0000000000004236
AUTHOR
Kookheon Char
The Role of Emission Layer Morphology on the Enhanced Performance of Light-Emitting Diodes Based on Quantum Dot-Semiconducting Polymer Hybrids
The influence of the morphology of quantum dot (QD)-semiconducting polymer hybrid emission layers on the performance of quantum dot-based light emitting diodes (QLEDs) is systematically investigated. Chemically grafted QD-semiconducting polymer hybrids are fabricated by the ligand exchange procedure between CdSe/CdxZn1−xS QDs and a new block copolymer consisting of a carbazole-based electroactive block with a low highest occupied molecular orbital level and a disulfide-based anchor block. The performance of QLEDs with hybrid emission layers is compared with QLEDs utilizing QD-only and physically mixed QD/polymer emission layers. It is shown that only in the emission layers formed by chemica…
Novel Amphiphilic Styrene-Based Block Copolymers for Induced Surface Reconstruction
This paper describes the synthesis of amphiphilic block copolymers by living radical polymerization (NMP) of new styrene-like monomers. The polar monomers (ethylene oxide side chains and free hydroxyl- or amino-groups after deprotection) were polymerized in a “protected form” to adjust the solubility of the monomers. In this way high molar mass polymers with a narrow polydispersity (around or below 1.2) were accessible. In the bulk state hydrophobic and hydrophilic domains demix. By exposing thin films of these polymers to vacuum (air) or alternatively to water or a hydrophilic surface it becomes possible to switch the surface polarity reversibly between contact angles of about 105° and 83°…
Covalently bonded layer-by-layer assembly of multifunctional thin films based on activated esters.
We demonstrate that chemically stable, multifunctional polymer thin films can be obtained using the layer-by-layer (LbL) deposition based on covalent bonds between adsorbing chains. Poly(pentafluorophenyl-4-vinylbenzoate) (P1) or poly(pentafluorophenylacrylate) (P2) polymers were assembled with poly(allyl amine) (PAAm) to yield LbL multilayer films through amide bond formation by the reaction between activated esters of P1 or P2 and amine groups in PAAm, which was quantitatively monitored by Fourier transform infrared spectroscopy (FT-IR). It was found that the difference in the solubility of P1 and P2 against ethanol, which was used as the solvent for PAAm, during the LbL deposition yields…
Cooperative Catechol-Functionalized Polypept(o)ide Brushes and Ag Nanoparticles for Combination of Protein Resistance and Antimicrobial Activity on Metal Oxide Surfaces
Prevention of biofouling and microbial contamination of implanted biomedical devices is essential to maintain their functionality and biocompatibility. For this purpose, polypept(o)ide block copolymers have been developed, in which a protein-resistant polysarcosine (pSar) block is combined with a dopamine-modified poly(glutamic acid) block for surface coating and silver nanoparticles (Ag NPs) formation. In the development of a novel, versatile, and biocompatible antibacterial surface coating, block lengths pSar were varied to derive structure-property relationships. Notably, the catechol moiety performs two important tasks in parallel; primarily it acts as an efficient anchoring group to me…
High-Performance TiO2 Nanoparticle/DOPA-Polymer Composites
Many natural materials are complex composites whose mechanical properties are often outstanding considering the weak constituents from which they are assembled. Nacre, made of inorganic (CaCO 3 ) and organic constituents, is a textbook example because of its strength and toughness, which are related to its hierarchical structure and its well-defi ned organic–inorganic interface. Emulating the construction principles of nacre using simple inorganic materials and polymers is essential for understanding how chemical composition and structure determine biomaterial functions. A hard multilayered nanocomposite is assembled based on alternating layers of TiO 2 nanoparticles and a 3-hydroxytyramine…
Functionalization and patterning of reactive polymer brushes based on surface reversible addition and fragmentation chain transfer polymerization
We present the synthesis of reactive polymer brushes prepared by surface reversible addition–fragmentation chain transfer polymerization of pentafluorophenyl acrylate. The reactive ester moieties can be used to functionalize the polymer brush film with virtually any functionality by simple post-polymerization modification with amines. Dithiobenzoic acid benzyl-(4-ethyltrimethoxylsilyl) ester was used as the surface chain transfer agent (S-CTA) and the anchoring group onto the silicon substrates. Reactive polymer brushes with adjustable molecular weight, high grafting density, and conformal coverage through the grafting-from approach were obtained. Subsequently, the reactive polymer brushes …
Strategy for good dispersion of well-defined tetrapods in semiconducting polymer matrices.
The morphology or dispersion control in inorganic/organic hybrid systems is studied, which consist of monodisperse CdSe tetrapods (TPs) with grafted semiconducting block copolymers with excess polymers of the same type. Tetrapod arm-length and amount of polymer loading are varied in order to find the ideal morphology for hybrid solar cells. Additionally, polymers without anchor groups are mixed with the TPs to study the effect of such anchor groups on the hybrid morphology. A numerical model is developed and Monte Carlo simulations to study the basis of compatibility or dispersibility of TPs in polymer matrices are performed. The simulations show that bare TPs tend to form clusters in the m…
A Bis(tridentate)cobalt Polypyridine Complex as Mediator in Dye‐Sensitized Solar Cells
Dye-sensitized solar cells equipped with cationic and neutral RuII-based sensitizers [Ru(ddpd){tpy(COOH)3}]2+ [12+; ddpd = N,N′-dimethyl-N,N′-di(pyridin-2-yl)pyridin-2,6-diamine, tpy(COOH)3 = 2,2″6′,2″-terpyridine-4,4′,4″-tricarboxylic acid] and [Ru(ddpd){tpy(COOH)(COO)2}] (2) with and without the coadsorbent chenodeoxycholic acid were constructed with I3–/I– or the CoIII/II-based redox mediators [Co(bpy)3]3+/2+ (33+/2+; bpy = 2,2′-bipyridine) and [Co(ddpd)2]3+/2+ (43+/2+) in the presence of LiClO4 and 4-tert-butylpyridine. The best photovoltaic performance was achieved by using the 43+/2+ shuttle and the neutral sensitizer 2 without coadsorbent. The higher short-circuit photocurrent densit…
Quantum dot-block copolymer hybrids with improved properties and their application to quantum dot light-emitting devices.
To combine the optical properties of CdSe@ZnS quantum dots (QDs) with the electrical properties of semiconducting polymers, we prepared QD/polymer hybrids by grafting a block copolymer (BCP) containing thiol-anchoring moieties (poly(para-methyl triphenylamine-b-cysteamine acrylamide)) onto the surfaces of QDs through the ligand exchange procedure. The prepared QD/polymer hybrids possess improved processability such as enhanced solubility in various organic solvents as well as the film formation properties along with the improved colloidal stability derived from the grafted polymer shells. We also demonstrated light-emitting diodes based on QD/polymer hybrids, exhibiting the improved device …
Strongly Coupled Cyclometalated Ruthenium Triarylamine Chromophores as Sensitizers for DSSCs
A series of anchor-functionalized cyclometalated bis(tridentate) ruthenium(II) triarylamine hybrids [Ru(dbp-X)(tctpy)](2-) [2 a](2-) -[2 c](2-) (H3 tctpy=2,2';6',2''-terpyridine-4,4',4''-tricarboxylic acid; dpbH=1,3-dipyridylbenzene; X=N(4-C6 H4 OMe)2 ([2 a](2-) ), NPh2 ([2 b](2-) ), N-carbazolyl [2 c](2-) ) was synthesized and characterized. All complexes show broad absorption bands in the range 300-700 nm with a maximum at about 545 nm. Methyl esters [Ru(Me3 tctpy)(dpb-X)](+) [1 a](+) -[1 c](+) are oxidized to the strongly coupled mixed-valent species [1 a](2+) -[1 c](2+) and the Ru(III) (aminium) complexes [1 a](3+) -[1 c](3+) at comparably low oxidation potentials. Theoretical calculati…
Living Light-Induced Crystallization-Driven Self-Assembly for Rapid Preparation of Semiconducting Nanofibers.
Well-defined nanostructures composed of conjugated polymers have attracted significant attention due to their intriguing electronic and optical properties. However, precise control of the size and uniformity of these semiconducting nanostructures is still rare and challenging, despite recent advances in strategies to obtain self-assembled nanostructures with narrow dispersions. Herein, we demonstrate the preparation of fluorescent conjugated block copolymers by one-shot polymerization and rapid formation of nanofibers in a few minutes via light-induced crystallization-driven self-assembly, driven by facile cis-to- trans photoisomerization of its poly( p-phenylenevinylene) blocks. Furthermor…
The effect of band gap alignment on the hole transport from semiconducting block copolymers to quantum dots
Semiconducting hole transporting block copolymers were chemically modified to adjust their energy levels to that of CdSe/CdS/CdZnS red quantum dots. Hybrids with optimized energy levels could be used to build strongly improved quantum dot based LEDs (QLEDs).
Morphology control in biphasic hybrid systems of semiconducting materials.
Simple blends of inorganic nanocrystals and organic (semiconducting) polymers usually lead to macroscopic segregation. Thus, such blends typically exhibit inferior properties than expected. To overcome the problem of segregation, polymer coated nanocrystals (nanocomposites) have been developed. Such nanocomposites are highly miscible within the polymer matrix. In this Review, a summary of synthetic approaches to achieve stable nanocomposites in a semiconducting polymer matrix is presented. Furthermore, a theoretical background as well as an overview concerning morphology control of inorganic NCs in polymer matrices are provided. In addition, the morphologic behavior of highly anisotropic na…
Toward mass producible ordered bulk heterojunction organic photovoltaic devices.
A strategy to fabricate nanostructured poly(3-hexylthiophene) (P3HT) films for organic photovoltaic (OPV) cells by a direct transfer method from a reusable soft replica mold is presented. The flexible polyfluoropolyether (PFPE) replica mold allows low-pressure and low- temperature process condition for the successful transfer of nanostructured P3HT films onto PEDOT/PSS-coated ITO substrates. To reduce the fabrication cost of masters in large area, we employed well-ordered anodic aluminum oxide (AAO) as a template. Also, we provide a method to fabricate reversed nanostructures by exploiting the self-replication of replica molds. The concept of the transfer method in low temperature with a fl…
Plasmon-enhanced photocurrent in quasi-solid-state dye-sensitized solar cells by the inclusion of gold/silica core–shell nanoparticles in a TiO2 photoanode
Direct evidence of the effects of the localized surface plasmon resonance (LSPR) of gold nanoparticles (Au NPs) in TiO2 photoanodes on the performance enhancement in quasi-solid-state dye-sensitized solar cells (DSCs) is reported by comparing gold/silica core–shell nanoparticles (Au@SiO2 NPs) and hollow silica nanoparticles with the same shell size of the core–shell nanoparticles. The Au nanoparticles were shelled by a thin SiO2 layer to produce the core–shell structure, and the SiO2 hollow spheres were made by dissolving the Au cores of the gold/silica core–shell nanoparticles. Therefore, the size and morphology of the SiO2 hollow spheres were the same as the Au@SiO2 NPs. The energy conver…
Copolymerization of Polythiophene and Sulfur To Improve the Electrochemical Performance in Lithium–Sulfur Batteries
We first report on the copolymerization of sulfur and allyl-terminated poly(3-hexylthiophene-2,5-diyl) (P3HT) derived by Grignard metathesis polymerization. This copolymerization is enabled by the conversion of sulfur radicals formed by thermolytic cleavage of S8 rings with allyl end-group. The formation of a C–S bond in the copolymer is characterized by a variety of methods, including NMR spectroscopy, size exclusion chromatography, and near-edge X-ray absorption fine spectroscopy. The S-P3HT copolymer is applied as an additive to sulfur as cathode material in lithium–sulfur batteries and compared to the use of a simple mixture of sulfur and P3HT, in which sulfur and P3HT were not covalent…
Characterization of quantum dot/conducting polymer hybrid films and their application to light-emitting diodes.
Quantum dot/conducting polymer hybrid films are used to prepare light-emitting diodes (LEDs). The hybrid films (CdSe@ZnS quantum dots excellently dispersed in a conducting polymer matrix, see figure) are readily prepared by various solution-based processes and are also easily micropatterned. The LEDs exhibit a turn-on voltage of 4 V, an external quantum efficiency greater than 1.5%, and almost pure-green quantum-dot electroluminescence.
Orientation of Polymer Functionalized Nanorods in Thin Films
A directed self assembly of anisotropic nanostructures offers a possibility to provide unique functional materials, which are e.g., important in optoelectronic devices. We use the liquid crystalline behavior of polymer functionalized TiO2 and ZnO nanorods to apply methods well known for low molecular liquid crystals to achieve oriented thin films. Convective forces in the meniscus on a structured substrate obtain thin layers of oriented nanoparticles with a ordering parameter of S = 0.7. As another method we present the orientation of polystyrene covered ZnO nanorods under an applied electric field. The method offers a perpendicular alignment of the rods to the surface.
Push‐Pull Design of Bis(tridentate) Ruthenium(II) Polypyridine Chromophores as Deep Red Light Emitters in Light‐Emitting Electrochemical Cells
Light-emitting electrochemical cells (LECs) with a simple device structure were prepared by using heteroleptic bis(tridentate) ruthenium(II) complexes [1](PF6)(2)-[3](PF6)(2) as emitters. The push-pull substitution shifts the emission energy to low energy, into the NIR region. The devices emit deep red light up to a maximum emission wavelength of 755 nm [CIE (International Commission on Illumination) coordinates: x = 0.731, y = 0.269 for [3](PF6)(2)], which, to the best of our knowledge, is the lowest emission energy for LECs containing bis(tridentate) ruthenium(II) complexes. A device structure of ITO/PEDOT:PSS/ruthenium(II) complex/Ag was used, and the thickness of the emitting layer was …
Tunable Phosphorescent Emission through Energy Transfer within Multilayer Thin Films Based on a Carbazole-Based Host and Ir(III)-Complex Guest System
A new method to tune both phosphorescence emission intensity and spectroscopic colors based on the alternatively structured host/guest multilayer thin films prepared by the spin-assisted LbL deposition is presented. Their emission characteristics are demonstrated with pairs of positively charged Ir-PEI complexes as guests and negatively charged CBZ-PAA as hosts. The phosphorescent emission of Ir-PEI complexes is enhanced by the energy transfer from the host to the guest and, additionally, this energy transfer can be finely tuned by the insertion of spacer layers between the phosphorescent donor and acceptor layers to vary the emission intensity as well as to render different emission colors.
Nanoporous Thin Films Based on Polylactide-Grafted Norbornene Copolymers
Thermally stable vinyl polymerized polynorbornene (PNB) is one of the challenging materials in porous low dielectric films for packaging applications. Nanoporous PNB thin films were obtained with poly(d,l-lactide) (PLA)-grafted norbornene copolymers. Thermally labile PLA chains act as pore generators in PNB films. Thermally stable PNB main chains were synthesized by Pd-catalyzed vinyl polymerization and PLA side chains were grafted onto the PNB main chains by ring opening polymerization. The brittle and poor processible properties of PNB could easily be controlled by the copolymerization with norbornene derivatives. In thin films, the PLA chains were found to thermally decompose at about 25…
Controlled Synthesis of CdSe Tetrapods with High Morphological Uniformity by the Persistent Kinetic Growth and the Halide-Mediated Phase Transformation
We report scalable controlled synthesis of CdSe tetrapods with high morphological uniformity based on the continuous precursor injection (CPI) approach with halide ligands. The CPI approach involves the successive injection of precursors into the seed solution at a controlled rate so that the reaction condition remains in the kinetic growth regime. To initiate the successful development of tetrapod structure, the controlled amount of halide ligands are added during the reaction, which triggered the formation of wurtzite arms on {111}-facets of the zincblende seeds. The formation of the wurtzite phase is responsible for the halide-mediated displacement of oleate ligands, destabilizing the em…
One-pot synthesis of PbS NP/sulfur-oleylamine copolymer nanocomposites via the copolymerization of elemental sulfur with oleylamine
A novel synthetic and processing strategy for converting elemental sulfur into polymeric and nanocomposite materials is reported. We describe a facile one-pot reaction using elemental sulfur and oleylamine as comonomers to prepare high sulfur content copolymers and lead sulfide nanoparticle (PbS NP) nanocomposites. This process enables the preparation of solution processable copolymers and nanocomposites, where the loading and dispersion of PbS NP inclusions could be precisely controlled. We demonstrate the dual roles of oleylamine with sulfur for both the copolymerization of sulfur copolymers as well as the in situ synthesis of PbS NPs in a one-pot fashion.
Facile Synthesis of Fluorescent Polymer Nanoparticles by Covalent Modification-Nanoprecipitation of Amine-Reactive Ester Polymers
Emission wavelength control in fluorescent nanoparticles (NPs) is crucial for their applications. In the case of inorganic quantum dots or dye-impregnated silica NPs, such a control is readily achieved by changing the size of the particles or choosing appropriate fluorescent dyes, respectively. A similar modular approach for controlling the emission wavelength of fluo-rescent polymer NPs, however, is difficult. This article reports on fluorescent polymer NPs, the synthesis of which provides a platform for a modular approach towards the preparation of fluorescent NPs of desired emission wavelength. Atom-transfer radical polymerization (ATRP) is employed to synthesize reactive ester polymers,…
Ultrastrong composites from dopamine modified-polymer-infiltrated colloidal crystals
Although strong and stiff synthetic composites have long been developed, the microstructure of today's most advanced composites has yet to achieve the sophisticated hierarchy of hybrid materials built up by living organisms. We have assembled hard and tough multilayered nanocomposites, which contain alternating layers of Fe3O4 nanoparticles and a 3-hydroxy-tyramine (dopamine) substituted polymer (dopamine modified polymer), strongly cemented together by chelation through infiltration of the polymer into the Fe3O4 mesocrystal. With a Young's modulus of 17 ± 3 GPa and a hardness of 1.3 ± 0.4 GPa the nanocomposite exhibits high resistance against elastic as well as plastic deformation. Key fea…
Reactive surface coatings based on polysilsesquioxanes: universal method toward light-responsive surfaces.
Reactive surface coatings were used as an ideal precursor coating for the fabrication of three different photoswitchable surface coatings in parallel. Different light-responsive moieties, such as azobenzene, salicylideneaniline, and spiropyran, were immobilized on glass, polycarbonate, and steel surfaces. Independent from the underlying substrate, wettability could be switched reversibly by UV irradiation. The maximum switching range was obtained after functionalization of the reactive coating with spiropyran, resulting in a contact angle difference between the two isomeric states of almost 30°.
Side-chain conjugated polymers for use in the active layers of hybrid semiconducting polymer/quantum dot light emitting diodes
Three monomers, M1–M3, with modified carbazole cores and styrene functionality were prepared for use in the active layers of hybrid polymer/quantum dot light emitting diodes. Utilizing reversible addition fragmentation chain transfer polymerization, side-chain conjugated polymers, P1–P3, with narrow polydispersities and disulfide end groups were obtained. The thermal, optical, and electrochemical properties of the polymers varied depending on the substituents of the carbazole cores. Through the disulfide end groups the polymers were chemically blended with quantum dots to obtain QD/polymer hybrids, which were further used as active layers in light emitting diodes. The fabricated devices ret…
Highly efficient and stable dye-sensitized solar cells based on SnO2nanocrystals prepared by microwave-assisted synthesis
Highly efficient dye-sensitized solar cells (DSSCs) with excellent long-term stability were fabricated based on tin(IV) oxide (SnO2) nanocrystals with tunable morphologies and band energy levels. The nanocrystals were prepared by a facile, fast, and energy-saving microwave-assisted solvothermal reaction. Through variation of the precursor base used during nanocrystal synthesis control over morphology was achieved—precursor metal cations are known to have a strong influence on the growth process of SnO2 nanostructures. A simple and economic way to prepare semiconducting pastes for photoanodes was devised. The photovoltaic performance of dye-sensitized solar cells based on SnO2 photoanodes wa…
Polymerizable Well-Defined Oligo(thiophene amide)s and their ROMP Block Copolymers
We report the synthesis of conjugated thiophene amide oligomers that constitute a new class of chromophores with potential for optoelectronic applications. The synthesis of defined norbornene-substituted oligothiophene amides using conventional coupling chemistry is described. Their electronic properties depend on the degree of oligomerization as UV/Vis and fluorescence spectroscopy demonstrate. A significant red shift in the spectra upon an increase in the oligomer length evidences conjugation of the thiophene rings via the amide linkages. ROMP of the norbornene-substituted oligomers gives homopolymers and block-copolymers with a solubilizing second block. The amphiphilic character of the …
Anchor‐Functionalized Push‐Pull‐Substituted Bis(tridentate) Ruthenium(II) Polypyridine Chromophores: Photostability and Evaluation as Photosensitizers
Stable push-pull substituted heteroleptic bis(tridentate) ruthenium(II) polypyridine complexes with COOH or 2,2′-bipyridine anchor groups have been prepared and characterized by 1H, 13C and 15N NMR 1D and 2D spectroscopy, infrared spectroscopy, elemental analysis, high-resolution ESI mass spectrometry, electrochemistry, UV/Vis absorption spectroscopy, luminescence spectroscopy, and density functional calculations. The complexes feature a pronounced electronic directionality and high absorption wavelengths up to λmax = 544 nm extending to 720 nm as a result of favorable push-pull substitutions. A remarkable photostability in the presence of water and coordinating ions (I–) was discovered for…
Reduced efficiency roll-off in light-emitting diodes enabled by quantum dot–conducting polymer nanohybrids
We demonstrate QLEDs implementing wider active layers (50 nm) based on QD–conducting polymer nanohybrids, which exhibit a stable operational device performance across a wide range of current densities and brightness. A comparative study reveals that the significant suppression of efficiency roll-off in the high current density regime is primarily attributed to a sufficient charge carrier distribution over the wider active layer and improved charge carrier balance within QDs enabled by the hybridization of QDs with conducting polymers. Utilization of this finding in future studies should greatly facilitate the development of high performance, stable QLEDs at high current density or luminance…