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1. Introduction
In recent years, more efficient cathodoluminescent
phosphors are being widely investigated for applications in monitors high definition television (HDTV),
and vacuum fluorescent displays (VFDs) [1, 2]. However, VFDs are operated by only 30 V d.c. or less when
they are used as indicators on aircraft control panels
or automobile dashboards [2]. Therefore, a range of
new phosphors such as ZnGa O for operating at low
2 4
voltages are being developed.
ZnGa O is a self-activated phosphor which emits
2 4
blue light under excitation by both ultraviolet light
and low voltage electrons (30 V d.c.). Excellent stability through the high temperature operating life test for
this phosphor has also been proven [5]. The stability
of zinc gallate phosphors in high vacuum and the
absence of corrosive gas emission under electron bombardment offer advantages over commonly used sulfide phosphors [3, 4]. However, the effect of
compositional change of zinc gallate on photoluminescence has not been reported. In the present
study the compositional change relationship between
the composition and the luminescence properties of
zinc gallate powders are investigated.
The 3d-series transition metal ions incorporated
into phosphors will act as emission centres. For
example, according to the different host materials,
doping with Mn2` (3d5) or Cl3` (3d3) will emit green
to red light [10, 14], or red light [7], respectively.
Information about the photoluminescence mechanism
of Mn-doped zinc gallate (Zn Mn Ga O ) remains
1~x
x 2 4
unclear. In this study, the effect of doping Mn2` in
09574522 ( 1998 Kluwer Academic Publishers
2. Experimental
The phosphor compositions of Zn Mn Ga O
1~x
x 2 4
with x ranging from 0 to 0.03 were synthesized
via a conventional solid state reaction. Starting powders of high purity ZnO (CERAC Ltd., 200 mesh,
99.999%), Ga O (CERAC Ltd., 325 mesh, 99.999%)
2 3
and dopant Mn(NO ) ) 2H O (AESAR Ltd., 99.98%),
32
2
as well as LiCl flux (CERAC Ltd., 60 mesh, 99.8%)
were weighed on an analytical balance to an
accuracy of $0.1 mg, thoroughly mixed for 10 h in
a Turbula shake mixer with alcohol solvent. The
mixed slurry was dried in a hot water bath, then
air-fired at 1200 C for 5 h and some Mn2 doped
samples were fired at 1300 C in vacuum for 1.5 h in
a covered alumina crucible to obtain homogeneous
phosphor powders [6]. After grinding, the phosphor
powders were washed with dilute nitric acid and then
rinsed with de-ionized water to remove the excessive
flux.
The grain size of the fired powder was measured
by a Shimadzu SA-CP3L centrifugal particle size
analyser.
The phases of the phosphors were characterized by
X-ray diffraction (XRD) using a Rigaku X-ray diffractometer with CuKa radiation at 40 kV, 15 mA and
4 (2h) min~1 scanning rate.
The photoluminescence emission and excitation
spectra of polycrystalline phosphors were obtained
283
using a Shimadzu RF-5301PC spectrofluorophotometer. The excitation spectra can be obtained from
scanning the wavelength from 220 to 700 nm
monitored at 450 or 506 nm. The emission wavelength
was scanned from 400 to 700 nm excited at 254 nm or
304 nm.
Phases in the
calcined powders
Relative emission
intensity
ZnO Ga O
2 3
A
B
C
D
E
44
47
50
53
55
56
53
50
47
45
ZnGa O #b-Ga O
58
2 4
2 3
ZnGa O
100
2 4
ZnGa O
65
2 4
ZnGa O #ZnO
32
2 4
ZnGa O #ZnO
27
2 4
4P
4D
4G
Levels in
tetrahedral
symmetry
4T
1
4E
4T
2
4E4A
1
4T
2
4T
1
Wavelength
(nm)
(cm~1)
304
358
385
429
454
584
32895
27933
25974
23310
22026
17123
the excitation light is 254 nm or 304 nm. The maximum emission intensity occurs as the Mn2` concentration of the sample x"0.006 and a decrease in
emission intensity is observed for the samples with
Mn2` higher or lower than this optimum amount.
This phenomenon implies the excess concentration of
activator would interfere with the energy transfer and
therefore weaken the emission peak. The fact can be
readily understood from concentration quenching.
Besides the shift of the emission peak from 470 nm to
506 nm after doping of Mn2` in zinc gallate, a green
light with better emission purity, the lower energy
excitation, 304 nm, can include the 506 nm emission,
too.
4. Conclusions
ZnGa O phosphor can be formed at a temperature
2 4
of 1050 C or above. As the temperature increased to
1200 C, ZnO and Ga O can react completely. X-ray
2 3
diffraction measurements show all the phosphors
with the mole ratio of ZnO and Ga O between
2 3
47/5350/50 are single phase and have the spinel crystal structure. ZnGa O emitted 375700 nm broad
2 2
light with the strongest wavelength at about 470 nm.
The highest emission intensity was that with the ZnO
and Ga O mole ratio of 47/53. The emission spec2 3
trum of ZnGa O doped Mn2` fired in air exhibited
2 4
Acknowledgements
The authors are grateful for the financial support
provided by the Tatung Company under the grant.
References
1. From Associated Press and Washington Post, in Roanoke
Times, World News, Section A3, May 26 (1993).
2. C. L. S L UP EK , Y. K A ZU YU K I , S . S HIN Y A, M . S U ZU K I ,
H. Y AM AG U C HI and G . W I R ES , Aut. Eng. 97 (1989) 47.
3. S. IT O H, M . Y O K OY A M A and K . M O R IM O T O , J. ac. Sci.
echnol, A5, (1987) 3430.
4. S. IT O H , T. K IM I Z UK A and T. TO N E GA W A , J. Electrochem. Soc. 136 (1989) 1819.
5. S. I TO H , H. T O KI , Y . S A TO , K. MO R I M OT O and
T . K I S HI N E, ibid. 138 (1991) 1509.
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