Study of dislocations in ZnSe and ZnS by scanning force microscopy

o. Nickolayev and V. F. Petrenko
Thayer School of Engineering. Dartmouth Col/ege. Hanover. New Hampshire 03755
(Received 29 December 1993; accepted 24 May 1994)
Images of grown-in and deformation-introduced dislocations penetrating cleaved {IIO} surfaces of
ZnSe and ZnS were obtained by scanning force microscopy. No electrical effects associated with
dislocations were found.
I. INTRODUCTION
Dislocations playa very significant role in the electrical
properties of semiconductors. Electronic states in the band
gap introduced by dislocations result in a high density of
electric charge at the dislocation cores which in turn results
in lower carrier mobility and lifetime, hence impairing the
device performance. A decade ago, significant progress in the
growth of defect-free crystals generated hope that the prob-
lem of defects was solved completely. Unfortunately, it
turned out to be otherwise. First, dislocations are produced in
the fabrication of integrated circuits due to the enormous
elastic stresses that build up (for example, during formation
of shallow isolation trenches I). Second. in such semiconduc-
tors as II - VI compounds dislocations are so mobile at room
temperature that they can easily multiply during the opera-
tion of optoelectronic devices. The multiplication is driven
by temperature gradients or electric fields.
2
These circum-
stances bring about a new interest in the study of the effect of
dislocations on the physical properties of semiconductors.
A very attractive idea is to use scanning tunneling micros-
copy (STM) or scanning force microscopy (SFM) for the
investigation of the electronic structure of dislocations. since
these methods combine atomic resolution with high sensitiv-
ity to electric fields. Dislocations intersecting the surface
have been studied by STM.'-9 In this article we report the
observation of dislocations penetrating cleaved {IIO} sur-
faces of ZnSe and ZnS by SFM. Unlike STM, SFM can be
used for the imaging of nonconducting samples and usually
does not require ultrahigh vacuum (UHV) conditions.
II. EXPERIMENTAL PROCEDURE
The experiments were performed using a NanoScope III
(Digital Instruments Inc.) operating in the contact and non-
contact modes under ambient conditions. During electrical
measurements the sample was isolated from the ambient
light to prevent charge carrier generation (due to photocon-
ductivity), which may lead to the screening of the dislocation
charge. as d i s c u ~ s e d in Sec. IV. The maximum scanning field
was 120X 120 /1-m2. The radius of the tip which limits the
lateral resolution was ~ 10 nm. Scan velocities were typi-
cally /0 f.1,m/s. All images were digitally processed to re-
move high-frequency noise. In addition, to eliminate large
height variations (arising due to tilt of the sample surface) a
best-fit line was subtracted from each of the scan lines.
Samples were cut from a monocrystal in such a way that
one of the surfaces was the plane of easy cleavage {II O} and
one of the surfaces was close to {OO I}; see Fig. I. Mono-
crystals were grown from the melt under pressure. The con-
ductivity was in the range 1O-6_1O-lofrlm-1 for ZnSe and
10-
8
_10-
12
0-
1
m-
1
for ZnS. The density of grown-in dis-
locations, revealed by chemical etching of fresh cleavages,
was between 10
6
and 10
8
m-
2
. Microindentation was used to
introduce new dislocations and to determine the exact orien-
tation of the specimen from the geometry of slip bands.
ZnSe and ZnS have the sphalerite structure with perfect
Burgers vectors of the type a/2< 110>.10 The primary slip
system is well established to be of the type < 11O>{ III}; see
Fig. 1. ZnS contains ~ 10% of wurtzite which results in only
one of the primary slip systems being active.
2
Directions
[110]. [112], and [112] on the surface of observation (011)
correspond to the < 111 >{ Ill} primary slip system; direc-
tions [221] and [221] correspond to the < II O>{ 112} system
(this will be used for data interpretation in Sec. III).
According to transmission electron microscopy (TEM)
studies, perfect dislocations in the primary slip system are
dissociated into Shockley partials with Burgers vectors of the
type aI6<II2>.2.11.12 The average distance between the
partials (stacking fault) in ZnSe is about 15 nm; 11 partials in
ZnS can move an arbitrarily large distance apart.
12
Since the
lateral resolution was 10 nm. individual partials in ZnSe
could not be resolved.
Samples were cleaved using razor edges in air. Some re-
gions of the resulting surface were covered with a dirt layer
(most probably of organic origin) with a typical thickness of
20 nm and some regions were atomically clean. A boundary
between atomically clean regions (on the left) and contami-
nated regions (on the right) is shown in Fig. 2(a). We found
that this dirt layer can be removed from the surface directly
by the cantilever tip in the contact mode. Figure 2(b) shows
a square (500x500 nm
2
) cleaned by the tip. The organic
material is collected on the perimeter of the square. No dam-
age to the tip could be seen after such an operation. Most of
the tests, however, were performed in the noncontact mode
using surface areas that were originally clean to avoid poten-
tial problems associated with contamination of the tip.
The amplitude of tip vibrations (noncontact mode) is a
function of the derivative of the force acting on the tip.
Changing the force derivative changes the effective spring
constant and hence the amplitude of the lever (tip) vibration.
Methods of noncontact imaging based on the monitoring of
very weak forces (electrostatic. magnetic) acting between the
sample and the tip have found wide use (a detailed treatment
is given in Ref. 13). These techniques are collectively termed
electric force microscopy (EFM). In our case the force is due
to the interaction between the tip and the charged dislocation.
2443 J. Vac. Sci. Techno\. B 12(4), Jul/Aug 1994 0734-211 X/94/12(4)12443/8/$1.00 @1994 American Vacuum Society 2443
2444 O. Nickolayev and V. F. Petrenko: Study of dislocations in ZnSe and ZnS by SFM 2444
[1
FI(i. I. Sample orientation.
surface of
observation
[110]
EFM allows of extremely small force deriva-
tives. The minimum force derivative typically detected is of
the order of 10-
4
N/m.
14
.
15
The minimum surface charge that
has been detected is 3e. with lateral resolution 0.2 tlm.15 The
minimum voltage induced in the tip that has been detected is
I m V, with a lateral resolution of 0.05 tlm.1 I> The sensitivity
to electric fields achieved in this study is discussed in detail
in Sec. IV.
III. EXPERIMENTAL RESULTS
All images presented in this section were acquired in the
noncontact mode. Contact atomic-scale images had signifi-
cantly poorer quality. Figures 3(a) and 4(a) show typical
(80X80 tlm") images of diamond-shape indentations and slip
bands emanating from them for ZnSe and ZnS, respectively.
These images acquired in the deflection mode when the
error signal (variation in the amplitude of cantilever oscilla-
tions) is captured instead of the voltage applied to the piezo.
This mode can reveal the orientation of small features (which
3 pm
a
TABl.E I. Dislocations in ZnSe.
Figure 3 Image size
icl 410 nm
Id) R40 nm
Ie) 560 nm
(f) 410 nm
Direction of the step
[l12J
[221J
[221] and [112]
[221J
Height of the step
2.1 :'::0.2 A
2.2:'::0.2 A
4.2:'::0.2 A
3.8:'::0.2 A
are not seen in the height mode) over scan areas with large
height variations. In the case of ZnSe at least three primary
slip systems are active; in the case of ZnS only one slip
system is active.
A (3X3 tlm2) image of a slip band parallel to the [112]
direction is shown in Fig. 3(b). The height of the step asso-
ciated with this slip band decreases from 10 nm. in the bot-
tom part of the picture, to zero. Unfortunately, no clear im-
ages of individual dislocations composing this slip band
were obtained. Note the presence of steps running in the
[112] direction emanating from the slip band. These steps
could be produced by dislocations which cross slipped from
the initial slip band. The height of these steps is in the range
2-5 A and was difficult to determine precisely because of
the presence of high topological features.
Figures 3(c)-3(f) display images of grown-in dislocations
in ZnSe. The heights and directions of surface steps originat-
ing from dislocations are summarized in Table 1. The values
of the heights were determined by taking the average of 20
sections across the step. Note that the step in Fig. 3(e)
changes its direction from [221] in the bottom part of the
picture to the direction close to n 12]. Note also that steps in
Figs. 3(d). 3(e). and 3(f) do not lie in the primary slip system
{lll}< 112>.
The height of a surface step produced by a dislocation
intersecting the surface is equal to the component of the Bur-
gers vector normal to the surface (see Sec. V). In sphalerite
the Burgers vectors of perfect dislocations are either perpen-
dicular (in case of (1/2[110)) or inclined at 30 0 to the surface
(in the case of a/2 [101] and a/2[011]); in the latter case, the
1.5 pm
b
FIG. 2. (a) A boundary between atomically clean and contaminated regions. (b) Atomically clean square cleaned by the cantilever tip in the contact mode.
J. Vac. Sci. Technol. e, Vol. 12, No.4, Jul/Aug 1994
2445
O. Nickolayev and V. F. Petrenko: Study of dislocations in ZnSe and ZnS by SFM
2445
80J..lm
a
410 nm
c
560 nm
e
3000 nm
b
840 nm
d
410 nm
f
FIG. 3. Surface steps produced by dislocations emerging on 111O} surface of ZnSe.
component normal to the surface is half the perfect Burgers
vector. Thus, theoretically we can expect values of the steps
to be 4.0 and 2.0 A, respectively (for ZnSe, a=5.67 A) in
reasonable agreement with the observed vaiues, see Table I.
Figure 4(b) shows a(IOX 10 ,um
2
) image revealing the
structure of grown-in dislocations in ZnS (deflection mode).
The direction of the steps is close to the primary slip system.
The places where surface steps terminate correspond to dis-
locations emerging at the surface. The dislocation density is
significantly higher than that determined by chemical etching
techniques.
JVST B - Microelectronics and Nanometer Structures
Figure 4(c) shows an image of a dislocation in ZnS (in-
troduced by indentation) on which a slip band emanating
from the indentation pit terminates. Figure 4(d) shows a
grown-in dislocation in ZnS. There is no apparent difference
between the images of grown-in and plastically introduced
dislocations. The parameters of the steps associated with
these dislocations are summarized in Table II.
Again, the heights of the steps are close to the expected
values of 1.95 A (the lattice parameter. a = 5.5 A). Both
steps lie in the primary slip system. These dislocations could
be either perfect 60° dislocations or isolated 30° partials with
2446 O. Nickolayev and V. F. Petrenko: Study of dislocations in ZnSe and ZnS by SFM
80 11m
a
'900 nm
c
e
'Ol1m
b
540 nm
d
PH;. 4. Surface steps produced hy dislocations emerging on {IIO} surface of ZnS.
J. Vac. Sci. Technol. B, Vol. 12, No.4, JuUAug 1994
2446
2447 O. Nickolayev and V. F. Petrenko: Study of dislocations in ZnSe and ZnS by SFM
2447
x
y
O.S
FiG. 5. Spatial distrihution of the electric potential produced hy a charged
dislocation.
a Burgers vector of the type a/6[1l2]. Since perfect disloca-
tions were never observed in ZnS, we believe that these are
isolated partials.
2
We did not observe dislocations producing
3.9 A steps (perfect screw dislocations), conforming to the
results of TEM studies.
2
Figure 4(e) shows a 3D image of the
dislocation from Fig. 4(d). Note the surface roughness which
is most probably due to thermal noise (discussed in Sec. IV).
Measurements of the dislocation charge were performed
in the lift mode. In this mode. first a normal scan is per-
formed with the feedback on. Then the feedback is switched
off. A second scan follows the topography from the preced-
ing scan with a constant tip-sample separation II (typically
h = 10 nm). The variation in the amplitude of tip oscillation
(which in our case is due to electric forces) is captured. The
tip is oscillated at the steepest slope of its resonant curve. To
increase sensitivity a dc bias was applied to the tip. The
maximum voltage that could be applied without deterioration
of the image quality was about 3 Y.
Both regular and metal coated cantilevers were tried. In
addition, to further increase sensitivity, an alternating voltage
V(!l) was appJied to the tip. The force derivative Fl (and
consequently the amplitude of tip vibrations) in this case is
modulated with the same frequency n. This signal is ampli-
fied using a lock-in amplifier.
No electrical effects associated with dislocations in either
method were observed. To make sure that our system is sen-
sitive to real surface charges we tried to deposit an electric
charge on the surface by applying short-voltage (40 V)
pulses to the tip. As a result, a significant amount of dirt was
accumulated in the spot where the voltage pulse was applied,
but again no evidence of electric charges was found. This
negative result is discussed in the following section.
IV. INTERACTION BETWEEN THE TIP AND THE
CHARGED DISLOCATION
A charged dislocation emerging at the surface produces an
electric field which interacts with the cantilever tip. Consider
JVST B • Microelectronics and Nanometer Structures
TARLE II. Dislocations in ZnS.
Figure J Image sife Direction of the step Height of the step
kl 1900 nm r 1121 n:'::O.2 A
Ill) 500 nm [112J 2.2:'::0.2 A
an electric charge Q located in the dielectric near the surface.
It can be shown that the potential produced by this charge in
vacuum is given by the formula
I 2 Q

4m:() 1+£ JrJ .
(I)
where £11 and e are the dielectric permittivity of vacuum and
semiconductor. respectively. and r is a vector between the
charge and the point of observation. The potential cp(x.r)
produced by a charged dislocation can be calculated by inte-
gration of Eq. (I) over the dislocation line and the screening
cylinder. The resulting potential (in the case of a dislocation
line normal to the surface) is plotted in cylindrical coordi-
nates (x.y) in Fig. 5. The integration can be performed ana-
lytically for the cases x = 0 (perpendicular to the surface) and
y=O (along the surface):
q 2 {
cp(x.O)=---- In ")
47Teo I + e _x
fl + -O.5}.
A, ,A, A,
(2)
CP(0.YI=-Q __ I_r
l2
)2].
47Tt:o I + £ ' Y , . A,
(3)
where q is the linear charge density at the dislocation core
and A 2 is the radius of the screening cylinder which is related
to q by the following formula:
(4)
where e is the electron charge and Nt! is the concentration of
shallow defects." Equations (2) and (3) are valid down to
distances of the order of a few atomic spacings. These func-
tions are plotted in Fig. 5 in thick lines. In fact. the linear
charge density q is not uniform along the dislocation line and
increases close to the surface. But this variation is not large
(about 20%) and can be neglected. t7 In the case of SFM, the
distance between the tip and the surface is typically much
less than the screening radius In this case Eq. (2)
reduces to
q 2
cp(x,0)=-4 - -1-ln(A/2x).
7T£(J + £
(5)
The potential at the tip (with respect to Fermi level) is equal
to the sum of cp(x.y) and the external bias V. The tip is
usually modeled as a conducting sphere (with a radius R). In
fact, the actual geometry corresponds to the case of a sphere
over a plane, but since on average the distance from the
sphere to the plane is much greater then R. the change of the
capacitance due to the presence of the plane can be ne-
2448 O. Nlckolayev and V. F. Petrenko: Study of dislocations in ZnSe and ZnS by SFM 2448
glected. The electrostatic energy of a spherical capacitor is
given by a well-known formula from electrostatics:
V(x) = 2 7TeoR[ c,o(x) + vf, (6)
where x corresponds to the position of the center of the
sphere (tip). The force on the sphere (tip) is equal to the
derivative of its energy. Substituting c,o(x,O) from Eq. (5) we
obtain
dV 2 I
=RVq-l- -.
x +e x
Usually the tip is vibrated on the steepest slope of the
resonant curve. In this case the change in amplitude of the tip
vibration 8A resulting from the change in the force deriva-
tiveF
I
is
(8)
where Ao is the amplitude of bimorph vibration, Q is the
quality factor, and k is the spring constant.
13
The amplitude
of the tip vibrations in this case is
(9)
The average value of the force derivative F I along the
path of tip oscillations can be found as
F(x min) - F(x max)

X
max
- Xmin
(10)
where Xmin = h + R and x max = h + R + 2A are the maximum
and the minimum distances between the center of the sphere
(tip) and the surface, h is the tip-sample separation in the lift
mode.
Substituting the following typical values (A 0 =0.18 nm,
A=30 nm, Q=300, k=30 N/m, R= 10 nm, V=3 V) and
for ZnSe q=0.6X 10-
10
C/m,2 we obtain F
I
=2X 10-
4
N/m and 8A = 0.5 A. The lateral size of the region of electric
potential is of the order of As as follows from Eq. (3) which
is much larger than the lateral resolution. A 8A of this mag-
nitude should have been detected. The thermal noise that
limits the sensitivity is
(II)
where k8 is the Boltzman constant and T is the absolute
temperature. In our case 8A
T
=0.1 A.
The absence of any observed electrical effects is most
probably due to the laser-induced impurity photoconductivity
of the samples. Though the helium-neon laser used had a
wavelength A=638 nm, which exceeds the wavelength of
fundamental absorption (466 nm for ZnSe and 344 nm for
ZnS), the laser light does generate a significant impurity
photoconductivity.ls The diameter of the laser beam shining
on the cantilever is larger than the lateral cantilever size (40
Mm) and an area outside the perimeter of the cantilever is
illuminated. Nonequilibrium charge carriers generated by the
laser can diffuse into the area shaded by the cantilever and
screen any electric charges. The diffusion length is
J. Vac. Sci. Technol. S, Vol. 12, No.4, Jul/Aug 1994
(12)
where D is diffusion coefficient and T is the lifetime of car-
riers. Substituting numerical values (for ZnSe
D
"5 ' -I 10-s)' b"
=L. cm" S,7= . s," we 0 tam tor Ad=20 Mm
which is comparable to the size of the shaded area under the
cantilever. The magnitude of the screening potential can be
estimated as
( 13)
where 0"1 and 0"0 are the conductivity under illumination and
in the dark, respectively. The conductivity under the illumi-
nation by the laser was measured to be approximately
0"1 = 10-
4
n - I m -I. Assuming the typical value of the con-
ductivity in the dark to be 0"0= IO-
R
n-
I
m -I, we obtain for
the magnitude of the screening potential cP, = 0.24 Y. This
potential is less than the potential associated with the dislo-
cation: E
F
-E
d
=O.5 V (for ZnSe\ where Er and Ed arc
the positions of the Fermi and the dislocation levels, respec-
tively. This implies that the screening can account for only a
partial reduction of the apparent dislocation charge. What is
more essential is that a dislocation is an extremely efficient
trap and recombination center for the minority charge carri-
ers (in our case, ho\es).2 Recombination of the minority
light-induced charge caITiers at the dislocation core may re-
sult in a dramatic reduction of the dislocation charge." In
addition, a scattered light with nm causes optical
transitions of electrons from a dislocation to the conduction
band, decreasing the dislocation charge. IS In summary, laser-
induced photoconductivity may account for the failure to ob-
serve any electrical effects associated with the dislocation
charge.
Another possible reason for the failure to observe electri-
cal phenomena is the presence of various impurities and ions
that can get stuck to the spot where a dislocation emerges at
the surface. However, such large objects should have been
clearly seen in our images and were not.
To confirm the validity of our model. we have measured
experimentally and calculated theoretically the change in the
amplitude of tip vibrations when a dc voltage was applied to
the tip. In this case the imaginary charge induced in the
sample plays the role of the surface charge. Experimental
and theoretical data were in agreement.
v. SURFACE MORPHOLOGY ASSOCIATED WITH
DISLOCATIONS
In this section the expected surface morphology in the
vicinity of a dislocation emerging at the surface is discussed.
The following simple estimation shows that in ZnSe and ZnS
dislocations come out perpendicular to the surface, i.e., a
rather long segment of the dislocation line adjacent to the
surface is always oriented normal to the surface. This occurs
because a dislocation is attracted to the surface and tends to
assume an equilibrium orientation with the lowest elastic en-
ergy: i.e., with the dislocation line normal to the surface. In
the region where these forces exceed the yield stress, the
2449 O. Nickolayev and V. F. Petrenko: Study of dIslocatIons in ZnSe and ZnS by SFM 2449
a
b
FIG. 6. Surface morphology associated with a screw (a) and an edge (b)
dislocations.
dislocation line is oriented normally to the surface. The force
per unit length with which dislocation is attracted to a free
surface is roughly
Eb
2
F=- (14)
x '
where x is the distance to the surface, E is Young's modulus,
and b is the magnitude of Burgers vector. The stress can be
estimated as F divided by b. Equating this stress to the yield
stress CTy, we obtain for the characteristic distance Xo over
which the dislocation line is normal to the surface:
E
xo=b- .
CTy
(15)
Substituting numbers E= 100 OPa and CTy=lO MPa,2 we
obtain x 0 = 5 ,um. This distance is very large, and for the
purpose of calculating the electric potential (Sec. IV) and
surface displacement, the dislocation line can be considered
to be normal to the surface. This simple calculation is sup-
ported by observations of lOO-,um-long straight dislocations
normal to the surface in CdS.
19
As was shown by Honda
2o
for an isotropic case, the sur-
face displacement Uscrew and Uedge produced by screw and
JVST B - Microelectronics and Nanometer Structures
edge dislocations, respectively, in the case of a dislocation
line normal to the surface are given by the following formu-
las:
vb
uedge=- sin cp,
1T
(16)
(I7)
where cp is the polar angle and v is the Poisson's ratio. The
surfaces corresponding to Eqs. (16) and (17) are plotted in
Figs. 6(a) and 6(b) [the scale in Fig. 6(b) is by a factor of 5
greater than in Fig. 6(a)]. The magnitude of surface displace-
ment associated with an edge dislocation is smaller than that
of a screw dislocation roughly by a factor of 5 (2Iv). This
makes it possible but quite difficult to resolve a surface dis-
tortion associated with the edge components of dislocations.
VI. CONCLUSIONS
SFM has been demonstrated to have an ability to identify
the type of dislocations in insulators and poor conductors.
Also SFM has an advantage over STM in the sense that it
can operate in air without UHV conditions. A sufficiently
high sensitivity of SFM to dislocation electric fields could be
achieved if the problem of the screening of the dislocation
charge by laser-induced charge carriers can be solved.
ACKNOWLEDGMENTS
The authors are very grateful to Digital Instruments, Inc.
who provided the NanoScope III used in this project and to
Dr. R. Whitworth for useful comments.
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Contact atomic-scale images had significantly poorer quality. in the latter case.2 surface of observation [1 [110] FI(i.2 [l12J [221J [221] and [112] [221J A A A 2. Vol. A (3X3 tlm2) image of a slip band parallel to the [112] direction is shown in Fig.8:'::0. The height of a surface step produced by a dislocation intersecting the surface is equal to the component of the Burgers vector normal to the surface (see Sec. These images wen~ acquired in the deflection mode when the error signal (variation in the amplitude of cantilever oscillations) is captured instead of the voltage applied to the piezo. III. 14 .4 N/m.2:'::0. EFM allows mea~urement of extremely small force derivatives. I. Unfortunately. (b) Atomically clean square cleaned by the cantilever tip in the contact mode. the n 3 pm 1. 3(e) changes its direction from [221] in the bottom part of the picture to the direction close to 12]. 2. Vac. 2444 TABl. Dislocations in ZnSe. The heights and directions of surface steps originating from dislocations are summarized in Table 1. Note that the step in Fig.2 A 4. J. and 3(f) do not lie in the primary slip system {lll}< 112>. EXPERIMENTAL RESULTS All images presented in this section were acquired in the noncontact mode.2 3. Figures 3(a) and 4(a) show typical (80X80 tlm") images of diamond-shape indentations and slip bands emanating from them for ZnSe and ZnS. The height of the step associated with this slip band decreases from 10 nm. e.5 pm a b FIG. IV. 3(d). 3(b). In sphalerite the Burgers vectors of perfect dislocations are either perpendicular (in case of (1/2[110)) or inclined at 30 0 to the surface (in the case of a/2 [101] and a/2[011]). Sample orientation. with a lateral resolution of 0. Petrenko: Study of dislocations in ZnSe and ZnS by SFM I. V).2 tlm. These steps could be produced by dislocations which cross slipped from the initial slip band. The values of the heights were determined by taking the average of 20 sections across the step. 15 The minimum surface charge that has been detected is 3e. F.15 The minimum voltage induced in the tip that has been detected is I m V.4. The minimum force derivative typically detected is of the order of 10. No. Nickolayev and V.1 I> The sensitivity to electric fields achieved in this study is discussed in detail in Sec. 3(e). Figures 3(c)-3(f) display images of grown-in dislocations in ZnSe.2:'::0.E Figure 3 icl Id) Ie) (f) Image size 410 R40 560 410 nm nm nm nm Direction of the step Height of the step 2. with lateral resolution 0. Sci. no clear images of individual dislocations composing this slip band were obtained. Technol. Jul/Aug 1994 . In the case of ZnSe at least three primary slip systems are active. 12. in the case of ZnS only one slip system is active. The height of these steps is in the range 2-5 A and was difficult to determine precisely because of the presence of high topological features.05 tlm. This mode can reveal the orientation of small features (which are not seen in the height mode) over scan areas with large height variations. Note the presence of steps running in the [112] direction emanating from the slip band. Note also that steps in Figs. in the bottom part of the picture.2444 O. (a) A boundary between atomically clean and contaminated regions. to zero.1 :'::0. respectively.

.0 A.um 2 ) image revealing the structure of grown-in dislocations in ZnS (deflection mode). Figure 4(b) shows a(IOX 10 . There is no apparent difference between the images of grown-in and plastically introduced dislocations. The places where surface steps terminate correspond to dislocations emerging at the surface. F. Again. Petrenko: Study of dislocations in ZnSe and ZnS by SFM 2445 80J. a = 5. theoretically we can expect values of the steps to be 4.Microelectronics and Nanometer Structures Figure 4(c) shows an image of a dislocation in ZnS (introduced by indentation) on which a slip band emanating from the indentation pit terminates.67 A) in reasonable agreement with the observed vaiues.2445 O. component normal to the surface is half the perfect Burgers vector. the heights of the steps are close to the expected values of 1. Both steps lie in the primary slip system.lm 3000 nm b a 410 nm 840 nm d c 560 nm e FIG. Surface steps produced by dislocations emerging on 111O} surface of ZnSe.0 and 2. The parameters of the steps associated with these dislocations are summarized in Table II. Thus. The dislocation density is significantly higher than that determined by chemical etching techniques. respectively (for ZnSe.95 A (the lattice parameter. Figure 4(d) shows a grown-in dislocation in ZnS. 410 nm f 3.5 A). These dislocations could be either perfect 60° dislocations or isolated 30° partials with . see Table I. Nickolayev and V. JVST B . a=5. The direction of the steps is close to the primary slip system.

No. Technol. 4. JuUAug 1994 . 12.2446 O. J. Surface steps produced hy dislocations emerging on {IIO} surface of ZnS. B. F.4. Petrenko: Study of dislocations in ZnSe and ZnS by SFM 2446 80 11m a 'Ol1m b '900 nm c 540 nm d e PH. Vol.. Vac. Sci. Nickolayev and V.

' Y .0)=-47T£(J 2 -1-ln(A/2x). (2) reduces to q cp(x. These functions are plotted in Fig. The tip is usually modeled as a conducting sphere (with a radius R). the distance between the tip and the surface is typically much less than the screening radius (X~A. t7 In the case of SFM. where £11 and e are the dielectric permittivity of vacuum and semiconductor. (I) FiG.2447 O. 5. respectively.)2 + I_~. Dislocations in ZnS. A. 2 Figure 4(e) shows a 3D image of the dislocation from Fig. No electrical effects associated with dislocations in either method were observed.2:'::0. The variation in the amplitude of tip oscillation (which in our case is due to electric forces) is captured. The resulting potential (in the case of a dislocation line normal to the surface) is plotted in cylindrical coordinates (x. F. In this case Eq.~.A. )2]. Note the surface roughness which is most probably due to thermal noise (discussed in Sec. (I) over the dislocation line and the screening cylinder. To increase sensitivity a dc bias was applied to the tip. an alternating voltage V(!l) was appJied to the tip. A second scan follows the topography from the preceding scan with a constant tip-sample separation II (typically h = 10 nm).2 A x an electric charge Q located in the dielectric near the surface. INTERACTION BETWEEN THE TIP AND THE CHARGED DISLOCATION A charged dislocation emerging at the surface produces an electric field which interacts with the cantilever tip. Then the feedback is switched off. In fact. but since on average the distance from the sphere to the plane is much greater then R.r) produced by a charged dislocation can be calculated by integration of Eq." Equations (2) and (3) are valid down to distances of the order of a few atomic spacings. Nickolayev and V. It can be shown that the potential produced by this charge in vacuum is given by the formula cp(rl=----~ I 2 Q y O. but again no evidence of electric charges was found. fl (2) CP(0. The potential cp(x.2 A 2. +£ (5) IV. Consider JVST B • Microelectronics and Nanometer Structures The potential at the tip (with respect to Fermi level) is equal to the sum of cp(x. the change of the capacitance due to the presence of the plane can be ne- . the actual geometry corresponds to the case of a sphere over a plane. ~(. To make sure that our system is sensitive to real surface charges we tried to deposit an electric charge on the surface by applying short-voltage (40 V) pulses to the tip. This negative result is discussed in the following section. . and r is a vector between the charge and the point of observation. we believe that these are isolated partials.O)=---. to further increase sensitivity.S 4m:() 1+£ JrJ .9 A steps (perfect screw dislocations). Petrenko: Study of dislocations in ZnSe and ZnS by SFM TARLE 2447 II. first a normal scan is performed with the feedback on. IV). A. In addition. Measurements of the dislocation charge were performed in the lift mode.In ") 47Teo I + e _x +~. This signal is amplified using a lock-in amplifier. a significant amount of dirt was accumulated in the spot where the voltage pulse was applied. The tip is oscillated at the steepest slope of its resonant curve. The integration can be performed analytically for the cases x = 0 (perpendicular to the surface) and y=O (along the surface): q 2 { \/~+x cp(x. Since perfect dislocations were never observed in ZnS. In this mode. conforming to the results of TEM studies.).5}. Both regular and metal coated cantilevers were tried.y) in Fig. Image sife Direction of the step Height of the step Figure J kl Ill) 1900 nm 500 nm r 1121 [112J n:'::O. A. The maximum voltage that could be applied without deterioration of the image quality was about 3 Y.y) and the external bias V.] -O. a Burgers vector of the type a/6[1l2]. As a result. Spatial distrihution of the electric potential produced hy a charged dislocation. 4(d). the linear charge density q is not uniform along the dislocation line and increases close to the surface. In fact. 5. The force derivative Fl (and consequently the amplitude of tip vibrations) in this case is modulated with the same frequency n. But this variation is not large (about 20%) and can be neglected. (3) where q is the linear charge density at the dislocation core and A2 is the radius of the screening cylinder which is related to q by the following formula: (4) where e is the electron charge and Nt! is the concentration of shallow defects. 2 We did not observe dislocations producing 3. 5 in thick lines. .YI=-Q_ _ 47Tt:o I + £ I_rl2 In(~)-I +(~.

which exceeds the wavelength of fundamental absorption (466 nm for ZnSe and 344 nm for ZnS). SURFACE MORPHOLOGY ASSOCIATED WITH DISLOCATIONS In this section the expected surface morphology in the vicinity of a dislocation emerging at the surface is discussed.2 Recombination of the minority light-induced charge caITiers at the dislocation core may result in a dramatic reduction of the dislocation charge. Q=300.I m -I. The conductivity under the illumination by the laser was measured to be approximately 4 0"1 = 10. The lateral size of the region of electric potential is of the order of As as follows from Eq.e. decreasing the dislocation charge.n . the laser light does generate a significant impurity photoconductivity. To confirm the validity of our model. IS In summary. respectively. The thermal noise that limits the sensitivity is (II) where 0"1 and 0"0 are the conductivity under illumination and in the dark." tam tor Ad=20 Mm which is comparable to the size of the shaded area under the cantilever. Assuming the typical value of the conductivity in the dark to be 0"0= IO.I m -I. In our case 8A T =0. we obtain for the magnitude of the screening potential cP. In this case the imaginary charge induced in the sample plays the role of the surface charge. Substituting c. Experimental and theoretical data were in agreement. Nonequilibrium charge carriers generated by the laser can diffuse into the area shaded by the cantilever and screen any electric charges.R n. However. V=3 V) and for ZnSe q=0. The magnitude of the screening potential can be estimated as ( 13) dV 2 I =RVq-l. What is more essential is that a dislocation is an extremely efficient trap and recombination center for the minority charge carriers (in our case.o(x. 13 The amplitude of the tip vibrations in this case is (9) The average value of the force derivative F I along the path of tip oscillations can be found as FI=----~------­ X max .Xmin F(x min) . The absence of any observed electrical effects is most probably due to the laser-induced impurity photoconductivity of the samples. k=30 N/m. Technol.5 V (for ZnSe\ where Er and Ed arc the positions of the Fermi and the dislocation levels.1 A. This implies that the screening can account for only a partial reduction of the apparent dislocation charge. Jul/Aug 1994 v.ls The diameter of the laser beam shining on the cantilever is larger than the lateral cantilever size (40 Mm) and an area outside the perimeter of the cantilever is illuminated.. a rather long segment of the dislocation line adjacent to the surface is always oriented normal to the surface. Nlckolayev and V. Another possible reason for the failure to observe electrical phenomena is the presence of various impurities and ions that can get stuck to the spot where a dislocation emerges at the surface. No.18 nm. Substituting numerical values (for ZnSe "5 ' -I D =L.5 A. S. a scattered light with ~=638 nm causes optical transitions of electrons from a dislocation to the conduction band.-. Sci. The electrostatic energy of a spherical capacitor is given by a well-known formula from electrostatics: V(x) = 2 7TeoR[ c. (6) where x corresponds to the position of the center of the sphere (tip). This potential is less than the potential associated with the dislocation: E F -E d =O. 12. laserinduced photoconductivity may account for the failure to observe any electrical effects associated with the dislocation charge." In addition.. Q is the quality factor. x +e x Usually the tip is vibrated on the steepest slope of the resonant curve. R= 10 nm. Petrenko: Study of dislocations in ZnSe and ZnS by SFM 2448 (12) glected. with the dislocation line normal to the surface.2448 O.4 N/m and 8A = 0.10 C/m. (5) we obtain F(x)=~d where D is diffusion coefficient and T is the lifetime of carriers. F. Substituting the following typical values (A 0 =0. A 8A of this magnitude should have been detected. In this case the change in amplitude of the tip vibration 8A resulting from the change in the force derivativeF I is (8) where Ao is the amplitude of bimorph vibration. A=30 nm. In the region where these forces exceed the yield stress. The diffusion length is J. such large objects should have been clearly seen in our images and were not. where k8 is the Boltzman constant and T is the absolute temperature. ho\es). = 0. i. Though the helium-neon laser used had a wavelength A=638 nm.F(x max) (10) where Xmin = h + R and x max = h + R + 2A are the maximum and the minimum distances between the center of the sphere (tip) and the surface. and k is the spring constant. we have measured experimentally and calculated theoretically the change in the amplitude of tip vibrations when a dc voltage was applied to the tip.o(x) + vf.2 we obtain F I =2X 10.4.24 Y. Vol. s.e. Vac. The force on the sphere (tip) is equal to the derivative of its energy. The following simple estimation shows that in ZnSe and ZnS dislocations come out perpendicular to the surface. respectively. h is the tip-sample separation in the lift mode. the . This occurs because a dislocation is attracted to the surface and tends to assume an equilibrium orientation with the lowest elastic energy: i. 7 = 10-s)' we 0 b" . cm" S .O) from Eq. (3) which is much larger than the lateral resolution.6X 10.

M. Adv. U.279 (1983). KrUger. G. Burt. Hashizume. Szynka. T. VI. Holt. Surface morphology associated with a screw (a) and an edge (b) dislocations. Phys. F. Alexander. S.. Khodos. (14) where x is the distance to the surface. IV) and surface displacement. Simon. G. Knipping. A. J. Dev. Schmid. ACKNOWLEDGMENTS The authors are very grateful to Digital Instruments. SA. B. KisielowskiKemmerich. R. Scanning Force Microscopy (Oxford University Press. Ry Mera. The surfaces corresponding to Eqs. S. 6(b) is by a factor of 5 greater than in Fig. K. V. Poppe. F. Mohler. who provided the NanoScope III used in this project and to Dr. and H. The stress can be estimated as F divided by b. Hirschom. Ebert. 6(a) and 6(b) [the scale in Fig. H. V. B 38. A. A 48. A. 9M. and T. and R. A. M. and 1. 35. Ultramicroscopy 42-44. Also SFM has an advantage over STM in the sense that it can operate in air without UHV conditions. 6. The force per unit length with which dislocation is attracted to a free surface is roughly Eb 2 F=x ' Ip. Biedermann. Wilson. Mis. Lett. Maeda. Inc. V.um-long straight dislocations normal to the surface in CdS. T. Zheng. 158 (1992). IBM 1. Fahey. Sarid. Lett. S. Rev. (I7) a where cp is the polar angle and v is the Poisson's ratio. Tsong. 69. Eades. Chern. Rev. V. V. 101 (1983). U. Osip'yan. Chiang. The magnitude of surface displacement associated with an edge dislocation is smaller than that of a screw dislocation roughly by a factor of 5 (2Iv). and b is the magnitude of Burgers vector.Microelectronics and Nanometer Structures A. B 9. A. E. lc Kriiger. 1353 (1962). and I. Poppe. Cox. J. 726 (1991). K. 1. 1. K. Nickolayev and V. 12780 (1988). Stiffler. K. and I. Osipyan. 925 (1992). Phys. \lD. Phys. K. Solids 23.2449 O. Sakurai. V. Graf. K. Petrenko. Petrenko. Rev. A sufficiently high sensitivity of SFM to dislocation electric fields could be achieved if the problem of the screening of the dislocation charge by laser-induced charge carriers can be solved. Yu. Zaretskii. M. 6(a)]. H. Mader. Technol. and T. Yu. Zaretskii. Graf. Miller. KisielowskiKemmerich. New York. Cox. Urban. Krinsley. I~A. in the case of a dislocation line normal to the surface are given by the following formulas: (16) vb uedge=1T sin cp. 1Iv. Phys. Alexander. . R. Ph. A. H. Mag. and I. C. 1991). E is Young's modulus. Phys. l. V. L. Leibsle. F. 100. 64. Phys. T. Sci. Stadler. Equating this stress to the yield stress CTy. 776 (1992). Lett. I. W. This simple calculation is supported by observations of lOO-. Urban. F. Rev. Petrenko: Study of dIslocatIons in ZnSe and ZnS by SFM 2449 edge dislocations. 1. Petrenko.915 (1992). 'G. Whitworth. Poppe. M. the surface displacement Uscrew and Uedge produced by screw and JVST B . A.2 we obtain x 0 = 5 . D. C. Philos. IN. Ultramicroscopy 4244. S. and H. 115 (1986). D. Szynka. respectively. CTy E (15) Substituting numbers E= 100 OPa and CTy=lO MPa. D. F. 19 As was shown by Honda2o for an isotropic case. 4G. D. 65. This distance is very large. 2402 (1990). dislocation line is oriented normally to the surface. K. Whitworth for useful comments. H. Aristov. "G. the dislocation line can be considered to be normal to the surface. Urban. Cox. and P. Phys. D. (16) and (17) are plotted in Figs. Zaretskii. Vac. Status Solidi A 75. R. Osip'yan. Strukova. J. U.um. R. Samsavar. Res. 36. Khodos. CONCLUSIONS b FIG. Varga. we obtain for the characteristic distance Xo over which the dislocation line is normal to the surface: xo=b. I. 2yU. This makes it possible but quite difficult to resolve a surface distortion associated with the edge components of dislocations. H. and K. Slinkrnan. SFM has been demonstrated to have an ability to identify the type of dislocations in insulators and poor conductors. Strukova. U. 1607 (1990). C. and for the purpose of calculating the electric potential (Sec.

"O. Strukova. K. '''v. 63. 1. e. Apr!. Terri. \\ilckrclIlla. No.. C. Solid State 22. Sci. 929 ( 19XOI.inghc. D. NicKolayev and V. 2450 . Vac. Rcv. "L. Phy. F Petrenko. K. Val' Sci. alld H. F. (I<)X91.. M. 61.n23119~71. F Petrenko lunpuhlished). Sov. 12. E. J. Solid State 19.YII. lIollJa. Jul/Aug 1994 .4. Apr\. 1. J. J. D.215 (1979). 154 (19771. Vo\. Phy'. 119911."f>2 R..ill)!he. Weaver and H. 2('K. Wic·krallla. Phys. C.1. Phys. J. So\. Nickolayev and V.2450 11'1'. O. "R. Petrenko: Study of dislocations in ZnSe and ZnS by SFM Martin. Stern. 2f>f>9 \1 •. Lett. K. Tedlllo!' H 9. Jpn.. and H. \lalllill. F Petrenko and G. J. 18.·illiaill'. Techno\. I'hy'. Rugar. C 'V. Kirichenko and V.

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