Π-conjugated Organic Semiconductors Research Articles

Effect of a Ag-rGO structure on the SERS activity of PEDOT:PSS films

π-Conjugated organic semiconductors with tunable electronic structures are new prospective active substrate materials for surface-enhanced Raman scattering (SERS). However, observing higher SERS activity when using organic semiconductors as substrates could be difficult because there is no plasmonic effect of hot electrons. Here, we designed a Ag-reduced graphene oxide (rGO) structure, introduced it into a poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS) solution, and spin-coated the solution to obtain a Ag-rGO/PEDOT:PSS (ARPP) film. Our analyses demonstrate that the introduction of this Ag-rGO structure can not only enhance the electromagnetic field effect based on plasmon resonance but also improve the interaction between the target molecule and the substrate in the ARPP film. This innovative approach not only improves the SERS activity of π-conjugated organic polymers but also provides novel ideas for the preparation of other organic semiconductor-based SERS substrates.

Molecular-Orbital Delocalization Enhances Charge Transfer in π-Conjugated Organic Semiconductors.

π-Conjugated organic semiconductors are promising materials for surface-enhanced Raman scattering (SERS)-active substrates based on the tunability of electronic structures and molecular orbitals. Herein, we investigate the effect of the temperature-mediated resonance-structure transitions of poly(3,4-ethylenedioxythiophene) (PEDOT) in poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT : PSS) films on the interactions between substrate and probe molecules, thereby affecting the SERS activity. Absorption spectroscopy and density functional theory calculations show that this effect occurs mainly due to delocalization of the electron distribution in molecular orbitals, effectively promoting the charge transfer between the semiconductor and probe molecules. In this work, we investigate for the first time the effect of electron delocalization in molecular orbitals on SERS activity, which will provide new design ideas for the development of highly sensitive SERS substrates.

Effective spin injection into the organic semiconductor PTCDA evaluated by a normalization method

Studies of spin current injection, transport, and interface control have drawn attention recently for efficient organic spintronic devices. In this study, we apply both spin pumping (SP) and the longitudinal spin Seebeck effect (LSSE) to inject spin currents into a π-conjugated organic semiconductor, perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), and characterize injection and transport by measuring inverse spin Hall voltage VISHE in spin detectors. A normalization factor introduced to SP analysis eliminates a contribution provoked by deviation of spin sources and leads to a more accurate determination of the spin diffusion length in PTCDA. While SP with Permalloy as a spin source is effective in generating detectable VISHE, the LSSE from yttrium iron garnet shows no convincing sign of spin injection. In addition, spin-flip scattering induced by hybrid states undermining electrical spin injection is negligible in SP. These results are attributed to interfaces between spin sources and PTCDA, indicative of the importance of injection methods and material choices.

Catalytic oxidation of ibuprofen over bulk heterojunction photocatalysts based on conjugated donor-acceptor configured benzoselenadiazole molecule

The use of photocatalysts for acquiring direct photon energy from sunlight is a promising way to clean the environment, particularly the remediation of contaminants from water. In this work, firstly π-conjugated organic semiconductor configuring benzoselenadiazole, 4-(3,5-bis(trifluoromethyl) phenyl)-7-(5′-hexyl-[2,2′-bithiophen]-5-yl)-benzo [c] (Kümmerer, 2009; Chen et al., 2018; Randeep et al., 201) selenadiazole, abbreviated as (RTh-Se-F), was synthesized. The designed RTh-Se-F with an extended π-conjugation showed good optical properties in the visible region and estimated a low optical band gap of ∼2.02 eV . The molecular orbitals i.e. HOMO (−5.33 eV) and LUMO (−3.31 eV) for RTh-Se-F organic semiconductor were suitably aligned to energy levels of (Madhavan et al., 2010Madhavan et al., 2010)-Phenyl-C71-butyric acid methyl esters (PC71BM) which resulted in the broadening of absorption and covering of entire visible region. RTh-Se-F was integrated with varied weight percentages (wt %) of PC71BM to obtain bulk heterojunction (BHJ) and applied as efficient visible light driven BHJ photocatalyst for an effective oxidation of ibuprofen. RTh-Se-F@PC71BM (1:2, wt %) BHJ photocatalyst showed the superior ibuprofen degradation of ∼93% within 90 min under visible light illumination. The maximum degradation rate by BHJ photocatalyst might be accredited to the broadening of absorption capacity and improved lifetime of photogenerated electron-hole pairs which might be resulted from high absorption properties of RTh-Se-F organic semiconductor.

Vapor-Phase Living Assembly of π-Conjugated Organic Semiconductors.

In contrast to well-studied amphiphilic block copolymers (BCPs) and π-stacked dyes, living assembly of hydrophobic π-conjugated materials has not yet been explored to date. Using a microspacing physical vapor transport (PVT) technique, the prefabricated microrods of organic semiconductors involving 9,10-dicyanoanthracene (DCA, A) or its binary alloy (B) can act as seeds to initiate living homoepitaxial growth from their ends, giving elongated microrods with controlled length. Red-green-red tricolor fluorescent microrod heterostructures with low dispersity are further realized by living heteroepitaxial growth of B microrod blocks on A seed microrod tips. Upon varying the growth sequence of each block, reverse triblock microrods are also accessible. Such a seed-induced living growth is applicable to triblock microrod heterostructures of more binary combinations as well as even more complex penta- and hepta-block heterostructures comprising A and B. By virtue of a convenient vapor-phase growth method, the present work demonstrates the generality of living assembly of π-conjugated materials.

Large π-Conjugated Metal-Organic Frameworks for Infrared-Light-Driven CO2 Reduction.

It remains challenging to excite traditional photocatalysts through near-infrared (NIR) light. Attempts to use NIR-light-response materials for photochemical reduction usually suffer from inapposite band position due to extremely narrow band gaps. Here, we report that large π-conjugated organic semiconductor engineered metal-organic framework (MOF) can result in NIR-light-driven CO2 reduction catalyst with high photocatalytic activity. A series of mesoporous MOFs, with progressively increased macrocyclic π-conjugated units, were synthesized for tuning the light adsorption range and catalytic performance. Attainment of these MOFs in single-crystal form revealed the identical topology and precise spatial arrangements of constituent organic semiconductor units and metal clusters. Furthermore, the ultrafast spectroscopic studies confirmed the formation of charge separation state and the mechanism underlying photoexcited dynamics. This combined with X-ray photoelectron spectroscopy and in situ electron paramagnetic resonance studies verified the photoinduced electron transfer pathway within MOFs for NIR-light-driven CO2 reduction. Specifically, tetrakis(4-carboxybiphenyl)naphthoporphyrin) MOF (TNP-MOF) photocatalyst displayed an unprecedentedly high CO2 reduction rate of over 6630 μmol h-1 g-1 under NIR light irradiation, and apparent quantum efficiencies (AQE) at 760 and 808 nm were over 2.03% and 1.11%, respectively. The photocatalytic performance outperformed all the other MOF-based photocatalysts, even visible-light-driven MOF-based catalysts.

OLED application of π-conjugated phenylimino carboxylic acid organic semiconductor material

The organic semiconductor materials which form Self-Assembled Monolayers (SAMs) on Indium Tin Oxide (ITO) surface have been synthesized and used in Organic Light Emitting Diode (OLED) applications. The synthesized molecules are bonded chemically to the hydrophilic and rough ITO surface and formed a new hydrophobic and smother surface of ITO by the effect of SAM formation. The synthesized SAM molecule is 4″, 4″″-[biphenyl-4,4″-diylbis(phenylimino)]dibiphenyl-4-carboxylic acid (MZ-187) that contains carboxylic acid head group to bond to ITO surface. The formation on ITO surface is analyzed by cyclic voltammetry (CV) and atomic force microscopy (AFM). Two configurations, ITO/SAM(MZ-187)/HTL/EML/LiF/Al (MZ187-OLED) and ITO/HTL/EML/LiF/Al (bare-OLED), are fabricated to investigate the effect of SAM layer on the performance of the OLED device. Current–voltage (I–V) characterization of OLED devices are carried out and the luminescence of the devices are measured by integrating sphere under nitrogen gas in a glow box system. The quantum efficiency is calculated to determine how to affects the SAM layers on OLEDs performance. As a consequence, it is determined that the OLED device containing MZ-187 SAM layer, a similar structure with N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD), is exhibited a better OLED performance compare to the device without SAM layer.

Organic Semiconductors with Benzoic Acid Based Additives for Solution- Processed Thin Film Transistors

Background: although solution-processed small molecular organic semiconductors have attracted great attention for organic electronic applications, the intrinsic crystal misorientation of the organic semiconductors still remains a challenging issue. Objective: two benzoic acid-based additives, i.e. 4-propylbenzoic acid (RBA) and 4-octylbenzoic acid (OBA), were employed to regulate the crystal growth and charge transport of organic semiconductors. Methods: RBA and OBA were mixed with a π-conjugated organic semiconductor 6,13- bis(triisopropylsilylethynyl) pentacene (TIPS pentacene), respectively. Organic thin-film transistors (OTFTs) with different bottom-gate, top-contact and bottom-gate, bottom-contact configurations were fabricated to investigate charge transport. Results: RBA and OBA share a similar benzoic acid structure with the same hydrophilic head but differ in the length of the hydrophobic tail. The benzoic acid-based additive forms a stratified selfassembled interfacial layer and maneuvers nucleation seed distribution via synergetic interactions with the silanol groups on silicon dioxide and with the bulky side chains of the semiconductor. The TIPS pentacene film with OBA additive exhibited a 10-fold reduction in misorientation angle as compared to the counterpart with RBA. Conclusion: Distinct thin film morphology in terms of crystal alignment and grain width was observed and correlated to the hydrophobic tail length. In particular, OTFTs incorporating the TIPS pentacene/benzoic acid mixture as the active layer showed a mobility of up to 0.15 cm2/Vs.

Influence of Various Doping Agents on Organic Semiconductors’ Physicochemical Properties

Due to the electron-reach π-conjugated organic semiconductors system, chemical so-called p-type doping is easily achievable. Oxidation by some molecules, atoms, or ions called “dopants” or “doping agents” force the molecule to accept the positive electrical charge. In general, there are several “theoretical” ways to increase the conductivity of the semiconductors by the introduction, as mentioned above, of the charge carriers into the structure of the molecule. For this reason, it was designed and synthesized a model molecule possessing: (a) acidic hydrogen—a fragment able to undergo chemical oxidation; (b) a unit having a pi-excess ring—vulnerable to electrochemical oxidation; (c) a free electron pair—susceptible to protonation and methylation; and finally (d) a fragment that is Lewis base in nature—that is, it can form adducts with Lewis acid. In this paper, we are reporting a comprehensive study (with the aid of DFT calculation) concerning the different doping agents’ influence on physicochemical properties of the model (namely 2,5-bis(2-(2-thienyl)-thien-5-yl)thiazolo[5,4-d]thiazole) organic semiconductor.

Donor-Acceptor Conjugated Macrocycles with Polyradical Character and Global Aromaticity.

SummaryPolyradical character and global aromaticity are fundamental concepts that govern the rational design of cyclic conjugated macromolecules for optoelectronic applications. Here, we report donor-acceptor (D−A) conjugated macromolecules with and without π-spacer derivatives to tune the antiferromagnetic couplings between the unpaired electrons. The macromolecules without π-spacer have a closed-shell electronic configuration and show global nonaromatic character in the singlet and lowest triplet states. However, the derivatives with π-spacer develop a nearly pure open-shell diradical and a very high polyradical character, not reported for D−A type macromolecules. Furthermore, the π-spacer derivatives display global nonaromaticity in the singlet ground state, but global aromaticity in the lowest triplet state, according to Baird's rule. The absorption spectra of the open-shell macromolecules calculated with time-dependent density functional theory indicate intensive light absorption in the near-infrared region and broadening to 2,500 nm, making these materials suitable for numerous optoelectronic applications.

Solution-Processed, Large-Area, Two-Dimensional Crystals of Organic Semiconductors for Field-Effect Transistors and Phototransistors.

Organic electronics with π-conjugated organic semiconductors are promising candidates for the next electronics revolution. For the conductive channel, the large-area two-dimensional (2D) crystals of organic semiconductors (2DCOS) serve as useful scaffolds for modern organic electronics, benefiting not only from long-range order and low defect density nature but also from unique charge transport characteristic and photoelectrical properties. Meanwhile, the solution process with advantages of cost-effectiveness and room temperature compatibility is the foundation of high-throughput print electrical devices. Herein, we will give an insightful overview to witness the huge advances in 2DCOS over the past decade. First, the typical influencing factors and state-of-the-art assembly strategies of the solution-process for large-area 2DCOS over sub-millimeter even to wafer size are discussed accompanying rational evaluation. Then, the charge transport characteristics and contact resistance of 2DCOS-based transistors are explored. Following this, beyond single transistors, the p–n junction devices and planar integrated circuits based on 2DCOS are also emphasized. Furthermore, the burgeoning phototransistors (OPTs) based on crystals in the 2D limits are elaborated. Next, we emphasized the unique and enhanced photoelectrical properties based on a hybrid system with other 2D van der Waals solids. Finally, frontier insights and opportunities are proposed, promoting further research in this field.

Growth and Characterization of TCNQ-Doped Ni(II)TAAB Thin Film As a New π-Conjugated Organic Semiconductor

The aim of this work was to obtain a π-conjugated organic semiconductor with the macrocycle Ni(II)(TAAB) ([tetrabenzo (b, f, j, n) [1,5,9,13]tetraazacyclohexadecine]Ni(II) and the electronic acceptor TCNQ (tetracyano-π-quinodimethane), in which hydrogen bonds are formed between TCNQ and Ni(II)(TAAB). Theoretical calculations based on DFT with dispersion force analysis were carried out in order to simulate molecular interaction and to establish the nature of the bonds between both fragments. Thin films of TCNQ-doped Ni(II)TAAB organic semiconductor were obtained through high vacuum evaporation and were structurally and morphological characterized by IR spectroscopy, X-ray diffraction analysis (XRD), and scanning electron microscopy (SEM). The absorption coefficient (α) and photon energy (hν) were calculated from UV–Vis spectroscopy and used to determine the Tauc band gap of the film. This quasi-experimental band gap was compared with that obtained by DFT; both results are in the range established for organic semiconductors. The electrical properties of the organic semiconductor have been obtained from a simple anode|TCNQ-doped Ni(II)TAAB|cathode device. The conductivity of this device was determined from electrical measurements of I(V). TCNQ-doped Ni(II)TAAB has semiconducting characteristics and its conductivity values are of order 10–5 S cm–1. Band gap determination and the I(V) study were both carried out in order to analyze the effect of doped TCNQ in the macrocycle. This work suggests that TCNQ-doped Ni(II)TAAB represents an alternative approach to obtaining a semiconductor-like behaviour that may be suitable for organic electronic applications.

Quantitative study of spin relaxation in rubrene thin films by inverse spin Hall effect

Spin relaxation properties of π-conjugated organic semiconductors are key indicators of the performance of organic spintronic devices. However, reliable determination of spin relaxation parameters in organic materials is hindered by complex interfacial phenomena at organic/ferromagnetic metal interfaces that couple spin injection with charge injection. Here, we study the spin pumping induced pure spin transport in Permalloy/rubrene/Pt trilayers and determine the spin diffusion length λs = 132 ± 9 nm and the spin relaxation time τs = 3.8 ± 0.5 ms in rubrene films at room temperature by using the inverse spin Hall effect. The determined spin diffusion length λs is found to be almost two times larger than that of ∼46.3 nm at 100 K extracted from rubrene spin valve devices in which charge carrier injection/detection occurs at organic/ferromagnetic metal interfaces. Our results demonstrate experimentally that the efficiency and the rate of spin polarized charge transport through the organic/ferromagnetic metal interface play a dominant role in determining the spin relaxation process of spin valve devices in which charge and spin currents are coupled.

Self-Assembly Polymorphism of Regioisomeric Diketopyrrolopyrrole-Based π-Conjugated Organic Semiconductors

Two-dimensional molecular assemblies of two structural isomers p-DBPy and d-DBPy containing a diketopyrrolopyrrole (DPP) unit relevant to the field of organic electronics are investigated on a grap...

The effect of side-chain length on the microstructure and processing window of zone-cast naphthalene-based bispentalenes

The solubilizing side-groups of solution-processable π-conjugated organic semiconductors affect both the crystal structure and microstructure of the respective thin films and thus charge-carrier mobility in devices.

Electro-optical interfacial effects on a graphene/π-conjugated organic semiconductor hybrid system.

The influence of graphene and retinoic acid (RA) – a π-conjugated organic semiconductor – interface on their hybrid system is investigated. The physical properties of the interface are assessed via scanning probe microscopy, optical spectroscopy (photoluminescence and Raman) and ab initio calculations. The graphene/RA interaction induces the formation of a well-organized π-conjugated self-assembled monolayer (SAM) at the interface. Such structural organization leads to the high optical emission efficiency of the RA SAM, even at room temperature. Additionally, photo-assisted electrical force microscopy, photo-assisted scanning Kelvin probe microscopy and Raman spectroscopy indicate a RA-induced graphene doping and photo-charge generation. Finally, the optical excitation of the RA monolayer generates surface potential changes on the hybrid system. In summary, interface-induced organized structures atop 2D materials may have an important impact on both design and operation of π-conjugated nanomaterial-based hybrid systems.

(Invited) Semiconductor Photocathode Materials for Direct Solar Fuel Production

The development of robust and inexpensive semiconducting materials that operate at high efficiency are needed to make the direct solar-to-fuel energy conversion by photoelectrochemical cells economically viable. In this presentation our laboratory’s progress in the development new light absorbing materials as photocathodes will be discussed along with the application toward overall solar water splitting tandem cells for H2 production. Specifically, this talk will highlight recent results with the ternary oxide CuFeO2, 2D transition metal dichalcogenides, and organic (π-conjugated) semiconductors as solution-processed photoelectrodes. With respect to CuFeO2, in our recent work [1] we demonstrate state-of-the-art sacrificial p-type photocurrent with optimized nanostructuring. Recent results addressing interfacial recombination by the electrochemical characterization of the surface states and attached co-catalysts will be presented along with approaches to overcome the limitations of this material. In addition, two-dimensional (2-D) transition metal dichalcogenides (TMDs) generally have intriguing electronic properties making them promising candidates for high-efficiency solar energy conversion. However, it is notoriously difficult to fabricate thin films of 2-D TMDs over the large areas required to convert solar energy on a practical scale. We recently developed a simple method to fabricate high-quality thin films of 2-D layered TMDs at low cost and with good efficiency towards solar-to-fuel energy conversion [2]. The challenges with charge transport, separation [3] and water redox catalysis in these systems will also be discussed with respect to the 2D flake size. Finally, with respect to π-conjugated organic semiconductors, in our recent work [4] we demonstrate a π-conjugated organic semiconductor for the sustained direct solar water oxidation reaction. Aspects of catalysis and charge-carrier separation/transport are discussed. [1] Prevot, M. S.; Li, Y.; Guijarro, N.; Sivula, K. J. Mater. Chem. A 2016, 4, 3018-3026. [2] Yu, X.; Prevot, M. S.; Guijarro, N.; Sivula, K., Nat. Commun. 2015, 6, 7596. [3] Yu, X.; Rahmanudin, A.; Jeanbourquin, X. A.; Tsokkou, D.; Guijarro, N.; Banerji, N.; Sivula, K. ACS Energy Lett. 2017, 2, 524. [4] Bornoz, P.; Prévot, M. S.; Yu, X.; Guijarro, N.; Sivula, K. J. Am. Chem. Soc. 2015, 137, 15338.

Nanostructured organic semiconductor films for molecular detection with surface-enhanced Raman spectroscopy

π-Conjugated organic semiconductors have been explored in several optoelectronic devices, yet their use in molecular detection as surface-enhanced Raman spectroscopy (SERS)-active platforms is unknown. Herein, we demonstrate that SERS-active, superhydrophobic and ivy-like nanostructured films of a molecular semiconductor, α,ω-diperfluorohexylquaterthiophene (DFH-4T), can be easily fabricated by vapour deposition. DFH-4T films without any additional plasmonic layer exhibit unprecedented Raman signal enhancements up to 3.4 × 103 for the probe molecule methylene blue. The combination of quantum mechanical computations, comparative experiments with a fluorocarbon-free α,ω-dihexylquaterthiophene (DH-4T), and thin-film microstructural analysis demonstrates the fundamental roles of the π-conjugated core fluorocarbon substitution and the unique DFH-4T film morphology governing the SERS response. Furthermore, Raman signal enhancements up to ∼1010 and sub-zeptomole (<10-21 mole) analyte detection were accomplished by coating the DFH-4T films with a thin gold layer. Our results offer important guidance for the molecular design of SERS-active organic semiconductors and easily fabricable SERS platforms for ultrasensitive trace analysis.

Tunable Semiconducting Polymer Nanoparticles with INDT-Based Conjugated Polymers for Photoacoustic Molecular Imaging

Photoacoustic imaging combines both excellent spatial resolution with high contrast and specificity, without the need for patients to be exposed to ionizing radiation. This makes it ideal for the study of physiological changes occurring during tumorigenesis and cardiovascular disease. In order to fully exploit the potential of this technique, new exogenous contrast agents with strong absorbance in the near-infrared range, good stability and biocompatibility, are required. In this paper, we report the formulation and characterization of a novel series of endogenous contrast agents for photoacoustic imaging in vivo. These contrast agents are based on a recently reported series of indigoid π-conjugated organic semiconductors, coformulated with 1,2-dipalmitoyl-sn-glycero-3-phosphocholine, to give semiconducting polymer nanoparticles of about 150 nm diameter. These nanoparticles exhibited excellent absorption in the near-infrared region, with good photoacoustic signal generation efficiencies, high photostability, and extinction coefficients of up to three times higher than those previously reported. The absorption maximum is conveniently located in the spectral region of low absorption of chromophores within human tissue. Using the most promising semiconducting polymer nanoparticle, we have demonstrated wavelength-dependent differential contrast between vasculature and the nanoparticles, which can be used to unambiguously discriminate the presence of the contrast agent in vivo.

Trends and challenges for microporous polymers.

Microporous polymers are covalently bound, entirely organic materials which possess very high surface areas. These materials have been intensively studied within recent years and various interesting properties and possible applications have been discovered and described. This review article starts with the question, what makes microporous polymers special and are there certain features which differentiate them from other microporous materials? Indeed, there are some special structural and functional features found in microporous polymers which make them really unique and merit further exploration. We focus here on microporous polymers which are solution-processable, can be produced as thin films on electrodes by oxidative polymerizations, are π-conjugated organic semiconductors, or which provide the possibility to introduce and exploit distinct functional groups in an otherwise non-functional highly porous environment. Emerging applications for these microporous polymers which make explicit use of these unique features are further presented.