Observation of optical, structure and electrical properties of samples in order to determining the role of transition metal (TM) ions in phosphate glass system and as a vital step on the road to realizing the huge potential of transition metal-CaO-P2O5 glasses for laser applications
Sample Measurement Phosphate glass is an excellent material for amplifier due to properties material for amplifier due to properties of good chemical durability, ion exchangeability, high gain coefficient, wide bandwidth capability and low upconversion emission. The nonradiative processes include processes characteristic of the host and processes characteristic of the active ion promoted by its concentration. Currently, all major high energy (J1kJ) solid-state laser systems in the US, Europe and Asia use phosphate based glasses as the gain medium. In some cases the quantity of glass installed in the laser is very large. Transition metal (TM) ions have been used as colouring agents in the glass industry for a long time. Recently, great attention has been paid to the TM ion doped glasses for development of new lasers or luminescence materials. One factor that degrades the performance of phosphate based laser glasses is OH impurities. Hydroxyl group reduce the lifetime (increase the decay rate) and thereby reduce stored energy in F3/2 state resulting in a corresponding degradation in the laser output energy. Phosphate glass hosts are particularly vulnerable to OH contamination because they tend to absorb water readily during melting. Consequently, sophisticated processing methods are used to dehydroxylate both the glass melt and the glass raw material. Despite these efforts, some residual hydroxyl groups remain in the glass.
1000
X-Ray Diffraction (Philips Model
MEMORY SWITCHI NG DEVICES
7602 EA Almelo)
FTIR (Perkin Elmer 1650
THICK FILM PASTE
Spectrometer) Dielectric (Novocontrol High Dielectric Resolution Analyzer)
LIGHT EMITTIN G DIODES
OPTICAL AMPLIFIE RS
Absorption (Uv-Visible Spectrophotometer – Camspec 1350) Ellipsometry (Abbe Refractometer)
OPTICAL FIBRES
Density (Archimedes
LASER
Displacement Method)
Essential Component of Laser
It is well known that a bright luminescence is emitted from Cu+ doped ions in inorganic solids by UV light radiation [Simonetti et al. 1977, Payne et al. 1984). Some studies have shown that these materials have potential to tunable laser [Tanimura et al 1985, Barrie et al 1987]. Especially, the gain coefficient in a Cu+ -doped aluminoborisilicate glass of 5 5 X 10-4 cm-1 and 1.1 X 10-3cm have been observed at 580 and 585 nm, respectively, using the fourth harmonic of a Nd : YAG laser for excitation [Kruglig et al. 1986]. However, Cu+ ions have the prospensity to oxidize to the Cu2+ state, whose charger transfer absorption in the UV region interferes with the excitation of Cu+. In general, 3d-ion lasers posses’ low gain (effective crosssection e of the order of 10-20 cm2) and relatively long emission lifetime of the order of 10-100 s; thus the large energy storage capabilities and high possible peak power operation expected [Struve et al. 1985]. However, copper doped with 50% P2O5 contents has been confirmed to show the favorable properties for laser applications [Tanaka et al. 1994).
1200
30 g
FTIR
CuO
CaO
2
Annealing (Furnace A) 3500C for 1 hour
2
MnO
CaO
10
PO 2
90
20
2500
2000
1500
1000
P O
20
70
4000
-1
3500
3000
Wavenumber (cm )
2500
2000
-1
1500
1000
4000
500
3500
CuO-1%
70
40
60
34
50
CuO-5%
32
CuO-7%
35
ZnO-7%
MnO-9%
20
ZnO-9%
18 16
(cm )
-1
25
-1
(cm )
-1
(cm )
18 16
20
10 8
10
6
6
5
4
2
10
300
400
500
600
700
2
0
800
300
400
Photon energy h(eV)
TMO
700
800
2
4
6
8
Photon energy h(eV)
Photon energy h(eV)
30
40
50
60
70
80
90
Fig. 5: Absorption Spectra of (MnO)x(CaO)30-x(P2O5)70 glass
Fig. 4: Absorption Spectra of (CuO)x(CaO)30-x (P2O5)1-x glass
Fig. 6: Absorption Spectra of (ZnO)x(CaO)30-x(P2O5)070 glass
REFRACTIVE INDEX 1.570
1.59
2.95
1.565
1.58
1.560 2.90
1.555
1.57 1.550 2.85
n
n
These materials shows characterization of amorphous materials through XRay Diffraction method. Polarisability and molar volume of a particular glass affect its refractive index. In ternary system the relationship between molar volume and compositions are more complex. It is well known that ionic radius and a highly charge can be related to ionic refractivity that contributes to molar refractivity. From the data we can see that molar volume decrease with the molar refractivity, due to the decreasing on ion size and ionic refractivity. The optical absorption spectra play an important role in analyzing the effect of doping of transition metal ions in calcium phosphate glasses. For TMOCaO-P2O5, optical band gap, Eopt decrease with increase of TM ion contents. Dielectric permittivity was measured in the temperature range of 25 to 300oC. The result showed that the dielectric permittivity and dielectric loss factor decreased with frequency and increase with temperature.
1.56
1.545
1.540
2.80
1.55
1.535
1.54 2.75
1.530
1.53
1.525 0
2
4
6
8
10
0
CuO (mol. %)
2
4
6
8
0
10
2
4
Fig. 8: Refractive Index of (MnO)x (CaO)30-x (P2O5)70 glass
Fig. 7: Refractive Index of (CuO)x(CaO)30-x(P2O5)70 glass
T25
T25
T50
T50
T75
T75
T100
4
10
T100
T125
T125
r
T150 T175
Department of Physics, Faculty of Science, Universiti Putra Malaysia, 43400 UPM,Serdang, Selangor, Malaysia.
[email protected] 019-6602415
Acknowledgement: The Financial Support Under IRPA (54249) is gratefully acknowledge
T150
3
10
"
T175 T200
T225 T250 T275
1
10
T300
T225
2
10
Dielectric Loss Factor,
Z.A. Talib, E.Z.M. Tarmizi, W.M.D.W. Yusoff W.M.M Yunus, H.A.A. Sidek and S.A. Halim
T250 T275 T300
1
10
0
10
-1
10
0
-2
10
10 -1
10
0
10
1
10
2
10
3
10
4
10
5
10
6
10
Frequency (Hz)
Fig.10: The frequency dependent of for CaO-P2O5 glasses doped with MnO
8
10
Fig. 9: Refractive Index of (ZnO)x (CaO)30-x (P2O5)70 glass
DIELECTRIC
T200
6
ZnO (mol. %)
MnO (mol. %)
Relative Dielectric Permittivity,
600
n
20
CONCLUSIONS
500
CaO
10
12
15
200
14
14
8
90 CaO
(PO 4 )
ZnO-5% 22
10
20
ZnO-3%
MnO-7%
30
12
30
80
10
500
ZnO-1%
MnO-5%
40
4
90
1000
24
22
40
70
20
80
1500
Fig. 3: FTIR spectra of (ZnO)x(CaO)30-x(P2O5)0.7 glass
MnO-3%
28
60
30
70
2000
MnO-1%
24
50
40
2500
ABSORBANCE
20
60
3000
-1
Fig. 2: FTIR spectra of (MnO)x(CaO)30-x(P2O5)70 glass
30
50
5
wavenumber (cm )
26
50
P=O (P-O 2 ) as (P-O 2 ) s P-O (P-O-P) as
2
wavenumber (cm )
80
30
60
40
CaO
5
500
CuO-3%
30
ZnO
90
10
80
(TMO)x(CaO)0.29-x(P2O5)0.70
5
ZnO-2%
P O
5
Fig. 1: FTIR spectra of (CuO)x(CaO)30-x (P2O5)70 glass
(CaO)x(P2O5)1-x
5
3000
Melt poured into a mould
Glass Forming Region PO
3500
3-
OH
-
(PO 4 )
OH
3-
(P-O-P)
(P-O 2 ) as
P=O
MnO-2%
2
4000
ZnO-5%
Transmittance (Arb unit)
CuO-2%
P O
ZnO-10%
MnO-5%
Transmittance (Arb unit)
Sample
(P-O 2 ) s P-O (P-O-P) as
-
OH (PO 4 )
3-
s
(P-O 2 ) s P-O (P-O-P) as
P=O (P-O 2 ) as
(P-O-P)
-
OH -
400
MnO-10%
CuO-5%
Transmittance (Arb unit)
OH
CuO-10%
s
-
s
Furnace B at 12000C for 31/2 hours
(P-O-P)
Furnace A at 10000C for 30 minutes
30 g of chemical substances in a crucible
-1
10
0
10
1
10
2
10
3
10
4
10
5
10
6
10
Frequency (Hz)
Fig.11: The frequency dependent of ˝ for CaO-P2O5 glasses doped with MnO
