A simple process has been developed to create large area, highly uniform microporous thin films. Multilayers of weak polyelectrolytes were assembled onto silicon substrates by the sequential adsorption of poly(acrylic acid) and poly(allylamine) from aqueous solution. These multilayers were then immersed briefly into acidic solution (pH ≈ 2.4) to effect a substantial and irreversible transformation of the film morphology. The resulting microporous structures are 2-3 times the thickness of the original films, possess a correspondingly reduced relative density of 1 /2 to 1 /3, and are stable against further rearrangement under ambient conditions. In addition, the microporous films may undergo a secondary reorganization in neutral water, leading to a morphology with more discrete throughpores. A mechanism is proposed for these transformations based on interchain ionic bond breakage and reformation in this highly protonating environment, leading to an insoluble precipitate on the substrate which undergoes spinodal decomposition with the solvent. FTIR (Fourier transform infrared spectroscopy) analysis supports the underlying chemical basis of this pH-induced phase separation, and AFM (atomic force microscopy), in situ ellipsometry, and SEM (scanning electron microscopy) have been used to monitor the morphological changes. The unique combination of properties exhibited by these microporous films makes them potential candidates for microelectronic and biomaterial applications.
In
this work, we introduce Cu2O thin films as a hole-transport
layer in planar perovskite solar cells. Here, a Cu2O layer
was formed through successive ionic layer adsorption and reaction
(SILAR) method. With methylammonium lead triiodide (MAPbI3) we form a direct structure (p–i–n), where the perovskite
layer is sandwiched between a layer of p-type Cu2O and
another layer of n-type PCBM (phenyl-C61-butyric acid methyl
ester), which acted as hole- and electron-transport materials, respectively.
We locate band edges of the materials with respect to their Fermi
energy by recording scanning tunneling spectroscopy that has correspondence
to their density of states (DOS). We observe that the energy levels
of the materials form type II band alignments at each of the two interfaces
(p–i and i–n) for charge separation and uninterrupted
carrier transport upon illumination. Such a band alignment enabled
charge transfer from MAPbI3 as evidenced from quenching
of its photoluminescence emission when the perovskite was in contact
with either the hole- or the electron-transport layer. With the direct
p–i–n structure having appropriate energy levels for
carrier separation, the planar perovskite solar cell (Cu2O/MAPbI3/PCBM) yielded an energy conversion efficiency
(η) of 8.23% under 1 sun illumination.
Approaches to tune the properties of hybrid halide perovskites and their performance in solar cells through metal substitution have been summarized in this review.
We have introduced functionalized multiwalled carbon nanotubes (CNTs) in donor/acceptor-type photovoltaic devices. We fabricated the devices based on heterostructure between polymer-CNT composite and buckminsterfullerene (C60) layers. Due to the functional groups of the CNTs, a homogeneous blend of CNT-polymer composite could be obtained. In the composite, the nanotubes acted as exciton dissociation sites and also hopping centers for hole transport. The CNTs in the polymer-CNT∕C60 device provided higher exciton dissociation volume and increased mobility for carrier transport. We have observed an increase in open-circuit voltage and short-circuit current in the polymer-CNT∕C60 devices as compared to the polymer∕C60 ones.
We have realized tuning of electronic memory-switching property via functional group modification in solidstate devices. Apart from their large ON/OFF ratio and long memory retention time, solid-state devices sustain repetitive switching between the two ON/OFF states at high frequencies. We have chosen several molecular systems with same backbone structure and tuned ON/OFF ratio from 4 to 300 000 simply by increasing the number of deactivating groups. A key to the large ON/OFF ratio in these devices has been the presence of acceptor groups in the molecules and consequently low OFF state current. We analyzed the appearance of ON state in terms of conjugation restoration of the molecules. A redox active group has been found to be necessary in the molecules for continuous flip-flop between "1" and "0" states for random access memory (RAM) applications.
We have observed electrical bistability and large conductance switching in functionalized carbon nanotube (CNT)-conjugated polymer composites at room temperature. The concentration of the CNTs in the polymer matrix controlled the degree of bistability. Conduction mechanism applicable in each of the conducting states has been identified. The switching had an associated memory phenomenon and was reversible in nature. In the bistable devices, the active layer retained its high-conducting state until a reverse voltage erased it. We could "write" or "erase" a state and "read" it for many cycles for random-access memory applications.
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