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# 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.