CN103468265A - Holmium-doped lanthanum trifluoride up-conversion luminescent material as well as preparation method and using method thereof - Google Patents
Holmium-doped lanthanum trifluoride up-conversion luminescent material as well as preparation method and using method thereof Download PDFInfo
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- CN103468265A CN103468265A CN201310416925XA CN201310416925A CN103468265A CN 103468265 A CN103468265 A CN 103468265A CN 201310416925X A CN201310416925X A CN 201310416925XA CN 201310416925 A CN201310416925 A CN 201310416925A CN 103468265 A CN103468265 A CN 103468265A
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Abstract
The invention discloses a holmium-doped lanthanum trifluoride up-conversion luminescent material which comprises lanthanum trifluoride, holmium trifluoride and ammonium fluoride or ammonium hydrogen fluoride. A preparation method of the holmium-doped lanthanum trifluoride up-conversion luminescent material comprises the steps of fully and evenly mixing the lanthanum trifluoride and the holmium trifluoride; then, under the protection of nitrogen or argon atmosphere, carrying out heat preservation for 2-10h at the temperature of 800-1300 DEG C to obtain the up-conversion luminescent material. When being used, the up-conversion luminescent material is excited by two or more near-infrared lights with the wave length range of 800-1200nm, so that the light intensity of the up-conversion luminescent material is 3-20 times higher than the light sum when the up-conversion luminescent material is excited by monochromatic light; after the using method is adopted, the excitation energy and rare earth ion energy level difference mismatch is obviously reduced, the probability of occurrence and the electron transition path in the up-conversion process during energy transfer can be greatly improved, the up-conversion luminescence efficiency is remarkably increased, and the up-conversion luminescent material has wide application prospect in the fields of a solar cell and photocatalysis.
Description
Technical field
The present invention relates to a kind of up-conversion luminescent material and preparation and application thereof, especially mix up-conversion luminescent material and the preparation and application thereof of holmium lanthanum trifluoride.
Background technology
Utilizing photovoltaic effect that solar energy converting is become to the solar cell of electric energy is one of current important device of rationally utilizing sun power.Yet at present institute's its effciency of energy transfer theoretical maximum of widely used silica-based solar cell only 30%, actual converted efficiency approximately 15%.Generally, arrive the about 1000W/ ㎡ of its energy of solar spectral (AM1.5) on ground, wavelength covers 200-2500 nm.Yet, for any solar cell, its utilization to sun power, only be confined in certain wavelength region, and most response all concentrates on visible-range.For example, for silica-based solar cell, only have energy be greater than the silicon solar cell energy gap (Eg > 1.12eV, λ<1100 nm) sunlight just can be absorbed (the current carrier thermalization also will reduce the efficiency of silion cell), and the sunlight (λ > 1100 nm) that energy is less than the silicon solar cell energy gap can not be absorbed and used.Absorb sunlight how more fully, more reasonably, the effciency of energy transfer that improves solar cell is one of focal issue of current extensive concern.Solar cell the expert once pointed out, the Research Thinking that improves the solar cell photoelectric efficiency of conversion recent decades is mainly performance, the composition optimizes of being devoted to material and device, and the further raising of following photoelectric transformation efficiency will mainly rely on the solar spectrum to inputting to be modulated.Modulation to solar spectrum mainly contains two technological lines: the lower conversion luminescence that absorbs two lower energy photons of a high-energy photon emission; Absorb the up-conversion luminescence of low energy infrared photon emission high energy optical photon.In recent years, due to prepared by up-conversion developing rapidly, by upper conversion method, convert infrared light to visible ray and obtain broad research for improving the solar cell photoelectric efficiency of conversion thereupon.Yet a large amount of experimental demonstration work all excite based on monochromatic infrared laser.
Therefore because solar spectrum has the wide spectrum characteristic, the utilization of sun power is had only based on wide band absorption and sets out and just can give full play to the effect of up-conversion.Efficient up-conversion adopts the rare earth ion doped energy transformation that realizes usually.The ground state of rare earth ion is absorbed in infra-red range and often is confined to limited wavelength.But rare earth ion excited state absorption, and phonon coupling absorption, be expected to realize the absorption to sunlight in broadband range.On the other hand, because the relative monochromatic ray of polychromatic light excites, excitation energy and rare earth ion energy level difference mismatch are obviously less, and have greatly improved probability of occurrence and the transition of electron approach of switching process on the transmission ofenergy, so its up-conversion luminescence efficiency obviously improves.Therefore, select suitable rare earth ion doped up-conversion, adopt the polychrome infrared light to excite to obtain up-conversion luminescence is the effective means that simultaneously realizes that the absorption of rare earth ion ground state, excited state absorption and phonon coupling absorb simultaneously, is a kind of novel method that has the raising solar cell photoelectric efficiency of conversion of potentiality and prospect.
Summary of the invention
The objective of the invention is to propose a kind of up-conversion luminescent material and preparation and application thereof of mixing the holmium lanthanum trifluoride, to strengthen the luminous intensity of up-conversion luminescent material, improve solar cell photoelectric efficiency of conversion and upper converting photocatalysis efficiency.
The up-conversion luminescent material of mixing the holmium lanthanum trifluoride of the present invention comprises lanthanum trifluoride, three holmium fluorides and Neutral ammonium fluoride or ammonium bifluoride, wherein the mol ratio of lanthanum trifluoride and three holmium fluorides is 1:1～99:1, and Neutral ammonium fluoride or ammonium bifluoride account for the 1%-20% of lanthanum trifluoride and three holmium fluoride total mole numbers.
The preparation method who mixes the up-conversion luminescent material of holmium lanthanum trifluoride of the present invention, its step is as follows:
By lanthanum trifluoride and the 1:1～99:1 mixing in molar ratio of three holmium fluorides; add again Neutral ammonium fluoride or ammonium bifluoride; Neutral ammonium fluoride or ammonium bifluoride account for the 1%-20% of lanthanum trifluoride and three holmium fluoride total mole numbers; after above-mentioned raw materials is fully mixed; under nitrogen or argon gas atmosphere protection; be incubated 2-10 hour at the temperature of 800～1300 ℃, obtain mixing the up-conversion luminescent material of holmium lanthanum trifluoride.
Mix the using method of the up-conversion luminescent material of holmium lanthanum trifluoride, it is characterized in that utilizing two kinds of the 800-1200nm wavelength region or two or more near infrared light to excite and mix holmium lanthanum trifluoride up-conversion luminescent material.
It is that near infrared light by two kinds or two or more mono-colour lasers excites simultaneously that above-mentioned two kinds or two or more near infrared light excite, or near-infrared light source is excited continuously.
Beneficial effect of the present invention is:
The up-conversion luminescent material of mixing the holmium lanthanum trifluoride of the present invention utilizes two kinds of the 800-1200nm wavelength region or two or more near infrared light to excite, with respect to the monochromatic ray of 800-1200nm wavelength region (for example, 980nm, 1150nm etc.) excite, its luminous intensity at green glow and ruddiness be monochromatic ray luminous summation while exciting 3-20 doubly.Above-mentioned using method can utilize the absorption of rare earth ion ground state, excited state absorption and phonon coupling to absorb simultaneously, the wide band absorption of realization to the near infrared region energy, therefore significantly reduce the requirement of up-conversion luminescence to light source power density, become sun power and directly excite the important leverage that produces up-conversion luminescence.Simultaneously, when two kinds or two or more near infrared light excite, excitation energy and rare earth ion energy level difference mismatch are obviously less, thereby significantly improve energy transfer efficiency and increase the transition of electron approach, energy efficient output by absorbed, make this up-conversion have broad application value in raising and the infrared band photocatalysis field of solar cell photoelectric efficiency of conversion.
The accompanying drawing explanation
Fig. 1 is monochromatic ray excitation light path figure;
Fig. 2 is two-beam excitation light path figure simultaneously;
Fig. 3 is upper switching emission spectrogram.
Embodiment
Below by embodiment, the invention will be further described, and specific embodiment is as follows:
Embodiment 1:
Mol ratio according to lanthanum trifluoride and three holmium fluorides is 99:1; Neutral ammonium fluoride accounts for 10% of three holmium fluorides and lanthanum trifluoride total mole number; raw materials weighing; after in agate mortar, ground and mixed mixes; move in the corundum Noah's ark; then the corundum Noah's ark is put into to tube furnace; pass under the nitrogen atmosphere protection; 1100 ℃ of insulations 3 hours; be radiated at (as shown in Figure 1) on sample with 970nm and 1150nm laser simultaneously; detect the luminous as seen of sample, use respectively 970nm and 1150nm laser radiation on sample (as shown in Figure 2), detect the luminous as seen of sample.Ho
3+ruddiness zone fluorescence intensity when comparing monochromatic ray 970nm and 1150nm and exciting respectively the intensity summation strengthened 20 times, as shown in Figure 3.
Embodiment 2:
Mol ratio according to lanthanum trifluoride and three holmium fluorides is 50:50; Neutral ammonium fluoride accounts for 1% of three holmium fluorides and lanthanum trifluoride total mole number; raw materials weighing; after in agate mortar, ground and mixed mixes; move in the corundum Noah's ark; then the corundum Noah's ark is put into to tube furnace; pass under the argon gas atmosphere protection; 800 ℃ of insulations 10 hours; with 800nm and 1200nm laser, be radiated on sample simultaneously; detect the luminous as seen of sample, use respectively 800nm and 1200nm laser radiation on sample, detect the luminous as seen of sample.Ho
3+green glow zone fluorescence intensity when comparing monochromatic ray 800nm and 1200nm and exciting respectively the intensity summation strengthened 3 times.
Embodiment 3:
Mol ratio according to lanthanum trifluoride and three holmium fluorides is 95:5; Neutral ammonium fluoride accounts for 20% of three holmium fluorides and lanthanum trifluoride total mole number; raw materials weighing; after in agate mortar, ground and mixed mixes; move in the corundum Noah's ark; then the corundum Noah's ark is put into to tube furnace; pass under the nitrogen atmosphere protection; 1300 ℃ of insulations 2 hours; with 1200nm and 970nm laser, be radiated on sample simultaneously; detect the luminous as seen of sample, use respectively 1200nm and 970nm laser radiation on sample, detect the luminous as seen of sample.Ho
3+ruddiness zone fluorescence intensity when comparing monochromatic ray 1200nm and 970nm and exciting respectively the intensity summation strengthened 8 times.
Claims (4)
1. a up-conversion luminescent material of mixing the holmium lanthanum trifluoride, it is characterized in that comprising lanthanum trifluoride, three holmium fluorides and Neutral ammonium fluoride or ammonium bifluoride, wherein the mol ratio of lanthanum trifluoride and three holmium fluorides is 1:1～99:1, and Neutral ammonium fluoride or ammonium bifluoride account for the 1%-20% of lanthanum trifluoride and three holmium fluoride total mole numbers.
2. prepare method of mixing the up-conversion luminescent material of holmium lanthanum trifluoride claimed in claim 1, its step is as follows:
By lanthanum trifluoride and the 1:1～99:1 mixing in molar ratio of three holmium fluorides; add again Neutral ammonium fluoride or ammonium bifluoride; Neutral ammonium fluoride or ammonium bifluoride account for the 1%-20% of lanthanum trifluoride and three holmium fluoride total mole numbers; after above-mentioned raw materials is fully mixed; under nitrogen or argon gas atmosphere protection; be incubated 2-10 hour at the temperature of 800～1300 ℃, obtain mixing the up-conversion luminescent material of holmium lanthanum trifluoride.
3. using method of mixing the up-conversion luminescent material of holmium lanthanum trifluoride claimed in claim 1, is characterized in that utilizing two kinds of the 800-1200nm wavelength region or two or more near infrared light to excite and mix holmium lanthanum trifluoride up-conversion luminescent material.
4. using method of mixing the up-conversion luminescent material of holmium lanthanum trifluoride according to claim 3, it is characterized in that it is that near infrared light by two kinds or two or more mono-colour lasers excites simultaneously that described two kinds or two or more near infrared light excite, or near-infrared light source is excited continuously.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897694A (en) * | 2014-03-24 | 2014-07-02 | 华南理工大学 | Upconversion luminescent material of erbium-doped barium dichloride as well as preparation method, using method and application thereof |
| CN104135230A (en) * | 2014-08-07 | 2014-11-05 | 鹤壁国立光电科技有限公司 | Solar cell module EL testing device and method under visible light |
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| CN102660801A (en) * | 2012-02-24 | 2012-09-12 | 长春理工大学 | Method for preparing erbium and ytterbium double-doped yttrium lithium tetrafluoride up-conversion luminescent nanobelt |
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| US20110063592A1 (en) * | 2008-03-10 | 2011-03-17 | Nikon Corporation | Fluorescent film, method of forming fluorescent film, multilayer dielectric film, optical element, optical system, imaging unit, optical property measuring apparatus, method of measuring optical property, exposure apparatus, exposure method, and method of manufacturing device |
| CN102660801A (en) * | 2012-02-24 | 2012-09-12 | 长春理工大学 | Method for preparing erbium and ytterbium double-doped yttrium lithium tetrafluoride up-conversion luminescent nanobelt |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897694A (en) * | 2014-03-24 | 2014-07-02 | 华南理工大学 | Upconversion luminescent material of erbium-doped barium dichloride as well as preparation method, using method and application thereof |
| CN103897694B (en) * | 2014-03-24 | 2016-03-02 | 华南理工大学 | A kind of up-conversion luminescent material of er-doped dichloride barium and preparation, using method and application |
| CN104135230A (en) * | 2014-08-07 | 2014-11-05 | 鹤壁国立光电科技有限公司 | Solar cell module EL testing device and method under visible light |
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Application publication date: 20131225 |