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Optical characterisation of gold using surface plasmon-polaritons

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1987 J. Phys. F: Met. Phys. 17 277
(http://iopscience.iop.org/0305-4608/17/1/031)
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J. Phys. F: Met. Phys. 17 (1987) 2 7 7 - 2 8 7 . Printed in the U K

Optical characterisation of gold using surface

plasmon-polaritons
R A Innes and J R Sambles
Department of Physics. University of Exeter. Exeter. Devon. UK
Received 24 March 1986
Abstract. Measurements are presented of the optical constants of a thin gold film over
primarily the visible region of the spectrum using the surface plasmon-polariton resonance
condition in the attenuated total-reflection configuration. Using this technique precise results
are obtained and these are compared with those found using other experimental methods and
also with the classical free-electron model.

1. Introduction

A surface plasmon-polariton (SPP) is a coupled electromagnetic field-charge density

oscillation that may occur at the boundary of a dielectric (ed > 0) and a material, usually a
metal or semiconductor, for which the dielectric constant ( E = E , + iei) has E , < 0. The
momentum of the localised (non-radiative) surface mode is always greater than that of an
electromagnetic wave in the dielectric, as is illustrated by the dispersion curve of figure 1.
Thus it is impossible to couple radiation directly into the SPP from the dielectric unless the
translational symmetry of the surface is broken by either roughness or a grating on the
surface. In effect there is then a Fourier component of the surface profile that will provide
the missing momentum and allow direct excitation of the SPP. However, rough or
corrugated surfaces are not readily modelled theoretically, particularly as they may have
substantially modified SPP dispersion curves. A far simpler method for coupling to the SPP
while leaving the surface flat uses attenuated total reflection (ATR). There are two possible
sample arrangements due to Otto (1 968) and Kretschmann and Raether (1968) basically
achieving the same result as a metal/dielectric interface being placed at a suitable distance
from a prism within which a light beam is being totally internally reflected. The totally
reflected beam evanescently decays away from the surface of the prism, while along the
surface it has a momentum that is enhanced by the refractive index of the prism. Such a
radiation field can now match both in energy and momentum to the SPP at a
metal/dielectric interface placed close to the prism surface.
In the experiments reported we have chosen to use the very convenient Kretschmann
geometry as illustrated in figure 2, which consists of a thin metal film evaporated onto one
face of a glass prism of refractive index n. Since surface charges are related to a
discontinuity in the normal component of E then it is clear that only p-polarised radiation
( E in the plane of incidence) may couple to the SPP. For such a p-polarised beam incident
with wave-vector of magnitude k at an angle Bi, which is greater than the critical angle,
0305-4608/87/010277 + 11%02.50

0 1987 IOP Publishing

Ltd

277

218

R A Innes and J R Sambles

/Light line

Figure 1. The two-media, single-interface dispersion curve for

momentum mismatch.

SPPS

showing the energy-

there is an evanescent wave decaying away from the prism face, which has a real wavevector of magnitude k, along the interface given by

k, = nk sin Oi.
The SPP has a complex wave-vector and hence the incident radiation cannot match
perfectly to it. However, at a particular angle of incidence, Ospp, k , will equal the real part
of the SPP wave-vector, which gives very strong coupling to the surface mode. Since the
SPP decays due to resistive losses in the metal (Joule heating) the momentum matching
condition is accompanied by a strong absorption of the incident radiation. This condition,
the SPP resonance absorption condition, is readily determined experimentally by observing
the reflectance of the p-polarised beam as the angle Oiis progressively increased beyond the
critical angle.
With careful sample preparation and a suitable choice of sample thickness almost
100% of the incident radiation may be absorbed into the metal. Typically the metal film is
a few tens of nanometres thick for coupling at room temperature. Such a simple layer
system is readily modelled using Fresnel's equations and experimental p-polarised

I \

1,

! '
SPP

on this intwfoce

Figure 2. The Kretschmann configuration.

Characterisation of gold using surface plasmons

279

reflectance data may be least-squares fitted to theory to yield values for E , , ci and d, the
metal film thickness. The only assumptions in the theory are that firstly the incident
radiation field is much greater in lateral extent than the propagation length of the SPP
(which is readily achieved for wavelengths less than 10 p m since propagation lengths are
typically micrometres) and that secondly the system is planar. This second assumption is
readily checked experimentally by monitoring the very low level of roughness-coupled reradiation emanating from the metal/dielectric (air) interface. A further check on the
theoretical modelling of the system is obtained by monitoring the apparent sample
thickness as a function of incident wavelength. This thickness must remain constant (to
within the precision of determination) over the whole range of A-values studied. Care with
sample production readily produces films that satisfy these constraints. However it must be
appreciated that while this technique then allows for precise determination of E for the
metal under study, the E will be sample-specific, varying from sample to sample as grainboundary, defect and surface scattering varies from sample to sample. Nevertheless it is a
simple and useful method for determining these important parameters for thin films.

2. Review of previous work on the optical constants of gold

The optical constants of gold have been measured by various reflectance and transmission
methods on samples of a variety of forms and thicknesses (see, e.g., Schulz 1954a, Schulz
and Tangherlini 1954, Hodgson 1968). Probably the most often quoted study is that of
Johnson and Christy (1972) who measured the optical constants for the noble metals in the
spectral range 0.5-6.5 eV. It also presents a brief review of the advantages and
disadvantages of some of the experimental techniques.
Surprisingly, while a substantial amount of work has been done on the optical
characterisation of silver films using the SPP resonance technique (Otto 1968,
Kretschmann and Raether 1968, Gugger et a1 1984) little work has been done on gold
using this method. Weber and McCarthy (1975) monitored the re-radiated light from the
SPP as a function of angle but for only two wavelengths. Barker (1973) performed a set of
measurements of the reflected intensity as a function of angle in the energy range
1.8-3 eV, but this work was not intended to be an accurate determination of the
optical constants of gold, rather a demonstration of the technique. Lopez-Rios and Vuye
(1977) present some interesting results for gold overlayers on silver using the ATR
technique. However these are very thin films which, with the additional possibility of
alloying with the silver, cannot be expected to have, and indeed do not have, the dielectric
constants of pure, bulk gold.
Probably the most thorough study using thin gold films is presented by Theye (1970).
In this case however the ATR technique was not employed. Nevertheless these are very
important results obtained for a range of films and over wavelengths extending from
200 nm to 2 pm. At the higher wavelengths the author finds very good agreement between
the simple free-electron model and the results. However there is substantial variation
between samples, depending upon the degree of annealing as well as the thickness of the
film. All the films studied by Theye were very thin (because of the use of transmission
measurements) being nowhere greater than 21 nm thick. Hence the electron scattering is
dominated by a mixture of grain-boundary and surface scattering-this of necessity varies
from sample to sample and is the primary cause of the variability of her results.
The most likely reason for this lack of data on SPP resonance on gold is that because of
the d-band electrons the SPP resonance becomes a very broad feature in the blue/green part

280

R A Innes and J R Sanibles

of the spectrum. Hence there is then a need for large-angle scans (experimentally difficult)
and careful detection of the very flat resonance curve. Given the availability of a system
that satisfies these latter constraints the SPP resonance technique provides a simple, quick
and accurate method for the determination of E , and for gold films from the ultraviolet to
the near infrared. Beyond this top wavelength, special sources and detectors need to be
used, while at the other end of the spectral range the very strong absorption eventually
prohibits the obtaining of high-quality data.

3. Experimental details
Thin gold films (around 45 nm) were produced by rapid evaporation (around 60 nm min-')
in a vacuum of
Pa onto one face of a high-index prism ( n r 1.8 at 632.8 nm). This fast
evaporation rate yields smooth (root mean square roughness less than a nanometre),
continuous, polycrystalline films with very small grain size (about 25 nm). These goldcoated prisms are then mounted on a stepper-motor-driven spectrometer table in the
apparatus shown schematically in figure 3. The primary source of radiation is a 150 W
tungsten filament which is used as the source for a single-grating monochromator (ruled
for A = 500 nm) with slits set to give a spectral width of 2 nm. A secondary source, used
primarily to align and calibrate the system, was a 10 mW HeNe laser beam which could be
substituted for the weak beam emanating from the monochromator. The chosen beam is
split into two beams of approximately equal intensity which are then separately polarised
at 90" to each other, producing both a p- and an s-polarised beam (polarised perpendicular
to the plane of incidence). These beams were then mechanically chopped at independent
frequencies. recombined and directed onto the same region of the sample.
From figure 3 it can be seen that the prism is placed in a retro-reflector arrangement
which allows a large-angle scan without motion of the reflected beam over the face of the
detector-thereby
avoiding any 'detector functions'. Nevertheless we monitored the s
reflectance as a check on possible small changes in the detector sensitivity. Phase-sensitive
detectors were used to monitor the signal obtained from the 'reference' and the 'signal'
photomultipliers. This procedure allowed for simultaneous monitoring of the p and s

Figure 3. The experimental apparatus. AD: analogue4gital converters; Au: gold film; BS:
beam-splitter: c: mechanical chopper: M C : microcomputer; M: monochromator; P: p
polariser; S : s polariser: PM: parabolic mirror; PMTI: 'signal' photomultiplier; P M T ~ :
'reference' photomultiplier: PSDs: phase-sensitive detectors; ST: spectrometer table.

Charocrerisarioti oj'gold

risitig

28 1

siirface plastmws

reflectance from the same region of the sample. At each wavelength the reflected intensit!,
was monitored as a function of the angle of incidence. Also at each wavelength the
refractive index of the prism was accurately determined by carefully measuring the critical
angle. With the obtained value of the prism index the reflectance data were first corrected
for the reflections at the entrance and exit faces of the prism and a least-squares fit to
theory was performed on the corrected data.

4. Results

Typical data. corrected for reflections at the prism faces, are shown in figure 4. The full
curves are theoretical fits. which are in excellent agreement with the data. All the values
obtained for c,. and d are given in table 1.
In the middle of the spectral range studied there is an excellent signal-to-noise ratio.
However at either end of the range this rapidly degrades. In particular at the upper
wavelength end the least-squares fitting procedure was constrained to fit only E , and E , . the
thickness d being held constant to that value found for E. < 7 2 5 nm. Even then the E-values
for iabove 7 5 0 n m are substantially less precise than those for the remainder of the
spectral range.
Figures 5(a) and 5(b) illustrate the behaviour of E , and E , as functions of ~ a v e l e n g t h .
On the same graphs we have plotted other authors' data for comparison. It is clear that the
Table 1. Experimentally determined balues of the real and imaginar). parts. E , and E , , of the
dielectric constant of gold at various wavelengths using the surface plasmon-polariton
technique.
W a \ elength
(nm)

400
413
425
437
450
475
5 00
525
550
575
600
632.8
650
675
687
700
712
725
737
750
762
715
787
800

6&,

t, I

0.3
0.2
0.53
--0.56
-- 0.78
1.16
2.30
-

~~

~~

~~

--4.14
- 6.02

1.72
9.50
11.84
-- 12.91
--- 14.78
-- 15.97
- 16.78
- 17.67
- - 18.44
19.7
20.6
--21.3
- 22.6
-- 23.5
24.8
--

~~

~~

~~

I
f0.1
0.05
10.02
i 0.02
10.02
2 0.02
i 0.02
0.02
i 0.02
t 0.02
e 0 02
f 0.02
i 0.02
f 0.02
t 0.02
+ 0.05
i 0.05

6.5
6.7
6.18
6.168
5.716
4.872
3.448
2.523
2.029
1.618
1.624
1.358
1.346
1.322
1.375
1.317
1.435
1.337

rO.l

1.51
I .57

ZO

t 0.3

t 0.5
i 0.5

0.5
2 0.5

6E,

E,

1.5
1.7
1.6
2.0

io.1
10.1
iO.01
i 0.005

iO.005
kO.005
r0.005
k0.005
t 0.005
i 0.005
f 0.005
r0.005
f0.005
c0.005

r0.005
i 0.005
i

0.01

kO.01
i 0.10

i0.15
0.2
i 0.2
0.2
0.2

*
*
*

Thickness. d
(nm)
45.6
45.2
45.6
45.3
45.5
45.3
45.0
45.1
45.4

44.5
45.7
45.6
45.9
45.9
44.9
45.4
45.1
45.7

45.3
45.3
45.3
45.3
45.3
45.3

6d
io4
i0 . 3
_L

0.2

20.1
0.1

i0.1
io.l
f0.I
io.l
rO.1

i0.I
rO.l
*O.l
*O.l
io.1
io.1
io.1
i 0. I

282

ce

R A ltines and J R Sambles

1;

31 8

L6 4
L6.4

4 6
AAng
ng.e

deg

Figure 4. Tlpical data at three wavelengths: (A) 425. (B) 550 and (C) 700 nm. Curves:
theoretical results. Crosses: experimental data.

general trends in all the sets of data are the same although there is variation beyond
individual error estimates due to the variation in sample type.

5. Discussion

I t is clear that there is excellent agreement between the experimental data and the threeparameter theoretical fits. From such fits the values obtained for E may be found and
compared with the free-electron model of metals. Recently Gugger el a1 (1984) have
performed a similar series of experiments on silver films for which they found close
agreement with the free-electron model. They found that the dielectric function of thin
silver films for frequencies below the inter-band absorption edge may be described by the
relationships
t, 2 Epr

o;/wz

E , =(E

-&,)/Or

where c , is the core polarisability and inter-band contribution to the DC dielectric

constant. wp is the plasma frequency (U;= ne2/cotn*,where n is the electron density and
m* the effective mass) and r is the electron relaxation time. For the noble metals the
scattering rate has the form

I/r= i/ro + p o 2 .
Theye found this dependence for gold with both ro, the DC relaxation time, and p
varying from sample to sample. We have tested the above relationship for our data. A plot
of - E , against i2,
which should in theory give a straight line of gradient ( w ~ / ~ xand
G )an
~

283

Characterisation of gold using surface plasmons

30

7'

6-

$1

..

0"

-E,

zc

.J

* 0'
L
10
3

tv
7

500

900

700

A 1nm1

Figure 5 . ( U ) The real part of the dielectric constant. E , . as a function of wavelength: 0 :this
work: 3: Schulz (19548) and Schuiz and Tangherlini (1954); V: Johnson and Christy (1972).
f h ) The imaginary part of the dielectric constant. E , , as a function of wavelength. The
sq"bo1s are as for ( a ) .

intercept of - E , , is shown in figure 6. As is to be expected the straight-line relationship is

only found for wavelengths greater than about 700 nm since this is sufficiently far from the
absorption edge for the theory to be valid. A least-squares straight-line fit in this region
yields a value for wp of (1.36 i 0.05) x 10l6rad s - ' . Naively treating gold as a freeelectron metal with one electron per gold atom in the conduction band and a cube spacing
of 0.408 nm we thus find

m* = 1.01 ri: 0.07me

where me is the free-electron mass. (This is in fact the effective mass of the s electrons. The
deviation from linearity in figure 6 at higher energies is due to excitation of d-band
electrons.) In table 2 we show this result together with other values from experiments both
on thin films and bulk gold taken from Theye. We see favourable comparison between our
determination and that of the other studies, the mean value being 1.01 0.05me. The
spread in results can largely be attributed to two effects. Firstly the crystalline order in the
gold films has an effect through the influence of the effective screening electrons. Those
electrons moving most nearly parallel to the surface are most effective at matching the
radiation and thus single-crystal gold surfaces of the (100) type may be different to
the ( 1 IO) type simply because of the influence of the necks on the Fermi surface of gold
in the ( 1 1 1 ) directions changing the concentration of effective electrons with crystal
orientation. Also d-band electrons should really be taken into account and this will give

284

R A Irrnes arid J R Sambles

25

-E-

151

..

I
2l

Figure 6. - E , as a function of i2
where ,iis the incident wavelength. Note the linear
relationship above i.= 700 nm.

directionally dependent effects. Thus we may anticipate that different effective masses
will be determined for different orientations of single-crystal surfaces. Therefore highly
polycrystalline gold, such as our sample, will show an average value from all surfaces,
while well annealed films which may well be dominated by (1 1 1 ) surfaces will have a
different apparent effective mass. Secondly the roughness of the film surface will have
some effect since a very rough surface will behave more like a cermet and thus cannot be
expected to give results in accord with smooth films. Well annealed, or electropolished,
Table 2. Values of the effective optical mass of electrons obtained from reflectance and
transmittance measurements on samples of various types.

Sample type
Polycrystalline thin film
Thick (opaque), annealed film
Thick (opaque), annealed film
Electropohshed bulk
Electropolished bulk
Thick (opaque), annealed film
interface)
Thick (opaque), annealed film
interface)
Various thin films

(free surface)
(free surface)

m*

Reference

1.01
I .03
1.06
1.04
1.06

This work
Hodgson (1968)
Motulevich and Shubin (1964)
Cooper ei a1 (1 965)
Beaglehole (1966)

0.98

Schulz(1954b)

0.96
0.94

Hodgson (1968)
Theye ( I 970)

(film/substrate
(film/substrate

Characterisation of gold using surface plasmons

285

samples often tend to be macroscopically rough and thus are not necessarily expected to
agree well with our data. In some senses it is surprising how close the values of m* are.
This agreement in the long-wavelength region is pleasing, and as can be seen from figure
5(a) there is close agreement between all our values of E , and other tabulations down to
500 nm. Below this wavelength substantial differences appear as the absorption edge is
approached, and as yet we can find no satisfactory explanation for this behaviour.
Turning to the imaginary part of the dielectric constant, we have seen that for noble
metals a straight line is expected for I/r against m 2 , where I / r is obtained from
Ilr=WE,/(c,

-cr)

and E , is obtained from figure 6. Once more this is true for wavelengths above about
700 nm. Such a plot is shown in figure 7 and a straight line may be fitted to the highly
scattered data above 700 nm to give an intercept a t zero frequency of I/ro = (1.1 i 0.2) x

ioi4

As a check on this simple free-electron model we also measured the DC electrical

resistivity of the gold film using the Van der Pauw (1958) method. This gave p =
45 + 1 nR m at 294 K which is. as expected, significantly enhanced over the bulk value of
24 nQ m. There are two major contributions to this enhancement, namely surface and
grain-boundary scattering. We may estimate the magnitude of these two scattering
processes.
We would anticipate the grain-boundary-enhanced resistivity to be (Mayadas et ai
1969. Sambles et ai 1982)

where p , is the bulk resistivity. A, the bulk mean free path, d, the grain size and R, the
grain-boundary reflection coefficient. With d, equal to about 25 nm, R , probably close
to 0. I 5 and a p x i , value of 0.96 fR m 2 (Sambles et a1 1982) (1, r 4 0 nm), then
pg = 4 2 nQ m, or Ap, = 18 nn m, where Ap, is the grain-boundary scattering contribution to the film resistivity.
For surface scattering alone, we may use the formula of Fuchs (1938) which, although
not really valid in this limit of i 1d, may be used to give an estimate for the surface term:
P,=P,[1

+d&ld)(l -P)l

where d is the film thickness and p the Fuchs specularity. F o r polycrystalline gold p is of

Figure 7. The experimentally derived electron scattering rate as a function of w 2 where w

the incident angular frequency for wavelengths 700-800 nm.

IS

286

R A Innes and J R Sumbles

order 0.75 (Sambles el a1 1982) (Theye also conlcuded that ~ 2 0 . 5 6and close to unity)
giving pI = 29.5 nR m, or Ap, = 5 . 5 nR m, where Ap, is the surface scattering contribution
to the film resistivity.
Thus we see from these simple estimates that grain-boundary scattering is likely to
dominate the resistivity and, since this will strongly influence the DC resistivity scattering
and the AC scattering in the same way (unlike surface scattering), we may expect close
agreement between our deduced value of 70 and the 7DC we are able to deduce from the
resistivity. We have for the DC resistivity p = m*/ne2rDc= 45 n R m giving T D C -- 1.35 x
s. Nevertheless the
s which agrees quite well with a value of r0 of (0.9 i 0. I ) x
ratio of 1.5 i 0.1 is sufficiently far from unity to be worthy of comment. Theye obtained an
almost identical ratio as shown from figure 7 of that study which suggests that the
difference in the two scattering rates is significant.
A probable explanation for this difference rests with the energy of the electrons that are
being scattered. For the DC resistivity the conduction electrons have energies close to the
Fermi energy with wavelengths close to the Fermi wavelength (about 0.52 nm) while for
the plasmon excitation the electrons have energies substantially above the Fermi energy,
with much shorter wavelengths, This change in energy and reduction in wavelength will
mean an increased rate of scattering from the surfaces. Soffer's theory (Soffer 1967) tells
us that the effective specularity for electrons incident at angle 0 to the surface varies a s

where h is the root mean square surface roughness and l e is the electron wavelength.
Sambles and Preist (1982) have recently shown how this expression may be used to
produce a similar equation to that of Fuchs of the form

where r = 4 n h / I b , . This approximate expression is strictly only valid for

p d ; however,
we may use it as a simple test of the above conjecture that it is the wavelength dependence
of surface scattering, through 4, that changes the scattering for the SPPS. For the Fermi
electrons in gold, { may be typically two (with an h of order 0.08 nm) giving p ss 30 nC2 m.
If we now increase the energy of the electrons from 5.5 eV (the Fermi energy) to an energy
of 7 eV, then in a free-electron picture with At varying as 1/E"2, we see increases from 2
to 2.26 and hence ps increases to 36 nC2 m-a doubling of the surface contribution. In
reality, since I , is of the order of d, more exact expressions need to be employed which
yield a greater enhancement of the surface scattering contribution. One further point to
note is that even this naive treatment gives an energy-dependent 7 in the Drude model for
E , , which is not contained within the approximations used and which will slightly modify
the form of the frequency dependence of The way in which this will occur depends upon
how significant surface scattering is in comparison with bulk scattering in the particular
sample under study. It would be expected that thinner samples should show even greater
disparity between rDC and ro extrapolated from optical studies.
Thus we conclude that the SPP resonance technique may be used as an accurate and
simple method for the determination of the optical constants of gold. The values obtained
for E over the visible region of the spectrum agree well with results obtained by other
techniques and conform closely to a free-electron theory for wavelengths above 700 nm.
The value of the discrepancy between the extrapolated DC scattering rate and that
measured directly at DC agrees with other values and implies significant differences

<

Cha ru crerisu r iorr oj' gold u s itig sU t:fu ce plus motis

287

between the influence of surface scattering upon DC and optical frequency resistivities. A
detailed theoretical model for this difference would be welcome. That, together with
experimental work examining the influence of systematic variations in film structure. may
well provide an explanation for this interesting discrepancy.
References
Barker A S 1973 P/i,vr. H w H 8 5418 26
f h i , , . Soc. 87 4 6 I
Heaglehole D 1966 P~YJC.
Cooper I3 R, Ehrenreich H and Philipp tl K 1965 / ' / I \ . < . H e t , . I38 A4Y4
Fuchs K 1 Y 3 H Proc. Ctrmh. Phil. Soc. 34 100-R
Guggrr t i , Jurich M and Swalen J D 1984 Phj8.s. H e r , . H 30 4lXY-YS
H O d g S O n J I968 J . /J/I,~',\,
Cheni. S ( J / i d \ 29 2 I 7 5
Johnson P B and Christy R W 1Y72 P h n Hcr,. H 6 4370-0
Krerschmann E and Raether ti I Y 6 H %. .Vatit</:l:a 23 2135
Lopez-Rios T ;tnd Vuye G 1977 .Vuoro C'i/nuito 39 82.7-7
Mayadas A F, Shatzkes M and Janak J F: IYhY Appi. / ' h ~ \ ./ . c l / , 14 345 7
Motulevich G P s n d Shubin A A 1Yh4 Y h . />/,\p Iror. k i z . 47 840 (Erigl, Tranbl. i W i 5 Sur,. /'/I,I~%.J / : 7 / ' 2 0
560)
Otto A 1968 Z . Phj.5. 216 398-310
Sambles J R. Elsom K C and Jarvis D J 1982 P h i / . 7'rciur. R . Soc. A 304 365-06
Sambles J R and Preist T V\ 1982 J . Ph\.\. I . : ,Jfc/. P h , ~ i 12
. 1971
Schulz L G 1954a J . Opr. Soc. A m . 44 357-62
-l 9 5 4 b J . Op/.SOC.
A tll. 44 540
Schulz L G and Tangherlini 1954 J . Opt. Soc. A m . 44 362-8
Soffer S B 1967 J . A p p l . Ph),r. 38 1710-5
Thepe M-L 1970 Phj,s. Rer. B 2 3060-78
Van der Pauw L J 1958 Philips Res. Rep. I3 1-9
Weber W H and McCarthy S L 1975 P h , n Rec. B 12 5643-50