Flash-photolysis Time-resolved Microwave Conductivity Research Articles

Crystal structure and carrier transport properties of a new 3D mixed-valence Cu(i)–Cu(ii) coordination polymer including pyrrolidine dithiocarbamate ligand

A novel mixed-valence Cu(i)-Cu(ii) coordination polymer having an infinite three-dimensional (3D) structure, {[Cu(I)(4)Cu(II)(2)Br(4)(Pyr-dtc)(4)]·CHCl(3)}(n) (1) (Pyr-dtc(-) = pyrrolidine dithiocarbamate), has been prepared and structurally characterized via X-ray diffraction. This complex consists of 1D Cu(i)-Br chains and bridging mononuclear copper(ii) units of Cu(II)(Pyr-dtc)(2), which form an infinite 3D network. A magnetic study indicates that this complex includes copper(ii) ions exhibiting a weak antiferromagnetic interaction (θ = -0.086 K) between the unpaired electrons of the copper(ii) ions present in the diamagnetic Cu(i)-Br chains. The carrier transport properties of 1 are investigated using an impedance spectroscopy technique and flash-photolysis time-resolved microwave conductivity measurement (FP-TRMC). The impedance spectroscopy reveals that this complex exhibits intriguing semiconducting properties at a small activation energy (E(a) = 0.29 eV (bulk)). The sum of the mobilities of the negative and positive carriers estimated via FP-TRMC is Σμ∼ 0.4 cm(2) V(-1) s(-1).

Structural and Electronic Properties of Extremely Long Perylene Bisimide Nanofibers Formed through a Stoichiometrically Mismatched, Hydrogen‐Bonded Complexation

Extremely long nanofibers, whose lengths reach the millimeter regime, are generated via co-aggregation of a melamine-appended perylene bisimide semiconductor and a substituted cyanurate, both of which are ditopic triple-hydrogen-bonding building blocks; they co-aggregate in an unexpected stoichiometrically mismatched 1:2 ratio. Various microscopic and X-ray diffraction studies suggest that hydrogen-bonded polymeric chains are formed along the long axis of the nanofibers by the 1:2 complexation of the two components, which further stack along the short axis of the nanofibers. The photocarrier generation mechanism in the nanofibers is investigated by time-of-flight (TOF) experiments under electric and magnetic fields, revealing the birth and efficient recombination of singlet geminate electron-hole pairs. Flash-photolysis time-resolved microwave conductivity (FP-TRMC) measurements revealed intrinsic 1D electron mobilities up to 0.6 cm(2) V(-1) s(-1) within nanofibers.

Supramolecular Structures and Photoelectronic Properties of the Inclusion Complex of a Cyclic Free‐Base Porphyrin Dimer and C60

A cyclic free-base porphyrin dimer H4-CPD(Py) (CPD = cyclic porphyrin dimer) linked by butadiyne moieties bearing 4-pyridyl groups self-assembles to form a novel porphyrin nanotube in the crystalline state. The cyclic molecules link together through nonclassical C-H⋅⋅⋅N hydrogen bonds and π–π interactions of the pyridyl groups along the crystallographic a axis. H4-CPD(Py) includes a C60 molecule in its cavity in solution. In the crystal structure of the inclusion complex (C60⊂H4-CPD(Py)), the dimer “bites” a C60 molecule by tilting the porphyrin rings with respect to each other, and there are strong π–π interactions between the porphyrin rings and C60. The included C60 molecules form a zigzag chain along the crystallographic b axis through van der Waals contacts with each other. Femtosecond laser flash photolysis of C60⊂H4-CPD(Py) in the solid state with photoexcitation at 420 nm shows the formation of a completely charge-separated state {H4-CPD(Py)·+ + C60·−}, which decays with a lifetime of 470 ps to the ground state. The charge-carrier mobility of the single crystal of C60⊂H4-CPD(Py) was determined by flash photolysis time-resolved microwave conductivity (FP-TRMC) measurements. C60⊂H4-CPD(Py) has an anisotropic charge mobility (Σμ = 0.16 and 0.13 cm2 V(−1) s(−1)) along the zigzag chain of C60 (which runs at 45° and parallel to the crystallographic b axis). To construct a photoelectrochemical cell, C60⊂H4-CPD(Py) was deposited onto nanostructured SnO2 films on a transparent electrode. The solar cell exhibited photovoltaic activity with an incident photon to current conversion efficiency of 17%.

The Effect of Nanoparticle Shape on the Photocarrier Dynamics and Photovoltaic Device Performance of Poly(3‐hexylthiophene):CdSe Nanoparticle Bulk Heterojunction Solar Cells

AbstractThe charge separation and transport dynamics in CdSe nanoparticle:poly(3‐hexylthiophene) (P3HT) blends are reported as a function of the shape of the CdSe‐nanoparticle electron acceptor (dot, rod, and tetrapod). For optimization of organic photovoltaic device performance it is crucial to understand the role of various nanostructures in the generation and transport of charge carriers. The sample processing conditions are carefully controlled to eliminate any processing‐related effects on the carrier generation and on device performance with the aim of keeping the conjugated polymer phase constant and only varying the shape of the inorganic nanoparticle acceptor phase. The electrodeless, flash photolysis time‐resolved microwave conductivity (FP‐TRMC) technique is used and the results are compared to the efficiency of photovoltaic devices that incorporate the same active layer. It is observed that in nanorods and tetrapods blended with P3HT, the high aspect ratios provide a pathway for the electrons to move away from the dissociation site even in the absence of an applied electric field, resulting in enhanced carrier lifetimes that correlate to increased efficiencies in devices. The processing conditions that yield optimum performance in high aspect ratio CdSe nanoparticles blended with P3HT result in poorly performing quantum dot CdSe:P3HT devices, indicating that the latter devices are inherently limited by the absence of the dimensionality that allows for efficient, prolonged charge separation at the polymer:CdSe interface.

Use of Side-Chain Incompatibility for Tailoring Long-Range p/n Heterojunctions: Photoconductive Nanofibers Formed by Self-Assembly of an Amphiphilic Donor-Acceptor Dyad Consisting of Oligothiophene and Perylenediimide

To tailor organic p/n heterojunctions with molecular-level precision, a rational design strategy using side-chain incompatibility of a covalently connected donor-acceptor (D-A) dyad has been successfully carried out. An oligothiophene-perylenediimide dyad, when modified with triethylene glycol side chains at one terminus and dodecyl side chains at the other (2(Amphi)), self-assembles into nanofibers with a long-range D/A heterojunction. In contrast, when the dyad is modified with dodecyl side chains at both termini (2(Lipo)), ill-defined microfibers result. In steady-state measurements using microgap electrodes, a cast film of the nanofiber of 2(Amphi) displays far better photoconducting properties than that of the microfiber of 2(Lipo). Flash-photolysis time-resolved microwave conductivity measurements, in conjunction with transient absorption spectroscopy, clearly indicate that the nanofiber of 2(Amphi) intrinsically allows for better carrier generation and transport properties than the microfibrous assembly of 2(Lipo).

Photogeneration of charge carrier correlated with amplified spontaneous emission in single crystals of a thiophene/phenylene co-oligomer

Thiophene/phenylene co-oligomers have substantial promise for the use of not only organic electronics but also organic optical devices. However, considerably less is known about the correlation between their optical and optoelectronic properties. We have investigated the charge carrier generation in 1,4-bis(5-phenylthiophen-2-yl)benzene (AC5) single crystals by flash-photolysis time-resolved microwave conductivity (TRMC) and transient absorption spectroscopy (TAS). It was found that the dependence of photocarrier generation efficiency on excitation photon density differed from that of emission efficiency once amplified spontaneous emission (ASE) and resultant spectrally narrowed emission occur upon exposure to 355 nm. In contrast, the dependences of emission and photocarrier generation efficiencies were identical when ASE was not involved at a different excitation wavelength (193 nm). An approximated analytical solution of rate equation considering ASE or singlet-singlet annihilation was applied to the experiments, exhibiting good agreement. On the basis of TRMC, TAS, and extinction coefficient of radical cation assessed by pulse radiolysis, the minimum charge carrier mobility was estimated, without electrodes, to be 0.12 cm(2) V(-1) s(-1). The dynamics of charge carrier and triplet excited state is discussed, accompanying with examination by time-dependent density functional theory. The present work would open the way to a deeper understanding of the fate of excited state in optically robust organic semiconducting crystals.

Physical Properties, Charge Carrier Mobility, and Photovoltaic Performance of Dendritic Oligothiophene Bearing Naphthalene Bis(dicarboximide) Groups

Dendritic oligothiophene having naphthalene bis(dicarboximide) (NDI) was synthesized, and its physical properties were investigated by ultraviolet–visible (UV–vis) spectroscopy and cyclic voltammetry. The charge carrier mobility measurements by organic field-effect transistor devices and flash-photolysis time-resolved microwave conductivity measurements revealed p-channel behavior. The photovoltaic performance of the dendritic oligothiophene–NDI dyad with PCBM exhibited a power conversion efficiency of 0.14%.

Ambipolar-transporting coaxial nanotubes with a tailored molecular graphene–fullerene heterojunction

Despite a large steric bulk of C(60), a molecular graphene with a covalently linked C(60) pendant [hexabenzocoronene (HBC)-C(60); 1] self-assembles into a coaxial nanotube whose wall consists of a graphite-like pi-stacked HBC array, whereas the nanotube surface is fully covered by a molecular layer of clustering C(60). Because of this explicit coaxial configuration, the nanotube exhibits an ambipolar character in the field-effect transistor output [hole mobility (micro(h)) = 9.7 x 10(-7) cm(2) V(-1) s(-1); electron mobility (micro(e)) = 1.1 x 10(-5) cm(2) V(-1) s(-1)] and displays a photovoltaic response upon light illumination. Successful coassembly of 1 and an HBC derivative without C(60) (2) allows for tailoring the p/n heterojunction in the nanotube, so that its ambipolar carrier transport property can be optimized for enhancing the open-circuit voltage in the photovoltaic output. As evaluated by an electrodeless method called flash-photolysis time-resolved microwave conductivity technique, the intratubular hole mobility (2.0 cm(2) V(-1) s(-1)) of a coassembled nanotube containing 10 mol % of HBC-C(60) (1) is as large as the intersheet mobility in graphite. The homotropic nanotube of 2 blended with a soluble C(60) derivative [(6,6)-phenyl C(61) butyric acid methyl ester] displayed a photovoltaic response with a much different composition dependency, where the largest open-circuit voltage attained was obviously lower than that realized by the coassembly of 1 and 2.

Impact of side-chain length on alternating current mobility of charge carriers in regioregular poly(3-alkylthiophene) films

The charge carrier mobility in films of regioregular polythiophenes substituted by n-alkyl side-chains, of butyl, hexyl, octyl, decyl, and dodecyl, was investigated by flash-photolysis time-resolved microwave conductivity (FP-TRMC), and transient photoabsorption spectroscopy excited at 355nm. The charge carrier concentration was estimated from inspecting radical anions of perylenecarboxydiimide (PDI), which also acts as an efficient electron acceptor to improve the yield of photocarrier generation. We discuss the dependence of side-chain length in terms of decay dynamics, quantum yield of charge carrier generation, and alternating current (ca. 9GHz) mobility, which exceeded 0.12cm2/(Vs).

Unusual Side‐Chain Effects on Charge‐Carrier Lifetime in Discotic Liquid Crystals

When hexa-peri-hexabenzocoronene (HBC) carries paraffinic side chains with ester-ether termini (1a-1c), a hexagonal columnar liquid-crystalline (LC) mesophase forms, which is characterized by a very wide temperature range (ca. 0-300 degrees C). The LC materials from these HBC derivatives show characteristic electronic properties with an extremely long photocarrier lifetime. For example, by means of a flash-photolysis time-resolved microwave conductivity technique, the photocarrier lifetime, observed for liquid-crystalline 1a, is as long as 14 ms, which is four-orders of magnitude longer than that of fully paraffinic HBC 4 (0.0011 ms). The maximum transient photoconductivities of liquid-crystalline 1a-1c are comparable to one another and also to those of HBCs without ester-ether terminals. Liquid-crystalline 1a exhibits an obvious photocurrent generation in response to light illumination.

Electrodeless Determination of Charge Carrier Mobility in Poly(3-hexylthiophene) Films Incorporating Perylenediimide as Photoconductivity Sensitizer and Spectroscopic Probe

The charge carrier mobility and its generation efficiency in regioregular and regiorandom poly(3-hexylthiophene) (P3HT) films upon exposure to light pulses are studied by flash-photolysis time-resolved microwave conductivity and transient absorption spectroscopy. For the full experimental determination of alternating current mobility without electrodes, we incorporated a perylenecarboxydiimide (PDI) derivative into the films not only to increase the photoconductivity but also estimate the quantum efficiency of charge generation by kinetic tracing of PDI radical anions. We discuss the mobility, quantum efficiency, decay of charge carriers, and film morphology observed by an X-ray diffraction and an atomic force microscope with various PDI concentrations. It is found that the three-dimensional mobility mainly attributed to the positive charges on regioregular P3HT is decreased from 0.12 to 0.070 cm2/Vs by addition of PDI which disturbs the intermolecular π-stacking, while that on regiorandom P3HT shows an almost constant value of 0.006 cm2/Vs. The quantum efficiency in regioregular P3HT reveals a peak at 6 mol % PDI for 355-nm excitation. The reason for the appearance of the peak is examined by changing excitation wavelength and inspecting the steady-state absorption and fluorescence spectra. The methodology and findings obtained by utilizing the additive as both an acceptor and a probe is proved to be useful for the investigations on optoelectronic properties of wide varieties of organic semiconductors.

Prominent Electron Transport Property Observed for Triply Fused Metalloporphyrin Dimer: Directed Columnar Liquid Crystalline Assembly by Amphiphilic Molecular Design

A triply fused copper porphyrin dimer, when site-specifically modified on its periphery with hydrophobic and hydrophilic wedges (1C12/TEG), self-assembles into a columnar liquid crystalline (LC) mesophase over a wide-temperature range from -17 to 99 degrees C but gives rise to an amorphous solid when modified with only hydrophobic (1C12/C12) or hydrophilic wedges (1TEG/TEG). A LC film of 1C12/TEG displays at 16 degrees C a top-class one-dimensional electron mobility (0.27 cm2/V x s), as evaluated from its maximum flash-photolysis time-resolved microwave conductivity.

Amphiphilic Molecular Design as a Rational Strategy for Tailoring Bicontinuous Electron Donor and Acceptor Arrays: Photoconductive Liquid Crystalline Oligothiophene−C60 Dyads

For tailoring solution-processable optoelectronic thin films, a rational strategy with amphiphilic molecular design is proposed. A donor-acceptor dyad consisting of an oligothiophene and C60, when modified with a hydrophilic wedge on one side and a paraffinic wedge on the other (1Amphi), forms over a wide temperature range a photoconducting smectic A liquid crystal having bicontinuous arrays of densely packed donor and acceptor units. In contrast, when modified with only paraffinic wedges (1Lipo), the dyad forms a smectic A liquid crystalline mesophase, which however is poorly conductive. As indicated by an absorption spectral feature along with a synchrotron radiation small-angle X-ray scattering profile, 1Lipo in the lamellar structure does not adopt a uniform head/tail orientation. Such defective donor and acceptor arrays likely contain a large number of trapping sites, leading to short-lived charge carriers, as observed by a flash photolysis time-resolved microwave conductivity study.

Quenching of Excitons by Holes in Poly(3-hexylthiophene) Films

The generation of excitons and their interaction with holes in films of neat regioregular poly(3-hexylthiophene) and the polymer blended with 1 wt% of the electron-acceptor [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) have been studied using flash-photolysis time-resolved microwave conductivity. The sublinear relationship between the photogenerated hole density and the incident light intensity, in both the neat polymer and the donor−acceptor blend, can be attributed to the quenching of excitons by holes, at a rate characterized by a second-order rate constant (γ2) of 3 × 10−8 cm3/s. This value is larger than that found for other, luminescent conjugated polymers; the difference may be attributed to a greater collision probability, due to the higher mobility of the interacting species, or to an enhancement of the quenching rate once they are in close proximity. The phenomenon has consequences for the ultimate efficiency of organic photovoltaic solar cells that are based on the simple polymer:PCBM bulk heterojunction, especially under conditions of solar concentration.

Intra-molecular mobility of charge carriers along oligogermane backbones studied by flash photolysis time-resolved microwave conductivity and transient optical spectroscopy techniques

Time-resolved microwave conductivity (TRMC) measurement has been performed for fullerene-doped thin films of oligo (dimethylgermane) at different excitation energies to evaluate the intra-molecular mobility of holes along their Ge backbones. Photo-induced electron transfer reaction between oligogermane and fullerene has been observed in the solution with a variety of solvent polarity using transient optical spectroscopy (TOS). The transient spectrum at 391 nm can be attributed to the radical cation of the oligomer under an excitation at 532-nm light, whereas the same spectrum (391 nm) is the overlapping of absorptions of radical cations and neutral radicals of oligogermanes upon exposure of 355-nm light in polar solvent. A combined TRMC and TOS experiments on the solutions of oligomer confirms the conductive transients originate from the radical cations on the backbone chains.

Superstructure‐Dependent Optical and Electrical Properties of an Unusual Face‐to‐Face, π‐Stacked, One‐Dimensional Assembly of Dehydrobenzo[12]annulene in the Crystalline State

To develop a novel pi-conjugated molecule-based supramolecular assembly, we designed and synthesized trisdehydrotribenzo[12]annulene ([12]DBA) derivative 2 with three carboxyl groups at the periphery. Recrystallization of 2 from DMSO gave a crystal of the solvate 23 DMSO. Crystallographic analysis revealed, to our surprise, that a face-to-face pi-stacked one-dimensional (1D) assembly of 2 was achieved and that the DMSO molecule played a significant role as a "structure-dominant element" in the crystal. This is the first example of [12]DBA to stack completely orthogonal to the columnar axis. To reveal its superstructure-dependent optical and electrical properties, 2 and its parent molecule 1, which crystallizes in a herringbone fashion, were subjected to fluorescence spectroscopic analysis and charge-carrier mobility measurements in crystalline states. The 1D stacked structure of 2 provides a red-shifted, broadened, weakened fluorescence profile (lambda(max) = 545 nm, phi(F) = 0.01), compared to 1 (lambda(max) = 491 nm, phi(F) = 0.12), due to strong interactions between the p orbitals of the stacked molecules. The charge-carrier mobility of the single crystal of 23 DMSO, as well as 1, was determined by flash photolysis time-resolved microwave conductivity (FP-TRMC) measurements. The single crystal of 23 DMSO revealed significantly-anisotropic charge mobility (sigma(mu) = 1.5x10(-1) cm(2) V(-1) s(-1)) along the columnar axis (crystallographic c axis). This value is 12 times larger than that along the orthogonal axis (the a axis).

Dynamics of photogenerated charge carrier and morphology dependence in polythiophene films studied by in situ time-resolved microwave conductivity and transient absorption spectroscopy

For the investigation of photoconductivity and charge carrier dynamics in regioregular poly(3-hexylthiophene) (RR-P3HT), an in situ flash-photolysis time-resolved microwave conductivity (FP-TRMC) and transient absorption spectroscopy (TAS) was performed using 6.4 and 3.5 eV photon excitation. Since the former energy is sufficiently higher than ionization potential of RR-P3HT, a direct ionization and consequent bulk charge recombination was observed. The dynamics of charge carriers of transient conductivity and photoabsorption kinetics are discussed in terms of the X-ray diffraction pattern and film morphology of RR-P3HT observed by tapping mode atomic force microscope.

Charge-carrier dynamics in polythiophene films studied by in-situ measurement of flash-photolysis time-resolved microwave conductivity (FP-TRMC) and transient optical spectroscopy (TOS)

An in-situ measurement system for flash-photolysis time-resolved microwave conductivity (FP-TRMC) and transient optical spectroscopy (TOS) has been developed to perform simultaneous measurements of photo-induced changes in conductivity and charge-carrier density in an organic thin film. The electric field in the resonant cavity designed for the present system was analysed by electrostatic simulation. Using the present system and the simulated electric field, the photoconductivity and transient absorption in a regioregular poly(3-hexyl thiophene) film were measured using one particular geometry under photon excitation energies of 6.39, 4.98, 3.48, and 2.34 eV. The dynamics of photogenerated charge carriers is discussed in terms of the excitation energy and incident photon intensity. The transient absorption spectrum induced by 3.48 eV light is presented and compared with the TRMC transient.

Photoconductivity in fullerene-doped polysilane thin films

Flash photolysis time-resolved microwave conductivity (FP-TRMC) measurements have been performed to study the transport properties of charge carriers in the polysilane films. The effect of C 60 concentrations on photoconductivity of poly(methylphenylsilane) (PMPS) and poly( n-hexylphenylsilane) (PHPS) films has been studied using a variety of excitation light sources. The value of ϕ ∑ μ , which is the product of quantum efficiency of photocarrier generation ( ϕ) and sum of moibilities of the carriers ( ∑ μ ), depends strongly on C 60 concentration upon exposure of 532 nm. The quantum efficiency reaches ∼0.06 with C 60 concentration at 5.7 mol%, and saturates at the higher concentrations. The ϕ ∑ μ value increases considerably upon exposure of 193 nm up to 1.22 × 10 −3 cm 2/Vs without significant dependence on C 60 concentration, suggesting the direct formation of electron-hole pair by 6.39 eV photon absorption with the higher ϕ value at ∼0.12. The present technique gave the estimates of intra-chain mobility of charge carriers in PMPS and PHPS, and one-order magnitude higher intra-chain mobility was observed in PHPS than that in PMPS. This is suggestive of a highly ordered Si backbone conformation in PHPS. The intra-chain mobility in PMPS, however, is at least two orders of magnitude higher than the mobility values estimated by conventional time-of-flight techniques. Thus we conclude that the higher mobility than ∼10 −3 cm 2/Vs ( E ∼ 0) is realizable even with PMPS by precise synthesis and device fabrication free from disordering, defects, impurities, etc.

Mobilities of Charge Carriers in Dendrite and Linear Oligogermanes by Flash Photolysis Time-resolved Microwave Conductivity Technique

Abstract The photoconductive properties of a series of oligogermanes with dendrite or linear skeleton have been studied by flash photolysis time-resolved conductivity (FP-TRMC) technique. The values of mobility (Σμ) and photocarrier generation yield (φ) have been discussed as a function of C60 concentration. The φΣμ values in the order of 10−4 to 10−3 cm2/Vs were observed for the oligogermanes upon exposure to 532, 355, and 193 nm light. The intrinsic value of mobility in the derivatives was also estimated without contribution from the additives, suggesting the presence of a highly conducting path along the Ge backbones of not only linear oligogermanes but also hyper-branched germanium dendrites.