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


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

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

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

Deposition of the gas on the cold germanium window was Fig. Once n has been established. is given by but was a breaking up of the film. it involves using Eq. This measurement window. and 0 is the incidence angle measured in the mass deposited on the crystal. and deposition occurred until a film thickness corresponding 5. Pyroelectric detector and col. For well-behaved de- parison of experimental transmittance data with theoretical posits.41 and 1. a quantity derived by com.6328 . 2n (1 . Transmittance measurements lection optics. From these this study. . 3. Wood and J. No. These refractive indices correspond to thickness . A quartz-crystal microbalance (QCM) mX T =(s (2) was used in conjunction with the dual-angle laser-beam in- terference technique to determine the density of each transmittance measurements. sin 2 6a)1/2 n1= (1. Schematic of the infrared optical transmission chamber with monitored by using two He-Ne-laser beams with the two- Fourier-transform spectrometer.158 in. reflected laser light.37.sn2 1 taminant. Before the water vapor was added.76 in. [1. in diameter). thick was formed that was so clear that it could not be measured incidence angles. At 80 K an H2 0 deposit off the germanium window for two different. was determined. spectively. A dual-angle laser-interference technique 2' 3 was used shattering phenomenon. where ma is the order of the interference These measurements were multiples of the thickness deter- maxima for incidence angle 0a.5 in. 16 to 25 thicknesses (interference maxima or minima) model-thickness data..He-Ne laser (O. The QCM operates on the principle that the crystal's vibration frequency changes linearly with changes where m = 1. by 27. beam (one of two shown) employed to measure cryofilm thickness. A special gas-addition system was used to introduce water vapor into the chamber to be cryopumped. were made when the interference maxima were reached. For both H 20 and NH 3 formed at for monitoring the film's thickness and the film's refractive 20 K. at cally cooled infrared window. 7. 3.B. 1. by 2. is readily calculated from ma X= 2nd1 condensed on the cryogenically cooled germanium window.5 in. the distilled water was boiled under vacuum while being pumped with a mechanical pump to remove gases ab- sorbed in the water. the Transmittance measurements were made of thin filrms of gases thickness of the film. 721 Chamber pressures in the low 10-8-Torr range were obtained when the germanium substrate. and the transfer lines were cooled to approximately 20 K with the cryostat (2-kW capacity). Am.(sin 2 0a/n2)]1/2. re- 1. adjacent to and just above the germanium window so that the In each case. Any error in absolute film thickness were obtained. On completion of the square (0. at 20 K. accurately 30 . because of terference patterns of different periods are monitored in the the shattering effect. and the film's thickness different incidence angles-approximately 18 and 68 deg in was determined from the interference patterns. two in. If the ratio of pattern periods is termed This effect was not the amorphous-to-cubic phase transition A. Opt. (2) for two ter) was determined from the QCM. Stainless-steel high-vacuum chamber. 38mm in diameter ( germanium. As the gas is condensed. Infrared beam. 72. 6. considerably on the particular gas. n. only a very small thickness (1-2 gin) could be reached index at X = 0.). 2. mined from the thin-film interference equation for reflection thickness monitor yielded thin-film refractive-index values maxima: accurate to within 2%. The surface density (in grams per square centime. before the entire deposit fractured or shattered. and so on. Samples of research-grade CO 2 and NH 3 were obtained from lecture bottles to be introduced into the chamber.. 4 mm thick by 70 mm which points the gas flow was shut off. 2-mW He-Ne laser. the refractive index n had to be measured mass-deposition rate would equal that of the germanium before a thickness could be calculated. 32 (sin2 Ob . a 2-. 8. NH 3 Deposited at 20 and 80 K Thin films of NH 3 gas were deposited on the germanium PROCEDURE window cooled to 80 and 20 K. thickness could be seen easily. The dual-angle laser-beam.. angle interference technique. 1. of n was described previously 3 . Roux Vol. The objective was to obtain transmittance measurements for as many thicknesses as possible during an experiment on the objective of the experiment was to determine the complex each gas. Michelson interferometer. The number of thicknesses obtained depended refractive index of the thin film. The QCM was located from the normal. 4. the holder.0 X 10-7 Torr by using the diffusion pump and the LN 2 liner. 2. For this investigation. Soc. 32)1/2 1 (1) RESULTS where 0a and 0 b (typically 18 and 68 deg) are the two laser- beam incidence angles. Infrared source and collimator to the next interference maximum was reached. whereas in some cases only a few thickness is directly introduced into the film's complex refractive-index measurements could be made because of a film fracture or results. A. two He-Ne laser beams are specularly reflected the film became highly scattering. However. 85 cm tall by 70 cm in diameter (33.5 in. then the refractive index of the film. detected with the naked eye. di. E.6328gAm) were 1. the gas flow was again started. The refractive indices at these The chamber was initially pumped down to approximately two temperatures (for X = 0. 6/June 1982/J.) and QCM. thickness is based on in- two values the film's density (in grams per cubic centimeter) terference maxima for 18-deg incidence. at which point Basically.

Opt.1-prm-thick solid NH 3 on 80-K germa. plained 4' 5 by the fact that amorphous NH3 ' which would not nium. In addition./Vol. 3) for thicknesses of 14.87 g/cm at 80. 2. which 3350 3375 3414 V3 3380 3385 corroborates the values of the refractive indices and densities measured.08 g/cm . The densities of the films at 80 and 20 K were derived by Solid Identifi. (Fig. Transmittance of 1. respectively. 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.6 The strong ab- . Lattice 525 535 spectively. as suggested by Wolff et al. was formed at 20 K. By comparing 80-K NH. re- 530 530 .2 Table 1.mtbetween interference maxima at 80 K and a thickness of 0. The CO 2 re- Wave Numbers fractive index showed the greatest ehange with temperature Fig. b Ref. A. 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. of all the gases condensable at both 80 and 20 K that were nium.722 J. 60 increments of 0. Transmittance of 12. 2500 2900 3300 3700 The lattice band seen at 525 cm. For an incidence angle of 18 deg.67 and 1.43-pm-thick solid NH 3 on 20-K germa. . studied. was found to be 0.7 This band was not observed for the 20-K films. 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.76 g/cm at 20 K. 2 and 3 was not Wave Numbers observed at 20 K in either Ref. F 20 CO 2 Deposited at 20 and 80 K Thin films of CO 2 were condensed on both 80. c Ref. which were clear-glassy in ap- pearance. the weak band observed at 3220 cm-' at 20 K is even weaker at 80 K. Soc. 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-'. . 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.0 sorption bands observed at 3385 cm. Conversely. were obtained for the 80. This was pointed out eartier. 3. Molecular Bands in NH 3 (cm-1) K. The complicated structure between 1340 and 1700 Fig.231 pm for interference maxima for 84 K and 3 0.43 at 80 K and 1. 40 Absorption-band locations and assignments are given in . the films formed at 20 K were more milky (exhibited more light scat- 60 tering) than the 80-K films. Am.227 . 6/June 1982 13.13. Spectra obtained for NH 3 condensed at Z these temperatures are shown in Figs.K and 3 0. values of 1.1/n 2 + 2)]. This was ex- Fig. 2) is seen as nium.. 5. where'P 5 is a tor- sional mode. and comparisons with results of other investigators4_8 0 E are made.43 pm. 5. 4 or Ref.238 Am for 20 K. The refractive indices at X = 0. 72. 2) for 80-K NH 3 is believed to be due to the combination band v4 + v5. No.27 at 20 K. Because there was more scattering in the 20-K a 40 films. 2) with 20-K NH13 2 20 (Fig. The 1050 1060 950 v2 1075 1065 Lorentz-Lorenz coefficient [(1/p(n2. 3. Wood and J. a Ref 4. this yields a film thickness of 0.7-pm-thick solid CO2 on 80-K germa- cm-' and centered at 1650 cm-' for 80 K ( Figs. this is normally associated with the amorphous structure. have a lattice band.and 20-K ger- manium substrates. Roux only one distinct band (V4) located at 1625 cm-1 for 20 K in 60 Fig. 2 and 3.8.and 20-K films.1 and 1. The densities were 0. with a possible contribution by the 2v 4 band. the thin-film interference pattern decayed at much thinner films than for the 80-K films.1 for 80 K and at 3380 'F 20 cm-' for 20 K are assigned to be the v3 vibration band. Transmittance of 14.257 pm between maxima for films at 20 Table 1. fracture 0 or shattering sometimes occurred for the films deposited on the 20-K germanium.155 cm /gm.6328 am 500 900 13W 1700 2100 2500 2900 3300 3700 were found to be 1. The descriptions of 4 5 those films ' and of the physical appearance of the films during deposition correspond to our observations. This band is believed to be due a 40 primarily to the v1 vibration. 1 500 900 1300 1700 2100 . A weak band at 1890 cm-1 (Fig. respectively. 4.

The absorption bands are identified in Table 2.88. and 80 K H20 films were condensed on the cryogenically cooled ger.C1 0 2 . The transmittance spectrum of an 80-K CO 2 film is shown in Fig. 3756 . The spectral-band lo- cations agree with the values observed for the 80-K spectrum ' 20 in Fig. 5. Molecular Bands in H20 (cm-') 6. The spectrum for 80 K is shown in Fig. 4. Soc.50-. 5. 4. 500 900 1300 1700 2100 2500 2900 3300 3700 Wave Numbers manium substrate at temperatures of 20. 0 nation V3 + lattice band is seen to occur at 2460 cm. d ence maximum for X = 0. Table 3.32 at X= (the 15th laser-interfer. The 20 strongest CO 2 band in the spectrum occurs at 2345 cm. is not shown in Fig. which corresponds to a film thickness of 1. The v1 band at 3260-3300 cm-' is solid H2 0 on 80-K germa- nium. 723 Table 2.1 and are the 2v2 + Fig. These bands are summarized in Table 3.C1302 2 2349 2343 2344 2345 2345 P3 . 3710 v1 + P3 a Ref. The corresponding V3 band for the carbon 13 isotope 13CO 2 occurs at 2285 cm-'.88-tm-thick solid CO 2 on 20-K germa- V3 and the P1 + P3 bands. 2455 2460 V3 + Lattice 3609 3600 3610 3600 3600 2v 2 + V3 3716 3710 3712 . 2245 2220 2220 P2 + PL studied. Films deposited at 50 and 20 K look essentially the same as the 80-K H20 data in Fig. 4 but was observed in some sets of mea- surements that were extended to 3950 cm-1. Transmittance of 3. Although transmittance data were taken for the 3700-3950-wave- 60 number range. Wood and J. 8. b Ref. which corresponds to 60 the 55th interference maximum. 50. 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. VL were all quite broad in contrast to those of the gases previously 1650 1595 1665 1665 1665 v2 . Observing 3300 3652 3255 3260 3300 i1 these bands in Fig. appear at 3600 and 3710 cm.6328. E. 5 for a film thickness of 3. 2370/2460 2379/2454. 6.50.1 . maximum. The transmittance spec- trum of a CO2 film deposited on 20-K germanium is shown in ' 40 Fig. and 80 K.m for these three tempera. Therefore. 72. d Ref. A. .C1202 667 660 660 660 665 2283 2282 2280 2282 2285 V3. Four absorption bands or regions were seen for H20. The combi. . as in Table 3.6328 gin). 9. 4. . 654 653 654 650 v2 . of the broadbands. and comparisons can be made with the work of other investigators. No. and . 4. 6/June 1982/J.50 gnm. Opt. .g 0 observed when the wave-number scale is expanded. 6 for the sixth interference Fig. the numbers refer to the approximate centers a Ref. H2 0 Deposited at 20. (30 K)a Vaporb 80 K 50 K 20 K Identification tures. they 750 .gm. respectively. where n = 1. but considerably weaker than the V3 band. Roux Vol. 4 -9 Although this is not readily E apparent from Fig.1 .1 and is the V3 12CO 2 band. 6 makes it obvious that the band locations . Essentially no differences were observed for the refractive Solid Present Work index of H20 at X = 0. The band at 3710 cm' nium. 4 for a film thickness of 12. These bands are . Ref. 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.. 8. one band is observed at 630 cm-1 .4m. Am. The I- 500 900 1300 1700 2100 2500 2900 3300 3700 Wave Numbers final two bands of significance. P3 are too broad to be designated by specific numbers.6328 . 40 two bands are seen at 650 and 665 cm. b Ref. 825 820 800 Libration .C1302 . Transmittance of 1. These bands are associated with the P2 13CO 2 and 12CO2 bands.

low wave numbers. The k value. Generally the nonlinear least-squares results (thin-film Transmittance data recorded for all deposits discussed here model) did converge. the Kramers-Kronig n's along with the least squares k's yielded good agreement when the k (v') -k (vmn)vm dv'.5 s-~ I- index also increases with temperature. the optical properties were obtained through use of an tion. As computed every 10 cm-'. fined. did not have this difficulty and n and k was used in conjunction with the nonlinear least. At small thicknesses.724 J. the k values were used with the Kronig relation is given by subtractive Kramers-Kronig relationship. the transmission is reduced to zero for the PI band. which is defined primarily by the mag- tine. and density are all where 11mis a reference frequency. thickness. Opt.. the period of the transmittance-versus-thickness curve at each surements for wave numbers between 700 and 3500 cm-. and a comparison of the Kramers- were digitized every 2 cm-'. i. was well defined over the whole spectral region (700 to 3700 squares determination of n. both approaches error. 72. and P indicates the Cauchy principle value of the in. A. PI = 700 cm-'.3 It is also seen that the location of the band shifts to higher wave numbers with decreasing temperature. Roux served to be deeper at the higher temperature.50 Am. as is that of the vL band. whereas the 2245-cm. the period mined by using this analytical transmission model' 2 -' 4 in of the interference as a function of thickness is not well de- conjunction with a nonlinear least-squares convergence rou.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.. tained from Eq. . in some in.V" Errors in the refractive index. or analytical model of film-plus-window transmission was used. the transmittance-versus-thickness (for The optical constants of the cryocontaminants were deter. The optical properties were Kronig and thin-film results is shown for NH 3 (Fig. Also.e. However. as a thick film. was assumed that the germanium substrate (window) acted linear least-squares determination.) This trend agrees with warmup data for H20 films studied by Thompson et a. Thus the depth of the absorption band increases with increasing temperature. (3). except in regions of strong absorp.Sqares ness of 0. Wood and J. Soc. a shift toward the opposite direction from the vPband.01 or tegral. The error in the absorption cm-'. each wave number) curve is not well defined.m (first interference maximum) the transmission 205 varies for the PI band from 30% at 80 K to 32% at 50 K and fi- nally to 34% at 20 K. the subtractive Kramers-Kronig relation between nitude of the transmittance. these new n values were then used in the analytical model (along with the k val- n(v) = nf(V) +2p vf2 k(v')v' . (3) were those determined slanted dashed line at the bottom of the absorption-index by the nonlinear least-squares technique. v2 = 3700 estimated to be within 42%. The values of k graphs. E. in which computations were performed every 2 cmi1. The v2 band at 1665 cm-' was independent _1 of temperature. refractive index of the germanium was a modification of that sorption or low wave number or for cases in which it was pos. O. illustrating the same trend observed for a the libration band. transmittance measurements. No. | ~ - ~ Ig raees-Krsn IlneariL. and therefore the smaller the k value the larger the zero or as a constant at the end-point values. For a thick. zs A. It The optical properties were initially computed by the non. The subtractive Kramers.'0 but is shifted at least 30 I 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". This usually occurred in regions of strong ab. For a film thickness I LO of 1. cm-'). . Integration was performed using the simple trape. (3) analytical model and transmittance data were compared. The value of n. whereas it was 3300 Wave Numbers cm-' for 20 K.1 band at 80 K shifted I ZI to 2220 cm-1 at 20 K. The n value appears to be defined primarily by ik) of the thin solid film from the IR-transmittance mea. and the absorption I L. The value of k can vary over several orders of mag- outside 700 cm-' < S < 3700 cm-' were considered either as nitude. index varies from about +2% at high k values (-0. the k values used in Eq. (V')2 . k(v)M ues) to see if good agreement occurred with the transmittance data./Vol. to determine n. 6/June 1982 B.25 . The spectral location of the latter band I agrees with the data of Bertie et al. (The central -7 ODD 13D 27W 27W 300 NSO location for the 80-K film was 3255 cm-'. greater) to a value that is inaccurate for values of k below the zoidal rule. the spectral location of this band is expected to be temperature WaveNumbers dependent. an wave number. and NH 3). and hence there was no phase coherence among stances. Fig. analytical model and the nonlinear least-squares method. For all wave numbers. this is because of the error limits on the film-substrate showed a negligible effect on the values of n that were ob. or high absorption. given by Herzberger and Salzberg"4 to account for the re- sible to form only a few thin deposit thicknesses (20-K H 20 fractive-index change that is due to the cryogenic tempera- . the program did not appear to converge upon a unique multiple internal reflected rays (inside the germanium). Am. OPTICAL CONSTANTS In order to determine the complex refractive index (n = n . 7). 7. Optical properties of NH3 condensed on 80-K germanium. A. Thus. stated.

9) were obtained by solidifying liquid ammonia. Am. The thin film (cryocontamination layer) was consid. 8 is a comparison of the present data at 20 K with the data of Thompson et al. 4 were shown only to 2400 cm-'. The data of Ref. The overall transmittance through the contamination layer on the germanium substrate is given by 0. NH3 bands is clearly seen in the n-versus-v plots of Figs. (4) ID Io 0. ng is the germanium refractive index. (4)] were determined. as was the 2 5 density.0 where n and k are the optical properties of the contamination layer. 8. as is noted Kramers-Kronig method.. 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. 6/June 1982/J. 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.50 to 20 Aum. 725 tures. Comparison of NH3 results at 80 K with those of Ref. The n values are higher at 80 K than at 20 K.5 Similar comparisons were made with Fig. 72.B. The Lambert absorption coefficient was deter- 0. these expressions involve Fres- nel's equations for the interface reflectances and transmit- tances.Arnold. Usually convergence was obtained at each wave number after about 1.0 mined by using thicknesses in the range from 0. Data of Ref. The tabulated results are given in Ref. In general the agreement is good. Sanderson.1 5 (Fig. 4 at 30 the results of Sill et al. 15 at generated improved values for n and k. Marts. 0. Also. Roux Vol. ngV. these were then 190 K. 8 and 9 are a comparison of the re- sults of this work with those of others.Thoson. 2.(300Rd.. respectively. 15 were WaneNumbers obtained at 190 K. the nonlinear least squares Fig. 10 illustrate the comparison with the WaneNumbers work of Pipes et al. No. Wane Numbers The exact expressions' for Eq. as5 Interference effects were not mentioned for these small thicknesses. 15 because of the use of CaF 2 windows. The results are shown in Figs. resubstituted to find an even better solution.) Shown in Fig. 1. v is 0 700 1000 lOW 2000 250 300 350D the wave number. The values of n and k were obtained by knowing v. (Results were limited to 950 cm-1 in Ref.4 at 30K.0 ered to be an optical thin film with properties n and k.. 16 (not shown) for NH3 at 80 K. 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. The anomalous dispersion at the two strong and 8. n and k. but the results of the present work yielded higher values for both n and k. 1 . Comparison of NH3 results at 20 K with those of Ref. nique was good. A. Soc. O. The n values were then determined by using the 0 700 1000 15W0 2000 25W 5 3000 W 3500 substractive Kramers-Kronig method. except that thin-film reflection data were recorded. This procedure was continued until convergence was obtained. 0 is the angle of incidence (here 0 = 0. The same techniques . whereas the present data were obtained at 80 K. However. (4) are algebraically long and tedious but straightforward. Results shown in Fig. and ng and measuring the value of T at known values of d (for CO 2 at 80-K. Wood and J. the results of Ref. the k values at the two major absorption bands . When an initial guess was Waee Numbere 3500 used for the solution for n and k. The K. 4 are greater at 80 K than at 20 K. agreement among all three is excellent. Values below by using both the nonlinear least-squares technique and the the dashed line are shown but may not be accurate. 7 and 8. 7 on the figures. The data given in Figs. which means normal incidence). For both temperatures the agreement between the three iterations. the agreement for the n values is very good. 25 values of r were measured at 25 known values of d). 9. and the agreement for k is generally good. Prent Work . E. d). The results of Rob- '5 ertson et al. Opt. Details of this standard method are available Kramers-Kronig method and nonlinear least-squares tech- in Ref. 4 were obtained by employing basically the same approach as that used in the present tests. k. and d is the contamination-layer thickness.5 T = T(n.

WIrk Rour. 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.5 nonlinear least-squares technique and the Kramers-Kronig 2.- I 70201O0 150 2WO 2520 300 3500 WaveNumbers 10 0 Inacou b7e1° nte 25.5 L5 c L ez'1!NaIL thlkoeventIy.t Is 6.5 NH3 . 11. No. 0K 2.2 ' L! I . - Present ----. 13. at 20 K. In some regions (i3300 cm-') the nonlinear least W-e.ScootM i8K. 72.726 J. the higher temperatures yielded higher values for n and II k as well as for the density. As was true for I I 1.Wave Fig.80K --. they were used in the analytical model to generate the theoretical curves. Roux 2. Comparison of NH3 results at 80 K with those of Ref.1t. L l I Determination of n and k for CO 2 at 80 K was made by J. 10./Vol. Fig. except that the present work employs a much better technique for determination of film thickness. Opt. Effect of substrate temperature on H2 0 optical properties stants for CO 2 at 80 and 20 K are available.. 13. H2 0 Optical Constants The optical constants for H2 0 at 80.'-. 5 at 80K. 3aI 35 Numbers . 12 for 80 K. Numbers Fig. E. The agreement between theory 0 700 loc 1520 2000 2020 3to 3500 and data is shown in Fig. 14 thicknesses were used. 50.0 Thickness. lnn Fig.. were used both in the present work and by Pipes et al. . 6/June 1982 B. the same research cell was also used. CO2 Optical Constants 20o0 250 3000 The optical constants for CO2 at 80 and 20 K were determined WaveNumbers and are shown in Fig. 50. Ret. Effect of substrate temperature on CO 2 optical properties (20 and 80 K). 11. <' To . Smith. A. r I using transmittance measurements at 25 thicknesses. After the n and k values WaveNumbers were determined. Possibly these n and k values are unique in the literature. Figure 11 shows the effect of temperature on the CO2 optical properties. Tabulated results for these con. Comparison of theory and data for 80-K solid CO 2 for three WaneNumbers different wave numbers. . Soc. and 80 K). 12. and 20 K are shown in Fig. Am. Wood and J.' Results of the (20.0 -20K 1.0 method were in good agreement. . --.-Pips. blmYss 10-3 .

C0 2 . the Kramers-Kronig method to generate n values. 10 at "Optical properties of cryodeposits on low scatter mirrors. E. The n and k values were determined by using absolute 8. A." J. 39. 10o3 NOTE: k values belnw thisline 2. CH 4 . B.70-20. From the trans- ------. E. Am. (As was mentioned earlier. Jr. . 15W0 .l L.. and A. 10-2 REFERENCES 1." AIAA J.6328 Am to permit accurate thickness measurement. U. G. Septembei 1979)." J. ensure good agreement. J. 1954). Additional n and k properties have been determined D)LLI for CO. J. -Thompson. pp. Princeton.0-. 3000 3500 Systems Command (AFSC) while the authors were with ARO. 16. A. Chem. Fig. Vol. Pipes. NO. N. for ecules (Van Nostrand." Appl. M. Roux. wavelength range).) For results10 in Fig.0 before shattering occurred. HCd. Then the 6. the data were a WaveNumbers obtained at 100 K. 6/June 1982/J. Cam- bridge.. Chem. P. graphical and tabular' form for a wave-number interval of 2 L A cm-1 . In Fig. These results are available in I. K. All the k values in Fig. ammonia. 55. Tempelmeyer.0 LA . "Infrared spectra and vapor least-squares k values and Kramers-Kronig n values were pressure isotope effect of crystallized ammonia and its deuterium used in the analytical model and compared with the data to derivatives. Ammonia and deutero- the error line and thus should be considered accurate values. and E. LabOW. Opt. 4 at crystal micdbalances (QCM's) and by calculating the re- 30 K. WaveNumbers The densities of the films were determined by using quartz- Fig. B. at 20 K only 8 thicknesses (-1. Figures 14 and 15 show comparisons of the present work LI with the results of Thompson et al. "Infrared the k values from the least-squares technique were used with transmission of contaminated cryocooled optical windows. a5 and the pressure was about 10-6 Torr. E. Roux. 4) used. 15. R. P. Comparison of H 2 0 results at 20 K with those of Ref.10 re- spectively. and B. J." AIAA could be formed before shattering occurred. Wood. Mass. Arnold. The infrared spectral transmittance was studied over the 500-3700-cm-1 range (the 2. 72. but the deposition pressure was not given. M. N 2 0. Infrared and Raman Spectra of Polyatomic Mol- transmittance measurements at 25 thicknesses for 80 K. W. N2 . Mills. Comparison of H2 0 results at 80 K with those of Ref. Roux Vol." in 100 X. andWhalley(IWKt. Smith.10 mittance data. 594-601 (1951). NH 3 . R.. SUMMARY Experimentally determined transmittance measurements of condensed gases on a cryogenically cooled germanium window were made. 1974).. Phys. 02. Wolff. M. A. F.. No. 17 thicknesses were used. 2274-2280 (1969). Tempelmeyer and D. Soc. Smith. 229-248.17 The work reported herein was conducted at the Arnold Engineering Development Center (AEDC). Wood and J. Thin films of NH3 . (Ref. "II I"A * Formerly with ARO. "IR optical properties of thin H2 0. Rollar. Thermophysics and Spacecraft Thermal Control. 19.B.7 . Sanderon. Air Force us A 700 15WD . an operating con- 1'S tractor for the AEDC. WaveNumbers Inc. 14. "The vibrational spectra of mol- ecules and codnplex ions in crystals. 1373-1378 (1971).. S.m) 2. for 20 K. Inc. H. Therefore 5. 984-990 (1978).4 and Bertie et al. 13 were above 7. "Angular distribution of visible and near IR radiation reflected 70 15W 15W 25W 25X 35W 35W from CO2 cryodeposits." AEDC-TR-79-57 (AD- A074913. 35 in Progress in Aeronautics and Astronautics (MIT Press-. E. Muller. F. and H.. and A. Reding and D. 15. 727 -Preent Work 50 K. At 50 K only 17 thicknesses could be formed (-2. Wood. and CO2 cryofilms. G. Smith. Sanderson. A. fractive index at 0. G. F.S. A. andMant (30k)(Ref. H. E.J. carbon dioxide cryodeposit. the optical properties n and k were determined for the 700-3700-cm-1 range. 14 the deposition temperature 4 was 30 K. squares did not converge on b unique value of n. Monty. Some fracture and shattering effects were PreentWork observed for the films condensed at 20 K. V. Hornig. Phys. Opt. Herzberg. Thompson. Scott. 2DO s . K. and Ar films. a Sverdrup Corporation company. 2968-2969 (1968). and H2 0 were deposited at 20 and 80 K. W. "Refractive index of mayte inaccurate. 7. Bertie. 8 thicknesses were Arnold. WaveNumbers 4. 3. the results4 were obtained through a thin-film re- 700 100 MW 2000 2500 325 3500 flectance analysis. The film thickness was accurately de- termined by using a two-angle laser-interference technique. Wolff. E.

Watney-Kaczer) (1980). J. Whalley. 14. 70. VI. Heavens. August 1980). A. "Absorptivity of ice I 15. Herzberger and C. E. H. S. W. Ockman. "Absorption coefficients of solid 7. Am. 52. and York." J. NH3 from 50 to 7000 cm-1 . . Carbon dioxide. R. No. Ar. M. 17. C. Chem. Osberg and D. A. Vasicek." Adv. 1965). (Interscience. 724-739 12. 65. N2 0. U. G. Opt. E. 10. New York. air cryofilms. R. Phys. and R. Phys. A. CH 4 . Downing. Hornig. Fink. HCl. 432-435 (1975). Am. H. M. Robertson. N. 0. D. Salzberg. optical materials and color correction of infrared lenses." J." J. 1960). and E. Chem. H. Soc. Ferraro. Roux. Am. 1345-1357 (1952). 50. A." J. and D. J. J. Roux 9. Sill. Phys. and J. Wood. Plyler. Opt. Williams. B. "The vibrational spectra of mol. 4501-4520 "Optical constants of solid ammonia in the infrared. Smith. "The infrared and raman spectra of ice. "Refractive indices of infrared ecules and complex ions and crystal. New optical properties of thin CO. "Infrared 13.728 J. Bertie. B. Am. E. Optics of Thin Films (Trans. 11. 6/June 1982 B. Curnutte." AEDC-TR-79-81 (AD-A088269. Optical Properties of Thin Films (Dover. N 2. Wood and J. 72. Opt." J. 16. NO./Vol. (1969). Soc. E. W. F. 20. Labbe. 420-426 (1962). Soc. 02. D. in the range 4000-30 cm-'. Soc. Opt. 199-220 (1957).