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CaAlSiN3. The XRD pattern of CaAlSiN3 is indexed with Figure 4. Crystallographic structure of CaAlSiN3 along the (a) [001] (on
the left side a polyhedral view of the structure and on the right a ball-stick
the TREOR 90 program package, and the calculation reveals representation) and (b) [100] directions.
that this compound is attributed to the orthorhombic system.
The space group determination is performed with the Table 1. Refined Structural Parameters, Atomic Coordinates,
Isotropic Displacement Parameters, and Selected Interatomic
CHECKCELL17 program. With regard to the symmetry and Distances of CaAlSiN3 Obtained from the Rietveld Refinement
space group of the initial compound, two space groups, Using Powder XRD Data
Cmc21 and Cmcm, are given as the best solutions. On the atom (site) x y z occupancy Uiso [Å2]
basis of the presented group-subgroup connection analysis
Ca (4a) 0 0.3156 0.9752 1 0.0167
of such AB2X3 compound according to Bärnighausen’s Al/Si (8b) 0.1714 0.8426 0.0489 1 0.0035
procedure,18 the space group of Cmc21 is chosen for further N1 (8b) 0.2123 0.8731 0.4067 1 0.0003
calculations. For the Rietveld refinement of CaAlSiN3, the N2 (4a) 0 0.2305 0.5000 1 0.0003
atomic coordinates of NaSi2N319 are employed as the starting CaAlSiN3 selected distances and angles
model, and the structure is refined with the software package
of FULLPROF SUITE.20 Figure 3 shows the comparison of formula weight 137.16 Ca-N1I 2.3995 N1I-Ca-N1II 118.896
crystal system orthorhombic Ca-N1II 2.3995 N1I-Ca-N2I 98.984
the calculated and observed CaAlSiN3 patterns as well as space group Cmc21 (No. 36) Ca-N2I 2.4433 N1I-Ca-N2II 115.529
the difference curve between them. The resultant crystal- cell parameters a ) 9.731(1) Å Ca-N2II 2.5637 N1II-Ca-N2I 98.984
lographic data and atomic coordinates are summarized in b ) 5.640(8) Å N1II-Ca-N2II 115.529
c ) 5.041(7) Å N2I-Ca-N2II 104.133
Table 1, and these data agree well with the work of Uheda’s volume 268.72 Å3 Ma-N1I 1.7357 N1I-M-N1II 107.628
group.13 The space group of Cmc21 is the maximum non- Z 4 M-N1II 1.8009 N1I-M-N1III 104.888
isomorphic subgroup of the ZnO type wurtzite group P63mc. density (calcd) 3.7919 g/cm3 M-N1III 1.8096 N1I-M-N2 111.570
R factors Rp ) 5.49% M-N2 1.8556 N1II -M-N1III 108.249
According to refinement results of the unit cell parameters, Rwp ) 9.86% N1II-M-N2 112.626
the CaAlSiN3 compound presents a normal tetrahedral N1III -M-N2 111.493
structure related to the wurtzite type a M ) Al/Si.
belong to Cmc21.
Figure 10. The temperature-dependent emission intensity of Ca1-xEuxAlSiN3 Figure 11. TG curve of Ca0.98Eu0.02AlSiN3 and (inset) the comparison of
samples with x ) 0.02 (a) and 0.05 (b), and the inset shows the emission intensity for the same sample before (solid line) and after (dotted
low-temperature emission of Ca0.98Eu0.02AlSiN3. line) the acid process.
only four nearest N3- are considered, the mean distance of Of course, the small stokes shift derived low transition
Ca-N bonds in the annealed sample is 2.4795 Å, and it is probability from the 4f65d to the 4f7 state cannot be excluded.
larger than that in the as-prepared one (2.4515 Å). A weaker
Furthermore, as a nitride phosphor, the optimized
crystal field strength, which is inversely proportional to R5
Ca0.98Eu0.02AlSiN3 shows excellent thermal and chemical
(R: chemical bond length between a cation with d orbital
stabilities. By the thermal gravity (TG) analysis up to 1000
electrons and the coordinating anion),37 is expected for the
°C (Figure 11), the oxidization of Ca0.98Eu0.02AlSiN3 is found
annealed sample. Induced by the lattice shrinkage, the Ca
to occur at a temperature higher than 400 °C and then
ion moves further to the bottom of the tetrahedron and almost
locates in the N1-N1-N2 plane (Figure 9c). This is in oxidized gradually to the corresponding Ca2Al2SiO7 and SiO2
accordance with the refinement of angles listed in Table 3. (by XRD analysis). The weight increase is observed to be
In this case, the fifth coordinated N3- ion (dCa-N ) 2.638) 19.2%, which is close to the stoichiometric value of 21.6%
has to be taken into account. Therefore, the variation of the for the above two compounds. The high threshold of
surrounding environment of doped Eu2+ ions results in the oxidization indicates that the Ca0.98Eu0.02AlSiN3 is oxygen-
narrowing of the excitation band and high-energy emission resistant before 400 °C, which is much higher than the
for the annealed sample. Though this annealed phosphor operating temperature of white LEDs. In addition, as shown
cannot be efficiently excited at 460 nm, its strong absorption in the inset of Figure 11, the emission intensity of
in the range of 380-420 nm indicates the application by Ca0.98Eu0.02AlSiN3 is compared before and after soaking in
combining with another type 405 nm blue LED chip. 5 mol/L nitric acid for 72 h for the chemical stability test.
In the white LED application, a low-temperature quench- After the acid soaking process, the intensity is slightly
ing effect is in favor of keeping the chromaticity and increased rather than decreased by acid corrosion, which
brightness of white light output. The temperature-dependent means that the target phosphor is chemically stable in the
emission intensity of the optimized Ca0.98Eu0.02AlSiN3 sample ambient atmosphere. The slight increase of emission intensity
is shown in Figure 10. As the temperature increases from 5 may be contributed to removal of some acid-soluble impuri-
to 280 K, the emission band peaking at 649 nm keeps the ties, such as the glass phase formed at high temperature.
position, and the intensity is decreased by 17% of the initial For the potential application of this phosphor to the white
value. With heating the samples up to 150 °C at which the LED illumination, the strong absorption in the range of 400-
white LEDs usually work, the emission intensity of 470 nm indicates that the Ca1-xEuxAlSiN3 phosphor can be
Ca0.98Eu0.02AlSiN3 and Ca0.95Eu0.05AlSiN3 remains at about efficiently excited by the blue light source of GaN and
90% and 83% of that measured at room temperature, while InGaN LEDs. The emission intensity of the optimized
at about 60% for the YAG:Ce3+ (P46-Y3) phosphor. The Ca0.98Eu0.02AlSiN3 phosphor by SHS is compared with the
widely accepted mechanism for the thermal quenching is the CaAlSiN3:Eu2+ sample prepared according to ref 13 (Mit-
electronic transition through the intersection between the 4f6- subishi Company provided) and commercially available
5d and 4f7 states. In addition, recently another mechanism YAG:Ce3+ (P46-Y3) standard. At the excitation of 460 nm,
of thermally activated ionization from the 4f65d to the the intensity reaches about 95% of that prepared by solid-
conduction band is proposed to elucidate the thermal state reaction at high temperature and pressure and 120% of
quenching behavior in the Eu2+ doped oxynitride SrSi2O2N2
the YAG:Ce3+ standard. The CIE (Commission Internatio-
host with a rigid structure framework.38 On the basis of the
nale del’Eclairage) 1931 chromaticity index of this phosphor
high quenching temperature and small stokes shift of the Eu2+
is (0.647, 0.347) which indicates the red emission of
ion in the rigid CaAlSiN3 host, the low thermal quenching
Ca0.98Eu0.02AlSiN3 phosphor has high color saturation. Thus,
effect is closely related to the thermally activated ionization.
this phosphor can be used to compensate the red color
deficiency of YAG:Ce3+-based white LEDs or to create white
(37) Kanou, T. Handbook of Phosphors; Ohm Press: Tokyo, 1987.
(38) Bachmann, V.; Jüstel, T.; Meijerink, A.; Ronda, C.; Schmidt, P. J. J. light by combining with a blue LED chip and another green
Lumin. 2006, 121, 441. phosphor.
Preparation of CaAlSiN3:Eu2+ Phosphors by SHS Chem. Mater., Vol. 19, No. 18, 2007 4599