JOURNAL OF THE OPTICAL SOCIETY OF AMERICA VOLUME 48, NUMBER 5 MAY, 1958

Optical Properties and Structure of Cerium Dioxide Films

G. HASS, J. B. RAMSEY,AND R. THUN
U. S. A rny Engineer Research and Development Laboratories, Fort Belvoir, Virginia
(Received November 6, 1957)

The refractive index n and the absorption coefficient k of evaporated CeO2 films were measured in the
wavelength region from 0.22ju to 1.01g. Films produced by direct evaporation of CeO2 were found to be
extremely durable and nonabsorbing in the visible and can be used as beam splitters and as high-index films
in multilayer film combinations. The refractive index of CeO2 films depends strongly on the temperature
of the substrate. An increase of the substrate temperature from 250 C to 300'C increases the refractive
index of the condensed film material at X= 550 miu,from about 2.2 to 2.4. The absorption of CeO2 films increases
strongly below 400 m~uand reaches a maximum at 300 m. Evaporated CeO2 films show the same cubic struc-
ture as compact material and crystallize without preferred orientation on amorphous substrates. The
crystal size in the condensed films increases with increasing temperature.

I. INTRODUCTION Maywood Chemical Works, was placed in the tungsten

WITHthe increasing use of multilayer coatings of boat and heated to evaporation temperature by passing
350 to 400 amperes through the boat. The glass plates
alternately low and high indexes of refraction,
high-index dielectrics suitable for producing durable to be coated were mounted about 18 inches above the
nonabsorbing films by evaporation in high vacuum are evaporation source. They could be cleaned by a dc
gaining in practical importance. The material most glow discharge using 5000 volts and 75 milliamperes
widely used for the deposition of high-index films is and could be heated up to 350'C with nichrome wire
zinc sulfide (ZnS). ZnS films, however, even if applied heating elements placed above them. A removable
under heat or put through a complicated baking process, Japanese fan type shutter was placed close to the glass
do not show completely satisfactory durability in the plates to avoid contamination of the plates while the
beginning and deteriorate quite frequently with aging. boat and CeO2 were being outgassed and brought up
A high-index film material of much better mechanical to constant evaporation speed. The pressure in the
and chemical durability is titanium dioxide (TiO2). vacuum chamber could be maintained at 1X10-5 mm
Unfortunately, however, TiO2 does not belong to the Hg during the film deposition or could be intentionally
substances which can be readily evaporated. It is increased by the use of a needle valve. The thickness of
reduced at the high temperature required for its the films was controlled during the evaporation process
evaporation and condenses as an absorbing film. Most by measuring their reflectance and transmittance with
of the nonabsorbing TiO2 films used as optical coatings monochromatic light during their deposition. The true
are, therefore, prepared by heat or anodic oxidation thickness t of the films was measured by a multiple beam
of evaporated titanium or slightly reduced titanium interferometer method as described by Tolansky.'
dioxide films.' The reflectance R and transmittance T of a great
Only recently a new film material, cerium dioxide number of films, deposited under various evaporation
(CeO2), was found to be qualified for producing ex- conditions onto glass and fused quartz were measured
tremely durable nonabsorbing high-index films by from 220 mgito 1000 mu with modified Beckman Model
direct evaporation in high vacuum.2 It is the purpose DU and DK Spectrophotometers. All R and T values
of this paper to present data on the optical properties reported in this paper were determined within 0.3%
and structure of CeO2 films prepared under various of the incident light, and the measurements were made
conditions, and to demonstrate their usefulness in at close to normal incidence. The measured R and T
multilayer film combinations. values were corrected for the effect of the back surface
reflection of the substrate and the substrate absorption,
II. EXPERIMENTAL TECHNIQUES and then used to determine the refractive index n and
Tungsten boats made of 0.4- to 0.5-mm thick sheet the absorption coefficient k iK of the various films.
material were used to evaporate CeO2. To remove To obtain the optical constants from R, T, and I
ignitible impurities and the water content of the strongly measurements, a graphical method was applied which
hydroscopic CeO2 powder, it was baked and sintered used a great number of curves displaying R and T as
in air at about 1100'C shortly before each evaporation. function of t/X for films of various n and k values on a
Unbaked material resulted in films with lower index nonabsorbing substrate of n 3=1.5. The graphs were
of refraction and unreproducible properties. The calculated from the equations developed by Hadley
sintered 99.5% pure CeO2, procured from Lindsay and Dennison4 and cover a range of values for n from
Chemical Company, A. D. MacKay, Inc., and from 3 S. Tolansky, Multiple Beam Interferometry of Films and
Surfaces
4
(Clarendon Press, Oxford, 1948).
IG. Hass, Vacuum II, 33 (1952). L. N. Hadley and D. M. Dennison, J. Opt. Soc. Am. 37,
2 G. Hass and J. B. Ramsey, J. Opt. Soc. Am. 45, 408A (1955). 451 (1947).
324
May 1958 CERIUM DIOXIDE FILMS 325

0 to 6 and for k from 0 to 5.* In the region of no absorp-

tion, the film indexes were also computed from the
reflectance values at the quarterwave positions.
The structure of CeO2 films was examined by electron
wa4
diffraction. The electron diffraction studies were made
with the RCA Electron Microscope Type EMU. Thin
Z3
films of silica, produced by evaporating silicon 4 >.~~~~X-550
'A
monoxide, were used as structureless supporting mem- ~22
branes. 5 Thus, the CeO2 films measured optically and
studied by electron diffraction were deposited onto the
same glass-like substrates. The crystal sizes in CeO2 50 100 150 200 250 300 350
SUBSTRATE
TEMPERATURE C)
films were computed from the half-widths of the
electron diffraction rings measured with a recording FIG. 2. Effect of substrate temperature on the refractive index of
microphotometer. CeO 2 films at X=450 m1Aand X= 550 m,.

III. OPTICAL PROPERTIES OF CeO2 FILMS fresh material. The use of a shutter in front of the glass
plates until evaporation speed and pressure reach
Figure 1 shows the visible reflectance and trans-
constant values is, therefore, most important for
mittance of two films of cerium dioxide, each one-
producing films with best mechanical and optical
quarter wavelength thick in the visible, deposited on a
properties. In all film preparations discussed in the
glass plate at 300C. The first film, called 1st evapora-
following parts of this paper, a removable shutter was
tion, was prepared with fresh material and without
used to avoid contamination of the glass plates with
vapor given off during the beginning of the evaporation.
w
Z6 70 r-FIRSTIVAPORATION
Figure 2 shows the effect of substrate temperature
2
i I
I- I- _:: on the refractive index of CeO 2 films at X= 450 my and
60 I
LSECONDIEVAPORANON X =550 mu, respectively. By increasing the substrate
so - temperature from 50C to 350C, the refractive index
I-
w
7SECONDIEVAPORATION
of the condensed film material increased from 2.18 to
R- =::
2.42 at X =550 myi and from 2.28 to 2.53 at X=450 myi.
C
,VAPORATION In contrast to the substrate temperature, other factors
20 such as deposition rate and pressure during the evapora-
10
450
-L
500
___
550
--- --- ---
7QU.
tion were found to have only very little effect on the
WAVELENGTH IN MILLIMICRONS optical properties of CeO2 films. If films of very high
index of refraction are desired, CeO2 should, therefore,
FIG. 1. Reflectance and transmittance of CeO2 films prepared
with fresh material and with material previously outgassed and be condensed on heated substrates. In addition, films
melted. Both films X/4 thick at X=600 mu deposited on glass at evaporated onto heated glass plates show much better
300°C. abrasion and scratch resistance than those condensed
at low temperatures.
using a shutter while the CeO2 was brought up to Figure 3 shows the dispersion curves of 200 A to
evaporation temperature. The second film, called 2nd 600 A thick films of CeO2 condensed at 50C and 300C.
evaporation, was prepared with material previously The absorption of CeO2 films increases strongly below
outgassed and melted. Both films show no appreciable 400 mu and reaches a maximum at 300 mit. This results
absorption in the visible, but the reflectance of the film in a maximum for n at 340 myuand a strong normal
prepared with melted and outgassed material is con- dispersion in the near ultraviolet and visible. The use of
siderably higher than that of the film produced with
fresh material. The glass plate coated in the second
3.2 .. ..-. .. .. .
evaporation has a maximum reflectance of 36.3% at 2.8
X=600 mu which corresponds to a refractive index 2.6
2.4
n= 2.38, while the maximum reflectance of the film 22
prepared with fresh material is only 32.5% and has, 2.0
2:°8
-- -- Ei E5 I 111 11
therefore, a refractive index of 2.30. Films with the
I.
highest possible refractive index can only be produced I 0 hjd~
with completely outgassed and melted material. In
addition, films produced with outgassed and melted
material are more durable than those prepared with 02 03 0.4 0.5 0.6 0.7 0.8 09 1.0

WAVELENGTH
IN MICRONS.
* The authors are indebted to Dr. L. N. Hadley for preparing
the graphs used in this paper to determine n and k. FIG. 3. Dispersion of CeO 2 films between 200 A and
5 G. Hass and H. Kehler, Optik 5, 48 (1948). 600 A thick from 0.2 to 1.0,.
326 RASS, RAMSEY, AND THUN Vol. 48

TEMPERATURE
(C)
200C and 250 0 C showed a lattice constant of 5.41 A
. lO 0 000 0
U)NN,2 0 which is identical with that of the compact material.
bc
AC Above 250C, the lattice constant increased slightly,
Z
probably due to an increase of the number of lattice
I- dislocations with temperature and a freezing in of these
4 4C
dislocations during the comparatively fast cooling
Q)

4
30 <1

Io -; 1;
L-
Tf3I
. -_
1 ^1 fI off rate of the film after its deposition. Although
subsequent heating of low-temperature films had no
appreciable effect on the optical constants, it resulted
O2
w i.8 Z4 6 Z 3.-3. 1- in a slight decrease of the lattice constant toward the
1.6. 1.8 2.0 22 2.4 2.6 2.8 310 3.2 X 10'" value of the bulk material.
lI TEMPERATURE
(K-') The density difference corresponding to the lattice
FIG. 4. Crystal size in CeO2 films as function of the
constant difference between films of low and high
substrate temperature during deposition. substrate temperatures accounts only for a small part
of their difference in the refractive indexes (about
CeO2 in multilayer film combinations below 400 m/ is 25%), as one can easily show by use of the Lorentz-
prohibited because of the absorption in this region. The Lorenz law.7 The main cause of the lesser density of
shapes of the n and k curves are fairly similar for both low-temperature substrate films must be sought,
substrate temperatures. This indicates that the smaller therefore, in a greater content of less dense packed
n and k values of the low-temperature films are caused boundary layers between the crystal grains and, corre-
mainly by a lower density and not by a different chemi-
100_ _ _
cal composition.
With increasing film thickness, CeO2 films show a
rapidly increasing surface roughness and, therefore, 80g6 ~~~~~R-
high scattering losses, especially in the ultraviolet.
60
This introduces a great uncertainty in the n and k
determination of thicker films (> 1000 A) in the
ultraviolet. It could, however, be established that the 40

refractive index of thicker CeO 2 films (t=2000 A to 20

3000 A) drops at the shorter wavelength side of the n
maximum to lower values than that of thin films C
450 500 550 600 650
(t= 200 A to 600 A).
WAVELENGTH
IN MILLIMICRONS
IV. STRUCTURE OF EVAPORATED CeO2 FILMS FIG. 5. Reflectance and transmittance of glass (N, = 1.51) with
a three-layer coating CeO2 -MgF 2 -CeO 2 as function of wave-
CeO2 is known to crystallize in a face-centered cubic length from 450 myt to 650 inp. Each layer X/4 thick at X= 525 mit.
lattice with a lattice constant a= 5.41 A.6 Substrate temperature during deposition: 300CC.
All evaporated CeO2 films showed the same cubic
structure and they crystallized without preferred spondingly, in a smaller average size of the crystal
orientation when deposited on amorphous substrates grains. This agrees well with the conditions found by
such as SiO or quartz glass. The lattice constant of films Riedmiller8 in evaporated metal films.
deposited at room temperature was measured to 5.44 A, The strong decrease of the crystal size with decreasing
while all films condensed at temperatures between substrate temperature was checked experimentally by
evaluating electron diffraction diagrams according to
TABLE I. Reflectance, transmittance and absorption of quarter
wavelength thick CeO2 films deposited on substrates of n, = 1.50 the Scherrer formula.' The result is given in Fig. 4.
at 300'C. The chosen presentation shows that the crystal size is,
over the observed range, fairly proportional to
Wavelength (A) % Reflectance % Transmittance % Absorption exp (- T- 1 ) where T is the temperature in K. This
3200 41.0 24.2 34.8 relation may be due to the dependence of the crystal
3400 46.0 32.3 21.7
3600 47.0 43.0 10.0
size on the mobility of the surface molecules during the
3800 45.5 50.7 3.8 condensation-crystallization process which will follow
4000 43.0 55.7 1.3 a similar law.
5000 35.5 64.5 0
6000 33.8 66.2 0
7000 33.4 66.6 0 V. APPLICATIONS OF CeO 2 FILMS
8000 33.1 66.9 0
9000 32.8 67.2 0 Single films of cerium dioxide already have a suffi-
10 000 32.6 67.4 0 ciently high reflectivity to be used as beam splitters
6 H. E. Swanson and E. Tatge, Natl. Bur. Standards Circular 7A. Sommerfeld, Optics (Academic Press, Inc., New York, 1954).
539 (1949). 8 R. Riedmiller, Z. Physik 102, 408 (1936).
May 1958 CERIUM DIOXIDE FILMS 327

satisfactory for many applications. They are not only

simple but yield also a broader high reflectance band 90
and, therefore, a more neutral intensity distribution z
I-.
80
over the used wavelength region than multiple film
beam splitters of comparable reflectivity with high 70
index layers of a lower refractive index. The highest 60
I-
reflectivities of a single layer CeO2 beam splitter 50_
obtainable on a substrate with an index of 1.5 are given .1 i
Of-
for different wavelengths in Table I. A .5 . 7 .8 . 0
ID .1 1.2 1.3 1.4

When beam splitters of high reflectance are desired, WAVELENGTH

IN MICRONS
CeO2 may be also used in multilayers, combined with
FIG. 7. Reflectance of evaporated Al with and without two
low index films of MgF 2 or SiO. The visible reflectance reflectance-increasing film pairs of MgF2 and CeO2 as function of
and transmittance of a 70-30 beam splitter are shown wavelength from 0.4 to 1.4 ,.
in Fig. 5. The reflecting surface of this beam splitter is
a three layer film of CeO 2 -MgF 2-CeO 2 , deposited broad spectral region by using pairs of dielectric films
onto a glass plate at 300C, each film a quarter wave- with alternately low and high indexes of refraction.
length thick at X= 525 mp. The film is not absorbing in To obtain highest reflectance, the dielectric films must
the visible and has a maximum reflectance of 71.5% be effectively one quarter wavelength thick and have
at the mentioned wavelength. to be applied in the following sequence: metal, low-
With an increasing number of high-index-low-index index film, high-index film. The visible reflectance of
film pairs, such combinations are showing more and evaporated aluminum with and without a reflectance
more filter properties. Nine and eleven layer coatings increasing film pair of MgF 2 and CeO 2 is shown in Fig. 6.
The coated aluminum surface has a maximum re-
10(
flectance of 96.3% and, at all wavelengths of the visible
z spectrum, higher reflectance than the uncoated alumi-
num film.
a 90 In some cases, it is desired to have very high re-
.1 flectance both in the visible and in the near infrared
at 1.0 to 1.3 ,. This can be obtained by coating alumi-
num with two reflectance-increasing film pairs of
AT
o
T T T MgF2 and CeO2, each film effectively one-quarter
450 500 550 600 650 wavelength thick at = 500 m/i. The reflectance charac-
WAVELENGTH
IN MILLIMICRONS
teristic of such a combination is shown from 0.4 to
FIG. 6. Reflectance of evaporated Al with and without a 1.6 A in Fig. 7. Over a great part of the visible spectrum,
reflectance-increasing film pair of MgF2 and CeO2 as function of
wavelength from 450 mguto 650 mju. the coated aluminum has a reflectance of more than
98%, while in the infrared from 1.0 to 1.4 , the
of CeO2 and MgF2 were prepared, either with maximum protected and the unprotected film show equal re-
reflectance in the visible as "cold reflectors" or with flectance of 95 to 96%.
highest reflectivity in the near infrared as heat reflecting Very durable reflectance-increasing film combinations
filters. These coatings showed excellent abrasion and of SiO and CeO2 , or of A12 0 3 and CeO 2 , have also been
corrosion resistance, even when exposed to salt water applied to evaporated aluminum with good results.
spray or when boiled in a 10% NaCl solution for several The given examples show only a few of the possible
hours. The resistance against thermal shocks, too, was applications of CeO2 films, but they may indicate at
remarkable. least the advantages of this material for certain optical
The reflectance of a metal can be increased over a coatings.