Solid State Communications, Vol. 26, pp. 99-102.

0 Pergamon Press Ltd. 1978. Printed in Great Britain

00381098/78/0408-0099-$02.00/O

VALENCE BAND PHOTOEMISSION SPECTROSCOPY OF A

TERNARY LAYERED SEMICONDUCTOR: ZnIn&
F. Cerrina* B , I. Abbatit g, L. Braicovicht 0, F.
* PUIS-Iaboratori

Levys, and G. Margaritondo* 5,

Nazionali di Frascati, 00044 Frascati (Roma), Italy

+ Istituto di Fisica de1 Politecnico, Milano, Italy

$ Laboratoire de Physique Appliquee de 1Ecole Polytechnique Fed&ale, Iausanne, Switzerland
(Received 12 November 1977 by F. Bassani)

UV photoemission spectroscopy (UPS) experiments have been carried out

on the layer compound ZnIn& employing several different photon
energies in the range liw = 9.5-21.2 eV. The energy distribution curves
(EDCs) exhibit four valence band density of states structures besides the
Zn 3d peak. These five peaks appear 0.90 eV, 1.6 eV, 4.3 eV, 5.8 eV and
8.7 eV respectively below the top of the valence band, EV. The atomic
orbital character of the shallowest peak A appears different from that of
the three deeper valence band peaks B, C and D and this is discussed in
terms of the more or less pronounced ionic character of the intralayer
chemical bonds. These results demonstrate that an overall understanding
of the electronic states in complex structures can be achieved by an
approach based on photoemission experiments and chemical bonding
considerations which has been widely used in the past to study simple
binary layer compounds.

THE EXTENSNE application of W photoemission

spectroscopy (UPS) techniques has recently produced
important improvements in the understanding of the
basic electronic properties of layer materials [ 1A] .
In many cases new photoemission techniques have been
tested while investigating compounds of this kind which
have a simple nearly-two-dimensional character [ 1,2] .
As a consequence the investigations have concerned
simple binary layer compounds rather than more complex layer compounds. The number of valence electrons
per unit cell is usually quite large even in simple binary
layer materials but these electrons do not participate
to many different kinds of chemical bonds. Therefore
the photoemission results have been often discussed in
terms of chemical bonds rather than in terms of band
structure [ 1,3] . It now appears necessary to further
test the validity of this approach by extending it to the
study of ternary layer compounds which exhibit a
larger variety of intralayer chemical bonds. In this
paper we present preliminary UPS results obtained for
the first time on a ternary layered semiconductor,
ZnInzS4, whose structure is shown in Fig. 1. It is found

that the states in the upper part of the valence band

exhibit a sulphur p-like atomic orbital character. The
states in the valence band deeper than - 1.5 eV from its
top , E,, have instead mixed sand p-like character.
These results will be discussed in terms of different kinds
of intralayer chemical bonds with more or less pronounced ionic character.
The experiments have been carried out in a ultrahigh vacuum chamber whose working pressure was
< 1.5 x lo- torr. The chamber was equipped with an
angle-integrated retarding field electron energy analyzer,
with a windowless W noble gas discharge lamp, a
monochromatized Hdischarge lamp, a low-energyelectron-diffraction (LEED) system, and sample
preparation facilities. The light was incident normally on
to the sample and photoelectons emitted in a solid angle
- 0.5 x 27rsterad around the normal to the sample were
collected and analyzed. Energy distribution curves
(EDCs) have been taken on freshly cleaved samples in
situ under ultrahigh vacuum conditions. The quality of
the cleave was tested by LEED and the face appeared to
be chemically stable so that the experimental results did
not change under the best pressure conditions over a
time period of several weeks. Several W photon

p Gruppo Nazionale di Struttura della Materia de1 CNR.

99

100

VALENCE BAND PHOTOEMISSION SPECTROSCOPY

I
-4

I
-2

Vol. 26, No. 2

ev

O=Ev

Energy (eV)

Fig. 1. Structure of a ZnIn& layer as given in [6] . The

plane labelled In, corresponds to tetrahedrally coordinated indium atoms while the plane labelled Inb corresponds to octahedrally coordinated indium atoms.

Znln2S4

Fig. 3. EDCs taken on ZnIns S4 with several different

photon energies from the H-discharge.
Table 1. Experimental energy position of the EDC peaks
for ZnInzS4

Peak

Average energy position*

A
B
C
D
Zn 3d

- 0.9 f 0.05
- 1.6kO.15
- 4.3 + 0.2
-5.8 +0.15
- 8.7 f 0.1

* Energies in eV, measured from E,.

I
-6

I
-4

I
0. Ev

Energy (eV1

Fig. 2. Energy distribution curves (EDCs) taken on

freshly cleaved ZnInzS4 employing He1 photons (hw =
21.2 eV) and NeI photons (I-U = 16.8 ev). The energy
scale is referred to the top of the valence band, E,. The
labelling of the EDC structures is explained in the text.
energies have been employed in the experiment including the 2 1.2 eV He1 radiation, the 16.8 eV NeI radiation
and a number of photon energies in the H-discharge
range. The results obtained with He1 and NeI photons
are shown in Fig. 2. The deepest peak appearing
- 8.7 eV below E, in the He1 EDCs corresponds to the
photoionization of the rather shallow 3d states of zinc
[5] . Above this peak one sees in Fig. 2 structures
related to the valence band over an energy range - 6 eV
wide. In particular a broad peak occupies the spectral
region between Ev and - 3 eV below it. We shall see that
this peak contains two different structures labelled
peak A and peak B in Fig. 2. Deeper in energy the He1

and NeI EDCs exhibit two weaker structures, peak C

and peak D respectively. Since the past experiments
[l-3] on binary layered semiconductors have shown
that the position and intensity of the EDC peaks may
depend much on the photon energy we have carried out
measurements with several more photon energies from
the H-discharge range. Figure 3 shows indeed that the
relative intensity of the shallowest valence band peak is
extremely enhanced at low photon energies. Moreover
the already mentioned fine structure of this peak is
much emphasized in the low photon energy EDCs and
it clearly consists of a main peak A and of a weaker
shoulder B whose relative intensity increases at
increasing photon energies. Table 1 summarizes the
energy positions of the valence band EDC peaks A, B, C
and D and of the Zn 3d peak.
Being a layer compound ZnInsS4 has strong intralayer chemical bonds but weak interlayer bonds which
play a minor role in determining the electronic properties of the material. As shown in Fig. 1 each layer consists of seven sheets of atoms piled up in the sequence
S-In-S-In-S-Zn-S.
The space group of the
structure is R3m-C 3. This corresponds to a tetrahedral
coordination of the sulphur atoms around the zinc
atoms. On the contrary the coordination of the sulphur

Vol. 26, No. 2

101

VALENCE BAND PHOTOEMISSION SPECTROSCOPY

atoms around the indium atoms may be either tetrahedral or octahedral. The two different coo&nations
correspond to the indium sites labelled as In,, and In,
respectively in Fig. 1 [6,7] .
Due to its rather interesting characteristics as good
photoconductor, as luminescent material and as nonohmic conductor with negative differential resistivity
behavior ZnIn& has been extensively studied in recent
years [8,13] . Many experimental results have been
obtained with transport measurements [8-l 1, 131 or
with optical measurements [8,9,12,13].
On the other
hand no band structure calculations have yet been
carried out for it. Nevertheless the valence band density
of states as revealed by our present experiments can be
interpreted to a good extent in terms of the intralayer
chemical bonds. An ionic character of all the chemical
bonds between In+3, Zn+ and S- would of course
result in a strong sulphur p-like character of the states in
\d valence band. However we have seen that the valence
band spectra of Figs. 2 and 3 exhibit different behavior
in different energy regions. The relative intensity of
peak A increases markedly when the photon energy
decreases. The contrary is true for peak B and to a
minor extent for peaks C and D. This indicates that the
atomic orbital character is not the same for peak A and
for peaks B, C and D. One should observe that the
measured values [6 ] of the intralayer bond lengths in
ZnIn2S4 indicate in some case a covalent rather than an
ionic character of the corresponding chemical bond.
For example the measured Zn-S bond length, 2.37 A,
is much closer to the sum of the covalent radii, 2.35 A,
than to the sum of the ionic radii, 2.58 A. Even more
interesting are the two measured values of the In-S
bond length corresponding to the two inequivalent
sites for In. Indeed the In,-S bond length, 2.40A, is
close to the sum of the covalent radii, 2.48 A, while the
Int,-S bond length, 2.69 A, is close to the sum of the

ionic radii, 2.65 A. In summary the ionic character

appears much weaker in the two cation-anion bonds
with cations in tetrahedral sites than in the Inr,-S bond!
corresponding to octahedral cation sites. As a consequence some cation contribution mostly s-like must be
present in the valence band together with the prevalent
sulphur p-like contributions [ 141. The main peak A
should have strong sulphur p-like character. The
difference in character between peak A and peaks B, C
and D Indicates that cation s-like contributions are
present in the three deeper peaks. There is no evidence
in our spectra of sulphur s-like contributions which
probably overlap the secondary electron peak in the
He1 EDCs.
In summary we have seen that the valence band
states of the ternary layered semiconductor ZnInzS4
exhibits four structures. Although the prevailing atomic
orbital character of the states in the valence band is
sulphur p-like some cation s-like contribution has also
been found. This is due to the rather covalent character
of the chemical bonds between sulphur atoms and
cation atoms in tetrahedral sites. It is clear from our
results that ZnIn2S4 would be an extremely interesting
subject for more sophisticated photoemission experiments [l-4] . Synchrotron radiation UPS should be
used to study in detail the chemical bonding properties
of the indium atoms in different sites. Even more
interesting would be to study the two-dimensional
theoretical band structure and the experimental dispersion of the valence band states in the k-space with
angle-resolved UPS [4, 151. This approach has been
successfully applied to several simple crystals with
either two- or three-dimensional character [4,15-181
but it has yet to be tested on more complex ternary
compounds with complicated band structure such as
ZnIn2S4.

REFERENCES
1.

See for instance: MARGARITONDO G., ROWE J.E. & CHRISTMAN S.B.,Phys. Rev. BlS, 3844 (1977) and
references therein.

2.

MARGARITONDO G., ROWE J.E., SCHLUTER M. & KASPER H., Solid Stare Commun. 22,753

3.

ROW J.E., MARGARITONDO G., KASPER H. & BALDERESCHI A., Solid Stare Commun. 20,92 1
(1976).

4.

PETROFF Y.,Proc. 5th Inr. Conf: on Vacuum UVRadWion Physics, Montepellier, 1977 (in press).

5.

The position of E, has been deduced by linear extrapolation of the highenergy edge of the EDCs.

(1977).

6.

LAPPE F., NIGGLI A., NITSCHE R. & WHITE J.G., Z. Krisrall. 117,146 (1962).

7.

It should be observed that similar to the indium atoms the possible sites for sulphur atoms are not equivalent
to each other. Thus one has two different kinds of In-S chemical bonds. This might cause some photon
polarization effect in the EDCs similar to what happens in Case-like III-VI compounds (see [ 1] and [3] ).

8.

GOMBIA E., ROMEO N., SBERVEGLIERI G. & PAORICI C., Phys. Status Solidi (a) 34,65 l(1976).

102
9.

VALENCE BAND PHOTOEMISSION SPECTROSCOPY

Vol. 26, No: 2

GRILL1 E. & GUZZI M., Phys. Srafus Solidi (a) 40,69 (1977).

10.

MORA S., PAORICI C. & ROMEO N.,J. Appl. Phys. 42,206l

(1971).

11.

NITSCHE R. & MERTZ W.S., Helv. Phys. Acta 35,274 (1962); BENN J.A., NITSCHE R. &
LICHTENSTEIGER M., Physicu (Utrecht) 26,647 (1960).

12.

SHIONOYA S. & TAMOTO Y., J. Phys. Sot. Japan 19,1142 (1964).

13.

SERPI A., J. Phys. D9,1881 (1976).

14.

Similar results have been obtained in the past for the binary layer compound SnSz where the sulphur atoms
are tetrahedrally coordinated around the tin atoms and one finds Sn s-like contributions in the valence band
photoemission spectra. See [2].

15.

See LARSEN PK., MARGARITONDO G., ROWE J.E., SCHLUTER M. & SMITH N.V., Phys. Lett. 58A,
423 (1976) and references therein.

16.

SMITH N.V., Proc. 5th Int. ConjI on Vmutun CJVRadiation Physics, Montpellier 1977 (in press).

17.

GRANDKE T., LEY L. & CARDONA M., Phys. Rev. Lett. 38,1033

18.

The same approach has recently been applied to study ordered chemisorbed overlayes. See: LARSEN PK.,
SMITH N.V. & FARRELL H.H., Extended Abstracts of the 5th ht. ConjI on Vacuum UVRadiation
Physics, Monfpellier, 1977 (Edited by CASTEX M.C., POUEY M. and POUEY N.),Vol. 2, p. 241. CNRS,
Meudon, France (1977).

(1977).