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JO U RN A L O F M AT E RIAL S S CIEN C E: M A TER I A LS IN ELE CT RO N I C S 9 (19 9 8) 283 28 8

A study of ZnGa2O4 phosphor prepared by the solid


method
KA I -H U NG HS U , M U -R O NG Y AN G , K O - SH AO CH E N
Department of Materials Engineering, Tatung Institute of Technology, Taipei, 104, Taiwan
In this study, the mixtures of ZnO and Ga2O3 powder with addition of LiCl flux were fired, the
raw material mixing ratio, doping with Mn2# and firing atmosphere effects on phosphor
characteristics were investigated. When fired at 1200 C, its phosphor powder emits
a broad-band spectrum range between 375 nm to 700 nm, with a peak at 470 nm. The optimal
composition of phosphors is about ZnO/Ga2O5"47/53. Manganese-doped ZnGa2O4, fired in
air, exhibits two new emission bands with peaks at 506 nm (Mn2# emission centre) and
666 nm (Mn4# emission centre). However, if fired under vacuum, the emission spectrum
presents only the 506 nm peak with increased intensity. The 666 nm emission peak derived
from a little Mn2 oxidized to Mn4# which substituted Ga3# to occupy the B sites of the spinel
structure. The emission intensity of the 506 nm peak of Zn [xMnxGa2O4 is strongest when
1
[Mn2#] x"0.006 and decreases markedly as the concentration of Mn2# exceeds x"0.01.
Most of the substitutional Mn2# doping species in spinel ZnGa2O4 occupy the zinc sites. The
luminescent band was associated to the spin-forbidden transition, 4T1(4G)P6A1 (6S). 1998
Kluwer Academic Publishers

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

zinc gallate on the spectrum shift and intensity will be


investigated.

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.

3. Results and discussion


3.1. Synthesis of phosphors
From the DTA analysis, the firing temperature of the
ZnO and Ga O mixed powder must be above
2 3
1050 C, and the optimal firing temperature of the
mixed powders is 1100 C [5, 15]. However, it takes
a longer time for firing pure ZnGa O phosphors at
2 4
this firing temperature and energy consumed is much
higher. For this reason, 1200 C for 5 h were chosen as
the firing temperature and time.
The effect of mole ratio of ZnO to Ga O on the
2 3
phase formations of fired ZnGa O is shown in Fig. 1
2 4
and summarized in Table I. The powders with mixed
compositions of ZnO/Ga O mole ratio were 47/53
2 5
and 50/50 showed the presence of ZnGa O spinel
2 2
phase only. It is clear that in the solid method of the
prepared ZnGa O the spinel phase exists over a wide
2 4
compositional range.
The particle size of fired phosphors was between
25 lm. However, the unfired ZnO and Ga O mixed
2 3
powder was about 12 lm. This indicated that the
ZnGa O phosphors fired at 1200 C for 5 h with LiCl
2 4
flux will promote the growth of the grain size.

3.2. Photoluminescence of ZnGa2O4


The luminescent characteristic of the samples with
various ZnO/Ga O ratios is shown in Figs 2 and 3.
2 3
The excitation spectrum of sample B with pure
ZnGa O phase monitored at 450 nm exhibits a max2 4
imum excitation peak only at about 246 nm, and indicates the optical bandgap is about 4.8 eV. Samples
D and E not only introduce an additional excitation
peak at 320 nm due to the existence of ZnO minor
phase, but also seriously decrease the intensity of both
excitation peak and emission peak of ZnGa O . The
2 4
emission spectrum under an exciting wavelength of
254 nm shows a broad-band emission extending from
375 to 700 nm with a maximum emission peak at
470 nm. However, sample A with excess Ga O de2 3
creases the intensity of the peak at 470 nm relatively
less. The optimum composition of ZnO/Ga O is
2 5
about 47/53.

3.3. The absorption spectrum of


ZnGa2O4 :Mn
The ZnGa O is a spinel compound with the unit cell
2 4
belonging to the cubic space group O7 (Fd3m). In this
)
structure there are two types of metal ion sites; A and
B. The A site has tetrahedral co-ordination with full
T symmetry and the B site has six-fold distorted
$
octahedral co-ordination belonging to the D
3$
point group. This compound is known to be almost
284

Figure 1 XRD patterns of zinc gallates with various mole ratios of


ZnO/Ga O .
2 3

TA BLE I Phase and emission intensity of calcined zinc gallate


samples
Samples Composition
(mol %)

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

perfectly normal ordered with the Zn ion occupying


the A sites and the Ga ions occupying the B sites [8].
There are five electrons in the (3d5) orbital of Mn2`.
According to Hunds rule and the fact that the splitting energy of Mn2` (*"7500 cm~1) is smaller than
its electron pairing energy (p"25 500 cm~1), these
five electrons in the 3d orbital should be in high
spin and weak crystal field [9]. Regardless of the
occupation site of Mn2` in spinel crystal, the
TanabeSugano (3d5) energy level diagram, can be
used to fit the energy splitting levels of ZnGa O :Mn
2 4
phosphors. The absorption spectrum and energy splitting levels of ZnGa O :Mn phosphors which were
2 4
fired in air are shown in Fig. 4 and summarized in
Table II. These absorption peaks match Tanabe
Sugano (3d) energy level diagram. The narrow, sharp
429 nm peak is a zero phonon line peak that is independent of the strength of the crystal field. Hence, it
fits the energy level of 4E4A(4G) which is parallel to
the horizontal axis. The B and C values of the Racah
parameter, which use derived from the observed energy levels of 4E4A(4G) and 4E(4D) are 660 cm~1 and
3342 cm~1, respectively. The crystal field parameter,
Dq is 564.8 cm~1. The fact that the 4E(4D) absorption
peak is very weak can be attributed to the shielding of
the ion transition band [10, 11]. Based on the peak of

Figure 4 The relationship of absorption spectrum and energy split


levels of Zn Mn Ga O (x"0.006).
1~x
x 2 2

TA BLE I I The absorption bands of Mn2` in ZnGa O phos2 4


phors
Free-ion
levels

Figure 2 Excitation spectra of zinc gallates with various mole ratios


of ZnO/Ga O , 15 samples AE.
2 3

4P
4D
4G

Figure 3 Emission spectra of zinc gallates with various mole ratios


of ZnO/Ga O , 15 samples AE.
2 3

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

emission spectrum fall at 506 nm, the luminescent


band matches the spin-forbidden transition, 4T (4G)
1
P6A (6S).
1
Fig. 5 shows the absorption spectrum of
ZnGa O :Mn phosphors which were fired in air and
2 4
vacuum. The intensity of the absorption spectrum of
samples fired in vacuum (&1.3 ph) is stronger than
samples fired in air, especially, the three highest intensity peaks are 245 nm (ZnGa O absorption peak),
2 4
304 nm (4T (4P)) and 626 nm (4T (4G)). These results
1
1
would suggest that (1) the doped Mn2` did not oxidize to Mn4`, (2) because of a lack of oxygen, this
created more defects in the spinel structure under
vacuum firing, and (3) all Mn2` (3d5) ions substitute
for Zn2` and occupy the A sites in the tetrahedral
structure. Therefore, the intensity of the absorption
spectrum is improved to its maximum.
If Mn2` substituted for the cation with a smaller
radii this would reduce the distance between Mn2`
and the co-ordinate anion. As a result, the emission
spectrum would shift to longer wavelength [12]. Since
the radii of Mn2`, Zn2` and Ga3` are 0.083, 0.072
and 0.062 nm, respectively, Mn2` substitutes for Zn2`
and occupies the A sites in the tetrahedral structure
which would cause the emission spectrum to shift from
470 nm (ZnGa O ) to 506 nm (ZnGa O :Mn). If
2 4
2 4
Mn2` substitutes for Ga3` and occupies the B sites in
285

Figure 5 Absorption spectrum monitored at 506 nm of


Zn Mn Ga O (x"0.01). (Dotted line: firing under vacuum;
1~x
x 2 2
Full line: firing in air).

the octahedral structure the emission spectrum would


shift to the long wavelength side even more. The
emission spectrum of ZnGa O :Mn phosphors fired
2 4
in air is shown in Fig. 6. Two emission bands, one
a main peak at 506 nm, the other a weak band at
666 nm, are seen. However, in the emission spectrum
of samples fired under vacuum, the weak band 666 nm
disappears. This implies that a little Mn2` oxidized to
Mn4` during the firing in air, and Mn4` substituted
for Ga3` to occupy the B sites of the octahedral
structure [13]. Due to the symmetry of the octahedral
structure [9], the intensity of spectrum is so weak that
the emission spectrum of 666 nm (red colour) can only
be detected through enlarging the slit width of the EX
or EM monochromator. Therefore, in ZnGa O fired
2 4
in air, most of the Mn2` occupy the A sites of the
tetrahedral structure and create the main wavelength
peak (506 nm), while some of the Mn4` occupy the
B sites of the octahedral structure and create the weak
wavelength peak (666 nm).

3.4. The emission spectrum of ZnGa2O4:Mn


Mn2` dopant will change the colour of zinc gallate
phosphors from white to a peach colour. The emission
peak of the phosphors doped with transition metal
ions varied with the host and ranged around
450750 nm at room temperature [10, 14]. The Mn2`
-doped ZnGa O host emission peaks at 506 nm are
2 4
shown in Fig. 6. Compared with the pure ZnGa O
2 4
shown in Fig. 3, the emission peak shifts from about
286

Figure 6 Emission spectrum excited by 304 nm of Zn Mn Ga O


1~x
x 2 2
(x"0.002). (Dotted line: firing under vacuum; Full line: firing in
air).

470 nm to about 506 nm under 254 nm excitation as


described elsewhere [15].
The Mn2` doping in ZnGa O will not only affect
2 4
the wavelength of the emission peak, but also narrows
the emission spectrum band at the emission peak. The
half-wave width at the emission peaks 470 nm and
506 nm are 110 nm and 23 nm, respectively. The
Mn2` doped ZnGa O has a narrower spectrum
2 2
band compared with an undoped sample and, consequently, better emission colour purity.
The amount of Mn2` addition affects the emission
intensity of ZnGa O phosphor. The emission spectra
2 4
of ZnGa O fired in air with various amounts of
2 4
Mn2` doping under 254 nm and 304 nm excitation
are shown in Figs 7 and 8, respectively. However,
regardless of whether the excitation wavelength is
254 nm or 304 nm, the emission spectra present
a weak band at 666 nm. Because of the weak red light
666 nm present, the intensity of the green light 506 nm
decreases. Nevertheless, the emission spectrum of
Zn Mn Ga O fired under vacuum exhibits
1~x
x 2 4
506 nm green light only, and increases the intensity of
the emission spectrum, as shown in Fig. 6. Hence, we
suggest that firing Zn Mn Ga O phosphors under
1~x
x 2 4
vacuum is much better than in air, as for firing ZnMnferrite would be in a protective atmosphere to avoid
Mn2` oxidizing to Mn4`.
It is indicated in Figs 7 and 8 that the emission
intensity increases with increasing Mn2` dopant in
zinc gallate regardless of whether the wavelength of

Figure 7 Emission spectrum of various amounts of Mn2` doped


ZnGa O excited by 254 nm light; (1) Zn Mn Ga O (x"
2 4
1~x
x 2 4
0.002); (2) Zn Mn Ga O (x"0.004); (3) Zn Mn Ga O
1~x
x 2 4
1~x
x 2 4
(x"0.006); (4) Zn Mn Ga O (x"0.008); (5) Zn Mn Ga O
1~x
x 2 4
1~x
x 2 4
(x"0.01).

Figure 8 Emission spectrum of various amounts of Mn2` doped


ZnGa O excited by 304 nm light; (1) Zn Mn Ga O
2 4
1~x
x 2 4
(x"0.002); (2) Zn Mn Ga O (x"0.004); (3) Zn Mn Ga O
1~x
x 2 4
1~x
x 2 4
(x"0.006); (4) Zn Mn Ga O (x"0.008); (5) Zn Mn Ga O
1~x
x 2 4
1~x
x 2 4
(x"0.01).

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.

two new bands, one peaks at 506 nm (Mn2` emission


centre), and another weak peak occurs at 666 nm,
which is derived from the presence of Mn4`. The
presence of Mn4` in phosphors will decrease the
506 nm emission intensity. The ZnGa O with Mn2`
2 4
doping fired under vacuum showed a green emission
spectrum only, and a stronger intensity than samples
fired in air. The concentration of Mn2` in phosphors
at maximum emission intensity is x"0.006. The emission spectrum of Zn Mn Ga O almost disappears
1~x
x 2 4
with an increase of Mn2` as the concentration of
Mn2` exceeds x"0.03.

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.

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Received 3 October 1997


and accepted 9 March 1998

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