High solid-state photoluminescence quantum yield of carbon-dot-derived molecular fluorophores for light-emitting devices.

Several recent studies of carbon dots (CDs) synthesized by bottom-up methods under mild conditions have reported the presence of organic molecular fluorophores in CD dispersions. These fluorophores have a tendency to aggregate, and their properties strongly depend on whether they are present in the form of discrete molecules or aggregates. The aggregation becomes more prominent in the solid state, which motivates the study of the properties of the fluorophores associated with CDs in the solid state. Here, we report the solid-state characterization of N4,N11-dimethyldibenzo[a,h]phenazine-4,11-diamine (BPD) - a molecular fluorophore that forms CDs. Discrete BPD molecules show excitation-wavelength-independent photoluminescence (PL) emission in the green wavelength region at ∼520 nm. However, additional blue PL is also observed due to aggregation, making the PL emission significantly broad. For detailed studies, BPD is mixed in different solid matrices, and it is observed that the PL quantum yield (PLQY) of BPD films strongly depends on the concentration of BPD in the solid matrices. Increasing the concentration of BPD results in a considerable decrease in the PLQY. The PLQY of the films with an optimum concentration of BPD is 75.9% and 40.2% in polymethyl methacrylate and polystyrene, respectively. At higher concentrations, these PLQY values decrease to ∼11%. The significant decrease in the PLQY is ascribed to reabsorption and nonradiative exciton decay that is facilitated by BPD aggregation at higher concentrations. Finally, light-emitting devices (LEDs) were fabricated with almost pure white emission color, having CIE (International Commission on Illumination) coordinates of (0.35, 0.37) using BPD in the color-converting layer of blue-pumped LEDs. The device shows a luminous efficiency 3.8 lm W-1 and luminance of 43 331 cd m-2.

Photostability of blue phosphorescent films on plasmonic surfaces.

Organometallic phosphors are an important class of emissive materials used in high-efficiency organic light-emitting devices. However, problems of low photostability arise for blue-emitting phosphors due to chemical and environmental degradation and triplet quenching processes. Various approaches have been developed to improve the photostability of such phosphors, including the design of new organometallic molecules and control of host-dopant composition in thin films. Here, we demonstrate a different approach for improving the photostability of blue organometallic phosphors that uses localized surface plasmon resonances to increase the triplet recombination rate. The increased recombination rate improves the photostability of the phosphor due to the reduction in triplet quenching pathways. We show that the lifetime of phosphorescence is decreased significantly by nanoparticle-based plasmonic surfaces, which improves the photostability of the blue organometallic phosphor by up to a factor of 3.6. Other plasmonic surfaces are also tested and exhibit less significant photostability improvements due to a reduced spectral overlap of the plasmonic modes with the emitter and lower mode confinement. The use of plasmonic surfaces to improve phosphor photostability at blue wavelengths is distinct from other approaches because it involves modification to the local electromagnetic environment of the phosphor rather than modifications to the phosphor molecular structure or the emitting material composition.

Self-Assembled Monolayers for Improved Charge Injection of Silver Back Electrodes in Inverted Organic Electronic Devices.

Self-assembled monolayers (SAMs) formed from thiol compounds bound to Ag and Au electrodes have been used as an important strategy in improving the stability and efficiency of optoelectronic devices. Thiol compounds provide only one binding site with the metal electrode which limits their influence. Dithiolane/dithiol compounds can provide multiple binding sites and could be useful in enhancing the performance of the device. In this study, inverted organic semiconducting hole-only devices were fabricated by using Ag back electrodes in conjunction with SAMs formed from disulfide lipoic acid-based compounds and were compared to a long aliphatic chain thiol. The binding and the electronic properties as well as electrical characteristics of the SAMs on silver were studied to look at the influence of their structure on charge injection in the organic semiconductor devices. It was found that the SAMs formed with (±)-α-lipoic acid, isolipoic acid, and (±)-4-phenylbutyl 5-(1,2-dithiolan-3-yl) pentanoate significantly improved the charge injection by either changing the work function of the Ag or altering the physical interaction between the polymer and the metal surface. This study may lead to an understanding of how the nature of the functional groups of the SAM and the number of bonds formed between each SAM molecule and the metal electrode influence the contact resistance and the performance of organic semiconductor devices.

Photon Recycling in Semiconductor Thin Films and Devices.

Photon recycling (PR) plays an important role in the study of semiconductor materials and impacts the properties of their optoelectronic applications. However, PR has not been investigated comprehensively and it has not been demonstrated experimentally in many different kinds of semiconductor materials and devices. In this review paper, first, the authors introduce the background of PR and describe how this phenomenon was originally identified in semiconductors. Then, the theory and modelling of PR is reviewed and some of the important parameters that are used to quantify PR are highlighted. Next, a variety of the methods used to achieve and characterize PR in materials and devices are discussed. Examples of how the performance parameters of different types of optoelectronic devices are affected by PR are described. Finally, a summary of the roles of PR in semiconductor materials and devices and an outlook on how PR can be used to solve existing problems and challenges in the field of optoelectronics are provided. From this review, it is apparent that PR can have a positive impact on optoelectronic device performance, and that further in-depth theoretical and experimental studies are needed to rigorously demonstrate the advantages and importance of PR.

Optical and Electrical Properties of Organic Semiconductor Thin Films on Aperiodic Plasmonic Metasurfaces.

Metal electrodes are playing an increasingly important role in controlling photon absorption and in promoting optimal light management in thin-film semiconductor devices. For organic optoelectronic devices, the conventional fabrication approach is to build the device on top of a transparent electrode, with metal electrode deposition as the last step. This makes it challenging to control the surface of the metal electrode to promote good light management properties. An inverted fabrication approach that builds the device on top of a metal electrode makes it possible to control the morphology of the metal surface independently of the organic semiconductor active layer to achieve a variety of photonic and plasmonic behaviors useful for devices. However, there are few reports of inverted fabrication of organic optoelectronic devices and its impacts on device properties. Silver (Ag) is the most suitable metal for fabrication of nanostructured electrodes with plasmonic behavior (i.e., plasmonic electrodes) because of its low parasitic absorption loss and high reflectivity. In this project, we describe the facile fabrication of silver nanoparticle (AgNP) aperiodic plasmonic metasurfaces and study their physical and optical characteristics. Then, we investigate the photonic and electrical behaviors of the aperiodic plasmonic metasurfaces when interfaced with poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) organic semiconducting polymer thin films. The luminescence quantum yield of F8BT thin films increases from 29% on planar Ag up to 66% on AgNP metasurfaces due to the Purcell effect and the improved extraction of emission coupled to surface plasmon polariton modes. In particular, we show that plasmonic enhancement can overcome ohmic losses associated with metals and metal-induced exciton quenching. According to the current-voltage characteristics of hole-only devices with and without aperiodic plasmonic metasurfaces, we conclude that AgNP aperiodic plasmonic metasurfaces have comparable electrical behavior to planar metal electrodes while having superior light management capability.

Plasmonic sphere-on-plane systems with semiconducting polymer spacer layers.

The optical properties of metal-film-coupled nanoparticles (NPs) are highly sensitive to physical and optical interactions between the NPs and the spacer medium in the gap between the NP and metal film. Here, we investigate the physical and optical interactions between gold NPs (AuNPs) and semiconducting conjugated polymer thin-film spacers in a "sphere-on-plane" type metal-film-coupled NP system, and their influence on the plasmonic scattering of individual AuNPs. We choose two different conjugated polymers: one with an absorption spectrum that is resonant with the plasmonic modes of the AuNPs and another that is non-resonant. By correlating dark-field back-scattering optical images with topographic atomic force microscope images, we find that partial embedding of the AuNPs occurs in both conjugated polymers to different extents. This can lead to partial quenching of certain plasmonic scattering modes, which results in a change of the back-scattering colors from the AuNPs. Pronounced, red-shifted scattering is observed due to deep embedding of the AuNPs, particularly for thicker conjugated polymer spacers that have resonant absorption with the plasmonic modes of the AuNPs. Polarization-controlled defocused dark-field imaging is employed to visualize the emergence of horizontally-polarized scattering modes upon embedding of AuNPs into the conjugated polymer spacer. These results demonstrate the importance of nanoparticle-spacer physical interactions to the control of the color and polarization of coupled plasmonic modes in nanoparticle-film systems relevant.

Controllable Cooperative Self-Assembly of PS-b-PAA/PS-b-P4VP Mixture by Tuning the Intercorona Interaction.

The cooperative self-assembly of amphiphilic polystyrene-block-poly(acrylic acid) (PS144-b-PAA22) and polystyrene-block-poly(4-vinylpyridine) (PS144-b-P4VP33) diblock copolymers in DMF/H2O mixtures has been investigated. Both copolymers self-assemble into small spherical micelles (SSMs) if used individually. However, the equimolar mixture of these two copolymers cooperatively self-assembles into vesicles. It is found that the formation of vesicles is attributed to the complex interactions between PAA and P4VP chains, including the hydrogen bonds between un-ionized acrylic acid units and pyridine units as well as the electronic attractions between ionized acrylic acid units and protonated pyridine units. Since these interactions between PAA and P4VP chains depend on pH value, the cooperatively self-assembled morphology can be easily tuned by the addition of HCl or NaOH. At high addition of H(+) or OH(-), the intercorona interaction is repulsive and the copolymer mixture tends to form SSMs (basic condition) or cylindrical micelles (acidic condition), whereas it prefers to aggregate into vesicles at low addition of H(+) or OH(-) because the intercorona interaction is attractive. Interestingly, the same morphology of the self-assembled aggregates can be obtained either at high H(+) addition or at low OH(-) addition, which results from the nonmonotonic variation of the intercorona interaction along with the addition of HCl or NaOH. The current study implies that it is the intercorona interaction rather than the chemical condition that dominates the cooperatively self-assembled morphology.

Aqueous-Processed Insulating Polymer/Nanocrystal Hybrid Solar Cells.

A novel kind of hybrid solar cell (HSC) was developed by introducing water-soluble insulating polymer poly(vinyl alcohol) (PVA) into nanocrystals (NCs), which revealed that the most frequently used conjugated polymer could be replaced by an insulating one. It was realized by strategically taking advantage of the characteristic of decomposition for the polymer at annealing temperature, and it was interesting to discover that partial decomposition of PVA left behind plenty of pits on the surfaces of CdTe NC films, enlarging surface contact area between CdTe NCs and subsequently evaporated MoO3. Moreover, the residual annealed PVA filled in the voids among spherical CdTe NCs, which led to the decrease of leakage current. An improved shunt resistance (increased by ∼80%) was achieved, indicating the charge-carrier recombination was effectively overcome. As a result, the new HSCs were endowed with increased Voc, fill factor, and power conversion efficiency compared with the pure NC device. This approach can be applied to other insulating polymers (e.g., PVP) with advantages in synthesis, type, economy, stability, and so on, providing a novel universal cost-effective way to achieve higher photovoltaic performance.

Layer-by-layer-assembled healable antifouling films.

Healable antifouling films are fabricated by the exponential layer-by-layer assembly of PEGylated branched poly(ethylenimine) and hyaluronic acid followed by post-crosslinking. The antifouling function originates from the grafted PEG and the extremely soft nature of the films. The rapid and multiple healing of damaged antifouling functions caused by cuts and scratches can be readily achieved by immersing the films in normal saline solution.