j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 1 9 9 ( 2 0 0 8 ) 412–416

journal homepage: www.elsevier.com/locate/jmatprotec

Control of the thickness distribution of evaporated

functional electroceramic NTC thermistor thin films

R. Schmidt ∗ , M. Parlak, A.W. Brinkman

University of Durham, Department of Physics, South Road, Durham DH1 3LE, United Kingdom

a r t i c l e i n f o a b s t r a c t

Article history: In this work the thickness distribution of NTC thermistor thin films produced by low depo-
Received 2 October 2006 sition rate (0.8 nm s−1 ) electron-beam evaporation is investigated. The target preparation,
Received in revised form deposition conditions and geometrical set-up of the evaporation mechanism are described
3 August 2007 in detail. The evaporation geometry is shown to be critical for the thickness distribution of
Accepted 8 August 2007 evaporated films. The film thickness distribution of evaporated layers was measured across
a macroscopic film surface using Alpha Step stylus profileometer. The thickness distribu-
tion was fitted using a geometrical model derived from evaporation theory, based on the
Keywords: Hertz–Knudsen equation and a modified version of the cosine law of emission. From this
Low rate electron-beam evaporation model, the sticking coefficient of the vapour on the substrates could be estimated to be
Thickness distribution 80 ± 1.5%.
NTC Thermistors © 2007 Elsevier B.V. All rights reserved.
Electroceramics

1. Introduction tion detection and stabilised temperature sensors (Parlak et

Negative temperature coefficient thermally sensitive resistor
(NTC thermistor) electroceramics based on nickel manganate
possess a partially inverse spinel structure and exhibit a neg-
ative temperature coefficient of resistance (NTCR), where the
resistance increases exponentially with decreasing tempera-
ture (Macklen, 1979). Despite optimisation of the production
processes of bulk material, severe problems of poor stabil-
ity and reproducibility remain in bulk materials due to high
porosity and incomplete inter-granular contact, which ham-
pers thermistor applications such as temperature sensors,
gas flow meters and attenuators. Therefore, film produc-
tion is interesting, for example in multilayer packages
with an NTC thermistor component. In an earlier com-
munication it was shown that in principle NiMn2 O4+ı thin
films may be produced by Electron-Beam Evaporation (EBE)
showing NTCR behaviour, and may be used in thermistor
applications such as multi-layer packages, infrared radia-
al., 1998; Schmidt and Brinkman, 2001). EBE is a physical
vapour deposition (PVD) process, and belongs to the same
class of deposition techniques as cathode arc evaporation
(Dobrzanski et al., 2006) or thermal evaporation (Boscornea et
al., 2001).
EBE is commonly used for evaporating metals (Au, Ag and
Al), transition metals such as Mo (Guillen and Herrero, 2003),
alloys (CoCrAlY) (Rybnikov et al., 1995), and more recently
for ceramic oxides such as YSZ based systems (Watanabe et
al., 2004). EBE is a rather simple technique, which makes it
favourable in principle over other thin film deposition pro-
cesses used for ceramic oxide depositions, for example rf
magnetron sputtering. In EBE the source powder can be of
any average grain size and grain size distribution and needs
no further developing, the deposition process often does not
require a specific gas atmosphere, and the deposition rate can
be varied easily by adjusting the beam current. An annealing
procedure of the sample is usually required after deposition.

∗
Corresponding author.
E-mail address: rainerxschmidt@googlemail.com (R. Schmidt).
0924-0136/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmatprotec.2007.08.014
 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 1 9 9 ( 2 0 0 8 ) 412–416
In most of the EBE studies quoted above, the process is used
for deposition of microscopic contacts, whereas in this study
a macroscopic film is deposited for device fabrication. In con-
trast to microscopic contacts, macroscopic film dimensions
make the thickness distribution of such coatings interesting.
In EBE the evaporation system geometry is the main factor to
predict and tailor the film thickness distribution, which is of
less importance for metal and alloy contact deposition of the
materials mentioned above. Thus, not much effort has been
made yet to describe and control the evaporation geometry,
and the resulting film thickness distribution.
Source–substrate distance, the electron-beam focus and
the size of the active source area are the main parame-
ters defining the evaporation geometry and determining
the thickness distribution. In this paper it is shown that
low deposition rate EBE allows thin films to be pro-
duced, where the thickness distribution can be predicted
precisely, based on a geometrical model derived from
evaporation theory, the cosine law of emission and the
Hertz–Knudsen equation. The theoretical model is derived
explicitly and extended by introducing a sticking coeffi-
cient, which is useful to predict film thickness. The EBE
geometry and all deposition parameters are described in
detail.
2. Experimental methods
NiMn2 O4+ı source powder was produced by mixing, grinding
and firing the precursor oxides NiO and Mn2 O3 . The oxides
were fired at 1200 ◦ C for 8 h and tempered at 800 ◦ C for up
to 50 h to restore phase purity (Wickham, 1964). Films were
grown on 1 mm thick soda lime glass substrates, which had
been cleaned with liquid detergent, followed by exposure to an
ultrasonic water bath containing dissolved decontamination
agent (Decon 90) and by applying a refluxing procedure in hot
isopropyl alcohol (iso-2-propanol) for 4 h. The EBE system used
is shown in Fig. 1(a) and in the schematic diagram in Fig. 1(b).
Electrons emitted from a tungsten filament were accelerated
through a variable high potential (HV) and focussed onto
the NiMn2 O4+ı source powder contained in a carbon crucible,
which was mounted on a water-cooled pedestal. During depo-
sition the substrates were heated to 100 ◦ C. The deposition
chamber was evacuated using a rotary backed oil diffusion
pump and the evaporation process was carried out at pres-
sures of ∼10−3 Pa. The following parameters proved to be
optimal for the film growth:
Distance source–substrate (h): 85 mm
Distance source–filament: 25 mm
Filament diameter: 15 mm
Beam current: 20 mA
High voltage: 5 kV
Radius of the electron spot on the 1.5 ± 0.3 mm
source surface (S):
The size of the electron-beam spot on the source surface
defines the active source area releasing the vapour, which is
highlighted in Fig. 1(b) and (c). In turn, the beam focus depends
413
on the filament diameter, filament current and the high volt-
age.
In order to obtain the thickness distribution of a grown
film, a regular array of holes was marked into a film
revealing the blank substrate underneath, as shown in
Fig. 2. The film thickness at each of the holes was mea-
sured using a Tencor Systems Alpha Step 200 stylus
profileometer.
3. Theoretical model
Following the approach of Maissel and Glang (1970), and
Ohring (1992), the mass flow rate  of evaporated particles
dNe per evaporating area Ae on the source can be described
by the following expression based on the Hertz–Knudsen
equation:
dNe
 m 1/2
 =m = p∗ (1)
Ae dt 2kB T
where m is the mass of an evaporated particle, T the tem-
perature and p* is the partial vapour pressure of the source
material. It was assumed here that only linear molecular flow
of evaporated particles occurred, which is a valid approach for
low rate evaporations where the density of emitted particles is
low. For high rate evaporations, significant contributions occur
from diffusive transport close to the source surface, where
a high particle density is exhibited (Schiller et al., 1983). For
this case complex analytical models have been developed to
approximate the thickness distribution (Chaleix et al., 1996;
Piot et al., 1997). During a full low rate deposition process of
time t, the total amount of evaporated material Me is given
by
 
Me = dAe dt (2)
t Ae
For an infinitesimal small substrate element dAr , the mass
fraction dMr deposited from a point source can be described
according to the cosine law of emission:
Me
dMr (ϕ) = cos ϕ dAr (3)
r2
where r is the distance of the point source to the substrate
element dAr and ϕ is the evaporation angle, as illustrated in
Fig. 1(b) and (c). A sticking coefficient  (0 <  < 1) was intro-
duced here to describe the fraction of evaporated material,
which sticks on the substrate without re-sublimation. The film
thickness d in dAr is given by
1 dMr
d= (4)
 dAr
where  is the volume density of the material. Eq. (3) was
substituted in (4), and the expression integrated over the full
circular active source area dAe = S d˛ dS, given in polar coordi-
414 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 1 9 9 ( 2 0 0 8 ) 412–416

Fig. 1 – (a) E-beam evaporator kit, (b) schematic diagram showing the basic principle of the electron-beam evaporation
system: source substrate distance h, evaporation angle ϕ, and (c) geometry of an E-beam deposition process (reproduced
from Maissel and Glang (1970)): evaporating area Ae on the source, radius S of the active source area, infinitesimal substrate
element dAr .

nates: parameter, which significantly influences the thickness d and

  the shape of the thickness distribution. Therefore, precise con-
Me 1 trol is desired.
d= 1−  (5)
2S2 1 + 4h2 S2 /(h2 − S2 + l2 )
2

4. Results and discussion

where the thickness d is expressed in terms of the stick-
ing coefficient , distance l of the film section to the normal
source–substrate axis, source–substrate distance h, total mass
of evaporated material Me and the radius of the active source
area S. Examination of Eq. (5) indicates that S is a critical
The profile of the film presented in Fig. 2 is drawn in Fig. 3 as a
plot of thickness versus position of the film section (X/Y Data).
From this distribution a cross-section through the thickness
maximum was taken parallel to the Y-axis. Both, this cross-
 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 1 9 9 ( 2 0 0 8 ) 412–416
Fig. 2 – E-beam evaporated film on soda lime glass
substrate with a regular array of exposed substrate for
thickness measurements.
section and the theoretical curve calculated from Eq. (5) using
the experimental parameters given in Section 2 were plotted
in Fig. 4. The theoretical and experimental curves are shifted
on the Y-axis in Fig. 4, but align perfectly if it is assumed
that a sticking coefficient  of 80 ± 1.5% occurred. This value
is reasonably high to conclude that the EBE process used is
appropriate to effectively deposit NTC thermistor layers.
The total evaporated mass Me was measured from the
weight loss of the source: 0.24 ± 0.01 g; and the density  of
the films was taken to be 5.25 g cm−3 , which is the theoretical
value of the NiMn2 O4+ı crystallographic spinel unit cell. For the
thin evaporated films investigated here, it was reasonable to
assume that the film density was very close to the theoretical
Fig. 3 – Film profile obtained from the sample shown in
Fig. 2.
415
Fig. 4 – Film profile, geometrical model and
source–filament–substrate trajectories; (–) theoretical curve;
(. . .) experimental thickness distribution; (– – –)
source–focusing cage–substrate trajectories.
value, because no pores or other irregularities were observ-
able in the films using scanning electron microscopy (SEM)
(Schmidt et al., 2004). On the other hand, this estimation might
contain a perceptible error as the crystallinity of as-deposited
films was rather poor (Schmidt et al., 2006). Post-deposition
annealing proved to be difficult as re-evaporation occurred by
annealing at 800 ◦ C, which is required to ensure phase purity.
From Fig. 4 it can be seen that the thickness drops dramati-
cally at the film periphery. This is due to the shadowing effect
of the focussing cage as demonstrated by the source–focusing
cage–substrate trajectories (see Fig. 1(b) and Fig. 4). The open-
ing angle of the trajectories was determined by the aperture
in the focusing cage, which was 12 mm in diameter.
5. Conclusions
The thickness distribution of NTC thermistor NiMn2 O4+ı thin
films deposited by low growth rate electron-beam evapora-
tion can be described with a model based on an extended
cosine law of emission and the Hertz–Knudsen equation.
Model and experiment showed excellent agreement and the
sticking coefficient of the vapour on the substrate could be
estimated from the derived model.
The thickness distribution function is a powerful tool to
predict the shape and thickness of low growth rate evaporated
thermistor films and enables a highly controlled evaporation
processes if the active area of the source is known precisely.
It has been shown previously that the film stoichiometry can
vary to the target composition (Schmidt and Brinkman, 2001),
but it is believed that the film stoichiometry may be predicted
effectively if well-controlled EBE is carried out under constant,
optimised and reproducible conditions. The method may be
regarded suitable for thermistor device fabrication and may
also be considered for the production of various other func-
tional ceramic oxide devices.
416 j o u r n a l o f m a t e r i a l s p r o c e s s i n g t e c h n o l o g y 1 9 9 ( 2 0 0 8 ) 412–416
Acknowledgement
R.S. wishes to thank Thomas Winiecki for advice about theo-
retical issues.
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