Surface potential images of polycrystalline organic semiconductors obtained by Kelvin probe force microscopy

P-type copper phthalocyanine (CuPc) and n-type hexadecafluorophthalocyanina-tocopper (F16CuPc) polycrystalline films were investigated by Kelvin probe force microscopy (KPFM). Topographic and corresponding surface potential images are obtained simultaneously. Surface potential images are related with the local work function of crystalline facets and potential barriers at the grain boundaries (GBs) in organic semiconductors. Based on the spatial distribution of surface potential at GBs, donor- and acceptor-like trapping states in the grain boundaries (GBs) of p-CuPc and n-F16CuPc films are confirmed respectively.

In-situ detection of defect formation in organic flexible electronics by Kelvin Probe Force Microscopy

Organic semiconductor technology has attracted considerable research interest in view of its great promise for large area, lightweight, and flexible electronics applications. Owing to their advantages in processing and unique physical properties, organic semiconductors can bring exciting new opportunities for broad-impact applications requiring large area coverage, mechanical flexibility, low-temperature processing, and low cost. In order to achieve highly flexible device architecture it is crucial to understand on a microscopic scale how mechanical deformation affects the electrical performance of organic thin film devices. Towards this aim, I established in this thesis the experimental technique of Kelvin Probe Force Microscopy (KPFM) as a tool to investigate the morphology and the surface potential of organic semiconducting thin films under mechanical strain. KPFM has been employed to investigate the strain response of two different Organic Thin Film Transistor with active layer made by 6,13-bis(triisopropylsilylethynyl)-pentacene (TIPS-Pentacene), and Poly(3-hexylthiophene-2,5-diyl) (P3HT). The results show that this technique allows to investigate on a microscopic scale failure of flexible TFT with this kind of materials during bending. I find that the abrupt reduction of TIPS-pentacene device performance at critical bending radii is related to the formation of nano-cracks in the microcrystal morphology, easily identified due to the abrupt variation in surface potential caused by local increase in resistance. Numerical simulation of the bending mechanics of the transistor structure further identifies the mechanical strain exerted on the TIPS-pentacene micro-crystals as the fundamental origin of fracture. Instead for P3HT based transistors no significant reduction in electrical performance is observed during bending. This finding is attributed to the amorphous nature of the polymer giving rise to an elastic response without the occurrence of crack formation.

Contrast Formation in Kelvin Probe Force Microscopy of Single π-Conjugated Molecules

We report the contrast formation in the local contact potential difference (LCPD) measured by Kelvin probe force microscopy (KPFM) on single charge-transfer complexes (CTCs) on a NaCl bilayer on Cu(111). At different tip heights, we found quantitatively different LCPD contrasts that characterize different properties of the molecule. In the small distance regime, the tip penetrates the electron density of the molecule, and the contrast is related to the size and topography of the electron shell of the molecule. For larger distances, the LCPD contrast corresponds to the electrostatic field above the molecule. However, in the medium-distance regime, that is, for tip heights similar to the size of the molecule, the nonspherical distribution of π- and σ-electrons often conceals the effect of the partial charges within the molecule. Only for large distances does the LCPD map converge toward the simple field of a dipole for a polar molecule.

Study of heterostructures of Cu3BiS3–buffer layer measured by Kelvin probe force microscopy measurements (KPFM)

The interface formed between Cu3BiS3 thin films and the buffer layer is a potentially limiting factor to the performance of solar cells based on Al/Cu3BiS3/buffer heterojunctions. The buffer layers of ZnS and In2S3 were grown by coevaporation, and tested as an alternative to the traditional CdS deposited by chemical bath deposition. From the Kelvin probe force microscopy measurements, we found the values of the work function of ZnS, In2S3, and CdS, layers deposited into Cu3BiS3. Additionally, different electronic activity was found for different grain boundaries (GBs), from studies under illumination, we also found the net doping concentration and the density of charged GB states for Cu3BiS3 and Cu3BiS3/CdS.

Probing charge screening dynamics and electrochemical processes at the solid–liquid interface with electrochemical force microscopy

The presence of mobile ions complicates the implementation of voltage-modulated scanning probe microscopy techniques such as Kelvin probe force microscopy (KPFM). Overcoming this technical hurdle, however, provides a unique opportunity to probe ion dynamics and electrochemical processes in liquid environments and the possibility to unravel the underlying mechanisms behind important processes at the solid–liquid interface, including adsorption, electron transfer and electrocatalysis. Here we describe the development and implementation of electrochemical force microscopy (EcFM) to probe local bias- and time-resolved ion dynamics and electrochemical processes at the solid–liquid interface. Using EcFM, we demonstrate contact potential difference measurements, consistent with the principles of open-loop KPFM operation. We also demonstrate that EcFM can be used to investigate charge screening mechanisms and electrochemical reactions in the probe–sample junction. We further establish EcFM as a force-based imaging mode, allowing visualization of the spatial variability of sample-dependent local electrochemical properties.

Colloidal drug probe : method development and validation for adhesion force measurement using atomic force microscopy

This study demonstrates a novel technique of preparing drug colloid probes to determine the adhesion force between the drug salbutamol sulphate (SS) and the surfaces of polymer microparticles to be used as carriers for the dispersion of drug particles from a dry powder inhaler (DPI) formulation. Initially model silica probes of approximately 4 μm size, similar to a drug particle used in DPI formulations, were coated with a saturated SS solution with the aid of capillary forces acting between the silica probe and the drug solution. The developed method of ensuring a smooth and uniform layer of SS on the silica probe was validated using X-Ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM). Using the same technique, silica microspheres preattached on the AFM cantilever were coated with SS. The adhesion forces between the silica probe and drug coated silica (drug probe) and polymer surfaces (hydrophilic and hydrophobic) were determined. Our experimental results showed that the technique for preparing the drug probe was robust and can be used to determine the adhesion force between hydrophilic/hydrophobic drug probe and carrier surfaces to gain a better understanding on drug carrier adhesion forces in DPI formulations.

Colloidal drug probe : Method development and validation for adhesion force measurement using Atomic Force Microscopy

This study demonstrates a novel technique of preparing drug colloid probes to determine the adhesion force between a model drug salbutamol sulphate (SS) and the surfaces of polymer microparticles to be used as carriers for the dispersion of drug particles from dry powder inhaler (DPI) formulations. Model silica probes of approximately 4 lm size, similar to a drug particle used in DPI formulations, were coated with a saturated SS solution with the aid of capillary forces acting between the silica probe and the drug solution. The developed method of ensuring a smooth and uniform layer of SS on the silica probe was validated using X-ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM). Using the same technique, silica microspheres pre-attached on the AFM cantilever were coated with SS. The adhesion forces between the silica probe and drug coated silica (drug probe) and polymer surfaces (hydrophilic and hydrophobic) were determined. Our experimental results showed that the technique for preparing the drug probe was robust and can be used to determine the adhesion force between hydrophilic/ hydrophobic drug probe and carrier surfaces to gain a better understanding on drug carrier adhesion forces in DPI formulations.

Length dependence of electron conduction for oligo(1,4-phenylene ethynylene)s: A conductive probe-atomic force microscopy investigation

The dependence of electron conduction of oligo(1,4-phenylene ethynylene)s (OPEs) on length, terminal group, and main chain structure was examined by conductive probe-atomic force microscopy (CP-AFM) via a metal substrate-molecular wire monolayer-conductive probe junction. The electron transport in the molecular junction was a highest occupied molecule orbital (HOMO)-mediated process following a coherent, non-resonant tunneling mechanism represented by the Simmons equation.

Conducting probe atomic force microscopy investigation of anisotropic charge transport in solution cast PBD single crystals induced by an external field

2-(4-Biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxdiazole (PBD) is a good electron-transporting material and can form single crystals from solution. In this work, solution cast PBD single crystals with different crystallographic axes (b, c) perpendicular to the Au/S substrates in large area are achieved by controlling the rate of solvent evaporation in the presence and absence of external electrostatic field, respectively. The orientation of these single crystals on Au/S substrate was characterized by transmission electron microscopy (TEM) and atomic force microscopy (AFM). Conducting probe atomic force microscopy (CP-AFM) was used to measure the charge transport characteristics of PBD single crystals grown on Au/S substrates. Transport was measured perpendicular to the substrate between the CP-AFM tip and the Au/S substrate. The electron mobility of 3 x 10(-3) cm(2)/(V s) for PBD single crystal along crystallographic b-axis is determined. And the electron mobility of PBD single crystal along the c-axis is about 2 orders of magnitude higher than that along the b-axis due to the anisotropic charge transport at the low voltage region.

Note: Design and development of an integrated three-dimensional scanner for atomic force microscopy

A compact scanning head for the Atomic Force Microscope (AFM) greatly enhances the portability of AFM and facilitates easy integration with other tools. This paper reports the design and development of a three-dimensional (3D) scanner integrated into an AFM micro-probe. The scanner is realized by means of a novel design for the AFM probe along with a magnetic actuation system. The integrated scanner, the actuation system, and their associated mechanical mounts are fabricated and evaluated. The experimentally calibrated actuation ranges are shown to be over 1 mu m along all the three axes. (c) 2013 AIP Publishing LLC.

Design and Evaluation of Torsional Probes for Multifrequency Atomic Force Microscopy

Multifrequency atomic force microscopy is a powerful nanoscale imaging and characterization technique that involves excitation of the atomic force microscope (AFM) probe and measurement of its response at multiple frequencies. This paper reports the design, fabrication, and evaluation of AFM probes with a specified set of torsional eigen-frequencies that facilitate enhancement of sensitivity in multifrequency AFM. A general approach is proposed to design the probes, which includes the design of their generic geometry, adoption of a simple lumped-parameter model, guidelines for determination of the initial dimensions, and an iterative scheme to obtain a probe with the specified eigen-frequencies. The proposed approach is employed to design a harmonic probe wherein the second and the third eigen-frequencies are the corresponding harmonics of the first eigen-frequency. The probe is subsequently fabricated and evaluated. The experimentally evaluated eigen-frequencies and associated mode shapes are shown to closely match the theoretical results. Finally, a simulation study is performed to demonstrate significant improvements in sensitivity to the second-and the third-harmonic spectral components of the tip-sample interaction force with the harmonic probe compared to that of a conventional probe.

Direct Measurement of Three-Dimensional Forces in Atomic Force Microscopy

Direct measurement of three-dimensional (3-D) forces between an atomic force microscope (AFM) probe and the sample benefits diverse applications of AFM, including force spectroscopy, nanometrology, and manipulation. This paper presents the design and evaluation of a measurement system, wherein the deflection of the AFM probe is obtained at two points to enable direct measurement of all the three components of 3-D tip-sample forces in real time. The optimal locations for measurement of deflection on the probe are derived for a conventional AFM probe. Further, a new optimal geometry is proposed for the probe that enables measurement of 3-D forces with identical sensitivity and nearly identical resolution along all three axes. Subsequently, the designed measurement system and the optimized AFM probe are both fabricated and evaluated. The evaluation demonstrates accurate measurement of tip-sample forces with minimal cross-sensitivities. Finally, the real-time measurement system is employed as part of a feedback control system to regulate the normal component of the interaction force, and to perform force-controlled scribing of a groove on the surface of polymethyl methacrylate.

Concentrated-Mass Cantilever Enhances Multiple Harmonics In Tapping-Mode Atomic Force Microscopy

The natural frequencies of a cantilever probe can be tuned with an attached concentrated mass to coincide with the higher harmonics generated in a tapping-mode atomic force microscopy by the nonlinear tip-sample interaction force. We provide a comprehensive map to guide the choice of the mass and the position of the attached particle in order to significantly enhance the higher harmonic signals containing information on the material properties. The first three eigenmodes can be simultaneously excited with only one carefully positioned particle of specific mass to enhance multiple harmonics. Accessing the interaction force qualitatively based on the high-sensitive harmonic signals combines the real-time material characterization with the imaging capability. (C) 2008 American Institute of Physics.

Ferromagnetic Resonance Force Microscopy

A new approach to magnetic resonance was introduced in 1992 based upon detection of spin-induced forces by J. Sidles [1]. This technique, now called magnetic resonance force microscopy (MRFM), was first demonstrated that same year via electron paramagnetic resonance (EPR) by D. Rugar et al. [2]. This new method combines principles of magnetic resonance with those of scanned probe technology to detect spin resonance through mechanical, rather than inductive, means. In this thesis the development and use of ferromagnetic resonance force microscopy (FMRFM) is described. This variant of MRFM, which allows investigation of ferromagnetic samples, was first demonstrated in 1996 by Z. Zhang et al. [3]. FMRFM enables characterization of (a) the dynamic magnetic properties of microscale magnetic devices, and (b) the spatial dependence of ferromagnetic resonance within a sample. Both are impossible with conventional ferromagnetic resonance techniques.

Ferromagnetically coupled systems, however, pose unique challenges for force detection. In this thesis the attainable spatial resolution - and the underlying physical mechanisms that determine it - are established. We analyze the dependence of the magnetostatic modes upon sample dimensions using a series of microscale yttrium iron garnet (YIG) samples. Mapping of mode amplitudes within these sample is attained with an unprecedented spatial resolution of 15μm. The modes, never before analyzed on this scale, fit simple models developed in this thesis for samples of micron dimensions. The application of stronger gradient fields induces localized perturbation of the ferromagnetic resonance modes. The first demonstrations of this effect are presented in this study, and a simple theoretical model is developed to explain our observations. The results indicate that the characteristics of the locally-detected ferromagnetic modes are still largely determined by the external fields and dimensions of the entire sample, rather than by the localized interaction volume (i.e., the locale most strongly affected by the local gradient field). Establishing this is a crucial first step toward understanding FMRFM in the high gradient field limit where the dispersion relations become locally determined. In this high gradient field regime, FMRFM imaging becomes analogous with that of EPR MRFM.

FMRFM has also been employed to characterize magnetic multilayers, similar to those utilized in giant magnetoresistance (GMR) devices, on a lateral scale 40 x 40μm. This is orders of magnitude smaller than possible via conventional methods. Anisotropy energies, thickness, and interface qualities of individual layers have been resolved.

This initial work clearly demonstrates the immense and unique potential that FMRFM offers for characterizing advanced magnetic nanostructures and magnetic devices.