Jpn. J. Appl. Phys. Vol. 41 (2002) pp.

814819
Part 1, No. 2A, February 2002
#2002 The Japan Society of Applied Physics

Al-Doped ZnO Films Deposited by Reactive Magnetron Sputtering

in Mid-Frequency Mode with Dual Cathodes
Masato KON* , Pung Keun SONG, Yuzo SHIGESATO, Peter FRACH1 , Akio M IZUKAMI2 and Koichi SUZUKI3
College of Science and Engineering, Aoyama Gakuin University, 6-16-1 Chitosedai, Setagaya-ku, Tokyo 157-8572, Japan
1
Fraunhofer Institut Elektronenstrahl- und Plasmatechnik, Winterbergstrasse 28, D-01277 Dresden, Germany
2
Nissin-seiki Co., Ltd., 913-4 Wakamiya, Ibaraki-chyo, Ibaraki 311-3123, Japan
3
SurfTech Transnational Co., Ltd., Fujishiro Bldg. 3F, 4-30-4 Shinbashi, Minato-ku, Tokyo 105-0004, Japan
(Received August 30, 2001; accepted for publication October 29, 2001)

Aluminum-doped zinc oxide (AZO) lms were deposited on heated (300
C) glass substrates by reactive mid-frequency (mf,
50 kHz) magnetron sputtering using dual magnetron cathodes with aluminumzinc alloy targets. In order to keep the very high
deposition rate, reactive gas control using plasma emission was carried out to stabilize the discharge in the transition region
of the reactive sputtering system. The highest deposition rate for the transparent conductive AZO lms by this dual magnetron
sputtering (DMS) system was 290 nm/min, which was higher than that for the conventional reactive sputtering system by one
order of magnitude. The lowest resistivity of the AZO lm was 3:9  104  cm. The structure and electrical properties of the
lms could be controlled systematically by the reactive gas control system in the transition region.
[DOI: 10.1143/JJAP.41.814]
KEYWORDS: transparent conductive film, ZnO, AZO, dual cathodes, DMS, plasma emission, reactive sputtering, transition region

1.

reactive gas control via plasma emission. The structure and

the electrooptical properties of the lms were analyzed in
relation to various deposition parameters.

Introduction

Transparent conductive oxide (TCO) lms have been used

extensively in electrooptical devices, such as transparent
electrodes in at panel displays or solar cells. Al- or Gadoped zinc oxide (AZO or GZO) lms are n-type, highly
degenerated, wide-gap semiconductors which, due to the low
resistivity of 103 104  cm and the lower material cost
compared with that of In, are expected as TCO materials that
may replace indium tin oxide (ITO) lms. They also have
advantages in terms of chemical stability in the reductive
plasma containing H used for hydrogenated a-Si depositions. DC magnetron sputtering using oxide targets has been
commonly adopted to deposit TCO because of its advantages of large-area uniform depositions of high-quality lms
with high reproducibility. Recently, there have been strong
industrial demands for a much higher deposition rate with
stable arc-free discharge in order to realize lower deposition
cost. On the other hand, the reactive magnetron sputtering
process using a metal target should have high potential for
lower cost deposition with a very high deposition rate.
However, high-quality ZnO lms with very low resistivity
were dicult to deposit with high reproducibility because
the ZnO lms should be deposited in the transition region
where the deposition rate changes markedly with increasing
O2 ow rate depending on the target surface condition.1) For
the reproducible and stable deposition at a high rate in the
transition region, a reactive gas control loop using the
optical light emission of the plasma as the measured
parameter characterizing the reactivity of the discharge
should be highly suitable to control the deposition rate and
the reactive gas ow precisely in the transition region.26)
Furthermore, dual magnetron sputtering (DMS) with midfrequency (mf) bipolar pulsing7,8) is considered to guarantee
reactive sputtering without arcing and nodule growth during
long time depositions.
In this study, AZO lms were deposited on Corning 7059
glass substrates using the mf DMS system with a set of
aluminumzinc alloy targets (Al: 1.5 wt%) and the fast

2.

Experimental Details

The reactive mf sputter deposition of AZO lms was

carried out with a DMS system (SSE-1, Nissin-seiki) in
which two cathodes with ZnAl (Al: 1.5 wt%) alloy targets
were mounted and the plasma control units (PCU) were sited
for each cathode (DMS400; Fraunhofer Institut Elektronenstrahl- und Plasmatechnik). The schematic illustration of the
DMS system is shown in Fig. 1. The two planar targets were
400  130 mm2 in size and they were connected with a
bipolar mf pulse generator so that the targets alternately
acted as a cathode and an anode of the dc discharge. The mf
pulse has the approximate shape of a square wave with the
frequency of 50 kHz. The reactive gas of O2 (purity:
99.999%) was introduced through piezoelectric valves that
were controlled by the PCU feedback system to stabilize the
discharge in the transition region. In the PCU, the plasma
emission of the neutral oxygen atomic radical O line at
777 nm was led into a photomultiplier through optical lters
and the optical intensity was transformed into the photovoltage. The photovoltage was initially calibrated to the
value of 0.7 V that was measured during discharge in an Ar
plasma at the discharge power of 2000 W. The PCU adjusted

substrate holder

Plasma
control
unit

Plasma
control
unit

MFC
Ar

O2

E-mail address: kon@candy.chem.aoyama.ac.jp

bipolar
pulse unit

power
supply

O2

Fig. 1. Schematic of the reactive m.f. DMS system.

814

Jpn. J. Appl. Phys. Vol. 41 (2002) Pt. 1, No. 2A

M. KON et al.

Table I. Sputtering parameters in reactive m.f. magnetron sputtering of

AZO lms.
Targets
Targetsubstrate distance

ZnAl (Al: 1.5 wt%) 400  130 mm2

115 mm

Substrate material

Corning 7059 glass

Substrate temperature (Ts )

300
C or room temperature (RT)

Sputter gas

Ar

Reactive gas

O2

Total gas pressure

0.50 Pa (baratron gauge)

Background pressure

<7:5  104 Pa (BA gauge)

Excitation mode
Pre-pre-sputtering

m.f. (bipolar pulse, 50 kHz)

>5 min (2000 W)

Sputtering power

2800 W (constant)

the photovoltage to the setpoint value by operating the

piezoelectric valve to control oxygen ow precisely and
rapidly. The chamber was evacuated to a pressure of less
than 7:5  104 Pa. Ar was introduced through a mass ow
controller (MFC). The total gas pressure was always kept at
0.50 Pa automatically by varying the Ar ow by feedback
control using the pressure value from a baratron gauge. The
pre-pre sputtering was carried out only with Ar in order to
remove the oxide layer at the target surface and to adjust the
zero setpoint of 0.7 V for the plasma emission, followed
by the pre-sputtering with the same ow ratio of Ar and O2
and the same power as in the deposition conditions. Other
deposition parameters are listed in Table I.
The lm thickness was measured with a dektak3 surface
proler (Sloan Technology). The crystallinity of the lms
was analyzed by X-ray diraction (XRD; XRD-6000,
Shimadzu) using Cu K1 radiation. Resistivity (), carrier
density (n) and Hall mobility () were estimated by the fourpoint probe method and Hall-eect measurements in the van
der Pauw geometry (Bio-Rad, HL5500PC). Optical properties were analyzed by optical spectroscopy using UV-3100
(Shimadzu) for the lms deposited on the fused silica glass.
3.

Results

Oxygen flow ratio FO2 / (FO2 + FAr) (%)

Figure 2 shows the oxygen ow ratio at various plasma

70
65
60

815

emission (O line) intensities. The experiment was carried

out by varying the setpoint of the plasma emission intensity
at the PCU. At a small value of the oxygen gas ow ratio of
<48%, all the oxygen gas is consumed in the reaction with
the metal being sputtered from the target, known as a
gettering eect, and the emission intensity shows almost no
increase. At a higher setpoint value of the plasma emission
intensity, the oxygen ow ratio decreases because of
increasing oxide coverage of the target, resulting in a
reduced gettering eect. When the target surface is fully
oxidized, the amount of the gettering eect becomes almost
constant at a lower value, so that the emission intensity
increases with increasing oxygen ow ratio. The shape of
this curve for the ZnO system is similar to that shown for the
AlOx 9) and TiOx 10) systems. In this gure, each setpoint of
the plasma emission intensity has only one point of the
oxygen ow ratio, allowing a precise process stabilization
also in the unstable transition region. In contrast, the oxygen
ow ratio corresponds to three dierent values of the plasma
emission intensity in the transition region. Therefore, the
oxygen ow cannot be used to stabilize the process in this
region. The dependence of the cathode voltage, cathode
current and deposition rate on the oxygen ow ratio
FO2 =FAr FO2 is shown in Fig. 3. The cathode voltage is
decreased by increasing the oxygen ow ratio caused by
oxidation of the target surface and hence increasing the
secondary electron emission coecient which results in
decreasing the plasma impedance. Figure 4 shows the
dependence of cathode voltage, cathode current and
deposition rate on the plasma emission intensity. It can
clearly be observed that the cathode voltage and deposition
rate change monotonically with the O plasma emission
intensity. In reactive sputtering, it is necessary to control a
balance between the ux being sputtered from the target and
oxygen partial pressure by varying the oxygen ow rate in
the transition region, where oxygen partial pressure,
gettering eect, deposition rate, sputtering yield and the
condition of the target surface are subtly linked together.
This unstable region makes precise control dicult,
generally. However, in this experiment, the PCU successfully maintained O emission intensity constantly so that we
could control the deposition rate monotonically in the
transition region. However, O plasma emission intensity is
not always in relation to oxygen partial pressure. This is
because the emission intensity is dominated by several
parameters. IO , the emission intensity of neutral oxygen
atomic radicals O , that corresponds to the transition
between two excited states (i ! j) is given by

55

IO NO Pi Tij g;

50

where NO is the concentration of O atoms, Tij is the

probability that the electron will decay to state j, and g is
the collected fraction of emitted photons. The probability Pi
of exciting an atom to state i is given by
Z
1
1
Pi p p Ee NeEe dEe ;
2
2me
Ee

45
40

1
2
3
4
5
O (777 nm) emission intensity (V)

Fig. 2. Oxygen ow ratio FO2 =FAr FO2 dependence on optical

emission intensity of the neutral atomic oxygen radical line (777 nm)
during sputtering with PCU at the discharge power of 2800 W.

where is the excitation cross section, Ne , me and Ee are the

electron concentration, mass and kinetic energy, respectively.11) The values of Tij and g are constant for each
emission line. With this equation, the emission intensity is a

Jpn. J. Appl. Phys. Vol. 41 (2002) Pt. 1, No. 2A

M. KON et al.

450

500

400

450
Cathode voltage (V)

Cathode voltage (V)

816

350
300
250

300

(a)

10

10
Cathode current (A)

11

200
11

9
8
7
6
5
600

(b)

500

8
7

(b)
5
600

400
300
200
100

(c)
0
40

6
Ts = 300 C
Ts = RT

45

50

55

60

65

70

Oxygen flow ratio FO2 / (FO2 + FAr) (%)

Deposition rate (nm/min)

Cathode current (A)

350

250

(a)
200
12

Deposition rate (nm/min)

400

400

function of not only the concentration of O atoms but also

the concentration of electrons. The lower deposition rate in
the region of low emission intensity (Fig. 4) on a heated
substrate at a temperature of 300
C is explained by the high
vapor pressure of Zn at such a high temperature, which gives
rise to partial re-evaporation of the metal atoms.12) At larger
oxygen ux, the formation of oxide improved and thereby
the probability of re-evaporation decreased. Further increasing the oxygen leads to a decrease of the deposition rate
caused by the increasing oxidation of the target surface due
to the rising oxygen portion in the sputtering atmosphere and
the lower sputtering yield of zinc oxide compared to zinc.
The dependences of the resistivity, Hall mobility and
carrier density on optical emission intensity are displayed in
Figs. 5(a)5(c), respectively. The lm which had the

(1.7)
(1.6)

300
200
100
0

Fig. 3. Dependence of cathode voltage (a), cathode current (b), and

deposition rate (c) on the oxygen ow ratio FO2 =FAr FO2 during
sputtering at discharge power of 2800 W controlling oxygen ow rate
with PCU.  and 4 in (c) indicate the substrate temperature of 300
C and
RT during sputtering, respectively.

Ts = 300 C
Ts = RT

500

(c)
0

1
2
3
4
5
O (777nm) emission intensity (V)

Fig. 4. Dependence of cathode voltage (a), cathode current (b), and

deposition rate (c) on the emission intensity during sputtering at discharge
power of 2800 W controlling oxygen ow rate with PCU. The arrow
labeled (1.6) indicates the transition from opaque to transparent layers,
and the arrow labeled (1.7) indicates the lm with the lowest resistivity of
3:9  104  cm. Labels correspond to the values of each emission
intensity during sputtering.  and 4 in (c) indicate the substrate
temperature of 300
C and RT during sputtering, respectively.

smallest resistivity of 3:9  104  cm [marked (1.7) in

Fig. 5] was obtained at an optimum emission intensity
corresponding to a larger deposition rate of 290 nm/min. The
decrease in resistivity was due to an increase in both carrier
density and Hall mobility.
Figure 6 shows transmittance and reectance of AZO
lms deposited at a substrate temperature of 300
C. Each
lm had high transmittance of over 90%. The transmittance
decreased in the region of long wavelength, where
reectance increased. This behavior is due to a reection

M. KON et al.

100

100

100

80

80

Resistivity (

cm)

Transmittance (%)

101

10-1
10-2
(1.7)

10-3

(a)

Ts = 300 C
Ts = RT

Hall mobility (cm2 / V s)

60

60
(1.7)
(2.2)
(3.0)

40

20

500

1000

1500

2000

2500

Wavelength (nm)

Ts = 300 C
Ts = RT

25

40

20
0

10-4
30

Fig. 6. Transmittance and reectance of lms deposited at substrate

temperature of 300
C under the emission intensity of 1.7, 2.2, 3.0 V (Film
thickness are 290, 271, 229 nm, respectively).

20
15
10
5

(b)

0
1021

Ts = 300 C
Ts = RT
Carrier density (cm-3)

817

Reflectance (%)

Jpn. J. Appl. Phys. Vol. 41 (2002) Pt. 1, No. 2A

1020

1019

(c)
1018

3
2
1.5
2.5
3.5
O (777nm) emission intensity (V)

Fig. 5. Dependence of (a) resistivity, (b) Hall mobility and (c) carrier
density on O (777 nm) emission intensity.  and 4 in (c) indicate the
substrate temperature of 300
C and RT during sputtering, respectively.

of the electromagnetic wave by the plasma oscillation of

conduction electrons, which is well known in degenerated
TCO lms with high carrier density.
XRD patterns of transparent lms deposited at a substrate
temperature of 300
C showed only one strong peak near
2 34:5
, attributed to the (002) line of the hexagonal ZnO
phase zincite [Fig. 7(a)]. The lm indicated as (1.8) in Fig.
7(a) had the largest crystallite sizes (77 nm) calculated from
the full-width at half maximum (FWHM) of the (002) XRDReex 2 according to the Scherrer formula. A (002)
peak location of high conductivity lms shifted toward a
large 2 value compared with randomly oriented ZnO
powder (JCPDS data 36-1451). Since the ionic radius of
Al3 (0.053 nm) is smaller than that of Zn2 (0.072 nm), the
length of the c-axis might become shorter. Park et al.13)

reported that the (002) peak location of XRD patterns of

AZO lms deposited by rf magnetron sputtering using an Aldoped ZnO target was shifted toward a larger 2 value from
that of pure ZnO lm with increasing Al content of target.
Therefore, these results could be explained in terms of the
substitutional replacements of Al atoms into Zn lattice sites.
On the other hand, the shift of the peak position of the (002)
plane toward a smaller 2 value is observed with the increase
in the optical emission intensity, accompanying the decrease
in the intensity and broadening of the peak. The decrease of
the intensity and broadening could be due to various
crystallite sizes, and the peak shift could be due to internal
strain in the lms.14) Ellmer et al.15,16) reported this variation
and explained that at higher and lower oxygen concentrations in sputtering atmosphere, alumina (Al2 O3 ) was formed,
which segregated as a separate phase introducing compressive strain in the lm. Figure 7(b) displays the (002)diraction peaks of lms deposited under dierent optical
emission intensities at the substrate temperature of RT. In
this gure, peak intensities and crystallite sizes decreased
compared with lms those of deposited at 300
C.
4.

Discussion

In AZO lms, carrier density is known to be dominated by

three kinds of donor sites: oxygen vacancies, interstitial Zn
atoms and substitutional trivalent Al atoms. The carrier
density on O plasma emission intensity exhibited a
maximum as observed in Fig. 5. The cause of scattering of
carriers which dominates the mobility is mainly charged
impurity scattering, neutral impurity scattering, grain
boundary scattering, lattice vibration scattering and dislocation scattering. Figure 8 shows the electrical properties of
AZO lms deposited at the substrate temperature of 300
C,
as a function of the measured temperature from 100 to
290 K. As shown in this gure, the mobility is not in relation
to temperature so that lattice vibration scattering and
dislocation scattering might be unimportant. From another
viewpoint, for good quality lms with high carrier densities,
the mean free path of free electrons was calculated using a
highly degenerated electron gas model17)

818

Jpn. J. Appl. Phys. Vol. 41 (2002) Pt. 1, No. 2A

M. KON et al.

30

( 10-4

(1.7) (1.6)

10
9
8
7
6
5
4

(2.2)
(1.7)

Hall mobility

(2.1)

20
15
(3.5)

10

(3.0)

(cm2 / V s)

(2.2)

25

30
20

(b)
Ts = RT

(1.9)
(2.1)

7
6

7
6
5
4

0
9

/cm3)

(5.0)

Carrier density

Intensity ( 104 counts)

35

Intensity ( 104 counts)

(1.8)

(a)
Ts = 300 C

40

Resistivity

45

cm)

JCPDS 36-1451

3
2

10

12

Temperature 103/T (K-1)

4
3
2

Fig. 8. Eect on measurement temperature on resistivity, Hall mobility,

and carrier density of AZO lms deposited at substrate temperature of
300
C.

(1.8)

(3.0)
(3.5)

(1.7)

1
34

34.2

34.4

34.6

34.8

35

2 (deg)
Fig. 7. XRD patterns of AZO lms prepared by m.f. sputtering at the
substrate temperature of (a) 300
C and (b) RT. The perpendicular line
shows the position of a ZnO-powder diraction (JCPDS number: 361451). The lm thickness were from (1.6) to (5.0): 246, 290, 307, 309,
271, 229, 175, 118 nm in (a), from (1.7) to (3.5): 253, 352, 287, 290, 319,
356 nm in (b). Labels correspond to the values of each emission intensity
during sputtering.

p
h 3 32 n
VF
m
lmfp

p
h 3 32
p ;
VF
e 2  3 n2

106
Absorption coefficient (cm-1)

105

104

(1.7)
(2.2)
(3.0)

103

102

3.5

4.5

Energy (eV)

where VF is the electron velocity at the Fermi surface, and

is the relaxation time, yielding the value of 1.5 nm which is
smaller than the average grain size estimated previously.
Therefore, the grain boundary scattering could be unimportant for lms with higher carrier density. At very low O
plasma emission intensity, the carrier density was lower,
which could be caused by bad crystallinity. On the other
hand, in the region of high O plasma emission intensity, the
carrier density was also lower, which could be due to a
decrease of oxygen vacancies. Further increase in the optical
emission intensity resulted in a further decrease in carrier
density, which could be caused by bad crystallinity (Fig. 7).
Figure 9 shows a logarithmic plot of the dependence of
absorption coecient on photon energy. Absorption edges
are almost vertical so that there would be almost no
interaction between photons and excitons in the compara-

Fig. 9. Logarithmic plot of the absorption coecient versus photon

energy near the bandgap for the AZO lms deposited at substrate
temperature of 300
C. Labels correspond to the values of each emission
intensity during sputtering.

tively narrow region of emission intensity, indicating that the

degree of short-range order of crystallinity could be high. A
plot of absorption coecient squared versus photon energy
is displayed in Fig. 10. When carrier density increased, an
optical energy band gap also increased. This is caused by a
shift of the Fermi level, the so-called BursteinMoss
eect,1820) which is a feature of a degenerate semiconductor.
In this way, the carrier density and Hall mobility hence
the resistivity change systematically with O plasma
emission intensity as shown in Fig. 5. The increase in O
plasma emission intensity does not always strengthen the

Absorption coefficient 2 ( 1010/cm2)

Jpn. J. Appl. Phys. Vol. 41 (2002) Pt. 1, No. 2A

M. KON et al.

result could be explained in terms of the substitutional

replacements of Al atoms into Zn lattice sites. Signicantly
increasing O plasma emission intensity resulted in lms
with bad crystallinity and with high resistivity. Therefore, it
is important to control the oxygen concentration in the
sputtering atmosphere in the transition region to achieve
high-quality transparent conductive AZO lms by reactive
sputtering.

3
2.5
2
1.5
1

Acknowledgements

(1.7)
(2.2)
(3.0)

0.5
0

3.5

4
Energy (eV)

4.5

This research was partially supported by the Science Fund

of Japan Private School Promotion Foundation.
5

Fig. 10. Absorption coecient squared versus photon energy for the
samples deposited at substrate temperature of 300
C. Labels correspond
to the values of each emission intensity during sputtering.

degree of the oxidation of lms within the transition region

as mentioned in 3, however, oxygen partial pressure might
rise with increase in O plasma emission intensity, as
indicated by the systematic changes of these electrical
properties, and assuming that oxygen is being introduced
into the deposited lms systematically.
5.

819

Conclusions

Transparent conductive AZO lms with the transparency

of over 90% were deposited by mf reactive magnetron
sputtering of ZnAl alloy targets at a deposition rate of
290 nm/min. Stable deposition was carried out in the
transition region, where the deposition rate changes rapidly
with reactive gas ow ratio, using PCU to control the oxygen
ow rate by a control loop using the emission intensity of
neutral atomic oxygen radicals. The lm with the resistivity
of 3:9  104  cm, the carrier density of 6:34  1020 /cm3
and the Hall mobility of 23.5 cm2 /(Vs) was obtained at a
substrate temperature of 300
C. Ionized scattering centers
and neutral scattering centers are important to the scattering
system for the lms with high carrier density. These lms
had a small lattice constant measured by XRD compared
with powdered ZnO having random orientation, caused by
the small ionic radius of Al3 compared with Zn2 . This

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