CN102181290A - Holmium-ytterbium-thulium three-doped calcium tungstate polycrystalline powder white light upconversion material and preparation method thereof - Google Patents
Holmium-ytterbium-thulium three-doped calcium tungstate polycrystalline powder white light upconversion material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a holmium-ytterbium-thulium three-doped calcium tungstate polycrystalline powder white light upconversion material and a preparation method thereof and relates to a rare earth element doped calcium tungstate polycrystalline powder white light upconversion material and the preparation method thereof. The chemical formula of the holmium-ytterbium-thulium three-doped calcium tungstate polycrystalline powder white light upconversion material is Ca1-x-y-0.01WO4: Hoy/Ybx/Tm0.01, wherein x is not less than 0.04 and not more than 0.08, and y is not less than 0.004 and not more than 0.01. The preparation method comprises the following steps: 1) weighing according to the chemical metering ratio of the chemical formula; 2) grinding and tabletting; and 3) performing high-temperature sintering. The holmium-ytterbium-thulium three-doped calcium tungstate polycrystalline powder white light upconversion material can emit bright upconversion white light under 980nm laser pumping within a wider exciting power range, and emit the uniform light. The holmium-ytterbium-thulium three-doped calcium tungstate polycrystalline powder white light upconversion material and the preparation method thereof can be applied in the field of solid state multi-color three-dimensional display and backlight lamps of white light sources.
Description
Technical field
The present invention relates to a kind of rare earth doped calcium wolframate polycrystalline whitewash light up-conversion and preparation method thereof.
Background technology
In recent years, owing to having important application prospects at aspects such as solid-state polychrome 3-D display and backlights, white light source causes extensive concern.Conversion can be transformed into versicolor visible light by non-linear multiphoton process with near infrared light on the frequency, is one of effective ways that produce white light.
Summary of the invention
The invention provides a kind of holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions and preparation method thereof.
The chemical formula of holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions is Ca
1-x-y-0.01WO
4: Ho
y/ Yb
x/ Tm
0.01, 0.04≤x≤0.08,0.004≤y≤0.01 wherein.
Above-mentioned holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions prepare by following step:
One, the stoichiometric ratio by holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversion chemical formulas takes by weighing lime powder, tungsten trioxide powder, holmium oxide powder, yttria powder and thulium oxide powder, and the chemical formula of holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions is Ca
1-x-y-0.01WO
4: Ho
y/ Yb
x/ Tm
0.01, 0.04≤x≤0.08,0.004≤y≤0.01 wherein;
Two, place agate mortar to grind 4 ± 0.5 hours in lime powder, tungsten trioxide powder, holmium oxide powder, yttria powder and the thulium oxide powder that takes by weighing, placing pressure then is the pressure environment compressing tablet 10min of 18MPa, obtains the sheet precast body;
Three, the sheet precast body is put into carried out high temperature sintering under the air atmosphere, sintering temperature is 1300 ± 50 ℃, and sintering time is 10 ± 0.5 hours, and naturally cooling promptly obtains holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions then.
Holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions of the present invention are made by lime powder, tungsten trioxide powder, holmium oxide powder, yttria powder and thulium oxide powder.Ho
3+Ion is red-green glow emission active ions, Tm
3+Ion is the blue emission active ions, and the present invention allocates substrate material (CaWO accurately
4) middle Ho
3+Ion and Tm
3+The ionic ratio, the emission of conversion white fluorescent in the realization.Yb in the holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions of the present invention
3+Ion can transmit energy excitation holmium ion and thulium ion up-conversion luminescence as sensitizing agent, and can also regulate indigo plant, green, red three-color light-emitting intensity.
Because calcium wolframate has excellent thermostability and chemical stability, therefore select its substrate material as holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions of the present invention.
Holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions of the present invention in the exciting power scope of 980nm laser pumping, broad (70mW～304mW), can both send bright last conversion of white light, and luminous evenly.
The preparation method of holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions of the present invention is simple, and the accurate control element doping of energy, and its resulting holmium ytterbium thulium three doped calcium tungstate polycrystalline powder have high-luminous-efficiency.
Description of drawings
Fig. 1 is the X-ray diffractogram of the holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions of embodiment 11 preparations.Fig. 2 be under embodiment seven to the ten prepared holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions condition that is 304mW in 980nm laser pumping, exciting power on the convert light spectrogram.Fig. 3 is the CIE chromatic graph under embodiment seven to the ten prepared holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions condition that is 304mW in 980nm laser pumping, exciting power.Fig. 4 is holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions convert light spectrogram under 980nm laser pumping, the different exciting power condition of embodiment 11 preparation.Fig. 5 is the CIE chromatic graph of holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions under 980nm laser pumping, different exciting power condition of embodiment 11 preparations.Fig. 6 be under embodiment 12 to the 15 prepared holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions condition that is 304mW in 980nm laser pumping, exciting power on the convert light spectrogram.Fig. 7 is the CIE chromatic graph under embodiment 12 to the 15 prepared holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions condition that is 304mW in 980nm laser pumping, exciting power.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the chemical formula of present embodiment holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions is Ca
1-x-y-0.01WO
4: Ho
y/ Yb
x/ Tm
0.01, 0.04≤x≤0.08,0.004≤y≤0.01 wherein.
Present embodiment holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions are doping Ho
3+, Tm
3+And Yb
3+CaWO
4The polycrystalline powder.
Embodiment two: the chemical formula of present embodiment holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions is Ca
1-x-y-0.01WO
4: Ho
y/ Yb
x/ Tm
0.01, 0.05≤x≤0.07,0.005≤y≤0.008 wherein.
Embodiment three: the chemical formula of present embodiment holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions is Ca
1-x-y-0.01WO
4: Ho
y/ Yb
x/ Tm
0.01, wherein x is 0.08,0.006≤y≤0.007.
Embodiment four: present embodiment holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions prepare by following step:
One, the stoichiometric ratio by holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversion chemical formulas takes by weighing lime powder, tungsten trioxide powder, holmium oxide powder, yttria powder and thulium oxide powder, and the chemical formula of holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions is Ca
1-x-y-0.01WO
4: Ho
y/ Yb
x/ Tm
0.01, 0.04≤x≤0.08,0.004≤y≤0.01 wherein;
Two, place agate mortar to grind 4 ± 0.5 hours in lime powder, tungsten trioxide powder, holmium oxide powder, yttria powder and the thulium oxide powder that takes by weighing, placing pressure then is the pressure environment compressing tablet 10min of 18MPa, obtains the sheet precast body;
Three, the sheet precast body is put into carried out high temperature sintering under the air atmosphere, sintering temperature is 1300 ± 50 ℃, and sintering time is 10 ± 0.5 hours, and naturally cooling promptly obtains holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions then.
CaO powder, WO in the present embodiment step 1
3Powder, Ho
2O
3Powder, Yb
2O
3Powder and Tm
2O
3The purity of powder is 99.99%.
The present embodiment step was ground in agate mortar 4 ± 0.5 hours, made lime powder, tungsten trioxide powder, holmium oxide powder, yttria powder and thulium oxide powder thorough mixing even.
Embodiment five: the difference of present embodiment and embodiment four is: the chemical formula of holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions is Ca
1-x-y-0.01WO
4: Ho
y/ Yb
x/ Tm
0.01, 0.05≤x≤0.07,0.005≤y≤0.008 wherein.Other step and parameter are identical with embodiment four.
Embodiment six: the difference of present embodiment and embodiment four is: the chemical formula of holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions is Ca
1-x-y-0.01WO
4: Ho
y/ Yb
x/ Tm
0.01, wherein x is 0.08,0.006≤y≤0.007.Other step and parameter are identical with embodiment four.
Embodiment seven: present embodiment holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions prepare by following step:
One, the stoichiometric ratio by holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversion chemical formulas takes by weighing lime powder, tungsten trioxide powder, holmium oxide powder, yttria powder and thulium oxide powder, and the chemical formula of holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions is Ca
0.906WO
4: Ho
0.004/ Yb
0.08/ Tm
0.01
Two, lime powder, tungsten trioxide powder, holmium oxide powder, yttria powder and the thulium oxide powder that takes by weighing placed agate mortar ground 4 hours, placing pressure then is the pressure environment compressing tablet 10min of 18MPa, obtains the sheet precast body;
Three, the sheet precast body is put into carried out high temperature sintering under the air atmosphere, sintering temperature is 1300 ℃, and sintering time is 10 hours, and naturally cooling promptly obtains holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions then; CaO powder, WO in the step 1
3Powder, Ho
2O
3Powder, Yb
2O
3Powder and Tm
2O
3The purity of powder is 99.99%.
Present embodiment accurately takes by weighing 0.03624mol CaO, 0.04mol WO
3, 0.00008mol Ho
2O
3, 0.0016mol Yb
2O
3With 0.0002mol Tm
2O
3
The doping volumetric molar concentration of holmium ion is 0.4% in the prepared holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions of present embodiment, the doping volumetric molar concentration of ytterbium ion is 8.0%, the doping volumetric molar concentration of thulium ion is 1.0%.
The holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions of present embodiment preparation in 980nm laser pumping, exciting power be can send under the condition of 304mW bright on conversion of white light, last inversion spectrum is shown in Fig. 2 curve b, the CIE colour code is shown in Fig. 3 mid point b, be positioned at white light field, and luminous even.
Embodiment eight: present embodiment holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions prepare by following step:
One, the stoichiometric ratio by holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversion chemical formulas takes by weighing lime powder, tungsten trioxide powder, holmium oxide powder, yttria powder and thulium oxide powder, and the chemical formula of holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions is Ca
0.905WO
4: Ho
0.005/ Yb
0.08/ Tm
0.01
Two, lime powder, tungsten trioxide powder, holmium oxide powder, yttria powder and the thulium oxide powder that takes by weighing placed agate mortar ground 4 hours, placing pressure then is the pressure environment compressing tablet 10min of 18MPa, obtains the sheet precast body;
Three, the sheet precast body is put into carried out high temperature sintering under the air atmosphere, sintering temperature is 1300 ℃, and sintering time is 10 hours, and naturally cooling promptly obtains holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions then; CaO powder, WO in the step 1
3Powder, Ho
2O
3Powder, Yb
2O
3Powder and Tm
2O
3The purity of powder is 99.99%.
Present embodiment accurately takes by weighing 0.0362mol CaO, 0.04mol WO
3, 0.0001mol Ho
2O
3, 0.0016mol Yb
2O
3With 0.0002mol Tm
2O
3
The doping volumetric molar concentration of holmium ion is 0.5% in the prepared holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions of present embodiment, the doping volumetric molar concentration of ytterbium ion is 8.0%, the doping volumetric molar concentration of thulium ion is 1.0%.
The holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions of present embodiment preparation in 980nm laser pumping, exciting power be can send under the condition of 304mW bright on conversion of white light, last inversion spectrum is shown in Fig. 2 curve c, the CIE colour code is shown in Fig. 3 mid point c, be positioned at white light field, and luminous even.
Embodiment nine: present embodiment holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions prepare by following step:
One, the stoichiometric ratio by holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversion chemical formulas takes by weighing lime powder, tungsten trioxide powder, holmium oxide powder, yttria powder and thulium oxide powder, and the chemical formula of holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions is Ca
0.904WO
4: Ho
0.006/ Yb
0.08/ Tm
0.01
Two, lime powder, tungsten trioxide powder, holmium oxide powder, yttria powder and the thulium oxide powder that takes by weighing placed agate mortar ground 4 hours, placing pressure then is the pressure environment compressing tablet 10min of 18MPa, obtains the sheet precast body;
Three, the sheet precast body is put into carried out high temperature sintering under the air atmosphere, sintering temperature is 1300 ℃, and sintering time is 10 hours, and naturally cooling promptly obtains holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions then; CaO powder, WO in the step 1
3Powder, Ho
2O
3Powder, Yb
2O
3Powder and Tm
2O
3The purity of powder is 99.99%.
Present embodiment accurately takes by weighing 0.03616mol CaO, 0.04mol WO
3, 0.00012mol Ho
2O
3, 0.0016mol Yb
2O
3With 0.0002mol Tm
2O
3
The doping volumetric molar concentration of holmium ion is 0.6% in the prepared holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions of present embodiment, the doping volumetric molar concentration of ytterbium ion is 8.0%, the doping volumetric molar concentration of thulium ion is 1.0%.
The holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions of present embodiment preparation in 980nm laser pumping, exciting power be can send under the condition of 304mW bright on conversion of white light, last inversion spectrum is shown in Fig. 2 curve d, the CIE colour code shown in Fig. 3 mid point d, and luminous evenly.
Embodiment ten: present embodiment holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions prepare by following step:
One, the stoichiometric ratio by holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversion chemical formulas takes by weighing lime powder, tungsten trioxide powder, holmium oxide powder, yttria powder and thulium oxide powder, and the chemical formula of holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions is Ca
0.903WO
4: Ho
0.007/ Yb
0.08/ Tm
0.01
Two, lime powder, tungsten trioxide powder, holmium oxide powder, yttria powder and the thulium oxide powder that takes by weighing placed agate mortar ground 4 hours, placing pressure then is the pressure environment compressing tablet 10min of 18MPa, obtains the sheet precast body;
Three, the sheet precast body is put into carried out high temperature sintering under the air atmosphere, sintering temperature is 1300 ℃, and sintering time is 10 hours, and naturally cooling promptly obtains holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions then; CaO powder, WO in the step 1
3Powder, Ho
2O
3Powder, Yb
2O
3Powder and Tm
2O
3The purity of powder is 99.99%.
Present embodiment accurately takes by weighing 0.03612mol CaO, 0.04mol WO
3, 0.00014mol Ho
2O
3, 0.0016mol Yb
2O
3With 0.0002mol Tm
2O
3
The doping volumetric molar concentration of holmium ion is 0.7% in the prepared holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions of present embodiment, the doping volumetric molar concentration of ytterbium ion is 8.0%, the doping volumetric molar concentration of thulium ion is 1.0%.
The holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions of present embodiment preparation in 980nm laser pumping, exciting power be can send under the condition of 304mW bright on conversion of white light, last inversion spectrum is shown in Fig. 2 curve e, the CIE colour code shown in Fig. 3 mid point e, and luminous evenly.
Detected result according to Fig. 2 is observed Ho
3+The increase of ionic concn sharply reduces blue emission intensity, and up-conversion emission intensity is almost constant on ruddiness and the green glow.
Detected result according to Fig. 3 is observed Ho
3+The ion volumetric molar concentration is that the colour code of 0.4% o'clock last conversion white fluorescent output is (0214,0.229); Ho
3+The ion volumetric molar concentration is that the colour code of 0.5% o'clock last conversion white fluorescent output is (0.236,0.246); Ho
3+The ion volumetric molar concentration is that the colour code of 0.6% o'clock last conversion white fluorescent output is (0.242,0.269); Ho
3+The ion volumetric molar concentration is that the colour code of 0.7% o'clock last conversion white fluorescent output is (0.253,0.272); Ho
3+The inclined to one side blue light of up-conversion luminescence when the ion volumetric molar concentration is low is along with Ho
3+The ion volumetric molar concentration increases, and chromaticity coordinates moves to the upper right side gradually, all drops in the 1931CIE chromatic graph in the horseshoe-shaped white light field.
Embodiment 11: present embodiment holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions prepare by following step:
One, the stoichiometric ratio by holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversion chemical formulas takes by weighing lime powder, tungsten trioxide powder, holmium oxide powder, yttria powder and thulium oxide powder, and the chemical formula of holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions is Ca
0.9WO
4: Ho
0.01/ Yb
0.08/ Tm
0.01
Two, lime powder, tungsten trioxide powder, holmium oxide powder, yttria powder and the thulium oxide powder that takes by weighing placed agate mortar ground 4 hours, placing pressure then is the pressure environment compressing tablet 10min of 18MPa, obtains the sheet precast body;
Three, the sheet precast body is put into carried out high temperature sintering under the air atmosphere, sintering temperature is 1300 ℃, and sintering time is 10 hours, and naturally cooling promptly obtains holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions then; CaO powder, WO in the step 1
3Powder, Ho
2O
3Powder, Yb
2O
3Powder and Tm
2O
3The purity of powder is 99.99%.
Present embodiment accurately takes by weighing 0.036mol CaO, 0.04mol WO
3, 0.0002mol Ho
2O
3, 0.0016mol Yb
2O
3With 0.0002mol Tm
2O
3
The doping volumetric molar concentration of holmium ion is 1.0% in the prepared holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions of present embodiment, the doping volumetric molar concentration of ytterbium ion is 8.0%, the doping volumetric molar concentration of thulium ion is 1.0%
The holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions of present embodiment preparation are in the 980nm laser pumping, exciting power is respectively 70mW, 117mW, 164mW, 210mW, can send bright last conversion of white light under the condition of 257mW and 304mW, (exciting power is that the last inversion spectrum of 70mW is shown in Fig. 4 curve f to last inversion spectrum as shown in Figure 4, exciting power is that the last inversion spectrum of 117mW is shown in Fig. 4 curve e, exciting power is that the last inversion spectrum of 164mW is shown in Fig. 4 curve d, exciting power is that the last inversion spectrum of 210mW is shown in Fig. 4 curve c, exciting power is that the last inversion spectrum of 257mW is shown in Fig. 4 curve b, exciting power is that the last inversion spectrum of 304mW is shown in Fig. 4 curve a), and luminous evenly.
Fig. 4 detected result shows that along with the enhancing of exciting power, it is faster that blue emission strength ratio green glow and red emission intensity increase.
The holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions of present embodiment preparation are respectively CIE colour code under the condition of 70mW, 117mW, 164mW, 210mW, 257mW and 304mW in 980nm laser pumping, exciting power and all drop in the 1931CIE chromatic graph in the horseshoe-shaped white light field.Exciting power during for 70mW on the colour code of conversion white fluorescent output be (0.378,0.379), exciting power during for 117mW on the colour code of conversion white fluorescent output be (0.342,0.362), exciting power during for 164mW on the colour code of conversion white fluorescent output be (0.309,0.340), exciting power during for 210mW on the colour code of conversion white fluorescent output be (0.282,0.314), exciting power during for 257mW on the colour code of conversion white fluorescent output be (0.263,0.256), exciting power during for 304mW on the colour code of conversion white fluorescent output be (0.240,0.269), observe enhancing according to the detected result of Fig. 5 along with exciting power, chromaticity coordinates gradually left the below move.
The X-ray diffraction analysis result of the holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions of present embodiment preparation as shown in Figure 1.Fig. 1 X-ray diffraction analysis result and standard x RD card (JCPDS 77-2236) match, and illustrate that the prepared holmium ytterbium thulium of present embodiment method three doped calcium tungstate polycrystalline whitewash light up-conversions have sheelite CaWO
4Structure.
Embodiment 12: present embodiment holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions prepare by following step:
One, the stoichiometric ratio by holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversion chemical formulas takes by weighing lime powder, tungsten trioxide powder, holmium oxide powder, yttria powder and thulium oxide powder, and the chemical formula of holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions is Ca
0.95WO
4: Ho
0.01/ Yb
0.04/ Tm
0.01
Two, lime powder, tungsten trioxide powder, holmium oxide powder, yttria powder and the thulium oxide powder that takes by weighing placed agate mortar ground 4 hours, placing pressure then is the pressure environment compressing tablet 10min of 18MPa, obtains the sheet precast body;
Three, the sheet precast body is put into carried out high temperature sintering under the air atmosphere, sintering temperature is 1300 ℃, and sintering time is 10 hours, and naturally cooling promptly obtains holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions then; CaO powder, WO in the step 1
3Powder, Ho
2O
3Powder, Yb
2O
3Powder and Tm
2O
3The purity of powder is 99.99%.
Present embodiment accurately takes by weighing 0.038mol CaO, 0.04mol WO
3, 0.0002mol Ho
2O
3, 0.0008mol Yb
2O
3With 0.0002mol Tm
2O
3
The doping volumetric molar concentration of holmium ion is 1.0% in the prepared holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions of present embodiment, the doping volumetric molar concentration of ytterbium ion is 4.0%, the doping volumetric molar concentration of thulium ion is 1.0%.
The holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions of present embodiment preparation in 980nm laser pumping, exciting power be can send under the condition of 304mW bright on conversion of white light, last inversion spectrum is shown in Fig. 6 curve a, the CIE colour code shown in Fig. 7 mid point d, and luminous evenly.
Embodiment 13: present embodiment holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions prepare by following step:
One, the stoichiometric ratio by holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversion chemical formulas takes by weighing lime powder, tungsten trioxide powder, holmium oxide powder, yttria powder and thulium oxide powder, and the chemical formula of holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions is Ca
0.93WO
4: Ho
0.01/ Yb
0.05/ Tm
0.01
Two, lime powder, tungsten trioxide powder, holmium oxide powder, yttria powder and the thulium oxide powder that takes by weighing placed agate mortar ground 4 hours, placing pressure then is the pressure environment compressing tablet 10min of 18MPa, obtains the sheet precast body;
Three, the sheet precast body is put into carried out high temperature sintering under the air atmosphere, sintering temperature is 1300 ℃, and sintering time is 10 hours, and naturally cooling promptly obtains holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions then; CaO powder, WO in the step 1
3Powder, Ho
2O
3Powder, Yb
2O
3Powder and Tm
2O
3The purity of powder is 99.99%.
Present embodiment accurately takes by weighing 0.0372mol CaO, 0.04mol WO
3, 0.0002mol Ho
2O
3, 0.001mol Yb
2O
3With 0.0002mol Tm
2O
3
The doping volumetric molar concentration of holmium ion is 1.0% in the prepared holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions of present embodiment, the doping volumetric molar concentration of ytterbium ion is 5.0%, the doping volumetric molar concentration of thulium ion is 1.0%.
The holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions of present embodiment preparation in 980nm laser pumping, exciting power be can send under the condition of 304mW bright on conversion of white light, last inversion spectrum is shown in Fig. 6 curve b, the CIE colour code shown in Fig. 7 mid point c, and luminous evenly.
Embodiment 14: present embodiment holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions prepare by following step:
One, the stoichiometric ratio by holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversion chemical formulas takes by weighing lime powder, tungsten trioxide powder, holmium oxide powder, yttria powder and thulium oxide powder, and the chemical formula of holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions is Ca
0.92WO
4: Ho
0.01/ Yb
0.06/ Tm
0.01
Two, lime powder, tungsten trioxide powder, holmium oxide powder, yttria powder and the thulium oxide powder that takes by weighing placed agate mortar ground 4 hours, placing pressure then is the pressure environment compressing tablet 10min of 18MPa, obtains the sheet precast body;
Three, the sheet precast body is put into carried out high temperature sintering under the air atmosphere, sintering temperature is 1300 ℃, and sintering time is 10 hours, and naturally cooling promptly obtains holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions then; CaO powder, WO in the step 1
3Powder, Ho
2O
3Powder, Yb
2O
3Powder and Tm
2O
3The purity of powder is 99.99%.
Present embodiment accurately takes by weighing 0.0368mol CaO, 0.04mol WO
3, 0.0002mol Ho
2O
3, 0.0012mol Yb
2O
3With 0.0002mol Tm
2O
3
The doping volumetric molar concentration of holmium ion is 1.0% in the prepared holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions of present embodiment, the doping volumetric molar concentration of ytterbium ion is 6.0%, the doping volumetric molar concentration of thulium ion is 1.0%.
The holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions of present embodiment preparation in 980nm laser pumping, exciting power be can send under the condition of 304mW bright on conversion of white light, last inversion spectrum is shown in Fig. 6 curve c, the CIE colour code shown in Fig. 7 mid point b, and luminous evenly.
Embodiment 15: present embodiment holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions prepare by following step:
One, the stoichiometric ratio by holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversion chemical formulas takes by weighing lime powder, tungsten trioxide powder, holmium oxide powder, yttria powder and thulium oxide powder, and the chemical formula of holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions is Ca
0.91WO
4: Ho
0.01/ Yb
0.07/ Tm
0.01
Two, lime powder, tungsten trioxide powder, holmium oxide powder, yttria powder and the thulium oxide powder that takes by weighing placed agate mortar ground 4 hours, placing pressure then is the pressure environment compressing tablet 10min of 18MPa, obtains the sheet precast body;
Three, the sheet precast body is put into carried out high temperature sintering under the air atmosphere, sintering temperature is 1300 ℃, and sintering time is 10 hours, and naturally cooling promptly obtains holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions then; CaO powder, WO in the step 1
3Powder, Ho
2O
3Powder, Yb
2O
3Powder and Tm
2O
3The purity of powder is 99.99%.
Present embodiment accurately takes by weighing 0.0364mol CaO, 0.04mol WO
3, 0.0002mol Ho
2O
3, 0.0014mol Yb
2O
3With 0.0002mol Tm
2O
3
The doping volumetric molar concentration of holmium ion is 1.0% in the prepared holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions of present embodiment, the doping volumetric molar concentration of ytterbium ion is 7.0%, the doping volumetric molar concentration of thulium ion is 1.0%.
The holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions of present embodiment preparation in 980nm laser pumping, exciting power be can send under the condition of 304mW bright on conversion of white light, last inversion spectrum is shown in Fig. 6 curve d, the CIE colour code shown in Fig. 7 mid point a, and luminous evenly.
Detected result according to Fig. 6 is observed Yb
3+The increase of ionic concn sharply reduces green glow and red emission intensity, and blue emission intensity is almost constant.
Detected result according to Fig. 7 is observed Yb
3+The ion volumetric molar concentration is that the colour code of 4.0% o'clock last conversion white fluorescent output is (0.348,0.403); Yb
3+The ion volumetric molar concentration is that the colour code of 5.0% o'clock last conversion white fluorescent output is (0.302,0.363); Yb
3+The ion volumetric molar concentration is that the colour code of 6.0% o'clock last conversion white fluorescent output is (0.275,0.325); Yb
3+The ion volumetric molar concentration is that the colour code of 7.0% o'clock last conversion white fluorescent output is (0.255,0.290); Yb
3+The inclined to one side ruddiness of up-conversion luminescence when the ion volumetric molar concentration is low is along with Yb
3+The ion volumetric molar concentration increases, chromaticity coordinates gradually left the below move, all drop in the 1931 CIE chromatic graphs in the horseshoe-shaped white light field.
Claims (7)
1. holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions is characterized in that the chemical formula of holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions is Ca
1-x-y-0.01WO
4: Ho
y/ Yb
x/ Tm
0.01, 0.04≤x≤0.08,0.004≤y≤0.01 wherein.
2. holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions according to claim 1 is characterized in that the chemical formula of holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions is Ca
1-x-y-0.01WO
4: Ho
y/ Yb
x/ Tm
0.01, 0.05≤x≤0.07,0.005≤y≤0.008 wherein.
3. holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions according to claim 1 is characterized in that the chemical formula of holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions is Ca
1-x-y-0.01WO
4: Ho
y/ Yb
x/ Tm
0.01, wherein x is 0.08,0.006≤y≤0.007.
4. the method for preparing the described holmium ytterbium of claim 1 thulium three doped calcium tungstate polycrystalline whitewash light up-conversions is characterized in that holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions prepare by following step:
One, the stoichiometric ratio by holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversion chemical formulas takes by weighing lime powder, tungsten trioxide powder, holmium oxide powder, yttria powder and thulium oxide powder, and the chemical formula of holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions is Ca
1-x-y-0.01WO
4: Ho
y/ Yb
x/ Tm
0.01, 0.04≤x≤0.08,0.004≤y≤0.01 wherein;
Two, place agate mortar to grind 4 ± 0.5 hours in lime powder, tungsten trioxide powder, holmium oxide powder, yttria powder and the thulium oxide powder that takes by weighing, placing pressure then is the pressure environment compressing tablet 10min of 18MPa, obtains the sheet precast body;
Three, the sheet precast body is put into carried out high temperature sintering under the air atmosphere, sintering temperature is 1300 ± 50 ℃, and sintering time is 10 ± 0.5 hours, and naturally cooling promptly obtains holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions then.
5. the preparation method of holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions according to claim 4 is characterized in that the chemical formula of holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions is Ca
1-x-y-0.01WO
4: Ho
y/ Yb
x/ Tm
0.01, 0.05≤x≤0.07,0.005≤y≤0.008 wherein.
6. the preparation method of holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions according to claim 4 is characterized in that the chemical formula of holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions is Ca
1-x-y-0.01WO
4: Ho
y/ Yb
x/ Tm
0.01, wherein x is 0.08,0.006≤y≤0.007.
7. according to the preparation method of claim 4,5 or 6 described holmium ytterbium thulium three doped calcium tungstate polycrystalline whitewash light up-conversions, it is characterized in that CaO powder, WO in the step 1
3Powder, Ho
2O
3Powder, Yb
2O
3Powder and Tm
2O
3The purity of powder is 99.99%.
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Application publication date: 20110914 |