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At least 703 records · Page 39

Suppression of Defects and Deep Levels Using Isoelectronic Tungsten Substitution in Monolayer MoSe 2

Chemical vapor deposition (CVD) is one of the most promising, scalable synthetic techniques to enable large-area synthesis of two-dimensional (2D) transition metal dichalcogenides (TMDs) for the realization of next generation optoelectronic devices. However, defects formed during the CVD growth process currently limit the quality and electronic properties of 2D TMDs. Effective synthesis and processing strategies to suppress defects and enhance the quality of 2D TMDs are urgently needed. In this work, isoelectrnic doping to produce stable alloy is presented as a new strategy to suppress defects and enhance photoluminescence (PL) in CVD-grown TMD monolayers. The random, isoelectronic substitution of W atoms for Mo atoms in CVD-grown monolayers of Mo 1-x W x Se 2 (0 2 monolayers. The resultant decrease in defect-medicated non-radiative recombination in the Mo 0.82 W 0.18 Se 2 monolayers yielded ~10 times more intense PL and extended the carrier lifetime by a factor of 3 compared to pristine CVD-grown MoSe 2 monolayers grown under similar conditions. Low temperatures (4 125 K) PL from defect-related localized states confirms theoretical predictions that isoelectronic W alloying should suppress deep levels in MoSe 2 , showing that the defect levels in Mo 1-x W x Se 2 monolayers are higher in energy and quenched more quickly than in MoSe 2 . Isoelectronic substitution therefore appears to be a promising synthetic method to control the heterogeneity of 2D TMDs to realize the scalable production of high performance optoelectronic and electronic devices.

36 MATERIALS SCIENCE↗

High-Performance Near-IR Photodetector Using Low-Bandgap MA 0.5 FA 0.5 Pb 0.5 Sn 0.5 I 3 Perovskite

Photodetectors with ultrafast response are explored using inorganic/organic hybrid perovskites. High responsivity and fast optoelectronic response are achieved due to the exceptional semiconducting properties of perovskite materials. However, most of the perovskite-based photodetectors exploited to date are centered on Pb-based perovskites, which only afford spectral response across the visible spectrum. This study demonstrates a high-performance near-IR (NIR) photodetector using a stable low-bandgap Sn-containing perovskite, (CH 3 NH 3 ) 0.5 (NH 2 CHNH 2 ) 0.5 Pb 0.5 Sn 0.5 I 3 (MA 0.5 FA 0.5 Pb 0.5 Sn 0.5 I 3 ), which is processed with an antioxidant additive, ascorbic acid (AA). The addition of AA effectively strengthens the stability of Sn-containing perovskite against oxygen, thereby significantly inhibiting the leakage current. Consequently, the derived photodetector shows high responsivity with a detectivity of over 10 12 Jones ranging from 800 to 970 nm. Such low-cost, solution processable NIR photodetectors with high performance show promising potential for future optoelectronic applications.

36 MATERIALS SCIENCE↗

The Relationship between Chemical Flexibility and Nanoscale Charge Collection in Hybrid Halide Perovskites

Hybrid organometal halide perovskites are known for their excellent optoelectronic functionality as well as their wide-ranging chemical flexibility. The composition of hybrid perovskite devices has trended toward increasing complexity as fine-tuned properties are pursued, including multi-element mixing on the constituent A, B, and halide sites. However, this tunability presents potential challenges for charge extraction in functional devices. Poor consistency and repeatability between devices may arise due to variations in composition and microstructure. Within a single device, spatial heterogeneity in composition and phase segregation may limit the device from achieving its performance potential. This article details how the nanoscale elemental distribution and charge collection in hybrid perovskite materials evolve as chemical complexity increases, highlighting recent results using non-destructive operando synchrotron-based X-ray nanoprobe techniques. In conclusion, the results reveal a strong link between local chemistry and charge collection that must be controlled to develop robust, high-performance hybrid perovskite materials for optoelectronic devices.

36 MATERIALS SCIENCE↗

Influence of Bulky Organo-Ammonium Halide Additive Choice on the Flexibility and Efficiency of Perovskite Light-Emitting Devices

Perovskite light-emitting diodes (LEDs) require small grain sizes to spatially confine charge carriers for efficient radiative recombination. As grain size decreases, passivation of surface defects becomes increasingly important. Also, polycrystalline perovskite flms are highly brittle and mechanically fragile, limiting their practical applications in flexible electronics. Here, the introduction of properly chosen bulky organo-ammonium halide additives is shown to be able to improve both optoelectronic and mechanical properties of perovskites, yielding highly efficient, robust, and flexible perovskite LEDs with external quantum efficiency of up to 13% and no degradation after bending for 10 000 cycles at a radius of 2 mm. Moreover, insight of the improvements regarding molecular structure, size, and polarity at the atomic level is obtained with first-principles calculations, and design principles are provided to overcome trade-offs between optoelectronic and mechanical properties, thus increasing the scope for future highly efficient, robust, and flexible perovskite electronic device development.

36 MATERIALS SCIENCE↗

Improving Charge Transport via Intermediate-Controlled Crystal Growth in 2D Perovskite Solar Cells

Reduced-dimensional hybrid perovskite semiconductors have recently attracted significant attention due to their promising stability and optoelectronic properties. However, the issue of poor charge transport in 2D perovskites limits its application. Here, studies on intermediate-controlled crystal growth are reported to improve charge carrier transport in 2D perovskite thin films. It is shown that the coordination strength of solvents with perovskite precursor affects the initial state of intermediate phase formation as well as the subsequent perovskite layer growth. Tuning the solvent composition with a mixture (5:5) of dimethyl formamide (DMF) and dimethyl sulfoxide (DMSO) leads to the growth of highly orientated 2D perovskite films with much-improved optoelectronic properties (faster transport by approx. ≈50x, longer carrier lifetime by approx. ≈4x, and lower defect density by approx. ≈30x) than the film prepared with pure DMF. Consequently, perovskite solar cells based on DMF/DMSO (5:5) show >80% efficiency improvement than the devices based on pure DMF.

14 SOLAR ENERGY↗

Direct Observation of Bandgap Oscillations Induced by Optical Phonons in Hybrid Lead Iodi.de Perovskites

Hybrid organic-inorganic perovskites such as methylammonium lead iodide have emerged as promising semiconductors for energy-relevant applications. The interactions between charge carriers and lattice vibrations, giving rise to polarons, have been invoked to explain some of their extraordinary optoelectronic properties. Here, time-resolved optical spectroscopy is performed, with off-resonant pumping and electronic probing, to examine several representative lead iodide perovskites. The temporal oscillations of electronic bandgaps induced by coherent lattice vibrations are reported, which is attributed to antiphase octahedral rotations that dominate in the examined 3D and 2D hybrid perovskites. The off-resonant pumping scheme permits a simplified observation of changes in the bandgap owing to the A(g) vibrational mode, which is qualitatively different from vibrational modes of other symmetries and without increased complexity of photogenerated electronic charges. The work demonstrates a strong correlation between the lead-iodide octahedral framework and electronic transitions, and provides further insights into the manipulation of coherent optical phonons and related properties in hybrid perovskites on ultrafast timescales.

coherent optical phonons↗

Identifying Photoinduced Dipolar Polarization and Orbit–Orbit Interaction between Excitons in Organic–Inorganic Hybrid Perovskites

Abstract Photoinduced polarization and orbit–orbit interaction are important issues in hybrid perovskites toward developing optoelectronic functionalities. This paper identifies that photoinduced polarization occurs in hybrid perovskites with mixed‐cation methylammonium (MA)/formamidinium (FA) (MA x FA (1− x ) PbI 3 ) by measuring bulk polarization at 1 MHz in a magnetic field. Interestingly, when the internal dipole moment is increased upon increasing the MA:FA ratio, the photoinduced dipolar polarization can be substantially enhanced, clarifying the controversial issue of whether photoexcitation can induce a dielectric polarization within dipolar polarization regime in hybrid perovskites. Furthermore, upon increasing photoinduced dipolar polarization, it is found that the intrinsic orbit–orbit interaction between excitons can be increased, revealed by monitoring photocurrent change (Δ J sc ) upon switching the photoexcitation between linear and circular polarizations. This presents that organic cations are directly involved in the orbit–orbit interaction within band structures. Clearly, the studies provide an insightful understanding of the dipole moment effects on photoinduced dipolar polarization and orbit–orbit interaction between excitons in hybrid perovskites toward controlling the optoelectronic properties.

Dou, Yixuan↗

Direct Observation of Photoinduced Ion Migration in Lead Halide Perovskites

Unique optoelectronic, electronic, and sensing properties of hybrid organic–inorganic perovskites (HOIPs) are underpinned by the complex interactions between electronic and ionic states. In this study, the photoinduced field ion migration in HOIPs is directly observed. Using newly developed local probe time-resolved techniques, more significant CH 3 NH 3 + migration than I – /Br – migration in HOIPs is unveiled. It is found that light illumination only induces CH 3 NH 3 + migration but not I – /Br – migration. By directly observing temporal changes in bias-induced and photoinduced ion migration in device conditions, it is revealed that light illumination suppresses the bias-induced ion redistribution in the lateral device. These findings, being a necessary compensation of previous understandings of ion migration in HOIPs based on simulations and static and/or indirect measurements, offer advanced insights into the distinct light effects on the migration of organic cation and halides in HOIPs, which are expected to be helpful for improving the performance and the long-term stability of HOIPs optoelectronics.

36 MATERIALS SCIENCE↗

Twisted Crystalline Organic Semiconductor Photodetectors

Optoelectronic properties of anisotropic crystals vary with direction requiring that the orientation of molecular organic semiconductor crystals is controlled in optoelectronic device active layers to achieve optimal performance. Here, in this work, a generalizable strategy to introduce periodic variations in the out-of-plane orientations of 5,11-bis(triisopropylsilylethynyl)anthradithiophene (TIPS ADT) crystals is presented. TIPS ADT crystallized from the melt in the presence of 16 wt.% polyethylene (PE) forms banded spherulites of crystalline fibrils that twist in concert about the radial growth direction. These spherulites exhibit band-dependent light absorption, photoluminescence, and Raman scattering depending on the local orientation of crystals. Mueller matrix imaging reveals strong circular extinction (CE), with TIPS ADT banded spherulites exhibiting domains of positive or negative CE signal depending on the crystal twisting sense. Furthermore, orientation-dependent enhancement in charge injection and extraction in films of twisted TIPS ADT crystals compared to films of straight crystals is visualized in local conductive atomic force microscopy maps. This enhancement leads to 3.3- and 6.2-times larger photocurrents and external quantum efficiencies, respectively, in photodetectors comprising twisted crystals than those comprising straight crystals.

36 MATERIALS SCIENCE↗

Enhancing Organic Semiconductor Molecular Packing Using Perovskite Interfaces to Improve Singlet Fission

Singlet fission, a process by which one singlet exciton is converted into two lower energy triplet excitons, is sensitive to the degree of electronic coupling within a molecular packing structure. Variations in molecular packing can be detrimental to triplet formation and triplet–triplet separation, ultimately affecting the harvesting of triplets for electricity in organic photovoltaic devices. Here, six phase-pure molecular packing structures of 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene) with varying optoelectronic properties are isolated using 2D lead halide perovskites as tunable, crystalline surfaces for crystallization. Transient absorption spectroscopy reveals that while triplet formation is fast (<100 fs) regardless of template structure, the increased ordering in perovskite-templated samples speeds up triplet–triplet separation and recombination, providing evidence that the benefits of phase-purity offset minor variations in molecular packing. Molecular dynamics modeling of the interface reveals that perovskite-templating allows for closer packing of TIPS-pentacene molecules for all perovskite templates. With an extensive number of organic molecule-perovskite pairings, this work provides a methodology to use ordered, periodic surfaces to elucidate structure–property relationships of small organic molecules in order to adjust structural or optoelectronic responses, such as molecular packing and singlet fission.

36 MATERIALS SCIENCE↗

Ligand‐Mediated Quantum Yield Enhancement in 1‐D Silver Organothiolate Metal–Organic Chalcogenolates

X-ray free electron laser (XFEL) microcrystallography and synchrotron single-crystal crystallography are used to evaluate the role of organic substituent position on the optoelectronic properties of metal–organic chalcogenolates (MOChas). MOChas are crystalline 1D and 2D semiconducting hybrid materials that have varying optoelectronic properties depending on composition, topology, and structure. While MOChas have attracted much interest, small crystal sizes impede routine crystal structure determination. A series of constitutional isomers where the aryl thiol is functionalized by either methoxy or methyl ester are solved by small molecule serial femtosecond X-ray crystallography (smSFX) and single crystal rotational crystallography. While all the methoxy examples have a low quantum yield (0-1%), the methyl ester in the ortho position yields a high quantum yield of 22%. Here, the proximity of the oxygen atoms to the silver inorganic core correlates to a considerable enhancement of quantum yield. Four crystal structures are solved at a resolution range of 0.8–1.0 Å revealing a collapse of the 2D topology for functional groups in the 2- and 3- positions, resulting in needle-like crystals. Further analysis using density functional theory (DFT) and many-body perturbation theory (MBPT) enables the exploration of complex excitonic phenomena within easily prepared material systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Probing the Nanoscale Excitonic Landscape and Confinement of Excitons in Gated Monolayer Semiconductors

Engineering and probing excitonic properties at the nanoscale remains a central challenge in quantum photonics and optoelectronics. While exciton confinement via electrical control and strain engineering has been demonstrated in 2D semiconductors, substantial nanoscale heterogeneity limits the scalability of 2D quantum photonic device architectures. Here, in this work, we use cathodoluminescence spectroscopy to probe the excitonic landscape of monolayer WS 2 under electrostatic gating. Exploiting the high spatial resolution of the converged electron beam, we resolve a homojunction arising between gated and ungated regions. Moreover, we reveal an exciton confinement channel arising from an unconventional doping mechanism driven by the interplay between the electron beam and the applied gate fields. These findings offer new insights into the optoelectronic behavior of monolayer semiconductors under the combined influence of electron-beam excitation and electrostatic gating. Our approach provides a pathway for exciton manipulation at the nanoscale and opens opportunities for controlling quantum-confined exciton transport in 2D materials.

2D materials↗

Isoelectronic tungsten doping in monolayer MoSe 2 for carrier type modulation

Doping and alloying are effective ways to engineer the band structure and modulate the optoelectronic functionality of monolayer transition metal dichalcogenides (TMDs). In this work, we explore the synthesis and electronic properties of monolayer Mo 1-x W x Se 2 (0 < x < 0.18) alloys with almost 100% alloying degree. The isoelectronic substitutional doping of tungsten for molybdenum in the monolayer MoSe 2 is shown to suppress its intrinsically n-type conduction behavior, with p-type conduction gradually emerging to become dominant with increasing W concentration in the alloys. Atomic resolution Z-contrast electron microscopy show that W is shown to substitute directly for Mo without the introduction of noticeable vacancy or interstitial defects, however with randomly-distributed W-rich regions ~2 nm in diameter. Scanning tunneling microscopy/spectroscopy measurements reveal that these W-rich regions exhibit a local band structure with the valence band maximum (VBM) closer to the Fermi level as compared with the Mo-rich regions in the monolayer Mo 1-x W x Se 2 crystal. These localized upshifts of the VBM in the local band structure appear responsible for the overall p-type behavior observed for the monolayer Mo 1-x W x Se 2 crystals. Stacked monolayers of n-type MoSe 2 and p-type Mo 1-x W x Se 2 were demonstrated to form atomically thin, vertically stacked p n homojunctions with gate-tunable characteristics, which appear useful for future optoelectronic applications. Lastly, these results indicate that alloying with isoelectronic dopant atoms appears to be an effective and advantageous alternate strategy to doping or alloying with electron donors or acceptors in two-dimensional TMDs.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Understanding Detrimental and Beneficial Grain Boundary Effects in Halide Perovskites

Abstract Grain boundaries play a key role in the performance of thin‐film optoelectronic devices and yet their effect in halide perovskite materials is still not understood. The biggest factor limiting progress is the inability to identify grain boundaries. Noncrystallographic techniques can misidentify grain boundaries, leading to conflicting literature reports about their influence; however, the gold standard – electron backscatter diffraction (EBSD) – destroys halide perovskite thin films. Here, this problem is solved by using a solid‐state EBSD detector with 6000 times higher sensitivity than the traditional phosphor screen and camera. Correlating true grain size with photoluminescence lifetime, carrier diffusion length, and mobility shows that grain boundaries are not benign but have a recombination velocity of 1670 cm s −1 , comparable to that of crystalline silicon. Amorphous grain boundaries are also observed that give rise to locally brighter photoluminescence intensity and longer lifetimes. This anomalous grain boundary character offers a possible explanation for the mysteriously long lifetime and record efficiency achieved in small grain halide perovskite thin films. It also suggests a new approach for passivating grain boundaries, independent of surface passivation, to lead to even better performance in optoelectronic devices.

Adhyaksa, Gede W. P.↗

Tunable Spin Characteristic Properties in Spin Valve Devices Based on Hybrid Organic–Inorganic Perovskites

The hybrid organic–inorganic perovskites (HOIPs) form a new class of semiconductors which show promising optoelectronic device applications. Remarkably, the optoelectronic properties of HOIP are tunable by changing the chemical components of their building blocks. Recently, the HOIP spintronic properties and their applications in spintronic devices have attracted substantial interest. Here the impact of the chemical component diversity in HOIPs on their spintronic properties is studied. Additionally, spin valve devices based on HOIPs with different organic cations and halogen atoms are fabricated. The spin diffusion length is obtained in the various HOIPs by measuring the giant magnetoresistance (GMR) response in spin valve devices with different perovskite interlayer thicknesses. In addition spin lifetime is also measured from the Hanle response. It is found that the spintronic properties of HOIPs are mainly determined by the halogen atoms, rather than the organic cations. The study provides a clear avenue for engineering spintronic devices based on HOIPs.

36 MATERIALS SCIENCE↗

A Noble-Transition Alloy Excels at Hot-Carrier Generation in the Near Infrared

Above-equilibrium “hot”-carrier generation in metals is a promising route to convert photons into electrical charge for efficient near-infrared optoelectronics. However, metals that offer both hot-carrier generation in the near-infrared and sufficient carrier lifetimes remain elusive. Alloys can offer emergent properties and new design strategies compared to pure metals. In this work, it is shown that a noble-transition alloy, Au x Pd 1-x , outperforms its constituent metals concerning generation and lifetime of hot carriers when excited in the near-infrared. At optical fiber wavelengths (e.g., 1550 nm), Au 50 Pd 50 provides a 20-fold increase in the number of ≈0.8 eV hot holes, compared to Au, and a threefold increase in the carrier lifetime, compared to Pd. The discovery that noble-transition alloys can excel at hot-carrier generation reveals a new material platform for near-infrared optoelectronic devices.

36 MATERIALS SCIENCE↗

Colloidal Quantum Dot Solar Cells: Progressive Deposition Techniques and Future Prospects on Large-area Fabrication

Colloidally grown nanosized semiconductors yield extremely high-quality optoelectronic materials. Many examples have pointed to near perfect photoluminescence quantum yields, meaning non-radiative optical processes (losses) can be completely suppressed allowing for technology-leading materials as high purity color centers in display technology and emitters in LEDs. Furthermore, because of high chemical yield, and improved understanding of the surfaces, these materials, particularly colloidal quantum dots (QDs) can also be ideal candidates for other optoelectronic applications. Given the strong drive toward carbon neutrality and limiting climate change, electricity from solar photovoltaics will play a large role in the power generation sector. QDs have been developed and shown dramatic improvements over the past 15 years as photoactive materials in photovoltaics and have unique potential with various innovative deposition properties which could lead to exceptionally low-cost and high-performance devices. Once the key issues related to charge transport in optically thick arrays are addressed, QD-based photovoltaic technology could become a better candidate for practical application. In this article, w e show how the possibilities of different deposition techniques could bring QD-based solar cells to the industrial level and discuss the challenges for perovskite QD solar cells in particular, to achieve large-area fabrication for further advancing technology to solve pivotal energy and environmental issues.

14 SOLAR ENERGY↗

Halide Perovskites and Their Derivatives for Efficient, High‐Resolution Direct Radiation Detection: Design Strategies and Applications

Abstract The past decade has witnessed a rapid rise in the performance of optoelectronic devices based on lead‐halide perovskites (LHPs). The large mobility‐lifetime products and defect tolerance of these materials, essential for optoelectronics, also make them well‐suited for radiation detectors, especially given the heavy elements present, which is essential for strong X‐ray and γ‐ray attenuation. Over the past decade, LHP thick films, wafers, and single crystals have given rise to direct radiation detectors that have outperformed incumbent technologies in terms of sensitivity (reported values up to 3.5 × 10 6 µC Gy air −1 cm −2 ), limit of detection (directly measured values down to 1.5 nGy air s −1 ), along with competitive energy and imaging resolution at room temperature. At the same time, lead‐free perovskite‐inspired materials (e.g., methylammonium bismuth iodide), which have underperformed in solar cells, have recently matched and, in some areas (e.g., in polarization stability), surpassed the performance of LHP detectors. These advances open up opportunities to achieve devices for safer medical imaging, as well as more effective non‐invasive analysis for security, nuclear safety, or product inspection applications. Herein, the principles behind the rapid rises in performance of LHP and perovskite‐inspired material detectors, and how their properties and performance link with critical applications in non‐invasive diagnostics are discussed. The key strategies to engineer the performance of these materials, and the important challenges to overcome to commercialize these new technologies are also discussed.

36 MATERIALS SCIENCE↗