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In situ transmission electron microscopy (TEM) is a powerful tool for advanced material characterization. It allows real-time observation of structural evolution at the atomic level while applying different stimuli such as heat. However, the validity of analysis strongly depends on the quality of the specimen, which has to be prepared by thinning the bulk material to electron transparency while maintaining the pristine properties. To address this challenge, a novel method of TEM samples preparation in plan-view geometry was elaborated based on the combination of the wedge polishing technique and an enhanced focused ion beam (FIB) workflow. It involves primary mechanical thinning of a broad sample area from the backside followed by FIB-assisted installation on the MEMS-based sample carrier. The complete step-by-step guide is provided, and the method’s concept is discussed in detail making it easy to follow and adapt for diverse equipment. The presented approach opens the world of in situ TEM heating experiments for a vast variety of fragile materials. The principle and significant advantage of the proposed method are demonstrated by new insights into the stability and thermal-induced strain relaxation of Ge Stranski–Krastanov islands on Si during in situ TEM heating. Graphical abstract

Advanced materials 35(5), 2208061 (2023). doi:10.1002/adma.202208061, Incorporating large organic cations to form 2D and mixed 2D/3D structures significantly increases the stability of perovskite solar cells. However, due to their low electron mobility, aligning the organic sheets to ensure unimpeded charge transport is critical to rival the high performances of pure 3D systems. While additives such as methylammonium chloride (MACl) can enable this preferential orientation, so far, no complete description exists explaining how they influence the nucleation process to grow highly aligned crystals. Here, by investigating the initial stages of the crystallization, as well as partially and fully formed perovskites grown using MACl, the origins underlying this favorable alignment are inferred. This mechanism is studied by employing 3-fluorobenzylammonium in quasi-2D perovskite solar cells. Upon assisting the crystallization with MACl, films with a degree of preferential orientation of 94%, capable of withstanding moisture levels of 97% relative humidity for 10 h without significant changes in the crystal structure are achieved. Finally, by combining macroscopic, microscopic, and spectroscopic studies, the nucleation process leading to highly oriented perovskite films is elucidated. Understanding this mechanism will aid in the rational design of future additives to achieve more defect tolerant and stable perovskite optoelectronics., Published by Wiley-VCH, Weinheim

In the present research, experiments on the formation and retention of nanoparticles (NPs) in the plasma of radio frequency (RF) capacitive discharge in acetylene were carried out with vertically positioned internal electrodes. It has been shown via SEM and TEM techniques that NPs found on the horizontal tube wall after the discharge operation have a spherical shape with a predominant diameter of approximately 400-600 nm. HRTEM analysis reveals their amorphous structure. At the same time, such NPs were not found on vertical electrodes, only a polymer film was deposited. To elucidate the possibility of NPs leaving the plasma in the direction of vertical electrodes, a model of NP retention in the near-electrode sheath of an RF capacitive discharge was elaborated. The model has shown that nanometer- and even micrometer-sized particles formed in the plasma cannot cross the near-electrode sheath and reach the electrode surface. For the plasma consisting of three charged components (positive ions, electrons, and NPs), an analytical model of ambipolar diffusion was developed. Applying this model, it has been shown that the ambipolar electric field can keep the micrometer-sized NPs in the plasma if their concentration is low. However, in the case of a high concentration of NPs, they can be retained with a diameter of no more than a few hundred nanometers due to a significant decrease in the ambipolar electric field. The calculation results are in agreement with our experimental data.

Wide range binary and ternary thin film combinatorial libraries mixing Al, Cu, and Ga were screened for identifying alloys with enhanced ability to withstand electromigration. Bidimensional test wires were obtained by lithographically patterning the substrates before simultaneous vacuum co-deposition from independent sources. Current-voltage measurement automation allowed for high throughput experimentation, revealing the maximum current density and voltage at the electrical failure threshold for each alloy. The grain boundary dynamic during electromigration is attributed to the resultant between the force corresponding to the electron flux density and the one corresponding to the atomic concentration gradient perpendicular to the current flow direction. The screening identifies Al-8 at. % Ga and Cu-5 at. % Ga for replacing pure Al or Cu connecting lines in high current/power electronics. Both alloys were deposited on polyethylene naphthalate (PEN) flexible substrates. The film adhesion to PEN is enhanced by alloying Al or Cu with Ga. Electrical testing demonstrated that Al-8 at. % Ga is more suitable for conducting lines in flexible electronics, showing an almost 50% increase in electromigration suppression when compared to pure Al. Moreover, Cu-5 at. % Ga showed superior properties as compared to pure Cu on both SiO2 and PEN substrates, where more than 100% increase in maximum current density was identified.

The online version contains supplementary material available at 10.1557/s43577-021-00255-5.

Composite memristors based on anodic oxidation of Hf superimposed on Ta thin films are studied. A layered structure is obtained by successive sputtering of Ta and Hf thin films. The deposition geometry ensured components' thickness gradient profiles (wedges) aligned in opposite directions. Anodization in citrate buffer electrolyte leads to a nanoscale columnar structuring of Ta2O5 in HfO2 due to the higher electrical resistance of the latter. Following the less resistive path, the ionic current forces Ta oxide to locally grow toward the electrolyte interface according to the Rayleigh-Taylor principle. The obtained composite oxide memristive properties are studied as a function of the Hf/Ta thickness ratio. One pronounced zone prominent for memristive applications is found for ratios between 4 and 5. Here, unipolar and bipolar memristors are found, with remarkable endurance and retention capabilities. This is discussed in the frame of conductive filament formation preferentially along the interfaces between oxides.

The aim of this work was to study nanoparticles that are formed in the plasma volume of a radio-frequency capacitive discharge in acetylene. The particles partially penetrate into the polymer film on the electrodes, and partially increase in size, and then fall on the tube wall. It is shown that even when deposited on vertically located electrodes, the polymer film contains nanoparticles with diameter of about 10 nm. In the plasma volume, nanoparticles can grow up to several hundred nanometers in diameter and then fall on the wall of the discharge tube. An analysis of the emission spectra showed that only hydrogen lines and a weak CH band (431 nm) are observed in a burning rf discharge in acetylene. A polymer film deposited on the tube wall effectively absorbs radiation lines in the blue part of the spectrum, while lines in the red and infrared parts of the spectrum are weakly absorbed.

In this paper, we study the mutual solid-state solubility in Au Ni nanoparticles with a mean size of ≈6 nm. Solid solution formation was probed via electron microdiffraction, EDX, and high-resolution STEM during sample heating in an electron microscope. As a result, a miscibility gap curve was constructed on the Au Ni phase diagram for ≈6 nm particles. It was shown that a quasi-homogeneous solid solution is already formed at 300–325 °C. The coarsening of particles induces decomposition of the solid solution and segregation of gold to the surface of nickel nanoparticles above 325 °C.

In the present work, we measured breakdown and extinction curves of radio-frequency discharge in acetylene as well as dependences of active current, power and gas pressure on the discharge burning time, and also optical emission spectra. It was found that in the region of low acetylene pressures (to the left of the minimum of the breakdown curve), the discharge can cover only a part of the electrode surface. Immediately after the ignition of the discharge, due to the intense deposition of the polymer film and the formation of dust particles in the plasma volume, the gas pressure decreases sharply (by the factor of 2-5), while the active current and power increase and then reach saturation. In the discharge with intense polymerization, the lines of atomic and molecular hydrogen dominate in the emission spectrum of the discharge. The film deposited on the surface of the electrodes and the tube walls, as well as the dust particles formed, are amorphous, the maximum peak of XRD spectrum is observed at 2θ = 18°, and the light absorption by the deposited films is highest at 440 nm wavelength.

Melting temperature is one of the principal parameters of phase equilibria thermodynamics and its value affects the majority of materials properties. Despite previous studies, the fundamental mechanisms of interphase interactions at melting in two-component nanomaterials are under consideration. We address these issues in a comprehensive experimental study of phase transformations in nanosized Ag-Ge eutectic system by means of in situ TEM techniques. The Ge/Ag/Ge and Ag/Ge layered films with thin Ag layer (1–50 nm) on top or in-between amorphous Ge films have been used as a model of a binary system of variable size. Morphology, crystalline structure and composition of Ag-Ge films have been examined in situ and ex situ by advanced (S)TEM techniques, the eutectic temperature (TE) and the Ge crystallization temperature have been measured as a function of Ag film thickness. A few hundred degrees lowering of TE with the film thickness reduction has been registered. Complex changes of the Ge/Ag/Ge films morphology below the eutectic temperature driven by Ag-mediated crystallization of amorphous Ge have been observed and related to the formation of metastable (liquid and/or Ag-Ge hcp) phases at the metal-semiconductor interface at 250 °C already.

Various oxides and especially their modifications are in actual scientific focus for memristors fabrication due to their applications in non-volatile memories. Such devices exceed most limits of conventional memory technology. Memristors are recognized as resistive random access memories (ReRAMs), in which the data storage profits from a non-volatile change in the material resistance. The switching between a high resistance state (HRS) and a low resistance state (LRS) depends on the selection of electrodes and active (oxide) layers. This generally impacts the conductive pathways (filaments) formation, which is mediated by oxygen vacancies and/or cations, and their field-activated movement inside the oxide. Anodic oxides of valve metals (Al, Hf, Ta, Ti, Nb, Zr) have shown remarkable performances as memristive elements. Studies on Hf- and Ta-based memristors reported excellent electrical and memory properties, such as multi-level switching, high endurance and data retention. Even though for research purposes the synthesis of such oxide layers is commonly done by atomic layer deposition or sputtering, the electrochemical anodization process should not be neglected. This is a faster, less complex and inexpensive method, with precise composition and oxide thickness control through electrochemical parameters. The value of this approach is clearly emphasized by its continuous industrial implementation in various sectors. Previous works have confirmed that the performance of Hf or Ta anodic memristors can be improved by carefully selecting the anodization electrolyte or other electrochemical parameters1,2. These play a crucial role in positioning and sizing of conductive filaments within the oxide. This approach directly leads to defect-engineered memristors fabrication, which is nowadays a major motivation for investigating devices based on mixed oxides formed in different electrolytes. Predicting the position and shape/thickness of a conducting filament may eventually lead to enhanced device stability and resistive states control. The focus of the current work is on the behavior of anodic memristors based on ultra-thin Hf superimposed on Ta films. The main idea linked to the control of resistive filaments is based on the particularities of the anodization process, when the interface between both oxides is dynamically changing. In situ oxide self-nanostructuring is already known for various superimposed valve metals, including Hf and Ta. Their anodization leads to nanoscale oxide columns (“fingers”) formation, when a metal producing a more resistive oxide is superimposed on a metal producing a less resistive one. This phenomenon is recognized as an electrical version of the Rayleigh-Taylor effect and results from the ionic current preferring the less resistive paths, enhancing the growth of the correspondent oxide. Oxide resistivities and structures, transport numbers, Pilling-Bedworth ratios are all considered as determining factors for the anodization process of such superimposed systems. In the current work, anodization of Hf/Ta system leads to Rayleigh-Taylor effects since HfO2 is the more resistive oxide. The boundary between Hf and Ta oxides may influence the conductive pathways required for the memristive effect, thus being most relevant for fabrication of highly stable and forming-free memristors. Additionally, the use of superimposed films with gradient but complementary thicknesses allows investigating the ideal Hf/Ta ratios for which the best memristive behavior is obtained.3 From this study, one pronounced zone prominent for memristive applications is found for Hf/Ta thickness ratios between 4 and 5. Here, unipolar and bipolar memristors are identified, with remarkable endurance and retention capabilities. The CFs positioning is predefined by the development of Ta2O5 columnar structures grown during the anodization process. It is also possible that few CFs may be found in parallel, according to TEM observations, showing more than one Ta2O5 “finger”. Previous studies on pure Hf anodic memristors have confirmed concurrent competing CFs formation.2 Thus, one could assume that the memristive switching mechanism can be conditioned by the formation of oxides with such structures. The identified Hf/Ta ratio could be an excellent choice for improved memristors fabrication. Controlled O vacancies generation is a critical factor in switching uniformity and reproducibility. Therefore, oxide “fingers” formation is a promising electrochemical approach towards defect-engineered memristors. Further investigation of the composite oxide formation, particularly in Hf/Ta superimposed system, is topical. Until now, such systems were not recognized in the literature for the ReRAM applications. This is highly promising since both memory and electrical characteristics are improved by the forming-free nature of the memristors with CFs mediated by oxide nanostructuring. I. Zrinski et al., Nanomaterials 11, 1 (2021) https://doi.org/10.3390/nano11030666 I. Zrinski et al. Appl. Surf. Sci. 565, 150608 (2021) https://doi.org/10.1016/j.apsusc.2021.150608 I. Zrinski et al., J. Phys. Chem. Lett. 12, 8917 (2021) https://doi.org/10.1021/acs.jpclett.1c02346 Figure 1

The conventional memory technology, based on von Neumann architecture, has challenged technical and scaling limitations. The architectures with separated memory and computing units have resulted in the low efficiency of computing systems. Hence, huge scientific attention has been recently drawn into the development of novel systems using the in-memory computing concept. Memristors are foreseen as a type of non-volatile memories that can fulfill such requirements but also as electronic components that can solve sneak path currents problems while consuming low power. The information storage mechanism is based on the resistance change of memristors which is driven by an applied external electric field. With this regard, the memory medium plays a crucial role, being an oxide layer sandwiched between the metallic bottom and top electrode. Valve metals and their oxides have shown promising switching properties when used as elements of metal-insulator-metal memristive (MIM) structures. The switching mechanism still depends on the nano-dimensional conductive filaments formation inside the oxide. Even though devices based on Hf, Nb, Ti, and Ta demonstrated a long lifetime, high data retention or resistive state ratio, devices are suffering from low lifetimes in the order of several thousand switching cycles, mainly due to the unpredictable size and position of conductive filaments being affected by the movement of cations or O species. Therefore, the development of materials for defect-engineered memristive applications is crucial. This was the main motivation for this study supported by the fact that memristors based on pure valve metals exhibited promising switching behavior. In this work, devices based on Ta, Nb, and their alloys were investigated. Since the goal was to improve the properties of devices based on pure metals, Nb and Ta were mixed and their alloys were used as bottom electrode for anodic memristors. It can be inferred that by mixing Ta and Nb, multifunctional devices can be produced. High number of Nb-Ta alloys were co-deposited by sputtering onto previously oxidized Si wafers. Afterwards, the samples were anodized for growing an insulating active layer for memristive devices. Onto the so-formed mixed oxides, Pt was deposited as top electrode. The compositional gradient was mapped by a scanning energy-dispersive X-ray spectroscopy (SEDX) system. The total compositional spread of the Nb-Ta library was ranging from Nb - 13 at.%Ta to Nb – 80 at% Ta over three Si wafers. Memristive devices based on Nb or Ta were also fabricated in identical conditions and used as reference samples. By using a combinatorial approach, the investigation of various electrical parameters could be established for more than 300 memristive devices produced per Si wafer. Electrical characterization was performed by a self-developed Gantry robot controlled via Labview software specifically designed for basic tests required for memristive characterization (I-U sweeps, endurance, retention tests). Electrical properties were screened with a compositional resolution of 1 at.%. The results have shown that memristive devices based on Ta reached a long lifetime and high resistive state ratio, whereas devices based on Nb indicated multi-level switching as well as non-volatile and threshold switching characteristics. The formation of Ta-oxyphosphate, responsible for conductive filaments pining, was confirmed by hard X-ray photoelectron spectroscopy. Similarly, multi-level switching characteristics were explained by the incorporation of electrolyte species in Nb2O5. However, Nb devices did not show reversible switching from unipolar to bipolar mode and vice versa. The improvement regarding reversible switching between unipolar and bipolar mode has been observed for memristive devices based on alloys containing Nb -35 at. % Ta. These memristors have also demonstrated longer endurance and data retention as compared to devices based on pure Nb and Ta. The switching mechanism was investigated by conductive filaments imaging using transmission electron microscopy. Conclusively, anodic memristors based on Nb and Ta exhibited non-volatile and threshold characteristics which can spread the range of memristive applications. Reversible switching behavior and multi-level switching possibilities are relevant for the development of memristive synapses and neuromorphic systems. The anodic growth of an insulating layer for devices based on Nb, Ta, and Nb/Ta alloys has simplified, speed up and decreased the cost of fabrication processes. The performance of anodic memristors based on metallic thin films containing Nb -35 at. % Ta indicated a substantial improvement. The switching mechanisms could be suggested based on the nanostructures found in oxide revealing the position and size of conductive filaments. I. Zrinski et al., Appl. Surf. Sci., 548, 149093 (2021) https://doi.org/10.1016/j.apsusc.2021.149093. I. Zrinski, et al., Appl. Mater. Today, accepted, (2021). I. Zrinski, et. al, J. Phys. Chem. Lett., 12, 8917 (2021) https://doi.org/10.1021/acs.jpclett.1c02346 Figure 1

We present a novel technique for investigating the melting and crystallization of nanomaterials in confinement. According to this method, the melting-crystallization phase transitions are traced by sharp changes of viscoelastic properties of matter using quartz resonator Q-factor analysis during heating-cooling cycles. Ge/Bi/Ge layered films, formed by successive condensation of components in high vacuum, were used as the model of nanoscale Bi confined in Ge matrix. Size dependences of the melting and crystallization temperatures have been systematically determined for the samples with Bi film thickness of 5-50 nm. The obtained data are in good agreement with the data obtained previously using in situ transmission electron microscopy techniques.

We present the results of a rigorous investigation of contact melting in thin Ag/Ge bilayers fulfilled via ex-situ TEM techniques based on tracing the abrupt changes of sample morphology and structure at melting. It has been revealed that the liquid-phase formation in the system at the eutectic temperature takes place only if the silver film mass thickness value is greater than the critical one (≈1.2 nm), which corresponds to ≈8 nm-sized Ag nanoparticles. The onset temperature of liquid nuclei formation at the metal-semiconductor interface was estimated to be 200 °C.

A combinatorial screening approach has been designed for identification of Hf-Ta anodic memristors with enhanced properties. Three distinct compositional zones with similar characteristics have been identified, two of which are relevant for memristive applications. In a Hf-poor zone, (

The results of experimental studies of melting and crystallization of Bi-Sn eutectic alloy on carbon, bismuth and tin substrates are presented. Bi-Sn layered films with different mass ratio of components have been used as model systems. The films have been formed by successive condensation of components in a high vacuum on the AT-cut of a quartz single crystal. The phase state of the system was traced in the heating-cooling cycles by a jump-like change of the quartz resonator Q-factor upon its excitation at the fundamental frequency. The values of supercooling during crystallization (89 K) and a wetting contact angle (112°) have been determined for Bi-Sn eutectic being in contact with the carbon substrate. The supercooling values for the liquid phase of the eutectic composition, which crystallizes on bismuth- (3 K) and tin-based (7 K) substrates, have been measured for the first time. The liquid-solid interfacial energy value of Bi-Sn eutectic alloy was assessed.

Anodic memristors obtained by electrochemical anodization of Ta in phosphate, borate and citrate buffer solutions are studied. Memristive behaviour is demonstrated by electrical switching between high and low conductive states. The endurance and retention of devices are analysed. The use of phosphate leads to 4 switching levels and the highest ratio between high and low resistive states. All studied oxides are stoichiometric Ta2O5 and only P is detected inside anodic memristors. The improved memristive characteristics of oxides anodized in phosphate are attributed to an increase of O vacancies due to the presence of Ta oxyphosphate, which is believed to mediate spatial pinning of conductive filaments positions during read/write. The anodic memristors show high stability, enhanced endurance and retention that combined with their active layer low fabrication cost makes them ideal candidates for industrial implementation.

We investigate the morphology and crystalline structure of Au/Ge films in a wide range of temperatures by in situ TEM heating. Au/Ge films with Au mass thickness of 0.2–0.3 nm and Ge thickness of 5 nm were produced in vacuum by the sequential deposition of components on a carbon substrate at room temperature. It has been shown that particles with an average size of 4 nm, formed by Au film de-wetting, melt on the germanium substrate at temperatures 110–160 °C, which are below the eutectic temperature for the bulk. The effect of crystallization-induced capillary motion of liquid eutectic particles over Ge surface has been found in this work. Formation of metastable fcc phase of Ge has been observed at the liquid–germanium interface and behind the moving particle. Formation of a liquid phase with its subsequent crystallization at the metal–semiconductor interface seems to play a key role in the metal-induced crystallization effect.

The group IV Ge–Sn system is a promising candidate for a variety of electronic and photonic applications due to its tunable bandgap and compatibility with Si-based technology. However, the peculiarities of the components interaction, phases evolution and, especially, their thermal stability are still far from a brimming comprehension. In the course of in situ TEM heating experiments, we demonstrate the high potential of using nanosized, layered Sn/amorphous-Ge films for the synthesis of Ge–Sn solid solutions with an enhanced Sn content. Particularly, we observe the formation of highly uniform, diamond structured Ge1-xSnx solid solution with Sn content of 33 at% by metal-induced crystallization (MIC) at 90 °C. The Ge0.67Sn0.33 alloy is stable in the range of 20–150 °C, whereat additional heating leads to partial Sn segregation and subsequent melting of the Sn-rich phase. The formation of the metastable and stable Sn-rich liquid phases, which was observed at 90 and 150–190 °C, respectively, has a key role in the system thermal stability. The temperatures and the observed complex interphase interactions are discussed in the frame of the size effects in nanoscaled structures.

Morphology of 7,5 nm thick polycrystalline Au-Ge layered film of a near eutectic composition has been studied in a wide temperature range by means of in situ TEM heating. It has been shown that de-wetting of the Au-Ge film on amorphous carbon substrate is activated at temperatures of about 150°C resulting in formation of large flatted islands with a mean thickness of 18 nm at pre-melting temperatures. An eutectic melting of the alloy film occurs at a temperature of 250°C inducing the conversion of flat islands to huge round-shaped binary particles. Correlation between coverage ratio and temperature of the film has been determined.

Effect of size on the mutual solubility of components in Ag-Cu films have been studied in a wide temperature range by means of in situ electron-microscopy technique. It was shown that there is the eutectic temperature shift to lower temperatures and a significant increase in the components mutual solubility (especially silver solubility in copper) with a decrease in the system characteristic size. It was shown that the system characteristic size reduction leads to the solid state solubility area shrinking on the phase diagram.

The results of studying the effect of the characteristic size on the rate of diffusion processes in nanometer Cu-Ni film systems have been reported. The film system has been prepared by sequential vacuum deposition of the components, and the activation energy of diffusion has been determined from a change in the electrical resistance of the film system in a heating-cooling cycle. It has been shown that the activation energy of grain-boundary diffusion decreases with decreasing characteristic size of the system and amounts to 0.25 eV for the film system with a characteristic size of 5 nm, which corresponds to an increase in the grain-boundary diffusion coefficient by 10 orders of magnitude with respect to massive samples.

The kinetics of homogenization of an Ag–Pd film system with a total thickness of 120 nm and a grain size of 5–10 nm has been studied by means of in situ TEM heating. The film system has been formed by the sequential deposition of components in a vacuum on the substrate at room temperature. It has been shown that diffusion processes are activated, starting from the temperature 453 K, resulting in complete homogenization of the film system at 573 K with preservation of its fine-grained structure. The effective diffusion coefficient in the Ag–Pd system was measured as 10−17–10−18 m2/s at 553 K. A possible mechanism of homogenization is discussed.

We investigate the melting behavior of Au/Ge bilayer (Ge: 5 or 2 nm; Au: 0.1–1.1 nm) thin films using transmission electron microscopy and high energy electron diffraction. It was found that the liquid-phase formation in the system at eutectic temperature takes place only if the gold film mass thickness values are greater than the critical one (0.2 nm). This effect is revealed to be independent of the contact-heating sequence of the components.