CN104479677B

CN104479677B - One class contains the up-conversion luminescence temperature-sensitive material of rare earth element, preparation method and applications

Info

Publication number: CN104479677B
Application number: CN201410748375.6A
Authority: CN
Inventors: 王旭升; 李俊; 洪渲清; 柴晓娜; 李艳霞; 赵海峰; 冯晓敏; 刘茜
Original assignee: Tongji University
Current assignee: Tongji University
Priority date: 2014-12-09
Filing date: 2014-12-09
Publication date: 2016-08-17
Anticipated expiration: 2034-12-09
Also published as: CN104479677A

Abstract

The present invention relates to a class containing the up-conversion luminescence temperature-sensitive material of rare earth element, preparation method and applications.The chemical general formula of described luminescent material is (A_0.5Re_0.5)TiO₃, in formula, A is selected from Rb, K, Na, one or more in Li or Ag, one or more in Er, Yb, Pr, Eu, Ho, Tm, Tb or Dy of Re.Described sensitive material can be used for preparing invention material, luminescent material prepared by the present invention has up-conversion luminescence performance and the temperature sensitivity energy of excellence, luminous intensity is high, temperature sensitivity is good, application wide temperature region, the stable chemical performance of material, physical size is controlled, it is easy to preparation, and cost is relatively low, at fluorescence temperature sensor, short wavelength emissions solid-state laser, biomolecule fluorescent labeling, infrared acquisition is with false proof, 3 D stereo shows, the field such as integrated optoelectronic device and solaode has broad application prospects.

Description

One class containing the up-conversion luminescence temperature-sensitive material of rare earth element, preparation method and Application

Technical field

The present invention relates to a class containing the up-conversion luminescence temperature-sensitive material of rare earth element, preparation method and applications, genus In Multifunctional photoelectric processor Material Field.

Background technology

Up-conversion refers to the infrared ray excited lower luminescent material that can send visible ray, and can convert infrared light into can See the material of light.Owing to its luminescence process runs counter to Stokes law, therefore it is also called anti-Stokes law luminescent material.Since 1966 Year Auzel reported first Er³⁺And Yb³⁺Codope CaWO₄Up-conversion starts, up-conversion luminescence process and corresponding material thereof Expect to be paid close attention to by more and more scientists.First up-conversion with practical value is Er³⁺And Yb³⁺Codope LaF₃, and within certain section time, become the focus of correlational study, also provide an effective way for obtaining visible waveband laser Warp.Dividing according to material system, up-conversion can be divided into rare earth fluoride (rare earth fluoride and rare earth fluorination compound with alkali metal Thing), rare earth halide, and rare earth oxide (single rare earth oxide and composite rare-earth oxide).Wherein, rare earth oxide phase Having heat stability than other two classes material and chemical stability is high, preparation technology is simple, and with low cost, preparation process is to environment Damage the advantages such as little, paid close attention to by some researcheres in recent years.The focus of research is concentrated mainly on to manage to improve and changes on it Luminous efficiency.

The feature that the up-conversion luminescence of material varies with temperature can be used to make temperature sensor.At present, fluorescence temperature Sensor is based primarily upon following three kinds of technology (seeing Chinese patent CN200910186444.8).It is that fluorescence intensity is with temperature respectively The technology that the ratio of the technology of change, technology that fluorescence lifetime varies with temperature and fluorescence intensity varies with temperature.Wherein, based on The technology that fluorescence intensity ratio varies with temperature has compared with other two kinds of technology not to be affected by input stimulus, should not by optical fiber The impact of power, the advantages such as data analysis is simple.This temperature sensor material requires that material has a following feature: first, material Material to have at a distance of nearer excited level, and the two energy level is preferably coupling level, and (beneficially sensor is from exciting merit The interference of the factor such as rate, fiber stress, the most beneficially theory analysis)；Second, fluorescence intensity ratio is temperature sensitive (beneficially to be improved The sensitivity of sensor), the 3rd, the physico-chemical property of material stable (beneficially interval the widening of thermometric).

High sensitivity and wide thermometric interval are two parameters of the most critical of such materials application.Preferably temperature sensing material Material should have high sensitivity simultaneously and wide thermometric is interval.But, sensitivity and thermometric interval are two vied each other for a pair Parameter.Usual highly sensitive material often its heat stability is poor.On the contrary, the material of usual Heat stability is good has wide survey Between warm area, but the ratio variation with temperature of its fluorescence intensity is the most notable (sensitivity is low).Such as, according to document Advanced Materials, 2012,24,1987-1993 reports, Yb₃Al₅O₁₂: the thermometric interval of Er-Mo material is the widest (295-973 K), the maximum of its sensitivity is 0.0048 K^-1.And document Applied Physics Letters reports BaTiO₃: Er nanocrystalline material has high sensitivity, and (maximum is 0.0052 K^-1), the thermometric interval of this material is the narrowest (only There is 322-466 K).It addition, according to Chinese patent CN201220402520.1, NaYF₃: Yb³⁺/Er³⁺Material has highly sensitive Degree (0.0137 K^-1), but its thermometric interval is only 25-180 DEG C, and its application is not coupling level.The most excellent Select host material, the composition of regulation material, or improve the preparation method of material so that sensitivity and thermometric interval are just balanced Seem and be even more important.

Owing to containing abundant physical phenomenon and peculiar physical property, perovskite structure oxide material is current advanced person One of field of functional materials is the most active, most active, and the most promising research material.In recent years, this kind of material, in luminescence, is situated between Electricity and piezoelectricity, many ferrum (ferroelectricity, ferromagnetic, ferrum bullet), giant magnetoresistance, metal-insulator phase transition, solid state ionic conductor, superconductor, optics The fields such as non-linear and opto-electronic conversion are paid close attention to the most widely.For up-conversion luminescent material, owing to material structure is stable, The advantages such as preparation technology is simple, with low cost and performance easy-regulating, perovskite structure oxide material is the most quite by the parent of researcher Look at.Root according to the literature, the CaTiO that rare earth erbium doping or erbium, ytterbium are co-doped with₃, SrTiO₃、BaTiO₃All show stronger upper turn Change optical phenomenon, see document Journal of Luminescence, 2008,128:797-799, Journal of Alloys and Compounds, 2006,415:280-283 and Optics Express, 2011,19 (3): 1824- 1829、Applied Physics Letters, 2004, 84(23): 4753-4755.But, according to Chinese patent CN102321575 reports, this Perovskite-type oxides material is as the up-conversion of substrate, and luminous efficiency is relatively low, limit Make its application.Recently, inventor place seminar reports a kind of with Na_0.5La_0.5TiO₃For substrate up-conversion (see Chinese patent CN102321575).This material is with appropriate rare earth element er³⁺、Ho³⁺、Tm³⁺、Yb³⁺Part substitutes La, wherein Er³ ⁺、Ho³⁺, or Tm³⁺As the centre of luminescence, rare earth element y b is as sensitizer, application solid state reaction, solvent thermal and collosol and gel etc. It is high that method is prepared for a class luminous intensity, and size is controlled, the oxide up-conversion luminescent material of Color tunable.

The present invention, on the basis of previous work, updates formula, uses new method to be prepared for a class containing rare earth element Up-conversion luminescence temperature-sensitive material.Research finds, material has up-conversion luminescence and the temperature sensitivity energy of excellence, has simultaneously The advantages such as having luminous intensity high, temperature sensitivity is good, application wide temperature region.Meanwhile, the stable chemical performance of material, physical size can Control, it is easy to preparation, cost is relatively low.Therefore, it is possible to it is envisioned that change material at fluorescence temperature sensor, short wavelength emissions solid-state laser, Biomolecule fluorescent labeling, infrared acquisition is with false proof, and 3 D stereo shows, integrated optoelectronic device, and the field such as solaode Have broad application prospects.

Summary of the invention

The shortcoming of prior art in view of the above, it is an object of the invention to provide the class upper conversion containing rare earth element Luminance temperature sensitive material, preparation method and applications, this materials application is in Multifunctional photoelectric processor Material Field.

For achieving the above object and other purpose, the present invention adopts the following technical scheme that realization:

The class that the present invention the provides up-conversion luminescence temperature-sensitive material containing rare earth element, the chemistry of described luminescent material Formula is (A_0.5Re_0.5)TiO₃, wherein: A is one or more in monoacidic base metallic element and transition metal Ag element, and Re is Lanthanide series rare-earth elements.

In the present invention, described A be selected from Rb, K, Na, one or more in Li or Ag, Re selected from Er, Yb, Pr, Eu, Ho, One or more in Tm, Tb or Dy.

What the present invention proposed the preparation method of the up-conversion luminescence temperature-sensitive material containing rare earth element, uses high energy ball In mill method, fused salt reaction method, solvent thermal reaction method or solid phase reaction method any one, its detailed step is the most such as Under:

1, high energy ball mill method

(1) the weighing of raw material: by chemical general formula (A_0.5Re_0.5)TiO₃The stoichiometric proportion of middle A, Re and Ti weighs following former Material: in the carbonate of element A, nitrate or hydroxide any one, the oxide of rare earth element Re or nitrate, element ti Oxide or chloride；

(2) high-energy ball milling: load weighted raw material is put into Special ball mill tank container, then be added thereto to a certain amount of firmly Fat acid, is simultaneously introduced a small amount of n-amyl alcohol (or adding appropriate amount of deionized water and dehydrated alcohol).Finally utilize high energy ball mill Ball milling, controls high speed ball milling 1-100 hour, and speed setting is 100-400 rev/min, rotating mode ball milling, Ball-milling Time and Time-out interval is respectively 10-200 minute and 5-60 minute；Stearic addition is the 0～300% of compound weight, n-amyl alcohol Addition is compound weight 1～50%；

(3) heat treatment: by the mixed material after ball milling with dehydrated alcohol dilute, static after tentatively remove stearic acid, then Application centrifuge separates, and takes out gained pretreatment powder body, then by this powder body 500～1100 DEG C of heat treatments 1～10 hours, Described up-conversion luminescence temperature-sensitive material is i.e. made after furnace cooling.

It is preferred that high energy ball mill described in step (2) use PULVERISETTE 5, speed setting be 100-400 turn/ Minute, ball milling 2-50 hour, Ball-milling Time and time-out interval are respectively 20-180 minute and 10-60 minute, in step (3), nothing During water-ethanol dilution, time of repose is 5-100 minute.

It is preferred that element A selects its carbonate or nitrate, Re element to select its oxide or nitrate in step (1), Element ti selects its oxide TiO₂Or chloride TiCl₄.Preferably；In step (2), stearic addition is compound weight 0～300%, the addition of n-amyl alcohol is the 1～50% of compound weight, and high energy ball mill utilizes PULVERISETTE 5, turn Speed is set as 100-400 rev/min, ball milling 2-50 hour, and Ball-milling Time and time-out interval are respectively 20-180 minute and 10-60 Minute.In step (3), during dehydrated alcohol dilution, time of repose is 5-100 minute, after centrifuge separates, and heat treatment temperature It it is 500～1000 DEG C.

Preferably, in step (2), stearic addition is the 10～200% of compound weight, and the addition of n-amyl alcohol is The 1～100% of compound weight, the speed setting of high energy ball mill is 150-380 rev/min, ball milling 2-50 hour, rotating Mode ball milling, Ball-milling Time and time-out interval are respectively 20-100 minute and 10-60 minute.In step (3), dehydrated alcohol dilutes Time, time of repose is 10-30 minute, and after centrifuge separates, heat treatment temperature is 500～1000 DEG C, and the time is 1～8 little Time.

Preferably, in step (2), stearic addition is the 10～100% of compound weight, and the addition of n-amyl alcohol is The 5～100% of compound weight, the speed setting of high energy ball mill is 300-380 rev/min, ball milling 2-20 hour, rotating Mode ball milling, Ball-milling Time and time-out interval are respectively 30 minutes and 20 minutes.In step (3), during dehydrated alcohol dilution, stand Time is 20 minutes, and after centrifuge separates, heat treatment temperature is 500～1000 DEG C, and the time is 2～8 hours.

2 molten-salt growth methods

(1) the weighing of raw material: by chemical general formula (A_0.5Re_0.5)TiO₃, A, Re and Ti element therein is chosen following respectively Raw material: elements A is selected from the chloride of A, and rare earth element Re is arbitrary in the oxide of Re, sulfate, nitrate or chloride Kind, element ti is selected from its oxide；

(2) prepared by predecessor: by chemical general formula (A_0.5Re_0.5)TiO₃In the stoichiometric proportion of A, Re and Ti weigh each at the beginning of Beginning raw material, and it is added thereto to the chloride of appropriate A as fused salt (initial feed is 1:0.5-1:10 with the mass ratio of ACl), This mixing raw material is ground 1-5 hour in agate mortar and is allowed to mix homogeneously, make the precursor powder of molten-salt growth method reaction.Again will This precursor powder is transferred in the corundum crucible added a cover, finally 700～1050 DEG C of heat treatments 1～10 hours, after furnace cooling I.e. make the predecessor of described up-conversion luminescence temperature-sensitive material；

(3) fused salt separates: is put into by the predecessor of step (2) gained in deionization warm water (water temperature 50-90 DEG C) and soaks (10-100h) it is allowed to soft (period can add deionized water to prevent it to be oven-dried).The most constantly change water repeatedly to wash Except the chloride of excess A, or filtering apparatus is used to filter off except excess fused salt.Finally by the pressed powder that obtains at 100-150 DEG C dry and to prepare described up-conversion luminescence temperature-sensitive material powder body.

It is preferred that in step (1), elements A is selected from the chloride of A, and rare earth element Re is selected from nitrate or the chloride of Re, Element ti is selected from its oxide (TiO₂)；In step (2), ACl is 1:1-1:2.5 with the mass ratio of initial feed, milling time For 2-3 hour, heat treatment temperature was 720-990 DEG C, heat treatment time 2～6 hours；In step (3), deionization warm water temperature is (water temperature 60-80 DEG C) soaks (10-72 h).

Preferably, in step (1), elements A is selected selected from the nitrate of Re, element ti selected from the chloride of A, rare earth element Re From its oxide (TiO₂)；In step (2), ACl is 1:1-1:2 with the mass ratio of initial feed, and milling time is 2-3 hour, Heat treatment temperature is 720-990 DEG C, heat treatment time 2～4 hours；In step (3), deionization warm water temperature is (water temperature 60-80 DEG C) middle immersion (10-72 h).

Preferably, in step (1), elements A is selected selected from the nitrate of Re, element ti selected from the chloride of A, rare earth element Re From its oxide (TiO₂)；In step (2), ACl is 1:1.5-1:2 with the mass ratio of initial feed, and milling time is 2 hours, Heat treatment temperature is 730-990 DEG C, heat treatment time 4 hours；In step (3), deionization warm water temperature is (water temperature 60-80 DEG C) Middle immersion (24-72 h).

3 solvent thermal reaction methods

(1) the choosing of raw material: by chemical general formula (A_0.5Re_0.5)TiO₃, A, Re and Ti element therein is chosen following respectively Raw material: elements A is selected from the hydroxide of A, and rare earth element Re is selected from nitrate or the chloride of Re, and element ti is selected from four chlorinations Titanium, four n-butyl titaniums (butyl titanate) or titanium tetraisopropylate.Solvent is chosen in deionized water, dehydrated alcohol or ethylene glycol arbitrary Kind；

(2) prepared by presoma: by chemical general formula (A_0.5Re_0.5)TiO₃In the stoichiometric proportion of A, Re and Ti weigh each at the beginning of Beginning raw material, and add deionized water, in one or more mixed solvents in dehydrated alcohol and ethylene glycol after the mixing of this raw material And be sufficiently stirred for being allowed to dissolve.Then the mol ratio adding appropriate AOH(AOH Yu Ti element in mixed solution is 1:1-20: 1) and make it fully dissolve.Again mixed solution being transferred in water heating kettle, carry out solvent thermal reaction, reaction temperature is 120 DEG C- 250 DEG C, the response time is 2 hours-48 hours；

(3) heat treatment: after solvent heat treatment, goes upper solution, and with deionized water repeatedly rinse precipitation powder body with Go out the RbOH of excess, finally take out gained pretreatment powder body, then by this powder body 400～1000 DEG C of heat treatments 1～10 hours, Described up-conversion luminescence temperature-sensitive material is i.e. made after furnace cooling.

It is preferred that in step (1), rare earth element Re is selected from titanium tetrachloride or four positive fourths selected from the nitrate of Re, element ti Alcohol titanium (butyl titanate)；Any one in deionized water, dehydrated alcohol or ethylene glycol chosen by solvent；AOH Yu Ti unit in step (2) The mol ratio of element is 1:1-15:1；Reaction temperature is 120-250 DEG C, and the response time is 6-36 hour；In step (3) at powder body heat Reason temperature is 400～1000 DEG C, and the time is 1～10 hour.

Preferably, in step (1), rare earth element Re is selected from titanium tetrachloride, four n-butyl alcohol selected from the nitrate of Re, element ti Titanium (butyl titanate)；Any one in deionized water, dehydrated alcohol or ethylene glycol chosen by solvent；AOH Yu Ti element in step (2) Mol ratio be 1:1-15:1, reaction temperature is 180-230 DEG C, and the response time is 12-36 hour；In step (3) at powder body heat Reason temperature is 600～980 DEG C, and the time is 1～10 hour.

Preferably, in step (1), rare earth element Re is selected from four n-butyl titaniums (metatitanic acid four selected from the nitrate of Re, element ti Butyl ester)；Any one in deionized water, dehydrated alcohol or ethylene glycol chosen by solvent；The mol ratio of AOH Yu Ti element in step (2) For 1:1-15:1, reaction temperature is 180-230 DEG C, and the response time is 12-36 hour；In step (3), powder body heat treatment temperature is 600～980 DEG C, the time is 1～10 hour.

4 solid phase reaction methods

(1) the choosing of raw material: by chemical general formula (A_0.5Re_0.5)TiO₃, A, Re and Ti element therein is chosen following respectively Raw material: elements A is selected from two selected from the carbonate of A, rare earth element Re selected from the oxide of Re, nitrate or chloride, element ti Titanium oxide (rutile, anatase or brockite)；

(2) raw material weighs and mixes: by chemical general formula (A_0.5Re_0.5)TiO₃In the stoichiometric proportion of A, Re and Ti weigh Each initial feed, the most volatile A raw material needs suitably excess (1-10%), and load weighted raw material side is entered Achates grinds In alms bowl, grind 2-5 hour after adding ethanol mix homogeneously；

(3) preheating: will grind after blended stock put into heat treatment in Muffle furnace, heat treatment temperature be 700～ 1000 DEG C, heat treatment time is 1～10 hour, then makes preburning powdered material with stove cooling down；

(4) double sintering: preburning powdered material is added dehydrated alcohol, regrinding 2-5 hour, then the powder body after this is ground 800～1200 DEG C of heat treatments 1～20 hours, after furnace cooling, i.e. make described up-conversion luminescence temperature-sensitive material powder Body.

Preferably, in step (1), elements A is selected from the carbonate of A, and rare earth element Re is selected from oxide or the nitrate of Re, Element ti is selected from titanium dioxide (rutile, anatase or brockite).

Preferably, in step (2), A raw material excess (1-5%), grinds 2-3 hour.

Preferably, in step (3), heat treatment temperature is 800～950 DEG C, and heat treatment time is 4～6 hours.

Preferably, step (4) the regrinding time is 2-3 hour, and heat treatment temperature is 900～1100 DEG C, during heat treatment Between be 4～10 hours.

The up-conversion luminescence temperature-sensitive material that the present invention proposes is applied to prepare ceramic material, target, and described target is used In preparing thick film or thin-film material.

The preparation method of the described ceramic material that the present invention proposes, specifically comprises the following steps that

(1) described up-conversion luminescence temperature-sensitive material is put in agate mortar and grind 1-2 hour, add dense wherein Degree be 1～15% polyvinyl alcohol as binding agent, be sufficiently stirred for, natural drying, pelletize, cross screen cloth, make spherical powder；

(2) spherical powder is put into grinding tool, under 10～100MPa pressure, is pressed into the green compact of certain thickness and diameter, Green compact are put in Muffle furnace 2-10 hour row of 500-600 DEG C of insulation again viscous, finally by sample at 950～1350 DEG C of sintering 1～ 10 hours, close power supply cooling after being cooled to uniform temperature, i.e. obtain described up-conversion luminescence temperature sensitive ceramic block material Material.

Preferably, adding polyvinyl alcohol concentration in step (1) is 2～10%, crosses 60 mesh and 160 mesh sieves.

Preferably, being incubated 10 hours at 500-600 DEG C when row is viscous in step (2), during sintering, temperature is 950～1350 DEG C, Sintering time is 2～8 hours.

In the present invention, described up-conversion luminescence temperature-sensitive material is at fluorescence temperature sensor, short wavelength emissions solid-state laser Device, biomolecule fluorescent labeling, infrared acquisition with false proof, 3 D stereo shows, integrated optoelectronic device or area of solar cell Application.

Up-conversion luminescence temperature-sensitive material prepared by the present invention has the luminescent properties of excellence, and luminous intensity is high, temperature Sensitivity is good, the stable chemical performance of material, and physical size is controlled, it is easy to preparation, and cost is relatively low, at fluorescence temperature sensor, Short wavelength emissions solid-state laser, biomolecule fluorescent labeling, infrared acquisition is with false proof, and 3 D stereo shows, integrated optoelectronic device, And the field such as solaode has broad application prospects.Preparation method of the present invention has that technique is simple, process stabilizing, be prone to The advantages such as industrialization promotion.

Accompanying drawing explanation

Fig. 1 is embodiment 4, (Na prepared by embodiment solid phase reaction method_0.5Er_0.5)TiO₃、(Na_0.5Eu_0.5)TiO₃、 (Na_0.5Ho_0.5)TiO₃And (Na_0.5Yb_0.5)TiO₃The XRD figure spectrum of powder sample；

Fig. 2 is that in embodiment 1, different time high-energy ball milling method prepares (Na_0.5Er_0.5)TiO₃The up-conversion luminescence figure of sample Spectrum, excitation source is 980 nanometers；

Fig. 3 and Fig. 4 is respectively the up-conversion luminescence spectrum of product in embodiment 2, and excitation source is 980 nanometers；

Fig. 5 is the up-conversion luminescence spectrum of product in embodiment 3, and excitation source is 980 nanometers；

Fig. 6 is the up-conversion luminescence spectrum of product in embodiment 4, and excitation source is 980 nanometers；

Fig. 7 is product up-conversion luminescence spectrum at different temperatures in embodiment 4；

Fig. 8 is the curve that in embodiment 4, the fluorescence intensity ratio of the up-conversion luminescence of product varies with temperature；

Fig. 9 is the curve that in embodiment 4, the sensitivity of the up-conversion luminescence of product varies with temperature；

Figure 10～13 is respectively the up-conversion luminescence spectral line of product in embodiment 5～8, and excitation source is 980 nanometers；

Figure 14 and Figure 15 is respectively the up-conversion luminescence spectrum of product under different temperatures in embodiment 12, and excitation source is 980 nanometers；

Figure 16 and Figure 17 is respectively the up-conversion luminescence spectrum of product under different temperatures in embodiment 16, and excitation source is 980 nanometers；

Figure 18 is the up-conversion luminescence spectrum of product in embodiment 20, and excitation source is 980 nanometers；

Figure 19 is the up-conversion luminescence spectrum of product in embodiment 22, and excitation source is 980 nanometers；

Figure 20 is the up-conversion luminescence spectrum of product in embodiment 30, and excitation source is 980 nanometers.

Detailed description of the invention

Below by way of specific instantiation, embodiments of the present invention being described, those skilled in the art can be by this specification Described content understands further advantage and effect of the present invention easily.The present invention can also be by the most different concrete realities The mode of executing is carried out or applies, the every details in this specification can also based on different viewpoints and application, without departing from Various modification or change is carried out under the spirit of the present invention.

Embodiment 1

High-energy ball milling method prepares (Na_0.5Er_0.5)TiO₃Powder body material, preparation method is as follows:

Use high pure sodium carbonate (99.8%), Erbia powder (99.9%), titania powder (99.9%), for raw material, press Stoichiometric proportion weighs raw material, is put in Special ball grinding jar by load weighted raw material, then is added thereto to a certain amount of stearic acid, It is simultaneously introduced a small amount of n-amyl alcohol.Finally utilize PULVERISETTE 5 high energy ball mill, high speed ball milling 4 hours, speed setting Being 350 revs/min, rotating mode ball milling, Ball-milling Time and time-out interval are respectively 20 minutes and 20 minutes.Again by after ball milling Mixed material dilute with dehydrated alcohol, static after tentatively remove stearic acid, then application centrifuge separates, and takes out gained Pretreatment powder body, then by this powder body 800 DEG C of heat treatments 10 hours, after furnace cooling, i.e. make described up-conversion luminescence temperature Sensitive material powder body；The up-conversion luminescence spectrum (excitaton source: 980 nm irasers) of different time high-energy ball milling sample is such as Fig. 2 Shown in.Luminescent material prepared by the present invention has preferable luminescent properties and temperature sensitivity energy, is especially suitable for making temperature sensing Device is applied.

Embodiment 2

Molten-salt growth method prepares (Na_0.5Er_0.5)TiO₃Powder body material, preparation method is as follows:

By chemical general formula (Na_0.5Er_0.5)TiO₃, initial feed is respectively high pure sodium chloride (NaCl, 98%), Erbia powder End (Er₂O₃, 99.9%), titania powder (TiO₂, 99.9%)；And weigh each initial feed by its stoichiometric proportion, and to it Middle addition lithium chloride is as fused salt (initial feed is 1:1.2 with the mass ratio of LiCl), by this mixing raw material in agate mortar Grind and be allowed to mix homogeneously in 3 hours, make the precursor powder of molten-salt growth method reaction.This precursor powder is transferred to the corundum added a cover again In crucible, finally 750 DEG C of heat treatments 10 hours, put into after furnace cooling in deionization warm water (water temperature 80 DEG C) and soak (36 h) It is allowed to soft (period can add deionized water to prevent it to be oven-dried).The most constantly change water repeatedly to wash to remove excess chlorination Lithium, or use sucking filtration instrument to filter off except excess fused salt.Finally by the pressed powder that obtains 120 DEG C dry prepare described upper Conversion luminance temperature sensitive material powder body.Under 980 nanometer light excite, (the Na of preparation_0.5Er_0.5)TiO₃Luminescent material upper turn Change luminescent spectrum as shown in Figures 3 and 4.Luminescent material prepared by the present invention has the luminescent properties of excellence, and luminous intensity is higher.

Embodiment 3

Solvent-thermal method prepares (Na_0.5Er_0.5)TiO₃Powder body material, preparation method is as follows:

By chemical formula (Na_0.5Er_0.5)TiO₃, wherein initial feed is respectively High Purity Hydrogen potassium oxide (NaOH, 99%), nitric acid Erbium [Er (NO₃)₃·5H₂O, 99.9%], four n-butyl titaniums (butyl titanate) liquid (C₁₆H₃₆O₄Ti, 98%)；By its stoichiometry Ratio weighs each initial feed.Solvent chooses deionized water, dehydrated alcohol, and ethylene glycol；Add after this raw material is mixed and go second two In alcohol and be sufficiently stirred for being allowed to be completely dissolved.Then in mixed solution, add appropriate NaOH and make it fully dissolve.Finally Mixed solution being transferred in water heating kettle, carry out solvent thermal reaction, reaction temperature is 180 DEG C, and the response time is 24 hours；Solvent After heat treatment, upper solution is gone, and with deionized water repeatedly rinse precipitation powder body with go out excess NaOH, finally take out Gained pretreatment powder body, then by this powder body 750 DEG C of heat treatments 4 hours, after furnace cooling, i.e. make described up-conversion luminescence Temperature-sensitive material powder body.(the Na prepared_0.5Er_0.5)TiO₃Luminescent material up-conversion luminescence under 980 nanometer light excite Spectrum is as shown in Figure 5.Luminescent material prepared by the present invention has the luminescent properties of excellence, and luminance conversion efficiency is high.

Embodiment 4

Solid phase method prepares (Na_0.5Er_0.5)TiO₃Powder body material, preparation method is as follows:

Use high-purity potassium carbonate (Na₂CO₃, 99.8%), Erbia powder (Er₂O₃, 99.9%), titania powder (TiO₂, 99.9%) it is raw material, stoichiometrically weighs raw material, put in agate mortar, after uniformly mixing with ethanol for solvent, ethanol The dry post-drying powder of mill, is placed in corundum boat in 750 DEG C of pre-burning 4 hours in atmosphere by the powder obtained, after cooling with Sample loading mode is ground and is dried.Again powder is placed in after drying in corundum boat in atmosphere 1100 DEG C calcine 10 hours.That prepares sends out The XRD of luminescent material composes as it is shown in figure 1, Fig. 6 gives the up-conversion luminescence spectrum (excitaton source: 980 nm are red under this material room temperature Outer laser), during as temperature sensing material, up-conversion luminescence spectrum under different temperatures as it is shown in fig. 7, its fluorescence intensity when Sensitivity variation with temperature curve is given the most in figs. 8 and 9.Luminescent material prepared by the present invention has the luminescence of excellence Performance, luminous intensity is high, temperature sensing excellent performance.

Embodiment 5

Solid phase method prepares (Na_0.5Pr_0.5)TiO₃Powder body material, preparation method is as follows:

Use high-purity potassium carbonate (Na₂CO₃, 99.8%), praseodymium oxide powder (Pr₅O₁₁, 99.9%), titania powder (TiO₂, 99.9%) and it is raw material, stoichiometrically weigh raw material, put in agate mortar, uniformly mix for solvent with ethanol After, the dry post-drying powder of ethanol mill, the powder obtained is placed in corundum boat in 750 DEG C of pre-burning 4 hours, coolings in atmosphere After grind drying in the same fashion.Again powder is placed in after drying in corundum boat in atmosphere 1100 DEG C calcine 10 hours.Preparation The XRD of the luminescent material gone out composes as it is shown in figure 1, Figure 10 gives the up-conversion luminescence spectrum (excitaton source: 980 nm are red of this material Outer laser).

Embodiment 6

Solid phase method prepares (Na_0.5Yb_0.5)TiO₃Powder body material, preparation method is as follows:

Use high-purity potassium carbonate (Na₂CO₃, 99.8%), yttrium oxide powder (Yb₂O₃, 99.9%), titania powder (TiO₂, 99.9%) it is raw material, stoichiometrically weighs raw material, put in agate mortar, after uniformly mixing with ethanol for solvent, ethanol The dry post-drying powder of mill, is placed in corundum boat in 750 DEG C of pre-burning 4 hours in atmosphere by the powder obtained, after cooling with Sample loading mode is ground and is dried.Again powder is placed in after drying in corundum boat in atmosphere 1000 DEG C calcine 10 hours.That prepares sends out The XRD of luminescent material composes as it is shown in figure 1, Figure 11 gives (Na_0.5Yb_0.5)TiO₃The up-conversion luminescence spectrum of powder body material (excites Source: 980 nm irasers).

Embodiment 7

Solid phase method prepares (Na_0.5Eu_0.5)TiO₃Powder body material, preparation method is as follows:

Use high-purity potassium carbonate (Na₂CO₃, 99.8%), europium oxide powder (Eu₂O₃, 99.9%), titania powder (TiO₂, 99.9%) it is raw material, stoichiometrically weighs raw material, put in agate mortar, after uniformly mixing with ethanol for solvent, ethanol The dry post-drying powder of mill, is placed in corundum boat in 750 DEG C of pre-burning 4 hours in atmosphere by the powder obtained, after cooling with Sample loading mode is ground and is dried.Again powder is placed in after drying in corundum boat in atmosphere 900 DEG C calcine 10 hours.The luminescence prepared The XRD spectrum of material is as it is shown in figure 1, Figure 12 gives the up-conversion luminescence spectrum (excitaton source: 980 nm irasers swash of this material Send out).

Embodiment 8

Solid phase method prepares (Na_0.5Ho_0.5)TiO₃Powder body material, preparation method is as follows:

Use high-purity potassium carbonate (Na₂CO₃, 99.8%), holmia powder (Ho₂O₃, 99.9%), titania powder (TiO₂, 99.9%) it is raw material, stoichiometrically weighs raw material, put in agate mortar, after uniformly mixing with ethanol for solvent, ethanol The dry post-drying powder of mill, is placed in corundum boat in 750 DEG C of pre-burning 4 hours in atmosphere by the powder obtained, after cooling with Sample loading mode is ground and is dried.Again powder is placed in after drying in corundum boat in atmosphere 1100 DEG C calcine 10 hours.That prepares sends out The XRD of luminescent material composes as it is shown in figure 1, Figure 13 gives the up-conversion luminescence spectrum (excitaton source: 980 nm irasers of this material Excite).

Embodiment 9

High-energy ball milling method prepares (K_0.5Er_0.5)TiO₃Powder body material, preparation method is as follows:

Use high-purity potassium carbonate (99.8%), Erbia powder (99.9%), titania powder (99.9%), for raw material, press Stoichiometric proportion weighs raw material, is put in Special ball grinding jar by load weighted raw material, then is added thereto to a certain amount of stearic acid, It is simultaneously introduced a small amount of n-amyl alcohol.Finally utilize PULVERISETTE 5 high energy ball mill, high speed ball milling 4 hours, speed setting Being 350 revs/min, rotating mode ball milling, Ball-milling Time and time-out interval are respectively 20 minutes and 20 minutes.Again by after ball milling Mixed material dilute with dehydrated alcohol, static after tentatively remove stearic acid, then application centrifuge separates, and takes out gained Pretreatment powder body, then by this powder body 900 DEG C of heat treatments 10 hours, after furnace cooling, i.e. make described up-conversion luminescence temperature Sensitive material powder body.

Embodiment 10

Molten-salt growth method prepares (K_0.5Er_0.5)TiO₃Powder body material, preparation method is as follows:

By chemical general formula (K_0.5Er_0.5)TiO₃, initial feed is respectively high purity potassium chloride (KCl, 99.8%), Erbia powder End (Er₂O₃, 99.9%), titania powder (TiO₂, 99.9%)；And weigh each initial feed by its stoichiometric proportion, and to it This mixing raw material, as fused salt (initial feed is 1:1.2 with the mass ratio of KCl), is ground in agate mortar by middle addition potassium chloride Grind and be allowed to mix homogeneously in 3 hours, make the precursor powder of molten-salt growth method reaction.This precursor powder is transferred to the corundum earthenware added a cover again In crucible, finally 950 DEG C of heat treatments 10 hours, put into after furnace cooling and deionization warm water (water temperature 80 DEG C) soaks (36h) make Soft (period can add deionized water to prevent it to be oven-dried).The most constantly change water repeatedly to wash to remove excess chlorination Potassium, or use filtering apparatus to filter off except excess fused salt.Finally by the pressed powder that obtains 120 DEG C dry prepare described upper Conversion luminance temperature sensitive material powder body.

Embodiment 11

Solvent-thermal method prepares (K_0.5Er_0.5)TiO₃Powder body material, preparation method is as follows:

By chemical formula (K_0.5Er_0.5)TiO₃, wherein initial feed is respectively High Purity Hydrogen potassium oxide (KOH, 99.8%), nitric acid Erbium [Er (NO₃)₃·5H₂O, 99.9%], four n-butyl titaniums (butyl titanate) liquid (C₁₆H₃₆O₄Ti, 98%)；By its stoichiometry Ratio weighs each initial feed.Solvent chooses deionized water, dehydrated alcohol, and ethylene glycol；Add after this raw material is mixed and go second two In alcohol and be sufficiently stirred for being allowed to be completely dissolved.Then in mixed solution, add appropriate KOH and make it fully dissolve.Finally will Mixed solution is transferred in water heating kettle, carries out solvent thermal reaction, and reaction temperature is 180 DEG C, and the response time is 24 hours；Solvent thermal After process, upper solution is gone, and with deionized water repeatedly rinse precipitation powder body with go out excess KOH, finally take out institute Pretreatment powder body, then by this powder body 850 DEG C of heat treatments 4 hours, after furnace cooling, i.e. make described up-conversion luminescence temperature Degree sensitive material powder body.

Embodiment 12

Solid phase method prepares (K_0.5Er_0.5)TiO₃Powder body material, preparation method is as follows:

Use high-purity potassium carbonate (K₂CO₃, 99.8%), Erbia powder (Er₂O₃, 99.9%), titania powder (TiO₂, 99.9%) it is raw material, stoichiometrically weighs raw material, put in agate mortar, after uniformly mixing with ethanol for solvent, ethanol The dry post-drying powder of mill, is placed in corundum boat in 750 DEG C of pre-burning 4 hours in atmosphere by the powder obtained, after cooling with Sample loading mode is ground and is dried.Again powder is placed in after drying in corundum boat in atmosphere 800-1050 DEG C calcine 10 hours.Cold with stove The most i.e. make described up-conversion luminescence temperature-sensitive material powder body.Figure 14 and Figure 15 sets forth 850 DEG C and 900 DEG C and forge Burn the up-conversion luminescence spectral line of 10 hours samples.

Embodiment 13

High-energy ball milling method prepares (Li_0.5Er_0.5)TiO₃Powder body material, preparation method is as follows:

Use pure Lithium Carbonate (99.8%), Erbia powder (99.9%), titania powder (99.9%), for raw material, press Stoichiometric proportion weighs raw material, is put in Special ball grinding jar by load weighted raw material, then is added thereto to a certain amount of stearic acid, It is simultaneously introduced a small amount of n-amyl alcohol.Finally utilize PULVERISETTE 5 high energy ball mill, high speed ball milling 4 hours, speed setting Being 350 revs/min, rotating mode ball milling, Ball-milling Time and time-out interval are respectively 20 minutes and 20 minutes.Again by after ball milling Mixed material dilute with dehydrated alcohol, static after tentatively remove stearic acid, then application centrifuge separates, and takes out gained Pretreatment powder body, then by this powder body 700-900 DEG C of heat treatment 10 hours, after furnace cooling, i.e. make described up-conversion luminescence Temperature-sensitive material powder body；Described up-conversion luminescence temperature-sensitive material powder body is i.e. made after furnace cooling.

Embodiment 14

Molten-salt growth method prepares (Li_0.5Er_0.5)TiO₃Powder body material, preparation method is as follows:

By chemical general formula (Li_0.5Er_0.5)TiO₃, initial feed is respectively industrial grade methanol (LiCl, 98%), Erbia powder End (Er₂O₃, 99.9%), titania powder (TiO₂, 99.9%)；And weigh each initial feed by its stoichiometric proportion, and to it Middle addition lithium chloride is as fused salt (initial feed is 1:1.2 with the mass ratio of LiCl), by this mixing raw material in agate mortar Grind and be allowed to mix homogeneously in 3 hours, make the precursor powder of molten-salt growth method reaction.This precursor powder is transferred to the corundum added a cover again In crucible, finally 750 DEG C of heat treatments 10 hours, put into after furnace cooling in deionization warm water (water temperature 80 DEG C) and soak (36h) It is allowed to soft (period can add deionized water to prevent it to be oven-dried).The most constantly change water repeatedly to wash to remove excess chlorination Lithium, or use filtering apparatus to filter off except excess fused salt.Finally by the pressed powder that obtains 120 DEG C dry prepare described upper Conversion luminance temperature sensitive material powder body.

Embodiment 15

Solvent-thermal method prepares (Li_0.5Er_0.5)TiO₃Powder body material, preparation method is as follows:

By chemical formula (Li_0.5Er_0.5)TiO₃, wherein initial feed is respectively High Purity Hydrogen potassium oxide (LiOH, 99%), nitric acid Erbium [Er (NO₃)₃·5H₂O, 99.9%], four n-butyl titaniums (butyl titanate) liquid (C₁₆H₃₆O₄Ti, 98%)；By its stoichiometry Ratio weighs each initial feed.Solvent chooses deionized water, dehydrated alcohol, and ethylene glycol；Add after this raw material is mixed and go second two In alcohol and be sufficiently stirred for being allowed to be completely dissolved.Then in mixed solution, add appropriate LiOH and make it fully dissolve.Finally Mixed solution being transferred in water heating kettle, carry out solvent thermal reaction, reaction temperature is 180 DEG C, and the response time is 24 hours；Solvent After heat treatment, upper solution is gone, and with deionized water repeatedly rinse precipitation powder body with go out excess LiOH, finally take out Gained pretreatment powder body, then by this powder body 750 DEG C of heat treatments 4 hours, after furnace cooling, i.e. make described up-conversion luminescence Temperature-sensitive material powder body.

Embodiment 16

Solid phase method prepares (Li_0.5Er_0.5)TiO₃Powder body material, preparation method is as follows:

Use high-purity potassium carbonate (Li₂CO₃, 99.8%), Erbia powder (Er₂O₃, 99.9%), titania powder (TiO₂, 99.9%) it is raw material, stoichiometrically weighs raw material, put in agate mortar, after uniformly mixing with ethanol for solvent, ethanol The dry post-drying powder of mill, is placed in corundum boat in 750 DEG C of pre-burning 4 hours in atmosphere by the powder obtained, after cooling with Sample loading mode is ground and is dried.Again powder is placed in after drying in corundum boat in atmosphere 750-1000 DEG C calcine 10 hours.Figure 16 and Figure 17 sets forth 10 hours (Li of 850 DEG C and 900 DEG C calcinings_0.5Er_0.5)TiO₃The up-conversion luminescence spectral line of powder sample.

Embodiment 17

High-energy ball milling method prepares (Rb_0.5Er_0.5)TiO₃Powder body material, preparation method is as follows:

Use high-purity rubidium carbonate (99.8%), Erbia powder (99.9%), titania powder (99.9%), for raw material, press Stoichiometric proportion weighs raw material, is put in Special ball grinding jar by load weighted raw material, then is added thereto to a certain amount of stearic acid, It is simultaneously introduced a small amount of n-amyl alcohol.Finally utilize PULVERISETTE 5 high energy ball mill, high speed ball milling 4 hours, speed setting Being 350 revs/min, rotating mode ball milling, Ball-milling Time and time-out interval are respectively 20 minutes and 20 minutes.Again by after ball milling Mixed material dilute with dehydrated alcohol, static after tentatively remove stearic acid, then application centrifuge separates, and takes out gained Pretreatment powder body, then by this powder body 900 DEG C of heat treatments 10 hours, after furnace cooling, i.e. make described up-conversion luminescence temperature Sensitive material powder body；

Embodiment 18

Molten-salt growth method prepares (Rb_0.5Er_0.5)TiO₃Powder body material, preparation method is as follows:

By chemical general formula (Rb_0.5Er_0.5)TiO₃, initial feed is respectively High Purity Rbcl (RbCl, 99.8%), Erbia Powder (Er₂O₃, 99.9%), titania powder (TiO₂, 99.9%)；And weigh each initial feed by its stoichiometric proportion, and to Wherein addition Rubinorm (Ifi). is as fused salt (initial feed is 1:1.2 with the mass ratio of RbCl), by this mixing raw material at agate mortar Middle grinding is allowed to mix homogeneously in 3 hours, makes the precursor powder of molten-salt growth method reaction.Be transferred to this precursor powder to add a cover is firm again In beautiful crucible, finally 950 DEG C of heat treatments 10 hours, put into after furnace cooling in deionization warm water (water temperature 80 DEG C) and soak (36h) it is allowed to soft (period can add deionized water to prevent it to be oven-dried).The most constantly change water repeatedly to wash to remove Amount Rubinorm (Ifi)., or use sucking filtration instrument to filter off except excess fused salt.Finally the pressed powder obtained is dried at 120 DEG C and prepare institute The up-conversion luminescence temperature-sensitive material powder body stated.

Embodiment 19

Solvent-thermal method prepares (Rb_0.5Er_0.5)TiO₃Powder body material, preparation method is as follows:

By chemical formula (Rb_0.5Er_0.5)TiO₃, wherein initial feed is respectively High Purity Hydrogen rubidium oxide (RbOH, 99.8%), nitre Acid erbium [Er (NO₃)₃·5H₂O, 99.9%], four n-butyl titaniums (butyl titanate) liquid (C₁₆H₃₆O₄Ti, 98%)；Based on its chemistry Amount ratio weighs each initial feed.Solvent chooses deionized water, dehydrated alcohol, and ethylene glycol；Add after this raw material is mixed and go second In glycol and be sufficiently stirred for being allowed to be completely dissolved.Then in mixed solution, add appropriate RbOH and make it fully dissolve.? After mixed solution is transferred in water heating kettle, carry out solvent thermal reaction, reaction temperature is 180 DEG C, and the response time is 24 hours；Molten After agent heat treatment, upper solution is gone, and with deionized water repeatedly rinse precipitation powder body with go out excess RbOH, finally take Go out gained pretreatment powder body, then by this powder body 850 DEG C of heat treatments 4 hours, i.e. make described upper conversion after furnace cooling and send out Light temperature-sensitive material powder body.

Embodiment 20

Solid phase method prepares (Rb_0.5Er_0.5)TiO₃Powder body material, preparation method is as follows:

Use high-purity rubidium carbonate (Rb₂CO₃, 99.8%), Erbia powder (Er₂O₃, 99.9%), titania powder (TiO₂, 99.9%) it is raw material, stoichiometrically weighs raw material, put in agate mortar, after uniformly mixing with ethanol for solvent, ethanol The dry post-drying powder of mill, is placed in corundum boat in 750 DEG C of pre-burning 4 hours in atmosphere by the powder obtained, after cooling with Sample loading mode is ground and is dried.Again powder is placed in after drying in corundum boat in atmosphere 900 DEG C calcine 10 hours.Figure 18 gives (Rb_0.5Er_0.5)TiO₃The up-conversion luminescence spectral line of powder sample.

Embodiment 21

High-energy ball milling method prepares (Ag_0.5Er_0.5)TiO₃Powder body material, preparation method is as follows:

Use high purity silver nitrate (99.8%), Erbia powder (99.9%), titania powder (99.9%), for raw material, press Stoichiometric proportion weighs raw material, is put in Special ball grinding jar by load weighted raw material, then is added thereto to a certain amount of stearic acid, It is simultaneously introduced a small amount of n-amyl alcohol.Finally utilize PULVERISETTE 5 high energy ball mill, high speed ball milling 4 hours, speed setting Being 350 revs/min, rotating mode ball milling, Ball-milling Time and time-out interval are respectively 20 minutes and 20 minutes.Again by after ball milling Mixed material dilute with dehydrated alcohol, static after tentatively remove stearic acid, then application centrifuge separates, and takes out gained Pretreatment powder body, then by this powder body 950 DEG C of heat treatments 10 hours, after furnace cooling, i.e. make described up-conversion luminescence temperature Sensitive material powder body.

Embodiment 22

Solid phase method prepares (Ag_0.5Er_0.5)TiO₃Powder body material, preparation method is as follows:

Use high purity silver nitrate (AgNO₃, 99.8%), Erbia powder (Er₂O₃, 99.9%), titania powder (TiO₂, 99.9%) it is raw material, stoichiometrically weighs raw material, put in agate mortar, after uniformly mixing with ethanol for solvent, ethanol The dry post-drying powder of mill, is placed in corundum boat in 750 DEG C of pre-burning 4 hours in atmosphere by the powder obtained, after cooling with Sample loading mode is ground and is dried.Again powder is placed in after drying in corundum boat in atmosphere 1050 DEG C calcine 10 hours.Figure 19 gives (Ag_0.5Er_0.5)TiO₃The up-conversion luminescence spectral line of powder sample.

Embodiment 23

High-energy ball milling method prepares [(Na_xK_1-x)_0.5Er_0.5]TiO₃Powder body material, preparation method is as follows:

Use high pure sodium carbonate (99.8%), potassium carbonate (99.8%), Erbia powder (99.9%), titania powder (99.9%), for raw material, stoichiometrically weigh raw material, load weighted raw material is put in Special ball grinding jar, then adds wherein Enter a certain amount of stearic acid, be simultaneously introduced a small amount of n-amyl alcohol.Finally utilize PULVERISETTE 5 high energy ball mill, clipping the ball Grinding 4 hours, speed setting is 350 revs/min, rotating mode ball milling, Ball-milling Time and time-out interval be respectively 20 minutes and 20 minutes.Again by the mixed material after ball milling with dehydrated alcohol dilute, static after tentatively remove stearic acid, then apply centrifuge Centrifugation, takes out gained pretreatment powder body, then by this powder body 900 DEG C of heat treatments 10 hours, i.e. makes institute after furnace cooling The up-conversion luminescence temperature-sensitive material powder body stated.

Embodiment 24

Molten-salt growth method prepares [(Na_xK_1-x)_0.5Er_0.5]TiO₃Powder body material, preparation method is as follows:

First prepare (K respectively by the method for embodiment 2 and embodiment 10_0.5Er_0.5)TiO₃(Na_0.5Er_0.5)TiO₃, then By chemical general formula [(Na_xK_1-x)_0.5Er_0.5]TiO₃Stoichiometric proportion weigh two kinds of powder, by this mixing raw material at agate mortar Middle grinding is allowed to mix homogeneously in 3 hours.Again this powder body is transferred in the corundum crucible added a cover, finally at 950 DEG C of heat treatments 10 Hour, furnace cooling i.e. obtains [(Na_xK_1-x)_0.5Er_0.5]TiO₃Up-conversion luminescence temperature-sensitive material powder body.

Embodiment 25

Solvent-thermal method prepares [(Na_xK_1-x)_0.5Er_0.5]TiO₃Powder body material, preparation method is as follows:

First prepare (K respectively by the method for example 3 and example 11_0.5Er_0.5)TiO₃(Na_0.5Er_0.5)TiO₃, then by changing Learn formula [(Na_xK_1-x)_0.5Er_0.5]TiO₃Stoichiometric proportion weigh two kinds of powder, this mixing raw material is ground in agate mortar Grind and be allowed to mix homogeneously in 3 hours.Again this powder body is transferred in the corundum crucible added a cover, finally 950 DEG C of heat treatments 10 hours, Furnace cooling i.e. obtains [(Na_xK_1-x)_0.5Er_0.5]TiO₃Up-conversion luminescence temperature-sensitive material powder body.

Embodiment 26

Solid phase method prepares [(Na_xK_1-x)_0.5Er_0.5]TiO₃Powder body material, preparation method is as follows:

Use high pure sodium carbonate (99.8%), potassium carbonate (K₂CO₃, 99.8%), Erbia powder (Er₂O₃, 99.9%), dioxy Change titanium powder (TiO₂, 99.9%) and it is raw material, stoichiometrically weigh raw material, put in agate mortar, equal with ethanol for solvent After even mixing, the dry post-drying powder of ethanol mill, the powder obtained is placed in corundum boat in 750 DEG C in atmosphere pre-burning 4 little Time, grind drying after cooling in the same fashion.Powder is placed in corundum boat 1050 DEG C of calcinings 10 in atmosphere again little after drying Time.

Embodiment 27

High-energy ball milling method prepares (Na_0.5Ho_0.5)TiO₃Powder body material, preparation method is as follows:

Use high pure sodium carbonate (99.8%), holmia powder (99.9%), titania powder (99.9%), for raw material, press Stoichiometric proportion weighs raw material, is put in Special ball grinding jar by load weighted raw material, then is added thereto to a certain amount of stearic acid, It is simultaneously introduced a small amount of n-amyl alcohol.Finally utilize PULVERISETTE 5 high energy ball mill, high speed ball milling 4 hours, speed setting Being 350 revs/min, rotating mode ball milling, Ball-milling Time and time-out interval are respectively 20 minutes and 20 minutes.Again by after ball milling Mixed material dilute with dehydrated alcohol, static after tentatively remove stearic acid, then application centrifuge separates, and takes out gained Pretreatment powder body, then by this powder body 900 DEG C of heat treatments 10 hours, after furnace cooling, i.e. make described up-conversion luminescence temperature Sensitive material powder body.

Embodiment 28

Molten-salt growth method prepares (Na_0.5Ho_0.5)TiO₃Powder body material, preparation method is as follows:

By chemical general formula (Na_0.5Er_0.5)TiO₃, initial feed is respectively high pure sodium chloride (NaCl, 99.8%), holmia Powder (Ho₂O₃, 99.9%), titania powder (TiO₂, 99.9%)；And weigh each initial feed by its stoichiometric proportion, and to Wherein addition sodium chloride is as fused salt (initial feed is 1:1.2 with the mass ratio of NaCl), by this mixing raw material at agate mortar Middle grinding is allowed to mix homogeneously in 3 hours, makes the precursor powder of molten-salt growth method reaction.Be transferred to this precursor powder to add a cover is firm again In beautiful crucible, finally 950 DEG C of heat treatments 10 hours, put into after furnace cooling in deionization warm water (water temperature 80 DEG C) and soak (36h) it is allowed to soft (period can add deionized water to prevent it to be oven-dried).The most constantly change water repeatedly to wash to remove Amount sodium chloride, or use filtering apparatus to filter off except excess fused salt.Finally the pressed powder obtained is dried at 120 DEG C and prepare institute The up-conversion luminescence temperature-sensitive material powder body stated.

Embodiment 29

Solvent-thermal method prepares (Na_0.5Ho_0.5)TiO₃Powder body material, preparation method is as follows:

By chemical formula (Na_0.5Ho_0.5)TiO₃, wherein initial feed is respectively high purity sodium hydroxide (NaOH, 99.8%), nitre Acid holmium [Er (NO₃)₃·5H₂O, 99.9%], four n-butyl titaniums (butyl titanate) liquid (C₁₆H₃₆O₄Ti, 98%)；Based on its chemistry Amount ratio weighs each initial feed.Solvent chooses deionized water, dehydrated alcohol, and ethylene glycol；Add after this raw material is mixed and go second In glycol and be sufficiently stirred for being allowed to be completely dissolved.Then in mixed solution, add appropriate NaOH and make it fully dissolve.? After mixed solution is transferred in water heating kettle, carry out solvent thermal reaction, reaction temperature is 180 DEG C, and the response time is 24 hours；Molten After agent heat treatment, upper solution is gone, and with deionized water repeatedly rinse precipitation powder body with go out excess NaOH, finally take Go out gained pretreatment powder body, then by this powder body 850 DEG C of heat treatments 4 hours, i.e. make described upper conversion after furnace cooling and send out Light temperature-sensitive material powder body.

Embodiment 30

Preparation (Na_0.5Er_0.5)TiO₃Ceramic material, its preparation method is as follows:

By any one (Na of preparation in embodiment 1 to 4_0.5Er_0.5)TiO₃Powder body is put in agate mortar, with ethanol is Solvent grinds 2 hours dries.Add the polyvinyl alcohol (PVA) that appropriate concentration is 5% wherein, as binding agent, to be sufficiently stirred for, Pelletize, crosses 60 mesh and 160 eye mesh screens, makes spherical powder；Then spherical powder is put into grinding tool, under 10～100MPa pressure It is pressed into the green compact of certain thickness and diameter, then it is viscous, finally by sample that green compact are put into 10 hours rows of 550 DEG C of insulations in Muffle furnace 950～1350 DEG C of (high-energy ball milling method 1000-1200 DEG C, molten-salt growth method 1050-1250 DEG C, solvent-thermal method 980-1180 DEG C, solid phases Reaction method 1050-1300 DEG C) sintering 2～6 hours, be cooled to after uniform temperature close power supply cooling, i.e. obtain described upper turn Change luminance temperature sensitive ceramic block materials.Figure 20 gives and sinters ceramics sample under these 1250 degrees Celsius at 980 nanometer lasers Up-conversion luminescence spectral line under exciting.

Embodiment 31

Preparation [(Na_xK_1-x)_0.5Er_0.5]TiO₃Ceramic material, its preparation method is as follows:

By any one [(Na of preparation in embodiment 23 to 26_xK_1-x)_0.5Er_0.5]TiO₃Powder body is put in agate mortar, Grind 2 hours with ethanol for solvent and dry.Add polyvinyl alcohol (PVA) that appropriate concentration is 5% wherein as binding agent, It is sufficiently stirred for, pelletize, crosses 60 mesh and 160 eye mesh screens, make spherical powder；Then spherical powder is put into grinding tool, 10～ It is pressed into the green compact of certain thickness and diameter under 100MPa pressure, then green compact are put into 10 hours rows of 550 DEG C of insulations in Muffle furnace Viscous, finally by sample at 950～1350 DEG C of (high-energy ball milling method 1000-1200 DEG C, molten-salt growth method 1050-1250 DEG C, solvent-thermal methods 980-1180 DEG C, solid reaction process 1050-1300 DEG C) 2～6 hours one-tenth porcelain of sintering, close power supply after being cooled to uniform temperature cold But, described up-conversion luminescence temperature sensitive ceramic block materials is i.e. obtained.

The principle of above-described embodiment only illustrative present invention and effect thereof, not for limiting the present invention.Any ripe Above-described embodiment all can be modified under the spirit and the scope of the present invention or change by the personage knowing this technology.Cause This, have usually intellectual such as complete with institute under technological thought without departing from disclosed spirit in art All equivalences become are modified or change, and must be contained by the claim of the present invention.

Claims

1. a preparation method for the up-conversion luminescence temperature-sensitive material containing rare earth element, described up-conversion luminescence temperature is sensitive The chemical general formula of material is (A_0.5Re_0.5)TiO₃, wherein: A is selected from Rb, K, Na, and one or more in Li or Ag, Re is selected from One or more in Er, Yb, Pr, Eu, Ho, Tm, Tb or Dy；It is characterized in that described sensitive material preparation method is high energy ball In mill method, molten-salt reaction method, solvent thermal reaction method or solid reaction process any one.

Preparation method the most according to claim 1, it is characterised in that specifically comprising the following steps that of described high-energy ball milling method

(1) the weighing of raw material: by chemical general formula (A_0.5Re_0.5)TiO₃, the stoichiometric proportion of A, Re and Ti weighs following raw material: A unit Carbonate, nitrate or the hydroxide of element any one, the oxide of rare earth element Re or nitrate, the oxide of element ti or Chloride；

(2) high-energy ball milling: load weighted raw material is put into Special ball mill tank container, then to its add stearic acid, n-amyl alcohol or Person adds deionized water and dehydrated alcohol, finally utilizes high energy ball mill ball milling, controls high speed ball milling 1-100 hour, and rotating speed sets Being set to 100-400 rev/min, rotating mode ball milling, Ball-milling Time and time-out interval are respectively divides for 10-200 minute and 5-60 Clock；Stearic addition is the 0～300% of compound weight, and the addition of n-amyl alcohol is the 1～50% of compound weight；

(3) heat treatment: by the mixing material after ball milling with dehydrated alcohol dilute, time of repose is 10-30 minute, then apply from Scheming centrifugation, takes out gained pretreatment powder body, then by this powder body 500～1100 DEG C of heat treatments 1～10 hours, cold with stove The most i.e. make described up-conversion luminescence temperature-sensitive material.

Preparation method the most according to claim 2, it is characterised in that in step (2), stearic addition is compound The 10～200% of weight, the addition of n-amyl alcohol is the 1～50% of compound weight, and the speed setting of high energy ball mill is 150- 380 revs/min, ball milling 2-50 hour, rotating mode ball milling, Ball-milling Time and time-out interval be respectively 20-100 minute and 10-60 minute；In step (3), during dehydrated alcohol dilution, time of repose is 10-30 minute, after centrifuge separates, at heat Reason temperature is 500～1000 DEG C, and the time is 1～8 hour.

Preparation method the most according to claim 2, it is characterised in that in step (2), stearic addition is compound The 10～100% of weight, the addition of n-amyl alcohol is the 5～50% of compound weight, and the speed setting of high energy ball mill is 300- 380 revs/min, ball milling 2-20 hour, rotating mode ball milling, Ball-milling Time and time-out interval are respectively 30 minutes and 20 points Clock；In step (3), during dehydrated alcohol dilution, time of repose is 20 minutes, and after centrifuge separates, heat treatment temperature is 500 ～1000 DEG C, the time is 2～8 hours.

Preparation method the most according to claim 1, it is characterised in that specifically comprising the following steps that of described molten-salt reaction method

(1) the weighing of raw material: by chemical general formula (A_0.5Re_0.5)TiO₃, A, Re and Ti element chooses following raw material respectively: elements A Selected from the chloride of A, rare earth element Re selected from the oxide of Re, sulfate, nitrate or chloride any one, element ti is selected from Its oxide；

(2) prepared by predecessor: by chemical general formula (A_0.5Re_0.5)TiO₃The stoichiometric proportion of A, Re and Ti weigh each initial feed, And to the chloride of its another addition element A as fused salt, the mass ratio controlling ACl and initial feed summation is 1:0.5-1:5, will Mixing raw material grinds at agate mortar and is allowed to mix homogeneously in 1-5 hour, makes the precursor powder of molten-salt growth method reaction；Again by this forerunner Powder body is transferred to the corundum crucible added a cover, and 700～1050 DEG C of heat treatments 1～10 hours, i.e. makes on described after furnace cooling The predecessor of conversion luminance temperature sensitive material；

(3) fused salt separates: the predecessor of step (2) gained is put into deionization warm water soaking, controls water temperature and is 50-90 DEG C, leaching The bubble time is 10-100h, is allowed to soft, and period can add deionized water to prevent it to be oven-dried；The most constantly change water repeatedly to wash Wash to remove the chloride of excess elements A, or use filtering apparatus to filter off except excess fused salt, the pressed powder that finally will obtain Dry at 100-150 DEG C and prepare described up-conversion luminescence temperature-sensitive material.

Preparation method the most according to claim 5, it is characterised in that in step (1), elements A is selected from the chloride of A, dilute Earth elements Re is selected from TiO selected from the nitrate of Re, element ti₂；In step (2), ACl is 1:1-1 with the mass ratio of initial feed: 2, milling time is 2-3 hour, and heat treatment temperature is 720-990 DEG C, heat treatment time 2～4 hours；In step (3), control Water temperature is 60-80 DEG C, and soak time is 10-72 h.

Preparation method the most according to claim 5, it is characterised in that in step (1), elements A is selected from the chloride of A, dilute Earth elements Re is selected from TiO selected from the nitrate of Re, element ti₂；In step (2), ACl is 1:1.5-with the mass ratio of initial feed 1:2, milling time is 2 hours, and heat treatment temperature is 730-990 DEG C, heat treatment time 4 hours；Controlling water temperature in step (3) is 60-80 DEG C, soak time is 24-72 h.

Preparation method the most according to claim 1, it is characterised in that specifically comprising the following steps that of described solvent thermal reaction method

(1) the choosing of raw material: by chemical general formula (A_0.5Re_0.5)TiO₃, A, Re and Ti element chooses following raw material respectively: elements A Selected from the hydroxide of A, rare earth element Re is selected from nitrate or the chloride of Re, and element ti is selected from titanium tetrachloride, four n-butyl alcohol Titanium (butyl titanate) or titanium tetraisopropylate, solvent choose deionized water, dehydrated alcohol or ethylene glycol any one；

(2) prepared by presoma: by chemical general formula (A_0.5Re_0.5)TiO₃The stoichiometric proportion of A, Re and Ti weigh each initial feed, And after being mixed by this raw material, adding deionized water, one or more mixed solvents of dehydrated alcohol and ethylene glycol also are sufficiently stirred for making Dissolving；Then adding AOH to mixed solution, the mol ratio controlling AOH Yu Ti element is 5:1-15:1, and makes it the most molten Solve；Finally mixed solution being transferred to water heating kettle, carry out solvent thermal reaction, reaction temperature is 120 DEG C-250 DEG C, and the response time is 2 hours-40 hours；

(3) heat treatment: diluted by the dehydrated alcohol of the mixed material after ball milling, then application centrifuge separates, and takes out institute Pretreatment powder body, then by this powder body 500～1000 DEG C of heat treatments 1～10 hours, i.e. make described upper after furnace cooling Conversion luminance temperature sensitive material.

Preparation method the most according to claim 8, it is characterised in that in step (1), rare earth element Re is selected from the nitric acid of Re Salt, element ti is selected from titanium tetrachloride, four n-butyl titaniums (butyl titanate)；Solvent chooses deionized water, dehydrated alcohol or second two Alcohol any one；In step (2), the mol ratio of AOH Yu Ti element is 5:1-15:1, and reaction temperature is 180-230 DEG C, the response time For 12-36 hour；In step (3), powder body heat treatment temperature is 600～980 DEG C, and the time is 1～10 hour.

Preparation method the most according to claim 8, it is characterised in that in step (1), rare earth element Re is selected from the nitre of Re Hydrochlorate, element ti is selected from four n-butyl titaniums (butyl titanate)；It is arbitrary that solvent chooses deionized water, dehydrated alcohol or ethylene glycol Kind；In step (2), the mol ratio of AOH Yu Ti element is 5:1-15:1, and reaction temperature is 180-230 DEG C, and the response time is 12-36 Hour；In step (3), powder body heat treatment temperature is 600～980 DEG C, and the time is 1～10 hour.

11. preparation methoies according to claim 1, it is characterised in that specifically comprising the following steps that of described solid reaction process

(1) the choosing of raw material: by chemical general formula (A_0.5Re_0.5)TiO₃, its A, Re and Ti element chooses following raw material respectively: unit Element A is selected from titanium dioxide selected from the carbonate of A, rare earth element Re selected from the oxide of Re, nitrate or chloride, element ti；

(2) raw material weighs and mixes: by chemical general formula (A_0.5Re_0.5)TiO₃The stoichiometric proportion of A, Re and Ti weigh each initially Raw material, its volatile A raw material needs excess 1-10wt%, and load weighted raw material side enters agate mortar, adds ethanol and mixes Grind 2-5 hour after closing uniformly；

(3) preheating: Muffle furnace heat treatment put into by the blended stock after grinding, and heat treatment temperature is 700～1000 DEG C, heat The process time is 1～10 hour, then makes preburning powdered material with stove cooling down；

(4) double sintering: preburning powdered material is added appropriate dehydrated alcohol, regrinding 2-5 hour, then the powder after this is ground Body, 800～1200 DEG C of heat treatments 1～10 hours, i.e. makes described up-conversion luminescence temperature-sensitive material after furnace cooling.

12. preparation methoies according to claim 11, it is characterised in that in step (1), elements A is selected from the carbonate of A, dilute Earth elements Re is selected from oxide or the nitrate of Re, and element ti is selected from titanium dioxide；A raw material excess 1-5 wt% in step (2), Grind 2-3 hour；In step (3), heat treatment temperature is 800～950 DEG C, and heat treatment time is 4～6 hours；In step (4) again Secondary milling time is 2-3 hour, and heat treatment temperature is 900～1100 DEG C, and heat treatment time is 4～10 hours.

The up-conversion luminescence temperature-sensitive material containing rare earth element that 13. 1 kinds of preparation methoies as claimed in claim 1 obtain should For preparing ceramic material, target, it is characterised in that described target is applied to prepare in thick film or thin-film material.

14. application according to claim 13, it is characterised in that the preparation method of described ceramic material, concrete steps are such as Under:

(1) up-conversion luminescence temperature-sensitive material powder body is put into agate mortar grind 1-2 hour, its add concentration be 1～ The polyvinyl alcohol of 15%, as binding agent, is sufficiently stirred for, natural drying, pelletize, crosses screen cloth, makes spherical powder；

(2) spherical powder is put into grinding tool, under 10～100MPa pressure, be pressed into the green compact of certain thickness and diameter, then will It is viscous that 2-10 hour row of Muffle furnace 500-600 DEG C insulation put into by green compact, is finally sintered 1～10 hour at 950～1350 DEG C by sample, Close power supply cooling after being cooled to uniform temperature, i.e. obtain described up-conversion luminescence temperature sensitive ceramic block materials.

15. application according to claim 14, it is characterised in that adding polyvinyl alcohol concentration in step (1) is 2～10%, Crossing 60 mesh and 160 mesh sieves, be incubated 10 hours at 500-600 DEG C when row is viscous in step (2), during sintering, temperature is 950～1350 DEG C, Sintering time is 2～8 hours.

The up-conversion luminescence temperature-sensitive material containing rare earth element that 16. 1 kinds of preparation methoies as claimed in claim 1 obtain exists Fluorescence temperature sensor, short wavelength emissions solid-state laser, biomolecule fluorescent labeling, infrared acquisition show with false proof, 3 D stereo Show, integrated optoelectronic device or the application of area of solar cell.