ADVANCESIN

COLLOIDAND
INTERFACE
Advances in Colloid and Interface Science SCIENCE
ELSEVIER 71-72 (1997) 165-182

Magic number and quasi-melting temperature

discovered in crystal growth and surface phase
transitions
Akitoshi Ishizaka a'b'c'*
aFunctional Properties Group, PrecursoryResearchfor Embryonic Science and Technology
(RESTO-Project), Research Development Corporation of Japan (JRDC)
bCentral Research Laboratory, Hitachi Ltd.
cJoint Research Centerfor Atom Technology (JRCAT)

Abstract

For crystal growth and surface phase transitions, we discovered a simple rule in the
relationship between surface structure and temperature. This rule states that changes in
crystal growth modes and those in surface structures occur at temperatures that are simple
fractions, such as 1/2, 2 / 3 , and 3 / 4 , of the melting temperature, T m, of the material. Here,
we first show our experimental results of transition temperatures for Si-MBE (molecular
beam epitaxy) on S i ( l l l ) and Si(001) substrates and for structure changes on S i ( l l l ) surface.
We then discuss them for other materials from the literature, having fcc (face centered
cubic) or diamond structures, which are similar crystal structures to Si. We found that the
transition temperatures were the same, regardless of material, depending on crystal surface
orientation. That is, transitions take place at the temperatures of 2 / 6 , 3 / 6 , 4 / 6 , 5 / 6 T m for
(111) surfaces, and 1/4, 2 / 4 , 3 / 4 T m for (001) surfaces, when transition temperatures are
normalized to the melting temperature of each material. We discuss the origin of these
fraction temperatures by consideration of surface atom energy based on the geometry of
atom arrangement on a crystal surface. We think that the reason why transition tempera-
tures were same is due to the same coordination numbers of the respective surface atoms if
material has similar crystal structure even if materials differ. We consider these fractions are
one kind of magic numbers, and also call these temperatures as quasi-melting temperatures,
from the analogy of the melting for bulk crystal. For example, at 1 / 2 Tm, atoms bound at
kink sites become free, i.e. kink melting occurs, since kink-site atoms have half the

* Present address Joint Research Center for Atom Technology (JRCAT) c / o National Institute for
Advanced Interdisciplinary Research 1-1-4 Higashi, Tsukuba, Ibaraki 305, Japan.

0001-8686/97/$32.00 © 1997 Elsever Science B.V. All rights reserved.

PllSOOO1-8686(97)OOO16-X
166 A. lshizaka /Adv. Colloid Interface Sci. 71-72 (1997) 165-182

coordination number of bulk atoms. Finally, we point out that it is important for understand-
ing various surface phenomena to consider the role of surface-defects such as terraces,
ledges, and kinks.

I. Introduction

In appearance, surface phenomena such as crystal growths a n d / o r surface phase

transitions seem to be too complex to understand, since such phenomenon differs
for each material, surface orientation, atmosphere, and so on. The purpose of this
review is to provide a simple guideline for understanding various phenomena seen
in crystal surfaces. We contend that a universal rule can be recognized by
extracting the features that are common to several material systems. In this study,
we discovered such rule for several phenomena seen in crystal surfaces. Specifi-
cally, we found that transitions in both the crystal growth mode and surface
structure occur at temperatures that are fixed ratios of the melting temperature of
the material. We call these ratios as 'magic numbers in surface phenomena'.
Simple, universal, and attractive laws are seen by chance in the phenomena of
nature. Magic numbers, above-mentioned, are one of these relationships. Various
kinds of magic numbers are known in nature. One of examples is seen in the
number of neutrons or protons in stable atomic nuclei. When the number of
neutrons or protons is 2, 8, 20, 28, 50, 82, or 126, an atomic nuclei is stable, and
these numbers are called as 'magic number'. The other is seen in the number of
atoms in stable micro-clusters of materials, e.g., Au clusters with 5, 7 or 9 atoms
are stable. The numbers of 60, 70, 76, 78, 82, 84, 90, and 96 found in the fullerene
(such as C60, C70, C82 etc.) are also one of magic numbers. For both eases, stable
and peculiar structures are formed at magic numbers. Finding such magic numbers
can provide powerful insight into fundamental mechanisms in phenomena, because
such numbers often reflect the nature of the phenomena.
This review is conducted in three stages. First, we show our experimental results
for growth mode transitions in Si-MBE (molecular beam epitaxy) on Si(lll) and
(001) substrates [1,2]. We also show our experimental results for surface phase
transitions in Si(lll) and (001) crystal surfaces [1,3]. We discovered that the
temperatures for the transitions in crystal growth mode and surface structure
occurred at certain fixed ratios, e.g., 1/2, 2/3, and 3/4, of the melting temperature
of the bulk Si. These simple ratios are thought to be one of 'magic numbers', which
reflect the universal law in the phenomena on crystal surfaces.
Secondly, to determine if these numbers apply to other materials, we searched
the literature for transition temperatures of MBE growth [4,10] and surface phase
transitions [5,9,11-15] for other materials having fee (face centered cubic) crystal
structure and diamond crystal structure. We found that magic numbers occur not
only in Si but also in other materials, such as Ge, GaAs, Au, Pt, etc. Specifically,
we found that the normalized transition temperature (defined as the ratio of
transition temperature to the melting temperature of the material) occurs at a
 A. lshizaka /Adv. Colloid Interface Sci. 71-72 (1997) 165-182 167

magic number. Therefore, we hypothesized that these fixed ratios on crystal

surface transitions are valid for any material having fee and diamond structure.
Thus, we call these numbers, magicnumbers, and these temperatures, quasi-melting
temperatures.
Finally, we discuss the origin of these magic numbers and quasi-melting temper-
atures by consideration an energy of surface atoms based on the geometry of atom
arrangement on a crystal surface, by considering a surface-defect crystal-structure
model in which the surface structure has terraces, ledges, and kinks (i.e. the
terrace-ledge-kink model).

2. Experimental method

In previous studies, we measured the temperature dependence in the crystal

quality of grown layers in Si-MBE [1,2] and that in the structural changes in Si
crystal surfaces [3] by using the reflective-high-energy-electron-diffraction method
(RHEED). Figure 1 shows a schematic of the RHEED method. Crystal quality of
epitaxial layers on Si(001) and Si(lll) substrates was judged by the sharpness (or
clarity) of the electron diffraction spot. Structural changes in the Si(001) and (111)
surfaces were judged by the electron diffraction intensity. Details of the experimen-

Pyrometer for Diffraction pattern Diffraction Pattern

F Spot Width ~ Crystallinlty of Grown Layer

Measurement~
L_ Spot Intensity ~ Surface Structure Transition
Fig. 1. Schematic of the apparatus used to determine RHEED diffraction patterns.
168 .4. lshizaka /Adv. Colloid Interface ScL 71-72 (1997) 165-182

tal procedure, such as sample conditions, sample preparations, and measurement

conditions, were previously reported [1-3].

3. Results

3.1. Growth mode changes in Si-MBE on Si(O01) and (111) substrates

Figure 2 shows in situ RHEED diffraction patterns for 100-nm-thick Si layers on

Si(001) substrates grown at various growth temperatures [1]. After the growth, the

Fig. 2. In situ RHEED diffraction patterns for 100-nm-thick MBE grown layers on Si(001) substrates as
a function of growth temperature.
 A. lshizaka /Adv. Colloid Interface ScL 71-72 (1997)165-182 169

substrates were cooled to room temperature and RHEED patterns were observed.
The halo seen in the patterns is due to the grown layers below 400 K being in an
amorphous phase (or micro crystals). At 473 K, diffuse diffraction spots were seen
to correspond to a reciprocal lattice of the bulk crystal, indicating that single
crystal layers with micro-rough surfaces grow at this temperature by two-dimen-
sional epitaxy on two-dimensional islands ( = quasi-three-dimensional epitaxy).
Above 573 K, 2 × 1 RHEED patterns and Kikuchi patterns were seen. Diffraction
spots became clearer as the substrate temperature increased from 573 K to 873 K.
Between 873 K and 1173 K, the diffraction size and sharpness did not change.
Figure 3 shows the relationship between the crystal quality of a grown layer and
the growth temperature for Si-MBE on (001) Si crystal substrates [2]. Here, the
growth temperature (T) was normalized by the melting temperature (Tm) of bulk
Si. The crystal quality was judged by the reciprocal of the (0,1) electron diffraction
spot width in Fig. 2. When the crystal quality was high, the diffraction spot was
sharp. Figure 3 shows that the temperature dependence of crystal quality of
Si-MBE layers. Crystal qualities changed at T / T m = 0.52 for both Si(001)-MBE
(shown by solid line) and Si-MBE on Si(lll) (shown by dotted line) in Fig. 3. We
defined these temperatures as the transition temperatures of the growth modes in
MBE. We compared these results for Si-MBE with those for GaAs-MBE on
GaAs(001) obtained by Metze and Calawa [4], shown by the gray line in Fig. 3. A
comparison between Si-MBE and GaAs-MBE will be discussed at section 4.2. Note
that surface orientation dependence on transition temperature was not found for
either (001) or (111) Si-MBE, and that the transition temperatures were almost
1/2 of the melting temperatures of the bulk material.

3.2 Systematic structural changes in Si(l l l ) surfaces

Figure 4 shows surface phase transitions as a function of T for clean surfaces of

Si(lll) [3]. Diffraction intensities of (1,0) integer spots and sum intensities of
( - 3/7, 0) + ( - 4/7, 0) + ( - 5/7, 0) super spots were measured as a function of T.
Intensities changed at T = 830 K, 1110 K, and 1413 K, corresponding to the
normalized temperatures of T / T m = 0.49 ( ~ 1/2), 0.66 ( ~ 2/3), and 0.83 ( - 5/6),
respectively. At T / T m ~ 1/2, the temperature dependence of the super-spot
intensity changed, but that of the integer-spot intensity did not. This change was
confirmed by Bennet and Webb [5] in experiments involving low electron energy
diffraction. Some relaxation in the 7 x 7 structure occurs above this temperature,
although details of the relaxation have not yet been clarified [6]. The intensity
change at T / T m ~ 2 / 3 is related to the well-known surface phase transition from
a 7 x 7 structure to a 1 X 1 structure [6-9]. At this temperature, the super-spot
intensity decreased, and the integer-spot intensity increased. Above it, the super
spots disappeared. At T / T m ~ 5/6, the integer-spot intensity dropped abruptly
due to surface disordering, namely, the occurrence of electron diffraction de-
creases in proportion to the disordering of surface atom sites above this tempera-
ture.
170 A. lshizaka /Ado. Colloid Interface Sci. 71-72 (1997) 165-182

Growth Temperature for Si-MBE (K)

600 800 1000
=====================! l=........ =================================!
• | ~l "'''''"

Growth 600Temperaturefor800GaAs-MBE 1(1<)000

10 5 I I I I I I 0.4

TransitionTe,mperature
o.3 ~
J

10 4 _ -0.2

ca :: :-:...,::'-'
0 e'-
.o_
_ 0.1
o
_. ~ : Si on Si(001) i:3
o. Si on Si(111 ) -
e" GaAs on GaAs(001)
10 3 ~ I ~ I ~ I 0.0
0.3 0.4 0.5 0.6 0.7
Normalized Growth Temperature T/Tm
Fig. 3. Growth temperature dependence of crystal quality for Si layers grown on Si(001) and (111)
substrates [1-3] and for GaAs layers grown on GaAs(001) substrates [4]. Crystal quality is represented
by the reciprocal of the width of the electron diffraction spots observed at room temperature for Si or
by the mobility of the charge carriers measured at 77 K for GaAs. Growth temperatures (T) were
normalized by the melting temperature (T m) of each material (T m = 1685 K for Si, T m = 1511 K for
GaAs).

Note that each transition temperature for an Si(lll) surface is given by n/6
(n = 3, 4, 5), creating ordered incremental increases of 1 / 6 T m. This demonstrates
the possibility that surface sites existed at which the energy changed with ordered
 A. lshizaka /Adv. Colloid Interface ScL 71-72 (1997) 165-182 171

Temperature ( K )
300 600 900 1200 1500 1800

I
1.0 _ - o ~ ~ . e . . ~ . . . . ~ ~ ~ Tm-

o.s !
g
~ o: (1,0) integer-spot ~m
t5 -": (-3/7, 0) + (-4/7,0) + (-5/7,0) super-spot
3/6 4/6 5/6 6/6

0.2 0.4 0.6 0.8 1.0

Normalized Temperature T / Tm
Fig. 4. Substrate temperature dependence of R H E E D diffraction intensities for S i ( l l l ) surfaces [4].
R H E E D intensities were normalized by those at room temperature. Intensities changed at T / T m = 0.49
(830 K), T / T m = 0.66 (1110 K) and T / T m = 0.83 (1413 K). (T m is the melting temperature of bulk Si).

increment. These systematic changes induced the surface structural changes at

temperature increments of 1/6 T m.

3.3. Surface orientation dependence on transition temperature

Figure 5 shows the R H E E D (1,0) diffraction intensities for clean surfaces of

Si(001) and Si(lll) as a function of substrate temperature [1]. The data for Si(lll)
are same as that in Fig. 4. For the Si(001) surface, the intensity decreased
monotonically with increasing temperature, and abruptly dropped at about 1310 K.
This temperature corresponds to 0.78 Tin, which is approximately 3 / 4 T m. This
drop can be explained by surface disordering. Note that both the Si(001) and
Si(lll) surfaces exhibited surface orientation dependence in the surface disorder-
ing temperature. In contrast, there was no such dependence for 1 / 2 T m.
172 A. lshizaka /Adv. Colloid Interface Sci. 71-72 (1997) 165-182

Temperature (K)
300 600 900 1200 1500 1800
I i ! I ' ' I i l I i , I l I

,'- 0.5
i
t--
Si(lO0)~ e,,,. i "
c-
. ~
O

t._

.=:_
a
/
0.1 I J I Y
0.2 0.4 0.6 0.8 1.0
Normalized Temperature T / T m
Fig. 5. RHEED diffraction intensities as a function of substrate temperature for clean Si(00l) and O l D
surfaces. The (1,0) spot intensities were measured.

This dependence was also found in Si-MBE [1]. Epitaxy-starting temperatures,

which defined as the lowest temperature of epitaxial growth, for Si(001) and Si(lll)
substrates were about 420 K and 600 K, corresponding to 0.25 T m and 0.34 Tin,
respectively, or approximately 1 / 4 T m and 1 / 3 T m.

4. Discussion

4.1 Results of our findings

Our findings on the transition temperatures in MBE and surface structure

changes for clean Si-crystal surfaces are as follows:
• Transition temperatures exist in both MBE for growth modes and surface
structure changes.
• Transition temperatures correspond to simple fractions of the melting tempera-
ture of Si.
• For a (111) surface plane, transition occurs at T / T m = 1/3, 1/2, 2/3, and 5 / 6 ,
i.e. T / T m = n/6, where n = 2, 3, 4 and 5. For a (001) surface plane, tramition
 A. lshizaka /Adv. Colloid Interface Sci. 71-72 (1997) 165-182 173

occurs at T / T m = 1/4, 1/2, and 3/4, i.e., T / T m = n/4, where n = 1, 2, and 3.

The transition temperature of T / T m = 1/2 is common to both (111) and (001)
surface orientations.

4.2 Transition temperatures ]'or MBE and surface structure changes for various materials

Our results show that temperatures for crystal growth mode transitions in
Si-MBE and for surface phase transitions on Si are fixed ratios of the melting
temperature. Here we look at transition temperatures for other materials reported
in the literature; specifically for (001), (111), and (110) surfaces of materials that
have fcc and diamond structures, which are similar crystal structures.
For MBE, Metze and Calawa [4] showed that the crystallinity of GaAs(001)-MBE,
changed at 0.51 Tm (Fig. 1). Crystallinity was judged by the mobility of electric
carrier measured at 77 K. Note that the transition temperature for GaAs(001)-MBE
is approximately 1/2 Tm, which is the same as our results for Si(111) and (001)
[1,2]. Ohshima et al. [10] showed that the growth mode transition temperature for
NiSi 2 on Si(111) heteroepitaxy was 0.53 Tm. Therefore, a transition temperature of
1 / 2 Tm occurs regardless of material or crystal surface orientation.
For surface phase transition, Abernathy et al. [11] showed that both Au(111) and
Pt(111) transform from a commensuration to a discommensuration-fluid phase at
0.65 Tm, which is quite the same as that for a 7 x 7 to 1 x 1 phase transition in
Si(111), i.e. 0.65 Tm. For a (110) surface plane of Au, Campuzano et al. [13] showed
that a 1 x 2 to 1 x 1 phase transition occurs at 650 K, corresponding to 0.49 Tm.
Frenken et al. [14] showed that surface melting occurs on a flat surface of Pb(ll0)
at 475 K, corresponding to 0.75 Tm. These results confirm that magic numbers are
found not only in (111) and (001) surfaces but also in (110) surfaces.
Table 1 lists the normalized transition temperatures for MBE growth transitions
[1,2,4,10] and surface structure transitions for different materials and substrate
orientations [3,6-9,11-15]. This table corroborates our findings described in sec-
tion 3.1, and shows that a T / T m = 1/2 is also valid for (110) surface orientations.
Note that transition does not always take place at all temperature shown by
magic numbers, although transition temperatures are represented by magic num-
bers. For example, on a Si(001) surface, growth mode changes occur at 1/2 "I'm,but
the surface phase transition does not occur at this temperature. Note also that
each surface listed in Table 1 has a different reconstruction structure and different
bond type, such as metallic, covalent, or ionic. This means that more effective
factor, which will be discussed at next section, should decide the 'magic number'
than those of such differences.

4.3 A model for magic numbers in surface phenomena

We now look at the physical meaning of these magic numbers. First, we consider
the meaning of temperature normalization. It is well known that the melting
temperature of a material is linear to its cohesive energy and also to its self-diffu-
sion activation energy, as shown in Fig. 6 [1]. Although cohesive energy is different
174 A. lshizaka /Adv. Colloid Interface Sci. 71-72 (1997) 165-182

Table 1
Normalized transition temperatures in MBE and surface structure change for various materials

Phenomena Material Normalized transition temperature T/T m

and 1/8 1/4 1/3 1/2 2/3 3/4 5/6
orientation (= 0.13) (= 0.25) (= 0.33) (= 0.50) (= 0.67) (= 0.75) (= 0.83)

MBE growth Si(lll) 0.34 0.52

GaAs(111) 0.51
Si(001) 0.25 0.52
GaAs(001) 0.24 0.51
InP(001) 0.28

Phase transition Si(lll) 0.49 0.66 0.83

Ge(lll) 0.49 0.83
Au(lll) 0.65
Pt(lll) 0.65
Si(001) 0.12 0.78
Ge(001) 0.17
Au(ll0) 0.48
Pt(110) 0.53
Pb(110) 0.75
Ni(110) 0.75
Cu(110) 0.75
Ag(llO) 0.80
At(110) 0.70
In(110) 0.69
For (11 I) surfaces, transition temperatures are presented by T/T m = n/6 (n = 2, 3, 4, 5).
For (001) surfaces, transition temperatures are presented by T/T m = n/8 (n = 1,2, 4, 6).
For (110) surfaces, transition temperatures are presented by T/T m = n/4 (n = 2, 3).
Transition temperature of T/T m = 1/2 is common irrespective of the surface plane of (111), (001) and
(110).

for each material, cohesive energy normalized by T m is a constant. This normaliza-

tion allows us to c o m p a r e properties o f the binding energy a m o n g different
materials.
Next, we consider a surface structure model. Because M B E growth and surface
phase transitions take place on the crystal surface, a c o m m o n , simple, and general
surface structure model which can apply to various materials must be discernible,
even when both the reconstruction structures and bonding types differ a m o n g the
materials. O n e such m o d e l that is applicable to various surfaces o f different
materials is the terrace-ledge-kink m o d e l (Fig. 7) p r o p o s e d by Kossel [16] and
Stranski [17].
T h e binding energies o f the terrace (Et), ledge (El), and kink (E k) atoms are
roughly proportional to their coordination numbers, w h e n we neglect the changes
in back-bond energies due to the dangling-bond formation. T h e binding energies
 A. lshizaka / Adu. Colloid Interface Sci. 71-72 (1997) 165-182 175

I I I
-10
o--'E c W
/
200
,~/Ta/°
---o-- : Q - -

-8
R

O
E >
150 oZrHof~° (D
.Pt/ ~,. - 6

,:,n 1 0 0 - N,~ oCr Nb"° %

InP~.~ / Fe " .-"'~,o -- - 4
o^'~ " V_oo" LU
/
A.G
00~% 1000 2000 30100 4000 0
T m (K)
Fig. 6. Relationship between cohesive energy (E c) and melting temperature (Tm), and between
activation energy of self diffusion (Q) and melting temperature [1].

increase in order, as if going upstairs; in other words, a zero-order estimation with

a simple cubic atom approximation (Fig. 7) shows that the ratio of E t : E m: E k : E b
is roughly 1 : 2 : 3 : 6. Therefore, the binding energy for each surface site is normal-
ized by that of the bulk for each material. Thus, binding energies of each surface
site is also normalized by T m even if the materials arc different, because the
binding energy of the bulk material (E b) is linear to the melting temperature for
each material (Fig. 6). Figure 8 shows our way of thinking for the relation of
binding energies between surface atoms and bull atoms, involving the normaliza-
tion for various materials.
Next, we use the terrace-ledge-kink model to explain the magic number of 1 / 2
found in MBE growth. Experimental results for MBE arc summarized as follows:
• Crystal growth takes place on the crystal surface [18-20].
176 A. lshizaka /Adv. Colloid Interface Sci. 71-72 (1997)165-182

Vacuum level

t EI
-k
A E
on terrace on terrace
C
at ledge
"b Eboc Tm
B
at kink Et<El<Ek< Eb
Ek/Eb= 1/2

D
in bulk
Fig. 7. Schematic of the geometry of the atom arrangement on a crystal surface determined using the
terrace-ledge-kink model. Potential levels are also shown.

. Two-dimensional ¢pitaxy (layer-by-layer growth) occurs in MBE [18-20].

• Growth modes in MBE is classified into two categories as shown in Fig. 3, and
the transition temperature between the growth modes is 1 / 2 Trn (our findings).
• A transition temperature of 1 / 2 Tm is common to both (001) and (111) surfaces
(our findings).
Growing atoms are incorporated on the sides of steps, because two-dimensional
layer-by-layer growth occurs in MBE. Therefore, among surface atomic sites, only
two sites are thought to be suitable for growing atoms: ledge sites and kink sites.
Kink-site atoms seem to determine the phenomena that takes place at 1 / 2 T m. The
binding energy of kink-site atoms is half that of bulk-site atoms because kink-site
atoms have half the coordination number of the bulk atoms, irrespective of surface
orientation. Therefore, kink-site atoms may play a role in the crystal growth (Fig.
3). Analogous to the melting of bulk crystal, an atom at a kink site will detach
above 1 / 2 Tm. This temperature is called the kink melting temperature. If we
 A. lshizaka /Adv. Colloid Interface SeL 71-72 (1997) 165-182 177

MeltingTempdTrn)

0 ~
~ 3 [ LinearRelation(see Fig.6) l

: l

ii
~" ~ " - ~; inding Energyof SurfaceAtom~ ~.
/

= "~ !---CAtomon Terrace)--/

o "g E i---(Atomat Ledge~---
•

i--.(.Atom~ Ledge~---
J
r r~~ ~
:,---(Atomin Bulk)
Fig. 8. Schematic diagram of the way of thinking for the relation of binding energies between bulk
atoms and surface atoms involving the normalization of various materials.

assume that growth starts at one straight step, then growing atoms will be
incorporated at every site along the step. When the growth temperature is lower
than 1 / 2 T m, as the growth proceeds, the shape of the growth front is zigzag, with
many kinks and short ledges, as shown in Fig. 9a [2]. The reason is that kink sites
act as pinning points. When the growth temperature is higher than 1 / 2 Tin, the
shape of the growth front is straight, as shown in Fig. 9b [2], because kink sites do
not act as pinning points and because a straight step has the minimum line tension.
The growing atoms at kink sites are bound more strongly and are thus in a more
stable state than are atoms at ledge sites. The crystal quality of the epitaxial layer
is therefore greatly improved above 1 / 2 T m.
Atoms at ledge sites will decompose above ( E t / E b ) T m. The value of (EI/Eb)T m
178 A. lshizaka /Adv. Colloid lnterface Sci. 71-72 (1997)165-182

(a) L e d g e G r o w t h
T < 1/2 Tm
(Kink Pinning)

(b) K i n k G r o w t h
T > 1/2 Tm
°t=(
(Kink Flow)

°~ ""

o=

d~ • (c) Island G r o w t h
RHEED Oscillation
Region
Homogeneous Nucl~
Growth on Terrace

• (d) Step G r o w t h
No RHEED Oscillatior
Region
Unnucleation Growth
at Steps

Fig. 9. Schematic of growth models for MBE. Two classifications of two-dimensional epitaxy are shown:
(a and b) ours and (c and d) proposed by Joyce et al. [1839] (a) Growing atoms incorporated at the
atomic sites of ledges and kinks. Because kink sites act as pinning points at temperatures lower than
1/2 Tm, the growth front becomes zigzag. (b) Growing atoms are incorporated and decomposed at
atomic sites of kinks at temperatures higher than l / 2 Tin. Growth front becomes smooth, because kink
sites do not act as pinning sites. (c) Two-dimensional nuclei and islands grow on terraces. Diffraction
intensities oscillate synchronously with each atomic layer growth. (d) Growth occurs at steps without
nucleation, No oscillation phenomena of diffraction intensities occur.

d e p e n d s o n t h e crystal o r i e n t a t i o n a n d structure o f t h e m a t e r i a l . T h e s e ledge-site

a t o m s a r e r e s p o n s i b l e f o r the surface o r i e n t a t i o n d e p e n d e n c e f o u n d in t h e p h e n o -
mena of epitaxial starting temperature.
 A. lshizaka /Ado. Colloid Interface Sci. 71-72 (1997) 165-182 179

Note that our classification for the two-dimensional epitaxy shown in Figs. 9a
and 9b differs from that proposed by Joyce et al. [18,19]. The model by Joyce et al.
explains the oscillation phenomenon of diffraction intensity, which changes syn-
chronously with each atomic layer growth. In model of Joyce et al., two-dimen-
sional islands grow on terraces following two-dimensional nuclei (Fig. 9c), or
growth takes place at step regions without nucleation (Fig. 9d). Note that the edges
of the two-dimensional islands in (c) are topologically equivalent to the steps, and
that the edges of islands consist of ledges and kinks, exactly like those at the edges
of steps. Therefore, ledge and kink growth proposed in our work can be applied to
both Figs. 9c and 9d. A fundamental difference in classification between 9a and 9b,
and between 9c and 9d, is whether growth occurs at atomic sites (ledges and kinks)
or at regions (steps and terraces). Note again that the growth model by Joyce et al.
(% and 9d) shows only whether nucleation takes place on terraces or nucleation-
less growth takes place at steps. Another difference is the transition temperature;
the transition temperature between 9c and 9d varies as a function of the growth
rate and the terrace width, because it is determined by the adatom mobility on
terraces and by the terrace width at which either nucleation growth on terraces or
nucleationless growth at steps occurs. On the other hand, the transition tempera-
ture between 9a and 9b is constant at 1 / 2 Tin, because it is related only to kink
sites. Therefore, our growth mechanism shown in Figs. 9a and 9b is the elemental
process for the incorporation of growing atoms.
The terrace-ledge-kink model is also applicable to surface phase transition. It is
well known that the phase transition from 7 x 7 to 1 x 1 for a clean Si(lll)
surface begins at the ledge (edge of a step) [9,21]. That is, this phase transition
(7 x 7 to a 1 x 1, or vice-versa) nucleate at ledges. On the other hand, this phase
transition takes place at T / T m -- 2 / 3 (Fig. 4). The binding energy of a step (or
ledge) relative to a bulk crystal needs to be estimated. Because the phase transition
from 1 x 1 to 7 x 7 took place at ledges at 2 / 3 T m, the Kossel-Stranski model can
be used [16,17], as shown in Fig. 7. According to this model, phase transition from
7 × 7 to 1 x I occurs as follows. Atoms incorporated in ledges begin to break free
at 2 / 3 Tin, leading to phase transformation, which can occur anywhere on the
steps. This hypothesis is consistent with direct REM observation by Osakabe et al.
[9] and STM observation by Kitamura et al. [21], for a phase transition from 1 x 1
to 7 x 7 initiated at steps.
Similarly, it is reasonable to interpret the mechanism of other changes in surface
structure for Si(lll) in terms of other surface sites, i.e. kinks and terraces, as one
of the explanation. According to the terrace-ledge-kink model with a simple cubic
atom approximation, the ratio of binding energies of kinks and terraces to that of
the bulk is 1 / 2 and 5/6, respectively. Therefore, these other sites provide a
possible interpretation for the systematic change in temperature increase or
decrease in ordered increments of 1/6T m seen in our experimental results (Fig. 4).
Crystal growth and surface structure transitions for Si(lll) can be explained by
the terrace-ledge-kink model. For surface phase transitions of other material
systems listed in Table 1, however, it may be premature to explain its transition
mechanism using the terrace-ledge-kink model. The reason is that the role of kinks
180 A. Ishizaka /Adv. Colloid Interface Sci. 71-72 (1997) 165-182

and steps has not yet been clarified by experimental observation at the atomic
level. Such clarification might lead to another explanation. However, it is certain
that coordination numbers of surface atoms and the symmetry of surface atom
arrangement play an important role in surface phenomena. We emphasize that
surface structure transition at the temperature corresponding to the magic num-
bers of 1/2, 2/3, 3/4, etc. was experimentally verified.
Analogous to the melting of bulk crystal at T m, atoms at ledge, kink, and terrace
sites will decompose above (E~/Eb)Tm, above 1 / 2 Tin, and above (Et/Eb)Tm,
respectively. These temperatures, which we call quasi-melting temperatures (in
contrast to the bulk melting temperature), correspond to the temperatures that
occur at the magic numbers.
Finally, it should be noted that crystal surfaces are not in homogeneous and
smooth from the view point of atomic scale. Indeed, existence of many kind of
surface defects, such as terraces, ledges, kinks, and so on, is certain on the crystal
surfaces. It is also certain that a consideration of the role of such surface defect
and heterogeneity is important for understanding the mechanism in various surface
phenomena, and that magic number in surface phenomena is also ascribed to
heterogeneity on crystal surfaces.

5. Conclusions

For crystal growth and surface phase transitions, we found out a simple rule in
the relationship between surface structure and temperature for the materials
having fcc or diamond structures. Results are as follows;
1. For (111) surfaces, transitions in the growth modes in crystal growth and surface
structures occur at temperatures approximately equal to simple values, such as
2/6, 3/6, 4/6, 5 / 6 T m, when transition temperatures are normalized to the
melting temperature, Tin, of each material.
2. For (001) surfaces, transitions in the growth modes in crystal growth and surface
structures occur at temperatures approximately equal to 1/4, 2/4, 3 / 4 T m of
each material.
3. Transition temperatures were the same, regardless of material, depending on
crystal surface orientation.
4. We call these characteristic numbers magic numbers and their corresponding
temperatures quasi-melting temperatures.
5. The origin of these magic numbers were thought to be ascribed to the same
coordination numbers of the respective surface atoms if material has similar
crystal structure evenif materials differ. As one of possible explanations, a
primitive interpretation showed that simple fractions such as 1/3, 1/2, 2/3, 3 / 4
etc. are thought to be the binding energy ratios of surface atoms bound at sites
of terraces, ledges and kinks to that of bulk material.
Although our interpretation of magic numbers and quasi-melting temperatures
contains simple and rough estimations based on speculation, we determined at
 A. lshizaka /Adv. Colloid lnterface Sci. 71-72 (1997) 165-182 181

least experimentally that there are features in transition temperatures which are
common to fee and diamond structure crystal surfaces regardless of material and
surface orientation. Magic numbers will provide new insights into various pheno-
mena in crystal surfaces.

Acknowledgements
I am grateful to Professor Kazutake Kohra for his encouragement and discus-
sions throughout this work. Also, I express my gratitude to Professor Yoshitada
Murata for his suggestion of the name magic number and for his helpful discus-
sions, and to Mr. Hirotaka Toyokawa for his suggestion of the name quasi-melting
temperature. Finally, I am thankful for vital suggestions from Drs. Eiichi Maruyama,
Seiichi Iwata, Toshikazu Shimada, Masahiro Kitada, Takahisa Doi, Masakazu
Ichikawa, Shin Sato, and Syu Kanehisa.
This work was partly performed at the Central Research Laboratory, Hitachi
Ltd. (until 1991), partly at the Institute for Solid State Physics, the University of
Tokyo under a PRESTO Program (1992-1994) of the Research Development
Corporation of Japan (JRDC). Since 1995, this work, partly supported by the New
Energy and Industrial Technology Development Organization (NEDO), was per-
formed in the Joint Research Center for Atom Technology (JRCAT) under the
joint research agreement between the National Institute for Advanced Interdisci-
plinary Research (NAIR) and the Angstrom Technology Partnership (ATP).

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