D-π-A conjugated molecules for optoelectronic applications.

Dipolar chromophores consisting of electron donor (D) and electron acceptor (A) groups connected through a conjugated π-bridge have been actively studied and integrated in optoelectronic and electronic devices. Generally, such π-conjugated molecules provide substantial delocalization of π-electrons over the molecules. Here, a brief overview of recent research on D-π-A dipolar chromophores including their syntheses and several promising applications is reported, especially in nonlinear optical devices and organic photovoltaics. Structure/property relationships are discussed in order to exploit the potentials by tuning the π-electron density, polarizability, and HOMO-LUMO band gap of the chromophores. Some of the examples may well set the stage for chip-scale integration of optoelectronics as well as the realization of an important array of new device technologies.

Photosensitive functionalized surface-modified quantum dots for polymeric structures via two-photon-initiated polymerization technique.

In this paper, the surface modification of CdSe- and CdZnS-based quantum dots (QDs) with a functional silica shell is reported. Functionalized silica shells are prepared by two routes: either by ligand exchange and a modified Stöber process or by a miniemulsion process with amphiphilic poly(oxyethylene) nonylphenylether also know as Igepal CO-520 (IG) as oligomeric amphiphile and modified silica precursors. The polymerizable groups on the functionalized silica shell allow covalent bonding to a polymer matrix and prevent demixing during polymerization and crosslinking. This allows the homogeneous incorporation of QDs in a crosslinked polymer matrix. This paper furthermore demonstrates that the resulting QDs, which are i) shielded with a proper silica shell and ii) functionalized with crosslinkable groups, can be used in two-photon-initiated polymerization processes in combination with different photoresists to obtain highly luminescent 3D structures. The resulting luminescent structures are attractive candidates for photonics and metamaterials research.

Triplet state formation in photovoltaic blends of DPP-type copolymers and PC71 BM.

The exciton dynamics in pristine films of two structurally related low-bandgap diketopyrrolopyrrole (DPP)-based donor-acceptor copolymers and the photophysical processes in bulk heterojunction solar cells using DPP copolymer:PC71 BM blends are investigated by broadband transient absorption (TA) pump-probe experiments covering the vis-near-infrared spectral and fs-µs dynamic range. The experiments reveal surprisingly short exciton lifetimes in the pristine poly-mer films in conjunction with fast triplet state formation. An in-depth analysis of the TA data by multivariate curve resolution analysis shows that in blends with fullerene as acceptor ultrafast exciton dissociation creates charge carriers, which then rapidly recombine on the sub-ns timescale. Furthermore, at the carrier densities created by pulsed laser excitation the charge carrier recombination leads to a substantial population of the polymer triplet state. In fact, virtually quantitative formation of triplet states is observed on the sub-ns timescale. However, the quantitative triplet formation on the sub-ns timescale is not in line with the power conversion efficiencies of devices indicating that triplet state formation is an intensity-dependent process in these blends and is reduced under solar illumination conditions, as free charge carriers can be extracted from the photoactive layer in devices.

Energy and charge transfer in nanoscale hybrid materials.

Hybrid materials composed of colloidal semiconductor quantum dots and π-conjugated organic molecules and polymers have attracted continuous interest in recent years, because they may find applications in bio-sensing, photodetection, and photovoltaics. Fundamental processes occurring in these nanohybrids are light absorption and emission as well as energy and/or charge transfer between the components. For future applications it is mandatory to understand, control, and optimize the wide parameter space with respect to chemical assembly and the desired photophysical properties. Accordingly, different approaches to tackle this issue are described here. Simple organic dye molecules (Dye)/quantum dot (QD) conjugates are studied with stationary and time-resolved spectroscopy to address the dynamics of energy and ultra-fast charge transfer. Micellar as well as lamellar nanostructures derived from diblock copolymers are employed to fine-tune the energy transfer efficiency of QD donor/dye acceptor couples. Finally, the transport of charges through organic components coupled to the quantum dot surface is discussed with an emphasis on functional devices.

Alkylated fullerene derivatives for solution-processable organic thin-film transistors and bulkheterojunction solar cells.

In this paper, we report synthesis and characterization of alkylated fullerene derivatives for solution-processable organic thin film transistors and solar cells. Their physical, thermal, and semiconducting properties have been studied. Organic thin-film transistors fabricated from C60TH-Oc exhibit electron mobilities as high as 3.2 x 10(-2) cm2 V(-1) s(-1) with 32 V of a threshold voltage. The best power conversion efficiency (PCE) was observed in a layered structure P3HT:C60TH-Oc (PCE = 0.44%), which was a twice value of P3HT:C60TH-Dd (PCE = 0.23%).

Feature issue introduction: quantum dots for photonic applications.

Quantum dots (QDs) are semiconductor nanocrystals with peculiar optoelectronic properties. Their wide application in light-emitting diodes, solar cells, and the medical and defense fields makes them a potential candidate in the area of photonics and biophotonics. In this feature issue of Optical Materials Express, together with Optics Express we focus on different aspects of semiconducting nanocrystals research, especially on the advances in the synthesis, physical properties, and application of QDs.

Synthesis and characterization of anthracene derivative for organic field-effect transistor fabrication.

Here we report on the synthesis and characterization of anthracene derivative for solution processable organic field-effect transistors. The transistor devices with bottom-contact geometry provided a maximum field-effect mobility of 3.74 x 10(-4) cm2 V(-1) s(-1) as well as current on/off ratio of 5.05 x 10(4) and low threshold voltage. Structural information in the solid state is obtained by thermal analysis and two-dimensional wide angle X-ray scattering (2D-WAXS). From the 2D-WAXS, it is clear that the planes of anthracene rings and benzene ring of the molecule are different in solid state. We assume similar arrangement in the thin-film which limit the effective hopping and thus charge mobility.

Synthesis and photophysical properties of two-photon absorbing spirofluorene derivatives.

New spirofluorene-based quadrupolar two-photon absorbing dyes having triphenylamine and N,N-dibutylaniline as electron donors at the end of molcules were designed and synthesized. The third-order nonlinear optical properties of these compounds were studied using a two-photon excited fluorescence method. They were found to have high two-photon absorption cross-section owing to extended conjugation of the spirofluorene moiety. The effect of varying the donor strength could be discerned by comparing the two compounds. They were successfully used as a photosensitizers for two-photon initiated polymerization of three-dimensional micro-objects.

Ultrafast exciton dissociation followed by nongeminate charge recombination in PCDTBT:PCBM photovoltaic blends.

The precise mechanism and dynamics of charge generation and recombination in bulk heterojunction polymer:fullerene blend films typically used in organic photovoltaic devices have been intensively studied by many research groups, but nonetheless remain debated. In particular the role of interfacial charge-transfer (CT) states in the generation of free charge carriers, an important step for the understanding of device function, is still under active discussion. In this article we present direct optical probes of the exciton dynamics in pristine films of a prototypic polycarbazole-based photovoltaic donor polymer, namely poly[N-11''-henicosanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT), as well as the charge generation and recombination dynamics in as-cast and annealed photovoltaic blend films using methanofullerene (PC(61)BM) as electron acceptor. In contrast to earlier studies we use broadband (500-1100 nm) transient absorption spectroscopy including the previously unobserved but very important time range between 2 ns and 1 ms, which allows us not only to observe the entire charge carrier recombination dynamics but also to quantify the existing decay channels. We determine that ultrafast exciton dissociation occurs in blends and leads to two separate pools of products, namely Coulombically bound charge-transfer (CT) states and unbound (free) charge carriers. The recombination dynamics are analyzed within the framework of a previously reported model for poly(3-hexylthiophene):PCBM (Howard, I. A. J. Am. Chem. Soc. 2010, 132, 14866) based on concomitant geminate recombination of CT states and nongeminate recombination of free charge carriers. The results reveal that only ~11% of the initial photoexcitations generate interfacial CT states that recombine exclusively by fast nanosecond geminate recombination and thus do not contribute to the photocurrent, whereas ~89% of excitons create free charge carriers on an ultrafast time scale that then contribute to the extracted photocurrent. Despite the high yield of free charges the power conversion efficiency of devices remains moderate at about 3.0%. This is largely a consequence of the low fill factor of devices. We relate the low fill factor to significant energetic disorder present in the pristine polymer and in the polymer:fullerene blends. In the former we observed a significant spectral relaxation of exciton emission (fluorescence) and in the latter of the polaron-induced ground-state bleaching, implying that the density of states (DOS) for both excitons and charge carriers is significantly broadened by energetic disorder in pristine PCDTBT and in its blend with PCBM. This disorder leads to charge trapping in solar cells, which in turn causes higher carrier concentrations and more significant nongeminate recombination. The nongeminate recombination has a significant impact on the IV curves of devices, namely its competition with charge carrier extraction causes a stronger bias dependence of the photocurrent of devices, in turn leading to the poor device fill factor. In addition our results demonstrate the importance of ultrafast free carrier generation and suppression of interfacial CT-state formation and question the applicability of the often used Braun-Onsager model to describe the bias dependence of the photocurrent in polymer:fullerene organic photovoltaic devices.

Autofocusing method using fluorescence detection for precise two-photon nanofabrication.

We propose a method capable of focusing a laser beam on a substrate automatically via fluorescence detection from the resin of a two-photon nanofabrication system. When two-photon absorption (TPA) occurs by focusing the laser beam in the resin, fluorescence is emitted from the focusing region in the visible range. The total pixel number above the threshold value of the fluorescence images obtained by a CCD camera is plotted on a graph in accordance with the focus position. By searching for the position when the total pixel number undergoes an abrupt change in the pre-TPA region, the correct configuration of the focused laser beam can be found. Through focusing tests conducted at four vertices of a 500 µm x 500 µm square placed arbitrarily inside SCR500 resin, the errors of the autofocusing method were found to range from -100 nm to + 200 nm. Moreover, this method does not leave any polymerized marks. To verify the usefulness of the autofocusing method, the fabrication of a pyramid structure consisting of 20 layers was attempted on a coverglass. It was completely fabricated without losing a layer.

Photopatternable quantum dots forming quasi-ordered arrays.

We have functionalized core-shell CdSe/ZnS quantum dots (QDs) with a photosensitive monolayer, rendering them solution processable and photopatternable. Upon exposure to ultraviolet radiation, films composed of this material were found to polymerize, forming interconnected arrays of QDs. The photoluminescence properties of the nanocrystal films increased with photocuring. The material was found to be suitable for spin casting and was used as the active layer in a green electroluminescent device. The electroluminescence efficiency of devices containing a photocured active layer was found to be largely enhanced when compared to devices containing nonphotocured active layers. The material also showed excellent adhesion to both organic and inorganic substrates because of the unique combination of a siloxane and a photopatternable layer as ligands. The pristine functionalized nanocrystals could easily be used for two-dimensional patterning on organic and inorganic substrates. The photopatternable quantum dots were uniformly dispersed into a photopolymerizable resin to fabricate QD embedded three-dimensional microstructures.

Spin-orbital coupling and slow phonon effects enabled persistent photoluminescence in organic crystal under isomer doping.

When periodically packing the intramolecular donor-acceptor structures to form ferroelectric-like lattice identified by second harmonic generation, our CD49 molecular crystal shows long-wavelength persistent photoluminescence peaked at 542 nm with the lifetime of 0.43 s, in addition to the short-wavelength prompt photoluminescence peaked at 363 nm with the lifetime of 0.45 ns. Interestingly, the long-wavelength persistent photoluminescence demonstrates magnetic field effects, showing as crystalline intermolecular charge-transfer excitons with singlet spin characteristics formed within ferroelectric-like lattice based on internal minority/majority carrier-balancing mechanism activated by isomer doping effects towards increasing electron-hole pairing probability. Our photoinduced Raman spectroscopy reveals the unusual slow relaxation of photoexcited lattice vibrations, indicating slow phonon effects occurring in ferroelectric-like lattice. Here, we show that crystalline intermolecular charge-transfer excitons are interacted with ferroelectric-like lattice, leading to exciton-lattice coupling within periodically packed intramolecular donor-acceptor structures to evolve ultralong-lived crystalline light-emitting states through slow phonon effects in ferroelectric light-emitting organic crystal.

Proportional enlargement of movement by using an optically driven multi-link system with an elastic joint.

Diverse movements using optical manipulation have been introduced. These are generally performed in the focal region of the laser beam. To achieve a wider range of movements based on precise motion transformation, an effective method for optical manipulation that overcomes the important obstacles such as small optical trapping forces, friction, and the viscosity of fluids is required. A multi-link system with an elastic joint is introduced that provides precise motion transformation and amplification. By considering the physical properties of the structure and the optical trapping force, an elastic micron-scale joint with the simple shape of a thin plate was designed. As a further example of a multi-link system with an elastic joint, a double 4-link system for motion enlargement was designed and fabricated. By performing experimental evaluations of the fabricated structures, it was confirmed that multi-link systems with an elastic joint were effective tools for precise motion transformation through optical manipulation.

Blue organic light-emitting diodes based on solution-processed fluorene derivative.

We report blue fluorescent organic light-emitting devices (OLED) by solution process utilizing a blue emitting small molecule, 2,7-bis[(9-ethyl-9H-carbazol-3-yl)ethenyl]-9,9-bis(4-n-octyloxyphenyl)-9H-fluorene (CB), which has good solubility in common organic solvent. The peak positions of absorption and emission spectra of a new fluorene-based molecule in tetrahydrofuran solution were observed at 399 and 439 nm, respectively. We achieved a maximum luminous efficiency of approximately 3 cd/A with CIE color coordinates of (0.15, 0.15) in our device.

Diethynylbenzene-based liquid crystalline semiconductor for solution-processable organic thin-film transistors.

We report here the synthesis and characterization of novel diethynylbenzene-based liquid crystalline semiconductor (P1) for organic thin-film transistors (OTFTs). Compound P1 was synthesized by the Sonogashira coupling reaction between 2-bromo-5-(4-hexylthiophen-2-yl)thieno[3,2-b]thiophene and 1,4-bis(dodecyloxy)-2,5-diethynylbenzene. Top contact OTFTs were fabricated by spin casting with 2 wt% solution of P1 in chloroform and their best performance, which exhibited a hole mobility of 4.5 x 10(-5) cm2/Vs, was showed after annealing of the films at liquid crystalline temperature. Time-of-flight (TOF) mobility measured at liquid crystalline phase was observed to be 1.5 x 10(-6) cm2/Vs for both positive and negative carriers. These results indicate that the liquid crystallinity helps to improve the molecular packing and enhance charge mobility for P1. These advantages can be applicable to design and construct solution-processable OTFT materials for electronic applications.

Synthesis and properties of a solution-processable truxene derivative for OLED devices.

A soluble truxene derivative (TR1) attached with triphenylamine at the peripheral position was designed and synthesized. The structure and purity of TR1 were carefully characterized by 1H NMR, UV/vis and photoluminescent spectroscopy, mass spectroscopy, and thermal analyses. It exhibited good solubility in common organic solvents and good film forming properties. The maximum absorption and emission peaks in THF solution were shown at 358 nm and 415 nm, respectively. Bright blue emission was observed in both solution and solid states under UV excitation. The fluorescent quantum efficiency was 0.46. The best luminous efficiency was found to be 3.65 cd/A with CIE coordinates of (0.163, 0.260) in electroluminescence devices.

Degenerate multi-photon properties of spirofluorene derivatives.

Two- and three-photon absorption properties of the fluorene-based chromophores have been investigated. The two- and three-photon absorption cross-section are found to be increased with the strength of the electron donor groups in the order of N-ethylcarbazoyl (1), triphenylamino (2), and N,N-dibutylanilino (3) groups. This nonlinear absorption enhancement can be interpreted by the increase of intramolecular charge transfer facilitated by strong electron donors and the decreased detuning energy (deltaE). Furthermore, direct laser microfabrication by two-photon photopolymerization with compound 2 as a two-photon sensitizer was carried out. Laser exposure time-dependent lateral voxel size has also been studied.

Exploring Orbit-Orbit Interaction in Relationship to Photoluminescence Quantum Efficiency in Perovskite Quantum Dots through Rashba Effect.

This study demonstrates the influence of the orbit-orbit interaction on the photoluminescence quantum efficiency (PLQE) of metal halide perovskite quantum dots (QDs) through the Rashba effect. The orbit-orbit interaction between excitons was characterized by using the minimal excitation intensity required to generate a photoluminescence difference (ΔPL) between linearly and circularly polarized photoexcitations. It was observed that changing the surface functionalization from PFOA-OA to PFSH-OAm and OA can largely increase the minimal excitation intensity for generating ΔPL. This indicates that the orbit-orbit interaction is essentially decreased in CsPbBr1I2 QDs with surface functionalization. Simultaneously, the PLQE is increased from 39% to 59 and 72% in CsPbBr1I2 QDs upon surface functionalization. Furthermore, the PL lifetime is decreased with increasing the PLQE in CsPbBr1I2 QDs upon surface functionalization. This phenomenon implies that decreasing the orbit-orbit interaction can essentially weaken the Rashba effect and consequently reduce the disallowed transitions, leading to an enhancement in the PLQE in perovskite QDs.

Photosensitive n-Type Doping Using Perovskite CsPbX3 Quantum Dots for Two-Dimensional MSe2 (M = Mo and W) Field-Effect Transistors.

Perovskite CsPbX3 (X = Br, Cl, and I) nanostructures have been intensively studied as they are luminescent, photovoltaic, and photosensitizing active materials. Two-dimensional (2D) transition-metal dichalcogenides (TMDCs) with MX2 (M = Mo, W; X = S, Se, Te, etc.) structures have been used in flexible optoelectronic devices. In this study, perovskite green-light-emitting CsPbBr2I1 quantum dots (QDs) and blue-light-emitting CsPb(Cl/Br)3-QDs are utilized to enhance the photoresponsive characteristics of 2D MSe2 (M = Mo and W)-based field-effect transistors (FETs). From laser confocal microscopy photoluminescence (PL) experiments, PL quenching of the perovskite CsPb(Cl/Br)3-QDs and CsPbBr2I1-QDs is observed after hybridization with MoSe2 and WSe2 layers, respectively, which reflects the charge-transfer effect. According to the characteristics of the FETs based on the WSe2, MoSe2, WSe2/CsPbBr2I1-QDs hybrid, and MoSe2/CsPb(Cl/Br)3-QDs hybrid, the p-channel current (with hole mobility) is considerably decreased after the hybridization with the QDs. Notably, under incident light, the n-channel photocurrent and photoresponsivity of the FET are substantially increased, and the threshold voltage is negatively shifted owing to the hybridization with the perovskite QDs. The results show that the photosensitive n-type doping effect on the 2D MoSe2 and WSe2 nanosystems originates from the photogating effect by the trap states after the hybridization with various perovskite CsPbX3-QDs.

Environmentally friendly quantum-dot color filters for ultra-high-definition liquid crystal displays.

This work reports the synthesis and application of highly tuned cadmium-free green and red InPZnSe1-xSx/ZnS quantum dots (QDs) in QD enhanced liquid crystal displays (LCD). The emissions of the quantum dots were synthetically tuned to sharp emissions at low full-width at half maximum. The QDs were incorporated in LCD devices as quantum dot enhancement film (QDEF) or as a quantum dot incorporated color filter (QDCF). Synthetic tuning of the gradient inter-shell in the QDs leads to reduced full width at half-maximum, resulting in sharp green and red emissions from both types of devices. The application of the same QDs to devices using these different integration techniques shows the superiority of QDCF devices over QDEF ones. The RGB color gamut of a QDCF-LCD was 81.4% of REC.2020 in the CIE 1931 color space compared to 71.2% obtained for a QDEF-LCD display. The improved performance of QDCF was mainly due to the optimal interactions between the green QDs and the green color filter. The superior performance of cadmium-free InPZnSe1-xSx/ZnS QDCFs in LCDs make them well-suited for ultra-high-definition TV formats.