Inorganic Semiconductors Research Articles

Electronic structure, mechanical, phonon, magnetic, and transport analysis of newly inorganic halide double perovskite semiconductors Rb2GeMnX6 (X = Cl, Br) from first-principles DFT calculations

Electronic structure, mechanical, phonon, magnetic, and transport analysis of newly inorganic halide double perovskite semiconductors Rb2GeMnX6 (X = Cl, Br) from first-principles DFT calculations

Hybrid MoSe2/P3HT Transistor for Real-Time Ammonia Sensing in Biofluids.

Organic and inorganic hybrid field-effect transistors (FETs), utilizing layered molybdenum diselenide (MoSe2) and an organic semiconductor poly(3-hexylthiophene) (P3HT), are presented for biosensing applications. A new hybrid device structure that combines organic (P3HT) and inorganic (MoSe2) components is showcased for accurate and selective bioanalyte detection in human bodily fluids to overcome 2D-transition metal dichalcogenides (TMDs) nonspecific interactions. This hybrid structure utilizes organic and inorganic semiconductors' high surface-to-volume ratio, carrier transport, and conductivity for biosensing. Ammonia concentrations in saliva and plasma are closely linked to physiological and pathological conditions of the human body. A highly sensitive hybrid FET biosensor detects total ammonia (NH4+ and NH3) from 0.5 μM to 1 mM concentrations, with a detection limit of 0.65 μM in human bodily fluids. The sensor's ammonia specificity in artificial saliva against interfering species is showcased. Furthermore, the fabricated hybrid FET device exhibits a stable and repeatable response to ammonia in both saliva and plasma, achieving a remarkable response level of 2300 at a 1 mM concentration of ammonia, surpassing existing literature by 10-fold. This hybrid FET biosensing platform holds significant promise for developing a precise tool for the real-time monitoring of ammonia concentrations in human biological fluids, offering potential applications in point-of-care diagnostics.

Optimizing charge transport in hybrid GaN-PEDOT:PSS/PMMADevice for advanced application

Organic–inorganic hybrid light-emitting devices have garnered significant attention in the last few years due to their potential. These devices integrate the superior electron mobility of inorganic semiconductors with the remarkable optoelectronic characteristics of organic semiconductors. The inquiry focused on analyzing the optical and electrical properties of a light-emitting heterojunction that combines p-type GaN with organic materials (PEDOT, PSS, and PMMA). This heterojunction is an organic–inorganic hybrid. The procedure entailed utilizing a spin-coating technique to apply a layer of either poly(methyl methacrylate) (PMMA) or a mixture of PMMA and poly(3,4ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT: PSS) onto an indium tin oxide (ITO) substrate. Subsequently, different Nd:YAG laser pulses (200, 250, and 300 pulses) were used to administer a GaN inorganic layer onto the prepared organic layer using a pulsed laser deposition approach. Subsequently, the thermal evaporation technique was employed to deposit an aluminum electrode on the top of the organic and inorganic layers, while laser pulses were fine-tuned for optimal performance. The Hall effect investigation verifies the p-type conductivity of the GaN material. The electroluminescence studies confirmed the production of blue light by the GaN-based devices throughout a range of voltage situations, spanning from 45 to 72 V.

Photoelectrochemical immunoassay of cardiac troponin I based on ZnTCPP/CdIn2S4 type-II heterojunction and co-catalyzed precipitation biolabeling.

CdIn2S4 and zinc tetrakis(4-carboxyphenyl)porphyrin (ZnTCPP) were synthesized by hydrothermal method, and an organic dye-sensitized inorganic semiconductor ZnTCPP/CdIn2S4 type II heterojunction was constructed on a fluorine-doped tin oxide (FTO) substrate electrode. Asandwich immunostructure forsignal-attenuation photoelectrochemical (PEC) detection of cardiac troponin I (cTnI) was constructed using the ZnTCPP/CdIn2S4/FTO photoanode and a horseradish peroxidase (HRP)-ZnFe2O4-Ab2-bovine serum albumin (BSA) immunolabeling complex. The bioenzyme HRP and the HRP-like nanozyme ZnFe2O4 can co-catalyze the oxidation of 4-chloro-1-naphthol (4-CN) by H2O2 to produce an insoluble precipitate on the photoanode, thus notably reducing the anodic photocurrent for quantitative determination of cTnI. Under the optimal conditions, the photocurrent at 0V vs. SCE in 0.1M phosphate buffer solution (pH 7.40) containing 0.1M ascorbic acid was linear with the logarithm of cTnI concentration from 500fg mL-1 to 50.0 ng mL-1, and the limit of detection (LOD, S/N = 3) is 0.15 pg mL-1. Spiked recoveries were 95.1% ~ 104% for assay of cTnI in human serum samples.

61‐2: Invited Paper: Light Emitting Diodes Based on Metal Halide Perovskites and Beyond

Light emitting diodes (LEDs) have wide applications from fullcolor displays to solid‐state lighting. Numerous types of luminescent materials have been explored for LEDs, ranging from inorganic semiconductors to metal complexes and quantum dots. Despite the rapid pace of development, LEDs have not achieved their full potentials in terms of performance and cost efficiency. Identifying new eco‐friendly materials for LEDs is of great interest. Recently, metal halide perovskites and perovskite‐related hybrid materials have emerged as new generation luminescent materials with unique optoelectronic properties. Here, some of our recent development of LEDs based on metal halide perovskites and perovskite‐related materials will be discussed.

Enhanced and Balanced Carrier Mobility Via n‐Type SnS Dopant Enables High‐Performance Non‐Fullerene Organic Solar Cells

AbstractThe unbalanced electron‐hole mobility is the major bottleneck for boosting the photovoltaic performance of organic solar cells. In this study, 2D n‐type inorganic semiconductor material tin sulfide (SnS) is prepared and introduced into the PM6:Y6 bulk heterojunction organic solar cells to improve photovoltaic performance. The incorporation of SnS promotes Y6 crystallization, and renders the face‐on orientation of Y6 molecules dominant. The improved active layer morphology suppresses carrier recombination and strengthens the electron transport. The electron mobility increases significantly from 4.71 × 10−4 cm2 V−1 s−1 to 7.61 × 10−4 cm2 V−1 s−1 with the hole/electron mobilities (µh/µe) value reducing from 1.67 to 1.11. With enhanced and balanced carrier mobility, the open‐circuit voltage, short‐circuit current density and fill factor of the SnS‐doped PM6:Y6 organic solar cells are improved simultaneously, and the power conversion efficiency is boosted from 16.66 to 18.50%. Additionally, the SnS doped devices exhibit better thermal and storage stability. The improved photovoltaic performance is further verified in PM6:L8‐BO and D18:Y6 based organic solar cells. This work demonstrates that n‐type SnS dopant is an efficient and universal method to improve photovoltaic performance of non‐fullerene organic solar cells.

An inorganic-blended p-type semiconductor with robust electrical and mechanical properties

Inorganic semiconductors typically have limited p-type behavior due to the scarcity of holes and the localized valence band maximum, hindering the progress of complementary devices and circuits. In this work, we propose an inorganic blending strategy to activate the hole-transporting character in an inorganic semiconductor compound, namely tellurium-selenium-oxygen (TeSeO). By rationally combining intrinsic p-type semimetal, semiconductor, and wide-bandgap semiconductor into a single compound, the TeSeO system displays tunable bandgaps ranging from 0.7 to 2.2 eV. Wafer-scale ultrathin TeSeO films, which can be deposited at room temperature, display high hole field-effect mobility of 48.5 cm2/(Vs) and robust hole transport properties, facilitated by Te-Te (Se) portions and O-Te-O portions, respectively. The nanosphere lithography process is employed to create nanopatterned honeycomb TeSeO broadband photodetectors, demonstrating a high responsibility of 603 A/W, an ultrafast response of 5 μs, and superior mechanical flexibility. The p-type TeSeO system is highly adaptable, scalable, and reliable, which can address emerging technological needs that current semiconductor solutions may not fulfill.

Shape-deformable Micro-LEDs for advanced displays and healthcare

Recently, flexible/stretchable micro-scale light-emitting diodes (LEDs), with dimensions significantly smaller than conventional diodes used for illuminations, have emerged for promising applications in areas such as deformable displays, wearable devices for healthcare, etc . For such applications, these devices must have some unusual features that common inorganic LEDs do not intrinsically own, including conformability, biocompatibility, mechanical flexibility, etc . This Perspective focuses on summarizing the most recent progress in developing such flexible emitters based on inorganic semiconductors, followed by reviewing their potential applications. Finally, major challenges and future research directions of deformable micro-scale LEDs are presented.

Indium oxide-based Z-scheme hollow core–shell heterostructure with rich sulfur-vacancy for highly efficient light-driven splitting of water to produce clean energy

Crafting an inorganic semiconductor heterojunction with defect engineering and morphology modulation is a strategic approach to produce clean energy by the highly efficient light-driven splitting of water. In this paper, a novel Z-scheme sulfur-vacancy containing Zn3In2S6 (Vs-Zn3In2S6) nanosheets/In2O3 hollow hexagonal prisms heterostructrue (Vs-ZIS6INO) was firstly constructed by an oil bath method, in which Vs-Zn3In2S6 nanosheets grew on the surfaces of In2O3 hollow hexagonal prisms to form a hollow core–shell structure. The obtained Vs-ZIS6INO heterostructrue exhibited much enhanced activity of the production of H2 and H2O2 by the light-driven water splitting. In particular, under visible light irradiation (λ > 420 nm), the rate of generation of H2 of Vs-ZIS6INO sample containing 30 wt% Vs-Zn3In2S6 (30Vs-ZIS6INO) could reach 3721 μmol g–1h−1, which was 87 and 6 times higher than those of Zn3In2S6 (43 μmol g–1h−1) and Vs-Zn3In2S6 (586 μmol g–1h−1), respectively. Meanwhile, 30Vs-ZIS6INO could exhibit the rate of H2O2 production of 483 μmol g–1h−1 through the dual pathways of indirect 2e– oxygen reduction (ORR) and water oxidation (WOR) without adding any sacrifice agents, far exceeding In2O3 (7 μmol g–1h−1) and Vs-Zn3In2S6 (58 μmol g–1h−1). The excellent photocatalytic activities of H2 and H2O2 generations of Vs-ZIS6INO sample might result from the synergistic effect of the sulfur vacancy, hollow core–shell structure, and Z-scheme heterostructure, which accelerated the electron delocalization, enhanced the absorption and conversion of solar energy, reduced the carrier diffusion distance, and ensured high REDOX ability. In addition, the possible photocatalytic mechanisms for the production of H2 and H2O2 were discussed in detail. This study provided a new idea and reference for constructing the novel and efficient inorganic semiconductor heterostructures by coordinating vacancy defect and morphology design to adequately utilize water splitting for the production of clean energy.

Semitransparent organic photovoltaics enabled by transparent p-type inorganic semiconductor and near-infrared acceptor

Semitransparent organic photovoltaics (STOPVs) have gained wide attention owing to their promising applications in building-integrated photovoltaics, agrivoltaics, and floating photovoltaics. Organic semiconductors with high charge carrier mobility usually have planar and conjugated structures, thereby showing strong absorption in visible region. In this work, a new concept of incorporating transparent inorganic semiconductors is proposed for high-performance STOPVs. Copper(I) thiocyanate (CuSCN) is a visible-transparent inorganic semiconductor with an ionization potential of 5.45 eV and high hole mobility. The transparency of CuSCN benefits high average visible transmittance (AVT) of STOPVs. The energy levels of CuSCN as donor match those of near-infrared small molecule acceptor BTP-eC9, and the formed heterojunction exhibits an ability of exciton dissociation. High mobility of CuSCN contributes to a more favorable charge transport channel and suppresses charge recombination. The control STOPVs based on PM6/BTP-eC9 exhibit an AVT of 19.0% with a power conversion efficiency (PCE) of 12.7%. Partial replacement of PM6 with CuSCN leads to a 63% increase in transmittance, resulting in a higher AVT of 30.9% and a comparable PCE of 10.8%.

Literature Review on Conjugated Polymers as Light-Sensitive Materials for Photovoltaic and Light-Emitting Devices in Photonic Biomaterial Applications

Due to their extended p-orbital delocalization, conjugated polymers absorb light in the range of visible–NIR frequencies. We attempt to exploit this property to create materials that compete with inorganic semiconductors in photovoltaic and light-emitting materials. Beyond competing for applications in photonic devices, organic conjugated compounds, polymers, and small molecules have also been extended to biomedical applications like phototherapy and biodetection. Recent research on conjugated polymers has focused on bioapplications based on the absorbed light energy conversions in electric impulses, chemical energy, heat, and light emission. In this review, we describe the working principles of those photonic devices that have been applied and researched in the field of biomaterials.

Electrical Doping of Metal Halide Perovskites by Co-Evaporation and Application in PN Junctions.

Electrical doping of semiconductors is a revolutionary development that enabled many electronic and optoelectronic technologies. While doping of many inorganic and organic semiconductors is well-established, controlled electrical doping of metal halide perovskites (MHPs) is yet to be demonstrated. In this work, efficient n- and p-type electrical doping of MHPs by co-evaporating the perovskite precursors alongside organic dopant molecules is achieved. It is demonstrated that the Fermi level can be shifted by up to 500 meV toward the conduction band and by up to 400 meV toward the valence band by n- and p-doping, respectively, which increases the conductivity of the films. The doped layers are employed in PN and NP diodes, showing opposing trends in rectification. Demonstrating controlled electrical doping by a scalable, industrially relevant deposition method opens the route to developing perovskite devices beyond solar cells, such as thermoelectrics or complementary logic.

Room temperature excitonic coupling in self-assembled copper – Fullerene hybrid films exposed to ambient air

Analytically sound combination of organic and inorganic semiconductors in designing functional hybrid nanomaterials promises new advances in nanoscience and in creation of next-generation optoelectronic devices. In this work, we report on combining two contrasting semiconductors (inorganic and organic) possessing attractive optical and electronic properties, namely Cu2O (in form of small single-crystalline nanoparticles, NPs) and C60-fullerene (as a medium supporting the NP ensemble), which were formed within the well-controlled Cux(Oy)C60 hybrid films through self-assembling and ambient air exposure of the vapour-deposited Cu and C60 mixture. The controllability of the hybrid film nanostructure was established and verified through systematic study of the films using Rutherford backscattering spectrometry, transmission electron microscopy, X-ray diffraction, Raman spectrometry and spectroscopic ellipsometry. The remarkable coincidence of the optical absorption peaks around 3.5 eV, reported for the Wannier-Mott (WM) excitons in a Cu2O crystal and detected for the Frenkel (F) excitons in the pristine C60 film, allowed us to observe room temperature polaritons as a product of the F-WM excitonic strong coupling. Quite high coupling energy of the FWM hybrid exciton estimated for the Cux(Oy)C60 films in the x interval of 5 < x < 15 (from 390 meV to 610 meV) implies the mediated effect of nanocavity photons and quantum confinement effect, strongly enhancing the hybrid exciton coupling energy. The implemented study discloses the self-assembled Cux(Oy)C60 hybrid films as promising material for application in optoelectronics and nonlinear optics.

Spatio-temporal strain analysis and thermal transport modulation in plastically deformed InSe van der Waals crystals

Contrary to typical inorganic semiconductors and functional materials with brittleness, InSe van der Waals crystals show remarkable room-temperature plasticity. Uncovering the mechanisms for the exceptional plasticity is of ultimate importance, and highly relies on the comprehension of strain state during deformation, which, however, remains an unresolved challenge. Moreover, the plastic deformation versus transport (e.g., thermal conductivity) correlation is yet to be quantitatively rationalized in these materials. Here, by using the digital-image-correlation (DIC) technique, we depict and analyze the spatio-temporal strain in InSe upon compression, providing straight evidence for the interlayer and cross-layer glides. Dense dislocations and grain boundaries are found to be created upon compression. As a result, the thermal conductivities are greatly reduced after plastic compression, being as low as 0.64 W/m K at room temperature and 0.38 W/m K at 600 K in a 50 % compressed specimen. Such a damped heat transport is well rationalized by incorporating the roles of multiple nanoscale defects as phonon scattering centers. This study provides new insight into the deformation mechanisms of 2D vdW crystals and shows that plastic deformation can be a powerful approach to modulate thermal properties of inorganic semiconductors for promising applications in energy utilization and heat management.

Machine Learning‐Enhanced Prediction of Inorganic Semiconductor Bandgaps for Advancing Optoelectronic Technologies

AbstractA pivotal challenge in advancing inorganics optoelectronic technologies, is the precise characterization of materials' electronic attributes, with the bandgap being a critical property. Conventional approaches, heavily reliant on time‐intensive and financially demanding experimental and computational methods, such as density functional theory (DFT) calculations, face limitations due to inherent estimation errors. Machine learning methodologies are developed for the prediction of bandgaps of inorganic semiconductors but most of them are employed for datasets created by DFT calculations, hence limiting their performance. Addressing this, the study leverages machine learning methodologies, harnessing both compositional and structural features, to predict the band gaps of inorganic semiconductors with enhanced accuracy. This advancement is reinforced by the employment of an experimental bandgap dataset, which, when integrated with structural descriptors obtained from the Materials Project, significantly improves prediction capabilities. This is evidenced by the model's exceptional performance across two distinct benchmark datasets. Furthermore, the model's adeptness in predicting formation energies underscores its versatility and applicability to a broad spectrum of electronic properties. These findings suggest that the predictive accuracy of this model can be further augmented through the inclusion of additional experimental bandgap measurements and the refinement of structural descriptors. This approach offers a promising and efficient alternative to traditional methodologies, potentially accelerating the development of optoelectronic technologies.

Effect of Hydrogen Bonding and Chirality in Star-Shaped Molecules with Peripheral Triphenylamines: Liquid Crystal Semiconductors and Gels.

Organic semiconductors with well-defined architectures pose a suitable alternative to amorphous silicon-based inorganic semiconductors. Encouraged by the development of organic semiconductors based on columnar liquid crystals, herein, we report on a family of C3-symmetric star-shaped mesogens based on triphenylamine (TPA), a functional unit with strong electron donor character. Highly stable columnar phases with high hole mobility values were obtained out of this nonplanar functional unit, and this was achieved by using flexible amide spacers to join the TPA units to a tris(triazolyl)triazine (T) star-shaped core, allowing the formation of intermolecular hydrogen bonds. The presence of hydrogen bonds results in a stabilization of the columnar architectures either in bulk or in the presence of solvents by reinforcing π-stacking and van der Waals interactions, as deduced by Fourier-transform infrared (FTIR) and X-ray diffraction (XRD) studies. Furthermore, the introduction of a stereogenic center in the flexible spacer prompts the formation of chiral aggregates in the liquid crystal state and in the organogel formed in 1-octanol, as demonstrated by circular dichroism spectroscopy.

Lewis acid catalysis of polydopamine electropolymerisation as a tool for shaping its morphology and electrochemical properties

Organic–inorganic semiconductor interfaces are of utmost importance in many photoelectrochemical applications, including water splitting and photodegradation of pollutants. The current work focuses on the fabrication and characterisation of transition metal-loaded polydopamine (PDA) electropolymerised on the surface of titania nanotubes. The structural studies via X-ray photoelectron spectroscopy and electron microscopy confirmed the catalytic effect of d-metal salts on the formation of the PDA layer during electropolymerisation. Cu and Ni loading leads to a significant enhancement of the visible absorption compared to that of the pristine PDA, also confirmed by the density functional theory calculations. Although the boost is greater for the thickest coatings, an excess amount of polymer suppresses the charge transfer and thus photocurrent generation. Synthesis in acidic conditions—optimal for photosensitisation—provides structures with a strong increase in the photocurrent quantum efficiency in the visible range, equal to 20% at 400 nm.Graphical

Semiconductor Membrane Exfoliation: Technology and Application

AbstractFlexible semiconductor film‐based optoelectronic devices have garnered significant attention in emerging fields such as the Internet of Things (IoT), wearable devices, and smart healthcare due to their wide range of applications. It is challenging to directly grow the foundational materials of optoelectronic devices, specifically semiconductor thin film structures, on flexible substrates. Instead, they are typically fabricated on conventional rigid thick semiconductor substrates. Consequently, the exfoliation and transfer of epitaxial semiconductor thin film structures onto substrates constitute pivotal steps in the production of flexible optoelectronic devices. The integration of hard inorganic semiconductor materials with flexible substrates offers a solution to the limitations of rigidity and brittleness associated with conventional optoelectronic devices and can be used to address challenges from design to manufacturing. This review provides a comprehensive overview of the working principles and recent advances of various techniques aimed at achieving the membrane exfoliation and transfer of semiconductor structures on conventional rigid substrates. It also reviews the possible applications of the transferred membrane in a variety of optoelectronic devices. Finally, it offers insights into the potential of high‐end semiconductor manufacturing and flexible semiconductor devices to play a critical role in advancing next‐generation optoelectronics technologies.

Superfluorescence in Metal Halide Perovskites

AbstractSuperfluorescence (SF) is a unique quantum optical phenomenon where an ensemble of atoms or molecules exhibit coherent emission of an intense burst of light of high directionality, with temporal coherence. SF exhibits ultrafast optical characteristics and is considerably explored in diverse inorganic and hybrid semiconductor materials at cryogenic temperatures, including inorganic and hybrid metal halide perovskites. Notably, SF is reported in different perovskites’ nanocrystal superlattices, alongside two examples in thin films, impressively achieving SF at room temperature. The density of quantum emitters, excited state characteristics, interaction strengths, and temperature all affect the SF threshold. Although significant progress is reported in the observance of SF phenomena, a full interpretation of the relationship between the factors that determine the SF threshold and the intrinsic material properties remains unclear. This review addresses the current state‐of‐the‐art observations of SF in perovskite systems, such as nanocrystal superlattices and thin films, elucidating the optical properties, ultrafast dynamics, and the proposed mechanisms for room‐temperature SF. The review concludes with a discussion on the existing challenges, unresolved questions, and future perspectives for advancing perovskite SF research

Vanadium-doped metal-organic framework@Znln2S4 core-shell heterojunction-attenuated photoelectrochemical immunoassay

Considering that cancer has become the second leading cause of death in humans, it is essential to develop an analytical approach that can sensitively detect tumor markers for early detection. We report an attenuated photoelectrochemical (PEC) immunoassay based on the organic-inorganic heterojunction 10MIL-88B(FeV)/ZnIn2S4 (10M88B(FeV)/ZIS) as a photoactive material for monitoring carcinoembryonic antigen (CEA). The 10M88B(FeV)/ZIS heterojunctions have excellent light-harvesting properties and high electrical conductivity, which are attributed to the advantages of both organic and inorganic semiconductors, namely, remarkable photogenerated carrier separation efficiency and long photogenerated carrier lifetime. Horseradish peroxidase (HRP) in the presence of H2O2 can catalyze 3,3′-diaminofenamide (DAB) producing brown precipitates (oxDAB), which is then loaded onto the 10M88B(FeV)/ZIS heterojunction to reduce the photocurrent and enable the quantitative detection of CEA. Under optimal conditions, the photocurrent values of the PEC biosensor are linearly related to the logarithm of the CEA concentrations, ranging from 0.01 ng mL−1 to 100 ng mL−1 with a detection limit (LOD) of 4.0 pg mL−1. Notably, the accuracy of the PEC biosensor is in agreement with that of the human CEA enzyme-linked immunosorbent assay (ELISA) kit.