720 J. Opt. Soc. Am./Vol. 72, No. 6/June 1982 B. E. Wood and J. A.

Roux

Infrared optical properties of thin H20, NH3 , and CO 2

cryofilms

B. E. Wood
Calspan Field Services, Inc., Arnold Air Force Station, Tennessee 37389

J.A. Roux*
Deportment of Mechanical Engineering, University of Mississippi, University, Mississippi38677

Received October 20, 1981

To identify and account for the effects from cryocontamination, the infrared spectral transmittances of cryofilms
formed by CO2, H20, and NH 3 were measured. These 0.25-14-pm-thick films were cryopumped onto 20-, 80-, and
in one case 50-K germanium substrates; the deposition pressures for the films deposited at 20 K and that for 80-K
films were approximately 2 x 10-6 Torr. Transmittance spectra were obtained for the 500-3700-cm-1 range with
a Fourier-transform spectrometer. Values of the optical properties (n, l) for the C02, H20, and NH3 cryofilms
were derived from the experimental data using a thin-film-transmittance analytical model and the nonlinear least-
squares method. Results from the least-squares method are compared with a Kramers-Kronig determination of
the refractive index (n). The optical properties (n, l) of such cryofilms are essential for predicting the degradation
of contaminated cryocooled optical surfaces.

INTRODUCTION source location. The chamber is an all-stainless-steel cell

Contamination of optical surfaces at cryogenic temperatures
by condensed atmospheric and rocket-exhaust-plume gases
is a serious problem to infrared-optical-system designers. On
contact with cold optical surfaces, these gases condense and
degrade system performance through thin-film interference
and vibrational-band absorption. Two of the most common
exhaust products from bipropellant engines [monomethyl
hydrazine/nitrogen tetroxide (N20 4 )] and atmospheric con-
stituents are carbon dioxide (CO 2) and water (H 20). Am-
monia (NH 3) is a common exhaust constituent from mono-
propellant [hydrazine (N2H4)] engines. Also, these species
are important for astrophysical observations of planetary
clouds and satellite surfaces.
To identify and account for cryocontamination effects, the
infrared (IR) spectra of H 20, C0 2, and NH 3 were measured.
The normal transmittance spectra were measured using 20-
and 80-K germanium as a substrate material.
Complete experimental details have been given elsewhere';
thus only a basic description of the chamber and apparatus
is presented here. The transmittances of thin solid films
ranging in thickness up to 14 gm are presented. Finally, a
theoretical model of window-plus-film transmission was de-
rived and used with the experimental results to determine the
complex refractive index (n = n - ik) of the pure species.
The subtractive Kramers-Kronig method for calculation of
the film's refractive index was also applied, and results were
compared with those of the nonlinear least-squares determi-
nation.
INSTRUMENTATION
Figure 1 shows the experimental apparatus and includes the
IR interferometer (Digilab Model FTS-14), the high-vacuum
chamber containing the cryocooled substrate, and the IR
equipped with a liquid nitrogen (LN 2 )-cooled liner, and a
vacuum of 10-8 Torr can be routinely obtained. The sub-
strate holder can be actively cooled with either LN 2 (80 K) or
gaseous helium (20 K). The three platinum resistors located
on the window holder yielded temperature measurements
accurate to within 0.5 K.
The spectral resolution of the interferometer system could
be selected between 16.0 and 0.5 cm-'1 , but 4-cm- 1 resolution
was found sufficient for all work reported herein. Trans-
mittance data were recorded in the 500-3700-wave-number
range. Transmittance measurements were performed by
rotating the germanium out of the beam and recording and
storing a reference power spectrum. Generally, 16 interfer-
ograms were added together to improve the signal-to-noise
ratio before execution of the Fourier transform. Next, the
window was rotated into the beam and the process repeated.
The reference file was then divided into the sample file and
plotted by a digital-incremental plotter, producing the final
data record on a linear ordinate scale of 0-100% transmit-
tance.
Controlled contamination of the cryocooled germanium
window was accomplished with a gas-induction system. Part
of the gas-induction system included a toroidal header with
36 0.16-cm-diameter orifices spaced 10 deg apart that directed
the gas toward the germanium window. The chamber pres-
sure rose from 1 X 10-3 to 2 X 10-7 or 2 X 10-6 Torr, respec-
tively, during deposition at 20 and 80 K. Gas was prevented
from condensing on the back of the germanium window by a
gas baffle positioned close to the back of the window holder.
The thin-film thickness was uniform across the exposed 5-
cm-diameter window area; the color of the reflected light from
the entire area of the cryofilm/germanium would change
uniformly with increasing film thickness. Film uniformity
and absolute thickness are two important parameters since

0030-3941/82/060720-09$01.00 1982 Optical Society of America

B. E. Wood and J. A. Roux
Fig. 1. Schematic of the infrared optical transmission chamber with
Fourier-transform spectrometer. 1, Pyroelectric detector and col-
lection optics. 2, Stainless-steel high-vacuum chamber, 85 cm tall
by 70 cm in diameter (33.5 in. by 27.5 in. in diameter). 3, Cryogeni-
cally cooled infrared window; germanium, 4 mm thick by 70 mm
square (0.158 in. by 2.76 in.) and QCM. 4,He-Ne laser (O.6328-,um)
beam (one of two shown) employed to measure cryofilm thickness.
5, Infrared beam, 38mm in diameter (1.5 in.). 6, 2-mW He-Ne laser.
7, Michelson interferometer. 8, Infrared source and collimator
mirror.
the objective of the experiment was to determine the complex
refractive index of the thin film, a quantity derived by com-
parison of experimental transmittance data with theoretical
model-thickness data. Any error in absolute film thickness
is directly introduced into the film's complex refractive-index
results. A dual-angle laser-interference technique 2' 3 was used
for monitoring the film's thickness and the film's refractive
index at X = 0.6328 ,gm.
Basically, two He-Ne laser beams are specularly reflected
off the germanium window for two different, accurately
measured incidence angles. As the gas is condensed, two in-
terference patterns of different periods are monitored in the
reflected laser light. If the ratio of pattern periods is termed
A, then the refractive index of the film, n, is given by
32
(sin2 Ob - sin 2 6a)1/2
n1= (1- 32)1/2 1 (1)
where 0a and 0 b (typically 18 and 68 deg) are the two laser-
beam incidence angles. Once n has been established, the
thickness of the film, di, is readily calculated from ma X= 2nd1
[1.- (sin 2 0a/n2)]1/2, where ma is the order of the interference
maxima for incidence angle 0a, The dual-angle laser-beam-
thickness monitor yielded thin-film refractive-index values
accurate to within 2%. A quartz-crystal microbalance (QCM)
was used in conjunction with the dual-angle laser-beam in-
terference technique to determine the density of each con-
taminant. The QCM operates on the principle that the
crystal's vibration frequency changes linearly with changes
in the mass deposited on the crystal. The QCM was located
adjacent to and just above the germanium window so that the
mass-deposition rate would equal that of the germanium
window. The surface density (in grams per square centime-
ter) was determined from the QCM, and the film's thickness
was determined from the interference patterns. From these
two values the film's density (in grams per cubic centimeter)
was determined.
PROCEDURE
The chamber was initially pumped down to approximately
1.0 X 10-7 Torr by using the diffusion pump and the LN 2 liner.
Vol. 72, No. 6/June 1982/J. Opt. Soc. Am. 721
Chamber pressures in the low 10-8-Torr range were obtained
when the germanium substrate, the holder, and the transfer
lines were cooled to approximately 20 K with the cryostat
(2-kW capacity).
Samples of research-grade CO 2 and NH 3 were obtained
from lecture bottles to be introduced into the chamber. A
special gas-addition system was used to introduce water vapor
into the chamber to be cryopumped. Before the water vapor
was added, the distilled water was boiled under vacuum while
being pumped with a mechanical pump to remove gases ab-
sorbed in the water.
Deposition of the gas on the cold germanium window was
monitored by using two He-Ne-laser beams with the two-
angle interference technique. Transmittance measurements
were made when the interference maxima were reached, at
which points the gas flow was shut off. On completion of the
transmittance measurements, the gas flow was again started,
and deposition occurred until a film thickness corresponding
to the next interference maximum was reached, and so on.
The objective was to obtain transmittance measurements
for as many thicknesses as possible during an experiment on
each gas. The number of thicknesses obtained depended
considerably on the particular gas. For well-behaved de-
posits, 16 to 25 thicknesses (interference maxima or minima)
were obtained, whereas in some cases only a few thickness
measurements could be made because of a film fracture or
shattering phenomenon. For both H 20 and NH 3 formed at
20 K, only a very small thickness (1-2 gin) could be reached
before the entire deposit fractured or shattered, at which point
the film became highly scattering. At 80 K an H2 0 deposit
30 ,im thick was formed that was so clear that it could not be
detected with the naked eye. However, at 20 K, because of
the shattering effect, a 2-,um thickness could be seen easily.
This effect was not the amorphous-to-cubic phase transition
but was a breaking up of the film.
RESULTS
Transmittance measurements were made of thin filrms of gases
condensed on the cryogenically cooled germanium window.
These measurements were multiples of the thickness deter-
mined from the thin-film interference equation for reflection
maxima:
mX
T =(s (2)
2n (1 - sn2 1
where m = 1, 2, 3, ... and 0 is the incidence angle measured
from the normal.
In each case, the refractive index n had to be measured
before a thickness could be calculated. This measurement
of n was described previously 3 ; it involves using Eq. (2) for two
different incidence angles-approximately 18 and 68 deg in
this study. For this investigation, thickness is based on in-
terference maxima for 18-deg incidence.
NH 3 Deposited at 20 and 80 K
Thin films of NH 3 gas were deposited on the germanium
window cooled to 80 and 20 K. The refractive indices at these
two temperatures (for X = 0.6328gAm) were 1.41 and 1.37, re-
spectively. These refractive indices correspond to thickness
722 J. Opt. Soc. Am./Vol. 72, No. 6/June 1982 13.13. Wood and J. A. Roux

only one distinct band (V4) located at 1625 cm-1 for 20 K in

60
Fig. 3. The relatively weak band seen at 3300 cm-' for 80 K
is much less significant for 20 K and is assigned to the 2v4
band. Conversely, the weak band observed at 3220 cm-' at
20 K is even weaker at 80 K. This band is believed to be due
a 40 primarily to the v1 vibration, with a possible contribution by
the 2v 4 band, as suggested by Wolff et al.6 The strong ab-
,0 sorption bands observed at 3385 cm- 1 for 80 K and at 3380
'F 20 cm-' for 20 K are assigned to be the v3 vibration band.
A weak band at 1890 cm-1 (Fig. 2) for 80-K NH 3 is believed
to be due to the combination band v4 + v5, where'P 5 is a tor-
sional mode.7 This band was not observed for the 20-K films.
1
500 900 1300 1700 2100 . 2500 2900 3300 3700 The lattice band seen at 525 cm- in Figs. 2 and 3 was not
Wave Numbers observed at 20 K in either Ref. 4 or Ref. 5. This was ex-
Fig. 2. Transmittance of 14.1-prm-thick solid NH 3 on 80-K germa- plained 4' 5 by the fact that amorphous NH3 ' which would not
nium. have a lattice band, was formed at 20 K. The descriptions of
4 5
those films ' and of the physical appearance of the films
during deposition correspond to our observations; the films
formed at 20 K were more milky (exhibited more light scat-
60 tering) than the 80-K films, which were clear-glassy in ap-
pearance; this is normally associated with the amorphous
structure. Because there was more scattering in the 20-K
a 40 films, the thin-film interference pattern decayed at much
thinner films than for the 80-K films. In addition, fracture
0 or shattering sometimes occurred for the films deposited on
the 20-K germanium.
F 20
CO 2 Deposited at 20 and 80 K
Thin films of CO 2 were condensed on both 80- and 20-K ger-
manium substrates. The refractive indices at X = 0.6328 am
500 900 13W 1700 2100 2500 2900 3300 3700 were found to be 1.43 at 80 K and 1.27 at 20 K. The CO 2 re-
Wave Numbers fractive index showed the greatest ehange with temperature
Fig. 3. Transmittance of 1.43-pm-thick solid NH 3 on 20-K germa- of all the gases condensable at both 80 and 20 K that were
nium. studied. For an incidence angle of 18 deg, this yields a film
thickness of 0.227 ,mtbetween interference maxima at 80 K
and a thickness of 0.257 pm between maxima for films at 20
Table 1. Molecular Bands in NH 3 (cm-1)
K. The densities of the films at 80 and 20 K were derived by
Solid Identifi- Present Work using the calculated thin-film thickness and the surface
0 3
30 K 80 Kb Vaporc cation 20 K 80 K density from the QCM; values of 1.67 and 1.08 g/cm , re-
530 530 - Lattice 525 535 spectively, were obtained for the 80- and 20-K films. The
1050 1060 950 v2 1075 1065 Lorentz-Lorenz coefficient [(1/p(n2- 1/n 2 + 2)], which is q
1625 1646 1682 V4 1625 1650 constant for a given wavelength regardless of the material
3
3200 3291 3336 VI 3215 3220 phase or temperature, was found to be 0.155 cm /gm, which
3350 3375 3414 V3 3380 3385 corroborates the values of the refractive indices and densities
measured.
a Ref 4.
b Ref. 5.
c Ref.8.

60
increments of 0.231 pm for interference maxima for 84 K and
3
0.238 Am for 20 K. The densities were 0.87 g/cm at 80.K and
3
0.76 g/cm at 20 K. Spectra obtained for NH 3 condensed at Z

these temperatures are shown in Figs. 2 and 3, respectively. . 40

Absorption-band locations and assignments are given in .2
Table 1, and comparisons with results of other investigators4_8 0
E
are made. By comparing 80-K NH,, (Fig. 2) with 20-K NH13
2 20
(Fig. 3) for thicknesses of 14.1 and 1.43 pm, respectively, it can
be seen that the bands near 1100 and 3300 cm-' for 20 K are
much broader than the corresponding bands at 80 K. This
was pointed out eartier. 4'5 The thin-film interference (or a
500 900 1300 1700 2100 2500 2900 3300 3700
channel spectra) can be observed between 2100 and 3100 Wave Numbers
cm-'. The complicated structure between 1340 and 1700 Fig. 4. Transmittance of 12.7-pm-thick solid CO2 on 80-K germa-
cm-' and centered at 1650 cm-' for 80 K (Fig. 2) is seen as nium.
B. E. Wood and J. A. Roux Vol. 72, No. 6/June 1982/J. Opt. Soc. Am. 723

Table 2. Molecular Bands in CO 2 (cm-')

Solid Present Work
Vapora 30 Kb 80 Kc 20 and 80 Kd (20 and 80 K) Identification

648 638 637 638 630 V2- C1302

- 654 653 654 650 v2 - C1202
667 660 660 660 665
2283 2282 2280 2282 2285 V3- C1302
2
2349 2343 2344 2345 2345 P3 - C1 0 2
- 2370/2460 2379/2454- 2455 2460 V3 + Lattice
3609 3600 3610 3600 3600 2v 2 + V3
3716 3710 3712 - 3710 v1 + P3

a Ref. 8.
b Ref. 4.
Ref. 9.
d Ref. 5.

The transmittance spectrum of an 80-K CO 2 film is shown

in Fig. 4 for a film thickness of 12.7,4m, which corresponds to 60
the 55th interference maximum. The absorption bands are
identified in Table 2, and comparisons can be made with the
work of other investigators. 4 -9 Although this is not readily E

apparent from Fig. 4, one band is observed at 630 cm-1 , and ,, 40

two bands are seen at 650 and 665 cm- 1 . These bands are .g
0
observed when the wave-number scale is expanded. These
bands are associated with the P2 13CO 2 and 12CO2 bands. The 20
strongest CO 2 band in the spectrum occurs at 2345 cm- 1 and
is the V3 12CO 2 band. The corresponding V3 band for the
carbon 13 isotope 13CO 2 occurs at 2285 cm-'. The combi- 0
nation V3 + lattice band is seen to occur at 2460 cm- 1 . The
I-
500 900 1300 1700 2100 2500 2900 3300 3700
Wave Numbers
final two bands of significance, but considerably weaker than
the V3 band, appear at 3600 and 3710 cm- 1 and are the 2v2 + Fig. 5. Transmittance of 3.88-tm-thick solid CO 2 on 20-K germa-
V3 and the P1 + P3 bands, respectively. The band at 3710 cm' nium.
is not shown in Fig. 4 but was observed in some sets of mea-
surements that were extended to 3950 cm-1. Although
transmittance data were taken for the 3700-3950-wave-
60
number range, the noise level past 3700 cm-' increased such
that accurate n's and k's could not be determined but spectral
features could still be easily seen. The transmittance spec-
trum of a CO2 film deposited on 20-K germanium is shown in ' 40
Fig. 5 for a film thickness of 3.88,um (the 15th laser-interfer- d
ence maximum for X = 0.6328 gin). The spectral-band lo-
cations agree with the values observed for the 80-K spectrum ' 20
in Fig. 4.

H2 0 Deposited at 20, 50, and 80 K

H20 films were condensed on the cryogenically cooled ger- 500 900 1300 1700 2100 2500 2900 3300 3700
Wave Numbers
manium substrate at temperatures of 20,50, and 80 K. The
spectrum for 80 K is shown in Fig. 6 for the sixth interference Fig. 6. Transmittance of 1.50-,um-thick solid H2 0 on 80-K germa-
nium.
maximum, which corresponds to a film thickness of 1.50 gnm,
where n = 1.32 at X= 0.6328,gm. Films deposited at 50 and
20 K look essentially the same as the 80-K H20 data in Fig. Table 3. Molecular Bands in H20 (cm-')
6. Essentially no differences were observed for the refractive Solid Present Work
index of H20 at X = 0.6328 ,m for these three tempera- (30 K)a Vaporb 80 K 50 K 20 K Identification
tures.
Four absorption bands or regions were seen for H20; they 750 - 825 820 800 Libration - VL

were all quite broad in contrast to those of the gases previously 1650 1595 1665 1665 1665 v2
- - 2245 2220 2220 P2 + PL
studied. These bands are summarized in Table 3. Observing
3300 3652 3255 3260 3300 i1
these bands in Fig. 6 makes it obvious that the band locations - 3756 - - - P3
are too broad to be designated by specific numbers, as in Table
3. Therefore, the numbers refer to the approximate centers a Ref. 4.
of the broadbands. The v1 band at 3260-3300 cm-' is ob- b Ref. 8.
724 J. Opt. Soc. Am./Vol. 72, No. 6/June 1982
served to be deeper at the higher temperature. For a thick-
ness of 0.25 ,m (first interference maximum) the transmission
varies for the PI band from 30% at 80 K to 32% at 50 K and fi-
nally to 34% at 20 K. Thus the depth of the absorption band
increases with increasing temperature, and the absorption
index also increases with temperature. For a film thickness
of 1.50 Am, the transmission is reduced to zero for the PI band.
It is also seen that the location of the band shifts to higher
wave numbers with decreasing temperature. (The central
location for the 80-K film was 3255 cm-', whereas it was 3300
cm-' for 20 K.) This trend agrees with warmup data for H20
films studied by Thompson et a.4 The libration band yL
observed in the solid at 825 cm-' at 80 K was observed at 800
cm-' for the 20-K films, a shift toward the opposite direction
from the vPband. The v2 band at 1665 cm-' was independent
of temperature, whereas the 2245-cm- 1 band at 80 K shifted
to 2220 cm-1 at 20 K, illustrating the same trend observed for
the libration band. The spectral location of the latter band
agrees with the data of Bertie et al.'0 but is shifted at least 30
cm-' from the 2190-cm-' value observed by Thompson et aLt4
The band at 2220 cm-' has been assigned as a combination
of the v2 and librational bands (v2 + PL) by Ockman"; the
spectral location of this band is expected to be temperature
dependent, as is that of the vL band.
OPTICAL CONSTANTS
In order to determine the complex refractive index (n = n -
ik) of the thin solid film from the IR-transmittance mea-
surements for wave numbers between 700 and 3500 cm-, an
analytical model of film-plus-window transmission was used.
The optical constants of the cryocontaminants were deter-
mined by using this analytical transmission model' 2 -' 4 in
conjunction with a nonlinear least-squares convergence rou-
tine. Also, the subtractive Kramers-Kronig relation between
n and k was used in conjunction with the nonlinear least-
squares determination of n. The subtractive Kramers-
Kronig relation is given by
n(v) = nf(V) +2p vf2 k(v')v' - k(v)M
k (v') -k (vmn)vm dv', (3)
(V')2 - V"
where 11mis a reference frequency, PI = 700 cm-', v2 = 3700
cm-', and P indicates the Cauchy principle value of the in-
tegral. Integration was performed using the simple trape-
zoidal rule; the k values used in Eq. (3) were those determined
by the nonlinear least-squares technique. The values of k
outside 700 cm-' < S < 3700 cm-' were considered either as
zero or as a constant at the end-point values; both approaches
showed a negligible effect on the values of n that were ob-
tained from Eq. (3).
Transmittance data recorded for all deposits discussed here
were digitized every 2 cm-'. The optical properties were
computed every 10 cm-', except in regions of strong absorp-
tion, in which computations were performed every 2 cmi1.
The optical properties were initially computed by the non-
linear least-squares determination. However, in some in-
stances, the program did not appear to converge upon a unique
value of n. This usually occurred in regions of strong ab-
sorption or low wave number or for cases in which it was pos-
sible to form only a few thin deposit thicknesses (20-K H 20
B. E. Wood and J. A. Roux
zs
A,
.
, | ~ -
~ Ig
raees-Krsn
IlneariL.,
A.Sqares
205
I L.5
s-~ I-
I LO
O.3
-7 ODD 13D 27W 27W 300 NSO
Wave Numbers
_1
I
ZI
a
I
I
WaveNumbers
Fig. 7. Optical properties of NH3 condensed on 80-K germanium.
and NH 3). The n value appears to be defined primarily by
the period of the transmittance-versus-thickness curve at each
wave number. At small thicknesses, or high absorption, or
low wave numbers, the transmittance-versus-thickness (for
each wave number) curve is not well defined; i.e., the period
of the interference as a function of thickness is not well de-
fined. The k value, which is defined primarily by the mag-
nitude of the transmittance, did not have this difficulty and
was well defined over the whole spectral region (700 to 3700
cm-'). Thus, to determine n, the k values were used with the
subtractive Kramers-Kronig relationship; these new n values
were then used in the analytical model (along with the k val-
ues) to see if good agreement occurred with the transmittance
data. For all wave numbers, the Kramers-Kronig n's along
with the least squares k's yielded good agreement when the
analytical model and transmittance data were compared.
Errors in the refractive index, thickness, and density are all
estimated to be within 42%. The error in the absorption
index varies from about +2% at high k values (-0.01 or
greater) to a value that is inaccurate for values of k below the
slanted dashed line at the bottom of the absorption-index
graphs. The value of k can vary over several orders of mag-
nitude, and therefore the smaller the k value the larger the
error; this is because of the error limits on the film-substrate
transmittance measurements.
Generally the nonlinear least-squares results (thin-film
model) did converge, and a comparison of the Kramers-
Kronig and thin-film results is shown for NH 3 (Fig. 7). As
stated, the optical properties were obtained through use of an
analytical model and the nonlinear least-squares method. It
was assumed that the germanium substrate (window) acted
as a thick film, and hence there was no phase coherence among
multiple internal reflected rays (inside the germanium). The
refractive index of the germanium was a modification of that
given by Herzberger and Salzberg"4 to account for the re-
fractive-index change that is due to the cryogenic tempera-
B. E. Wood and J. A. Roux Vol. 72, No. 6/June 1982/J. Opt. Soc. Am. 725

tures. The thin film (cryocontamination layer) was consid- 2.0

ered to be an optical thin film with properties n and k. The

overall transmittance through the contamination layer on the
germanium substrate is given by 0.5

T = T(n, k, O, ngV, d), (4) ID

Io
0.0
where n and k are the optical properties of the contamination
layer, 0 is the angle of incidence (here 0 = 0, which means
normal incidence), ng is the germanium refractive index, v is 0 700 1000 lOW 2000 250 300 350D
the wave number, and d is the contamination-layer thickness. Wane Numbers

The exact expressions' for Eq. (4) are algebraically long and
tedious but straightforward; these expressions involve Fres-
nel's equations for the interface reflectances and transmit-
tances. The values of n and k were obtained by knowing v,
0, and ng and measuring the value of T at known values of d
(for CO 2 at 80-K, 25 values of r were measured at 25 known
values of d). Mathematically it was required to have at least
two values of r at two known values of d in order to have two
equations for the two unknowns, n and k. By using the
nonlinear least-squares convergence method the values of n
and k that produce the least error (in the least-squares sense)
among all the data (25 values for 80-K C0 2) and the analytical
700 1000 1500 20D0 2500 -3000
model [Eq. (4)] were determined. When an initial guess was Waee Numbere
3500

used for the solution for n and k, the nonlinear least squares Fig. 9. Comparison of NH3 results at 80 K with those of Ref. 15 at
generated improved values for n and k; these were then 190 K.
resubstituted to find an even better solution. This procedure
was continued until convergence was obtained. Usually
convergence was obtained at each wave number after about 1. For both temperatures the agreement between the
three iterations. Details of this standard method are available Kramers-Kronig method and nonlinear least-squares tech-
in Ref. 1. nique was good. The slanted dashed line on the k-versus-v
plots represents the minimum imaginary refractive-index
NH3 Optical Constants values that can be determined because of the error limits on
The optical constants for NH 3 at 80 and 20 K were determined the film-substrate transmission measurements. Values below
by using both the nonlinear least-squares technique and the the dashed line are shown but may not be accurate, as is noted
Kramers-Kronig method. The results are shown in Figs. 7 on the figures. The anomalous dispersion at the two strong
and 8, respectively. The tabulated results are given in Ref. NH3 bands is clearly seen in the n-versus-v plots of Figs. 7 and
8. The n values are higher at 80 K than at 20 K, as was the
2 5
density. Also, the k values at the two major absorption bands
. 1
- Prent
Work
- - - - Thoson,Arnold,
Sanderson.
Marts.(300Rd. 4
are greater at 80 K than at 20 K.
The data given in Figs. 8 and 9 are a comparison of the re-
sults of this work with those of others. The results of Rob-
'5 ertson et al.1 5 (Fig. 9) were obtained by solidifying liquid
ammonia. The Lambert absorption coefficient was deter-
0.0
mined by using thicknesses in the range from 0.50 to 20 Aum.
as5 Interference effects were not mentioned for these small
thicknesses. The n values were then determined by using the
0 700 1000 15W0 2000 25W 5
3000 W
3500
substractive Kramers-Kronig method. Data of Ref. 15 were
WaneNumbers obtained at 190 K, whereas the present data were obtained at
80 K. However, the agreement for the n values is very good,
and the agreement for k is generally good. (Results were
limited to 950 cm-1 in Ref. 15 because of the use of CaF 2
windows.)
Shown in Fig. 8 is a comparison of the present data at 20 K
with the data of Thompson et al.4 at 30K. The data of Ref.
4 were obtained by employing basically the same approach as
that used in the present tests, except that thin-film reflection
data were recorded. In general the agreement is good, but the
results of the present work yielded higher values for both n
and k; the results of Ref. 4 were shown only to 2400 cm-'.
Results shown in Fig. 10 illustrate the comparison with the
WaneNumbers work of Pipes et al.5 Similar comparisons were made with
Fig. 8. Comparison of NH3 results at 20 K with those of Ref. 4 at 30 the results of Sill et al. 16 (not shown) for NH3 at 80 K. The
K. agreement among all three is excellent. The same techniques
726 J. Opt. Soc. Am./Vol. 72, No. 6/June 1982 B. E. Wood and J. A. Roux

2.
-
Present
----- -Pips,.
WIrk
Rour,
Smith,ScootM
i8K, Ret.5
nonlinear least-squares technique and the Kramers-Kronig
2.0
method were in good agreement. Figure 11 shows the effect
of temperature on the CO2 optical properties. As was true for
I
I 1.5 NH3 , the higher temperatures yielded higher values for n and
II
k as well as for the density.
L l
I Determination of n and k for CO 2 at 80 K was made by
J. r I using transmittance measurements at 25 thicknesses; at 20
K, 14 thicknesses were used. The agreement between theory
0 700 loc 1520 2000 2020 3to 3500
and data is shown in Fig. 12 for 80 K. After the n and k values
WaveNumbers
were determined, they were used in the analytical model to
generate the theoretical curves.
No n or k values in the wave-number range of interest were
found in existing studies with which the present work could
be compared. Possibly these n and k values are unique in the
literature.
H2 0 Optical Constants
The optical constants for H2 0 at 80, 50, and 20 K are shown
in Fig. 13. In some regions (i3300 cm-') the nonlinear least

W-e. Numbers

Fig. 10. Comparison of NH3 results at 80 K with those of Ref. 5 at

80K.

.2

' L!

I .t
Is
6.0
Thickness, lnn

Fig. 12. Comparison of theory and data for 80-K solid CO 2 for three
WaneNumbers
different wave numbers.

--- 80K
--- 0K
2.0 -20K

1.5
L5

c L

ez'1!NaIL thlkoeventIy,.
blmYss

10-3 ;'-,1t; <' To - - -

I 70201O0 150 2WO 2520 300 3500

WaveNumbers

10 0 Inacou
b7e1 nte 25. 3aI 35
Numbers
.Wave

Fig. 11. Effect of substrate temperature on CO 2 optical properties

(20 and 80 K).

were used both in the present work and by Pipes et al. the
same research cell was also used, except that the present work
employs a much better technique for determination of film
thickness.

CO2 Optical Constants

20o0 250 3000
The optical constants for CO2 at 80 and 20 K were determined WaveNumbers

and are shown in Fig. 11. Tabulated results for these con- Fig. 13. Effect of substrate temperature on H2 0 optical properties
stants for CO 2 at 80 and 20 K are available.' Results of the (20, 50, and 80 K).
B. E. Wood and J. A. Roux Vol. 72, No. 6/June 1982/J. Opt. Soc. Am. 727

-Preent Work 50 K, 17 thicknesses were used; for 20 K, 8 thicknesses were

Arnold,
Sanderon,
-Thompson,.
andMant (30k)(Ref.
4)
used. At 50 K only 17 thicknesses could be formed (-2.7 ,m)
2.0
before shattering occurred; at 20 K only 8 thicknesses (-1.0
LA
,um) could be formed before shattering occurred.
Figures 14 and 15 show comparisons of the present work
LI
with the results of Thompson et al.4 and Bertie et al.,10 re-
spectively. In Fig. 14 the deposition temperature 4 was 30 K,
a5
and the pressure was about 10-6 Torr. (As was mentioned
earlier, the results4 were obtained through a thin-film re-
700 100 MW 2000 2500 325 3500
flectance analysis.) For results10 in Fig. 15, the data were
a
WaveNumbers

obtained at 100 K, but the deposition pressure was not

given.

SUMMARY
Experimentally determined transmittance measurements of
condensed gases on a cryogenically cooled germanium window
were made. Thin films of NH3 , C0 2 , and H2 0 were deposited
at 20 and 80 K. The infrared spectral transmittance was
studied over the 500-3700-cm-1 range (the 2.70-20.0-,um
wavelength range). The film thickness was accurately de-
termined by using a two-angle laser-interference technique.
WaveNumbers The densities of the films were determined by using quartz-
Fig. 14. Comparison of H 2 0 results at 20 K with those of Ref. 4 at crystal micdbalances (QCM's) and by calculating the re-
30 K. fractive index at 0.6328 Am to permit accurate thickness
measurement. Some fracture and shattering effects were
PreentWork
observed for the films condensed at 20 K. From the trans-
------- Bertie,
LabOW,
andWhalley(IWKt,
(Ref.10 mittance data, the optical properties n and k were determined
for the 700-3700-cm-1 range. These results are available in
I.l L.
graphical and tabular' form for a wave-number interval of 2
L A cm-1 . Additional n and k properties have been determined
D)LLI for CO, NO, CH 4 , HCd, N 2 0, 02, N2 , and Ar films.17
The work reported herein was conducted at the Arnold
Engineering Development Center (AEDC), U.S. Air Force
us
A
700 15WD
.

15W0
.

2DO s
..

3000 3500 Systems Command (AFSC) while the authors were with ARO,
WaveNumbers
Inc., a Sverdrup Corporation company, an operating con-
1'S
tractor for the AEDC.

"II
I"A * Formerly with ARO, Inc.

10-2
10o3
70 15W 15W 25W
WaveNumbers
Fig. 15. Comparison of H2 0 results at 80 K with those of Ref. 10 at
100 X.
squares did not converge on b unique value of n. Therefore
the k values from the least-squares technique were used with
the Kramers-Kronig method to generate n values. Then the
least-squares k values and Kramers-Kronig n values were
used in the analytical model and compared with the data to
ensure good agreement. All the k values in Fig. 13 were above
the error line and thus should be considered accurate values.
The n and k values were determined by using absolute
transmittance measurements at 25 thicknesses for 80 K; for
REFERENCES
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A074913, Septembei 1979).
NOTE:
k values
belnw
thisline
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