Appl. Phys.
A 61, 637-641 (1995)
Origin of the defect states at ZnS/Si interfaces
P. Hazdra 1, D.J. Reeve 2, D. Sands 2
1Department of Microelectronics,Faculty of Electrical Engineering,Czech Technical University,
Prague, Czech Republic
~Department of Applied Physics, Universityof Hull, Hull HU6 7RX, UK
(Fax: + 44-482/465606)
Received: 4 February 1994"/Accepted: 21 February 1995
Abstract. Electrical characterisation of silicon surfaces
contaminated by a zinc-sulphide overlayer has been car-
ried out by forming Schottky diodes on the silicon after
the ZnS has been etched off. The techniques include cur-
rent-voltage, capacitance-voltage, and deep-level transi-
ent spectroscopy. The Schottky diodes show clear "mem-
ory" of the presence of the ZnS overlayer and the electrical
characteristics are far from ideal. Five deep levels in the
sub-surface region of the silicon are detected, correspond-
ing to the Zn+, Zn + +, S-, S - - states and probably to
a Zn-B complex (p-type). Diffusion of the zinc and sul-
phur into the silicon is therefore confirmed and this diffu-
sion is thought to create a compensated layer at the
interface. These impurity states control the electrical char-
acteristics of the surface in these diodes.
PACS: 73.20. - r; 73.30. + y
The density of electronic states at the interface between
(100) p-Si and an overlying thin film of ZnS have been
measured in the past using A1-ZnS-Si Metal-Insula-
tor-Semiconductor (MIS) capacitors [1]. This informa-
tion is essential to an understanding of proposed electro-
luminescent devices [2-33 in which the MIS capacitor is
biased into deep depletion so that current flowing through
the device is limited by generation within the silicon
depletion region. P-silicon is used therefore to provide an
electron current by minority carrier generation, but a high
density of interface states will prevent inversion by pinn-
ing the Fermi level and the devices will not operate [13.
It has not been possible with the above measurements
to place the measured density of states energetically in the
gap because the resistivity of ZnS, while high, is not high
enough to allow the quasi-static capacitance measurement
needed to determine the surface potential. Therefore, the
origin of the states has not been identified conclusively,
though a peak in the density of states close to mid-gap has
been observed which appears to be related to the diffusion
of sulphur into the silicon. The diffusion of zinc into the
Applied Materials
P h y s i c s A Processing
Sc,en0e
9 Springer-Verlag 1995
silicon is also indicated from Secondary Ion Mass Spec-
trometry (SIMS), but the effect of this on the interface
state density is not known.
In the present paper investigations into the properties
of the silicon surface are reported. Zinc-sulphide thin
films were evaporated onto n- and p-silicon and chemic-
ally removed so that Schottky diodes could be fabricated
on the silicon. Capacitance-voltage (C-V) characteristics,
current-voltage (I-V) characteristics and deep-level tran-
sient spectra have all been measured on the Schottky
diodes to provide information on the interface states and
the existence or not of deep levels in the silicon depletion
region.
1 Experimental
Thin films of zinc sulphide were evaporated in high vac-
uum (base pressure 5 x 10 .6 Torr) to a thickness ranging
from 200 to 500 nm onto (100) silicon. Several types of
silicon were used.
(a) 6 gm p-epilayer, 10-35 f2 cm, supplied by Wacker;
(b) 6 gm n-epilayer, 9-15 f~cm, supplied by Southampton
University (UK);
(c) p-type Czochralski, 3.75-6.25flcm, supplied by
Southampton University (UK);
(d) Shallow P+-n junctions fabricated in the Technical
University, Prague, by 10 keV implantation of BF2 art
5 x 1015 cm -2 into phosphorous-doped (1.3 x 1025
cm -3) (100) silicon. The implants were annealed at
800 ~ to give a junction depth of ~ 160 nm.
Following the deposition of zinc sulphide, the films
were annealed in situ at 580~ for 1,2, or 3 h. Back
contacts to the silicon were made by moderately rapidly
thermally annealing a layer of evaporated aluminium at
800 ~ for 40 s (p-type) and 60 s (n-type), respectively. The
zinc sulphide was etched in HC1 for 3 h and top contacts
of A1 or Au (p- and n-type, respectively) were evaporated
through a shadow mask. The area of the contacts was
0.020 cm 2.
638

The electrical measurements were performed in the i 0 -2. ' I 0 -~

dark using a Keithley 487 picoammeter/voltage source for lo -3 'v A1/Si(P) l o -~
! *.
the I-V, and an H P 4275 LCR meter for the C-V. Deep- 10 - ' ~"~ 10 -+
level measurements (DLTS) were made on an in-house
i 0 -67 "'"~"QI" 91 o -~
built system based around the Boonton 72B capacitance
meter.
Z
l o -< " _"' ............ 72_1-2~2. . . . . . . . I

i0 -": , a n o ZnS i
2 Results 10 ', t
-~ a ZnS l h a n n e a l i n g I 0 -"
I0 ZnS 2h annealing I0-m
Figure 1 shows typical I - V characteristics for Schottky
10 -11 . . . . , . . . . ~. . . . , . . . . *
diodes in p-type silicon (type (a) above). The reference - -. - 8 - 2 - 1 '"lL -"

characteristics for a silicon surface on which no ZnS has u~ Iv]

been deposited are shown alongside the characteristics for
silicon surfaces on which a ZnS layer was annealed for Fig. 1. I - V characteristics for Schottky diodes on p-type silicon,
1 and 2 h, respectively. The Schottky diodes on the uncon- (untreated: [B) and coated with ZnS and annealed for l(*) a n d 2 h
(A), respectively before etching in HC1. The data were measured at
taminated (clean) surface are well-behaved with evidence
0.1 V intervals b u t a limited n u m b e r of points are m a r k e d for clarity
of some series resistance in the forward bias for currents
greater than 2 x 10 -~ A. However, for diodes in which the
silicon has been covered in ZnS, annealed, and then
cleaned in HC1, the forward bias characteristics are modi- I0 -2 :--i0 -2
fied considerably. Extrapolating the straight line portion i0 < Au/Si(N) .~<.,.; :io_~
of the curve back to zero voltage shows a steady decrease i0 -4 :ri0 -4
in the intercept, from 7 x 1 0 - S A to 6 x 1 0 - 9 A and
2 x 1 0 - 1 ~ for 1 and 2 h annealing, respectively. The < io -~ i,f
reverse bias characteristics show only a slight change in i0-8 ........ -,- . . . . . . . ', ,: :-I0-6 <

the magnitude of the current, with the 2 h annealing 10 -~ .............. ~, . . . . . . -% '/ 10 -7

exhibiting a slight recovery over the 1 h annealing. i o -" u no ZnS - '~i
~/ :i0-8
For n-type silicon (Fig. 2) similar trends are evident; 1 0 -~ n ZnS l h a n n e a l i n g ~ i 1 0 -~
well-behaved characteristics for untreated silicon, with i0 -~o * ZnS 2 h a n n e a l i n g ~' ilO-to
modification of the forward bias t - V for annealed silicon. !
As with Fig. 1, the characteristics change in both shape -10 -8 -6 -4 -2 0 1 2 8
and magnitude of the current so that it is not clear which uMs [v]
has been affected more; silicon annealed for one hour to
two. The reverse bias characteristics show a much greater Fig. 2. I - V characteristics for S c h o n k y diodes on n-type silicon
variation, but the silicon annealed for two hours again corresponding to the same treatments as in Fig. 1
exhibiting some recovery.
Figures 3 and 4 show 1 MHz C-V characteristics for
these Schottky diodes. For the p-type substrates (Fig. 3), 250,
the untreated silicon surface displays ideal behaviour, but
for samples annealed for one and two hours there are A1/Si(P) 1 MHz
20O
some deviations from the ideal. Most noticeably, there is ~ il cn no ZnS
a kink in the curve at zero bias which is indicative of ~ ~, A ZnS lh annealing
a large density of traps being filled in response to a change I50
~x m~,, 0 ZnS 2h annealing
in voltage. Finally, for the l-V, and C-V characteristics
no effects were observed when the ZnS was deposited onto o 100
the shallow p +-n junctions. In all cases, the characteristics
were near ideal and the data are not shown. 5O
The C-V and I - V characteristics point to contamina-
tion of the silicon surface by the ZnS layer. DLTS reveals
that the contamination is confined mainly to the surface of - 0 1 2 3 4 5

the silicon. A quiescent reverse bias U~ = _+ IV (the top IV]

sign applies to p-Si and the bottom to n-Si) with an
excitation voltage Ue, = -T-0.5 V, 200 ms duration was
used to probe the silicon to a depth of approximately
1.5 gm. N o significant deep-level spectrum was observed
in either uncontaminated silicon or on contaminated sur-
faces annealed for one and two hours. However, for both
p- and n-type samples,, ia the voltage range _+ 0.5 >
U~ > -T-Ue, that is, with excitation into forward bias,
a broad and complex spectrum is observed which has
a remarkably broad peak at high temperatures (Figs. 5, 6).
Fig. 3. 1 M H z C - V characteristics on p-Si corresponding to the I - V
characteristics of Fig. I
There appear to be four identifiable contributions
(H l-H4) in the p-type and three in the n-type (El-E3), but
these are themselves broad compared with the signal
characteristic of discrete (bulk-like) states at well-defined
energies. The precise position of the DLTS signal depends
 639

Ec
250~Au/Si(N) 1 MHz
~..1"

1.0"
2001 D no zn~ /
.9
~ 1~01 A ZnS1h .....ling //
.8
- J 0 ZnS 2h annealing i"
CD
.7
o I00 i ~ ~-" 7//~,///x,./,~./////,r2,//////. , (-I--)
.6
50 ~ .5
Z
.4

-5 -4 -3 -2 -1 0 .3 zo
[V] .2
Fig. 4. 1 MHz C V characteristics on n-Si corresponding to the I - V .1 - - z.B( ?)
characteristics of Fig. 2
0 i ~ i i i i E7
-1.5 -I -0.5 0 0.5

~F U. o [v]
0.08
0.07 A1/Si(P) ,A Fig. 7. The activation energy of the states as determined by "ener-
O 0.06
getically resolved" DLTS is shown as a ffmction of the quiescent bias
on the sample (n-Si: r~; p-Si: A; p+-Si: o). Also shown are the known

t
c)
0.05
energies of states associated with Zn and S in Si
0.04
<
z 0.03
O9 0.02
O9 0.0l Table 1. Characteristics of the states identified by "high pulse"
0.00 , , excitation DLTS on both p- and n-Si
7O 120 170 220 270 320
TEMPERATURE [K] Deep Energy level Capture cross Silicon
level [eV] section [ c m 2] type
Fig. 5. DLTS spectrum under "high pulse" excitation of a p-Si/A1
Schottky diode annealed for i h before removal of the ZnS. Note the H1 Ev + 0.15 0.18 1 • 10 -19 p
broad peak at elevated temperatures which is typical of all the H2 Ev + 0.29-0.33 1 x 10 17-1 • 10 - I 6 p
Schottky diodes in which the silicon has been contaminated, irre- H3 Ev+0.48 0.53 t x t 0 16 p
spective of substrate type or annealing time H4 Ev + 0.57-0.16 1 x 10 -is p
E1 Ec - 0.28 1 x 10 -18 n
E2 Eo -- 0.54 1 x 10 -16 n
E3 Ec - 0.62 5 x 10 -is n
~7 0.20

Au/Si(N)
cO 0.15
<D
0.i0 states a r o u n d certain energies was observed. That is to
Z
say, with small changes in the dc voltage sudden changes
0.05 in the activation energies occurred (Fig. 7), along with
O9
a large change in the estimated capture cross section. The
states are listed in Table 1. The estimated activation en-
0.00
7O 120 170 220 270 320 370 ergy at zero volts applied bias for hole emission for sam-
TEMPERATURE [K] ples fabricated on low-doped p-substrates was within the
interval Ev + 0 . 5 - 0.57 eV, i.e., near mid-gap. F o r the
Fig. 6. DLTS (high pulse) spectrum of an n-Si/Au Schotttky diode m o r e heavily d o p e d p-substrates, the activation energy
annealed for 1 before removal of the ZnS was Ev + 0.33 eV. In order to estimate the density of
states, "high pulse" excitation [4,5] was used with
Uex = -7 2 . 5 V and a pulse durable of lOOms, and
slightly on the voltage applied to the structure, implying U r = _+0.5V. The average density of states was
an ill-defined energy associated with the states. A strong 2 x 1 0 1 2 c m - 2 in both n- and p-type diodes annealed for
excitation into forward bias leads to positive-going D L T S 1 h. F o r diodes annealed for 2 h, the spectrum has an
signals, indicative of minority-carrier capture and sub- identical shape but the amplitude of the signal is nearly
sequent emission. twice as big.
In order to establish the energetical spectrum of the D L T S measurements on shallow p + - n junctions gave
deep levels involved (assumed to be located close to the no observable spectrum, regardless of the surface treat-
surface), a small excitation of ~ 50 m V superimposed on ment. This is a clear indication that zinc and sulphur have
a variable dc level has been used. A localisation of the not diffused d o w n to the junction.
640
3 Discussion
The present work identifies the seven characteristic states
(four in p-Si and three in n-Si) at the ZnS/Si interface listed
in Table 1. However, H4 and E3 have energies and cap-
ture cross-sections which overlap, as do the states H4 and
E2, so probably there are states at five localised energies.
The variation of the activation energy of the states as
measured by energetically resolved DLTS is shown in
Fig. 7. Also shown (shaded bands) are the known energies
of states caused by the presence of zinc and sulphur [6-9]
and the coincidence between these and our experimen-
tally measured deep levels identifies the origins as
S-, S2 -, Zn +, Zn 2+, and Zn-B complex. Two additional
states associated with sulphur complexes are not seen and
would not be expected at the low diffusion temperatures
used here [9]. The presence of zinc in the silicon surface is
therefore confirmed. The states we have measured, parti-
cularly those near mid-gap, are seen clearly to have a dis-
tribution of energies lying largely within the bounds de-
fined by the shaded areas, but we can't say at present
whether the states actually form bands at the surface or
other phenomena, such a surface potential fluctuations,
cause an apparent spread in the measured energies. How-
ever, the range of measured activation energies within
a band is consistent with the observation of an ill-defined
energy, as illustrated by the variation of the "high pulse"
peak position with applied dc bias.
The physical location of the states is not known pre-
cisely. Almost certainly, the states reside in the silicon and
not in a surface compound or alloy. Channeling RBS [10]
has excluded this by placing an upper limit of a few ppm
on the surface concentrations of both Zn and S. In trying
to estimate the depth of diffusion, extrapolation of the
diffusion coefficients of S [11] and Zn [12] in Si is unlikely
to yield useful results since the coefficients have been
determined at temperatures well in excess of 1000~
Quite likely, the traps extend from the surface into the
silicon to a depth less than 200 nm, the depth of the p+-n
junction which remains free of any contaminants. The fact
of similar active concentrations of the two elements, as
indicated by similar densities of traps, might be a conse-
quence of similar diffusion lengths but it might also be
a consequence of similar solid solubilities [-6J. The max-
imum values recorded have been measured at 1300 ~ and
are 6 x 1016 and 3 x 1016 cm -3 for Zn and S, respectively.
These values cannot be extrapolated to 580 ~ but they do
provide upper limits on the concentrations of electrically
active Zn and S available.
Having excluded the existence of an interfacial layer
from the present Schottky diodes, the possibility still exists
that such a layer is present at the ZnS/Si interface but is
removed during etching. Such a layer could give rise to
a continuum of states at the interface. Therefore, we have
examined MIS structures on p-Si with DLTS using both
"high pulse" and energetically resolved methods. The re-
sults are very similar to those obtained from the Schottky
diodes. The "high pulse" spectrum is nearly identical to
that in Fig. 5 and the energetically resolved measurements
identify three discrete states which have the same charac-
teristics as H2, H3 and H4 in Table 1. We conclude from
this that there are no additional states at the ZnS/Si
interface and probably no intermediate layer other than
the compensated silicon present in the Schottky diodes.
Given that the states arise from the diffusion of Zn and
S into the silicon and that the states are located close to
the surface, the C - V characteristics can be interpreted
better. After annealing, the zero-bias capacitance is re-
duced and similar in both p-Si and n-Si diodes. The
doping density is the same in both cases, so the Fermi-
level positions with respect to the majority carrier band
edges must be nearly identical. Given that the activation
energy of the states is Ec-(0.58-0.6) eV for p-type
structures, putting the Fermi level at mid-gap near the
surface, and that the estimated depletion width is
1.5 ~tm, corresponding to a potential drop of ~ 1 V at
bulk doping densities, the potential profile of the depletion
region must be quite complicated. Quite probably, the
surface has an opposite charge to the rest of the depletion
region, arising from nearly equal densities of doubly
charged donor and acceptor states. The presence of defect
states close to the surface is also indicated by the slight
kink in the C - V around 0 V, suggesting some filling of the
traps in response to a change in voltage rather than
a change in the depletion region.
The I - V characteristics are a little more difficult to
understand and a full interpretation is not presented here.
Uncontaminated silicon has nearly ideal characteristics,
with some evidence of a small series resistance in the
forward bias currents in p-Si. However, after annealing
the deviations from ideality become considerable. For
n-Si annealed for 1 h, the smooth curve in the forward I - V
might imply nothing more complicated than an increase
in series resistance. After annealing for two hours, though,
there is evidence of two slopes, implyig some mechanism
other than simple series resistance. It would seem from the
energetically resolved DLTS that the Fermi level at the
surface changes abruptly from one pinning position to
another with dc bias, implying a voltage-dependent bar-
rier height. Such a mechanism is possible and has been
observed in Au/CdTe junctions [13]. A simple analysis
can show that the presence of discrete states at two or
more energies can lead to an abrupt change in the barrier
height of a Schottky diode in forward bias, and that
change in barrier height must necessarily lead to a higher
ideality factor. The arguments have been set out in detail
elsewhere [131 but will be summarised below.
The equilibrium pinning position of the Fermi energy
will be given by the condition for charge neutrality, taking
into account the ionised dopants, the charge of full and
empty traps, and band bending in the metal, which is
usually neglected but can be larg e. In fact, for a variable
Fermi level at the surface, such as we are suggesting here,
band bending in the metal is essential, either before the
Fermi level moves or after. Application of a forward bias
causes the bulk Fermi level in the semiconductor to shift
relative to the metal Fermi level and it is usually assumed
that the Fermi level is constant across the depletion re-
gion. Microscopically, this cannot be the case because
there must be continuity at the interface, but a precise
formulation of the Fermi level in this region requires
knowledge of the exact charge state and the probability of
capture and emission of the traps by Shockley-Read stat-
istics or by communication with the metal (tunneling).

Some states will alter their occupancy with applied bias,
however, and the Fermi level will begin to move through
the discrete states. Once the states are full, the Fermi level
is no longer pinned and is free to j u m p to the next
unoccupied level. The voltage dropped across a dipole
layer at the surface (to which band bending in the metal
makes a contribution) must therefore change in order to
preserve the total voltage across the junction. Such a mecha-
nism must lead to a change in slope of the ln(/)-V curve and
is of course consistent with the abrupt change in activation
energy seen in D L T S when the forward bias is altered.
The present measurements clarify our knowledge of
the ZnS/Si interface. Conductance measurements on
A1/ZnS/p-Si MIS diodes cannot provide the energy of the
states unless accompanied by a quasi-static C - V curve.
Moreover, conductance measurements have indicated
only one deep state near mid-gap in addition to a high
background U-shaped density of interface states, but the
present work shows quite clearly that there are two states
near mid-gap and that the states are essentially bulk states
rather than strictly interface states. In consequence, they
occur at distinct energies rather than form a continuum
throughout the whole band gap. The conductance tech-
nique is probably not sensitive enough to resolve the
different peaks, either because of its limited energy range
(~0.3 eV from mid-gap in Si) or because other states
within a range of energies at least 8 k T either side of the
Fermi level will contribute to the measured signal [14].
4 Conclusion
D L T S measurements have been performed on silicon
Schottky diodes, p + - n junctions and MIS diodes. The
measurement conditions are unusual for D L T S so
extraction of level densities is only approximate.
However, activation energies have been extracted which
agree well with the known energies for Z n - B complex,
641
Z n + , Z n 2 + , S - and S2-. We propose that these are the
dominant, and perhaps only, energy levels of states at the
ZnS/Si interface. The Zn and S appears to have diffused
into the silicon to some depth less than 200 nm, in concen-
trations such that a compensated region of silicon exists.
Electrical measurements are consistent with the presence
of discrete states at the surface, indicating both trapping
and perhaps a voltage-dependent barrier height. N o evid-
ence exists for the formation of an interracial alloy or
compound.
Acknowledgements. We are grateful to Dr C.G. Scott (Hull), Chris
Jeynes (Surrey University), and Colin Starbuck (Southampton Uni-
versity) for their assistance.
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