Professional Documents
Culture Documents
pubs.acs.org/JPCC
■ INTRODUCTION
Colloidal semiconductor quantum dots (QDs) have optoelec-
addition, we have observed a drastic, repeatable, and rapid
increase in the conductivity of QDs by up to 10 orders of
tronic properties that greatly differ from their bulk counter- magnitude within 1 ms, under a small threshold field on the
parts. Both n-type and p-type bulk lead chalcogenide crystals order of 0.1 V/μm.
exhibit unusual positive temperature coefficients of resistance
(resistance increases with increasing temperature).1 On the
other hand, colloidal lead selenide (PbSe) QDs show negative
■ EXPERIMENTAL DETAILS
PbSe QDs were synthesized using standard air-free techniques
temperature coefficients of resistance in almost all reports to as described elsewhere.14 The QDs were transferred and stored
date.2−5 This difference is likely caused by a weak electronic in a N2 glovebox (O2 < 10 ppm, H2O < 0.1 ppm) where all
coupling among QDs, where the low temperature conduction EDT treatment and subsequent electrical measurements were
behaviors can be described very well by the variable range performed. Planar devices with bottom contact to QDs were
hopping mechanism.5−7 Improving the coupling, while made on 300 nm SiO2 covered Si wafer previously patterned
maintaining quantum confinement, can lead to more efficient with interdigitated Cr/Au (5/25 nm) electrodes by photo-
carrier extraction and better electronic devices based upon
lithography (Figure 1a). The electrodes consisted of 350 pairs
QDs.
of 10 μm wide, 7 mm long Au pads with 10 μm gap. The QDs
QDs have also recently been studied as potential building
were dispersed in a 9:1 mixture of hexane/octane and passed
blocks for electrically driven memory devices,8−12 which take
through a 0.2 μm PTFE filter before being drop cast on the
advantage of the low fabrication cost and tunable electronic
prepatterned substrate. The film was then placed in 0.1 M EDT
properties of QDs. The investigation of the memory effect can
in anhydrous acetonitrile for 2−3 min and was subsequently
also shed light on the charge transport mechanism in QD thin
films. Bistable conduction of QD thin films is typically achieved dried in N2 without rinsing.
by embedding the QDs in a polymer matrix, where the Small angle X-ray scattering (SAXS) and X-ray diffraction
application of a voltage pulse changes the conductivity of the measurements were performed with a Bruker D8 Discover X-
system between two metastable conductive states.8−10,13 The ray diffractometer. Absorption spectra were taken with a
bistability in the QD/polymer system has been attributed to an Nicolet 6700 Fourier transform infrared (FTIR) spectrometer.
electric field induced charge transfer from QDs to the Atomic force microscopic (AFM) images were measured with a
conducting polymers. Recently, there have been reports of Veeco Dimension 3100 system. Electrical characterization was
bistable conduction of pure QD thin films.9,12,13 However, the made with a NI data acquisition system and a Stanford
memory switching mechanism of devices composed solely of Research Systems model SR570 current preamplifier. The QD
QDs is not well understood. devices were transferred into a cryostat without exposure to air
Here, we report a positive temperature coefficient of and placed under vacuum with a base pressure of ∼20 mTorr
resistance in strongly coupled PbSe QD thin films. While the
QDs in the films treated with 1,2-ethanedithiol (EDT) still Received: July 11, 2012
show clear quantum confined absorption peaks, conductivity Revised: January 22, 2013
increases with decreasing temperature, as in the bulk PbSe. In Published: January 25, 2013
© 2013 American Chemical Society 3713 dx.doi.org/10.1021/jp306893e | J. Phys. Chem. C 2013, 117, 3713−3717
The Journal of Physical Chemistry C Article
Figure 1. (a) Schematic of a planar device with a QD thin film on top of prepatterned interdigitated electrodes. (b) Absorption spectra of PbSe QDs
with different diameters. (c) X-ray diffraction spectrum of PbSe QDs.
for temperature dependent measurements. To ensure an inert spacing within a couple angstroms after treatment, consistent
and water free environment, the device was transferred into the with the length of an EDT molecule.16 The SAXS result
cryostat inside the glovebox. The cryostat was then sealed and confirms that the compact EDT ligands have successfully
transferred out of the glovebox and placed under vacuum for replaced the bulky oleic acid ligands and the QDs are in near
characterization. direct contact with each other after EDT treatment.
■
We then took the absorption spectra of the QD thin films
RESULTS AND DISCUSSION before and after EDT treatment. After EDT treatment, QDs
maintained the discrete peaks indicating the QDs were still
1. X-ray Diffraction and Spectroscopy Character- quantum confined. The slight increase in the peak width can be
ization. The QD sizes were determined from the first exciton attributed to the electron enhanced coupling.17 The first
peak positions following the literature (Figure 1b).15 The first exciton absorption peak of the QD thin films red-shifted by 61
exciton absorption peaks of the PbSe QDs were narrow (<40 meV after EDT treatment, while maintaining discrete energy
meV), corresponding to a size distribution of <10% for all three levels (Figure 2b). The red-shift in our films was significantly
samples (Figure 1b). XRD measurements confirmed the rock larger than that of thicker spin-coated films (27−32 meV) or
salt structure of the PbSe QDs (Figure 1c). The final film films created by the layer-by-layer method (23 meV).3,16 The
thickness after EDT treatment was typically around 40 nm as red-shift is caused by the increase in electronic coupling
measured by AFM. The entire film had a RMS roughness of between QDs or by other effects, such as the change in the
about 15 nm, corresponding to 2−3 monolayers of QDs. dielectric environment. Liu et al. has observed a 22 meV red-
In order to determine the interdot spacing, we performed shift due to noncoupling effect,16 from which we can estimate
SAXS measurements before and after EDT treatment. The QD
our coupling energy, hΓ, is approximately 39 meV, correspond-
samples were exposed to air during the SAXS measurements,
ing a charge transfer rate, Γ, of 9.4 × 1012 s−1. This coupling
and we observed that the results slowly changed over hours due
energy is significantly higher than the previously reported 10
to oxidation. The following data was taken immediately after
meV,16 indicating that our QDs are very strongly coupled. This
the samples were removed from the glovebox, and before a
large shift in the absorption spectrum is consistent with the
significant change occurred. SAXS measurements of the QD
small interdot distance indicated by the large SAXS shift. A
thin films before EDT treatment exhibited clear superlattice
large red-shift in the absorption spectrum has also been
peaks indicating the film had a long-range order. After EDT
observed previously in thiocyanate treated CdSe QDs
treatment, these peaks were greatly diminished and broadened,
exhibiting bandlike transport.17
signaling that the film transitioned to a more disordered
2. Charge Transport. We now present the electronic
structure. The scattering intensity for spherical particles of
characterization of the PbSe QD thin films. The QD thin films
uniform radius R is proportional to the form factor F(q) = (4/
exhibited a bistable conduction detailed in the later section and
3)πR3{3[sin(qR) − qR cos(qR)]/(qR)3}, where q = (4π sin θ)/
λ . We extracted R by setting the derivative of F(q) to zero and here we first focus on their charge transport behavior in the
plugging in θ at maximum scattering intensity. By analyzing the conductive state. The as-deposited films were completely
SAXS data this way, the interdot spacing was found to decrease insulating beyond the detection limit of our setup (σ < 10−11
by approximately 1.6 nm (Figure 2a), bringing the interdot S/cm). The EDT treatment led to an increase in film
conductivity of at least 10 orders of magnitude (σ ∼ 10−1 S/
cm) after the film conductance was turned on by applying an
overthreshold bias voltage. Our film conductivity was 1−2
orders of magnitude higher than that in earlier reports,3,16
indicating a stronger electronic coupling between neighboring
QDs and consistent with our larger absorption peak shift and
small interdot spacing. We prepared our QD films by drop
casting instead of a layer-by-layer method or spin-casting as in
previous reports. It should be noted that the electrical
properties of QD thin films are sensitive to the details of the
film preparation, as the charge transfer rate exponentially
depends on the interdot distance and is strongly influenced by
Figure 2. (a) SAXS data showing a 1.6 nm reduction in interdot the surface traps. This sensitivity has been noted by other
spacing. (b) Spectral shift of 3.9 nm diameter PbSe QDs after EDT groups as well.5,14
treatment. Upper blue line, EDT treated thin film; middle black line, as We want to make two notes regarding to the electrical
deposited thin film; bottom red line, QD solution. measurements. (1) The interdigitated electrode structure
3714 dx.doi.org/10.1021/jp306893e | J. Phys. Chem. C 2013, 117, 3713−3717
The Journal of Physical Chemistry C Article
allowed us to greatly increase the electrode area and thus CdSe QDs.17 The bandlike transport in our QD films is
overall conductance; however, it prevented us from making 4- consistent with our other observations: near direct contact
point measurements. Though the measurements were made in between neighboring QDs confirmed by SAXS and strong
2-point devices, our linear I−V curves (even at low temper- electronic coupling indicated by the absorption peak red-shift.
atures) and high conductivity in the conductive state strongly The observed positive temperature coefficient of resistance
indicate ignorable contact barriers. (2) These films only showed further suggests that strong electronic coupling lead to
temporary gate response as in earlier reports.3 In our films, the extended electronic states and electronic band formation. The
gate response decayed on the order of seconds, preventing us 40% resistivity increase in our PbSe QD thin films from 78 to
from separating the current generated by the gate pulse from 300 K is significantly smaller than the 10-fold increase in bulk
the temporary increase in carrier concentration. This decay is PbSe, indicating the carrier scattering at the boundary of the
not understood, but it has been attributed to a slow screening QDs still play an important role in the QD thin film.
of the applied gate field by trapped carriers.3 The instability in The other possibility is that the films have already undergone
gate response prohibits us from extracting the field effect a metal−insulator transition at room temperature.18 This would
mobilities. explain the absence of a persistent gate response. However,
To better understand the charge transport mechanism, we given the positive temperature coefficient of bulk PbSe, along
cooled a device incorporating a QD thin film to approximately with the observations of bandlike transport in QD thin films by
78 K and slowly warmed, while the conductance was measured other groups,17,19 we believe it is more likely that the observed
at 1 V bias so that the device stayed in its conductive state. The positive temperature coefficient in PbSe QD thin films is caused
conductance decreased by approximately 40% as the temper- by a bandlike transport.
ature increased from 78 to 300 K (Figure 3), showing a positive 3. Bistable Conduction. At room temperature, the EDT
treated films showed a strong hysteresis in their I−V curves
(Figure 4). Upon reaching a threshold voltage (Vth), the film
temperature coefficient of resistance. We measured the conductivity increased abruptly from ∼10−11 to 10−1 S/cm
temperature dependence of four devices, and all exhibited a (Figure 4b). This increased conductivity was maintained even
positive temperature coefficient of resistance. This positive after the bias was reduced below Vth. The film returned to its
temperature coefficient is the first such observation for insulating state once the voltage was reduced below a holding
chemically treated QDs. Previously a positive temperature voltage Vhold. Vth and Vhold could have the same or opposite
coefficient has been seen only below 110 K in laser ablated and polarity depending on sample, but |Vhold| was always much
ligand free PbSe QDs,18 which has been attributed to an smaller than |Vth| and near 0 V. The I−V curves were usually
insulator-to-metal transition at low temperature. On the other symmetric and the film switched to the conductive state as the
hand, bulk PbSe crystals also exhibit a positive temperature voltage reached a more negative bias (V−th). The time required
coefficient, with a resistivity increase by a factor of 10 from 78 for switching was measured to be less than 1 ms, limited by the
to 300 K. The resistivity change of bulk crystals is mainly temporal resolution of the preamplifier.
caused by the drastic increase in carrier mobility at low This memory switching was robust, and a device could be
temperature because of reduced carrier-phonon scattering.1 As switched on and off many times. For a given device, Vth
mentioned previously, our devices do not show a persistent remained constant upon repeated switching (Figure 5). While
gate response, even at low temperature, preventing us from Vth usually varies from 0.2 to 2 V in the more than 21 devices
directly measuring the mobility, but we can deduce the sign of measured, a couple of devices showed Vth as high as 10 V. This
dμ/dT from the negative sign of dσ/dT. The conductivity, σ, is variation was observed even when the films were composed of
determined by the product of the carrier mobility μ and the the same batch of QDs and fabricated with the same procedure.
carrier density n (σ = neμ). As temperature increases, σ This Vth variation made it difficult to identify any size
decreases and n is expected to increase or remain constant if dependence. Out of the 21 devices measured, 16 devices
acceptor states are completely ionized at given temperature. showed conductance change over 10 orders of magnitude,
Thus, μ must decrease with temperature, suggesting bandlike while other devices exhibited smaller on/off ratios. Hysteresis
transport through extended electronic states. A negative dμ/dT in chemically treated CdSe QD thin films has been seen in the
has been previously observed, as a signature of bandlike past,9 but not with such drastic on/off ratios and with such a
transport, in CdSe QDs capped with molecular metal rapid transition. The direction of hysteresis observed in CdSe
chalcogenide complexes (MCCs)19 and thiocyanate treated QDs was clockwise in contrast to our counterclockwise
3715 dx.doi.org/10.1021/jp306893e | J. Phys. Chem. C 2013, 117, 3713−3717
The Journal of Physical Chemistry C Article
■
QDs could be the cause of such a reaction. Because lead only
acts as short connection between QDs, the conductance is
expected to be dominated by the PbSe QDs and our early CONCLUSION
discussion on the positive temperature coefficient of resistivity In summary, we have observed a positive temperature
still holds. At room temperature, such metallic filaments are not coefficient of resistance in strongly coupled PbSe QD thin
stable at zero-bias and will likely react with Se, returning the films. The large red shift of the absorption peak, high film
film to the insulating state. At low temperature (<160 K), the conductivity, and SAXS results are all consistent with a strong
3716 dx.doi.org/10.1021/jp306893e | J. Phys. Chem. C 2013, 117, 3713−3717
The Journal of Physical Chemistry C Article
electronic coupling between QDs. This finding demonstrates (12) Das, B. C.; Pal, A. J. Memory Applications and Electrical
semiconductor nanocrystal solids can show bandlike transport Bistability of Semiconducting Nanoparticles: Do the Phenomena
properties when the neighboring QDs are strongly coupled, Depend on Bandgap? Small 2008, 4, 542−547.
which can lead to improved charge extraction and possibly (13) Kim, T. H.; Jang, E. Y.; Lee, N. J.; Choi, D. J.; Lee, K.-J.; Jang, J.-
t.; Choi, J.-s.; Moon, S. H.; Cheon, J. Nanoparticle Assemblies as
higher mobilities in QD devices. EDT treated PbSe QD thin Memristors. Nano Lett. 2009, 9, 2229−2233.
films also exhibit bistable conduction. The conductivity (14) Wehrenberg, B. L.; Wang, C.; Guyot-Sionnest, P. Interband and
increases abruptly by up to 10 orders of magnitude when the Intraband Optical Studies of PbSe Colloidal Quantum Dots. J. Phys.
bias reaches a threshold, and remains high until the bias is Chem. B 2002, 106, 10634−10640.
reduced much lower than the threshold. We attribute the (15) Moreels, I.; Lambert, K.; De Muynck, D.; Vanhaecke, F.;
insulating state to the Coulomb repulsion by the trapped Poelman, D.; Martins, J. C.; Allan, G.; Hens, Z. Composition and Size-
charges, and the conductive state to the reduced charging Dependent Extinction Coefficient of Colloidal PbSe Quantum Dots.
energy due to extended charge carrier wave function. Chem. Mater. 2007, 19, 6101−6106.
Alternatively, we acknowledge that the bistability could be (16) Liu, Y.; Gibbs, M.; Puthussery, J.; Gaik, S.; Ihly, R.; Hillhouse,
due to the formation of conductive filaments in the QD thin H. W.; Law, M. Dependence of Carrier Mobility on Nanocrystal Size
and Ligand Length in PbSe Nanocrystal Solids. Nano Lett. 2010, 10,
films. The drastic and fast memory switching may find
1960−1969.
applications in memory devices.
■
(17) Choi, J.-H.; Fafarman, A. T.; Oh, S. J.; Ko, D.-K.; Kim, D. K.;
Diroll, B. T.; Muramoto, S.; Gillen, J. G.; Murray, C. B.; Kagan, C. R.
AUTHOR INFORMATION Bandlike Transport in Strongly Coupled and Doped Quantum Dot
Corresponding Author Solids: A Route to High-Performance Thin-Film Electronics. Nano
*E-mail: yu@physics.ucdavis.edu. Lett. 2012, 12, 2631−2638.
(18) Dedigamuwa, G.; Lewis, J.; Zhang, J.; Jiang, X.; Mukherjee, P.;
Notes Witanachchi, S. Enhanced Charge-Transport in Surfactant-Free PbSe
The authors declare no competing financial interest. Quantum Dot Films Grown by a Laser-Assisted Spray Process. Appl.
■ ACKNOWLEDGMENTS
This work was supported by the Startup fund by University of
Phys. Lett. 2009, 95, 122107−122103.
(19) Lee, J.-S.; Kovalenko, M. V.; Huang, J.; Chung, D. S.; Talapin,
D. V. Band-Like Transport, High Electron Mobility and High
Photoconductivity in All-Inorganic Nanocrystal Arrays. Nat. Nano-
California at Davis and the Hellman fellowship. We thank Prof. tehnol. 2011, 6, 348−352.
P. Guyot-Sionnest for helpful discussions. We also acknowledge (20) Talapin, D. V.; Murray, C. B. PbSe Nanocrystal Solids for N-
Prof. Y. Takamura and Peter Greene for their assistance with and P-Channel Thin Film Field-Effect Transistors. Science 2005, 310,
the SAXS measurements. 86−89.
■
(21) Elteto, K.; Antonyan, E. G.; Nguyen, T. T.; Jaeger, H. M. Model
REFERENCES for the Onset of Transport in Systems with Distributed Thresholds for
Conduction. Phys. Rev. B 2005, 71, 064206.
(1) Dalven, R. A Review of Semiconductor Properties of PbTe, PbSe,
PbS and PbO. Infrared Phys. 1969, 9, 141.
(2) Hu, Z.; Fischbein, M. D.; Drndić, M. Local Charge Transport in
Two-Dimensional PbSe Nanocrystal Arrays Studied by Electrostatic
Force Microscopy. Nano Lett. 2005, 5, 1463−1468.
(3) Luther, J. M.; Law, M.; Song, Q.; Perkins, C. L.; Beard, M. C.;
Nozik, A. J. Structural, Optical, and Electrical Properties of Self-
Assembled Films of PbSe Nanocrystals Treated with 1,2-Ethanedithiol.
ACS Nano 2008, 2, 271−280.
(4) Mentzel, T. S.; Porter, V. J.; Geyer, S.; MacLean, K.; Bawendi, M.
G.; Kastner, M. A. Charge Transport in PbSe Nanocrystal Arrays. Phys.
Rev. B 2008, 77, 075316.
(5) Wehrenberg, B. L.; Yu, D.; Ma, J.; Guyot-Sionnest, P.
Conduction in Charged PbSe Nanocrystal Films. J. Phys. Chem. B
2005, 109, 20192−20199.
(6) Yu, D.; Wang, C.; Wehrenberg, B. L.; Guyot-Sionnest, P. Variable
Range Hopping Conduction in Semiconductor Nanocrystal Solids.
Phys. Rev. Lett. 2004, 92, 216802.
(7) Zabet-Khosousi, A.; Dhirani, A. A. Charge Transport in
Nanoparticle Assemblies. Chem. Rev. 2008, 108, 4072−4124.
(8) Ouyang, J.; Chu, C.-W.; Szmanda, C. R.; Ma, L.; Yang, Y.
Programmable Polymer Thin Film and Non-Volatile Memory Device.
Nat. Mater. 2004, 3, 918−922.
(9) Fischbein, M. D.; Drndic, M. CdSe Nanocrystal Quantum-Dot
Memory. Appl. Phys. Lett. 2005, 86, 193106.
(10) Bozano, L. D.; Kean, B. W.; Beinhoff, M.; Carter, K. R.; Rice, P.
M.; Scott, J. C. Organic Materials and Thin-Film Structures for Cross-
Point Memory Cells Based on Trapping in Metallic Nanoparticles.
Adv. Funct. Mater. 2005, 15, 1933−1939.
(11) Son, D. I.; You, C. H.; Kim, W. T.; Jung, J. H.; Kim, T. W.
Electrical Bistabilities and Memory Mechanisms of Organic Bistable
Devices Based on Colloidal Zno Quantum Dot-Polymethylmethacry-
late Polymer Nanocomposites. Appl. Phys. Lett. 2009, 94, 132103−
132103.