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JOURNAL OF MATERIALS SCIENCE: MATERIALS IN ELECTRONICS 9 (1998) 283 288

A study of ZnGa 2 O 4 phosphor prepared by the solid method

KAI-HUNG HSU, MU-RONG YANG, KO-SHAO CHEN

Department of Materials Engineering, Tatung Institute of Technology, Taipei, 104, Taiwan

In this study, the mixtures of ZnO and Ga 2 O 3 powder with addition of LiCl flux were fired, the raw material mixing ratio, doping with Mn 2# 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/Ga 2 O 5 "47/53. Manganese-doped ZnGa 2 O 4 , fired in air, exhibits two new emission bands with peaks at 506 nm (Mn 2# emission centre) and 666 nm (Mn 4# 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 Mn 2 oxidized to Mn 4# which substituted Ga 3# to occupy the B sites of the spinel structure. The emission intensity of the 506 nm peak of Zn x Mn x Ga 2 O 4 is strongest when [Mn 2# ] x"0.006 and decreases markedly as the concentration of Mn 2# exceeds x"0.01. Most of the substitutional Mn 2# doping species in spinel ZnGa 2 O 4 occupy the zinc sites. The luminescent band was associated to the spin-forbidden transition, 4 T 1 (4G)P 6 A 1 (6S). 1998

Kluwer Academic Publishers

1. Introduction

In recent years, more efficient cathodoluminescent phosphors are being widely investigated for applica- tions in monitors high definition television (HDTV), and vacuum fluorescent displays (VFDs) [1, 2]. How- ever, 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 voltages are being developed. ZnGa O is a self-activated phosphor which emits blue light under excitation by both ultraviolet light and low voltage electrons (30 V d.c.). Excellent stabil- ity 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 bom- bardment offer advantages over commonly used sul- fide phosphors [3, 4]. However, the effect of compositional change of zinc gallate on photo- luminescence 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 Mn (3d ) or Cl (3d ) 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 unclear. In this study, the effect of doping Mn in

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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 with x ranging from 0 to 0.03 were synthesized via a conventional solid state reaction. Starting pow- ders of high purity ZnO (CERAC Ltd., 200 mesh, 99.999%), Ga O (CERAC Ltd., 325 mesh, 99.999%) and dopant Mn(NO ) ) 2H O (AESAR Ltd., 99.98%), 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 Mn 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 diffrac- tometer with CuK radiation at 40 kV, 15 mA and 4° (2 ) min scanning rate. The photoluminescence emission and excitation spectra of polycrystalline phosphors were obtained

283

using a Shimadzu RF-5301PC spectrofluoropho-

tometer. 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

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

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

phase formations of fired ZnGa O is shown in Fig. 1

and summarized in Table I. The powders with mixed

compositions of ZnO/Ga O mole ratio were 47/53

and 50/50 showed the presence of ZnGa O spinel

phase only. It is clear that in the solid method of the

prepared ZnGa O the spinel phase exists over a wide

compositional range.

The particle size of fired phosphors was between

25 m. However, the unfired ZnO and Ga O mixed

powder was about 12 m. This indicated that the

ZnGa O phosphors fired at 1200 °C for 5 h with LiCl

flux will promote the growth of the grain size.

  • 3.2. Photoluminescence of ZnGa 2 O 4

The luminescent characteristic of the samples with

various ZnO/Ga O ratios is shown in Figs 2 and 3.

The excitation spectrum of sample B with pure

ZnGa O phase monitored at 450 nm exhibits a max-

imum excitation peak only at about 246 nm, and indi-

cates 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

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 de-

creases the intensity of the peak at 470 nm relatively

less. The optimum composition of ZnO/Ga O is

about 47/53.

  • 3.3. The absorption spectrum of ZnGa 2 O 4 :Mn

The ZnGa O is a spinel compound with the unit cell

belonging to the cubic space group O (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

point group. This compound is known to be almost

284

using a Shimadzu RF-5301PC spectrofluoropho- tometer. The excitation spectra can be obtained from scanning the wavelength

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

ZnO/Ga O .

TABLE I Phase and emission intensity of calcined zinc gallate

samples

Samples Composition

 

(mol%)

ZnO

Ga O

A

44

56

B

47

53

C

50

50

D

53

47

E

55

45

Phases in the

calcined powders

ZnGa O # -Ga O

ZnGa O

ZnGa O

ZnGa O #ZnO

ZnGa O #ZnO

Relative emission

intensity

58

100

65

32

27

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 (3d ) orbital of Mn .

According to Hund’s rule and the fact that the split-

ting energy of Mn ( "7500 cm ) is smaller than

its electron pairing energy (p"25 500 cm ), these

five electrons in the 3d orbital should be in high

spin and weak crystal field [9]. Regardless of the

occupation site of Mn in spinel crystal, the

TanabeSugano (3d ) energy level diagram, can be

used to fit the energy splitting levels of ZnGa O :Mn

phosphors. The absorption spectrum and energy split-

ting levels of ZnGa O :Mn phosphors which were

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 inde-

pendent of the strength of the crystal field. Hence, it

fits the energy level of E A(4G) which is parallel to

the horizontal axis. The B and C values of the Racah

parameter, which use derived from the observed en-

ergy levels of E A(4G) and E(4D) are 660 cm and

3342 cm , respectively. The crystal field

parameter,

Dq is 564.8 cm . The fact that the E(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 2 Excitation spectra of zinc gallates with various mole ratios of ZnO/Ga O , 1

Figure 2 Excitation spectra of zinc gallates with various mole ratios

of ZnO/Ga O , 15 samples AE.

Figure 2 Excitation spectra of zinc gallates with various mole ratios of ZnO/Ga O , 1

Figure 3 Emission spectra of zinc gallates with various mole ratios

of ZnO/Ga O , 15 samples AE.

Figure 2 Excitation spectra of zinc gallates with various mole ratios of ZnO/Ga O , 1

Figure 4 The relationship of absorption spectrum and energy split

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

TABLE I I The absorption bands of Mn in ZnGa O phos-

phors

Free-ion

levels

Levels in

tetrahedral

symmetry

Wavelength

(nm)

(cm )

4P

4D

4G

T

E

T

E A

T

T

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, T (4G)

P A (6S).

Fig. 5 shows the absorption spectrum of

ZnGa O :Mn phosphors which were fired in air and

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 inten-

sity peaks are 245 nm (ZnGa O absorption peak),

  • 304 nm ( T (4P)) and 626 nm ( T (4G)). These results

would suggest that (1) the doped Mn did not oxi-

dize to Mn , (2) because of a lack of oxygen, this

created more defects in the spinel structure under

vacuum firing, and (3) all Mn (3d ) ions substitute

for Zn and occupy the A sites in the tetrahedral

structure. Therefore, the intensity of the absorption

spectrum is improved to its maximum.

If Mn substituted for the cation with a smaller

radii this would reduce the distance between Mn

and the co-ordinate anion. As a result, the emission

spectrum would shift to longer wavelength [12]. Since

the radii of Mn , Zn and Ga are 0.083, 0.072

and 0.062 nm, respectively, Mn substitutes for Zn

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

Mn substitutes for Ga and occupies the B sites in

285

Figure 5 Absorption spectrum monitored at 506 nm of
Figure 5 Absorption
spectrum
monitored
at
506 nm
of

Zn Mn Ga O (x"0.01). (Dotted line: firing under vacuum;

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

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 Mn oxidized to

Mn during the firing in air, and Mn substituted

for Ga 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

in air, most of the Mn occupy the A sites of the

tetrahedral structure and create the main wavelength

peak (506 nm), while some of the Mn occupy the

B sites of the octahedral structure and create the weak

wavelength peak (666 nm).

3.4. The emission spectrum of ZnGa 2 O 4 :Mn

Mn 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 Mn

-doped ZnGa O host emission peaks at 506 nm are

shown in Fig. 6. Compared with the pure ZnGa O

shown in Fig. 3, the emission peak shifts from about

286

Figure 5 Absorption spectrum monitored at 506 nm of Zn Mn Ga O ( x "

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

(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 Mn doping in ZnGa O will not only affect

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

Mn doped ZnGa O has a narrower spectrum

band compared with an undoped sample and, conse-

quently, better emission colour purity.

The amount of Mn addition affects the emission

intensity of ZnGa O phosphor. The emission spectra

of ZnGa O fired in air with various amounts of

Mn 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

  • 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

vacuum is much better than in air, as for firing ZnMn-

ferrite would be in a protective atmosphere to avoid

Mn oxidizing to Mn .

It is indicated in Figs 7 and 8 that the emission

intensity increases with increasing Mn dopant in

zinc gallate regardless of whether the wavelength of

Figure 7 Emission spectrum of various amounts of Mn doped ZnGa O excited by 254 nm

Figure 7 Emission spectrum of various amounts of Mn doped

ZnGa O excited by 254 nm light; (1) Zn Mn Ga O (x"

0.002); (2) Zn Mn Ga O (x"0.004); (3) Zn Mn Ga O

(x"0.006); (4) Zn Mn Ga O (x"0.008); (5) Zn Mn Ga O

(x"0.01).

Figure 7 Emission spectrum of various amounts of Mn doped ZnGa O excited by 254 nm

Figure 8 Emission spectrum of various amounts of Mn doped

ZnGa O excited by 304 nm light; (1) Zn Mn Ga O

(x"0.002); (2) Zn Mn Ga O (x"0.004); (3) Zn Mn Ga O

(x"0.006); (4) Zn Mn Ga O (x"0.008); (5) Zn Mn Ga O

(x"0.01).

the excitation light is 254 nm or 304 nm. The max-

imum emission intensity occurs as the Mn concen-

tration of the sample x"0.006 and a decrease in

emission intensity is observed for the samples with

Mn 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 Mn 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

of 1050 °C or above. As the temperature increased to

1200 °C, ZnO and Ga O can react completely. X-ray

diffraction measurements show all the phosphors

with the mole ratio of ZnO and Ga O between

47/5350/50 are single phase and have the spinel crys-

tal structure. ZnGa O emitted 375700 nm broad

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 spec-

trum of ZnGa O doped Mn fired in air exhibited

two new bands, one peaks at 506 nm (Mn emission

centre), and another weak peak occurs at 666 nm,

which is derived from the presence of Mn . The

presence of Mn in phosphors will decrease the

506 nm emission intensity. The ZnGa O with Mn

doping fired under vacuum showed a green emission

spectrum only, and a stronger intensity than samples

fired in air. The concentration of Mn in phosphors

at maximum emission intensity is x"0.006. The emis-

sion spectrum of Zn Mn Ga O almost disappears

with an increase of Mn as the concentration of

Mn exceeds x"0.03.

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

288