Al2O3 Atomic Layer Deposition with Trimethylaluminum and Ozone Studied by in Situ
Transmission FTIR Spectroscopy and Quadrupole Mass Spectrometry
David N. Goldstein, Jarod A. McCormick, and Steven M. George*,,
Department of Chemistry and Biochemistry, and Department of Chemical and Biological Engineering,
UniVersity of Colorado, Boulder, Colorad, 80309
ReceiVed: May 14, 2008; ReVised Manuscript ReceiVed: September 25, 2008
The atomic layer deposition (ALD) of Al2O3 using sequential exposures of Al(CH3)3 and O3 was studied by
in situ transmission Fourier transform infrared (FTIR) spectroscopy and quadrupole mass spectrometry (QMS).
The FTIR spectroscopy investigations of the surface reactions occurring during Al2O3 ALD were performed
on ZrO2 particles for temperatures from 363 to 650 K. The FTIR spectra after Al(CH3)3 and ozone exposures
showed that the ozone exposure removes surface AlCH3* species. The AlCH3* species were converted to
AlOCH3* (methoxy), Al(OCHO)* (formate), Al(OCOOH)* (carbonate), and AlOH* (hydroxyl) species. The
TMA exposure then removes these species and reestablishes the AlCH3* species. Repeating the TMA and O3
exposures in a sequential reaction sequence progressively deposited the Al2O3 ALD film as monitored by the
increase in absorbance for bulk Al2O3 infrared features. The identification of formate species was confirmed
by separate formaldehyde adsorption experiments. The formate species were temperature dependent and were
nearly absent at temperatures g650 K. QMS analysis of the gas phase species revealed that the TMA reaction
produced CH4. The ozone reaction produced mainly CH4 with small amounts of C2H4 (ethylene), CO, and
CO2. Transmission electron microscopy (TEM) was also used to examine the Al2O3 ALD films deposited on
the ZrO2 particles. These TEM images observed conformal Al2O3 ALD films with thicknesses that were
consistent with an Al2O3 ALD growth rate of 1.1 /cycle. The surface species after the O3 exposures and the
mass spectrometry results lead to a very different mechanism for Al2O3 ALD growth using TMA and O3
compared with Al2O3 ALD using TMA and H2O.
I. Introduction
Atomic layer deposition (ALD) is an ideal technique to
deposit ultrathin films with high conformality and precise
thickness control.1,2 Traditional methods to deposit Al2O3 with
ALD involve sequential surface reactions of Al(CH3)3 (trimethylaluminum (TMA)) and water.3-6 These sequential reactions allow conformal Al2O3 film growth with thickness control
on a variety of substrates including polymers,7 porous membranes,3,8
and nanopowders.9 The details of the Al2O3 ALD reaction have
been extensively studied by a variety of techniques, including
the quartz crystal microbalance measurements,10,11 Fourier
transform infrared (FTIR) spectroscopy,3,12 ellipsometry,4,5 and
X-ray photoelectron spectroscopy (XPS).13 Al2O3 ALD is a
model system and serves as a reference point for other ALD
systems.
The semiconductor industry is interested in growing Al2O3
films with ozone instead of water as the oxygen source. Al2O3
is a high-k dielectric that is used as a dielectric film for both
DRAM and MOS-FETs.14 When ozone is used as the oxidant,
the Al2O3 ALD films can have leakage current densities that
are reduced by two orders of magnitude in comparison with
Al2O3 ALD films deposited with water.15 This improvement and
smaller flat band voltage shifts allow Al2O3 ALD films grown
using ozone to make better gate oxides.15,16 There are also other
advantages when replacing H2O with ozone. Water desorbs
slowly from substrates and requires longer purge times.10 Water
can also leave unreacted hydroxyl groups in the Al2O3 ALD
* Corresponding author.
Department of Chemistry and Biochemistry.
Department of Chemical and Biological Engineering.
TEM studies help to clarify the surface chemistry and thin film
growth mechanism during Al2O3 ALD with TMA and ozone.
II. Experimental Section
The surface chemistry and thin film growth during Al2O3
ALD was studied using sequential exposures of TMA and O3
at various temperatures. Al2O3 ALD films were grown on ZrO2
particles in an ALD reactor designed for in situ FTIR spectroscopy studies.12,20 Figure 1 presents a schematic of the ALD
reactor. The reactor was a warm-wall reactor where the chamber
walls were heated to 350 K while the sample could be
independently heated to >900 K. Figure 2 shows a schematic
of all the inlet and outlet connections to the ALD reactor. Two
argon mass flow controllers (MFC) regulated the flow of argon
Goldstein et al.
Figure 3. FTIR difference spectra after (a) last water exposure, (b)
next TMA exposure, (c) first ozone exposure, and (d) next TMA
exposure. All exposures were performed at 450 K. C ) carbonate, F
) formate.
Goldstein et al.
Figure 5. FTIR difference spectra after (a) third TMA exposure, (b)
third ozone exposure, (c) fourth TMA exposure, and (d) fourth ozone
exposure. All exposures were performed at 550 K. F ) formate.
Goldstein et al.
Figure 11. TEM image of ZrO2 particles coated with Al2O3 after 40
reaction cycles of TMA and ozone.
lit. (cm-1)
exptl (cm-1)
Al-O phonon
(s) C-O (m)
Sym. Al-CH3 def
(s) OCO (c)
(s) OCO (f)
CH (f, m)
asym CH3 def (m)
(as) OCO (f)
(a) OCO (c)
(s) CH3 (m)
(as) CH3 (m)
(s) OCO + CH (f)
110026,29,30,32,38
11973,12
131525
138026,29,30,32,38
139526,29,30,32,38
145026,29,30,32,38
159526,29,30,32,38
171025
284626,29,30,32,38
295026,29,30,32,38
297026,29,30,32,38
900-1000
1089
1212
1320
1388
1404
1475
1597
1720
2850
2923
3016
Figure 10. Absolute FTIR spectra showing the growth of the bulk
Al-O bulk absorbance feature after various numbers of TMA and O3
reaction cycles.
Figure 12. (a) Mass spectrum during the first O3 micropulse showing
CH4 and C2H4 at 550 K. (b) Mass spectrum during the 55th O3
micropulse showing CH4, CO, and CO2 at 550 K.
Figure 13. (a) Mass spectrum during the first TMA micropulse
showing CH4 and CO at 550 K. (b) Mass spectrum during the 55th
TMA micropulse showing TMA at 550 K.
Goldstein et al.
COOH)* (carbonate), and AlOH* (hydroxyl) species. The TMA
exposure then removes the methoxy, formate, carbonate, and
hydroxyl species and reestablishes the AlCH3* species. The
identification of formate species in the FTIR spectra was
confirmed by separate formaldehyde adsorption experiments on
Al2O3 ALD surfaces. The formate species were temperature
dependent and were nearly absent from the FTIR spectra at
g650 K.
Repeating the TMA and O3 exposures in a sequential reaction
sequence progressively deposited an Al2O3 ALD film as
monitored by the absorbance increase for bulk Al2O3 infrared
features. TEM was used to examine the Al2O3 ALD films
deposited on the ZrO2 particles. The Al2O3 ALD films were
very conformal to the underlying ZrO2 particles. These TEM
images were consistent with an Al2O3 ALD growth rate of 1.1
/cycle at 550 K. QMS analysis of the gas phase species
revealed that the TMA reaction produced CH4. The ozone
reaction then produced mainly CH4 with a small amount of C2H4
(ethylene), CO, and CO2.
On the basis of the surface species observed by the FTIR
studies and the gas phase species monitored by the QMS
investigations, a very different mechanism is suggested for Al2O3
ALD growth using TMA and O3 compared with Al2O3 ALD
using TMA and H2O. During Al2O3 ALD using ozone, both
Al-C and C-H bond insertion occurs when O3 reacts with
AlCH3* species to create methoxy and AlCH2OH* species. The
methoxy species decompose to formate and carbonate species.
The formate and carbonate species release CO and CO2 to
produce AlOH* species. Two AlCH2OH* species also eliminate
C2H4 and produce two AlOH* species.
Acknowledgment. This work was supported by the National
Science Foundation (CHE-0715552). Some of the equipment
used in this research was provided by the Air Force Office of
Scientific Research. The authors thank Dr. Thomas Giddings
for assistance with the TEM analysis.
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