CN106753379A - A kind of preparation method of terbium ion doping fluoride solid luminescent material - Google Patents

Abstract

A kind of preparation method of terbium ion doping fluoride solid luminescent material, is related to a kind of preparation method of solid luminescent material.Cannot low temperature synthetic crystallization degree CeF higher the present invention is to solve existing method₃And CeF₃：Tb³⁺Fluorescent material, simultaneously synthesizing process needs to introduce organic matter, to the disagreeableness problem of environment.Method：First, by chemical formula Ce_1‑xF₃：xTb³⁺Stoichiometric proportion weigh Ce (NO₃)₃·6H₂O、NaF、NaNO₃And KNO₃Sample；2nd, sample is put into agate mortar, adds ethanol to grind to obtain mixture；3rd, mixture is transferred in alumina crucible and is heated, keeping temperature, cooling, product washing is dried overnight, and obtains Ce_1‑xF₃：xTb³⁺Powder.The method has easy to operate, easily repeats, and raw material used is inexpensive, be easy to get, the low advantage of sintering temperature.The present invention is for preparing solid luminescent material.

Description

A kind of preparation method of terbium ion doping fluoride solid luminescent material

Technical field

The present invention relates to a kind of preparation method of solid luminescent material.

Background technology

As the important rare earth fluoride of a class, binary fluoride REF₃Structure is due to its VHD, and the response time is short With radiant emissivity high, there is potential application in optics, photoelectronics and fluorescence labeling and receive significant attention.

As the representative instance of binary fluoride, CeF₃It is hexagonal phase structure, it has P3 ∣ c1 (D_3d ⁴) space group, each Structure cell is by six molecular compositions.CeF₃Ce in crystal³⁺Ion is by nine F^-Coordination, and with C₂Site symmetry.Additionally, CeF₃There is bigger Stokes shift (10000cm as the luminescent material with 100% activator concentration^-1).It is this big Stokes shift and resulting less spectra overlapping prevent Ce³⁺Resonant energy transfer between ion, so that Reduce the probability being quenched by energy transmission generation concentration.Additionally, CeF₃Excited in room temperature ultraviolet (UV) lower with amount high Sub- efficiency and emission spectrum wide, this makes it suitable for the exploitation of adjustable short pulse solid-state laser.Especially, Ce³⁺Due to D-f transition, stronger absorption and shorter fluorescence lifetime is shown in UV regions, is a kind of excellent sensitizer.Tb³⁺It is green The outstanding emitter of transmitting, and it is widely used in illumination and the biomarker of green emitting phosphor.Due to Ce³⁺To Tb³⁺It is high-effect Amount transfer, in Ce³⁺And Tb³⁺Co-doped material such as LaPO₄, NaYF₄Strong green emission is observed in fluorescent material.It is so far Only, it has been reported that excessively many to prepare CeF₃And CeF₃：Tb³⁺Method, including high temperature solid-state method, polyol process, ultrasonic-microwave Method, microemulsion method etc..

However, above-mentioned synthetic method is limited by complicated technology and equipment, it usually needs synthesis temperature higher, system Standby process also needs to introduce organic matter, therefore develops a kind of efficient cryogenic and environment-friendly synthetic method is for realizing above material Preparation it is critical that.

The content of the invention

Cannot low temperature synthetic crystallization degree CeF higher the present invention is to solve existing method₃And CeF₃：Tb³⁺Fluorescent material, together When building-up process need introduce organic matter, to the disagreeableness problem of environment, there is provided a kind of terbium ion doping fluoride solid luminescent The preparation method of material.

A kind of preparation method of terbium ion doping fluoride solid luminescent material of the present invention, comprises the following steps：

First, by chemical formula Ce_1-xF₃：xTb³⁺Stoichiometric proportion weigh Ce (NO₃)₃·6H₂O、NaF、NaNO₃And KNO₃Sample Product, wherein x are 0~0.8；

2nd, the sample that step one is weighed is put into agate mortar, adding the amount of appropriate ethanol, ethanol can own Sample dissolves, and grinds 20~30 minutes, obtains mixture；

Three and then mixture is transferred to it is heated to 320~350 DEG C in alumina crucible, and keep 4 at such a temperature~ 5 hours, after being cooled to room temperature, product was washed with deionized for several times, is then dried overnight at 80~100 DEG C, obtains Ce_{1- x}F₃：xTb³⁺Powder.

Beneficial effects of the present invention：

(1) present invention uses NaNO₃And KNO₃As reaction medium, low temperature synthetic crystallization degree CeF higher₃And CeF₃：Tb^{3 +}Fluorescent material.The method has easy to operate, easily repeats, and raw material used is inexpensive, be easy to get, the low advantage of sintering temperature.

(2) in CeF₃：Tb³⁺In sample, Tb³⁺Generation lattice replaces, and photoluminescence intensity is had a significant impact.Burst of ultraviolel Under, with doping Tb³⁺Concentration increase, Ce_1-xF₃：xTb³⁺Strong green emission is produced, maximum is reached in x=0.2.Together When compared to other Ce, Tb is co-doped with system, and energy transfer efficiency is up to 98.2%.

(3) under the exciting of denoted low voltage electron beam, CeF₃：Tb³⁺Fluorescent material shows the Tb similar to photoluminescent property³⁺'s Characteristic emission, shows that sample stability is preferable.Excellent photism makes sample have very in display, sensor and field of telecommunications Big application potential.

Brief description of the drawings

Fig. 1 is CeF₃With CeF under different levels of doping₃：xTb³⁺The XRD of sample；

Fig. 2 is CeF₃The XPS analysis result of phosphor；

Fig. 3 is undoped p Tb³⁺The CeF of ion₃SEM figure；

Fig. 4 is Ce0.95F₃：0.05Tb³⁺The SEM figures of sample；

Fig. 5 is Ce_0.6F₃：0.4Tb³⁺The SEM figures of sample；

Fig. 6 is CeF₃The excitation and emission spectra of sample；

Fig. 7 is Ce_0.8F₃：0.2Tb³⁺The excitation and emission spectra of sample；

Fig. 8 is the different Tb under burst of ultraviolel³⁺Doped in concentrations profiled Ce_1-xF₃：xTb³⁺The spectrum of sample；Wherein 1-5 is right respectively It is 0.8,0.4,0.2,0.1 and 0.05 to answer doping concentration；

Fig. 9 is Ce_0.8F₃：0.2Tb³⁺The CL figures of sample, wherein accelerating potential is 4kV, and heater current is 90mA；

Figure 10 be accelerating potential 85mA under, Ce_0.8F₃：0.2Tb³⁺The CL Strength Changes figures of sample；

Figure 11 be heater current 90mA under, Ce_0.8F₃：0.2Tb³⁺The CL Strength Changes figures of sample；

Figure 12 is that the CeF that 6h is obtained is reacted at 800 DEG C using high temperature solid-state method₃The XRD of sample.

Specific embodiment

Technical solution of the present invention is not limited to act specific embodiment set forth below, also including between each specific embodiment Any combination.

Specific embodiment one：The preparation method of present embodiment terbium ion doping fluoride solid luminescent material, including Following steps：

First, by chemical formula Ce_1-xF₃：xTb³⁺Stoichiometric proportion weigh Ce (NO₃)₃·6H₂O、NaF、NaNO₃And KNO₃Sample Product, wherein x are 0~0.8；

2nd, the sample that step one is weighed is put into agate mortar, adds ethanol sample dissolution, ground 20~30 minutes, Obtain mixture；

Three and then mixture is transferred to it is heated to 320~350 DEG C in alumina crucible, and keep 4 at such a temperature~ 5 hours, after being cooled to room temperature, product was washed with deionized 3~5 times, is then dried overnight at 80~100 DEG C, obtains Ce_1-xF₃：xTb³⁺Powder.

Specific embodiment two：Present embodiment from unlike specific embodiment one：X is 0.05 in step one.Its It is identical with specific embodiment one.

Specific embodiment three：Present embodiment from unlike specific embodiment one：X is 0.1 in step one.Other It is identical with specific embodiment one.

Specific embodiment four：Present embodiment from unlike specific embodiment one：X is 0.2 in step one.Other It is identical with specific embodiment one.

Specific embodiment five：Present embodiment from unlike specific embodiment one：X is 0.4 in step one.Other It is identical with specific embodiment one.

Specific embodiment six：Present embodiment from unlike specific embodiment one：X is 0.8 in step one.Other It is identical with specific embodiment one.

Specific embodiment seven：Unlike one of present embodiment and specific embodiment one to six：Ground in step 2 Mill 25 minutes.Other are identical with one of specific embodiment one to six.

Specific embodiment eight：Unlike one of present embodiment and specific embodiment one to seven：Will in step 3 Mixture is heated to 330~340 DEG C in being transferred to alumina crucible.Other are identical with one of specific embodiment one to seven.

Specific embodiment nine：Unlike one of present embodiment and specific embodiment one to eight：Produced in step 3 Thing is washed with deionized 3~5 times, is then dried overnight at 90 DEG C.Other are identical with one of specific embodiment one to eight.

Embodiments of the invention are elaborated below, following examples are entered under premised on technical solution of the present invention Row is implemented, and gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following realities Apply example.

Embodiment 1：The preparation method of the present embodiment terbium ion doping fluoride solid luminescent material, comprises the following steps：

In molar ratio 1:3:50:25 weigh Ce (NO₃)₃·6H₂O、NaF、NaNO₃And KNO₃Sample, is put into agate mortar, Appropriate ethanol is added, is ground 30 minutes, obtain mixture, then the mixture is transferred in alumina crucible and is heated to 350 DEG C, and kept for 4 hours at such a temperature, after being cooled to room temperature, product is washed with deionized for several times, is then done at 100 DEG C It is dry overnight, obtain CeF₃Powder.

Embodiment 2：The preparation method of the present embodiment terbium ion doping fluoride solid luminescent material, comprises the following steps：

In molar ratio 0.95:0.05:3:50:25 weigh Ce (NO₃)₃·6H₂O、Tb(NO₃)₃、NaF、NaNO₃And KNO₃Sample Product, are put into agate mortar, add appropriate ethanol, grind 30 minutes, obtain mixture, and the mixture then is transferred into oxidation 350 DEG C are heated in aluminium crucible, and are kept for 4 hours at such a temperature, after being cooled to room temperature, product is washed with deionized number It is secondary, then it is dried overnight at 100 DEG C, Ce_0.95F₃：0.05Tb³⁺Powder.

Embodiment 3：The preparation method of the present embodiment terbium ion doping fluoride solid luminescent material, comprises the following steps：

In molar ratio 0.9:0.1:3:50:25 weigh Ce (NO₃)₃·6H₂O、Tb(NO₃)₃、NaF、NaNO₃And KNO₃Sample, It is put into agate mortar, adds appropriate ethanol, grind 30 minutes, obtain mixture, the mixture is then transferred to aluminum oxide 350 DEG C are heated in crucible, and are kept for 4 hours at such a temperature, after being cooled to room temperature, product is washed with deionized for several times, Then it is dried overnight at 100 DEG C, Ce_0.9F₃：0.1Tb³⁺Powder.

Embodiment 4：The preparation method of the present embodiment terbium ion doping fluoride solid luminescent material, comprises the following steps：

In molar ratio 0.8:0.2:3:50:25 weigh Ce (NO₃)₃·6H₂O、Tb(NO₃)₃、NaF、NaNO₃And KNO₃Sample, It is put into agate mortar, adds appropriate ethanol, grind 30 minutes, obtain mixture, the mixture is then transferred to aluminum oxide 350 DEG C are heated in crucible, and are kept for 4 hours at such a temperature, after being cooled to room temperature, product is washed with deionized for several times, Then it is dried overnight at 100 DEG C, Ce_0.8F₃：0.2Tb³⁺Powder.

Embodiment 5：The preparation method of the present embodiment terbium ion doping fluoride solid luminescent material, comprises the following steps：

In molar ratio 0.6:0.4:3:50:25 weigh Ce (NO₃)₃·6H₂O、Tb(NO₃)₃、NaF、NaNO₃And KNO₃Sample, It is put into agate mortar, adds appropriate ethanol, grind 30 minutes, obtain mixture, the mixture is then transferred to aluminum oxide 350 DEG C are heated in crucible, and are kept for 4 hours at such a temperature, after being cooled to room temperature, product is washed with deionized for several times, Then it is dried overnight at 100 DEG C, Ce_0.6F₃：0.4Tb³⁺Powder.

Embodiment 6：The preparation method of the present embodiment terbium ion doping fluoride solid luminescent material, comprises the following steps：

In molar ratio 0.2:0.8:3:50:25 weigh Ce (NO₃)₃·6H₂O、Tb(NO₃)₃、NaF、NaNO₃And KNO₃Sample, It is put into agate mortar, adds appropriate ethanol, grind 30 minutes, obtain mixture, the mixture is then transferred to aluminum oxide 350 DEG C are heated in crucible, and are kept for 4 hours at such a temperature, after being cooled to room temperature, product is washed with deionized for several times, Then it is dried overnight at 100 DEG C, Ce_0.2F₃：0.8Tb³⁺Powder.

Following detection and analysis are carried out to sample prepared by above example：

(1) composition of sample and phase purity

CeF₃With CeF under different levels of doping₃：xTb³⁺The XRD of sample is as shown in Figure 1.A is obtained by embodiment 1 in Fig. 1 The CeF for obtaining₃Typical XRD, there's almost no miscellaneous peak, be CeF₃Hexagonal phase pure phase.Wherein lattice parameter a=7.112 and c= 7.279(JCPDS No.08-0045；Space group：P63/mcm(193)).B-E respectively illustrates Ce in Fig. 1_0.95F₃：0.05Tb^{3 +}, Ce_0.9F₃：0.1Tb³⁺, Ce_0.8F₃：0.2Tb³⁺, Ce_0.6F₃：0.4Tb³⁺The XRD of sample.Compared to CeF₃, in addition to moving to right, institute There are four samples to show pure six sides CeF₃Characteristic peak.This is due to Tb³⁺Ionic radius be less than Ce³⁺Ionic radius, lattice Shrink what is caused.By replacing Ce³⁺, Tb³⁺Effectively occupy CeF₃In host lattice case.For Ce_0.2F₃： 0.8Tb³⁺Sample (F in Fig. 1), except several CeF₃Outside the small peak of phase, diffraction maximum substantially with orthogonal TbF₃Phase (JCPDS No.37-1487 it is) consistent.Work as Tb³⁺When the doping concentration of ion is 100mol%, can also obtain under the same conditions with height The pure TbF of crystallinity₃Sample (G in Fig. 1).The average crystallite size of all samples can estimate from Scherrer equations, D= 0.89 λ/β cos θ, wherein D is particle mean size, and λ is X-ray wavelength (0.15405nm), and β and θ is that overall with is respectively observation peak The half high and angle of diffraction.

In CeF₃In the building-up process of phosphor, NaNO is used₃-NKO₃As medium of fused salt.Due to NO^3-With strong oxygen The property changed, can be by Ce³⁺Partial oxidation is Ce⁴⁺.In order to solve this problem, we provide protective atmosphere and carry out protection system.In order to Confirm Ce⁴⁺Do not exist, to CeF₃Phosphor carries out XPS analysis, such as Fig. 2.Can return respectively in the combination of 883.1 and 903.3eV Belong to Ce 3d_5/2And 3d_3/2Peak.F peaks can be belonged in the combination of 685.7eV, while the oxygen and carbon that are detected in XPS tests Air is can come from, is not detected from Ce⁴⁺Peak, show in systems do not exist Ce⁴⁺。

As it was previously stated, doping for stable product crystalline phase and size it is critical that.Therefore, CeF₃Nanocrystal In high concentration Tb³⁺The form and size of strong influence sample.Fig. 3-Fig. 5 is depicted with different Tb³⁺The Ce of concentration_{1- x}F₃：xTb³⁺Representative SEM image.In figure 3, undoped p Tb³⁺Ion (pure CeF₃) sample by size in 50 to 300nm Six prisms and some small cubes nano particles constitute, six prism patterns occupy major part.Work as Tb³⁺When concentration increases to 0.05 (Fig. 4), occurs in that some nanometer of disc structure, for Ce_0.6F₃：0.4Tb³⁺(Fig. 5), hence it is evident that it was observed that size range is 30- The nanocube of 200nm is main.In CeF₃Adulterate different amounts of Tb in structure³⁺Ion, the change of shape and size is By CeF₃(hexagonal phase) and TbF₃What the different crystal structure between (orthorhombic phase) caused, but it is overall more equal to obtain sample granularity It is even.

(2) photoluminescence performance

Ce³⁺Unmasked electronic shell it is very sensitive to host lattice, and launch wavelength depends on surrounding environment.Fig. 6 gives CeF is gone out₃The excitation and emission spectra of sample.Under the burst of ultraviolel of 253nm (Fig. 6 left sides peak), it was observed that in 340nm extremely Broadband in the range of 500nm, maximum at 375nm, this be due to ground state division (²F_5/2With²F_7/2), form two and cleave peak.But It is the failure to capture Ce³⁺Current split, this is probably widening due to the spectral line that small-size effect causes.

Due to CeF₃Fluorophor is doped with Tb³⁺Ion, they show strong Tb in the case where UV is excited³⁺Green emitted.Fig. 7 Give Ce_0.8F₃：0.2Tb³⁺The excitation and emission spectra of sample.Ce³⁺The presence of excitation band shows energy from Ce³⁺It is transferred to Tb^{3 +}.Ce is energized into 253nm³⁺There is Tb in band³⁺'s⁵D₄ ^-7F₆(489nm),⁵D₄-⁷F₅(543nm),⁵D₄-⁷F₄(583nm) and⁵D₄-⁷F₃ (620nm), the appearance of these characteristic peaks is because f-f is in Tb³⁺4f⁸There is f-f transition in electronics.

Ce_1-xF₃：xTb³⁺The emissive porwer of sample is by doping Tb³⁺The strong influence of concentration, it is dense that Fig. 8 gives different doping The spectrogram of the lower sample of degree.It can be seen that Tb³⁺Emissive porwer with Tb³⁺The increase of concentration and gradually increase, Doped parameterx reaches maximum when being 0.2, then reduces, this and Ce³⁺Emissive porwer conversely, show using this method prepare CeF₃：x Tb³⁺Tb in sample³⁺The doping concentration optimal result of green emitted is 0.2.

Tb³⁺The launching efficiency of itself is very low, can improve luminous efficiency by doping, the mode of energy transmission.We In method, Ce³⁺As sensitizer, Tb³⁺As activator, i.e., by Ce³⁺Exciting for ion can obtain strong Tb³⁺Emission peak.It is logical Cross equation η_T=I_S/I_SoTo calculate different Tb³⁺The energy transfer efficiency of sample, wherein η under doping concentration_TIt is energy transfer effect Rate, I_SAnd I_SoIt is respectively exist and in the absence of Tb⁴⁺'s⁵D₄Corresponding luminous sensitizing agent intensity during energy level.Energy transfer efficiency with Tb³⁺Increase to 0.2 from 0.05 and increase, be then gradually reduced.This is due to from Ce³⁺To Tb³⁺Energy transmission tend to full With Tb³⁺Concentration continues to increase, and causes the Tb in high concentration³⁺-Tb³⁺Harmful energy transmission is produced between ion, causes to light The reduction of efficiency.For Ce_0.8F₃：0.2Tb³⁺, it is 98.2% to estimate rate of energy transfer, shows Ce_0.8F₃：0.2Tb³⁺Sample In from Ce³⁺To Tb³⁺Energy transfer it is highly effective.

(3) cathodoluminescence performance

In the case where denoted low voltage electron beam is excited, Ce_1-xF₃：Tb³⁺The cathodoluminescence property of sample is similar to photoluminescent property.Fig. 9 It is Ce_0.8F₃：0.2Tb³⁺The representative CL spectrum of sample.Tb in figure³⁺Corresponded respectively in the characteristic emission of 543nm and 489nm⁵D₄-⁷F₅With⁵D₄-⁷F₆Tb³⁺Transition.Then study Ce_0.8F₃：0.2Tb³⁺The CL emissive porwers of fluorophor and heater current and plus The relation of fast voltage.When heater current is fixed on 85mA, CL intensity is with accelerating potential from 2.0 to 4.0kV (such as Figure 10 institutes Show).Similarly, under 4.0kV electron-beam excitations, CL intensity increases to 93mA (such as Figure 11 institutes also with heater current from 85 Show).Result above shows that the photostability of sample is preferable.

Compared with conventional solid reacts, the temperature of this method is lower, and generally generally only needs the shorter reaction time, With little residual impurity.Using solid phase method at 800 DEG C in N₂Sample is prepared in atmosphere as a comparison, corresponding XRD in Figure 12 There is bad crystallization, CeO in the bright product of chart₂Impurities phase occupy major part.When using the hot method preparation CeF of hydrothermal/solvent₃It is glimmering Body of light, their normal yields are low, and need the reaction time long to react.Additionally, before the poisonous organic metal used in the pyrolysismethod Body and/or corrosive acid have resulted in serious environmental problem.

To sum up, the preferable CeF of crystallization can conveniently be prepared by this method₃And CeF₃：Tb³⁺Fluorescent material.In CeF₃：Tb³⁺ In sample, Tb³⁺Generation lattice replaces, and the phase of sample, size, pattern change, while have impact on the luminescent properties of sample. CeF₃：Tb³⁺In sample, Ce³⁺While carrying out strong UV absorptions, Tb³⁺Strong green emission is produced, is occurred by Ce³⁺To Tb³⁺Energy Amount transmission, while being estimated critical distance, the as shown by data energy transfer efficiency of calculating is higher.Tb³⁺Doping concentration It is optimum doping concentration 0.2 or so.CeF₃：Tb³⁺The cathode-ray luminescence property of sample is similar with photoluminescent property, Show Tb³⁺Characteristic emission.Excellent luminous intensity and efficient energy transmission makes sample have in solid luminescent Material Field There is very big application potential.

Claims (9)

1. a kind of preparation method of terbium ion doping fluoride solid luminescent material, it is characterised in that the method includes following step Suddenly：

First, by chemical formula Ce_1-xF₃：xTb³⁺Stoichiometric proportion weigh Ce (NO₃)₃·6H₂O、NaF、NaNO₃And KNO₃Sample, its Middle x is 0~0.8；

2nd, the sample that step one is weighed is put into agate mortar, adds ethanol sample dissolution, ground 20~30 minutes, obtain mixed Compound；

Three and then mixture is transferred to it is heated to 320~350 DEG C in alumina crucible, and keeps 4~5 small at such a temperature When, after being cooled to room temperature, product is washed with deionized 3~5 times, is then dried overnight at 80~100 DEG C, obtains Ce_{1- x}F₃：xTb³⁺Powder.

2. a kind of preparation method of terbium ion doping fluoride solid luminescent material according to claim 1, its feature exists X is 0.05 in step one.

3. a kind of preparation method of terbium ion doping fluoride solid luminescent material according to claim 1, its feature exists X is 0.1 in step one.

4. a kind of preparation method of terbium ion doping fluoride solid luminescent material according to claim 1, its feature exists X is 0.2 in step one.

5. a kind of preparation method of terbium ion doping fluoride solid luminescent material according to claim 1, its feature exists X is 0.4 in step one.

6. a kind of preparation method of terbium ion doping fluoride solid luminescent material according to claim 1, its feature exists X is 0.8 in step one.

7. a kind of preparation method of terbium ion doping fluoride solid luminescent material according to claim 1, its feature exists Ground 25 minutes in step 2.

8. a kind of preparation method of terbium ion doping fluoride solid luminescent material according to claim 1, its feature exists Mixture is transferred in step 3 330~340 DEG C are heated in alumina crucible.

9. a kind of preparation method of terbium ion doping fluoride solid luminescent material according to claim 1, its feature exists Product is washed with deionized 3~5 times in step 3, is then dried overnight at 90 DEG C.