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.     

Device performance and density of trap states of organic and inorganic field-effect transistors

Trap states, present in any semiconductor, have a large influence on charge transport as well as various other physical processes relevant for device performance. Therefore, quantifying the density of trap states (trap DOS) in a semiconductor is a crucial step towards understanding and improving field-effect transistors (FET), organic photovoltaic cells (OPV) and organic light-emitting diodes (OLED). We present a method to determine the free vs. total charge carrier density in FETs, and therefore the trap DOS, through full normalization of the transfer curve. We apply this method to many different materials, prepared under a wide range of processing conditions, e.g. organic single crystals, thermally evaporated and inkjet printed thin-films, leading to various degrees of order/disorder. They are compared to inorganic thin-films. A quantitative analysis of the spectral density of the trap DOS reveals the trap DOS in p- and n-type semiconductors to be very similar provided they have a similar morphology. The variation by 3 orders of magnitude is dominated by the degree of crystalline order. Further, the trap DOS in organic materials is essentially the same as in inorganic materials, again, provided they have a similar morphology. Surprisingly, ink-jet printed organic polymers have a relatively low trap DOS, which is in between the one of organic single crystals and thin-films.     

Dependence of general Einstein relation on density of state for organic semiconductors

The Einstein relation (ER) about the diffusion coefficient D and mobility μ of charge carriers has been suspected for disordered organic semiconductors. The general Einstein relation (GER) is popular in recent years, and usually been calculated based on the Gaussian DOS. A clearly cutting inverse-exponential (CCIE) DOS [Org. Elect. 30 (2016) 60–66] is proposed. The mobility is obtained by solving variable range hopping (VRH) equations. The results show that the experimental mobility-density data can be well fitted by using single CCIE DOS in the wide ranges of density, but cannot be fitted by using single Gaussian or un-cutting exponential-type DOS. In this work, the coefficient ζ in the GER (D/μ = ζkT/q) is calculated based on the Gaussian and CCIE DOSs. The variations of coefficient ζ with temperature and density are analyzed. It is shown that the ζ are a gradually decreasing function with temperature and similar for both DOSs. But variations of ζ with density are very different for both DOSs. The ζ is a gradually increasing function of density for the Gaussian DOS, but a non-monotonously increasing function of density for the CCIE DOS with a platform located in the typical range of density. The ζ is assumed as a constant to analyze the data of ideality factor for two organic diodes based on rr-P3HT and OC₁C₁₀-PPV in literature, the theoretical results are in agreement with experimental data.     

Unifying Energetic Disorder from Charge Transport and Band Bending in Organic Semiconductors

Characterizing the density of states (DOS) width accurately is critical in understanding the charge‐transport properties of organic semiconducting materials as broader DOS distributions lead to an inferior transport. From a morphological standpoint, the relative densities of ordered and disordered regions are known to affect charge‐transport properties in films; however, a comparison between molecular structures showing quantifiable ordered and disordered regions at an atomic level and its impact on DOS widths and charge‐transport properties has yet to be made. In this work, for the first time, the DOS distribution widths of two model conjugated polymer systems are characterized using three different techniques. A quantitative correlation between energetic disorder from band‐bending measurements and charge transport is established, providing direct experimental evidence that charge‐carrier mobility in disordered materials is compromised due to the relaxation of carriers into the tail states of the DOS. Distinction and quantification of ordered and disordered regions of thin films at an atomic level is achieved using solid‐state NMR spectroscopy. An ability to compare solid‐state film morphologies of organic semiconducting polymers to energetic disorder, and in turn charge transport, can provide useful guidelines for applications of organic conjugated polymers in pertinent devices.     

High operational stability of solution-processed organic field-effect transistors with top-gate configuration

Electrical characteristics of top-gate field-effect transistors based on a wide range of solution-processed organic semiconductors are systematically investigated. The top-gate field-effect transistors based on different organic semiconductors—from an amorphous polymer semiconductor to a polycrystalline molecular semiconductor—exhibit higher operational stability compared with bottom-gate organic field-effect transistors reported in literature, in spite of significant difference in field-effect mobility. The correlation between charge transport and operational stability is discussed to gain insight into high operational stability of top-gate organic field-effect transistors.     

A charge-separated interfacial hole transport semiconductor for efficient and stable perovskite solar cells

Perovskite solar cells (PSCs) with high efficiency and high stability are still a challenge to produce although remarkable successes have been achieved since they were first reported in 2009. One strategy to effectively improve both the performance as well as the stability is to introduce an interfacial layer between perovskite and hole transport material. Herein, we report a charge-separated (CS) organic semiconductor as the interfacial layer that forms cascaded energy levels between perovskite and hole transportation material. This CS semiconductor displays high hole and electron mobilities by converting long-lived CS states in solution into permanent polarons (charged carriers) in films. Doping with iodinehydride is able to improve the surface morphology of the CS semiconductor layer. Our devices with an iodinehydride-doped CS semiconductor layer exhibit an efficiency of 17.87%, which is increased by ~25% in comparison with 14.24% of the reference devices that have no interfacial layer. This additional CS semiconductor layer also enhances the unsealed device stability by maintaining 90% of initial PCE, while the reference devices degraded by 35% at a relative humidity of 20–30%, temperature of 25 °C and ambient light for 240 h. This result reveals that the utilization of CS states is an alternative approach to construct high charge transport organic semiconductors. An interfacial semiconductor with proper energy level and a matching hole transport mobility can improve the hole extraction, speed up hole transport and suppress charge recombination of PSCs, and thus may be an effective strategy to improve their efficiency and stability.     

Generation-recombination in disordered organic semiconductor: Application to the characterization of traps

The presence of traps in organic semiconductor based electronic devices affects considerably their performances and their stability. The Shockley-Read-Hall (SRH) model is generally used to extract the trap parameters from the experimental results. In this paper, we propose to adapt the SRH formalism to disordered organic semiconductors by considering a hopping transport process and Gaussian distributions for both mobile and trapped carriers. The model is used to extract multiple trap parameters from charge based Deep Level Transient Spectroscopy (Q-DLTS) spectrum. Calculation of the charge transients are given in detail. The model predicts that the activation energy of the trap should not follow an Arrhenius plot on large temperature ranges. Also, the charge transients are no longer exponential when considering Gaussian trap distributions, enlarging the Q-DLTS peaks. The model fits the Q-DLTS spectra measured on organic diodes with a limited number of trap contributions with a good agreement. It is found that an increase of the material rate of disorder reduces the extracted trap energy distances to the LUMO but has no influence on the extracted trap distribution widths. This work shows the importance of considering the specific properties of organic materials to study their properties and their trap distributions.     

Characterisation of charge carrier transport in thin organic semiconductor layers by time-of-flight photocurrent measurements

The paper reviews recent advances in characterisation of charge carrier transport in organic semiconductor layers by time-of-flight photocurrent measurements, with the emphasis on the measurements of the samples with co-planar electrodes. These samples comprised an organic semiconductor layer whose thickness is on the order of a μm or less, and thus mimic the structures of organic thin film transistors. In the review we emphasise the importance of considering spatial variation of electric field in these, essentially two-dimensional structures, in interpretation of photocurrent transients. We review the experimental details of this type of measurements and give examples that demonstrate exceptional sensitivity of the method to minute concentration of electrically active defects in the organic semiconductors as well as the capability of probing charge transport along the channels of different mobility that reside in the same sample.     

Phase-breaking effect on polaron transport in organic conjugated polymers

Despite intense investigations and many accepted viewpoints on theory and experiment, the coherent and incoherent carrier transport in organic semiconductors remains an unsettled topic due to the strong electron-phonon coupling. Based on the tight-binding Su-Schrieffer-Heeger (SSH) model combined with a non-adiabatic dynamics method, we study the effect of phase-breaking on polaron transport by introducing a group of phase-breaking factors into π-electron wave-functions in organic conjugated polymers. Two approaches are applied: the modification of the transfer integral and the phase-breaking addition to the wave-function. Within the former, it is found that a single site phase-breaking can trap a polaron. However, with a larger regular phase-breaking a polaron becomes more delocalized and lighter. Additionally, a group of disordered phase-breaking factors can make the polaron disperse in transport process. Within the latter approach, we show that the phase-breaking can render the delocalized state in valence band discrete and the state in the gap more localized. Consequently, the phase-breaking frequency and intensity can reduce the stability of a polaron. Overall, the phase-breaking in organic systems is the main factor that degrades the coherent transport and destroys the carrier stability.     

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.     

Photomultiplication in Disordered Unipolar Organic Materials

Photomultiplication in conventional inorganic semiconductors has been known and used for decades, the underlying mechanism being multiplication by impact ionization triggered by hot carriers. Since neither carrier heating by an electric field nor avalanche multiplication are possible in strongly disordered organic solids, charge multiplication seems to be highly unlikely in these materials. However, here the photomultiplication observed in the bulk of a unipolar disordered organic semiconductor is reported. The proportion of extracted carriers to incident photons is experimentally determined to be in excess of 3000 % in a single‐layer device of the air‐stable, n‐type organic semiconductor F₁₆CuPc (Pc: phthalocyanine). This effect is explained in terms of exciton quenching by localized charges, the subsequent promotion of these detrapped charges to the high‐mobility energy band of the density‐of‐states (DOS) distribution, and subsequent slow equilibration within this broad intrinsic DOS. Such a mechanism allows multiple replenishment of the optically released charge by mobile carriers injected from an Ohmic electrode. Also shown is photomultiplication in double‐layer devices composed of layers of donor and acceptor small‐molecule materials. This result implies that, apart from exciton dissociation at a donor/acceptor interface, exciton energy transfer to trapped carriers is a complementary photoconductivity process in organic solar cells. This new insight paves the way to cheap, highly efficient organic photodetectors on flexible substrates for numerous applications.     

有机半导体研究进展

1977年人们发现通过掺杂可以使聚乙炔膜的电导率提高 1 2个量级 ,由绝缘体变成导体 ,从此掀起了有机半导体的研究热潮。其研究工作包括有机高分子材料、有机小分子材料和有机分子晶体材料的电学、光学等性质。有机半导体中的载流子除了电子和空穴外 ,还有孤子、极化子等。人们已经获得低温迁移率高达 1 0 5cm2 /V.s的高质量有机半导体晶体 ,在其中观察到量子霍尔效应 ,并用其制成有机半导体激光器。如今有机半导体彩色显示屏已进入实用阶段。     

Mapping the Density of States Distribution of Organic Semiconductors by Employing Energy Resolved–Electrochemical Impedance Spectroscopy

Although the density of states (DOS) distribution of charge transporting states in an organic semiconductor is vital for device operation, its experimental assessment is not at all straightforward. In this work, the technique of energy resolved–electrochemical impedance spectroscopy (ER-EIS) is employed to determine the DOS distributions of valence (highest occupied molecular orbital (HOMO)) as well as electron (lowest unoccupied molecular orbital (LUMO)) states in several organic semiconductors in the form of neat and blended films. In all cases, the core of the inferred DOS distributions are Gaussians that sometimes carry low energy tails. A comparison of the HOMO and LUMO DOS of P3HT inferred from ER-EIS and photoemission (PE) or inverse PE (IPE) spectroscopy indicates that the PE/IPE spectra are by a factor of 2–3 broader than the ER-EIS spectra, implying that they overestimate the width of the distributions. A comparison of neat films of MeLPPP and SF-PDI₂ or PC(61)BM with corresponding blends reveals an increased width of the DOS in the blends. The results demonstrate that this technique does not only allow mapping the DOS distributions over five orders of magnitude and over a wide energy window of 7 eV, but can also delineate changes that occur upon blending.     

Charge current polarization and magnetoresistance in ferromagnetic/organic semiconductor/ferromagnetic devices

Spin-polarized injection and transport in ferromagnetic/organic semiconductor/ferromagnetic devices are studied theoretically. Based on the spin diffusion theory and Ohm’s law, we obtain the charge current polarization and the magnetoresistance, which takes into account the special carriers in organic semiconductors. From the calculation, it is found that the charge current polarization decreases exponentially from the ferromagnetic layer into the organic layer and polarons are effective spin carriers in organic semiconductors for polarized charge current. To get an apparent magnetoresistance in an organic device, it is better to adopt a spin-dependent interface, and the thickness of the organic interlayer is much smaller than the spin diffusion length. Spin polarons are effective carriers for gaining remarkable magnetoresistance in ferromagnetic/organic semiconductor/ferromagnetic devices.     

Nanoscale Conducting Channels at the Surface of Organic Semiconductors Formed by Decoration of Molecular Steps with Self‐Assembled Molecules

Under certain conditions, self‐assembling molecules preferentially bind to molecular steps at the surface of crystalline organic semiconductors, inducing a strong local doping effect. This creates macroscopically long conducting paths of nanoscale width (a single crystalline analogue of organic nanowires) that can span distances of up to 1 cm between electrical contacts. The observed effect of molecular step decoration opens intriguing possibilities for visualization, passivation, and selective doping of surface and interfacial defects in organic electronic devices and provides a novel system for research on nanoscale charge transport in organic semiconductors. In addition, this effect sheds light on the microscopic origin of nucleation and growth of self‐assembled monolayers at organic surfaces. It can also have implications in electronic patterning, nanoscale chemical sensors, integrated interconnects and charge‐transfer interfaces in organic transistors and solar cells.     

Electric potential mapping by thickness variation: A new method for model-free mobility determination in organic semiconductor thin films

Charge transport, with charge carrier mobility as main parameter, is one of the fundamental properties of semiconductors. In disordered systems like most organic semiconductors, the effective mobility is a function of the electric field, the charge carrier density, and temperature. Transport is often investigated in a space-charge limited current (SCLC) regime in thin film single carrier devices, where an electric current is driven in the direction perpendicular to the surface. Direct evaluation of the current–voltage characteristics, however, is problematic, because parasitic contributions from injection or extraction barriers can falsify results.     

Performance enhancement of p-type organic thin-film transistors by surface modification of hybrid dielectrics

The quality of the dielectric/organic semiconductor interface is a critical issue, because it determines the charge transport properties in organic thin-film transistors (OTFTs). High-k organic-inorganic hybrid films have received considerable attention for their outstanding dielectric properties, including low leakage currents, high breakdown fields, and suitable band offsets against the organic semiconductor. However, Hf and Zr hybrid gate dielectrics on p-type OTFTs show poor charge transport properties in the organic semiconductor channel, due to the polaron disorder elicited by the high-k properties and the presence of the –N(CH₃)₂ polarity (hole trapper) on the dielectric/semiconductor interface. In this report, the surface of the Hf and Zr hybrid dielectrics was capped by an ultra-thin poly-1,3,5-trivinyl-1,3,5,-trimethyl-cyclosiloxane (pV3D3) layer formed via an initiated chemical vapor deposition (iCVD) process, to modify the hybrid dielectrics/semiconductor interface. The pV3D3-capped Hf and Zr hybrid OTFTs show an enhanced V_T stability while a large amount of V_T shift was observed from the Hf and Zr hybrid OTFTs. This large amount of V_T shift is attributed to the hole trap sites originated by –N(CH₃)₂ on the uncapped hybrid dielectrics. Furthermore, the p-type OTFTs with the pV3D3-capped hybrid dielectrics show a higher mobility than those with the uncapped hybrid dielectrics. The presence of the non-polar/low-k pV3D3 on the hybrids contribute to narrow the density of state (DOS) in the organic channel, improving the charge transport properties. This combined approach using the bulk layer of Hf and Zr hybrid films and the pV3D3 capping layer can overcome the limitations of single-layer hybrid dielectrics and improve the overall device performance of the OTFTs.     

Molecular orientation and thermal stability of thin-film organic semiconductors

Molecular orientation in organic semiconductors plays a critical role in maximizing external quantum efficiencies of organic light-emitting diodes. It was generally believed that the molecular packing of organic semiconductors is either amorphous or liquid-crystal-like with a preferred molecular orientation distributed uniformly throughout the film. In this paper, however, we report that the orientation of organic molecules in physical-vapor deposited films varies drastically depending on thickness. The thermal stability of the molecular network, measured by its characteristic glass transition temperature, also varies as a function of the film thickness. Based on a two-layered film-structure model, we propose a simple function to quantify the molecular dipole orientation S parameter as a function of film thickness. This function describes well experimental data. In addition to contributing to external quantum efficiency, the molecular orientation parameter S is found to have a strong impact on disruptive change in material density after thermal anneal and glass transition.     

Generation-recombination processes in semiconductors

A unified methodical approach to investigate the transport phenomena in semiconductors is formulated. Various recombination models used in studying the transport phenomena and the establishment of equilibrium in semiconductor structures are analyzed. New expressions describing the recombination processes under the steady-state conditions in arbitrary temperature fields are derived. The recombination process in the hot-carrier theory used when the temperatures of the charge carriers and phonons do not coincide was analyzed. Manifestations of the quasi-neutrality condition in thermodynamic equilibrium and transport phenomena are studied.