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Abstract. Electrical characterisation of silicon surfaces silicon is also indicated from Secondary Ion Mass Spec-
contaminated by a zinc-sulphide overlayer has been car- trometry (SIMS), but the effect of this on the interface
ried out by forming Schottky diodes on the silicon after state density is not known.
the ZnS has been etched off. The techniques include cur- In the present paper investigations into the properties
rent-voltage, capacitance-voltage, and deep-level transi- of the silicon surface are reported. Zinc-sulphide thin
ent spectroscopy. The Schottky diodes show clear "mem- films were evaporated onto n- and p-silicon and chemic-
ory" of the presence of the ZnS overlayer and the electrical ally removed so that Schottky diodes could be fabricated
characteristics are far from ideal. Five deep levels in the on the silicon. Capacitance-voltage (C-V) characteristics,
sub-surface region of the silicon are detected, correspond- current-voltage (I-V) characteristics and deep-level tran-
ing to the Zn+, Zn + +, S-, S - - states and probably to sient spectra have all been measured on the Schottky
a Zn-B complex (p-type). Diffusion of the zinc and sul- diodes to provide information on the interface states and
phur into the silicon is therefore confirmed and this diffu- the existence or not of deep levels in the silicon depletion
sion is thought to create a compensated layer at the region.
interface. These impurity states control the electrical char-
acteristics of the surface in these diodes.
1 Experimental
PACS: 73.20. - r; 73.30. + y
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.
The density of electronic states at the interface between
(100) p-Si and an overlying thin film of ZnS have been (a) 6 gm p-epilayer, 10-35 f2 cm, supplied by Wacker;
measured in the past using A1-ZnS-Si Metal-Insula- (b) 6 gm n-epilayer, 9-15 f~cm, supplied by Southampton
tor-Semiconductor (MIS) capacitors [1]. This informa- University (UK);
tion is essential to an understanding of proposed electro- (c) p-type Czochralski, 3.75-6.25flcm, supplied by
luminescent devices [2-33 in which the MIS capacitor is Southampton University (UK);
biased into deep depletion so that current flowing through (d) Shallow P+-n junctions fabricated in the Technical
the device is limited by generation within the silicon University, Prague, by 10 keV implantation of BF2 art
depletion region. P-silicon is used therefore to provide an 5 x 1015 cm -2 into phosphorous-doped (1.3 x 1025
electron current by minority carrier generation, but a high cm -3) (100) silicon. The implants were annealed at
density of interface states will prevent inversion by pinn- 800 ~ to give a junction depth of ~ 160 nm.
ing the Fermi level and the devices will not operate [13.
It has not been possible with the above measurements Following the deposition of zinc sulphide, the films
to place the measured density of states energetically in the were annealed in situ at 580~ for 1,2, or 3 h. Back
gap because the resistivity of ZnS, while high, is not high contacts to the silicon were made by moderately rapidly
enough to allow the quasi-static capacitance measurement thermally annealing a layer of evaporated aluminium at
needed to determine the surface potential. Therefore, the 800 ~ for 40 s (p-type) and 60 s (n-type), respectively. The
origin of the states has not been identified conclusively, zinc sulphide was etched in HC1 for 3 h and top contacts
though a peak in the density of states close to mid-gap has of A1 or Au (p- and n-type, respectively) were evaporated
been observed which appears to be related to the diffusion through a shadow mask. The area of the contacts was
of sulphur into the silicon. The diffusion of zinc into the 0.020 cm 2.
638
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 -"
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
Some states will alter their occupancy with applied bias, Z n + , Z n 2 + , S - and S2-. We propose that these are the
however, and the Fermi level will begin to move through dominant, and perhaps only, energy levels of states at the
the discrete states. Once the states are full, the Fermi level ZnS/Si interface. The Zn and S appears to have diffused
is no longer pinned and is free to j u m p to the next into the silicon to some depth less than 200 nm, in concen-
unoccupied level. The voltage dropped across a dipole trations such that a compensated region of silicon exists.
layer at the surface (to which band bending in the metal Electrical measurements are consistent with the presence
makes a contribution) must therefore change in order to of discrete states at the surface, indicating both trapping
preserve the total voltage across the junction. Such a mecha- and perhaps a voltage-dependent barrier height. N o evid-
nism must lead to a change in slope of the ln(/)-V curve and ence exists for the formation of an interracial alloy or
is of course consistent with the abrupt change in activation compound.
energy seen in D L T S when the forward bias is altered.
The present measurements clarify our knowledge of Acknowledgements. We are grateful to Dr C.G. Scott (Hull), Chris
the ZnS/Si interface. Conductance measurements on Jeynes (Surrey University), and Colin Starbuck (Southampton Uni-
A1/ZnS/p-Si MIS diodes cannot provide the energy of the versity) for their assistance.
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 References
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near mid-gap and that the states are essentially bulk states sulphide on silicon. Dissertation, University of Bradford (1987)
rather than strictly interface states. In consequence, they 2. J.M. Gallego, H.S. Reehal, C.B. Thomas: IEEE Trans. ED-30,
475 (1983)
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(19811
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10. C. Jeynes: Private communication
D L T S measurements have been performed on silicon 11. P.L. Gruzin, S.V. Zemsky, A.D. Bulkin, N.M. Makarov: Fiz.
Schottky diodes, p + - n junctions and MIS diodes. The Tekh. Poluprovaln. 7, 1853 (1973) (in Russian)
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