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skevi
cius
b,
*
, Ramutis Drazdys
b
a
Department of Materials Science and Engineering, The University of Shefeld, Sir Robert Hadeld Building, Mappin Street, Shefeld S1 3JD, UK
b
Optical Coatings Laboratory, Centre for Physical Sciences and Technology, Savanoriu Ave. 231, LT-02300 Vilnius, Lithuania
a r t i c l e i n f o
Article history:
Received 5 February 2014
Received in revised form
23 April 2014
Accepted 25 April 2014
Keywords:
Zirconium oxide
Hafnium oxide
Reactive magnetron sputtering
a b s t r a c t
Target voltage (V
T
) feedback-based closed-loop gas ow control is one of the most cost-effective and
well-known methods to regulate reactive oxide thin lm sputtering processes. However, it can be
difcult to perform due to target voltage non-linearity, changes in signal direction and drifts in the case
of Zr and Hf sputtering in an Ar/O
2
ambient. We show in this paper that the use of the ratio of V
T
over the
O* (oxygen plasma emission, or alternatively oxygen partial pressure) as a feedback signal in a closed-
loop control, enables stable operation anywhere in the transition region (the region between metal and
fully poisoned sputtering target states) as well as extending into the forbidden parts of it. The result of
using V
T
over the O* ratio as the main feedback signal is a stable process exhibiting constant sputter
target state and partial pressure of oxygen as well as high deposition rate (e.g. 6.4
A/s
for HfO
2
at D
TeS
20 cm by pulse-DC sputtering). Such a process is able to deliver ZrO
2
and HfO
2
coatings
that exhibit a low extinction coefcient in the near UV (0.0002 for HfO
2
and 0.001 for ZrO
2
at 350 nm)
and a high refractive index (2.05 for HfO
2
and 2.16 for ZrO
2
at 1000 nm), without any ion/plasma
assistance, at low substrate temperature (20e50
C) and no nitrogen addition.
2014 Elsevier Ltd. All rights reserved.
1. Introduction
Zirconium and hafnium oxide (ZrO
2
and HfO
2
) layers are used
widely in electronic and precision optical component layer stacks.
Many established techniques to deposit these layers exist and are
often adequate in terms of lms electrical and optical properties.
Rapid developments in the high power UV laser industry, however,
exert new pressures on optical components. Optical characteristics
and the Laser Induced Damage Threshold (LIDT) of components has
become the main limitation to the application of UV lasers [1]. ZrO
2
and HfO
2
exhibit a large transparent range from near-UV (above
350 nm) to mid-IR (w8000 nm), a high LIDT as well as good optical
and mechanical properties [2,3] and are therefore considered to be
the most important high index oxides for use in optical components
operating in the UV (e.g. high LIDT mirrors, polarizers, antireective
coatings and even chirped mirrors for group velocity dispersion
compensation in ultra-short laser pulse technology). The furthering
of the application of single compound layers in UV optical
components will involve mixtures, such as ZrO
2
/SiO
2
, HfO
2
/SiO
2
and HfO
2
/Al
2
O
3
[4e6].
Reactive pulse-DC sputtering is a well-established PVD tech-
nology for depositing oxide layers [7e16]. Literature surveys
(below) reveal however that ZrO
2
and HfO
2
are often not produced
in optimal conditions, in terms of process stability, deposition rate
and resultant lm properties.
Active feedback reactive sputtering process control is an
enabling technology that is relatively well-understood and has now
been practiced for decades [17]. High rate high quality reactive
sputter deposition of mixed oxides is even possible when operating
two processes simultaneously (co-sputtering), both in the transi-
tion region.
In 1997 Sproul et al. [11] reported the use of a closed-loop
process control system, based on a mass spectrometer, to deposit
zirconia and hafnia lms.
Other published work (e.g. papers by Venkataraj et al. [18] and
Zhao et al. [19]) reported production of ZrO
2
or HfO
2
lms while
operating the sputter target in or very near the fully poisoned
[20,21] target state, the disadvantages of which are well known.
In 2002, the addition of nitrogen was reported to provide im-
provements in process stability, arcing-avoidance and deposition
* Corresponding author. Tel.: 370 60405132.
E-mail addresses: m.audronis@yahoo.co.uk (M. Audronis),
kestutisjuskevicius18@gmail.com (K. Juskevicius).
Contents lists available at ScienceDirect
Vacuum
j ournal homepage: www. el sevi er. com/ l ocat e/ vacuum
http://dx.doi.org/10.1016/j.vacuum.2014.04.025
0042-207X/ 2014 Elsevier Ltd. All rights reserved.
Vacuum 107 (2014) 159e163
rate when operating in the fully poisoned state without closed-
loop control [22]. This was later conrmed by other groups [13,14].
Pervak et al. in their 2007 paper [12] on mediumfrequency (MF)
reactive HfO
2
sputter deposition said the lm quality was found to
degrade at a high rate. A good lm quality was realized at a rate of
around 0.3 nm/s. This was done using a system with a lambda
sensor for oxygen monitoring. Lambda sensors, however, have
many disadvantages, such as a slow response time, need for con-
stant air reference, need for heating, repeatability issues as well as
ability to work well only close to fully poisoned target state [20].
Target voltage (V
T
) feedback-based closed-loop gas ow control
(often termed Impedance Control) [23] is one of the most cost-
effective and well-known methods to regulate reactive oxide lm
sputtering processes (i.e. sputtering from a metal target). However,
this technique is difcult to performwith Zr and Hf oxide processes
due to target voltage non-linearity, changes in signal direction (i.e.
bidirectional signal changes caused by unidirectional changes in
gas ow rate) and drifts that are a known characteristics of reactive
Zr and Hf sputtering in an Ar/O
2
ambient [24]. Also, the use of V
T
-
based control allows reliable operation only on one of the slopes in
the transition zone and no stable operation is possible at the point
where V
T
peaks.
Optical Emission Spectrometry based process control (often
termed Plasma Emission Monitoring or PEM) [16] and mass
spectrometry-based process control [10] are able to x the partial
pressure of reactive gas or ux of sputtered metal species, but they
are not able to maintain the Hf or Zr sputtering target state con-
stant, which means the process control works only partially.
Also, it is not clear if nitrogen addition is needed when active
feedback process control is used.
The aim of this study was therefore to develop a simple coating
method that enables: i) quick and easy reactive Zr and Hf oxide
sputtering process stabilization anywhere in the transition zone,
ultimately providing stable processes in the most unstable point e
i.e. at max V
T
and ii) precise control of coating deposition processes
in a way that both target state (using Impedance Control) and
partial pressure of oxygen (using PEM) are constant during coating
deposition runs e thus the choice of V
T
and O* as feedback signals.
We demonstrate in this paper that the developed technology based
on the use of V
T
over the O* (oxygen plasma emission at 777 nm)
ratio as a feedback signal for closed-loop reactive gas ow control
(without nitrogen) allows stable and reproducible ZrO
2
and HfO
2
coating processes to be realized. Operation anywhere in the tran-
sition region (the region between metal and fully poisoned
sputtering target states) and extending into the forbidden parts, as
described further in the paper, is possible. Such processes can yield
routinely very high deposition rates (6.4
A/s for
HfO
2
at D
TeS
20 cm) and excellent optical properties in the near
UV.
2. Experimental
Fig. 1 shows schematically the deposition chamber setup. A K.J.
Lesker system equipped with a four-inch diameter circular Torus
sputter cathode was used. This cathode was tted with either Zr or
Hf (purity e 99.95%) target, each 6 mm thick, 101.6 mm diameter
and non-bonded. The target-to-substrate distance (D
TeS
) was
200 2 mm. The system was initially pumped down with a cryo-
genic pump (Cryo-Torr 8F series from Helix Technology Corpora-
tion; 1500 L/s air) to a base pressure below 5 10
7
Torr
(6.7 10
5
Pa). The ambient (Ar/O
2
or Ar/O
2
N
2
) pressure during
sputtering runs was always between 2.4 mTorr and 2.6 mTorr. Prior
to depositing HfO
2
and ZrO
2
lms, the target was pre-sputtered for
3 min in pure Ar