Theoretical study of the influence of the morphology in polymer-based devices functioning

It is well known that the morphology of polymer-based optoelectronic devices can influence their efficiency, since the ways that polymer chains pack inside the active layer can influence not only the charge transport but also the optic properties of the device. By using a mesoscopic model we carried out computer experiments to study the influence of the polymer morphology on the processes of charge injection, transport, recombination and collection by the electrodes opposite to those where the injection of bipolar charge carriers take place. Our results show that for polymer layers where the conjugated segments have perpendicular and random orientation relative to the electrodes surface, the competition between charge collection and charge recombination is affected when the average conjugation length of the polymer strands increase. This effect is more pronounced with the increase of the potential barrier at polymer/electrode interfaces that limit charge injection and increase charge collection. For these molecular arrangements the intra-molecular charge transport plays a major role in device performance, being this effect negligible when the polymer molecules have their axis parallel to the electrodes. Although the polymer morphology modelled in this work is far from real, we believe that our model can give some insights on the role of the microstructure on the functioning of polymer-based devices.     

Modelling the effects of the anode work function in PPV LED

Transparent conducting oxides are widely used as the transparent electrode in polymer light emitting diodes (PLEDs). The physical properties of these materials and consequently device performance strongly depend on their processing and surface treatment. The injection of charge from the transparent electrode into the polymer layer occurs by tunnelling through a potential barrier from the electrode to molecules close to it. This barrier is influenced by the difference in the relevant energy levels of electrode material and polymer molecules, the external applied potential, the Coulomb potential of the charges present in the polymer layer and the potential of their image charges on the electrodes, and may also be altered by electrode degradation effects. A better understanding of the effect of varying this potential barrier on the functioning of PLED is necessary to achieve further improvements in these applications. Here we present a theoretical study of the influence of changes in the potential barrier at the transparent electrode, on bipolar charge evolution through thin polymer layers, in the absence of defects and impurity states, while the other electrode functions as an ohmic contact. Results of a mesoscopic model provide insight into bipolar charge injection, charge and recombination distribution throughout the polymer layer, and may suggest new materials and processing methods to optimize these optoelectronic devices.     

Gate‐Controlled BP–WSe2 Heterojunction Diode for Logic Rectifiers and Logic Optoelectronics

p–n junctions play an important role in modern semiconductor electronics and optoelectronics, and field‐effect transistors are often used for logic circuits. Here, gate‐controlled logic rectifiers and logic optoelectronic devices based on stacked black phosphorus (BP) and tungsten diselenide (WSe₂) heterojunctions are reported. The gate‐tunable ambipolar charge carriers in BP and WSe₂ enable a flexible, dynamic, and wide modulation on the heterojunctions as isotype (p–p and n–n) and anisotype (p–n) diodes, which exhibit disparate rectifying and photovoltaic properties. Based on such characteristics, it is demonstrated that BP–WSe₂ heterojunction diodes can be developed for high‐performance logic rectifiers and logic optoelectronic devices. Logic optoelectronic devices can convert a light signal to an electric one by applied gate voltages. This work should be helpful to expand the applications of 2D crystals.     

High-performance organic optoelectronic devices enhanced by surface plasmon resonance

The surface plasmon effect on polymer solar cells and polymer light-emitting diodes is demonstrated by using metal nanoparticles prepared from block copolymer templates. Light absorption of the polymer thin layer is increased with the incorporation of metallic nanostructures, resulting in a significant surface plasmon effect in the optoelectronic devices.     

Effects of electric field and charge distribution on nanoelectronic processes involving conducting polymers

The injection of charge carriers in conducting polymer layers gives rise to local electric fields which should have serious implications on the charge transport through the polymer layer. The charge distribution and the related electric field inside the ensemble of polymer molecules, with different molecular arrangements at nanoscale, determine whether or not intra-molecular charge transport takes place and the preferential direction for charge hopping between neighbouring molecules. Consequently, these factors play a significant role in the competition between current flow, charge trapping and recombination in polymer-based electronic devices. By suitable Monte Carlo calculations, we simulated the continuous injection of electrons and holes into polymer layers with different microstructures and followed their transport through those polymer networks. Results of these simulations provided a detailed picture of charge and electric field distribution in the polymer layer and allowed us to assess the consequences for current transport and recombination efficiency as well as the distribution of recombination events within the polymer film. In the steady state we found an accumulation of electrons and holes near the collecting electrodes giving rise to an internal electric field which is greater than the external applied field close to the electrodes and lower than the one in the central region of the polymer layer. We also found that a strong variation of electric field inside the polymer layer leads to an increase of recombination events in regions inside the polymer layer where the values of the internal electric field are lower.     

Conjugated Polyelectrolytes Bearing Various Ion Densities: Spontaneous Dipole Generation,Poling‐Induced Dipole Alignment,and Interfacial Energy Barrier Control for Optoelectronic Device Applications

Conjugated polyelectrolytes (CPEs) with π‐delocalized main backbones and ionic pendant groups are intensively studied as interfacial layers for efficient polymer‐based optoelectronic devices (POEDs) because they facilitate facile control of charge injection/extraction barriers. Here, a simple and effective method of performing precise interfacial energy level adjustment is presented by employing CPEs with different thicknesses and various ion densities under electric poling to realize efficient charge injection/extraction of POEDs. The effects of the CPE ion densities and electric (positive or negative) poling on the energy level tuning process are investigated by measuring the open‐circuit voltages and current densities of devices with the structure indium tin oxide/zinc oxide/CPE/organic active layer/molybdenum oxide/gold while changing the CPE film thickness. The performances of inverted polymer light‐emitting diodes and inverted polymer solar cells are remarkably improved by precisely controlling the interfacial energy level matching using optimum CPE conditions.     

Self-assembly of highly ordered conjugated polymer aggregates with long-range energy transfer

Applications of conjugated polymers (CP) in organic electronic devices such as light-emitting diodes and solar cells depend critically on the nature of electronic energy transport in these materials. Single-molecule spectroscopy has revealed their fundamental properties with molecular detail, and recent reports suggest that energy transport in single CP chains can extend over extraordinarily long distances of up to 75 nm. An important question arises as to whether these characteristics are sustained when CP chains agglomerate into a neat solid. Here, we demonstrate that the electronic energy transport in aggregates composed of tens of polymer chains takes place on a similar distance scale as that in single chains. A recently developed molecular-level understanding of solvent vapour annealing has allowed us to develop a technique to control the CP agglomeration process. Aggregates with volumes of at least 45,000 nm(3) (molecular weight ≈ 21 MDa) maintain a highly ordered morphology and show pronounced fluorescence blinking behaviour, indicative of substantially long-range energy transport. Our findings provide a new lens through which the ordering of single CP chains and the evolution of their morphological and optoelectronic properties can be observed, which will ultimately enable the rational design of improved CP-based devices.     

Interface and Defect Engineering for Metal Halide Perovskite Optoelectronic Devices

Metal halide perovskites have been in the limelight in recent years due to their enormous potential for use in optoelectronic devices, owing to their unique combination of properties, such as high absorption coefficient, long charge‐carrier diffusion lengths, and high defect tolerance. Perovskite‐based solar cells and light‐emitting diodes (LEDs) have achieved remarkable breakthroughs in a comparatively short amount of time. As of writing, a certified power conversion efficiency of 22.7% and an external quantum efficiency of over 10% have been achieved for perovskite solar cells and LEDs, respectively. Interfaces and defects have a critical influence on the properties and operational stability of metal halide perovskite optoelectronic devices. Therefore, interface and defect engineering are crucial to control the behavior of the charge carriers and to grow high quality, defect‐free perovskite crystals. Herein, a comprehensive review of various strategies that attempt to modify the interfacial characteristics, control the crystal growth, and understand the defect physics in metal halide perovskites, for both solar cell and LED applications, is presented. Lastly, based on the latest advances and breakthroughs, perspectives and possible directions forward in a bid to transcend what has already been achieved in this vast field of metal halide perovskite optoelectronic devices are discussed.     

3D Printed Polymer Photodetectors

Extrusion‐based 3D printing, an emerging technology, has been previously used in the comprehensive fabrication of light‐emitting diodes using various functional inks, without cleanrooms or conventional microfabrication techniques. Here, polymer‐based photodetectors exhibiting high performance are fully 3D printed and thoroughly characterized. A semiconducting polymer ink is printed and optimized for the active layer of the photodetector, achieving an external quantum efficiency of 25.3%, which is comparable to that of microfabricated counterparts and yet created solely via a one‐pot custom built 3D‐printing tool housed under ambient conditions. The devices are integrated into image sensing arrays with high sensitivity and wide field of view, by 3D printing interconnected photodetectors directly on flexible substrates and hemispherical surfaces. This approach is further extended to create integrated multifunctional devices consisting of optically coupled photodetectors and light‐emitting diodes, demonstrating for the first time the multifunctional integration of multiple semiconducting device types which are fully 3D printed on a single platform. The 3D‐printed optoelectronic devices are made without conventional microfabrication facilities, allowing for flexibility in the design and manufacturing of next‐generation wearable and 3D‐structured optoelectronics, and validating the potential of 3D printing to achieve high‐performance integrated active electronic materials and devices.     

Nanoparticle‐Enhanced Silver‐Nanowire Plasmonic Electrodes for High‐Performance Organic Optoelectronic Devices

Improved performance in plasmonic organic solar cells (OSCs) and organic light‐emitting diodes (OLEDs) via strong plasmon‐coupling effects generated by aligned silver nanowire (AgNW) transparent electrodes decorated with core–shell silver–silica nanoparticles (Ag@SiO₂NPs) is demonstrated. NP‐enhanced plasmonic AgNW (Ag@SiO₂NP–AgNW) electrodes enable substantially enhanced radiative emission and light absorption efficiency due to strong hybridized plasmon coupling between localized surface plasmons (LSPs) and propagating surface plasmon polaritons (SPPs) modes, which leads to improved device performance in organic optoelectronic devices (OODs). The discrete dipole approximation (DDA) calculation of the electric field verifies a strongly enhanced plasmon‐coupling effect caused by decorating core–shell Ag@SiO₂NPs onto the AgNWs. Notably, an electroluminescence efficiency of 25.33 cd A^?1 (at 3.2 V) and a power efficiency of 25.14 lm W^?1 (3.0 V) in OLEDs, as well as a power conversion efficiency (PCE) value of 9.19% in OSCs are achieved using hybrid Ag@SiO₂NP–AgNW films. These are the highest values reported to date for optoelectronic devices based on AgNW electrodes. This work provides a new design platform to fabricate high‐performance OODs, which can be further explored in various plasmonic and optoelectronic devices.     

Progress in the growth and characterization of nonpolar ZnO films

Zinc oxide (ZnO) is an important material for its potential applicability to short-wavelength optoelectronic devices such as light emitting diodes (LEDs) and laser diodes (LDs). Nonpolar ZnO materials have been developed in recent years to avoid the strong internal electric fields in active regions of optoelectronic devices and improve luminescence efficiency. The growth and physical properties of nonpolar ZnO films, which are essential for fabricating optoelectronic devices and improving device performance, still remains not well understood. In this review, the technologies for preparation of nonpolar ZnO epitaxial films are summarized, and recent developments are described. Then the main characteristics of nonpolar ZnO films are discussed with the deviations from those of polar ZnO films, including morphology, structural defects, anisotropic strain, optical, and electrical properties. The anisotropic electron transport and strains correlated strongly with the anisotropic surface morphologies of nonpolar ZnO films. Fabricating nonpolar ZnO films with high quality should be further developed to decrease the structural defect densities for substantial improvement of device performance, and intensive studies on their characteristics are especially important for device applications.     

Semiconducting polymer LEDs

Technologies based on organic semiconductors may answer the increasing demands that consumers make in the areas of large-area electronics, lightweight displays, and portable computing. Advances in scientific understanding, technology, and device performance have occurred particularly rapidly in the area of polymer light-emitting diodes (LEDs). Material properties and economic considerations suggest that polymer LEDs are the devices most likely to win the race to applications that produce light on inorganic substrates such as glass and silicon, as well as plastic substrates.The field of semiconducting polymers has its root in the 1977 discovery of the semiconducting properties of polyacetylene¹. This breakthrough earned Alan Heeger, Alan MacDiarmid, and Hideki Shirakawa the 2000 Nobel Prize in Chemistry for ‘the discovery and development of conductive polymers’2, 3, 4, 5. Other review articles capture how more than two decades of developments in the physical and chemical understanding of these novel materials has led to new device applications as active and passive electronic and optoelectronic devices ranging from diodes and transistors to polymer LEDs, photodiodes, lasers, and solar cells6, 7, 8, 9, 10, 11. Much interest in plastic devices derives from the opportunities to use clever control of polymer structure combined with relatively economical polymer synthesis and processing techniques to obtain simultaneous control over electronic, optical, chemical, and mechanical features⁵. This article focuses on the advances leading to polymer LEDs12, 13, 14.     

Synergistic Cascade Carrier Extraction via Dual Interfacial Positioning of Ambipolar Black Phosphorene for High-Efficiency Perovskite Solar Cells

2D black phosphorene (BP) carries a stellar set of physical properties such as conveniently tunable bandgap and extremely high ambipolar carrier mobility for optoelectronic devices. Herein, the judicious design and positioning of BP with tailored thickness as dual-functional nanomaterials to concurrently enhance carrier extraction at both electron transport layer/perovskite and perovskite/hole transport layer interfaces for high-efficiency and stable perovskite solar cells is reported. The synergy of favorable band energy alignment and concerted cascade interfacial carrier extraction, rendered by concurrent positioning of BP, delivered a progressively enhanced power conversion efficiency of 19.83% from 16.95% (BP-free). Investigation into interfacial engineering further reveals enhanced light absorption and reduced trap density for improved photovoltaic performance with BP incorporation. This work demonstrates the appealing characteristic of rational implementation of BP as dual-functional transport material for a diversity of optoelectronic devices, including photodetectors, sensors, light-emitting diodes, etc.     

Reversible tuning of plasmon coupling in gold nanoparticle chains using ultrathin responsive polymer film

We demonstrate large and reversible tuning of plasmonic properties of gold nanoparticles mediated by the reversible breaking and making of linear and branched chains of gold nanoparticles adsorbed on an ultrathin (1 nm) responsive polymer film. Atomic force microscopy revealed that at pH below the isoelectric point of the polybase (extended state of the polymer chains), gold nanoparticles adsorbed on the polymer layer existed primarily as individual nanoparticles. On the other hand, at higher pH, the polymer chains transition from coil to globule (collapsed) state, resulting in the formation of linear and branched chains with strong interparticle plasmon coupling. Reversible aggregation of the nanoparticles resulted in large and reversible change in the optical properties of the metal nanostructure assemblies. In particular, we observed a large redistribution of the intensity between the individual and coupled plasmon bands and a large shift (nearly 95 nm) in the coupled plasmon band with change in pH. Large tunability of plasmonic properties of the metal nanostructure chains reported here is believed to be caused by the chain aggregates of nanoparticles and un-cross-linked state of the adsorbed polymer enabling large changes in polymer chain conformation.     

Internal electrical field distribution in double layer polymer stacks as studied by electroabsorption

We report on the application of in situ electroabsorption measurements for the evaluation of local electric field distributions in double layer polymer films. The temporal dependence of the measured signal indicates that besides the relation of ohmic resistivities of the different polymer layers, the influence of the electric properties of polymer/electrode and polymer/polymer interfaces must also be considered for the DC field, which is present in the electrooptic active layer.     

Significant vertical phase separation in solvent-vapor-annealed poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) composite films leading to better conductivity and work function for high-performance indium tin oxide-free optoelectronics

In the present study, a novel polar-solvent vapor annealing (PSVA) was used to induce a significant structural rearrangement in poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) films in order to improve their electrical conductivity and work function. The effects of polar-solvent vapor annealing on PEDOT:PSS were systematically compared with those of a conventional solvent additive method (SAM) and investigated in detail by analyzing the changes in conductivity, morphology, top and bottom surface composition, conformational PEDOT chains, and work function. The results confirmed that PSVA induces significant phase separation between excess PSS and PEDOT chains and a spontaneous formation of a highly enriched PSS layer on the top surface of the PEDOT:PSS polymer blend, which in turn leads to better 3-dimensional connections between the conducting PEDOT chains and higher work function. The resultant PSVA-treated PEDOT:PSS anode films exhibited a significantly enhanced conductivity of up to 1057 S cm(-1) and a tunable high work function of up to 5.35 eV. The PSVA-treated PEDOT:PSS films were employed as transparent anodes in polymer light-emitting diodes (PLEDs) and polymer solar cells (PSCs). The cell performances of organic optoelectronic devices with the PSVA-treated PEDOT:PSS anodes were further improved due to the significant vertical phase separation and the self-organized PSS top surface in PSVA-treated PEDOT:PSS films, which can increase the anode conductivity and work function and allow the direct formation of a functional buffer layer between the active layer and the polymeric electrode. The results of the present study will allow better use and understanding of polymeric-blend materials and will further advance the realization of high-performance indium tin oxide (ITO)-free organic electronics.     

Evaluation of reactive ion etching processes for fabrication of integrated GaAs/AlGaAs optoelectronic devices

Reactive ion etching (RIE) was used for the fabrication of GaAs/AlGaAs optoelectronic devices (laser diodes and photodetectors) for optical interconnect applications. Smooth, vertical sidewalls with a smooth surface at the field were obtained after optimizing RIE conditions in BCl₃-formed plasma. Accurate in-situ monitoring of the etching process was realized by laser interferometry end-point detection. This led to good process control and reproducibility of the demanding fabrication of the optoelectronic devices. The RIE etching process did not affect the electrical properties of the device by increasing the surface recombination currents. Lasers with etched mirrors exhibited a threshold current density of 970 A cm⁻², which is one of the best values ever reported. The feasibility of a simple technology for the fabrication of optoelectronic circuits, based on a BCl₃ RIE process for laser mirror etching, has been demonstrated.     

Influence of the thickness of electrochemically deposited polyaniline used as hole transporting layer on the behaviour of polymer light-emitting diodes

An experimental study about the influence of the thickness of electrochemically deposited polyaniline (PANI), used as hole-transporting layer, on the behaviour of polymer light emitting diodes is presented. Two sets of devices with a different conjugated polymer used as active layer were prepared. Poly(9-vinylcarbazole) was used for the first type of devices, whereas Poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylene-vinylene] was used for the second type. Each set consists of five polymeric diodes in which the hole-transporting layer has been varied. In one case of each set no layer was deposited, in other one a Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) layer was deposited, and in the rest of the diodes a different thickness of electrochemically deposited PANI was employed. The optic and electronic characterization of the devices show that controlling the thickness of the PANI hole transporting layer, both the maximum emission peak of the electroluminescence curves and the driving voltage could be tuned. Furthermore, an exponential behaviour has been demonstrated for the maximum intensity of the electroluminescence curves as a function of the applied excitation voltage between anode and cathode.     

Efficiency enhancement in organic solar cells with ferroelectric polymers

The recombination of electrons and holes in semiconducting polymer-fullerene blends has been identified as a main cause of energy loss in organic photovoltaic devices. Generally, an external bias voltage is required to efficiently separate the electrons and holes and thus prevent their recombination. Here we show that a large, permanent, internal electric field can be ensured by incorporating a ferroelectric polymer layer into the device, which eliminates the need for an external bias. The electric field, of the order of 50 V μm(-1), potentially induced by the ferroelectric layer is tens of times larger than that achievable by the use of electrodes with different work functions. We show that ferroelectric polymer layers enhanced the efficiency of several types of organic photovoltaic device from 1-2% without layers to 4-5% with layers. These enhanced efficiencies are 10-20% higher than those achieved by other methods, such as morphology and electrode work-function optimization. The devices show the unique characteristics of ferroelectric photovoltaic devices with switchable diode polarity and tunable efficiency.     

Two‐Dimensional Materials for Halide Perovskite‐Based Optoelectronic Devices

Halide perovskites have high light absorption coefficients, long charge carrier diffusion lengths, intense photoluminescence, and slow rates of non‐radiative charge recombination. Thus, they are attractive photoactive materials for developing high‐performance optoelectronic devices. These devices are also cheap and easy to be fabricated. To realize the optimal performances of halide perovskite‐based optoelectronic devices (HPODs), perovskite photoactive layers should work effectively with other functional materials such as electrodes, interfacial layers and encapsulating films. Conventional two‐dimensional (2D) materials are promising candidates for this purpose because of their unique structures and/or interesting optoelectronic properties. Here, we comprehensively summarize the recent advancements in the applications of conventional 2D materials for halide perovskite‐based photodetectors, solar cells and light‐emitting diodes. The examples of these 2D materials are graphene and its derivatives, mono‐ and few‐layer transition metal dichalcogenides (TMDs), graphdiyne and metal nanosheets, etc. The research related to 2D nanostructured perovskites and 2D Ruddlesden–Popper perovskites as efficient and stable photoactive layers is also outlined. The syntheses, functions and working mechanisms of relevant 2D materials are introduced, and the challenges to achieving practical applications of HPODs using 2D materials are also discussed.