Emergence of superconductivity in the cuprates via a universal percolation process

A pivotal step toward understanding unconventional superconductors would be to decipher how superconductivity emerges from the unusual normal state upon cooling. In the cuprates, traces of superconducting pairing appear above the macroscopic transition temperature $T_c$, yet extensive investigation has led to disparate conclusions. The main difficulty has been the separation of superconducting contributions from complex normal state behaviour. Here we avoid this problem by measuring the nonlinear conductivity, an observable that is zero in the normal state. We uncover for several representative cuprates that the nonlinear conductivity vanishes exponentially above $T_c$, both with temperature and magnetic field, and exhibits temperature-scaling characterized by a nearly universal scale $T_0$. Attempts to model the response with the frequently evoked Ginzburg-Landau theory are unsuccessful. Instead, our findings are captured by a simple percolation model that can also explain other properties of the cuprates. We thus resolve a long-standing conundrum by showing that the emergence of superconductivity in the cuprates is dominated by their inherent inhomogeneity

Facile fabrication of complex networks of memristive devices

We describe the memristive properties of cluster-assembled gold films. We show that resistive switching is observed in pure metallic nanostructured films at room temperature and atmospheric pressure, in response to applied voltage inputs. In particular, we observe resistance changes up to 400% and archetypal switching events that have remarkable symmetry with the applied voltage. We associated this symmetry with 'potentiation' and 'anti-potentiation' processes involving the activation of synapses and of pathways comprising multiple synapses. The stability and reproducibility of the resistance switching, which lasted over many hours, make these devices ideal test-beds for exploration of the basic mechanisms of the switching processes, and allow convenient fabrication of devices that may have neuromorphic properties

Characterization of Electronic and Ionic Transport in Soft and Hard Functional Materials

Control over concurrent transport of multiple carrier types is desired in both soft and hard materials. For both types of materials, I demonstrate ways to characterize and execute governance over both electronic and ionic transport, and apply these concepts in the fabrication of devices with applications in conducting composites, photovoltaics, electrochemical energy storage, and memristors. In soft materials, such as polymers, the topology of the binary polymer mesoscale morphology has major implications on the charge/ion transport. Traditional approaches to co-continuous structures involve either using blends of polymers or diblock copolymers. In polymer blends, the structures are kinetically trapped and thus have poor long term stability. In diblock polymers, such morphologies are not universally accessible to non-random coil polymers. I discuss an approach to binary polymer mesoscale morphologies via the assembly of polymer nanoparticles. In this strategy, polymers are assembled into spherical nanoparticles, which are then assembled into hierarchical mesoscale structures. First, I demonstrate, experimentally and computationally, that the electrical transport in semiconducting/insulating polymer nanoparticle assemblies can be predictably tuned according to power law percolation scaling. Then I show that nanoparticle assemblies can be utilized for tunable concurrent transport of electrons and holes for photovoltaics, and for electronic and ionic charges aimed at applications in electrochemical energy storage. For hard materials, I detail the characterization of mixed electronic and ionic transport in hybrid organic/inorganic lead triiodide perovskites. I used the understanding of mixed electronic and ionic transport in these materials to explain poorly understood phenomena such as photo-instability and current-voltage hysteresis. Then, I show several examples of interfacial materials, and the characterization and implications of their respective work functions, as charge transport materials to control selective charge extraction from perovskites. And finally, I show how interfacial charge transport materials with ionic functionality can be used to change the interfacial chemistry at perovskite/charge transport material interfaces to control both electronic and ionic transport. In this regard, I demonstrate how an adsorbing interface for mobile ions can be used to control current-voltage hysteresis and state-dependent resistance, introducing a novel paradigm of interfacial ion adsorption to fabricate novel perovskite-based memristor devices

Low firing temperature thick-film piezoresistive composites:properties and conduction mechanism

Thick-film technology has found applications on miniaturised hybrid circuits in various fields (automotive electronics, televisions, ...). This technology is also now widely used for the fabrication of force and pressure sensors that use the piezoresistive properties of thick-film resistors. The goal of this work has been generated by the fact that usual piezoresistive pastes / inks were optimised for applications on alumina, which is the standard substrate for thick-film technology, but ill suited for more flexible substrates such as aluminium, steel or Ti alloys. We were limited by the process conditions of the commercial pastes, in particular the too high firing process that does not allow the use of substrates with melting temperature < 850°C. This technological lack leads to manufacture a new generation of piezoresistive pastes with low firing temperatures (Tf: 500 ... 700°C). In parallel, we aim to optimise the electrical properties (resistance R, temperature coefficient of resistance TCR and gauge factor GF values) by highlighting the link with the structural evolution during the firing process and the obtained properties, and by understanding the conduction process in such percolative systems. Study of usual commercial piezoresistive pastes allowed us to determine that such piezoresistive pastes are composed of a percolating network of nanoconductive RuO2 grains embedded in a lead borosilicate glassy matrix. Evolution during the firing process was emphasised and showed the importance of controlling the firing parameters to assure the best properties for the final thick-film. Commercial pastes are characterised by a TCR value close to 0 ppm/°C, a reasonable sheet resistance value (R ~ 10 kOhms) and a gauge factor comprise between 10-12, that can be influenced by structural and process parameters. Indeed, complementary studies on sensitivity and stability were realised, because of limited available information in literature concerning the effect of firing schedule, particularly of quenching, and have shown that these properties are very dependent on the conditions of firing, although the main commercial pastes showed a moderate stability. In fact, this study showed that a compromise should be found between the different properties (for instance, high GF pastes presents a poor stability), and emphasises the fact that they should be optimised. A manufacturing process has been developed, process never well described in the literature, leading to the realisation of different lead borosilicate glasses. It has resulted in the ability to realise three series of model piezoresistive pastes with different ranges of firing temperatures corresponding to high (700°C), low (600°C) and very low (500°C) firing temperatures. The control of several parameters (glass composition, conductive phase concentration, grain size, firing temperature...) allowed us to direct precisely our research to elucidate the principle of conduction in such percolative systems and the reactions occurring between the elements and their influence on the electrical properties. Structural and electrical properties were studied by varying diverse parameters such as conductive grain size, concentration and firing temperature, and a coherence was found between the electrical behaviour (conduction process) and its relation to the complex nanostructure. In other words, this key chapter presents the results and their interpretation by a model of conduction based on a nonuniversal tunnelling percolation theory and based on a previously unpublished hypothesis. Indeed, it was demonstrated that the piezoresistive response of the pastes changed dramatically depending on whether the composites were universal or not. For the composites with critical exponent t ~ 2, the piezoresistive factor Γ showed no dependence upon the RuO2 volume fraction x, whereas the nonuniversal composites displayed a logarithmic divergence of Γ near the percolation threshold. We have interpreted the piezoresistivity results as being due to a strain dependence of the critical exponent when this was nonuniversal. We have brought forth a microscopic formulation to the phenomenological level proposed by Balberg, and we can now assert that thick-film resistors (TFR) are mainly nonuniversal compounds showing transport exponent t larger than the universal limit t = 2.0. This exponent t depends on strain and leads to a logarithmic divergence of the gauge factor. The possibility of influencing t by external means (e. g. strain) has never been studied so far. We have proposed a new way to investigate percolative systems by studying the behaviour of piezoresistive pastes. After having elucidated the conduction mechanism in such piezoresistive pastes, we studied the influence of different parameters (Tf, grain size, concentration, dwell time) on the main electrical properties (R, TCR and GF). Structural analysis gave a possible interpretation of the results. RuO2 parameters have direct effects on the R, TCR and GF values. Tf acts on microstructure provoking interactions between the bulk components and the substrate (in case of high Tf), and consequently leading to a modification of the electrical properties. The same complementary studies as commercial pastes on stability showed a combined influence of the cooling rate and the temperature dwell-time on R and TCR values. The results are in coherence with commercial pastes. The evolution of the values can be explained by diffusion phenomenon and local microscopic strains due to important cooling rates. The evolution of R upon annealing 250°C was found to depend strongly on the cooling rate for commercial and model pastes, but this observed trend tends to saturate. These new series of low firing temperature were shown to be not as stable as the "best" commercial pastes, but their variations are much similar to "medium" commercial one's. At 250°C, possible evolution mechanisms could involve Ru in glass (dissolved or in clusters), or mechanical relaxation that can be extrinsic (macroscopic thermal mismatch between resistor and substrate) or intrinsic (local thermal mismatch between glass and conductive phase), and which can later relax during annealing. During this analysis, technological problems have been emphasised and a section was dedicated to resolve the problem of the unsuitability of the substrate to the very low firing temperature system, which showed local strain that induced cracks and leading to electrical instability. Moreover, it was shown that these new pastes could be optimised by additives or used on more adapted substrates. However, these obtained series offers a large range of TCR and R values for different low Tf and it would be useful for technological goals. The best proof of the success of our study was the realisation of sensor prototypes based on different substrates such as steel, aluminium and even glass. This work has allowed to realise a detailed study of piezoresistive pastes and to complete previous research in this field concerning the influence of firing parameters (quenching) and annealing studies. From a scientific point of view, this first step allowed to show that nanostructure, conduction mechanism and electrical properties are intimately linked. By choosing adequate and relevant compositions, structure and firing, we proposed a new way to unveil the conduction process that has not been yet elucidated. From a technical point of view, their stability could be enhanced with a higher GF or adapted TCR. However, they present a large range of applications because of their different Tf and their different TCRs. Thanks to this particularity, these pastes could be used on different substrates, and we could expect a larger technological impact by optimising our piezoresistive pastes by additives to better control their properties

Water Based Polyurethane Multi-Functional Composites

Polyurethanes (PUs) are a class of versatile polymers that exhibit various mechanical, physical, chemical and biological properties depending on their structure and morphology. Polyurethanes (PUs) have been employed in a variety of industrial applications including foams, coatings, textiles, machinery, sporting, transportation, vehicles and construction. However, the potentials of PUs in the emerging technology fields such as soft and wearable electronics, energy storage devices, biosensors, actuators, photovoltaic devices and stimuli-responsive materials are largely unexplored. The major objective of the thesis research is to develop PU composites for such emerging applications as e-textiles, self-healing electronics, and smart windows. In this project, we select water-based polyurethane (WPU) as the main polymer matrix to develop a variety of ink systems for multiple applications. Firstly, to investigate the application of WPU in flexible and stretchable electronics, we develop a WPU-silver and WPU-polypyrrole (PPy) conductive ink for textile. The effective penetration of obtained ink makes the textile conductive and mechanically robust. The electrical conductivity of the PU-silver textile is high but drops significantly under stretching due to the intrinsically rigid property of metal. In contrast, the WPU-PPy textile shows a stable conductive performance under large elongation, however the electrical conductivity is four orders of magnitude lower than that of WPU-silver textile. Secondly, taking advantage of the ionic properties of WPU, we develop a self-healing elastomer through WPU/polyethylenimine (PEI) latex polyelectrolyte coacervation system, which contains opposite charges but is stable in water solution. Self-healing is achieved via water through two types of non-covalent bonds: ionic interaction between WPU and PEI, and polymer entanglement of WPU itself. This WPU-PEI dispersion can be combined with conductive filler such as silver flakes for printable self-healing soft antenna, indicating the potential applications in soft electronics industries. Finally, we replace the positively charged PEI with negatively charged poly methacrylic acid sodium salt (PMANa) to functionalize the WPU dispersion. The WPU-PMANa film shows a sharp change in transparency under mechanical strain, which can be used as robust mechanoresponsive smart windows. Additionally, the polyurethane smart window is multi-functional, its potential applications in the field of camouflage and dynamic optical gratings have been explored.

Development of modelling and testing for analysis of degradation of Ni-YSZ anode in solid oxide fuel cells

The ability to predict the lifetime performance of an SOFC can give guidelines for where improvements can be made in terms of production, operating parameters and cell design. Microstructural analysis ofNi-YSZ anode samples under varying steam and temperature regimes was investigated to determine trends in the anode Ni particle growth. Increasing the steam content produced larger mean Ni radii for a given temperature. Higher operating temperatures (900°C) were shown to have a significant accelerating effect on the particle size change. Further analysis of the microstructural data highlighted profiles for Ni-pore contact angle 9 values, as well as Triple Phase Boundary points and overlap length which both showed a decrease over time, highlighting differences in the rate of performance loss in the anode. Using models derived for the degradation mechanisms combined with a particle packing model, Matlab® coding was developed to predict the Ni particle growth rate and the relative change in conductivity and TPB length per unit volume. Ni particle growth rate predictions were compared to experimental results and showed good correlation. The data can be used to help design accelerated testing procedures for SOFC anodes to determine the long term performance of a given anode composition

Report / Institute für Physik

The 2016 Report of the Physics Institutes of the Universität Leipzig presents a hopefully interesting overview of our research activities in the past year. It is also testimony of our scientific interaction with colleagues and partners worldwide. We are grateful to our guests for enriching our academic year with their contributions in the colloquium and within our work groups

Bimodal Gate Oxide Breakdown in Sub-100 nm CMOS Technology

In the last three decades, the electronic industry has registered a tremendous progress. The continuous and aggressive downsizing of the transistor feature sizes (CMOS scaling) has been the main driver of the astonishing growth and advancement of microelectronic industry. Currently, the CMOS scaling is almost reaching its limits. The gate oxide is now only a few atomic layers thick, and this extremely thin oxide causes a huge leakage current through the oxide. Therefore, a further reduction of the gate oxide thickness is extremely difficult and new materials with higher dielectric constant are being explored. However, the phenomena of oxide breakdown and reliability are still serious issues in these thin oxides. Oxide breakdown exhibits a soft breakdown behavior at low voltages, and this is posing as one of the most crucial reliability issues for scaling of the ultra-thin oxides. In addition, the stress-induced leakage current (SILC) due to oxide has emerged as a scaling problem for the non-volatile memory technologies. In this dissertation, a percolation modeling approach is introduced to study and understand the dramatic changes in the conductivity of a disordered medium. Two different simulation methods of percolative conduction, the site and bond percolation, are studied here. These are used in simulating the post-breakdown conduction inside the oxide. Adopting a Monte-Carlo method, oxide breakdown is modeled using a 2-D percolation theory. The breakdown statistics and post-breakdown characteristics of the oxide are computed using this model. In this work, the effects of different physical parameters, such as dimension and the applied stress are studied. The simulation results show that a thinning of oxide layer and increasing the oxide area result in softening of breakdown. It is observed that the breakdown statistics appear to follow Weibull characteristics. As revealed by simulations, the Weibull slope changes linearly with oxide thickness, while not having a significant change when the area is varied and when the amount of the applied stress is varied. It is shown that the simulation results are well correlated with the experimental data reported in the literature. In this thesis, studying the conduction through the oxide using percolation model, it was discovered that a critical or a quasi-critical phenomenon occurs depending on the oxide dimensions. The criticality of the phase-transition results in a hard breakdown while the soft breakdown occurs due to a quasi-critical nature of percolation for ultra-thin oxides. In the later part of the thesis, a quantum percolation model is studied in order to explain and model the stress induced leakage current. It is explained that due to the wave nature of electrons, the SILC can be modeled as a tunneling path through the stressed oxide with the smaller tunneling threshold compared to the virgin oxide. In addition to the percolation model, a Markov chain theory is introduced to simulate the movement of electron as a random walk inside the oxide, and the breakdown is simulated using this random-walk of electron through the accumulated traps inside the oxide. It is shown that the trapping-detrapping of electrons results in an electrical noise in the post-breakdown current having 1/f noise characteristics. Using simulation of a resistor network with Markov theory, the conductance of the oxide is computed. An analytical study of a 2-D site percolation system is conducted using recursive methods and useful closed-form expressions are derived for specialized networks