In situ examination of tin oxide atomic layer deposition using quartz

crystal microbalance and Fourier transform infrared techniques

X. Du
Department of Chemical and Biological Engineering, University of Colorado, Boulder, Colorado 80309
Y. Du
Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309
S. M. Georgea兲
Department of Chemical and Biological Engineering, and Department of Chemistry and Biochemistry,
University of Colorado, Boulder, Colorado 80309
共Received 9 November 2004; accepted 21 March 2005; published 7 June 2005兲
The atomic layer deposition 共ALD兲 of tin oxide thin films has been examined using in situ quartz
crystal microbalance 共QCM兲 and Fourier transform infrared 共FTIR兲 techniques. The SnOx films
were deposited using sequential exposures of SnCl4 and H2O2 at temperatures from 150 to 430 °C.
The linear growth of the tin oxide ALD films was observed by both the mass gain during QCM
measurements and the background infrared absorbance increase during FTIR investigations. The
FTIR spectra revealed the loss and gain of the O–H stretching vibrations of the hydroxyl group for
the SnCl4 and H2O2 exposures, respectively. The background infrared absorbance also oscillated
after each SnCl4 and H2O2 exposure. The background absorbance increased after SnCl4 exposure
and decreased after H2O2 exposure. QCM measurements were consistent with a tin oxide ALD
growth rate of ⬃60 ng cm−2 per cycle. This mass change corresponds to a growth rate of
⬃0.7 Å / cycle at 325 °C assuming a SnO2 density of 6.9 g cm−3. Additional ex situ surface analysis
using x-ray photoelectron spectroscopy 共XPS兲 and Auger electron spectroscopy 共AES兲 revealed that
the SnOx films grown at 325 °C were defined by x ⬍ 2. Atomic force microscope 共AFM兲 results also
showed that the SnOx ALD films deposited on Si共100兲 wafers have a very rough surface.

24 February 2025 13:07:45

Understanding and controlling the growth of tin oxide ALD films should be useful to enhance the
sensitivity of SnOx gas sensors. © 2005 American Vacuum Society. 关DOI: 10.1116/1.1914810兴

I. INTRODUCTION coverage, returns the free electron charge carriers to the

SnO2 metal oxide and increases the electrical conductivity.11
SnO2 is an n-type semiconductor metal oxide that has
Highest sensitivities for SnO2 gas sensors are expected
many applications in various fields due to its special optical,
when the film thickness is comparable with the surface
electrical, and chemical properties. Many of these properties
depletion layer thickness. This expectation is supported by
result from the ability of SnO2 to form oxygen vacancies,
gas sensor sensitivity studies on nanoparticles.7,12 The sur-
dislocations or interstitial atoms that produce electron charge
carriers. For example, SnO2 is a transparent conducting ma- face depletion layer is the length over which an adsorbed gas
terial and is widely used in flat panel displays and solar can perturb the underlying metal oxide. The depth of this
cells.1,2 SnO2 is a possible high capacity anode for next gen- space-charge region is measured by the Debye length which
eration lithium ion batteries.3,4 SnO2 can also be used as a is defined by LD = 共⑀ kT/ nq2兲1/2 where ⑀ is the static dielec-
catalyst for oxidation of CO, CH4 and the other organic tric constant, n is the charge carrier concentration, and q is
molecules.5,6 the carrier charge.13 The Debye length for a thin sputtered
Tin oxide can also change its resistivity corresponding to SnO2 film has been reported to be as small as 3 nm at
gas adsorption and is widely used as a gas sensing material 250 °C.14
for the detection of combustible and toxic gases.7,8 The oxy- Charge carriers in SnO2 are conducted by the entire film
gen vacancies in SnO2 yield high conductivity and low elec- thickness. If the Debye length is only a fraction of the entire
trical resistivity typically around ⬃10−2 ⍀ cm. The adsorp- film thickness, the sensitivity of the film to an adsorbed gas
tion of O2 from air removes the electron charge carriers from will be low because the majority of the charge carriers will
the surface region of SnO2 and is believed to form O2− , O−, not be perturbed by the surface space-charge region. If the
and O2− oxygen surface species at certain temperatures.9,10 Debye length and the entire film thickness are nearly equal,
The resulting electron-depleted space-charge region has a large sensitivities can be obtained because the charge carriers
much lower electrical conductivity. When exposed to com- will be confined to travel in the surface space-charge
bustible gases, the surface oxygen species react to form com- region.15 The film conductivity will then be expected to
bustion products. This reaction lowers the oxygen species change dramatically with gas adsorption.
Although most discussions of tin oxide focus on SnO2,
a兲
Electronic mail: [Link]@[Link] oxygen is easily lost from SnO2 to form SnOx where x ⬍ 2.

581 J. Vac. Sci. Technol. A 23„4…, Jul/Aug 2005 0734-2101/2005/23„4…/581/8/$22.00 ©2005 American Vacuum Society 581
582 Du, Du, and George: In situ examination of tin oxide atomic layer deposition 582

X-ray photoelectron studies have shown that annealing SnOx ALD using in situ techniques. Optimization of the sen-
amorphous tin oxide films at 300 °C can reduce the Sn:O sitivity of tin oxide ALD films as gas sensors will be greatly
stoichiometry at the film surface from 1:2 to 1:1.4.16 Addi- facilitated using in situ techniques to monitor simultaneously
tional XPS studies have also identified SnO on the surface of both SnOx ALD film growth and the electrical properties of
tin oxide films.17 SnO is a semiconductor and is active as a SnOx ALD films.
gas sensor.18,19 Nonstoichiometric mixtures of SnO and SnO2 In this study, tin oxide ALD is examined using quartz
with Sn2+ and Sn4+ oxidation states, respectively, are semi- crystal microbalance 共QCM兲 and transmission Fourier trans-
conductors and may also act as gas sensors.16 Given the fa- form infrared 共FTIR兲 in situ techniques. The QCM and FTIR
cility of SnO2 to lose oxygen, the tin oxide ALD films will techniques can be conducted concurrently in a viscous flow
be described as SnOx where x ⬍ 2. ALD reactor designed for in situ analysis. The QCM mea-
Atomic layer deposition 共ALD兲 techniques may be useful surements can monitor the mass changes during SnOx ALD.
to deposit an ultrathin tin oxide film on a high surface area The FTIR investigations can observe the surface species dur-
substrate to produce a SnOx gas sensor with enhanced sensi- ing SnOx ALD. In addition, the background absorbance of
tivity. ALD is a thin film deposition technique that employs the FTIR spectra is dependent on the electrical conductance
sequential self-limiting surface reactions.20–22 ALD can de- of the SnOx ALD film. Additional ex situ techniques such as
posit ultrathin films with high conformality and precise x-ray photoelectron spectroscopy 共XPS兲, Auger electron
thickness control. Tin oxide ALD can be accomplished using spectroscopy 共AES兲, x-ray diffraction 共XRD兲, and atomic
sequential exposures of SnCl4 and H2O at temperatures from force microscopy 共AFM兲 were also used to determine the
300 to 600 °C.23 The proposed surface chemistry for tin ox- composition and structure of the tin oxide ALD films.
ide ALD using SnCl4 and H2O is:
共A兲 SnOH* + SnCl4 → SnOSnCl3* + HCl, 共1兲 II. EXPERIMENT
The tin oxide films were grown in a viscous flow ALD
共B兲 SnCl* + H2O → SnOH* + HCl, 共2兲 reactor designed for in situ QCM and FTIR studies. The
basic design of this viscous flow ALD reactor has been de-
where the asterisks indicate the surface species. Alternating scribed previously.30 The viscous flow reactor is composed
ABAB… reactions have been reported to deposit tin oxide of three basic sections: Reactant delivery lines; a specially

24 February 2025 13:07:45

with a growth rate of ⬃0.15 Å per AB cycle at 300 °C.23 The designed four-way cross with 2.75 in. Conflat flanges for the
tin oxide ALD growth rate can be increased slightly and the in situ probing; and the vacuum pumping system. A sche-
growth temperature can be reduced to 250 °C using H2O2.24 matic of the four-way cross for the in situ QCM and FTIR
For the H2O2 reactant, the proposed surface reactions are: probing techniques is shown in Fig. 1.
共A兲 2SnOH* + SnCl4 → SnO共SnCl2兲*OSn + 2HCl, 共3兲 The IR beam passes through CsI salt windows installed
on the two side ports of the four-way cross. The gas line
feeding the reactants is attached to the front port. The sample
共B兲 SnCl2* + H2O2 → Sn共OH兲2* + Cl2 . 共4兲
mount holding the QCM and the sample for the transmission
Compared with the SnCl4 and H2O reactions given by FTIR studies is installed at the back port through a standard
Eqs. 共1兲 and 共2兲, the SnCl4 and H2O2 reaction given by Eqs. six-way cross. This assembly is pumped by an Alcatel 2015
共3兲 and 共4兲 are the more thermodynamically favored reac- mechanical pump. In addition, a Baratron is also attached to
tions. The SnCl4 + 2H2O → SnO2 + 4HCl reaction has a reac- the six-way cross to monitor the pressure inside the reactor
tion enthalpy of ⌬H = + 4.5 kcal/ mol. In contrast, the SnCl4 chamber. Outside of the four-way cross is a ceramic heater.
+ H2O2 → SnO2 + 2HCl+ Cl2 reaction has a reaction enthalpy Temperatures inside the reactor are controlled with a preci-
of ⌬H = −34.6 kcal/ mol. Even though some oxygen may be sion of ±0.05 ° C. The ability to keep this temperature con-
lost from SnO2 to create SnOx where x ⬍ 2, direct SnO ALD stant enables the QCM to operate at relatively high tempera-
is not thermodynamically favored. The SnCl4 + H2O → SnO tures.
+ 2HCl+ Cl2 reaction has a reaction enthalpy of ⌬H Ultrahigh purity nitrogen is supplied by mass flow con-
= + 61.4 kcal/ mol. The 2SnCl4 + H2O2 → 2SnO+ 2HCl+ 3Cl2 trollers with a maximum throughput of 1000 sccm. This N2
reaction has a reaction enthalpy of ⌬H = + 83.7 kcal/ mol. carrier gas delivers the SnCl4 and H2O2 reactants. The N2
These reaction enthalpies were calculated at the primary also serves as the gas purge between the reactant exposures.
growth temperature of 325 °C using the HSC CHEMISTRY 5.11 The base pressure inside the ALD reactor stabilizes at
thermochemistry program from Outokumpu Research Oy in ⬃0.9 Torr using a total nitrogen throughput of 100 sccm. At
Pori, Finland. this gas flow rate, the flow velocity is 1.4 m / s. Under these
Many previous investigations have examined tin oxide viscous flow conditions, the reactant gases are entrained in
and various applications of tin oxide ALD. Several studies the N2 carrier flow and the reactants and products can be
have observed very rough SnOx ALD films.25,26 SnOx ALD easily delivered and swept from the ALD reactor.
has been demonstrated on high surface area porous silicon SnCl4 with a purity of ⬎95% was obtained from Gelest.
substrates.27,28 SnOx ALD at lower growth temperatures has Hydrogen peroxide was 50% by weight and was obtained
also been employed to fabricate smooth amorphous gas sens- from Sigma-Aldrich. The SnCl4 liquid source was used at
ing films.29 However, this previous research has not explored room temperature. The H2O2 source was held at 30 °C using

J. Vac. Sci. Technol. A, Vol. 23, No. 4, Jul/Aug 2005