Journal of The Electrochemical Society, 152 共4兲 G271-G276 共2005兲 G271

0013-4651/2005/152共4兲/G271/6/$7.00 © The Electrochemical Society, Inc.

Etch Characteristics of Al2O3 in ICP and MERIE Plasma

Etchers
Stefan Tegenz and Peter Moll
Infineon Technologies SC300, 01099 Dresden, Germany

The etch characteristics of Al2O3 films were investigated for magnetically enhanced reactive ion etching 共MERIE兲 and inductively
coupled plasma 共ICP兲 etch systems as a function of bias power, source power, and gas chemistry. Compared to pure Ar sputtering,
F-, Cl-, and Br-based plasma provided a significant chemical enhancement. Fluorine containing plasma produced higher etch rates
compared to Cl and Br. The selectivity for Al2O3 over other semiconductor materials is low for all of the investigated two-gas
mixtures. A polymerizing C4F6 chemistry provides acceptable selectivity to Si, and was used for a patterning of an Al2O3 hard
mask. These structures have been transferred into the Si wafer.
© 2005 The Electrochemical Society. 关DOI: 10.1149/1.1865912兴 All rights reserved.

Manuscript submitted July 26, 2004; revised manuscript received September 24, 2004. Available electronically March 7, 2005.

As Al2O3 is one of the potential materials as gate dielectric1 or
for a novel memory capacitor dielectric 共IEDM Infineon 2002兲,2 the
etch characteristics at wafer level are of growing interest in the
pursuit of suitable plasma etch processes for the removal of these
layers. Other conventional applications for Al2O3 are in magnetic
stacks used for hard disks 共magnetic read/write heads兲3 and as a
tunnel barrier in magnetic random access memory 共MRAM兲 cells4
and in electroluminescent displays.5
Al2O3 is known as a very hard material which is difficult to
remove by reactive ion etching 共RIE兲; therefore it is proposed as a
new hard mask material or as an etch barrier material.6-9 To function
as a hard mask, a well controlled etch process, with good profile
control and sufficient selectivity to photoresist or another mask ma-
terial, is needed.
In this paper, we describe the characterization and development
of the Al2O3 etch process beginning with sputter rates on different
types of etch chambers up to the use of the material as a hard mask.
Experimental
Al2O3 films were deposited by atomic layer deposition 共ALD兲
on 8 in. wafers with low carbon content, resulting in highly uniform
Al2O3 films. The deposition process is described in detail in Ref. 10.
Typical film thickness was 100 nm, and the films were not annealed
after deposition. In Ar sputter experiments, no etch rate differences
between annealed and nonannealed wafers have been observed.
The plasma etch experiments were performed with two commer-
cially available inductively coupled plasma 共ICP兲 chambers 共LAM
TCP and Applied Materials DPS+兲 and a magnetically enhanced
reactive ion etching 共MERIE兲 tool 共Applied Materials eMax兲. On
the ICP chambers, both targeted for Si/conductor etch applications,
the plasma is ignited inductively by the source power; at the eMax,
designed for dielectric etch, the plasma is ignited capacitivly by
the cathode.
The dc bias voltage values mentioned in this paper are those
supplied by the tools and software. They are not directly measured
but calculated from the Vpp values.
The etch rates were determined by measuring the film thick-
nesses before and after processing on a Rudolph spectral ellipsom-
eter 共S200兲, based on multi-wavelength laser ellipsometry and full
spectrum reflectometry.
Unless otherwise mentioned, the following experimental setup
for plasma etching is used: The eMax has a 13.56 MHz RF cathode,
the pressure is set to 10 mTorr, the cathode temperature to ⫺15°C,
the magnetic field to 60 Gauss with a B field ratio of 0.25 and a
backside pressure of 20 Torr is used for both inner and outer cooling
zone.
On the DPS+ we set the process pressure to 10 mTorr as well. A
source power of 1000 W was used to ignite the plasma and a bias
z
E-mail: stefan.tegen@infineon.com
power of 200 W 共with a frequency of 13.56 MHz兲 was applied to
control the ion current towards the wafer. This value was often var-
ied to investigate the influence of the ion current and energy on
the etch rates. The wafers were held with a chuck voltage of 650 V
to the cathode which had been set to a temperature of 50°C. A
helium back side pressure of 8 Torr for the inner and 12 Torr for
the outer cooling zone of the chuck was used to control the wafer
temperature.
Process pressure on the TCP was held at 10 mTorr as well, but
source power was set to 600 W 共also with a frequency of 13.56
MHz兲 and bias power to 200 W. A chuck temperature of 50°C and a
He cooling pressure of 8 Torr was applied. The E-chuck voltage
was 700 V.
On all three chambers the standard gas flow was 100 sccm
per gas.
Error discussion.—Film thickness measurement.—The given
values for the etch rate are the difference of the mean values of the
pre and post etch measurement of nine points on the wafer. Due to a
large nonuniformity on some wafers, the etch rate differs from wafer
edge to center. On some wafers, certain points could not be mea-
sured. In the case of polymer formation on the wafer surface, zero
removal was assumed to calculate the wafer mean etch rate. A sys-
tematic error of the post-etch-measurement cannot be excluded, due
to possible film density change caused by ion bombardment and the
polymer formation. Overall, the error due to the measurement accu-
racy and the changes in surface stochiometry and film morphology
is assumed to be in the order of 10% 共1 sigma兲.
By repeating experiments on different days, and randomizing the
order of parameter variations, the error due to reproducibility and
systematic tool drift was minimized.
dc Bias.—One important parameter for comparing the experiments
performed on different tools is the dc/bias. The given values were
calculated from Vpp measurements by the tool and software, with no
direct outside access for calibrating. Because the method is tool
specific 共calibrated by the tool vendor兲, systematic difference in the
absolute dc-bias values may exist.
Process parameters.—The process parameters, including gas flows,
magnetic field, pressure, and radio-frequency 共rf兲 power setting were
calibrated either during the startup of the tool or on regular intervals.
The assumed error is low and does not play a significant role for the
discussed results.
Ar Sputter Etching
The set of experiments was done on all three chambers: the
eMax and the two different ICP chambers, where the DPS+ has been
operated with two different source powers of 500 and 1000 W. One
SiO2 sputter rate is included for comparison purposes. The SiO2 has
been processed on the DPS+ with 1000 W source power.
The results of our experiments for the eMax, the DPS+, and the
TCP are shown in Figs. 1a, b, and c, respectively. The sputter rates

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 G272 Journal of The Electrochemical Society, 152 共4兲 G271-G276 共2005兲
Figure 1. Sputter rate as function of the bias power 共a兲 eMax, 共b兲 DPS+, and
共c兲 TCP.
共in nm/min兲 are plotted against the applied bias power 共in W兲. In all
curves the sputter rate increases faster than linear with the applied
bias power for small power values.
A similar curve is observed for the SiO2 sputter rate, but
the absolute removal rates are five times higher. A comparable rela-
tionship between the sputter rates has been found by Day et al. in
Ref. 11.
The Ar sputter rate can be effectively suppressed by adding oxy-
gen to the plasma 共see Fig. 1a兲. With 100 sccm O2/100 sccm Ar at
1000 W source power, 400 W bias power on the DPS+, the Al2O3
sputter rate is reduced from 8 nm/min for Ar alone down to 1 nm/
min; with O2 alone, 0.8 nm/min have been achieved.
The bias power dependence of the sputter rate can be explained
in terms of the Ar ion current and energy.
With the eMax 共Fig. 1a兲, the plasma was ignited capacitively, so
the plasma density increases with the bias power. Therefore, one
should expect a linear dependence of the etch rate on this parameter,
what we do find in our experiments.
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Figure 2. Al2O3 etch rate of CF4/Ar on a DPS+ as a function of the source
power
For the ICP chambers 共Fig. 1b and c兲 the plasma density is domi-
nated by the source power and the ion current towards the wafer is
a parameter that can be set nearly independently by the bias power.
Therefore, one should expect different sputter rates for different
source power values, as can be seen for the DPS+ operated at 500
and 1000 W.
At zero bias power, only a small number of ions reach the wafer
surface. If the bias power is switched on, more and more of them
reach the cathode because they are accelerated by an increasing bias
voltage. Therefore, the sputter rate augments faster than linear at
small bias power, until a power value where a constant amount of
the ions reach the Al2O3 surface.
Reactive Ion Etching
In this section we present and discuss the influence of the cham-
ber settings on the Al2O3 etch rates obtained from ICP chambers and
for gases and gas combinations typically used for RIE in semicon-
ductor industry.
With these investigations we pursue three aims:
1. To demonstrate the influence of chamber parameters that are
typically varied to optimize an etch process. These parameters in-
clude: source power, bias power, pressure, chuck temperature, and
gas mixture;
2. To demonstrate high and low Al2O3 etch rates; and
3. To achieve high/low selectivities to other materials.
These investigations were performed on the two ICP chamber
types mentioned above, which are equipped with different kind of
halogen containing gases.
Source power.—In an ICP chamber, the source power ignites the
plasma and mainly determines the degree of ionization and the frag-
mentation of the gas molecules.
In a series of experiments the Al2O3 etch rate on the DPS+ for
CF4 with the addition of Ar were measured at different source power
values. The other chamber settings remained unchanged. As shown
in Fig. 2, the Al2O3 etch rate increases with increasing source
power. This relationship is linear for the investigated source power
interval and gas mixture.
Bias power.—The bias power determines the electrical field be-
tween the plasma and the bottom electrode. This field accelerates the
charged particles toward the wafer. Ion energy is therefore con-
trolled by the source power.
It is varied in a number of experiments that have been performed
on the TCP and on the DPS+. Figure 3a shows the result for CF4,
HCl, Cl2, and HBr, all with the addition of Ar, on the LAM TCP. For
comparison, the sputter rates of Ar are also shown. In Fig. 3b dif-
ferent F-containing gases 共SF6, CF4, NF3, and CHF3, all of them
with Ar兲 have been tested on the DPS+. Again, the values for Ar
alone are plotted in this graph.
 Journal of The Electrochemical Society, 152 共4兲 G271-G276 共2005兲
Figure 3. Etch rate of Al2O3 with different fluorine containing gases as
function of the bias power on the TCP 共a兲 and on the DPS+ 共b兲.
As with the source power, the etch rate increases linearly with
increasing bias power for both ICP chambers. At zero bias power no
Al2O3 removal was observed, and the curves indicate that a certain
threshold power of some 10 W 共depending on the chamber and the
gas used兲 is needed to etch the material.
In Fig. 3a, CF4 removes the Al2O3 three times faster than Cl- or
Br-based chemistries. The difference in the etch rate between Ar/
CF4 and Ar alone is nearly one order of magnitude. This can also be
observed in Fig. 3b. Comparing the two figures, it can be seen that
under comparable chamber settings, all F-based plasma processes
etch the Al2O3 faster than Cl- or Br-based ones.
In Fig. 3b the etch rate increases with increasing F-content of the
gas molecules: SF6 ⬎ CF4 ⬎ NF3, with the exception of CHF3. Un-
der equal chamber settings, CHF3 removes the Al2O3 at the same
rate as SF6.
Cl2, HCl, and HBr yield comparable etch rates 共Fig. 3a兲, where
the Ar/Cl2 gives slightly higher etch rates than HCl or HBr. This
corresponds to an investigation on a MERIE chamber,17 where BCl3
is reported to give significantly higher etch rates than HCl or Cl2.
Two conclusions can be drawn from these results: (i) the Al2O3
etch rate increases with increasing source power. This relationship is
essentially linear for the investigated gas mixtures; and (ii) under
comparable chamber settings CF4 etches the Al2O3 by a factor three
faster than Cl2 or HBr and ten times faster than Ar alone. This
indicates a significant chemical enhancement of the etch rate.
Pressure.—By varying the pressure in the RIE process, the ratio
between ions and radicals arriving on the wafer can be changed over
a wide range.12 At low pressure, the ion bombardment is dominant
over the influence of radicals and neutrals; at high pressure the situ-
ation is reversed. The plasma density is also influenced by pressure.
To observe pressure impacts on Al2O3 etch rate, the pressure was
varied from 3 to 80 mTorr in the DPS+ chamber while source power
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G273
Figure 4. Al2O3 etch rate for CF4/Ar and HBr/Ar as a function of the
pressure. The chamber settings have been 1000 W source/200 W bias power
for CF4/Ar and 1000 W source/400 W bias power for HBr/Ar. The gas flow
was 100 sccm for each gas.
and gas flow were held constant at 1000 W and 100 sccm for each
gas, respectively; bias power was set to 200 W for CF4/Ar and to
400 W for HBr/Ar.
With Ar/CF4 it can be seen 共Fig. 4兲 that the etch rate decreases
from high values at low pressures 共27 nm/min at 3 mTorr兲 down to
below 5 nm/min at 35 mTorr. At 80 mTorr, nearly no etching takes
place. For the case of Ar/HBr pressure effects on the etch rate were
analogous 共Fig. 4兲.
A comparable pressure dependence can be found in other
publications. It has been observed for CF4 in an ICP chamber,8
for CF4/O29 in a CCP reactors 共capacitivly coupled plasma兲 and
also for SF65,8 and HCl.13
Temperature.—The chuck temperature influences the adsorption
and desorption rate of gas particles and the chemical reaction rate at
the wafer surface.
For chambers used in production, temperature can only be varied
within a small range. The E-chuck of the DPS+ is capable of oper-
ating between 20 and 90°C.
Figure 5 shows the Al2O3 etch rate as a function of the chuck
temperature for the DPS+ for Cl2/Ar at two different bias power
values 共100 and 400 W兲 and for HBr/Ar at 400 W. The other cham-
ber parameters had been set to the standard values.
In the investigated temperature range there is essentially no de-
pendence of the etch rate on this chamber parameter, maybe the data
indicate a slight decrease of the etch rate with rising temperature.
Gas combinations.—In Fig. 3a the Cl and Br containing chem-
istries show fairly the same etch rates, regardless of Ar is added or
Figure 5. Al2O3 etch rate on the DPS+ as a function of the chuck
temperature.
 G274 Journal of The Electrochemical Society, 152 共4兲 G271-G276 共2005兲
Figure 6. Al2O3 etch rate as a function of the Ar content in Ar/XFn gas
mixtures
not. For F-based plasma the situation depends on the gas used, here
a strong dependence on the Ar-addition for NF3, CHF3 and SF6 共Fig.
3b兲 can be observed, while the CF4 etch rates remain essentially
unchanged.
To investigate the role of the F-content on the etch process, the
Ar content in Ar/XFn gas mixtures was changed in a series of ex-
periments from 0 to 100%. The power was held constant at 1000 W
共source兲 and 200 W 共bias兲, the pressure at 10 mTorr and the total gas
flow at 100 sccm.
It can be seen in Fig. 6 that, with CF4, small amounts of this gas
already augment the Al2O3 etch rate significantly. With a further
increase in the amount of CF4 the etch rate improves slightly, reach-
ing a maximum value around 80% and decreasing a little for pure
CF4.
For CHF3/Ar gas mixtures the maximum etch rate is reached at
about 40% CHF3, well below the CF4 values. Toward higher CHF3
flows the values diminish; at 100% CHF3 no etching but deposition
takes place. This polymer formation seems to be reduced at 400 W
bias power 共Fig. 3兲, but it may nevertheless limit the etch rates there.
The slightly reduced etch rate for pure CF4 共compared to 80
sccm CF4/20 sccm Ar兲 may also be caused by this effect.
The addition of oxygen to a CF4 plasma is a possible way to
remove polymers from the wafer surface and to enlarge the amount
of reactive particles. 20% O2 can double the etch rate of Si.12 The
underlying mechanism is reported to be the enhanced amount of free
F in the plasma.
The influence of the O2 addition is presented in Fig. 7. Adding 10
sccm O2 to the CF4/Ar gas mixture increases the Al2O3 etch rate by
40%. A higher O2 flow leads to only slightly higher etch rates.
Figure 7. Al2O3 etch rate of an Ar/CF4 plasma as a function of the O2 flow
added.
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Figure 8. Selectivity of different materials to Al2O3 as a function of the O2
flow in an Ar/CF4 plasma on the DPS+.
This contrasts with two investigations made on CCP chambers.
For a CF4/O2 plasmas no influence of the O2-content on the etch rate
has been observed.9 One reason for this discrepancy may be the high
pressure of 13 Pa 共about 98 mTorr兲 used in that publication. Above,
we report very low etch rates measured at these high pressures.
In another publication, the addition of O2 to a CHF3 plasma was
found to reduce the etch rate.14 The reason for this is thought to be
a re-oxidation of the Al2O3 surface and a scavenge of the carbon by
the oxygen.
An addition of O2 to an Ar plasma reduces the sputter rate dra-
matically 共see section 3兲, but an O2-plasma alone is reported not to
change the stochiometry of Al2O3.15 A reoxidation of the Al by the
oxygen should slow down the etching in this case, which cannot be
observed in our experiment.
Our results indicate that the influence of the oxygen in this pro-
cess is mainly an enhancement of the content of free F in the
plasma. They and/or fluorine containing molecules 共like CF+3 for
example兲 lead to the higher etch rates.
Selectivity
The aim of the investigations presented here is to analyze the
plasma processes investigated for Al2O3 etching with respect to se-
lectivities. For some applications, it is necessary to etch Al2O3 se-
lective to other materials, such as photoresist, Si, Si3N4, or SiO2 and
vice versa. Therefore effective processes for Al2O3 etching have
been tested on these materials to perform an Al2O3 hardmask open
process. On the other hand, it is interesting to look for processes
slowly removing Al2O3 to structure Si, Si3N4, or SiO2 with an
Al2O3 hardmask. This turned out to be an easier task, as the selec-
tivity of Al2O3 to other materials is typically well below 1:1.
All experiments presented here have been performed on the
eMax or on the DPS+.
CF4.—CF4 containing chemistries are widely used in the semi-
conductor industry and have been studied intensively. Therefore, our
investigations were started with this type of process.
With CF4, the highest Al2O3 removal rates have been obtained,
but it also etches Si very effectively, so one cannot hope that high Si
to Al2O3 selectivities can be achieved.
In a first series of experiments, the influence of an oxygen addi-
tion to a CF4/Ar plasma was investigated. This is known to intensify
the Si etch rate, and, as seen above, this has been found to also
enhance the Al2O3 etch rate. The O2 flow has been varied in this
experiment between 0 and 40 sccm.
The selectivities S of Si, Si3N4, and SiO2 to Al2O3 have been
plotted in Fig. 8. They decrease with increasing O2 flow from values
of 14 and 13 for SiO2 and Si3N4, respectively, at pure Ar/CF4 down
to S = 7 for SiO2 共⫺46%兲 and S = 10 for Si3N4 共⫺32%兲 with 40
sccm O2 added. For Si, the decrease is less pronounced; it starts at
 Journal of The Electrochemical Society, 152 共4兲 G271-G276 共2005兲 G275

Table I. Selectivity of different materials to Al2O3 for different

plasma processes.

Si Si3N4 SiO2
Ar/CHF3 3:1 1.5 4.8 4.8
Ar/CHF3 2:1 2.0 5.3 5.5
Ar/CHF3 1:1 2.1 5.2 4.8
CHF3 4.8 11.1 9.0
Ar/CF4/0 O2 9.6 13.8 12.7
Ar/CF4/10 O2 8.3 10.5 8.5
Ar/CF4/20 O2 8.3 10.2 7.9
Ar/CF4/40 02 7.2 9.5 6.9
50Ar/50CF4/10 O2 62.0 57.1 39.6
Ar + SF6 19.7 9.2 5.4
SF6 32.1 14.1 8.3
Ar/C12 共10 m Torr兲 69.7 25.8 4.0
Ar/HBr 共20 m Torr兲 8.7 1.4 3.9
CI/Br 55.7 1.4 2.0 Figure 9. Selectivity of Al2O3 to different materials in a CHxFy/Ar plasma
C4F6 0.85 2.6 17.2 on the eMax.

about 10 and ends at a value around 7 共⫺25%兲. The reason for this
behavior is the strong enhancement of Si removal with the oxygen
flow, it is nearly as strong as for the Al2O3. In opposition to this, the
etch rate of SiO2 decreases slightly with increasing O2 flow, and so
is the SiO2 to Al2O3 selectivity. The behavior of Si3N4 lies some-
where between the two extremes.
As seen above, increasing pressure has been identified as one
important parameter to suppress the Al2O3 etch rate. The selectivity
results of an experiment made at 40 mTorr are listed in Table I. A
reduced source power of 500 W 共bias power 200 W兲 gives a very
high Si to Al2O3 selectivity of 62. For SiO2 and Si3N4 we obtained
57 and 40, respectively, the highest values found in these experi-
ments. In this process the gas flows have been reduced to 50 sccm
Ar, 50 sccm CF4, and 10 sccm O2.
An increase of selectivity with increasing process pressure and
decreasing bias power for CF4 and SF6 on a ICP tool have also been
observed in Ref. 8.
Due to the suppressed Al2O3 etch rate at higher process pressure
it is thus easy to etch Si, Si3N4, or SiO2 with an Al2O3 hardmask at
very high selectivities. Pressure, decoupled power, and gas flows are
parameters in this recipe which should give a sufficient process win-
dow for profile control, uniformity over the wafer, etch rates etc.
Adding some CHF3 might increase the profile control for Si3N4 or
SiO2 etching without too great a drop in selectivity.
The opposite of this, a selective etching of Al2O3 to one of these
materials, seems to be impossible with this process, even at higher
O2 flow rates or at reduced process pressure.
CHF3.—CHF3 is used to remove SiO216 or Si3N4 and a selective
etching of SiO2 or Si3N4 to Si is possible with this chemistry. High
Al2O3 etch rates have been found for this gas if the polymer depo-
sition on the surface is suppressed by sufficient sputtering 共see
above兲. To obtain a better selectivity to Si, processes with different
Ar to CHF3 ratios were tested. The process parameters are: 10
mTorr, a source power of 1000 W and a bias power of 400 W. The
result of this experiment is summarized in Table I.
All selectivities decrease with increasing Ar share in the gas flow
and a Si/Al2O3value of 1.5 is reached for 150 sccm Ar/50 sccm
CHF3. Because of the high sputter part of the process, the Si etch
uniformity is low. In the wafer center the material is removed
slower, here the selectivity reaches unity. At the wafer edge, fewer
polymers were formed on the wafer surface or they are sputtered
away more effectively. Here, the Si is etched two times faster, while
the Al2O3 etch rate remains constant. Thus, a selectivity of two is
obtained in this region.
This nonuniformity will be difficult to overcome and might be a
challenge if one wants to use an Ar/CHF3 plasma to etch an Al2O3
layer with a Si mask.
CHxFy chemistries.—One interesting aspect is, if the Al2O3 etch
can be enhanced by having a larger amount of a reduction agent like
hydrogen in the plasma. Unfortunately, pure H2 is normally not
available on standard gas configurations, so the experiments were
performed on the eMax with CHxFy, with x = 0, 1, 2, or 3 and y
= 4−x. Therefore, the hydrogen concentration is always changed in
combination with fluorine concentration. Figure 9 shows the selec-
tivity to SiO2 decreasing with higher H-content, the selectivity to Si
increases up to CH2F2, but does not increase further for CH3F.
This may be an effect of two mechanisms: the reduction of
Al2O3 with formation of H2O and thus enhancing the probability
of AlF3 formation, and the changed polymer formation and sur-
face passivation of the surface. The etch rate of the Al2O3 decreases
substantially with a higher H-content 共and lower F-content兲, so
that a reduction of the Al2O3 can not be determined out of these
experiments.
This leads to the question of whether the F-content is limiting for
this kind of etch.
A series of experiments with a decreasing CF4 content in a mix-
ture with Ar shows no indication of this trend, so at least for the CF4
the etch rate seems not to be limited by the supply of fluorine. This
matches to the expectations, since the Al2O3 etch rate is low com-
pared to SiO2.
The process with the best selectivity has been found on the
eMax. It runs at 1800 W rf power, 40 mTorr pressure, and 100 G
magnetic field with an Ar/C4F6/CHF3/O2 gas mixture.
In Table I, the selectivities for Al2O3 to Si, SiO2, and Si3N4 are
shown. For Si the lowest value of our experiments, S = 0.85, has
been achieved. In this process, the selectivity is mainly determined
by balancing the CF/H based polymer deposition and the removal of
this polymer by sputtering and CO/CO2 formation by oxygen. On
surfaces with O containing materials like SiO2, the polymer removal
is enhanced due to the higher local O concentration out of the reac-
tion products. A similar mechanism is believed to produce a lower
CF-polymer thickness on the Al2O3 compared to Si, and so sup-
pressing the normally substantially higher Si etch rate in F-
containing plasma conditions.
SF6.—SF6 etches Si very fast and isotropically. The Al2O3 etch
rate of this gas can also be quite high. Therefore, one can expect
only a moderate selectivity in Ar/SF6 plasmas. The result of
such an experiment, where the bias power has been set to 400 W,
is presented in Table I. The selectivities can be increased by using
SF6 alone, as the sputter component is decreased in this case.
For SF6 alone we obtained a remarkable Si to Al2O3 selectivity of
32. A higher process pressure or lower bias power are process con-
ditions that would further increase this value.8

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 G276 Journal of The Electrochemical Society, 152 共4兲 G271-G276 共2005兲
Figure 10. SEMs of Al2O3 mask open 共left兲 and following Si-structuring
with Al2O3 mask 共right兲 in different magnifications.
This etch chemistry can therefore be used to stop an isotropic Si
recess on a Al2O3 liner.
Cl, Br.—As seen above, relatively low Al2O3 etch rates have
been found even at high bias powers for Cl and Br based chemistries
which do not contain fluorine. This kind of etch process is often
used for anisotropic etching of Si, so the selectivities are tested. The
result for one Ar/Cl2 experiment, one Ar/HBr plasma, and for a more
complex chemistry, which contains beneath HBr and Cl2 also HeO2
and NF3 are also listed in Table I. With Ar/Cl2 the highest selectivity
value for Si to Al2O3, nearly 70, was obtained, a value that could
certainly be improved by higher pressure 共for the etch rate depen-
dence on the process pressure in a HCl-plasma, see Ref. 13兲 or
lower bias power.
This dependency can be seen for the case of Ar/HBr. As reported
above, the Al2O3 etch rate can be suppressed at a pressure of 40
mTorr. This leads to very high Si to Al2O3 selectivities at higher
process pressures. The etch rate of SiO2 in an Ar/HBr plasma is also
zero at high pressures, so here no selectivity to Al2O3 can be ob-
tained.
But Si can be etched with very thin Al2O3 hard masks if one uses
this chemistry and it is our recommended process for this task.
With the Cl2/HBr/HeO2/NF3 chemistry 共labeled ClBr兲 the value
for the Si to Al2O3 selectivity is also very good. This highly aniso-
tropic process has been developed to obtain excellent Si to SiO2 and
Si to Si3N4 selectivities. This is why the selectivities of the two
dielectrics to Al2O3 are small, it is the smallest selectivity to Si3N4
in our experiments 共S = 1.4兲. Because of the good etch uniformity
over the wafer, one can use this process to remove Al2O3 with a
Si3N4 or SiO2 mask. Unfortunately the etch rate for Al2O3 is with 7
nm/min very small, so this will only be an option to structure very
thin layers of oxidized aluminum.
Structurization of Al2O3/HM
Due to the high etch resistance, a use of Al2O3 as a hardmask for
structuring is a possible application. Therefore, a typical high selec-
tivity process for SiO2 and Si3N4 etching with a higher selectivity to
other materials like resist or Si was investigated, to enable the struc-
turing of the Al2O3 itself.
A dense contact layer in a 0.17 µm technology was successfully
transferred into a 110 nm thick Al2O3 film 共Fig. 10兲. A patterned 300
nm Si film was used as a hardmask.
The sidewall angle of the contacts shows less than the typical
taper of a sputter-based etch with nonvolatile reaction products, due
to a long overetch into the Si3N4 underlayer 共Fig. 10兲.
Finally, a high power Si etch, normally used for forming the
dynamic random access memory trench capacitor structures was
performed using this hardmask 共Fig. 10兲.
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The selectivity of Si to the hard mask was about 11-12, only
marginally higher than for SiO2 共⬃10兲. The etch recipe has a rf
power of 1200 W, producing ions with a kinetic energy of up to 700
eV. The low difference in selectivity values for Al2O3 compared to
SiO2 values show, that for this Si etch, the mask removal rate is
mainly caused by sputter removal of the high energy ions.
Conclusions
The etch characteristics of Al2O3 films were investigated for
MERIE and ICP plasma etch reactors as a function of chamber
settings and gas chemistry.
Compared to pure Ar sputtering, F-, Cl-, and Br-based plasma
provided a significant chemical enhancement. Fluorine containing
plasma produce higher etch rates compared to Cl and Br.
The investigation of different chamber parameters revealed some
useful dependencies of the Al2O3 etch rate. Increasing source and
bias power linearly increases the Al2O3 etch rate, while no influence
of the chuck temperature has been found between 20 and 90°C.
Decreasing pressure has been identified as one important parameter
to enlarge the Al2O3 etch rate
The etch selectivity for Al2O3 over other typical materials used
in the semiconductor industry is quite low for most of the investi-
gated gas mixtures, but an Ar/CHF3 and a C4F6 containing process
with an acceptable Al2O3 to Si selectivity has been identified.
With the Ar/CHF3 process an Al2O3 hardmask has been opened
and the structures were successfully transferred into the wafer with a
conventional Si etching chemistry.
Acknowledgments
We thank Kimberly Wilson and Stephan Wege for helpful
discussions.
The work for this paper was supported by the EFRE fund of the
European Community and by funding of the State of Saxony of the
Federal Republic of Germany 共project no. 8214兲. The authors are
responsible for the content of the paper.
Infineon Technologies SC300 assisted in meeting the publication costs of
this article.
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