Thin Solid Films 405 (2002) 270–275

Nanostructural characterisation of SnO2 thin films prepared by reactive

r.f. magnetron sputtering of tin
M.A. Gubbins1, V. Casey*, S.B. Newcomb
Materials and Surface Science Institute, University of Limerick, Limerick, Ireland

Received 30 May 2001; received in revised form 5 October 2001

Abstract

Tin oxide thin films have been deposited on oxidised silicon substrates using a reactive r.f. magnetron sputter process with a
tin target in a mixed oxygenyargon gas environment. Process parameters such as oxygen composition, substrate temperature and
r.f. power have been varied and the resulting films characterised structurally using X-ray diffraction, atomic force microscopy and
transmission electron microscopy (TEM). TEM has demonstrated that the films are composed of an amorphous matrix as well as
columnar grains of SnO2 which are interspersed with pores. The deposition method is shown to be a useful way of fabricating
nanocrystalline particles of tin oxide within an amorphous matrix and the results are briefly discussed in relation to their
significance for the fabrication of tin oxide quantum dots and nanoclusters. 䊚 2002 Elsevier Science B.V. All rights reserved.

Keywords: Tin oxide; Transmission electron microscopy (TEM); Atomic force microscopy (AFM); Nanostructures

1. Introduction being used to deposit SnO2 thin films. Some of the

Tin oxide thin films are technologically important
materials and find application in areas such as electro-
luminescent displays w1x, heat reflectors w2x, mechanical
surface coatings w3x and sensors w4x. Recently, it has
been shown that the sensitivity of thin film tin oxide
gas sensors increases as the particle size is reduced with
nanometer sized particles yielding improved response
and recovery times w5x. Sensor sensitivity and dynamic
characteristics may be increased further by the presence
of pores in the films, which provide channels for gas
transport that increases the resistivity response and helps
gas evacuation during recovery w6x. Fabrication routes
for tin oxide nanoparticles and nanoclusters are thus of
increasing interest, particularly if such routes can be
optimised so that particle parameters such as size and
composition can be controlled. In general, film proper-
ties are strongly influenced by the choice of deposition
method and an ever increasing range of techniques is
* Corresponding author. Tel.: q353-61-202290; fax: q353-61-
202423.
E-mail address: vincent.casey@ul.ie (V. Casey).
1
Now at: Seagate, 1 Disk Drive, Springtown Industrial Estate,
Londonderry BT48 OBF, Northern Ireland.
more common deposition techniques include dip coating
w7x, reactive thermal evaporation w8x, CVD w9x, r.f.
magnetron sputtering w10x, r.f. reactive sputtering w11x,
spray pyrolysis w12x, plasma polymerisation w13x and
glow discharge decomposition of tin compounds w14x.
Sputter techniques using modern vacuum technology
allow tight control over critical process parameters and
this contributes greatly to the reproducibility of the
films. For this reason, sputtering is used extensively in
the fabrication of functional electronic thin films in the
semiconductor industry. More generally, any fabrication
route which facilitates the control of particle properties
such as size and composition on a nanometer scale is
significant because of the novel electronic and optical
properties expected for nanocluster and quantum dot
structures.
In this paper, we describe an r.f. reactive magnetron
sputter deposition process which has been used to
prepare films containing semiconducting SnO2 nanopar-
ticles embedded in an amorphous insulating matrix. The
effects of process parameters such as substrate temper-
ature and oxygen pressure on film structural properties
and particle size are described.

0040-6090/02/$ - see front matter 䊚 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 4 0 - 6 0 9 0 Ž 0 1 . 0 1 7 2 8 - X
 M.A. Gubbins et al. / Thin Solid Films 405 (2002) 270–275
2. Experimental
Tin oxide thin films were deposited by reactive r.f.
magnetron sputtering using a Leybold Lab500 system.
The magnetron cathode (ION’X-3) with a water-cooled
copper backing plate accommodates the 76 mm diameter
tin target and is positioned at an angle of 458 to the
rotating substrate holder normal and at a distance of 12
cm from the substrate. The substrate holder also incor-
porates an in-built heaterytemperature control which
allows substrate heating to temperatures within the range
of 20–600 8C.
Oxidised silicon wafers were used as substrates. The
chamber was evacuated to a pressure of 1.0 mPa and
the substrate heater was allowed to reach the set point
temperature before the introduction of argon. Flow rates
were adjusted in order to attain an argon pressure of
0.53–0.60 Pa which was found to be the optimum
pressure for plasma ignition. The target surface was
cleaned by sputtering for 5 min in argon at an r.f. power
of 60 W. The argon and oxygen flow rates were adjusted
in order to give the desired gas composition while
keeping the total pressure at 0.71 Pa. A rotation speed
of 1.8 rev.ymin was used for the substrate holder and
shutter control was used to set the deposition time. The
substrate was allowed to cool to less than 100 8C before
venting the chamber and removing the sample.
Tin oxide thin films were deposited at two power
levels, 40 and 80 W. Four substrate temperatures (330,
400, 440 and 480 8C) and three gas compositions (10,
20 and 30% oxygen in argon) were used in this study.
Deposition times of 20 min were used for films depos-
ited at 40 W, and 10 min for films deposited at 80 W.
X-Ray diffraction (XRD) of the tin oxide films was
carried out using a Philips X-Pert diffractometer oper-
ated in the u–2u mode over angles in the range of 20–
608. A Topometrix Explorer Atomic Force Microscope
(AFM) was also used to elucidate the structure of the
films. It was operated in the non-contact mode using a
scanner with a maximum range in the xyy plane of 2.3
mm and a maximum z-range of 0.8 mm. Image repro-
ducibility was verified by recording topography-forward,
-reverse and internal-sensor images. Images were proc-
essed using SPMlab first-order levelling and shading in
order to aid interpretation. Samples for transmission
electron microscopy (TEM) were prepared using
focused ion beam (FIB) thinning. Small rectangular bars
measuring some 3=1=0.05 mm were milled in an FEI
200 workstation and the electron transparent regions
were examined in a JEOL 2000FX operated at 200 keV.
3. Results and discussion
We begin by describing the data obtained using XRD
and AFM and then outline the TEM microstructural
observations.
271
Table 1
XRD and TEM diffraction data for a tin oxide film deposited at low
oxygen in argon composition (10%) and low power (40 W)
XRD TEM Bulk SnO2
2u Counts d-Spacing Ring no. d-Spacing d-Spacing hkl
(nm) (nm) (nm)
26.6 100 0.335 1 0.3289 0.335 110
2 0.2838
33.921 75 0.264 3 0.2539 0.264 101
37.98 21 0.237 4 0.2316 0.237 200
51.826 57 0.176 5 0.1703 0.176 211
3.1. X-Ray diffraction
Table 1 indicates that peaks characteristic of the
tetragonal SnO2 phase were identified in a thin film
sample deposited at low oxygen percentage composition
(10%) and low power (40 W) conditions. Such peaks
were not, however, seen for films deposited at the same
oxygen pressure but a higher power (80 W) and this is
indicative of the fact that the increased sputter rate of
tin at 80 W leads to the formation of the metallic phase
andyor SnO rather than SnO2. More critically, there is
clear evidence that at 40 W the low oxygen composition
is sufficient to oxidise the tin although changes in the
deposition temperature (330–480 8C) were found not
to lead to any structural modification of the oxide.
Comparisons were made for thin films deposited at
oxygen in argon compositions of 20 and 30%. XRD
indicated that crystalline SnO2 was present for all
combinations of temperature (330–480 8C) and power
(40 and 80 W) and in this way there were few, if any,
differences between the 40 W film deposited at an
oxygen composition of 10%. Peak broadening was seen
in XRD spectra taken from thin films deposited at 80
W and this indicates that a relatively fast deposition rate
promotes the formation of a fine grain sized oxide. The
grain size of the oxide was found to be in the range of
6–29 nm. Larger grain sizes tended to be seen in
samples deposited at low power although no relationship
was apparent between the grain size of the oxide and
the temperature at which it was deposited.
3.2. Atomic force microscopy
AFM images and the corresponding particle size
histograms for films deposited at 20% oxygen in argon
composition, 80 W and temperatures of 330, 400, 440
and 480 8C are shown in Fig. 1. The AFM images of
all samples displayed a granular structure with an overall
grain size ranging from 8 to 54 nm, which is small
relative to films obtained using other deposition methods
but not uncommon for sputtered films. There would
appear to be a discrepancy between the XRD and AFM
grain sizes. As we will see from the TEM data below,
272 M.A. Gubbins et al. / Thin Solid Films 405 (2002) 270–275

Fig. 1. AFM images of the surfaces of oxides deposited at a 20% oxygen in argon composition, 80 W and temperatures of (a) 330 8C, (b) 400
8C, (c) 440 8C and (d) 480 8C. The grain size distribution histograms for each temperature are also shown.

the film contains dagger-like crystallites with the ‘thick
end’ of the crystallite at the surface and the ‘thin end’
within the film. The AFM grain sizes are averages over
the surface of the film (relatively large crystallites)
whereas the XRD averages over the entire thickness of
the film (large and small crystallites) and so provides a
lower estimate of grain size. The AFM data provides
clear evidence for the way in which the grain size of
the oxide increases with substrate temperature and this
is in apparent contrast to the X-ray analysis where no
such trend was observed. The surfaces of the films were
found to be reasonably smooth and exhibited surface
roughness values which varied from 0.4 to 1.0 nm. This
is in marked contrast to the much higher roughness (50–
100 nm) seen in films of similar thickness deposited by
MOCVD w15x. No relationship was found between
 M.A. Gubbins et al. / Thin Solid Films 405 (2002) 270–275 273

tion of this oxide, Table 1, demonstrating that there is a

good correlation between the TEM and XRD data
described. The origin of the weak reflections seen at a
d-spacing of 0.2838 nm was not, however, determined,
but is likely to originate from the capping layer used to
protect the surface during ion beam milling of the
sample.
The microstructure of the layer deposited at an oxygen
in argon composition of 10% was examined in further
detail and a number of interesting features were
observed. The thin film deposit was found to be banded,
as demonstrated by the pair of under- and over-focus
bright field images shown in Fig. 3a,b, respectively.
Here a series of ‘layers’ of alternating light and dark
contrast can be observed which were found to extend
across the full thickness of the deposit. Such localised
changes in contrast are indicative of a modulation in the
Sn content of the film, the low contrast ‘sub-layers’
being of apparently lower Sn content than those exhib-
iting relatively strong absorption contrast. Given the
way in which the target lies at an inclined angle to the
plane of the substrate, the variation in Sn content is
likely to originate from rotation of the substrate during
deposition of the thin film. This view is supported by

Fig. 2. A tin oxide film deposited at 40 W, 440 8C and a 10% oxygen

in argon composition showing (a) a low magnification bright field
image of the layer (A, tin oxide; B, SiO2; C, Si; D, capping layer)
and (b) a diffraction pattern taken from the deposit (ring numbers
relate to Table 1).

surface roughness and deposition temperature whilst

increases in the oxygen in argon composition to 30%
gave surface roughness values which tended to the lower
end of the range (0.4–0.6 nm) for both power levels.

3.3. Transmission electron microscopy

The microstructures of the thin film oxide deposits

have been examined using TEM and comparisons made
as a function of the different oxygen in argon compo-
sition (10, 20 and 30%) used for films fabricated at 40
W and a substrate temperature at 440 8C. Fig. 2a shows
a cross-sectional low magnification micrograph of a
typical region of the thin film formed at the low oxygen
composition (10%). Here the fully continuous deposit,
which has a thickness of some 330 nm, has been marked
at A and the underlying SiO2 and Si substrate at B and
C, respectively. An electron diffraction pattern taken
from the deposit is shown in Fig. 2b and Table 1 gives
Fig. 3. Higher magnification (a) under-focus and (b) over-focus bright
the measured d-spacings. Comparisons can be made field micrographs of the tin oxide film deposited at 40 W, 440 8C and
with the tabulated d-spacings for the tetragonal SnO2 10% oxygen in argon (X, crystallite region; Y, amorphous region; P,
phase and this provides further evidence for the forma- pore).
274 M.A. Gubbins et al. / Thin Solid Films 405 (2002) 270–275
Fig. 4. A dark field image of the tin oxide film deposited at 40 W,
440 8C and 10% oxygen in argon composition showing the presence
of amorphous (A) and crystalline (C) oxide phases.
the closeness of the length of time per rotation of the
substrate (33 s) and the estimated time for the deposition
of each pair of sub-layers within the deposit (40 s). The
latter was determined from a knowledge of the total
deposition time (1200 s), the overall film thickness (330
nm) and the average thickness of a pair of sub-layers
(11 nm). The oxide deposit was also examined in dark
field, as typified by the image shown in Fig. 4. Here
the critical point is the way in which the thin film was
found to contain both crystalline and amorphous SnO2
phases, the latter being confirmed by the objective
aperture size dependent nature of the speckle contrast
w16x seen in regions such as that marked at A. Compar-
ison with the diffraction pattern shown earlier in Fig.
2b indicates the presence of the diffuse halo marked at
A and this provides further evidence for the formation
of the amorphous phase. Figs. 3 and 4 not only indicate
the way in which approximately the lower third of the
deposit contains only the amorphous oxide but also that
the thin film clearly contains a number of crystallites.
Such grains exhibit a tendency to have a high aspect
ratio common in tin oxide thin films w15,17x, whilst
there is an apparent relationship between the presence
of crystallites at the surface of the deposit and local
increases in surface roughness. Compare, for example,
the local areas marked at X and Y in Fig. 3a. The
defocus images are also of interest for the way in which
they show that the crystalline parts of the deposit are
interspersed with pores. The visibility of the pores has
been enhanced using Fresnel contrast as a function of
the defocus conditions in Fig. 3 and examples of the
vertically aligned pores have been marked at P in Fig.
3a.
TEM examination of samples deposited at the higher
oxygen in argon composition of 20 and 30% displayed
similar characteristics to the sample described above.
Fig. 5 shows an example of a thin film layer deposited
at the highest oxygen composition (30%). Here the
thickness of the deposit is as low as 50 nm but as before
tapered columnar crystallites can be seen to penetrate
downward from the surface into an otherwise amorphous
matrix. Crystallite diameters vary from 3 to 10 nm and
vertical pores are also evident but the compositional
modulation observed in the sample deposited at 10%
oxygen composition was not evident.
4. Discussion and conclusions
The tin oxide films deposited using the method
described have been shown to contain both crystalline
and amorphous SnO2. The crystallites tended to be
columnar in nature and were interspersed with fine
pores. The banding composition evident in the films
produced at the low oxygen composition (10%) is likely
to originate from the fact that the cathode is not oxidised
at this low oxygen pressure and so deposition occurs
primarily from a metallic tin target. The compositional
variation across the thin film originates from the effec-
tive variation of the target to substrate distance due to
the rotation of the substrate as explained above. At
higher oxygen pressures, the target is oxidised and the
deposition occurs from a tin oxide surface, as evidenced
by a marked reduction in the sputter yield at higher
oxygen pressures.
The properties of nanostructured materials are deter-
mined by the interplay of three main parameters: domain
size; composition; and interfaces. The sputter process
tends to produce small grain sizes and is thus inherently
suited to the production of nanocrystalline thin films.
The morphological structure of the films includes sig-
nificant interface regions between the nanocrystallites.
However, the semiconducting nature of the polycrystal-
line SnO2 phase may give rise to a dominance of the
interfacial regions in determining the electronic proper-
ties of the overall film. Grain surface depletion layers
may extend through a large portion of the grains and in
such a case carriers will be confined to a volume that
Fig. 5. A bright field TEM micrograph of the tin oxide film deposited
at 40 W, 440 8C and an oxygen in argon composition of 30% (A,
SnO2; B, SiO2; C, Si).
 M.A. Gubbins et al. / Thin Solid Films 405 (2002) 270–275
is significantly less than the geometric size of the film.
This in turn may lead to quantum size effects in the
electrical transport properties of the film. The existence
of an amorphous (non-conducting) matrix between the
columnar grains is interesting as it offers the possibility
of generating SnO2 quantum dot and nanocluster struc-
tures via the deposition route described.
Quantum dots need to meet several conditions in
order to be useful for room temperature operation. In
addition to the obvious maximum size restriction, the
size distribution must be uniform since the energy bandy
level structure varies with dot size. Defect densities
should be low as localised defects produce variations in
the electrical and optical properties between dots. It is
also desirable to know the shape of the dots in order to
calculate the energy band structure. The deposition
technique used here offers some promise for the produc-
tion of semiconducting quantum dots: a significant
energy offset between the energy structure of the grains
and the amorphous matrix is expected; grain sizes and
shapes are relatively narrowly defined and the grains
are structurally stable. However, the approach suffers
from some of the short-comings common with other
quantum dot fabrication routes such as colloidal suspen-
sions. Grain surfaces and interfaces will be dominated
by electronic defects so making it difficult to reproduce
the exact band structure whilst there is significant
connectivity, at least physically, between the
nanoparticles.
Acknowledgments
The authors would like to acknowledge the Irish
Higher Education Authority (HEA) for a grant under
its Capital Equipment Scheme which was used to pur-
chase the Lab500 system. One of the authors (Mark A.
275
Gubbins) would like to acknowledge both Enterprise
Ireland and the UL Physics Department for partial
support for this work.
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