CN109161968A - A kind of red long-afterglow single crystal material and preparation method thereof - Google Patents
A kind of red long-afterglow single crystal material and preparation method thereof Download PDFInfo
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- CN109161968A CN109161968A CN201810977502.8A CN201810977502A CN109161968A CN 109161968 A CN109161968 A CN 109161968A CN 201810977502 A CN201810977502 A CN 201810977502A CN 109161968 A CN109161968 A CN 109161968A
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- afterglow
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
- C30B29/30—Niobates; Vanadates; Tantalates
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/36—Single-crystal growth by pulling from a melt, e.g. Czochralski method characterised by the seed, e.g. its crystallographic orientation
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- Crystallography & Structural Chemistry (AREA)
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- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a kind of red long-afterglow crystalline materials and preparation method thereof.The long-afterglow material is monocrystal, and structure belongs to trigonal system, ABO3Type, chemical formula LiNbO3:Mg2+,Pr3+.In formula, LiNbO3For matrix, Mg2+And Pr3+For doping component.Doping component Mg2+Content be matrix 1 ~ 6mol%, doping component Pr3+Content be matrix 1 ~ 3mol%.Preparation method includes ingredient, pre-sintering and Czochralski grown.The long-persistence luminous crystal of red lanthanide prepared by the present invention, can be excited by ultraviolet light, can also be excited by x-ray bombardment, be emitted red light (619 nanometers of central wavelength), and have long after-glow.The present invention can have many advantages, such as low cost, high thermal stability and mechanical stability in the applications such as ultraviolet light and X-ray detection, optical storage, security identifier, high temp sensitive and power sensing.
Description
Technical field
The invention belongs to long after glow luminous material fields, specifically, being related to a kind of red long afterglow material and its preparation
Method.
Background technique
Long-afterglow material refers to that material is receiving high energy excitation (visible light, ultraviolet light, X-ray, ray and electron beam etc.)
Afterwards, the optical phenomena to shine for a long time in visible light wave range or near infrared band.It is such to shine, it can stop from excitation
Continue a few minutes, a few houres even several days after only.Based on this special function, long-afterglow material is widely used in safety
Mark, luminous energy storage, power and temperature sensor, biological living image, treatment of cancer, solar energy photoelectric conversion and photocatalysis etc. are all
It is multi-field.In recent years, the research in relation to long-afterglow material be concentrated mainly on expansion excitation and transmitting range and it is longer luminous when
Between etc., and as photoelectric device is integrated and the fast development of multifunction, integrated multi-functional long-afterglow material will be
One important development direction in the field.It is a kind of or more by using ferroelectricity, piezoelectricity, ferromagnetic, electric light and press polish etc. is provided simultaneously with
The basis material of kind characteristic is realized and is regulated and controled to the various dimensions of long afterglow property, will be the important of the following multi-functional long-afterglow material
Feature.
Lithium columbate crystal has excellent ferroelectricity, piezoelectricity, electric light and turns as a kind of famous multifunctional optical material
Change and the performances such as press polish conversion, or a kind of important integrated optical material.Optical property in relation to niobic acid lithium material, shine spy
Property research be current basal research and application study hot topic.However, existing by the long afterglow of basis material of lithium columbate crystal
As not having been reported that yet so far.
Summary of the invention
For overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of lithium niobate crystals with long afterglow performance
Body material can be excited by ultraviolet light and X-ray, emit feux rouges and have longer persistence.
The technical solution adopted in the present invention is as follows:
A kind of red long-afterglow crystalline material, chemical formula LiNbO3:Pr3+:Mg2+, wherein doping component Pr3+Concentration be 1
~ 3mol% adulterates component Mg2+Concentration be 1 ~ 5mol%.The monocrystal material has the red long-afterglow characteristics of luminescence.Its exciting light
For near ultraviolet and blue light, near ultraviolet region wavelength is 300-410nm, and blue region wavelength is 460-470n.Its exciting light
It may be X-ray.
The preparation method of above-mentioned red long-afterglow crystalline material, comprising the following steps:
(1) ingredient: pure Lithium Carbonate and niobium pentaoxide are prepared according to molar ratio Li/Nb=0.946:1, be added magnesia and
The mixing of praseodymium oxide powder, is placed in ground and mixed in ball mill；
(2) it is sintered: the resulting uniform mixed-powder of step (1) being added in platinum crucible, is placed in Muffle furnace and is warming up to
It 700 DEG C, is kept for 3 hours, then with 250 DEG C/h of rates, is warming up to 1150 DEG C and is kept for 10 hours, be then slowly dropped to room temperature,
To polycrystalline material；
(3) crystal growth: by step (2) polycrystalline material as in platinum crucible, and crucible is placed in Czochralski grown dress
In setting, 1230 DEG C or more are heated to, using c to the seed crystal seeding of cutting, grows crystal along c-axis.
In the preparation method of above-mentioned red long-afterglow monocrystal material: step (3) described crystal is consolidated along what c-axis was grown
Liquid interface temperature gradient maintains 28 DEG C/mm.
In the preparation method of above-mentioned red long-afterglow monocrystal material: the brilliant rotary speed of step (3) described crystal is 15
Rev/min.
In the preparation method of above-mentioned red long-afterglow monocrystal material: step (3) the Czochralski grown device mentions
Pulling rate degree is 1.5 mm/h.
Compared with current material and technology, advantages of the present invention and useful effect are:
(1) material of the present invention can also use X-ray other than it can use ultraviolet excitation and be excited with visible blue light
Excitation, has the potentiality as X-ray detection and energy stores.
(2) in addition to having long afterglow qualities, material of the present invention is also equipped with ferroelectricity, piezoelectricity and abundant optical
Can, it provides the foundation to regulate and control long afterglow performance by means such as ferroelectricity, piezoelectricity and mechanical forces.
(3) integrated optical material that material of the present invention is famous as one kind, has excellent performance is long-afterglow material
It is integrated to provide possibility.
(4) material of the present invention has excellent thermal stability and mechanical performance, can be used as the high temperature of function admirable
Sensor and force snesor.
(5) preparation process of material of the present invention is suitable for industrialization large-scale production, low in cost, has very high
Application potential.
Detailed description of the invention
Fig. 1 is the exciting light spectrogram of red long-afterglow crystalline material；
Fig. 2 is red long-afterglow crystalline material respectively by the launching light spectrogram of ultraviolet excitation and excitation of X-rays；
Fig. 3 is the burst of ultraviolel and excitation of X-rays decay curve figure of red long-afterglow crystalline material.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are not
It is limited to this.
Embodiment 1:
(1) pure Lithium Carbonate and niobium pentaoxide are prepared according to molar ratio Li/Nb=0.946:1, magnesia and praseodymium oxide is added
Powder mixing, is placed in ground and mixed 48 hours in ball mill.
(2) the resulting uniform mixed-powder of step (1) is added in platinum crucible, is placed in Muffle furnace and is warming up to
It 700 DEG C, is kept for 3 hours, then with 250 DEG C/h of rates, is warming up to 1150 DEG C and is kept for 10 hours, be then slowly dropped to room temperature,
To polycrystalline material.
(3) by step (2) polycrystalline material as in platinum crucible, and crucible is placed in Czochralski grown device,
1230 DEG C or more are heated to, using c to the seed crystal seeding of cutting, grows crystal along c-axis.It, will by automatic temperature control technology
Crystal growth temperature gradient of solid-liquid interface maintains 28 DEG C/mm, and brilliant rotary speed is 15 revs/min, and pull rate is 1.5 mm/h.
(4) growth 60 hours is maintained by step (3), by 50 DEG C/h of near room temperatures of rate of temperature fall, obtains good niobic acid
Lithium monocrystal.
(5) the crystal vertical-growth direction of growth is sliced, and is polished, obtain sample wafer.
The excitation spectrum of red long-afterglow crystalline material manufactured in the present embodiment is as shown in Figure 1, at 300 nanometers -420 nanometers
There are a wide excitation band, there are three excitation peaks for 462 nanometers, 487 nanometers and 501 nanometers.
The emission spectrum of red long-afterglow crystalline material manufactured in the present embodiment is as shown in Fig. 2, wherein red solid line is 365
The emission spectrum of nano-ultraviolet light excitation, emission peak are 619 nanometers；Blue dotted line is the emission spectrum of excitation of X-rays, emission peak
It also is 619 nanometers.
The long afterglow curve of red long-afterglow crystalline material manufactured in the present embodiment is as shown in figure 3, wherein blue dotted line is X
The decay curve of ray excitation；Red solid line is the decay curve of ultraviolet excitation.Persistence is 10 minutes.
Claims (7)
1. a kind of red long-afterglow monocrystal material, which is characterized in that chemical formula LiNbO3:Pr3+:Mg2+, wherein adulterating component
Pr3+Concentration be 1 ~ 3mol%, adulterate component Mg2+Concentration be 1 ~ 5mol%.
2. red long-afterglow crystalline material as described in claim 1, which is characterized in that its exciting light be near ultraviolet and blue light,
Near ultraviolet region wavelength is 300-410nm, and blue region wavelength is 460-470n.
3. red long-afterglow crystalline material as described in claim 1, which is characterized in that its exciting light is X-ray.
4. the preparation method of red long-afterglow monocrystal material described in claim 1, which comprises the steps of:
(1) ingredient: pure Lithium Carbonate and niobium pentaoxide are prepared according to molar ratio Li/Nb=0.946:1, be added magnesia and
The mixing of praseodymium oxide powder, is placed in ground and mixed in ball mill；
(2) it is sintered: the resulting uniform mixed-powder of step (1) being added in platinum crucible, is placed in Muffle furnace and is warming up to
It 700 DEG C, is kept for 3 hours, then with 250 DEG C/h of rates, is warming up to 1150 DEG C and is kept for 10 hours, be then slowly dropped to room temperature,
To polycrystalline material；
(3) crystal growth: by step (2) polycrystalline material as in platinum crucible, and crucible is placed in Czochralski grown dress
In setting, 1230 DEG C or more are heated to, using c to the seed crystal seeding of cutting, grows crystal along c-axis.
5. the preparation method of red long-afterglow monocrystal material according to claim 4, it is characterised in that: step (3) is described
Crystal maintains 28 DEG C/mm along the temperature gradient of solid-liquid interface that c-axis is grown.
6. the preparation method of red long-afterglow monocrystal material according to claim 4, it is characterised in that: step (3) is described
The brilliant rotary speed of crystal is 15 revs/min.
7. the preparation method of red long-afterglow monocrystal material according to claim 4, it is characterised in that: step (3) is described
The pull rate of Czochralski grown device is 1.5 mm/h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109763171A (en) * | 2019-03-27 | 2019-05-17 | 焦作科尔光电科技有限公司 | One kind mixing praseodymium lithium columbate crystal and preparation method thereof |
| CN112898967A (en) * | 2021-01-30 | 2021-06-04 | 济南大学 | Low-temperature solution method synthesis process of novel long-afterglow perovskite crystal |
| CN114907847A (en) * | 2022-05-18 | 2022-08-16 | 五邑大学 | Fluorescent temperature measuring material and preparation method and application thereof |
| CN115873594A (en) * | 2022-12-06 | 2023-03-31 | 济南大学 | Low-temperature solution method synthesis process of transparent cadmium-based long-afterglow crystal |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109763171A (en) * | 2019-03-27 | 2019-05-17 | 焦作科尔光电科技有限公司 | One kind mixing praseodymium lithium columbate crystal and preparation method thereof |
| CN112898967A (en) * | 2021-01-30 | 2021-06-04 | 济南大学 | Low-temperature solution method synthesis process of novel long-afterglow perovskite crystal |
| CN112898967B (en) * | 2021-01-30 | 2022-11-25 | 济南大学 | Low-temperature solution method synthesis process of novel long-afterglow perovskite crystal |
| CN114907847A (en) * | 2022-05-18 | 2022-08-16 | 五邑大学 | Fluorescent temperature measuring material and preparation method and application thereof |
| CN114907847B (en) * | 2022-05-18 | 2023-01-03 | 五邑大学 | Fluorescent temperature measuring material and preparation method and application thereof |
| CN115873594A (en) * | 2022-12-06 | 2023-03-31 | 济南大学 | Low-temperature solution method synthesis process of transparent cadmium-based long-afterglow crystal |
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| CN109161968B (en) | 2021-01-08 |
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