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.

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.

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.

Surface-Modified Industrial Acrylonitrile Butadiene Styrene 3D Scaffold Fabrication by Gold Nanoparticle for Drug Screening.

Biocompatibility is very important for cell growth using 3D printers, but biocompatibility materials are very expensive. In this study, we investigated the possibility of cell culture by the surface modification of relatively low-cost industrial materials and an efficient three-dimensional (3D) scaffold made with an industrial ABS filament for cell proliferation, spheroid formation, and drug screening applications. We evaluated the adequate structure among two-layer square shape 3D scaffolds printed by fused deposition modeling with variable infill densities (10-50%). Based on the effects of these scaffolds on cell proliferation and spheroid formation, we conducted experiments using the industrial ABS 3D scaffold (IA3D) with 40% of infill density, which presented an external dimension of (XYZ) 7650 µm × 7647 µm × 210 µm, 29.8% porosity, and 225 homogenous micropores (251.6 µm × 245.9 µm × 210 µm). In the IA3D, spheroids of cancer HepG2 cells and keratinocytes HaCaT cells appeared after 2 and 3 days of culture, respectively, whereas no spheroids were formed in 2D culture. A gold nanoparticle-coated industrial ABS 3D scaffold (GIA3D) exhibited enhanced biocompatible properties including increased spheroid formation by HepG2 cells compared to IA3D (1.3-fold) and 2D (38-fold) cultures. Furthermore, the cancer cells exhibited increased resistance to drug treatments in GIA3D, with cell viabilities of 122.9% in industrial GIA3D, 40.2% in IA3D, and 55.2% in 2D cultures when treated with 100 µM of mitoxantrone. Our results show that the newly engineered IA3D is an innovative 3D scaffold with upgraded properties for cell proliferation, spheroid formation, and drug-screening applications.

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.

Magnetically Actuated SiCN-Based Ceramic Microrobot for Guided Cell Delivery.

A silicon carbonitride (SICN) ceramic microrobot, biocompatible and magnetically activable, is developed for the delivery of viable cells to defective tissue by sequential steps of microstructuring, magnetization, and cell loading. The ceramic carrier of porous cylindrical framework is fabricated by 3D laser lithography using a photocurable preceramic polymer, chemically modified polyvinylsilazane, and subsequent pyrolysis at 600 °C under an inert atmosphere. Magnetic nanoparticles (MNP) are integrated into the surface-modified ceramic carrier by thiol-ene click reaction. Finally, the microrobot is loaded with fibroblast cells, which can be guided by a rotating external magnetic field. The proposed ceramic microrobot is mechanically durable, adequately controllable with external magnetic field, and quite compatible with mammalian cells.

Feature issue introduction: biophotonic materials and applications.

Biophotonics can be defined as the interplay of light and biological matter. The percolation of new optical technology into the realm of biology has literally shed new light into the inner workings of biological systems. This has revealed new applications for optics in biology. In a parallel trend, biomolecules have been investigated for their optical applications. Materials are playing a central role in the development of biophotonics. New materials, fabrication methods, and structures are enabling new biosensors, contrast agents, imaging strategies, and assay methods. Similarly, biologic materials themselves can be used in photonic devices. In this context, two open-access, rapid-publication journals from The Optical Society of America (OSA), Optical Materials Express and Biomedical Optics Express, will publish a joint feature issue covering advances in biophotonics materials.

3D Hierarchical, Pyramid-Based Cancer Cell Chip for the Detection of Anticancer Drug Effects.

In this study, we developed a novel three-dimensional (3D) cancer cell chip using a three-floor hierarchical 3D pyramid structure (3D pyramid) to simulate 3D tumor cell growth in vitro and to detect anticancer drugs. The proposed 3D pyramidbased cancer cell chip offered substantial advantages for the agglomerate formation of tumor cells, in which cells could be maintained as tumor spheroids for up to 3 weeks. Soon after HeLa tumor cells adhered to the micropatterned pillar sidewalls, they were suspended between the pillars based on scanning electron microscopy images. Treatment with the anticancer drug oleanolic acid resulted in 46.33% and 5.86% apoptotic cells on the 2D plate and 3D pyramid-based cell chip, respectively, compared with only 0.06% apoptotic cells in the control. The increase in chemoresistance to anticancer drugs in the 3D pyramid-based cell chip might be a result of cell confluence and hypoxia due to the spheroid formation of tumor cells in the 3D pyramid structure. These results indicated that the proposed cell chip could potentially be used for anticancer drug screening or can be incorporated into other models aimed at prolonging various cell functions in culture.

Photodynamic assembly of nanoparticles towards designable patterning.

Recent advancements in nanotechnology have continued to stimulate the development of functional devices based on nanomaterials. However, the controllable assembly of these tiny nanomaterials into functional structures is still a big challenge for further applications; nowhere is this more obvious than in the field of nanodevices. Currently, despite the fact that self-assembly technologies have revealed great potential to reach this end, serious problems with respect to morphology control, designable assembly and even flexible patterning set huge obstacles to the fabrication of functional devices. Nowadays, in addition to self-assembly technologies that make use of interaction forces between different objects, photodynamic assembly (PDA) technology has emerged as a promising route to architect functional materials with the help of optical driving forces towards device fabrication. In this review, we summarize the recent developments in PDA technology for the designable patterning of nanoparticles (NPs). The basic fundamentals of PDA that resort to optical trapping (OT) and typical examples regarding far-field/near-field OT for the PDA of various NPs have been reviewed. In particular, femtosecond laser induced photodynamic assembly (FsL-PDA), which enables the designable patterning of NPs through a direct writing manner, has been introduced. Finally, the current challenges and future prospects of this dynamic field are discussed based on our own opinions.

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.

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.

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.

Effect of core quantum-dot size on power-conversion-efficiency for silicon solar-cells implementing energy-down-shift using CdSe/ZnS core/shell quantum dots.

Silicon solar cells mainly absorb visible light, although the sun emits ultraviolet (UV), visible, and infrared light. Because the surface reflectance of a textured surface with SiNX film on a silicon solar cell in the UV wavelength region (250-450 nm) is higher than ∼27%, silicon solar-cells cannot effectively convert UV light into photo-voltaic power. We implemented the concept of energy-down-shift using CdSe/ZnS core/shell quantum-dots (QDs) on p-type silicon solar-cells to absorb more UV light. CdSe/ZnS core/shell QDs demonstrated clear evidence of energy-down-shift, which absorbed UV light and emitted green-light photoluminescence signals at a wavelength of 542 nm. The implementation of 0.2 wt% (8.8 nm QDs layer) green-light emitting CdSe/ZnS core/shell QDs reduced the surface reflectance of the textured surface with SiNX film on a silicon solar-cell from 27% to 15% and enhanced the external quantum efficiency (EQE) of silicon solar-cells to around 30% in the UV wavelength region, thereby enhancing the power conversion efficiency (PCE) for p-type silicon solar-cells by 5.5%.

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%).

Spectroscopic properties and orientation of molecules in Langmuir-Blodgett layers of selected functionalized fullerenes.

Vibrational properties of two fullerene derivatives: C60TZ-OT-5 (1) and C60TH-3HX (2) have been studied using infrared absorption and Raman scattering spectroscopies. Additionally, quantum chemical calculations of the equilibrium geometry and normal mode vibrations of these functionalized fullerenes were performed. It was stated that despite of distinct structural differences between the investigated molecules, their experimental spectra are quite similar and correspond well with the calculated ones. The orientation of the molecules in the Langmuir-Blodgett films was evaluated.

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.

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.