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polymers,[2] functional polyimide,[3] polymers with specific Block copolymers have been extensively studied recently
pendent chromophore,[4] polymer composites (carbon since they can self-organize into an ordered nano-morphol-
nanotube,[5a,5b] fullerene,[5c,5d,5e] metal nanoparticle,[5f] or ogy[6] or be used to control the aggregated size of polymer
graphene oxide[5g]). The polymer composites, using charge composites.[7] Functional block copolymer composites were
transfer or charge trapping-detrapping, has been widely used to control fullerene domain size through specified
explored for memory device application.[1] The controlled physical interaction.[8] However, only relatively limited
aggregation domain of the guest material embedded in the block copolymers based composites were explored for
host polymer matrix is the main issue for nano-scale high- memory device,[9] and the supramolecular materials
density memory devices. approach was not used as far as we know.
In this paper, we report the memory device character-
istics based on 1%, 5% and 10% PCBM:P(St-Fl)-b-P2VP
composite with a configuration of ITO/composite/Al device
as shown in Figure 1(a). In addition, the memory devices
prepared from PCBM:polystyrene-block-poly(2-vinylpyri-
dine) (PS-b-P2VP) and PCBM:poly(fluorenylstyrene) (P(St-
Fl)) composites were also used for comparison. The
photophysical properties were used to explore the inter-
action between P(St-Fl)-b-P2VP block copolymer and PCBM.
Atom force microscopy (AFM), and transmission electron
microscopy (TEM) were performed to characterize the
morphology of the prepared composites. The obtained
electrical characteristics were further analyzed by the
appropriate conduction model. The experimental results
suggested that the memory characteristics could be
controlled by the loading ratio and corresponding PCBM
aggregated size in the block copolymer composites.
Experimental Part
Materials
P(St-Fl) homopolymer and P(St-Fl)-b-P2VP diblock copolymer were
synthesized via living anionic polymerization as reported pre-
viously.[10] The molecular weight (Mn ) of P(St-Fl) was 11 500 g mol1
with a polydispersity index (PDI) value of 1.08. The molecular weights
of P(St-Fl) and P2VP blocks on P(St-Fl)-b-P2VP were 8 900 and 1 500
g mol1, respectively. PS-b-P2VP was purchased from Polymer
Source Inc. (Dorval, Canada), with the block molecular weight of
16 000 (PS) and 3 500 g mol1 (P2VP), respectively, and a poly-
dispersity index of 1.06. [6,6]-phenyl-C61-butyric acid methyl ester
(PCBM) was obtained from Nano-C Inc. The anhydrous solvents were
purchased from Acros Organics (Geel, Belgium) or Aldrich (Missouri,
USA) and used as received without any purification.
Characterization
UV-Vis optical absorption and photoluminescence spectra were
obtained using Hitachi U-4100 spectrometer and Fluorolog-3
Spectrofluorometer (Jobin Yvon), respectively. Electrochemistry
was performed with a CHI 611B electrochemical analyzer using an
ITO plate as working electrode, platinum wire as counter electrode,
and Ag/AgCl as reference electrode at a sweep rate 0.1 V s1.
Figure 1. a) Chemical structures of the studied materials. The thickness of polymer film was measured with a Microfigure
b) Optical absorption spectra of the PCBM:P(St-Fl)-b-P2VP com- Measuring Instrument (Surfcorder ET3000, Kosaka Laboratory Ltd.).
posite in chloroform solution. c) Photoluminescence spectra of Transmission electron microscopy (TEM) was performed using a
P(St-Fl)-b-P2VP and 5% PCBM:P(St-Fl)-b-P2VP thin films. JEOL 1230 operated at an acceleration voltage of 100 kV. The
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samples for TEM measurement were prepared by spin-coating on The solution and film absorption spectra of P(St-Fl)-b-
NaCl substrate, and then put into water. The polymer films were P2VP block copolymer are shown in Figure S3(a) (Support-
left on the water surface and picked up onto 200-mesh copper grids. ing Information). The absorption maximum in thin film
The morphologies of polymer film surface was also obtained with a
state around 317 nm are attributed to the p-p transition of
Nanoscope 3D Controller atomic force micrographs (AFM, Digital opt
the fluorene moiety The optical band gap (Eg ) from the
Instruments) operated in the tapping mode at room temperature.
onset absorbance edge of P(St-Fl)-b-P2VP thin film is 3.60 eV.
The corresponding energy level of HOMO and LUMO of P(St-
Fl)-b-P2VP are estimated from cyclic voltammogram
Fabrication and Measurement of the Memory Devices
(Figure S3(b), Supporting Information) to be 5.94 and
The electrical properties of memory devices were fabricated with 2.34 eV, respectively, which are both slightly stabilized than
the configuration of ITO/polymer/Al, similar to our previous those of P(St-Fl) homopolymer (5.86 and 2.29 eV)[4a]
study.[3b,3c,4a] A chloroform solution of P(St-Fl)-b-P2VP (10 mg ml1) probably due to the weak electron-withdrawing P2VP block.
containing calculated PCBM, was stirred overnight to form
The morphology of the PCBM:polymer composite was
homogeneous solutions. Thereafter, the solution was filtered
further analyzed by TEM images. The TEM images of 5%
through 0.22 mm pore size of PTFE membrane syringe filter and
spin-coated at 1 000 rpm for 60 s onto the ITO substrate. The
PCBM:P(St-Fl)-b-P2VP and 5% PCBM:P(St-Fl) are shown in
polymer thin films were dried under vacuum (106 Torr) for 2 h to Figure 2(a) and 2(b). The size of PCBM aggregated size in P(St-
remove all of the solvents used. The thickness of the prepared thin Fl)-b-P2VP matrix is around 5 nm, which is much smaller
film was estimated to be 90100 nm. Finally, the 200 nm thick Al compared to that in P(St-Fl) matrix around 30 nm. It
top electrode (recorded active area of 0.5 0.5 mm2) was thermally suggests that the charge transfer interaction between the
evaporated through the shadow mask at a pressure of 106 Torr P2VP block and PCBM and the microphase separation of
s1). The electrical characteriza-
with a slow deposition rate (1.2 A P(St-Fl)-b-P2VP[10a] reduces the PCBM aggregation size. The
tion of the memory device was performed by a Keithley 4200-SCS
semiconductor parameter analyzer in a glove box.
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PCBM aggregated size in the TEM image of 10% PCBM:P(St- b-P2VP composites films estimated from AFM is around
Fl)-b-P2VP composite is estimated to be 7 nm and also more 1.0 nm, as shown in the Figure S6 (Supporting Information).
obvious density of PCBM clusters as shown in Figure S4 The electrical properties of P(St-Fl)-b-P2VP diblock copoly-
(Supporting Information). On the other hand, the PCBM mer without the PCBM content still keep in a low
aggregated size is insignificant in 1% PCBM:P(St-Fl)-b-P2VP conductivity state with the external applied voltage. It
as shown in Figure S5 (Supporting Information). Such suggests the insulating characteristic of the pristine P(St-
difference on the PCBM aggregation varies the switching Fl)-b-P2VP, similar to polystyrene reported previously.[4a,5d]
characteristic. The well-dispersion with suitable domain By incorporation of a small amount PCBM into P(St-Fl)-b-
size of PCBM aggregation in P(St-Fl)-b-P2VP block copoly- P2VP matrix, it exhibits an interesting non-volatile memory
mers is recognized to form transition of high conductance and the conductance of the memory device changes
electron channel. significantly with the applied writing voltage. The device
based on 1% PCBM:P(St-Fl)-b-P2VP thin film is scanned
through three voltage sequences: 0 to 4.0 V (sweep 1),
Memory Device Performance based on PCBM:Block
0 to 4.0 V (sweep 2) and 0 to 4.0 V (sweep 3) in steps of 0.1 V.
Copolymers Composites
As the first negative voltage from 0 to 3.2 V (sweep 1), the
Figure 3(a) exhibits typical current density-voltage (J-V) current density initially remains at a low conductance (OFF
curves of the devices with the configuration of state). Until the threshold voltage (3.2 V), the current
ITO/PCBM:P(St-Fl)-b-P2VP/Al. All the thickness of active density increases abruptly with several orders of magni-
memory films was adjusted to be 90100 nm. The smooth tude and changes to a high conduction state, indicating the
root-mean-square surface roughness of the PCBM:P(St-Fl)- transition from the OFF state to the ON state. The electrical
transition of this memory device serves as the writing
process. The current density maintains at ON state for the
subsequent negative sweep from 0 to 4.0 V (sweep 2) and
positive sweep from 0 to 4.0 V (sweep 3). The memory
device could not return to the OFF state even after turning
off the power or applying a reverse bias, suggesting the
write-once-read-many-times (WORM) memory behavior
with a high observed ON/OFF current ratio of 105 at 1 V.
The threshold voltage is in the range of 2.5 to 3.2 V. The
memory device of 5% PCBM:P(St-Fl)-b-P2VP composite film
also exhibits a similar WORM memory behavior using the
same voltage swept. The threshold voltage and ON/OFF
current ratio are in the range of 1.6 1.8 V and
around 103, respectively. Both 1% and 5% PCBM:P(St-Fl)-b-
P2VP composite film of WORM device can be measured in
the at least 10 memory cells of the same device with
reproducible data. The retention time tests on the above
WORM memory devices for the OFF and ON states are
shown in Figure 3(b) and Figure S7 of the Supporting
Information. The read voltage of the memory devices at
1.0 V for the ON or OFF state could remain over 104 s
without obvious degradation which suggests the excellent
device stability. However, the memory device of 10%
PCBM:P(St-Fl)-b-P2VP exhibits only a high conduction
characteristic, due to the further increase in the high
conductivity of PCBM content.
The J-V curves of the corresponding device with the PS-b-
P2VP block copolymers or P(St-Fl) homopolymer and PCBM
composite films are exhibited in Figure S8 (Supporting
Information) for comparison. The root-mean-square sur-
face roughness of the PCBM:PS-b-P2VP composites is
Figure 3. a) Current density vs. voltage plots for ITO/PCBM:P(St- around 1.1 nm, as shown in Figure S6 (Supporting
Fl)-b-P2VP/Al composites devices. b) Retention times of the ITO/ Information). The electrical characteristic of the 1% or 5%
1%PCBM:P(St-Fl)-b-P2VP/Al. PCBM:PS-b-P2VP composite films shows a low conduction
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state without any memory behavior. On the other hand, the whole injection from the ITO or electron injection from Al to
electrical behavior of 5% PCBM:P(St-Fl) composite film the active memory layer under the first negative sweep
exhibits a single state conductor behavior without a probably result in a low conductance state. Therefore, the
memory behavior. It suggests the significance of PCBM OFF state is confirmed by charge injection-dominated
aggregated size on the memory characteristics. thermionic emission, similar to those reported in the
literature.[5b,5c,5e] When the voltage swept above the
threshold voltage, the electron-donating pendent fluorene
Mechanism of the PCBM:P(St-Fl)-b-P2VP Composite
moiety of the P(St-Fl)-b-P2VP probably formed charge
Devices
transfer with the electron acceptor PCBM and the generated
The memory device characteristics of the polymer compo- carriers consequently exhibit sharp increase in current
sites with 0%, 1%, 5%, and 10% of PCBM in the P(St-Fl)-b- density. Thus, Poole-Frenkel emission is the field-induced
P2VP matrix are insulator, WORM, WORM, and conductor, transport-dominated mechanism in the ON state. The
respectively. The obtained J-V data for 5% PCBM:P(St-Fl)-b- stabilized charge separated state may not easily be
P2VP WORM memory devices in the OFF and ON state were recombined even under the reverse field and the high
further analyzed using appropriate conductance models, as conductance state can be retained for a long time in the
shown in Figure 4 and S9 (Supporting Information). For the observed WORM device.
two states, the voltage sweep from 0 to 1.6 V (sweep 1) and The ITO/10% PCBM:P(St-Fl)-b-P2VP/Al memory device,
0 to 4 V (sweep 2) represents characteristics of the OFF and the plot of ln(J) versus ln(V) shows a straight line with a slop
ON state, respectively. The plot of ln(J) versus V1/2 in the OFF of 1.0 as shown in Figure S11 (Supporting Information). It
state can be fitted to a straight line in the region before suggests that the ohmic conduction is the dominated
electrical transition. The thermionic emission is probably mechanism and the continuous percolation pathway can
the carrier transport mechanism in the OFF state. On the be formed effectively in the high conductance of 10%
other hand, the plot of ln(J/V) versus V1/2 in the ON state PCBM:P(St-Fl)-b-P2VP device, which is the same case for 5%
shows linearity characteristic as shown in Figure 4. Poole- PCBM:P(St-Fl) device in Figure S12 (Supporting Information).
Frenkel emission is probably the operation mechanism in The difference in PCBM aggregated domain from TEM
the ON state.[5e] images could provide a strong correlation on the memory
From the energy level of the composite system, the performance. Both P2VP block and P(St-Fl) block could
HOMO and LUMO are 5.94 and 2.34 eV for P(St-Fl)-b- interact with PCBM. Therefore, the loading amounts of
P2VP and 6.1 and 3.7 eV for PCBM, respectively. The PCBM in the block polymer matrix allow the device to tune
corresponding energy diagram was shown in Figure S10 the threshold voltage and ON/OFF current ratio since the
(Supporting Information). The P(St-Fl)-b-P2VP and PCBM separation of the PCBM domain can be controlled through
can be viewed as donor and acceptor in the thin film aggregated PCBM in the microphase-separated block
composite, respectively. The high energy barriers for the copolymers matrix. The 5% PCBM:P(St-Fl)-b-P2VP device
exhibit smaller threshold voltage and ON/OFF current ratio
than the 1% PCBM:P(St-Fl)-b-P2VP due to the decrease
distance between isolated PCBM domains. The highest
PCBM concentration (10%) with larger aggregated size
probably form electrically connected channels from two
electrodes (ITO and Al) and thus short-circuits the devices.
As compared to 5% PCBM in P(St-Fl) homopolymer, ohmic
J-V curve is observed due to the highly aggregated PCBM
cluster domain. However, the 5% PCBM:PS-b-P2VP compo-
site thin film still behaves like an insulting state perhaps
since only the P2VP block can complex with PCBM and thus
the composite could not undergo effective charge transfer
process through the PCBM domain that can conduct the
channel. Besides, the switching behavior can be observed
even in only 1% PCBM:P(St-Fl)-b-P2VP composite thin film
based on the charge-transfer interaction between PCBM
and pendent 2-vinylpyridine or fluorene chromophores and
thus the field-induced charge transfer effect occurred. This
study suggests the importance of supramolecular approach
Figure 4. Analysis of J-V characteristics of the ITO/5% PCBM:P(St- using the block copolymer composite for advanced memory
Fl)-b-P2VP/Al device in the OFF and ON states. device applications.
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