Investigation of charge carrier mobility and recombination in PBDTTPD thin layer structures

In this paper we present investigation of hole transport properties in sandwich and OFET structures with single active layer of PBDTTPD (Poly[(5,6-dihydro-5-octyl-4,6-dioxo-4H-thieno[3,4-c]pyrrole-1,3-diyl)[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl]]). Sandwich structures were investigated by photo-CELIV and TOF techniques, obtained results showed strongly time dependent hole mobility and non-Gaussian DOS tail. Photogenerated charge carrier decay experiment demonstrated that bimolecular recombination coefficient is smaller than calculated Langevin recombination coefficient and this was explained by faster holes escaping recombination area and not participating in Langevin recombination process. Organic field-effect transistor structure was investigated by current transients technique to find hole mobility near the dielectric layer and to study OTS treatment influence on hole transport. The study of hole mobility dependence on temperature was performed in order to evaluate energetic disorder of interface DOS in the channel of OFET structures.     

Charge carrier mobility,bimolecular recombination and trapping in polycarbazole copolymer:fullerene (PCDTBT:PCBM) bulk heterojunction solar cells

Organic photovoltaic devices based on the donor:acceptor blend of poly[N-9″-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT) and [6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM) have received considerable attention in recent years due to their high power conversion efficiencies and the ability to achieve close to 100% internal quantum efficiency. However, the highest efficiencies were all attained using active layers of less than 100 nm, which is not ideal for either maximised potential performance or commercial viability. Furthermore, more recent reports have documented significant charge carrier trapping in these devices. In this paper two charge extraction techniques (photo-CELIV and time-of-flight) have been used to investigate the mobility and recombination behaviour in a series of PCDTBT:PCBM devices. The results not only confirm significant charge carrier trapping in this system, but also reveal close to Langevin-type bimolecular recombination. The Langevin recombination causes a short charge carrier lifetime that results in a short drift length. The combination of these two characteristics (trapping and fast bimolecular recombination) has a detrimental effect on the charge extraction efficiency when active layers greater than ∼100 nm are used. This accounts for the pronounced decrease in fill factor with increasing active layer thickness that is typically observed in PCDTBT:PCBM devices.     

Time-independent charge carrier mobility in a model polymer:fullerene organic solar cell

The technique of photo-CELIV (charge extraction by linearly increasing voltage) is one of the more straightforward and popular approaches to measure the faster carrier mobility in measurement geometries that are relevant for operational solar cells and other optoelectronic devices. It has been used to demonstrate a time-dependent photocarrier mobility in pristine polymers, attributed to energetic relaxation within the density of states. Conversely, in solar cell blends, the presence or absence of such energetic relaxation on transport timescales remains under debate. We developed a complete numerical model and performed photo-CELIV experiments on the model high efficiency organic solar cell blend poly[3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-naphthalene] (PDPP-TNT):[6,6]-phenyl-C₇₁-butyric-acid-methyl-ester (PC70BM). In the studied solar cells a constant, time-independent mobility on the scale relevant to charge extraction was observed, where thermalisation of photocarriers occurs on time scales much shorter than the transit time. Therefore, photocarrier relaxation effects are insignificant for charge transport in these efficient photovoltaic devices.     

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.     

Evolution in crystal structure and electrical performance of thiophene-based polymer field effect transistors: A remarkable difference between thermal and solvent vapor annealing

We report the various conformational structures of long pendant side-chains, and the effects of thermal and solvent vapor annealing (SVA) with the corresponding charge carrier mobilities of thiophene-based conjugated polymers, poly[5,5′-bis(3-dodecyl-2-thienyl)-2,2′-bithiophene] (PQT-12) and poly(4,4′-bis-decyloxymethylquaterthiophene) (POQT), by correlated study of their extraordinary polymorphic crystal structures. In substitution for alkyl chains in polythiophenes, ether alkyl chains induce a favorable non-covalent interaction between the oxygen and sulfur atoms and help the polymer chains planar with lower torsion angles between conjugated backbone units showing a reduced π–π stacking distance. However, the flexibility and conformational freedom with such long side-chains dominantly induce polymorphic crystallites from bent and extended side-chains. Especially, POQT exhibit two polymorphic crystallite phases in a similar ratio probably due to the increased freedom of ether alkyl chains. Therefore, the field effect mobility of POQT is decreased gradually with the increase of annealing temperature from 0.024 (at 80 °C) to 3.96 × 10⁻⁴ cm²/V s (at 170 °C). Contrary to the thermal annealing method, solvent-vapor-annealed POQT films show highly ordered and single-phase crystallites with edge-on orientation to the substrate, which ultimately provides an effectively improved charge carrier mobility from 0.023 (pristine) to 0.076 cm²/V s after adequate solvent vapor exposure.     

Effect of dihydropyrazine on structures and charge transport properties of N-heteropentacenes matters: A theoretical investigation

A family of N-heteropentacenes acted as promising candidates for organic semiconductor materials is of immense interest. It should be attributed to the following reasons that (1) the positions, numbers and valence-states of N atom in N-heteropentacenes can effectively tune their electronic structure, stability, solubility, and molecular stacking; (2) diverse intermolecular interaction and π-stacking motifs appear in their crystals. The effect of the position and number of the 6-π-pyrazine on their structures and charge-transport properties has been systematically investigated in our previous work (J. Phys. Chem. C 115 (2011) 21416). Therefore, in this work, the study on the role of 8-π-dihydropyrazine with another valence-state N atoms is our focus. Density functional theory, Marcus electron transfer theory and Brownian diffusion assumption coupled with kinetic Monte-Carlo simulation are applied into this investigation. Our theoretical results indicate that in contrast with pyrazine, dihydropyrazine introduced is more helpful for promoting p-type organic semiconductor materials. For molecule 4, hole mobility of its single crystal theoretically reach 0.71 cm² V⁻¹ s⁻¹, and coupled with its fine hole-injection ability, it should be a promising candidate for p-type organic semiconductor materials. Although the lowest triplet-state energies of the molecules studied are very small, introduction of dihydropyrazine is very helpful for increasing the energies.     

Estimation of charge carrier mobility in amorphous organic materials using percolation corrected random-walk model

A computationally simple yet predictive multi-scale simulation scheme is introduced to estimate zero-field charge mobilities for amorphous OSC materials. A percolating charge model is utilized to describe inhomogeneity of hopping trajectories of carriers in amorphous media. The prediction scheme is composed of the following stages: quantum chemical calculation of Marcus inner sphere reorganization energies, molecular dynamics simulations of the amorphous condensed phase bulk structure, automated quantum chemical calculations of the electronic coupling for dimer pairs in the amorphous solid, and calculation of the Marcus theory charge hopping rates and an estimated bulk mobility using the Einstein relation, corrected for the inhomogeneous hopping network of the solid. Comparisons with independent experimental measurements of hole mobility for ten OSC compounds show that this approach gives good correlation between predictions and measurements suitable for ranking systems, and useful quantitative agreement. This low-cost model with minimal complexity is well-suited for incorporation into a virtual materials discovery framework for advanced OSC solutions.     

Investigation of structural and optoelectronic properties of annealed nickel phthalocyanine thin films

Thin films of nickel phthalocyanine (NiPc) were prepared by thermal evaporation and the effects of annealing temperature on the structural and optical properties of the samples were studied using different analytical methods. Structural analysis showed that the grain size and crystallinity of NiPc films improved as annealing temperature increased from 25 to 150 °C. Also, maximum grain size (71.3 nm) was obtained at 150 °C annealing temperature. In addition, NiPc films annealed at 150 °C had a very smooth surface with an RMS roughness of 0.41 nm. Optical analysis indicated that band gap energy of films at different annealing temperatures varied in the range of 3.22–3.28 eV. Schottky diode solar cells with a structure of ITO/PEDOT:PSS/NiPc/Al were fabricated. Measurement of the dark current density–voltage (J–V) characteristics of diodes showed that the current density of films annealed at 150 °C for a given bias was greater than that of other films. Furthermore, the films revealed the highest rectification ratio (23.1) and lowest barrier height (0.84 eV) demonstrating, respectively, 23% and 11% increase compared with those of the deposited NiPc films. Meanwhile, photoconversion behavior of films annealed at 150 °C under illumination showed the highest short circuit current density (0.070 mA/cm²) and open circuit voltage of (0.55 V).     

Charge trapping in organic transistor memories: On the role of electrons and holes

In this work, we study charge trapping in organic transistor memories with a polymeric insulator as gate dielectric. We found that the mechanism of charge trapping is tunneling from the semiconductor channel into the gate dielectric. Depending on the semiconductor and its processing, charge trapping can result in large bi-directional threshold voltage shifts, in case the semiconductor is ambipolar, or in shifts in only one direction (unipolar semiconductor). These results indicate that optimal memory performance requires charge carriers of both polarities, because the most efficient method to lower the programming field is by overwriting a trapped charge by an injected charge of opposite polarity.     

Controlling organization of conjugated polymer films from binary solvent mixtures for high performance organic field-effect transistors

We investigate the effect of a binary solvent blend as a solvent for poly{[N,N′-bis(2-octyldodecyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)} P(NDI2OD-T2) on the characteristics of n-channel organic field-effect transistors (OFETs). To make the binary solvent blend, the low-boiling-point non-solvent propylene glycol methyl ether acetate (PGMEA, b.p ∼146 °C) is added to the high-boiling-point good solvent 1,2-dichlorobenzene (O-DCB, b.p ∼180 °C) at various mixing ratio from 0 to 40 v%. UV–vis spectra of P(NDI2OD-T2) solution dissolved in the binary solvent clearly show the formation of polymer aggregates through a gradual red shift of the intramolecular charge transfer band with the addition of high concentrations of non-solvent PGMEA. Higher edge-on oriented crystallinity is observed for P(NDI2OD-T2) films spin-coated from the binary solvent with 5–10 v% PGMEA by out-of-order x-ray diffraction. P(NDI2OD-T2) films are applied as the active layer in top-gate/bottom-contact OFETs. Improved n-type field-effect mobility of the P(NDI2OD-T2) semiconducting layer up to 0.59 cm²/Vs was achieved for on-center spin coated films compared to 1.03 cm²/Vs for off-center (parallel alignment) spin-coated films respectively employing the binary solvent with 10 v% PGMEA.     

Structural phase transition in pentacene caused by molecular doping and its effect on charge carrier mobility

The structural properties and charge carrier mobility of pentacene doped by 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) and 2,2-(perfluoronaphthalene-2,6-diylidene) dimalononitrile (F6-TCNNQ) are studied by X-ray diffraction, scanning electron microscopy, field effect transistor measurements, and space charge limited currents (SCLC). We observe the presence of polycrystalline and amorphous domains within the doped pentacene film grown under co-deposition conditions. The appearance of the amorphous phase is induced by the molecular dopants F4-TCNQ and F6-TCNNQ. A strong drop of crystallite size is obtained at a doping concentration of around 7 and 4 wt.%, respectively. The loss of the polycrystalline structure is correlated to a strong decrease of the charge carrier mobility in pentacene in horizontal and vertical film structures. We discuss typical scenarios of charge transport for polycrystalline and amorphous thin films in order to explain the observed loss of mobility originated by the doping induced structural phase transition. In this way an optimum doping concentration for highest conductivity with acceptable mobility is determined which can help to improve the performance of organic solar cells and organic high-frequency rectification diodes.     

Interface effect in pentacene field-effect transistors from high energy proton beam irradiation

We report the effect of irradiation using 10 MeV high energy proton beams on pentacene organic field-effect transistors (OFETs). The electrical characteristics of the pentacene OFETs were measured before and after proton beam irradiation with fluence (dose) conditions of 10¹², 10¹³, and 10¹⁴ cm⁻². After proton beam irradiation with fluences of 10¹² or 10¹³ cm⁻², the threshold voltage of the OFET devices shifted to the positive gate voltage direction with an increase in the current level and mobility. In contrast, for a high proton beam fluence condition of 10¹⁴ cm⁻², the threshold voltage shifted to the negative gate voltage direction with a decrease in the current level and mobility. It is evident from the electrical characteristics of the pentacene OFETs treated with a self-assembled monolayer that these experimental observations can be attributed to the trapped charges in the dielectric layer and pentacene/SiO₂ interface. Our study will enhance the understanding of the influence of high energy particles on organic field-effect transistors.     

Enhanced photoconductivity and trapping rate through control of bulk state in organic triphenylamine-based photorefractive materials

In organic optical semiconductors, it is rather challenging to achieve precise control of photoconductivity and charge trapping, which determines the device performance. This paper reports on enhanced photorefractive response rate through control of the photoconductivity and trapping rate in organic triphenylamine-based photorefractive materials by means of bulk state tuning. The bulk state in organic triphenylamine-based photorefractive composites was controlled through a rapid cooling process from various melting temperatures during sample fabrication. The photoconductivity and trapping rate were determined from photocurrent measurements. Fabrication at lower melting temperatures enhanced the trapping rate for deep traps, whereas it reduced the trapping rate for shallow traps. As a result, a faster photorefractive response was obtained.     

Transient electroluminescence determination of carrier mobility and charge trapping effects in heavily doped phosphorescent organic light-emitting diodes

Transient electroluminescence (EL) was used to measure the delay between the excitation pulse and onset of emission in OLEDs based on phosphorescent bis[3,5-bis(2-pyridyl)-1,2,4-triazolato] platinum(ΙΙ) doped into 4,4′-bis(carbazol-9-yl) triphenylamine (CBP), from which an electron mobility of 3.2 × 10⁻⁶ cm²/V s was approximated. Delayed recombination was observed after the drive pulse had been removed and based on its dependence on frequency and duty cycle, ascribed to trapping and de-trapping processes associated with disorder-induced carrier localization at the interface between the emissive layer and electron blocker. The data suggests that the exciton recombination zone is at, or close to the interface between the emissive layer and electron blocker. Despite the charge trapping effects, a peak power efficiency of 24 lm/W and peak external quantum efficiency of 10.64% were obtained. Mechanisms for the electroluminescence and delayed recombination are proposed.     

The mutual influence of surface energy and substrate temperature on the saturation mobility in organic semiconductors

We report on a mutual correlation between the substrate temperature during semiconductor deposition and the surface energy of the gate dielectric on the charge carrier mobility in bottom gate top contact organic field effect transistors (OFETs) with N,N′-diphenyl-3,4,9,10-perylene tetracarboxylic diimide (DP-PDI) as organic semiconductor.     

Charge extraction by a linearly increasing voltage of photo-generated carriers: The influence of two mobile carrier types,bimolecular recombination,and series resistance

The charge extraction by a linearly increasing voltage (CELIV) technique is a well-known and commonly used method to characterize charge transport in low-mobility materials. In the original CELIV theory it is assumed that one type of charge carrier is mobile and the other fixed and that recombination during the extraction pulse is negligible. However, this is in general not the case, especially in photo-CELIV where both electrons and holes are generated by light excitation. Moreover, RC effects induced by the series or load resistance of the external circuit are typically assumed to be negligible. In this work, we use drift-diffusion modelling and analytical derivations to show that the standard equations used for calculating the mobility in the moderate conductivity regimes generally leads to errors in the mobility determination in the case when i) two carrier types of similar mobility, ii) recombination, iii) an electric-field-dependent mobility, and iv) RC effects are present in the device. The effect of the external series resistance on the mobility determination becomes of particular importance in devices with relatively large mobilities and/or high carrier concentrations, where the original CELIV theory might give rise to an underestimation of the mobility by several orders of magnitude.     

The metal-induced crystallization of poly-Si and the mobility enhancement of thin film transistors fabricated on a glass substrate

In this study, we report on the fabrication of poly-crystalline silicon (poly-Si) using the metal-induced crystallization (MIC) method and its application to thin film transistors (TFTs). The top gate of the p-type TFTs, whose active layer used MIC poly-Si annealed for 1 h at 650 °C, showed a field effect mobility (μ_FE) of 7.5 cm²/V s. By increasing the crystallization time to 5 h, the quality of the MIC poly-Si was improved. The μ_FE increased from 7.5 to 15 cm²/V s. In order to enhance the channel mobility, the Si dangling bonds, which were produced during the transformation from the amorphous phase to the poly-crystalline phase of silicon (Si), were reduced by using plasma hydrogenation. Measurements show that the μ_FE reached 45 cm²/V s after passivation by an inductively coupled plasma chemical vapor deposition (ICPCVD) system.     

The role of local potential minima on charge transport in thin organic semiconductor layers

We have performed a systematic study of dependence of time-resolved photocurrent on the point of charge excitation within the organic semiconductor channel formed by two coplanar metal electrodes. The results confirm that spatial variation of electric field between the electrodes crucially determines transport of photogenerated charge carriers through the organic layer. Time-of-flight measurements of photocurrent demonstrate that the transit time of photogenerated charge carrier packets drifting between the two electrodes decreases with increasing travelling distance. Such counterintuitive result cannot be reconciled with the spatial distribution of electric field between coplanar electrodes, alone. It is also in contrast to expected role of space-charge screening of external electric field. Supported by Monte Carlo simulations of hopping transport in disordered organic semiconductor layer, we submit that the space-charge screens the external electric field and captures slower charge carriers from the photogenerated charge carrier packet. The remaining faster carriers, exhibit velocity distribution with significantly higher mean value and shorter transit time.     

Charge transport and recombination in PDPP5T:[70]PCBM organic solar cells: The influence of morphology

The performance of organic bulk heterojunction solar cells is strongly dependent on the donor/acceptor morphology. Morphological parameters, such as the extent and the composition of donor- and acceptor-rich domains, influence both the charge generation and the charge transport throughout the active layer. This work focuses on a polymer:fullerene system based on a small bandgap diketopyrrolopyrrole–quinquethiophene alternating copolymer (PDPP5T) mixed with [6,6]-phenyl-C₇₁-butyric acid methyl ester ([70]PCBM) that is capable of efficiencies higher than 6%. By changing the processing conditions, the morphology can be varied from a coarse separated morphology, with fullerene domains (blobs) embedded in a polymer-rich matrix, to a completely mixed layer.     

Interface optimization using diindenoperylene for C60 thin film transistors with high electron mobility and stability

C₆₀-based organic thin film transistors (OTFTs) with high electron mobility and high operational stability are achieved with (1 1 1) oriented C₆₀ films grown by using template effects of diindenoperylene (DIP) under layer on the SiO₂ gate insulator. The electron mobility of the C₆₀ transistor is significantly increased from 0.21 cm² V⁻¹ s⁻¹ to 2.92 cm² V⁻¹ s⁻¹ by inserting the template-DIP layer. Moreover much higher operational stability is also observed for the DIP-template C₆₀ OTFTs. A grazing incidence X-ray diffraction and ultrahigh-sensitivity photoelectron spectroscopy measurements indicate that the improved electron mobility and stability arise from the decreased density of trap states in the C₆₀ film due to increased (1 1 1) orientation of C₆₀-grains and their crystallinity on the DIP template.