Study of excited states of doped CaS phosphors using Laser excitation

H.S. BHATTI, SUKHVINDER SINGH, N.K. VERMA*, SUNIL KUMAR*

Department of Physics, Punjabi University, Patiala-147002 (PB)-India
*School of Basic and Applied Sciences, T.I.E.T, Patiala-147004
Email: sunilkumar32@yahoo.co.in

Abstract
Short lived excited state phosphorescence decays of CaS phosphors, doped with Barium
& Aluminium activators having variable concentrations have been detected and analysed
using N2- laser as the excitation source (pulsewidth of 10 nanosecond and high peak
power output) .The measured short lived excited state phosphorescence lifetimes of the
doped CaS phosphors range in the microsecond region. These investigations have been
carried out at room (300 K) as well as at liquid nitrogen temperature(77 K).
Introduction
CaS phosphors doped with activators having variable concentrations are very useful for a
variety of applications. The experimental determination of short lived excited state
lifetimes have become more reliable with modern laser techniques coupled with photon
counting system (1-2) for various states spread over a wide energy and time range. Pulsed
N2-laser having operating wavelength in UV region, short pulsewidth, large photon flux
density and high repetition rate is especially useful to excite shallow trapping states and
record the short lived decays from the shallow tapping levels.
Experimental set-up
The CaS doped phosphors were prepared by the flux method (3) starting from pure CaS.
For room temperature (300 K) studies, the sample was taken in the form of a pellet. The
low temperature studies at 77 K were carried out employing a liquid nitrogen Cryostat.
The short lived phosphorescence from the sample at an angle of 90 to the incident beam
was collected by a fast photomultiplier tube through an assembly of monochromator and
glass slab as a filter for UV radiation. The hyperbolic decay signals from phosphors were
recorded by storage oscilloscope and analysed by using computer simulations to
accurately calculate the three lifetime values in almost all the phosphors.
Theoretical background
The probability that in time dt an electron returns to the ground state with the emission of
light is given by npdt, where n is the number of electrons in the excited state at time, t,
after switching off the exciting radiation, and, p, is transition probability
for a crystal at a given temperature. So the rate of deacy of electron is

dn/dt = -pn

(1)

n = noe-pt
I = Ioe-pt

(2)
(3)

By monitoring the intensity of the decay, the life time of the excited state can be
estimated. The values of the lifetime for different transitions have been shown in Table.1.
Results and Discussions
In the present paper, hyperbolic decay curves have been observed. Pure exponential
components of decay curves were extracted from the hyperbolic decays. Decay rate
increases with the lowering of the temperature. The effect of concentration on the
lifetimes is generally mixed. An interesting feature of the studies is the fact that all the
lifetimes are in the microsecond time domain. It is worth noting that the short-lived
phosphorescence in these phosphors is mainly due to the presence of relatively shallow
trapping states as compared to the other phosphors.
Table-1
Life-Time values (s) of CaS doped phosphors ( s )
300 K
Phosphor

CaS:(Ba)
0.03 %
0.10 %
0.20 %
0.30 %
0.40 %
CaS:(Al)
0.03 %
0.10 %
0.20 %
0.30 %
0.40 %

77 K

37.15
31.00
28.75
27.12
24.19

10.56
9.35
9.10
9.20
8.37

3.58
3.21
2.68
3.24
2.49

11.29
11.89
11.23
11.97
11.23

3.73
3.21
3.90
3.89
3.56

2.57
2.35
2.68
2.70
2.56

31.56
31.47
29.67
28.45
27.18

4.67
4.38
4.78
3.89
3.69

1.67
1.78
1.88
1.56
1.45

12.78
13.35
12.89
13.45
13.59

2.79
2.90
2.78
2.89
2.85

1.35
1.45
1.68
1.38
1.17

References
1. Imasaka T., Kawabata V. and Ishibashi N., Rev. Sc. Instr., 52(4), 572 (1981).
2. Hoek A.V. and Visser A.J.W.G., Rev. Sc. Instr., 52(8), 1199 (1981).
3. Pham-Thi M and Ravaux G, J Electrochem Soc, (U.S.A), 138(4), 1103-6 (1991).

Table 1

Measured LifeTime Values of ZnS Doped Phosphors at 300 K and 77 K ( s )

* values are in ms
300 K

77 K

Phosphor

ZnS:(Cu)
0.03 %
0.10 %
0.20 %
0.30 %
0.40 %

23.12
21.40
21.16
21.36
20.54

5.30
4.97
3.77
4.81
3.82

2.23
1.89
1.97
1.86
1.89

ZnS:(Ag)
0.03 %
0.10 %
0.20 %
0.30 %
0.40 %

10.42
7.64
9.87
8.52
7.96

3.47
4.77
4.92
4.67
4.29

0.87
1.46
1.31
1.22
1.16

2.33
2.33
2.31
2.40
2.36

ZnS:(Mn)*
0.03 %
0.10 %
0.20 %
0.30 %
0.40 %

1.02
0.99
0.83
0.81
0.72

0.27
0.20
0.18
0.21
0.20

0.13
0.08
0.05
0.05
0.04

0.98
0.94
0.96
0.94
0.91

ZnS:(Fe)

1
13.87
13.34
13.47
13.21
13.39

3.49
3.20
3.19
3.14
3.26

0.87
0.84
0.82
0.81
0.82

0.22
0.21
0.21
0.20
0.20

0.07
0.07
0.07
0.06
0.06

0.03 %
0.10 %
0.20 %
0.30 %
0.40 %

15.33
15.87
15.72
14.91
14.94

4.32
3.73
4.04
3.86
3.91

0.90
1.62
1.38
1.28
1.33

5.07
4.85
4.93
4.69
4.72

2.17
2.29
2.23
2.16
2.12

0.99
1.13
1.09
1.01
1.00

ZnS:(Co)
0.03 %
0.10 %
0.20 %
0.30 %
0.40 %

20.43
20.32
20.18
20.06
20.08

4.43
3.01
3.84
3.78
3.79

1.58
1.88
1.72
1.70
1.70

15.92
15.85
15.88
15.77
15.60

6.13
6.06
6.05
6.04
6.00

2.10
2.11
2.12
2.09
2.02

ZnS:(Ni)
0.03 %
0.10 %
0.20 %
0.30 %
0.40 %

13.37
11.48
11.12
10.77
10.40

5.18
4.64
4.74
4.59
4.31

2.88
2.18
2.08
2.09
2.02

5.90
5.85
5.86
5.81
5.80

2.28
2.28
2.29
2.27
2.26

0.87
0.86
0.86
0.84
0.82

ZnS:(Mg)
0.03 %
0.10 %
0.20 %
0.30 %
0.40 %

16.01
15.95
15.59
14.67
14.72

5.25
4.95
4.12
4.01
4.01

2.82
2.18
2.15
2.01
2.02

2.94
2.71
2.86
2.84
2.79

2.00
1.99
2.02
2.01
1.97

0.81
0.82
0.82
0.81
0.80

ZnS:(Sr)
0.03 %
0.10 %
0.20 %
0.30 %
0.40 %

6.86
8.69
9.30
8.96
8.72

3.28
4.27
4.57
4.42
4.23

1.45
2.38
2.55
1.96
1.96

4.80
4.77
4.79
4.69
1.39

1.32
1.25
1.27
1.23
1.20

0.80
0.79
0.81
0.77
0.74

ZnS:(Ba)
0.03 %
0.10 %
0.20 %
0.30 %
0.40 %

12.41
11.18
11.14
10.89
10.64

3.47
3.97
2.92
3.08
3.12

1.09
2.07
1.29
1.24
1.19

4.03
4.06
4.09
4.12
4.08

1.42
1.41
1.41
1.43
1.40

0.66
0.65
0.68
0.72
0.71

ZnS:(Al)
0.03 %
0.10 %
0.20 %
0.30 %
0.40 %

14.03
13.10
12.49
12.30
12.92

4.64
4.31
3.89
3.71
3.97

2.92
2.46
1.97
1.84
1.96

8.65
7.89
8.32
8.07
7.74

ZnS:(Bi)
0.03 %
0.10 %
0.20 %
0.30 %
0.40 %

13.03
12.31
12.13
11.84
11.96

3.41
4.96
4.62
4.51
4.46

1.74
1.83
1.51
1.39
1.41

10.21
7.70
9.21
8.74
7.34

1.86
1.20
1.42
1.31
1.20

0.98
0.89
0.91
0.92
0.86

Table 2
Oscillator Strengths ( 10-5) of ZnS Phosphor Doped with
Different Concentrations of Activators
Phosphor

f1

300 K
f2

f3

ZnS:(Cu)
0.03 %
0.10 %
0.20 %
0.30 %
0.40 %

1.08
1.17
1.18
1.17
1.21

4.72
5.03
6.64
5.20
6.55

11.22
13.24
12.70
13.46
13.24

1.80
1.87
1.85
1.89
1.86

ZnS:(Ag)
0.03 %
0.10 %
0.20 %
0.30 %
0.40 %

3.18
4.33
3.35
3.88
4.16

9.55
6.94
6.73
7.09
7.72

38.09
22.70
25.29
27.16
28.57

14.22
14.22
14.34
13.80
14.04

ZnS(Mn)*
0.03 %
0.10 %
0.20 %
0.30 %
0.40 %

3.52
3.60
4.38
4.41
5.06

13.32
18.03
20.01
17.27
18.05

27.81
45.23
72.33
72.36
90.41

ZnS:(Fe)
0.03 %
0.10 %
0.20 %
0.30 %
0.40 %

1.86
1.80
1.82
1.92
1.91

6.62
7.67
7.08
7.41
7.32

ZnS:(Co)
0.03 %
0.10 %
0.20 %
0.30 %
0.40 %

1.27
1.28
1.29
1.29
1.29

5.87
8.65
6.78
6.88
6.87

* values are multiplied by 10-7

f1

77 K
f2

f3

7.17
7.82
7.84
7.97
7.68

28.78
29.80
30.53
30.91
30.53

36.02
38.07
37.04
38.02
39.01

16.40
17.24
17.24
18.01
18.01

51.61
51.61
51.61
60.20
60.20

31.81
17.67
20.74
22.36
21.52

5.64
5.90
5.80
6.10
6.06

13.19
12.50
12.83
13.25
13.50

28.91
25.33
26.26
28.34
28.62

16.48
13.85
15.13
15.31
15.31

1.63
1.64
1.63
1.65
1.66

4.24
4.29
4.30
4.31
4.34

12.40
12.34
12.28
12.45
12.89

f1

f2

f3

f1

f2

f3

ZnS:(Ni)
0.03 %
0.10 %
0.20 %
0.30 %
0.40 %

2.26
2.63
2.71
2.80
2.90

5.83
6.51
6.38
6.58
7.01

10.50
13.87
14.53
14.46
14.97

5.12
5.16
5.16
5.20
5.21

13.26
13.26
13.20
13.32
13.38

34.76
35.16
35.16
36.00
36.88

ZnS:(Mg)
0.03 %
0.10 %
0.20 %
0.30 %
0.40 %

1.52
1.52
1.56
1.65
1.65

4.63
4.91
5.91
6.07
6.07

8.63
11.16
11.32
12.11
12.05

8.28
8.98
8.51`
8.57
8.72

12.17
12.23
12.05
12.11
12.36

30.06
29.69
29.69
30.06
30.43

ZnS:(Sr)
0.03 %
0.10 %
0.20 %
0.30 %
0.40 %

3.57
2.82
2.63
2.73
2.81

7.48
5.74
5.37
5.55
5.80

16.92
10.31
9.62
12.52
12.52

5.11
5.14
5.12
5.23
5.59

18.59
19.63
19.32
19.95
20.45

30.68
31.07
30.30
31.87
33.16

ZnS:(Ba)
0.03 %
0.10 %
0.20 %
0.30 %
0.40 %

2.30
2.56
2.56
2.62
2.69

8.25
7.21
9.80
9.29
9.17

26.26
13.83
22.19
23.08
24.05

7.10
7.05
6.99
6.94
7.01

20.16
20.30
20.30
20.02
20.44

43.37
44.04
42.10
39.76
40.32

ZnS:(Al)
0.03 %
0.10 %
0.20 %
0.30 %
0.40 %

1.81
1.94
2.03
2.06
1.96

5.48
5.90
6.53
6.85
6.40

8.71
10.34
12.91
13.82
12.97

2.94
3.05
3.05
3.15
3.28

ZnS:(Bi)
0.03 %
0.10 %
0.20 %
0.30 %
0.40 %

2.36
2.50
2.53
2.60
2.57

9.02
6.20
6.66
6.82
6.90

17.69
16.82
20.39
22.15
21.83

3.01
3.99
3.34
3.52
4.19

16.55
25.65
21.68
23.50
25.65

31.41
34.59
33.83
33.46
35.80

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