Journal of Non-Crystalline Solids 22 (1976) 29-35

© North-Holland Publishing Company

THE CRYSTALLIZATION OF AMORPHOUS GERMANIUM FILMS

Norman A. BLUM and Charles FELDMAN

The Johns Hopkins University, Applied Physics Laboratory, Laurel, Maryland 2081 O, USA

Received 15 September 1975

Germanium thin films were prepared in an amorphous form by vacuum deposition on-
to room temperature fused silica substrates. The amorphous-crystalline transition was stu-
died as a function of time and temperature by measuring the optical transmission near
0.65 ~tm, where the absorption constant is most sensitive to the phase transformation. At
a fixed temperature, the time for half the volume of the sample to become crystallized was
found to be consistent with the relation t c = r exp(Eo/kT), with an activation energy Eo =
2.96 eV.

1. Introduction

It was shown in an earlier publication [ 1 ] that the amorphous-crystalline transfor

mation o f thin silicon films depends upon time and temperature consistent with

t c = r exp(E0/kT) , (1)

where t c is the time to crystallize, r is proportional to an attempt period, and E 0 is

an activation energy. A heuristic derivation of eq. (1) based on a simple rate model
was given in the earlier paper. The purpose of this paper is to show that eq. (1) is
also applicable to the amorphous-crystalline transformation in Ge films. This infor-
mation is useful both for crystallizing the films at the lowest temperatures and in the
shortest times to minimize introduction of impurities, and for studying the tempera-
ture-dependent properties of amorphous films without crystallizing the samples.

2. Sample preparation and analysis

The samples were prepared by evaporation o f zone-refined (40 g2-cm) p-type

polycrystalline Ge from a joule-heated tungsten boat onto optically polished pure
fused silica substrates. The pressure in the vacuum chamber was less than 3 X 10 - 7
Torr during the deposition. The deposition rate was approximately 800 A/min. The
source-substrate distance was 15 cm at an evaporation angle o f near 90 °. The sub-

29
30 N.A. Blum, C Feldman / Crystallization o f a-Ge films

strate temperature varied from 23 to 38°C during the deposition. Film thicknesses
ranged between 2300 and 3300 A.
Following deposition, the samples were heated in a fused silica tube furnace
flowing with ultra-pure helium (<l ppm 02) which was further purified by flowing
through a heated (900°C) titanium inert gas purifier and then through a liquid-ni-
trogen cooled trap filled with zeolite. A prior investigation [2] indicated that this
technique may result in the introduction of fewer impurities than vacuum heating.
Samples which were analyzed by sputter-ion source mass spectrometry showed
that they consisted of nearly pure germanium (~200 ppm total impurities) through-
out most of their bulk, irrespective of their heating history. Some surface contami-
nation (mostly oxygen) was detected in two samples which were heated for over
20 hs.

3. Experimental

As samples transform from the amorphous to the crystalline state, the optical trans-
mission changes most rapidly in the wavelength range 0.60 ~< X < 0.75/am. In this
region of the spectrum, the optical absorption coefficients (a a and ac) are sufficiently
large that interference effects in the films may be neglected. The optimum wavelength
which was chosen for the measurements depends slightly upon sample thickness,
and is 0.70 p.rn for a sample about 3000 A thick. Optical transmission was measured
by scanning a double-beam recording spectrophotometer over the range of maximum
variation in transmission. The optical transmission of each sample was measured in
the as-deposited state and again after each heating cycle until the sample crystallized.
In general, further heating did not change the transmission within experimental error,
although a trend toward slightly more transparency was noticed for a few of the
samples. This slight increase in transmission may be attributed to the development
of small cracks, pinholes or possibly oxidation along the interstices exposed by the
cracks and pinholes. The optical transmission could not be monitored continuously
during the transformation because Ge becomes degenerate (i.e. opaque) at tempera-
tures necessary for crystallization.

4. Results

A plot of external optical transmission versus total heating time (for T = 438°C)
is shown in fig. 1 with a smooth curve drawn through the points. While the curve
in fig. 1 contains only a small number of data points, examination of approximately
25 such plots with different quantities and distributions of points indicate that the
transmission versus time curve has the general shape shown by the smooth curve.
The optical criterion for crystallization is that the sample transmission be halfway
between its amorphous and fully crystallized values. This criterion leads to a relati-
 N.A. Blum, C FeMman/Crystallization of a-Gefilms 31
1.25 5.0
I I I

"~ 1.00 - t , , ~ , .... -2 4.0

>

E 0.75 3.0 8
- 1/7 -
t~ ¢ I
o.5o 2.0 g

-- ,,,,.,I"
>o 0.25 1.0

5.0 10.0 15.0 20.0

Total Heating Time (hours)

Fig. 1. Transmission at X = 0.70 tzm (solid line), and fractional volume transformed (dashed line)
of a Ge film, 0.25/~m thick, as a function of heating time at T = 438°C.

vely precise determination of the crystallization time, since tile time interval over
which the transmission changes from near its minimum to near its maximum value
is small compared with the total time for which the sample has been heated at a
given temperature.
The fractional volume crystallized, Vc/V, may be expressed in terms of the mea-
sured optical transmission T and the known optical constants of the pure amor-
phous and crystalline phases as
Vc In [7'/(1 - R ) 2] + a a d
V d(ot a _ O~c) , (2)

where a a and a c are the absorption coefficients of the amorphous and crystalline
phases, respectively, R is the reflectivity of the air-grim interface, and d is the mea-
sured f'rim thickness. In deriving eq. (2) the following assumptions are made: (1) the ef-
fects of multiple reflections can be ignored; (2) the substrate has the same refrac-
tive index as air; (3) R has the same value for both the crystalline and amorphous
f'rims; (4) scattering within the film due to the difference in refractive indices be-
tween amorphous and crystalline regions can be neglected; and (5) the thickness
d does not change with the transformation. None of these assumptions is strictly
true; however, they lead to errors in Vc/V which are believed to be less than those
propagated by the measurement uncertainties in T and d. It is further assumed that
there are only two distinct a's in the transformation process; the crystalline regions
a c grow at the expense of the amorphous regions %. The transmissions shown in
fig. 1 were converted to Vc/V and plotted in the same figure. Comparison of the
two curves indicates that the transmission is especially sensitive to changes in Vc/V
near Vc/.V = 0.75, and insensitive for Vc,/V < 0.25. This is because of the exponen-
tial dependence of transmission upon the ct's with the absorption coefficient of
the amorphous phase being about double that of the crystalline phase.
The values of t c obtained from curves similar to fig. 1 for different heating tern-
32 N.A. glum, C. Feldman / Crystallization of a-Ge films

Temperature (oc)
525 500 475 450 425
50
I I [ I ~____~/
20

10.0 _ C

5.0
=o
v

2.0i
E
1.C

0.5

{J
0.2

0.1 /~" J. Amorphous --

0.05 ¢5/- I

0.02

0.01 I I I I I
1.25 1.30 1.35 1.40 1.45
103/T (o K - 1)

Fig. 2. Log o f the crystallization time versus reciprocal temperature for Ge films. The solid
line (solid circles with error bars) corresponds to the T c = (Txtal + Tamor)/2 criterion, and the
dashed line ( × 's without error bars) corresponds to the Vc/V = 0.5 criterion.

peratures are plotted in fig. 2 for both the optical criterion, T c = (Txtal + Tamor)/2,
and the volumetric criterion (Vc/V=0.5). These data were fit by straight lines on a
semilog plot, using a least-squares method which ignored the explicit probable errors
assigned to the individual measurements. The lines shown are parallel and fit eq. (1)
with E 0 = 2.96 eV. The intercept is r ~ 4 X 10 -17 s for the solid line (optical crite-
rion), and r ~ 2 X 10 -17 s for the dashed line (volumetric criterion).
Studies were performed to determine whether the number of times a sample was
heated and then cooled had any effect on the measurements of t c. There was a trend
in the data which indicated that frequent cycling had the effect of slightly decreasing
t c. A single heating cycle, for a period of time corresponding to t c obtained from a
series of shorter cycles, in most instances left the sample on the amorphous side of
the crystallinity criterion. However, effects of variations in film thickness, exact
34 N.A. Blum, C. Feldman /Crystallization o f a-Ge films

The isothermal transformation curves (fig. 1) contain inadequate data for a detailed
comparison with the kinetic theory of transformation; however, the curves have the
sigmoidal shape and general characteristics predicted by the theory [eq. (3)]. Insofar
as the optical measurements are concerned, as long as internal scattering is neglected,
the results are independent of whether the system contains amorphous and crystalline
macroscopic regions characterized by absorption coefficients cta and t~c, respectively,
or whether an intermediate "state" (degree of amorphicity) exists which is charac-
terized by an absorption coefficient a' such that a a < a' < ctc. There is general agree-
ment on the value of a c. The amorphous state absorption coefficient o~a would vary
depending upon the method and details of sample preparation.
Previous studies of the crystallization of amorphous Ge films have emphasized
the effects of substrate temperature during deposition [8-10], employed measure-
ment techniques which are predominantly surface sensitive [11,12], or used metal-
lic contacts for transport measurements [13]. The properties of amorphous films
are known to be very sensitive to the details of sample preparation: sample purity,
thickness, deposition conditions, and the substrate type and temperature during
deposition greatly affect the crystallization temperatures [8,11 ] and sharpness of
the optical absorption edge [9,10]. These properties of the films are also sensitive
to stress resulting from deposition conditions or differential expansion with respect
to the substrate [11 ]. The results reported here are consequently strictly valid only
for films prepared according to the method described. In comparing these results
with those of others, it is useful to note that the time to crystallize a film at a
given temperature may be, according to Paul et al., "an indication of the freedom
of the disordered film from large defects and impurities which act as nucleation
sites" [9]; volume crystallization has been reported to occur two to three orders
of magnitude more slowly than surface crystallization [9]; and crystallization has
been shown to occur at lower temperatures in regions of metal-amorphous semi-
conductor contact than in the absence of metal contact [14]. The measurements
reported here are relatively insensitive to surface crystallization, are unaffected by
possible electrode problems and tend to give transformation temperatures as high
or higher than have been reported by other techniques [8,9,11-13].

Acknowledgement

We are grateful to Dr. F.G. Satkiewicz for the mass spectra analysis of our samples
and are pleased to acknowledge the capable technical assistance of Messrs. K.G.
Hoggarth and E.W. Koldewey. The Applied Physics Laboratory is supported by the
Naval Sea Systems Command under contract no. N00017-72-4401.
 N.A. Blum, C. Feldman / Crystallization of a-Ge films 35

References

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[5] H. Letaw, Jr., W.M. Portnoy and L. Slifkin, Phys. Rev. 102 (1956) 636.
[6] G.D. Watkins and J.W. Corbett, Phys. Rev. 134 (1964) A 1359.
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