Electrochemical strain microscopy probes morphology-induced variations in ion uptake and performance in organic electrochemical transistors.

Ionic transport phenomena in organic semiconductor materials underpin emerging technologies ranging from bioelectronics to energy storage. The performance of these systems is affected by an interplay of film morphology, ionic transport and electronic transport that is unique to organic semiconductors yet poorly understood. Using in situ electrochemical strain microscopy (ESM), we demonstrate that we can directly probe local variations in ion transport in polymer devices by measuring subnanometre volumetric expansion due to ion uptake following electrochemical oxidation of the semiconductor. The ESM data show that poly(3-hexylthiophene) electrochemical devices exhibit voltage-dependent heterogeneous swelling consistent with device operation and electrochromism. Our data show that polymer semiconductors can simultaneously exhibit field-effect and electrochemical operation regimes, with the operation modality and its distribution varying locally as a function of nanoscale film morphology, ion concentration and potential. Importantly, we provide a direct test of structure-function relationships by correlating strain heterogeneity with local stiffness maps. These data indicate that nanoscale variations in ion uptake are associated with local changes in polymer packing that may impede ion transport to different extents within the same macroscopic film and can inform future materials optimization.

Lithium-doping inverts the nanoscale electric field at the grain boundaries in Cu2ZnSn(S,Se)4 and increases photovoltaic efficiency.

Passive grain boundaries (GBs) are essential for polycrystalline solar cells to reach high efficiency. However, the GBs in Cu2ZnSn(S,Se)4 have less favorable defect chemistry compared to CuInGaSe2. Here, using scanning probe microscopy we show that lithium doping of Cu2ZnSn(S,Se)4 changes the polarity of the electric field at the GB such that minority carrier electrons are repelled from the GB. Solar cells with lithium-doping show improved performance and yield a new efficiency record of 11.8% for hydrazine-free solution-processed Cu2ZnSn(S,Se)4. We propose that lithium competes for copper vacancies (forming benign isoelectronic LiCu defects) decreasing the concentration of ZnCu donors and competes for zinc vacancies (forming a LiZn acceptor that is likely shallower than CuZn). Both phenomena may explain the order of magnitude increase in conductivity. Further, the effects of lithium doping reported here establish that extrinsic species are able to alter the nanoscale electric fields near the GBs in Cu2ZnSn(S,Se)4. This will be essential for this low-cost Earth abundant element semiconductor to achieve efficiencies that compete with CuInGaSe2 and CdTe.

Electrical and optical properties of semiconductor nanocrystals.

Application of semiconductor nanocrystals in optoelectronic devices requires an understanding not only of their emission and absorption properties, but also of the processes of charge injection and transport in nanocrystalline films. Here, we present measurements of the electrical properties of nanocrystalline films and of blends of nanocrystals with conjugated polymers. We also describe the attachment of nanocrystals to semiconductor surfaces, and we investigate the emission of nanocrystalline films in microcavity structures and at high excitation intensities.

Direct patterning of modified oligonucleotides on metals and insulators by dip-pen nanolithography.

The use of direct-write dip-pen nanolithography (DPN) to generate covalently anchored, nanoscale patterns of oligonucleotides on both metallic and insulating substrates is described. Modification of DNA with hexanethiol groups allowed patterning on gold, and oligonucleotides bearing 5'-terminal acrylamide groups could be patterned on derivatized silica. Feature sizes ranging from many micrometers to less than 100 nanometers were achieved, and the resulting patterns exhibited the sequence-specific binding properties of the DNA from which they were composed. The patterns can be used to direct the assembly of individual oligonucleotide-modified particles on a surface, and the deposition of multiple DNA sequences in a single array is demonstrated.

Signals for a transition from surface to bulk emission in thermal multifragmentation.

Excitation-energy-gated two-fragment correlation functions have been studied between E(*)/A = (2-9)A MeV for equilibriumlike sources formed in 8-10 GeV/c pi(-) and p+197Au reactions. Comparison with an N-body Coulomb-trajectory code shows an order of magnitude decrease in the fragment emission time in the interval E(*)/A = (2-5)A MeV, followed by a nearly constant breakup time at higher excitation energy. The decrease in emission time is strongly correlated with the onset of multifragmentation and thermally induced radial expansion, consistent with a transition from surface-dominated to bulk emission expected for spinodal decomposition.