Short Notes phys. s t a t . sol.

( b )

K109

165,K109

(1991)

Subject classification: 78.30; S10.1 Institute of Physics, Belgrade )

I n f r a r e d and R a m a n Spectra of C d O
BY Z . V . POPOVId, G . STANIsId, D . STOJANOVId, and R . KOSTId
Introduction Cadmium oxide is the only IIb-VI compound with a cubic structure

of the NaCl type. This crystal structure has Oh space group symmetry with only one optically active mode (IR-active Flu mode / l / ) . The assignment of this mode in CdO is rather difficult because of the high free carrier concentration 1 2 , 3 / . Namely, CdO is an n-type semiconductor of non-stoichiometric composition (oxygen deficient). Thus, single crystals and sintered samples usually exhibit / 4 / a free electron concentration greater than CdO samples were analysed

lo1

The infrared spectra of sintered interaction

1 2 , 3/ using a photon-plasmon-phonon

model. One oscillator with a TO frequency a t (262 f 2)cmm1 (300 K ) was observed. samples. In addition to the wTO Experimental The CdO In this short note we present infrared and Raman spectra of sintered CdO -1 = 262 cm oscillator, two-phonon vibration modes samples studied were obtained by the standard

may also be observed. The assignment of these modes is discussed. procedure used to fabricate ceramic oxides. The CdO powder ( 5 N purity) was cold pressed ( p = 3 . 9 ~ 1 0Pa) into disc-shaped pellets that were sintered a t different ~ temperatures (between 500 and 800 K ) over 1 to 3 h . They were sintered in air and under flowing oxygen. Samples for optical measurements were polished in an
A1203

water 50 to

suspension 1200 cm-l.

(fine Raman

grain

size 0.3 were

pm).

The infrared in the

reflectivity

measurements were made on a Bruker IFS 113v spectrometer in the spectral range from spectra observed geometry. The excitation source was the 514.5 nm line of an A r -ion laser. A Spex model 1403 monochromator with a R C A 31034A photomultiplier as detector and a standard photon counting system were used. Results and discussion The CdO reflectivity spectrum from 100 to 1200 cm-l depicted by dots in Fig. l a is for a sample sintered a t 800 K for 3 h . Its shape is time is longer than the longitudinal mode frequency (T typical of the plasmon-phonon interaction where the inverse free carrier relaxation -1 > wLo /3/). This

backscattering

spectrum was least-squares fitted using the plasmon-phonon interaction model:

I )

P . O . Box 5 7 , YU-11000 Belgrade, Yugoslavia.

KllO
T a b l e
1

physica status solidi ( b ) 165

Optical parameters (in cm ) of phonons and plasmons obtained by oscillator fitting of the CdO reflection spectrum (OiToppYjTO 270
444 13
100

-1

w jL0
380 448

'jL0 125

wp

-1

805
20

555.56

6.8

where ujTO, wjTO, phonons, time, and

E~

yjTo, y,jLo are thefrequenciesanddampings of the TO and LO

w

respectively,

is plasma frequency, T is the free carrier relaxation P the high frequency dielectric constant.

For a single oscillator ( j = 1 in (l)),

occurs in the 350 to 450 cm-' under different conditions.

satisfactory agreement between the

theoretical and experimental spectra cannot be attained. The greatest difference range, where the reflection spectrum exhibits a novel structure. In an attempt to explain this phenomenon, we sintered samples The samples were sintered in flowing oxygen and measurements were made a t different temperatures in order to decrease the free carrier concentration, whereupon an increase in structure detail was not observed. Relatively good agreement between computation and experimental data
is

obtained with two oscillators. This spectrum is shown a s the solid line in Fig. l a . Its best fit parameters are listed in Table 1. The appearance of an additional infrared active phonon mode may be explained in terms of the usual appearance of secondary modes of higher and lower frequency with respect to the basic mode in all NaCl structure type materials. They are due to two-phonon absorption in these materials /l/. Two-phonon spectra in most of the alkali halide crystals are well known / 5 / . This is not the case for CdO because no theoretical phonon dispersion relations exist for it. Thus, the modes listed in Table 1 were assigned by analogy to NaCl and other two-atom crystals of the same crystal structure. Namely, the 270 cm-' mode is a CdO Brillouin zone center LO modes are two-phonon combinations. These mode is a TO mode whereas the 448 cm-' mode. The remaining 380 and 444 cm-'

combination bands obey infrared selection rules. It is known that for NaCl crystal structure type materials two-phonon combinations a r e not allowed a t T o r X points of the Brillouin zone but are possible at the L point, with the exception of TO + LO and TA + LA, and that all overtones are forbidden. With all this in mind we believe that the 380 and 444 cm-I modes a r e an LO mode and a inode due to a TO + TA combination a t the Brillouin zone L point, respectively. This mode assignment
is also given in Fig. l b . The high concentration of free carriers in CdO makes a detailed experimental analysis of two-phonon absorption in this material impossible.

Short Notes
7.0

Klll

40 . 8 1

0.6

0.4

0.2
0

I
37 5

I
925
1,

650

'b

f
1.0

08

06
0.4
300

a-..
500 wave number (cm-')

400

600

Fig. 1. a ) Infrared reflection spectra of polycrystalline CdO at 300 K in the spectral region from 100 to 1200 em-'. Experimental data are represented by open circles and the solid line is calculated by a fitting procedure based on the model described by (1) with parameter values given in Table 1; b ) Raman and infrared spectra of the same sample a t 300 K in the spectral region from 100 and 650 cm-'. L are laser plasma lines

The Raman scattering spectrum for the same sample, together with the infrared spectrum is shown in Fig. l b . Though one-phonon Raman scattering f o r this type of crystal structure is not allowed, non-stoichiometry degracks the symmetry, i. e. modes in the Raman spectrum appear that are exclusively infrared active according

t o the selection rules.

in Fig.

This is the case for the modes at 267 and 380 cm-'

observed in Fig. l b a t almost the same frequencies as the TO and LO active modes l a . The remaining 320 cm-l mode in Fig. l b , in analogy t o NaC1, is

K112

physica status solidi ( b ) 165

assigned as t w o - p h o n o n

c o m b i n a t i o n 2LA( A ) , because this mode is the s t r o n g e s t intensity R a m a n mode in alkali halide crystals / 6 / . In conclusion, w e observed i n f r a r e d and R a m a n spectra of p o l y c r y s t a l l i n e C d O and assigned one- and t w o - p h o n o n m o d e s to the observed peaks. The obtained

data will prove u s e f u l in lattice d y n a m i c s studies of C d O . For a m o r e detailed

analysis of the v i b r a t i o n a l properties of C d O , single crystal s a m p l e s of low f r e e

carrier concentration have t o be studied w h i c h w e plan to do in the f u t u r e .

References

/ I / H. B I L Z , D . S T R A U C H , and R . K . WEHNER, V i b r a t i o n a l I n f r a r e d and Raman Spectra of Non-Metals , H d b . Phys., Vol. X X V l Z d , Licht und Materie Id, S p r i n g e r - V e r l a g ,
B e r l i n 1984 ( p . 1 5 7 ) . / 2 / H. FINKENRATH and N . UHLE, Solid State Commun. / 3 / Z . V . P O P O V I d , Fizika

5,

875 ( 1 9 6 7 ) .

17,145

(1985).

/ 4 / H. KOEHLER, Solid State Commun. 11, 1687 ( 1 9 7 2 ) . / 5 / R . F . WALLIS and M. BALKANSKI, M a n y - B o d y A s p e c t s of Solid State Spectroscopy, N o r t h - H o l l a n d , A m s t e r d a m 1988 ( p . 1 2 6 ) . / 6 / J.L. BIRMAN, T h e o r y of C r y s t a l Space G r o u p s and I n f r a r e d

and R a m a n L a t t i c e Processes of Insulating C r y s t a l s ,

H d b . P h y s . , Vol. X X V / 2 b , L i c h t und Materie Id, S p r i n g e r - V e r l a g , B e r l i n 1974 ( p . 2 1 9 ) . ( R e c e i v e d A p r i l 30, 1991)