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Jens Meyer , * Rebecca Khalandovsky , Patrick Grrn , and Antoine Kahn
MoO
3
Films Spin-Coated from a Nanoparticle Suspension
for Efcient Hole-Injection in Organic Electronics
Dr. J. Meyer , R. Khalandovsky , Dr. P. Grrn , Prof. A. Kahn
Department of Electrical Engineering
Princeton University
Princeton, NJ 08544, USA
E-mail: jensm@princeton.edu
DOI: 10.1002/adma.201003065
Signicant advances in organic electronic devices such as
organic light-emitting diodes or organic photovoltaic cells
(OPV) have occurred in the last two decades, due in part to
tailored organic molecules, novel device concepts and more
cost effective deposition techniques.
[

13

]
Indium tin oxide
(ITO) has been an ubiquitous electrode material for these
devices in view of its high transparency and large conductivity.
However, a direct hole-injection (extraction) from ITO in most
organic transport material is inefcient because of a signi-
cant energetic mismatch at the interface. High operating volt-
ages are needed to overcome the injection barrier, resulting
in reduced efciency. Therefore, various hole-injection layers
(HIL) are being used to circumvent this issue and provide a
bridge between different material transport levels. A widely
used HIL is polyethylene dioxythiophene:polystyrene sulfonate
(PEDOT:PSS).
[

4

,

5

]
However, the aqueous PEDOT:PSS disper-
sion can cause degradation due to the presence of moisture,
leading to reduced device lifetime.
[

6

]
The acidic nature of the
materials is also an issue.
[

7

]
Moreover, PEDOT:PSS exhibits
a work function (5.05.1 eV) that can limit charge injection
into materials with large ionization energy. A promising alterna-
tive is offered by transition metal-oxides such as molybdenum-,
nickel-, rhenium-, vanadium- or tungsten-oxides (MoO
3,

NiO, ReO
3
, V
2
O
5
, and WO
3
).
[

813

]
MoO
3
and WO
3
in par-
ticular exhibit remarkably deep lying electronic states and
are strongly n-doped by oxygen vacancies.
[

14

]
The electron
afnity (EA), work function (WF) and ionization energy (IE) of
vacuum-grown MoO
3
were found to be 6.7 eV, 6.9 eV and
9.7 eV, respectively
[

14

]
. Efcient hole-injection into organic
materials with deep-lying HOMO levels was demonstrated
from an ITO electrode covered with a MoO
3
or WO
3
HIL. Sim-
plied device structures consisting only of one or two organic
layers can therefore be realized.
[

9

,

15

]
In addition, long lifetimes
of metal-oxide based devices have been reported.
[

16

]
Of impor-
tance for this study is also the fact that MoO
3
and WO
3
are
stable against energetic particle bombardment emerging in
plasma processes, and can therefore act as a protection layer
for organic materials.
[

1719

]

The unique energetics of WO
3
and MoO
3
mentioned above
have so far been accessible only for lms thermally evaporated
under vacuum, which is a drawback in terms of low-cost, large-
area manufacturing processing. Here we report on MoO
3
lms
spin-coated from a suspension of nanoparticles (NP), which
offers energetics nearly identical to those of thermally evapo-
rated MoO
3
lms. To prevent agglomeration due to van der
Waals interactions and facilitate the formation of homogeneous
lms, the NPs are dressed with a polymeric dispersing agent.
However, this protective polymer shell also shields the NP and
their electronic properties, preventing the lm to act as a HIL
in a device. We demonstrate that the dispersing agent can be
fully removed by a short O
2
-plasma treatment, allowing the for-
mation of homogenous, neat MoO
3
thin lms with interesting
electronic properties. Device studies show that the spin-coated
MoO
3
lms feature electronic properties identical to those of
their thermally evaporated counterparts, and improved proper-
ties compared to PEDOT:PSS. The concept introduced here is
efcient and easy to implement, and therefore applicable for
low-cost manufacturing processes.
Our MoO
3
lms are spin-coated on ITO from a suspension
containing 2.5 wt% of crystalline MoO
3
NP and 1 wt% of a
block copolymer dispersing agent in xylene. Note that the initial
presence of the dispersing agent is essential to the formation
of homogenous lms.
[

20

]
The mean size of the NPs is 15 nm.
O
2
-plasma treatment is a well-established technique to clean
the surface of transparent conducting oxides and modify their
work function. Here the MoO
3
lms are treated for 1 min in
a 200 W/0.2 Torr O
2
-plasma. On the non-treated lms, X-ray
photoemission spectroscopy (XPS) shows the O 1s, Mo 3d and
C 1s peaks that are characteristic of the MoO
3
NP dressed with
the dispersing agent ( Figure 1a ). Following O
2
-plasma treat-
ment, the C 1s peak is nearly completely eliminated and the
O 1s and Mo 3d peaks are more intense, indicating that the
process effectively removes the block copolymer from the NPs
and leads to a nearly neat MoO
3
layer. Two additional peaks
corresponding to the In 3d and Mo 3p core levels arise after
O
2
-plasma treatment. The In peak corresponds to the ITO sub-
strate. The inuence of the MoO
3
thickness and roughness is
discussed later in this article. The Mo 3p core level centered
at 398.1 eV corresponds to a nearly stoichiometric MoO
3
lm
composition.
[

21

]
This is conrmed by the more intense Mo 3d
core level shown in Figure 1b . The maximum peak intensity of
the Mo 3d 5/2 component is found at 232.5 eV, identical to the
value found for vacuum evaporated MoO
3
.
[

22

]
Moreover, the Mo
3d peaks from the as-deposited and O
2
-plasma treated MoO
3

lms are identical and can be tted by two GaussianLorentzian
curves. Thus, the plasma process does not, in rst approxima-
tion, change the stoichiometry of the spin-coated MoO
3
lms.
The 0.2 eV core level shift toward lower binding energies after
O
2
-treatment is due to the elimination of the dispersing agent
and the concomitant enhanced electronic coupling to the sub-
strate and small charge transfer from ITO to the high work
function oxide lm.
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The photoemission onset is shown in the left panel, while the
center panel displays the magnied spectra of the density of
states near the oxide valence band edge. Vertical lines mark the
photoemission onset and valence band edge The comparison
of spectra of sMoO
3
with published data on evaporated MoO
3

(eMoO
3
) demonstrates that the lms offer the same electronic
states with a distinct peak near the valence band edge and two
very low features around 6.5 eV and 9 eV, respectively.
[

23

,

25

]

The photoemission onset of non-annealed sMoO
3
is found at
15.8 eV, which corresponds to a WF of 5.4 eV. Annealing shifts
the onset towards higher binding energies, indicating a WF
increase to 5.6 eV and 6.0 eV for 100 C and 200 C, respec-
tively. At the same time the valence band edge shifts slightly
to higher binding energy. The IE of the 200 C annealed lm
is found to be 8.9 eV. The conduction band edge, measured via
IPES, shifts toward E
F
upon annealing to 200 C, as depicted
in the right panel of Figure 2 , leading to an electron afnity of
5.8 eV.
The energy levels of eMoO
3
and sMoO
3
before and after
annealing are compared in Figure 3 . The solution-processed
samples were exposed to air for a short time. As mentioned
earlier, air exposure affects the position of the vacuum level,
and thus IE, EA and WF. Hence, to accomplish a meaningful
comparison, eMoO
3
was also exposed to air for 3 min. Even
without annealing, sMoO
3
exhibits energetics very similar to
In the following, the solution-based MoO
3
lms post-treated
by an O
2
-plasma process are denoted as sMoO
3
. It is impor-
tant to note that these sMoO
3
samples were transferred in air
from the O
2
-plasma chamber to an ultra-high vacuum analysis
chamber. It has been reported that the energetics of thermally
evaporated MoO
3
lms are affected by air exposure.
[

23

,

24

]
A
3 min ambient exposure reduces the WF, EA and IE by about
1 eV with respect to the freshly evaporated lm,
[

23

]
though the
material remains strongly n-doped and the Fermi level (E
F
)
remains very close to the conduction band minimum. The
decrease in WF, EA and IE is therefore purely a surface effect,
i.e. lowering of the vacuum level due to adsorption of adventi-
tious species.
The UPS spectra of sMoO
3
before and after annealing
in UHV for 1 h at 100 C and 200 C, are given in Figure 2 .
Figure 1 . Photoemission (XPS) spectra of solution-based MoO
3
lms
taken before and after O
2
-plasma treatment. (a) Full scans indicating
a vanishing C 1s core level peak after O
2
-plasma treatment. (b) Mo
3d core level shifts towards lower binding energy when O
2
-plasma
treated.
Figure 2 . UPS and IPES spectra of a sMoO
3
lm measured at room
temperature (RT), and after heating to 100 C and 200 C, respectively.
Photoemission onset (left), magnied section of the evolution of the den-
sity of states near the oxide valence band edge (center) and conduction
band edge (right).
Figure 3 . Energy levels of solution-based MoO
3
(left), vacuum evapo-
rated MoO
3
(center) and solution-based MoO
3
after annealing to 200 C
(right). All samples were air-exposed for a short time before measuring.
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the injection properties of annealed sMoO
3
layers were investi-
gated as well. As discussed earlier, the energetics of air-exposed
sMoO
3
can be improved by annealing, leading to values of
WF, EA and IE that are comparable to those of vacuum-grown,
non-exposed MoO
3
surfaces. The IV characteristics of 100 C
and 200 C annealed sMoO
3
(Figure 4b ) show nearly identical
hole-injection properties compared to a non-annealed HIL.
Thus, even without annealing, sMoO
3
produces a very low
interface barrier with TFB and an efcient hole-injection. Like-
wise, it was reported that a short contamination by air exposure
of an eMoO
3
lm does not signicantly affect its hole-injection
property.
[

23

]

In summary, we demonstrated that MoO
3
lms formed by
spin-coating of nanoparticles in suspension possess electronic
properties comparable to those achieved via vacuum thermal
evaporation. Following spin-coating, the dispersing agent
that protects the nanoparticle is easily removed by a short
O
2
-plasma treatment, forming a neat homogenous MoO
3
layer.
eMoO
3
. The main difference consists in a slightly larger energy
difference between E
F
and the CB edge, and a lower vacuum
level. Annealing eliminates this difference and raises the
vacuum level. The band gaps of eMoO
3
and sMoO
3
are found
equal to 3.1 eV, with E
F
about 0.2 eV below CB. The vacuum
level of annealed sMoO
3
is even 0.3 eV higher than that of
eMoO
3
, and therefore closer to the original position found on
freshly vacuum evaporated MoO
3
. These details clearly show
that adsorbates are responsible for the original difference in
energetics. It is important to stress that sMoO
3
, like vacuum-
deposited MoO
3
, is a strongly n-type doped metal-oxide. Even
though XPS shows nearly stoichiometric lms, a relatively small
density of oxygen vacancies, which is below the experimental
resolution of the measurement, causes the n-type doping.
Atomic force microscopy (AFM) of a sMoO
3
and neat ITO
substrate (provided as support information) shows that the
solution-processing leads to a homogenous lm on ITO. The
mean crystallite size is less than 40 nm, however, some larger
clusters of around 100 nm can also be observed. The lm rough-
ness depends on various parameters, such as the substrate
surface preparation, the spin-speed and the MoO
3
NP concen-
tration. A detailed study is in progress and will be reported
elsewhere. In the present study, non-optimized sMoO
3
lms
with an average RMS roughness of around 25 nm are used.
As shown below, this is not a limiting factor for testing hole
injection in simple organic devices, and the hole-injection ef-
ciency afforded by these lms is identical to that achieved with
their thermally evaporated counterpart. Note that the thickness
of the sMoO
3
lms is limited by the NP size, which averages
15 nm in diameter. Thus, layer thicknesses of less than 40 nm
are not easily accessible.
Current-voltage ( IV) characteristics of hole-only devices
are shown in Figure 4 . The device structure consists of an
ITO bottom electrode, three different HILs, namely sMoO
3
,
eMoO
3
and PEDOT:PSS, all 40 nm in thickness, a 100 nm
thick spin-coated layer of poly(9,9 -dioctyluorene-co-bis- N , N -
(4-butylphenyl)diphenylamine) (TFB) and a top electrode
formed by a Hg-droplet probe station. TFB is a polymer with
IE = 5.5 eV,
[

26

]
and the hole-current injected from ITO (here
WF = 4.3 eV) is strongly injection-limited (Figure 4 ). The IV
characteristics show that the hole-injection is signicantly
improved when using one of the HILs. For both sMoO
3
and
eMoO
3
, very efcient and nearly identical hole-injection proper-
ties can be observed, allowing for high current-densities at low
bias voltage. This derives from the formation of a small energy
barrier between the oxide conduction band and the HOMO of
TFB. As demonstrated previously,
[

25

]
hole injection proceeds
via electron extraction from the organic HOMO through the
oxide CB. In comparison, the PEDOT:PSS layer shows about
the same hole-injection onset voltage of 0.6 V, however, the IV
characteristic shifts to a linear slope at higher current densities.
Fong et al. reported on the limiting hole-injection properties
of PEDOT:PSS into TFB with increasing electric eld,
[

27

]
and
speculated that ohmic losses in PEDOT:PSS affect the injec-
tion in materials with high mobility such as TFB. Another
important factor that emerges from Figure 4a is the very low
leakage-current below the onset voltage of the sMoO
3
device.
Hence, even the relatively rough sMoO
3
layer (as compared to
PEDOT:PSS) does not affect the device performance. Finally,
Figure 4 . Current density-voltage characteristics of hole-only devices.
Holes are injected from ITO electrode. (a) Comparison of different hole-
injection layers. (b) sMoO
3
measured before and after post-treatment at
100 C and 200 C, respectively.
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Device studies conrm that spin-coated MoO
3
lms provide
the same hole-injection efciency as thermally evaporated
MoO
3
, and improved properties compared to PEDOT:PSS.
This new concept is efcient and easy to implement at the
same time, which is important for low-cost manufacturing
processing.
Experimental Section
ITO substrates were cleaned by sonication in acetone and methanol
followed by exposure to UV ozone for 30 min. The MoO
3
suspension
(5 wt%, surfactant stabilized by an undisclosed block copolymer),
developed by Nanograde GmbH (Product No. 3007), was dispensed
on ITO using a syringe with a 0.45 m PTFE lter. Pre-screening
studies conducted by Kelvin-Probe and AFM showed that a diluted
MoO
3
suspension of 2.5 wt% spun in N
2
at 5000 rpm for 40 sec forms
homogenous 40 nm lms. The samples were then baked in N
2
at
100 C for 10 min on a hot plate. To remove the dispersing agent,
the samples were treated in an O
2
-plasma (1 min, 200 W, 0.2 Torr,
gas ow 40 sccm) generated in a reactive-ion etching system. For
photoemission spectroscopy the samples were transferred in air
to an analysis chamber ( < 10
10
Torr). UPS was done with both He I
(21.22 eV) and He II (40.8 eV) radiation lines from a discharge lamp,
with an experimental resolution of 0.15 eV. IPES was carried out in
the isochromat mode, with a resolution of 0.45 eV. XPS was done
with the Al K (1486.6 eV) photon line with a spectral resolution of
0.8 eV.
The IV measurements were done with a Hg-probe station in a N
2
-
atmosphere. The Hg-probe droplet size was carefully measured with
a microscope camera. The average physical contact area was around
0.75 mm
2
. The devices comprised MoO
3
either thermally evaporated in a
UHV growth chamber (10
9
Torr) from a temperature-controlled Knudsen
cell or spin-coated from solution, followed by various treatments, as
described in the text. PEDOT:PSS ( Baytron P VP CH 8000 ) was rst
ltered (0.45 m PEET), then spun at 3000 rpm for 80 sec and nally
baked at 180 C for 45 min. TFB was dissolved in p-xylene (25.9 mg/cc).
The solution was dispensed on the substrate using a 0.45 m PTFE
lter and spun at 3000 rpm for 40 sec. The samples were then baked at
130 C for 10 min on a hot plate. This procedure led to TFB lms about
100 nm thick.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This work was supported by the Ofce of Science DOE Energy Frontier
Research Center for Interface Science: Solar Electric Materials (DE-
SC0001084), the National Science Foundation (Grant No. DMR-1005892)
and the Princeton MRSEC of the NSF (Grant No. DMR-0819860). P.G.
thanks the Alexander von Humboldt-Foundation for a Feodor Lynen
Fellowship. J.M. acknowledges the Deutsche Forschungsgemeinschaft
(DFG) for generous support within the postdoctoral fellowship program.
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Revised: September 16, 2010
Published online: October 26, 2010