Charge Transport in Amorphous Organic Semiconductors: Effects of Disorder,Carrier Density,Traps, and Scatters

In real devices, organic semiconductors are largely amorphous. Because accurate molecular packing in them cannot be obtained, the relationship between the molecular structure and the material properties can be difficult to understand. Nevertheless, knowing the charge transport processes is essential to material and device engineering. In amorphous organic semiconductors, charge transport is often apprehended as a hopping process that can be described using the Marcus or Miller Abrahams equations. The intrinsic disorder and frequently present traps have a great influence on the charge mobility. Carrier density, which would affect the effective density of states and create space charge perturbations, is also one important factor in the charge transport process. Herein, recent advances in the charge transport mechanism in amorphous organic semiconductors are summarized. The influences of disorder, carrier density, traps, and scatters are discussed in detail.     

High photoelectric conversion efficiency of metal phthalocyanine/fullerene heterojunction photovoltaic device

This paper introduces the fundamental physical characteristics of organic photovoltaic (OPV) devices. Photoelectric conversion efficiency is crucial to the evaluation of quality in OPV devices, and enhancing efficiency has been spurring on researchers to seek alternatives to this problem. In this paper, we focus on organic photovoltaic (OPV) devices and review several approaches to enhance the energy conversion efficiency of small molecular heterojunction OPV devices based on an optimal metal-phthalocyanine/fullerene (C(60)) planar heterojunction thin film structure. For the sake of discussion, these mechanisms have been divided into electrical and optical sections: (1) Electrical: Modification on electrodes or active regions to benefit carrier injection, charge transport and exciton dissociation; (2) Optical: Optional architectures or infilling to promote photon confinement and enhance absorption.     

Ferrocene-terminated monolayers covalently bound to hydrogen-terminated silicon surfaces. Toward the development of charge storage and communication devices

The combination of monocrystalline silicon's well-defined structure and the ability to prepare hydrogen-terminated surfaces (Si-H) easily and reproducibly has made this material a very attractive substrate for immobilizing functional molecules. The functionalization of Si-H using the covalent attachment of organic monolayers has received intense attention due to the numerous potential applications of controlled and robust organic/Si interfaces. Researchers have investigated these materials in diverse fields such as molecular electronics, chemistry, and bioanalytical chemistry. Applications include the preparation of surface insulators, the incorporation of chemical or biochemical functionality at interfaces for use in photovoltaic conversion, and the development of new chemical and biological sensing devices. Unlike those of gold, silicon's electronic properties are tunable, and researchers can directly integrate silicon-based devices within electronic circuitry. Moreover, the technological processes used for the micro- and nanopatterning of silicon are numerous and mature enough for producing highly miniaturized functional electronic components. In this Account, we describe a powerful approach that integrates redox-active molecules, such as ferrocene, onto silicon toward electrically addressable systems devoted to information storage or transfer. Ferrocene exhibits attractive electrochemical characteristics: fast electron-transfer rate, low oxidation potential, and two stable redox states (neutral ferrocene and oxidized ferrocenium). Accordingly, ferrocene-modified silicon surfaces could be used as charge storage components with the bound ferrocene center as the memory element. Upon application of a positive potential to silicon, ferrocene is oxidized to its corresponding ferrocenium form. This redox change is equivalent to the change of a bit of information from the "0" to "1" state. To erase the stored charge and return the device to its initial state, a low potential must be applied to reduce the whole generated ferrocenium. In this type of application, the electron is transferred from the ferrocene headgroups to the underlying conducting silicon surface by a tunneling process across the monolayer. To produce a stable and reproducible electrical response, this process must be efficient, fast, and reversible. The stability, charge density, and capacitance performances of high-quality ferrocene-terminated monolayers could compete with those of the existing semiconductor-based memory devices, such as dynamic random access memories, DRAMs. Moreover, we provide experimental evidence that a series of immobilized ferrocene centers can efficiently communicate via a lateral electron hopping process. Using these modified interfaces, we demonstrate that the thin redox-active monolayer can behave as a purely conducting material, highlighting an unprecedented very fast electron communication between immobilized redox groups. Perhaps more importantly, the surface coverage of ferrocene allows us to precisely control the rate of this process. Such characteristics are relevant not only for electrocatalytic reactions but also for widening the potential applications of these assemblies to novel molecular electronic devices (e.g. chemiresistors, chemically sensitive field-effect transistors (CHEMFETs)) and redox chemistry on insulating surfaces.     

Toward the ideal organic light-emitting diode. The versatility and utility of interfacial tailoring by cross-linked siloxane interlayers

Small molecule and polymer organic light-emitting diodes (OLEDs) show promise of revolutionizing display technologies. Hence, these devices and the materials that render them functional are the focus of intense scientific and technological interest. The archetypical multilayer OLED heterostructure introduces numerous chemical and physical challenges to the development of efficient and robust devices. It is demonstrated here that robust, pinhole-free, conformal, adherent films with covalently interlinked structures are readily formed via self-assembling or spin-coating organosilane-functionalized molecular precursors at the anode-hole transport layer interface. In this manner, molecularly "engineered" hole transport and hydrocarbon anode functionalization layers can be introduced with thicknesses tunable from the angstrom to nanometer scale. These investigations unequivocally show that charge injection and continuity at the anode-hole transport layer interface, hence OLED durability and efficiency, can be substantially enhanced by these tailored layers.     

On the phase behaviour of organic semiconductors

The physical organisation, from the molecular to the macroscale, of functional organic matter such as polymer semiconductors can profoundly affect the properties and features of the resulting architectures and their consequent performance when used as active layers in organic optoelectronic devices, including organic thin‐film field‐effect transistors, organic light‐emitting diodes or organic photovoltaic cells. Here, we present a survey on the principles of structure development from the liquid phase of this interesting and broad class of materials with focus on how to manipulate their phase transformations and solid‐state order to tailor and manipulate the final ‘morphology’ towards technological and practical applications. Copyright © 2012 Society of Chemical Industry     

Solid‐state dye‐sensitized and bulk heterojunction solar cells using TiO2 and ZnO nanostructures: recent progress and new concepts at the borderline

In the field of photovoltaic energy conversion, hybrid inorganic/organic devices represent promising alternatives to standard photovoltaic systems in terms of exploiting the specific features of both organic semiconductors and inorganic nanomaterials. Two main categories of hybrid solar cells coexist today, both of which make much use of metal oxide nanostructures based on titanium dioxide (TiO₂) and zinc oxide (ZnO) as electron transporters. These metal oxides are cheap to synthesise, are non‐toxic, are biocompatible and have suitable charge transport properties, all these features being necessary to demonstrate highly efficient solar cells at low cost. Historically, the first hybrid approach developed was the dye‐sensitized solar cell (DSSC) concept based on a nanostructured porous metal oxide electrode sensitized by a molecular dye. In particular, solid‐state hybrid DSSCs, which reduce the complexity of cell assembly, demonstrate very promising performance today. The second hybrid approach exploits the bulk heterojunction (BHJ) concept, where conjugated polymer/metal oxide interfaces are used to generate photocurrent. In this context, we review the recent progress and new concepts in the field of hybrid solid‐state DSSC and BHJ solar cells based on TiO₂ and ZnO nanostructures, incorporating dyes and conjugated polymers. We point out the specificities in common hybrid device structures and give an overview on new concepts, which couple and exploit the main advantages of both DSSC and BHJ approaches. In particular, we show that there is a trend of convergence between both DSSC and BHJ approaches into mixed concepts at the borderline which may allow in the near future the development of hybrid devices for competitive photovoltaic energy conversion. Copyright © 2011 Society of Chemical Industry     

Organic Solar Cells: Understanding the Role of F?rster Resonance Energy Transfer

Organic solar cells have the potential to become a low-cost sustainable energy source. Understanding the photoconversion mechanism is key to the design of efficient organic solar cells. In this review, we discuss the processes involved in the photo-electron conversion mechanism, which may be subdivided into exciton harvesting, exciton transport, exciton dissociation, charge transport and extraction stages. In particular, we focus on the role of energy transfer as described by Förster resonance energy transfer (FRET) theory in the photoconversion mechanism. FRET plays a major role in exciton transport, harvesting and dissociation. The spectral absorption range of organic solar cells may be extended using sensitizers that efficiently transfer absorbed energy to the photoactive materials. The limitations of Förster theory to accurately calculate energy transfer rates are discussed. Energy transfer is the first step of an efficient two-step exciton dissociation process and may also be used to preferentially transport excitons to the heterointerface, where efficient exciton dissociation may occur. However, FRET also competes with charge transfer at the heterointerface turning it in a potential loss mechanism. An energy cascade comprising both energy transfer and charge transfer may aid in separating charges and is briefly discussed. Considering the extent to which the photo-electron conversion efficiency is governed by energy transfer, optimisation of this process offers the prospect of improved organic photovoltaic performance and thus aids in realising the potential of organic solar cells.     

One-dimensional self-assembly of planar pi-conjugated molecules: adaptable building blocks for organic nanodevices

In general, fabrication of well-defined organic nanowires or nanobelts with controllable size and morphology is not as advanced as for their inorganic counterparts. Whereas inorganic nanowires are widely exploited in optoelectronic nanodevices, there remains considerable untapped potential in the one-dimensional (1D) organic materials. This Account describes our recent progress and discoveries in the field of 1D self-assembly of planar pi-conjugated molecules and their application in various nanodevices including the optical and electrical sensors. The Account is aimed at providing new insights into how to combine elements of molecular design and engineering with materials fabrication to achieve properties and functions that are desirable for nanoscale optoelectronic applications. The goal of our research program is to advance the knowledge and develop a deeper understanding in the frontier area of 1D organic nanomaterials, for which several basic questions will be addressed: (1) How can one control and optimize the molecular arrangement by modifying the molecular structure? (2) What processing factors affect self-assembly and the final morphology of the fabricated nanomaterials; how can these factors be controlled to achieve the desired 1D nanomaterials, for example, nanowires or nanobelts? (3) How do the optoelectronic properties (e.g., emission, exciton migration, and charge transport) of the assembled materials depend on the molecular arrangement and the intermolecular interactions? (4) How can the inherent optoelectronic properties of the nanomaterials be correlated with applications in sensing, switching, and other types of optoelectronic devices? The results presented demonstrate the feasibility of controlling the morphology and molecular organization of 1D organic nanomaterials. Two types of molecules have been employed to explore the 1D self-assembly and the application in optoelectronic sensing: one is perylene tetracarboxylic diimide (PTCDI, n-type) and the other is arylene ethynylene macrocycle (AEM, p-type). The materials described in this project are uniquely multifunctional, combining the properties of nanoporosity, efficient exciton migration and charge transport, and strong interfacial interaction with the guest (target) molecules. We see this combination as enabling a range of important technological applications that demand tightly coupled interaction between matter, photons, and charge. Such applications may include optical sensing, electrical sensing, and polarized emission. Particularly, the well-defined nanowires fabricated in this study represent unique systems for investigating the dimensional confinement of the optoelectronic properties of organic semiconductors, such as linearly polarized emission, dimensionally confined exciton migration, and optimal pi-electronic coupling (favorable for charge transport). Combination of these properties will make the 1D self-assembly ideal for many orientation-sensitive applications, such as polarized light-emitting diodes and flat panel displays.     

How the structural deviations on the backbone of conjugated polymers influence their optoelectronic properties and photovoltaic performance

The design of novel conjugated polymers with appropriate frontier orbital energy levels, low band gap (LBG) and suitable carrier transport properties are needed to improve the power conversion efficiency (PCE) of organic photovoltaic devices. In this review, a detailed structure-property relationship study is presented, by identifying those chemical entities in the backbone of conjugated polymers that are responsible for the modification of optoelectronic properties towards high photovoltaic performance.     

Improving the performance of inverted organic solar cells by embedding silica‐coated silver nanoparticles deposited by electron‐beam evaporation

Embedding metallic nanoparticles (MNPs) in organic solar cells (OSCs) is proposed as one of the promising strategies to enhance their photovoltaic performance owing to localized surface plasmon resonance, light scattering effects or a synergy of both effects derived from the MNPs. However, it has been demonstrated that MNPs wrapped by a thin dielectric silica shell can lead to better photovoltaic yield than bare MNPs due to the presence of the dielectric shell which avoids direct contact between the active layer and the MNPs, reducing the charge recombination and the exciton quenching loss at the metal surface. In this study, we report an alternative solution using an ultrathin dielectric layer coating silver nanoparticles (Ag NPs) for improving the performance of plasmonic inverted OSCs instead of the use of metal–dielectric core–shell NPs. A silica (SiO₂) layer 5 nm thick coating evaporated Ag NPs with an average size of 60 nm is deposited on top of the zinc oxide (ZnO) layer used as the electron transport layer, leading to a significant improvement in the short‐circuit current density (J_sc) and the power conversion efficiency (PCE) of the inverted OSCs. The electron‐beam evaporation method is employed for controlled deposition of Ag NPs and SiO₂ on the ZnO layer. The plasmonic devices resulted in an 18% and 14.1% enhancement of the J_sc and PCE, respectively, compared to reference devices. This increase of the photoelectric parameters in plasmonic devices is attributed not only to the plasmonic effects originating from the Ag NPs but also to the ultrathin silica layer which can contribute to facilitating charge extraction. © 2019 Society of Chemical Industry     

Simplified p-i-n organic light-emitting diodes using an universal ambipolar material

A simplified p-i-n organic light-emitting diode with only one organic material in the emitting layer and the charge transport layer was developed. A blue light-emitting material, 2-methyl-9,10-di(2-naphthyl) anthracene (MADN), was used as a host in the light-emitting layer, a hole transport material and an electron transport material. P type and n type dopants were doped into the MADN and the p-doped and n-doped MADN layers were used as charge transport layers to fabricate p-i-n type devices. The p-i-n type simple blue device with the MADN in all organic layers showed better power efficiency than the conventional organic light-emitting diodes.     

Effect of the regioregularity of poly(3‐hexylthiophene) on the performances of organic photovoltaic devices

BACKGROUND: The highest efficiencies of bulk‐heterojunction solar cells from poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl C₆₁‐butyric acid methyl ester (PCBM) reported so far are close to 6%. Phenomena occurring during the photovoltaic process, such as the creation, diffusion and separation of excitons, as well as charge carrier transport, are governed by the active layer morphology. The latter phenomenon, which depends on the self‐organization of P3HT, can be influenced by its degree of regioregularity. The aim of this work is to clarify the relationship between the regioregularity of P3HT, the composition of P3HT/PCBM blends and the performances of photovoltaic devices. RESULTS: Two types of P3HTs with different degrees of regioregularity have been synthesized and used as active layers with PCBM in photovoltaic cells. The higher performances in photovoltaic devices are obtained for high‐regioregular P3HT and can be explained considering the self‐organizing properties of high‐regioregular P3HT, leading to higher sunlight absorption and higher hole mobilities. In addition, this report demonstrates the importance of the ratio of P3HT versus PCBM in correlation with the regioregularity of P3HT on the optical properties, charge transport and characteristics of photovoltaic cells. CONCLUSION: We have investigated the dependence of the photovoltaic properties of P3HT/PCBM blend‐based photovoltaic devices on the degree of regioregularity of P3HT. We find that the best performance is exhibited by devices based on highly regioregular P3HT. Also, the best performances are not obtained for the same P3HT:PCBM weight ratios for high‐regioregular P3HT (1:0.8) and low‐regioregular P3HT (1:3). Copyright © 2007 Society of Chemical Industry     

Electrochemical oxidation-induced polymerization of 5,10,15,20-tetrakis[3-(N-ethylcarbazoyl)]porphyrin. Formation and characterization of a novel electroactive porphyrin thin film

The formation and characterization of novel polymer modified Pt and ITO electrodes obtained by electropolymerization is depicted. The presences of porphyrin, a powerful optical and redox active center, together with carbazole, a well-known hole-transporting material, confer to the polymer electric and optical activity, with potential application in the development of organic optoelectronic devices. 5,10,15,20-Tetrakis[3-(N-ethylcarbazoyl)]porphyrin form conductive, stable and reproducible electropolymer films. Combined electrochemical and spectroscopic studies show that the electropolymerization mechanism involves the dimerization of carbazole units. During coupling of carbazole radicals, protons are released to the media and porphyrin film is protonated, generating the porphyrin dication. The observation of the characteristic porphyrin electronic spectrum after reduction of the film indicates that the tetrapyrrolic macrocycle remains unaltered in the electrogenerated polymer. The formation of a broad band that extends into the near-IR region upon polymer oxidation is in agreement with the presence of a conducting polymer with good charge transport capability.     

Organic solar cell materials and active layer designs—improvements with carbon nanotubes: a review

Organic solar cells offer an opportunity to diversify renewable energy sources owing to their low technological cost. They are amenable to large surfaces and can easily be integrated into buildings. It is necessary, however, to improve their energy efficiency and durability for the development of a sustainable technology. In these devices, photovoltaic conversion is based on the separation of photogenerated charges at an interface between electron donor and acceptor materials, which imposes some constraints on the photoactive layer of the cells. In this paper, which includes some of our studies, we address optimization of the active layer: absorption and exciton dissociation steps, the open‐circuit voltage and the active layer morphology. A promising direction proposed to improve the active layer morphology and cell efficiency is the incorporation of highly anisotropic nanoparticles such as carbon nanotubes, which may facilitate charge transport to the electrodes. Dispersion and orientation of the nanotubes in the organic matrix are discussed and we suggest an ideal model polymer solar cell which will maximize performance of the cells by using carbon nanotubes in the active layer. Copyright © 2012 Society of Chemical Industry     

Photoelectronic and transport properties of polypyrrole doped with a dianionic dye

Polypyrrole (PPy) doped with dodecylsulfate (DS) and an organic dye (indigo carmine, IC) was electrochemically prepared and characterized by Raman spectroscopy and X-ray diffraction (XRD). The photoelectrochemical properties of PPy-DS and PPy-DS-IC in contact with an electrolytic solution containing a redox couple were studied using the theories for the semiconductor ∣ electrolyte interface. Results indicate that the system containing IC presents a higher photocurrent density under polychromatic illumination and faster response time when compared with PPy-DS. This fact was assigned to the formation of molecular-scale paths in PPy-DS-IC. The IC molecules lying perpendicularly between PPy chains, as confirmed by the X-ray analysis, could facilitate the mass transport at the interface and increase the ordering degree to provide better electronic charge transfer in the bulk. Although the photoelectrochemical devices presented here do not present all the properties of inorganic-based devices, we discuss some strategies to enhance the photoelectrochemical properties and response time of conducting polymers used in these type of systems.     

Photovoltaic performance and impedance spectroscopy of ZnS-Cu-Go nanocomposites

In this work, novel, non-toxic and cost effective ZnS-Cu-GO nanocomposite is synthesized via wet chemical route to study its photovoltaic properties. Three samples including ZnS,ZnS-Cu and ZnS-Cu-GO were prepared and deposited as sensitizers on ZnO coated FTO substrates to assemble PV devices.The samples were characterized using UV–Vis NIR spectroscopy, Atomic force microscopy (AFM).Electrochemical impedance spectroscopy (EIS) and AM 1.5 Sun Simulator. It was observed that ZnS-Cu-GO exhibitedsuperiorchargetransport, remarkably high open circuit voltage(0.8 V) and Fill factor (0.806).The current density significantly enhanced and maximum solar cell efficiency was observed for ZnS-Cu-GO based PV device. A pronounced red shift of 360 nm in the absorption spectra was observed in the ZnS-Cu-GO due to fine dispersion of GO sheets.The AFM analysis showed that incorporation of GO and Cu maximized grain density and trench like grain boundaries in ZnS-Cu-GO which facilitated charge transport mechanism.A detailed electrochemical impedance study to probe charge dynamics in the prepared PV devices is presented herein.     

Conjugated polyelectrolytes: A new class of semiconducting material for organic electronic devices

This feature article presents a short review of the recent developments in the synthesis of conjugated polyelectrolytes (CPEs) along with their applications in organic optoelectronic devices with particular focus on the molecular structures of CPEs with ionic functionality, synthetic approaches, and their utilization as an interfacial layer. The orthogonal solubility of the CPEs allows the simple preparation of multilayer organic devices by solution casting on top of a nonpolar organic photoactive layer without disturbing the interfaces, showing their effectiveness in tuning the electronic structures at the interfaces for improving the charge carrier transport and resulting device properties. These achievements highlight the dynamic nature of CPEs and their applicability to a wide range of optoelectronic devices.     

Charge Migration in Organic Materials: Can Propagating Charges Affect the Key Physical Quantities Controlling Their Motion?

Charge migration is a ubiquitous phenomenon with profound implications throughout many areas of chemistry, physics, biology, and materials science. The long-term vision of designing functional materials with tailored molecular-scale properties has triggered an increasing quest to identify prototypical systems where truly molecular conduction pathways play a fundamental role. Such pathways can be formed due to the molecular organization of various organic materials and are widely used to discuss electronic properties at the nanometer scale. Here, we present a computational methodology to study charge propagation in organic molecular stacks at nano and sub-nanoscales and exploit this methodology to demonstrate that moving charge carriers strongly affect the values of the physical quantities controlling their motion. The approach is also expected to find broad application in the field of charge migration in soft matter systems.     

Comprehensive approach to intrinsic charge carrier mobility in conjugated organic molecules, macromolecules, and supramolecular architectures

Si-based inorganic electronics have long dominated the semiconductor industry. However, in recent years conjugated polymers have attracted increasing attention because such systems are flexible and offer the potential for low-cost, large-area production via roll-to-roll processing. The state-of-the-art organic conjugated molecular crystals can exhibit charge carrier mobilities (μ) that nearly match or even exceed that of amorphous silicon (1-10 cm(2) V(-1) s(-1)). The mean free path of the charge carriers estimated from these mobilities corresponds to the typical intersite (intermolecular) hopping distances in conjugated organic materials, which strongly suggests that the conduction model for the electronic band structure only applies to μ > 1 cm(2) V(-1) s(-1) for the translational motion of the charge carriers. However, to analyze the transport mechanism in organic electronics, researchers conventionally use a disorder formalism, where μ is usually less than 1 cm(2) V(-1) s(-1) and dominated by impurities, disorders, or defects that disturb the long-range translational motion. In this Account, we discuss the relationship between the alternating-current and direct-current mobilities of charge carriers, using time-resolved microwave conductivity (TRMC) and other techniques including field-effect transistor, time-of-flight, and space-charge limited current. TRMC measures the nanometer-scale mobility of charge carriers under an oscillating microwave electric field with no contact between the semiconductors and the metals. This separation allows us to evaluate the intrinsic charge carrier mobility with minimal trapping effects. We review a wide variety of organic electronics in terms of their charge carrier mobilities, and we describe recent studies of macromolecules, molecular crystals, and supramolecular architecture. For example, a rigid poly(phenylene-co-ethynylene) included in permethylated cyclodextrin shows a high intramolecular hole mobility of 0.5 cm(2) V(-1) s(-1), based on a combination of flash-photolysis TRMC and transient absorption spectroscopy (TAS) measurements. Single-crystal rubrene showed an ambipolarity with anisotropic charge carrier transport along each crystal axis on the nanometer scale. Finally, we describe the charge carrier mobility of a self-assembled nanotube consisting of a large π-plane of hexabenzocoronene (HBC) partially appended with an electron acceptor. The local (intratubular) charge carrier mobility reached 3 cm(2) V(-1) s(-1) for the nanotubes that possessed well-ordered π-stacking, but it dropped to 0.7 cm(2) V(-1) s(-1) in regions that contained greater amounts of the electron acceptor because those molecules reduced the structural integrity of π-stacked HBC arrays. Interestingly, the long-range (intertubular) charge carrier mobility was on the order of 10(-4) cm(2) V(-1) s(-1) and monotonically decreased when the acceptor content was increased. These results suggest the importance of investigating charge carrier mobilities by frequency-dependent charge carrier motion for the development of more efficient organic electronic devices.