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Hybrid inorganic–organic semiconductor (HIOS) interfaces are of interest for new photovoltaic devices operating above the Shockley–Queisser limit. Predicting energy band alignment at the interfaces is crucial for their design, but represents a challenging problem due to the large scales of the system, the energy precision required and a wide range of physical phenomena that occur at the interface. To tackle this problem, many-body perturbation theory in the non-self-consistent GW approximation, orbital relaxation corrections for organic semiconductors, and line-up potential method for inorganic semiconductors which allows for tractable and accurate computing of energy band alignment in crystalline van-der-Waals hybrid inorganic–organic semiconductor interfaces are used. In this work, crystalline tetracene physisorbed on the clean hydrogen-passivated 1 × 2 reconstructed (100) silicon surface is studied. Using this computational approach, it is found that the energy band alignment is determined by an interplay of the mutual dynamic dielectric screening of two materials and the formation of a dipole layer due to a weak hybridization of atomic/molecular orbitals at the interface. The significant role of the exchange-correlation effects in predicting band offsets for the hybrid inorganic–organic semiconductor interfaces is also emphasized.

Liquid metals (LMs) are emerging as unique fluids for a variety of applications, but their nanoscale solvation properties remain largely understudied. In this work, a combination of atomic force microscopy (AFM) and molecular dynamics (MD) simulations are used to investigate the structure of the interface between the bulk room temperature liquid metal (RTLM) and the LM oxide in nanodroplet systems of gallium, EGaIn (75.5% gallium, 24.5% indium), and Galinstan (68.5% gallium, 21.5% indium, 10% tin). Field's metal (51% indium, 32.5% bismuth, 16.5% tin) is also investigated, which melts at ≈62 °C, as a contrast to the other systems. AFM measurements reveal distinct sub‐oxide nanostructured layering in all three RTLM systems, and Field's metal above the melting point, to differing degrees. EGaIn and Galinstan show multiple penetration events between 20 and 30 nm, with smaller, less complex events in Ga. MD simulations suggest that this layering is a result of the near‐surface ordering of LM atoms beneath the oxide layer. Importantly, the atoms in this region do not behave as solids but are more ordered than in a pure disordered liquid system. The surface nanostructure elucidated here significantly expands the understanding of LM systems and their behavior at interfaces. [ABSTRACT FROM AUTHOR]

Crystallization of alloys from a molten state is a fundamental process underpinning metallurgy. Here the direct imaging of an intermetallic precipitation reaction at equilibrium in a liquid‐metal environment is demonstrated. It is shown that the outer layers of a solidified intermetallic are surprisingly unstable to the depths of several nanometers, fluctuating between a crystalline and a liquid state. This effect, referred to herein as crystal interface liquefaction, is observed at remarkably low temperatures and results in highly unstable crystal interfaces at temperatures exceeding 200 K below the bulk melting point of the solid. In general, any liquefaction process would occur at or close to the formal melting point of a solid, thus differentiating the observed liquefaction phenomenon from other processes such as surface pre‐melting or conventional bulk melting. Crystal interface liquefaction is observed in a variety of binary alloy systems and as such, the findings may impact the understanding of crystallization and solidification processes in metallic systems and alloys more generally. [ABSTRACT FROM AUTHOR]

The absorption spectra of congenetic wurtzite (WZ) and zincblende (ZB) CdS magic-sized clusters are investigated. We demonstrate that the exciton peak positions can be tuned by up to 500 meV by varying the strong coupling between X-type ligands and the semiconductor cores, while the addition of L-type ligands primarily affects cluster midgap states. When Z-type ligands are displaced by L-type ligands, red shifts in the absorption spectra are observed, despite the fact there is a small decrease in cluster size. Density functional theory calculations are used to explain these findings and they reveal the importance of Cd and S dangling bonds on the midgap states during the Z- to L-type ligand exchange process. Overall, ZB CdS clusters show higher chemical stability than WZ clusters but their optical properties exhibit greater sensitivity to the solvent. Conversely, WZ CdS clusters are not stable in a Lewis base-rich environment, resulting in various changes in their spectra. Our findings enable researchers to select capping ligands that modulate the optical properties of semiconductor clusters while maintaining precise control over their solvent interactions. [ABSTRACT FROM AUTHOR]

A variety of deposition methods for two-dimensional crystals have been demonstrated; however, their wafer-scale deposition remains a challenge. Here we introduce a technique for depositing and patterning of wafer-scale two-dimensional metal chalcogenide compounds by transforming the native interfacial metal oxide layer of low melting point metal precursors (group III and IV) in liquid form. In an oxygen-containing atmosphere, these metals establish an atomically thin oxide layer in a self-limiting reaction. The layer increases the wettability of the liquid metal placed on oxygen-terminated substrates, leaving the thin oxide layer behind. In the case of liquid gallium, the oxide skin attaches exclusively to a substrate and is then sulfurized via a relatively low temperature process. By controlling the surface chemistry of the substrate, we produce large area two-dimensional semiconducting GaS of unit cell thickness (∼1.5 nm). The presented deposition and patterning method offers great commercial potential for wafer-scale processes.

Continued industrial growth along with population growth is putting pressure on clean water supplies. Photocatalysis is an eco-friendly and cost-effective technology that can treat polluted water. As a visible-light-responsive photocatalyst, polymeric carbon nitride (CN) has shown significant potential for photocatalytic pollutant degradation. However, the fast charge recombination, slow charge transport and relatively large band gap restrict its photocatalytic performance. To overcome these challenges and develop a highly efficient photocatalyst, CN with robust visible-light photoactivity was solvothermally synthesised through defect engineering by carbon doping and surface vacancy modification. The additional carbon induces charge delocalization for enhancing charge tranfer and broadens the wavelength range of absorbance. The introduction of surface cyano functionality (–C≡N) not only enhances charge separation but also serves as electron-rich sites, thereby facilitating the generation of superoxide radicals. The controlled introduction of the C dopant and surface cyano group by simply introducing citric acid and varying the LiOH volume during synthesis demonstrated their synergy in optimising the electronic structure and the charge transport. As a consequence, there was a substantial generation of superoxide radicals when exposed to visible light (wavelengths > 420 nm), facilitating the efficient photodegradation of pollutants, such as tetracycline and Rhodamine B. Furthermore, the defect-engineered CN exhibited exceptional performance in the degradation of real-world wastewater. These findings underscore the promising potential of engineered CN for the advancement of visible-light-driven water purification technologies. [ABSTRACT FROM AUTHOR]

The positively charged nitrogen vacancy (NV +) center in diamond has been traditionally treated as a dark state due to the experimental lack of an optical signature. Recent computational studies have shown that it is possible for the NV + defect to have an excited state transition equivalent to that of the negatively charged (NV −) center, but no photoluminescence (PL) predictions have been reported so far. We report the first ab initio calculation showing that the NV + center presents quantum emission, with zero phonon line at 765 nm and a non-zero transition dipole moment, approximately one quarter of the transition dipole moment of NV −. We calculate the energy levels of the multielectron states under the time-dependent density functional theory (singlet and triplet E states), and using our recently developed frequency cutoff method, we predict the full PL spectrum. Our results suggest that this state cannot be considered intrinsically "dark" and charge specific quenching mechanisms should be investigated as the cause of the lack of optical activity in experimental characterizations. [ABSTRACT FROM AUTHOR]

Inorganic lead‐free halide perovskites, devoid of toxic or rare elements, have garnered considerable attention as photocatalysts for pollution control, CO2 reduction and hydrogen production. In the extensive perovskite design space, factors like substitution or doping level profoundly impact their performance. To address this complexity, a synergistic combination of machine learning models and theoretical calculations were used to efficiently screen substitution elements that enhanced the photoactivity of substituted Cs2AgBiBr6 perovskites. Machine learning models determined the importance of d10 orbitals, highlighting how substituent electron configuration affects electronic structure of Cs2AgBiBr6. Conspicuously, d10‐configured Zn2+ boosted the photoactivity of Cs2AgBiBr6. Experimental verification validated these model results, revealing a 13‐fold increase in photocatalytic toluene conversion compared to the unsubstituted counterpart. This enhancement resulted from the small charge carrier effective mass, as well as the creation of shallow trap states, shifting the conduction band minimum, introducing electron‐deficient Br, and altering the distance between the B‐site cations d band centre and the halide anions p band centre, a parameter tuneable through d10 configuration substituents. This study exemplifies the application of computational modelling in photocatalyst design and elucidating structure–property relationships. It underscores the potential of synergistic integration of calculations, modelling, and experimental analysis across various applications. [ABSTRACT FROM AUTHOR]

Organic–inorganic perovskite solar cells (PSCs) are promising candidates for next‐generation, inexpensive solar panels due to their commercially competitive cost and high power conversion efficiencies. However, PSCs suffer from poor stability. A new and vast subset of PSCs, quasi‐two‐dimensional Ruddlesden–Popper PSCs (quasi‐2D RP PSCs), has improved photostability and superior resilience to environmental conditions compared to three‐dimensional metal‐halide PSCs. To accelerate the search for new quasi‐2D RP PSCs, this work reports a combinatorial, machine learning (ML) enhanced high‐throughput perovskite film fabrication and optimization study. This work designs a bespoke experimental strategy and produces perovskite films with a range of different compositions using only spin‐coating free, reproducible robotic fabrication processes. The performance and characterization data of these solar cells are used to train a ML model that allow materials parameters to be optimized and direct the design of improved materials. The new, ML‐optimized, drop‐cast quasi‐2D RP perovskite films yield solar cells with power conversion efficiencies of up to 16.9%. [ABSTRACT FROM AUTHOR]

The functionalization of small‐molecule hole‐transport materials (HTMs) heavily relies on the rational design of molecular geometry, which can optimize both intrinsic HTM properties and interfacial properties for realizing high‐performance and stable lead halide perovskite solar cells (LHPSCs). Herein, two fluorene‐based donor–π linker–donor HTMs are seen, FL01 and FL02, whose side chains are tailored with planar phenyl‐carbazole groups and twisted triphenylamine groups, respectively. Benefiting from the high conformational flexibility of twisted side chains, the strong and oriented interaction via PbO bonding is well coordinated at the perovskite and FL02 interface, which favors the interfacial charge transfer as well as the protection of perovskite layer by effectively blocking or mitigating the diffusion of hygroscopic dopants toward the perovskite surface. Consequently, the performance of FL02 HTM‐based n–i–p LHPSCs is significantly enhanced by achieving a power conversion efficiency of 17.8%, which is twice higher than that (8.6%) of FL01 HTM‐based ones and comparable with the case (18.8%) of conventional spiro‐OMeTAD HTM‐based devices. More importantly, the FL02‐based devices exhibit impressively high operation and storage stabilities with T80 and TS80 lifetimes of >98 h and ≈270 days, respectively, which are among the longest lifespans for the type of hygroscopically doped LHPSCs. [ABSTRACT FROM AUTHOR]

Miniaturization and energy consumption by computational systems remain major challenges to address. Optoelectronics based synaptic and light sensing provide an exciting platform for neuromorphic processing and vision applications offering several advantages. It is highly desirable to achieve single‐element image sensors that allow reception of information and execution of in‐memory computing processes while maintaining memory for much longer durations without the need for frequent electrical or optical rehearsals. In this work, ultra‐thin (<3 nm) doped indium oxide (In2O3) layers are engineered to demonstrate a monolithic two‐terminal ultraviolet (UV) sensing and processing system with long optical state retention operating at 50 mV. This endows features of several conductance states within the persistent photocurrent window that are harnessed to show learning capabilities and significantly reduce the number of rehearsals. The atomically thin sheets are implemented as a focal plane array (FPA) for UV spectrum based proof‐of‐concept vision system capable of pattern recognition and memorization required for imaging and detection applications. This integrated light sensing and memory system is deployed to illustrate capabilities for real‐time, in‐sensor memorization, and recognition tasks. This study provides an important template to engineer miniaturized and low operating voltage neuromorphic platforms across the light spectrum based on application demand. [ABSTRACT FROM AUTHOR]

Gallium nitride (GaN) technology has matured and commercialised for optoelectronic devices in the ultraviolet (UV) spectrum over the last few decades. Simultaneously, atomically thin materials with unique features have emerged as contenders for device miniaturization. However, the lack of successful techniques to produce ultra‐thin GaN prevents access to these new predicted properties. Here, this important gap is addressed by printing millimeter‐large ultra‐thin GaN nanosheets (NS) (≈1.4 nm) using a simple two‐step process that simultaneously introduces nitrogen point defects. This extends the photoelectrical spectral response from UV (280 nm) to near infrared (NIR) (1080 nm). The GaN‐based photodetectors display excellent figures of merit, having a responsivity (2.72 × 104 A W−1) up to four orders of magnitude higher than the commercial photodetectors at room temperature, despite being 102–103 times thinner. The photodetectors exhibit fast switching, with rise and decay time in the range of microseconds. The state‐of‐the‐art device performance originates from the ultra‐thin nature of GaN NS coupled with nitrogen point vacancies in the synthesis process. This work presents the opportunity to significantly expand the reach of GaN semiconductor technology and may lead to applications in high‐performance miniaturized imaging systems, spectroscopy, communication, and integrated optoelectronic circuits. [ABSTRACT FROM AUTHOR]

This work presents algorithms for the efficient enumeration of configuration spaces following Boltzmann-like statistics, with example applications to the calculation of non-radiative rates, and an open-source implementation. Configuration spaces are found in several areas of physics, particularly wherever there are energy levels that possess variable occupations. In bosonic systems, where there are no upper limits on the occupation of each level, enumeration of all possible configurations is an exceptionally hard problem. We look at the case where the levels need to be filled to satisfy an energy criterion, for example, a target excitation energy, which is a type of knapsack problem as found in combinatorics. We present analyses of the density of configuration spaces in arbitrary dimensions and how particular forms of kernel can be used to envelope the important regions. In this way, we arrive at three new algorithms for enumeration of such spaces that are several orders of magnitude more efficient than the naive brute force approach. Finally, we show how these can be applied to the particular case of internal conversion rates in a selection of molecules and discuss how a stochastic approach can, in principle, reduce the computational complexity to polynomial time. [ABSTRACT FROM AUTHOR]

Measuring the photoluminescence of defects in crystals is a common experimental technique for analysis and identification. However, current theoretical simulations typically require the simulation of a large number of atoms to eliminate finite-size effects, which discourages computationally expensive excited state methods. We show how to extract the room-temperature photoluminescence spectra of defect centers in bulk from an ab initio simulation of a defect in small clusters. The finite-size effect of small clusters manifests as strong coupling to low frequency vibrational modes. We find that removing vibrations below a cutoff frequency determined by constrained optimization returns the main features of the solid-state photoluminescence spectrum. This strategy is illustrated for the negatively charged nitrogen vacancy defect in diamond (NV −) presenting a connection between defects in solid state and clusters; the first vibrationally resolved ab initio photoluminescence spectrum of an NV − defect in a nanodiamond; and an alternative technique for simulating photoluminescence for solid-state defects utilizing more accurate excited state methods. [ABSTRACT FROM AUTHOR]

Geometries and electronic structures of germanium trimer clusters doped with titanium TiGe3−/0 were studied making use of the complete active space self-consistent field followed by second-order perturbation theory explicitly correlated coupled cluster singles and doubles method with perturbative triples corrections CCSD(T)-F12 and Tao-Perdew-Staroverov-Scuseria methods. Two electronic states (²A′ and ²A″) of the anion (pyramid shape) were determined to be nearly degenerate and energetically competing for the anionic ground state of TiGe3−. These two anionic states are believed to be concurrently populated in the experiment and induce six observed anion photoelectron bands. Total 14 electronic transitions starting from the ²A′ and ²A″ states were assigned to five out of six visible bands in the experimental anion photoelectron spectrum of TiGe3−. Each band was proven to be caused by multiple one-electron detachments from two populated anionic states. The last experimental band with the highest detachment energy is believed to be the result of various inner one-electron removals. [ABSTRACT FROM AUTHOR]