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Groner 2004
Groner 2004
Groner 2004
Al2O3 films were deposited by atomic layer deposition (ALD) at temperatures as low as 33
°C in a viscous-flow reactor using alternating exposures of Al(CH3)3 (trimethylaluminum
[TMA]) and H2O. Low-temperature Al2O3 ALD films have the potential to coat thermally
fragile substrates such as organic, polymeric, or biological materials. The properties of low-
temperature Al2O3 ALD films were investigated versus growth temperature by depositing
films on Si(100) substrates and quartz crystal microbalance (QCM) sensors. Al2O3 film
thicknesses, growth rates, densities, and optical properties were determined using surface
profilometry, atomic force microscopy (AFM), QCM, and spectroscopic ellipsometry. Al2O3
film densities were lower at lower deposition temperatures. Al2O3 ALD film densities were
3.0 g/cm3 at 177 °C and 2.5 g/cm3 at 33 °C. AFM images showed that Al2O3 ALD films grown
at low temperatures were very smooth with a root-mean-squared (RMS) roughness of only
4 ( 1 Å. Current-voltage and capacitance-voltage measurements showed good electrical
properties of the low-temperature Al2O3 ALD films. Elemental analysis of the films using
forward recoil spectrometry revealed hydrogen concentrations that increased with decreasing
growth temperature. No other elements were observed by Rutherford backscattering
spectrometry except the parent aluminum and oxygen concentrations. Low-temperature Al2O3
ALD at 58 °C was demonstrated for the first time on a poly(ethylene terephthalate) (PET)
polymeric substrate. Al2O3 ALD coatings on PET bottles resulted in reduced CO2 gas
permeabilities.
gas switching valves and the gas reservoirs. The gas switching
valves allow for a rapid turn-on and shut-off of the reactant
gases for short ALD cycle times. This short time is facilitated
by pumping the gas reservoirs with separate mechanical
pumps after the reactant exposures.17
The time for one complete Al2O3 ALD cycle ranged from 12
s at 177 °C to 203 s at 33 °C. This cycle time was defined by
(t1, t2, t3, t4) where t1 is the TMA exposure time, t2 is the N2
purge time following the TMA reactant exposure, t3 is the H2O
exposure time, and t4 is the N2 purge time following the H2O
reactant exposure. All times are in units of seconds. Longer
purge times were required at lower temperatures to avoid
Figure 1. Diagram of the viscous-flow reactor used for low- Al2O3 chemical vapor deposition (CVD) resulting from insuf-
temperature Al2O3 ALD. A special flow tube was employed to ficient purge times.
accommodate a 510-mL PET bottle. A nitrogen purge line was Quartz crystal microbalance (QCM) studies of Al2O3 ALD
used to suspend and pressurize the PET bottle during Al2O3 were performed in situ using a Maxtek TM400 thin-film
ALD. deposition monitor. The QCM crystal housing was sealed and
purged to prevent deposition on the backside and positioned
properties of such films. This study explores the condi- horizontally in the flow reactor tube. A detailed description of
tions necessary for low-temperature Al2O3 ALD and the QCM for monitoring ALD has been presented in a previous
publication.17
examines the properties of the resulting films. Low- Al2O3 ALD films were deposited on PET bottles at 58 °C.
temperature Al2O3 ALD was also applied for the first To accommodate the 510-mL PET bottles, the standard reactor
time to a poly(ethylene terephthalate) (PET) polymer flow tube was replaced with a larger 10-cm diameter tube as
substrate. Reduced gas permeabilities were observed for shown in Figure 1. This tube consisted of the bottom halves
Al2O3 ALD-coated PET bottles. of two vacuum traps joined by an O-ring and a clamp. The
bottles were suspended in this enlarged reactor tube by a
custom-made cap and purge line that allowed the bottle to be
2. Experimental Section pressurized with N2 gas during Al2O3 ALD. The pressurization
A. Chemicals and Substrates. Al2O3 ALD films were prevented bottle deformation during and after the Al2O3 ALD
grown using H2O (Fisher, optima grade) and Al(CH3)3 [tri- film growth.
methylaluminum (TMA)] (Akzo-Nobel, semiconductor grade, C. Al2O3 Film Characterization. Al2O3 film thicknesses
99.9999%). The carrier gas in the viscous flow reactor was N2 and refractive indices were measured using a J. A. Woollam
(Airgas, ultrahigh purity). Moderately doped n-type Si(100) M44 variable-angle spectroscopic ellipsometer (VASE). Mea-
wafers from Montco Silicon Technologies, Inc., with a boron surements were obtained over the spectral range from 406 to
doping density of ∼2 × 1017 cm-3 were used as substrates. 806 nm using an incidence angle of 75°. Al2O3 and SiO2 have
A variety of chemicals were used for etching and cleaning virtually identical optical constants. Consequently, a simple
of the Si substrates. These chemicals included 5% HF (general ellipsometric measurement yields only the sum of the Al2O3
chemicals class 10 water/HF (10:1) mix), water (HPLC grade), and SiO2 film thicknesses. To determine the true Al2O3
sulfuric acid, and hydrogen peroxide (30%). Prior to deposition, thickness and the thickness of any interfacial SiO2 layer on
the silicon wafers were cut into ∼2.5 cm × 2.5 cm pieces, Si(100), a procedure was employed that utilized simultaneous
cleaned in a ∼60 °C Piranha solution for 15 min, and then Al2O3 ALD growth on both an HF-etched Si wafer and a Si
HF etched for 60 s. wafer with a native oxide. This procedure was described in
For gas diffusion tests, uncoated poly(ethylene terephtha- detail in another publication.11 A 13 ( 2 Å thick interfacial
late) (PET) bottles were supplied by Applied Films Corp. The SiO2 layer was determined to be present at the Al2O3/Si
bottles were 510-mL Coke Contour bottles. These PET bottles interface after Al2O3 ALD. This SiO2 thickness was subtracted
had a weight of 28 g and a petalloid shaped base. The PET from the ellipsometric measurements to determine the Al2O3
bottles were cleaned with Micro cleaner/oxide remover (Inter- layer thickness.
national Products Corp.) prior to deposition. Atomic force microscope (AFM) images of the Al2O3 films
B. Al2O3 ALD Film Growth in Viscous-Flow Reactor. and substrates were obtained using an AutoProbe CP Research
Al2O3 films were grown by ALD in a viscous-flow ALD reactor. scanning probe microscope (SPM) instrument from Thermo-
This reactor has been described in detail in other publica- Microscopes. RMS surface roughness values were calculated
tions.11,17 TMA and H2O were alternately entrained in the N2 on the basis of 1 µm2 contact-mode AFM scans. Profilometry
carrier flow using gas switching valves.17 The N2 carrier gas was performed using a Dektak 3 surface profile measuring
pressure was ∼1.0 Torr. TMA and H2O pressure transient system from Veeco Metrology Group. Al2O3 film thicknesses
increases of ∼0.1 Torr were measured by a Baratron when the were determined by measuring step heights using profilometry
reactants were introduced into the N2 carrier flow. and contact-mode AFM. Well-defined steps needed for AFM
The Al2O3 ALD film growth proceeded according to two self- imaging were created by masking part of the sample with a
limiting surface reactions. The TMA and H2O yield Al2O3 ALD small piece of high-temperature aluminum foil tape (3M, Type
according to the following two reactions:9,10 433) during Al2O3 ALD. Other methods, such as clamping
another piece of silicon to the substrate, were found to produce
poorly defined steps that were too wide to be imaged by AFM.
(A) Al-OH* + Al(CH3)3 f Al-O-Al(CH3)2* + CH4
Electrical measurements were performed using a MDC 811
mercury probe from the Materials Development Corporation.
(B) Al-CH3* + H2O f Al-OH* + CH4 These electrical measurements have been described in another
publication.11 The mercury probe makes contact to the front
where the asterisks denote the surface species. When per- surface of the Al2O3 films by drawing up a well-defined column
formed in an ABAB... reaction sequence, these sequential of Hg with a surface area of 0.437 mm2. Current-voltage (IV)
reactions produce linear, atomic-layer controlled Al2O3 growth. measurements were obtained using a Keithley 487 picoam-
Many previous studies have confirmed linear and conformal meter/voltage source. Capacitance-voltage (CV) measure-
growth using TMA and H2O.9,11,15,17 ments were performed using a Stanford Research Systems
The standard flow tube was used to deposit Al2O3 ALD films SR720 LCR meter. The experiments were computer-controlled
on Si substrates or the QCM.17 Figure 1 shows the reactor with using LabView from National Instruments.
a larger-than-normal flow tube designed to accommodate the Elemental analysis was performed at the Ion Beam Analysis
PET bottles. Figure 1 also shows a simplified diagram of the Laboratory in the Institute of Technology Characterization
Low-Temperature Al2O3 Atomic Layer Deposition Chem. Mater., Vol. 16, No. 4, 2004 641
tion in the Al2O3 ALD films grown at lower tempera- (BIF) are desired for commercial applications. Light
tures. Figure 10 also shows that the dielectric constant microscopy images of the surface of the PET bottle
did not decrease with decreasing growth temperatures. revealed apparent scratches and/or cracks on the surface
However, the scatter in the measurements may have of the Al2O3 ALD-coated bottles. These scratches and/
masked a small change. or cracks may explain the low BIF for these Al2O3 ALD
E. Film Composition. The RBS analysis of the Al2O3 films compared with typical BIFs for SiO2 coatings.24
ALD films obtained O/Al ratios close to the expected
ratio of 1.5. In addition, FReS analysis revealed hydro- 5. Conclusions
gen concentrations in Figure 11 that increased with
decreasing growth temperatures. The increasing hydro- Al2O3 ALD growth has been demonstrated at tem-
gen concentrations continue a trend that was observed peratures as low as 33 °C. Many of the properties of
in a previous study for Al2O3 ALD growth temperatures these low-temperature Al2O3 ALD films were compa-
from 350 to 125 °C.11 The increasing hydrogen concen- rable with the properties of Al2O3 ALD films grown at
tration at low temperatures may be directly related to higher temperatures of g177 °C. The low-temperature
the lower density of the Al2O3 ALD films at lower Al2O3 ALD films exhibited very low surface roughness
growth temperature. values, low leakage currents, high dielectric constants,
At lower temperatures, the hydroxyl surface coverage and growth rates in excess of 1 Å/cycle. Good thin film
is higher on Al2O3 surfaces.9,10 In addition, the TMA properties were observed despite decreasing densities
reaction with the Al-OH surface species groups does and increasing hydrogen concentrations observed at
not go to completion at low temperatures.9,10 During lower temperatures. Increased ALD cycle times were
Al2O3 ALD, the hydroxyl species can build up in the necessary at lower temperatures because of the slower
growing Al2O3 film. At 180 °C, the hydroxyl concentra- reaction rates and longer required purge times for the
tion in the film after 10 AB cycles is equal to ap- H2O reactant. Improvements in reactor design and the
proximately the full hydroxyl coverage.10 Annealing at use of alternate oxygen sources could help overcome this
1000 K can reduce hydroxyl accumulation in Al2O3 ALD problem. Low-temperature Al2O3 ALD may have ap-
films.10 These previous studies support the idea that the plications for coating thermally fragile substrates such
H atoms in the low-temperature Al2O3 ALD films are as organic, polymeric, or biological material. As a
present in the form of Al-OH species. demonstration of the possible applications, low-temper-
Despite the high hydrogen concentrations at low ature Al2O3 ALD films were grown on PET bottles to
temperatures, the Al2O3 ALD films still exhibited reduce gas diffusion. The Al2O3 ALD-coated PET bottles
remarkably good properties. Low-temperature Al2O3 displayed lower CO2 gas diffusion rates than uncoated
ALD films may be used for various applications where PET bottles.
the high hydrogen concentration is not crucial. On the
basis of the results at 33 °C, growing Al2O3 ALD films Acknowledgment. Funding for this research was
at room temperature is possible. The major problem is research was provided by Applied Films Corporation.
slow H2O desorption from the reactor walls and very Additional support was provided by the Air Force Office
long required H2O purge times. Shorter cycle times of Scientific Research. We thank Russell Black and
could be achieved using a modified reactor design and Elisabeth Sommer at Applied Films Corp. for providing
alternate oxygen sources such as N2O,22 NO2,16 or the PET bottles and for performing CO2 gas diffusion
alkoxides.23 tests on the PET bottles coated with Al2O3 ALD films.
F. Gas Diffusion Tests. The PET bottles coated with Yongqiang Wang at the Ion Beam Analysis Laboratory
300 reaction cycles of Al2O3 ALD at 58 °C displayed a in the Institute of Technology Characterization Facility
decrease in CO2 gas diffusion rates. However, lower CO2 at the University of Minnesota performed the RBS and
diffusion rates and higher barrier improvement factors FReS analysis of the Al2O3 ALD samples.
(22) Kumagai, H.; Toyoda, K.; Matsumoto, M.; Obara, M. Jpn. J. CM0304546
Appl. Phys. 1993, 32, 6137.
(23) Ritala, M.; Kukli, K.; Rahtu, A.; Raisanen, P. I.; Leskela, M.;
Sajavaara, T.; Keinonen, J. Science 2000, 288, 319. (24) Chatham, H. Surf. Coat. Technol. 1996, 78, 1.