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Martensitic transformation was investigated by the combination of electron backscatter diffraction and in situ atomic force microscope (AFM). The metastable tetragonal phase in the plasma-sprayed 3 mol% Y2O3-ZrO2 coating showed a strong basal texture with the {001}t plane parallel to the surface. The habit plane (108)t of a pair of V-arranged monoclinic variants was determined on the basis of the lattice correspondence of (001)m//(100)t, [100]m//[010]t, and [010]m//[001]t and an included angle of 14°. Additionally, the direction of residual stress in the coatings was revealed by the periodic corrugation patterns of AFM, which matched approximately with 10° deflection of the basal texture. This was further confirmed by an in situ reverse transformation from the monoclinic phase to tetragonal phase and the formation of parallel microcracks after stress release during heat treatment.

An electrothermal piezoresistive cantilever (EPC) sensor is a low-cost MEMS resonance sensor that provides self-actuating and self-sensing capabilities. In the platform, which is of MEMS-cantilever shape, the EPC sensor offers several advantages in terms of physical, chemical, and biological sensing, e.g., high sensitivity, low cost, simple procedure, and quick response. However, a crosstalk effect is generated by the coupling of parasitic elements from the actuation part to the sensing part. This study presents a parasitic feedthrough subtraction (PFS) method to mitigate a crosstalk effect in an electrothermal piezoresistive cantilever (EPC) resonance sensor. The PFS method is employed to identify a resonance phase that is, furthermore, deployed to a phase-locked loop (PLL)-based system to track and lock the resonance frequency of the EPC sensor under cigarette smoke exposure. The performance of the EPC sensor is further evaluated and compared to an AFM-microcantilever sensor and a commercial particle counter (DC1100-PRO). The particle mass–concentration measurement result generated from cigarette-smoke puffs shows a good agreement between these three detectors.

In this study, we investigate the performance of two piezoresistive micro-electro-mechanical system (MEMS)-based silicon cantilever sensors for measuring target analytes (i.e., ultrafine particulate matters). We use two different types of cantilevers with geometric dimensions of 1000 &times, 170 &times, 19.5 &micro, m3 and 300 &times, 100 &times, 4 &micro, m3, which refer to the 1st and 2nd types of cantilevers, respectively. For the first case, the cantilever is configured to detect the fundamental in-plane bending mode and is actuated using a resistive heater. Similarly, the second type of cantilever sensor is actuated using a meandering resistive heater (bimorph) and is designed for out-of-plane operation. We have successfully employed these two cantilevers to measure and monitor the changes of mass concentration of carbon nanoparticles in air, provided by atomizing suspensions of these nanoparticles into a sealed chamber, ranging from 0 to several tens of &micro, g/m3 and oversize distributions from ~10 nm to ~350 nm. Here, we deploy both types of cantilever sensors and operate them simultaneously with a standard laboratory system (Fast Mobility Particle Sizer, FMPS, TSI 3091) as a reference.

Copyright © 2019 American Chemical Society. Accessing the thermal properties of materials or even full devices is a highly relevant topic in research and development. Along with the ongoing trend toward smaller feature sizes, the demands on appropriate instrumentation to access surface temperatures with high thermal and lateral resolution also increase. Scanning thermal microscopy is one of the most powerful technologies to fulfill this task down to the sub-100 nm regime, which, however, strongly depends on the nanoprobe design. In this study, we introduce a three-dimensional (3D) nanoprobe concept, which acts as a nanothermistor to access surface temperatures. Fabrication of nanobridges is done via 3D nanoprinting using focused electron beams, which allows direct-write fabrication on prestructured, self-sensing cantilever. As individual branch dimensions are in the sub-100 nm regime, mechanical stability is first studied by a combined approach of finite-element simulation and scanning electron microscopy-assisted in situ atomic force microscopy (AFM) measurements. After deriving the design rules for mechanically stable 3D nanobridges with vertical stiffness up to 50 N m-1, a material tuning approach is introduced to increase mechanical wear resistance at the tip apex for high-quality AFM imaging at high scan speeds. Finally, we demonstrate the electrical response in dependence of temperature and find a negative temperature coefficient of -(0.75 ± 0.2) 10-3 K-1 and sensing rates of 30 ± 1 ms K-1 at noise levels of ±0.5 K, which underlines the potential of our concept. ©

Suspended membranes of two-dimensional (2D) materials are of interest for many applications. Much of their characterization relies on scanning probe microscopy (SPM) techniques such as atomic force microscopy (AFM) or scanning tunneling microscopy (STM). Unlike rigid samples, the suspended atomically thin 2D membranes are, however, flexible and do not remain mechanically undisturbed during SPM measurements. Local deformations can occur at the location of the scanning tip and thus result in measurements that misrepresent actual membrane topography and nanomechanical properties. Exact levels of such SPM tip-induced deformations in 2D membranes remain largely unknown, as they are to date only indirectly accessible via dual probe microscope concepts that either are not mechanically independent (e.g., SPM-SPM setups resulting in complicated imaging crosstalk) or suffer from intrinsically limited lateral resolution (e.g., optical far-field techniques as the second probe). Circumventing these shortcomings, we here demonstrate that by coupling an AFM with a scanning electron microscope (SEM) as the second, mechanically independent probe, we can directly and in situ visualize by SEM at high resolution 2D membrane deformations that result from controllable AFM tip manipulations in the nN range. Employing few-layer graphene as model membranes, we discuss the experimental realization of our coupled in situ AFM-SEM approach.

The sensitivity and detection speed of cantilever-based mechanical sensors increases drastically through size reduction. The need for such increased performance for high-speed nanocharacterization and bio-sensing, drives their sub-micrometre miniaturization in a variety of research fields. However, existing detection methods of the cantilever motion do not scale down easily, prohibiting further increase in the sensitivity and detection speed. Here we report a nanomechanical sensor readout based on electron co-tunnelling through a nanogranular metal. The sensors can be deposited with lateral dimensions down to tens of nm, allowing the readout of nanoscale cantilevers without constraints on their size, geometry or material. By modifying the inter-granular tunnel-coupling strength, the sensors' conductivity can be tuned by up to four orders of magnitude, to optimize their performance. We show that the nanoscale printed sensors are functional on 500 nm wide cantilevers and that their sensitivity is suited even for demanding applications such as atomic force microscopy., Reducing the size of cantilever-based sensors increases the sensitivity and detection speed of techniques such as atomic force microscopy. Here, the authors demonstrate a nanomechanical readout method that can be easily scaled down in size by using electron co-tunnelling through a nanogranular metal.

Background: Focused electron beam induced deposition (FEBID) is a direct-writing technique with nanometer resolution, which has received strongly increasing attention within the last decade. In FEBID a precursor previously adsorbed on a substrate surface is dissociated in the focus of an electron beam. After 20 years of continuous development FEBID has reached a stage at which this technique is now particularly attractive for several areas in both, basic and applied research. The present topical review addresses selected examples that highlight this development in the areas of charge-transport regimes in nanogranular metals close to an insulator-to-metal transition, the use of these materials for strain- and magnetic-field sensing, and the prospect of extending FEBID to multicomponent systems, such as binary alloys and intermetallic compounds with cooperative ground states.Results: After a brief introduction to the technique, recent work concerning FEBID of Pt–Si alloys and (hard-magnetic) Co–Pt intermetallic compounds on the nanometer scale is reviewed. The growth process in the presence of two precursors, whose flux is independently controlled, is analyzed within a continuum model of FEBID that employs rate equations. Predictions are made for the tunability of the composition of the Co–Pt system by simply changing the dwell time of the electron beam during the writing process. The charge-transport regimes of nanogranular metals are reviewed next with a focus on recent theoretical advancements in the field. As a case study the transport properties of Pt–C nanogranular FEBID structures are discussed. It is shown that by means of a post-growth electron-irradiation treatment the electronic intergrain-coupling strength can be continuously tuned over a wide range. This provides unique access to the transport properties of this material close to the insulator-to-metal transition. In the last part of the review, recent developments in mechanical strain-sensing and the detection of small, inhomogeneous magnetic fields by employing nanogranular FEBID structures are highlighted.Conclusion: FEBID has now reached a state of maturity that allows a shift of the focus towards the development of new application fields, be it in basic research or applied. This is shown for selected examples in the present review. At the same time, when seen from a broader perspective, FEBID still has to live up to the original idea of providing a tool for electron-controlled chemistry on the nanometer scale. This has to be understood in the sense that, by providing a suitable environment during the FEBID process, the outcome of the electron-induced reactions can be steered in a controlled way towards yielding the desired composition of the products. The development of a FEBID-specialized surface chemistry is mostly still in its infancy. Next to application development, it is this aspect that will likely be a guiding light for the future development of the field of focused electron beam induced deposition.

Binary systems of Pt-Si are prepared by electron-beam-induced deposition using the two precursors, trimethyl(methylcyclopentadienyl)platinum(IV) (MeCpPt(Me)(3)) and neopentasilane (Si(SiH(3))(4)), simultaneously. By varying the relative flux of the two precursors during deposition, we are able to study composites containing platinum and silicon in different ratios by means of energy-dispersive X-ray spectroscopy, atomic force microscopy, electrical transport measurements, and transmission electron microscopy. The results show strong evidence for the formation of a binary, metastable Pt(2)Si(3) phase, leading to a maximum in the conductivity for a Si/Pt ratio of 3:2.

The electron transfer processes at the interface between 3,4,9,10-perylene-tetracarboxylic acid dianhydride (PTCDA) and Ag(111) have been studied using time- and angle-resolved two-photon photo-emission (2PPE). For this system a dispersing unoccupied interface state can be identified that is located 0.6 eV above the Fermi level with an effective electron mass of 0.39 me at the $\overline{\Gamma}$ -point. The lifetime of 54 fs for the interface state is relatively short indicating a large penetration of the wavefunction into the metal. Supported by model calculations this interface state is interpreted as predominantly arising from an upshift of the occupied Shockley surface state of the clean metal substrate due to the interaction with the PTCDA overlayer. Coverage dependent measurements show a second long-lived component in the time-resolved measurements for higher PTCDA coverages that can be associated to charge transfer processes from the PTCDA multilayers into the metal substrate. Additionally the influence of the PTCDA adlayers on the image-potential states is studied indicating that the n = 1 image-potential state is localized in the first two monolayers of the PTCDA film.

Focused electron beam induced deposition presents a promising technique for the fabrication of nanostructures. However, due to the dissociation of mostly organometallic precursor molecules employed for the deposition process, prepared nanostructures contain organic residues leading to rather low conductance of the deposits. Post-growth treatment of the structures by electron irradiation or in reactive atmospheres at elevated temperatures can be applied to purify the samples. Recently, an in-situ conductance optimization process involving evolutionary genetic algorithm techniques has been introduced leading to an increase of conductance by one order of magnitude for tungsten-based deposits using the precursor W(CO)6. This method even allows for the optimization of conductance of nano-structures for which post-growth treatment is not possible or desirable. However, the mechanisms responsible for the observed enhancement have not been studied in depth. In this work, we identified the dwell-time dependent change of conductivity of the samples to be the major contributor to the change of conductance. Specifically, the chemical composition drastically changes with a variation of dwelltime resulting in an increase of the metal content by 15 at% for short dwell-times. The relative change of growth rate amounts to less than 25 % and has a negligible influence on conductance. We anticipate the in-situ genetic algorithm optimization procedure to be of high relevance for new developments regarding binary or ternary systems prepared by focused electron or ion beam induced deposition.

We present the application of an evolutionary genetic algorithm for the in situ optimization of nanostructures that are prepared by focused electron-beam-induced deposition (FEBID). It allows us to tune the properties of the deposits towards the highest conductivity by using the time gradient of the measured in situ rate of change of conductance as the fitness parameter for the algorithm. The effectiveness of the procedure is presented for the precursor W(CO)6 as well as for post-treatment of Pt–C deposits, which were obtained by the dissociation of MeCpPt(Me)3. For W(CO)6-based structures an increase of conductivity by one order of magnitude can be achieved, whereas the effect for MeCpPt(Me)3 is largely suppressed. The presented technique can be applied to all beam-induced deposition processes and has great potential for a further optimization or tuning of parameters for nanostructures that are prepared by FEBID or related techniques.

Incorporating resistive strain-sensing elements into MEMS devices is a long-standing approach for electronic detection of the device deformation. As the need for more sensitivity trends the device dimensions downwards, the size of the strain-sensor may become comparable to the device size, which can have significant impact on the mechanical behaviour of the device. To study this effect, we modelled a submicron-thickness silicon nitride AFM cantilever with strain-sensing element. Using finite element analysis, we calculated the strain in the sensor elements for a deflected cantilever. The sensor element contributes to a local stiffening effect in the device structure which lowers the strain in the sensor. By varying the sensor geometry, we investigated the degree to which this effect impacts the strain. Minimizing the sensor size increases the strain, but the reduction in sensor cross-sectional area increases the resistance and expected sensor noise. The optimal sensor geometry must therefore account for this effect. We used our analysis to optimize geometric variations of nanogranular tunnelling resistor (NTR) strain sensors arranged in a Wheatstone bridge on a silicon nitride AFM cantilever. We varied the dimensions of each sensor element to maintain a constant cross-sectional area but maximize the strain in the sensor element. Through this approach, we expect a 45% increase in strain in the sensor and corresponding 20% increase in the Wheatstone bridge signal. Our results provide an important consideration in the design geometry of resistive strain-sensing elements in MEMS devices.

The ion beam induced nanoscale synthesis of platinum nanowires using the trimethyl (methylcyclopentadienyl)platinum(IV) (MeCpPt(IV)Me3) precursor is investigated using helium and neon ion beams in the gas field ion microscope. The He(+) beam induced deposition resembles material deposited by electron beam induced deposition with very small platinum nanocrystallites suspended in a carbonaceous matrix. The He(+) deposited material composition was estimated to be 16% Pt in a matrix of amorphous carbon with a large room-temperature resistivity (∼3.5 × 10(4)-2.2 × 10(5) μΩ cm) and temperature-dependent transport behavior consistent with a granular material in the weak intergrain tunnel coupling regime. The Ne(+) deposited material has comparable composition (17%), however a much lower room-temperature resistivity (∼600-3.0 × 10(3) μΩ cm) and temperature-dependent electrical behavior representative of strong intergrain coupling. The Ne(+) deposited nanostructure has larger platinum nanoparticles and is rationalized via Monte Carlo ion-solid simulations which show that the neon energy density deposited during growth is much larger due to the smaller ion range and is dominated by nuclear stopping relative to helium which has a larger range and is dominated by electronic stopping.

We present temperature-dependent conductivity data obtained on a sample set of nanogranular Pt-C with finely tuned intergrain tunnel coupling strength g. For samples in the strong-coupling regime gg(C), characterized by a finite conductivity for T→0, we find a logarithmic behavior at elevated temperatures and a crossover to a √T behavior at low temperatures over a wide range of coupling strengths g(C) ≈ 0.25g ≤ 3. The experimental observation for g1 is in very good agreement with recent theoretical findings on ordered granular metals in three spatial dimensions. The results indicate a validity of the predicted universal conductivity behavior that goes beyond the immediate range of the approach used in the theoretical derivation.

The hopping rate for hydrogen diffusion from one to the other Si atom of a dimer on the Si(001) surface was investigated at high temperatures by means of laser-induced thermal heating in combination with scanning tunneling microscopy. A lower limit for the diffusion rate of $1\ifmmode\times\else\texttimes\fi{}{10}^{9}\text{ }{\text{s}}^{\ensuremath{-}1}$ was determined at 1400 K. This value is more than two orders of magnitude larger than expected from extrapolation of data measured between 470 and 570 K.

This paper introduces a new methodology for the fabrication of strain-sensor elements for MEMS and NEMS applications based on the tunneling effect in nano-granular metals. The strain-sensor elements are prepared by the maskless lithography technique of focused electron-beam-induced deposition (FEBID) employing the precursor trimethylmethylcyclopentadienyl platinum [MeCpPt(Me)(3)]. We use a cantilever-based deflection technique to determine the sensitivity (gauge factor) of the sensor element. We find that its sensitivity depends on the electrical conductivity and can be continuously tuned, either by the thickness of the deposit or by electron-beam irradiation leading to a distinct maximum in the sensitivity. This maximum finds a theoretical rationale in recent advances in the understanding of electronic charge transport in nano-granular metals.

Hydrogen diffusion across DB steps on Si(001) surfaces is investigated by means of variable-temperature scanning tunneling microscopy and first-principles calculations. Experimentally, the hopping rate for diffusion from the step sites to the Si dimers of the upper terrace was found to be more than one order of magnitude higher than that for diffusion to the lower terrace. This clear preference, opposite to the trend for the respective binding energies, is explained by first-principles calculations that identify a metastable intermediate to be responsible for the unexpected lowering of the energy barrier for upward diffusion.

The rearrangement of silicon dangling bonds induced by pulsed laser heating of monohydride-covered Si(001) surfaces has been studied by means of scanning tunneling microscopy (STM). The initial configurations, which were created by laser-induced thermal desorption, consist of isolated pairs of dangling bonds at two adjacent dimers and represent an excited state of the surface. Hydrogen diffusion causes this arrangement to change during only a few nanosecond laser pulses into the equilibrium configuration with most of the dangling bonds being paired up at a single dimer. STM images taken after different numbers of heating pulses show snapshots of the surface configuration frozen at various stages of the fast equilibration process. In this way, hydrogen diffusion associated with rates as high as ${10}^{8}\phantom{\rule{0.3em}{0ex}}{\mathrm{s}}^{\ensuremath{-}1}$ could be monitored with atomic resolution. Comparison with Monte Carlo simulations of the diffusion processes allows for the precise determination of both the diffusion rates and the pairing energies between dangling bonds at high surface temperature.

Focused electron beam induced deposition as a direct-write approach possesses great potential to meet the demands for superconducting nanostructure fabrication especially regarding its 3D patterning capabilities combined with the high resolution in the nanometer regime. So far, however, it was not possible to fabricate superconducting structures with this technique. In this work, we present a lead-based superconductor prepared by focused electron beam induced deposition by dissociation of the precursor tetraethyllead. The as-grown structures exhibit metallic behavior and a minimum resistivity in the normal state of ρ = 16 μΩcm at T = 9 K followed by a superconducting transition at Tc = 7.2 K.

We have prepared the new amorphous superconductor MoxCyGazOδ with a maximum critical temperature Tc of 3.8 K by the direct-write nano-patterning technique of focused (gallium) ion beam induced deposition (FIBID) using Mo(CO)6 as precursor gas. From a detailed analysis of the temperature-dependent resistivity and the upper critical field, we found clear evidence for proximity of the samples to a disorder-induced metal-insulator transition. We observed a strong dependence of Tc on the deposition parameters and identified clear correlations between Tc, the localization tendency visible in the resistance data and the sample composition. By an in-situ feedback-controlled optimization process in the FIB-induced growth, we were able to identify the beam parameters which lead to samples with the largest Tc-value and sharpest transition into the superconducting state.

We have fabricated Pt-containing granular metals by focused electron beam induced deposition from the $(CH_3)_3CH_3C_5H_4Pt$ precursor gas. The granular metals are made of platinum nanocrystallites embedded in a carbonaceous matrix. We have exposed the as-grown nanocomposites to low energy electron beam irradiation and we have measured the electrical conductivity as a function of the irradiation dose. Postgrowth electron beam irradiation transforms the matrix microstructure and thus the strength of the tunneling coupling between Pt nanocrystallites. For as-grown samples (weak tunnel coupling regime) we find that the temperature dependence of the electrical conductivity follows the stretched exponential behavior characteristic of the correlated variable-range hopping transport regime. For briefly irradiated samples (strong tunnel coupling regime) the electrical conductivity is tuned across the metal-insulator transition. For long-time irradiated samples the electrical conductivity behaves like that of a metal. In order to further analyze changes of the microstructure as a function of the electron irradiation dose we have carried out transmission electron microscope (TEM), micro-Raman and atomic force microscopy (AFM) investigations. TEM pictures reveal that the crystallites' size of long-time irradiated samples is larger than that of as-grown samples. Furthermore we do not have evidence of microstructural changes in briefly irradiated samples. By means of micro-Raman we find that by increasing the irradiation dose the matrix changes following a graphitization trajectory between amorphous carbon and nanocrystalline graphite. Finally, by means of AFM measurements we observe a reduction of the volume of the samples with increasing irradiation time which we attribute to the removal of carbon molecules.