into corundum crucible, in air atmosphere, with 5
DEG C/heating rate of min is warming up to 1350 DEG C, after keeping the temperature primary roasting 15 hours, cool to room temperature with the furnace.Resulting materials are point
Spar phase, emission wavelength range is between 600-850nm, and the peak position of emission peak is located at 694nm or so, and twilight sunset can continue for 24 hours
More than.
Claims (8)
1. a kind of near-infrared long after glow luminous material of matrix containing silicon spinel, it is characterised in that the chemistry expression of the luminescent material
Formula are as follows:
Zn2+aGaa(2-x)SiO4+4a:xCr3+
In formula: 0 < a≤20,0.001≤x≤0.1.
2. one kind near-infrared long after glow luminous material of matrix containing silicon spinel according to claim 1, it is characterised in that 0.1
≤ a≤10,0.002≤x≤0.03.
3. one kind near-infrared long after glow luminous material of matrix containing silicon spinel according to claim 1, it is characterised in that 2≤
A≤7,0.003≤x≤0.015；Preferably a=5 or 6,0.005≤x≤0.01.
4. a kind of preparation method of the near-infrared of matrix containing silicon spinel long after glow luminous material according to claim 1,
It is characterized in that using zinc compound, gallium-containing compound, silicon-containing compound, contains chromium compound as raw material, using high temperature solid-state legal system
Silicon spinel matrix near-infrared long after glow luminous material must be contained.
5. the method for the near-infrared of matrix containing silicon spinel long after glow luminous material according to claim 4, it is characterised in that
The following steps are included:
1) chemical expression Zn is pressed2+aGaa(2-x)SiO4+4a:xCr3+In stoichiometric ratio, weigh the raw material of corrresponding quality respectively
Zinc compound, silicon-containing compound, contains chromium compound at gallium-containing compound, and solid powder raw material is ground to obtain presoma；
2) presoma is put into crucible, under air or nitrogen atmosphere, 1100 DEG C of -1400 DEG C of temperature is warming up in high temperature furnace
Lower roasting 1-3 times, gained product of roasting is crushed, grinds to obtain the near-infrared long after glow luminous material of matrix containing silicon spinel.
6. the method for the near-infrared of matrix containing silicon spinel long after glow luminous material according to claim 5, it is characterised in that
Grinding carries out in agate or corundum mortar, milling time 10-30min.
7. the method for the near-infrared of matrix containing silicon spinel long after glow luminous material according to claim 5, it is characterised in that
Raw material is the oxide of each element, preferably zinc oxide, gallium oxide, silica, chromium oxide.
8. the method for the near-infrared of matrix containing silicon spinel long after glow luminous material according to claim 5, it is characterised in that
Each calcining time is 3-24 hours in step 2), and heating rate is 5 DEG C/min~15 DEG C/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810778552.3A CN108998017A (en) | 2018-07-16 | 2018-07-16 | One kind near-infrared long after glow luminous material of matrix containing silicon spinel and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810778552.3A CN108998017A (en) | 2018-07-16 | 2018-07-16 | One kind near-infrared long after glow luminous material of matrix containing silicon spinel and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108998017A true CN108998017A (en) | 2018-12-14 |
Family
ID=64598426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810778552.3A Pending CN108998017A (en) | 2018-07-16 | 2018-07-16 | One kind near-infrared long after glow luminous material of matrix containing silicon spinel and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108998017A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110713831A (en) * | 2019-10-30 | 2020-01-21 | 广东省稀有金属研究所 | Near-infrared long-afterglow luminescent material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103131409A (en) * | 2013-03-20 | 2013-06-05 | 广东工业大学 | Red long-afterglow gallate and preparation method thereof |
| CN103923653A (en) * | 2014-05-05 | 2014-07-16 | 青岛大学 | Red long-afterglow luminescent material and preparation method thereof |
| CN105754595A (en) * | 2016-03-28 | 2016-07-13 | 武汉大学 | Long-afterglow nanomaterial based on ion doping as well as preparation method and application of long-afterglow nanomaterial |
-
2018
- 2018-07-16 CN CN201810778552.3A patent/CN108998017A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103131409A (en) * | 2013-03-20 | 2013-06-05 | 广东工业大学 | Red long-afterglow gallate and preparation method thereof |
| CN103923653A (en) * | 2014-05-05 | 2014-07-16 | 青岛大学 | Red long-afterglow luminescent material and preparation method thereof |
| CN105754595A (en) * | 2016-03-28 | 2016-07-13 | 武汉大学 | Long-afterglow nanomaterial based on ion doping as well as preparation method and application of long-afterglow nanomaterial |
Non-Patent Citations (2)
| Title |
|---|
| MATHIEU ALLIX ET AL.: "Considerable Improvement of Long-Persistent Luminescence in Germanium and Tin Substituted ZnGa2O4", 《CHEM. MATER.》 * |
| 张万鑫: "红色和近红外长余辉材料的探索", 《中国优秀硕士学位论文全文数据库基础科学辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110713831A (en) * | 2019-10-30 | 2020-01-21 | 广东省稀有金属研究所 | Near-infrared long-afterglow luminescent material and preparation method and application thereof |
| CN110713831B (en) * | 2019-10-30 | 2022-02-22 | 广东省稀有金属研究所 | Near-infrared long-afterglow luminescent material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kemere et al. | Luminescence properties of Eu, RE3+ (RE= Dy, Sm, Tb) co-doped oxyfluoride glasses and glass–ceramics | |
| CN108998018A (en) | A kind of Cr3+The stanniferous mixing spinelle near-infrared long after glow luminous material and preparation method thereof of doping | |
| CN110194593B (en) | Method for promoting crystallization of all-inorganic perovskite quantum dots in glass by adding fluoride | |
| CN108285272A (en) | A kind of CsPb2Br5Quantum dot microcrystal glass material and preparation method thereof | |
| CN112877069B (en) | Cr (chromium) 3+ Doped gallium aluminate near-infrared long-afterglow luminescent material and preparation method thereof | |
| CN108998016A (en) | A kind of Cr3+Mixing spinelle matrix near-infrared long after glow luminous material of doping and preparation method thereof | |
| Shan et al. | Luminescent properties of Tb3+ doped high density borogermanate scintillating glasses | |
| CN110257064A (en) | Chromium ion-doped germanium silicate near-infrared long after glow luminous material and preparation method thereof | |
| CN112342021A (en) | Near-infrared broadband emission luminescent material, preparation method thereof and luminescent device comprising material | |
| CN108623167A (en) | A kind of laser glass material and preparation method thereof | |
| CN101723593A (en) | Luminous glass ceramic used for LED white-light illumination and preparation method thereof | |
| CN109021973A (en) | A kind of double-perovskite type molybdate red phosphor and preparation method thereof | |
| Qiang et al. | ZnAl2O4: Cr3+ translucent ceramic phosphor with thermally stable far-red luminescence | |
| CN104403668A (en) | Silicate green fluorescent powder and preparation method thereof | |
| Zhang et al. | Pr3+/Ho3+ co-doped glass phosphors for application in warm white light-emitting diodes | |
| CN108998017A (en) | One kind near-infrared long after glow luminous material of matrix containing silicon spinel and preparation method thereof | |
| CN105670622A (en) | Red fluorescent material for LED lamps for plant growth and preparation method of red fluorescent material | |
| CN100386405C (en) | Red long afterglow luminescent material and its prepn | |
| CN103014864B (en) | A kind of mid-infrared luminescent crystal material, and preparation method and application | |
| CN106753347A (en) | A kind of near ultraviolet excitated red fluorescence powder and preparation method thereof | |
| CN102051175B (en) | Lanthanide series gallate luminous material and preparation method thereof | |
| CN108690617B (en) | White light L ED fluorescent material and preparation method thereof | |
| CN104059640B (en) | A kind of borate fluorescent powder substrate and the preparation method of fluorescent material | |
| CN104445929A (en) | Heavy metal oxide block glass material for up-conversion of white light and method for enhancing illumination intensity of heavy metal oxide block glass material | |
| CN108148583A (en) | A kind of near-infrared long after glow luminous material of aluminate-base and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181214 |
|
| RJ01 | Rejection of invention patent application after publication |