Ultrafast terahertz photoconductivity of bulk heterojunction materials reveals high carrier mobility up to nanosecond time scale

The few-picosecond (ps) decay of terahertz (THz) photoconductivity typically observed for conjugated polymer:fullerene blends (at excitation fluencies ~10(15) photons/cm(2) per pulse) is shown to be a result of charge pair annihilation for two polymer:PCBM blends. At a factor of 100 lower excitation density, the THz decay is in the hundreds of ps time scale, implying that very high carrier mobility (~0.1 cm(2) V(-1) s(-1)) prevails for long time after charge formation, of importance for free charge formation in organic solar cells.     

Electrical conductivity and translational diffusion in the 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid

Broadband dielectric and terahertz spectroscopy (10(-2)-10(+12) Hz) are combined with pulsed field gradient nuclear magnetic resonance (PFG-NMR) to explore charge transport and translational diffusion in the 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid. The dielectric spectra are interpreted as superposition of high-frequency relaxation processes associated with dipolar librations and a conductivity contribution. The latter originates from hopping of charge carriers on a random spatially varying potential landscape and quantitatively fits the observed frequency and temperature dependence of the spectra. A further analysis delivers the hopping rate and enables one to deduce--using the Einstein-Smoluchowski equation--the translational diffusion coefficient of the charge carriers in quantitative agreement with PFG-NMR measurements. By that, the mobility is determined and separated from the charge carrier density; for the former, a Vogel-Fulcher-Tammann and for the latter, an Arrhenius temperature dependence is obtained. There is no indication of a mode arising from the reorientation of stable ion pairs.     

A Molecular Photosensor Based on Photoswitching of Charge Carrier Mobility

Polymer photoelectronic device based on interaction between π-conjugated polymer matrices and photochromic molecules was fabricated. The theoretical and experimental studies proved that the photochromic reaction in studied devices should eventuate in changes of optical and electrical properties of polymers such as luminescence and conductivity. The quantum chemical calculations showed that the presence of dipolar species in the vicinity of a polymer chain modifies the on-chain site energies and consequently increases the width of the distribution of hopping transport states. Optical switching was studied using standard absorption and photoluminescence spectroscopy. A strong photoluminescence quenching after the photochromic conversion caused by radiative energy transfer was observed. The influence of photoswitchable charge carrier traps on charge transport were evaluated by Space Charge Limited Current (SCLC) method. It was shown that deep traps may significantly affect the energy of the transport level, and thus modulate the transport of charge carriers.     

Charge carrier mobility and concentration as a function of composition in AgPO3-AgI glasses

Conductivity data of the xAgI(1 - x)AgPO(3) system (0 ≤ x ≤ 0.5) were collected in the liquid and glassy states. The difference in the dependence of ionic conductivity on temperature below and above their glass transition temperatures (T(g)) is interpreted by a discontinuity in the charge carrier's mobility mechanisms. Charge carrier displacement occurs through an activated mechanism below T(g) and through a Vogel-Fulcher-Tammann-Hesse mechanism above this temperature. Fitting conductivity data with the proposed model allows one to determine separately the enthalpies of charge carrier formation and migration. For the five investigated compositions, the enthalpy of charge carrier formation is found to decrease, with x, from 0.86 to 0.2 eV, while the migration enthalpy remains constant at ≈0.14 eV. Based on these values, the charge carrier mobility and concentration in the glassy state can then be calculated. Mobility values at room temperature (≈10(-4) cm(2) V(-1) s(-1)) do not vary significantly with the AgI content and are in good agreement with those previously measured by the Hall-effect technique. The observed increase in ionic conductivity with x would thus only be due to an increase in the effective charge carrier concentration. Considering AgI as a weak electrolyte, the change in the effective charge carrier concentration is justified and is correlated to the partial free energy of silver iodide forming a regular solution with AgPO(3).     

Increase in the mobility of photogenerated positive charge carriers in polythiophene

We report the increase in the mobility of charge carriers in regioregular poly 3-hexyl thiophene (RR-P3HT) films by mixing them with tetracyanoethylene (TCNE), which is examined by in situ time-resolved microwave conductivity (TRMC) and transient optical spectroscopy (TOS). TCNE acts not only as an electron acceptor which increases the number of charge carriers on photoexposure but also as a functional additive which enhances the mobility of the charge carriers. This conclusion was deduced from the results of fluorescence quenching, transient optical absorption and photobleaching, and comparison of the TRMC signal with the TOS signal. The combination of the TRMC and TOS techniques represents a comprehensive and fully experimental approach to the determination of the intrinsic carrier mobility in conjugated polymers.     

Two-dimensional materials toward Terahertz optoelectronic device applications

Two-dimensional (2D) materials have become a worldwide hot topic due to their fascinating properties, including high carrier mobility, tunable bandgap, ultra-broadband optical absorption and response. The versatility of 2D materials enable it hold great potential to achieve high performance Terahertz (THz) optoelectronic devices. However, the THz radiation, range from infrared to microwave, known as the THz gap, much less investigated than that of other electromagnetic wave. Motivated by this lack of knowledge, we reviewed the recent advances of research into 2D materials based THz optoelectronic devices. Firstly, we introduced the background and motivation of this review. Then, the suitable 2D material candidates are exhibited, followed by a comprehensive review of their applications in THz generation devices, modulator, THz shielding, and photodetectors. Finally, the challenges and further development directions are concluded. We believe that some milestone investigations of 2D materials based THz optoelectronic devices will emerge soon, which will bring about great industrial revelations in 2D materials-based nanodevice commercialization.     

Simultaneous large enhancements in thermopower and electrical conductivity of bulk nanostructured half-Heusler alloys

Large reductions in the thermal conductivity of thermoelectrics using nanostructures have been widely demonstrated. Some enhancements in the thermopower through nanostructuring have also been reported. However, these improvements are generally offset by large drops in the electrical conductivity due to a drastic reduction in the mobility. Here, we show that large enhancements in the thermopower and electrical conductivity of half-Heusler (HH) phases can be achieved simultaneously at high temperatures through coherent insertion of nanometer scale full-Heusler (FH) inclusions within the matrix. The enhancements in the thermopower of the HH/FH nanocomposites arise from drastic reductions in the "effective" carrier concentration around 300 K. Surprisingly, the mobility increases drastically, which compensates for the decrease in the carrier concentration and minimizes the drop in the electrical conductivity. Interestingly, the carrier concentration in HH/FH nanocomposites increases rapidly with temperature, matching that of the HH matrix at high temperatures, whereas the temperature dependence of the mobility significantly deviates from the typical T(-α) law and slowly decreases (linearly) with rising temperature. This remarkable interplay between the temperature dependence of the carrier concentration and mobility in the nanocomposites results in large increases in the power factor at 775 K. In addition, the embedded FH nanostructures also induce moderate reductions in the thermal conductivity leading to drastic increases in the ZT of HH(1 - x)/FH(x) nanocomposites at 775 K. By combining transmission electron microscopy and charge transport data, we propose a possible charge carrier scattering mechanism at the HH/FH interfaces leading to the observed anomalous electronic transport in the synthesized HH(1 - x)/FH(x) nanocomposites.     

Efficient charge transport along phenylene-vinylene molecular wires

We have studied the motion of charge carriers along isolated phenylene-vinylene (PV) chains using a combination of experimental and theoretical methods. The conductive properties of positive charges along PV chains in dilute solution were studied by using the pulse-radiolysis time-resolved microwave conductivity (TRMC) technique. This technique enables the measurement of high-frequency (tens of GHz) charge carrier mobilities along isolated PV chains without the use of electrodes. The charge carrier mobility along PV chains with finite and infinite length was studied theoretically by charge transport simulations with parameters from density functional theory (DFT) calculations. The high-frequency charge carrier mobility is found to depend strongly on the conjugation length of the PV chains and is found to increase both with increasing length of the PV chain and with increasing conjugation fraction. The experimental results are in good agreement with the calculated results. On the basis of this combined experimental and theoretical study an intrachain charge carrier mobility of a few tens of cm2/Vs is expected for an infinitely long PV chain without conjugation breaks.     

Electrical Methods to Elucidate Charge Transport in Hybrid Perovskites Thin Films and Devices

The panchromatic light absorption and excellent charge carrier transport properties in organo lead halide perovskites allowed to achieve an unprecedented power conversion efficiency in excess of 25 % for thin film photovoltaics fabrication. To understand the underlying phenomena, various comprehensive set of optical and electrical techniques have been employed to investigate the charge carrier dynamics in such devices. In this perspective, we aim to summarize the electrical transport properties of perovskite thin films by using (i) impedance spectroscopy (IS), (ii) space charge limited current (SCLC), (iii) field‐effect transistors (FETs) and (iv) time‐of‐flight (TOF) methods. We have deliberated various equivalent circuit used to model the perovskite solar cells by means of IS. The SCLC technique provide vital electrical parameters such as mobility, activation energy, traps density and distribution, carrier concentration, density of states, etc. The TOF technique measures mobility as a primary parameter while the FETs configuration provide a valuable insight into the in‐plane charge transport in perovskites thin films. We believe that these notable understanding will provide insights into charge carrier dynamics in perovskite materials and devices.     

High-mobility field-effect transistors from large-area solution-grown aligned C60 single crystals

Field-effect transistors based on single crystals of organic semiconductors have the highest reported charge carrier mobility among organic materials, demonstrating great potential of organic semiconductors for electronic applications. However, single-crystal devices are difficult to fabricate. One of the biggest challenges is to prepare dense arrays of single crystals over large-area substrates with controlled alignment. Here, we describe a solution processing method to grow large arrays of aligned C(60) single crystals. Our well-aligned C(60) single-crystal needles and ribbons show electron mobility as high as 11 cm(2)V(-1)s(-1) (average mobility: 5.2 ± 2.1 cm(2)V(-1)s(-1) from needles; 3.0 ± 0.87 cm(2)V(-1)s(-1) from ribbons). This observed mobility is ~8-fold higher than the maximum reported mobility for solution-grown n-channel organic materials (1.5 cm(2)V(-1)s(-1)) and is ~2-fold higher than the highest mobility of any n-channel organic material (~6 cm(2)V(-1)s(-1)). Furthermore, our deposition method is scalable to a 100 mm wafer substrate, with around 50% of the wafer surface covered by aligned crystals. Hence, our method facilitates the fabrication of large amounts of high-quality semiconductor crystals for fundamental studies, and with substantial improvement on the surface coverage of crystals, this method might be suitable for large-area applications based on single crystals of organic semiconductors.     

MWNTs/HDPE复合体系在太赫兹波段的光电性质

利用太赫兹时域光谱技术和电导测量研究了多壁碳纳米管/高密度聚乙烯(MWNTs/HDPE)复合体系的光电性质. 直流电导率结果表明, 复合体系的逾渗阈值在5%左右; 交流电导率则随频率的变化出现一个拐点, 拐点的位置与颗粒浓度以及导电颗粒的存在状态密切相关. 加入碳纳米管后, 复合体系在太赫兹波段的吸收系数和折射率均有很大的提高. 通过假定在此波段导电颗粒在聚合物中的介电行为类似于偶极子的弛豫, 利用Cole-Cole理论对复合材料的介电性质进行了解释.     

Electrical properties of σ-conjugated polymers with additives and their applications in sensors

The charge carrier transport in poly[methyl(phenyl)silylene] (PMPSi) proceeds predominantly along the σ-delocalized Si backbone with participation of interchain hopping and polaron formation. The charge carrier mobility increases with increasing electron affinity of acceptor dopands having zero dipole moments. On the other band, the hole drift mobility is influenced by the dipole moment of the dopand. The electrostatic charge-dipole interactions cause a broadening of the energy distribution of transport states, which results in a decrease in the charge carrier mobility. An addition of organic salts leads, under the conditions of increased humidity, to an increase in electrical conductivity and capacitance. This is demonstrated on the layers PMPSi/1,5-dimorpholino-1,5-diphenylpentamethinium perchlorate.     

Mott-Schottky Analysis and Impedance Spectroscopy of TiO2/6T and ZnO/6T devices

Schottky junctions have been realized by evaporating gold spots on top of sexithiophen (6T), which is deposited on TiO 2 or ZnO with e-beam and spray pyrolysis. Using Mott-Schottky analysis of 6T/TiO2 and 6T/ZnO devices acceptor densities of 4.5x10(16) and 3.7x10(16) cm(-3) are obtained, respectively. For 6T/TiO2 deposited with the e-beam evaporation a conductivity of 9x10(-8) S cm(-1) and a charge carrier mobility of 1.2x10(-5) cm2/V s is found. Impedance spectroscopy is used to model the sample response in detail in terms of resistances and capacitances. An equivalent circuit is derived from the impedance measurements. The high-frequency data are analyzed in terms of the space-charge capacitance. In these frequencies shallow acceptor states dominate the heterojunction time constant. The high-frequency RC time constant is 8 micros. Deep acceptor states are represented by a resistance and a CPE connected in series. The equivalent circuit is validated in the potential range (from -1.2 to 0.8 V) for 6T/ZnO obtained with spray pyrolysis.     

Electrodynamic investigations of conduction processes in humid microcrystalline cellulose tablets

The conduction mechanism in microcrystalline cellulose (MCC) tablets at varying relative humidity (RH) has been investigated by using the techniques of low frequency dielectric spectroscopy and transient current analysis at room temperature. The dependence on RH on the measured conductivity and charge carrier density indicates that a high-power-law-exponent percolation process of cations being conducted on water molecules occupying available 6-OH units on the cellulose chains is the dominating dc conduction mechanism at RH below 3 wt % of moisture content. The experimentally observed decrease in charge carrier mobility with increasing moisture content shows that protons and H3O+ ions that are being blocked at empty 6-OH sites also contribute to the charge transport process in cellulose at low moisture contents.     

Reinvestigation of carrier transport properties in liquid crystalline 2-phenylbenzothiazole derivatives

We have reinvestigated the charge carrier transport properties in a liquid crystal of 2-(4'-heptyloxyphenyl)-6-dodecylthiobenzothiazole (7O-PBT-S12), for which the electronic conduction was first established in rodlike liquid crystals and for which the highest hole mobility in the smectic A (SmA) phase ever achieved was reported. We found that 7O-PBT-S12 exhibited three crystal phases, one of which appeared in a limited temperature range of 10 degrees just below the phase transition temperature from the SmA phase. In this crystal phase, nondispersive transient photohole currents were observed in time-of-flight experiments, and its hole mobility was determined to be 8 x 10(-3) cm(2)/Vs, slightly higher than that reported previously in the SmA phase. For the SmA phase, however, the hole mobility was 1 x 10(-4) cm(2)/Vs. Furthermore, we established the electron transport in the SmA phase of purified 7O-PBT-S12, whose mobility was the same as the hole mobility in that phase. In order to confirm generality of the new findings in 7O-PBT-S12, we investigated the carrier transport properties of its derivative having a short hydrocarbon chain, 2-(4'-heptyloxyphenyl)-6-butylthiobenzothiazole (7O-PBT-S4), and obtained comparable results. The present results correct a mistake in the previous report and give an idea of what a typical mobility in the SmA phase is. On the basis of these results, we discuss what determines the charge carrier mobility in smectic mesophases.     

Charge carrier transport in poly[methyl(phenyl)silylene]: the effect of additives

Poly[methyl(phenyl)silylene], PMPSi, was doped with compounds of the electron acceptor type. The charge carrier mobility increases with increasing electron affinity of the acceptors having zero dipole moments. At the same time the energy distribution of hopping states narrows. On the other hand, the hole drift mobility is influenced by the dipole moment of the dopand. The electrostatic charge carrier‐dipole interaction causes a broadening of the energy distribution of transport states which results in a decrease in the charge carrier mobility. The charge carrier transport can be explained by the disordered polaronic theory, according to which the activation energy of charge carrier mobility has contributions based on the dynamic disorder, i.e. the polaronic barrier, and on the static disorder, i.e. the variation of the energy of transport states as a result of the environment. Copyright © 2001 John Wiley & Sons, Ltd.     

Photoinduced charge carrier generation in a poly(3-hexylthiophene) and methanofullerene bulk heterojunction investigated by time-resolved terahertz spectroscopy

We report on the ultrafast photoinduced charge separation processes in varying compositions of poly(3-hexylthiophene) (P3HT) blended with the electron acceptor [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). Through the use of time-resolved terahertz spectroscopy, the time- and frequency-dependent complex photoconductivity is measured for samples with PCBM weight fractions (WPCBM) of 0, 0.2, 0.5, and 0.8. By analysis of the frequency-dependent complex conductivity, both the charge carrier yield and the average charge carrier mobility have been determined analytically and indicate a short (<0.2 nm) carrier mean free path and a suppressed long-range transport that is characteristic of carrier localization. Studies on pure films of P3HT demonstrate that charge carrier generation is an intrinsic feature of the polymer that occurs on the time scale of the excitation light, and this is attributed to the dissociation of bound polaron pairs that reside on adjacent polymer chains due to interchain charge transfer. Both interchain and interfacial charge transfer contribute to the measured photoconductivity from the blended samples; interfacial charge transfer increases as a function of increasing PCBM. The addition of PCBM to the polymer films surprisingly does not dramatically increase the production of charge carriers within the first 2 ps. However, charge carriers in the 0.2 and 0.5 blended films survive to much longer times than those in the P3HT and 0.8 films.     

磁控溅射中靶-基底距离与Si共掺对ZnO:Al薄膜性质的影响

使用射频磁控溅射, 在正方形石英衬底上沉积透明导电掺Al的ZnO(AZO)和Si共掺AZO(AZO:Si)薄膜. 系统研究了靶-基底距离(D_st)和Si共掺对AZO薄膜电学、光学性质的影响. 电阻率、载流子浓度和迁移率都强烈地依赖于靶-基底距离, 随着靶-基底距离的减少, 载流子浓度和迁移率都有显著的增加, 电导率也随之提高. 在靶-基底距离为4.5 cm处, 得到最低电阻率4.94×10^-4 Ω·cm, 此时的载流子浓度和迁移率分别是3.75×10²⁰ cm^-3和33.7 cm²·V^-1·s^-1. X射线光电子能谱(XPS)、X射线衍射(XRD)和边界散射模型被用于分析载流子浓度、迁移率和靶-基底距离的关系. 透射谱显示, 在可见-近红外范围内所有样品均有大于93%的平均透射率, 同时随着靶基距离的减少, 吸收边蓝移. AZO:Si表现出可与AZO相比拟的高电导和高透射光学特性, 但在热湿环境中却有着更好的电阻稳定性, 这在实际使用中很有意义.     

Improving the Performance of TIPS-pentacene Thin FilmTransistors via Interface Modification

Understanding the structure-performance relationship is crucial for optimizing the performance of organic thin film transistors. Here, two interface modification methods were applied to modulate the thin film morphology of the organic semiconductor, 6,13-bis(triisopropylsilylethynyl)pentacene(TIPS-pentacene). The resulting different film morphologies and packing structures led to distinct charge transport abilities. A substantial 40-fold increase in charge carrier mobility was observed on the octadecyltrichlorosilane(OTS)-modified sample compared to that of the transistor on the bare substrate. A better charge mobility greater than 1 cm²·V^-1·s^-1 is realized on the p-sexiphenyl(p-6P)- modified transistors due to the large grain size, good continuity and, importantly, the intimate π-π packing in each domain.     

Stable polythiophene semiconductors incorporating thieno[2,3-b]thiophene

This work describes a new design methodology that allows the preparation of air stable, semiconducting thiophene polymers with high charge carrier mobilities. The incorporation of thieno[2,3-b]thiophene into a polythiophene backbone introduces cross-conjugated double bonds that disfavor full delocalization, leading to high ionization potential in comparison to a fully conjugated polythiophene, with no reduction in charge carrier mobility. The resulting solution processable polymers exhibit charge carrier mobilities up to 0.15 cm2/V s and on/off ratios greater than 105 when measured in air. Transistors exhibit lifetimes of several months in air with no encapsulation necessary.