Over the last decades, the development of micro- and nanoparticle pastes (nanopastes) for sinter-bonding (sintering) has been a major research effort in the field of micro- and nanojoining, firstly of Ag-based pastes, and more recently also of Cu-based pastes. One classical application scenario is semiconductor die attach for power electronics, where sintering can provide bonds with superior temperature stability as well as thermal and electrical conductivity. A recently proposed novel application field is the use of sinter-bonding for transfer and integration of functional thin films: thin films and 2D materials can offer unique properties, e.g. for sensing, catalysis, and electronics. However, film manufacturing often requires distinct growth conditions. For subsequent film integration into a functional device, the films must be transferred and bonded to a suitable host structure. Current transfer methods often lead to film damage and/or insufficient bond qualities. In this work, we present sinter-bonding with nanopastes as a flexible and easy-to-use method to realise high-quality thin-film transfers and provide an in-depth discussion of the process steps and bonding mechanisms.
In solid-state compounds, the valence of europium can sometimes be mixed – which is especially favored in structures with several positions for the europium atoms. In this work, we study the Eu-based intermetallic noncentrosymmetric system Eu_10Hg_55 which has 65 atoms per unit cell and 4 distinct crystallographic positions for europium and 17 positions for mercury. Our detailed analysis of magnetism of large single crystals suggests that europium in Eu_10Hg_55 might be present in two valence states, resulting in a fragile magnetic ground state. Due to the cage-like structure with a large distance between the Eu atoms, those atoms are weakly ferromagnetically coupled and Eu_10Hg_55 orders at low temperatures, below T_1 = 5.5 K, with a subsequent spin re-orientation at T_2 = 4.3 K. There is no sign of magnetic frustration. Interestingly, the magnetic ordering of europium sub-lattices results in a magnetization pole reversal with a weak ferrimagnetic ground state. Additional magnetic phases can be induced by application of a modest external magnetic field.
The transport and magnetic properties of the Magnéli phase tungsten oxide WO2.90, prepared via spark plasma sintering, were investigated across a broad temperature range of 4–550 K, including the previously unexplored low-temperature region below 300 K. Microstructure analysis shows that obtained pellets are fully dense, enabling reliable measurement of transport properties. Resistivity measurements reveal typical metallic behavior of WO2.90 at low temperatures. Above room temperature, resistivity tends to saturate by reaching a maximum value near 430 K. The resistivity saturation indicates that Mott-Ioffe-Regel limit is approached, where the charge carrier mean free path becomes comparable to the interatomic spacing. The temperature dependence of the resistivity can be well described by the phenomenological parallel resistor model. Significant positive magnetoresistance was observed at low temperatures, with an unusual linear dependence on the magnetic field. Despite its metallic conductivity, WO2.90 displays weak diamagnetism, likely due to the substantial core diamagnetism of tungsten and the bipolaronic pairing of charge carriers.
Colloidal quantum dots (cQDs), semiconductor materials with widely tunable properties, can be printed in submicrometer patterns through electrohydrodynamic printing, avoiding aggressive photolithography steps. Postprinting ligand exchange determines the final optoelectronic properties of the cQD structures. However, achieving a complete bulk exchange is challenging, and the conventional vibrational analysis lacks the required spatial resolution. Infrared nanospectroscopy enables quantitative analysis of vibrational signals and structural topography on the nanometer scale upon ligand substitution on lead sulfide cQDs. A solution of ethanedithiol led to rapid (∼60 s) exchange of ≤90% of the ligands, in structures up to ∼750 nm thick. Prolonged exposures (>1 h) caused the degradation of the microstructures, with a systematic removal of cQDs regulated by surface:bulk ratios and solvent interactions. This study establishes a method for the development of devices through a combination of tunable photoactive materials, additive manufacturing of microstructures, and their quantitative nanometer-scale analysis.
MXenes are 2D transition metal carbides, nitrides, and/or carbonitrides that can be intercalated with cations through chemical or electrochemical pathways. While the insertion of alkali and alkaline earth cations into Ti3C2Tx MXenes is well studied, understanding of the intercalation of redox-active transition metal ions into MXenes and its impact on their electronic and electrochemical properties is lacking. In this work, we investigate the intercalation of Cu ions into Ti3C2Tx MXene and its effect on its electronic and electrochemical properties. Using X-ray absorption spectroscopy (XAS) and ab initio molecular dynamics (AIMD), we observe an unusual phenomenon whereby Cu2+ ions undergo partial reduction upon intercalation from the solution into the MXene. Furthermore, using in situ XAS, we reveal changes in the oxidation states of intercalated Cu ions and Ti atoms during charging. We show that the pseudocapacitive response of Cu-MXene originates from the redox of both the Cu intercalant and Ti3C2Tx host. Despite highly reducing potentials, Cu ions inside the MXene show an excellent stability against full reduction upon charging. Our findings demonstrate how electronic coupling between Cu ions and Ti3C2Tx modifies electrochemical and electronic properties of the latter, providing the framework for the rational design and utilization of transition metal intercalants for tuning the properties of MXenes for various electrochemical systems.
Colloidal quantum dots (cQDs) recently emerged as building blocks for semiconductor materials with tuneable properties. Electro-hydrodynamic printing can be used to obtain sub-micrometre patterns of cQDs without elaborate and aggressive photolithography steps. Post-deposition ligand exchange is necessary for the introduction of new functionalities into cQD solids. However, achieving a complete bulk exchange is challenging and conventional infrared spectroscopy lacks the required spatial resolution. Infrared nanospectroscopy (AFM-IR) enables quantitative analysis of the evolution of vibrational signals and structural topography on the nano-metre scale upon ligand substitution on lead sulphide (PbS) cQDs. A solution of ethane-dithiol in acetonitrile demonstrated rapid ( 60 s) and controllable exchange of approximately 90 encompassing structures up to 800 nm in thickness. Prolonged exposures (>1 h) led to the degradation of the microstructures, with a systematic removal of cQDs regulated by surface-to-bulk ratios and solvent interactions. This study establishes a method for the development of devices through a combination of tuneable photoactive materials, additive manufacturing of microstructures, and their quantitative nanometre-scale analysis.
In the past 5 years, the transfer of epitaxial oxide thin films has drawn a renewed interest in the scientific community. The major challenge in this technology is to minimize the appearance of extended bulk defects such as plastic deformations, cracks, and delamination, which are induced by the transfer process to a new host substrate. In this work, a procedure for the transfer of epitaxial oxide films where a rigid bond to the final host holder is obtained via a metallic Au/Ag bonding layer is presented. Here, the transfer of SrRuO 3 (SRO) and SrRuO 3 /SrTiO 3 (STO) epitaxial films grown on a water‐soluble Sr 3 Al 2 O 6 sacrificial layer is reported. These epitaxial films are grown on a STO substrate and transferred onto a Si host substrate. Roughness values lower than 1nm are observed for the transferred SRO membranes. Cross‐section analysis shows straight interfaces without plastic deformation of the membranes. X‐ray diffraction rocking‐curve analysis evidences that mechanical damage is minimized and the membranes remain close to their initial quality. This procedure represents an important step forward in the development of advanced technologies for membrane transfer of epitaxial oxides and superstructures.
MXenes are 2D transition metal carbides, nitrides, and/or carbonitrides, capable of intercalation by various cations through chemical or electrochemical means. Previous research has primarily focused on intercalating alkaline and alkaline earth cations, such as Li+, K+, Na+, Mg2+ or alkylammonium cations, into Ti3C2Tx MXenes. However, the impact of intercalated transition metal (TM) ions on the electronic and electrochemical properties of MXenes remains largely unexplored. In this study, we investigated the effects of pre-intercalated Cu ions on Ti3C2Tx MXenes and vice versa to gain a comprehensive understanding of how the electronic and electrochemical properties of both intercalated TM ion and MXene host are altered. Using in-situ X-ray absorption spectroscopy (XAS), we reveal changes in the oxidation states of intercalated Cu ions and Ti atoms during charging and their corresponding role in charge storage mechanisms. Our findings show that electronic coupling between Ti3C2Tx and Cu ions results in modified electrochemical and electronic properties compared to pristine Ti3C2Tx. These insights lay the foundation for the rational design and utilization of TM ion intercalants to tailor the properties of MXenes for various electrochemical systems and beyond.
It has been proposed by Müller and Shengelaya that underdoped ultrathin layers of copper-oxide high-temperature superconductors (HTSs) sandwiched between high-dielectric-constant insulator layers could manifest increased superconducting critical temperature $$T_c$$ T c . To check this hypothesis, we investigated structural and transport properties of YBa $$_{2}$$ 2 Cu $$_{3}$$ 3 O $$_{7-\delta }$$ 7 - δ (YBCO) thin films sandwiched between SrTiO $$_{3}$$ 3 (STO) layers. Scanning transmission electron microscopy (STEM) showed that a high-quality interface is formed between YBCO and the top STO layers. An increase of $$T_c$$ T c up to $$\Delta$$ Δ T $$\approx$$ ≈ 20 K was observed at these interfaces in case of underdoped YBCO films.
It has been proposed by Müller and Shengelaya that underdoped ultrathin layers of copper-oxide high-temperature superconductors (HTSs) sandwiched between high-dielectric-constant insulator layers could manifest increased superconducting critical temperature $$T_c$$ . To check this hypothesis, we investigated structural and transport properties of YBa $$_{2}$$ Cu $$_{3}$$ O $$_{7-\delta }$$ (YBCO) thin films sandwiched between SrTiO $$_{3}$$ (STO) layers. Scanning transmission electron microscopy (STEM) showed that a high-quality interface is formed between YBCO and the top STO layers. An increase of $$T_c$$ up to $$\Delta$$ T $$\approx$$ 20 K was observed at these interfaces in case of underdoped YBCO films.
It has been proposed by Müller and Shengelaya that underdoped ultrathin layers of copper-oxide high-temperature superconductors (HTSs) sandwiched between high-dielectric-constant insulator layers could manifest increased superconducting critical temperature T_c . To check this hypothesis, we investigated structural and transport properties of YBa _2 Cu _3 O _7-δ (YBCO) thin films sandwiched between SrTiO _3 (STO) layers. Scanning transmission electron microscopy (STEM) showed that a high-quality interface is formed between YBCO and the top STO layers. An increase of T_c up to Δ T ≈ 20 K was observed at these interfaces in case of underdoped YBCO films.
Within the emerging field of proton-conducting fuel cells, BaZr0.9Y0.1O3-δ (BZY10) is an attractive material due to its high conductivity and stability. The fundamentals of conduction in sintered pellets and thin films heterostructures have been explored in several studies; however, the role of crystallographic orientation, grains, and grain boundaries is poorly understood for proton conduction. This article reports proton conduction in a self-assembled multi-oriented BZY10 thin film grown on top of a (110) NdGaO3 substrate. The multiple orientations are composed of different lattices, which provide a platform to study the lattice-dependent conductivity through different orientations in the vicinity of grain boundary between them and the substrate. The crystalline stacking of each orientation is confirmed by X-ray diffraction analysis and scanning transmission electron microscopy. The transport measurements are carried out under different gas atmospheres. The highest conductivity of 3.08 × 10-3 S cm-1 at 400 °C is found under a wet H2 environment together with an increased lattice parameter of 4.208 Å, while under O2 and Ar environments, the film shows lower conductivity and lattice parameter. Our findings not only demonstrate the role of crystal lattice for conduction properties but also illustrate the importance of self-assembled strategies to achieve high proton conduction in BZY10 thin films.
Computationally guided high-throughput synthesis is used to explore the Zn-V-N phase space, resulting in the synthesis of a novel ternary nitride Zn$_2$VN$_3$. Following a combinatorial PVD screening, we isolate the phase and synthesize polycrystalline Zn$_2$VN$_3$ thin films with wurtzite structure on conventional borosilicate glass substrates. In addition, we demonstrate that cation-disordered, but phase-pure (002)-textured, Zn$_2$VN$_3$ thin films can be grown using epitaxial stabilization on {\alpha}-Al2O3 (0001) substrates at remarkably low growth temperatures well below 200 {\deg}C. The structural properties and phase composition of the Zn$_2$VN$_3$ films are studied in detail using XRD and (S)TEM techniques. The composition as well as chemical state of the constituent elements are studied using RBS/ERDA as well as XPS/HAXPES methods. These analyses reveal a stoichiometric material with no oxygen contamination, besides a thin surface oxide. We find that Zn$_2$VN$_3$ is a weakly-doped p-type semiconductor demonstrating broadband room-temperature photoluminescence spanning the range between 2 eV and 3 eV. In addition, the electronic properties can be tuned over a wide range via isostructural alloying on the cation site, making this a promising material for optoelectronic applications.
Nanomultilayers are complex architectures of materials stacked in sequence with layer thicknesses in the nanometer range. Their application in microelectronics is challenged by their thermal stability, conductivity, and interface reactivity, which can compromise their performance and usability. By using different materials as thermal barriers and by changing their thickness, it is possible to manipulate interfacial effects on thermal transport. In this work, we report on the thermal conductivity of Cu/W, Cu/Ta, and Cu/TaN sputter deposited nanomultilayers with different thicknesses. The resistive interfacial effects are rationalized and discussed also in relation to the structural transformation into a nano-composite upon high-temperature annealing.
The temperature and magnetic field dependence of resistivity in WO2.9 was investigated. The variation of resistivity with temperature displayed unusual features, such as a broad maximum around 230 K and a logarithmic increase of resistivity below 16 K. In the temperature range 16–230 K, we observed metallic-like behavior with a positive temperature coefficient. The combined analysis of resistivity and magnetoresistance (MR) data shows that these unusual transport properties of WO2.9 can be understood by considering the (bi)polaronic nature of charge carriers. In contrast to magnetization data, superconducting transition below Tc = 80 K was not detected in resistivity measurements, indicating that the superconductivity is localized in small regions that do not percolate. We found a strong increase in positive MR below 80 K. This effect is similar to that observed in underdoped cuprates, where the substantial increase of MR is attributed to superconducting fluctuations in small clusters. Therefore, the temperature dependence of MR indicates the presence of non-percolating superconducting clusters in WO2.9 below 80 K in agreement with magnetization data.
The role of epitaxial strain and chemical termination in selected interfaces of perovskite oxide heterostructures is under intensive investigation because of emerging novel electronic properties. SrTiO 3 (STO) is one of the most used substrates for these compounds, and along its < 001 > direction allows for two nonpolar chemical terminations: TiO2 and SrO. In this paper, we investigate the surface morphology and crystal structure of SrO epitaxial ultrathin films: from 1 to about 25 layers grown onto TiO 2 -terminated STO substrates. X-ray diffraction and transmission electron microscopy analysis reveal that SrO grows along its [ 111 ] direction with a 4% out-of-plane elongation. This large strain may underlay the mechanism of the formation of self-organized pattern of stripes that we observed in the initial growth. We found that the distance between the TiO 2 plane and the first deposited SrO layer is 0.27 ( 3 ) nm, a value which is about 40% bigger than in the STO bulk. We demonstrate that a single SrO-deposited layer has a different morphology compared to an ideal atomically flat chemical termination.
Europium (Eu) and dysprosium (Dy) co-doped strontium aluminate (SrAl2O4) (SA:Eu, Dy) is one of the most widely applied long persistent phosphors due to its strong emission intensity and long afterglow. However, the difficulty to get crystalline SA:Eu, Dy thin films in the as-deposited state strongly limited their applications in devices and surface coatings. In this study, we present a breakthrough in the synthesis of single-crystal SA:Eu, Dy films via direct-epitaxial growth on sapphire substrate by means of pulsed layer deposition. A threshold temperature of 900 degrees C is identified, only above which the mobility of adatoms is high enough to form crystalline films. By avoiding the nucleation process via introducing a homo-buffer layer, this temperature can be significantly reduced by 200 degrees C. The direct-epitaxial growth ensures a good surface quality, while the temperature reduction may prevent interdiffusion in applications involving hetero multilayer structures. The films are single crystals composed of twinned domains. The constraint effect from substrate significantly limits the freedom for twinning, which leads to much less twin variants in films compared to powders. The high-quality epitaxial films obtained in this study are useful for understanding the unique phosphorescence mechanism in SA:Eu, Dy, which may further help to design new phosphor materials with higher performance.
In this work we study the catastrophic optical damage (COD) of graded-index separate confinement heterostructure quantum well (QW) laser diodes based on AlGaAs/GaAs. The emphasis is placed on the impact that the nanoscale physical properties have on the operation and degradation of the active layers of these devices. When these laser diodes run in continuous-wave mode with high internal optical power densities, the QW and guide layers can experiment very intense local heating phenomena that lead to device failure. A thermomechanical model has been set up to study the mechanism of degradation. This model has been solved by applying finite element methods. A variety of physical factors related to the materials properties, which play a paramount role in the laser degradation process, have been considered. Among these, the reduced thicknesses of the QW and the guides lead to thermal conductivities smaller than the bulk figures, which are further reduced as extended defects develop in these layers. This results in a progressively deteriorating thermal management in the device. To the best of our knowledge, this model for laser diodes is the first one to have taken into account low scale mechanical effects that result in enhanced strengths in the structural layers. Moreover, the consequences of these conflicting size-dependent properties on the thermo-mechanical behaviour on the route to COD are examined. Subsequently, this approach opens the possibility of taking advantage of these properties in order to design robust diode lasers (or other types of power devices) in a controlled manner.