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12784 J. Phys. Chem.

C 2010, 114, 1278412791

Surface Treatment of CdSe Nanoparticles for Application in Hybrid Solar Cells: The Effect
of Multiple Ligand Exchange with Pyridine

Irina Lokteva, Nikolay Radychev, Florian Witt, Holger Borchert, Jurgen Parisi, and
Joanna Kolny-Olesiak*
Energy and Semiconductor Research Laboratory, Department of Physics, UniVersity of Oldenburg,
Carl-Von-Ossietzky-Strasse 9-11, 26129 Oldenburg, Germany
ReceiVed: April 13, 2010; ReVised Manuscript ReceiVed: June 15, 2010

Colloidal CdSe quantum dots (QDs) are suitable as electron acceptors in polymer/nanoparticle bulk
heterojunction hybrid solar cells. For this application, a thick organic ligand shell which is typically surrounding
the QDs after synthesis needs to be removed. Ligand exchange with pyridine is the most widely used method
for this purpose. Although this approach is already 15 years old, detailed studies on the effectiveness of
ligand exchange with pyridine for solar cell applications are still missing. In the present work hybrid solar
cells were prepared from CdSe QDs initially capped with oleic acid (OA), and the impact of single and
multiple pyridine treatment was thoroughly investigated. NMR was applied to determine the composition of
the ligand shell as well as to distinguish the bound and free ligands before and after ligand exchange. It is
shown that after a single pyridine treatment some amount of OA is still present in the samples. By using
thermal gravimetric analysis (TGA) we could obtain also quantitative information about the effectiveness of
subsequent pyridine treatments. In a series of one-, two-, and threefold ligand exchange, the estimated surface
coverage by OA decreased from 26% to 12%, whereas that of pyridine increased from 54% to 80%. Laboratory
solar cells with pyridine-capped CdSe QDs and poly(3-hexylthiophene) (P3HT) were characterized by
current-voltage (I-V) measurements, and in order to get deeper insight into charge carrier generation and
recombination processes, CdSe/P3HT blends were studied by light-induced electron spin resonance (l-ESR).
Although repeated pyridine treatment was found to have a beneficial effect in the sense that more complete
ligand exchange was achieved, which in turn enabled more efficient charge transfer, the performance of the
solar cells was found to be reduced. This fact correlates with increased aggregation tendency of repeatedly
pyridine-treated particles, negatively influencing the morphology of the blends, as well as with a larger amount
of surface defects in particles stabilized by the weak pyridine ligand shell.

Introduction original ligands when it is used in excess. Surprisingly, although


the ligand exchange is essentially important for solar cell
Presently, CdSe nanocrystals are one of the most intensively applications, the question of its effectiveness and impact on the
studied systems for ligand chemistry and can be prepared in a
solar cell performance has not been studied in enough detail
high quality by using the colloidal synthesis with different
yet. There are a few reports showing that a single pyridine
organic ligands.1-6 The choice of the ligands for the synthesis
treatment is not able to replace entirely the original ligand shell
is crucial to obtain samples with a narrow size distribution and
of CdSe quantum dots (QDs) capped with tributylphosphine or
to control the shape of the nanocrystals.7-10 Fatty acids, long-
trioctylphosphine and trioctylphosphine oxide (TBP/TOPO or
chain amines, phosphines, and phosphonic acids turned out to
be suitable ligands allowing controlling the structural properties TOP/TOPO).26,27 In these cases even after repeating the treat-
of nanocrystals. However, in many cases these ligands of as- ment several times 10-15% of original ligands can be found
synthesized CdSe nanoparticles are not suitable for their further on the surface. A detailed analysis of the surface conducted in
application and a modification of the surface properties is the Bawendi group revealed that the species remaining on the
required.11-14 By ligand exchange solubility of the nanoparticles surface are TOPO or TOPSe molecules, probably occupying
in special solvents can be obtained,15,16 new functional groups bridging positions over several Cd atoms.27 Carboxylic acids
can be introduced onto the surface,17 or the thickness of the being weaker ligands than TOPO,28 one could expect the ligand
ligand shell can be reduced. An exchange of the original ligand exchange with pyridine to be possible more easily in the case
shell by smaller molecules is especially important for applica- of oleic acid (OA)-stabilized NPs. However, detailed studies
tions based on charge transfer between nanoparticles, since long of the ligand exchange of OA-capped CdSe NPs with pyridine
carbon chains bound to the surface of nanoparticles form a are missing so far. Furthermore, it is still unexplored how
barrier to charge carriers.18,19 multiple pyridine treatments influence the stability of the
For many applications, e.g., photovoltaics, exchange of the colloids, the tendency for aggregation of the nanoparticles, and
initial ligand shell with pyridine turned out to be a good way surface defects. For these reasons, the exact knowledge of the
to reduce the thickness of the ligand shell.20-25 Pyridine is a composition of the ligand shell after single and multiple pyridine
weak ligand, but it binds to the surface Cd atoms replacing the treatment can be highly important for the further application of
these nanocrystals. In this work, we carefully studied the effect
* Corresponding author. E-mail: joanna.kolny@uni-oldenburg.de. of multiple pyridine treatments on the surface of CdSe nano-
10.1021/jp103300v 2010 American Chemical Society
Published on Web 07/01/2010
Surface Treatment of CdSe Nanoparticles J. Phys. Chem. C, Vol. 114, No. 29, 2010 12785

crystals initially capped with OA and investigated the suitability (samples further referred to as CdSePy2 and CdSePy3, respec-
of differently treated particles for application in hybrid solar tively) carried out analogously to the first one. In this way, a
cells. series of samples was generated that were treated once, two
times, and three times with pyridine.
Experimental Section Characterization of CdSe QDs.
UV-Vis spectra were recorded in hexane or pyridine on a
Materials. Cadmium oxide (CdO, 99%) was purchased from Cary 100 absorption spectrophotometer (Varian), using 1 cm
Fluka; tri-n-octylphosphine (TOP, 90%) and OA (90%) were path length quartz cells. The absorbance values of the first
from Aldrich; 1-octadecene (ODE) was from Merck; selenium absorption maximum were used to calculate the molar particle
powder (Se, 99.99%) was from ChemPur; regioregular poly(3- extinction coefficients, the concentrations of the nanocrystals,
hexylthiophene) (P3HT) was from Rieke Metals; PEDOT/PSS and their diameter using empiric formulas developed in ref 31.
was from H. C. Starck. All reagents were used as received Thermal gravimetric analysis (TGA) was performed under
without further purification. All solvents were obtained from N2 atmosphere on a TGA/SDTA-851e instrument from Mettler-
commercial sources and used as received. In the cases where Toledo, using a heating rate of 2.5 C/min up to a temperature
the manipulation of the materials required inert atmosphere, a of 500 C.
standard glovebox technique was used. 1
H and 31P NMR spectra were recorded on Bruker DRX
Synthesis of CdSe Nanocrystal Quantum Dots. The CdSe
500 and Bruker Avance III 500 NMR spectrometers operating
QDs were synthesized in analogy to a previously reported
at 500 and 202.772 MHz, respectively. The spectra were
procedure for CdTe QDs.29 First, the Se precursor solution (0.4
referenced to tetramethylsilane (TMS) at 0.0 and the residual
M), containing 0.316 g of Se and 10 mL of TOP, was prepared
proton signal of CDCl3 at 7.24 in the case of 1H NMR
in the glovebox; the solution was permanently stirred until
spectra, and to an external phosphoric acid standard set at P
complete dissolution of Se. Second, 0.1024 g of CdO, 800 L
0.0 in the case of 31P NMR spectra. 1H NMR analysis was
of OA, and 20 mL of ODE were mixed and heated to 100 C
carried out either by dissolving a powder of a nanocrystal sample
under vacuum. Then this red-colored mixture was heated to 300
in CDCl3 or by using recovered ligands dissolved in CDCl3.
C under nitrogen, resulting in the formation of a homogeneous
To obtain the recovered ligands, purified nanocrystals were first
transparent solution, due to the formation of cadmium oleate
digested by a DCl-D2O solution, and then the organic ligands
(Cd(OA)2). This solution of Cd(OA)2 in ODE was allowed to
were extracted by CDCl3 from the D2O solution, this procedure
be boiled at 300 C without restriction, which led to the
being adopted from ref 32. 31P NMR analysis was performed
formation of a grayish precipitate that can be attributed to
using both purified nanocrystals and recovered ligands as well.
crystalline Cd0 nanoparticles in analogy to the CdTe synthesis.29
An amount of 4 mL of the Se/TOP solution was loaded into a Powder X-ray diffraction (XRD) data were collected on a
syringe, thus providing the initial molar excess of Se in Philips XPert-MPD diffractometer using Cu KR radiation;
comparison to Cd (molar ratio of Cd/Se ) 1:2). This amount samples were deposited on special glass slides, suitable to avoid
was rapidly injected into the reaction flask, immediately after contributions of the sample holder to the diffraction patterns.
the precipitation of Cd0 nanoparticles. The reaction temperature Transmission electron microscopy (TEM) images were
was then reduced to 250 C for the growth of the CdSe QDs. collected by using a Zeiss EM 902A transmission electron
After 7 min of growth the heating mantel was removed and the microscope operating at an acceleration voltage of 80 kV. TEM
reaction solution rapidly cooled to the room temperature. The samples of pure nanoparticles were prepared by putting a 10
CdSe nanocrystal solution was separated from the metallic Cd0 L aliquot of nanocrystals dissolved in hexane or pyridine onto
precipitate by centrifugation. For further treatment the CdSe a carbon-coated copper grid, which was dried in air. For
QDs were purified by an extraction and precipitation procedure investigation of polymer/nanoparticle blends, CdSe/P3HT films,
adopted from ref 30. Briefly, 20 mL of the solution of CdSe prepared by the standard procedure (see below), were floated
nanocrystals capped by the original ligands (further denoted as from the water-soluble PEDOT/PSS substrate onto the surface
CdSeOA) in ODE with a concentration of 0.16 mmol/L was of deionized water and picked up with a copper TEM grid.
diluted with 6 mL of hexane, and 14 mL of methanol was used Preparation and Characterization of Laboratory Solar
to extract the excess of reaction byproducts. The nanocrystals Cells.
dispersed in the hexane-ODE phase were precipitated with Hybrid nanoparticle/polymer blends of CdSe and P3HT
excess acetone and methanol (5:1 v/v ratio of acetone/methanol were prepared as follows: Colloidal solutions of CdSe nano-
to the hexane-ODE solution containing the nanocrystals). The particles in pyridine obtained after the first, second, and third
nanocrystals were isolated through centrifugation and decanta- pyridine treatment steps were blended with P3HT dissolved in
tion. The precipitation/redissolution procedure was repeated chlorobenzene. The weight ratio of CdSe/P3HT was 10:1, and
several times. After the last precipitation step, the nanocrystals the volume ratio of chlorobenzene/pyridine was 4:1 in all cases.
were finally redissolved in 7 mL of pure pyridine. Laboratory solar cells were prepared with a bulk hetero-
Pyridine Treatment of CdSe QDs. For exchange of the junction layer of the CdSe/P3HT blends sandwiched between
ligands, the purified CdSe QDs redissolved in pyridine were an indium-tin oxide (ITO)-coated glass substrate covered with
heated in a water bath for 3 h at 65 C under permanent stirring. a PEDOT/PSS layer as anode and an Al layer as cathode (see
Afterward, the nanocrystal/pyridine solution was stirred over- Figure 1). To avoid short circuits, half of the ITO coating was
night at room temperature. Excess hexanes were added to the etched away with HCl and zinc powder. Subsequently, the
nanocrystal/pyridine solution to precipitate the CdSe QDs. The substrates were cleaned with acetone and isopropyl alcohol in
nanocrystal precipitate was isolated by centrifugation and an ultrasonic bath. The last cleaning step was O2 plasma etching.
decantation and finally redissolved in 0.65 mL of pyridine (in The interfacial layer of PEDOT/PSS (Clevios ph, H. C. Starck)
order to obtain a final concentration of the CdSe QDs in pyridine between the active layer and ITO, used for improving the energy
of 215 mg/mL). The solution obtained at this step will be further conversion efficiency,33 was spin-coated on the cleaned substrate
referred to as CdSePy1. Part of this CdSePy1 solution was and dried at 180 C under nitrogen atmosphere for 20 min. The
subjected to a second and a third pyridine treatment step active layer was deposited by spin-coating the CdSe/P3HT
12786 J. Phys. Chem. C, Vol. 114, No. 29, 2010 Lokteva et al.

Figure 1. Schematic representation of the laboratory solar cells.

solution on top of the PEDOT/PSS layer under inert atmosphere.


It is well-known that annealing of the P3HT/CdSe composite
films near the glass transition temperature of the polymer can
on the one hand enhance the hole mobility in the polymer phase
and partly eliminate pyridine ligands for better electron transport
between nanocrystals on the other hand.34 Furthermore, the Figure 2. Absorption spectra of the CdSeOA QDs (solid line) and
removal of interfacial pyridine can also improve charge transfer CdSePy1, CdSePy2, and CdSePy3 QDs (dashed lines).
between the CdSe QDs and the host polymer P3HT.35 Therefore,
heat treatments of the composite thin films of CdSe/P3HT were
applied at 140 C for 20 min under inert atmosphere. Finally,
the devices were completed by thermal evaporation of about
100 nm Al on top as cathode.
Current-voltage (I-V) measurements were used to char-
acterize the performance of the laboratory solar cells under AM
1.5 conditions. A K. H. Steuernagel class B solar simulator was
used for this purpose. (The intensity of the solar simulator (1000
W/m2) was calibrated using a calibrated Si (mono-Si, Fraunhofer
ISE, Freiburg, Germany) reference solar cellsspectral mismatch
was not taken into account.) All measurements were done at
room temperature.
Electron spin resonance (ESR) spectroscopy was used to
study the charge-transfer process in the nanoparticle/polymer
blends. An amount of 60 L of the prepared solution was drop-
cast on Mitsubishi Hostaphan plastic sheets (1 cm2 per
sample). After drying in inert atmosphere the samples were
annealed at 140 C for 10 min and cut to 10 slices, which were
transferred in ESR quartz tubes and sealed under vacuum. ESR
spectra were taken with a Bruker Elexys 500 X-band spectrom-
eter at 9.44 GHz. Low temperatures were accessible via an
Oxford ESR 900 L-He flow cryostat with a minimum operation
Figure 3. TEM images of (a) CdSeOA QDs and (b-d) CdSePy1,
temperature of 4.2 K. Measurements were performed at ambient CdSePy2, and CdSePy3 QDs, respectively.
temperatures and 20 K with a microwave power of 6 mW. For
light excitation a solid-state semiconductor laser at 532 nm grid well-separated by their initial ligand shells (Figure 3a). After
wavelength and 20 mW laser power was used. removal of this ligand shell the size of the particles does not
change, but the distance between them decreases, and their
Results and Discussion
tendency to form aggregates on the TEM grid increases with
Study of the CdSe Ligand Shell before and after the the number of subsequent pyridine treatments (Figure 3b-d).
Ligand Exchange. Pyridine is known to form weak and It has to be noted, however, that this aggregation due to the
reversible bonds with the surface cadmium ions of cadmium thinner and weaker ligand shell seems to occur only during the
chalcogenide nanocrystals.36 In Figure 2 the absorption spectra drying process on the TEM grid, because the absorption spectra
of CdSe QDs (mean diameter 3.04 nm) before and after pyridine did not provide any evidence for aggregation in the colloidal
treatment are represented. As the pyridine-treated CdSe QDs solutions of the pyridine-treated QDs.
maintain the original optical spectra (in particular the position XRD analysis of the original and pyridine-treated CdSe QDs
and the width of the first exciton did not change), it means that has revealed that both samples have a zinc blende structure (see
no oxidation, etching, and aggregation of the nanocrystals have Figure 4). With the original ligand shell present, it was difficult
occurred.36 The absorption spectra have three well-defined to obtain a powder. Even after a very thorough cleaning
absorption maxima, indicating a high quality of the synthesized procedure samples could be obtained only in the form of a
nanocrystals. viscous paste, suggesting that there was still some excess
Although the optical spectra of the CdSe QDs before and organics left which are difficult to remove by standard cleaning
after ligand exchange show almost no differences, TEM images procedures. The presence of organic impurities is confirmed by
of the corresponding samples demonstrate obvious changes in the presence of an additional reflection in the XRD pattern in
the nanoparticles tendency for aggregation (see Figure 3). the case of the CdSeOA QDs (Figure 4a). In contrast, the XRD
Before pyridine treatment the QDs can be found on the TEM pattern of the pyridine-capped nanocrystals (Figure 4b) has no
Surface Treatment of CdSe Nanoparticles J. Phys. Chem. C, Vol. 114, No. 29, 2010 12787

Figure 4. XRD patterns of (a) CdSeOA QDs and (b) CdSePy1 QDs.

additional peaks besides the Bragg reflections belonging to Figure 5. 1H NMR spectra of (a) pure oleic acid, (b) intact CdSeOA
CdSe, which shows that the pyridine treatment is an effective QDs, and (c) recovered ligand shell of CdSeOA QDs.
way to get rid of the organic impurities. The effectiveness of
this method and the composition of the ligand shell were further
studied by nuclear magnetic resonance (NMR) spectroscopy and
TGA analysis.
NMR spectroscopy allows both the analysis of the composi-
tion of the ligand shell and distinguishing between bound and
free ligands. In order to obtain detailed information about the
ligand shell we measured both a solution of purified nanocrystals
and the recovered ligand shell. In the NMR spectra the signals
from ligands bound to the surface are usually broadened; some
of them can disappear and they can be shifted.36 Signals coming
from the parts of the ligands being in the direct neighborhood
of the surface are influenced in the strongest way. Therefore,
the composition of the ligand shell can be only reliably studied
if the ligands are not bound to the surface. That is why we
destroyed the nanoparticles and investigated the recovered ligand
shell. Since the absence of free ligands was confirmed by the
NMR measurements of intact particles (see discussion below)
these measurements revealed the composition of the organic
ligand shell bound to the surface. Figure 6. 1H NMR spectra of (a) pure pyridine, (b) intact CdSePy1
In the first step the composition of the ligand shell of the QDs, and (c) recovered ligand shell of CdSePy1 QDs.
as-synthesized nanoparticles was investigated. These nanocryst-
als grow in presence of OA and TOP, two kinds of possible The high intensity of the signals at 0.9 and 1.25 ppm that can
surfactant molecules. However, the 31P NMR analysis did not be assigned to hydrogen atoms bound to an aliphatic carbon
prove the presence of any phosphorus compound in the ligand chain indicates the presence of some additional organic material
shell of the nanocrystals (spectra not shown for brevity). This in the sample. This could be polymerized ODE molecules. ODE
result was obtained both with intact QDs and the recovered shows a strong tendency to form oligomers upon heating, which
ligand shell. In this way we could exclude the possibility that can be seen both in 1H NMR spectra, as decreasing intensity of
TOP was present on the surface of the QDs but not measurable the protons in the neighborhood of the double bond compared
by NMR because of the immobilization on the surface. On the to the remaining signals, and in mass spectra, where masses
basis of these results we can conclude that the ligand shell of corresponding to oligomers composed of two, three, and four
the CdSe QDs before pyridine treatment is only composed of ODE molecules could be found (data not shown for brevity).
OA molecules. This was further confirmed by 1H NMR These oligomers are difficult to remove from the samples by
measurements. The 1H NMR spectra of a CdSe nanocrystal standard cleaning procedures.
sample capped with the original ligands from synthesis is shown The NMR spectra of the CdSe QDs after one pyridine
in Figure 5b and that of the recovered ligands in Figure 5c. treatment are shown in Figure 6b (intact particles) and Figure
Two very small peaks in the nanoparticles sample at 5.00 and 6c (recovered ligand shell). The results of the measurement of
5.83 ppm belong to ODE, which shows the difficulty to remove intact CdSe QDs confirm the binding of pyridine to their surface
it completely. In the NMR spectra of intact CdSe QDs (Figure (Figure 6b). Three peaks at 7.30, 7.68, and 8.62 ppm correspond
5b), the signals from the parts of OA molecules in the direct to pyridine (the first one overlapped by the signal of CDCl3).
neighborhood of the CdSe surface are broadened and no signal We do not find signals from free pyridine molecules (compare
from free OA can be observed, though in the 1H NMR spectrum Figure 6, parts a and b) in this spectrum, which would be shifted
of the recovered ligand shell (Figure 5c) one can clearly observe to smaller ppm values. This makes it possible to conclude that
the presence of all typical OA peaks (Figure 5a). The integrals the pyridine is bound on the nanocrystals surface. Also no peaks
of these signals, however, do not match those of the pure OA. that could be specifically assigned to OA molecules can be found
12788 J. Phys. Chem. C, Vol. 114, No. 29, 2010 Lokteva et al.

TABLE 1: Summary of the Results Calculated from TGA


Curves for CdSePy1, CdSePy2, and CdSePy3 QDsa
no. of molecules , %
sample OA Py OA Py overall surface coverage, %
CdSePy1 36 74 26.2 53.9 80.1
CdSePy2 28 101 20.2 72.9 93.1
CdSePy3 17 110 12.1 79.9 92.0
a
All nanoparticles were estimated to have 138 surface Cd atoms,
and is the fraction of surface Cd atoms bound to coordinating
species.

to 73%, which indicates the presence of large quantities of


the organic material, in accordance with the XRD and NMR
results. The TGA curves for pyridine-treated nanocrystals
(Figure 8) exhibit already more than one step. The total weight
Figure 7. TGA curve of the CdSeOA QDs.
losses for particles after the first, second, and third step of the
pyridine treatment are 21%, 21%, and 18%, respectively,
which clearly shows that the pyridine treatment is a good way
to remove organic impurities from the samples. However, not
all of the original ligands can be replaced by pyridine even after
three pyridine treatments. This is evident, even after three
pyridine treatments, by the persistence of a step at 420 C
that was also observed in the case of the OA-capped nanoparticles.
Assuming that weight loss above 285 C (at this temperature
the TGA curves approach an intermediate plateau) is due to
strongly bound OA ligands we estimated the fraction of surface
sites capped by pyridine (py) and OA ligands (OA) on the
surface of CdSe QDs after each pyridine treatment using a
method described in detail in ref 38. On the basis of the size of
the nanocrystals calculated from the absorption spectrum (3.33
nm) we estimated the number of surface Cd atoms to be 138.
Then, assuming that the ligand molecules only bind to Cd and
not to Se atoms, from the weight loss in the TGA measurements
we have calculated for the samples CdSePy1, CdSePy2, and
Figure 8. TGA data showing pyridine-treated CdSe QDs: (A) CdSePy3 (see Table 1). After each pyridine treatment additional
CdSePy1, (B) CdSePy2, and (C) CdSePy3. (The arbitrary scaling on OA molecules are substituted with pyridine molecules. The
the ordinate is different for the three samples.) overall surface coverage (concerning again only the Cd surface
atoms) increases from 80% to 90% after the second pyridine
in the spectrum of pyridine-treated CdSe QDs. A comparison treatment and does not change significantly after the third
with the NMR spectrum of the recovered ligand shell (Figure pyridine treatment. This shows that the change of the values
6c) reveals that this is due to a broadening of the signal in is really due to an exchange of stronger OA ligands by weaker
molecules bound to the CdSe surface, since all the OA signals pyridine ligands and not a result of a binding of additional
can be identified in the NMR spectrum after destroying the CdSe pyridine molecules to the surface. In this way the TGA results
particles with a DCl-D2O solution. Pyridine signals are missing confirm the observation made by TEM (increasing aggregation
in the spectrum of the recovered ligand shell, because pyridine tendency) that the stabilization of the nanocrystals gets weaker
is better miscible with the DCl-D2O phase than with CDCl3 after each pyridine treatment.
used for the NMR measurements. So, taking both measurements Impact of the Ligand Shell on Polymer/Nanoparticle
into account (intact nanoparticles and recovered ligand shell) Hybrid Solar Cells. To study the impact of the ligand shell on
we can conclude that the ligand shell after the pyridine treatment the suitability for application of CdSe nanocrystals in photo-
is composed of both OA and pyridine. The NMR analysis clearly voltaic devices, differently treated CdSe particles were now
reveals that both kinds of molecules are bound to the surface incorporated into hybrid solar cells based on a bulk heterojunc-
of the nanocrystals. tion of conductive polymer (P3HT) and CdSe nanoparticles.
To corroborate the NMR results, TGA analysis was performed Nanoparticles of the samples CdSePy1, CdSePy2, and CdSePy3
for the samples CdSeOA (Figure 7) as well as CdSePy1, were used to study systematically the influence of repeated
CdSePy2, and CdSePy3 (Figure 8). In the sample of OA-capped ligand exchange on the device performance. (It is noted that
nanocrystals the weight loss starts at 160 C and continues until solar cells with CdSeOA particles are not included into this
470 C, the derivative of this curve having a maximum at 420 comparison, because without any ligand exchange the device
C. This high desorption temperature indicates that the particles efficiency is almost zero.)
are covered by strongly binding ligands, which is in accordance In Figure 9a the current-voltage characteristics of the hybrid
with the NMR results, showing that the ligand shell is composed system CdSe/P3HT are shown in semilogarithmic representation
of OA molecules. OA is known to bind strongly to the CdSe in the dark and under illumination. All of the solar cells behave
surface and to decompose from the surface only at high like a rectifying diode and exhibit a photoresponse. In Figure 9b
temperatures in TGA experiments.37 The total weight loss equals the fourth quadrant of the I-V curves is shown. For the solar cells
Surface Treatment of CdSe Nanoparticles J. Phys. Chem. C, Vol. 114, No. 29, 2010 12789

QDs remains almost unaffected by the multiple pyridine


treatments as evidenced by the UV-vis spectra (see Figure 2).
However, pyridine being a weaker capping agent, coagulation
of CdSe QDs can occur much easier after the ligand exchange.
The observation of the TEM images (see Figure 10) clearly
demonstrates increasing agglomeration of the CdSe QDs in the
active layer after each step of pyridine treatment. Although the
blend prepared with CdSePy1 particles (Figure 10a) is homo-
geneous, and almost no aggregation of nanoparticles can be
observed, already the second pyridine treatment leads to large
clusters of aggregated CdSe nanoparticles that are not well-
dispersed in the P3HT host matrix (Figure 10b). This behavior
is even more pronounced with the sample CdSePy3 (Figure 10c),
showing a pronounced phase separation between the polymer
and the QDs. So, the aggregation of the CdSe nanocrystals in
the P3HT matrix results in an inhomogeneous active layer, with
the phase separation increasing after each pyridine treatment.
Due to the aggregation of the nanoparticles, pure polymer
domains with dimensions exceeding the double of the exciton
diffusion length (estimated to be only 8 nm in P3HT41) appear,
meaning that part of the photogenerated excitons cannot reach
the donor/acceptor interface within their lifetime.
Figure 9. I-V characteristics of the hybrid solar cells in the dark and To study the charge carrier generation in the different P3HT/
under illumination with simulated AM 1.5G radiation for cells with
CdSe blends ESR measurements were performed. It has been
CdSePy1, CdSePy2, and CdSePy3 QDs: (a) I-V curves in the dark
and under illumination in semilogarithmic representation; (b) fourth demonstrated with organic P3HT/PCBM blends that positive
quadrant in linear representation for the I-V curves under illumination. polaron states in P3HT show an ESR signal at a Lande factor
of g ) 2.0022, whereas the signal of the negative polaron in
PCBM appears at g ) 1.99.42 ESR measurements on P3HT/
TABLE 2: Characteristic Parameters of Solar Cells with PCBM blends under laser illumination (l-ESR) could show that
CdSePy1, CdSePy2, and CdSePy3 QDsa
an increase of the P3HT signal under illumination is related to
treatment FF Jsc, mA/cm2 Voc, V the splitting of photogenerated singlet excitons to a polaron pair
1 0.49 1.15 0.5 at the material interface. In blends with inorganic semiconductor
2 0.44 0.41 0.32 nanoparticles so far no signal related to the generated electrons
3 0.34 0.5 0.26 was found, but a comparable l-ESR behavior of the positive
a
FF, fill factor; Jsc, short-circuit current density; Voc, open-circuit polarons in P3HT was resolved.43 In a previous work44 it was
voltage. demonstrated that both the polaron generation and recombination
rate in P3HT/CdSe blends occur on two time scales at low
with CdSePy1 nanoparticles, the open-circuit voltage (Voc), the temperatures. A first, fast rate occurs in the subsecond regime
short-circuit current density (Jsc), and the power conversion and a second long process in the hour regime. While the first
efficiency () were 0.5 V, 1.15 mA/cm2, and 0.3%, respectively. process is connected to weakly bound polarons, the latter is
These values are slightly lower than usually possible with blends related to deep traps, where the diffusion of the charge carriers
of P3HT and quasi-spherical CdSe nanocrystals where efficiencies is suppressed. By investigating the temporal behavior of charge
can approach 1% with optimized preparation parameters such carrier generation and recombination in dependence of the
as mixing ratios and film thickness.30,39,40 However, the efficiencies pyridine treatment steps the influence of the ligand exchange
obtained in this series of experiments are still a reasonable starting on the occurrence of traps can be determined.
point for comparison with cells prepared with CdSe particles treated For each sample, first a spectrum was measured without light
several times with pyridine. excitation (dark signal). Figure 11 shows as an example the
As shown by NMR and TGA in this study, a large part of dark signal for the CdSePy1 sample, measured at T ) 20 K.
the OA shell was removed and the fraction of the nanoparticle The signal can be attributed to positive polarons in the P3HT
surface covered with pyridine increased after each step of the phase. The position of the peak (minimum) was now determined,
pyridine treatment. Pyridine is a weaker stabilizing agent than and the magnetic field was fixed to this value. The intensity
OA so that surface passivation in the pyridine-treated nanopar- (absolute value referenced to the baseline) of the minimum of
ticles is reduced.26 Furthermore, pyridine is a much smaller the spectrum which is a measure for the amount of polarons
molecule than OA resulting in a thinner ligand shell which was then recorded over time while the laser irradiation (P )
should facilitate charge transfer between the polymer and the 20 mW, ) 532 nm) was switched on and off.
CdSe nanoparticles as well as charge transport between neigh- In Figure 12 the time evolvement of the intensity is shown
bored nanoparticles. For these reasons one should expect an for all three samples. For the sample with CdSePy1 particles,
improvement of the device efficiency after each repetition of the curve resembles the measurement in ref 44. The increasing
the pyridine treatment. However, repeated pyridine treatment intensity after switching on the laser gives a clear indication
of the solution of CdSe nanoparticles was found to strongly for successful charge separation at the polymer/nanoparticle
decrease the main characteristic parameters of the solar cells interface. After switching off the excitation source, a fast decay
(see Figure 9 and Table 2). of the signal due to recombination of relatively mobile charge
This behavior seems to be correlated with the morphology carriers and a very slow decay due to the recombination of
of the hybrid blends. The size distribution of the colloidal CdSe deeply trapped charge carriers are observable. The curves for
12790 J. Phys. Chem. C, Vol. 114, No. 29, 2010 Lokteva et al.

Figure 10. TEM images of CdSe/P3HT films with (a) CdSePy1, (b) CdSePy2, and (c) CdSePy3 QDs.

higher level after multiple pyridine treatments, meaning that


more charge carriers are confined in deep traps in these samples.
Thus, whereas the surface passivation of the nanoparticles
decreases with every treatment step, the amount of surface traps
seems to increase. The traps that are additionally induced by
multiple pyridine treatments seem, however, not to be as deep
as the traps present already after the first treatment. This is
evidenced by the higher recombination rate in the slow regime
that is observed for CdSePy3. The observation of a higher trap
density provides an additional reason for the reduced device
performance.
Thus, repeated pyridine treatment was found to have a
beneficial effect in the sense that it leads to more complete ligand
exchange which in turn enables more efficient charge transfer.
However, the density of trap states for charge carriers seems to
Figure 11. ESR signal of positive polarons in P3HT/CdSe blends (with increase as well, probably because of the less passivated
CdSePy1 particles). The spectrum was measured at T ) 20 K, nanoparticle surface. Together with negative effects due to a
microwave power PMW ) 6 mW, microwave frequency ) 9.44 GHz higher tendency for the formation of large nanoparticle ag-
(black, taken in the dark; green, taken after illumination experiment).
gregates, this was found to overcompensate the positive effects
so that the device efficiency decreased after multiple pyridine
treatment.

Summary and Conclusion


In summary, the impact of single and multiple ligand
exchange procedures with pyridine on the performance of hybrid
solar cells based on a bulk heterojunction of P3HT and CdSe
nanoparticles was investigated. For this purpose, OA-capped
CdSe nanoparticles were synthesized and subjected to repeated
treatments with pyridine. The comparison of the absorption
spectra of all samples revealed that the size of the nanoparticles
did not change during the ligand exchange process; furthermore,
no hints for an aggregation of pyridine-treated particles in
solution could be found. The surface properties of the nano-
particles before and after each of the pyridine treatment steps
have been studied by NMR and TGA. The initial ligand shell
Figure 12. Time dependence of the ESR signal of P3HT/CdSe blends was found to consist of OA only, although TOP was present in
taken at the same conditions as in Figure 11, laser power PL ) 20 the synthesis as well. The overall surface coverage was found
mW. to increase only slightly from the first to the third pyridine
treatment, but we could observe changes of the ligand shell
the other two samples show slight deviations from this behavior. composition. The OA molecules could be gradually removed
Both samples show an increased charge carrier generation rate, by repeated treatments with pyridine, but about 10% of the
best pronounced in the sample with CdSePy2. In the fast surface Cd sites remained passivated by OA even after the third
recombination regime the sample with CdSePy3 shows the ligand exchange step. Structural characterization of the samples
smallest decrease. However, in the second regime the decrease was carried out by TEM and XRD measurements. In this way
is enhanced compared to the other samples. As mentioned before we could also confirm that the size of the nanoparticles was
a higher charge generation rate was expected in the second and not influenced by the ligand exchange; however, a higher
third sample due to better ligand exchange efficiency. This can tendency to form aggregates on the TEM grid could be observed
be confirmed by the ESR measurements. in the samples being treated more often with pyridine. This is
Furthermore, a possible explanation for the reduced solar cell in accordance with the finding that the ligand shell after repeated
performance after multiple pyridine treatment can be provided. pyridine treatments is composed of more weakly stabilizing
In the slow recombination regime the ESR signal remains on a ligands.
Surface Treatment of CdSe Nanoparticles J. Phys. Chem. C, Vol. 114, No. 29, 2010 12791

Even though the repeated pyridine treatment results in a (10) Nair, P. S.; Fritz, K. P.; Scholes, G. D. Small 2007, 3, 481.
thinner ligand shell that should facilitate the charge transfer (11) Wang, X.; Wu, J.; Li, F.; Li, H. Nanotechnology 2008, 19, 205501.
(12) Munro, A. M.; Bardecker, J. A.; Liu, M. S.; Cheng, Y.-J.; Niu,
between nanoparticles and a polymer, we found that the Y.-H.; Plante, I. J.-L.; Jen, A. K.-Y.; Ginger, D. S. Microchim. Acta 2008,
efficiency of laboratory solar cells made of blends of differently 160, 345.
pyridine-treated CdSe nanoparticles and P3HT decreases with (13) Liu, I.-S.; Lo, H.-H.; Chien, C.-T.; Lin, Y.-Y.; Chen, C.-W.; Chen,
Y.-F.; Su, W.-F.; Liou, S.-C. J. Mater. Chem. 2008, 18, 675.
every additional pyridine treatment. The efficiency of hybrid (14) Querner, C.; Reiss, P.; Sadki, S.; Zagorska, M.; Pron, A. Phys.
solar cells being strongly dependent on the blend morphology, Chem. Chem. Phys. 2005, 7, 3204.
one possible reason for the negative effect of repeated pyridine (15) Wuister, S. F.; de Mello Donega, C.; Meijerink, A. J. Am. Chem.
treatments on the performance of solar cells is the nanoparticles Soc. 2004, 126, 10397.
(16) Li, L.; Daou, T. J.; Texier, I.; Kim Chi, T. T.; Liem, N. Q.; Reiss,
increasing tendency to form aggregates, which results in a too P. Chem. Mater. 2009, 21, 2422.
strong phase segregation in the blend. ESR studies of the (17) Kim, S.; Bawendi, M. G. J. Am. Chem. Soc. 2003, 125, 14652.
generation and recombination of polarons indicated that not only (18) Greenham, N. C.; Peng, X.; Alivisatos, A. P. Phys. ReV. B 1996,
the blend morphology is responsible for lower efficiencies. 54, 17628.
(19) Seo, J.; Kim, W. J.; Lee, K.-S.; Cartwright, A. N.; Prasad, P. N.
Removing more of the original ligand shell by repeating the Appl. Phys. Lett. 2009, 94, 133302.
ligand exchange procedure was found to have a beneficial effect (20) Kumar, S.; Scholes, G. D. Microchim. Acta 2008, 160, 315.
on the charge carrier generation, but on the other hand repeated (21) Afzaal, M.; OBrien, P. J. Mater. Chem. 2006, 16, 1597.
pyridine treatments were also found to increase the amount of (22) Sun, B.; Greenham, N. C. Phys. Chem. Chem. Phys. 2006, 8, 3557.
(23) Zhang, C.; OBrien, S.; Balog, L. J. Phys. Chem. B 2002, 106,
trap states. Together with the aggregation tendency this effect 10316.
lowers the solar cells efficiency. So, even if multiple pyridine (24) Li, Q.; Sun, B.; Kinloch, I. A.; Zhi, D.; Sirringhaus, H.; Windle,
treatments turned out to be a suitable way to reduce the amount A. H. Chem. Mater. 2006, 18, 164.
(25) Huynh, H. U.; Dittmer, J. J.; Alivisatos, A. P. Science 2002, 295,
of OA on the nanocrystals surface, which resulted in an 2425.
increased charge carrier generation under illumination, the (26) Katari, J. E. B.; Colin, V. L.; Alivisatos, A. P. J. Phys. Chem. 1994,
negative effects related to the reduced surface passivation 98, 4109.
overcompensated this influence and lowered the solar cell (27) Kuno, M.; Lee, J. K.; Dabbousi, B. O.; Mikulec, F. V.; Bawendi,
M. G. J. Chem. Phys. 1997, 106, 9869.
performance. (28) Puzder, A.; Williamson, A. J.; Zaitseva, N.; Galli, G.; Manna, L.;
Alivisatos, A. P. Nano Lett. 2004, 4, 2361.
Acknowledgment. We thank Erhard Rhiel and Heike Oetting (29) Kolny-Olesiak, J.; Kloper, V.; Osovsky, R.; Sashchiuk, A.; Lifshitz,
for assistance in obtaining TEM images, Marlies Rundshagen E. Surf. Sci. 2007, 601, 2667.
(30) Zutz, F.; Lokteva, I.; Radychev, N.; Kolny-Olesiak, J.; Riedel, I.;
and Dieter Neemeyer for assistance in obtaining NMR data, Borchert, H.; Parisi, J. Phys. Status Solidi A 2009, 206, 2700.
Mareike Ahlers and Katja Riess for assistance in obtaining TGA (31) Yu, W. W.; Qu, L.; Guo, W.; Peng, X. Chem. Mater. 2003, 15,
data, and Gunda Sangerlaub for assistance in obtaining XRD 2854.
data. We gratefully acknowledge funding of the EWE research (32) Yu, W. W.; Wang, Y. A.; Peng, X. Chem. Mater. 2003, 15, 4300.
(33) Alem, S.; Bettignies, R.; Nunzi, J. M.; Cariou, M. Appl. Phys. Lett.
group Thin Film Photovoltaics by the EWE AG, Oldenburg. 2004, 84, 2178.
Furthermore, this work was partly supported by the Federal (34) Ginger, D. S.; Greenham, N. C. J. Appl. Phys. 2000, 87, 1361.
Ministry of Education and Research (BMBF, project no. (35) Huynh, W. U.; Dittmer, J. J.; Libby, W.; Whiting, G. L.; Alivisatos,
A. P. AdV. Funct. Mater. 2003, 13, 73.
03SF0338C) and by the State of Lower Saxony and the (36) Ji, X.; Copenhaver, D.; Sichmeller, C.; Peng, X. J. Am. Chem. Soc.
Vokswagen Foundation, Hannover, Germany. 2008, 130, 5726.
(37) Khanna, P. K.; Srinivasa Rao, K.; Patil, K. R.; Singh, V. N.; Mehta,
References and Notes B. R. J. Nanopart. Res. 2010, 12, 101.
(38) Foos, E. E.; Wilkinson, J.; Makinen, A. J.; Watkins, N. J.; Kafafi,
(1) Liu, H.; Owen, J. S.; Alivisatos, A. P. J. Am. Chem. Soc. 2007, Z. H.; Long, J. P. Chem. Mater. 2006, 18, 2886.
129, 305. (39) Han, L.; Qin, D.; Jang, X.; Liu, Y.; Cao, Y. Nanotechnology 2006,
(2) Van Embden, J.; Mulvaney, P. Langmuir 2005, 21, 10226. 17, 4736.
(3) De Mello Donega, C.; Hickey, S. G.; Wuister, S. F.; Vanmaekel- (40) Liu, Y.; Wang, L.; Cao, Y. Front. Chem. China 2007, 2, 383.
bergh, D.; Meijerink, A. J. Phys. Chem. B 2003, 107, 489. (41) Shaw, P. E.; Ruseckas, A.; Samuel, I. D. W. AdV. Mater. 2008,
(4) Murray, C. B.; Norris, D. J.; Bawendi, M. G. J. Am. Chem. Soc. 20, 3516.
1993, 115, 8706. (42) Dyakonov, V.; Zoriniants, G.; Scharber, M.; Brabec, C. J.; Janssen,
(5) Pradhan, N.; Reifsnyder, D.; Xie, R.; Aldana, J.; Peng, X. J. Am. R. A. J.; Hummelen, J. C.; Sariciftci, N. S. Phys. ReV. B 1999, 59, 8019.
Chem. Soc. 2007, 129, 9500. (43) Pientka, M.; Dyakonov, V.; Meissner, D.; Rogach, A.; Talapin,
(6) Wu, D.; Kordesch, M. E.; Van Patten, P. G. Chem. Mater. 2005, D.; Weller, H.; Lutsen, L.; Vanderzande, D. Nanotechnology 2004, 15, 163.
17, 6436. (44) Heinemann, M. D.; Von Maydell, K.; Zutz, F.; Kolny-Olesiak, J.;
(7) Lee, S.; Cho, S.; Cheon, J. AdV. Mater. 2003, 15, 441. Borchert, H.; Riedel, I.; Parisi, J. AdV. Funct. Mater. 2009, 19, 3788.
(8) Jun, Y.; Choi, J.; Cheon, J. Angew. Chem., Int. Ed. 2006, 45, 3414.
(9) Kumar, S.; Nann, T. Small 2006, 2, 316. JP103300V