Impact of Blend Morphology on Interface State Recombination in Bulk Heterojunction Organic Solar Cells

This work is a reinvestigation of the impact of blend morphology and thermal annealing on the electrical performance of regioregular‐P3HT:PC₆₀BM bulk heterojunction organic solar cells. The morphological, structural, and electrical properties of the blend are experimentally investigated with atomic force microscopy, X‐ray diffraction, and time‐of‐flight measurements. Current–voltage characteristics of photodiode devices are measured in the dark and under illumination. Finally, the existence of exponential electronic band tails due to gap states is experimentally confirmed by measuring the device spectral response in the subband gap regime. This method reveals the existence of a large density of gap states, which is partially and systematically reduced by thermal annealing. When the band tails are properly accounted for in the drift and diffusion simulations, experimentally measured charge transport characteristics, under both dark and illuminated conditions and as a function of annealing time, can be satisfactorily reproduced. This work further confirms the critical impact of tails states on the performance of solar cells.     

Naphthacenodithiophene Based Polymers—New Members of the Acenodithiophene Family Exhibiting High Mobility and Power Conversion Efficiency

Wide‐bandgap conjugated polymers with a linear naphthacenodithiophene (NDT) donor unit are herein reported along with their performance in both transistor and solar cell devices. The monomer is synthesized starting from 2,6‐dihydroxynaphthalene with a double Fries rearrangement as the key step. By copolymerization with 2,1,3‐benzothiadiazole (BT) via a palladium‐catalyzed Suzuki coupling reaction, NDT‐BT co‐polymers with high molecular weights and narrow polydispersities are afforded. These novel wide‐bandgap polymers are evaluated as the semiconducting polymer in both organic field effect transistor and organic photovoltaic applications. The synthesized polymers reveal an optical bandgap in the range of 1.8 eV with an electron affinity of 3.6 eV which provides sufficient energy offset for electron transfer to PC₇₀BM acceptors. In organic field effect transistors, the synthesized polymers demonstrate high hole mobilities of around 0.4 cm² V^–1 s^–1. By using a blend of NDT‐BT with PC₇₀BM as absorber layer in organic bulk heterojunction solar cells, power conversion efficiencies of 7.5% are obtained. This value is among the highest obtained for polymers with a wider bandgap (larger than 1.7 eV), making this polymer also interesting for application in tandem or multijunction solar cells.     

Nanostructure and Optoelectronic Characterization of Small Molecule Bulk Heterojunction Solar Cells by Photoconductive Atomic Force Microscopy

Photoconductive atomic force microscopy is employed to study the nano­scale morphology and optoelectronic properties of bulk heterojunction solar cells based on small molecules containing a benzofuran substituted diketopyrrolopyrrole ( DPP ) core (3,6‐bis(5‐(benzofuran‐2‐yl)thiophen‐2‐yl)‐2,5‐bis(2‐ethylhexyl)pyrrolo[3,4‐c]pyrrole‐1,4‐dione, DPP(TBFu)₂ , and [6,6]–phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) , which were recently reported to have power conversion efficiencies of 4.4%. Electron and hole collection networks are visualized for blends with different donor:acceptor ratios. Formation of nanostructures in the blends leads to a higher interfacial area for charge dissociation, while maintaining bicontinuous collection networks; conditions that lead to the high efficiency observed in the devices. An excellent agreement between nanoscale and bulk open‐circuit voltage measurements is achieved by surface modification of the indium tin oxide (ITO) substrate by using aminopropyltrimethoxysilane. The local open‐circuit voltage is linearly dependent on the cathode work function. These results demonstrate that photoconductive atomic force microscopy coupled with surface modification of ITO substrate can be used to study nanoscale optoelectronic phenomena of organic solar cells.     

Photovoltaic device performance of highly regioregular fluorinated poly(3-hexylthiophene)

Highly regioregular poly(3-hexylthiophene) derivatives with varying degrees of fluorine substitution on the thiophene moieties have been demonstrated in photovoltaic devices and characterized using ultraviolet and inverse photoelectron spectroscopy. As fluorine content is increased, an increase in ionization energy of 0.3 eV is observed for 50% fluorination compared to non-fluorinated poly(3-hexylthiophene). The electron affinity is observed to increase to a lesser extent with increased fluorination, consistent with a systematic increase in the optical bandgaps of up to 0.12 eV. Bulk heterojunction photovoltaic devices made from polymer:PC₆₁BM blends achieve power conversion efficiencies of 3%, however film morphologies measured using atomic force microscopy indicate that strong phase separation with increasing fluorination limits device performance. UV–vis spectra of thin films of the fluorinated materials exhibit a long tail in the red, extending to longer wavelengths than non-fluorinated poly(3-hexylthiophene). Photovoltaic devices similarly exhibit non-zero quantum efficiency in this region. This behavior has been attributed to a low energy, interchain charge transfer state.     

Effects of Pre‐reducing Sb‐Doped SnO2 Electrodes in Viologen‐Anchored TiO2 Nanostructure‐Based Electrochromic Devices

In this paper, we investigate the effects of pre‐reducing Sb‐doped SnO₂ (ATO) electrodes in viologen‐anchored TiO₂ (VTO) nanostructure–based electrochromic devices. We find that by pre‐reducing an ATO electrode, the operating voltage of a VTO nanostructure–based electrochromic device can be lowered; consequently, such a device can be operated more stably with less hysteresis. Further, we find that a pre‐reduction of the ATO electrode does not affect the coloration efficiency of such a device. The aforementioned effects of a pre‐reduction are attributed to the fact that a pre‐reduced ATO electrode is more compatible with a VTO nanostructure–based electrochromic device than a non‐pre‐reduced ATO electrode, because of the initial oxidized state of the other electrode of the device, that is, a VTO nanostructure–based electrode. The oxidation state of a pre‐reduced ATO electrode plays a very important role in the operation of a VTO nanostructure–based electrochromic device because it strongly influences charge movement during electrochromic switching.     

Vertical Phase Separated Cesium Fluoride Doping Organic Electron Transport Layer: A Facile and Efficient “Bridge” Linked Heterojunction for Perovskite Solar Cells

In perovskite solar cells (PSCs), the interfaces of the halide perovskite/electron transport layer (ETL) and ETL/metal oxide electrode (MOE) always attract and trap free carriers via the surface electrostatic force, altering quasi‐Fermi level (E_Fq) splitting of contact interfaces, and significantly limit the charge extraction efficiency and intrinsic stability of devices. Herein, a graded “bridge” is first reported to link the MOE and perovskite interfaces by self vertical phase separation doping (PSD), diminishing the side effect of notorious ionic defects via both reinforced interface E_bi and the vacancies filling. Experimental and theoretical results prove that the inhomogeneous distribution of CsF in the bulk or surface of PC₆₁BM would not only form metal–oxygen (M–O) dipole on MOE, reinforcing the interface E_bi, but also create a graded energy bridge to alleviate the disadvantage of band offset raised by the enhanced interface E_bi, which significantly avoid the carrier accumulation and recombination at defective interfaces. Employing PSD, the power conversion efficiency of the devices approaches 21% with a high open‐circuit voltage (1.148 V) and delivers a high stability of 89% after aging 60 days in atmosphere without encapsulation, which is the highest efficiency of organic electron transport layers for n–i–p PSCs.     

CMOS负阻单元逻辑电路及其发展前景

在回顾了多值逻辑(MVL)电路的优点、分析了共振隧穿器件(RTD)电路的特点和比较了各种类型负阻器件性能的基础上,提出了利用CMOS型负阻单元作为基础性器件设计并实现CMOS型逻辑电路的新概念,并指出了此研究领域的几个重点研究内容和方向。     

Air‐Stable Cesium Lead Iodide Perovskite for Ultra‐Low Operating Voltage Resistive Switching

CsPbX₃ (X = halide, Cl, Br, or I) all‐inorganic halide perovskites (IHPs) are regarded as promising functional materials because of their tunable optoelectronic characteristics and superior stability to organic–inorganic hybrid halide perovskites. Herein, nonvolatile resistive switching (RS) memory devices based on all‐inorganic CsPbI₃ perovskite are reported. An air‐stable CsPbI₃ perovskite film with a thickness of only 200 nm is successfully synthesized on a platinum‐coated silicon substrate using low temperature all‐solution process. The RS memory devices of Ag/polymethylmethacrylate (PMMA)/CsPbI₃/Pt/Ti/SiO₂/Si structure exhibit reproducible and reliable bipolar switching characteristics with an ultralow operating voltage (<+0.2 V), high on/off ratio (>10⁶), reversible RS by pulse voltage operation (pulse duration < 1 ms), and multilevel data storage. The mechanical flexibility of the CsPbI₃ perovskite RS memory device on a flexible substrate is also successfully confirmed. With analyzing the influence of phase transition in CsPbI₃ on RS characteristics, a mechanism involving conducting filaments formed by metal cation migration is proposed to explain the RS behavior of the memory device. This study will contribute to the understanding of the intrinsic characteristics of IHPs for low‐voltage resistive switching and demonstrate the huge potential of them for use in low‐power consumption nonvolatile memory devices on next‐generation computing systems.     

Nanoscale Morphology of Conjugated Polymer/Fullerene‐Based Bulk‐ Heterojunction Solar Cells

The relation between the nanoscale morphology and associated device properties in conjugated polymer/fullerene bulk‐heterojunction “plastic solar cells” is investigated. We perform complementary measurements on solid‐state blends of poly[2‐methoxy‐5‐(3,7‐dimethyloctyloxy)]‐1,4‐phenylenevinylene (MDMO‐PPV) and the soluble fullerene C₆₀ derivative 1‐(3‐methoxycarbonyl) propyl‐1‐phenyl [6,6]C₆₁ (PCBM), spin‐cast from either toluene or chlorobenzene solutions. The characterization of the nanomorphology is carried out via scanning electron microscopy (SEM) and atomic force microscopy (AFM), while solar‐cell devices were characterized by means of current–voltage (I–V) and spectral photocurrent measurements. In addition, the morphology is manipulated via annealing, to increase the extent of phase separation in the thin‐film blends and to identify the distribution of materials. Photoluminescence measurements confirm the demixing of the materials under thermal treatment. Furthermore the photoluminescence of PCBM clusters with sizes of up to a few hundred nanometers indicates a photocurrent loss in films of the coarser phase‐separated blends cast from toluene. For toluene‐cast films the scale of phase separation depends strongly on the ratio of MDMO‐PPV to PCBM, as well as on the total concentration of the casting solution. Finally we observe small beads of 20–30 nm diameter, attributed to MDMO‐PPV, in blend films cast from both toluene and chlorobenzene.     

A Novel Fluorene‐Triphenylamine Hybrid That is a Highly Efficient Host Material for Blue‐, Green‐, and Red‐Light‐Emitting Electrophosphorescent Devices

TFTPA (tris[4‐(9‐phenylfluoren‐9‐yl)phenyl]amine), a novel host material that contains a triphenylamine core and three 9‐phenyl‐9‐fluorenyl peripheries, was effectively synthesized through a Friedel‐Crafts‐type substitution reaction. Owing to the presence of its sterically bulky 9‐phenyl‐9‐fluorenyl groups, TFTPA exhibits a high glass transition temperature (186 °C) and is morphologically and electrochemically stable. In addition, as demonstrated from atomic force microscopy measurements, the aggregation of the triplet iridium dopant is significantly diminished in the TFTPA host, resulting in a highly efficient full‐color phosphorescence. The performance of TFTPA ‐based devices is far superior to those of the corresponding mCP‐ or CBP‐based devices, particularly in blue‐ and red‐emitting electrophosphorescent device systems. The efficiency of the FIrpic‐based blue‐emitting device reached 12 % (26 cd A^–1) and 18 lm W^–1 at a practical brightness of 100 cd m^–2; the Ir(piq)₂acac‐based red‐emitting device exhibited an extremely low turn‐on voltage (2.6 V) and a threefold enhancement in device efficiency (9.0 lm W^–1) relative to those of reference devices based on the CBP host material.     

Acceptor‐Substituted S,N‐Heteropentacenes of Different Conjugation Length: Structure–Property Relationships and Solar Cell Performance

The synthesis, optoelectronic, and photovoltaic properties of novel acceptor–donor–acceptor (A–D–A) based π‐conjugated functional molecules 1 – 3, comprising a planar S,N‐heteropentacene as central donor substituted with various terminal acceptor units, such as 1,1‐dicyanovinylene (DCV) and 1‐(1,1‐dicyanomethylene)‐cyclohex‐2‐ene (DCC), are reported. The structural variation of the end groups provides molecules 1 – 3 with gradually increased π‐conjugation due to a rising number of double bonds, which comes from the DCC unit(s). From optoelectronic investigation, structure–property relationships are deduced and the novel A–D–A heteropentacenes 1 – 3 are implemented as photoactive donor component in solution‐processed bulk heterojunction solar cells together with [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester as acceptor. The structural variation in the S,N‐heteropentacenes leads to clear trends in the photovoltaic performance and power conversion efficiencies of up to 4.9% are achieved. Furthermore, due to extension of the double bonds a clear trade‐off between the open circuit voltage (V _OC) and the short circuit current density (J _SC) values is observed. The role of additives on the optimization of the nanoscale morphology and device performance is investigated. The findings presented herein demonstrate that depending on the types of materials the additive may have significantly different effects on the active layer morphology and the device performance.     

Nanoscale Defect Engineering and the Resulting Effects on Domain Wall Dynamics in Ferroelectric Thin Films

Defect engineering is one of the cornerstones of the modern electronics industry. Almost all electronic devices include materials that have been doped by ion bombardment. For materials where crystallinity is essential, such as ferroelectrics, defect type and concentration can vastly influence properties and are often used to optimize device performance. This study shows a method to effectively control the density and position on the nanoscale of defect sites in thin films of Pb(Zr,Ti)O₃ via focused ion beam microscopy. This allows for exceptional clarity of observation of the role of defects in nucleation, polarization switching, and domain wall interaction through investigation with piezoresponse force microscopy and transmission electron microscopy, adding insight to accepted but seldom‐demonstrated facts on defect‐induced effects. This nanoscale defect engineering can be used as a tool to control material properties, and furthermore, a route is demonstrated toward a practical application.     

Difluorobenzothiadiazole‐Based Small‐Molecule Organic Solar Cells with 8.7% Efficiency by Tuning of π‐Conjugated Spacers and Solvent Vapor Annealing

The synthesis of a series of tetrafluorine‐substituted, wide‐bandgap, small molecules consisting of various π‐conjugated spacers (furan, thiophene, selenophene) between indacenodithiophene as the electron‐donating core and the electron‐deficient difluorobenzothiadiazole unit is reported and the effect of the π‐conjugated spacers on the photovoltaic properties is investigated. The alteration of the π‐conjugated spacer enables fine‐tuning of the photophysical properties and energy levels of the small molecules, and allows the adjustment of the charge‐transport properties, the morphology of the photoactive films, as well as their photovoltaic properties. Moreover, most of these devices exhibit superior device performances after CH₂Cl₂ solvent annealing than without annealing, with a high fill factor (0.70–0.75 for all cases). Notably, the devices based on the new molecule BIT4FTh (with thiophene as the spacer) show an outstanding PCE of 8.7% (with an impressive FF of 0.75), considering its wide‐bandgap (1.81 eV), which is among the highest efficiencies reported so far for small‐molecules‐based solar cells. The morphologies of the photoactive layers with/without CH₂Cl₂ solvent annealing are characterized by atomic force microscopy, transmission electron microscopy and two‐dimensional grazing incidence X‐ray diffraction analysis. The results reported here clearly indicate that highly efficient small‐molecules‐based solar cells can be achieved through rational design of their molecular structure and optimization of the phase‐separated morphology via an adapted solvent–vapor annealing process.     

Current-mode CMOS multiple-valued logic circuits

Current-mode CMOS circuits are receiving increasing attention. Current-mode CMOS multiple-valued logic circuits are interesting and may have applications in digital signal processing and computing. In this paper we review several of the current-mode CMOS multiple-valued logic (MVL) circuits that we have studied over the past decade. These circuits include a simple current threshold comparator, current-mode MVL encoders and decoders, current-mode quaternary threshold logic full adders (QFAs), current-mode MVL latches, current-mode latched QFA circuits, and current-mode analog-to-quaternary converter circuits. Each of these circuits is presented and its performance described     

Synthesis of 2H‐1T′ WS2‐ReS2 Heterophase Structures with Atomically Sharp Interface via Hydrogen‐Triggered One‐Pot Growth

2D transition metal chalcogenides (TMDs) with different compositions, phase structures, and properties offer giant opportunities for building novel 2D lateral heterostructures. However, the studies to date have been largely limited to homophase TMD heterostructures, while the construction of heterophase TMD heterostructures remains a challenge. Herein, the synthesis of 2H‐1T′ WS₂‐ReS₂ heterophase junctions with high‐quality interface structure via a hydrogen‐triggered one‐pot growth approach is reported. Sequential introduction of hydrogen during growth system, which acts as a “switch” to selectively turn off the growth of ReS₂ while turning on the growth of WS₂, allows WS₂ to seamlessly grow around ReS₂ to form the WS₂‐ReS₂ heterojunction. Moreover, WS₂ prefers to nucleate at the vertices of ReS₂ grain with fixed lattice orientation, which makes the surrounding WS₂ grains merge into single crystal. Scanning transmission electron microscopy reveals high crystal quality of the heterojunction with an atomically sharp 2H‐1T′ heterophase interface. Transient absorption spectroscopy indicates that the photocarriers can effectively separate at the heterophase interface. Based on the high quality heterophase junction, prominent rectification characteristics and polarization‐dependent photodiode properties are achieved. This study provides a robust way for the controlled synthesis of 2D heterophase structures, which is essential for their fundamental studies and device applications.     

Energy Quantization in Solution‐Processed Layers of Indium Oxide and Their Application in Resonant Tunneling Diodes

The formation of quantized energy states in ultrathin layers of indium oxide (In₂O₃) grown via spin coating and thermally annealed at 200 °C in air is studied. Optical absorption measurements reveal a characteristic widening of the optical band gap with reducing In₂O₃ layer thickness from ≈43 to ≈3 nm in agreement with theoretical predictions for an infinite quantum well. Through sequential deposition of In₂O₃ and gallium oxide (Ga­₂O₃) layers, superlattice‐like structures with controlled dimensionality and spatially varying conduction band characteristics are demonstrated. This simple method is then explored for the fabrication of functional double‐barrier resonant tunneling diodes. Nanoscale current mapping analysis using conductive atomic force microscopy reveals that resonant tunneling is not uniform but localized in specific regions of the apparent device area. The latter observation is attributed to variation in the layer(s) thickness of the In₂O₃ quantum well and/or the Ga₂O₃ barrier layers. Despite the nonidealities, the tremendous potential of solution‐processable oxide semiconductors for the development of quantum effect devices that have so far been demonstrated only via sophisticated growth techniques is demonstrated.     

Identifying a Threshold Impurity Level for Organic Solar Cells: Enhanced First‐Order Recombination Via Well‐Defined PC84BM Traps in Organic Bulk Heterojunction Solar Cells

Small amounts of impurity, even one part in one thousand, in polymer bulk heterojunction solar cells can alter the electronic properties of the device, including reducing the open circuit voltage, the short circuit current and the fill factor. Steady state studies show a dramatic increase in the trap‐assisted recombination rate when [6,6]‐phenyl C₈₄ butyric acid methyl ester (PC₈₄BM) is introduced as a trap site in polymer bulk heterojunction solar cells made of a blend of the copolymer poly[N‐9″‐hepta‐decanyl‐2,7‐carbazole‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole) (PCDTBT) and the fullerene derivative [6,6]‐phenyl C₆₁ butyric acid methyl ester (PC₆₀BM). The trap density dependent recombination studied here can be described as a combination of bimolecular and Shockley–Read–Hall recombination; the latter is dramatically enhanced by the addition of the PC₈₄BM traps. This study reveals the importance of impurities in limiting the efficiency of organic solar cell devices and gives insight into the mechanism of the trap‐induced recombination loss.     

Influence of the Relative Humidity on the Performance of Polymer/TiO2 Photovoltaic Cells

Hydrolysis of titanium(IV ) isopropoxide (TTIP) is a well‐known method for the fabrication of TiO₂. Normally it is made via a sol–gel reaction in the presence of water. In this paper we report on the preparation of flat TiO₂ films for conjugated polymer/TiO₂ photovoltaic cells, from a TTIP/isopropanol solution. It is shown that the morphological structure of the TiO₂ film is strongly dependent on the relative humidity during spin‐coating of the TTIP/isopropanol solution. In bilayer devices consisting of TiO₂/poly[2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylene vinylene] (MDMO‐PPV), a low relative humidity (< 25 %, room temperature) is needed in order to form smooth, transparent TiO₂ films. Increasing the relative humidity results in porous TiO₂ films with a high surface roughness, which leads to shunted devices. Apart from bilayer devices, bulk‐heterojunction (BHJ) hybrid TiO₂:MDMO‐PPV photovoltaic cells have been made, by spin‐coating a mixture of TTIP and MDMO‐PPV in toluene. Again a strong relation was found between the relative humidity during spin‐coating and the current–voltage characteristics of the devices. However, in contrast to the bilayer devices, the best BHJ devices were made at higher relative humidity. The observed performance dependence on relative humidity is discussed in relation to the TiO₂ morphology.     

Nanoscale Resistive Switching in Amorphous Perovskite Oxide (a‐SrTiO3) Memristors

Memristive devices are the precursors to high density nanoscale memories and the building blocks for neuromorphic computing. In this work, a unique room temperature synthesized perovskite oxide (amorphous SrTiO₃: a‐STO) thin film platform with engineered oxygen deficiencies is shown to realize high performance and scalable metal‐oxide‐metal (MIM) memristive arrays demonstrating excellent uniformity of the key resistive switching parameters. a‐STO memristors exhibit nonvolatile bipolar resistive switching with significantly high (10³–10⁴) switching ratios, good endurance (>10⁶I–V sweep cycles), and retention with less than 1% change in resistance over repeated 10⁵ s long READ cycles. Nano‐contact studies utilizing in situ electrical nanoindentation technique reveal nanoionics driven switching processes that rely on isolatedly controllable nano‐switches uniformly distributed over the device area. Furthermore, in situ electrical nanoindentation studies on ultrathin a‐STO/metal stacks highlight the impact of mechanical stress on the modulation of non‐linear ionic transport mechanisms in perovskite oxides while confirming the ultimate scalability of these devices. These results highlight the promise of amorphous perovskite memristors for high performance CMOS/CMOL compatible memristive systems.     

Ultrahigh Stability 3D TI Bi2Se3/MoO3 Thin Film Heterojunction Infrared Photodetector at Optical Communication Waveband

Infrared (IR) detection at 1300–1650 nm (optical communication waveband) is of great significance due to its wide range of applications in commerce and military. Three dimensional (3D) topological insulator (TI) Bi₂Se₃ is considered a promising candidate toward high‐performance IR applications. Nevertheless, the IR devices based on Bi₂Se₃ thin films are rarely reported. Here, a 3D TI Bi₂Se₃/MoO₃ thin film heterojunction photodetector is shown that possesses ultrahigh responsivity (R_i), external quantum efficiency (EQE), and detectivity (D*) in the broadband spectrum (405–1550 nm). The highest on–off ratio of the optimized device can reach up to 5.32 × 10⁴. R_i, D*, and the EQE can reach 1.6 × 10⁴ A W^?1, 5.79 × 10¹¹ cm² Hz^1/2 W^?1, and 4.9 × 10⁴% (@ 405 nm), respectively. Surprisingly, the R_i can achieve 2.61 × 10³ A W^?1 at an optical communication wavelength (@ 1310 nm) with a fast response time (63 µs), which is two orders of magnitude faster than that of other TIs‐based devices. In addition, the device demonstrates brilliant long‐term (>100 days) environmental stability under environmental conditions without any protective measures. Excellent device photoelectric properties illustrate that the 3D TI/inorganic heterojunction is an appropriate way for manufacturing high‐performance photodetectors in the optical communication, military, and imaging fields.