CN109294581A - A kind of erbium ion-doped niobic acid ytterbium material and preparation method thereof - Google Patents

A kind of erbium ion-doped niobic acid ytterbium material and preparation method thereof Download PDF

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CN109294581A
CN109294581A CN201811076434.4A CN201811076434A CN109294581A CN 109294581 A CN109294581 A CN 109294581A CN 201811076434 A CN201811076434 A CN 201811076434A CN 109294581 A CN109294581 A CN 109294581A
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niobic acid
erbium ion
erbium
acid ytterbium
ytterbium
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钱艳楠
唐巽泽
张海燕
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Guangdong University of Technology
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Guangdong University of Technology
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    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • 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
    • C09K11/7767Chalcogenides
    • C09K11/7769Oxides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/054Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
    • H01L31/055Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means where light is absorbed and re-emitted at a different wavelength by the optical element directly associated or integrated with the PV cell, e.g. by using luminescent material, fluorescent concentrators or up-conversion arrangements
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/52PV systems with concentrators

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Abstract

The invention discloses a kind of erbium ion-doped niobic acid ytterbium materials and its preparation method and application.The chemical general formula of the erbium ion-doped niobic acid ytterbium material is YbNbO3:xEr3+, wherein 0.5≤x≤2.2.The present invention, which is entered bait ion doping in matrix niobic acid ytterbium lattice using solvent thermal reaction, obtains a kind of erbium ion-doped niobic acid ytterbium material of up-conversion luminescent material, wherein for erbium ion as the centre of luminescence, preparation method of the present invention is simple using niobic acid ytterbium as host material;For the limitation of solar cell semiconductor material energy gap, 980nm and 1550nm wave band near infrared light will be converted to the visible light that can be absorbed by solar battery by erbium ion-doped niobic acid ytterbium material prepared by the present invention simultaneously using switch technology on erbium ion, 510 ~ 570nm and 640 ~ 680nm wave band up-conversion fluorescence can be generated, so that the photoelectric conversion efficiency for improving battery can be applied to area of solar cell, medicine, photocatalysis and anti-counterfeit field.

Description

A kind of erbium ion-doped niobic acid ytterbium material and preparation method thereof
Technical field
The present invention relates to optical material technical field, more particularly, to a kind of erbium ion-doped niobic acid ytterbium material and its Preparation method.
Background technique
Niobic acid ytterbium is a kind of ABO4It is normal to have good thermochemical property, no pollution to the environment, high dielectric for ternary oxide The advantages that several, low Phonon frequency, photoelasticity and nonlinear optics, can be applied to solar battery, cathode-ray tube, fluorescent lamp and The optical devices such as solid state laser.There are two types of crystal structures for rare earth niobates tool, another one is monocline crystal phase at low temperature Kind is the tetragonal phase of the scheelite-type structure formed under high temperature.Possess the NbO at self-activate luminescence center in rare earth niobates lattice4 3- Group can obtain very strong blue light in ultraviolet region by excitation.Currently, to the research of rare earth niobates to be related to mostly Lanthanum, lutetium, gadolinium and yttrium (Y) etc. have not yet to see report, and the application to niobic acid ytterbium to rear-earth-doped niobic acid ytterbium up-conversion luminescent material It is limited only to film applications.
The research and development of solar energy power generating is the research hotspot that current international community is paid close attention to jointly, can become and solve The reserves exhaustion and one of the effective way to severe environmental pollution that traditional fossil energy faces.However, due to semiconductor material The limitation of itself energy gap, near infrared band sunlight cannot be absorbed and be utilized by solar battery, but as useless thermal energy It slatterns, which limits the optical-electronic transfer efficiencies of solar battery.Therefore, using in erbium ion-doped niobic acid ytterbium material The spectral response range of switch technology extension solar battery, efficient to absorb and utilize sunlight on erbium ion, to mention High cell photoelectric transfer efficiency becomes problem in the urgent need to address in solar battery research field.
Based on this, it is necessary to provide a kind of rear-earth-doped niobic acid ytterbium up-conversion luminescent material, and realize same using the material When by 980nm and 1550nm light conversion can by solar battery absorb visible light.
Summary of the invention
Primary and foremost purpose of the invention is to overcome the defect and deficiency of the above-mentioned material of rare earth niobates in the prior art, provides one The erbium ion-doped niobic acid ytterbium material of kind.For the erbium ion-doped niobic acid ytterbium material using niobic acid ytterbium as matrix, rare earth erbium ion is hair Light center, the material will can be converted to visible light simultaneously on 980nm and 1550nm wavelength laser, the centre of luminescence is respectively, Green light and 645 ~ 685nm wave band feux rouges are converted on 510 ~ 570nm wave band.
It is a further object of the present invention to provide a kind of preparation methods of erbium ion-doped niobic acid ytterbium material.
It is yet another object of the invention to provide a kind of erbium ion-doped niobic acid ytterbium materials in area of solar cell Using.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of erbium ion-doped niobic acid ytterbium material, chemical general formula YbNbO3: xEr3+, wherein 0.5≤x≤2.2.
Rare earth niobates material in compared with the prior art, erbium ion-doped niobic acid ytterbium material of the invention is for the first time with niobium Sour ytterbium is used as sensitizer again while being used as host material, prepared sample is equal under 980nm and 1550nm laser excitation Capable of emitting up-conversion fluorescence.
Preferably, the chemical formula of the erbium ion-doped niobic acid ytterbium material is YbNbO3: 2Er3+
A kind of preparation method of erbium ion-doped niobic acid ytterbium material, comprising the following steps:
S1. erbium source and ytterbium source are dissolved in the water, ethylene glycol is added, obtains mixed solution;
S2. niobium source and lithium source are added in above-mentioned S1 mixed solution, react 12 at 260 ~ 270 DEG C ~ for 24 hours, and it separates, it is dry, 0.5 ~ 2h is calcined at 900 ~ 1050 DEG C, obtains erbium ion-doped niobic acid ytterbium material.
Preferably, the erbium source, ytterbium source and niobium source molar ratio are 1 ~ 4.335: 21.67 ~ 30: 63.41 ~ 137.73.
It is highly preferred that the erbium source, ytterbium source and niobium source molar ratio are 3.8639: 29.06: 89.34.
Preferably, the volume ratio of water described in S1 and ethylene glycol is 1: 1 ~ 1.2.
It is highly preferred that the volume ratio of water described in S1 and ethylene glycol is 1: 1.
Preferably, niobium source described in S2 is niobium pentaoxide.
Preferably, erbium source described in S1 is erbium nitrate.
Preferably, ytterbium source described in S1 is ytterbium nitrate.
Preferably, lithium source described in S2 is Lithium hydroxide monohydrate.
A kind of application of above-mentioned erbium ion-doped niobic acid ytterbium material in solar battery, medicine, photocatalysis and anti-counterfeit field Also within the scope of the present invention.
The present invention prepares erbium ion-doped niobic acid ytterbium material using solvent-thermal method, wherein using niobic acid ytterbium as matrix, rare earth erbium Ion is the centre of luminescence;Under 980nm and 1550nm laser excitation, green light and 640 is converted on capable of emitting 510 ~ 570nm wave band Feux rouges is converted on ~ 680nm wave band, near infrared light effectively will be converted to the visible light that can be absorbed by battery, extend battery Spectral response range, and further increase the photoelectric conversion efficiency of battery.
Compared with prior art, the invention has the following beneficial effects:
The present invention provides a kind of above-mentioned erbium ion-doped niobic acid ytterbium material and preparation method thereof, by solvent-thermal method by bait ion Doping, which enters in matrix niobic acid ytterbium lattice, obtains a kind of up-conversion luminescent material, and preparation method is simple, erbium ion-doped niobic acid ytterbium Material is and the sensitization as 980nm wave band near-infrared excitaton source simultaneously for the first time using ytterbium as one of host material component Agent enhances up-conversion luminescence efficiency, and erbium ion-doped niobic acid ytterbium material of the invention is under 980nm and 1550nm laser excitation, 510 ~ 570nm and 640 ~ 680nm wave band up-conversion fluorescence can be generated, the spectral response range for extending solar battery is conducive to, The photoelectric conversion efficiency for further increasing battery can be applied to area of solar cell, medicine, photocatalysis and anti-counterfeit field.
Detailed description of the invention
Fig. 1 is the XRD diagram of the erbium ion-doped niobic acid ytterbium of embodiment 1.
Fig. 2 is the up-conversion fluorescence spectrogram of the erbium ion-doped niobic acid ytterbium of embodiment 1, and (1) is 980nm wavelength exciting light Upconversion emission figure under excitation, (2) are the upconversion emission figure under 1550nm wavelength excitation.
Specific embodiment
In order to become apparent from, completely describe technical solution of the present invention, further specifically below by way of specific embodiment The bright present invention, it should be understood that described herein the specific embodiments are only for explaining the present invention, is not intended to limit the present invention, Various changes can be carried out in the range of right of the present invention limits.
Embodiment 1
A kind of erbium ion-doped niobic acid ytterbium material, chemical general formula YbNbO3: 2Er3+
Preparation method is as follows:
S1. five water ytterbium nitrate of 0.0018mol and five water erbium nitrate solution of 0.2452mmol are added into 40mL second in 40mL water Glycol obtains mixed solution;
S2. 0.6421mmol Lithium hydroxide monohydrate and 0.0057mol niobium pentaoxide are added in above-mentioned S1 mixed solution, 12h is reacted at 270 DEG C, is separated, it is dry, 2h is calcined at 900 DEG C, obtains erbium ion-doped niobic acid ytterbium material.
Fig. 1 is the XRD diagram of erbium ion-doped niobic acid ytterbium described in embodiment 1.Wherein a is niobic acid ytterbium standard card PDF#81- 1976, b be prepared sample.Compared by observation it is found that one kind is c five there are the diffraction maximum of two kinds of substances in made sample b Two niobiums are aoxidized, another kind is d ytterbium oxide.
Fig. 2 is the up-conversion fluorescence spectrogram of erbium ion-doped niobic acid ytterbium described in embodiment 1, wherein (1) is 980nm wavelength Upconversion emission figure under excitation, (2) are the upconversion emission figure under 1550nm wavelength excitation.Observation is compared Figure (1) and scheme (2) it is found that the niobic acid ytterbium material under the excitation of 980nm and 1550nm wavelength, launch 510 ~ It is converted on 570nm wave band on green light and 640 ~ 680nm wave band and converts feux rouges.Under 980nm wavelength excitation, upper conversion green light Luminous intensity is better than feux rouges, and under 1550nm wavelength excitation, upper conversion red light-emitting intensity is then better than green light.
Embodiment 2
A kind of erbium ion-doped niobic acid ytterbium material, chemical general formula YbNbO3: 2Er3+.Preparation method and embodiment 1 are basic Unanimously, difference is, the reaction temperature in step S2 is 270 DEG C, and the reaction time is for 24 hours.
The performance for the erbium ion-doped niobic acid ytterbium material being prepared using the above method is similar to Example 1, in 980nm Under 1550nm wavelength excitation, it can launch and turn on conversion green light and 640 ~ 680nm wave band on 510 ~ 570nm wave band Change feux rouges.
Embodiment 3
A kind of erbium ion-doped niobic acid ytterbium material, chemical general formula YbNbO3: 2Er3+.Preparation method and embodiment 1 are basic Unanimously, difference is, the calcination temperature in step S2 is 1050 DEG C, reaction time 0.5h.
The performance for the erbium ion-doped niobic acid ytterbium material being prepared using the above method is similar to Example 1.The erbium from Son doping niobic acid ytterbium material can be launched and convert on 510 ~ 570nm wave band under 980nm and 1550nm wavelength excitation Feux rouges is converted on green light and 640 ~ 680nm wave band.
Embodiment 4
A kind of erbium ion-doped niobic acid ytterbium material, chemical general formula YbNbO3: 2Er3+.Preparation method and embodiment 1 are basic Unanimously, difference is, the volume of the water in step S1 is 36.36mL, and the volume of ethylene glycol is 43.64mL.
The performance for the erbium ion-doped niobic acid ytterbium material being prepared using the above method is similar to Example 1, in 980nm Under 1550nm wavelength excitation, it can launch and turn on conversion green light and 640 ~ 680nm wave band on 510 ~ 570nm wave band Change feux rouges.
Embodiment 5
A kind of erbium ion-doped niobic acid ytterbium material, chemical general formula YbNbO3:0.5Er3+.Preparation method and 1 base of embodiment This is consistent, and difference is, five water ytterbium nitrates in step S1 are 0.003mol, and five water erbium nitrates are 0.01mmol;In step S2 Niobium pentaoxide be 0.0137mol.
The performance for the erbium ion-doped niobic acid ytterbium material being prepared using the above method is similar to Example 1, in 980nm Under 1550nm wavelength excitation, under 980nm and 1550nm wavelength excitation, it can launch 510 ~ 570nm wave It is converted in section on green light and 640 ~ 680nm wave band and converts feux rouges.
Embodiment 6
A kind of erbium ion-doped niobic acid ytterbium material, chemical general formula YbNbO3: 2.2Er3+.Preparation method and 1 base of embodiment This is consistent, and difference is, five water ytterbium nitrates in step S1 are 0.0025mol, and five water erbium nitrates are 0.0433mmol;Step S2 In niobium pentaoxide be 0.1012mol.
The performance for the erbium ion-doped niobic acid ytterbium material being prepared using the above method is similar to Example 1, in 980nm Under 1550nm wavelength excitation, it can launch and turn on conversion green light and 640 ~ 680nm wave band on 510 ~ 570nm wave band Change feux rouges.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate examples made by the present invention, and is not to this The restriction of the embodiment of invention.It will be appreciated by those skilled in the art that can also make on the basis of the above description other Various forms of variations or variation, there is no necessity and possibility to exhaust all the enbodiments.It is all in spirit of the invention With any modifications, equivalent replacements, and improvements made within principle etc., the protection scope of the claims in the present invention should be included in Within.

Claims (10)

1. a kind of erbium ion-doped niobic acid ytterbium material, which is characterized in that its chemical general formula is YbNbO3 : xEr3+, wherein 0.5≤x ≤2.2。
2. erbium ion-doped niobic acid ytterbium material as described in claim 1, which is characterized in that its chemical formula is YbNbO3 : 2Er3+
3. a kind of preparation method of erbium ion-doped niobic acid ytterbium material, which comprises the following steps:
S1. ytterbium source and erbium source are dissolved in the water, add ethylene glycol, obtain mixed solution;
S2. niobium source and lithium source are added in the mixed solution of above-mentioned S1,12 ~ 24 h is reacted at 260 ~ 270 DEG C, separated, done It is dry, 0.5 ~ 2h is calcined at 900 ~ 1050 DEG C, obtains erbium ion-doped niobic acid ytterbium material.
4. preparation method as claimed in claim 3, which is characterized in that the molar ratio in the erbium source, ytterbium source and niobium source is 1 ~ 4.335: 29.06~30 : 63.41~137.73。
5. preparation method as claimed in claim 3, which is characterized in that the molar ratio in the erbium source, ytterbium source and niobium source is 3.8639: 29.06 : 89.34。
6. preparation method as claimed in claim 3, which is characterized in that the volume ratio of water described in S1 and ethylene glycol be 1: 1 ~ 1.2。
7. preparation method as claimed in claim 3, which is characterized in that erbium source described in S1 is erbium nitrate.
8. preparation method as claimed in claim 3, which is characterized in that ytterbium source described in S1 is ytterbium nitrate.
9. preparation method as claimed in claim 3, which is characterized in that lithium source described in S2 is Lithium hydroxide monohydrate.
10. a kind of erbium ion-doped niobic acid ytterbium material as claimed in claim 1 or 2 is in solar battery, medicine, photocatalysis and anti-fake The application in equal fields.
CN201811076434.4A 2018-09-14 2018-09-14 A kind of erbium ion-doped niobic acid ytterbium material and preparation method thereof Pending CN109294581A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101014683A (en) * 2004-07-14 2007-08-08 德国捷德有限公司 Valuable document
DE102010034256A1 (en) * 2010-08-13 2012-02-16 Giesecke & Devrient Gmbh Luminescent substance exhibiting a host lattice doped with a luminescent activator, useful in a diagnostic or therapeutic method or a tissue labeling method in vivo or in vitro, where the diagnostic method is graphical angiographic method
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Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101014683A (en) * 2004-07-14 2007-08-08 德国捷德有限公司 Valuable document
DE102010034256A1 (en) * 2010-08-13 2012-02-16 Giesecke & Devrient Gmbh Luminescent substance exhibiting a host lattice doped with a luminescent activator, useful in a diagnostic or therapeutic method or a tissue labeling method in vivo or in vitro, where the diagnostic method is graphical angiographic method
CN103265954A (en) * 2013-05-16 2013-08-28 同济大学 Potassium-sodium niobate based oxide up-conversion luminescent material and preparation method thereof

Non-Patent Citations (3)

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Title
MASANORIHIRANO等: "Intense up-conversion luminescence of Er3+/Yb3+ co-doped YNbO4 through hydrothermal route", 《JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A: CHEMISTRY》 *
O.S.DYMSHITS等: "Structural characteristics and spectral properties of novel transparent lithium aluminosilicate glass-ceramics containing (Er,Yb)NbO4 nanocrystals", 《JOURNAL OF LUMINESCENCE》 *
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