CN105295911B - Praseodymium-doped perovskite type red afterglow luminescent material for AC-LED and preparation method thereof - Google Patents

Abstract

The invention provides a praseodymium-doped perovskite type red afterglow luminescent material for AC-LED and a preparation method thereof. The luminescent material is prepared by using alkaline earth metal titanate as a substrate, Pr＜3+＞ as an activating agent and other co-doped ions as a defect center, and has a general formula of M(3-x-y-z)Zr2O7:xPr＜3+＞, yRe＜3+＞ and zT＜3+＞, wherein M is one or more elements of Mg, Ca, Sr and Ba, Re is one of Dy, Tm and Yb, T is one or two of B, Al, Ga, In and Bi, x is more than or equal to 0.005 and less than or equal to 0.02, y is more than or equal to 0 and less than or equal to 0.05, and z is more than or equal to 0 and less than or equal to 0.05. The invention further provides a method for preparing the praseodymium-doped perovskite type red afterglow luminescent material. The luminescent material can generate red light to be emitted under blue ray excitation, bright red light afterglow emission can still be observed after the excitation light source is removed, and tests show that the service life of the red light afterglow is 13 milliseconds. While the material is expected to make up strobe of AC-LEG, the color quality (color rendering index and color temperature) of a luminescent device can be improved.

Description

A kind of AC-LED praseodymium doped Ca-Ti ore type redness afterglow materials and its preparation Method

Technical field

The present invention relates to solid luminescent material field, more particularly, to a kind of AC-LED with red afterglow materials and its Preparation method.

Background technology

At present, whether family, industry and commerce or public electricity-using, almost all depend on exchange (Alternating Current, AC) mode is powered, and conventional white light LED illumination must be driven in direct current mode (Direct Current, DC), because This, AC-DC conversion equipment is to realize the essential accessory of White-light LED illumination.But, the electric energy of AC-DC conversion equipment The high shortcoming restriction of loss high (15-30%), built-in electrolysis condenser easily damaged (generally below 10,000 hours life-span), price The practical application of DC-LED products and popularization.

AC-LED has given up AC/DC changeover switch from design, uses the longevity in LED lamp reduces cost, miniaturization, prolongation The aspects such as life have obvious advantage.However, AC-LED occurs continuous light and shade conversion phenomenon --- stroboscopic when working, to people Eye injury is larger.How " Radix Clematidis Clarkeanae " that " stroboscopic " problem have become development AC-LED technology is solved.Recently, Chinese patent CN 101705095 disclose a kind of aY towards AC-LED applications₂O₃·bAl₂O₃·SiO₂:MCenBxNayP yellow twilight sunset Fluorescent material, describes its afterglow (twilight sunset life-span：The stroboscopic of device is successfully compensate for 5-20ms).Chinese patent CN 102468413 disclose and various are suitable for the AC-LED lamp polychrome persistence phosphors that UV/blue chip is excited.This class has The fluorescent material for having power-off light-decay characteristic is development low frequency sudden strain of a muscle of new generation, the key of long-life AC-LED.

It is well known that consider from colorimetry angle, as long as the three primary colories that afterglow intensity and die-away time are close to (red, green, It is blue) afterglow materials mix in specific proportions, can just produce white afterglow.At present, the indigo plant with the millisecond twilight sunset life-span Color or the existing some reports of green persistence phosphor, but the red afterglow materials with the millisecond twilight sunset life-span are still very Shortcoming, therefore the excellent white afterglow of chromaticity (color rendering index, colour temperature) can not be produced.

The content of the invention

In order to, while AC-LED stroboscopics are improved, improve white light chromaticity, the invention provides one kind is in the case where blue light is excited Praseodymium doped Ca-Ti ore type red fluorescence powder with the millisecond twilight sunset life-span, its chemical general formula are M_3-x-y-zZr₂O₇:xPr³⁺,yRe³⁺, zT³⁺, wherein：

One or more elements of the M selected from Mg, Ca, Sr and Ba；

One or more in La, Nd, Gd, Tb, Dy, Er, Yb and Lu of Re；

One or more in B, Al, Ga, In, Bi of T；

0.005≤x≤0.02；0.005≤y≤0.02；0.005≤z≤0.02.

In the present invention, the Re of introducing³⁺Or T³⁺Ion can introduce defect in substrate, so as to regulate and control persistence and twilight sunset Brightness.

The preparation method of above-mentioned praseodymium doped Ca-Ti ore type redness twilight sunset fluorescent material is additionally provided in the present invention, its feature exists In using high temperature solid phase synthesis.

According to the present invention, the preparation method comprises the steps：

Powder material is mixed according to certain component proportion, ethanol in proper amount grinding is added, is subsequently placed in square crucible, plus Heat, insulation are allowed to solid state reaction, and last furnace cooling obtains required fluorescent material sample.

According to the present invention, after powder material mixing, ethanol need to be added, about 30-120 minutes are fully ground；

According to the present invention, after powder material grinding is uniform, need to be placed in batch-type furnace and be heated to 1000-1300 DEG C, preferably 1150-1250 DEG C, and 2-8 hours are incubated, preferred 4-6 hours；

According to the present invention, the preparation method specifically includes following steps：

Powder material is mixed according to certain component proportion, ethanol in proper amount is added, and is ground 60 minutes, be subsequently placed in square In crucible, be heated in batch-type furnace 1250 DEG C, insulation be allowed within 5 hours solid state reaction, needed for last furnace cooling is obtained Fluorescent material sample.

In the present invention, M can be obtained using said components and preparation technology_3-x-y-zZr₂O₇:xPr³⁺,yRe³⁺,zT³⁺It is red remaining Brightness fluorescent material, which has following luminescence feature：Can effectively be excited by the exciting light in 400-500 nanometers interval, cardiac wave in generation The long red emission for being located at 612 nanometers；After exciting light stops, bright red afterglow still can be observed, its twilight sunset longevity Order as 13 milliseconds.

The invention further relates to a kind of application of praseodymium doped Ca-Ti ore type redness persistence phosphor, it is characterised in that for structure Build the high chromaticity white light AC-LED that blue chip is excited.

The fluorescent material preparation process is simple of the present invention, with low cost, nontoxic pollution-free are steady with good physics, chemistry It is qualitative.

Description of the drawings

Fig. 1 is Ca in example 1_2.75Zr₂O₇:0.005Pr³⁺,0.01Dy³⁺,0.01In³⁺The X-ray of afterglow materials is spread out Penetrate figure；

Fig. 2 is Pr in example 1³⁺The excitation emission spectra of doped samples；Wherein excitation wavelength is 460 nanometers, the transmitting of monitoring Wavelength is 612 nanometers.

Fig. 3 is the room temperature decay of afterglow time graph (λ of sample in example 1_ex=460 nanometers, λ_em=612 nanometers).

Specific embodiment

Example 1：

By analytically pure material powder CaO, ZrO₂、Pr₆O₁₁、Dy₂O₃、In₂O₃, by Ca²⁺:Zr⁴⁺:Pr³⁺:Dy³⁺:In³⁺= 2.975:0.005:0.01:It is placed in agate mortar after the proportioning accurate weighing of 0.01 (mol ratio), adds ethanol, be fully ground About 30 minutes, it is allowed to uniform mixing；Be subsequently placed in square crucible, be heated in batch-type furnace 1300 DEG C, insulation be allowed within 2 hours Generation solid state reaction；Last furnace cooling, ground, mistake mesh sieve, fluorescent material sample needed for obtaining.According to X-ray analyses result (as shown in Figure 1), the luminescent material of acquisition is pure phase Ca₃Zr₂O₇.Its room temperature is measured with FLS920 fluorescence spectrophotometer to excite and send out Spectrum (as shown in Figure 2) is penetrated, in the case where 460 nanometers of light are excited, sample shows Pr³⁺Feature¹D₂→³H₄Red emission；Closing is excited After light source, red afterglow is can observe.With the decay of afterglow curve of FLS920 fluorescence spectrophotometer measurement as shown in figure 3, Jing Calculate, its persistence is 13 milliseconds.

Example 2：By analytically pure material powder SrO, ZrO₂、Pr₆O₁₁、Tm₂O₃、Al₂O₃, by Sr²⁺:Zr⁴⁺:Pr³⁺:Tm³⁺: Al³⁺=2.97:0.005:0.01:It is placed in agate mortar after the proportioning accurate weighing of 0.015 (mol ratio), adds ethanol, fill Divide grinding about 60 minutes, be allowed to uniform mixing；Be subsequently placed in square crucible, be heated in batch-type furnace 1250 DEG C, insulation it is 4 little When be allowed to solid state reaction；Last furnace cooling, ground, mistake mesh sieve, fluorescent material sample needed for obtaining.According to X-ray point Analysis result, the luminescent material of acquisition is pure phase Sr₃Zr₂O₇.In the case where 460 nanometers of light are excited, sample shows that bright HONGGUANG is sent out Penetrate；After closing excitation source, red afterglow is can observe.Decay of afterglow with FLS920 fluorescence spectrophotometer measuring samples is bent Line, is computed, and its persistence is 18 milliseconds.

Example 3：By analytically pure material powder MgO, ZrO₂、Pr₆O₁₁、Yb₂O₃、B₂O₃, by Mg²⁺:Zr⁴⁺:Pr³⁺:Yb³⁺:B^{3 +}=2.965:0.005:0.01:It is placed in agate mortar after the proportioning accurate weighing of 0.02 (mol ratio), adds ethanol, fully Grinding about 120 minutes, is allowed to uniform mixing；Be subsequently placed in square crucible, be heated in batch-type furnace 1000 DEG C, insulation it is 6 little When be allowed to solid state reaction；Last furnace cooling, ground, mistake mesh sieve, fluorescent material sample needed for obtaining.According to X-ray point Analysis result, the luminescent material of acquisition is pure phase Mg₃Zr₂O₇.In the case where 460 nanometers of light are excited, sample shows that bright HONGGUANG is sent out Penetrate；After closing excitation source, red afterglow is can observe.Decay of afterglow with FLS920 fluorescence spectrophotometer measuring samples is bent Line, is computed, and its persistence is 20 milliseconds.

Example 4：By analytically pure material powder BaO, ZrO₂、Pr₆O₁₁、Yb₂O₃、Ga₂O₃, by Ba²⁺:Zr⁴⁺:Pr³⁺:Yb³⁺: Ga³⁺=2.98:0.005:0.01:It is placed in agate mortar after the proportioning accurate weighing of 0.005 (mol ratio), adds ethanol, fill Divide grinding about 45 minutes, be allowed to uniform mixing；Be subsequently placed in square crucible, be heated in batch-type furnace 1050 DEG C, insulation it is 4 little When be allowed to solid state reaction；Last furnace cooling, ground, mistake mesh sieve, fluorescent material sample needed for obtaining.According to X-ray point Analysis result, the luminescent material of acquisition is pure phase Ba₃Zr₂O₇.In the case where 460 nanometers of light are excited, sample shows that bright HONGGUANG is sent out Penetrate；After closing excitation source, red afterglow is can observe.Decay of afterglow with FLS920 fluorescence spectrophotometer measuring samples is bent Line, is computed, and its persistence is 18 milliseconds.

Example 5：By analytically pure material powder CaO, ZrO₂、Pr₆O₁₁、Dy₂O₃、Bi₂O₃, by Ca²⁺:Zr⁴⁺:Pr³⁺:Dy³⁺: Bi³⁺=2.96:0.005:0.015:It is placed in agate mortar after the proportioning accurate weighing of 0.02 (mol ratio), adds ethanol, fill Divide grinding about 35 minutes, be allowed to uniform mixing；Be subsequently placed in square crucible, be heated in batch-type furnace 1100 DEG C, insulation it is 8 little When be allowed to solid state reaction；Last furnace cooling, ground, mistake mesh sieve, fluorescent material sample needed for obtaining.According to X-ray point Analysis result, the luminescent material of acquisition is pure phase Ca₃Zr₂O₇.In the case where 330 nanometers of light are excited, sample shows that bright HONGGUANG is sent out Penetrate；After closing excitation source, red afterglow is can observe.Decay of afterglow with FLS920 fluorescence spectrophotometer measuring samples is bent Line, is computed, and its persistence is 15 milliseconds.

Claims (4)

1. a kind of praseodymium doped Ca-Ti ore type redness afterglow materials, its chemical general formula is M_3-x-y-zZr₂O₇:xPr³⁺,yRe³⁺,zT^{3 +}, one or more element of M=Mg, Ca, Sr, Ba, one kind in Re=Dy, Tm, Yb, in T=B, Al, Ga, In, Bi in formula One or two, 0.005≤x≤0.02；0<y≤0.05；0<z≤0.05.

2. red afterglow materials according to claim 1, it is characterised in that：The red afterglow materials can quilt 400 nanometers of -500 nanometers of exciting lights are effectively excited, and produce the red afterglow that centre wavelength is positioned at 612 nanometers, its twilight sunset longevity Order as 13 milliseconds.

3. the M in a kind of claim 1_3-x-y-zZr₂O₇:xPr³⁺,yRe³⁺,zT³⁺The preparation method of red afterglow materials, its It is characterised by, powder material is weighed according to certain component molar proportioning and is mixed, adds ethanol in proper amount, and grind 30-120 point Clock, is subsequently placed in square crucible, be heated in batch-type furnace 1000-1300 DEG C, insulation 2-8 hours be allowed to solid phase it is anti- Should, last furnace cooling obtains required fluorescent material sample.

4. the application of the red afterglow materials any one of a kind of claim 1-3, which is used to build blue chip The high chromaticity white light AC-LED for exciting.