Fundamental optical attenuation limits in the liquid and glassy state with

application to fiber optical waveguide materials

D.A. Pinnow, T.C. Rich, F.W. Ostermayer, and M. DiDomenico

Citation: Appl. Phys. Lett. 22, 527 (1973); doi: 10.1063/1.1654495

View online: http://dx.doi.org/10.1063/1.1654495
View Table of Contents: http://apl.aip.org/resource/1/APPLAB/v22/i10
Published by the American Institute of Physics.

Additional information on Appl. Phys. Lett.

Journal Homepage: http://apl.aip.org/
Journal Information: http://apl.aip.org/about/about_the_journal
Top downloads: http://apl.aip.org/features/most_downloaded
Information for Authors: http://apl.aip.org/authors

Downloaded 12 Dec 2012 to 152.3.102.242. Redistribution subject to AIP license or copyright; see http://apl.aip.org/about/rights_and_permissions
Fundamental optical attenuation limits in the liquid and glassy state with
application to fiber optical waveguide materials
D.A. Pinnow, T.e. Rich, F.W. Ostermayer, Jr., and M. DiDomenico, Jr.
Bell Laboratories, Murray Hill, New Jersey 07974
(Received 26 January 1973; in final form 20 March 1973)

Fundamental optical scattering and absorption mechanisms have been identified which limit
light transmission in fiber optical waveguide materials. These mechanisms, which are in-
timately associated with the random structure in the liquid and glassy state, are described
and then used as a basis for comparing fiber optical waveguide materials. It is concluded
that pure fused silica is a preferred waveguide material, having ultimate total losses of
1.2 dB/km at the Nd: YAG laser wavelength of 1.061', 3.0 dB/km at the Ga,.A1l_xAs emis-
sion wavelength of approximately 0.8 Il, and 4.8 dB/km at the GaP: Zn,O emission wave-
length centered at 0.7 1'.

It is well known that the optical attenuation in fiber
optical waveguides is due to the sum of the bulk material
attenuation and attenuation due to imperfections in the
waveguide structure. It is further known that bulk atten-
uation is comprised of two parts, absorption and scatter-
ing, both of which may be influenced by impurities in
the glass. However, it has not been broadly appreciated
that fundamental mechanisms in chemically pure liquids
and glasses cause intrinsic optical absorption and
scattering loss. Both of these mechanisms are intimate-
ly associated with the random structure of the liquid and
vitreous state. The purpose of this letter is to compare
potential fiber optical waveguide materials on the basis
of their ultimate intrinsic loss characteristics. In doing
this we describe the nature and magnitude of these
losses.
Scattering loss in liquids and glasses is known to be due
to microscopic variations in the local dielectric constant
associated with the random molecular structure of these
materials. 1 For pure liquids, such as carbon tetrachlo-
ride (CC1 4), the variation in local dielectric constant is
due principally to thermally driven fluctuations in the
number of molecules within a region having dimensions
substantially less than an optical wavelength. The mag-
nitude of the optical scattering coefficient due to this
effect can be shown, by using claSSical electromagnetic
theory and thermodynamics, to be
(1)
where A is the optical wavelength, n is the index of re-
fraction, P is the photoelastic coeffiCient, k is Boltz-
mann's constant, T is the absolute temperature, and
{3T is the isothermal compressibility of the material.
Qualitative insight into this expression can be gained
by noting that kT is the driving force for the denSity
fluctuations, {3T is a measure of the compliancy of the
medium to the driving force, and napz is a term which
converts denSity fluctuations into dielectric constant
fluctuations. It should also be noted that this expression
has the explicit A-4 Rayleigh dependence, indicating that
the scatter loss substantially decreases at longer wave-
lengths. Since the parameters in Eq. (1) are known for
simple liquids, it is possible to immediately calculate
their scattering loss. Results are shown in Fig. 1 for
CC1 4, which has been conSidered as a waveguide
material. z
The expression given in Eq. (1) is based on the assump-
tion of thermodynamic equilibrium, which is valid for
liquids but not for glasses. The random structure of
glasses is not determined by the ambient temperature,
but by its fictive temperature, which is closely related
to the softening point or more precisely the temperature
at which the glass, if heated, would come into thermo-
dynamic equilibrium. By incorporating the fictive tem-
perature concept, Pinnow et al. 3 were able to account
for light scattering in Single-component glasses such as
fused silica. Since glasses are known to be substantially
less compliant than liquids, one would qualitatively
infer from Eq. (1) that the scattering loss would tend to
be less in glasses than liquids. However, this effect is
partially mitigated by the higher effective temperature
of the glass structure, which leads to increased scatter-
ing. Results are shown in Fig. 1 for fused silica, which
has a fictive temperature of apprOximately 1700 oK.
These results were obtained by the Brillouin spectro-
scopic method recently described by Rich and Pinnow. 4
The scatter loss due to density fluctuations is predicted3
to be less in lower-softening-point glasses than in fused
silica. An interesting example is soda-lime-silicate
glass (20% NazO, 10% CaO, 70% SiOz) which has a fictive
temperature of approximately 800 OK. High-purity sam-
ples of this glass have been prepared since it is re-
garded as a potential waveguide material. 5 The scatter
loss in these pure samples has been found experimental-
ly to be greater than that in fused silica. The resolution
of this apparent discrepancy is that scattering due to
density fluctuations is indeed low; however, there is an
additional mechanism which contributes to the scatter
loss in multi component glasses. This mechanism is
attributable to the statistically random distribution of
the polarizable components, which leads to an additional
contribution to the local variations in the dielectric
constant. Ostermayer and Pinnow6 have recently devel-
oped a quantitative model to account for this effect. The
resulting scattering coefficient due only to concentration
fluctuations in a host glass modified with m constituents
is 6
(2)
where n is the refractive index, A is the wavelength, p

527 Appl. Phys. Lett., Vol. 22, No. 10,15 May 1973 Copyright © 1973 American Institute of Physics 527

Downloaded 12 Dec 2012 to 152.3.102.242. Redistribution subject to AIP license or copyright; see http://apl.aip.org/about/rights_and_permissions
528 Pinnow et al.: Fundamental optical attenuation limits 528

100r-~~r---'---'---~~--.-----------------~ with energy as

(
E-E~
\ exp ~J' (3)
\
, ,
Q abS '"

\, \ CCl 4 Here E is the photon energy, E, is the effective energy

gap of the material, and il.E is a parameter which is
\, \ constant for each material. At present the theoretical
model is not suffiCiently sophisticated to establish the
\ \
\ magnitude of Q abs or the value of il.E. We note however
that the exponential form given in Eq. (3) is insensitive
E
10 ' \II
,, '\ SODA- LIME-SILICATE
to the detailed nature of the microfields and is therefore
,, \
.><
.....
CD useful in fitting experimental data as well as gaining
~
,, inSight into the effect. For example, it can be observed
,, \
(JJ
(JJ
0
that the larger-energy-band-gap materials such as fused
...J
<?
z
,, silica should have lower intrinsic absorption than the
narrower-gap soda-lime-silicate glasses, provided both
it:
<oj
t-
, \ , glasses have comparable il.E values.
t- \
<l
u
(JJ
\
, \ Although experimental absorption data are still sketchy
1.0 \
,, and encumbered by extrinsic impurity effects, we have
,, \ been able to extract what we believe to be the intrinsic
absorption tail in fused silica and soda-lime-silicate
, \ \
\
glass after studying many samples of extremely-high-
purity materials. 13 The results are exhibited in Fig. 2.
\ ,
\ ,,
, WAVELENGTH (MICRONS)

\ ,
o.IoL.4.,-----'----=-'"::-----L-....,-L--.l.----'-::-------------~2.0 /
0/
WAVELENGTH
/
FIG. 1. Intrinsic scattering loss vs optical wavelength for
liquid CC1 4 and vitreous fused silica and soda-lime-silicate.
100,000
o SODA-LIME-SILICATE I r/
0/
00
10,000 00 /
is the denSity, NA is Avogadro's number, and M j and o /
o /
Xj are the molecular weight and the weight fraction, 00/
respectively, of the jth modifier. The partial derivates ........E 0/
of n can be evaluated from the Gladstone-Dale relation7 1,000 /
and the partial derivatives of p from the Huggins-Sun
'"
"t>
o /
formula. 8 By using published data on the soda-lime-
V)
U)
/
0
...J /
silicate system, 9 the scattering coefficient calculated
from Eq. (2), when added to the scattering coefficient
due to denSity fluctuations calculated from Eq. (1), re-
Q
Z

t-
o..
f
0/
II: FUSED SILICA x
00/
sults in a total scattering loss in agreement with the ex- 0
U)
/
perimentally determined value shown in Fig. 1. '"
«
/
It is known that the random molecular structure in /
/
liquids and glasses gives rise to varying local electric /
fields on a microscopic scale. Recent theoretical devel-
opments by Dow and Redfield, 10 as well as experimental
and theoretical work by Wood and Tauc ll on chalcogenide
glasses, provide convincing evidence that such local
microfields cause intrinsic absorption loss in chemical-
0.1 L----'-__-'-__L-----'-_-'-__L-----'-__-'-__L-----'-__-'-----l
ly pure materials in what is normally the transparent
I 2 3 4 5 6 7
region below the fundamental interband absorption edge.
Similar experimental results have been observed in the PHOTON ENERGY (eV)

amorphous III-V semiconductor compounds. 12 The

mechanism for the loss is due basically to local field- FIG. 2. Intrinsic absorption loss vs photon energy for fused
induced broadening of the excitonic levels which are silica and soda-lime-silicate. These curves represent lower
.created in optical absorption for energies close to but bounds for all experimental absorption data. Shown are some
of the experimental data points used to develop these curves.
below the interband edge. The broadening of the exciton The rather broad gap in data for fused silica in the range of
levels can be shown,10 to produce a tail on the ultraviolet 2.5-4.5 eV is due to the limitations in sensitivity and wave-
interband absorption edge which varies exponentially length of the measurement techniques described in the text.

Appl. Phys. Lett., Vol. 22, No. 10, 15 May 1973

Downloaded 12 Dec 2012 to 152.3.102.242. Redistribution subject to AIP license or copyright; see http://apl.aip.org/about/rights_and_permissions
529 Pinnow et al.: Fundamental optical attenuation limits
IOOr--,---.-----,-----,------r-----,-----r-----,
"', ,
"' "' "
E ,SODA-LlME-
, ...
SILICATE
..><
.....
..,III ... ........
..... .....
Ul
Ul
..........
.... .... ....
9
u
Vi
z encouraging if one considers that they are less sensitive
1i:
I-
~
1.0
...J
~ and near infrared the scattering loss alone in CC1 4 ex-
0.1 '--____-'---____...I..-_ _ _ _...L..._ _ _ _....L.._ _ _--'-_ _.......--'-_ _ _ _- - '
0.5
WAVELENGTH (MICRONS)
FIG. 3. Total intrinsic loss in fused silica and soda-Ume-
silicate. The emission wavelengths corresponding to the most
promising optical sources are marked on the abscissa.
These data extend from the near-infrared through to the
near-ultraviolet portion of the spectrum. The ultraviolet
data pOints shown in this figure were obtained by using
a commercial spectrophotometer (Cary 14) operated to
the limit of its sensitivity. The lower-loss data points
in the visible and near infrared were obtained by the
calorimetric technique of Rich and Pinnow~ using vari -
ous emisSion wavelengths from argon, krypton, and
Nd: YAG lasers. These results convincingly fit the ex-
ponential form given in Eq. (3), although it is apparent
that impurity effects, such as the noticeable excess ab-
sorption band in the soda-lime-silicate centered at 3300
A, have not yet been completely eliminated. Neverthe-
less, the exponential trend in the data, which continues
over apprOximately six decades in attenuation and over
5 eV in photon energy, appears to be intrinsic and not
governed by impurity ions which exhibit known charac-
teristic spectral absorption bands 14 rather than the ob-
served exponential dependence. The t.E values deter-
mined from the slopes in Fig. 2 are 0.3 and 0.5 eV for
soda -lime-silicate and fused Silica, respectively. These
values are quite Similar to the 0.4 eV observed for
amorphous AS 2S3 11 and GaP. 15 Such similarities in the
absorption characteristics of greatly different glass
types is remarkable. Preliminary data taken on anum-
ber of liquids and glasses indicate that t.E is directly
proportional to kT" where Tf is the fictive temperature.
This implies that in random molecular structures the
fictive temperature gives a direct measure of the mag-
nitude of the average local microelectric field term in
the Dow -Redfield model for the exponential absorption
edge.
In appraising the merits of prospective fiber optical
waveguide materials it is useful to consider their funda-
mental loss limitations. In addition, since these losses
are dependent on optical wavelength, it is also possible
to establish not only the preferred material but also the
preferred optical sources for communications
applications.
Appl. Phys. Lett .• Vol. 22. No. 10.15 May 1973
Downloaded 12 Dec 2012 to 152.3.102.242. Redistribution subject to AIP license or copyright; see http://apl.aip.org/about/rights_and_permissions
529
To unify the data presented above, we have plotted in
Fig. 3 the total intrinsic loss (scattering plus absorp-
tion) of pure fused silica and pure soda-lime-silicate,
two of the most promising waveguide materials. The
data are plotted directly as a function of wavelength out
to 1. 1 J.1., which corresponds to the cutoff wavelength of
silicon photodetectors. Although the optical loss con-
...... tinues to decrease beyond this wavelength, the prospect
of using narrower-band-gap detector materials is not
and may require COOling. Carbon tetrachlOride was not
included in Fig. 3 because its absorption loss is not
known. However, it should be pointed out that in the red
ceeds the total loss of fused silica. Of the two glasses
Nd:YAJ!G
Shown in Fig. 3, it is apparent that fused silica is the
preferred material by a factor of 3-4 in loss. Further,
1.1 1.2
it is noted that the total loss in this material decreases
with increasing optical wavelength. As a practical con-
sequence, the repeater spacing in a fiber optical com-
munications system limited by intrinSic waveguide loss
could be over two times greater at a wavelength of 1. 06
J.1. (Nd:YAG laser) than at 0.8 J.1. (~Al1_%As source).
The ultimate loss at 1. 06 J.1. in fused silica is 1. 2 dB/km.
The authors wish to thank S. H. Wemple and D. Aspnes
for helpful discussions, and A.D. Pearson and W.G.
French for preparing the high-purity soda-lime-silicate
test samples. The authors also wish to thank P. Kaiser
for providing some complementary loss data on the
soda -lime silicate materials. The experimental assis-
tance of D. D. Badding is gratefully acknowledged.
II. L. Fabelinskii, Molecular Scattering of Light (Plenum,
New York, 1968), pp. 1-47.
2J. stone, Appl. Phys. Lett. 20, 239 (1972).
3D.A. Pinnow, S.J. Candau, J. T. LaMacchia, and T.A.
Litovitz, J. Acoust. Soc. Am. 43, 131 (1968). An earlier
but qualitative discussion of the relationship between fictive
temperature and light scattering was given by R. D. Maurer,
J. Chem. Phys. 25, 1206 (1956).
4T.C. Rich and D.A. Pinnow, Appl. Phys. Lett. 20,264
(1972).
5A. D. Pearson, AIME Technical Conference on Recent Ad-
vances in Electronic, Optical and Magnetic Materials, San
Francisco, Calif. 1971 (unpublished).
6 F . W. Ostermayer and D.A. Pinnow, Annual Meeting of the
American CeramiC Society, Cincinnati, Ohio, 1973
(unpublished) •
7J. H. Gladstone and T. P. Dale, ProC. Roy. Soc. Lond. 153,
317 (1863). Pro". Roy. Soc. Lond. 153, 337 (1863).
8M. L. Huggins and K. -H. Sun, J. Am. Ceram. Soc. 26, 4
(1943).
9G. W. Morey, The Properties of Glass, 2nd ed. (Reinhold,
New York, 1954), Chap. X and XVI.
IOJ.D. Dow and D. Redfield, Phys. Rev. Lett. 26, 762 (1971);
Phys. Rev. B 5, 594 (1972).
I1 D. L. Wood and J. Tauc, Phys. Rev. B 5, 3144 (1972).
12J. Stuke and G. Zimmer, Phys. Status Solidi B 49, 513
(1972).
13The highest-purity fused silica materials have been Suprasil
W1, supplied by Amersil, Inc. The highest-purity soda-lime-
silicate materials have been prepared by A. D. Pearson and
W. G. French of Bell Laboratories.
14Modern Aspects of the Vitreous State, edited by J. D. Mac-
Kenzie (Butterworth, Washington, D. C. , 1952), pp. 195-
254.
15S. H. Wemple (private communication).