Organic bipolar transistors.

Devices made using thin-film semiconductors have attracted much interest recently owing to new application possibilities. Among materials systems suitable for thin-film electronics, organic semiconductors are of particular interest; their low cost, biocompatible carbon-based materials and deposition by simple techniques such as evaporation or printing enable organic semiconductor devices to be used for ubiquitous electronics, such as those used on or in the human body or on clothing and packages1-3. The potential of organic electronics can be leveraged only if the performance of organic transistors is improved markedly. Here we present organic bipolar transistors with outstanding device performance: a previously undescribed vertical architecture and highly crystalline organic rubrene thin films yield devices with high differential amplification (more than 100) and superior high-frequency performance over conventional devices. These bipolar transistors also give insight into the minority carrier diffusion length-a key parameter in organic semiconductors. Our results open the door to new device concepts of high-performance organic electronics with ever faster switching speeds.

Highly Ordered Small Molecule Organic Semiconductor Thin-Films Enabling Complex, High-Performance Multi-Junction Devices.

Organic semiconductors have opened up many new electronic applications, enabled by properties like flexibility, low-cost manufacturing, and biocompatibility, as well as improved ecological sustainability due to low energy use during manufacturing. Most current devices are made of highly disordered thin-films, leading to poor transport properties and, ultimately, reduced device performance as well. Here, we discuss techniques to prepare highly ordered thin-films of organic semiconductors to realize fast and highly efficient devices as well as novel device types. We discuss the various methods that can be implemented to achieve such highly ordered layers compatible with standard semiconductor manufacturing processes and suitable for complex devices. A special focus is put on approaches utilizing thermal treatment of amorphous layers of small molecules to create crystalline thin-films. This technique has first been demonstrated for rubrene─an organic semiconductor with excellent transport properties─and extended to some other molecular structures. We discuss recent experiments that show that these highly ordered layers show excellent lateral and vertical mobilities and can be electrically doped to achieve high n- and p-type conductivities. With these achievements, it is possible to integrate these highly ordered layers into specialized devices, such as high-frequency diodes or completely new device principles for organics, e.g., bipolar transistors.

Efficient and low-voltage vertical organic permeable base light-emitting transistors.

Organic light-emitting transistors, three-terminal devices combining a thin-film transistor with a light-emitting diode, have generated increasing interest in organic electronics. However, increasing their efficiency while keeping the operating voltage low still remains a key challenge. Here, we demonstrate organic permeable base light-emitting transistors; these three-terminal vertical optoelectronic devices operate at driving voltages below 5.0 V; emit in the red, green and blue ranges; and reach, respectively, peak external quantum efficiencies of 19.6%, 24.6% and 11.8%, current efficiencies of 20.6 cd A-1, 90.1 cd A-1 and 27.1 cd A-1 and maximum luminance values of 9,833 cd m-2, 12,513 cd m-2 and 4,753 cd m-2. Our simulations demonstrate that the nano-pore permeable base electrode located at the centre of the device, which forms a distinctive optical microcavity and regulates charge carrier injection and transport, is the key to the good performance obtained. Our work paves the way towards efficient and low-voltage organic light-emitting transistors, useful for power-efficient active matrix displays and solid-state lighting.

Band gap engineering in blended organic semiconductor films based on dielectric interactions.

Blending organic molecules to tune their energy levels is currently being investigated as an approach to engineer the bulk and interfacial optoelectronic properties of organic semiconductors. It has been proven that the ionization energy and electron affinity can be equally shifted in the same direction by electrostatic effects controlled by blending similar halogenated derivatives with different energetics. Here we show that the energy gap of organic semiconductors can also be tuned by blending. We use oligothiophenes with different numbers of thiophene rings as an example and investigate their structure and electronic properties. Photoelectron spectroscopy and inverse photoelectron spectroscopy show tunability of the single-particle gap, with the optical gaps showing similar, but smaller, effects. Theoretical analysis shows that this tuning is mainly caused by a change in the dielectric constant with blend ratio. Further studies will explore the practical impact of this energy-level engineering strategy for optoelectronic devices.

Molecular parameters responsible for thermally activated transport in doped organic semiconductors.

Doped organic semiconductors typically exhibit a thermal activation of their electrical conductivity, whose physical origin is still under scientific debate. In this study, we disclose relationships between molecular parameters and the thermal activation energy (EA) of the conductivity, revealing that charge transport is controlled by the properties of host-dopant integer charge transfer complexes (ICTCs) in efficiently doped organic semiconductors. At low doping concentrations, charge transport is limited by the Coulomb binding energy of ICTCs, which can be minimized by systematic modification of the charge distribution on the individual ions. The investigation of a wide variety of material systems reveals that static energetic disorder induced by ICTC dipole moments sets a general lower limit for EA at large doping concentrations. The impact of disorder can be reduced by adjusting the ICTC density and the intramolecular relaxation energy of host ions, allowing an increase of conductivity by many orders of magnitude.

Modulating the Electronic and Solid-State Structure of Organic Semiconductors by Site-Specific Substitution: The Case of Tetrafluoropentacenes.

The properties as well as solid-state structures, singlet fission, and organic field-effect transistor (OFET) performance of three tetrafluoropentacenes (1,4,8,11: 10, 1,4,9,10: 11, 2,3,9,10: 12) are compared herein. The novel compounds 10 and 11 were synthesized in high purity from the corresponding 6,13-etheno-bridged precursors by reaction with dimethyl 1,2,4,5-tetrazine-3,6-dicarboxylate at elevated temperatures. Although most of the molecular properties of the compounds are similar, their chemical reactivity and crystal structures differ considerably. Isomer 10 undergoes the orbital symmetry forbidden thermal [4+4] dimerization, whereas 11 and 12 are much less reactive. The isomers 11 and 12 crystallize in a herringbone motif, but 10 prefers π-π stacking. Although the energy of the first electric dipole-allowed optical transition varies only within 370 cm-1 (0.05 eV) for the neutral compounds, this amounts to roughly 1600 cm-1 (0.20 eV) for radical cations and 1300 cm-1 (0.16 eV) for dications. Transient spectroscopy of films of 11 and 12 reveals singlet-fission time constants (91±11, 73±3 fs, respectively) that are shorter than for pentacene (112±9 fs). OFET devices constructed from 11 and 12 show close to ideal thin-film transistor (TFT) characteristics with electron mobilities of 2×10-3 and 6×10-2  cm2 V-1 s-1 , respectively.

Insight into doping efficiency of organic semiconductors from the analysis of the density of states in n-doped C60 and ZnPc.

Doping plays a crucial role in semiconductor physics, with n-doping being controlled by the ionization energy of the impurity relative to the conduction band edge. In organic semiconductors, efficient doping is dominated by various effects that are currently not well understood. Here, we simulate and experimentally measure, with direct and inverse photoemission spectroscopy, the density of states and the Fermi level position of the prototypical materials C60 and zinc phthalocyanine n-doped with highly efficient benzimidazoline radicals (2-Cyc-DMBI). We study the role of doping-induced gap states, and, in particular, of the difference Δ1 between the electron affinity of the undoped material and the ionization potential of its doped counterpart. We show that this parameter is critical for the generation of free carriers and influences the conductivity of the doped films. Tuning of Δ1 may provide alternative strategies to optimize the electronic properties of organic semiconductors.

Fully sp2 -Carbon-Linked Crystalline Two-Dimensional Conjugated Polymers: Insight into 2D Poly(phenylenecyanovinylene) Formation and its Optoelectronic Properties.

Cyano-substituted polyphenylene vinylenes (PPVs) have been the focus of research for several decades owing to their interesting optoelectronic properties and potential applications in organic electronics. With the advent of organic two-dimensional (2D) crystals, the question arose as to how the chemical and optoelectronic advantages of PPVs evolve in 2D compared with their linear counterparts. In this work, we present the efficient synthesis of two novel 2D fully sp2 -carbon-linked crystalline PPVs and investigate the essentiality of inorganic bases for their catalytic formation. Notably, among all bases screened, cesium carbonate (Cs2 CO3 ) plays a crucial role and enables reversibility in the first step with subsequent structure locking by formation of a C=C double bond to maintain crystallinity, which is supported by density functional theory (DFT) calculations. A quantifiable energy diagram of a "quasi-reversible reaction" is proposed, which allows the identification of further suitable C-C bond formation reactions for 2D polymerizations. Moreover, the narrowing of the HOMO-LUMO gap is delineated by expanding the conjugation into two dimensions. To enable environmentally benign processing, the post-modification of 2D PPVs is further performed, which renders stable dispersions in the aqueous phase.

Influence of the average molar mass of poly(N-vinylpyrrolidone) on the dimensions and conductivity of silver nanowires.

We investigate the influence of the average molar mass (Mw) of the capping agent poly(N-vinylpyrrolidone) (PVP) on the conductivity of a silver nanowire (AgNW) network. During the polyol process, the chain length of PVP is known to influence the AgNW diameters and lengths. By altering the reaction temperature and time and using PVP of different chain lengths, we synthesized AgNWs with varying diameters, lengths and PVP coverage. The obtained plethora of AgNWs is the basis for conductivity investigations of networks made of AgNWs with a diameter of either 60 nm or 80 nm. The results show a negative influence of long-chain PVP on the conductivity of the subsequent network if 60 nm thick AgNWs are employed. Overall, we obtain well performing AgNW transparent electrodes on glass with RS = 24.4 Ω sq-1 at 85.5%T550nm.

Coherent perfect absorption in wedged organic thin films: a method to determine optical properties.

We investigate coherent perfect absorption in layered thin-film structures with organic small molecules as absorbing material. We focus on strongly asymmetric resonator structures, realized with a high-optical-quality dielectric-distributed Bragg reflector and a thermally evaporated wedged organic layer on top. The optical properties of these devices are systematically investigated by selective optical pumping and probing of the structure along the wedge. We show that phases and amplitudes of all waves and their balance relations can be tuned such that coherent perfect absorption is achieved, i.e., almost all incident radiation is absorbed within the thin organic layer. We show that such wedged structures on highly reflective dielectric mirrors can be used as a novel approach to measure optical dispersion relations of absorbing materials in a broad spectral range without requiring any specific a priori knowledge of the absorbing film.

Doped Organic Transistors.

Organic field-effect transistors hold the promise of enabling low-cost and flexible electronics. Following its success in organic optoelectronics, the organic doping technology is also used increasingly in organic field-effect transistors. Doping not only increases device performance, but it also provides a way to fine-control the transistor behavior, to develop new transistor concepts, and even improve the stability of organic transistors. This Review summarizes the latest progress made in the understanding of the doping technology and its application to organic transistors. It presents the most successful doping models and an overview of the wide variety of materials used as dopants. Further, the influence of doping on charge transport in the most relevant polycrystalline organic semiconductors is reviewed, and a concise overview on the influence of doping on transistor behavior and performance is given. In particular, recent progress in the understanding of contact doping and channel doping is summarized.

Small Molecule Near-Infrared Boron Dipyrromethene Donors for Organic Tandem Solar Cells.

Three furan fused boron dipyrromethenes (BODIPYs) with a CF3 group on the meso-carbon are synthesized as near-infrared absorbing materials for vacuum processable organic solar cells. The best single junction device reaches a short-circuit current (jsc) of 13.3 mA cm-2 and a power conversion efficiency (PCE) of 6.1%. These values are highly promising for an electron donor material with an absorption onset beyond 900 nm. In a tandem solar cell comprising a NIR BODIPY subcell and a matching "green" absorber subcell, complementary absorption is achieved, resulting in PCE of ∼10%.

Impact of mesoscale order on open-circuit voltage in organic solar cells.

Structural order in organic solar cells is paramount: it reduces energetic disorder, boosts charge and exciton mobilities, and assists exciton splitting. Owing to spatial localization of electronic states, microscopic descriptions of photovoltaic processes tend to overlook the influence of structural features at the mesoscale. Long-range electrostatic interactions nevertheless probe this ordering, making local properties depend on the mesoscopic order. Using a technique developed to address spatially aperiodic excitations in thin films and in bulk, we show how inclusion of mesoscale order resolves the controversy between experimental and theoretical results for the energy-level profile and alignment in a variety of photovoltaic systems, with direct experimental validation. Optimal use of long-range ordering also rationalizes the acceptor-donor-acceptor paradigm for molecular design of donor dyes. We predict open-circuit voltages of planar heterojunction solar cells in excellent agreement with experimental data, based only on crystal structures and interfacial orientation.

Optical display film as flexible and light trapping substrate for organic photovoltaics.

We demonstrate flexible small molecular solar cells on periodically patterned plastic substrate (LCD display film) using a highly transparent poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) ( PEDOT: PSS) electrode with flexible thin atomic layer deposited (ALD) AlOx top and bottom encapsulation. The organic photovoltaic device (OPV) on this display film shows a power conversion efficiency of 7.48%, which is a 13.0% improvement as compared to a device fabricated on a planar poly-ethylen-terephtalate (PET) substrate (6.62%) and even higher than the efficiency of a device using planar glass substrate (7.15%). The improvement is mainly due to an enhanced harvesting of photons with wavelengths shorter than 500 nm. Moreover, the fully encapsulated device is sufficiently flexible to withstand a bending with a 10 mm radius for more than 50 cycles at ambient condition. These results indicate that the use of standard optical display films is a cheap, simple and efficient way to increase the photocurrent and overall efficiency of organic photovoltaic devices.

White organic light-emitting diodes with fluorescent tube efficiency.

The development of white organic light-emitting diodes (OLEDs) holds great promise for the production of highly efficient large-area light sources. High internal quantum efficiencies for the conversion of electrical energy to light have been realized. Nevertheless, the overall device power efficiencies are still considerably below the 60-70 lumens per watt of fluorescent tubes, which is the current benchmark for novel light sources. Although some reports about highly power-efficient white OLEDs exist, details about structure and the measurement conditions of these structures have not been fully disclosed: the highest power efficiency reported in the scientific literature is 44 lm W(-1) (ref. 7). Here we report an improved OLED structure which reaches fluorescent tube efficiency. By combining a carefully chosen emitter layer with high-refractive-index substrates, and using a periodic outcoupling structure, we achieve a device power efficiency of 90 lm W(-1) at 1,000 candelas per square metre. This efficiency has the potential to be raised to 124 lm W(-1) if the light outcoupling can be further improved. Besides approaching internal quantum efficiency values of one, we have also focused on reducing energetic and ohmic losses that occur during electron-photon conversion. We anticipate that our results will be a starting point for further research, leading to white OLEDs having efficiencies beyond 100 lm W(-1). This could make white-light OLEDs, with their soft area light and high colour-rendering qualities, the light sources of choice for the future.

Molecular-scale simulation of electroluminescence in a multilayer white organic light-emitting diode.

In multilayer white organic light-emitting diodes the electronic processes in the various layers--injection and motion of charges as well as generation, diffusion and radiative decay of excitons--should be concerted such that efficient, stable and colour-balanced electroluminescence can occur. Here we show that it is feasible to carry out Monte Carlo simulations including all of these molecular-scale processes for a hybrid multilayer organic light-emitting diode combining red and green phosphorescent layers with a blue fluorescent layer. The simulated current density and emission profile are shown to agree well with experiment. The experimental emission profile was obtained with nanometre resolution from the measured angle- and polarization-dependent emission spectra. The simulations elucidate the crucial role of exciton transfer from green to red and the efficiency loss due to excitons generated in the interlayer between the green and blue layers. The perpendicular and lateral confinement of the exciton generation to regions of molecular-scale dimensions revealed by this study demonstrate the necessity of molecular-scale instead of conventional continuum simulation.

Coherent mode coupling in highly efficient top-emitting OLEDs on periodically corrugated substrates.

Bragg scattering at one-dimensional corrugated substrates allows to improve the light outcoupling from top-emitting organic light-emitting diodes (OLEDs). The OLEDs rely on a highly efficient phosphorescent pin stack and contain metal electrodes that introduce pronounced microcavity effects. A corrugated photoresist layer underneath the bottom electrode introduces light scattering. Compared to optically optimized reference OLEDs without the corrugated substrate, the corrugation increases light outcoupling efficiency but does not adversely affect the electrical properties of the devices. The external quantum efficiency (EQE) is increased from 15 % for an optimized planar layer structure to 17.5 % for a corrugated OLED with a grating period of 1.0 µm and a modulation depth of about 70 nm. Detailed analysis and optical modeling of the angular resolved emission spectra of the OLEDs provide evidence for Bragg scattering of waveguided and surface plasmon modes that are normally confined within the OLED stack into the air-cone. We observe constructive and destructive interference between these scattered modes and the radiative cavity mode. This interference is quantitatively described by a complex summation of Lorentz-like resonances.

Correlation between temperature activation of charge-carrier generation efficiency and hole mobility in small-molecule donor materials.

In organic solar cells, free charge carriers are generated at the interface between an electron-donating and an electron-accepting material. The detailed mechanisms of the generation of free charge carriers are still under discussion. In this work, we investigate the influence of temperature on the generation efficiency of free charge carriers in blends of dicyanovinyl substituted oligothiophene (DCVnT) molecules and C60 by quasi-steady-state photoinduced absorption (PIA) measurements. The observed positive temperature dependence of charge-carrier generation can be directly correlated to the charge-transport behavior. The determined activation energy scales inversely with the hole mobility for all investigated DCVnT derivatives, suggesting higher dissociation probability of bound interfacial charge pairs at high mobility. Furthermore, the energetic disorder parameter, σ, determined by CELIV (charge extraction by linearly increasing voltage) measurements for a DCV6T derivative, matches the activation energy from the PIA measurements. In conclusion, these results underline the need for high-mobility donor materials for optimal charge-pair dissociation in organic solar cells.

Tuning Charge-Transfer States by Interface Electric Fields.

Intermolecular charge-transfer (CT) states are extended excitons with a charge separation on the nanometer scale. Through absorption and emission processes, they couple to the ground state. This property is employed both in light-emitting and light-absorbing devices. Their conception often relies on donor-acceptor (D-A) interfaces, so-called type-II heterojunctions, which usually generate significant electric fields. Several recent studies claim that these fields alter the energetic configuration of the CT states at the interface, an idea holding prospects like multicolor emission from a single emissive interface or shifting the absorption characteristics of a photodetector. Here, we test this hypothesis and contribute to the discussion by presenting a new model system. Through the fabrication of planar organic p-(i-)n junctions, we generate an ensemble of oriented CT states that allows the systematic assessment of electric field impacts. By increasing the thickness of the intrinsic layer at the D-A interface from 0 to 20 nm and by applying external voltages up to 6 V, we realize two different scenarios that controllably tune the intrinsic and extrinsic electric interface fields. By this, we obtain significant shifts of the CT-state peak emission of about 0.5 eV (170 nm from red to green color) from the same D-A material combination. This effect can be explained in a classical electrostatic picture, as the interface electric field alters the potential energy of the electric CT-state dipole. This study illustrates that CT-state energies can be tuned significantly if their electric dipoles are aligned to the interface electric field.

High-performance vertical organic transistors.

Vertical organic thin-film transistors (VOTFTs) are promising devices to overcome the transconductance and cut-off frequency restrictions of horizontal organic thin-film transistors. The basic physical mechanisms of VOTFT operation, however, are not well understood and VOTFTs often require complex patterning techniques using self-assembly processes which impedes a future large-area production. In this contribution, high-performance vertical organic transistors comprising pentacene for p-type operation and C60 for n-type operation are presented. The static current-voltage behavior as well as the fundamental scaling laws of such transistors are studied, disclosing a remarkable transistor operation with a behavior limited by injection of charge carriers. The transistors are manufactured by photolithography, in contrast to other VOTFT concepts using self-assembled source electrodes. Fluorinated photoresist and solvent compounds allow for photolithographical patterning directly and strongly onto the organic materials, simplifying the fabrication protocol and making VOTFTs a prospective candidate for future high-performance applications of organic transistors.