Fast Thermodynamic Study on a Silicon Nanotransistor at Cryogenic Temperatures.

Cryogenic temperatures are crucial for the operation of semiconductor quantum electronic devices, yet the heating effects induced by microwave or laser signals used for quantum state manipulation can lead to significant temperature variations at the nanoscale. Therefore, probing the temperature of individual devices in working conditions and understanding the thermodynamics are paramount for designing and operating large-scale quantum computing systems. In this study, we demonstrate high-sensitivity fast thermometry in a silicon nanotransistor at cryogenic temperatures using RF reflectometry. Through this method, we explore the thermodynamic processes of the nanotransistor during and after a laser pulse and determine the dominant heat dissipation channels in the few-kelvin temperature range. These insights are important to understand thermal budgets in quantum circuits, with our techniques being compatible with microwave and laser radiation, offering a versatile approach for studying other quantum electronic devices in working conditions.

Time-Resolved Photoionization Detection of a Single Er3+ Ion in Silicon.

The detection of charge trap ionization induced by resonant excitation enables spectroscopy on single Er3+ ions in silicon nanotransistors. In this work, a time-resolved detection method is developed to investigate the resonant excitation and relaxation of a single Er3+ ion in silicon. The time-resolved detection is based on a long-lived current signal with a tunable reset and allows the measurement under stronger and shorter resonant excitation in comparison to time-averaged detection. Specifically, the short-pulse study gives an upper bound of 23.7 µs on the decay time of the 4I13/2 state of the Er3+ ion. The fast decay and the tunable reset allow faster repetition of the single-ion detection, which is attractive for implementing this method in large-scale quantum systems of single optical centers. The findings on the detection mechanism and dynamics also provide an important basis for applying this technique to detect other single optical centers in solids.

High-rate nanofluidic energy absorption in porous zeolitic frameworks.

Optimal mechanical impact absorbers are reusable and exhibit high specific energy absorption. The forced intrusion of liquid water in hydrophobic nanoporous materials, such as zeolitic imidazolate frameworks (ZIFs), presents an attractive pathway to engineer such systems. However, to harness their full potential, it is crucial to understand the underlying water intrusion and extrusion mechanisms under realistic, high-rate deformation conditions. Here, we report a critical increase of the energy absorption capacity of confined water-ZIF systems at elevated strain rates. Starting from ZIF-8 as proof-of-concept, we demonstrate that this attractive rate dependence is generally applicable to cage-type ZIFs but disappears for channel-containing zeolites. Molecular simulations reveal that this phenomenon originates from the intrinsic nanosecond timescale needed for critical-sized water clusters to nucleate inside the nanocages, expediting water transport through the framework. Harnessing this fundamental understanding, design rules are formulated to construct effective, tailorable and reusable impact energy absorbers for challenging new applications.

Engineering long spin coherence times of spin-orbit qubits in silicon.

Electron-spin qubits have long coherence times suitable for quantum technologies. Spin-orbit coupling promises to greatly improve spin qubit scalability and functionality, allowing qubit coupling via photons, phonons or mutual capacitances, and enabling the realization of engineered hybrid and topological quantum systems. However, despite much recent interest, results to date have yielded short coherence times (from 0.1 to 1 µs). Here we demonstrate ultra-long coherence times of 10 ms for holes where spin-orbit coupling yields quantized total angular momentum. We focus on holes bound to boron acceptors in bulk silicon 28, whose wavefunction symmetry can be controlled through crystal strain, allowing direct control over the longitudinal electric dipole that causes decoherence. The results rival the best electron-spin qubits and are 104 to 105 longer than previous spin-orbit qubits. These results open a pathway to develop new artificial quantum systems and to improve the functionality and scalability of spin-based quantum technologies.

Chlorination of a Zeolitic-Imidazolate Framework Tunes Packing and van der Waals Interaction of Carbon Dioxide for Optimized Adsorptive Separation.

Molecular separation of carbon dioxide (CO2) and methane (CH4) is of growing interest for biogas upgrading, carbon capture and utilization, methane synthesis and for purification of natural gas. Here, we report a new zeolitic-imidazolate framework (ZIF), coined COK-17, with exceptionally high affinity for the adsorption of CO2 by London dispersion forces, mediated by chlorine substituents of the imidazolate linkers. COK-17 is a new type of flexible zeolitic-imidazolate framework Zn(4,5-dichloroimidazolate)2 with the SOD framework topology. Below 200 K it displays a metastable closed-pore phase next to its stable open-pore phase. At temperatures above 200 K, COK-17 always adopts its open-pore structure, providing unique adsorption sites for selective CO2 adsorption and packing through van der Waals interactions with the chlorine groups, lining the walls of the micropores. Localization of the adsorbed CO2 molecules by Rietveld refinement of X-ray diffraction data and periodic density functional theory calculations revealed the presence and nature of different adsorption sites. In agreement with experimental data, grand canonical Monte Carlo simulations of adsorption isotherms of CO2 and CH4 in COK-17 confirmed the role of the chlorine functions of the linkers and demonstrated the superiority of COK-17 compared to other adsorbents such as ZIF-8 and ZIF-71.

The micromechanical model to computationally investigate cooperative and correlated phenomena in metal-organic frameworks.

Computational insight into the impact of cooperative phenomena and correlated spatial disorder on the macroscopic behaviour of metal-organic frameworks (MOFs) is essential in order to consciously engineer these phenomena for targeted applications. However, the spatial extent of these effects, ranging over hundreds of nanometres, limits the applicability of current state-of-the-art computational tools in this field. To obtain a fundamental understanding of these long-range effects, the micromechanical model is introduced here. This model overcomes the challenges associated with conventional coarse-graining techniques by exploiting the natural partitioning of a MOF material into unit cells. By adopting the elastic deformation energy as the central quantity, the micromechanical model hierarchically builds on experimentally accessible input parameters that are obtained from atomistic quantum mechanical or force field simulations. As a result, the here derived micromechanical equations of motion can be adopted to shed light on the effect of long-range cooperative phenomena and correlated spatial disorder on the performance of mesoscale MOF materials.

Quantifying the Likelihood of Structural Models through a Dynamically Enhanced Powder X-Ray Diffraction Protocol.

Structurally characterizing new materials is tremendously challenging, especially when single crystal structures are hardly available which is often the case for covalent organic frameworks. Yet, knowledge of the atomic structure is key to establish structure-function relations and enable functional material design. Herein, a new protocol is proposed to unambiguously predict the structure of poorly crystalline materials through a likelihood ordering based on the X-ray diffraction (XRD) pattern. Key of the procedure is the broad set of structures generated from a limited number of building blocks and topologies, which is submitted to operando structural characterization. The dynamic averaging in the latter accounts for the operando conditions and inherent temporal character of experimental measurements, yielding unparalleled agreement with experimental powder XRD patterns. The proposed concept can hence unquestionably identify the structure of experimentally synthesized materials, a crucial step to design next generation functional materials.

Strongly Reducing (Diarylamino)benzene-Based Covalent Organic Framework for Metal-Free Visible Light Photocatalytic H2O2 Generation.

Photocatalytic reduction of molecular oxygen is a promising route toward sustainable production of hydrogen peroxide (H2O2). This challenging process requires photoactive semiconductors enabling solar energy driven generation and separation of electrons and holes with high charge transfer kinetics. Covalent organic frameworks (COFs) are an emerging class of photoactive semiconductors, tunable at a molecular level for high charge carrier generation and transfer. Herein, we report two newly designed two-dimensional COFs based on a (diarylamino)benzene linker that form a Kagome (kgm) lattice and show strong visible light absorption. Their high crystallinity and large surface areas (up to 1165 m2·g-1) allow efficient charge transfer and diffusion. The diarylamine (donor) unit promotes strong reduction properties, enabling these COFs to efficiently reduce oxygen to form H2O2. Overall, the use of a metal-free, recyclable photocatalytic system allows efficient photocatalytic solar transformations.

Single Rare-Earth Ions as Atomic-Scale Probes in Ultrascaled Transistors.

Continued scaling of semiconductor devices has driven information technology into vastly diverse applications. The performance of ultrascaled transistors is strongly influenced by local electric field and strain. As the size of these devices approaches fundamental limits, it is imperative to develop characterization techniques with nanometer resolution and three-dimensional (3D) mapping capabilities for device optimization. Here, we report on the use of single erbium (Er) ions as atomic probes for the electric field and strain in a silicon ultrascaled transistor. Stark shifts on the Er3+ spectra induced by both the overall electric field and the local charge environment are observed. Changes in strain smaller than 3 × 10-6 are detected, which is around 2 orders of magnitude more sensitive than the standard techniques used in the semiconductor industry. These results open new possibilities for 3D mapping of the local strain and electric field in the channel of ultrascaled transistors.

Reliably Modeling the Mechanical Stability of Rigid and Flexible Metal-Organic Frameworks.

Over the past two decades, metal-organic frameworks (MOFs) have matured from interesting academic peculiarities toward a continuously expanding class of hybrid, nanoporous materials tuned for targeted technological applications such as gas storage and heterogeneous catalysis. These oft-times crystalline materials, composed of inorganic moieties interconnected by organic ligands, can be endowed with desired structural and chemical features by judiciously functionalizing or substituting these building blocks. As a result of this reticular synthesis, MOF research is situated at the intriguing intersection between chemistry and physics, and the building block approach could pave the way toward the construction of an almost infinite number of possible crystalline structures, provided that they exhibit stability under the desired operational conditions. However, this enormous potential is largely untapped to date, as MOFs have not yet found a major breakthrough in technological applications. One of the remaining challenges for this scale-up is the densification of MOF powders, which is generally achieved by subjecting the material to a pressurization step. However, application of an external pressure may substantially alter the chemical and physical properties of the material. A reliable theoretical guidance that can presynthetically identify the most stable materials could help overcome this technological challenge. In this Account, we describe the recent research the progress on computational characterization of the mechanical stability of MOFs. So far, three complementary approaches have been proposed, focusing on different aspects of mechanical stability: (i) the Born stability criteria, (ii) the anisotropy in mechanical moduli such as the Young and shear moduli, and (iii) the pressure-versus-volume equations of state. As these three methods are grounded in distinct computational approaches, it is expected that their accuracy and efficiency will vary. To date, however, it is unclear which set of properties are suited and reliable for a given application, as a comprehensive comparison for a broad variety of MOFs is absent, impeding the widespread use of these theoretical frameworks. Herein, we fill this gap by critically assessing the performance of the three computational models on a broad set of MOFs that are representative for current applications. These materials encompass the mechanically rigid UiO-66(Zr) and MOF-5(Zn) as well as the flexible MIL-47(V) and MIL-53(Al), which undergo pressure-induced phase transitions. It is observed that the Born stability criteria and pressure-versus-volume equations of state give complementary insight into the macroscopic and microscopic origins of instability, respectively. However, interpretation of the Born stability criteria becomes increasingly difficult when less symmetric materials are considered. Moreover, pressure fluctuations during the simulations hamper their accuracy for flexible materials. In contrast, the pressure-versus-volume equations of state are determined in a thermodynamic ensemble specifically targeted to mitigate the effects of these instantaneous fluctuations, yielding more accurate results. The critical Account presented here paves the way toward a solid computational framework for an extensive presynthetic screening of MOFs to select those that are mechanically stable and can be postsynthetically densified before their use in targeted applications.

Optical addressing of an individual erbium ion in silicon.

The detection of electron spins associated with single defects in solids is a critical operation for a range of quantum information and measurement applications under development. So far, it has been accomplished for only two defect centres in crystalline solids: phosphorus dopants in silicon, for which electrical read-out based on a single-electron transistor is used, and nitrogen-vacancy centres in diamond, for which optical read-out is used. A spin read-out fidelity of about 90 per cent has been demonstrated with both electrical read-out and optical read-out; however, the thermal limitations of the former and the poor photon collection efficiency of the latter make it difficult to achieve the higher fidelities required for quantum information applications. Here we demonstrate a hybrid approach in which optical excitation is used to change the charge state (conditional on its spin state) of an erbium defect centre in a silicon-based single-electron transistor, and this change is then detected electrically. The high spectral resolution of the optical frequency-addressing step overcomes the thermal broadening limitation of the previous electrical read-out scheme, and the charge-sensing step avoids the difficulties of efficient photon collection. This approach could lead to new architectures for quantum information processing devices and could drastically increase the range of defect centres that can be exploited. Furthermore, the efficient electrical detection of the optical excitation of single sites in silicon represents a significant step towards developing interconnects between optical-based quantum computing and silicon technologies.

On the importance of anharmonicities and nuclear quantum effects in modelling the structural properties and thermal expansion of MOF-5.

In this article, we investigate the influence of anharmonicities and nuclear quantum effects (NQEs) in modelling the structural properties and thermal expansion of the empty MOF-5 metal-organic framework. To introduce NQEs in classical molecular dynamics simulations, two different methodologies are considered, comparing the approximate, but computationally cheap, method of generalised Langevin equation thermostatting to the more advanced, computationally demanding path integral molecular dynamics technique. For both methodologies, similar results were obtained for all the properties under investigation. The structural properties of MOF-5, probed by means of radial distribution functions (RDFs), show some distinct differences with respect to a classical description. Besides a broadening of the RDF peaks under the influence of quantum fluctuations, a different temperature dependence is also observed due to a dominant zero-point energy (ZPE) contribution. For the thermal expansion of MOF-5, by contrast, NQEs appear to be only of secondary importance with respect to an adequate modelling of the anharmonicities of the potential energy surface (PES), as demonstrated by the use of two differently parametrised force fields. Despite the small effect in the temperature dependence of the volume of MOF-5, NQEs do however significantly affect the absolute volume of MOF-5, in which the ZPE resulting from the intertwining of NQEs and anharmonicities plays a crucial role. A sufficiently accurate description of the PES is therefore prerequisite when modelling NQEs.

Gigahertz Single-Electron Pumping Mediated by Parasitic States.

In quantum metrology, semiconductor single-electron pumps are used to generate accurate electric currents with the ultimate goal of implementing the emerging quantum standard of the ampere. Pumps based on electrostatically defined tunable quantum dots (QDs) have thus far shown the most promising performance in combining fast and accurate charge transfer. However, at frequencies exceeding approximately 1 GHz the accuracy typically decreases. Recently, hybrid pumps based on QDs coupled to trap states have led to increased transfer rates due to tighter electrostatic confinement. Here, we operate a hybrid electron pump in silicon obtained by coupling a QD to multiple parasitic states and achieve robust current quantization up to a few gigahertz. We show that the fidelity of the electron capture depends on the sequence in which the parasitic states become available for loading, resulting in distinctive frequency-dependent features in the pumped current.

Influence of a Confined Methanol Solvent on the Reactivity of Active Sites in UiO-66.

UiO-66, composed of Zr-oxide bricks and terephthalate linkers, is currently one of the most studied metal-organic frameworks due to its exceptional stability. Defects can be introduced in the structure, creating undercoordinated Zr atoms which are Lewis acid sites. Here, additional Brønsted sites can be generated by coordinated protic species from the solvent. In this Article, a multilevel modeling approach was applied to unravel the effect of a confined methanol solvent on the active sites in UiO-66. First, active sites were explored with static periodic density functional theory calculations to investigate adsorption of water and methanol. Solvent was then introduced in the pores with grand canonical Monte Carlo simulations, followed by a series of molecular dynamics simulations at operating conditions. A hydrogen-bonded network of methanol molecules is formed, allowing the protons to shuttle between solvent methanol, adsorbed water, and the inorganic brick. Upon deprotonation of an active site, the methanol solvent aids the transfer of protons and stabilizes charged configurations via hydrogen bonding, which could be crucial in stabilizing reactive intermediates. The multilevel modeling approach adopted here sheds light on the important role of a confined solvent on the active sites in the UiO-66 material, introducing dynamic acidity in the system at finite temperatures by which protons may be easily shuttled from various positions at the active sites.

A Probabilistic Finite State Logic Machine Realized Experimentally on a Single Dopant Atom.

Exploiting the potential of nanoscale devices for logic processing requires the implementation of computing functionalities departing from the conventional switching paradigm. We report on the design and the experimental realization of a probabilistic finite state machine in a single phosphorus donor atom placed in a silicon matrix electrically addressed and probed by scanning tunneling spectroscopy (STS). The single atom logic unit simulates the flow of visitors in a maze whose topology is determined by the dynamics of the electronic transport through the states of the dopant. By considering the simplest case of a unique charge state for which three electronic states can be resolved, we demonstrate an efficient solution of the following problem: in a maze of four connected rooms, what is the optimal combination of door opening rates in order to maximize the time that visitors spend in one specific chamber? The implementation takes advantage of the stochastic nature of electron tunneling, while the output remains the macroscopic current whose reading can be realized with standard techniques and does not require single electron sensitivity.

Implementation of Multivariable Logic Functions in Parallel by Electrically Addressing a Molecule of Three Dopants in Silicon.

To realize low-power, compact logic circuits, one can explore parallel operation on single nanoscale devices. An added incentive is to use multivalued (as distinct from Boolean) logic. Here, we theoretically demonstrate that the computation of all the possible outputs of a multivariate, multivalued logic function can be implemented in parallel by electrical addressing of a molecule made up of three interacting dopant atoms embedded in Si. The electronic states of the dopant molecule are addressed by pulsing a gate voltage. By simulating the time evolution of the non stationary electronic density built by the gate voltage, we show that one can implement a molecular decision tree that provides in parallel all the outputs for all the inputs of the multivariate, multivalued logic function. The outputs are encoded in the populations and in the bond orders of the dopant molecule, which can be measured using an STM tip. We show that the implementation of the molecular logic tree is equivalent to a spectral function decomposition. The function that is evaluated can be field-programmed by changing the time profile of the pulsed gate voltage.

Charge-Insensitive Single-Atom Spin-Orbit Qubit in Silicon.

High fidelity entanglement of an on-chip array of spin qubits poses many challenges. Spin-orbit coupling (SOC) can ease some of these challenges by enabling long-ranged entanglement via electric dipole-dipole interactions, microwave photons, or phonons. However, SOC exposes conventional spin qubits to decoherence from electrical noise. Here, we propose an acceptor-based spin-orbit qubit in silicon offering long-range entanglement at a sweet spot where the qubit is protected from electrical noise. The qubit relies on quadrupolar SOC with the interface and gate potentials. As required for surface codes, 10^{5} electrically mediated single-qubit and 10^{4} dipole-dipole mediated two-qubit gates are possible in the predicted spin lifetime. Moreover, circuit quantum electrodynamics with single spins is feasible, including dispersive readout, cavity-mediated entanglement, and spin-photon entanglement. An industrially relevant silicon-based platform is employed.

Acidity Constant (pKa ) Calculation of Large Solvated Dye Molecules: Evaluation of Two Advanced Molecular Dynamics Methods.

pH-Sensitive dyes are increasingly applied on polymer substrates for the creation of novel sensor materials. Recently, these dye molecules were modified to form a covalent bond with the polymer host. This had a large influence on the pH-sensitive properties, in particular on the acidity constant (pKa ). Obtaining molecular control over the factors that influence the pKa value is mandatory for the future intelligent design of sensor materials. Herein, we show that advanced molecular dynamics (MD) methods have reached the level at which the pKa values of large solvated dye molecules can be predicted with high accuracy. Two MD methods were used in this work: steered or restrained MD and the insertion/deletion scheme. Both were first calibrated on a set of phenol derivatives and afterwards applied to the dye molecule bromothymol blue. Excellent agreement with experimental values was obtained, which opens perspectives for using these methods for designing dye molecules.