Intermittent-contact local dielectric spectroscopy of nanostructured interfaces.

Local dielectric spectroscopy (LDS) is a scanning probe method, based on dynamic-mode atomic force microscopy (AFM), to discriminate dielectric properties at surfaces with nanometer-scale lateral resolution. Until now a sub-10 nm resolution for LDS has not been documented, that would give access to the length scale of fundamental physical phenomena such as the cooperativity length related to structural arrest in glass formers (2-3 nm). In this work, LDS performed by a peculiar variant of intermittent-contact mode of AFM, named constant-excitation frequency modulation, was introduced and extensively explored in order to assess its best resolution capability. Dependence of resolution and contrast of dielectric imaging and spectroscopy on operation parameters like probe oscillation amplitude and free amplitude, the resulting frequency shift, and probe/surface distance-regulation feedback gain, were explored. By using thin films of a diblock copolymer of polystyrene (PS) and polymethylmethacrylate (PMMA), exhibiting phase separation on the nanometer scale, lateral resolution of at least 3 nm was demonstrated in both dielectric imaging and localized spectroscopy, by operating with optimized parameters. The interface within lamellar PS/PMMA was mapped, with a best width in the range between 1 and 3 nm. Changes of characteristic time of the secondary (ß) relaxation process of PMMA could be tracked across the interface with PS.

Tuning-fork-based piezoresponse force microscopy.

Surface displacements of a few picometers, occurring after application of an electric potential to piezoelectric materials, can be detected and mapped with nanometer-scale lateral resolution by scanning probe methods, the most notable being piezoresponse force microscopy (PFM). Yet, absolute determination of such displacements, giving access for instance to materials' piezoelectric coefficients, are hindered by both mechanical and electrostatic side-effects, requiring complex experimental and/or post-processing procedures for carrying out reliable results. The employment of quartz tuning-fork force sensors in an intermittent contact mode PFM is able to provide measurements of electrically-induced surface displacements that are not influenced by electrostatic side-effects typical of more conventional cantilever-based PFM. The method is shown to yield piezoeffect mapping on standard ferroelectric test crystals (periodically-poled lithium niobate and triglycine sulfate), as well as on a ferroelectric polymer (PVDF), with no visible influence from the applied dc electric potential.

Lateral resolution of electrostatic force microscopy for mapping of dielectric interfaces in ambient conditions.

The attainable lateral resolution of electrostatic force microscopy (EFM) in an ambient air environment on dielectric materials was characterized on a reference sample comprised of two distinct, immiscible glassy polymers cut in a cross-section by ultramicrotomy. Such a sample can be modeled as two semi-infinite dielectrics with a sharp interface, presenting a quasi-ideal, sharp dielectric contrast. Electric polarizability line profiles across the interface were obtained, in both lift-mode and feedback-regulated dynamic mode EFM, as a function of probe/surface separation, for different cases of oscillation amplitudes. We find that the results do not match predictions for dielectric samples, but comply well or are even better than predicted for conductive interfaces. A resolution down to 3 nm can be obtained by operating in feedback-regulated EFM realized by adopting constant-excitation frequency-modulation mode. This suggests resolution is ruled by the closest approach distance rather than by average separation, even with probe oscillation amplitudes as high as 10 nm. For better comparison with theoretical predictions, effective probe radii and cone aperture angles were derived from approach curves, by also taking into account the finite oscillation amplitude of the probe, by exploiting a data reduction procedure previously devised for the derivation of interatomic potentials.

Model of frequency-modulated atomic force microscopy for interpretation of noncontact piezoresponse measurements.

A model to describe the behavior of the probe of an atomic force microscope (AFM) operated in frequency modulation (FM) dynamic mode with constant excitation (CE) is developed, with the aim of describing recent experiments after the introduction of a noncontact piezoresponse force microscopy (PFM) method based on such an operation mode, named CE-FM-PFM (Labardi et al 2020 Nanotechnology 31, 075707). The model provides insight into improving the accuracy of converse piezoelectric coefficient (d 33) measurements on the local scale in this PFM mode. Its rather general applicability helps to quantify the residual electrostatic contribution in local piezoresponse measurements by AFM, which is anticipated to be strongly mitigated in the CE-FM-PFM compared to the more standard contact-mode PFM.

Piezoelectric displacement mapping of compliant surfaces by constant-excitation frequency-modulation piezoresponse force microscopy.

A simple experimental method for piezoresponse force microscopy (PFM) measurements for reliable evaluation of piezoelectric surface displacements even on compliant surfaces is proposed based on atomic force microscopy (AFM) operated in frequency-modulation (FM) dynamic mode with constant excitation (CE), by using non-contact mode cantilevers. Surface displacement by piezoelectric effect after application of an electric potential to the conductive AFM probe translates into a likewise variation of the probe oscillation amplitude, while the related electrostatic forces mainly affect the oscillator resonant frequency, and cantilever bending is limited due to their high stiffness. Our non-contact CE-FM-PFM method is shown to reduce electrostatic force contributions as compared to contact-PFM modes. Converse piezoelectric effect mapping is demonstrated on poly(vinylidenefluoride) nanofibers obtained by electrospinning.

Dynamics of poly(vinyl methyl ketone) thin films studied by local dielectric spectroscopy.

Local dielectric spectroscopy, which entails measuring the change in resonance frequency of the conducting tip of an atomic force microscope to determine the complex permittivity of a sample with high spatial (lateral) resolution, was employed to characterize the dynamics of thin films of poly(vinyl methyl ketone) (PVMK) having different substrate and top surface layers. A free surface yields the usual speeding up of the segmental dynamics, corresponding to a glass transition suppression of 6.5° for 18 nm film thickness. This result is unaffected by the presence of a glassy, compatible polymer, poly-4-vinyl phenol (PVPh), between the metal substrate and the PVMK. However, covering the top surface with a thin layer of the PVPh suppresses the dynamics. The speeding up of PVMK segmental motions observed for a free surface is absent due to interfacial interactions of the PVMK with the glass layer, an effect not seen when the top layer is an incompatible polymer.

Effect of Interface Interaction on the Segmental Dynamics of Poly(vinyl acetate) Investigated by Local Dielectric Spectroscopy.

The segmental dynamics of poly(vinyl acetate) (PVAc) thin films were measured in the presence of an aluminum interface and in contact with an incompatible polymer, poly(4-vinylpyridine). The local dielectric relaxation was found to be faster in thin films than in the bulk; however, no differences were observed for the various interfaces, including a PVAc/air interface. These results show that capping of thin films, even with a rigid material, does not necessarily affect the dynamics, the speeding up herein for capped PVAc was equivalent to that for the air interface. The insensitivity of the dynamics to the nature of the interface affords a means to engineer thin films while maintaining desired mechanical properties. Our findings for PVAc also may explain the discordant results that have been reported in general for the effect of air versus rigid interfaces on the local segmental relaxation of thin films.

Balanced homodyning for apertureless near-field optical imaging.

A quadrature optical detection technique, based on polarized balanced-homodyne interferometry, has been developed for specific application to apertureless near-field scanning optical microscopy (ANSOM). With such technique, multiplicative background interference, inficiating quantitative optical imaging in standard homodyne-based ANSOM, can be suppressed. Periodic modulation of interferometric optical phase, typically employed in heterodyne-based ANSOMs even to such purpose, is not needed in the present configuration. Homodyne detection also facilitates detection of harmonic components of the ANSOM optical signal at the probe/sample distance modulation frequency, necessary for near-field discrimination and suppression of artifacts. Furthermore, since amplitude signal is not affected by phase fluctuations generated in the optical path of the interferometer, an optical fiber could be included in one interferometer arm, to couple the ANSOM head to the detection system, obtaining improved versatility of the instrument. A demonstration of the interferometer performance is given by a test confocal optical scan of a mirror surface. This technique, as applied to near-field microscopy, is anticipated to provide absolute values of optical contrast not depending on background interference and topography artifacts.

Mapping local field enhancements at nanostructured metal surfaces by second-harmonic generation induced in the near field.

We report on an aperture scanning near-field optical microscope in which femtosecond pulses are coupled to a hollow-pyramid aperture sensor. Such probe displays high throughput and preserves pulse duration and polarization, enabling the achievement of sufficiently high peak power in the near field to perform nonlinear optics on the nanoscale. We use the system to observe the nonlinear optical response of nanostructured metal surfaces with sub-100-nm spatial resolution. We study second-harmonic generation from gold nanoparticles both isolated and in high-density patterns, highlighting a strong dependence of the generation efficiency on the shape and on the fine structure of the nanoemitter. In particular, we present results on closely packed gold triangles as well as on nanoellipsoids with different local surface plasmon resonances.

Dynamics of probes attached to quartz tuning forks for the detection of surface forces.

The dynamics of force microscopy probes attached to quartz tuning fork piezoelectric sensors has been investigated, by simply modeling the tuning fork/probe system as two coupled damped harmonic oscillators. Depending on how probes are applied to the tuning fork prong, they could show appreciable compliance along the direction of approach to the surface. In particular, buckling or bending deformation of the probe may account for unexpectedly long interaction ranges found in experimental approach curves. Some peculiar curves found in the literature in the case of lateral probe oscillation (shear force) are well reproduced by the present model. In particular, a 'clamping' effect is observed when the probe is substantially more compliant than the tuning fork. By calculating the actual probe motion along with the tuning fork response, the correct distance control operation regimes are pointed out for the shear-force case, even when using compliant probes. The model can be readily extended to the case of normal oscillation, at least for small amplitudes. Furthermore, it could be applied to a 'mixed' case of shear-force detection performed with very compliant probes. The present analysis can help to improve data interpretation and operation conditions in dynamic force microscopy and spectroscopy.

Highly efficient second-harmonic nanosource for near-field optics and microscopy.

A nanometric source of second-harmonic (SH) light with unprecedented efficiency is demonstrated; it exploits the grazing-incidence illumination of a metal tip, which is conventionally used for atomic force microscopy, by 25-fs laser pulses of a high-energy Ti:sapphire oscillator. Tip scanning around the beam focus shows that the SH generation is strongly localized at its apex. The polarization dependence of the SH light complies with the model of an on-axis nonlinear oscillating dipole.

A versatile multipurpose scanning probe microscope.

A combined scanning probe microscope has been developed that allows simultaneous operation as a non-contact/tapping mode atomic force microscope, a scattering near-field optical microscope, and a scanning tunnelling microscope on conductive samples. The instrument is based on a commercial optical microscope. It operates with etched tungsten tips and exploits a tuning fork detection system for tip/sample distance control. The system has been tested on a p-doped silicon substrate with aluminium depositions, being able to discriminate the two materials by the electrical and optical images with a lateral resolution of 130 nm.

Optical near-field harmonic demodulation in apertureless microscopy.

Spatial derivatives of the optical fields scattered by a surface can be investigated by apertureless near-field optical microscopy by modulating sinusoidally the probe to sample distance and detecting the optical signal at the first and higher harmonics. Demodulation up to the fifth harmonic order has been accomplished on a sample of close-packed latex spheres by means of the silicon tip of a scanning interference apertureless microscope. The working principles of such microscope are reviewed. The experimental configuration used comprises a tuning-fork-based tapping-mode atomic force microscope for the distance stabilization, and a double-modulation technique for complete separation of the topography tracking from the optical detection. Simple modelling provides first indications for the interpretation of experimental data. The technique described here provides either artefact-free near-field optical imaging, or detailed information on the structure of the near fields scattered by a surface.

Serum HBV DNA and intrahepatic hepatitis B core antigen (HBcAg) in chronic hepatitis B virus infection: correlation with infectivity and liver histology.

In this study we investigated the HBeAg/anti HBeAg status, the liver histological features, the intrahepatic localization of HBcAg, and the presence of serum HBV DNA in a group of 79 HBsAg-positive patients. We found a close relationship between the presence of HBV DNA and intrahepatic HBcAg in HBeAg-positive patients. Among the 56 anti-HBeAg-positive patients considered, 13 (23.2%) showed the presence of intrahepatic HBcAg and serum HBV DNA. In this group of patients, active viral replication was associated with a chronic inflammatory liver disease and particularly with CAH. Furthermore, a prevalent cytoplasmic localization of HBcAg was found in 66.6% of patients affected by CAH, showing that this peculiar distribution of HBcAg seems to be associated with a poor prognosis.