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.

Strategy to improve synaptic behavior of ion-actuated synaptic transistors-the use of ion blocking layer to improve state retention.

Synaptic transistors (STs) with a gate/electrolyte/channel stack, where mobile ions are electrically driven across the solid electrolyte, have been considered as analog weight elements for neuromorphic computing. The current (ID) between the source and drain in the ST is analogously updated by gate voltage (VG) pulses, enabling high pattern recognition accuracy in neuromorphic systems; however, the governing physical mechanisms of the ST are not fully understood yet. Our previous physics-based simulation study showed that ion movement in the electrolyte, rather than the electrochemical reactions that occur in the channel, plays an important role in switching. In this study, we experimentally explore the properties of the HfOx electrolyte and show that by tuning the density of oxygen vacancies, it can assume the dual role of electrolyte and channel. We demonstrate analog synaptic behavior using a novel ST with a two-layer stack of CuOx/HfOx, where the CuOx is the gate and Cu ion reservoir, and the HfOx is the electrolyte and channel. To improve state retention and linearity, we introduce a Cu ion transport barrier in the form of a dense and stoichiometric Al2O3 layer. The CuOx/Al2O3/HfOx exhibits excellent state retention and improved potentiation and depression response. Energy dispersive spectroscopy mapping following potentiation confirms the role of the Al2O3 layer in confining the Cu ions in the HfOx layer. We also show that a two-step programming scheme can further enhance synaptic response and demonstrate high recognition accuracy on the Fashion-MNIST dataset in simulation.

Optimized Doping of Diffusion Blocking Layers and Their Impact on the Performance of Perovskite Photovoltaics.

The roll-to-roll printing production process for hybrid organic-inorganic perovskite solar cells (PSCs) demands thick and high-performance solution-based diffusion blocking layers. Inverted (p-i-n) PSCs usually incorporate solution-processed PC70BM as the electron-transporting layer (ETL), which offers good electron charge extraction and passivation of the perovskite active layer grain boundaries. Thick fullerene diffusion blocking layers could benefit the long-term lifetime performance of inverted PSCs. However, the low conductivity of PC70BM significantly limits the thickness of the PC70BM buffer layer for optimized PSC performance. In this work, we show that by applying just enough N-DMBI doping principle, we can maintain the power conversion efficiency (PCE) of inverted PSCs with a thick (200 nm) PC70BM diffusion blocking layer. To better understand the origin of an optimal doping level, we combined the experimental results with simulations adapted to the PSCs reported here. Importantly, just enough 0.3% wt N-DMBI-doped 200 nm PC70BM diffusion blocking layer-based inverted PCSs retain a high thermal stability at 60 °C of up to 1000 h without sacrificing their PCE photovoltaic parameters.

Zn-Doped P-Type InAs Nanocrystal Quantum Dots.

Doped heavy metal-free III-V semiconductor nanocrystal quantum dots (QDs) are of great interest both from the fundamental aspects of doping in highly confined structures, and from the applicative side of utilizing such building blocks in the fabrication of p-n homojunction devices. InAs nanocrystals (NCs), that are of particular relevance for short-wave IR detection and emission applications, manifest heavy n-type character poising a challenge for their transition to p-type behavior. The p-type doping of InAs NCs is presented with Zn - enabling control over the charge carrier type in InAs QDs field effect transistors. The post-synthesis doping reaction mechanism is studied for Zn precursors with varying reactivity. Successful p-type doping is achieved by the more reactive precursor, diethylzinc. Substitutional doping by Zn2+ replacing In3+ is established by X-ray absorption spectroscopy analysis. Furthermore, enhanced near infrared photoluminescence is observed due to surface passivation by Zn as indicated from elemental mapping utilizing high-resolution electron microscopy corroborated by X-ray photoelectron spectroscopy study. The demonstrated ability to control the carrier type, along with the improved emission characteristics, paves the way towards fabrication of optoelectronic devices active in the short-wave infrared region utilizing heavy-metal free nanocrystal building blocks.

Persistent Ion Accumulation at Interfaces Improves the Performance of Perovskite Solar Cells.

The mixed ionic-electronic nature of lead halide perovskites makes their performance in solar cells complex in nature. Ion migration is often associated with negative impacts-such as hysteresis or device degradation-leading to significant efforts to suppress ionic movement in perovskite solar cells. In this work, we demonstrate that ion trapping at the perovskite/electron transport layer interface induces band bending, thus increasing the built-in potential and open-circuit voltage of the device. Quantum chemical calculations reveal that iodine interstitials are stabilized at that interface, effectively trapping them at a remarkably high density of ∼1021 cm-3 which causes the band bending. Despite the presence of this high density of ionic defects, the electronic structure calculations show no sub-band-gap states (electronic traps) are formed due to a pronounced perovskite lattice reorganization. Our work demonstrates that ionic traps can have a positive impact on device performance of perovskite solar cells.

Radiofrequency Schottky Diodes Based on p-Doped Copper(I) Thiocyanate (CuSCN).

Schottky diodes based on inexpensive materials that can be processed using simple manufacturing methods are of particular importance for the next generation of flexible electronics. Although a number of high-frequency n-type diodes and rectifiers have been demonstrated, the progress with p-type diodes is lagging behind, mainly due to the intrinsically low conductivities of existing p-type semiconducting materials that are compatible with low-temperature, flexible, substrate-friendly processes. Herein, we report on CuSCN Schottky diodes, where the semiconductor is processed from solution, featuring coplanar Al-Au nanogap electrodes (<15 nm), patterned via adhesion lithography. The abundant CuSCN material is doped with the molecular p-type dopant fluorofullerene C60F48 to improve the diode's operating characteristics. Rectifier circuits fabricated with the doped CuSCN/C60F48 diodes exhibit a 30-fold increase in the cutoff frequency as compared to pristine CuSCN diodes (from 140 kHz to 4 MHz), while they are able to deliver output voltages of >100 mV for a VIN = ±5 V at the commercially relevant frequency of 13.56 MHz. The enhanced diode and circuit performance is attributed to the improved charge transport across CuSCN induced by C60F48. The ensuing diode technology can be used in flexible complementary circuits targeting low-energy-budget applications for the emerging internet of things device ecosystem.

14 GHz Schottky Diodes Using a p-Doped Organic Polymer.

The low carrier mobility of organic semiconductors and the high parasitic resistance and capacitance often encountered in conventional organic Schottky diodes hinder their deployment in emerging radio frequency (RF) electronics. Here, these limitations are overcome by combining self-aligned asymmetric nanogap electrodes (≈25 nm) produced by adhesion lithography, with a high mobility organic semiconductor, and RF Schottky diodes able to operate in the 5G frequency spectrum are demonstrated. C16 IDT-BT is used, as the high hole mobility polymer, and the impact of p-doping on the diode performance is studied. Pristine C16 IDT-BT-based diodes exhibit maximum intrinsic and extrinsic cutoff frequencies (fC ) of >100 and 6 GHz, respectively. This extraordinary performance is attributed to the planar nature of the nanogap channel and the diode's small junction capacitance (<2 pF). Doping of C16 IDT-BT with the molecular p-dopant C60 F48 improves the diode's performance further by reducing the series resistance resulting to intrinsic and extrinsic fC of >100 and ≈14 GHz respectively, while the DC output voltage of an RF rectifier circuit increases by a tenfold. Our work highlights the importance of the planar nanogap architecture and paves the way for the use of organic Schottky diodes in large-area RF electronics of the future.

Doped Organic Hole Extraction Layers in Efficient PbS and AgBiS2 Quantum Dot Solar Cells.

The efficiency of PbS quantum dot (QD) solar cells has significantly increased in recent years, strengthening their potential for industrial applications. The vast majority of state-of-the-art devices utilize 1,2-ethanedithiol (EDT)-coated PbS QD hole extraction layers, which lead to high initial performance, but result in poor device stability. While excellent performance has also been demonstrated with organic extraction layers, these devices include a molybdenum trioxide (MoO3) layer, which is also known to decrease device stability. Herein, we demonstrate that organic layers based on a poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) polymer doped with C60F48 can serve as hole extraction layers for efficient EDT-free and MoO3-free QD solar cells. Such layers are shown to offer high conductivity for facile hole transport to the anode, while effectively blocking electrons due to their low electron affinity. We show that our approach is versatile and is applicable also to AgBiS2 QD solar cells.

Effect of the Organic Semiconductor Side Groups on the Structural and Electronic Properties of Their Interface with Dopants.

Two derivatives of [1]benzothieno[3,2-b][1]benzothiophene (BTBT), namely, 2,7-dioctyl-BTBT (C8-BTBT) and 2,7-diphenyl-BTBT (DPh-BTBT), belonging to one of the best performing organic semiconductor (OSC) families, have been employed to investigate the influence of the substitutional side groups on the properties of the interface created when they are in contact with dopant molecules. As a molecular p-dopant, the fluorinated fullerene C60F48 is used because of its adequate electronic levels and its bulky molecular structure. Despite the dissimilarity introduced by the OSC film termination, dopant thin films grown on top adopt the same (111)-oriented FCC crystalline structure in the two cases. However, the early stage distribution of the dopant on each OSC film surface is dramatically influenced by the group side, leading to distinct host-dopant interfacial morphologies that strongly affect the nanoscale local work function. In this context, Kelvin probe force microscopy and photoelectron emission spectroscopy provide a comprehensive picture of the interfacial electronic properties. The extent of charge transfer and energy level alignment between OSCs and dopant are debated in light of the differences in the ionization potential of the OSC in the films, the interface nanomorphology, and the electronic coupling with the substrate.

Hybrid image sensor of small molecule organic photodiode on CMOS - Integration and characterization.

Organic photodiodes (OPDs) for its interesting optoelectronic properties has the potential to be utilized with complementary metal-oxide-semiconductor (CMOS) circuit for imaging, automotive, and security based applications. To achieve such a hybrid device as an image sensor, it is imperative that the quality of the OPD remains high on the CMOS substrate and that it has a well-connected optoelectronic interface with the underneath readout integrated circuit (ROIC) for efficient photogeneration and signal readout. Here, we demonstrate seamless integration of a thermally deposited visible light sensitive small molecule OPD on a standard commercial CMOS substrate using optimized doped PCBM buffer layer. Under a standard power supply voltage of 3 V, this hybrid device shows an excellent photolinearity in the entire bias regime, a high pixel sensitivity of 2 V/Lux.sec, a dynamic range (DR) of 71 dB, and a low dark leakage current density of 1 nA/cm2. Moreover, the integrated OPD has a minimum bandwidth of 400 kHz. The photoresponse nonuniformity being only 1.7%, achieved under research lab conditions, strengthens the notion that this fully-CMOS compatible technology has the potential to be applied in high-performance large-scale imaging array.

Double Beneficial Role of Fluorinated Fullerene Dopants on Organic Thin-Film Transistors: Structural Stability and Improved Performance.

The present work assesses improved carrier injection in organic field-effect transistors by contact doping and provides fundamental insight into the multiple impacts that the dopant/semiconductor interface details have on the long-term and thermal stability of devices. We investigate donor [1]benzothieno[3,2-b]-[1]benzothiophene (BTBT) derivatives with one and two octyl side chains attached to the core, therefore constituting asymmetric (BTBT-C8) and symmetric (C8-BTBT-C8) molecules, respectively. Our results reveal that films formed out of the asymmetric BTBT-C8 expose the same alkyl-terminated surface as the C8-BTBT-C8 films do. In both cases, the consequence of depositing fluorinated fullerene (C60F48) as a molecular p-dopant is the formation of C60F48 crystalline islands decorating the step edges of the underlying semiconductor film surface. We demonstrate that local work function changes along with a peculiar nanomorphology lead to the double beneficial effect of lowering the contact resistance and providing long-term and enhanced thermal stability of the devices.

Structure-Property Relation in Organic-Metal Oxide Hybrid Phototransistors.

We report an optoelectronic device consisting of a solution-processed indium gallium zinc oxide (IGZO) thin-film transistor and vacuum-deposited small organic molecules. Depending on the configurations of the organic materials, either bulk heterojunction or planar heterojunction (PHJ), the device assumes the functionality of either a photosensor or a photoinduced memory, respectively. Under λ = 625 nm light illumination, the photosensor shows response and recovery time of ∼50 ms, responsivity of ∼5 mA/W, sensitivity above 104, and a linear response. The mechanism of the photoinduced memory is studied experimentally and verified using a device simulation. We find that the memory is due to long charge retention time at the organic PHJ interface which is stable for over 9 days. It is correlated with the low leakage current found in ordered organic junctions having low subgap tail states. The presented integration of the PHJ with the transistor constitutes a new design of write-once-read-many-times memory device that is likely to be attractive for low-cost applications.

Surface specificity and mechanistic pathway of de-fluorination of C60F48 on coinage metals.

We provide experimental and theoretical understanding on fundamental processes taking place at room temperature when a fluorinated fullerene dopant gets close to a metal surface. By employing scanning tunneling microscopy and photoelectron spectroscopies, we demonstrate that the on-surface integrity of C60F48 depends on the interaction with the particular metal it approaches. Whereas on Au(111) the molecule preserves its chemical structure, on more reactive surfaces such as Cu(111) and Ni(111), molecules interacting with the bare metal surface lose the halogen atoms and transform to C60. Though fluorine-metal bonding can be detected depending on the molecular surface density, no ordered fluorine structures are observed. We show the implications of the metal-dependent de-fluorination in the electronic structure of the molecules and the energy alignment at the molecule-metal interface. Molecular dynamics simulations with ReaxFF reactive force field corroborate the experimental facts and provide a detailed mechanistic picture of the surface-induced de-fluorination, which involves the rotation of the molecule on the surface. Outstandingly, a thermodynamic analysis indicates that the effect of the metal surface is lowering and diminishing the energy barrier for C-F cleave, demonstrating the catalytic role of the surface. The present study contributes to in-depth knowledge of the mechanisms that affect the degree of stability of chemical species on surfaces, which is essential to advance our understanding of the chemical reactivity of metals and their role in on-surface chemical reactions.

Enhancing the Open-Circuit Voltage of Perovskite Solar Cells by Embedding Molecular Dipoles within Their Hole-Blocking Layer.

Engineering the energetics of perovskite photovoltaic devices through deliberate introduction of dipoles to control the built-in potential of the devices offers an opportunity to enhance their performance without the need to modify the active layer itself. In this work, we demonstrate how the incorporation of molecular dipoles into the bathocuproine (BCP) hole-blocking layer of inverted perovskite solar cells improves the device open-circuit voltage (VOC) and, consequently, their performance. We explore a series of four thiaazulenic derivatives that exhibit increasing dipole moments and demonstrate that these molecules can be introduced into the solution-processed BCP layer to effectively increase the built-in potential within the device without altering any of the other device layers. As a result, the VOC of the devices is enhanced by up to 130 mV, with larger dipoles resulting in higher VOC. To investigate the limitations of this approach, we employ numerical device simulations that demonstrate that the highest dipole derivatives used in this work eliminate all limitations on the VOC stemming from the built-in potential of the device.

Nanoparticulate Metal Oxide Top Electrode Interface Modification Improves the Thermal Stability of Inverted Perovskite Photovoltaics.

Solution processed γ-Fe2O3 nanoparticles via the solvothermal colloidal synthesis in conjunction with ligand-exchange method are used for interface modification of the top electrode in inverted perovskite solar cells. In comparison to more conventional top electrodes such as PC(70)BM/Al and PC(70)BM/AZO/Al, we show that incorporation of a γ-Fe2O3 provides an alternative solution processed top electrode (PC(70)BM/γ-Fe2O3/Al) that not only results in comparable power conversion efficiencies but also improved thermal stability of inverted perovskite photovoltaics. The origin of improved stability of inverted perovskite solar cells incorporating PC(70)BM/ γ-Fe2O3/Al under accelerated heat lifetime conditions is attributed to the acidic surface nature of γ-Fe2O3 and reduced charge trapped density within PC(70)BM/ γ-Fe2O3/Al top electrode interfaces.

Effect of Injection Layer Sub-Bandgap States on Electron Injection in Organic Light-Emitting Diodes.

It is generally considered that the injection of charges into an active layer of an organic light-emitting diode (OLED) is solely determined by the energetic injection barrier formed at the device interfaces. Here, we demonstrate that the density of surface states of the electron-injecting ZnO layer has a profound effect on both the charge injection and the overall performance of the OLED device. Introducing a dopant into ZnO reduces both the energy depth and density of surface states without altering the position of the energy levels-thus, the magnitude of the injection barrier formed at the organic/ZnO interface remains unchanged. Changes observed in the density of surface states result in an improved electron injection and enhanced luminescence of the device. We implemented a numerical simulation, modeling the effects of energetics and the density of surface states on the electron injection, demonstrating that both contributions should be considered when choosing the appropriate injection layer.

Small Molecule/Polymer Blend Organic Transistors with Hole Mobility Exceeding 13 cm(2) V(-1) s(-1).

A ternary organic semiconducting blend composed of a small-molecule, a conjugated polymer, and a molecular p-dopant is developed and used in solution-processed organic transistors with hole mobility exceeding 13 cm(2) V(-1) s(-1) (see the Figure). It is shown that key to this development is the incorporation of the p-dopant and the formation of a vertically phase-separated film microstructure.

A Comprehensive study of the Effects of Chain Morphology on the Transport Properties of Amorphous Polymer Films.

Organic semiconductors constitute one of the main components underlying present-day paradigm shifting optoelectronic applications. Among them, polymer based semiconductors are deemed particularly favorable due to their natural compatibility with low-cost device fabrication techniques. In light of recent advances in the syntheses of these classes of materials, yielding systems exhibiting charge mobilities comparable with those found in organic crystals, a comprehensive study of their charge transport properties is presented. Among a plethora of effects arising from these systems morphological and non morphological attributes, it is shown that a favorable presence of several of these attributes, including that of rapid on-chain carrier propagation and the presence of elongated conjugation segments, can lead to an enhancement of the system's mobility by more than 5 orders of magnitude with respect to 'standard' amorphous organic semiconductors. New insight for the formulation of new engineering strategies for next generation polymer based semiconductors is thus gathered.

Self-assembled metallic nanowire-based vertical organic field-effect transistor.

We report on in situ, self-assembly, solution-processing of metallic (Au/Ag) nanowire-based transparent electrodes integrated to vertical organic field-effect transistors (VOFETs). In the VOFET architecture, the nanowires' microstructure facilitates current modulation by the gate across the otherwise shielding sandwiched source electrode. We show N-type VOFETs operation with on/off ratio ∼1 × 10(5) and high current density (>1 mA cm(-2) at VDS = 5 V). The integration of the device design and the transparent electrode deposition methods offers a potential route for all-solution processing-based, large-area, high-efficiency organic electronics.

Coating and enhanced photocurrent of vertically aligned zinc oxide nanowire arrays with metal sulfide materials.

Hybrid nanostructures combining zinc oxide (ZnO) and a metal sulfide (MS) semiconductor are highly important for energy-related applications. Controlled filling and coating of vertically aligned ZnO nanowire arrays with different MS materials was achieved via the thermal decomposition approach of single-source precursors in the gas phase by using a simple atmospheric-pressure chemical vapor deposition system. Using different precursors allowed us to synthesize multicomponent structures such as nanowires coated with alloy shell or multishell structures. Herein, we present the synthesis and structural characterization of the different structures, as well as an electrochemical characterization and a photovoltaic response of the ZnO-CdS system, in which the resulting photocurrent upon illumination indicates charge separation at the interface.