CN101899307A - Up-conversion fluorescent powder codoped with Er3+and Dy3+and preparation method thereof - Google Patents

Up-conversion fluorescent powder codoped with Er3+and Dy3+and preparation method thereof Download PDF

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CN101899307A
CN101899307A CN2010101268160A CN201010126816A CN101899307A CN 101899307 A CN101899307 A CN 101899307A CN 2010101268160 A CN2010101268160 A CN 2010101268160A CN 201010126816 A CN201010126816 A CN 201010126816A CN 101899307 A CN101899307 A CN 101899307A
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preparation
solution
conversion phosphor
mixed solution
fluorescent powder
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雷亮
任益超
杨云霞
袁双龙
陈国荣
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East China University of Science and Technology
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East China University of Science and Technology
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Abstract

The invention discloses Er<3+> and Dy<3+> codoped upconversion fluorescent powder and a preparation method thereof, and relates to conversion fluorescent powder and a preparation method thereof. The invention solves the problems of high synthesis temperature, nonuniform particle size distribution, foreign phases in crystal and low spectral absorption in infrared spectrum region when the prior art is used for producing the upconversion fluorescent material. The structural formula of the upconversion fluorescent powder is NaY1-x-y(ErxDyy)F4. The preparation method thereof comprises the following steps: proportionally mixing the required raw materials, stirring, maintaining the temperature, cooling, taking out the reactants, centrifugating, cleaning and drying to obtain the Er<3+> and Dy<3+> codoped upconversion fluorescent powder. Due to the adoption of the hydrothermal method, the invention has the advantages of simple preparation technique, low synthesis temperature (only 160-200 DEG C) and low cost; and the obtained product is in micron grade, and has the advantages of uniform particle size distribution (5-10 mu m), high crystal form purity and no other foreign phases, so that the infrared spectrum region has stronger absorption spectral peak.

Description

A kind of Er that mixes altogether 3+, Dy 3+Up-conversion phosphor and preparation method thereof
Technical field
The present invention relates to a kind of up-conversion phosphor and preparation method thereof.
Background technology
Over nearly 30 years, solar utilization technique is being researched and developed, is being commercially produced, all obtaining tremendous development aspect the market development, become the world fast, one of the new industry of steady progression.And solar photovoltaic generating wherein be in the world save energy, advocate a kind of main new high-tech industry of green electric power supply.The development photovoltaic industry has become global various countries and has solved one of optimal path of contradiction between the energy and Economic development, the environment protection.But because the restriction of the forbidden band of silicon materials itself, silicon solar cell mainly is by the sunlight that absorbs in the visible-range opto-electronic conversion to take place at present, is utilized by us.Spectrum at infrared region can not be by solar absorption, and this also is the very important bottleneck that the present photoelectric transformation efficiency of silicon solar cell can't break through.At present, a kind of up-conversion phosphor coating is painted on the back side of two-sided solar cell, and can not have influence on the performance of entire cell device because of the ENERGY E＞Eg of incident photon.This fluorescent material has been proved to be higher last efficiency of conversion, and can be coated in the back side of two-sided battery then easily by mixing with tamanori.
Last conversion be one after process than the energy photons continuous absorption, then be the luminous two-phonon process of higher-energy photon.This mechanism can be used on the solar cell, and the loss of photovoltaic sub-band crack is minimized.Its main advantage is: a. absorbing wavelength scope is higher than 1100nm; B. radiative wavelength is lower than 1100nm; C. low excitation intensity; D. high last efficiency of conversion; E. through the light after the last conversion high transmitance is arranged.Rear-earth-doped material has ideal up-conversion luminescence performance, also is used on a lot of transformation applications from the near infrared light to the visible light.This fluorescent material has been used in the back side of double-sided solar battery, and the also verified absorption near infrared region strengthens to some extent.By last conversion, the nonabsorbable near infrared light of those silicon solar cells, convert its absorbent light to, improve the efficient of battery.
The yttrium fluoride natrium matrix that the ytterbium erbium ion is mixed altogether is proved has efficiency of conversion on the highest near red visible light, wherein the efficiency of conversion of hexagonal structure yttrium fluoride natrium be higher than far away again the cubic yttrium fluoride natrium (Chem.Mater.200719,727-734).For this reason, yttrium fluoride natrium is to be used to study the matrix of changing on the near infrared, is that the inferior forbidden band of silicon photovoltaic near infrared spectrographic improves desired.
In various types of up-conversion luminescent materials of preparation at present; as Chinese patent (publication number: CN101067083A; publication number: CN1386817A; publication number: CN1539917A); in above-mentioned several preparation methods, mostly need to carry out high temperature, for a long time solid state reaction; even need atmosphere protection, thereby complicated process of preparation and energy consumption height.Wherein (publication number: CN101067083A) disclosed a kind of general formula is NaY 1-X-Y(Yb xEr y) F 4Be fertile material, synthesis temperature is up to 450～570 ℃, the product particle size distribution is inhomogeneous, and crystalline purity is not high, there are other dephasigns to influence its up-conversion luminescence performance, and the absorption of fluorescent material also is not suitable for being used as the basic thing of conversion coating on the sun power back side only in visible-range.
Summary of the invention
To the present invention seeks to produce in order solving in the prior art that upconverting fluorescent material synthesis temperature height, size-grade distribution are inhomogeneous, dephasign to be arranged in the crystal and, and a kind of up-conversion phosphor and preparation method thereof is provided in the few problem of infrared spectral region spectral absorption.
The system structure formula of the up-conversion phosphor that can increase the infrared region absorption spectrum described in the present invention is: NaY 1-x-y(Er xDy y) F 4, 0.01≤x≤0.05,0.001≤y≤0.05 wherein.
The preparation method of the up-conversion phosphor that can increase the infrared region absorption spectrum described in the present invention is by mixed solution of rare earth and the NaCl aqueous solution and NH 4The mixed solution of F and EDTA aqueous solution are adjusted the pH value, transfer to then in the reactor, and insulation is dried after eccentric cleaning at a certain temperature, obtains up-conversion phosphor.
Realize according to the following steps:
1), rare-earth chloride solution is by YCl 3, ErCl 3, DyCl 3The water-soluble in molar ratio mixed solution of rare earth A that obtains; Mixed solution A is YCl in molar ratio 3: ErCl 3: DyCl 3=1: 0.01～0.06: 0.001～0.06 is soluble in water; The mixed solution total concn is 0.1～0.3mol/L.
2), with the NaCl aqueous solution and NH 4F presses NaCl: NH 4F mol ratio=1: 4～8 mixing obtain mixed liquid B;
3), with mixed solution of rare earth A and mixing solutions B and EDTA aqueous solution, stirring the back, to adjust pH value with ammoniacal liquor be 6～7, join then in the reactor, 160～200 ℃ down 46～50 hours postcooling of insulation arrive room temperature;
4), take out reactant and after eccentric cleaning, dry, obtain up-conversion phosphor; Wherein: the size distribution of up-conversion phosphor is 5～10 μ m.
In step 1), the optimum concn of described mixed solution of rare earth is 0.2mol/L.Concentration is during less than 0.1mol/L, and the volume of required reactor is excessive; Concentration is during greater than 0.3mol/L, add the volume inconvenience control of solution.Work as DyCl 3: (YCl 3+ ErCl 3+ DyCl 3) mol ratio=0.001～0.005: 1 o'clock, DyCl 3The optimum concn of solution is 0.01mol/L.Work as DyCl 3The concentration of solution is greater than 0.01mol/L, and the inconvenience of the volume of solution is controlled; Work as DyCl 3The concentration of solution is less than 0.01mol/L, and the volume of total solution is excessive.
In step 2) in, described NaCl: NH 4F mol ratio=1: 4～8.When ratio greater than 1: 4 or during less than 1: 8, the crystal formation of the fluorescent material that obtains is impure.
In step 3), described mixed solution of rare earth A: mixing solutions B: the volume ratio of the EDTA aqueous solution=12～13: 1: 10～20.Described ammonia soln is a water by volume: the solution that obtains is mixed in ammoniacal liquor=1: 0.5～2, adjusts the pH value of mixed solution with ammonia soln, add ammonia soln amount be ammonia soln: the volume ratio of mixed solution of rare earth=1: 4～6.Described mixed solution is incubated 46～50 hours down at 160～240 ℃.
The crystal formation of present embodiment gained up-conversion phosphor is a hexagonal structure; Under 980nm laser excitation, send green glow, good luminous performance; Along with Dy 3+Mix, the absorption peak in the near-infrared region obviously increases, and can increase the utilization of solar cell to sunlight.
Description of drawings
Fig. 1 is the X-ray diffractogram of the embodiment of the invention 1.
Fig. 2 is the last inversion spectrum of the embodiment of the invention 1, the emmission spectrum of embodiment 1 sample under the 980nm laser apparatus excites.
Fig. 3 is the absorption spectrum of the embodiment of the invention 1.
Embodiment:
Example example 1
NaY 0.949(Er 0.05Dy 0.001) F 4The preparation of fluorescent material, concrete preparation process is as follows:
1) mol ratio by above-mentioned stoichiometric equation takes by weighing Y 2O 3(4N) generate YCl behind 5.645g and the hydrochloric acid reaction 3, add the standardized solution that water is made into the 0.2mol/L of 500ml; Er 2O 3(4N) generate ErCl behind 1.9125g and the hydrochloric acid reaction 3, add the standardized solution that water is made into the 0.2mol/L of 50ml; Dy 2O 3(4N) generate DyCl behind 0.3734g and the hydrochloric acid reaction 3, add the standardized solution that water is made into the 0.01mol/L of 100ml.Solution after the configuration is got YCl respectively 3, ErCl 3, DyCl 3Solution 23.73ml, 1.25ml, 0.5ml mix mixed solution of rare earth A.
2) mol ratio by above-mentioned stoichiometric equation takes by weighing NaCl (AR) 5.844g, adds the standardized solution that water is made into 100ml.Measure the NaCl standardized solution of 2ml, take by weighing NH again 4F (AR) 1.11g, mix stir mixed liquid B.
3) weighing EDTA (AR) 33.6231g adds the standardized solution that water is made into 500ml.Measure the EDTA standardized solution of 30ml.And mixed solution of rare earth A, mixing solutions B, EDTA aqueous solution stirred.
4) measure the ammoniacal liquor of 50ml, add the ammonia soln that water 50ml is made into 100ml.The ammonia soln of measuring 5ml again is added drop-wise in the mixed solution in (3), and adjusting the pH value is 6.7.Mixed solution is put into the reactor of 100ml.
5) reactor is put into baking oven, 180 ℃ are incubated 48 hours postcooling down to room temperature, take out reactant then to dry after eccentric cleaning, obtain up-conversion phosphor.
6) take out and to comprise in the reactant aftertreatment cleaning process that ethanol washes and wash.Bake out temperature is 100 ℃.
The composition of the sample for preparing is NaY 0.949(Er 0.05Dy 0.001) F 4, the size distribution of up-conversion phosphor is 5～10 μ m.
Example example 2
NaY 0.9(Er 0.05Dy 0.05) F 4The preparation of fluorescent material, concrete preparation process is as follows:
1) mol ratio by above-mentioned stoichiometric equation takes by weighing Y 2O 3(4N) generate YCl behind 5.645g and the hydrochloric acid reaction 3, add the standardized solution that water is made into the 0.2mol/L of 500ml; Er 2O 3(4N) generate ErCl behind 1.9125g and the hydrochloric acid reaction 3, add the standardized solution that water is made into the 0.2mol/L of 50ml; Dy 2O 3(4N) generate DyCl behind 9.3250g and the hydrochloric acid reaction 3, add the standardized solution that water is made into the 0.2mol/L of 250ml.Solution after the configuration is got YCl respectively 3, ErCl 3, DyCl 3Solution 22.5ml, 1.25ml, 1.25ml mix mixed solution of rare earth A.
2) mol ratio by above-mentioned stoichiometric equation takes by weighing NaCl (AR) 5.844g, adds the standardized solution that water is made into 100ml.Measure the NaCl standardized solution of 2ml, take by weighing NH again 4F (AR) 1.11g, mix stir mixed liquid B.
3) weighing EDTA (AR) 33.6231g adds the standardized solution that water is made into 500ml.Measure the EDTA standardized solution of 30ml.And mixed solution of rare earth A, mixing solutions B, EDTA aqueous solution stirred.
4) measure the ammoniacal liquor of 50ml, add the ammonia soln that water 50ml is made into 100ml.The ammonia soln of measuring 5ml again is added drop-wise in the mixed solution in (3), and adjusting the pH value is 6.7.Mixed solution is put into the reactor of 100ml.
5) reactor is put into baking oven, 180 ℃ are incubated 48 hours postcooling down to room temperature, take out reactant then to dry after eccentric cleaning, obtain up-conversion phosphor.
6) take out and to comprise in the reactant aftertreatment cleaning process that ethanol washes and wash.Bake out temperature is 100 ℃.
The composition of the sample for preparing is NaY 0.9(Er 0.05Dy 0.05) F 4, the size distribution of up-conversion phosphor is 5～10 μ m.

Claims (9)

1. up-conversion phosphor and preparation method thereof is characterized in that the chemical formula of this up-conversion phosphor system is: NaY 1-x-y(Er xDy y) F 4, 0.01≤x≤0.05,0.001≤y≤0.05 wherein; Its preparation method is: one, rare-earth chloride solution is by YCl 3, ErCl 3, DyCl 3The water-soluble in molar ratio mixed solution of rare earth A that obtains; Two, with the NaCl aqueous solution and NH 4F presses NaCl: NH 4F mol ratio=1: 4～8 mixing obtain mixed liquid B; Three, with mixed solution of rare earth A and mixing solutions B and EDTA aqueous solution, stirring the back is 6～7 with ammoniacal liquor adjustment pH value, joins then in the reactor, and 160～200 ℃ are incubated 46～50 hours postcooling down to room temperature; Four, take out reactant and after eccentric cleaning, dry, obtain up-conversion phosphor; The size distribution that it is characterized in that up-conversion phosphor is 5～10 μ m.
2. the described mixed solution of rare earth A of claim 1 is YCl in molar ratio 3: ErCl 3: DyCl3 =1: 0.01～0.06: 0.001～0.06 is soluble in water; The mixed solution total concn is 0.1～0.3mol/L.
3. the volumetric molar concentration of the described NaCl aqueous solution of claim 1 is: 2～3mol/L.
4. the volumetric molar concentration of the described EDTA aqueous solution of claim 1 is: 0.1～0.3mol/L.
5. claim 1 middle-weight rare earths mixed solution A: mixing solutions B: the volume ratio of the EDTA aqueous solution is=12～13: 1: 10～20.
6. ammonia soln is a water by volume in the claim 1: the solution that obtains is mixed in ammoniacal liquor=1: 0.5～2, adjusts the pH value of mixed solution with ammonia soln, and the ammonia soln add-on is 4～6ml.
7. the preparation method of up-conversion phosphor according to claim 1 is characterized in that the mixed solution in the claim 1 is incubated 46～50 hours down at 160～240 ℃.
8. the preparation method of up-conversion phosphor according to claim 1 is characterized in that in the step 4, comprises in the aftertreatment cleaning process that ethanol washes and wash, and bake out temperature is 90～110 ℃.
9. the preparation method of up-conversion phosphor according to claim 1, the size distribution that it is characterized in that up-conversion phosphor is 5～10 μ m.
CN2010101268160A 2010-03-18 2010-03-18 Up-conversion fluorescent powder codoped with Er3+and Dy3+and preparation method thereof Pending CN101899307A (en)

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Publication number Priority date Publication date Assignee Title
US20120307344A1 (en) * 2011-05-30 2012-12-06 Boe Technology Group Co., Ltd. Electronic paper display device and displaying method
CN105001866A (en) * 2015-06-30 2015-10-28 中山大学 Lutetium-base fluoride up-conversion luminescence nanocrystal and preparation method thereof
US10652683B2 (en) 2014-01-10 2020-05-12 Samsung Electronics Co., Ltd. Method and apparatus for reproducing three-dimensional audio

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120307344A1 (en) * 2011-05-30 2012-12-06 Boe Technology Group Co., Ltd. Electronic paper display device and displaying method
US10652683B2 (en) 2014-01-10 2020-05-12 Samsung Electronics Co., Ltd. Method and apparatus for reproducing three-dimensional audio
US10863298B2 (en) 2014-01-10 2020-12-08 Samsung Electronics Co., Ltd. Method and apparatus for reproducing three-dimensional audio
CN105001866A (en) * 2015-06-30 2015-10-28 中山大学 Lutetium-base fluoride up-conversion luminescence nanocrystal and preparation method thereof

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Application publication date: 20101201