1. nv. CAR soly, Vol. 39. p).

133440
QPqmoaPmsW..I97s. RiuediuGmlBraa

ELECTRICAL PROPERTIES OF a-MnS

H. H. Herrtms,t C. F. VAN BRUGGENand C. HMS

Laboratory of Inorganic Chemistry. Materials Sc.knce Center of tbc University, Nijcnborgh 16. 9747 AG
Groningcn.The Ncthcrlands

(Receiwd IO Nombrr l9n: occcptad 27 lknber 1977)

Abrtrd-Ekctrical data including tbamocktic power. Hal effect and nsistivity on iodine-growncrystals of
p-type a-MnS are reported. A study of the temperaturedependence reveals that the conductivityoccursby holes
in a 3d-baad (Mn*) and that the mobility of the hoks is not thermally activated.Photoelectronspectraco&m the
3d chrncter of the top of the valence band. Accmatcanalysisof the electricaldata givesa satisfactoryexplanation
of the extrinsic and intisic bcbaviour;tbc simuhancouspresenceof donors(substitutionaliodine) and acceptors
(manganesevacancies)is responsibk for the observedphenomena

I. lNlmmlm
Because little is known ahout the band structure of
binary 3d transition-metal cbalcogenides with a small
existence region, measurements of their electrical pro-
perties might contribute to a better understanding of
criteria and models that are valid.
Several models have been used to explain tbe semi-
conducting properties of these compounds. Charge car-
riers may be small polarons. more or less strongly cou-
pled to the lattice, or may move in some sort of a narrow
band, or in a broad energy band [ I].
In case of small polaroos, tbe conduction mechanism
is considered to he a thermally-activated diflusion
process of conduction electrons (bopping model)[2.3].
The activation energy is a consequence of the trapping of
boles by a lattice polrrization, caused by tbe bole itself.
In the bopping model one expects a mobility increasing
exponentially with temperature. The electrical properties
of Lidoped Ma0 have heen interpreted in terms of this
model, in which the small-polaron character of the boks
is thougbt to be connected with static Jabn-Teller
deformations caused by the boles.
A close analysis of many results on the electrical
properties has led to the conclusion that the assumption
of tbe bopping model for many transition-metal
compounds, like NiO and COO. was not justified[4]. Tbe
mobility of charge carriers appeared not to involve an
activation energy, and only tbe number of charge carriers
depends strongly on tbe temperature. The transport
properties of tbe free charge carriers in these compounds
can be described witb a large-polaron band model.
Most investigations on the character of conduction
mechanisms have been applied to transition-metal
oxides. Tbe transition-metal sulfides and selenides have
been investigated less thoroughly. Since the early work
of Heikes. reviewed in Ref. [2], no definitive answer has
heen given to questions about tbe type of conduction,
effective mass, mobility, effective density of states, etc.
in the transition-metal sulfides and selenides. One of the
Wrcsent Address: Oc&Ncdcrland B. V.. Venlo. Tbe Nethex-
l&S.
reasons was the failureto detect the Hall effect. Also,
grain-boundary effects and s&ring at bigher tempera-
tures may have obscured tbe results.
In order to understand better the nature of the trans-
port properties of a-M&, tbe Seebeck effect a, the Hall
effect RH and the electrical resistivity p were measured
as a function of temperature. These observations will be
discussed; moreover, from the sign of a and RH,predic-
tions about the nature bf the charge carriers can be
made. From the temperatlaedependent hebaviour of a,
RH and p, the mobility, the number of charge carriers
and the effective density of states are calculated.
To investigate tbe position of the Mn 3d band relative
to the valence band, a study was made of X-ray pboto-
electron spectra of polycrystalline samples of a-MnS.
tmnwMmrAL.mxPWIIBS
Singk crystals of a-MnS were prepared by chemical
transport reactions with iodine[S+. Due to transport via
the gaseous mixture of MI& and s2, single crystals of
a-MnS are deposited in the colder zone of tbe transport
tube. Among the transported material there are several
platelets from I to 7 mm width, with a thickness ranging
from several microns to about I mm. In addition a large
number of small octahedra and pyramides (l-2 mm) are
obtained. Chemical analysis revealed the presence of
0.2mol 96 iodine. From tbe temperature dependence of
the magnetic susceptibility we calculated that up to
0.14 mol 96 of Mn is present in the form of MnL[9].
Measurements of the electrical resistivity and tbe
thermoelectric power were carried out on single crystals.
For the Hall measurements we used polycjstalline a-
MnS prepared by heating appropriate amounts of the
elements in evacuated quartz ampoules at about 750°C.
Previously the Mn ties were etched in order to remove
any oxide layers, and m&d. The polycrystalline a-MnS
was pressed for 2br with a pressure of 8ooo kgcm-’ in
vacuum. The obtained polycrystalline bars were sintered
in vacuum at 750°C during one week, and subsequently
annealed in N2 atmosphere up to SOOT in tbe sample
bolder. Tbe ekctrical resistivity and tbe Hall effect were
measured using tbe standard rectangular four-contact

833
834
and five-contact geometry, respectively; for the Hall
measurements three voltage contacts are used to eli-
minate unwanted ohmic voltages. When pressure
contacts or Pt paste were used at the edges of the
pressed samples, the contacts were always ohmic. In
order to remove possible oxide layers, the surface of the
sample was carefully scraped off before applying the
contacts. Conventional current- and field-reversal pro-
cedures were used during the Hall measurements to
eliminate parasitic effects.
Seebeck measurements were carried out in a special
holder with a thermal gradient across the sample; various
gradients were applied. The sample was situated between
two golden, spring-loaded, pressure contact-blocks. The
Seebeck coefficient was corrected for the contribution of
gold.
All electrical measurements were carried out in a
nitrogen or helium atmosphere free from oxygen and
water vapour.
Photoelectron spectra were collected on an AEI-ES
200 spectrometer using MgKa radiation (energy
1253.6eV, linewidth 0.7 eV) and monochromatiied AlKa
radiation (energy 1486.3eV and linewidth 0.3eV). The
samples were maintained at a temperature of +lo”C
during the measurements. Special precautions were
taken to prevent surface oxidation of the samples: they
have been described in a previous paper( lo].
The photoelectron spectra of a-MnS were compared
with spectra of MgS, Mn& and NiS. MgS was chosen as
a reference material because of the absence of metal 3d
electrons, and the great resemblance of the cell edges of
a-MnS and MgS(81. In this paper the valence-band
regions only will be shown.
During the measurements on the insulator MgS (pres-
sed into In foil), it appeared that the position and
consequently the overall shape of the peaks was strongly
tin the calculations of the activation energies it is assumed
that the effective density of states NV 01 T’n, as in the case of a
broad band semiconductor.
FM.I. Temperaturedependence of the Seebeck coefficient CI of a single crystal of a-MnS, grown by iodine-vapour
transport and quenched from 600 K. Fust heating curve: (a), second heating curve: (b), ultimate behaviour: (c).
H. H. HEIKENS er al.
influenced by a gradual increase of the charging of the
sample during the measurement. In order to eliminate
this effect, MgS was fixed on Scotch tape. In this way, a
constant charge of the sample was obtained at once.
A method to obtain the position of the Fermi level is
calibration on the C Is peak, which is observed because
of a contamination of the sample space with carbon-
containing compounds. As a standard, the position of the
C 1s peak in the spectrum of a Cu foil (C Is: binding
energy = 284.6 eV) was taken for the spectra of a-MnS,
Mn& and NiS.
The uncertainty in the position of the Fermi level in
semiconductors (and insulators) hampers the charac-
terization of the spectra. The Fermi level may be near
the top of the valence band or higher, due to the
presence of acceptors or donors. Therefore, in order to
obtain comparable spectra of a-MnS and MgS, the
energy levels of MgS were shifted in such a way that the
sulfur 2p levels are the same in a-MnS and MgS. This
procedure corresponds to the assumption, that the nature
of the sulfur ions in a-MnS and MgS is essentially the
same.
3. RESULTS
3. I Thermoelecrric power
The measurements were carried out on various crys-
tals of a-MnS; representative results are shown in Fig.
I. The sign of the Seebeck coefficient a is positive in the
whole temperature range. Changes in the a vs T-’
relation appear during the first measurements, when the
crystal was heated up to 715 K. The curves are all
characterized by a maximum and a minimum. In the
subsequent heating curves the maximum in a shifts from
235 K to 295 K and the minimum from 415 K to 475 K. At
the same time the slope of a vs T-’ in the region
between the maximum and the minimum, changes from
about 0.10-0.18eV to 0.31 kO.01 eV.t After heating the
crystal up to 715 k twice. the a vs T-’ curve does not
change anymore (curve c). The ultimate behaviour of a
vs T-l IS . qualitatively similar to that of Li,Ni,-,O
(Xz 0) [4].
 Electrical
3.2 Hall tffect
Attempts to measure the Hall effect of a-MnS have
been reported in the literature in Refs. (11, 121.In both
cases the authors reported the Hall effect to be too small
to be detectable. We have been able to detect a small
Hall voltage on a sintered bar of a-MnS; unfortunately,
we could not detect the Hall effect of single crystals of
a-M&.
The results of a tem~rat~ede~ndent me~~ement
of a sintered bar are shown in Fig. 2, where RH is plotted
Fig. 2. Hail coefficientRH of a sintcred bar of a-&S
function of temperature.
9
(ohm cm I
Fii. ‘3. Temperature dependence of the resistivity p of a sia& crystal of o-MnS, grown by i~ine-v~
transport aad quenchedfrom 600K.
propertiesof a-MnS 835
as a function of the reciprocal temperature. At T < 400 K
RH is positive and decreases exponentially with increas-
ing temperature; the corresponding activation energy is
0.30 20.02 eV. RH is zero, or at least too small to be
detectable, in the temperature region 400< T < 475 K.
R,, is negative at 7’> 488 K and lR,,l decreases with
increasing temperature.
3.3 Ektticai resistivity
The tem~rat~e dependence of the resistivity p of
iodine-transported single crystals of a-h&S shows (just
like the Seebeck effect) a gradual change, when the
sample is heated several times up to about 700K. A
representative result is shown in Fig. 4 where p has been
plotted as a function of the inverse temperature. The first
heating curve (Pig. 3) exhibits an exponential decrease of
p with a corresponding activation energy of 0.17eV for
170~ T<415 K. At temperature T < 170K p bends off
with decreasing temperature. At temperatures T 7 475 K
the activation energy has increased to 1.5020.02eV.
After the crystal has been heated once, the second
heating curve is linear up to 435 K with a slope
d In &f( T-‘) = 0.31 -+O.OleV; in the tem~rat~e region
435 < T ~590 K p is almost constant. At higher
temperatures again a linear decrease of p is observed,
with a slope of 1.5OeV (which is the same as in the first
heating curve). A third heating curve yields the same
behaviour. The ultimate behaviour of In p vs T-’ is very
similar to that of LixNil-,O (for low values of x)[4] and
of Li,Mn&je (for low values of x)[13].
3.4 X-rcry photoelectron spectra
The Mn 3d character at the top of the S 3p band in
as a a-MnS, as revealed by the transport data, is coked
by the XPS spectrum of the valence-band region. Figure 5
836

good agreement with the value of 0.9eV obtained from

reflection spectra of o-MnS(161). This implies that the
top of the valence band has mainly a M-e, character.
The u overlap of the 3d-e, orbit& of Mn with the 3p
orbiis of S gives rise to a rather broad peak, as in-
dicated by the slope at the band edge around the Fermi
levei. The spectrum of Mnsl is very similar to that of
a-?&S. In the case of NB, the slope at the band edge is
much targer. This is due to the fact that the band edge of
NiS is m&y determined by thezcon~~tion of the ‘T,
(&~t final state, in which the 36-r, electrons give ?r
overlap with S 3p electrons. Because r bonding is
weaker than D bonding, the tD band is expected to be
narrower than the e, band.

4.1 Nature of the canductivity

The change in the temperature dependence of the
resistivity at low temperatures, and the appearance of a
maximum in the Seebeck effect is probably caused by
the stylus presence of two different conduction
schisms* In the following, we will de~ns~te the
relation between the impurity conduction at tow
temperatures and the initial non-reversible behaviour of
a and p.
From the positive sign of o and RH (at T c 475 K), it
can be concluded that the (majority) charge carriers are
holes. The dependence of the electrical conductivity at
high temperatures on the partial % or HS pressure of
the gas with which the compound was equilibrated, in-
dicates the presence of doubly-ionized Mn vacancies at
high temperatures{l7, t8]:

%t
v”,, G== v-, + h’ (11
I
f%i c
v,e v;;,+it . (21

Impurity conduction at low temperatures is possible, if

besides acceptors also donors are present. The donors
will loose their electrons to the acceptors and then
electrons can hop from an occupied to an empty ac-
ceptor. Impurity-band conduction appears when the
states, associated with each acceptor, form a (narrow)
partiy E!.ledband.

The mobility of the charge carriers responsible for the

gives
this spectrum
and the comspondii spectnrof impurity conduction is quite small; therefore, impurity
h&S, Mt&(l4] and NiS[l5$. conduction will be of importance only at iow tempera-
Comparison of the valence bands of a-MnS and MgS tures, where the concentration of charge carriers in the
valence band is small.
indicates that the shoulder and the peaks at about 5.5 and
3.8 eV in the spectnun of ~-MIS correspoud to the S 3p In the low-temperature region tbe conductivity is given
by the sum of hva contributions, viz. that of the holes in
band. The remaining structural features, viz. the sboul-
the valence band (formed by excitation of electrons to
ders at 1.5 eV and 2.5 eV, can then be associated with the
Mn 3aL-like final states. empty acceptor kvels) a,, and that of impurity conduc-
The initial 3& &b-spin con&W&ion of a-A&l!+ leadstion in the acceptor levels (rr:
to two fit& 38’ high-spin states, viz. ‘E <t&e,“, and‘Z-2
r&+3. In the xps sptctrum the cxxrmpo* bin&IQ W-oii-ob. (31
energies are I.5 and ZSeV, respectively. This COP
responds to a crystaMeid spfitting lODq= 1.0 eV (in The See+t coet?jcient is determined by the position of
 Uectricalpropertiesof a-M16
the Fermi level EF with respect to the two conduction
levels and by the relative cont.riitions of the two
different conduction mechanisms [ I, 41:
p[A+z]
&31ep+!$p
u cr
+o’
u [
A,+ EF-EA
-F-’ 11
The constants A and A’ are related to the heat of
transfer of the charge carriers. For charge carriers in
broad energy bands, the value of A depends on the
scattering mechanism. For the low-mobility impurity
conductivity the heat of transfer is presumably small, i.e.
A’ = O[l]. EF is the Fermi level with respect to the top of
the vaience band, and E, is the position of the impurity
energy level (with respect to the top of the valence band)
in which the impurity conduction takes place.
In the temperature region where the conduction is
determined by the free-hole conductivity u,, a is deter-
mined by the lirst term on the r.h.s. of eqn (4) and will
increase with decreasing temperature. At very low
temperatures or dominates the conduction, and a is
determined by the second term on the r.h.s. of eqn (4).
The interference of the two terms leads to a maximum in
the Q vs T-’ curve, as observed (at X).
For a crystal of a-MnS which was originally quen-
ched, a shift of T, to higher temperatures was observed
when the crystal was heated several times, successively.
This implies that as a consequence of the heating, the
contribution of the impurity conduction increases. At the
same time a change in slope of both the u and p vs T-’
curves is observed.
There are several possibilities to account for these
phenomena: (a) The change in slope can be explained by
an increase of the number of donors ND or a decrease of
the number of acceptors NA, upon heating to about
700K. Consider as an example the simple case of NA
single acceptors and ND single donors, with N* + ND In
Fig. 6 the relation between the number of positive charge
carriers p and the reciprocal temperature is shown (see
for example Ref. [I]). The intrinsic region at high
temperatures has been omitted.
Several regions can be distinguished:
(1) p is very small: p 4 NA - ND and p 4 ND, with
log P
I
p=NA-No
----
p_.,o
I J
s 7
Fig. 6. Tk number of poritivc charge carriers,given as log p, of
a partly mmpeasrted crystal with aiogly-ionizedvacancies, a~ a
functba of tcmpermre.
831
p=iNv(v)exp(-EJkT) (5)
(2) intermediate region: ND 4 p 4 N,, - ND and
(6)
(4)
P=
4 1
i Nv(NA - ND) exp (-E,JZkT)
(3) exhaustion region, where all acceptors and donors
are ionized:
p=NA-Na (7)
According to this model, a doubling of the slope of log p
vs T-’ will be observed at a temperature T, where p is
equal to the number of donors. When ND is very small,
however, this doubling will not be observed experiment-
ally in the a and p vs T-’ curves, because it will happen
at a very low temperature where the impurity behaviour
dominates; and a slope equal to EJ2 will be measured.
If the number of donors ND has increased after the hrst
heating-cooling cycle, the curve of log p has changed in
character: ND will approach N,,- ND When ND =
N,, - ND (or ND = (1/2)N,,) the temperatures T, and 7’2
(Fig. 6) coincide, and the slope of In p vs T-’ is equal to
E,, (and has been doubled).
A draw-back of this model is that it requires the
crystal to stabilize after several heat treatments at a
donor concentration of just ND = (1/2)N,,, which
represents a rather accidental situation. Therefore, this
model does not offer a very likely interpretation of the
observed data.
(b) Another mechanism for the change in slope is
possible, if we assume the presence of double acceptors.
Assume the crystal to contain N,, double acceptors
(ionization energies EAI and EA2) and ND single donors.
Suppose ND -ZN,; then the donors will loose their elec-
trons to acceptors which become partly compensated
(Fig. 7a). Because ND< N,, only single ionization takes
place. At low temperatures impurity conduction takes
place by hopping of electrons from occupied to empty
acceptors. At higher temperatures thermal activation of
electrons from the valence band to empty vacancies
occurs with an activation energy E,,, (eqn 1). Conduction
takes place by the holes which are formed in this way in
the valence band.
Now, suppose that the number of donors increases by
the heat treatment. The mechanism of the increase of the
donor concentration might be due to the following reac-
tion. It is known from magnetic measurements[9] that
a-MnS crystals, grown with the vapour-transport
method, contain a small amount of Mn12 as a second
phase. This MnL has presumably been formed at low
temperatures by precipitation of iodine which was dis-
solved in the crystal at higher temperatures. Annealing at
715 K would lead to partly dissolving again the M&
The dissolved iodine ions act as donors.
The uhimate behaviour which was observed after
heating the single crystal of a-&S two times up to
715 K is illustrated in Fig. 7b, where it is supposed that
the number of donors ND has been increased due to the
838 H. H. HEIKENS

(Cl1 (b)

Condua~~ band Caduction band conductiml band Conduction band

N, donors: D+ - -- - - - ’ D+..__-_-_-_____- ______ _ _ ____

N4 acceptors: F M”

Valence band Valence band Vaknce band Valance band

Law temperatures) (Higher twnpemtures) I Low temperoturus) (Higher temperatures)
Impurity conduction p-type conduction in impwity conduction in P-type ccoduction In
the valence band I
in aaxptor level Vi, acceptor level Vi, the valence band

Fii. 7. Energy-levelschemeof U-MI& with singk donors nod doubk acceptors. (a): before annealing, No < NA.
(b): after aartaahg, NA < No < 2N.+

previous heating: N., < ND <2N,. Again the donors 4.3 Lktmnination of N.,, No and Nv
loose their electrons to the acceptors, but now acceptor In this section we will analyze the resistivity and the
level Vlc. wiIl be compensated completely and level Seebeck data in the intermediate-temperature region, i.e.
V& partly. Again, at low temperatures impurity the region of extrinsic band conduction. In this region
conduction occurs, but now in acceptor level VL,, and u=pepP and a =(k/e)(A t In(Nvlp)). We assume the
m( Vi,,) is not necessarily equal to or (Vii,,). At higher presence of double acceptors (Mn vacancies), partly
temperatures, again thermal activation of electrons from compensated by single donors (iodine at sulfur sites).
the valence band to an acceptor level takes place; The quations descriii the charge carrier concentra-
because level V-ii,, is filled completely, the activation tions wet
energy in this case will be EA2 (qn 2). Experimentally
we will observe a huger slope E,,l in the a and p vs T-’ w = i NV exp (-E,JkT) (8)
curves because E,u > EA,.
Model (a) predicts a change of the activation energy by
2Nv exp (- EdkT) (9)
a factor 2; the observed activation energies. of 0.17~ %?=
0.03 eV and 0.31+ 0.02 eV are not inconsistent with this.
N~=[V”ti]+]V,]+]v;(n] (10)
This model, however, requires an accidental donor
concentration ND = (1/2)N,. p+ND=[V-L,,]+2[VL,,]. (11)
Model (b) appears to be consistent with the obser-
vations and we think it represents the most-likely It is assumed that all donors ND are ionized, and that
explanation of the observed behaviour. It is known from ND c 2N,, and n * p. We discuss the two cases of inter-
thermodynamic data that Mn vacancies act indeed as est, before and after annealing.
double acceptors in a-MnS. Le Bruq[l8] calculated the Before annealii (Fig. I curve a) the Iirst acceptor
second ionization energy of a metal vacancy; the level is partly compensated, i.e.
obtained value of 0.34eV is in good agreement with the
observed slopes of 0.31 ?O.O2eV. Moreover, the dis- ND’<N* and [VA*N,,
solving of iodine donors up to a concentration ND 2 N,,
is not accidental. In fact, the value of ND = NA forms a where ND0 is the donor concentration before annealing.
natural solubiity limit for donors in a p-type crystal: the In this case the hole concentration is given by
enthalpy of dissolving donors in p-type crystals depends
on the energy of the levels which will be occupied by the
2Nv exp (-E,,,/kT). (12)
electrons from the donors. For ND< N.., these donor
electrons can be accomodated at the V-i& acceptor level.
For N, < ND <2N, the donor electrons are ac- For P * ND’ and p 4 N., - ND’, we obtain
comodated at the higher VL level. Therefore, at ND 2:
N,. the enthaipy for dissolving donors increases by P = ~42Nv(N~ - ND?] exp (- E,&kT) (13)
EA2-Ea.,.
and for p 4 ND0

tThc statisticalweightsfor hoks bound to the acceptor (V&, p = 2NV(NA - ND9 exp (_E A,kT) .
and Va depend on tba precise nature of theacceptorstates.If (14)
NV
the boaad holes UXrespoadcsselltiauyto bin* (38) ion8 ill the
vicinity of the Mn vecaacy, there will be an additional spin
~neracy. This will rli&ty alter the numerical vahua of the We observe indeed a chaqe of slope in curve (a) at
parameterscalculatedin this paragraph, but it has little inUoeoce about T,=317K; for T<317K the slope is 0.18*
on the geoefel cooclusions. 0.03 eV, for T > 317 the slope is 0.10 5 0.03 eV. Accord-
 Fkctricd propertiesof a-l&S
ing to eqns (14) and (13), these values correspond to E,,,
and EJ2, respectively. Therefore the temperature
dependence of curve (a) is connected witb E,, =
0.18~0.03eV.
After annealing #ii. 1 curve c), the second acceptor
level is partly compensated, i.e. NA c ND < 2NA and
[V&J rf NA. The hole concentration in this case is given
bY
p= K4W.t - ND)
2(ND_N
A
) expt-&dkv.
From the experimental values of curve c (It@. 1).
we obtain (assuming A = 2): E,,* = 0.31 eV and ND =
1.126N,,.
In the p vs T-’ curve (FQ. 4) a plateau is observed,
which characterixes the exhaustion region with alI ac-
ceptors (and donors) ionized and
p=2N.,-Na
From tbe Hall coefficient
R,, = (pe)-’
we find: p = 2NA - ND = 2.8 x 10” crnm3and with ND =
1.126NA we find
NA = 3.2 x 10” cme3 and No = 3.6 x 10’”cme3.
We calculate the effective density of states (with A = 2):
NV = 1.03x ld’ cm-” at T = 435 K.
This corresponds to a relative effective mass m*/mo=
8.2. Comparison with the values for a small-polaron
hopper (viz. MnO: m*lmo=67.5[19,20]) and for a
broadband semiconductor (viz. ZnS: m*/mo= OS
1.0[211),reveals that the experimental value for a-MnS
is in between. This is a clear indication that the boles
have 3d character. This conclusion is in agreement with
X-ray photoelectron spectra, which show the Mn 3d
character of the top of tbe valence band.
From the resistivity
P = (PeC’
we calculate the (Hall) mobility of tbe holes:
pi’ = 0.065 cm* V-’ set-’ at 435 K.
For a, RH and p activation energies of 0.31,0.30 and
0.31 eV are found, which are equal within the error
limits. This indicates that the mobility has only a small
temperature dependence, and rules out the mechanism of
~~y-~ti~ hopping as the conduction process.
839
4.4 High-ttmperatwe region
At T=575 K the resistivity curves show a marked
deviation of the activation energies to a higher value
(1.5 eV). Because of the negative Hall coefficient in this
temperature region, it is likely that the charge carriers,
responsible for the conduction, are electrons. The ab-
sence of changes in the Seebeck effect indicates that
these electrons have a small effective mass, and that
probably in this temperature region intrinsic conduction
dominates. If so, the activation energy of 1.5eV cor-
responds to a value of E, 2 3.0 eV for the forbidden-
energy gap.
This value is in agreement with theoretical predictions of
Wilson, viz. EI =3.2eV[22]. Huffman and Wild(23],
however, interpreted the observed optical absorption edge
(16) (3.2 eV) as valence-baud-localized-state transitions,
From the experimental data for p and RH (ex-
trapolated to 625 K), we derive for the Hall mobility of
the electrons at 625 K: em” * 10cm* V-l set-’ (which is
the same as observed for Li-doped MnO[l]).
5. coNcLusior@s
From the analysis of the electrical properties discussed
above, it appears that a satisfactory explanation of the
(17) extrinsic and intrinsic properties of iodine-transported
a-MnS can be given. In an annealed crystal three
regions can be discerned:
(a) An impurity region at very low temperatures,
(18) where the acceptors are partly compensated by donors.
f$) An intermediate region, where the transport pro-
perties are determined by free holes in the valence band.
(c) An intrinsic region at high temperatures.
The mobility of the holes in the valence band is not
achy activated. A possible reason, that all authors
up to now have arrived at the. hopping model from the
experimental results, might be that none of them was
able to detect a Hail effect.
We succeeded to detect a Hall effect, the sign and
temperature dependence of which leads to the
conclusion that, apart from the extrinsic p-type
behaviour at intermediate temperatures,mobile electrons
with a relatively high mobility are responsible for the
conductivity at higher temperatures.
Acknowirdgcmenfs-The authors wish to thank Miss R. Haange
and Mr. H. Druiven,J. Slijkbuis and P. Rohde for tbeir contribu-
tions in tbe synthesis and electricalrne~~emen~ of tbc various
types of samples. and Mr. A. Heeres for running the XPS spectra.
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