Nanopatterning in Langmuir-Blodgett monolayers of a thermoresponsive double hydrophilic block copolymer studied by atomic force microscopy

The microphase-separation of Langmuir-Blodgett (LB) monolayers of a rhodamine B (RhB) end-labeled double hydrophilic block copolymer (DHBC), RhB-Poly(N,N-dimethylacrylamide)-b-poly(N,N-diethylacryl-amide) (RhB-PDMA(207)b-PDEA177) and the 1:1 segmental mixture of PDEA and RhB-PDMA homopolymers was followed by AFM. The DHBC LB films revealed a loose distribution of nano-aggregates with variable geometries below the lower critical solution temperature (LCST) of PDEA (32 degrees C) and low surface pressure (3 mN m(-1)). By increasing either the temperature above the LCST of PDEA or the surface pressure beyond the immersion regime of PDMA in the subphase (7 mN m(-1)) a dense nanopatterning was obtained. The absence of a corresponding regular nanopatterning in LB films of mixed homopolymers with the same composition highlights the role of the covalent bonding between PDEA and PDMA on the self-segregation of the two blocks at the air-water interface.     

Mesoporous block copolymer nanorods by swelling-induced morphology reconstruction

Engineering the topography of thin block copolymer (BCP) films by surface reconstruction associated with selective swelling of one of the blocks has been investigated intensively. Here we show that swelling-induced structural transitions in nanorods consisting of amphiphilic BCPs involve pronounced reshaping of the nonswollen glassy domains in the course of the transition from the equilibrium morphology of the molten BCP in cylindrical confinement to that of the BCP dissolved in the swelling agent. The reconstruction process can be quenched to retain intermediate nonequilibrium morphologies. The collapse of the swollen chains upon drying yields polymeric nanorods exhibiting complex nanoscopic architectures characterized by a variety of mesopore structures and surface topographies, including channels along the nanorods, bunches of partially interconnected strands, and strings of spheres. The complex BCP nanorods thus obtained can be used as soft templates for the rational arrangement of metal nanoparticles.     

Combined atomic force microscopy and optical microscopy measurements as a method to investigate particle uptake by cells

We propose a combination of atomic force microscopy (AFM) and optical microscopy for the investigation of particle uptake by cells. Positively and negatively charged polymer microcapsules were chosen as model particles, because their interaction with cells had already been investigated in detail. AFM measurements allowed the recording of adhesion forces on a single-molecule level. Due to the micrometer size of the capsules, the number of ingested capsules could be counted by optical microscopy. The combination of both methods allowed combined measurement of the adhesion forces and the uptake rate for the same model particle. As a demonstration of this system, the correlation between the adhesion of positively or negatively charged polymer microcapsules onto cell surfaces and the uptake of these microcapsules by cells has been investigated for several cell lines. As is to be expected, we find a correlation between both processes, which is in agreement with adsorption-dependent uptake of the polymer microcapsules by cells.     

Mapping van der Waals forces with frequency modulation dynamic force microscopy

Nanometre-size gold clusters supported on MoS(2)(0001) are investigated by means of ultrahigh-vacuum frequency modulation dynamic force microscopy. Topography and frequency shift images are simultaneously obtained using the average tunnelling current to regulate the tip-substrate distance. Two families of clusters are observed, giving different frequency shift images. While the topographic and frequency shift profiles have similar shapes on small clusters (size [Formula: see text]?nm), they are quite different near the top of large clusters (size [Formula: see text]?nm): the topographic profile is rounded, but the frequency shift profile exhibits rather steep edges and a depression near the centre of the island. It is demonstrated that these differences result from the finite range of van der Waals forces. On small islands, the frequency shift is dominated by the interaction of the tip with the substrate. On large islands, it is dominated by the interaction with the island. The particular observed shape results from the geometry of the island. These interpretations are comforted by analytical and numerical calculations. In particular, the characteristic shape of the frequency shift profiles on large islands can be reproduced by introducing realistic parameters and considering only the contribution of van?der?Waals forces.     

Morphology-driven modulation of charge transport in radical/ion-containing, self-assembled block copolymer platform

A TEMPO-substituted ionic liquid was selectively incorporated into well-defined, self-assembled block copolymer templates, which served as an active layer for organic nonvolatile memory. Phase structures (sphere, cylinder, and lamellae) and their orientation modulated the resistive switching behavior, which demonstrated the unprecedented, morphology-driven charge transport in the organic electronic devices.     

Measuring phase shifts and energy dissipation with amplitude modulation atomic force microscopy

By recording the phase angle difference between the excitation force and the tip response in amplitude modulation AFM it is possible to image compositional variations in heterogeneous samples. In this contribution we address some of the experimental issues relevant to perform phase contrast imaging measurements. Specifically, we study the dependence of the phase shift on the tip-surface separation, interaction regime, cantilever parameters, free amplitude and tip-surface dissipative processes. We show that phase shift measurements can be converted into energy dissipation values. Energy dissipation curves show a maximum (～10?eV/cycle) with the amplitude ratio. Furthermore, energy dissipation maps provide a robust method to image material properties because they do not depend directly on the tip-surface interaction regime. Compositional contrast images are illustrated by imaging conjugated molecular islands deposited on silicon surfaces.     

Characterization of materials' nanomechanical properties by force modulation and phase imaging atomic force microscopy with soft cantilevers

Soft cantilevers, although having good force sensitivity, have found limited use for investigating materials' nanomechanical properties by conventional force modulation (FM) and intermittent contact (IC) atomic force microscopy. This is due to the low forces and small indentations that these cantilevers are able to exert on the surface, and to the high amplitudes required to overcome adhesion to the surface. In this paper, it is shown that imaging of local elastic properties of surface and subsurface layers can be carried out by employing electrostatic forcing of the cantilever. In addition, by mechanically exciting the higher vibration modes in contact with the surface and monitoring the phase of vibrations, the contrast due to local surface elasticity is obtained.     

The emergence of multifrequency force microscopy

In atomic force microscopy a cantilever with a sharp tip attached to it is scanned over the surface of a sample, and information about the surface is extracted by measuring how the deflection of the cantilever - which is caused by interactions between the tip and the surface - varies with position. In the most common form of atomic force microscopy, dynamic force microscopy, the cantilever is made to vibrate at a specific frequency, and the deflection of the tip is measured at this frequency. But the motion of the cantilever is highly nonlinear, and in conventional dynamic force microscopy, information about the sample that is encoded in the deflection at frequencies other than the excitation frequency is irreversibly lost. Multifrequency force microscopy involves the excitation and/or detection of the deflection at two or more frequencies, and it has the potential to overcome limitations in the spatial resolution and acquisition times of conventional force microscopes. Here we review the development of five different modes of multifrequency force microscopy and examine its application in studies of proteins, the imaging of vibrating nanostructures, measurements of ion diffusion and subsurface imaging in cells.     

Nanopatterned carbon films with engineered morphology by direct carbonization of UV-stabilized block copolymer films

Nanopatterned thin carbon films were prepared by direct and expeditious carbonization of the block copolymer polystyrene- block-poly(2-vinylpyridine) (PS- b-P2VP) without the necessity of slow heating to the process temperature and of addition of further carbon precursors. Carbonaceous films having an ordered "dots-on-film" surface topology were obtained from reverse micelle monolayers. The regular nanoporous morphology of PS- b-P2VP films obtained by subjecting reverse micelle monolayers to swelling-induced surface reconstruction could likewise be transferred to carbon films thus characterized by ordered nanopit arrays. Stabilization of PS- b-P2VP by UV irradiation and the concurrent carbonization of both blocks were key to the conservation of the film topography. The approach reported here may enable the realization of a broad range of nanoscaled architectures for carbonaceous materials using a block copolymer ideally suited as a template because of the pronounced repulsion between its blocks and its capability to form highly ordered microdomain structures.     

Direct measurement of interaction force between hydrophilic silica surfaces in triblock copolymer solutions with salt by atomic force microscopy

Triblock copolymers composed of polyethylene oxide (PEO) and polypropylene oxide (PPO) are used in various fields as nonionic surfactants. In this study, we measured interaction forces between untreated hydrophilic silica surfaces in solutions with two typical triblock copolymers, Pluronic P123 (PEO₂₀PPO₇₀PEO₂₀) and F127 (PEO₉₉PPO₆₅PEO₉₉), in the presence of 1 mM and 500 mM NaCl using atomic force microscopy (AFM). In solutions at the copolymer concentration of 1 µM, which is below the critical micelle concentration (CMC), the measured interaction forces were monotonically repulsive in the presence of 1 mM NaCl, which suggested the brush-like conformation of copolymers on the surfaces. When the concentration of NaCl was increased to 500 mM, interaction forces became attractive, which indicated the bridging of adsorbed polymers onto surfaces, the strength of which varied depending on the affinity and adsorption density of copolymers. The interactions at the copolymer concentration of 1 mM, which were above the CMC of both copolymers, were steric repulsions between adsorbed micelles on the surfaces with 1 mM of NaCl. For 500 mM of NaCl, an attractive jump after a steric repulsion was observed only in the force curve for P123, which inferred that the displacement of micelles from the surfaces was presumably due to a decrease in the strength of adsorption caused by the dehydration of EO groups. These results indicated that the length of the EO group considerably affected the interactions.     

PMMA-b-PHEA嵌段共聚物的制备和表征

采用分步法合成了两嵌段共聚物聚甲基丙烯酸甲酯-b-聚丙烯酸-2-羟乙酯(PMMA-b-PHEA):首先采用AIBN作为引发剂,FeCl3/PPh3作为催化体系,通过MMA的反向原子转移自由基聚合(RA-TRP),得到含端基Cl的M-n为17128聚合物PMMA-Cl;然后以PMMA-Cl为大分子引发剂,FeCl2/PPh3为催化体系,引发丙烯酸-2-羟乙酯(HEA)的原子转移自由基聚合(ATRP),得到的产物PMMA-b-PHEA分子量分布达到1.32,凝胶渗透色谱(GPC)、红外光谱(FTIR)、核磁共振(1HNMR)、差示扫描量热仪(DSC)和热重分析仪(TGA)对产物结构进行了表征,证实了嵌段共聚物PMMA-b-PHEA的生成。     

Energy dissipation distributions and dissipative atomic processes in amplitude modulation atomic force microscopy

Instantaneous and average energy dissipation distributions in the nanoscale due to short and long range interactions are described. We employ both a purely continuous and a semi-discrete approach to analyze the consequences of this distribution in terms of rate of heat generation, thermal flux, adhesion hysteresis, viscoelasticity and atomic dissipative processes. The effects of peak values are also discussed in terms of the validity of the use of average values of power and energy dissipation. Analytic expressions for the instantaneous power are also derived. We further provide a general expression to calculate the effective area of interaction for fundamental dissipative processes and relate it to the energy distribution profile in the interaction area. Finally, a semi-discrete approach to model and interpret atomic dissipative processes is proposed and shown to lead to realistic values for the atomic bond dissipation and viscoelastic atomic processes.     

Effects of frequencies of AC modulation voltage on piezoelectric-induced images using atomic force microscopy

Lead zirconate titanate (PZT) thin film is prepared by sol-gel method on Pt/Ti electrode/SiO₂/Si wafer. Local poling is performed on the PZT film using an atomic force microscope (AFM). The topography and piezoelectric-induced (PEI) images on the polarized PZT film are recorded using AFM at piezo-responsive mode, operated with an AC voltage at varying frequencies. The best PEI image was obtained at the frequency around 300 kHz. It is explained that the change of piezoelectric vibrations and input noise signals with the frequency of AC modulation voltage affects the intensity of PEI images.     

Morphologies of block copolymer melts

Morphology formation by block copolymers in the melt is reviewed, considering both theoretical and experimental aspects. Comprehensive tables provide information on morphology identification for many block copolymer systems. A particular focus is on recent structural studies on ABC triblocks and rod–coil copolymers.     

A force modulation study on crystallization process in ferroelectric vinylidene fluoride and trifluoroethylene copolymer films

This paper introduces the Force Modulation technique to the study of crystallization process in ferroelectric vinylidene fluoride and trifluoroethylene copolymer films. Using this technique we have successfully visualized ferroelectric crystalline domains and observed that these ferroelectric domains grow out from amorphous phase, unite into strip-like structures, and finally congregate into a union. Force Modulation can weaken the influence of topography on imaging of ferroelectric domains, and reveal more details, which are difficult to be observed in topographical image.