Solar Energy Materials and Solar Cells 168 (2017) 136–145

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Solar Energy Materials and Solar Cells

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

Tailoring anatase nanotubes for the photovoltaic device by the anodization MARK
process on behalf of microstructural features of titanium thin film
⁎
V. Mandića, , M. Plodineca, I. Kerekovića, K. Juraića, V. Janickia, D. Gracina, A. Gajovića,
A. Moguš-Milankovića, M.G. Willingerb
a
Ruđer Bošković Institute, 54 Bijenička cesta, HR-10 000 Zagreb, Croatia
b
Fritz Haber Institute of the Max Planck Society, Faradayweg 4-6, D-14195 Berlin, Germany

A R T I C L E I N F O A B S T R A C T

Keywords: We prepared the anatase nanotubes (NT) and other nanostructured titania as electron accepting/transmitting
Titanium layers in solar cells, using titanium anodization. Upon gaining control over the anodization, the parameters were
Electron beam evaporation held constant in order to observe the role of the deposited layers (by electron beam evaporation and magnetron
Magnetron sputtering sputtering) on the NT yield. The structural and microstructural parameters were investigated using FIB-FEG-
Anatase nanotubes
SEM, XRD, Raman and GIXRD. Differences in the titanium layers play a significant role on the type of titania
Anodization
Charge transfer solar cell material
nanostructures achieved. Only dense homogeneous titanium layer surface, uniform in thickness and without
cracks at macroscale, with uniformly seized isotropic nanoparticles, will enable uniform electrochemical etching
and thus favourable, reproducible formation of the titania NT, and upon thermal treatment the anatase NT.
Transparent conductive oxide (TCO) layers, which are not in direct contact to the NT, can also exhibit influence
on the morphology of the titania NT charge transfer layer. In order to reach large uniform areas of nanotubes,
which is required for solar cell application, the preparation of titanium layer has to be tailored.

1. Introduction transparent conductive oxide (TCO) layer is concerned as one of the

critical parameters in active material-to-electrode electron transport.
Photovoltaic devices seem to be the most lucrative answer (clean, The main disadvantageous process in the solar cells is the non-radiative
free, unlimited, low maintenance, etc.) to the large demands of the recombination which is more probable at the interfaces of grains in the
future [1]. In a 3rd generation photovoltaic device, like dye sensitized active material, but will also occur at the defect states in bulk of the
solar cell (DSSC), or perovskite based solar cell (PSC), electron active materials. Having in mind a multi-layer assembly of a solar cell,
transmitting material (ETM) layer is considered to be the curtail for limits in the control of the interfaces can be nominated as one of the
enabling high efficiency in the overall performance of solar cell [2,3]. main reasons why nowadays all (familiar) types of solar cell (SC)
Namely, when excited by the light, active material will yield excitons materials still fail to get closer to the theoretical efficiency limits.
and the electron transmitting material which is underlaying the active While literature agrees that the most important task is the optical,
material will ensure separation of the charge carriers and their further electrical and structural compatibility of active and passive layers, there
transfer to the electrode in order to finally yield electricity. The better is no consensus on mechanisms of processes at boundaries (for example
the process, the higher performance of overall solar cell is achieved. charge transfer, charge recombination, etc.) which cause discrepancies
The problem lies within the short lifetime of the photogenerated charge in optimisation efforts [1–22]. Thus, in the bottom-top solar cell
carriers, therefore the layer has to remain thin. Implementation of assembly processes, much attention is devoted to the strategy of
various nanostructural forms of the buffer layers ensures the increase of overlaying the CTO layers. The upgrade in efficiency of modern solar
specific surface area, and enables more efficient charge transfer without cell is known to depend not only on the chemical composition of the
the need to increase the thickness of the layers. Majority of non- active material but also significantly on the morphology of materials at
inverted solar cells (SC) repose on the transparent conductive oxide the interface between active and transport layers. Having in mind the
(TCO) layer in order to serve as a transparent electrode underlying the chemical composition, titania is recognised as photoactive, photocata-
electron transmitting material. Actually, the interface between the lytic, semiconducting material with known application as both charge
overlaying charge transfer oxide (CTO) layer and the underlaying transfer and active absorbing material [4]. In the case of special

⁎
Corresponding author.
E-mail addresses: [email protected], [email protected] (Vilko Mandić).

http://dx.doi.org/10.1016/j.solmat.2017.04.028
Received 26 October 2016; Received in revised form 18 March 2017; Accepted 13 April 2017
0927-0248/ © 2017 Elsevier B.V. All rights reserved.
V. Mandić et al. Solar Energy Materials and Solar Cells 168 (2017) 136–145

morphology, i.e. tailored self-organisation, for the titania thin films one manner [42]. In the literature, much attention is dedicated to the
can expect very favourable charge transfer properties, for example in geometry of anodization derived TiO2 NT layers, as it is presumed it is
the case of titania nanotube based thin films [5]. Such thin film can mainly responsible for the solar cell performance efficiency. The use of
show significant enhancement of solar cell properties when used as an anatase nanotubes in solar cells is known to be more favourable in the
electron transmitting material, i.e. when placed between the absorbing non-inverted setup, meaning the light enters the cell on the titania side.
material and the conductive transparent oxide layer, i.e. electrode. Common substrate that ensures mechanical strength for the cell and
When compared to a nanoparticle film, TiO2 nanotubes (NT) have a transparency is glass. On top of glass one should have transparent
large area-to-volume ratio, superior lifetime and provide optimal electrode. For a transparent conductive oxide layer, aluminium doped
pathways for electron percolation, thus the ability to produce ordered zincite (AZO) is commonly used. Alloy of indium tin oxide (ITO) and
self-assembled anatase nanotubes presented a huge milestone [6]. A fluorine doped tin oxide (FTO) are renowned candidates as well. In
25% increase in the charge collection efficiency of nanotube-based solar order to produce the nanotubes, it is necessary to deposit a thin film of
cell when compared to nanoparticle-based solar cells occurs due to the titanium on top of TCO layer. Understanding of the transport mechan-
enhanced light scattering and slower electron recombination [7]. isms in titania nanotubes (with respect to their geometry), as well as the
Namely, morphology and self-organisation of CTO ensure enlarged reproducibility of the preparation process (on all type of substrates) are
specific surface area, i.e. contact to active material, while CTO remains still a matter of controversy and act as a milestone in the future upgrade
thin enough to overcome the problem of the short lifetime of photo- of the titania NT-based solar cell performance [18,39].
generated charge carriers. The use of various nanostructural forms of In this work, the influence of titanium layer (structure, morphology,
inorganic materials in different crystal sizes in hybrid solar cells may uniformity, thickness, etc.) deposited on the TCO layer, on formation of
allow additional tuning of the optical and electrical properties. The well-defined homogeneous, ordered, self-organised, self-standing tita-
literature nominates various nano structures like tubes, rods, wires, nia nanotubes was studied in terms of the morphology of achieved
fibers, particles, etc. [8]. Furthermore, tailoring of the optical gap and nanotubes and reproducibility of the anodization process. The use of
surface chemistry is employed to enhance the transfer of photo- various nanostructured arrays may allow additional tuning to ensure
generated carriers towards the external circuit. Currently, efficiencies the overall compatibility of all layers. The controlled deposition of the
of up to 13% were achieved for the titania NT-based DSSC, while above starting titanium layer was shown to be a prerequisite for successful
20% for the NT-based PSC [9,10]. It is important to point out that these anodization. The results of this work show that interface properties of
materials are the most cost effective solar cell constituent layers, both in layers underlaying the derived titania nanotubes (TCO, Ti) may
terms of material and preparation (both laboratory and scale up) costs significantly attribute to the behaviour of the solar cell.
vs. power conversion efficiency. Subsequently, all of the above-men-
tioned influence the efficiency/stability of SC. 2. Experimental
Layer deposition techniques also play an important role in the
previously mentioned high efficiency separation of charge carriers and 2.1. Synthesis parameters
their transport from the absorbing material to the electrode. Achieving
affordable and reliable deposition technique is the continuous matter of The syntheses of porous TiO2 structures or TiO2 nanotubes by the
scientific effort [11–15]. Preparing the titania nanotube layer reposes anodization process were performed on Ti layer deposited by electron
on the starting Ti-layer. The successfulness of Ti deposition (with beam evaporation or magnetron sputtering under marginally different
respect to structure, morphology, thickness, particle size, uniformity, conditions on glass substrate with TCO layer. Thereafter, the prepared
etc.), anodization (with respect to deposition parameters), and thermal titanium samples were microstructurally and structurally characterised.
treatment (with respect to anodization parameters) is a necessity for the Subsequently, the titanium thin films were anodized to titania nano-
homogeneous surface which is needed for the solar cell application. In tubes and thermally treated to anatase nanotubes (all under the same
this case, a fully controllable and reproducible preparation procedure conditions) (Fig. 1) and then microstructurally and structurally char-
on all type of substrates still presents a challenge [16–18]. Namely, the acterised again. The only process parameters that were differed are
Ti anodization process was introduced as a convenient way to produce brought up in Table 1. Few steps were performed during the prepara-
the TiO2 NT with various geometries in terms of nanotube length, tion:
diameter and wall thickness (basically a electrochemical etching Glass substrates with transparent conductive electrode (aluminium
process of the titanium in the ammonium fluoride electrolyte solution zincite – AZO, Aldrich, United Kingdom; indium tin oxide – ITO, Ossila,
of various concentrations under different currents, where intermediate United Kingdom; fluorine tin oxide – FTO, Aldrich, United Kingdom) for
titanium fluoride is dissoluted to form amorphous titania nanotubes) the depositions of titanium had to be cleaned. The cleaning procedure
[19–29], whereas the subsequent thermal treatment is required to includes 3-step washing in ultrasonic bath cleaner (US) in: (i) detergent,
promote the crystal transformation to anatase [30]. The process (ii) acetone, (iii) ethanol, and subsequent boiling in MilliQ H2O.
depends on many parameters, such as the F− ion concentration Electron beam evaporation (EBE) for the titanium deposition was
[31,32], the type of solvent [33], temperature [34,35], stirring [36] performed in a modified Varian 3117 chamber, where parameters
and anodization potential [34,37]. Yet anodization voltage and ammo-
nium fluorite solution concentration are nominated as the most
important. By changing these parameters, the nanotube parameters
can be controlled, i.e. inner and outer tube diameters and the wall
thickness [25]. The easiest way to control the length of the tubes is
through the duration of the anodization process [38,39]. Very low
water content in polar organic solvents may considerably decrease the
rate of chemical dissolution and thus increase the nanotube length
[40,41]. The presented anodization process was generalised as simple
and facile. Namely, it was usually performed on commercial titanium
foils. Such titanium materials were usually homogeneous with well-
defined morphologies. XRD of such material yields the titanium with
hexagonal crystal lattice. The need to produce the anatase nanotubes on
different substrates, like the transparent substrates, brings about the
problems in their preparation in micro- and macroscopically uniform Fig. 1. Scheme of the anatase nanotubes preparation by titanium anodization.

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Table 1
Titanium deposition conditions; electron beam evaporation conditions, magnetron sputtering conditions.

Substrate No Electron beam evaporation Magnetron sputtering

Base pressure / Pa·10−4 Depos. rate /Ås−1 Substrate preheat /°C Cell pressure / Pa·10−5 Argon pressure / Pa Depos. power / W Substrate temp. /°C

E1 6.6 8.0 230 – – – –

E2 6.6 1.0 230 – – – –
E3 6.6 7.5 RT – – – –

M4 – – – 1 0.5 60 RT
M5 – – – 1 0.5 60 RT
M6 – – – 1 0.5 60 RT

E – electron beam evaporation, M – magnetron sputtering.

under control are given in Table 1. Starting material was 99% Ti hydroxides (TiO(OH)2) [45,46] can be formed (Eq. (5)) in the reaction
0.2–1.5 mm granulate (Balzers, USA). The substrates were positioned with water or hydroxide ion (available from the hydrolysis reaction of
onto a rotating calotte to ensure a uniform thickness of the layers over F-). Simultaneously, at the cathode hydrogen evolution takes place (Eq.
the sample surface. The substrates were preheated to 230 °C. Ti layers (6)).
with targeted mass thickness ~800 nm were deposited. Mass thickness
Ti4+ + (2+n)H2O → TiO2-n(OH)2n + 4H+ (5)
of the layers was controlled by a quartz crystal monitor. Base pressure
was 6.6·10−4 Pa.
Titanium layers ~800 nm thick were deposited at room temperature 2H2O + 2e- → H2 + 2OH- (6)
by DC magnetron sputtering (MS) (60 W power) on TCO coated glass
The final porous oxide layer is formed as a result of the continuous
substrates. Working gas was argon, target to substrate distance was
process, which involves competition between chemical dissolution of
140 mm. Base chamber pressure was 10−5 Pa and working gas pressure
oxide and anodic oxide formation [24]. The TiO2 nanotube arrays were
during deposition was 0.5 Pa (Table 1).
fabricated at 30 V. Anodization parameters are given in Table 2. For the
According to TCO and deposition technique, surfaces were denomi-
whole time of anodization, current was monitored and recorded in the
nated as electron beam evaporated titanium on AZO; E1, E2 and E3,
form of I-t graphs. After anodization, the specimens were cleaned using
while magnetron sputtered on AZO; M4, M5 and M6. Subsequently,
isopropyl alcohol (IPA, (C3H8O, p.a. Kemika, Croatia)) and MilliQ H2O
magnetron sputtered Ti on AZO, ITO and FTO were denominated as
treatment in UZV bath and dried in a nitrogen gas stream. Anodized
MAZO, MITO and MFTO, respectively (Table 1).
samples were thermally treated at 450 °C for 1 h, in order to transform
The anodization was carried out at room temperature in a conven-
from amorphous to crystalline TiO2 NT, the heating and cooling was
tional two-electrode cell using a direct current (DC) power supply. A Pt
performed at the rate of 1 °C/min.
foil was used as the counter electrode and a deposited Ti layer served as
According to previous surfaces denomination, anodized and ther-
the anode. The electrolyte was 0.9 wt% ammonium fluorite (NH4F, p.a.
mally treated nanostructured samples were denominated as E1A, E2A,
Kemika, Croatia) and 2 wt% milliQ H2O in ethylene glycol (C2H6O2,
E3A, M4A, M5A and M6A. NT samples on AZO, ITO and FTO were
p.a. Kemika, Croatia). A radial surface having diameter of 1 cm was
denominated as MAZOA, MITOA and MFTOA, respectively (Table 2).
exposed to the anodization; until mostly transparent.
The formation of a nanoporous structure during the anodization can
2.2. Characterisation techniques
be summarised as the result of three simultaneous processes: (1) field
assisted oxidation of Ti and formation of TiO2, (2) field assisted oxide
Morphology of the surfaces was investigated using field emission
dissolution (dissolution of Ti4+ in the solution), and (3) chemical
gun scanning electron microscopy (FEG-SEM) device JEOL model
dissolution of Ti and TiO2, due to etching by fluoride ions [43,44]. At
7000F equipped by energy dispersive spectroscopy (EDS) system.
first, due to the applied electrical field, metal cations are formed (Eq.
Micrographs were analysed using fast Fourier transformation algorithm
(1)) and afterwards a compact oxide is created on the metal/electrolyte
(FFT) in order to achieve information on the periodically repeating
interface in the reaction with oxygen anion from water (Eq. (2)).
features and their dimensions.
Ti → Ti4+ + 4e- (1) For the scanning electron microscopy cross section of the TiO2
nanotubes arrays at different substrates, samples were prepared by
using focused ion beam scanning electron microscopy system (FIB-SEM)
Ti4+ + 2H2O → TiO2 + 4H+ (2)
FEI Helios Nanolab. Pt protective strap was deposited on the area of
Since the system is under constant voltage, the applied field enables interest. The specimens were milled using 30 keV Ga ions to obtain the
transport of ions through the oxide lattice. Further oxide growth occurs
on metal/oxide interface owing to the field assisted transport of O2- Table 2
Anodization process parameters and outcome of the nanostructured TiO2 layer.
downwards and on the oxide/electrolyte interface due to the transport
of Ti4+ upwards [19]. In presence of the F- the oxide growth becomes Substrate No Anodization parameters Nanostructured TiO2
less straight-forward as TiO2 chemically dissolves. During that process,
soluble [TiF6]2- complex is produced (Eq. (3)). It is possible that the Etching voltage / V Etching time / min NT formation
reaction occurs at oxide/electrolyte as well at metal/oxide interface.
E1A 30 15 +
Direct complexation (Eq. (4)) at the oxide/electrolyte interface is also a E2A 30 30 0
possible way of [TiF6]2- formation due to Ti4+ transport. E3A 30 45 –

TiO2 + 6HF → [TiF6]2- + 2H2O + 2H+ (3) M4A 30 60 +

M5A 30 70 –
M6A 30 60 –
Ti4+ + 6 F- → [TiF6]2- (4)
E – electron beam evaporation, M – magnetron sputtering, A – anodized to TiO2.
In addition, on the oxide/electrolyte interface hydroxides or oxy- (+): favourable NT formation; (−): unfavourable NT; (0): other nanostructures formed.

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cross section area of interest. micrographs side view (shown in Fig. 4 and in Supplementary
The powder X–ray diffraction (XRD) was accomplished using material). NT in all of these lengths should be acceptable for DSSC.
Shimadzu diffractometer XRD 6000 with CuKα radiation at accelera- For PSC, the success of infiltration of active material decreases with NT
tion voltage of 40 kV and current of 30 mA. Data were collected depth, so average length of tubes of 800 nm should be appropriate.
between 20–75°2θ in a step scan mode with steps of 0.02°2θ and Upon thermal treatment, the nanotubes were confirmed as anatase
counting time of 0.6 s. Grazing indecent XRD (GI XRD) measurements using Raman spectroscopy (Eg modes at 639, 197 and 144 cm−1, A1g/
were performed on Bruker ASX D8 Discover device 20–75°2θ in a step B1g modes at 516 cm−1 and B1g mode at 399 cm−1) and GI XRD (ICDD
scan mode with steps of 0.01°2θ and counting time of 0.1 s at angle of PDF#21–1272) (Fig. 5ab) [50]. The interpretation is focused on the
1.5°θ at acceleration voltage of 40 kV and current of 40 mA. The microscopic features of the nanostructures, while the macroscopical
average crystallite size of titanium was calculated from the broadening overview of the samples may reveal additional aspects that may
of several diffraction peak using Scherrer's equation: D=kλ/(Bcosθ), significantly contribute to the applicability of the samples in the solar
where D is the average crystallite diameter, k is Scherrer's constant, λ is cell device. The desirable sample characteristic would be a large scale
the X–ray wavelength, B is full width at the half height of the diffraction homogeneity and uniformity, and absence of all defects and cracks.
peak corrected for instrumental broadening, and θ is the diffraction Some properties of the starting titanium layer may also influence the
angle. XRD scans embed also the horizontal surfaces beyond the macroscopic features of the titania nanotube layer. This will be
boundaries of anodized region. commented later. Also, some samples show debris on top of the titania
The micro-Raman spectroscopy measurements were performed ordered nanotubes, whereas the EDS chemical composition suggests
using a Horiba Jobin-Yvon T64000 system equipped with a Coherent, this material is also titania. This material is only superficially adsorbed
Innova 400 argon ion laser operating at 514.5 nm for the excitation. to the surface and can be removed using ultrasonic tip. For all samples
The laser power of 20 mW was focused on the samples using a 50× where such effect was evidenced, the debris layer was removed by
magnification distance objective. treatment in US bath.
The UV–vis spectrum of the prepared samples were obtained using
Perkin Elmer Lambda 900 in transmission mode. The spectra were 3.3. Titanium layer properties
recorded at room temperature in the wavelength range 200–800 nm
with step of 1 nm and integrating time of 0.8 s. 3.3.1. Structural parameters
The nanotubes were assigned as anatase using GI XRD (Fig. 5b).
3. Results and discussion Titanium occurs also as the area where diffraction signal was collected
extend beyond the anodized circle.
3.1. Titania based solar cell prerequisites More attention was dedicated to the as-deposited starting layers; all
titanium samples show similar diffractograms (Fig. 6b). Major feature is
It has to be ensured that the glass substrate and the transparent the zincite (ICDD PDF#36-1451). It is common for zincite thin films to
conductive oxide layer are perfectly uniform and clean, only then may have quite strong [002] reflection due to a preferred orientation which
they be excluded as the process parameter. Then the parameters of the occurs for all measured samples. Titanium phase is visible in all samples
deposition process may be held responsible for the differences in and it is assigned as α-titanium hexagonal close packing (hcp) (ICDD
nanostructured products, assuming all anodization parameters were PDF#44-1294). Beside the α-titanium, there might be a presence of
held constant [47]. This is necessary to ensure good adhesion of body centred cubic (bcc) β-titanium phase (ICDD PDF#88-2321). No
deposited layer. Non-inverted setup, which requires Ti deposition on additional phases were present. Even though the conditions for stable
TCO, seems to be more appropriate. Methods applied to deposit growth of β-titanium phase were not reached, local existence of β-
titanium on equally prepared glass substrates with TCO layer mainly titanium is not excluded. The more the peak intensity in the diffracto-
differ on applied energy; magnetron sputtering was used as a high grams differs from α-titanium ICDD data in terms of both preferred
energy deposition method, while electron beam evaporation was used orientation or possible β-phase existence, the less favourable thin film
as a low energy deposition method [48,49]. Both deposition methods microstructure turns out to be. It was observed that titanium thin films
were performed under just marginally different conditions. also show a strong preferred orientation, again on behalf of the
reflection [002]. Previous investigation shows that the more power is
3.2. Anodized nanostructured titania layer properties employed during the deposition, the derived titanium particles turn out
to have a stronger preferred orientation [51], while further increase in
Scanning electron microscopy micrographs of all anodized titanium power will yield surface porosity. We observed that different deposition
layers are presented on Fig. 2. One can observe that several nanos- methods also strongly favour different preferred orientation (at differ-
tructural features arise; tubes, porous structures, wormholes, and comb- ent planes), while other conditions determinate if the achieved texture
like blend of all the mentioned morphologies. Among the plethora of will be favourable. It could be said that for the deposition at lower
samples, only those having distinctively different morphologies were temperatures the strain remains in samples. Namely, some shifts in
selected; 3 for EBE derived (Fig. 2a,b,c), and 3 for MS derived [002] position point out that the interplanar distances of the unit cell
(Fig. 2d,e,f) (additional info in Supplementary material). However, it are affected by different deposition conditions. Similar effects were
is important to bear in mind that the selected morphologies do not observed by Chawla et al. [52] for different levels of energy during the
relate to their abundance. The favourable products are the nanotubes deposition. This all may be attributed to the fact that the different
(Fig. 2a,d), while the formation of other type of nanostructures is not surface free energies are associated with different planes. One should
favourable (Fig. 2b). We observed a variety of inhomogeneous surfaces, not forget that different materials with different thermal expansion
where wormhole-like structures with different content of tubes were coefficients are interfaced. Obviously, there is a presence of competition
formed (Fig. 2c,e,f). The best samples display uniformly distributed, between deposition energy and surface free energy affecting the
equally shaped self-standing nanotubes (Fig. 2a,d). Based on the textures of the grains, which altogether heavily depends on the different
anodization voltage, the tubes displayed the inner tube diameter in deposition parameters, all of which are related with substrate proces-
range from 20 to 35 nm, and outer in range 40–70 nm, which was sing temperature, pressure, power and other substrate properties in
confirmed using FFT analysis of the micrographs. FFT analysis of complex manner [52–56]. The non-isotropic particles, i.e. the 1D or 2D
sample M4A (Fig. 2d) was shown in Fig. 3. The authors were successful growth of crystals may be the main cause for such result. Therefore, the
in preparation of favourable NT in lengths from 200 up to 2000 nm, yet normalised relative ratios of the selected reflections [002] and [103] to
mainly lengths around 800 nm were prepared, as observed from SEM the ICDD card data were plotted (Fig. 7a). Values significantly different

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Fig. 2. Micrographs of the titania morphology and organisation forms derived by anodization of titanium thin films deposited by electron beam evaporation; a) sample E1A, b) sample
E2A and c) sample E3A, and by magnetron sputtering; d) sample M4A, d) sample M5A and d) sample M6A.

Fig. 3. Example of FFT micrograph analysis of the sample M4A (Fig. 2d); dimensions of
the periodical units, Insets: micrograph of analysed area of the sample M4A and FFT
image of the micrograph.

Fig. 5. Anatase spectra on samples E1A and M4A: a) Raman with active modes, b) GI XRD
than 1 (especially bigger values) suggest presence of non-isotropic with assignation and crystal planes.
crystallites and strain. It could be concluded that successful nanotubes
will be derived from the titanium thin film consisting of mainly reasonable for all samples. One can only assume higher energy method
isotropic particles. Limited number of titanium peaks hinders the will cause higher extent of preferred orientation. Literature also
deeper structural insight in these presumptions, especially in the case strongly relates the degree of orientation on the texture and roughness
of Ti deposited by magnetron sputtering where this quantification is not of underlying material [57], whereas magnetron sputtered Ti thin films

Fig. 4. Sideview micrographs of the NTs anodized from titanium thin films deposited by magnetron sputtering on top of a) AZO, b) FTO and c) ITO; additionally available in
Supplementary material.

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underlaying surface and deposition conditions will be discussed later.

Based on the diffraction parameters, the average crystallite sizes were
calculated; results are shown in Fig. 7b. The sizes range from 40 to
180 nm. It was observed that smaller crystallites of used deposited
titanium lead to more successful nanotubes, as will be shown later. The
particle size is usually determined by the temperature of the deposition,
yet this investigation shows that other parameters can also be respon-
sible for the grain size change.

3.3.2. Microstructural parameters

In order to confirm the structural results, morphologies of titanium
layers deposited by electron beam evaporation and magnetron sputter-
ing were investigated with FEG-SEM; (Fig. 7). Different morphologies
were observed even though the deposition parameters differed mini-
mally (Table 1). Several types of surfaces can be observed; dense,
almost absent of pores, homogeneous with narrow size distribution of
isotropic particles (E1) (Fig. 7a), less dense with 2D flakes and irregular
Fig. 6. XRD diffractograms of the titanium layers deposited by electron beam evaporation particles of roughly the same size that form significant amount of pores
and magnetron sputtering, assignation and crystal planes presented below. and holes (E2) (Fig. 7b), less dense surface consisting of 2D objects,
flakes and 1D pillars, agglomerated, in brush style, again with lot of
porosity (E3) (Fig. 7c), dense surface with expressed roughness, almost
absent of pores, homogeneous with equally sized isotropic particles
(M4) (Fig. 7d), less dense with randomly oriented 2D and irregular
particles that form significant amount of pores and holes (M5) (Fig. 7e),
dense with 2D particles that also display porous surface with holes (M6)
(Fig. 7f). The results are in concordance with the XRD structural
analysis; smaller and more uniform titanium particles yield more
successful titania nanotubes. It seems that titanium surface with 1D,
2D, generally non-isotropic, non-uniformly size distributed and gen-
erally larger particles will allow excess etching that will prevent
formation of a homogeneous, ordered titania nanotube layer at a
microscale, and without defects and cracks at a macroscale. Only the
dense homogeneous titanium layer surface, uniform in thickness at
macroscale, having uniformly seized isotropic nanoparticles will enable
uniform etching and thus favourable reproducible formation of the
nanotubes. The results enable us to offer relation of the achieved
titanium morphology type to the type of morphology and self-organisa-
tion of the derived anatase tubes at the nano level. Titanium-to-titania
(titanium morphology leading to titania nanotubes formation) relation
Fig. 7. Structural parameters of the; a) relative ratio of the hcp Ti reflections [002] and
[103] (dimensionality insight) and b) Schererr crystallites size. was summarised on the scheme in Fig. 8.
Successful NT layer was achieved at the titanium surface (sample
generally show [100], [103], and [101] crystallographic orientations of E1) using electron beam evaporation at base pressure of 6.6·10−4 Pa,
crystallites parallel to the surface. Only a special modification of the deposition rate of 8.0 Ås−1 on substrates preheated at 230 °C (Table 1).
magnetron sputtering process (closed-field unbalanced, pulsed), can Successful NT layer was achieved at the titanium surface (sample M4)
bring up the number of various and independent deposition parameters, prepared using magnetron sputtering at starting pressure of 10−5 Pa,
i.e. can enable optimizing of deposited layers [58]. Influences of working Ar pressure of 0.5 Pa and deposition power of 60 W at room
temperature (Table 1). Generally, somewhat more homogeneous sur-

Fig. 8. Scheme showing different titanium thin film morphology exhibit different susceptibility to anodization, i.e. the existence of preferred routes and spots for electrochemical etching,
and relation to derived titania morphology as a consequence of the starting morphology. From left to right: i) worst-case scenario occur in the case of microstructure consisting of 1D Ti
particles which yields porous nanostructure due to multiple electrolyte penetration points in the course of the anodization; ii) 2D-type of Ti particles and iii) generally non-isotropic Ti
particles yield various blends of porous, wormhole and NT products, also considered as porous; iv) bigger isotropic Ti particles yield favourable NT on micro level with unfavourable
cracks on macrolevel, while finally v) smaller isotropic Ti particles yield favourable micro and macro homogeneous titania NT layer.

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Fig. 9. Micrographs of the titanium layers deposited by electron beam evaporation; a) surface E1, b) surface E2 and c) surface E3, and by magnetron sputtering; d) surface M4, d) surface
M5 and d) surface M6.

faces appear to be achieved by magnetron sputtering. However, it can the abrupt changes in current obviously point out to local resistivity
be observed that even the surfaces that appear to be similar (in terms of increase as nonconductive titania layer is formed and the resistivity
microstructural homogeneity) (Fig. 9d,e,f) do not always yield same decreases when nanotubes form. The electric mechanism of reaction is
nanotubes (Fig. 2d,e,f). A different level of titanium particles adhesion not offered. However, empirically it was observed that, after the
is achieved using different deposition methods, whereas magnetron starting current decay, sudden current increase may be a good
sputtering, as a higher energy deposition method, obviously exhibits indication that NT are formed. Additionally, very “noisy” current decay
the surfaces where somewhat stronger bonds are achieved. Although may present the new NT formation and thus is more favourable than
magnetron sputtering should be nominated as the method of choice very stable decay. Absence of the current increase in the later stage of
based on this theoretical consideration, equally favourable NT can be anodization may prevent the penetration of the layers, i.e. excess
prepared at titanium thin films deposited by electron beam evapora- etching. I-t curves can serve only as marginal parameter in the
tion. anodization process; they are hardly a reliable indicator that the
electrochemical etching process is executed in concise and homoge-
3.3.3. Electrochemical etching conditions neous manner and offer little information on the type of morphology
The course of the anodization process which leads to formation of and organisation of the TiO2 NT achieved. Probably the I-t effects arise
different morphologies may be monitored by anodization currents as a consequence of macroscopical issues on the treated surfaces as
(Fig. 10a). Contrary to general belief, very stable decay of current will well.
not yield ideal nanotubes, only the porous surface. That may be related The macroscopical issues observed on micrographs of the nanos-
to the mechanisms of etching, which occur in a stepwise manner. So, tructured titania (Fig. 2a) may also originate from the properties of the

Fig. 10. a) Anodization current vs time plot; scale inserted; b) micrograph of the excess etching: NT etched trough deposited titanium to the TCO ZnO:Al, c) UV–vis transmittance of
anodized and thermally treated samples; scale inserted.

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titanium layer. For example, it was observed that higher surface proportional to the temperature of the substrate during sputtering,
roughness of the titanium layer will in turn give more cracks in the although it is not apparent if it directly influences NT growth mechan-
nanotube layer. However, majority of the cracks seem to be caused by ism and morphology [18,56,61,62]. To enhance Ti layer density and
the contamination particles. Based on that and the lack of statistics on grain size, an increase in sputtering substrate temperature or subse-
these observations, the macroscopical effects on the nanotube surface quent thermal treatment may be suggested, and in order to influence
should not be related solely to the starting titanium layer parameters. the dimensionality of achieved particles the deposition power optimisa-
For the photovoltaic device application, it is important to achieve tion may be suggested [48,49]. However, the temperature increase
uniform etching to the titania nanotubes. Namely, insufficient etching inevitably enlarges grain size which was found as unfavourable. It is
will cause the leftovers of titanium layer. This will lead to reduction or better to say that smaller particles are more favourable for successful
complete lack of transparency required for the solar cell to work. NT growth, but only when good layer density and adhesion of Ti layer is
Alternatively, the excess etching will dissolve the entire layer trough to achieved (with constant strain and preferred orientation) despite the
the TCO layer (Fig. 10b). This will cause the short circuit and the solar deposition method employed. Practically, the difference in samples may
cell will not work. Optimisation of deposition requires the titanium arise as the distinctive deposition session exhibit marginal differences
layer with uniform and known thickness all over the sample. Lengths of due to minor pressure corrections, cooling conditions, cathode material
anodized TIO2 NT usually correspond to Ti thin-film thickness, whereas wear, etc. Overall, this investigation shows more parameters lay behind
under some minimum Ti thin-film thickness value the NT will not be the control of the deposition of the Ti thin-films exhibiting appropriate
formed. The use of organic viscous electrolytes may allow additive morphology for appropriate etching susceptibility.
growth, yielding NT that surpasses the thickness of the consumed Ti
layer several times [56,59]. In our case, the Ti layer thickness was 3.4. Influence of TCO on CTO
approx. 0.8 µm which was reported as sufficient for the NT [51,60].
Following the acceptable Ti layer, in the next step the duration of the Previously it was mentioned that underlaying material may sig-
anodization (with all other parameter constant) has to be optimised in nificantly influence the parameters of the overlaying [57]. In order to
order to yield (in ideal case) complete anodization of the titanium layer check if the influence on titania nanotubes may be somehow related to
without penetration into the TCO layer. In practice, titanium layer the type of the material used for TCO layer, subsequently the NT
leftover with thickness of several nanometers will ensure reasonable samples were prepared on different transparent conductive oxides
titania nanotube layer with sufficient transparency. The thermal (aluminium zinc oxide (AZO), fluorine tin oxide (FTO) and indium tin
treatment to anatase will further increase the transparency to more oxide (ITO)). By relating XRD (Fig. 11) and SEM (Fig. 12abc) data, it
than 80% (UV–vis spectra shown in Fig. 10c). Of course the better the was observed that titanium morphology and structure derived on these
NT morphology turns out to be, the more transparent are the layers, layers show very little differences. XRD shows well defined structures
while for all samples the bandgap is only marginally affected. with crystallite sizes ranging from 46 to 57 nm, which was previously
determined as desirable. Morphologies observed in FEG-SEM micro-
3.3.4. Deposition conditions graphs, in general resemble to the description of surfaces previously
Is it possible to exactly define the ideal conditions to derive titanium shown to be favourable for the growth of the NT by anodization.
that would yield continuous and uniform layer of titania nanotubes? However, deeper insight reveals one important deviation from the ideal
For the evaporation method, the ideal conditions would be those morphology; it is the size of the Ti particles or the particle agglomer-
that yield smaller, homogeneous isotropic particles. Namely, the ates, i.e. surface roughness. Anodized nanotubes (Fig. 12def) also do
electron beam evaporation is low energy deposition method, meaning not significantly differ, but follow the previously established rule where
the particle density in the deposited layer will not be very high (thus the smaller Ti particles yield better NT. Thus, the deposition is responsible
adhesion between the particles will not be very strong). Therefore, for the achieved titanium morphology (and structurally preferred
much will depend on the extent of the sites favourable for etching. morphology) and influence on anodization, while the boundary to
When big particles are in contact, big voids are enabled. Same applies TCO layer has less influence on subsequent layers, i.e. titanium layer
for the non-isotropic particles. The electron beam evaporation condi- and nanotubes anodized thereof. One should not neglect the fact that
tions have complex mutual dependency. However, high deposition rate the TCO surface morphology may be transferred on the Ti surface
without substrate preheating seems to be more favourable than the low morphology. Thereby the use of FTO (typically showing surface
deposition rate with substrate preheating.
The magnetron deposition conditions seem to have less influence on
the nanotubes outcome and more influence on the general layer
properties. Magnetron sputtering is a high energy deposition method,
meaning the particle density in the deposited layer will be high, i.e. all
the deposited particles show strong adhesion, so voids leading to excess
etching will be reachable less often. However, the issue here is the
presence of cracks in the derived nanotubes layer. This may be due to
the difference in thermal expansion coefficients of TCO and titanium.
Usually very thick or very thin layers show more favourable behaviour
but that somewhat limits the availability of the nanotube lengths.
Although the magnetron sputtering should be the method of choice
based on these theoretic considerations, there are still no conclusive
practical arguments to backup these claims. For Ti thin film deposition,
it was observed that the substrate temperature during the process
strongly influences the quality of the thin film and its adhesion to the
substrate, which are crucial for obtaining free standing NT on TCO. Low
temperatures of substrate heating yield poor connection of Ti and the
substrate (whether because of poor adhesion or high residual stress),
which will cause problems in subsequent anodization due to irregular Fig. 11. XRD diffractograms of the titanium thin films samples MAZO, MFTO and MITO
film etching or peeling off. The exact reason for this effect is not clear, deposited by magnetron sputtering on top of AZO, FTO and ITO; assignation and crystal
but it has been reported that the size of Ti crystalline grains is reversely planes presented below, Inset: Ti Schererr crystallites size.

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V. Mandić et al. Solar Energy Materials and Solar Cells 168 (2017) 136–145

Fig. 12. Micrographs of the titanium thin films deposited by magnetron sputtering on top of: a) AZO – surface MAZO, b) FTO – surface MFTO and c) ITO – surface MITO, and
nanostructures anodized thereof: d) AZO – sample MAZOA, e) FTO – sample MFTOA and f) ITO – sample MITOA.

constituted of large particles or more agglomerated particles or higher Acknowledgement

surface roughness) may be less favourable than the AZO or ITO
(typically showing fine particles and low surface roughness). Authors The financial support of the ESF project No HR.3.2.01-0312 “Titania
observe lower success rate (not statistically analysed). Best samples nanotubes for photovoltaic application”, COST MP 1307 STSM project
containing glass substrate/TCO/Ti/anatase nanotubes/ should be fa- No 32084 “The electric compatibility of TCO and CT layers in DSSC and
vourable for the DSSC or PSC solar cell assembly. OPV solar cells” and CSF project No 9419 “Zinc Oxide and Titanium
Dioxide Nanocomposites for Photovoltaic Application” are gratefully
acknowledged.
4. Conclusions
Appendix A. Supplementary material
The prepared titanium samples yield some difference in surface
morphologies. Based on that, samples having different morphologies Supplementary data associated with this article can be found in the
were also found to exhibit different susceptibility to successful and online version at http://dx.doi.org/10.1016/j.solmat.2017.04.028.
reproducible anodization. Differences in the growth of the TiO2 NT with
constant main anodization parameters were attributed to different References
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