A Theory of Sensitized Luminescence in Solids (original) (raw)

Skip Nav Destination

Research Article| May 01 1953

D. L. Dexter

Metallurgy Division, Naval Research Laboratory, Washington, D. C.

Search for other works by this author on:

Crossmark: Check for Updates

J. Chem. Phys. 21, 836–850 (1953)

The term ``sensitized luminescence'' in crystalline phosphors refers to the phenomenon whereby an impurity (activator, or emitter) is enabled to luminesce upon the absorption of light in a different type of center (sensitizer, or absorber) and upon the subsequent radiationless transfer of energy from the sensitizer to the activator. The resonance theory of Förster, which involves only allowed transitions, is extended to include transfer by means of forbidden transitions which, it is concluded, are responsible for the transfer in all inorganic systems yet investigated. The transfer mechanisms of importance are, in order of decreasing strength, the overlapping of the electric dipole fields of the sensitizer and the activator, the overlapping of the dipole field of the sensitizer with the quadrupole field of the activator, and exchange effects. These mechanisms will give rise to ``sensitization'' of about 103−104, 102, and 30 lattice sites surrounding each sensitizer in typical systems. The dependence of transfer efficiency upon sensitizer and activator concentrations and on temperature are discussed. Application is made of the theory to experimental results on inorganic phosphors, and further experiments are suggested.

REFERENCES

The edge emission of CdS [F. A. Kröger, reference 31,

C. C.

Klick

,

Phys. Rev.

89

,

274

(

1953

)] may prove to be an example of true lattice emission. A number of more complicated inorganic crystals, CaMoO4 and CaWO4, for example (see references 8 and 12), apparently luminesce even in the absence of imperfections, as do a number of organic crystals, e.g., anthracene and napthalene.

P. Pringsheim, Fluorescence and Phosphorescence (Interscience Publishers, Inc., New York, 1949).

H. W. Leverenz, Introduction to Luminescence of Solids (John Wiley and Sons, Inc., New York, 1950).

S.

Rothschild

,

Physik. Z.

35

,

557

(

1934

);

S.

Rothschild

,

37

,

757

(

1936

).,

Phys. Z.

Schulman

,

Evans

,

Ginther

, and

Murata

,

J. Appl. Phys.

18

,

732

(

1947

).

J. B.

Merrill

and

J. H.

Schulman

,

J. Opt. Soc. Am.

38

,

471

(

1948

).

H. C.

Froelich

,

J. Electrochem. Soc.

93

,

101

(

1948

).

F. A. Kroger, Some Aspects of the Luminescence of Solids (Elsevier Publishing Company, Inc., Houston, Texas, 1948).

Th. P. J.

Botden

and

F. A.

Kröger

,

Physica

XIV

,

553

(

1948

).

F. A.

Kroger

,

Physica

XV

,

801

(

1949

).

Schulman

,

Ginther

, and

Klick

,

J. Electrochem. Soc.

97

,

123

(

1950

).

Th. P. J.

Botden

,

Philips Research Repts.

6

,

425

(

1951

).

J.

Franck

and

R.

Livingston

,

Revs. Modern Phys.

21

,

505

(

1949

). This paper contains references to work on organic systems.

N. F. Mott and R. W. Gurney, Electronic Process in Ionic Crystals (Oxford University Press, New York, 1940), p. 207.

For references to the original work see, for example, references 2 and 13.

H.

Kallmann

and

F.

London

,

Z. Physik. Chem.

B2

,

207

(

1929

).

J.

Perrin

,

Compt. Rend. Paris

,

184

,

1097

(

1927

).

F.

Perrin

,

J. Phys. et Radium

7

,

1

(

1936

).

Th.

Forster

, (a)

Ann. Physik

2

,

55

(

1948

);

(b) Fluoresezenz organische Verbindungen (Vandenhoeck and Ruprecht, Gottingen, 1951);

(c)

Z. Elektrochem.

53

,

93

(

1949

).

The latest paper on this subject,

W. R.

Heller

and

A.

Marcus

,

Phys. Rev.

84

,

809

(

1951

), contains references to other previous work.

D. L.

Dexter

and

W. R.

Heller

,

Phys. Rev.

84

,

377

(

1951

).

A second practical benefit of sensitization comes from the double degradation of the absorbed energy, as a result of a Stokes’ shift in both the sensitizing and activating center. For example, the Hg 2537 line can be used for excitation, and emission can be obtained in the visible, as in the ordinary fluorescent lamp. (In this example it is probable that internal transitions to lower excited states of the Mn ion are responsible for part of the shift.)

See, for example, L. I. Schiff, Quantum Mechanics (McGraw‐Hill Book Company, Inc., New York, 1949), p. 189.

For a discussion of this type of normalization see, for example, H. Bethe, Handbuch der Physik (1933), (2) 24/1, p. 273, and references contained therein. The discussion of normalization given below is similar to that in reference 19.

See, for example, N. F. Mott and I. N. Sneddon, Wave Mechanics and Its Applications (Oxford University Press, New York, 1948), p. 253 ff; note that there are several misprints on p. 257.

K.

Husimi

,

Proc. Phys. Math. Soc. Japan

22

,

264

(

1940

).

E. U. Condon and G. H. Shortley, The Theory of Atomic Spectra (Cambridge University Press, Cambridge, 1935), p. 96.

See

M.

Lax

,

J. Chem. Phys.

20

,

1752

(

1952

) for further references.

R.

Peierls

,

Ann. Physik

13

,

905

(

1932

).

Paul Leurgans, thesis, to be published.

(a) A manuscript is in preparation discussing concentration quenching from the point of view of resonance transfer of energy, i.e., S–S transfer, in ordinary systems containing one impurity. It is concluded that S–S transfer is the critical process for systems of low dielectric constant and small Stokes’ shift.

F. A. Kroger, Luminescence in Solids Containing Manganese (Van Campen, Amsterdam, 1940).

C. C.

Klick

and

J. H.

Schulman

,

J. Opt. Soc. Am.

42

,

910

(

1952

).

L.

Apker

and

E.

Taft

,

Phys. Rev.

83

,

479

(

1951

), and several earlier papers.

Th.

Botden

,

Philips Research Rept.

7

,

197

(

1952

).

This content is only available via PDF.

© 1953 American Institute of Physics.

1953

American Institute of Physics

You do not currently have access to this content.

Sign in

Sign In

You could not be signed in. Please check your credentials and make sure you have an active account and try again.

Username ?

Password

Pay-Per-View Access

$40.00