Maxim P. Nikiforov

Morphology characterization in organic and hybrid solar cells

Organic and hybrid organic–inorganic photovoltaics are among the most promising options for low-cost and highly scalable renewable energy. In order to fully realize the potential of these technologies, power conversion efficiencies and stability will both have to be improved beyond the current state-of-the-art. The morphology of the active layer is of paramount importance in the photon to electron conversion process in organic and hybrid solar cells, with all length scales, from molecular ordering to intradevice composition variability, playing key roles. Given the central influence of morphology, characterizing the structure of these surprisingly complex material systems at multiple length scales is one of the grand challenges in the field. This review addresses the techniques, some of which have only recently been applied to organic and hybrid photovoltaics, available to scientists and engineers working to understand—and ultimately improve—the operation of these fascinating devices.

Self-assembly of highly ordered peptide amphiphile metalloporphyrin arrays.

Long fibers assembled from peptide amphiphiles capable of binding the metalloporphyrin zinc protoporphyrin IX ((PPIX)Zn) have been synthesized. Rational peptide design was employed to generate a peptide, c16-AHL(3)K(3)-CO(2)H, capable of forming a β-sheet structure that propagates into larger fibrous structures. A porphyrin-binding site, a single histidine, was engineered into the peptide sequence in order to bind (PPIX)Zn to provide photophysical functionality. The resulting system indicates control from the molecular level to the macromolecular level with a high order of porphyrin organization. UV/visible and circular dichroism spectroscopies were employed to detail molecular organization, whereas electron microscopy and atomic force microscopy aided in macromolecular characterization. Preliminary picosecond transient absorption data are also reported. Reduced hemin, (PPIX)Fe(II), was also employed to highlight the materials versatility and tunability.

Probing the temperature dependence of the mechanical properties of polymers at the nanoscale with band excitation thermal scanning probe microscopy

Understanding local mechanisms for temperature-induced phase transitions in polymers requires quantitative measurements of the thermomechanical behavior, including glass transition and melting temperatures as well as temperature dependent elastic and loss modulus and thermal expansion coefficients in nanoscale volumes. Here, we demonstrate an approach for probing local thermal phase transitions based on the combination of thermal field confinement by a heated SPM probe and multi-frequency thermomechanical detection. The local measurement of the glass transition temperature is demonstrated and the detection limits are established.

Local thermomechanical characterization of phase transitions using band excitation atomic force acoustic microscopy with heated probe

An approach for thermomechanical characterization of phase transitions in polymeric materials (polyethyleneterephthalate) by band excitation acoustic force microscopy is developed. This methodology allows the independent measurement of resonance frequency, Q factor, and oscillation amplitude of a tip-surface contact as a function of tip temperature, from which the thermal evolution of tip-surface spring constant and mechanical dissipation can be extracted. We demonstrate a heating protocol which keeps the contact area and contact force constant, thus allowing for reproducible measurements and quantitative extraction of material properties including temperature dependence of indentation-based elastic and loss moduli.

Defect-Mediated Polarization Switching in Ferroelectrics and Related Materials: From Mesoscopic Mechanisms to Atomistic Control

The plethora of lattice and electronic behaviors in ferroelectric and multiferroic materials and heterostructures opens vistas into novel physical phenomena including magnetoelectric coupling and ferroelectric tunneling. The development of new classes of electronic, energy-storage, and information-technology devices depends critically on understanding and controlling field-induced polarization switching. Polarization reversal is controlled by defects that determine activation energy, critical switching bias, and the selection between thermodynamically equivalent polarization states in multiaxial ferroelectrics. Understanding and controlling defect functionality in ferroelectric materials is as critical to the future of oxide electronics and solid-state electrochemistry as defects in semiconductors are for semiconductor electronics. Here, recent advances in understanding the defect-mediated switching mechanisms, enabled by recent advances in electron and scanning probe microscopy, are discussed. The synergy between local probes and structural methods offers a pathway to decipher deterministic polarization switching mechanisms on the level of a single atomically defined defect.

Local bias-induced phase transitions

Electrical bias-induced phase transitions underpin a wide range of applications from data storage to energy generation and conversion. The mechanisms behind these transitions are often quite complex and in many cases are extremely sensitive to local defects that act as centers for local transformations or pinning. Using ferroelectrics as an example, we review methods for probing bias-induced phase transitions and discuss the current limitations and challenges for extending the methods to field-induced phase transitions and electrochemical reactions in energy storage, biological and molecular systems.

Combined Atomic Force Microscope-Based Topographical Imaging and Nanometer Scale Resolved Proximal Probe Thermal Desorption/Electrospray Ionization-Mass Spectrometry

Nanometer- scale proximal probe thermal desorption/electrospray ionization mass spectrometry (TD/ESI-MS) was demonstrated for molecular surface sampling of caffeine from a thin film using a 30 nm diameter nanothermal analysis (nano-TA) probe tip in an atomic force microscope (AFM) coupled via a vapor transfer line and ESI interface to a MS detection platform. Using a probe temperature of 350 °C and a spot sampling time of 30 s, conical desorption craters 250 nm in diameter and 100 nm deep were created as shown through subsequent topographical imaging of the surface within the same system. Automated sampling of a 5 × 2 array of spots, with 2 μm spacing between spots, and real time selective detection of the desorbed caffeine using tandem mass spectrometry was also demonstrated. Estimated from the crater volume (∼2 × 10(6) nm(3)), only about 10 amol (2 fg) of caffeine was liberated from each thermal desorption crater in the thin film. These results illustrate a relatively simple experimental setup and means to acquire in an automated fashion submicrometer scale spatial sampling resolution and mass spectral detection of materials amenable to TD. The ability to achieve MS-based chemical imaging with 250 nm scale spatial resolution with this system is anticipated.

Double-Layer Mediated Electromechanical Response of Amyloid Fibrils in Liquid Environment

Harnessing electrical bias-induced mechanical motion on the nanometer and molecular scale is a critical step toward understanding the fundamental mechanisms of redox processes and implementation of molecular electromechanical machines. Probing these phenomena in biomolecular systems requires electromechanical measurements be performed in liquid environments. Here we demonstrate the use of band excitation piezoresponse force microscopy for probing electromechanical coupling in amyloid fibrils. The approaches for separating the elastic and electromechanical contributions based on functional fits and multivariate statistical analysis are presented. We demonstrate that in the bulk of the fibril the electromechanical response is dominated by double-layer effects (consistent with shear piezoelectricity of biomolecules), while a number of electromechanically active hot spots possibly related to structural defects are observed.

Photoinduced charge dynamics on BaTiO3 (001) surface characterized by scanning probe microscopy

The surface potential of a multidomain BaTiO3 (001) surface was imaged in the presence and absence of ultraviolet (UV) illumination. The UV radiation induces a decrease in the surface potential contrast between c+ and c− domains with a time constant of a few seconds due to redistribution of photocarriers and screening. A slower process of recovery was observed after illumination. In addition, scanning a conducting atomic force microscopy tip in contact under UV illumination destabilizes some ferroelectric domains.

Nanofabrication of insulated scanning probes for electromechanical imaging in liquid solutions.

In this paper, the fabrication and electrical and electromechanical characterization of insulated scanning probes have been demonstrated in liquid solutions. The silicon cantilevers were sequentially coated with chromium and silicon dioxide, and the silicon dioxide was selectively etched at the tip apex using focused-electron-beam-induced etching (FEBIE) with XeF(2). The chromium layer acted not only as the conductive path from the tip, but also as an etch-resistant layer. This insulated scanning probe fabrication process is compatible with any commercial AFM tip and can be used to easily tailor the scanning probe tip properties because FEBIE does not require lithography. The suitability of the fabricated probes is demonstrated by imaging of a standard topographical calibration grid as well as piezoresponse force microscopy (PFM) and electrical measurements in ambient and liquid environments.