CN106479498A - A kind of Nitrogen oxide blue fluorescent powder and preparation method and application - Google Patents
A kind of Nitrogen oxide blue fluorescent powder and preparation method and application Download PDFInfo
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
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Abstract
The invention provides a kind of Nitrogen oxide blue fluorescent powder and preparation method and application, the chemical general formula of this fluorescent material is Ba1‑x‑y‑z‑mA1xA2yA3zSi2O2N2:mEu2+, A1 is at least one in Sr, Ca, Mg, Mn, Zn or Cu, and A2 is at least one in Li, Na or K, and A3 is at least one in Y, Sc, La, Ga, Gd or Lu；0≤x≤0.1 in formula, 0≤y≤0.1,0≤z≤0.1,0 ＜ m ＜ 0.2.This fluorescent material pass through ball milling mixing raw material, carry out in reducing atmosphere double sintering and post-treated be obtained.The fluorescent material simple production process of the present invention, workable it is easy to industrialized production；It can be by by blue light ultraviolet excitation, and transmitting peak wavelength scope is 490 ~ 500nm, half-peak width（30nm<FWHM<36nm）, light efficiency is high, quenching temperature is high, quantum efficiency is high, acid and alkali-resistance and high-temp resisting high-humidity resisting；It can be mated with blue chip, UV chip makes luminescent device, or is applied in white light LEDs, display, full spectrum special lighting and multiple illuminator.
Description
Technical field
The present invention relates to a kind of luminescent material, specifically a kind of Nitrogen oxide blue fluorescent powder and preparation method thereof with
Application.
Background technology
Fluorescent material conversion of white light diode (LED) has energy-saving and environmental protection, safety, broken colour, specular removal, long-life, driving
Voltage is low and many advantages, such as anti-vibration, it has also become the main flow implementation pattern of white light on market.At present, mainly adopt InGaN blue
Optical chip excites YAG:Ce3+Fluorescent material produces the gold-tinted complementary with blue light, and then mixes to realize common White-light LED illumination.But
It is red color light component disappearance, product color rendering index low (70 about) in white light LEDs produced by this pattern, and colour temperature is higher
(more than 5500K), requires (3000～5000K) to there is certain deviation with the optimum visual of human eye, is therefore not used to family and shines
Bright.
In display field, for obtaining high color rendering index (CRI), the different white light LEDs heating up mainly adopt blue chip+bloom+red
Powder or blue chip+Hydrargyri Oxydum Rubrum+green powder (RGB) method, but the white light LEDs colour developing obtained by blue chip+bloom+Hydrargyri Oxydum Rubrum method refers to
Number is difficult to more than 90；And the requirement more and more higher in RGB scheme, to color rendering index R1～R15.With regard to state-of-the art
Speech, in RGB scheme, in addition to R12 saturated blue colors, remaining R1～R11, R13～R15 all can reach more than 90, R12 then to be become
The limiting factor of high-end display field.With the maturation of black light (380～410nm) chip LED technology, use black light core
The design of piece excitated fluorescent powder white light LEDs will be more noticeable.Because human visual is insensitive to ultraviolet light, then black light
The white light LEDs colour stable that the white light LEDs of chip excite than blue chip, color reducibility and color rendering index are high.Near ultraviolet core
Piece+RGB white light LEDs have become as the emerging pattern of white light LEDs, therefore urgently develop a kind of spoke under blue light and ultraviolet excitation
Project blue light and the good fluorescent material of quantum efficiency height, half-peak width, thermal quenching temperature height, hydrothermal stability.
At present, main flow backlight green emitting phosphor includes LuAG, GAG, orthosilicate and β-Sialon, and wherein LuAG, GAG is same
Belong to YAG system, half-peak breadth (FWHM) is typically larger than 100nm, and excitation is good, its spectrum the shortest for 510nm；Although orthosilicate
Quantum efficiency is very high, and half-peak breadth (FWHM) is 65nm, but the stability of silicate systems and temperature quenching poor performance, only
Suitable small-power, cheap field of backlights, its spectral region is the shortest to be only 510nm；β-Sialon belongs to SiON system, stability pole
Good, half-peak breadth (FWHM) is 51nm, but up to 2000 DEG C of its synthesis temperature and need high pressure, production cost is expensive, in short-term
Interior be difficult to extensively apply, its spectral region be 535～540nm, also can not meet blue wave band radiation requirement.
Orthosilicate quantum efficiency is high and cheap, and β-Sialon system stability is good, and all contains in both core elements
There is Si and O, therefore, the MSiON system between orthosilicate and Sialon system has obtained increasing concern.Patent
A kind of M is disclosed in CN1856561(1-c)Si2O2N2:Dc, it is the nitrogen oxides of divalent europium doping, and luminous material layer is by chip
Exposed portion or be completely converted into dominant wavelength λdomGreen glow for 550～570nm.Non-patent literature Color Point
Tuning for(Sr,Ca,Ba)Si2O2N2:Eu2+In for White Light LEDs, MSiON system has been carried out M case Sr,
Quantum efficiency of Ca, Ba element doping rule, activator concentration variation tendency and each composition etc. has carried out systematic analysiss；Patent
In CN101775292A, embodiment 4 shows a kind of once sintered preparation method of Eu doped nitric oxide blue powder fluorescent material, its
When λ ex=306nm and λ ex=388nm excites, there is blue emission at 495nm.Above three belongs to MSi2O2N2System,
But its thermal quenching temperature and hydrothermal stability are not illustrated, and in actual applications, this system has encapsulated result
Thermal quenching and the heat-labile phenomenon of moisture-proof.
Content of the invention
It is an object of the invention to provide a kind of Nitrogen oxide blue fluorescent powder and preparation method and application, to solve
MSi2O2N2System blue colour fluorescent powder light efficiency is low, thermal quenching and the problems such as moisture-proof thermally labile.
The object of the present invention is achieved like this：
A kind of Nitrogen oxide blue fluorescent powder, its chemical general formula is Ba1-x-y-z-mA1xA2yA3zSi2O2N2:mEu2+, A1 is
At least one in Sr, Ca, Mg, Mn, Zn or Cu, A2 is at least one in Li, Na or K, and A3 is Y, Sc, La, Ga, Gd or Lu
In at least one；0≤x≤0.1 in chemical general formula, 0≤y≤0.1,0≤z≤0.1,0 ＜ m ＜ 0.2.
Preferably, chemical general formula Ba1-x-y-z-mA1xA2yA3zSi2O2N2:mEu2+In, 0≤x≤0.1,0<Y≤0.1,0<z≤
0.1,0 ＜ m ＜ 0.2.
The purpose of the present invention can also be achieved in that：
A kind of preparation method of Nitrogen oxide blue fluorescent powder, comprises the steps：
A () is according to chemical general formula Ba1-x-y-z-mA1xA2yA3zSi2O2N2:mEu2+The mol ratio of middle each element, weighs respectively
The oxide of each element or carbonate in Ba, A1, A2, A3, Si and Eu, using ball mill mix homogeneously, obtain mixed material；
B () said mixture material is placed in high-temperature tubular sintering furnace, be warming up to 1250 under hydrogen or nitrogen and hydrogen mixture
～1450 DEG C, it is incubated 3～7h, is cooled to room temperature, obtains presoma (Ba, A1, A2, A3)2SiO4Crude product；
C () is by gained presoma (Ba, A1, A2, A3)2SiO4Crude product crushes, sieves, obtain presoma (Ba, A1, A2,
A3)2SiO4；
D () is by presoma (Ba, A1, A2, A3)2SiO4With Si3N4And the mixing of 0.1～10wt% flux, grind, obtain
Double sintering mixture；
E double sintering mixture is placed in high-temperature tubular sintering furnace by (), be warming up to 1300～1550 DEG C under reducing atmosphere,
Insulation 2～6h, is cooled to room temperature, obtains fluorescent material crude product；
F fluorescent material crude product is crushed, sieves by (), pickling, ball milling, moisture and drying, obtain final product Nitrogen oxide blue fluorescent powder.
In step (a), the ball milling mixing time is 5～10h, preferably 8h, makes mixed material mix homogeneously.
In nitrogen and hydrogen mixture described in step (b), the volume fraction of hydrogen is 10%～100%.
Preferably 1300～1400 DEG C of sintering temperature in step (b).
The sieve number that in step (c), presoma sieves is 200 mesh.
In step (d), flux is NH4F、NaF、KF、CaF2、AlF3、MgF2、SrF2、BaF2、NH4Cl、MgCl2、SrCl2、
BaCl2、CaCl2、ZnCl2In at least one, preferably add 2～5wt% flux, more preferably BaF2With MgCl2Mixture,
And BaF2∶MgCl2=2wt%: 1wt%.
Reducing atmosphere described in step (e) is hydrogen or nitrogen and hydrogen mixture, and in nitrogen and hydrogen mixture, the volume fraction of hydrogen is
10%～100% it is preferable that in nitrogen and hydrogen mixture hydrogen volume fraction be 75%～100%.
The temperature of step (e) high temperature pipe type sintering furnace is preferably 1400～1500 DEG C, temperature retention time preferably 4～5h.
In step (f), the acid solution of pickling is hydrochloric acid, the pH of described hydrochloric acid<3, preferably 1.5 ＜ pH ＜ 3.
In step (f), baking temperature is 100～300 DEG C, and drying time is 1～3h.
The purpose of the present invention can also be achieved in that：
A kind of application of Nitrogen oxide blue fluorescent powder, it is excited by blue-violet light, in white light LEDs, display and full light
Application in spectrum special lighting.
The present invention is in BaSi2O2N2:On the basis of Eu, Ba is replaced using Sr, Ca, Mg, Mn, Zn, Cu element2+Case, adopt
Y, Sc, La, Ga, Gd, Lu replace Ba2+Case and charge compensation is carried out to it by Li, Na, K element.Due to replacing ion
Radius is less than Ba2+Radius, Charge-compensating ions K+、Na+Ionic radius is close to or smaller than Ba2+Radius so that distortion of lattice
Reduce, compensate for the lattice defect in MSiON system, promote crystallization, so that half-peak breadth is narrowed, and lifted to UV-blue light
Absorption efficiency and luminous efficiency, increase luminous intensity, thus improving light efficiency, system thermal quenching temperature and hydrothermal stability.
The Nitrogen oxide blue fluorescent powder simple production process of the present invention, workable it is easy to industrialized production；Made
Standby Nitrogen oxide blue fluorescent powder can be excited by blue-violet light, and transmitting peak wavelength scope is 490～500nm, half-peak
Width (30nm<FWHM<36nm), light efficiency is high, quenching temperature is high, quantum efficiency height, acid and alkali-resistance and high-temp resisting high-humidity resisting；It can be with indigo plant
Optical chip, UV chip coupling make luminescent device, or are applied to white light LEDs, display and full spectrum special lighting, also can be
Office lighting systems, industrial light system, home lighting systems, roadway lighting system, decorative lightening system, automotive lighting system
The field such as system and indicator illuminator is extensively applied.
Brief description
Fig. 1 is the temperature quenching curve of comparative example 1 and sample prepared by embodiment 13,37,57,78.
Fig. 2 is double 85 experiment brightness flop curves of comparative example 1 and sample prepared by embodiment 13,37,57,78.
Fig. 3 is double 85 experiment x chromaticity coordinates change curves of comparative example 1 and sample prepared by embodiment 13,37,57,78.
Fig. 4 is the SEM figure of sample prepared by embodiment 37.
Fig. 5 is the launching light spectrogram of sample prepared by embodiment 37.
Specific embodiment
Embodiment 1
According to Ba1.8K0.04Y0.04SrSiO4:0.12Eu2+The carbonate of middle each element or oxide stoichiometries ratio, weigh
16.91g BaCO3、0.13g K2CO3、0.22g Y2O3、3.62g SiO2With 1.01g Eu2O3, it is placed in batch mixing 8h in ball mill,
Obtain mixed material.Mixed material is placed in corundum crucible, uncaps, crucible is placed in high temperature process furnances, in the mixing of nitrogen hydrogen
It is warming up to 1350 DEG C with the speed of 10 DEG C/min under gas (10% hydrogen) atmosphere, after insulation 4h, naturally cool to room temperature, before obtaining
Drive body crude product.Presoma crude product is taken out broken, cross 200 mesh sieves, obtain presoma needed for double sintering.Weigh 10g above-mentioned before
Drive body, 3.87g Si3N4、0.28g BaF2With 0.14g MgCl2Flux, mixed grinding 30min, it is placed in molybdenum Noah's ark crucible,
Do not add a cover, crucible is placed in high temperature process furnances, be passed through hydrogen and be sintered, programming rate controls in 5～10 DEG C/min, heat up
To 1400 DEG C, naturally cool to room temperature after insulation 5h, obtain fluorescent material crude product.Gained fluorescent material crude product is crushed, crosses 200 mesh
Sieve, using the chlorohydric acid pickling of pH=2.5, ball milling 2h, moisture, dries 3h at 200 DEG C, obtains Ba0.90K0.02Y0.02Si2O2N2:
0.06Eu2+Nitrogen oxide blue fluorescent powder.
Embodiment 2～32
Nitrogen oxide blue fluorescent powder prepared by embodiment 2～32 is carried out not to Ba case as different from Example 1
Replacement with element：Y, Sc, La, Ga, Gd, Lu, wherein respectively with Y2O3、Sc2O3、La2O3、Ga2O3、Gd2O3、Lu2O3Form
It is added in mixture, other process conditions are all same as Example 1, repeat no more.
Fluorescent material prepared by embodiment 1～32 is carried out with relative luminance, peak wavelength, half-peak breadth test, concrete test
The results are shown in Table 1.
Table 1
Embodiment 33～44
Nitrogen oxide blue fluorescent powder prepared by embodiment 33～44 is as different from Example 1 to Ba2+Case is carried out
Different elements and different amounts of replacement, other process conditions are all same as Example 1, repeat no more.
Relative luminance, peak wavelength, half-peak breadth are carried out to the Nitrogen oxide blue fluorescent powder prepared by embodiment 33～44
Test, concrete test result is shown in Table 2；The SEM spectrogram of the Nitrogen oxide blue fluorescent powder prepared by embodiment 37 and emission spectrum
Figure is as shown in Figure 4, Figure 5.
Table 2
Embodiment 52
According to Ba1.96SiO4:0.04Eu2+The carbonate of middle each element or oxide stoichiometries ratio, weigh 18.42g
BaCO3、3.62g SiO2With 0.34g Eu2O3, it is placed in batch mixing 8h in ball mill, obtain mixed material.Mixed material is placed in just
In beautiful crucible, uncap, crucible is placed in high temperature process furnances, with 10 DEG C/min's under nitrogen and hydrogen mixture (10% hydrogen) atmosphere
Speed is warming up to 1350 DEG C, naturally cools to room temperature, obtain presoma crude product after insulation 4h.Presoma crude product is taken out broken,
Cross 200 mesh sieves, obtain presoma needed for double sintering.Weigh the above-mentioned presoma of 10g, 3.82g Si3N4Flux with 0.14g NaF
Agent, mixed grinding 30min, it is placed in molybdenum Noah's ark crucible, does not add a cover, crucible is placed in high temperature process furnances, be passed through hydrogen and carry out
Sintering, programming rate controls in 5～10 DEG C/min, is warmed up to 1400 DEG C, naturally cools to room temperature, obtain fluorescent material after insulation 5h
Crude product.Gained fluorescent material crude product is crushed, crosses 200 mesh sieves, using the chlorohydric acid pickling of pH=2.5, ball milling 2h, moisture, at 200 DEG C
Lower drying 3h, obtains Ba0.98Si2O2N2:0.02Eu2+Nitrogen oxide blue fluorescent powder.
Comparative example 1
Repeated experiment is carried out according to embodiment in patent CN101775292A 4, dosage etc. is than expansion.
Reaction raw materials are 18.6g BaCO3、3.5g SiO2、6.4g Si3N4With 0.2g Eu2O3, raw material is placed in Achatess and grinds
Alms bowl, adds appropriate dehydrated alcohol as abrasive media, is ground to dehydrated alcohol and all volatilizees, mixture is scraped off, put into
100mL beaker, adds appropriate dehydrated alcohol, carries out ultrasonic 30min, then dry sample.Mixture after drying is placed in
Aluminium oxide porcelain boat, puts horizontal pipe furnace into, is passed through nitrogen and is calcined.Calcining heat is 1500 DEG C, temperature retention time 8h.Gained produces
Thing is slightly ground broken, obtains final product blue-green fluorescent powder Ba0.98Si2O2N2:Eu0.02.
Embodiment 53～59
Ba prepared by embodiment 53～590.98Si2O2N2:Eu0.02Nitrogen oxide blue fluorescent powder, with embodiment 52 institute not
Same is species and the amount of auxiliary (accounting for the wt% of mixture) changing auxiliary agent, and other process conditions are all identical with embodiment 52,
Repeat no more.
Relative luminance, peak wavelength, half-peak breadth are carried out to the fluorescent material prepared by comparative example 1 and embodiment 52～59, tool
Body examination test result is shown in Table 3.
Table 3
Embodiment 60
According to Ba1.88Sr0.02SiO4:0.12Eu2+The carbonate of middle each element or oxide and flux stoichiometric proportion
Weigh raw material BaCO317.66g、SrCO30.14g、SiO23.62g and Eu2O31.01g mixes, and is placed in batch mixing 8h in ball mill
Afterwards, be placed in corundum crucible, uncap, crucible is placed in high temperature process furnances, under nitrogen and hydrogen mixture (10% hydrogen) atmosphere with
The speed of 10 DEG C/min is warming up to 1350 DEG C, naturally cools to room temperature, obtain presoma crude product after insulation 4h.By presoma crude product
Take out broken, cross 200 mesh sieves, obtain presoma needed for double sintering.Weigh the above-mentioned presoma of 10g, 3.19g Si3N4、0.28g
BaF2With 0.14g MgCl2Flux, mixed grinding 30min, it is placed in molybdenum Noah's ark crucible, does not add a cover, crucible is placed in high temperature pipe
In formula stove, it is passed through nitrogen and hydrogen mixture and is sintered, programming rate controls in 5～10 DEG C/min, be warmed up to 1400 DEG C, after insulation 5h
Naturally cool to room temperature, obtain fluorescent material crude product.Gained fluorescent material crude product is crushed, crosses 200 mesh sieves, using the salt of pH=2.5
Pickling, ball milling 2h, moisture, dry 3h at 200 DEG C, obtain Ba0.93Sr0.01Si2O2N2:0.06Eu2+Nitrogen oxides blueness is glimmering
Light powder.
Nitrogen oxide blue fluorescent powder prepared by embodiment 61～81 is carried out to Ba case from unlike embodiment 60
The replacement of different elements：Sr, Ca, Mg, Mn, Zn, Cu, wherein respectively with SrCO3、CaO、MgO、MnCO3, the form of ZnO, CuO adds
It is added in mixture, other process conditions are all identical with embodiment 60, repeat no more.
Nitric oxide fluorescent powder prepared by embodiment 60～81 is carried out with relative luminance, peak wavelength, half-peak breadth test,
Concrete test result is shown in Table 4.
Table 4
Embodiment 82
The sample weighing respectively in 1g comparative example 1 is glimmering with the nitrogen oxides obtained by the embodiment of the present invention 13,37,57,78
Light powder carries out thermal quenching experiment, and experimental apparatus used are Hitachi spectrofluorophotometer F7000, λ ex=450nm, test 300K
The different relative luminance of sample in～500K temperature range, test result is as shown in table 5 and Fig. 1.
Table 5
As can be seen from Table 5, the thermal quenching performance of Nitrogen oxide blue fluorescent powder prepared by the present invention is superior to comparative example
1.
Embodiment 83
Weigh the nitric oxide fluorescent powder that the sample of 1g comparative example 1 is obtained with the embodiment of the present invention 13,37,57,78 respectively
Temperature be 85 DEG C, humidity be to carry out double 85 experiments in the environment of 85%, predominantly detecting index is the change of quality, x chromaticity coordinates
Change, the change of brightness, every 200h detect once, interruption carry out 1000h, to detect its stability, result such as table 6, Fig. 2
With shown in Fig. 3.
Table 6
Can be seen that the resistance to of Nitrogen oxide blue fluorescent powder prepared by embodiment 13,37,57 and 78 from table 6, Fig. 2 and Fig. 3
Hydrothermal stability is better than comparative example 1.
Claims (10)
1. a kind of Nitrogen oxide blue fluorescent powder is it is characterised in that its chemical general formula is Ba1-x-y-z-mA1xA2yA3zSi2O2N2:
mEu2+, A1 be Sr, Ca, Mg, Mn, Zn or Cu at least one, A2 be Li, Na or K at least one, A3 be Y, Sc, La,
At least one in Ga, Gd or Lu；0≤x≤0.1 in chemical general formula, 0≤y≤0.1,0≤z≤0.1,0 ＜ m ＜ 0.2.
2. Nitrogen oxide blue fluorescent powder according to claim 1 is it is characterised in that in described chemical general formula, and 0≤x≤
0.1,0<Y≤0.1,0<Z≤0.1,0 ＜ m ＜ 0.2.
3. a kind of preparation method of Nitrogen oxide blue fluorescent powder is it is characterised in that comprise the steps：
（a）According to chemical general formula Ba1-x-y-z-mA1xA2yA3zSi2O2N2:mEu2+The mol ratio of middle each element, weigh respectively Ba, A1,
The oxide of each element or carbonate in A2, A3, Si and Eu, using ball mill mix homogeneously, obtain mixed material；
（b）Said mixture material is placed in high-temperature tubular sintering furnace, under hydrogen or nitrogen and hydrogen mixture, is warming up to 1250 ~ 1450
DEG C, it is incubated 3 ~ 7h, be cooled to room temperature, obtain presoma (Ba,A1,A2,A3)2SiO4Crude product；
（c）By gained presoma (Ba,A1,A2,A3)2SiO4Crude product crushes, sieves, and obtains presoma (Ba,A1,A2,A3)2SiO4；
（d）By presoma (Ba,A1,A2,A3)2SiO4With Si3N4And the mixing of 0.1 ~ 10wt% flux, grind, obtain double sintering
Mixture；
（e）Double sintering mixture is placed in high-temperature tubular sintering furnace, is warming up to 1300 ~ 1550 DEG C under reducing atmosphere, be incubated 2
~ 6h, is cooled to room temperature, obtains fluorescent material crude product；
（f）Fluorescent material crude product is crushed, sieves, pickling, ball milling, moisture and drying, obtain final product Nitrogen oxide blue fluorescent powder.
4. preparation method according to claim 3 is it is characterised in that step（b）Described in hydrogen in nitrogen and hydrogen mixture
Volume fraction is 10% ~ 100%.
5. preparation method according to claim 3 is it is characterised in that step（d）Described in flux be NH4F、NaF、KF、
CaF2、AlF3、MgF2、SrF2、BaF2、NH4Cl、MgCl2、SrCl2、BaCl2、CaCl2、ZnCl2In at least one.
6. preparation method according to claim 5 is it is characterised in that step（d）Described in flux be BaF2With MgCl2
Mixture, and BaF2∶MgCl2=2wt%∶1wt%.
7. preparation method according to claim 3 is it is characterised in that step（e）Described in reducing atmosphere be hydrogen or nitrogen
Hydrogen gaseous mixture, in described nitrogen and hydrogen mixture, the volume fraction of hydrogen is 10% ~ 100%.
8. preparation method according to claim 3 is it is characterised in that step（f）Middle pickling is carried out using hydrochloric acid, and hydrochloric acid
PH<3.
9. preparation method according to claim 3 is it is characterised in that step（f）Middle baking temperature is 100 ~ 300 DEG C, does
The dry time is 1 ~ 3h.
10. the Nitrogen oxide blue fluorescent powder any one of a kind of claim 1 ~ 9 is excited by blue-violet light, white
Application in light LED, display and full spectrum special lighting.
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| CN113249126B (en) * | 2021-05-20 | 2023-08-15 | 中国科学院长春光学精密机械与物理研究所 | Cyan-induced luminescent material capable of increasing number of low-temperature traps, and preparation method and application thereof |
| CN115477941A (en) * | 2021-06-16 | 2022-12-16 | 厦门稀土材料研究所 | Blue fluorescent powder excited by near ultraviolet light with high thermal stability and preparation method thereof |
| CN115477941B (en) * | 2021-06-16 | 2023-12-26 | 厦门稀土材料研究所 | Blue fluorescent powder excited by near ultraviolet light with high thermal stability and preparation method thereof |
| CN114525131A (en) * | 2022-03-01 | 2022-05-24 | 中国计量大学 | High-thermal-stability blue-green fluorescent powder and preparation method thereof |
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