CN110184063A - A kind of rare earth luminescent material and the preparation method and application thereof - Google Patents

A kind of rare earth luminescent material and the preparation method and application thereof Download PDF

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CN110184063A
CN110184063A CN201910463186.7A CN201910463186A CN110184063A CN 110184063 A CN110184063 A CN 110184063A CN 201910463186 A CN201910463186 A CN 201910463186A CN 110184063 A CN110184063 A CN 110184063A
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郭崇峰
张智喻
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    • C09K11/77Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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    • C09K11/7773Halogenides with alkali or alkaline earth metal
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    • G01J5/00Radiation pyrometry, e.g. infrared or optical thermometry
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J5/00Radiation pyrometry, e.g. infrared or optical thermometry
    • G01J2005/0077Imaging

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Abstract

The invention discloses a kind of rare earth luminescent materials and the preparation method and application thereof.Disclosed materials chemistry formula are as follows: NaY(1‑x‑y)F4:xYb3+/yEr3+@NaY(1‑z)F4:zNd3+@SiO2@IR780, wherein 0≤x≤20%, 1%≤y≤5%, 10%≤y≤30%.Disclosed preparation method includes being prepared using thermal decomposition method and microemulsion method.Material of the invention is used for photo-thermal therapy material, near-infrared temperature sensing material and optical imagery material.Material of the invention is in nanostructure, has stronger absorption in the near infrared region, and show 500-1350 nanometers of characteristic emission, wherein rare earth ion Yb3+、Er3+、Nd3+808 nanometers of excitation light source can effectively be absorbed and generate the visible/near infrared transmitting of up/down conversion for temperature sensing and optical imagery, secondly the excitation light source that light thermit powder IR780 can effectively absorb 808 nanometers generates heat, light thermit powder is avoided to improve the accuracy of its temperature sensing to the absorption of the transmitting light (500-580 nanometers, 900-1350 nanometers) for temperature sensitive range.

Description

A kind of rare earth luminescent material and the preparation method and application thereof
Technical field
The invention belongs to the inorganic nano luminescent material technical fields in physics, and in particular to a kind of compound rare earth Luminescent material and the preparation method and application thereof.
Background technique
The characteristics of luminescence that rare earth luminescent material has other materials incomparable as fluorescence labeling material of new generation, example Such as energy level abundant, longer luminescent lifetime, narrow emission lines, high colour purity, the rare earth ion based on doping itself are special Electronic configuration and obtain from ultraviolet to visible (Kumar, the R. abundant of shining to infrared light district again;Nyk, M.; Ohulchanskyy,T.Y;Flask, C.A.;Pras, P.N., Combined Optical and MR Bioimaging Using Rare Earth Ion Doped NaYF4 Nanocrystals.Adv.Funct.Mater, 2009,19,853- 859.),
And visible and near infrared emission shows following advantage in organism: having in biological tissues low-down spontaneous The light penetration depth of fluorescence, high detection sensitivity and depth.
Since inorganic material is more stable, it can be greatly lowered and be made an uproar as fluorescence labeling material using rare earth luminescent material The influence of sound, therefore rare earth luminescent material can be applied to many fields, such as infrared light detecting, short-wave laser and bioluminescence mark The fields such as note.
In recent years, there is the interference, relatively for reducing background auto-fluorescence based on the light activated rare earth luminescent material of near-infrared A series of advantages such as high tissue penetration and excellent photostability, rear-earth-doped nano luminescent material is in biological tissue More and more extensive concern is obtained in oncotherapy.Using the light activated rear-earth-doped Illuminant nanometer material of near-infrared for biology Body treatment not only needs to carry out temperature detection to organism also to carry out effective photo-thermal therapy to it.
Summary of the invention
For the defects or inadequacies for existing technologies, the purpose of the present invention is to provide a kind of rare earth luminescent materials.
Its chemical formula of material provided by the present invention are as follows: NaY(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+@ SiO2@IR780, wherein 0≤x≤20%, 1%≤y≤5%, 10%≤y≤30%.
The preparation method of material of the present invention includes:
(1) NaY is prepared using thermal decomposition method(1-x-y)F4:xYb3+/yEr3+
(2) NaY prepared with step (1)(1-x-y)F4:xYb3+/yEr3+NaY is prepared using thermal decomposition method for raw material(1-x-y) F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+
(3) NaY prepared with step (2)(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+Micro emulsion is used for raw material Liquid method prepares NaY(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+@SiO2@IR780。
Present invention simultaneously provides can above-mentioned material be used to prepare photo-thermal therapy material, near-infrared temperature sensing material and light Learn the application of image forming material.
Compared with prior art, the invention has the following advantages that
Yb provided by the invention3+、Er3+、Nd3+Doped ions are made under the excitation of 808 nanometer lasers by energy transmission Have the function of the imaging and temperature sensing of visible light and near infrared light simultaneously.
Photo-thermal therapy (PTT) is to absorb luminous energy by light absorber and convert light energy into heat, kills cancer using thermal energy For cell to achieve the purpose that treatment, the validity of photo-thermal therapy depends mainly on effective conversion that light turns heat.Due to noble metal Nano particle has special physical property, they are widely used in the fields such as catalysis and biological diagnosis and treatment.Existing Au, Ag, The inorganic light thermit powder such as CuS has excellent surface plasmon absorption effect, but absorption region is wider, while can absorb The accuracy of temperature sensing is influenced for the range of temperature sensing emission peak, and light thermit powder IR780 provided by the invention inhales The switching emission up and down of nanoparticle can be avoided effectively to improve imaging effect and temperature sensing accuracy by receiving range.
Shell Nd of the invention3+Adulterate NaYF4It can effectively be excited by 808 nanometers of laser, be transmitted by energy transmission To Yb3+And Er3+, to show visible and near-infrared characteristic emission within the scope of 500-1350nm, for temperature sensing and Optical imagery, the excitation light source that secondly light thermit powder IR780 can effectively absorb 808 nanometers generate heat, avoid light thermit powder to being used for The absorption of the transmitting light (500-580 nanometers, 900-1350 nanometers) of temperature sensitive range is to improve the accurate of its temperature sensing Degree.Therefore, which may be implemented the integrated function of photo-thermal therapy, accurate thermometric and optical imagery.
Synthetic method of the present invention is simple, and the sample particle diameter of synthesis is about 18 nanometers, is easy to be dispersed in aqueous solution, from And there is good biological tissue's compatibility.
Detailed description of the invention
Fig. 1 is the NaYF of the embodiment4:Yb3+/Er3+@NaYF4:Nd3+@SiO2The flow chart of@IR780 synthesis and each mistake Corresponding transmission electron microscope(TEM) picture in journey;(a) column figure is the illustraton of model of the embodiment synthesis flow, and it is corresponding for (b) arranging figure The transmission electron microscope(TEM) picture of synthesis step, (c) arranging figure is corresponding high resolution transmission electron microscope photo.
Fig. 2 (a), (b) and (c) are respectively the NaYF of embodiment4:Yb3+/Er3+、NaYF4:Yb3+/Er3+@NaYF4:Nd3+、 NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2The XRD spectrum of@IR780;
Fig. 3 is embodiment NaYF4:Yb3+/Er3+(core),NaYF4:Yb3+/Er3+@NaYF4:Nd3+(core- shell),NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2The VISIBLE LIGHT EMISSION map of@IR780 (core-shell-IR780);
Fig. 4 is embodiment NaYF4:Yb3+/Er3+(core),NaYF4:Yb3+/Er3+@NaYF4:Nd3+(core- shell),NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2The near infrared light of@IR780 (core-shell-IR780) emits figure Spectrum;
Fig. 5 is embodiment NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2The temperature sensing of@IR780 near infrared light is sensitive It writes music line;
Fig. 6 is to monitor sample heat production respectively with laser power with the near-infrared temperature sensing and thermal infrared imager of embodiment Situation of change;
Fig. 7 is the NaYF of the embodiment4:Yb3+/Er3+@NaYF4:Nd3+@SiO2@IR780 is in different control groups to large intestine The ablation of bacillus.
Specific implementation method
The present invention provides Yb3+、Er3+、Nd3+The chemical general formula of the nano material of three doping are as follows: NaY(1-x-y)F4:xYb3+/ yEr3+@NaY(1-z)F4:zNd3+@SiO2@IR780, wherein x, y, z is respectively Yb3+、Er3+、Nd3+Mole percent doping, And x=18%, y=2%, y=20%.
"@" indicates the relationship of core-shell structure, such as " NaY in the present invention(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4: zNd3+@SiO2@IR780 " indicates " NaY (1-z) F4:zNd3+Coat NaY(1-x-y)F4:xYb3+/yEr3+", " SiO2Cladding NaY(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+", behind and so on.
The preparation of multi-functional nanometer material of the present invention is synthesized using thermal decomposition method and microemulsion method, and basic synthesis step can divide For three big steps, including (1) NaY(1-x-y)F4:xYb3+/yEr3+Preparation;(2)NaY(1-x-y)F4:xYb3+/yEr3+@NaY(1-z) F4:zNd3+Preparation;(3)NaY(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+@SiO2The preparation of@IR780.
Wherein: NaY(1-x-y)F4:xYb3+/yEr3+Preparation thermolysis process in the prior art preparation can be used.It is a kind of It is specific the preparation method is as follows:
(1) it is dilute that six water yttrium chlorides, six water ytterbium chlorides, six water erbium chlorides, the quantitative oleic acid of addition and 18 are weighed in proportion, Solution A is obtained after hybrid reaction under ar gas environment protection preference temperature;Wherein six water yttrium chlorides can use acetic acid yttrium substitution, six water Ytterbium chloride can be replaced with acetic acid ytterbium, six water erbium chlorides can be replaced with acetic acid erbium;
(2) by solution A under argon gas sustainable protection Temperature fall to room temperature;
(3) appropriate ammonium fluoride is dissolved in proper amount of methanol solution and obtains clear solution B, appropriate sodium hydroxide is dissolved in appropriate first Clear solution C is obtained in alcoholic solution;
(4) solution B and C are added drop-wise in solution A dropwise simultaneously, hybrid reaction obtains suspension D under the conditions of room temperature argon gas;
(5) after suspension D being warming up to suitable temperature heat preservation, continue heating and heat preservation;
(6) argon gas is closed, is continually fed into argon gas after vacuumizing to reaction environment;
(7) it is then cooled to room temperature after heating and heat preservation, closes argon gas gas cylinder, after obtained solution E centrifuge washing NaYF4:Yb3+/Er3+, can be by NaYF4:Yb3+/Er3+It is scattered in hexamethylene as solution F, for future use.
NaY(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+Preparation thermal decomposition side in the prior art can be used Method preparation.It is a kind of specific the preparation method is as follows:
(1) it weighs six water yttrium chlorides, neodymium chloride six hydrate in proportion, quantitative oleic acid and 18 dilute is added, is protected in ar gas environment It is mixed to get clear solution G under shield, appropriate temperature conditions, wherein six water yttrium chlorides can be replaced with acetic acid yttrium, neodymium chloride six hydrate It can be replaced with acetic acid neodymium;
(2) it is based on solution G, implements " NaY according to the above method(1-x-y)F4:xYb3+/yEr3+Preparation method " step (2)- (4) it operates, obtains suspension H, solution F is then added dropwise, be warming up to suitable temperature heat preservation, be then normally cooled to room temperature, close Argon gas gas cylinder is NaYF after obtained solution centrifuge washing4:Yb3+/Er3+@NaYF4:Nd3+, desirable partially liq hexamethylene It is dried for standby under preference temperature after alkane and absolute alcohol washing centrifugation;
NaY(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+@SiO2The preparation of@IR780 can be used in the prior art Microemulsion method synthesis.It is a kind of specific the preparation method is as follows:
By NaYF4:Yb3+/Er3+@NaYF4:Nd3+It is scattered in quantitative dehydrated alcohol and deionized water solution, is added quantitative Ammonium hydroxide instills quantitative tetraethyl orthosilicate, and subsequent instillation IR780 is mixed, and resulting solution is dried to obtain into centrifuge washing is crossed NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2@IR780。
It is specific NaYF below4: 18%Yb3+/ 2%Er3+@NaYF4: 20%Nd3+@SiO2@IR780 multifunctional nano light The building and preparation method thereof of heat cure platform, to be further explained explanation to technical solution of the present invention.
Embodiment:
The embodiment is that thermal decomposition method and microemulsion method prepare NaYF4: 18%Yb3+/ 2%Er3+@NaYF4: 20%Nd3+@ SiO2@IR780, specific preparation process are as follows:
NaYF4: 18%Yb3+/ 2%Er3+Preparation:
Y in molar ratio3+:Yb3+:Er3+The stoichiometric ratio of=0.8:0.18:0.02 weighs YCl3·6H2O(AR) 0.5400g、YbCl3·6H2O(AR)0.1395g、ErCl3·6H2O (AR) 0.0153g, raw material is poured into reaction vessel and is added 12ml oleic acid and 30ml 18 are dilute, are mixed to get clear solution under the conditions of argon gas protection and 160 DEG C or so, persistently protect in argon gas Lower Temperature fall is protected to room temperature;
NH is weighed in molar ratio4F (AR) 0.2963g, NaOH (AR) 0.2000g is dissolved in 20ml and 10ml methanol solution respectively In obtain clear solution;By NH4F and NaOH solution instill in clear solution obtained by above-mentioned steps, react under the conditions of room temperature argon gas Obtain suspension;
Suspension is warming up to 60 DEG C or so rear heat preservations 20 minutes, 108 DEG C or so is continuously heating to and keeps the temperature 5 minutes;
It closes argon gas, vacuumize, vacuum pump is closed in lasting pumping after twenty minutes, leads to argon gas, Continuous aeration;
It is continuously heating to 300 DEG C and keeps the temperature one hour, be then normally cooled to room temperature, close argon gas gas cylinder, it is obtained molten Sample NaYF is obtained after liquid centrifuge washing4:Yb3+/Er3+, it is scattered in spare in 20ml hexamethylene.Take partially liq hexamethylene and Absolute alcohol washs 70 DEG C of drying after 3 centrifugations, is fully ground and tests its optical property;
NaYF4: 18%Yb3+/ 2%Er3+@NaYF4: 20%Nd3+Preparation:
Y in molar ratio3+:Nd3+The stoichiometric ratio of=0.8:0.2 weighs YCl3·6H2O(AR)0.4854g、NdCl3· 6H2O (AR) 0.1435g, by raw material pour into reaction vessels be added 12ml oleic acid and 30ml 18 it is dilute, ar gas environment protection under 160 DEG C stir to get clear solution, and Temperature fall is to room temperature under argon gas sustainable protection;
NH is weighed in molar ratio4F (AR) 0.2963g, NaOH (AR) 0.2000g is dissolved in 20ml and 10ml methanol solution respectively In obtain clear solution;By NH4F and NaOH solution instill in clear solution, stir to get suspension under the conditions of room temperature argon gas;
The NaYF being scattered in 20ml hexamethylene is added dropwise in suspension4:Yb3+/Er3+, it is warming up to 60 DEG C later, maintains 20 Minute, it is continuously heating to 108 DEG C and stablizes 5 minutes;Argon gas gas circuit to be closed, is vacuumized, vacuum pump is closed in lasting pumping after twenty minutes, Logical argon gas, Continuous aeration;
300 degrees Celsius are continuously heating to, maintains one hour, is then normally cooled to room temperature, closes argon gas gas cylinder, it is acquired Solution centrifuge washing after obtain sample NaYF4: 18%Yb3+/ 2%Er3+@NaYF4: 20%Nd3+
NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2The preparation of@IR780:
By NaYF4:Yb3+/Er3+@NaYF4:Nd3+It is scattered in quantitative dehydrated alcohol and deionized water solution, is added quantitative Ammonium hydroxide, instills 200 microlitres of tetraethyl orthosilicates, 2 milliliters of IR780 of subsequent instillation, stirring at normal temperature, and resulting solution is washed into centrifugation is crossed It washs drying and obtains NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2@IR780。
Optical property is carried out to material prepared by the embodiment, using fluorescence intensity ratio thermometric skill disclosed in document [1] Art obtains the relation curve of its sensitivity and temperature, as a result as shown in Figure 5.It is strong using the comparison fluorescence of method disclosed in document [2] The superiority than thermometry and the comparative illustration fluorescence intensity ratio thermometry of thermal infrared imager thermometric is spent, as a result such as Fig. 6 institute Show.With superior photo-thermal effect, as a result material prepared by the embodiment is demonstrated using sterilization experiment disclosed in document [3] As shown in Figure 7.
[1]H.Suo,X.Zhao,Z.Zhang,R.Shi,Y.Wu,J.Xiang,C.Guo.Local Symmetric Distortion Boosted Photon Up-conversion and Thermometric Sensitivity in lanthanum Oxide Nanospheres.Nanoscale,2018,10,9245–9251.
[2]Suo,H.,Zhao,X.,Zhang,Z.,Guo,C.808nm Light-triggered Thermometer- Heater Up-converting Platform based on Nd3+-sensitized Yolk-shell GdOF@ SiO2.ACS Appl.Mater.Interfaces 2017,9,43438-43448.
[3]Z.Zhang,H.Suo,X.Zhao,D.Sun,L.Fan,C.Guo.NIR-to-NIR Deep Penetrating Nanoplatforms Y2O3:Nd3+/Yb3+@SiO2@Cu2S towards Highly Efficient Photothermal Ablation.ACS applied materials&interfaces,2018,10,14570-14576.
Fig. 1 is the NaYF of the embodiment4:Yb3+/Er3+@NaYF4:Nd3+@SiO2The flow chart of@IR780 synthesis and each mistake Corresponding transmission electron microscope(TEM) picture, illustrates the core-shell structure of sample in journey.
Fig. 2 (a) is the NaYF of the embodiment4:Yb3+/Er3+XRD spectrum, Fig. 1 (b) be the embodiment NaYF4:Yb3+/ Er3+@NaYF4:Nd3+XRD spectrum, Fig. 1 (c) be the embodiment NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2@IR780's XRD spectrum.
Fig. 3 is embodiment NaYF4:Yb3+/Er3+(core),NaYF4:Yb3+/Er3+@NaYF4:Nd3+(core- shell),NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2The VISIBLE LIGHT EMISSION map of@IR780 (core-shell-IR780). Illustrate that material of the invention is greatly improved in VISIBLE LIGHT EMISSION intensity.
Fig. 4 is embodiment NaYF4:Yb3+/Er3+(core),NaYF4:Yb3+/Er3+@NaYF4:Nd3+(core- shell),NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2The near infrared light of@IR780 (core-shell-IR780) emits figure Spectrum.Illustrate that material of the invention is greatly improved near infrared light emissive porwer.
Fig. 5 is the NaYF of the embodiment4:Yb3+/Er3+@NaYF4:Nd3+@SiO2The near infrared light temperature sensing spirit of@IR780 Acuity curve.
Fig. 6 is the NaYF of the case study on implementation4:Yb3+/Er3+@NaYF4:Nd3+@SiO2@IR780 swashs 808 nanometer lasers It gives, the heat generated in the pigeon breast meat tissue with a thickness of 1mm, and the material made from the embodiment and thermal infrared imager point The case where other monitoring temperature is with changed power.Illustrate the obtained temperature of the material as made from the embodiment compared to infrared heat As the biological tissue surface temperature that instrument monitors is more accurate.
Fig. 7 is the NaYF of the embodiment4:Yb3+/Er3+@NaYF4:Nd3+@SiO2@IR780 is in different control groups to large intestine The ablation of bacillus.And heat is produced under the excitation of 808nm laser by comparative illustration material of the present invention, to bacterium It has arrived ablation.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (5)

1. a kind of rare earth luminescent material, which is characterized in that its chemical formula of the material are as follows: NaY(1-x-y)F4:xYb3+/yEr3+@NaY (1-z)F4:zNd3+@SiO2@IR780, wherein 0≤x≤20%, 1%≤y≤5%, 10%≤y≤30%.
2. the preparation method of rare earth luminescent material described in claim 1, which is characterized in that method includes:
(1) NaY is prepared using thermal decomposition method(1-x-y)F4:xYb3+/yEr3+
(2) NaY prepared with step (1)(1-x-y)F4:xYb3+/yEr3+NaY is prepared using thermal decomposition method for raw material(1-x-y)F4: xYb3+/yEr3+@NaY(1-z)F4:zNd3+
(3) NaY prepared with step (2)(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+Microemulsion method is used for raw material Prepare NaY(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+@SiO2@IR780。
3. the application that material described in claim 1 is used to prepare photo-thermal therapy material.
4. the application that material described in claim 1 is used to prepare near-infrared temperature sensing material.
5. the application that material described in claim 1 is used to prepare optical imagery material.
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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN116891742A (en) * 2023-06-07 2023-10-17 西安邮电大学 Rare earth luminescent material and preparation method and application thereof

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