Thin Solid Films 587 (2015) 2027

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Thin Solid Films

journal homepage: www.elsevier.com/locate/tsf

Inductive couple plasma reactive ion etching characteristics of TiO2

thin lms
Adrian Adalberto Garay, Su Min Hwang, Chee Won Chung
Department of Chemistry and Chemical Engineering, Center for Design and Applications of Molecular Catalysts, Inha University, 100 Inharo, Nam-gu, Incheon 402-751, Republic of Korea

a r t i c l e

i n f o

Available online 22 November 2014

Keywords:
Titanium dioxide
Thin lms
Inductively coupled plasma reactive ion etching
HBr/Ar gas
Cl2/Ar gas
C2F6/Ar gas
Hard mask

a b s t r a c t
Changes in the inductively coupled plasma reactive ion etching characteristics of TiO2 thin lms in response to
the addition of HBr, Cl2 and C2F6 to Ar gas were investigated. As the HBr, Cl2 and C2F6 concentration increased,
the etch rate increased; however, the etch prole degree of anisotropy followed a different trend. As HBr
concentration increased, the greatest anisotropic etch prole was obtained at 100% HBr, while the greatest
anisotropic etch prole was obtained at concentrations of 25% when etching was conducted under C2F6 and
Cl2. Field emission scanning electron microscopy revealed that 25% C2F6 generated the greatest vertical etch
prole; hence, etch parameters were varied at this concentration. The effects of rf power, dc-bias voltage and
gas pressure on the etch rate and etch prole were also investigated. The etch rate and degree of anisotropy in
the etch prole increased with increasing rf power and dc-bias voltage and decreasing gas pressure. X-ray
photoelectron spectroscopy analysis of the lms etched under a C2F6/Ar gas mixture revealed the existence of
etch byproducts containing F (i.e. TiFx) over the lm. CxFy compounds were not detected on the lm surface,
probably due to contamination with atmospheric carbon.
2014 Elsevier B.V. All rights reserved.

1. Introduction
The etching of electronic materials is a crucial step in the fabrication
of semiconductor devices because improper conditions can lead to
defects such as faceting, trenching, redeposition, and plasma damage
to the lm. There has been a continuous and rapid implementation of
new techniques and materials that could improve the scalability and
performance of these devices owing to a rapid density growth and
physical limitations of semiconductor storage devices [1].
Conventional inorganic hard masks such as SiO2 and SiC cannot be
employed in the next generation of electronic devices owing to their
low selectivity and severe faceting during etching. Metallic and organic
hard mask materials have been proposed as possible replacements for
previously conventional inorganic hard masks owing to their better
hard mask capabilities [2].
The etching of hard mask materials such as Ta, Ti, TiN and TiO2 under
several etch chemistries has recently been widely investigated [3,4].
TiO2 has received a great deal of attention due to its numerous applications in solar cells, light-emitting diodes, photo catalysts, photosplitting of water and gas sensors [5,6]. In the semiconductor industry,
TiO2 has been proposed as a replacement for SiO2 dielectrics of capacitors owing to its high dielectric constant and low leakage current [7,8],
Corresponding author at: 244E, 2nd building, Inha University, 100 Inharo, Nam-gu,
Incheon, 402-751, Republic of Korea. Tel: +82 32 860 7473; fax: +82 32 872 0959.
E-mail address: cwchung@inha.ac.kr (C.W. Chung).

http://dx.doi.org/10.1016/j.tsf.2014.11.055
0040-6090/ 2014 Elsevier B.V. All rights reserved.

and as a hard mask material owing to its high selectivity and strong
adhesion.
The etch properties of TiO2 thin lms under an inductively coupled
plasma (ICP) were previously investigated under Cl2, HBr, BCl3, CF4
and non-corrosive gases such as CH4/H2/Ar. The results of these studies
indicated that, as the concentration of halogen gas in the gas mixture
increases, the etch rate increases and aggressive etch parameters appear to produce further improvement of the etch rate and etch prole
[912].
The etch rates, etch selectivity, plasma modeling, etch mechanisms
and surface analysis of TiO2 thin lms have previously been discussed
[913], but physical evidence of redeposition-free etch proles with a
high degree of anisotropy is scarce. Development of nanoscale anisotropic etching processes for TiO2 thin lms and their characterization
is necessary for their future applications in semiconductor devices and
as a hard mask material.
In this study, we investigated the inductively coupled plasma reactive ion etching (ICPRIE) of TiO2 thin lms. The etch rate and etch prole
of a variety of gases (Cl2, HBr, C2F6, Ar) were examined, and the effects of
etch parameters including coil rf power, dc-bias voltage, gas pressure
and gas concentration on the etch prole and etch mechanism were investigated. The etch rates were obtained using a surface prolometer
and etch proles were observed by eld emission scanning electron
microscopy (FESEM). Additionally, the surface chemistry of TiO2 lms
under the proper etch gas was analyzed by X-ray photoelectron
spectroscopy (XPS).

A.A. Garay et al. / Thin Solid Films 587 (2015) 2027

200

2. Experimental details

3. Results and discussion

Etching of TiO2 thin lms was carried out under various HBr/Ar, Cl2/
Ar and C2F6/Ar concentrations at an ICP power of 800 W, dc-bias voltage
to substrate of 300 V and gas pressure of 0.67 Pa.
Fig. 1 shows the etch rate of TiO2 thin lms and the etch selectivity of
TiO2 over PR etched under the HBr/Ar gas mixture. The etch rate increased from a minimum of 23.81 nm/min at 100% Ar gas to a maximum
of 64.62 nm/min at 75% HBr gas. At 100% HBr, the etch rate decreased to
63.12 nm/min. The etch rate of PR increased from a minimum of 22.02
nm/min under pure Ar to a maximum of 160.3 nm/min at 25% HBr,
then decreased to 116.2 nm/min at 100% HBr. We consider this decrease
in etch rate of TiO2 thin lms at 100% HBr to be related to plasma instabilities and/or the considerable reduction of ion bombardment onto the
sample due to the absence of Ar gas. The etch selectivity underwent a
rapid decrease from 1.08 nm/min under pure argon to a minimum of
0.197 at 25% HBr, after which it increased to a maximum value of
0.543 at 100% HBr. FESEM micrographs that describe the etch prole
of TiO2 thin lms etched under various HBr concentrations are shown
in Fig. 2. PR patterned TiO2 thin lms before etching are shown in
Fig. 2(a). Fig. 2(b) shows the etch prole of TiO2 thin lms etched in
pure Argon. Heavy sidewall redeposition and a slanted slope could
clearly be seen, probably due to the absence of any chemical reactions
and the dominance of physical sputtering. As HBr concentrations

2
TiO2
PR
TiO2/PR

150

100

Selectivity

Etch Rate (nm/min)

ICPRIE of TiO2 thin lms was conducted using HBr/Ar, Cl2/Ar and
C2F6/Ar gas mixtures. Additionally, 100 nm TiO2 thin lms were prepared on a SiO2/Si substrate by rf magnetron reactive sputtering using
a Ti target in a Ar (35 sccm)/O2 (5 sccm) atmosphere.
Photolithography was carried out on TiO2 thin lms using a 1.2 m
thick photoresist (PR: AZ1512) to pattern the lm. The lms were patterned as parallel lines of different widths. The TiO2 thin lms were
then etched using a conventional ICPRIE system (A-Tech System,
Korea) equipped with a main chamber and a load lock chamber. To dissipate the heat generated during the etching process while avoiding
damage to the sample, a cold uid around 12 C to 15 C was circulated
through the susceptor, while circular void channels between the substrate and the susceptor were lled with He to improve sample cooling.
High density plasma was generated by a coil located at the top of the
main chamber, that was connected to a 13.56 MHz rf power supply. To
control the kinetic energy of the ions generated on the plasma, a selfinduced dc bias voltage was generated by an rf power generator at
13.56 MHz that was capacitively coupled to the susceptor. The vacuum
condition of the main chamber was generated by a turbo molecular
pump backed up by a mechanical pump, making it possible to obtain
base pressures lower than (2.74) 104 Pa.
The HBr/Ar, Cl2/Ar and C2F6/Ar gas mixtures used as etch gases were
fed into the main chamber at a rate of 40 sccm. The etch rates, etch selectivity and etch proles of the TiO2 thin lm and photoresist were examined under varying concentrations of HBr/Ar, Cl2/Ar and C2F6/Ar.
Additionally, the effects of etch parameters such as ICP rf power, dcbias voltage to the substrate, and gas pressure on the etch rate and prole were investigated. Etch by products and the surface chemistry of
TiO2 lms prepared under the proper etch gas were analyzed by XPS.
The etch rates were obtained using a surface prolometer (Tencor P1) and etch proles were observed by FESEM (FESEM-Hitachi 4300SE) at
an operating voltage of 15 kV. Etch byproducts, the surface chemistry
and etch mechanism of TiO2 lms under the proper etch gas were analyzed by using an ex-situ K-alpha source XPS analyzer (ThermoScientic
K-Alpha). All XPS analysis samples were TiO2 thin lms without photoresist. To remove any contamination from the lm surface, all samples
were Argon pre-sputtered for 30 s at beam acceleration energy and
beam current of 1 keV and 2 A, respectively. The binding energies
were calibrated using Au 4f7/2 = 84.00 eV as a reference.

21

50

25

50

75

100

% HBr in HBr/Ar
Fig. 1. Etch rate of TiO2 thin lms and PR, and etch selectivity of TiO2/PR under varying TiO2
concentrations in HBr/Ar mixtures and the following etch conditions: ICP rf power of
800 W, dc bias voltage of 300 V and gas pressure of 0.667 Pa.

increased from 25% to 75% (Fig. 2(c) to (e)), there was a slight improvement in the etch slope and no redeposition could be seen near the sidewall. At 100% HBr (Fig. 2(f)), the etch slope clearly improved relative to
other samples, but the angle was still less than 60. In general, the introduction of 25% HBr was sufcient to obtain a slanted, but redeposition
free etch prole that improved as concentration increased.
Fig. 3 depicts the etch rate of TiO2 thin lms and the etch selectivity
of TiO2 over PR etched under a Cl2/Ar gas mixture. The etch rate slowly
increased from a minimum of 23.81 nm/min at 100% Ar gas to a
maximum of 134.76 nm/min at 100% Cl2. The etch rate of PR underwent
a steeper increase from a minimum of 22.02 nm/min to a maximum of
447.6 nm/min. The etch selectivity showed a maximum value of 1.08 at
100% Ar that gradually decreased to its minimum value of 0.3 at 100%
Cl2.
Fig. 4 depicts the FESEM micrographs of the TiO2 thin lms etched
under various Cl2/Ar concentrations. Fig. 4(a) and (b) shows the
transition of the etch prole from 100% Ar and 25% Cl2/Ar, respectively.
The sample etched in pure Ar showed heavy sidewall redeposition,
while the prole of the sample etched at 25% Cl2 improved considerably.
A further increase in Cl2 concentration led to negative effects on the etch
prole degree of anisotropy (Fig. 4(c) to (d)).
Fig. 5 shows the etch rate and selectivity of the TiO2 thin lms etched
under C2F6/Ar gas mixture at varying concentrations. The etch rate of
TiO2 and PR increased from a minimum of 23.81 nm/min and 22.02
nm/min at 100% Ar to a maximum of 105.6 nm/min and 221.2 nm/min
at 100% C2F6, respectively. The etch selectivity gradually decreased
from a maximum of 1.08 at 100% Ar to a minimum of 0.477 at 100%
C2F6. The etch selectivity of TiO2 thin lms over PR mask showed the tendency of slightly decreasing with increasing C2F6 concentration, while
the etch rate increased. Although an unsaturated uorocarbon protective layer is formed when the lms are etched in a C2F6/Ar plasma, the
etch rate of PR is so fast that the sidewall of TiO2 cannot be properly
protected. It is believed that the etch selectivity of TiO2 lm over PR
mask can somehow inuence the overall etch prole. Fig. 6 shows the
FESEM micrographs of the TiO2 samples etched under a variety of C2F6
concentrations. The TiO2 samples etched in pure Ar showed heavy sidewall redeposition (Fig. 6(a)), while the addition of 25% C2F6 to Ar gas
(Fig. 6(b)) revealed an etch slope with a high degree of anisotropy. As
the C2F6 concentration increased from 50% to 100% (Fig. 6(c) to (e)),
the etch slope became more slanted and the surface roughness increased
considerably. At 100% C2F6, the formation of an area near the sidewall
that differed in height from the rest of the lm was clearly evident.
These ndings suggest the existence of a polymer layer, presumably
containing CxFy compounds, over the surface.
All halogen gas chemistries explored above showed a chemical enhancement of the TiO2 etch rate over pure Ar sputtering, but the etch

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A.A. Garay et al. / Thin Solid Films 587 (2015) 2027

(a)

(b)

300nm

Photoresist

TiO2
SiO2

TiO2

(d)

(c)

(e)

(f)

Fig. 2. FESEM micrographs of TiO2 thin lms before etching (a) and etched in (b) pure argon, (c) 25% HBr, (d) 50% HBr, (e) 75% HBr, and (f) 100% HBr.

rate of TiO2 thin lms in Cl2/Ar was the fastest, followed by C2F6/Ar and
HBr/Ar. The high etch rates in the Cl2/Ar gas mixture may be associated
with the higher total ux of neutral reactive species, as well as the
higher volatility of TiClx etch byproducts compared to TiBrx etch by
products [11]. Both Cl2/Ar and HBr/Ar appear to follow an ion enhanced
etching mechanism commonly known as reactive ion etching [14]. The
500

2
PR
TiO2/PR

400
300

1
200

Selectivity

Etch Rate (nm/min)

TiO2

100
0

25

50

75

100

% Cl2 in Cl2/Ar
Fig. 3. Etch rate of TiO2 thin lms and PR, and etch selectivity of TiO2/PR under varying TiO2
concentrations in Cl2/Ar mixtures and the following etch conditions: ICP rf power of
800 W, dc bias voltage of 300 V and gas pressure of 0.667 Pa.

etch rates of TiO2 thin lms under SF6/Ar gas mixtures have been reported to be much faster than those under Cl2/Ar gas mixtures, which brings
into question the reasons why the etch rates of TiO2 thin lms etched
under a C2F6/Ar gas mixture were considerably lower than those obtained under a Cl2/Ar gas mixture [9]. We believe that etching of TiO2 thin
lms in a C2F6/Ar gas mixture is hindered by the formation of an inhibition layer over the lm, similar to those generated in response to freon
feed gases (e.g., C2F6 and CHF4) that yield unsaturated polymer-forming
species in plasmas [14].
The SEM micrographs of the TiO2 thin lms etched under HBr/Ar,
Cl2/Ar and C2F6/Ar revealed that the best etch prole was obtained at
25% C2F6/Ar. We believe that there is a balance between the formation
of an inhibition layer and its removal by the effect of Ar sputtering at
this concentration, which helps maintain the high degree of anisotropy
in the etch slope. Based on the results obtained upon etching of TiO2 thin
lms in varying gas mixtures and concentrations, 25% C2F6 was selected
as the standard gas concentration for evaluation of the etching parameters due to its degree of anisotropy and plasma stability. The standard
conditions were 25% C2F6 in a C2F6/Ar gas mixture at an ICP rf power
of 800 W, dc-bias voltage to substrate of 300 V and gas pressure of
0.67 Pa.
Fig. 7(a) shows the etch rates of TiO2 thin lms and PR together with
the selectivity of TiO2 thin lms to PR for a variation of ICP power while
the other conditions were xed. As the ICP rf power increased from
700 W to 900 W, the etch rates of TiO2 thin lms and PR increased

A.A. Garay et al. / Thin Solid Films 587 (2015) 2027

23

(b)

(a)

300nm

(c)

(d)

(e)

Fig. 4. FESEM micrographs of TiO2 thin lms etched in (a) pure argon, (b) 25% Cl2, (c) 50% Cl2, (d) 75% Cl2, and (e) 100% Cl2.

and etch selectivity increased slightly. The increase in the etch rate of
TiO2 thin lms as rf power increased can be attributed to an increase
of both neutral species and ions. The increase in rf power causes increases in the densities and uxes of positive ions and F atoms through
an increase in both dissociation and ionization rates, which leads to an

200

1
100

25

50

75

100

Selectivity

Etch Rate (nm/min)

TiO2
PR
TiO2/PR

% C2F6 in C2F6/Ar
Fig. 5. Etch rate of TiO2 thin lms and PR, and etch selectivity of TiO2/PR under varying TiO2
concentrations in C2F6/Ar mixtures and the following etch conditions: ICP rf power of
800 W, dc bias voltage of 300 V and gas pressure of 0.667 Pa.

increase in the etch rate of TiO2 thin lms [12]. FESEM micrographs of
TiO2 thin lms etched at various ICP rf powers are shown in
Fig. 7(b) to (d). The etch prole of the sample etched at 700 W shows
a slanted etch slope with no redeposition near the sidewall (Fig. 7(b)).
Fig. 7(c) depicts the sample etched at 800 W (standard conditions).
The etch prole seemed to be similar to those observed in response to
varying C2F6/Ar concentrations, suggesting good reproducibility. As
the rf power increased to 900 W (Fig. 7(d)), the etch slope appeared
to improve slightly compared to TiO2 thin lms etched at 800 W.
The effects of dc-bias voltage on the etch rates and selectivity of the
TiO2 thin lms and PR are presented in Fig. 8(a). As the DC bias increased from 200 V to 400 V, the etch rate of both TiO2 thin lms and
PR rapidly increased relative to the rf power variation. The etch selectivity of TiO2 thin lms to PR steadily increased from 200 V to 300 V, but a
further increase in the dc bias to 400 V caused a decrease in the etch selectivity. FESEM micrographs revealed that the etch slope became
slanted and the etch depth near the sidewall differed greatly from the
average etch depth at a dc-bias voltage of 200 V (Fig. 8(b)). The etch
slope at a dc-bias voltage of 400 V (Fig. 8(c)) was steeper than that at
200 V. The increase in dc-bias voltage caused an increase in the overall
ion energy, increasing the ion bombardment onto the lm surface.
This caused an expedited increase in the sputtering effect of the lm
that enhanced the bond breaking and desorption of etch products
from the TiO2 surface, resulting in an increased etch rate and improved
etch prole.

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A.A. Garay et al. / Thin Solid Films 587 (2015) 2027

(a)

(b)

300nm

(c)

(d)

(e)

Fig. 6. FESEM micrographs of TiO2 thin lms etched in (a) pure argon, (b) 25% C2F6, (c) 50% C2F6, (d) 75% C2F6, and (e) 100% C2F6.

Fig. 9(a) shows the etch rate and selectivity of TiO2 thin lms etched
at different gas pressures. As pressure increased from 0.133 Pa to
1.33 Pa, the etch rate of the TiO2 thin lms and PR decreased, while
the etch selectivity of TiO2 over PR decreased slightly. The SEM micrograph of the sample etched at 0.133 Pa (Fig. 9(b)) revealed a steep
etch slope with no visible redeposition along the sidewall, while the
etch prole of the sample etched at 1.33 Pa (Fig. 9(c)) exhibited a
slanted etch slope. In general, lowering the pressure leads to a proportional decrease in the concentration of neutral etchant, while the relative rate of energetic ion-enhanced etching increases [15]. At low
pressures (0.133 Pa), ion bombardment onto the sample is enhanced
because high energy and low incident angle ions are abundant due to
the large mean free path. This results in an increased etch rate and degree of anisotropy of the etch prole. Conversely, at high pressures
(1.33 Pa), many ions with relatively low energy and high-incident angles exist. The lack of high energy ions and diminished ion bombardment consequently reduce the etch rate due to inefcient TiO bond
breaking and/or the formation of a greater amount of etch byproducts.
We suspect that the increase in neutral active species (chemical etching) at high pressures results in the formation of a polymer layer over
the lm, which reduces the etch rate and degree of anisotropy of the
etch prole [14,16].

XPS analysis was conducted to elucidate the etch mechanism and

determine whether etch byproducts were present on lms etched
under a C2F6/Ar gas mixture. Bare TiO2 thin lms without photoresist
masks were used for the analysis and all species were pre-sputtered
prior to analysis to remove contaminants from the surface.
Fig. 10(a) shows the narrow scan of Ti 2p3/2 peaks for TiO2 thin lms.
The narrow scan of the as-deposited lm reveals the chemical state of
pure TiO2 (~458.8 eV) and Ti2O3 (~456.9 eV) [17]. However, when the
TiO2 thin lms were etched in 25% C2F6/Ar (low C2F6 concentration)
and 75% C2F6 (high C2F6 concentration), the main Ti 2p3/2 peak shifted
to a higher energy of around 459 eV. The shift of the peak indicates
that compounds containing Ti were formed on the surface of TiO2 thin
lms [12]. Fig. 10(b) presents the narrow scans of the F 1s peaks. The
F 1s peaks of the as-deposited lm were not observed; however, the existence of main peaks of 684.5 eV to 685.1 eV after the sample was
etched in 25% and 75% C2F6/Ar gas mixtures suggests the existence of
TiFx compounds over the lm [18]. Additionally, the presence of secondary peaks located at approximately 683.8 eV suggests the presence
of structures corresponding to oxyuoride (FTiO) functional
groups over the TiO2 surface [19]. In addition to the existence of TiFx
or TiO2 xFx compounds after etching of TiO2 thin lms in a C2F6/Ar
gas mixture, we expected to obtain signals corresponding to CxFy

A.A. Garay et al. / Thin Solid Films 587 (2015) 2027

TiO2

(a)

PR
TiO2/PR

200

Selectivity

Etch Rate (nm/min)

250

25

150
100
50
0

700

800

900

rf power

(b)

(c)

300nm

(d)

Fig. 7. (a) Etch rate of TiO2 thin lms and PR, and etch selectivity of TiO2/PR under varying coil rf power and the following etch conditions: 25% C2F6 in C2F6/Ar gas mixture, dc bias voltage of
300 V and gas pressure of 0.667 Pa. FESEM micrographs of TiO2 thin lms etched at the following coil rf power: (b) 700 W, (c) 800 W, and (d) 900 W.

compounds; however, the Ti 2p3/2 and C 1s narrow scan (gure not

shown) revealed the absence of this etch byproduct. Hazra et al. reported that uorinated carbon residues over the lm were extremely difcult to detect unless in situ XPS measurements were carried out after
etching [20].
The Ti 2p3/2 and F 1s spectra conrmed that F related compounds
were formed over the TiO2 layer after etching under C2F6 plasma chemistries. Even though the etch rate increased as the C2F6 concentration increased, Ti, O and/or F containing compounds formed over the lm,
even at low C2F6 concentrations (Figs. 6(b) and 10). Furthermore, detailed inspection of Fig. 6 FESEM micrographs clearly showed that the
TiO2 surface became irregular and rougher as the C2F6 concentration increased, which was likely due to the formation of a much denser layer of
etch byproducts (TiFx compounds, CxFy polymers, oxyuorides, etc.)
over the lm at high C2F6 concentrations. The Ti 2p3/2 spectrum
(Fig. 10(a)) Ti2O3 peak intensity increased with C2F6 addition compared
to the as deposited lm. The destruction of TiO bonds by ion sputtering
generated highly reactive sites that not only increased the chemical
etching rate of the C2F6 neutral species, but also induced bonding

between the Ti and O elements of the lm to form several types of Ti

oxides.
4. Conclusions
The ICPRIE characteristics of PR patterned TiO2 thin lms were investigated using HBr/Ar, Cl2/Ar and C2F6/Ar gas mixtures. The etch
rates and etch proles of TiO2 thin lms were examined by individually
varying the HBr, Cl2 and C2F6 concentrations. Generally, as the HBr, Cl2
and C2F6 concentration in the Ar gas mixture increased, the etch rates
of TiO2 thin lm and PR increased, except for the HBr/Ar gas mixture.
The etching of TiO2 thin lms using HBr/Ar, Cl2/Ar and C2F6/Ar gas mixtures was found to follow the conventional reactive ion etching mechanism. FESEM images revealed heavy sidewall redeposition on the TiO2
samples etched in pure Ar, but as the HBr concentration increased, the
degree of anisotropy increased while for Cl2 and C2F6 it decreased as
concentration increased. Among the three halogen gases employed,
the most anisotropic etch proles were obtained in a C2F6/Ar gas mixture. At 25% C2F6, the etch slope appeared to be greater than 80, with

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A.A. Garay et al. / Thin Solid Films 587 (2015) 2027

TiO2

200

(a)

PR
TiO2/PR

150

Selectivity

Etch Rate (nm/min)

250

100
50
0

200

300

400

dc bias

(b)

(c)

300nm
Fig. 8. (a) Etch rate of TiO2 thin lms and PR, and etch selectivity of TiO2/PR under varying dc-bias voltage and etch conditions of: 25% C2F6 in C2F6/Ar gas mixture, ICP rf power of 900 W and
gas pressure of 0.667 Pa. FESEM micrographs of TiO2 thin lms etched at the following coil rf power: (b) 200 V and (c) 400 V.

(a)

TiO2

PR
TiO2/PR

200

Selectivity

Etch Rate (nm/min)

250

150
100
50
0

10

Pressure

(b)

(c)

300nm
Fig. 9. (a) Etch rate of TiO2 thin lms and PR, and etch selectivity of TiO2/PR under varying gas pressures and etch conditions of: 25% C2F6 in C2F6/Ar gas mixture, ICP rf power of 900 W and
dc bias voltage of 300 V. FESEM micrographs of TiO2 thin lms etched at varying gas pressures of: (b) 0.133 Pa and (c) 1.33 Pa.

A.A. Garay et al. / Thin Solid Films 587 (2015) 2027

(a)

75% C2F6/Ar
25% C2F6 /Ar

(b)

F 1s

Intensity (arb.unit)

Intensity (arb.unit)

Ti 2p3/2

27

75% C2F6/Ar

25% C2F6 /Ar

As deposited
As deposited

462

460

458

456

454

Binding Energy (eV)

690

688

686

684

682

680

Binding Energy (eV)

Fig. 10. XPS narrow scans of the Ti 2p3/2 (a) and F 1s (b) spectra for TiO2 thin lms etched under the following etch conditions: ICP rf power of 800 W, dc bias voltage of 300 V and process
pressure of 0.667 Pa.

no visible redeposition near the sidewall; however, as the concentration

increased to pure C2F6, the lm surface became irregular and the etch
depth varied greatly with position, with the depth near the sidewall
being deeper than between patterns. These changes may have been
due to the reduction of physical sputtering at this concentration, as
well as the formation of layers of CxFy and etch byproducts over the lm.
The etch parameters were explored using 25% C2F6 as the standard
gas concentration. The etch rate, selectivity and degree of anisotropy
of TiO2 thin lms increased with increasing rf power, dc-bias voltage
and decreasing gas pressure.
XPS analysis of partially etched TiO2 blanket lms conrmed that the
chemical reaction between TiO2 and C2F6 left etch byproducts, mainly
TiFx compounds, on the etched TiO2 surface. The existence of a CxFy polymer layer over the TiO2 thin lm could not be conrmed due to contamination with atmospheric carbon. These ndings suggest that etching
TiO2 thin lms in a 25% C2F6/Ar gas mixture is suitable for obtaining patterns with a high degree of anisotropy, even though post treatment of
the lms might be necessary to reduce or eliminate uorine etch
byproducts from the lm.
Acknowledgments
This research was supported by a grant from the R&D Program for
Industrial Core Technology funded by the Ministry of Trade, Industry
and Energy (MOTIE), Republic of Korea (grant no. 10044723). This
work was supported by an Inha University research grant (grant no.
50047).
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