The transition from bipolaron to triplet-polaron magnetoresistance in a single layer organic semiconductor device

We measure the current–voltage–luminescence (I–V–L) and Magneto-Conductance (MC) response of a poly(3-hexyl-thiophene) (P3HT) based device (Au/P3HT(300 nm)/Al) in forward and reverse bias. In reverse bias (<1 V), the negative MC is described by a single non-Lorentzian function, consistent with the bipolaron theory. In forward bias, the transition from negative saturation MC (low bias) to positive saturation MC (high bias) occurs when the current density exceeds ∼10⁻² A cm⁻² and coincides with electroluminescence. Under these conditions the triplet density (∼10¹⁵ cm⁻³) becomes comparable to the hole density (∼10¹⁶ cm⁻³), consistent with the triplet-polaron interaction theory. From the current density dependence of the MC we conclude that in forward bias both mechanisms must be occurring simultaneously, within a given device, and that the overall sign of the MC results from competition between the two mechanisms.     

Fluorene-centered perylene monoimides as potential non-fullerene acceptor in organic solar cells

A fluorene-centered perylene monoimide dimer, PMI-F-PMI with a partly non-coplanar configuration has been developed as a potential non-fullerene acceptor for organic solar cells (OSCs). The optimum power conversion efficiency (PCE) of the OSC based on PMI-F-PMI as acceptor and poly (3-hexyl thiophene) (P3HT) as donor is up to 2.30% after annealing at 150 °C. The PCE of 2.30% is the highest value for the OSCs based on P3HT donor and non-fullerene acceptor lies in that PMI-F-PMI’s lowest unoccupied molecular orbital (LUMO) level around −3.50 eV matches well with the donor P3HT to produce higher open-circuit voltage (V_oc) of 0.98 V. Meanwhile, PMI-F-PMI makes remarkable contribution to devices’ light absorption as the maximum EQE (30%) of the devices is at 512 nm, same to the maximum absorption wavelength of PMI-F-PMI. The other favorable characteristics of PMI-F-PMI in bulk heterojunction (BHJ) active layers is proved through the photo current density measures, the relatively balanced electron–hole transport, and the smooth morphology with root mean square (RMS) value of 1.86 nm. For these advantages, PMI-F-PMI overwhelms its sister PMI-F and parent PMI as an acceptor in BHJ solar cells.     

Effective protection of sequential solution-processed polymer/fullerene bilayer solar cell against charge recombination and degradation

Both charge recombination and degradation in sequential solution processed polymer/fullerene bilayer organic photovoltaics (OPV) are effectively reduced by the insertion of a TiO₂ inter-layer between the bilayer and Al electrode. The polymer/fullerene bilayer composed of a poly(3-hexylthiophene) (P3HT) bottom-layer and a [6,6] phenyl C61-butyric acid methyl ester (PCBM) top-layer shows significant change in morphology due to the substantial inter-penetration of P3HT and PCBM during the thermal annealing process. Consequently, the bilayer surface becomes P3HT rich resulting in significant charge recombination at the bilayer/Al interface of the bilayer OPV. The charge recombination rate of the bilayer OPV is reduced by one order of magnitude upon the insertion of a TiO₂ nanoparticle inter-layer between the bilayer and the Al electrode after the thermal annealing process. In contrast, when the thermal annealing process is conducted after insertion of the inter-layer, the effect of the TiO₂ inter-layer becomes insignificant. The V_OC and efficiency of the bilayer OPV is greatly enhanced from 0.37 to 0.66 V and 1.2% to 3.7%, respectively by utilizing the properly constructed TiO₂ inter-layer in the bilayer OPV. Additionally, insertion of the TiO₂ inter-layer significantly improves the stability of the bilayer OPV. The bilayer OPV with a TiO₂ inter-layer maintains 51% of its initial PCE after storage under dark ambient conditions for 700 h without encapsulation, whereas the bilayer OPV without a TiO₂ inter-layer did not show any solar cell performance after 200 h under the same conditions.     

Charge transport properties and microstructure of polythiophene/polyfluorene blends

We present a combined charge transport and X-ray diffraction study of blends based on regioregular poly(3-hexylthiophene) (P3HT) and the polyfluorene co-polymer poly((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(3-hexylthien-5-yl)-2,1,3-benzothiadiazole]-2′,2′′-diyl) (F8TBT) that are used in efficient all-polymer solar cells. Hole mobility is observed to increase by nearly two orders of magnitude from less than 10^?7 cm² V^?1 s^?1 for as spin-coated blends to 6 × 10^?6 cm² V^?1 s^?1 for blends annealed at 453 K at a field of 2.7 × 10⁵ V/cm, but still significantly below the time-of-flight mobility of unblended P3HT of 1.7 × 10^?4 cm² V^?1 s^?1. The hole mobility of the blends also show a strong negative electric-field dependence, compared with a relatively flat electric-field dependence of unblended P3HT, suggestive of increased spatial disorder in the blends. X-ray diffraction measurements reveal that P3HT/F8TBT blends show a phase separation of the two components with a crystalline part attributed to P3HT and an amorphous part attributed to F8TBT. In as-spun and mildly annealed blends, the measured d-values and relative intensities of the 100, 200 and 300 P3HT peaks are noticeably different to unblended P3HT indicating an incorporation of F8TBT in P3HT crystallites that distorts the crystal structure. At higher anneal temperatures the blend d-values approach that of unblended P3HT suggesting a well separated blend with pure P3HT crystallites. P3HT crystallite size in the blend is also observed to increase with annealing from 3.3 to 6.1 nm, however similar changes in crystallite size are observed in unblended P3HT films with annealing. The lower mobility of P3HT/F8TBT blends is attributed not only to increased P3HT structural disorder in the blend, but also due to the blend morphology (increased spatial disorder). Changes in hole mobility with annealing are interpreted in terms of the need to form percolation networks of P3HT crystallites within an F8TBT matrix, with a possible contribution due to the intercalation of F8TBT in P3HT crystallites acting as defects in the as-prepared state.     

Hydrophilic self-assembly monolayers for pentacene-based thin-film transistors

A series of hydrophilic alkanethiols, HS(CH₂)_nOH with n = 3, 4, 6, 8, 9 and 11, have been self-assembled on gold electrodes of pentacene-based thin-film transistors. The multi-parametric and ultra-sensitive response of these devices allows us to characterize both charge–injection and electrical stability moving from vacuum to air. The decay exponent β of charge injection is found to be 0.7–1.1 Å^?1 in agreement with earlier measurements of charge tunneling done by electrochemistry and large-area molecular junctions. We find that the intermediate chain lengths (n = 4 and 6) yield an optimum response as they represent the best compromise in terms of decrease of the contact-resistance and bias stress.     

Aggregation,crystallization, and resistance properties of poly(3-hexylthiophene-2,5-diyl) solid films gel-cast from CHCl3/p-xylene mixed solvents

In this study we found that the gelation time and crystallinity of P3HT solid films are adjustable when aging and casting from CHCl₃/p-xylene mixed solvents. After aging for 36 h in pure p-xylene, CHCl₃, or various mixtures of the two as cosolvents, we found that the solid P3HT film gel-cast from 20 vol% CHCl₃ had the highest degree of crystallinity of its main chain (ϕ_m = 0.54), highest melting point of its main chain (T_m = 232.7 °C), fastest gelation time (30 min), largest melting enthalpy of its main chain (ΔH_m = 19.81 J g⁻¹), and lowest resistance (R_P = 0.76 MΩ); the latter value was three orders and one order of magnitude lower than those of the films cast from pure CHCl₃ (ca. 110 MΩ) and pure p-xylene (ca. 4.4 MΩ), respectively. In differential scanning calorimetry scans, we attribute the presence of melting peaks near 75 °C to the solid-to-solid phase transition of the side chain crystallites of P3HT, thereby affecting the aggregation of the P3HT main chain and resulting in the changes in resistance, crystallinity, melting enthalpy, and melting point of the gel-cast P3HT solid films.     

Characterization of solution processed,p-doped films using hole-only devices and organic field-effect transistors

We report a solution processed, p-doped film consisting of the organic materials 4,4′,4″-tris(3-methylphenylphenylamino)triphenylamine (MTDATA) as the electron donor and 2-(3-(adamantan-1-yl)propyl)-3,5,6-trifluorotetracyanoquinodimethane (F3TCNQ-Adl) as the electron acceptor. UV–vis–NIR absorption spectra identified the presence of a charge transfer complex between the donor and acceptor in the doped films. Field-effect transistors were used to characterize charge transport properties of the films, yielding mobility values. Upon doping, mobility increased and then slightly decreased while carrier concentration increased by two orders of magnitude, which in tandem leads to conductivity increasing from 4 × 10^?10 S/cm when undoped to 2 × 10^?7 S/cm at 30 mol% F3TCNQ-Adl. The hole density was calculated based on mobility values extracted from OFET data and conductivity values extracted from bulk I–V data for the MTDATA: x mol% F3TCNQ-Sdl films. These films were then shown to function as the hole injection/hole transport layer in a phosphorescent blue OLED.     

Efficient ternary blend polymer solar cells with a bipolar diketopyrrolopyrrole small molecule as cascade material

We present a ternary strategy to enhance the power conversion efficiency (PCE) of bulk heterojunction polymer solar cells (PSCs) with a bipolar small molecule as cascade material. A bipolar diketopyrrolopyrrole small molecule (F(DPP)₂B₂), as the second electron acceptor, was incorporated into poly(3-hexylthiophene) (P3HT): [6,6]-phenyl-C₆₁-butyric-acidmethyl-ester (PC₆₁BM) blend to fabricate ternary blend PSCs. The introduction of the bipolar compound F(DPP)₂B₂ can not only broaden the light absorption of the active layer because of its absorption in near infrared region but also play a bridging role between P3HT and PC₆₁BM due to the cascaded energy level structure, thus improving the charge separation and transportation. The optimized ternary PSC with 5 wt% F(DPP)₂B₂ content delivered a high PCE of 3.92% with a short-circuit current density (J_sc) of 9.63 mA cm⁻², an open-circuit voltage (V_oc) of 0.62 V and a fill factor (FF) of 64.90%, showing an 23% improvement of PCE as compared to the binary systems based on P3HT:PC₆₁BM (3.18%) or P3HT:F(DPP)₂B₂ (3.17%). The results indicate that the ternary PSCs with a bipolar compound have the potential to surpass high-performance binary PSCs after carefully device optimization.     

Characterization of scaled MANOS nonvolatile semiconductor memory (NVSM) devices

We have modeled and characterized scaled Metal–Al₂O₃–Nitride–Oxide–Silicon (MANOS) nonvolatile semiconductor memory (NVSM) devices. The MANOS NVSM transistors are fabricated with a high-K (K_A = 9) blocking insulator of ALD deposited Al₂O₃ (8 nm), a LPCVD silicon nitride film (8 nm) for charge-storage, and a thermally grown tunneling oxide (2.2 nm). A low voltage program (+8 V, 30 μs) and erase (?8 V, 100 ms) provides an initial memory window of 2.7 V and a 1.4 V window at 10 years for an extracted nitride trap density of 6 × 10¹⁸ traps/cm³ eV. The devices show excellent endurance with no memory window degradation to 10⁶ write/erase cycles. We have developed a pulse response model of write/erase operations for SONOS-type NVSMs. In this model, we consider the major charge transport mechanisms are band-to-band tunneling and/or trap-assisted tunneling. Electron injection from the inversion layer is treated as the dominant carrier injection for the write operation, while hole injection from the substrate and electron injection from the gate electrode are employed in the erase operation. Meanwhile, electron back tunneling is needed to explain the erase slope of the MANOS devices at low erase voltage operation. Using a numerical method, the pulse response of the threshold voltages is simulated in good agreement with experimental data. In addition, we apply this model to advanced commercial TANOS devices.     

Effect of thermal annealing on the electrical properties of P3HT:PC70BM nanocomposites

We studied the electrical properties of organic photovoltaic (OPV) devices based on poly (3-hexylthiophene) and fullerene derivative [6, 6]-Phenyl-C₇₀-butyric acid methyl ester nanocomposite (P3HT:PC₇₀BM) as a function of the annealing temperature. Thermal annealing enables crystallization of the polymer and diffusion of the PC₇₀BM molecules. Diode parameters, such as the barrier height ϕ_b and the ideality factor n were calculated. They were found to be depend strongly on the annealing temperature. This dependence is attributed to surface states, inhomogeneity in the material and series resistance. Best OPV devices had a short circuit current density of 3.35 mA/cm², an open circuit voltage of 0.68 V, a fill factor of 0.45, and a power conversion efficiency of 2.2%, by applying a thermal annealing temperature of 150 °C for 10 min.     

Mechanism of mobility enhancement in Ge p-channel metal-oxide-semiconductor field-effect transistor due to introduction of Al atoms into SiO2/GeO2 gate stack

In this paper, we present comprehensive results on Al-postmetallization annealing (Al-PMA) effect for the SiO₂/GeO₂ gate stack on a Ge substrate, which were fabricated by a physical vapor deposition method. The effective oxide thickness of metal-oxide-semiconductor (MOS) capacitor (CAP) was ~7 nm, and the Al-PMA was performed at a temperature in the range of 300–400 °C. The flat band voltage (V_FB), the hysteresis (HT), the interfacial states density (D_it), and the border traps density (D_bt) for MOSCAPs were characterized by a capacitance–voltage method and a constant-temperature deep-level transient spectroscopy method. The MOSCAP without Al-PMA had an electrical dipole of ~−0.8 eV at a SiO₂/GeO₂ interface, which was disappeared after Al-PMA at 300 °C. The HT, D_it, and D_bt were decreased after Al-PMA at 300 °C and were maintained in the temperature range of 300–400 °C. On the other hand, the V_FB was monotonically shifted in the positive direction with an increase in PMA temperature, suggesting the generation of negatively charged atoms. Structural analyses for MOSCAPs without and with Al-PMA were performed by a time-of-flight secondary ion mass spectroscopy method and an X-ray photoelectron spectroscopy method. It was confirmed that Al atoms diffused from an Al electrode to a SiO₂ film and reacted with GeO₂. The dipole disappearance after Al-PMA at 300 °C is likely to be associated with the structural change at the SiO₂/GeO₂ interface. We also present the device performances of Al-gated p-channel MOS field-effect transistors (FET) with PMA treatments, which were fabricated using PtGe/Ge contacts as source/drain. The peak field-effect mobility (μ_h) of the p-MOSFET was reached a value of 468 cm²/Vs after Al-PMA at 325 °C. The μ_h enhancement was explained by a decrease in the total charge densities at/near the GeO₂/Ge interface.     

Computational studies on the radiative and nonradiative processes of luminescent N-heteroleptic platinum(II) complexes

Three N-heteroleptic Pt(II) complexes, [Pt(C^C)(O^O)] [O^O = acetylacetonate, C^C = 1-phenyl-1,2,4-triazol-5-ylidene (1), C^C = 4-phenyl-1,2,4-triazol-5-ylidene (2), C^C = 2-phenylpyrazine (3)] have been investigated with density functional theory (DFT) and time-dependent density functional theory (TDDFT). The radiative decay rate constants of complexes 1–3 have been discussed with the oscillator strength (f_n), the strength of spin–orbit coupling (SOC) interaction between the lowest energy triplet excited state (T₁) and singlet excited states (S_n), and the energy gaps between E(T₁) and E(S_n). To illustrate the nonradiative decay processes, the transition states between triplet metal-centered (³MC) and T₁ states have been optimized and were verified with the calculations of vibrational frequencies and intrinsic reaction coordinate (IRC). In addition, the minimum energy crossing points (MECPs) between ³MC and ground states (S₀) were optimized. At last, the potential energy curves relevant to the nonradiative decay pathways are simulated. The results show that complex 3 has the biggest photoluminescence quantum yield because the complex 3 has the biggest radiative decay rate constant and the smallest nonradiative decay rate constant in complexes 1–3.     

Energy level alignment and morphology of interfaces between molecular and polymeric organic semiconductors

Ultraviolet photoelectron spectroscopy (UPS) was used to determine the energy level alignment at organic–organic conductor–semiconductor and semiconductor–semiconductor hetero-interfaces that are relevant for organic optoelectronic devices. Such interfaces were formed by in situ vacuum sublimation of small molecular materials [C₆₀ and pentacene (PEN)] and ex situ spin-coating of poly(3-hexylthiophene) (P3HT), all on the common substrate poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS). We found that the deposition sequence had a significant impact on the interface energetics. The hole injection barrier (HIB) of C₆₀ on PEDOT:PSS could be changed from 1.0 eV (moderate hole injection) to 1.7 eV (good electron injection) by introducing a layer of P3HT. The HIB of P3HT/PEDOT:PSS was increased by 0.35 eV due to an interfacial PEN layer. However, PEN deposited on PEDOT:PSS and P3HT/PEDOT:PSS exhibited the same value. These observations are explained by material-dependent dipoles at the interfaces towards PEDOT:PSS and substrate dependent inter-molecular conformation.     

Fabrication of a planar water gated organic field effect transistor using a hydrophilic polythiophene for improved digital inverter performance

A planar water gated OFET (WG-OFET) structure is fabricated by patterning gate, source and drain electrodes on the same plane at the same time. Transistor output characteristics of this novel structure employing commercial regioregular poly(3-hexylthiophene) (rr-P3HT) as polymer semiconductor and deionized (DI) water as gate dielectric show successful field effect transistor operation with an on–off current ratio of 43 A/A and transconductance of 2.5 μA/V. These output characteristics are improved using P3HT functionalized with poly(ethylene glycol) (PEG) (P3HT-co-P3PEGT), which is more hydrophilic, leading to on–off ratio of 130 A/A and transconductance of 3.9 μA/V. Utilization of 100 mM NaCl solution instead of DI water significantly increases the on–off ratio to 141 A/A and transconductance to 7.17 μA/V for commercial P3HT and to 217 A/A and to 11.9 μA/V for P3HT-co-P3PEGT. Finally, transistors with improved transconductances are used to build digital inverters with improved characteristics. Gain of the inverters employing P3HT and P3HT-co-P3PEGT are measured as 2.9 V/V and 10.3 V/V, respectively, with 100 mM NaCl solution.     

High mobility and low operation voltage organic field effect transistors by using polymer-gel dielectric and molecular doping

In this work, we present a method to increase the performance in solution processed organic field effect transistors (OFET) by using gel as dielectric and molecular doping to the active organic semiconductor. In order to compare the performance improvement, Poly (methylmethacrylate) (PMMA) and Poly (3-hexylthiophene-2,5-diyl) P3HT material system were used as a reference. Propylene carbonate (PC) is introduced into PMMA to form the gel for using as gate dielectric. The mobility increases from 5.72×10⁻³ to 0.26 cm² V s^–1 and operation voltage decreases from −60 to −0.8 with gel dielectric. Then, the molecular dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) is introduced into P3HT via co-solution. The mobility increases up to 1.1 cm² V s^–1 and the threshold voltage downs to −0.09 V with doping. The increase in performance is discussed in terms of better charge inducing by high dielectric properties of gel and trap filling due to the increased carrier density in active semiconductor by molecular doping.     

N-doped ZnO based fast response ultraviolet photoconductive detector

We report a study on the fabrication and characterization of ultraviolet photodetectors based on N-doped ZnO films. Highly oriented N-doped ZnO films with 10 at.% N doping are deposited using spray pyrolysis technique onto glass substrates. The photoconductive UV detector based on N-doped ZnO thin films, having a metal–semiconductor–metal (MSM) configuration are fabricated by using Al as a contact metal. I–V characteristic under dark and UV illumination, spectral and transient response of ZnO and N-doped ZnO photodetector are studied. The photocurrent increases linearly with incident power density by more than two orders of magnitude. The photoresponsivity (580 A/W at 365 nm with 5 V bias, light power density 2 μW/cm²) is much higher in the ultraviolet region than in the visible.     

Increase in hole mobility in poly (3-hexylthiophene-2,5-diyl) films annealed under electric field during the solvent drying step

Higher electrical charge carrier mobility in polymer semiconductor films is important to build electronic and opto-electronic devices with improved performance. Application of electric field of the order of 2000 V cm⁻¹ during the solvent drying step for the formation of poly (3-hexyl thiophene-2,5-diyl) (P3HT) film is shown to significantly increase the hole carrier mobility. The reasons for increase in mobility by this novel technique are investigated in this paper. The X-ray diffraction measurements confirm the increase in crystallinity of the films for electric-field annealed samples, while the analysis of the data shows increase in the size of the ‘crystallites’ in those films. The current density–voltage data corresponding to the space charge limited currents at various low temperatures for hole-only devices with P3HT film when fitted to the empirical model for electric-field annealed samples, show an increase in zero field mobility (μ₀) and correspondingly a decrease in activation energy (E_a) and the field dependence pre-factor (γ). The data fitted to the Gaussian disorder model also shows a decrease in the energetic disorder (σ) in the polymer films due to electric-field annealing – indicative of increased ordering of molecules in those films. The analysis confirms the improvement of ordering of the polymer in the film formed due to application of electric field during the solvent drying step of the film formation – a simple processing technique which may be implemented to fabricate higher mobility polymer films for building improved organic electronic devices.     

Effective mobility in amorphous organic transistors: Influence of the width of the density of states

The temperature dependence of poly(3-hexylthiophene-2,5-diyl) (P3HT)/polystyrene (PS) blend organic transistor current/voltage (I–V) characteristics has been experimentally and theoretically studied. The planar transistors, realized by drop casting the P3HT/PS ink, exhibit high mobilities (over 5 × 10⁻³ cm² V⁻¹ s⁻¹) and good overall characteristics. A transistor model accounting for transport mechanisms in disordered organic materials was used to fit the measured characteristics. Using a single set of parameters, the measured effective mobility versus gate bias, either increasing or decreasing with the gate bias depending on temperature, is well reproduced over a wide temperature range (130–343 K). A Gaussian density of states width of 0.045 eV was determined for this P3HT/PS blend. The transistor I–V characteristics are very well described considering disordered material properties within a self-consistent transistor model.     

Effect of fullerene doping on the electrical properties of P3HT/PCBM layers

Poly (3-hexylthiophene-2, 5-diyl) (P3HT) and its blend with Phenyl-C₆₁-Butyric acid-Methyl-Ester (PCBM) and fullerene (C₆₀) thin films were prepared and their electrical properties for memory applications were studied. Due to doping, a sharp decrease in the resistance for a P3HT:PCBM:C₆₀ device was observed at around 70 °C which makes it useful for thermal switching applications. Addition of C₆₀ to P3HT:PCBM blend gave a high value for R_RESET/R_SET in thermal switching. For bias switching, threshold voltage reduces to 1.4 V from 25 V with the addition of C₆₀ to P3HT layer.     

Characterization of current transport in ferroelectric polymer devices

We report the charge injection characteristics in poly(vinylidene fluoride-trifluoroethylene), P(VDF-TrFE), as a function of electrode material in metal/ferroelectric/metal device structures. Symmetric and asymmetric devices with Al, Ag, Au and Pt electrodes were fabricated to determine the dominant carrier type, injection current density, and to propose transport mechanisms in the ferroelectric polymer. Higher work function metals such as Pt are found to inject less charges compared to lower work function metals, implying n-type conduction behavior for P(VDF-TrFE) with electrons as the dominant injected carrier. Two distinct charge transport regimes were identified in the P(VDF-TrFE) devices; a Schottky-limited conduction regime for low to intermediate fields (E < 20 MV/m), and a space-charge limited conduction (SCLC) regime for high fields (20 < E < 120 MV/m). Implication of these results for degradation in P(VDF-TrFE) memory performance are discussed.