Phys. Status Solidi A 211, No. 2, 357–367 (2014) / DOI 10.1002/pssa.
201330130
Atomic layer deposition of functional
films for Li-ion microbatteries
Ola Nilsen*, Ville Miikkulainen, Knut B. Gandrud, Erik Østreng, Amund Ruud, and Helmer Fjellvåg
Department of Chemistry, Centre for Materials Science and Nanotechnology (SMN), University of Oslo, P.O. Box 1033,
Blindern 0315, Oslo Norway
Received 17 October 2013, revised 22 October 2013, accepted 25 October 2013
Published online 5 December 2013
Keywords atomic layer deposition, lithium ion batteries, microbatteries, thin films
* Corresponding author: e-mail ola.nilsen@kjemi.uio.no
The lithium ion battery concept is a promising energy storage
system, both for larger automotive systems and smaller
mobile devices. The smallest of these, the microbatteries, are
commonly based on the all-solid state concept consisting of
thin layers of electroactive materials separated by a solid state
electrolyte. The fact that solid state electrolytes are required
puts rather severe constraints on the materials in terms of
electronic and ionic conductivity, as well as lack of pinholes
otherwise leading to self-discharge. The atomic layer deposi-
tion (ALD) technology is especially suitable for realization of
1 Introduction Recent developments show a rapid
growing need for versatile energy storage systems, in
particular for electric energy storage in mobile applications,
ranging from microbatteries in miniature sensors and RFID
cards to electric cars and boats. The power requirements for
all these applications vary over many orders of magnitude,
but the common desire is to be able to charge these batteries
as fast as possible. To enable such rapid charging without
significant deterioration of the performance puts severe
constraints on the microstructure of the battery. One solution
is to increase the internal surface area of the electrodes by 3D
structuring to reduce the specific power load per area. This
would be to follow the architecture of the energy sources of
the cells in our bodies, the mitochondria, in how they have
increased the overall activity and mobility of protons through
the cell membranes during oxidative phosphorylation by
increasing their surface area significantly.
Similar types of microstructuring would benefit all-
solid state microbatteries and simultaneously increase their
energy capacity significantly. Even though 2D all-solid state
microbatteries are already offered commercially, they suffer
from an overall limited capacity of ca. 1.25 mAh cm
2
(corresponding to ca. 4.5 C cm
2) [1]. 3D structuring of such
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such microbatteries for the Li-ion technology. ALD has an
inherent nature to deposit conformal and pinhole free layers on
complex geometrical shapes, an architecture most commonly
adopted for microbattery designs. The current paper gives an
overview of ALD-type deposition processes of functional
battery materials, including cathodes, electrolytes, and anodes
with the aim of developing all-solid-state batteries. Deposition
of Li-containing materials by the ALD technique appears
challenging and the status of current efforts is discussed.
ß 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
batteries would easily increase the areal capacity with a
factor of 30, while maintaining a high power density [2].
Several different schemes for structuring microbatteries have
been put forward. A recent overview of this field is given by
Oudenhoven et al. [2] where different structuring concepts as
well as types of suitable materials for realization of 3D
batteries is discussed.
In order to realize 3D structured all-solid state micro-
batteries, structured templates and homogeneous deposition
techniques are required. Electroplating has proven most
suitable as deposition technique for selected cathode
materials [3, 4], but has specific constraints by being a
wet chemical technique. The atomic layer deposition (ALD)
method suits this application area well by its conformal
growth over complex geometrical shapes via the gas phase.
The ALD technique relies on self-limiting reactions between
a volatile precursor and active sites on the surface. The self-
limiting process ensures uniform coverage on the whole
substrates and also on complex three-dimensional features.
The technique is recognized for providing pinhole free films
under suitable conditions [5].
The ALD technique is considered slow since just sub-
monolayers of material are deposited per cycle. This holds
ß 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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when bulk-like structures are to be deposited, for instance
thicker layers of cathode and anode materials. However, for
deposition of thinner layers such as interfaces, barriers, and
especially in this context, electrolytes, the deposition speed
is comparable to the loading and unloading time of the
samples. One of the real strongholds of ALD is its scalability
and the fact that it can do batch processes. In such settings, a
traditional slow growth process is turned into an overall fast
process. This has now been demonstrated for growth of
passivation layers for the photovoltaic industry, where
deposition units matching the process lines of more than
2000 wafers per hour are in use (Beneq TFS NX300 offers
2000 wafers h
1 in batch mode. SoLayTec InPassion ALD
offers up to 2500 wafer h
1 in sequential mode for four
deposition units working together). For construction of more
complex 3D structured batteries, the feature size of the
structures will nevertheless be small and require limited
amount of cathode and anode material before filling the
structure, hence within the realm of the ALD technique. As is
also more frequently demonstrated, by constructing the
batteries of thinner layers, a larger proportion of the material
will remain electrochemically active throughout its use [6–9].
The ALD technique has previously been successfully
applied for coating barrier layers on cathode and anode
materials in order to minimize SEI formation. This has
resulted in superior electrode material with respect to long
term cycling. An overview of such applications is given in
prior reviews such as [10–12], and are not a topic of the
present paper.
This review focuses on the current status in deposition of
active battery materials by ALD suitable to be implemented
into microbatteries, with emphasis on deposition of Li-
containing materials. This ALD field is still quite immature
and new deposition routes and new materials are frequently
reported. Below we provide an overview of the present status
in deposition of Li-containing materials by ALD, before
going into details on the cathode, electrolyte, and anode
materials deposited by ALD until now.
2 Li-materials by ALD The ALD deposition process-
es used for Li-containing materials known so far are given in
Table 1, together with some characteristics, and an overview
of the Li-precursors are given in Fig. 1. While some Li-
precursors work fine for deposition of certain materials, they
are not necessarily transferable to other material combina-
tions. Until now, a total of 11 different types of precursors
have been evaluated, and of these, three are in more
widespread use (Li(thd), Li(OtBu), and LiHMDS), see
Table 1. This range of precursors was first introduced in the
papers [13] and [14], and will undoubtedly be followed by
more precursor types in the future. The range of possibilities
in commercially available Li-precursors is large because
they are frequently used as starting reactants in most organic
and metalorganic syntheses.
2.1 Li(thd) The first growth of a Li-containing
material by ALD was reported in 2009 [13] where Li(thd)
ß 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
O. Nilsen et al.: Atomic layer deposition of functional films
was combined with O3 to form Li2CO3. Li(thd) is a stable
powder material which is easy to handle in air, but requires
some temperature to obtain a suitable vapor pressure. ALD
growth has been reported using sublimation in the range
175–200 8C. Its reactivity is low and ozone is typically
required as an oxygen source. However, this frequently
results in incorporation of carbonates in the film, as shown
in [13] where the [Li(thd) þ O3] process is combined
with the [La(thd)3 þ O3] process to form Li–La–O materials.
For this precursor combination, it was possible to control
the Li-content over the whole Li/La range. Retrospectively,
the deposition of carbonate was perhaps a lucky key
aspect for proving that Li-containing materials could be
deposited successfully by ALD with self-limiting growth. As
will be discussed later, attempts to deposit Li2O or LiOH
frequently result in uneven growth and troublesome ex situ
characterization procedures – quite regardless of the type of
Li-precursor.
Formation of carbonates during deposition is likely
connected to the basicity of the deposited material in its
ability to absorb CO2. The [Li(thd) þ O3] process has
recently been combined with the [Mn(thd)3 þ O3] process in
successful deposition of a highly electroactive spinel phase
where the overall amount of carbonate was negligible [15],
see Fig. 2. In the same work it is shown that sequential
cycles of [Li(thd) þ O3] on previously deposited MnO2 or
V2O5 films resulted in post lithiation of the films rather than
an additional layer of Li2CO3. In this manner lithiated
cathode materials in the form of LixMn2O4 and LixV2O5
were obtained. The fact that such postlithiation processes are
possible indicates that the mobility of Li during deposition
is rather high, and that the traditional ALD view with self-
saturating surface reactions is challenged.
LiFePO4 is reported to form by combining the processes
[Li(thd) þ O3], [Fe(thd)3 þ O3], and [Me3PO4 þ (H2O þ
O3)] [16]. The films are amorphous as deposited, but
crystallized to the LiFePO4 phase upon annealing in 10% H2
in Ar at 500 8C. The electrochemical activity was not
reported.
Lithium fluoride can be formed by combining Li(thd)
with TiF4 in a sequential manner, producing films of
crystalline LiF at a growth rate of 1.5–1.0 Å/cycle in the
temperature range 250–350 8C [17]. The same authors
showed that introduction of Mg(thd)2 into the deposition
sequence aids the formation of LiF without introducing Mg-
impurities in the films [18]. Deposition of LiF is most
relevant for optical materials, however, LiF is furthermore an
important constituent in Li-ion conducting materials such as
Li3AlF6 and Li2NiF4 that show room temperature conduc-
tivities of the order 10
6 S cm
1 [32].
2.2 Li(OtBu) Li(OtBu) was also tested as Li-precursor
together with H2O in 2009 [13] resulting in films which
clearly changed appearance when exposed to air. Highly
hygroscopic and CO2 absorbing films of Li2O/LiOH was
likely formed. Li(OtBu) is an air sensitive solid which is
reported to sublime in one step at ca. 110 8C as measured by
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Phys. Status Solidi A 211, No. 2 (2014) 359

Table 1 Overview of the current Li-based ALD processes reported in the literature together with some of its characteristics such as
deposition temperature, growth rate, and film uniformity.
precursor combination result references

Li(thd) TG analysis, sublimes without significant residue [13, 14]

[Li(thd) þ O3] Li2CO3 (185–300 8C), ca. 0.30 Å/cycle [13]
[Li(thd) þ O3] þ [La(thd)3 þ O3] Li–La–O with carbonate formation (225 8C), good [13]
controllable Li-content
[Li(thd) þ O3] þ [Mn(thd)3 þ O3] LiMn2O4 (225 8C), ca. 0.5 Å/cycle, uniform films [15]
[Li(thd)] þ [Mn(thd)3 þ O3] LiMn2O4 (225 8C), non-uniform films [15]
[Li(thd) þ O3] þ [Fe(thd)3 þ O3] þ [Me3PO4 þ (H2O þ O3)] LiFePO4 (250 8C), amorphous as-deposited, crystallized in [16]
10% H2 at 500 8C
[Li(thd) þ TiF4] LiF (250–350 8C), 1.5–1.0 Å/cycle [17]
[Li(thd) þ TiF4] þ [Mg(thd)2 þ TiF4] LiF (300–350 8C), 1.4 Å/cycle [18]
Li(OtBu) TG analysis, sublimes without residue [14]
[Li(OtBu) þ H2O] air sensitive film [13]
[Li(OtBu) þ H2O] LiOH (225 8C) QCM analysis [19]
[Li(OtBu) þ H2O þ CO2] Li2CO3 (225 8C) QCM analysis [19]
[Li(OtBu) þ Me3PO4] Li3PO4 (225–275 8C) ca. 0.7 Å/cycle [14]
[LiOtBu þ H2O] þ [TMA þ O3] LiAlO2 (225 8C), uniform films, 2.8 Å/cycle, QCM analysis [20]
[LiOtBu þ H2O] þ [TMA þ H2O] LiAlO2 (225 8C), QCM analysis [20]
[Li(OtBu) þ H2O] þ [TMA þ H2O] QCM þ FTIR analysis (225 8C) [21]
[Li(OtBu) þ H2O] þ [Ti(OiPr)4 þ H2O] Li4Ti5O12 on N-CNT (250 8C) ca. 0.61 Å/cycle [22]
[Li(OtBu) þ H2O] þ [Ti(OiPr)4 þ H2O] Li4Ti5O12, (225 8C), 0.55 Å/cycle, good controllable [23]
Li-content, crystalline as-deposited and air stable films
[Li(OtBu) þ H2O] þ [TiCl4 þ H2O] LixTiyOz (225 8C), 1.5 Å/cycle, low concentration of Li [23]
and air sensitive films
[Li(OtBu) þ H2O] þ [TiCl4 þ H2O] þ [La(thd)3 þ O3] Li0.32La0.30TiOz (225 8C), 0.45 Å/cycle, uniform films. [24]
non-linear variation of Li-content with Li-pulsing
[Li(OtBu) þ H2O] þ [La(thd)3 þ O3] þ [TiCl4 þ H2O] LixLayTiOz (225 8C), non-uniform films [24]
[Li(OtBu) þ O2-plasma] þ [CoCp2 þ O2-plasma] LiCoO2 (325 8C), 0.6 Å/cycle and uniform films [25, 26]
[Li(OtBu) þ H2O] þ [Mn(thd)3 þ O3] LiMn2O4 (250 8C), uniform films [15]
[Li(OtBu) þ H2O] þ [Mn(EtCp)2 þ H2O] etching or poisoning of MnO growth (250 8C) [15]
[Li(OtBu) þ H2O] þ [TMA þ H2O] þ [TEOS þ H2O] LiAlSiO4 (290 8C), amorphous as-deposited [27]
LiHMDS TG analysis, sublimes without residue [14]
[LiHMDS þ H2O] Li2O/LiOH (186 8C) non-uniform film, uncontrollable [28]
growth
[LiHMDS þ H2O þ CO2] Li2CO3, (89–380 8C) ca. 35 Å/cycle, uniform Si-free films [28]
[LiHMDS þ NH3] Li3N, (167 8C) 0.95 Å/cycle [28]
[LiHMDS þ O3] Li2SiO3 (200–300 8C) QCM þ MS analysis [29]
[LiHMDS þ O3] Li2SiO3 (150–400 8C) 0.3–1.7 Å/cycle [30]
[LiHMDS þ Me3PO4] Li3PO4, (275–350 8C) 0.4–1.3 Å/cycle [14]
[LiHMDS þ H2O] þ [Nb(OEt)5 þ H2O] LiNbO3, (235 8C) 0.5 Å/cycle. Si-free films. good [31]
controllable Li-content
[LiHMDS þ H2O] þ [Mn(thd)3 þ O3] LiMn2O4 (200 8C) non-uniform and XRD amorphous films [15]
[LiHMDS þ H2O] þ [Mn(EtCp)2 þ H2O] etching or poisoning of MnO growth (200 8C) [15]
[Li(Cp) þ H2O] non-reproducible film at depositions above 300 8C. [13]
sublimed at 185 8C
[n-BuLi þ H2O] uncontrolled growth (160 8C). Sublimed at 113 8C [13]
[Li(dicyclohexylamide) þ H2O] partial decomposition at sublimation at 250 8C [13]
Li(hfac) TG analysis, sublimes without residue at ca. 250 8C [14]
Li(acac) TG analysis, substantial residue [14]
Li(Piv)(H2O) TG analysis, two step sublimation without residue [14]
at 100 þ 400 8C
Li(CH3SiMe3) TG analysis, substantial residue [14]
Li(tBu2Cp) TG analysis, substantial residue [14]

thermogravimetric analysis (TG) [14] and is reported used in Deposition of LiOH is shown to proceed according to the
ALD processes by sublimation in the range 130–170 8C. ALD principles for relatively thin films, while the growth
Formation of LiOH has been proved by in situ becomes more dependent on absorption of water into the
techniques when Li(OtBu) is combined with water [19]. bulk for thicker films. The bulk behaves probably as a

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Figure 2 Discharge capacities and first cycle potentiograms

(insets) for a 86-nm MnO2 treated with 200 cycles of LiOtBu þ
H2O, 1000 charge–discharge cycles with 200 mA. Based on data
in Ref. [15].

trimethylaluminium) to form LiAlO2 in an ALD manner

with a surprisingly high growth rate of 2.8 Å/cycle [20]. This
process has also been studied in situ by QCM [20, 21] and
FTIR [21], which show that there is an enhanced mass
increase between TMA and the prior deposition cycles
of [Li(OtBu) þ H2O]. The mass increase during the next
TMA exposure depends on the number of preceding
[Li(OtBu) þ H2O] cycles, while the overall growth is not
affected by the number of [TMA þ H2O] cycles, see Fig. 3.

Figure 1 An overview of the Li-precursors reported for ALD of

Li-containing materials.

reservoir for water which takes part in the preceding

reactions and hampers the surface limited mechanism. By
adding pulses of CO2 to the [Li(OtBu) þ H2O] process,
the more stable Li2CO3 is formed, and the films become
uniform [19].
Li(OtBu) can also react directly with trimethylphosphate
(TMPO) in an ALD manner to form crystalline Li3PO4 with
a growth rate of ca. 0.7 Å/cycle [14]. Despite the fact that
crystalline Li3PO4 has a bit too high electronic conductivity,
this work is clearly a contribution towards deposition of Figure 3 Frequency change during one LiOtBu þ H2O subcycle
the highly desired electrolyte material, lithium phosphorus (*) as a function of the number of preceding TMA þ H2O
oxynitride (LiPON), which also show good electrochemical subcycles, and frequency change during one TMA þ H2O subcycle
stability towards metallic Li. (&) as a function of the number of preceding LiOtBu þ H2O
The [Li(OtBu) þ H2O] process has been combined with subcycles at 225 8C. Reprinted with permission from Ref. [20].
the [TMA þ O3] and [TMA þ H2O] processes (TMA ¼ Copyright 2011, American Chemical Society.

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This behavior makes it difficult to control the Li content

of the Li–Al–O material for higher contents of Li where
possibly water is absorbed and released by the bulk material
during cycling, forming a reservoir effect which increases
the growth rate significantly, see Fig. 4.
The ionic conductivity of the LiAlO2 material was
characterized by impedance spectroscopy to be in the
range 1  10
7 S cm
1 at 90 8C [20]. Its ionic conductivity
is perhaps too low for an ideal electrolyte material, but it
is stable towards current anode materials, and has been
suggested as barrier layer between anodes and alternative
electrolytes [33] and also as protection layer on cathode
materials to prolong their stability under cycling [21].
The [Li(OtBu) þ H2O] process can also be combined
with titanium as [Ti(OiPr)4 þ H2O] [19, 20] (Ti(OiPr)4 ¼
titanium tetra-isopropoxide) or [TiCl4 þ H2O] [23] for
formation of the electroactive material Li4Ti5O12. Although
the work in [22] and [23] describe the same precursor Figure 5 Film growth per cycle and the Li:Ti TOF-ERDA
combinations, they use different pulsing sequences, and elemental ratio of LixTiyOz films versus the Li:Ti pulsing ratio
hence require different pulse stoichiometries, to obtain deposited using Ti(OiPr)4 as the titanium source. The line
the desired material. When [Ti(OiPr)4 þ H2O] was used, corresponds to the linear fit of the Li:Ti ratio in the film versus
the composition of Li could be controlled well over a large the Li:Ti pulsing ratio. Reproduced by permission of The Royal
Society of Chemistry [23].
range [23], and as-deposited crystalline films which were
seemingly air stable were obtained, see Fig. 5. By application
of [TiCl4 þ H2O] it was only possible to obtain films with
rather low concentration of Li, and despite this, the films according to Eq. (1) is only 0.3%. The material is therefore
were rather air sensitive [23]. highly suitable for realization of durable structures in all-
Li4Ti5O12 can be used as both cathode and anode solid state Li-ion batteries. The electrochemical properties of
material depending on the electrochemical potential of its the material developed in Ref. [23] has previously been
counterpart. The electrochemical potential of Li4Ti5O12 presented in [34] and show good cyclability but an overall
towards Li/Liþ is ca. 1.55 V, hence the titanate will not capacity of only 35 mAh g
1 as compared to its theoretical
enter into high voltage batteries. The clear benefit of capacity of 175 mAh g
1, see Fig. 6. A possible origin for
Li4Ti5O12 is that the volumetric change upon cycling this may be formation of carbonates or alternative phases
which removes part of the lithium from electrochemical
cycling.

L4 Ti5 O12 þ 3Liþ þ 3e
! L7 Ti5 O12 : ð1Þ

Li(OtBu) has also been combined with both [TiCl4 þ

H2O] and [La(thd)3 þ O3] to form the perovskite based
electrolyte Li0.32La0.30TiOz (LLT) [24]. This collection of

Figure 4 Li–Al–O growth rate measured by ellipsometry as a

function of % LiOH ALD cycles. Gray shaded area designates the
region of stable growth with constant, linear growth as function of
ALD cycles. Reprinted with permission from Ref. [21]. Copyright Figure 6 Discharge capacity versus cycle number for L4Ti5O12,
2013, American Chemical Society. as presented in Ref. [34].

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precursors was also tested in two different combination
schemes: Ti – La – Li, or Ti – Li – La. When Li was
introduced after the Ti-precursor, the films were rough and
air sensitive. By rather introducing Li after the La-precursor,
uniform films were obtained with a significant amount of Li.
The resulting pulsing scheme for variations of the Li-content
became 1  [TiCl4 þ H2O] þ 3  [La(thd)3 þ O 3] þ n 
[Li(OtBu) þ H2O], which showed that it was only possible
to control the Li-content up to a level of 20 at%, see Fig. 7.
Lithium lanthanum titanates [(Li,La)xTiyOz, LLT] are
considered as very promising solid-state lithium ion
conductors and are foreseen to replace LIPON in all-solid
state lithium ion thin film batteries since they may have much
higher Li-ion conductivity [35]. However, the electrolyte
has limited electrochemical stability towards reduction
and would require a barrier layer of e.g., LiAlO2 towards
common anodes in Li-ion batteries.
The Li(OtBu) precursor has also been used in plasma
processes in combination with CoCp2 for formation of the
cathode material LiCoO2 [25, 26]. The films have been
deposited using O2 plasma for both precursors with a growth
rate of 0.6 Å/cycle at a deposition temperature of 325 8C,
showing well saturative behavior of the pulses. A subsequent
post annealing at 700 8C resulted in the electrochemically
active LiCoO2 material showing good electrochemical
cycling although a maximum of 60% of the deposited
material was electrochemically active, Fig. 8. The origin of
the reduced activity may be similar to those mentioned for
deposition of Li4Ti5O12 above.
In the same manner as was shown for deposition of
LixMn2O4 using Li(thd), it is possible to use the [Li(OtBu) þ
H2O] process in combination with [Mn(thd)3 þ O3] to obtain
the phase pure spinel [15]. The [Li(OtBu) þ H2O] process
has also been tested in combination with the [Mn(EtCp)2 þ
H2O] process to obtain a Li–Mn–O material, but this rather
Figure 7 Lithium content of the films, as measured by TOF-
ERDA, as a function of number of subsequent lithium subcycles
n in the pulsing scheme of 400  (1  TiO2 þ 3  La2O3 þ n 
Li2O). Reproduced with permission of The Royal Society of
Chemistry [24].
ß 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
O. Nilsen et al.: Atomic layer deposition of functional films
Figure 8 Constant current (CC) (dis)charge cycling between
3.0 and 4.1 V (0.35 C-rate) for an ALD-deposited LiCoO2 (x ¼ 4)
film on Si/TiO2/Pt, using LiClO4 in ethylene carbonate/diethyl
carbonate (EC/DEC 1/1) as liquid electrolyte. The electrochemical
storage capacity upon cycling showing data for x ¼ 2 and x ¼ 4,
where x notes the Co/Li pulsing ratio. Reproduced from Ref. [25]
with permission from The Electrochemical Society.
resulted in lack of incorporation of Li and an actual loss of
Mn from the deposited film [15]. Whether this was due to
chemical etching of the MnO or by surface deactivation
remains to be investigated.
It is also reported that the processes [Li(OtBu) þ H2O],
[TMA þ H2O], and [TEOS þ H2O] (TEOS ¼ tetraethyl
orthosilane) have been combined to form lithium aluminum
silicate [27]. The material was amorphous as deposited at
290 8C but crystallized into LiAlSiO4 upon annealing at
900 8C.
2.3 LiHMDS LiHMDS was first introduced in 2012
by formation of Li2SiO3 [30] and also Li3PO4 [14], and has
in a very short time become a frequently used precursor
for formation of Li-containing materials. The LiHMDS
precursor is a relatively stable powder which may be handled
in air for moderate times prior to deposition. The precursor
is relatively volatile and is reported used by subliming at
temperatures from 60 to 75 8C.
LiHMDS will react with water to form LiOH with the
result of uncontrolled growth with rather large thickness
gradients [28]. This appearance is most probably due to
the mentioned reservoir effect of LiOH which result in
uncontrolled content of H2O for thicker films of LiOH.
The growth can be completely controlled by adding a
CO2 pulse to form the pulsing scheme [LiHMDS þ H2O þ
CO2]. This result in formation of Li2CO3 with a growth rate
of ca. 0.35 Å/cycle and has been demonstrated for the
deposition range 89–380 8C [28]. Even though the LiHMDS
precursor contains silicon, the deposited films are almost
free from silicon, indicating a simple reaction mechanism
probably of ligand exchange type.
LiHMDS will also react directly with NH3 to form the
nitride Li3N, which is a rather air sensitive compound and
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Phys. Status Solidi A 211, No. 2 (2014)
requires capping in order to be analyzed [28]. The nitride
was deposited uniformly at 167 8C with a growth rate of
0.95 Å/cycle and required rather shorter pulse times of
LiHMDS for saturation than what was required for formation
of Li2CO3. This indicates that LiHMDS reacts slower with a
carbonate surface than a NHx-terminated surface.
Lithium nitride is a rather good ionic conductor [36],
however, with a too low break down voltage for practical
use in batteries in its pure state [37]. The motivation for
formation of such a nitride may therefore be regarded as one
step towards development of more suitable materials for
Li-ion batteries.
The LiHMDS precursor may be used as a single source
precursor for deposition of lithium silicates such as Li2SiO3
by reacting with ozone in a sequential manner [29, 30].
The ozone will also oxidize the ligands resulting in a
film containing both lithium and silicon. The growth rate
is strongly temperature dependent and varies from 0.3 to
1.7 Å/cycle in the deposition range between 150 and 400 8C
although proving good uniformity and control over the
thickness. The stoichiometry of the deposited film changed
somewhat with temperature providing a decreasing Li
content with increasing deposition temperature. The growth
has been investigated by in situ techniques such as QCM
and MS at different temperatures [29]. The investigation
indicates a somewhat complex reaction path which does
not involve direct ligand exchange between hydroxyl
and LiHMDS. The reaction mechanism is most probably
a successive reaction with hydroxyl groups on the surface
and sequential decomposition of the ligands. The reaction
mechanism is proven to be temperature sensitive which
affects the Li:Si stoichiometry, see Fig. 9.
The lithium silicates are potential electrolyte materials
although the reported conductivities of Li2SiO3 and Li4SiO4
are in the range of 10
8 to 10
7 S cm
1 [38]. There is hope to
increase this conductivity to practical values by alloying with
other elements.
Figure 9 Possible reaction pathways for the adsorption of
LiHMDS on a hydroxylated surface. Reprinted with permission
from Ref. [29]. Copyright 2013, American Chemical Society.
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In the same manner as reported above for Li(OtBu),
LiHMDS may also be reacted directly with TMPO in
an ALD manner to form crystalline Li3PO4 [14]. The
growth rate increases from about 0.4 Å/cycle up to around
1.3 Å/cycle for depositions in the range 275–350 8C.
The [LiHMDS þ H2O] process has also been combined
with the [Nb(OEt)5 þ H2O] process with formation of the
ferroelectric LiNbO3 [31]. The deposition was performed at
235 8C and with no significant amount of Si in the films. It
proved possible to control the Li content over large ranges
by varying the pulsing ratio of the precursors. The films
were uniform and proved self-limiting process apart from
the Li-rich compositions which resulted in large gradients.
During deposition of LiNbO3 it proved necessary to
passivate the reaction chamber with a layer of pure
Nb2O5 between each run in order to obtain suitable high
quality samples.
Despite the fact that LiNbO3 is most popularly known as
a ferroelectric material, it may also act as a Li-ion conductor
with conductivities in the range of 10
9 to 10
5 S cm
1
depending on crystallinity with the largest values for the
amorphous material [39–41]. Such properties were not the
focus of the work in Ref. [31].
The [LiHMDS þ H2O] process has also been attempted
combined with the [Mn(thd)3 þ O3] and the [Mn(EtCp)2 þ
H2O] processes with aim to form the lithium manganese
spinel [15]. However, for the [LiHMDS þ H2O] þ
[Mn(thd)3 þ O3] combination, non-uniform and XRD
amorphous films were obtained. For the [LiHMDS þ
H2O] þ [Mn(EtCp)2 þ H2O] combination, a similar appear-
ance as mentioned above for the combination with Li(OtBu)
was observed, i.e., lack of incorporation of Li and an actual
loss of Mn from the deposited film [15].
2.4 Alternative Li-precursors There are relatively
limited reports for application of the remaining Li-precursors
mentioned in Table 1. The [Li(Cp) þ H2O] process is reported
to provide films, although not well reproducible [13]. The
[n-BuLi þ H2O] process show clear non self-limiting growth
even at 160 8C [13], and Li(dicyclohexylamide) is reported
to decompose during sublimation [13]. Li(hfac) is reported
to sublime completely in one step by TG analysis [14], while
Li(acac), Li(Piv)(H2O), Li(CH3SiMe3), and Li(tBu2Cp)
either show substantial solid residue or stepwise sublimation
as measured by TG [14].
3 Deposition of non-lithiated battery materials
The ALD technique is one out of many methods for
production of electroactive materials in the form of thin
films. As mentioned in the introduction, one of its strengths
is its capability to form conformal coating on geometrically
challenging objects, such as porous materials. While
deposition of Li-containing materials by ALD may have
been driven by a motivation in development of new
deposition processes, deposition of non-lithiated materials
may have been more driven by synthesis of model materials
for fundamental understanding of the processes during
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electrochemical cycling, and for closing the gap towards
supercapacitors by deposition on high surface area supports.
For both these applications, it is important to be able to
control the film thickness with high precision, and to affect
the deposited crystallinity and texture. These are all well
within the possibilities of the ALD technique.
Deposition of non-lithiated battery materials have
therefore been mostly focused on traditionally known
ALD processes until lately. Titanium oxides and vanadium
oxides are the most frequently encountered anode and
cathode materials deposited by ALD. Both are relatively
easily deposited in a conformal manner and offer the
possibility to be deposited in many crystalline modifications.
3.1 Vanadium oxides by ALD The first report on
application of ALD for deposition of Li-ion cathode material
was in 2003 where V2O5 was used as model material for
investigation of the lithium intercalation mechanism [42].
The vanadium oxide was produced using the
[VO(OiPr)3 þ H2O] (VO(OiPr)3 ¼ vanadyl triisopropoxide)
process at a deposition temperature of 105 8C. This resulted
in as-deposited amorphous films, which crystallized to
V2O5 after annealing in air at 400 8C. The uniform and
homogeneous films were very well suited for determination
of diffusion coefficients of Li as function of Li content
and type of phase of V2O5. This work proves that the
concentration dependence of the diffusion coefficient
should be taken into account when interpreting the
intercalation process [42]. The electrochemical properties
of similar amorphous V2O5 films have been investigated
as model material in Ref. [6] proving superior properties
as compared to crystalline films. The amorphous material
was capable of reversible intercalation of Li up to a Li
content of Li2.9V2O5 without showing the limitations of
non-reversible phase transitions of v- and g-V2O5, resulting
in a capacity of 455 mAh g
1 for a 200 nm film cycled
between 4 and 1.5 V. The specific capacity decreased for
thicker films.
There are several reasons why V2O5 is a good model
material for investigation of electrochemical processes.
It offers a high specific capacity of up to 441 mAh g
1
if three Li are intercalated into a V2O5 unit. During such
high level of intercalation it experiences several phase
changes (a, e, d, v, g) which also affects the Li-diffusivity.
Some of these phase transitions are also not completely
reversible (v, g). Unfortunately the electronic conductivity
of bulk V2O5 is rather low and requires combination with
a support or additive with higher electronic conductivity.
This also implies that the electrochemical properties of
V2O5 should be thickness dependent where the specific
capacity will be reduced for thicker layers [6–8].V2O5
may therefore be more suitable as a cathode material for
high power applications as coated on nanostructured
templates functioning as current collectors. Some of the
reported nanostructured supports are: Multiwalled carbon
nanotubes [43], nickel plated Tobacco mosaic virus [44],
anodic aluminum oxide [45].
ß 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
O. Nilsen et al.: Atomic layer deposition of functional films
Figure 10 High discharge rate cycling stability test performed at
120 C for a 10 nm film of V2O5. The gray band indicates 80%
capacity loss relative to the initial capacity (55 mAh g
1 at 120 C).
The capacity is stable up to 650 cycles and drops below 80% of the
initial capacity only after 1530 cycles. Based on data in Ref. [8].
The surface area of the vanadium oxide may also be
increased without the aid of a template by depositing it in
a crystalline state and exploiting the roughness which
develops during deposition. The electrochemical properties
of films deposited by the processes [VO(OiPr)3 þ H2O] and
[VO(OiPr)3 þO3] has been compared in Ref. [7] where
the processes results in amorphous and smooth, and
crystalline and rough textures, respectively. The crystalline
films prove better than the amorphous counterpart in terms of
capacity for 1Li/V2O5 and 2Li/V2O5, though their capacities
are comparable for 3Li/V2O5.
Even more recently, films of V2O5 with a particularly
developed rough texture has been deposited using the
[VO(thd)2 þ O3] process at 235 8C [8]. The films show an
electrochemical capacity of up to 105 mAh g
1, depending
on the film thickness for cycling in the range 2.75–3.80 V at
1 C. The current cycling range corresponds to insertion of
1 Li per V2O5 and a theoretical capacity of 147 mAh g
1.
The capacity at high rate discharge is surprisingly good
for this material. For cycling at 120 C a capacity of ca.
55 mAh g
1 is maintained for 650 cycles, and the cell last
for 1530 cycles before dropping below 80% of its initial
capacity, see Fig. 10.
3.2 Titanium oxides by ALD Titanium oxide has
become a popular anode material for Li-ion batteries and
exists in several different phases such as anatase, rutile,
brookite, hollandite, ramsdellite, amorphous, and possible
more. Of these phases, anatase is the most electroactive
material capable of inserting 0.5 Li per TiO2 formula unit
with a potential towards Li/Liþ of 1.55 V [46]. The
drawback of its higher potential, as compared to anodes,
should be balanced by the lack of SEI formation for TiO2
and its improved safety [47].
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Phys. Status Solidi A 211, No. 2 (2014)
Anatase type TiO2 is commonly produced by ALD using
a range of different precursors [48]. The major focus on
application of ALD-type TiO2 in Li-ion batteries has been in
formation of high surface area nanostructures to enable rapid
cycling.
The areal capacity of TiO2 has been increased by a factor
of 10 by coating a structure of nanorods of aluminum [49].
An interpenetrating TiO2 structure has also been formed
using a 3D-porous anodic alumina structure [50]. TiO2 has
also been deposited as anode material on Ni-plated Tobacco
mosaic virus (TMV) [51], showing increased areal capacity
and greatly improved cyclability. Hollow nanoribbons of
TiO2 has been produced using a sacrificial template of
peptide assembly [52]. The width of the templates is in the
range 100–200 nm, with a wall thickness of ca. 15 nm TiO2.
The hollow structure is particularly beneficial since it
enables storage of electrolyte within the hollow structure as
well.
The size dependent properties of TiO2 have been studied
by varying the thickness of TiO2 layers coated inside anodic
alumina templates [53]. The best overall properties were
found for 5 nm thick films which gave a capacity of
330 mAh g
1, proving excellent performance.
TiO2 has also been suggested used in supercapacitors by
coating on graphene [54], or carbon nanowires [55].
3.3 Additional materials As mentioned previously,
LiFePO4 has been reported deposited by ALD [16]. Its
unlithiated compound, amorphous FePO4, has also been
deposited by ALD and proven to have excellent electro-
chemical capacity with capacity reaching its theoretical
limit of 178 mAh g
1 for 1 C charge–discharge rates and
cycling properties proving stable capacity over at least 600
cycles [9].
Traditional electrode materials are chosen to give as little
structural change as possible upon lithium cycling in order to
provide good reversibility while maintaining its capacity.
This has been the common approach for identifying good
intercalation materials such as the cathode material LiCoO2.
However, another approach would be to extend capacity
by exploiting the complete redox range of the metal from
its oxide to the metallic state. Such an approach involves
complete conversion of the electrode material, and is
thus called conversion electrodes. The volumetric change
involved in such transitions is substantial and deteriorates
the materials cyclability severely. One approach to circum-
vent such capacity fade with cycling would be to constrict
the amount of conversion electrode to thin films capable
of tolerating the stress involved. Cobalt oxide (Co3O4)
deposited by ALD has been suggested used as conversion
anode in Li-ion batteries [56] with a potential capacity of
8 Li per Co3O4 according to the reaction in Eq. (2).
Co3 O4 þ 8Li ¼ 3Co þ 4Li2 O; E  ¼ 1:87 V: ð2Þ
The films were deposited using [CoCp2 þ O2 plasma],
and 40 nm films of Co3O4 was capable of delivering a
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Figure 11 Capacity of a Co3O4 electrode versus cycle number.
The electrode was cycled between 20 mV and 3 V at 10 mA (0.22 C)
with a half hour resting period in between the cycles, using LiPF6
in ethylene carbonate/diethyl carbonate (EC/DEC, 1/1) as liquid
electrolyte. Reproduced from Ref. [56], with permission from
Elsevier Science.
capacity of 1000 mAh g
1 for at least 70 cycles, Fig. 11,
proving the potential of ALD to stabilize conversion
materials towards mechanical degradation.
4 Outlook The number of examples for deposition of
Li-containing materials will undoubtedly increase in the near
future. One of the lessons which may be learned from the
selection presented here is that many of the Li-containing
materials, especially such as LiOH, may function as a
reservoir for water during the deposition by dehydrating and
hydrating during Li and water pulses, respectively. This
behavior will result in almost uncontrolled levels of water
released for reaction during the following metal pulses and
hence result in non-feasible ALD growth. Such processes
may be converted to the more stable Li2CO3 during
deposition by adding an additional CO2 pulse and provide
uniform films which are easily characterized ex situ. In
this manner, we would assume that several of the presented
negative results may be revisited to show more suitable
growth systems.
By comparing the processes where TiCl4 is used, it
becomes evident that the growth is affected in a negative
manner if the Li-precursor is introduced after the [TiCl4 þ
H2O] cycle. It is sufficient to add another material in
between to obtain uniform films, such as for deposition
in the lithium lanthanum titanates (LLT) system where
[La(thd)3 þ O3] is inserted. It is also possible to replace
the TiCl4 precursor with Ti(OiPr)4 to obtain more even
growth. This indicates that chlorine based processes
affects the deposition of Li. It would be natural to assume
that this would be due to formation of the stable LiCl,
however, for the mentioned cases where TiCl4 was used
as precursor, the content of Cl in the film was surprisingly
low which was also the case for the Li-content in the same
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films, indicating that the adsorption of the Li-precursor
was affected.
When comparing the similar processes where the Li-
precursors Li(OtBu) and LiHMDS are exposed to the MnO
surface from the [Mn(EtCp)2 þ H2O] processes, it is evident
that the element Li plays a role in loss or deactivation of
MnO, since both Li-precursors behaves in a similar manner.
The origin of this appearance remains to be investigated,
but it should be noted that such behavior is not seen when
these Li-precursors are combined with the [Mn(thd)3 þ O3]
process.
When depositing active materials for Li-ion batteries,
one should also recognize that the Li-ions are hopefully
mobile at the deposition temperatures, which may lead to a
more bulk controlled growth than pure surface limited
reactions. Indications of such bulk controlled growth is seen
for the [Li(thd) þ O3] þ [Mn(thd)3 þ O3] combination [15].
The ALD technique has additionally proven most
suitable in deposition of thin layers of electroactive materials
capable of delivering high powers over numerous cycles,
such as the V2O5 and FePO4 materials reported in Refs. [8]
and [9], respectively. By combining these ALD-grown
materials with nanostructured templates, one would expect
to achieve electrochemical electrodes offering much
higher specific energy at extremely high specific power
when compared to normal batteries, thus closing the gap
towards present supercapacitors.
More examples of cathode and anode materials will
undoubtedly be demonstrated in the near future where
also the main focus will be electrochemical cycling of thin
films under extreme rates. The ALD technique may have its
limitations when it comes to deposition of large amounts of
electroactive materials to obtain high capacity. However, it
is inherent ability to achieve conformal coatings is most
beneficial for conversion of nanostructured templates into
highly active electrochemical structures.
The ALD technique is inherently also optimal for
production of thin solid state Li-ion electrolytes, although
the materials demonstrated so far do not meet the require-
ments in electronic and/or ionic conductivity. The field
is still to be considered as immature and new types of
electrolytes which are electrochemically stable towards
lithium are to be expected.
Acknowledgement We would like to thank the Research
Council of Norway for their funding (Project number 200030).
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