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Sol-gel synthesized, low-temperature processed, reduced molybdenum

peroxides for organic optoelectronics applications

Article in Journal of Materials Chemistry C · May 2014

DOI: 10.1039/C4TC00301B

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Journal of
Materials Chemistry C
PAPER

Sol–gel synthesized, low-temperature processed,

reduced molybdenum peroxides for organic
Cite this: J. Mater. Chem. C, 2014, 2,
6290 optoelectronics applications†
Antonios M. Douvas,*a Maria Vasilopoulou,a Dimitra G. Georgiadou,a
Anastasia Soultati,ab Dimitris Davazoglou,a Nikolaos Vourdas,a
Konstantinos P. Giannakopoulos,a Athanassios G. Kontos,a Stella Kennouc
and Panagiotis Argitisa

Reduced molybdenum peroxides with varying degrees of reduction were synthesized following a modified
sol–gel peroxo method and the respective films were employed as anode interfacial layers in organic
optoelectronics applications, such as organic light emitting diodes (OLEDs) and organic photovoltaics
(OPVs). The degree of reduction was controlled through both the synthesis route and the thermal
treatment protocol of the obtained films. The films were thoroughly investigated with a variety of
spectroscopic, diffraction, and electron microscopy methods (UV-Vis, FT-IR, XPS, UPS, Raman, XRD,
SEM, and TEM). These films were found to be considerably sub-stoichiometric with a relatively high
Received 13th February 2014
Accepted 23rd May 2014
content of hydrogen. When they were used as anode interfacial layers in OLED and OPV devices, high
efficiencies and adequate temporal stability were achieved. The enhanced hole injection/extraction
DOI: 10.1039/c4tc00301b
properties of the reduced molybdenum peroxide films were attributed to the improved charge transport
www.rsc.org/MaterialsC facilitated through the gap states present in these materials.

1. Introduction
Transition metal oxides (TMOs)1 and their molecular
analogues, polyoxometalates (POMs),2,3 have been extensively
used in a wide variety of applications ranging from catalysis4 to
molecular electronics5 and organic optoelectronic devices.6,7
More specically, in organic electronic devices, such as organic
light emitting diodes (OLEDs) and organic photovoltaics
(OPVs), TMOs have been widely used as charge selective inter-
facial layers between the electrodes and the active polymeric
layer to enhance charge transport from/to the electrodes. Thus,
tungsten (WO3), molybdenum (MoO3), vanadium (V2O5) and
nickel (NiO) oxides have been mainly used as hole transport
a
Institute of Nanoscience and Nanotechnology (INN), National Center for Scientic
Research “Demokritos”, 15310 Aghia Paraskevi, Athens, Greece. E-mail: adouvas@
imel.demokritos.gr; Fax: +30 210 6511723; Tel: +30 210 6503231
b
Department of Chemical Engineering, National Technical University of Athens, 15780
Athens, Greece
c
Department of Chemical Engineering, University of Patras, 26504 Patra, Greece
† Electronic supplementary information (ESI) available: (1) UV-Vis monitoring of
ox/red Mo peroxides in solution, (2) FT-IR changes in water content during
thermal treatment of ox/red Mo peroxide lms, (3) FT-IR changes during
thermal treatment of a solution-reduced Mo peroxide lm, (4) Raman study of
ox/red Mo peroxide lms, (5) XRD characterization of ox/red Mo peroxide lms,
(6) optical characterization of ox/red Mo peroxide lms using spectroscopic
ellipsometry, and (7) morphological characterization of ox/red Mo peroxide
lms using SEM/TEM. Fig. S1–S7. See DOI: 10.1039/c4tc00301b
layers (HTLs), whereas TiO2, ZnO and ZrO2 have been used as
electron transport layers (ETLs).8 For those applications,
however, the current trend is to synthesize TMO lms using
solution-based methods owing to lower cost and more conve-
nient implementation in an industrial process, as compared
with vacuum deposition-based methods (such as thermal
vacuum evaporation, laser vapor deposition, etc.).
Especially for molybdenum oxide – one of the most popular
materials for use as an anode interlayer in organic optoelec-
tronic devices – four main wet chemistry-based synthetic
methods have been hitherto reported in the literature. The rst
method is based on an acidied aqueous dispersion of
ammonium molybdate leading to the formation of MoO3 lms,
though with considerable surface roughness.9 The second route
is based on MoO3 nanoparticles dispersed in xylene along with a
block copolymer, followed by treatment with oxygen plasma
and thermal annealing at relatively high temperature (200
C) of
the MoO3 lms.10 The third method is based on MoO2(acac)2
(acac ¼ acetylacetonate) precursors, which undergo hydrolysis
and condensation to Mo2O5(OH)2(H2O)4 and in a limiting case
to [Mo6O19]2 clusters leading nally to the formation of MoOx
lms.11,12 Finally, the fourth route is based on a sol–gel method
involving dissolution of MoO3 in hydrogen peroxide, and then
dispersion with polyethylene glycol and 2-methoxyethanol,
resulting in smooth MoO3 lms aer high temperature (275
C)
thermal treatment.13,14

6290 | J. Mater. Chem. C, 2014, 2, 6290–6300 This journal is © The Royal Society of Chemistry 2014
Paper
Three weak points can be discerned in the above solution-
based synthetic methods for molybdenum oxides lms, which
may ultimately decrease their hole-transporting efficiency
when they become part of an organic optoelectronic device.
The rst point is the inadequately homogeneous surface of
molybdenum oxide lms that are usually formed. The second
point is the high temperature thermal treatment along with
additional process steps (such as oxygen plasma treatment)
that are generally needed aer spin coating of the precursor
solution. The third and most critical point is that the majority
of the aforementioned synthetic routes aim to the formation
of oxidized MoO3 lms (a requirement that is usually inter-
related to the high temperature thermal treatment). However,
as it has been reported in the recent literature, solution-pro-
cessed hydrogen molybdenum bronze lms and hydrogen
vanadium bronze lms exhibit higher hole-transporting effi-
ciency than their corresponding oxidized lms when used as
anode interfacial layers in bulk heterojunction (BHJ) OPVs.15
Similar results have also been reported recently by our group
for oxygen decient hydrogen molybdenum bronze lms
deposited by thermal vacuum evaporation.16 In that case, the
superior hole transporting efficiency of the hydrogen molyb-
denum bronzes was attributed to their favourable energy level
alignment with the highest occupied molecular orbital
(HOMO) of the organic semiconductor owing to the intro-
duction of gap states near the Fermi level without a signi-
cant decrease of molybdenum oxide's work function.
Furthermore, we showed recently that solution-processed
hydrogen molybdenum bronzes resulted in improved power
conversion efficiency and stability when they were used as
anode interfacial layers in BHJ OPV devices.17 However, no
detailed characterisation of the properties of the obtained
material (dened as hydrogen molybdenum bronzes) was
presented in that work.
In this article, we aim to make a clear correlation between
the exact synthesis route and the subsequent processing
conditions with the optoelectronic, crystalline and morpho-
logical properties of the obtained lms. It is shown that the
degree of reduction, stoichiometry and, consequently, the
electronic characteristics of the synthesized lms can be
precisely tuned both through simple modications in the
solution synthesis and also by applying specic lm
annealing protocols. To this end, a combination of spectro-
scopic, diffraction and electron microscopy characterization
techniques (UV-Vis, FT-IR, Raman, ellipsometry, XPS, UPS,
XRD, SEM, and TEM) were employed to provide insight
into the properties of the obtained material. Finally, OLED
and OPV devices were fabricated to highlight the importance
of controlling the exact material composition in optoelec-
tronic applications. It was found that the devices imple-
menting as anode interfacial layers reduced molybdenum
peroxide lms, which were thermally treated at relatively low
temperature, demonstrated enhanced efficiency and
adequate stability. Therefore, it could be substantiated that
solution-processed reduced molybdenum peroxide lms
constitute a viable choice for large area, low-cost organic
optoelectronic devices.
This journal is © The Royal Society of Chemistry 2014
Journal of Materials Chemistry C
2. Results and discussion
2.1 Sol–gel synthesis of ox/red Mo peroxide lms
The Mo peroxide lms were synthesized through a modied
previously reported sol–gel peroxo method.13,14 The initial per-
oxo route was introduced by Kurusu,18 but it was established
and subsequently modied by Kudo et al. to synthesize stoi-
chiometric molybdenum peroxides.19–22 Recently, it has been
combined with the sol–gel process to obtain more homoge-
neous lms, while keeping at the same time the advantages of a
solution-based synthesis method, i.e. composition control,
large area deposition and low cost.13 In the present work, MoO3
powder is dissolved in H2O2 rich (31%) aqueous solution under
reux at 80
C. Subsequently, polyethylene glycol (PEG) is mixed
with the molybdenum peroxide solution for the adjustment of
the homogeneity/viscosity of the initial solution. Up to this
stage, the solution exhibits a clear yellow colour, an indication
that the synthesized molybdenum peroxide is in a fully or nearly
stoichiometric oxidation state. Then, 2-methoxyethanol (2ME)
is added to promote the reduction of the synthesized molyb-
denum peroxide (aer having removed the excess of H2O2) and
turning therefore the solution colour into blue. It will be shown
that the amount of added 2ME is critical, since it may promote
the reduction of molybdenum peroxide in the precursor solu-
tion. Therefore, oxidized (ox) or reduced (red) Mo peroxides can
be formed by controlling the amount of 2ME. Films are then
spin-coated on different substrates from the synthesized solu-
tions and subjected to various annealing protocols to produce
fully oxidized or reduced molybdenum peroxides depending on
the type of the solution (ox/red) and the annealing temperature,
as discussed below. More details on the exact synthesis proce-
dure and lm preparation are given in the Experimental
section.
2.2 Reduction of Mo peroxides
2.2.1 UV-Vis monitoring of ox/red-Mo peroxide lms. The
reduction of oxidized molybdenum peroxide lms can be easily
monitored using UV-Vis absorption spectroscopy through the
appearance of a new band in the visible/near IR region in the
reduced lms.23 Fig. 1 and 2 depict the absorption spectra of
100 nm thick Mo peroxide lms, before and aer thermal
treatment, in order to compare the effect of thermal annealing
in lms derived by two slightly different synthetic routes. In
Fig. 1, the initial product of the synthetic route followed was an
oxidized (ox) Mo peroxide lm, which was reduced only aer
being thermally treated. The second process (Fig. 2) involved
the addition of an excess amount of 2ME in the solution, which
resulted in the formation of a reduced (red) Mo peroxide lm,
and then the effect of further annealing was studied. In both
cases, the reduced lms were reoxidized aer annealing at high
temperatures.
More specically, Fig. 1a depicts the UV-Vis/NIR absorption
region of an ox-Mo peroxide lm, which was annealed from RT
up to 130
C. The rst observation is that the non-treated lm
and the one treated at temperatures up to 60
C are completely
transparent below 500 nm. Furthermore, the band at 356 nm
J. Mater. Chem. C, 2014, 2, 6290–6300 | 6291
Journal of Materials Chemistry C
Fig. 1 UV-Vis absorption spectra of an ox-Mo peroxide film upon
thermal treatment: (a) from RT to 130
C (thermal reduction of the
film); inset: magnification of the UV region and (b) from 100 to 230
C
(thermal reoxidation).
Fig. 2 UV-Vis absorption spectra of a red-Mo peroxide film: (a) in
comparison with an ox-Mo peroxide film and (b) upon thermal treat-
ment from 150 to 300
C (thermal reoxidation of the film). In (b), the
spectra are normalized to demonstrate the red-shift of the NIR peak
(IVCT band).
in the oxidized state, which is assigned to the peroxo (O–O)
group,24 gradually decreases in intensity and red-shis to
375 nm. This is the rst indication that the thermal reduction of
the ox-Mo peroxide lm proceeds through the reduction of the
peroxo group. Upon thermal annealing of the ox-Mo peroxide
lm at 100
C, a new broad band at 778 nm appears, which blue-
shis by 20 nm (to 757 nm) when further annealed at 130
C.
That band is attributed to the intervalence charge transfer
(IVCT, MoV / MoVI) band indicating that the Mo peroxide lm
is thermally reduced. Furthermore, upon thermal treatment at
T $ 100
C, a new big shoulder at 305 nm appears, whereas
the shoulder at 225 nm increases in intensity (see the inset in
Fig. 1a). Both of these bands have been ascribed to charge
transfer (CT) bands of the Mo6+]O2 bond with the 305 nm
shoulder being indicative of octahedrally coordinated Mo ions,
whereas the 225 nm band indicative of both tetrahedrally and
6292 | J. Mater. Chem. C, 2014, 2, 6290–6300
Paper
octahedrally coordinated Mo ions.23–26 Thus, it seems that the
thermal reduction of the ox-Mo peroxide lm at 130
C is
possibly accompanied by a tetrahedral-to-octahedral change in
the coordination of Mo ions.
Fig. 1b shows that upon further increase of annealing
temperature at T $ 160
C, the IVCT band gradually decreases
in intensity and red-shis. The latter changes indicate that the
(thermally) reduced Mo peroxide lm is gradually being ther-
mally reoxidized at T $ 160
C, whereas at 230
C it has been
almost completely reoxidized in accordance with the litera-
ture.18,24 It is also noteworthy that the peroxo group does not
reform upon thermal reoxidation of the (thermally) reduced Mo
peroxide lm. That nding indicates that the thermal reduction
of the peroxo group in ox-Mo peroxide lms is irreversible.
A similar thermal reoxidation was observed in a Mo peroxide
lm formed by a reduced solution (i.e. with the addition of
excess of 2ME) and the spectra are shown in Fig. 2. In particular,
the red-Mo peroxide lm shows that the characteristic IVCT
band considerably blue-shied, i.e. 757 / 728 nm (Fig. 2a),
indicating that it is possibly much more reduced than in the
previous case of thermal reduction of ox-Mo peroxide lms.
Moreover, the characteristic peroxo band at 367 nm vanishes
(Fig. 2a), indicating that the reduction of ox-Mo peroxide in
solution proceeds here also through the reduction of the peroxo
group. Upon thermal treatment of the red-Mo peroxide lm at
200
C, the IVCT band signicantly red-shis (i.e. 728 / 787
nm; Fig. 2b), indicating that the lm has been completely
reoxidized at T > 200
C. Analogous observations have also been
made during thermal treatment of ox/red-Mo peroxides in
solution (ESI, Fig. S1†).
2.2.2 FT-IR monitoring of ox/red-Mo peroxide lms. FT-IR
spectroscopy was performed to investigate the chemical bonds
between molybdenum, oxygen, carbon and other atoms present
in the synthesized materials and to study the structural changes
in Mo peroxide lms induced by reduction through either the
solution synthesis route or the thermal treatment of lms.
Initially, an ox-Mo peroxide lm, as obtained from the synthesis
route, presents the following peaks (spectrum (1), Fig. 3): (a) a
broad band at 2877 cm1 and a shoulder at 2930 cm1 attrib-
uted to symmetric and antisymmetric stretching vibration of
CH2 groups of PEG, respectively. (b) A strong broad band at 1099
cm1, ascribed to stretching vibration of both C–OH and C–O–C
groups of PEG.27 (c) Two strong peaks at 983 and 955 cm1,
attributed possibly to two stretching modes (symmetric and
antisymmetric) of terminal Mo]O bonds indicating the pres-
ence of a MoO2 (O]Mo]O) group similar to the one observed
in dioxomolybdenum(VI) complexes.26,28,29 (d) A strong band at
919 cm1, attributed to the stretching vibration of the peroxo
group (O–O), although slightly red-shied (10–15 cm1) in
comparison with molybdenum peroxo complexes and vana-
dium peroxo complexes reported in the literature, possibly
because of intermolecular H-bonding interactions.24,34 (e) A
weak band at 802 cm1, attributed to Mo–O–Mo bridges, indi-
cating that a small percentage of Mo–O–Mo bridges exist in
the initial Mo peroxide lm.24,26,30–33 (f) Two bands at 633 and
520 cm1, attributed possibly to symmetric and antisymmetric
stretching modes of the Mo(O2) peroxo group, respectively.
This journal is © The Royal Society of Chemistry 2014
Paper
Fig. 3 FT-IR spectra of an oxidized and a reduced Mo peroxide film
before and after annealing at 220
C: (1) ox-Mo peroxide as synthe-
sized, (2) ox-Mo peroxide after annealing at 220
C, (3) red-Mo
peroxide as synthesized, and (4) red-Mo peroxide after annealing at
220
C.
Those bands are also signicantly shied (30–40 cm1) to lower
and higher energy respectively, possibly because of intermo-
lecular H-bonding interactions of peroxo groups.34 (g) Infrared
peaks, attributed to water (ESI, Fig. S2a and b†), indicate that
coordinated water molecules mostly exist in the Mo peroxide
lm, whereas a small percentage of adsorbed water molecules is
also present. From the above FT-IR and UV-Vis results, the
structure of Mo peroxide compounds synthesised in the present
work could be written as: MoO2(O2)$H2O or, generally,
MoO3$H2O2$H2O, dispersed in PEG.18,22,24
Upon annealing an ox-Mo peroxide lm from RT to 220
C
(spectrum (2), Fig. 3) the following infrared changes are
observed: (a) almost vanishing of the PEG vibration bands at
2930, 2877, and 1099 cm1 indicating that PEG is removed upon
heating. (b) Disappearance of the peroxo group bands at 919,
633, and 520 cm1 giving clear evidence that the peroxo group is
destroyed upon thermal treatment. These results are in agree-
ment with the previous UV-Vis absorption ndings showing
that the thermal reduction of an ox-Mo peroxide lm proceeds
mainly through the reduction/destruction of the peroxo group
and that during thermal reoxidation of the lm at a higher
temperature (T > 130
C), the peroxo group does not reform. (c)
Vanishing of one of the two Mo]O stretching mode bands
(preferably the symmetric stretching mode band at 983 cm1),
resulting in the formation of a broad Mo]O stretching band
with intermediate position (967 cm1). (d) The weak band of
Mo–O–Mo bridges at 802 cm1 slowly vanishes and a very broad
band at 852 cm1 appears, indicating that Mo–O–Mo bridges
possibly form during annealing of the lm. (e) Two new bands
at 679 and 563 cm1 appear during thermal treatment possibly
coming from the corresponding bands of the peroxo group (at
633 and 520 cm1 respectively), indicating that possibly new
Mo–O–Mo bridges form as a result of peroxo groups' cleavage.
The gradual decrease of the number of Mo]O stretching bands
(from 2 to 1) in combination with the increase of Mo–O–Mo
bridges observed upon annealing of an ox-Mo peroxide lm in
This journal is © The Royal Society of Chemistry 2014
Journal of Materials Chemistry C
spectra (1) and (2) suggests progressive change in conguration
(possibly from tetrahedral to octahedral) of Mo ions up to
220
C.18,24,26 (f) Finally, the number of coordinated water
molecules in the Mo peroxide lm seems to progressively
increase, especially upon heating at a high temperature (T $
170
C; ESI, Fig. S2a and b†).35–37
Analogous structural changes to those observed during the
thermal reduction of an ox-Mo peroxide lm were also detected
in a red-Mo peroxide lm (i.e. reduced through the synthesis
route) and the IR spectra are also presented in Fig. 3. In brief, by
comparing the spectra (3) and (1) (Fig. 3), the following changes
are observed: (a) signicant decrease of the peroxo group bands
at 917, 633, and 517 cm1 and formation of two new bands at
673 and 565 cm1 indicating that the reduction in solution (red-
Mo peroxide) proceeds also through reduction/destruction of
the peroxo group, and (b) the appearance of a shoulder at 1123
cm1 indicates that PEG is affected by the reduction of Mo
peroxide in solution (possibly PEG is also oxidized in solution).
The structural changes that were observed during thermal
treatment of the red-Mo peroxide lm are also depicted in Fig. 3
(see spectrum (4) and Discussion in the ESI†). It is noteworthy
that both lms obtained at the end of thermal treatment (i.e. at
220
C) seem to be molybdenum trioxide regardless of the
initial lm that was formed (compare spectra (2) and (4), Fig. 3).
Similar results were obtained by using Raman spectroscopy
during thermal treatment of ox/red-Mo peroxide lms (ESI,
Fig. S3†). Further characterisation (crystal structure, optical
properties, surface and bulk morphology) of the above lms as a
function of annealing temperature is presented in the ESI
(Fig. S4–S7†).
2.3 Chemical structure and electronic characterization of ox/
red-Mo peroxide lms
2.3.1 Determination of stoichiometry using XPS. Next,
X-ray photoelectron spectroscopy (XPS) analysis of lms
deposited from either the oxidized or the reduced solution and
annealed at different temperatures was performed in order to
investigate the chemical composition of the outermost lm
layers. In the wide scan spectra (not shown), no appreciable
charging effects were observed and only carbon, oxygen and
molybdenum related signals were detected on the lms'
surface. The presence of carbon may be due to surface
contamination but it might be also related to incomplete
decomposition (such as PEG) of the precursor solution.
Despite the presence of contaminants, for the lms depos-
ited from the oxidized solution and heat treated at 220
C
(Fig. 4a and Table 1), the Mo 3d surface signal was typical of Mo
in the VI oxidation state. In fact, the Mo 3d5/2 and Mo 3d3/2
binding energy (BE) values at 232.7 (FWHM ¼ 1.40 eV) and
235.8 eV (FWHM ¼ 1.47 eV) can be attributed to molybdenum
cations being at the highest oxidation state (Mo6+) in accor-
dance with the literature.16,17,38–41 It is evident that in this case
the lm exists almost exclusively as MoO3. In the case of lms
deposited also from the oxidized solution and heat treated at a
lower temperature (i.e. at 170
C; Fig. 4b), the energy peaks were
lower and broader than before. The lower and broadened energy
J. Mater. Chem. C, 2014, 2, 6290–6300 | 6293
Journal of Materials Chemistry C Paper

percentage of Mo5+ cations was estimated to be 31% of the

overall Mo states, whereas no evidence for the existence of the
lowest oxidation states Mo4+ was obtained.
The O 1s peaks of the XPS spectra of the above lms are also
presented in Fig. 5. All lms present a broad peak which is
further broadened to higher BEs for those deposited from the
reduced solutions. Deconvolution of this peak allowed to
identify the presence of an intense peak at 530.8 eV, which can
be attributed to the O 1s binding energy of Mo–O bonds,16,17,40,42
and of two smaller broad peaks at 531.6 and 532.3 eV.
Regarding the origin of these peaks, they can be assigned to

Fig. 4 Mo 3d XPS spectra of (a and b) an ox-Mo peroxide film and (c

and d) a red-Mo peroxide film. The films were thermally treated at (a
and c) 220
C and (b and d) 170
C.

peaks were associated with the lower oxidation state of the Mo

cations, which tends to result in lower BE.41–44 From the
deconvolution of these peaks it was proven that a new doublet
appeared at 231.4 eV (FWHM ¼ 1.45 eV) and 234.6 eV (FWHM ¼
1.50 eV) with a spin–orbit split of 3.2 eV, which was attributed to
Mo 3d5/2 and Mo 3d3/2, respectively, of Mo cations at a lower
oxidation state (Mo5+). The percentage of the Mo5+ oxidation
state to the total Mo cations (Mo5+/Mo5+/6+) was estimated to
be 20%.
For lms deposited from the reduced (blue) solutions and
thermally treated at 220
C, the Mo 3d signal resulted more
broadened towards lower BEs (Fig. 4c), again suggesting the
presence of Mo oxidation states lower than VI. Indeed, decon-
volution of the latter spectrum allowed identifying the presence
of two distinct doublets as in the case of the ox-Mo peroxide lm
annealed at 170
C, attributed to Mo species being at 6+ and 5+
oxidation states. In that case, the percentage of Mo5+ cations
was estimated to be 27% of the overall Mo states. Finally,
when the red-Mo peroxide lm was thermally treated at 170
C
(Fig. 4d), the Mo 3d peaks were further decreased and broad- Fig. 5 O 1s XPS spectra of (a and b) an ox-Mo peroxide film and (c and
d) a red-Mo peroxide film. The films were thermally treated at (a and c)
ened evidence for further reduction of the Mo species. The
220
C and (b and d) 170
C.

Table 1 Electronic properties of ox/red-Mo peroxide films synthesized using a slightly modified sol–gel peroxo method

Mo peroxide formula Synthesized solutiona Tb (
C) Mo5+/(Mo5+/6+)c (%) Peroxo + OH/Ototald (%) WFe (eV) VBMe (eV)

MoO3 Ox 220 0 17 5.6 3.0

HxMoO2.9 Ox 170 20 21 5.3 3.0
HxMoO2.75 Red 220 27 29 5.3 3.0
HxMoO2.45 Red 170 31 42 5.2 2.7
a
Oxidized or reduced Mo peroxide in the precursor solution. b Temperature of lm thermal treatment. c Results obtained from Mo 3d XPS spectra.
d
Results obtained from O 1s XPS spectra. e Results obtained from UPS spectra.

6294 | J. Mater. Chem. C, 2014, 2, 6290–6300 This journal is © The Royal Society of Chemistry 2014
Paper
hydroxyl (–OH) and to peroxo groups, respectively, bound to Mo
atoms,42 while the former peak may have a contribution from
adsorbed water molecules. The relative intensity of this peak is
quite large and becomes larger in the lms obtained from the
reduced solution and/or heat treated at lower temperatures,
which argues against surface contamination and represents
rather strong evidence of stable Mo-peroxide bonds. From the
Mo 3d and O 1s XPS spectra the materials’ stoichiometry was
estimated and is presented in Table 1.
2.3.2 Valence band prole analysis with UPS. Next, the UPS
photoemission spectra of ox/red-Mo peroxide lms were
analyzed (Fig. 6). The UPS spectrum of an ox-Mo peroxide lm
annealed at 220
C is structureless with a single peak indicating
an amorphous (defect-free) MoO3 lm (Fig. 6a and Table 1).16,17
The valence band of MoO3 consists mainly of O 2p orbitals with
a maximum (VBM) at 3.0 eV below the Fermi level as expected
for a fully stoichiometric Mo oxide (right panel).16,17,43,44 The
high binding energy cut-off of MoO3 is 15.6 eV, corresponding
to a work function (WF) of 5.6 eV, a value which is very close to
the values reported in the literature for solution prepared MoO3
lms.15,17 Thus, the ionization energy (IE) is estimated to be
8.6 eV. When an ox-Mo peroxide lm was annealed at a lower
temperature (i.e. 170
C; Fig. 6b) the VBM was practically
constant at 3.0 eV below the Fermi level, whereas the high BE
cut-off increased (at 15.9 eV) resulting in a WF value of 5.3 eV. It
is noteworthy that in this case, the formation of a broad set of
gap states near the Fermi level, located at 2.2 eV, can be
observed. Those gap states may be attributed to intervalence
electrons transferred to the initially empty Mo 4d orbitals of the
antibonding p* band near the Fermi level during the thermal
reduction of peroxo groups.16,43 Similar results concerning the
Fig. 6 UPS photoemission spectra of (a and b) an ox-Mo peroxide film
and (c and d) a red-Mo peroxide film. The films were thermally treated
at (a and c) 220
C and (b and d) 170
C.
This journal is © The Royal Society of Chemistry 2014
Journal of Materials Chemistry C
VBM and WF (3.0 and 5.3 eV, respectively) were also obtained,
when a red-Mo peroxide lm was thermally treated at 220
C
(Fig. 6c). The only difference in that case is the signicant
increase in the density of occupied gap states located at 2.2 eV,
near the Fermi level, indicating that molybdenum oxide is
further reduced. Finally, when a red-Mo peroxide lm was
annealed at 170
C (Fig. 6d) a considerable decrease in both
VBM and WF (2.7 and 5.2 eV, respectively), accompanied by a
further increase of the density of gap states located near the
Fermi level, was observed.
2.4 Mo peroxide lms as anode interfacial layers in organic
optoelectronic devices
2.4.1 Performance of OLEDs. Aer having established a
direct correlation of the preparation conditions of the Mo
peroxide lms with their electronic structure and physical
properties, those Mo peroxide lms were employed as anode
interlayers in OLEDs. The fabricated device structure was ITO/
Mo-peroxide/F8BT (emissive layer)/PW12/Al, where PW12 is 12-
phosphotungstic acid (H3PW12O40), a polyoxometalate (POM)
previously reported by our group as a highly efficient electron
injection/extraction layer (EIL/EEL) in OLEDs and OPVs,7,45
which can be cast from alcohol-based solvents, that are
orthogonal with regard to the polymeric layer underneath.
Reference devices based on poly(3,4-ethylenedioxythio-
phene) : poly(styrene sulfonate) (PEDOT-PSS) for hole injection
were also fabricated for comparison purposes.
In Fig. 7a, the current density–voltage–luminance ( J–V–L)
and in Fig. 7b, the current efficiency–voltage characteristics for
devices with an optimized thickness of 20 nm Mo-peroxide lm
or 40 nm PEDOT-PSS as the anode interlayer and a 2 nm thin
polyoxometalate (PW12) as the cathode interlayer are shown.
The main results are summarized in Table 2. In the device based
on the ox-Mo peroxide lm (MoO3, thermally processed at
220
C), an overall low light emission (the peak luminance was
7000 cd m2 at current density equal to 1800 A m2) and device
efficiency (3.9 cd A1) is observed. Slightly higher efficiency
(4.2 cd A1) is obtained for the material processed from the
oxidized solution that was thermally treated at 170
C (namely
HxMoO2.9).
On the other hand, for the devices incorporating reduced Mo
peroxide lms, high peak current densities and luminances are
obtained. The device with the reduced HxMoO2.75 (thermally
treated at 220
C) reaches luminance values up to 34 000 cd m2
and current densities of 3200 A m2. As a result, the peak
current efficiency rises to 10.6 cd A1, representing a more than
100% improvement relative to the device with the ox-Mo
peroxide interlayer. Moreover, the device with the highest
degree of reduction and hydrogen content, namely HxMoO2.45
(i.e. red-Mo peroxide heated at 170
C), exhibits a slightly
increased performance with efficiency reaching 10.9 cd A1.
Note that the reference device with PEDOT-PSS at its anode
interface exhibits luminance values up to 9200 cd m2 and
current densities of 2300 A m2, resulting in a maximum
current efficiency of 4 cd A1.
J. Mater. Chem. C, 2014, 2, 6290–6300 | 6295
Journal of Materials Chemistry C Paper

exhibit a work function (WF) of the order of 5.2–5.6 eV which is

Fig. 7 (a) Current density–voltage (solid symbols) and luminance–
voltage (open symbols) characteristic curves of OLEDs with the
structure ITO/Mo-peroxide (20 nm) or PEDOT-PSS (40 nm)/F8BT/
PW12 (2 nm)/Al devices. (b) Current efficiency–voltage curves of the
same OLED devices. (c) Stability measurements for non-encapsulated
OLEDs based on Mo-peroxides as HILs are presented as plots of
luminance versus time of operation in air at room temperature under a
constant driving current density of 200 A m2.
The efficiency enhancement of the devices using Mo-perox-
ides, and especially the reduced ones at the anode interface, can
be explained as follows: as discussed above these materials
sufficient enough to reduce the barrier for hole injection from
the metallic anode to the organic active layer (namely F8BT
having an ionization energy IE in the order of 5.0 eV)16 through
the formation of an interfacial dipole with its positive pole
pointing towards the anode contact.8 However, WF alone cannot
explain the efficiency enhancement. For instance, the device
based on ox-MoO3 with the higher WF values exhibits poor
performance in comparison with the devices based on red-Mo
peroxides. To explain this, we have to take into account that
fully stoichiometric metal oxides are wide band-gap semi-
conductors, adding a large series resistance to the device. In
contrast, the red-Mo peroxides exhibit occupied gap states near
the energy level of the highest occupied molecular orbital
(HOMO) of the active layer and thus may facilitate hole trans-
port. The increased performance of devices based on the red-Mo
peroxides may thus be attributed to the large density of occu-
pied gap states near their Fermi level.
Furthermore, the stability of the devices operating in air was
tested in a period of 700 hours. Fig. 7c depicts that all the Mo
peroxide lm-based devices showed better stability when
compared with the device using a PEDOT-PSS layer for hole
injection. This is a very promising result, making those mate-
rials attractive candidates for future industrial implementation,
since the temporal stability is an important issue in organic
optoelectronic devices.
2.4.2 Hole only devices. For an in-depth understanding on
how the Mo-peroxide’s chemical composition affects the device
operation and supports our argument about the enhanced hole
transport within the device, we next fabricated hole only
devices. To this end, we replaced the PW12/Al cathode with a
simple Au electrode, which causes a large barrier for electron
injection/extraction to/from the LUMO of F8BT from/to the
electrode. Therefore, the resulting current is expected to be
dominated by holes. In Fig. 8, the corresponding dark J–V
characteristics of devices with the structure ITO (anode)/Mo-
peroxide (20 nm) or PEDOT-PSS (40 nm)/F8BT (70 nm)/Au
(cathode) are shown in a semi-log scale. From the J–V charac-
teristics, it is evident that the hole current density for the
devices with the red-Mo peroxide layers is about one order of
magnitude higher than the corresponding current in the
devices with either the ox-Mo peroxide or the PEDOT-PSS layer.
Most signicantly, the devices with the red-Mo peroxide layers
show space-charge limited current (SCLC) behaviour, as veried
by the overlap of the experimental data with the calculated J–V
characteristics using the equation J ¼ 93o3rmV2/8L3 (where J is

Table 2 Device characteristics (and statistics obtained from a batch of 24 devices) of OLEDs having the structure ITO/Mo-peroxide or PEDOT-
PSS (HIL)/F8BT/PW12 (EIL)/Al

Anode interfacial Vturn-on (V) Max. current efficiency

layer (at 10 cd m2) Jmax (A m2) Lmax (cd m2) (cd A1) [at voltage]

MoO3 2.7 1800 (0.5) 7000 (0.5) 3.9 (0.2) (5.0 V)

HxMoO2.9 2.6 2500 (0.5) 10 500 (0.5) 4.2 (0.2) (5.0 V)
HxMoO2.75 2.6 3200 (0.5) 34 000 (0.5) 10.6 (0.2) (4.5 V)
HxMoO2.45 2.6 3400 (0.5) 37 000 (0.5) 10.9 (0.2) (4.5 V)
PEDOT-PSS 2.6 2300 (0.5) 9200 (0.5) 4.0 (0.2) (4.5 V)

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Paper Journal of Materials Chemistry C

Fig. 8 Current density–voltage (J–V) curves of hole only devices ITO/

Mo-peroxide (20 nm) or PEDOT-PSS (40 nm)/F8BT (70 nm)/Au
(cathode). The SCLC was also calculated.

the current density, V is the applied voltage, 3o3r is the dielectric

permittivity, m is the carrier mobility, and L is the thickness of
the F8BT active layer) of the SCLC model at low applied voltages.
From Fig. 8, it can also be seen that the hole mobility is
increased in devices with the red-Mo peroxide layers. The
formation of an ohmic contact at the anode interface, which
highly facilitates hole injection/transport, can also be deduced
and attributed to the energy level alignment due to both the
formation of a favourable interfacial dipole and the occupation
of gap states near the device Fermi level.
2.4.3 Performance of OPVs. To further highlight the impact
of the above ndings on the operation of organic electronic
devices, OPV cells incorporating ox/red-Mo peroxide layers as
hole-selective interlayers were fabricated. The device architec- Fig. 9 (a) Photocurrent–voltage and (b) dark current–voltage (J–V)
ture was ITO/Mo-peroxide (20 nm)/active layer (100 nm)/PW12 curves of organic cells with the structure ITO/Mo-peroxide (20 nm)/
(5 nm)/Al. The active layer was based on the bulk heterojunction P3HT:PC71BM (100 nm)/PW12 (5 nm)/Al. (c) The IPCEs of the same
devices.
blend of the P3HT polymer donor and the PC71BM fullerene
acceptor.46 In Fig. 9a, the current density versus voltage ( J–V)
characteristics of the OPV devices under AM 1.5G illumination
processed from the reduced solution exhibits a larger turn-on
are presented. It is evident that the incorporation of Mo
voltage (in the range of 0.55–0.65 V) relative to that with the
peroxide layers induces large improvement in short-circuit
Mo peroxide layers processed from the oxidized solution (0.45–
current density (Jsc) from 8.3 mA cm2 for the devices with the
0.55 V). This implies that the built-in potential (Vbi) across the
ox-MoO3 anode interlayer to 10.2 and 10.4 mA cm2 (25%
device, which is the voltage responsible for exciton dissociation
improvement) for the devices with the reduced HxMoO2.75 and
and the upper limit for the attainable Voc, is increased upon the
HxMoO2.45 peroxide layers, respectively (the maximum recorded
insertion of the Mo peroxide layer. In addition, a large increase
and mean values of devices' operational characteristics are
of the diode forward current and a small suppression of the
summarized in Table 3). Similarly, the ll factor (FF) is
reverse current aer the incorporation of the Mo peroxide lms
improved from 0.52 to a maximum of 0.58 and the open-circuit
are observed. This proves that the introduction of these layers
voltage (Voc) increases from 0.59 V to 0.66 V in the devices with
creates a highly conductive path for hole-extraction, which can
the reduced Mo-peroxide layers. As a consequence, a high PCE
also explain the enhanced FF of these devices.
of 3.9% and slightly higher of 4.0% was estimated for the
Fig. 9c compares the incident photon-to-current collection
devices based on the reduced HxMoO2.75 and HxMoO2.45
efficiency (IPCE) spectra of the above devices. The devices with
peroxides, respectively. Again, the devices with the red-Mo
the MoO3 and HxMoO2.9 layers show the typical spectral
peroxide lms exhibit the largest increase in performance,
response of P3HT:PC71BM blends with a maximum IPCE of
probably due to the increase of the density of occupied gap
57% and 59%, respectively, which are consistent with previous
states, as discussed above.
studies for P3HT:PC71BM devices exhibiting similar short-
The above ndings are further supported by the dark current
circuit currents and overall external quantum efficiencies.46 For
versus voltage characteristics presented in Fig. 9b. It can be
the devices with the reduced HxMoO2.75 and HxMoO2.45 inter-
clearly seen that the device with the Mo peroxide layers
layers, the results demonstrate an enhancement of 25%

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Journal of Materials Chemistry C
Table 3 Device characteristics of P3HT:PC71BM OPV cells with the structure ITO/Mo-peroxide/P3HT:PC71BM/PW12/Ala
Anode interfacial layer Jsc (mA cm2) Voc (V)
MoO3 8.3 (7.95  0.25) 0.59
HxMoO2.9 8.8 (8.61  0.2) 0.63
HxMoO2.75 10.2 (10.14  0.10) 0.66
HxMoO2.45 10.4 (10.32  0.16) 0.66
a
Data and statistics based on 24 cells of each type. Numbers in bold are the maximum recorded values.
(reaching maximum values of 78% at the wavelength of 510
nm in both cases) in the IPCE over the entire spectral region,
where the photoactive layer absorbs. These values are correlated
with the corresponding enhancements in short-circuit currents
measured in the red-Mo peroxide based devices relatively to the
ox-Mo peroxide based device. The increased IPCEs in the devices
incorporating such red-Mo peroxide layers are mainly attributed
to corresponding enhanced extraction rates through the occu-
pied gap states of those layers, which are not present in the ox-
Mo peroxide. Thus, it is evident that a direct correlation between
the Mo peroxide composition/electronic structure and the
device performance can be accomplished.
3. Conclusions
Reduced molybdenum peroxide lms with varying reduction
degrees were synthesized using a modied sol–gel peroxo
method with the critical steps being the addition of an appro-
priate amount of 2-methoxy ethanol to the precursor solution
and the annealing of deposited lms in a broad temperature
range. Those lms were then characterized in detail and nally
used as anode interfacial layers in organic optoelectronics
applications, such as F8BT based-OLEDs and OPVs based on
P3HT:PC71BM as the photoactive layer. From spectroscopic
measurements it was found that the reduction of molybdenum
peroxides both in solution (during the synthesis route aer the
addition of an excess of alcohol) and in lms (during annealing)
proceeds mainly through the reduction of the peroxo group. The
gradual removal of PEG during the thermal treatment of the Mo
peroxide lms was also evidenced. The chemical composition of
the surface of each Mo peroxide lm was determined by XPS
based on Mo 3d and O 1s core level spectra and showed that a
higher degree of reduction can be obtained through the addi-
tion of an appropriate amount of alcohol during synthesis,
whereas ne tuning of the stoichiometry can be made by
decreasing the lm annealing temperature. Finally, it was found
that when solution-reduced Mo peroxide lms were used as
anode interfacial layers, a signicant improvement of OLED
and OPV device characteristics was achieved. This is due to the
enhancement in charge transport induced by the occupation of
gap states in the reduced Mo peroxide lms.
4. Experimental
4.1 Materials
4.1.1 Synthesis of ox/red-molybdenum peroxide lms. Ox/
red molybdenum peroxide lms were synthesized by modifying
6298 | J. Mater. Chem. C, 2014, 2, 6290–6300
Paper
FF PCE (%) Rs (U cm2)
(0.57  0.02) 0.52 (0.51  0.026) 2.6 (2.4  0.18) 18
(0.61  0.02) 0.55 (0.54  0.021) 3.1 (3.0  0.14) 15
(0.65  0.01) 0.58 (0.58  0.014) 3.9 (3.8  0.11) 5
(0.65  0.01) 0.58 (0.57  0.014) 4.0 (3.9  0.13) 4
the sol–gel peroxo route proposed by Lin.13 In detail, 3 g of
molybdenum oxide powder (99%, Panreac) was dissolved in
20 mL of hydrogen peroxide (H2O2, 31%, Merck). The solution
was reuxed at 80
C for 2 h and then cooled to room temper-
ature (RT) for 24 h. The MoO3 powder was completely dissolved
and a clear yellow solution was obtained. Subsequently, poly-
ethylene glycol (PEG, Mn 400, Merck) was added in a varying
volume ratio of MoO3-sol : PEG (optimal ratio, 1 : 0.25) in order
to improve the lm forming properties due to better homoge-
neity of the resultant solution. The solution was reuxed at 70
C
for 0.5 h and then cooled to RT. Next, 2-methoxyethanol (2ME,
98%, Ferak Berlin) was added in a varying volume ratio of MoO3-
sol : 2ME (1 : 1, 1 : 2, 1 : 3, 1 : 4, and 1 : 6; optimal ratio: 1 : 3),
the solution was reuxed at 60
C for 0.5 h and then cooled to
RT. The resultant solutions displayed intense blue colour for
increased contents of 2ME aer having evaporated the excess of
H2O2. The molybdenum peroxide solutions were spin coated on
the substrate at a spinning rate of 1500–6000 rpm for 40 s giving
approximately 20–200 nm thick lms (optimal thickness for
device operation is approximately 20 nm). Prior to that step, spin
coating of 2ME (at 6000 rpm) was found to improve adhesion
and quality of Mo peroxide lms. Coated Mo peroxide lms were
heated on a hot plate at 60–360
C for 5–15 min. The heat
treatment was performed in air since there was no indication
that oxygen affects the reduction of Mo compounds.
4.2 Device fabrication
For both OLED and OPV fabrication, glass/indium tin oxide
(ITO) substrates (20 U cm1) were used as anode electrodes. The
substrates were ultrasonically cleaned with a sequence of
solutions/solvents (0.026 M aqueous solution of tetramethyl-
ammonium hydroxide (TMAH), water, acetone, and isopropyl
alcohol, for 15 min each). In OLEDs, on top of the ox/red-Mo
peroxide lm, a 70 nm thick emissive layer (EML) of the green-
emitting copolymer, poly[(9,9-dioctyluorenyl-2,7-diyl)-co-1,4-
benzo-{2,1,3}-thiadiazole] (F8BT, American Dye Source) was
spin coated from a chloroform solution (6 mg mL1) and
thermally treated at 80
C for 10 min. Then, a thin electron
injection/transport layer (EIL/ETL) of polyoxometalate (POM,
12-tungstophosphoric acid, H3PW12O40, Sigma-Aldrich) was
spin-coated from a methanol solution (10 mg mL1). Subse-
quently, a 150 nm thick Al cathode layer was deposited in a
dedicated thermal evaporator under a high vacuum of 106
Torr. Reference devices were also prepared with poly(3,4-ethyl-
enedioxythiophene) : poly(styrene sulfonate) (PEDOT-PSS, Her-
aus) as anode interfacial layer. The active area of the fabricated
This journal is © The Royal Society of Chemistry 2014
Paper Journal of Materials Chemistry C

devices was 0.1256 cm2. In OPVs, the active layer was a 100 nm unit. Luminance and electroluminescence (EL) spectral char-
thick lm of a blend (1 : 0.8 wt% ratio) of poly(3-hexyl thio- acteristics were recorded with an Ocean Optics USB 2000 ber
phene-2,5-diyl) (P3HT, 98% RR, Mw 54 000–75 000, Rieke optic spectrophotometer, assuming a Lambertian emission
Metals) and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM, prole (for luminance measurements). For the stability
Sigma-Aldrich), spin-coated from a chloroform solution (10 mg measurements the devices were stored in nitrogen between
mL1) and annealed at 135
C for 10 min. measurements. Current density–voltage characteristics of the
fabricated solar cells were measured with a Keithley 2400
4.3 Methods source-measure unit. Cells were illuminated with a Xe lamp and
an AM 1.5G lter to simulate solar light illumination conditions
4.3.1 Spectroscopic methods. UV-Vis absorption spectra of
with an intensity of 100 mW cm2 (1 sun), as was recorded with
(ox/red) molybdenum peroxides in solution and lms, along
a calibrated silicon photodiode. Incident photon-to-current
with polymer lms, were obtained on quartz cuvettes (with 1 cm
efficiencies (IPCE) were measured on an Autolab PGSTAT-30
path length) and quartz slides (2  2 cm2), respectively, using a
potentiostat, using a 300 W Xe lamp in combination with an
Perkin-Elmer UV-Vis Lambda 40 spectrophotometer. FT-IR
Oriel 1/8 monochromator for dispersing the light in an area of
transmittance spectra of Mo peroxide lms were obtained on
0.5 cm2. A Thorlabs silicon photodiode was used for the cali-
silicon wafers (at 4 cm1 resolution and 128 scans) using a
bration of the IPCE spectra. Film preparation and device
Bruker Tensor 27 FT-IR spectrometer with a DTGS detector.
measurements were performed in air.
Chemical analysis of all Mo peroxide lms was performed by
XPS measurements in an ultra-high vacuum VG ESCALAB210.
The spectra were obtained aer excitation using Mg Ka (1253.6 Acknowledgements
eV) radiation of a twin anode in a constant analyzer energy mode
This research was co-nanced by the European Union (Euro-
with a pass energy of 30 eV. All binding energies were referred to
pean Social Fund – ESF) and Greek national funds through the
the C 1s peak at 284.8 eV and to the O 1s peak at 530.2 eV of the
Operational Program “Education and Lifelong Learning” of the
surface adventitious carbon and oxygen, respectively. The Mo-
National Strategic Reference Framework (NSRF) – Research
peroxides' stoichiometry was estimated using the XPS-measured
Funding Program: ARCHIMEDES III. Investing in knowledge
Mo 3d core levels, respectively, and the corresponding O 1s core-
society through the European Social Fund.
level spectra. To this extent, the areas under the photoemission
peaks were integrated by tting the O 1s and Mo 3d spectra with
asymmetric Gaussian–Lorentzian curves. The peroxo and –OH References
groups versus total oxygen content were estimated by tting the
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