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CN103897695B - A kind of orange red rare earth long-afterglow luminescent material being applicable near ultraviolet excitation and preparation method thereof - Google Patents

A kind of orange red rare earth long-afterglow luminescent material being applicable near ultraviolet excitation and preparation method thereof Download PDF

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CN103897695B
CN103897695B CN201410009895.5A CN201410009895A CN103897695B CN 103897695 B CN103897695 B CN 103897695B CN 201410009895 A CN201410009895 A CN 201410009895A CN 103897695 B CN103897695 B CN 103897695B
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rare earth
luminescent material
orange red
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afterglow luminescent
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CN103897695A (en
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汪正良
胡芬芬
周美丽
朱怡雯
程萍
郭俊明
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Yunnan Minzu University
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Yunnan Minzu University
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Abstract

The present invention relates to white light emitting diode field, disclose a kind of preparation method being applicable to the orange red rare earth long-afterglow luminescent material of near ultraviolet excitation.The chemical constitution of orange red rare earth long-afterglow luminescent material of the present invention is: M iI 3 (1-x-y)m iII 2o 5cl 2: xEu 2+, yR iII.M iIfor alkaline-earth metal ions Sr 2+, Ba 2+in one two several; M iIIfor Al 3+, B 3+in one or both; R iIIfor Dy 3+, Nd 3+, La 3+, Pr 3+in one; X, y are the relative M of corresponding dopant ion iImolar percentage coefficient shared by ion, 0.0≤x≤0.50,0.0≤y≤0.20.Orange red rare earth long-afterglow luminescent material of the present invention adopts high temperature solid-state method preparation.Orange red fluorescent powder of the present invention is under near ultraviolet excitation, and be emitted as master with the orange of 600nm, luminous efficiency is high; Be placed in camera bellows at ultra violet lamp 30 min of 365nm, its time of persistence can reach 4h.

Description

A kind of orange red rare earth long-afterglow luminescent material being applicable near ultraviolet excitation and preparation method thereof
Technical field
The present invention relates to a kind of orange red rare earth long-afterglow luminescent material and preparation method thereof, specifically, is a kind of orange red rare earth long-afterglow luminescent material being applicable near ultraviolet excitation and preparation method thereof.Belong to rare earth material preparation field.
Background technology
The problems such as current environment pollution and energy dilemma have caused countries in the world extensive concern, and novel " energy-conservation " and " green " have become the study hotspot of material science.Long after glow luminous material (also known as long persistence luminescent powder) is a kind of novel energy-saving and environmental protection shaped material, it does not need external power source to provide energy, the energy of energy automatic absorption sunlight or light, and portion of energy is wherein stored in the material, then the energy stored in material by the form slow release of visible ray out.Utilize its this characteristic, long after glow luminous material beautifies in low light illuminant, emergent Warning Mark, building and is with a wide range of applications with the field such as technique U.S., information storage, imaging display, biological label art.
Early stage long after glow luminous material mainly mixes the sulfide of transition metal ion, and the luminosity of long persistence luminous sulfide material is low, and luminous time of persistence is short, can not meet whole noctilucent requirement.What current people's research was the most ripe is alkali earth metal aluminate green long afterglow luminescent material, and its luminous efficiency is high, and time of persistence is long, but meets water unstable, and color is single.In addition rare-earth activated silicate long-afterglow material is also an important subject of present long-afterglow material.Silicate, compared with oxide compound, sulfide, aluminate etc., has acidproof, alkaline-resisting, water-fast, and good chemical stability.The research of silicate long-afterglow material.This type of long-afterglow material mainly comprises Sr 2mgSi 2o 7: Eu 2+, Dy 3+, Ca 2mgSi 2o 7: Eu 2+, Tb 3+, Ba 2mgSi 2o 7: Eu 2+, Tm 3+, Sr 3mgSi 2o 8: Eu 2+, Dy 3+, Ca 3mgSi 2o 8: Eu 2+, Dy 3+, Ba 3mgSi 2o 8: Eu 2+, Dy 3+deng.Although the research of silicate long-afterglow material obtains very large progress in recent years, in general, the afterglow property of silicate systems does not reach the level of aluminates system yet.
It is a kind of inorganic fluorescent powder out newly developed in recent years that alkaline-earth metal halogen aluminate mixes rare earth luminescent material.Alkaline-earth metal halogen aluminate substrate is stablized, and according to their composition, proportioning is different and have different crystalline structure; Rare earth ion with alkaline-earth metal ions radius (as Sr 2+) close, be conducive to the doping of rare earth ion, therefore alkaline-earth metal halogen aluminate is suitable as the luminous host of rare earth ion.For current long after glow luminous material study immature, we propose research Novel alkali earth metals halogen aluminate and mix rare earth long-afterglow luminescent material tool and have very important significance.
Summary of the invention
The object of the invention is the deficiency for existing rare earth long-afterglow luminescent material, provide that a kind of luminous efficiency is high, good stability, be suitable for the orange red rare earth long-afterglow luminescent material of near ultraviolet excitation.
Another object of the present invention is to provide the preparation method of above-mentioned rare earth long-afterglow luminescent material.
To achieve these goals, the orange red rare earth long-afterglow luminescent material being applicable near ultraviolet excitation of the present invention, its chemical constitution is:
M II 3(1-x-y)M III 2O 5Cl 2: xEu 2+, yR III。M iIfor alkaline-earth metal ions Sr 2+, Ba 2+in one two several; M iIIfor Al 3+, B 3+in one or both; R iIIfor Dy 3+, Nd 3+, La 3+, Pr 3+in one; X, y are the relative M of corresponding dopant ion iImolar percentage coefficient shared by ion, 0.0≤x≤0.50,0.0≤y≤0.20.The mass percentage of raw material type used in the present invention and each raw material is respectively: Strontium carbonate powder (SrCO 3): 0 ~ 51.70 %; Barium carbonate (BaCO 3): 0 ~ 54.99 %; Six water strontium chloride (SrCl 26H 2o): 0 ~ 37.15 %; Bariumchloride (BaCl 2): 0 ~ 25.48 %; Aluminium hydroxide [Al (OH) 3]: 0 ~ 21.73 %; Boric acid (H3BO3): 0 ~ 18.04 %, europiumsesquioxide (Eu2O3): 0 ~ 21.46 %; Dysprosium trioxide (Dy2O3): 0 ~ 12.88 %; Neodymium sesquioxide (Nd2O3): 0 ~ 12.88 %; Lanthanum sesquioxide (La2O3): 0 ~ 12.88 %; Praseodymium trioxide (Pr6O11): 0 ~ 12.88 %.
Work as M iIfor alkaline-earth metal ions Sr 2+, Ba 2+in two kinds time, the emission peak half-peak width of sample can become large relative to wherein one, and and the emissive porwer of sample can be significantly improved; M iIIfor Al 3+, B 3+in two kinds time relative to time wherein a kind of, emissive porwer and the twilight sunset life time of sample can be significantly improved.
Near-ultraviolet light of the present invention, refers to the near-ultraviolet light sending out 380 ~ 410 nm.
The preparation method of above-mentioned rare earth orange-red long afterglow Luminescent Material, adopts high temperature solid-state method, comprises the steps: various raw material to mix in agate mortar in proportion, pre-burning 3 ~ 6 hours at 400 ~ 500 DEG C, be chilled to room temperature, take out grinding again evenly, in 1000 ~ 1200 DEG C of H 2sintering 4 ~ 10 hours is reduced, by levigate for gained sinter the finished product in atmosphere.
Rare earth orange-red long afterglow Luminescent Material of the present invention has very strong orange red light emission (emission peak is positioned at about 600 nm) under near ultraviolet excitation, and luminous efficiency is high.Be placed in camera bellows at ultra violet lamp 30 min of 365nm, its time of persistence can reach 4 h.
Accompanying drawing explanation
Fig. 1 is room temperature excitation spectrum (monitoring wavelength is 600 nm) and the emmission spectrum (excitation wavelength is 400 nm) of orange-red long afterglow Luminescent Material of the present invention;
Fig. 2 is the decay of afterglow curve of orange-red long afterglow Luminescent Material of the present invention.
Embodiment
Embodiment 1:
Take Strontium carbonate powder (SrCO 3): 2.8 g (43.67 %), bariumchloride (BaCl 2): 2.08 g(32.44 %), aluminium hydroxide [Al (OH) 3]: 1.17 g(18.25 %), boric acid (H 3bO 3): 0.325 g(5.08 %), europiumsesquioxide (Eu 2o 3): 0.0176 g(0.27 %), Dysprosium trioxide (Dy 2o 3): 0.0187 g(0.29 %) fully grind in agate mortar and after mixing, at 500 DEG C, pre-burning 4 hours, is chilled to room temperature, it is even to take out grinding again, in 1200 DEG C of H 2sintering 4 hours is reduced, by levigate for gained sinter the finished product Sr in atmosphere 1.9baAl 1.5b 0.5o 5cl 2: 0.05Eu 2+, 0.05Dy 3+.
The luminescent properties of this fluorescent material as shown in Figure 1, sample has at near-ultraviolet light district (250 nm ~ 450 nm) and very strong excites broadband excitation. and the emmission spectrum under 400 nm optical excitation is as shown in Figure 1, the transmitting of sample is the orange red light emission based on about 600 nm, this Eu corresponded to 2+4f 65d 1-4f 7transition.
Figure 2 shows that the decay of afterglow curve of sample.Work as Eu 2+when ion is excited, its portions of electronics can by RE 3+(RE=Dy 3+, Nd 3+, La 3+, Pr 3+) produce trap level captured, at room temperature enter hot activation and get back to Eu 2+ion t 2energy level or eenergy level, then produces twilight sunset phenomenon.Be placed in camera bellows at ultra violet lamp 30 min of 365 nm, its time of persistence can reach 4 h.
Embodiment 2:
Take Strontium carbonate powder (SrCO 3): 2.8 g (39.62 %), six water strontium chloride (SrCl 26H 2o): 2.67 g(37.78 %), aluminium hydroxide [Al (OH) 3]: 1.56 g(22.09 %), europiumsesquioxide (Eu 2o 3): 0.0176 g(0.25 %), Dysprosium trioxide (Dy 2o 3): 0.0187 g(0.26 %) fully grind in agate mortar and after mixing, at 500 DEG C, pre-burning 4 hours, is chilled to room temperature, it is even to take out grinding again, in 1200 DEG C of H 2sintering 6 hours is reduced, by levigate for gained sinter the finished product Sr in atmosphere 2.9al 2o 5cl 2: 0.05Eu 2+, 0.05Dy 3+.
Embodiment 3:
Take Strontium carbonate powder (SrCO 3): 2.8 g (39.99 %), six water strontium chloride (SrCl 26H 2o): 2.67 g(38.14 %), aluminium hydroxide [Al (OH) 3]: 1.17 g(16.71 %), boric acid (H 3bO 3): 0.325 g(4.64 %), europiumsesquioxide (Eu 2o 3): 0.0176 g(0.25 %), Dysprosium trioxide (Dy 2o 3): 0.0187 g(0.27 %) fully grind in agate mortar and after mixing, at 500 DEG C, pre-burning 4 hours, is chilled to room temperature, it is even to take out grinding again, in 1200 DEG C of H 2sintering 4 hours is reduced, by levigate for gained sinter the finished product Sr in atmosphere 2.9al 1.5b 0.5o 5cl 2: 0.05Eu 2+, 0.05Dy 3+.
Embodiment 4:
Take Strontium carbonate powder (SrCO 3): 2.8 g(40.37 %), six water strontium chlorides: (SrCl 26H 2o) 2.67 g(38.49 %), aluminium hydroxide [Al (OH) 3]: 0.78 g(11.25 %), boric acid (H 3bO 3): 0.61 g(9.37 %), europiumsesquioxide (Eu 2o 3): 0.0176 g(0.25 %), neodymium sesquioxide (Nd 2o 3): 0.0168 g(0.24 %), fully grind and after mixing, at 500 DEG C, pre-burning 6 hours, is chilled to room temperature in agate mortar, it is even to take out grinding again, in 1200 DEG C of H 2sintering 2 hours is reduced, by levigate for gained sinter the finished product Sr in atmosphere 2.9alBO 5cl 2: 0.05Eu 2+, 0.05Nd 3+.
Embodiment 5:
Take Strontium carbonate powder (SrCO 3): 2.66 g (38.22 %), six water strontium chlorides: (SrCl 26H 2o) 2.67 g(38.37 %), aluminium hydroxide [Al (OH) 3]: 1.56 g(22.42 %), europiumsesquioxide (Eu 2o 3): 0.0352 g(0.51 %), neodymium sesquioxide (Nd 2o 3): 0.0336 g(0.48 %) fully grind in agate mortar and after mixing, at 500 DEG C, pre-burning 4 hours, is chilled to room temperature, it is even to take out grinding again, in 1200 DEG C of H 2sintering 8 hours is reduced, by levigate for gained sinter the finished product Sr in atmosphere 2.8al 2o 5cl 2: 0.1Eu 2+, 0.1Nd 3+.
Embodiment 6:
Take Strontium carbonate powder (SrCO 3): 2.66 g (38.24 %), six water strontium chlorides: (SrCl 26H 2o) 2.67 g(38.37 %), aluminium hydroxide [Al (OH) 3]: 1.56 g(22.42 %), europiumsesquioxide (Eu 2o 3): 0.0352 g(0.51 %), lanthanum sesquioxide (Nd 2o 3): 0.0325 g(0.46 %) fully grind in agate mortar and after mixing, at 500 DEG C, pre-burning 4 hours, is chilled to room temperature, it is even to take out grinding again, in 1200 DEG C of H 2sintering 8 hours is reduced, by levigate for gained sinter the finished product Sr in atmosphere 2.8al 2o 5cl 2: 0.1Eu 2+, 0.1La 3+.
Embodiment 7:
Take Strontium carbonate powder (SrCO 3): 2.66 g (38.23 %), six water strontium chlorides: (SrCl 26H 2o) 2.67 g(38.37 %), aluminium hydroxide [Al (OH) 3]: 1.56 g(22.42 %), europiumsesquioxide (Eu 2o 3): 0.0352 g(0.51 %), Praseodymium trioxide (Pr 6o 11): 0.0340 g(0.47 %) fully grind in agate mortar and after mixing, at 500 DEG C, pre-burning 4 hours, is chilled to room temperature, it is even to take out grinding again, in 1200 DEG C of H 2sintering 10 hours is reduced, by levigate for gained sinter the finished product Sr in atmosphere 2.8al 2o 5cl 2: 0.1Eu 2+, 0.1Pr 3+.

Claims (3)

1. be applicable to an orange red rare earth long-afterglow luminescent material near ultraviolet excitation, its chemical constitution is: M iI 3 (1-x-y)m iII 2o 5cl 2: xEu 2+, yR iII.M iIfor alkaline-earth metal ions Sr 2+and Ba 2+combination; M iIIfor Al 3+, B 3+in combination; R iIIfor Dy 3+, Nd 3+, La 3+, Pr 3+in one; X, y are the relative M of corresponding dopant ion iImolar percentage coefficient shared by ion, 0.0≤x≤0.50,0.0≤y≤0.20; Described orange red rare earth long-afterglow luminescent material is placed in camera bellows at ultra violet lamp 30 min of 365nm, and its time of persistence can reach 4 h.
2. be applicable to the orange red rare earth long-afterglow luminescent material of near ultraviolet excitation as claimed in claim 1, it is characterized in that described near-ultraviolet light refers to that wavelength is the light of 380 ~ 410nm.
3. the preparation method of an orange red rare earth long-afterglow luminescent material as claimed in claim 1, it is characterized in that preparation method comprises the steps: to take Strontium carbonate powder: 2.8 g, bariumchloride: 2.08 g, aluminium hydroxide: 1.17 g, boric acid: 0.325 g, europiumsesquioxide: 0.0176 g, Dysprosium trioxide: 0.0187 g fully grinds and after mixing in agate mortar, pre-burning 4 hours at 500 DEG C, be chilled to room temperature, take out grinding again evenly, in 1200 DEG C, H 2sintering 4 hours is reduced, by levigate for gained sinter the finished product Sr in atmosphere 1.9baAl 1.5b 0.5o 5cl 2: 0.05Eu 2+, 0.05Dy 3+.
CN201410009895.5A 2014-01-09 2014-01-09 A kind of orange red rare earth long-afterglow luminescent material being applicable near ultraviolet excitation and preparation method thereof Expired - Fee Related CN103897695B (en)

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KR101689989B1 (en) * 2016-01-27 2016-12-26 티오켐 주식회사 Process for Producing Phosphorescent Pigments Having Excellent Afterglow
CN107353894A (en) * 2016-05-09 2017-11-17 云南民族大学 Microwave synthesizes a kind of white rare earth long-afterglow luminescent material of ultraviolet excitation
CN108690608A (en) * 2017-11-02 2018-10-23 王小琴 A kind of carrousel
CN112143491A (en) * 2020-10-21 2020-12-29 岭南师范学院 Long-afterglow light conversion agent and application thereof
CN113999672B (en) * 2021-11-22 2023-05-12 厦门理工学院 Stress luminescent material with orange afterglow and preparation thereof

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Publication number Priority date Publication date Assignee Title
CN101191253A (en) * 2006-11-27 2008-06-04 中国科学院理化技术研究所 Alkali metal boroaluminate compound and single crystal and preparation method thereof
CN101899297A (en) * 2010-07-15 2010-12-01 兰州大学 Orange-yellow long-afterglow luminescent material and preparation method thereof
CN102191045A (en) * 2011-03-28 2011-09-21 彩虹集团公司 Preparation method of nitrogen oxide green fluorescent powder material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101191253A (en) * 2006-11-27 2008-06-04 中国科学院理化技术研究所 Alkali metal boroaluminate compound and single crystal and preparation method thereof
CN101899297A (en) * 2010-07-15 2010-12-01 兰州大学 Orange-yellow long-afterglow luminescent material and preparation method thereof
CN102191045A (en) * 2011-03-28 2011-09-21 彩虹集团公司 Preparation method of nitrogen oxide green fluorescent powder material

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