Temperature effect on polaron recombination in conjugated polymers

The microcosmic mechanism of electroluminescence in polymer light emitting diodes (PLEDs) is the recombination of the oppositely charged polarons. In previous studies, it has been demonstrated that the temperature-induced irregular lattice vibration may have non-negligible influence on polaron dynamics. Nevertheless, there are few reports about thermal effect on recombination process between polaron pair, although it is very important for the performance of PLEDs. In this paper, we adopt the modified one-dimensional tight-binding model, including to which the thermal random force, and explore the temperature effect on polaron collision driven by electric field with different strengths. The dynamical simulation is performed by using the non-adiabatic evolution method. The results show that under the influence of electric field, the oppositely charged polarons could recombine into either an exciton with one lattice distortion, or the mixed state of polaron pair and exciton with two lattice distortions. It depends on both field strength and temperature. Anyway, after including temperature effect, a significant improvement of exciton yield is obtained. In addition, the new-formed exciton could perform a random walk along the polymer chain driven by the thermal random force when its strength is large enough. If we further increase the temperature, the stability of exciton would become worse.     

Theoretical investigation of voltage effect on magnetoresistance in an organic small molecule device

We theoretically study the voltage effect on organic magnetoresistance (OMAR) in a weak disordered small molecule device on the basis of the quantum dynamics. It is found that with the increase of the voltage, the OMAR effect is reduced. The results show a good agreement with the experimental data. In addition, the carrier density effect on OMAR has also been discussed.     

Simulations of polaron spin inversion in an organic semiconductor: Comparison of two mechanisms

We present a model study of the effects of two mechanisms, the Rashba spin–orbit coupling and the spin-flip term, on the polaron spin inversion in an organic semiconductor. We find that, while both mechanisms can impact the polaron spin by changing the polaron level from a spin eigenstate to a spin superposition state, substantial difference can be observed in the static and dynamical properties of the polaron. Given the values of model parameters relevant to conjugated polymers, the magnitude of the polaron spin inversion caused by the spin–orbit coupling is much smaller than that by the spin-flip term. When the dynamical properties of the polaron are considered, spin oscillations induced by both mechanisms are observed when the polaron moves along the polymer chain driven by external electric field. Interestingly, the length of the polaron motion during one spin oscillation period remains constant in the case of spin–orbit coupling, while it is enhanced with increasing the driven electric field in the case of spin-flip term, in which larger spin diffusion length and longer spin relaxation time can be expected.     

Spin-charge disparity of polarons in organic ferromagnets

Polaron formation in quasi-one-dimensional organic ferromagnets is studied based on an extended Su–Schrieffer–Heeger model combined with a Kondo term. The charge distribution of the polaron is found to be highly asymmetric under spatial reflection, due to the spin radicals. On the contrary, the spin density is nearly symmetric; the spin asymmetry introduced by the extra electron inducing the polaron formation is nearly compensated by the spin polarization of the lower-energy states. We discuss these results on the basis of real-space mean-field calculations and symmetry arguments.     

Spin injection and transport in organic spin-valves based on fullerene C60

We report the fabrication and magnetoresistance (MR) of the La_0.67Sr_0.33MnO₃/C₆₀/Co spin valves. The introduction of 1.5 nm AlO_x barrier between the C₆₀ layer and cobalt top electrode prevents effectively interfacial diffusion and Co penetration, and thus an appreciable positive MR (as large as 3.65%) at room temperature was exhibited for the devices in the thickness range (5–40 nm) of C₆₀ studied. Possible mechanisms on the MR polarity are proposed. Furthermore, based on the temperature- and thickness- dependent MR and I–V characteristics, we have obtained clear evidences that the MR of C₆₀-based spin-valves originates from the tunneling of spin-polarized electrons at the low thickness of C₆₀, however at the larger thickness (>20 nm) the electrons are injected into and subsequently hopping transport within the C₆₀ spacer.     

The effect of thermal annealing on dopant site choice in conjugated polymers

Solution-processed organic electronic devices often consist of layers of polar and non-polar polymers. In addition, either of these layers could be doped with small molecular dopants. It is extremely important for device stability to understand the diffusion behavior of these molecular dopants under the thermal stress and whether the dopants have preference for the polar or the non-polar polymer layers. In this work, a widely used molecular dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) was chosen to investigate dopant site preference upon thermal annealing between the polar thiophene poly(thiophene-3-[2-(2-methoxy-ethoxy)ethoxy]-2,5-diyl) (S–P3MEET) and non-polar thiophene poly(3-hexylthiophene) (P3HT). F4TCNQ is able to p-type dope both P3HT and S–P3MEET. Further doping studies of S–P3MEET using near edge X-ray absorption fine structure spectroscopy, conductivity measurements and atomic force microscopy show that the F4TCNQ additive competes for doping sites with the covalently attached dopants on the S–P3MEET. Calorimetry measurements reveal that the F4TCNQ interacts strongly with the side-chains of the S–P3MEET, increasing the melting temperature of the side-chains by 30 °C with 5 wt% dopant loading. Next, the thermal stability of doping in the polar/non-polar (S–P3MEET/P3HT) bilayer architectures was investigated. Steady-state absorbance and fluorescence results show that F4TCNQ binds much more strongly in S–P3MEET than P3HT and very little F4TCNQ is found in the P3HT layer after annealing. In combination with reflectometry measurements, we show that F4TCNQ remains in the SP3MEET layer with annealing to 210 °C even though the sublimation temperature for neat F4TCNQ is about 80 °C. In contrast, F4TCNQ slowly diffuses out of P3HT at room temperature. We attribute this difference in binding the F4TCNQ anion to the ability of the ethyl-oxy side-chains of the S–P3MEET to orient around the charged dopant molecule and thereby to stabilize its position. This study suggests that polar side-chains could be engineered to increase the thermal stability of molecular dopant position.     

Electrical instability in short channel organic thin-film transistors induced by lucky-polaron mechanism

In this work we study the electrical stability under both gate bias stress and gate and drain bias stress of short channel (L = 5 μm) bottom contact/top gate OTFTs made on flexible substrate with solution-processed organic semiconductor and fluoropolymer gate dielectric. These devices show high field-effect mobility (μ_FE> 1 cm²V⁻¹s⁻¹) and excellent stability under gate bias stress (bias stress V_ds = 0V). However, after prolonged bias stress performed at high drain voltage, V_ds, the transfer characteristics show a decreased threshold voltage, degradation of the subthreshold slope and an apparent increase in the field effect mobility. Furthermore, the output characteristics show an asymmetry when measured in forward and reverse mode. These experimental results can be explained considering that the bias stress induces the damage of a small part of the device channel, localized close to the source contact. The analysis of the experimental data through 2D numerical simulations supports this explanation showing that the electrical characteristics after bias stress at high V_ds can be reproduced considering the creation of donor-like interface states and trapping of positive charge into the gate dielectric at the source end of the device channel. In order to explain this degradation mechanism, we suggest a new physical model that, assuming holes injection from the source contact into the channel in bounded polarons, envisages the defect creation at the interface near the source end of the channel induced by injection of holes that gained energy from both the high longitudinal electric fields and the polaron dissolution.     

Dynamic recombination of polaron pair with impurity in conjugated polymers

The dynamic collision of an on-chain same charged polaron pair with an off-chain counterion trapped in an impurity molecule, under the influence of an external electric field, has been investigated using a nonadiabatic evolution method. We demonstrate that the bipolaron, the exciton and the trion are the main products in such a reaction, and that the trion can be formed by both the direct recombination of a positive polaron pair with a counterion and the secondary recombination of the formed bipolaron with either a trapped polaron, a charged defect, or an impurity of the opposite sign, which is consistent with the experimental evidence qualitatively. Meanwhile, our results show that the strength of the applied electric field and the impurity potential play important roles in the polaron pair-impurity collision. These results are expected to be helpful to understand the electroluminescence and conductivity in conjugated polymers.     

Assessing the width of Gaussian density of states in organic semiconductors

The Density of States (DOS) is an ingredient of critical importance for the accurate physical understanding of the optoelectronic properties of organic semiconductors. The disordered nature of this class of materials, though, renders the task of determining the DOS far from trivial. Its extraction from experimental measurements is often performed by driving the semiconductor out of thermal equilibrium and therefore requires making assumptions on the charge transport properties of the material under examination. This entanglement of DOS and charge transport models is unfavorable since transport mechanisms in organic semiconductors are themselves still subject of debate. To avoid this, we propose an alternative approach which is based on populating and probing the DOS by means of capacitive coupling in Metal Insulator Semiconductors (MIS) structures while keeping the semiconductor in thermal equilibrium. Assuming a Gaussian shape, we extract the DOS width by numerical fitting of experimental Capacitance–Voltage curves, exploiting the fact that the DOS width affects the spatial distribution of accumulated charge carriers which in turn concurs to define the MIS capacitance. The proposed approach is successfully tested on two benchmark semiconducting polymers, one of n-type and one of p-type and it is validated by verifying the robustness of the extraction procedure with respect to varying the insulator electrical permittivity. Finally, as an example of the usefulness and effectiveness of our approach, we study the static characteristics of thin film transistors based on the aforementioned polymers in the framework of the Extended Gaussian Disorder transport model. Thanks to the extracted DOS widths, the functional dependence of current on the gate voltage is nicely predicted and physical insight on transistor operation is achieved.     

Effects of disorder on charge transport in semico++ nducting polymers

Polaron transport process in semiconducting polymers with disordered structure and morphology is simulated using a nonadiabatic evolution method. The simulations are performed within the framework of an extended version of the Su–Schrieffer–Heeger model modified to include diagonal disorder, off-diagonal disorder and an external electric field. It is found that the polaron transport mechanism is determined by the competition between the disorder and the electric field. For the case of pure diagonal disorder, the polaron transport undergoes a crossover from adiabatic drift to nonadiabatic hopping under a large scope of electric field (E < 2.0 mV/Å), whereas the field-assisted tunneling dominates charge transport for a higher electric field. For the combined disorder, it is demonstrated that the competition effects and the synergetic effects between the diagonal and off-diagonal disorder are equally important. The effects of diagonal disorder are negative in most cases, and the energetically easier pathways for charge transport are mainly opened by the off-diagonal disorder.     

Disorder-mediated ordering by self-interfactant effect in organic thin film growth of pentacene on silicon

We have studied the morphology of pentacene films on different silicon surfaces with orientations between Si(1 1 1) and Si(0 0 1). Pentacene molecules are immobile on the Si surface, covering and passivating reactive defect sites. Molecules deposited on top of a closed amorphous wetting layer exhibit isotropic diffusion with diffusion lengths of several tens of micrometers. Neither steps, nor the surface structure affect the film morphology. The wetting layer thus acts as an interfactant, and isolates the molecular film from the substrate, explaining the high quality of pentacene films.     

Effect of trap states on the electrical doping of organic semiconductors

We demonstrate that direct charge transfer (CT) from trap states of host molecules to the p-dopant molecules raises the doping effect of organic semiconductors (OS). Electrons of the trap states in 4,4′-N,N′-dicarbazolyl-biphenyl (CBP) (E_HOMO = 6.1 eV) are directly transferred to the p-dopant, 2,2′-(perfluoronaphthalene-2,6-diylidene) dimalononitrile (F6-TCNNQ) (ELUMO = 5.4 eV). This doping process enhances the conductivity of doped OS by different ways from the ordinary doping mechanism of generating free hole carriers and filling trap states of doped OS. Trap density and trap energy are analysed by impedance spectroscopy and it is shown that the direct charge transfer from deep trap states of host to dopants enhances the hole mobility of doped OS and the I–V characteristics of hole only devices.     

High-speed organic transistors with three-dimensional organic channels and organic rectifiers based on them operating above 20 MHz

Three-dimensional organic transistors (3D-OFETs) comprising vertical short channels are developed to raise the operational speed of organic transistors. The devices with a short-channel length of 0.8 μm and reduced parasitic capacitance operate at up to 20 MHz with an applied drain voltage of −15 V. Organic rectifiers based on the diode-connected 3D-OFETs are also demonstrated to operate at above 20 MHz, even with an applied effective voltage of about 4 V, which is higher than the speed of radio frequency identification tags of 13.56 MHz required in near field communication. These techniques boost the performance of organic transistors and can help to realize the breakthrough for practical applications of organic logic circuits used as key components in various flexible or plastic devices.     

Exponential-type density of states with clearly cutting tail for organic semiconductors

It was recently demonstrated that the density of states (DOS) is the key factor to determine charge transport, photoelectric and contact properties in disordered organic semiconductors. However, the density of states in organic semiconductors is unclear at present. Although the Gaussian DOS is the most popular, some works support the exponential DOS or combination of both forms. In this paper, we propose three exponential-type DOS, one has complete exponential tail, and other two cuts tails at some places. The variations of mobility with carrier density are obtained through numerically solving variable range hopping (VRH) equations. It is shown that the relationships of mobility with density and Fermi level are very different among results obtained from Gaussian, un-cutting and cutting exponential-type DOS. The results show that the experimental mobility-density data can be well fitted by using single cutting exponential-type DOS in the wide ranges of density, but cannot be fitted by using single Gaussian and un-cutting exponential-type DOS. Instead of the Gaussian and pure exponential DOS, the DOS with exponential core and clearly cutting tail is recommended.     

Modeling of charge transport across disordered organic heterojunctions

Organic electronic devices often consist of a sandwich structure containing several layers of disordered organic semiconductors. In the modeling of such devices it is essential that the charge transport across the organic heterojunctions is properly described. The presence of energetic disorder and of strong gradients in both the charge density and the electric field at the heterojunction complicates the use of continuum drift-diffusion approaches to calculate the electrical current, because of the discrete positions of the sites involved in the hopping transport of charges. We use the results of three-dimensional Monte Carlo simulations to construct boundary conditions in a one-dimensional continuum drift-diffusion approach that accurately describe the charge transport across the junction. The important effects of both short- and long-range Coulomb interactions at the junction are fully accounted for. The developed approach is expected to have a general validity.     

Organic temperature sensors and organic analog-to-digital converters based on p-type and n-type organic transistors

We present an organic temperature detector that consists of an organic temperature sensor and an organic complementary read-out circuit. The temperature sensor is a Wheatstone bridge composed of temperature-sensitive polymer films and metal films. The read-out circuit receives an analog temperature signal from the temperature sensor and outputs a 1-bit digital signal that reflects whether the temperature has exceeded a threshold temperature or not. For more detailed read-out, detection of the temperature range the temperature sensor is within also demonstrated using an organic 2-bit analog-to-digital converter as a read-out circuit.     

Transition metal oxides on organic semiconductors

Transition metal oxides (TMOs) on organic semiconductors (OSs) structure has been widely used in inverted organic optoelectronic devices, including inverted organic light-emitting diodes (OLEDs) and inverted organic solar cells (OSCs), which can improve the stability of such devices as a result of improved protection of air sensitive cathode. However, most of these reports are focused on the anode modification effect of TMO and the nature of TMO-on-OS is not fully understood. Here we show that the OS on TMO forms a two-layer structure, where the interface mixing is minimized, while for TMO-on-OS, due to the obvious diffusion of TMO into the OS, a doping-layer structure is formed. This is evidenced by a series of optical and electrical studies. By studying the TMO diffusion depth in different OS, we found that this process is governed by the thermal property of the OS. The TMO tends to diffuse deeper into the OS with a lower evaporation temperature. It is shown that the TMO can diffuse more than 20 nm into the OS, depending on the thermal property of the OS. We also show that the TMO-on-OS structure can replace the commonly used OS with TMO doping structure, which is a big step toward in simplifying the fabrication process of the organic optoelectronic devices.     

A new photon source for ultraviolet photoelectron spectroscopy of organic and other damage-prone materials

Accurate measurements of the valence electronic structures of organic semiconductors are important for the development and understanding of organic electronic devices, materials, and interfaces. Ultraviolet photoelectron spectroscopy (UPS) is a well-established technique for probing valence electronic structures; however, many organic semiconductors undergo rapid sample degradation upon exposure to traditional laboratory-based vacuum ultraviolet (VUV) photon sources. Here, we report on a novel VUV photon source for UPS measurements that utilizes H Lyman-α emission with a narrow linewidth and a widely tunable intensity, and apply it to a number of organic materials of interest to show its ability to overcome this hurdle of sample degradation. Furthermore, the H Lyman-α source displays no measureable higher energy emission lines, which significantly reduces the background over typical He I discharge sources and allows for the onset of the density of states to be clearly observed over several orders of magnitude.     

High-speed organic single-crystal transistors gated with short-channel air gaps: Efficient hole and electron injection in organic semiconductor crystals

Short-channel, high-mobility organic filed-effect transistors (OFETs) are developed based on single crystals gated with short-channel air gaps. The high hole mobility of 10 cm²/Vs for rubrene, and high electron mobility of 4 cm²/Vs for PDIF-CN₂ crystals are demonstrated even with a short channel length of 6 μm. Such performance is due to low contact resistance in these devices estimated to be as low as ～0.5 kΩ cm at gate voltage of ?4 V for rubrene. With the benefit of the short channel length of 4.5 μm in a new device architecture with less parasitic capacitance, the cutoff frequency of the rubrene air–gap device was estimated to be as high as 25 MHz for drain voltage of ?15 V, which is the fastest reported for p-type OFETs, operating in ambient conditions.