Metal-Oxide Heterojunction Optoelectronic Synapse and Multilevel Memory Devices Enabled by Broad Spectral Photocarrier Modulation.

Broad spectral response and high photoelectric conversion efficiency are key milestones for realizing multifunctional, low-power optoelectronic devices such as artificial synapse and reconfigurable memory devices. Nevertheless, the wide bandgap and narrow spectral response of metal-oxide semiconductors are problematic for efficient metal-oxide optoelectronic devices such as photonic synapse and optical memory devices. Here, a simple titania (TiO2 )/indium-gallium-zinc-oxide (IGZO) heterojunction structure is proposed for efficient multifunctional optoelectronic devices, enabling widen spectral response range and high photoresponsivity. By overlaying a TiO2 film on IGZO, the light absorption range extends to red light, along with enhanced photoresponsivity in the full visible light region. By implementing the TiO2 /IGZO heterojunction structure, various synaptic behaviors are successfully emulated such as short-term memory/long-term memory and paired pulse facilitation. Also, the TiO2 /IGZO synaptic transistor exhibits a recognition rate up to 90.3% in recognizing handwritten digit images. Moreover, by regulating the photocarrier dynamics and retention behavior using gate-bias modulation, a reconfigurable multilevel (≥8 states) memory is demonstrated using visible light.

Three-dimensional imaging performance of photoelectrochemical cells.

A photoelectrochemical (PEC) cell produces hydrogen energy using solar energy and an electrochemical reaction. In the hydrogen production process with water decomposition, electrons move from the anode to the cathode, and by measuring the current value at this time, the PEC cell can generate hydrogen and function as an image sensor at the same time. Due to the characteristics of the PEC cell that can perform both functions simultaneously, it can be applied as a device that can detect and respond to the surrounding environment without the need for an observation system such as a camera. We present the imaging performance of PEC cells. The effectiveness of the experiment was confirmed by applying the PEC cells to integral imaging, one of the three-dimensional (3D) imaging techniques.

SWIR imaging using PbS QD photodiode array sensors.

We fabricated a 1 × 10 PbS QD photodiode array with multiple stacked QD layers with high-resolution patterning using a customized photolithographic process. The array showed the average responsivity of 5.54 × 10-3 A/W and 1.20 × 10-2 A/W at 0 V and -1 V under 1310- nm short-wavelength infrared (SWIR) illumination. The standard deviation of the pixel responsivity was under 10%, confirming the uniformity of the fabrication process. The response time was 2.2 ± 0.13 ms, and the bandwidth was 159.1 Hz. A prototype 1310-nm SWIR imager demonstrated that the QD photodiode-based SWIR image sensor is a cost-effective and practical alternative for III-V SWIR image sensors.

Integral imaging using a MoS2 Schottky diode.

We report the performance of a MoS2 Schottky diode on three-dimensional (3D) integral imaging. The MoS2 Schottky diode has asymmetric Pt electrodes for the Schottky contact and Ti/Au electrodes for the ohmic contact. Such a Schottky diode exhibits an excellent rectification ratio of 103, a broad spectral photoresponse in the 450-700 nm range, an almost ideal linearity of 1, and a wide linear dynamic range of 106 dB. We successfully conduct object pickup experiments using integral imaging and validate the feasibility of a single-pixel imager as a 3D image sensor.

All 2D WSe2/MoS2 heterojunction photodiode and its image sensor application.

Two-dimensional (2D) layered van der Waals atomic crystals exhibit many fascinating properties. In particular, their dangling-bond-free nature enables different 2D materials to be stacked on the top of each other without restraint, thereby forming a heterostructure. In this study, a high-performance all 2D WSe2/MoS2 heterojunction photodiode with a graphene contact as an electrode is demonstrated. It exhibits an excellent electrical performance (ideality factor of 1.2 and rectification ratio of 104), a broad spectral photoresponse (from 450 to 980 nm), and a remarkable linearity with a linear dynamic range of 113 dB. Finally, a self-powered single pixel imager is demonstrated as a feasible optoelectronic application.

Impact of H-Doping on n-Type TMD Channels for Low-Temperature Band-Like Transport.

Band-like transport behavior of H-doped transition metal dichalcogenide (TMD) channels in field effect transistors (FET) is studied by conducting low-temperature electrical measurements, where MoTe2 , WSe2 , and MoS2 are chosen for channels. Doped with H atoms through atomic layer deposition, those channels show strong n-type conduction and their mobility increases without losing on-state current as the measurement temperature decreases. In contrast, the mobility of unintentionally (naturally) doped TMD FETs always drops at low temperatures whether they are p- or n-type. Density functional theory calculations show that H-doped MoTe2 , WSe2 , and MoS2 have Fermi levels above conduction band edge. It is thus concluded that the charge transport behavior in H-doped TMD channels is metallic showing band-like transport rather than thermal hopping. These results indicate that H-doped TMD FETs are practically useful even at low-temperature ranges.

High-Speed Colloidal Quantum Dot Photodiodes via Accelerating Charge Separation at Metal-Oxide Interface.

With ever-growing technological demands in the imaging sensor industry for autonomous driving and augmented reality, developing sensors that can satisfy not only image resolution but also the response speed becomes more challenging. Herein, the focus is on developing a high-speed photosensor capable of obtaining high-resolution, high-speed imaging with colloidal quantum dots (QDs) as the photosensitive material. In detail, high-speed QD photodiodes are demonstrated with rising and falling times of τr = 28.8 ± 8.34 ns and τf = 40 ± 9.81 ns, respectively, realized by fast separation of electron-hole pairs due to the action of internal electric field at the QD interface, mainly by the interaction between metal oxide and the QD's ligands. Such energy transfer relations are analyzed and interpreted with time-resolved photoluminescence measurements, providing physical understanding of the device and working principles.

Black Phosphorus-Zinc Oxide Nanomaterial Heterojunction for p-n Diode and Junction Field-Effect Transistor.

Black phosphorus (BP) nanosheet is two-dimensional (2D) semiconductor with distinct band gap and attracting recent attention from researches because it has some similarity to gapless 2D semiconductor graphene in the following two aspects: single element (P) for its composition and quite high mobilities depending on its fabrication conditions. Apart from several electronic applications reported with BP nanosheet, here we report for the first time BP nanosheet-ZnO nanowire 2D-1D heterojunction applications for p-n diodes and BP-gated junction field effect transistors (JFETs) with n-ZnO channel on glass. For these nanodevices, we take advantages of the mechanical flexibility of p-type conducting of BP and van der Waals junction interface between BP and ZnO. As a result, our BP-ZnO nanodimension p-n diode displays a high ON/OFF ratio of ∼10(4) in static rectification and shows kilohertz dynamic rectification as well while ZnO nanowire channel JFET operations are nicely demonstrated by BP gate switching in both electrostatics and kilohertz dynamics.

Dual Gate Black Phosphorus Field Effect Transistors on Glass for NOR Logic and Organic Light Emitting Diode Switching.

We have fabricated dual gate field effect transistors (FETs) with 12 nm-thin black phosphorus (BP) channel on glass substrate, where our BP FETs have a patterned-gate architecture with 30 nm-thick Al2O3 dielectrics on top and bottom of a BP channel. Top gate dielectric has simultaneously been used as device encapsulation layer, controlling the threshold voltage of FETs as well when FETs mainly operate under bottom gate bias. Bottom, top, and dual gate-controlling mobilities were estimated to be 277, 92, and 213 cm(2)/V s, respectively. Maximum ON-current was measured to be ∼5 µA at a drain voltage of -0.1 V but to be as high as ∼50 µA at -1 V, while ON/OFF current ratio appeared to be 3.6 × 10(3) V. As a result, our dual gate BP FETs demonstrate organic light emitting diode (OLED) switching for green and blue OLEDs, also demonstrating NOR logic functions by separately using top- and bottom-input.

Enhanced light scattering and trapping effect of Ag nanowire mesh electrode for high efficient flexible organic solar cell.

Ag nanowire (NW) mesh is used as transparent conducting electrode for high efficient flexible organic solar cells (OSCs). The Ag NW mesh electrode facilitates light scattering and trapping, allowing enhancement of light absorption in the active layer. OSCs incorporating Ag NW mesh electrode exhibit maximum power conversion efficiency (PCE) of 4.47%, 25%, higher than that of OSCs with a conventional ITO electrode (3.63%).

Effect of geometric lattice design on optical/electrical properties of transparent silver grid for organic solar cells.

Silver (Ag) grid transparent electrode is one of the most promising transparent conducting electrodes (TCEs) to replace conventional indium tin oxide (ITO). We systematically investigate an effect of geometric lattice modifications on optical and electrical properties of Ag grid electrode. The reference Ag grid with 5 µm width and 100 µm pitch (duty of 0.05) prepared by conventional photo-lithography and lift-off processes shows the sheet resistance of 13.27 Ω/sq, transmittance of 81.1%, and resultant figure of merit (FOM) of 129.05. Three different modified Ag grid electrodes with stripe added-mesh (SAM), triangle-added mesh (TAM), and diagonal-added mesh (DAM) are suggested to improve optical and electrical properties. Although all three of SAM, TAM, and DAM Ag grid electrodes exhibit the lower transmittance values of about 72 - 77%, they showed much decreased sheet resistance of 6 - 8 Ω/sq. As a result, all of the lattice-modified Ag grid electrodes display significant improvement of FOM and the highest value of 171.14 is obtained from DAM Ag grid, which is comparable to that of conventional ITO electrode (175.46). Also, the feasibility of DAM Ag gird electrode for use in organic solar cell is confirmed by finite difference time domain (FDTD) simulations. Unlike a conventional ITO electrode, DAM Ag grid electrode can induce light scattering and trapping due to the diffuse transmission that compensates for the loss in optical transparency, resulting in comparable light absorption in the photo active layer of poly(3-hexylthiophene) (P3HT): [6,6]-phenyl-C61-butyric acid methyl ester (PC60BM). P3HT:PC60BM based OSCs with the DAM Ag grid electrode were fabricated, which also showed the potential for ITO-free transparent electrode.

Self-Powering Sensory Device with Multi-Spectrum Image Realization for Smart Indoor Environments.

The development of organic-based optoelectronic technologies for the indoor Internet of Things market, which relies on ambient energy sources, has increased, with organic photovoltaics (OPVs) and photodetectors (OPDs) considered promising candidates for sustainable indoor electronic devices. However, the manufacturing processes of standalone OPVs and OPDs can be complex and costly, resulting in high production costs and limited scalability, thus limiting their use in a wide range of indoor applications. This study uses a multi-component photoactive structure to develop a self-powering dual-functional sensory device with effective energy harvesting and sensing capabilities. The optimized device demonstrates improved free-charge generation yield by quantifying charge carrier dynamics, with a high output power density of over 81 and 76 µW cm-2 for rigid and flexible OPVs under indoor conditions (LED 1000 lx (5200 K)). Furthermore, a single-pixel image sensor is demonstrated as a feasible prototype for practical indoor operating in commercial settings by leveraging the excellent OPD performance with a linear dynamic range of over 130 dB in photovoltaic mode (no external bias). This apparatus with high-performance OPV-OPD characteristics provides a roadmap for further exploration of the potential, which can lead to synergistic effects for practical multifunctional applications in the real world by their mutual relevance.

Atto-Scale Noise Near-Infrared Organic Photodetectors Enabled by Controlling Interfacial Energetic Offset through Enhanced Anchoring Ability.

The near-infrared (NIR) sensor technology is crucial for various applications such as autonomous driving and biometric tracking. Silicon photodetectors (SiPDs) are widely used in NIR applications; however, their scalability is limited by their crystalline properties. Organic photodetectors (OPDs) have attracted attention for NIR applications owing to their scalability, low-temperature processing, and notably low dark current density (JD), which is similar to that of SiPDs. However, the still high JD (at NIR band) and few measurements of noise equivalent powers (NEPs) pose challenges for accurate performance comparisons. This study addresses these issues by quantitatively characterizing the performance matrix and JD generation mechanism using electron-blocking layers (EBLs) in OPDs. The energy offset at an EBL/photosensitive layer interface determines the thermal activation energy and directly affects JD. A newly synthesized EBL (3PAFBr) substantially enhances the interfacial energy barrier by forming a homogeneous contact owing to the improved anchoring ability of 3PAFBr. As a result, the OPD with 3PAFBr yields a noise current of 852 aA (JD = 12.3 fA cm⁻2 at V → -0.1 V) and several femtowatt-scale NEPs. As far as it is known, this is an ultralow of JD in NIR OPDs. This emphasizes the necessity for quantitative performance characterization.

Negative Photoresponse Switching via Electron-Hole Recombination at The Type III Junction of MoTe2 Channel/SnS2 Top Layer.

Extensive study on 2D van der Waals (vdW) heterojunctions has primarily focused on PN diodes for fast-switching photodetection, while achieving the same from 2D channel phototransistors is rare despite their other advantages. Here, a high-speed phototransistor featuring a type III junction between p-MoTe2 channel and n-SnS2 top layer is designed. The photodetecting device operates with a basis of negative photoresponse (NPR), which originates from the recombination of photoexcited electrons in n-SnS2 and accumulated holes in the p-MoTe2 channel. For the NPR to occur, high-energy photons capable of exciting SnS2 (band gap ≈2.2 eV) are found to be effective because lower-energy photons simply penetrate the SnS2 top layer only to excite MoTe2 , leading to normal positive photoresponse (PPR) which is known to be slow due to the photogating effects. The NPR transistor showcases 0.5 ms fast photoresponses and a high responsivity over 5000 A W-1 . More essentially, such carrier recombination mechanism is clarified with three experimental evidences. The phototransistor is finally modified with Au contact on n-SnS2 , to be a more practical device displaying voltage output. Three different photo-logic states under blue, near infrared (NIR), and blue-NIR mixed photons are demonstrated using the voltage signals.

Chiral Diketopyrrolopyrrole-Based Conjugated Polymers with Intramolecular Rotation-Isomeric Conformation Asymmetry for Near-Infrared Circularly Polarized Light-Sensing Organic Phototransistors.

Recent advances in chiral nanomaterials interacting with circularly polarized (CP) light open new expectations for optoelectronics in various research fields such as quantum- and biology-related technology. To fully utilize the great potential of chiral optoelectronic devices, the development of chiral optoelectronic devices that function in the near-infrared (NIR) region is required. Herein, we demonstrate a NIR-absorbing, chiroptical, low-band-gap polymer semiconductor for high-performance NIR CP light phototransistors. A newly synthesized diketopyrrolopyrrole-based donor-acceptor-type chiral π-conjugated polymer with an asymmetric alkyl side chain exhibits strong chiroptical activity in a wavelength range of 700-1000 nm. We found that the attachment of an enantiomerically pure stereogenic alkyl substituent to the π-conjugated chromophore backbone led to strong chiroptical activity through symmetry breaking of the π-conjugation of the backbone in a molecular rotational motion while maintaining the coplanar backbone conformation for efficient charge transport. The NIR CP light-sensing phototransistors based on a chiral π-conjugated polymer photoactive single channel layer exhibit a high photoresponsivity of 26 A W-1 under NIR CP light irradiation at 920 nm, leading to excellent NIR CP light distinguishability. This study will provide a rationale and strategy for designing chiral π-conjugated polymers for high-performance NIR chiral optoelectronics.

Chiroptical Synaptic Heterojunction Phototransistors Based on Self-Assembled Nanohelix of π-Conjugated Molecules for Direct Noise-Reduced Detection of Circularly Polarized Light.

High-performance chiroptical synaptic phototransistors are successfully demonstrated using heterojunctions composed of a self-assembled nanohelix of a π-conjugated molecule and a metal oxide semiconductor. To impart strong chiroptical activity to the device, a diketopyrrolopyrrole-based π-conjugated molecule decorated with chiral glutamic acid is newly synthesized; this molecule is capable of supramolecular self-assembly through noncovalent intermolecular interactions. In particular, nanohelix formed by intertwinded fibers with strong and stable chiroptical activity in a solid-film state are obtained through hydrogen-bonding-driven, gelation-assisted self-assembly. Phototransistors based on interfacial charge transfer at the heterojunction from the chiroptical nanohelix to the metal oxide semiconductor show excellent chiroptical detection with a high photocurrent dissymmetry factor of 1.97 and a high photoresponsivity of 218 A W-1 . The chiroptical phototransistor demonstrates photonic synapse-like, time-dependent photocurrent generation, along with persistent photoconductivity, which is attributed to the interfacial charge trapping. Through the advantage of synaptic functionality, a trained convolutional neural network successfully recognizes noise-reduced circularly polarized images of handwritten alphabetic characters with better than 89.7% accuracy.

Probing Optical Multi-Level Memory Effects in Single Core-Shell Quantum Dots and Application Through 2D-0D Hybrid Inverters.

Challenges in the development of a multi-level memory (MM) device for multinary arithmetic computers have posed an obstacle to low-power, ultra-high-speed operation. For the effective transfer of a huge amount of data between arithmetic and storage devices, optical communication technology represents a compelling solution. Here, by replicating a floating gate architecture with CdSe/ZnS type-I core/shell quantum dots (QDs), a 2D-0D hybrid optical multi-level memory (OMM) device operated is demonstrated by laser pulses. In the device, laser pulses create linear optically trapped currents with MM characteristics, while conversely, voltage pulses reset all the trapped currents at once. Assuming electron transfer via the energy band alignment between MoS2 and CdSe, the study also establishes the mechanism of the OMM effect. Analysis of the designed device led to a new hypothesis that charge transfer is difficult for laterally adjacent QDs facing a double ZnS shell, which is tested by separately stimulating different positions on the 2D-0D hybrid structure with finely focused laser pulses. Results indicate that each laser pulse induced independent MM characteristics in the 2D-0D hybrid architecture. Based on this phenomenon, we propose a MM inverter to produce MM effects, such as programming and erasing, solely through the use of laser pulses. Finally, the feasibility of a fully optically-controlled intelligent system based on the proposed OMM inverters is evaluated through a CIFAR-10 pattern recognition task using a convolutional neural network.

Easily reducible materials from the reactions of diselenopheno[3,2-b:2',3'-d]pyrrole and dithieno[3,2-b:2',3'-d]pyrrole with tetracyanoethylene.

A new core, 4H-diselenopheno[3,2-b:2',3'-d]pyrrole (DSP), was reacted with tetracyanoethylene, and three products, mono-tricyanovinyl, bis-tricyanovinyl, and quinoidal, were isolated and compared with the respective 4H-dithieno[3,2-b:2',3'-d]pyrrole (DTP) derivatives using cyclic voltammetry, UV-vis absorption, and differential scanning calorimetry analyses. Organic field-effect transistors were fabricated using solution-processed films, and only one derivative, bis-tricyanovinyl-DSP, exhibited transistor behavior with µ(e) reaching 8.7 × 10(-4) cm(2)/V·s. This enhancement of the electron-transporting properties in comparison with DTP derivative is attributed to stronger LUMO-LUMO interaction due to a larger size of selenium atom, which in the case of the bis-tricyanovinyl derivative, has wave function density on the chalcogen.

Organic photodiode with dual functions of indoor photovoltaic and high-speed photodetector.

Energy harvesting and light detection are key technologies in various emerging optoelectronic applications. The high absorption capability and bandgap tunability of organic semiconductors make them promising candidates for such applications. Herein, a poly(3-hexylthiophene-2,5-diyl) (P3HT):indene-C60 bisadduct (ICBA) bulk heterojunction-based organic photodiode (OPD) was reported, demonstrating dual functionality as an indoor photovoltaic (PV) and as a high-speed photodetector. This OPD demonstrated decent indoor PV performance with a power conversion efficiency (PCE) of (11.6 ± 0.5)% under a light emitting diode (LED) lamp with a luminance of 1000 lx. As a photodetector, this device exhibited a decent photoresponsivity of 0.15 A/W (green light) with an excellent linear dynamic range (LDR) of over 127 dB within the optical power range of 3.74 × 10-7 to 9.6 × 10-2 W/cm2. Furthermore, fast photoswitching behaviors could be observed with the rising/falling times of 14.5/10.4 µs and a cutoff (3 dB) frequency of 37 kHz. These results might pave the way for further development of organic optoelectronic applications.

Graphene Bridge Heterostructure Devices for Negative Differential Transconductance Circuit Applications.

Two-dimensional van der Waals (2D vdW) material-based heterostructure devices have been widely studied for high-end electronic applications owing to their heterojunction properties. In this study, we demonstrate graphene (Gr)-bridge heterostructure devices consisting of laterally series-connected ambipolar semiconductor/Gr-bridge/n-type molybdenum disulfide as a channel material for field-effect transistors (FET). Unlike conventional FET operation, our Gr-bridge devices exhibit non-classical transfer characteristics (humped transfer curve), thus possessing a negative differential transconductance. These phenomena are interpreted as the operating behavior in two series-connected FETs, and they result from the gate-tunable contact capacity of the Gr-bridge layer. Multi-value logic inverters and frequency tripler circuits are successfully demonstrated using ambipolar semiconductors with narrow- and wide-bandgap materials as more advanced circuit applications based on non-classical transfer characteristics. Thus, we believe that our innovative and straightforward device structure engineering will be a promising technique for future multi-functional circuit applications of 2D nanoelectronics.