High Thermoelectric Performance in Solution-Processed Semicrystalline PEDOT:PSS Films by Strong Acid-Base Treatment: Limitations and Potential.

Thermoelectric (TE) generation with solution-processable conducting polymers offers substantial potential in low-temperature energy harvesting based on high tunability in materials, processes, and form-factors. However, manipulating the TE and charge transport properties accompanies structural and energetic disorders, restricting the enhancement of thermoelectric power factor (PF). Here, solution-based strong acid-base treatment techniques are introduced to modulate the doping level of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) thin films with preserving its molecular orientation, enabling to achieve a remarkably high PF of 534.5 µW m-1  K-2 . Interestingly, theoretical modeling suggested that further de-doping can increase the PF beyond the experimental value. However, it is impossible to reach this value experimentally, even without any degradation of PEDOT crystallinity. Uncovering the underlying reason for the limitation, an analysis of the relationship among the microstructure-thermoelectric performance-charge transport property revealed that inter-domain connectivity via tie-chains and the resultant percolation for transport are crucial factors in achieving high TE performance, as in charge transport. It is believed that the methods and fundamental understandings in this work would contribute to the exploitation of conducting polymer-based low-temperature energy harvesting.

Reduced dopant-induced scattering in remote charge-transfer-doped MoS2 field-effect transistors.

Efficient doping for modulating electrical properties of two-dimensional (2D) transition metal dichalcogenide (TMDC) semiconductors is essential for meeting the versatile requirements for future electronic and optoelectronic devices. Because doping of semiconductors, including TMDCs, typically involves generation of charged dopants that hinder charge transport, tackling Coulomb scattering induced by the externally introduced dopants remains a key challenge in achieving ultrahigh mobility 2D semiconductor systems. In this study, we demonstrated remote charge transfer doping by simply inserting a hexagonal boron nitride layer between MoS2 and solution-deposited n-type dopants, benzyl viologen. A quantitative analysis of temperature-dependent charge transport in remotely doped devices supports an effective suppression of the dopant-induced scattering relative to the conventional direct doping method. Our mechanistic investigation of the remote doping method promotes the charge transfer strategy as a promising method for material-level tailoring of electrical and optoelectronic devices based on TMDCs.

Mechanochemistry-driven engineering of 0D/3D heterostructure for designing highly luminescent Cs-Pb-Br perovskites.

Embedding metal-halide perovskite particles within an insulating host matrix has proven to be an effective strategy for revealing the outstanding luminescence properties of perovskites as an emerging class of light emitters. Particularly, unexpected bright green emission observed in a nominally pure zero-dimensional cesium-lead-bromide perovskite (Cs4PbBr6) has triggered intensive research in better understanding the serendipitous incorporation of emissive guest species within the Cs4PbBr6 host. However, a limited controllability over such heterostructural configurations in conventional solution-based synthesis methods has limited the degree of freedom in designing synthesis routes for accessing different structural and compositional configurations of these host-guest species. In this study, we provide means of enhancing the luminescence properties in the nominal Cs4PbBr6 powder through a guided heterostructural configuration engineering enabled by solid-state mechanochemical synthesis. Realized by an in-depth study on time-dependent evaluation of optical and structural properties during the synthesis of Cs4PbBr6, our target-designed synthesis protocol to promote the endotaxial formation of Cs4PbBr6/CsPbBr3 heterostructures provides key insights for understanding and designing kinetics-guided syntheses of highly luminescent perovskite emitters for light-emitting applications.

Enhanced Thermoelectric Power Factor in Carrier-Type-Controlled Platinum Diselenide Nanosheets by Molecular Charge-Transfer Doping.

2D transition metal dichalcogenides (TMDCs) have revealed great promise for realizing electronics at the nanoscale. Despite significant interests that have emerged for their thermoelectric applications due to their predicted high thermoelectric figure of merit, suitable doping methods to improve and optimize the thermoelectric power factor of TMDCs have not been studied extensively. In this respect, molecular charge-transfer doping is utilized effectively in TMDC-based nanoelectronic devices due to its facile and controllable nature owing to a diverse range of molecular designs available for modulating the degree of charge transfer. In this study, the power of molecular charge-transfer doping is demonstrated in controlling the carrier-type (n- and p-type) and thermoelectric power factor in platinum diselenide (PtSe2 ) nanosheets. This, combined with the tunability in the band overlap by changing the thickness of the nanosheets, allows a significant increase in the thermoelectric power factor of the n- and p-doped PtSe2 nanosheets to values as high as 160 and 250 µW mK-2 , respectively. The methodology employed in this study provides a simple and effective route for the molecular doping of TMDCs that can be used for the design and development of highly efficient thermoelectric energy conversion systems.

Channel-Length-Modulated Avalanche Multiplication in Ambipolar WSe2 Field-Effect Transistors.

Recently there has been growing interest in avalanche multiplication in two-dimensional (2D) materials and device applications such as avalanche photodetectors and transistors. Previous studies have mainly utilized unipolar semiconductors as the active material and focused on developing high-performance devices. However, fundamental analysis of the multiplication process, particularly in ambipolar materials, is required to establish high-performance electronic devices and emerging architectures. Although ambipolar 2D materials have the advantage of facile carrier-type tuning through electrostatic gating, simultaneously allowing both carrier types in a single channel poses an inherent difficulty in analyzing their individual contributions to avalanche multiplication. In ambipolar field-effect transistors (FETs), two phenomena of ambipolar transport and avalanche multiplication can occur, and both exhibit secondary rise of output current at high lateral voltage. We distinguished these two competing phenomena using the method of channel length modulation and successfully analyzed the properties of electron- and hole-initiated multiplication in ambipolar WSe2 FETs. Our study provides a simple and robust method to examine carrier multiplication in ambipolar materials and will foster the development of high-performance atomically thin electronic devices utilizing avalanche multiplication.

Plasmonic phenomena in molecular junctions: principles and applications.

Molecular junctions are building blocks for constructing future nanoelectronic devices that enable the investigation of a broad range of electronic transport properties within nanoscale regions. Crossing both the nanoscopic and mesoscopic length scales, plasmonics lies at the intersection of the macroscopic photonics and nanoelectronics, owing to their capability of confining light to dimensions far below the diffraction limit. Research activities on plasmonic phenomena in molecular electronics started around 2010, and feedback between plasmons and molecular junctions has increased over the past years. These efforts can provide new insights into the near-field interaction and the corresponding tunability in properties, as well as resultant plasmon-based molecular devices. This Review presents the latest advancements of plasmonic resonances in molecular junctions and details the progress in plasmon excitation and plasmon coupling. We also highlight emerging experimental approaches to unravel the mechanisms behind the various types of light-matter interactions at molecular length scales, where quantum effects come into play. Finally, we discuss the potential of these plasmonic-electronic hybrid systems across various future applications, including sensing, photocatalysis, molecular trapping and active control of molecular switches.

Proton irradiation effects on mechanochemically synthesized and flash-evaporated hybrid organic-inorganic lead halide perovskites.

A hybrid organic-inorganic halide perovskite is a promising material for developing efficient solar cell devices, with potential applications in space science. In this study, we synthesized methylammonium lead iodide (MAPbI3) perovskites via two methods: mechanochemical synthesis and flash evaporation. We irradiated these perovskites with highly energetic 10 MeV proton-beam doses of 1011, 1012, 1013, and 4 × 1013protons cm-2and examined the proton irradiation effects on the physical properties of MAPbI3perovskites. The physical properties of the mechanochemically synthesized MAPbI3perovskites were not considerably affected after proton irradiation. However, the flash-evaporated MAPbI3perovskites showed a new peak in x-ray diffraction and an increased fluorescence lifetime in time-resolved photoluminescence under high-dose conditions, indicating considerable changes in their physical properties. This difference in behavior between MAPbI3perovskites synthesized via the abovementioned two methods may be attributed to differences in radiation hardness associated with the bonding strength of the constituents, particularly Pb-I bonds. Our study will help to understand the radiation effect of proton beams on organometallic halide perovskite materials.

Molecular Dopant-Dependent Charge Transport in Surface-Charge-Transfer-Doped Tungsten Diselenide Field Effect Transistors.

The controllability of carrier density and major carrier type of transition metal dichalcogenides(TMDCs) is critical for electronic and optoelectronic device applications. To utilize doping in TMDC devices, it is important to understand the role of dopants in charge transport properties of TMDCs. Here, the effects of molecular doping on the charge transport properties of tungsten diselenide (WSe2 ) are investigated using three p-type molecular dopants, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4 -TCNQ), tris(4-bromophenyl)ammoniumyl hexachloroantimonate (magic blue), and molybdenum tris(1,2-bis(trifluoromethyl)ethane-1,2-dithiolene) (Mo(tfd-COCF3 )3 ). The temperature-dependent transport measurements show that the dopant counterions on WSe2 surface can induce Coulomb scattering in WSe2 channel and the degree of scattering is significantly dependent on the dopant. Furthermore, the quantitative analysis revealed that the amount of charge transfer between WSe2 and dopants is related to not only doping density, but also the contribution of each dopant ion toward Coulomb scattering. The first-principles density functional theory calculations show that the amount of charge transfer is mainly determined by intrinsic properties of the dopant molecules such as relative frontier orbital positions and their spin configurations. The authors' systematic investigation of the charge transport of doped TMDCs will be directly relevant for pursuing molecular routes for efficient and controllable doping in TMDC nanoelectronic devices.

Ultrasensitive Photodetection in MoS2 Avalanche Phototransistors.

Recently, there have been numerous studies on utilizing surface treatments or photosensitizing layers to improve photodetectors based on 2D materials. Meanwhile, avalanche breakdown phenomenon has provided an ultimate high-gain route toward photodetection in the form of single-photon detectors. Here, the authors report ultrasensitive avalanche phototransistors based on monolayer MoS2 synthesized by chemical vapor deposition. A lower critical field for the electrical breakdown under illumination shows strong evidence for avalanche breakdown initiated by photogenerated carriers in MoS2 channel. By utilizing the photo-initiated carrier multiplication, their avalanche photodetectors exhibit the maximum responsivity of ≈3.4 × 107 A W-1 and the detectivity of ≈4.3 × 1016 Jones under a low dark current, which are a few orders of magnitudes higher than the highest values reported previously, despite the absence of any additional chemical treatments or photosensitizing layers. The realization of both the ultrahigh photoresponsivity and detectivity is attributed to the interplay between the carrier multiplication by avalanche breakdown and carrier injection across a Schottky barrier between the channel and metal electrodes. This work presents a simple and powerful method to enhance the performance of photodetectors based on carrier multiplication phenomena in 2D materials and provides the underlying physics of atomically thin avalanche photodetectors.

Crystallinity-dependent device characteristics of polycrystalline 2D n = 4 Ruddlesden-Popper perovskite photodetectors.

Ruddlesden-Popper (RP) perovskites have attracted a lot of attention as the active layer for optoelectronic devices due to their excellent photophysical properties and environmental stability. Especially, local structural properties of RP perovskites have shown to play important roles in determining the performance of optoelectronic devices. Here, we report the photodetector performance variation depending on the crystallinity of n = 4 two-dimensional (2D) RP perovskite polycrystalline films. Through controlling the solvent evaporation rate, 2D RP perovskite films could be tuned between highly- and randomly-orientated phases. We investigated how different factors related to the film crystallinity are reflected in the variation of photodetector performances by considering grain boundary and low energy edge state effects in n = 4 RP perovskites. Better understanding the interplay between these factors that govern the photophysical properties of the devices would be beneficial for designing high-performance RP perovskite-based optoelectronic devices.

Crystal Size Effect on Carrier Transport of Microscale Perovskite Junctions via Soft Contact.

To reduce the size of optoelectronic devices, it is essential to understand the crystal size effect on the carrier transport through microscale materials. Here, we show a soft contact method to probe the properties of irregularly shaped microscale perovskite crystals by employing a movable liquid metal electrode to form a self-adaptative deformable electrode-perovskite-electrode junction. Accordingly, we demonstrate that (1) the photocurrents of perovskite quantum dot films and microplatelets show profound differences regarding both the on/off ratio and the response time upon light illumination; and (2) small-size perovskite (<50 µm) junctions may show negative differential resistance (NDR) behavior, whereas the NDR phenomenon is absent in large-size perovskite junctions within the same bias regime. Our studies provide a method for studying arbitrary-shaped crystals without mechanical damage, assisting the understanding of the photogenerated carriers transport through microscale crystals.

Controllable deposition of organic metal halide perovskite films with wafer-scale uniformity by single source flash evaporation.

Conventional solution-processing techniques such as the spin-coating method have been used successfully to reveal excellent properties of organic-inorganic halide perovskites (OHPs) for optoelectronic devices such as solar cell and light-emitting diode, but it is essential to explore other deposition techniques compatible with large-scale production. Single-source flash evaporation technique, in which a single source of materials of interest is rapidly heated to be deposited in a few seconds, is one of the candidate techniques for large-scale thin film deposition of OHPs. In this work, we investigated the reliability and controllability of the single-source flash evaporation technique for methylammonium lead iodide (MAPbI3) perovskite. In-depth statistical analysis was employed to demonstrate that the MAPbI3 films prepared via the flash evaporation have an ultrasmooth surface and uniform thickness throughout the 4-inch wafer scale. We also show that the thickness and grain size of the MAPbI3 film can be controlled by adjusting the amount of the source and number of deposition steps. Finally, the excellent large-area uniformity of the physical properties of the deposited thin films can be transferred to the uniformity in the device performance of MAPbI3 photodetectors prepared by flash evaporation which exhibited the responsivity of 0.2 A/W and detectivity of 3.82 × 1011 Jones.

Highly Stable Contact Doping in Organic Field Effect Transistors by Dopant-Blockade Method.

In organic device applications, a high contact resistance between metal electrodes and organic semiconductors prevents an efficient charge injection and extraction, which fundamentally limits the device performance. Recently, various contact doping methods have been reported as an effective way to resolve the contact resistance problem. However, the contact doping has not been explored extensively in organic field effect transistors (OFETs) due to dopant diffusion problem, which significantly degrades the device stability by damaging the ON/OFF switching performance. Here, the stability of a contact doping method is improved by incorporating "dopant-blockade molecules" in the poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT) film in order to suppress the diffusion of the dopant molecules. By carefully selecting the dopant-blockade molecules for effectively blocking the dopant diffusion paths, the ON/OFF ratio of PBTTT OFETs can be maintained over 2 months. This work will maximize the potential of OFETs by employing the contact doping method as a promising route toward resolving the contact resistance problem.

Intrinsic Optoelectronic Characteristics of MoS2 Phototransistors via a Fully Transparent van der Waals Heterostructure.

In the past decade, intensive studies on monolayer MoS2-based phototransistors have been carried out to achieve further enhanced optoelectronic characteristics. However, the intrinsic optoelectronic characteristics of monolayer MoS2 have still not been explored until now because of unintended interferences, such as multiple reflections of incident light originating from commonly used opaque substrates. This leads to overestimated photoresponsive characteristics inevitably due to the enhanced photogating and photoconductive effects. Here, we reveal the intrinsic photoresponsive characteristics of monolayer MoS2, including its internal responsivity and quantum efficiency, in fully transparent monolayer MoS2 phototransistors employing a van der Waals heterostructure. Interestingly, as opposed to the previous reports, the internal photoresponsive characteristics do not significantly depend on the wavelength of the incident light as long as the electron-hole pairs are generated in the same k-space. This study provides a deeper understanding of the photoresponsive characteristics of MoS2 and lays the foundation for two-dimensional materials-based transparent phototransistors.

High-Performance Solution-Processed Organo-Metal Halide Perovskite Unipolar Resistive Memory Devices in a Cross-Bar Array Structure.

Resistive random access memories can potentially open a niche area in memory technology applications by combining the advantages of the long endurance of dynamic random-access memory and the long retention time of flash memories. Recently, resistive memory devices based on organo-metal halide perovskite materials have demonstrated outstanding memory properties, such as a low-voltage operation and a high ON/OFF ratio; such properties are essential requirements for low power consumption in developing practical memory devices. In this study, a nonhalide lead source is employed to deposit perovskite films via a simple single-step spin-coating method for fabricating unipolar resistive memory devices in a cross-bar array architecture. These unipolar perovskite memory devices achieve a high ON/OFF ratio up to 108 with a relatively low operation voltage, a large endurance, and long retention times. The high-yield device fabrication based on the solution-process demonstrated here will be a step toward achieving low-cost and high-density practical perovskite memory devices.

Unidirectional Real-Time Photoswitching of Diarylethene Molecular Monolayer Junctions with Multilayer Graphene Electrodes.

We fabricate and characterize vertical molecular junctions consisting of self-assembled monolayers of diarylethene (DAE) contacted by a multilayer graphene (MLG) electrode on the top and gold on the bottom. The DAE molecular junctions show two stable electrical states, a closed state (high conductance) or an open state (low conductance), which are created upon illumination with UV or visible light, respectively. For the Au-DAE-MLG junction structure, we observe that the current levels between the two conductance states are separated by 2 orders of magnitude. However, in a real-time measurement, we observe only unidirectional switching behavior from the open to the closed state.

Enhanced Charge Injection Properties of Organic Field-Effect Transistor by Molecular Implantation Doping.

Organic semiconductors (OSCs) have been widely studied due to their merits such as mechanical flexibility, solution processability, and large-area fabrication. However, OSC devices still have to overcome contact resistance issues for better performances. Because of the Schottky contact at the metal-OSC interfaces, a non-ideal transfer curve feature often appears in the low-drain voltage region. To improve the contact properties of OSCs, there have been several methods reported, including interface treatment by self-assembled monolayers and introducing charge injection layers. Here, a selective contact doping of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4 -TCNQ) by solid-state diffusion in poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT) to enhance carrier injection in bottom-gate PBTTT organic field-effect transistors (OFETs) is demonstrated. Furthermore, the effect of post-doping treatment on diffusion of F4 -TCNQ molecules in order to improve the device stability is investigated. In addition, the application of the doping technique to the low-voltage operation of PBTTT OFETs with high-k gate dielectrics demonstrated a potential for designing scalable and low-power organic devices by utilizing doping of conjugated polymers.

Contact-Engineered Electrical Properties of MoS2 Field-Effect Transistors via Selectively Deposited Thiol-Molecules.

Although 2D molybdenum disulfide (MoS2 ) has gained much attention due to its unique electrical and optical properties, the limited electrical contact to 2D semiconductors still impedes the realization of high-performance 2D MoS2 -based devices. In this regard, many studies have been conducted to improve the carrier-injection properties by inserting functional paths, such as graphene or hexagonal boron nitride, between the electrodes and 2D semiconductors. The reported strategies, however, require relatively time-consuming and low-yield transfer processes on sub-micrometer MoS2 flakes. Here, a simple contact-engineering method is suggested, introducing chemically adsorbed thiol-molecules as thin tunneling barriers between the metal electrodes and MoS2 channels. The selectively deposited thiol-molecules via the vapor-deposition process provide additional tunneling paths at the contact regions, improving the carrier-injection properties with lower activation energies in MoS2 field-effect transistors. Additionally, by inserting thiol-molecules at the only one contact region, asymmetric carrier-injection is feasible depending on the temperature and gate bias.