Regioisomerism in Thienothiophene-Based Covalent Organic Frameworks─A Tool for Band-Gap Engineering.

The craft of tuning optical properties is well-established for crystalline inorganic and hybrid solids. However, a far greater challenge is to tune the optical properties of organic materials systematically by design. We now introduce a synthesis concept that enables us to alter the optical properties of crystalline covalent organic frameworks (COFs) systematically using isomeric structures of thienothiophene-based building blocks (T23/32T) combined with a variety of tetratopic aromatic amines, e.g., the Wurster moiety (W-NH2). This concept is demonstrated for the synthesis of COFs in bulk and film forms and provides highly crystalline and porous isomeric COFs featuring predesigned photophysical properties. The band gap of the framework can be tuned continuously and precisely by chemically doping the pristine W23TT COF with its related constitutional isomer building block. Density-functional theory investigations of COF model compounds indicate that the extent of π-conjugation is among the key characteristics enabling the band-gap engineering.

Role of Hydrophobic Modification in Spermine-Based Poly(ß-amino ester)s for siRNA Delivery and Their Spray-Dried Powders for Inhalation and Improved Storage.

After RNAi was first discovered over 20 years ago, siRNA-based therapeutics are finally becoming reality. However, the delivery of siRNA has remained a challenge. In our previous research, we found that spermine-based poly(ß-amino ester)s are very promising for siRNA delivery. However, the role of hydrophobic modification in siRNA delivery of spermine-based poly(ß-amino ester)s is not fully understood yet. In the current work, we synthesized spermine-based poly(ß-amino ester)s with different percentages of oleylamine side chains, named P(SpOABAE). The chemical structures of the polymers were characterized by 1H NMR. The polymers showed efficient siRNA encapsulation determined by SYBR Gold assays. The hydrodynamic diameters of the P(SpOABAE) polyplexes from charge ratio N/P 1 to 20 were 30-100 nm except for aggregation phenomena observed at N/P 3. Morphology of the polyplexes was visualized by atomic force microscopy, and cellular uptake was determined by flow cytometry in H1299 cells, where all the polyplexes showed significantly higher cellular uptake than hyperbranched polyethylenimine (25 kDa). The most hydrophobic P(SpOABAE) polyplexes were able to achieve more than 90% GFP knockdown in H1299/eGFP cells. The fact that gene silencing efficacy increased with hydrophobicity but cellular uptake was affected by both charge and hydrophobic interactions highlights the importance of endosomal escape. For pulmonary administration and improved storage stability, the polyplexes were spray-dried. Results confirmed the maintained siRNA activity after storage for 3 months at room temperature, indicating potential for dry powder inhalation.

Merged Molecular Switches Excel as Optoacoustic Dyes: Azobenzene-Cyanines Are Loud and Photostable NIR Imaging Agents.

Optoacoustic (or photoacoustic) imaging promises micron-resolution noninvasive bioimaging with much deeper penetration (>cm) than fluorescence. However, optoacoustic imaging of enzyme activity would require loud, photostable, NIR-absorbing molecular contrast agents: which remain unknown. Most organic molecular contrast agents are repurposed fluorophores, with severe shortcomings of photoinstability or phototoxicity under optoacoustic imaging, as consequences of their slow S1→S0 electronic relaxation. We now report that known fluorophores can be rationally modified to reach ultrafast S1→S0 rates, without much extra molecular complexity, simply by merging them with molecular switches. Here, we merge azobenzene switches to cyanine dyes to give ultrafast relaxation (<10 ps, >100-fold faster). Without even adapting instrument settings, these azohemicyanines display outstanding improvements in signal longevity (>1000-fold increase of photostability) and signal loudness (here: >3-fold even at time zero). We show why this simple but unexplored design strategy can still offer stronger performance in the future, and can also increase the spatial resolution and the quantitative linearity of photoacoustic response over extended longitudinal imaging. By bringing the world of molecular switches and rotors to bear on problems facing optoacoustic agents, this practical strategy will help to unleash the full potential of optoacoustic imaging in fundamental studies and translational uses.

Advances in Tip-Enhanced Near-Field Raman Microscopy Using Nanoantennas.

Tip-enhanced near-field Raman microscopy spectroscopy is a scanning probe technique that is capable of providing vibrational spectroscopic information on single nanoobjects and surfaces at (sub-) nanometer spatial resolution and high detection sensitivity. In this review, we first illustrate the physical principle of optical nanoantennas used in tip-enhanced near-field Raman microscopy and tip-enhanced Raman scattering (TERS) to efficiently couple light to Raman excitations on nanometer length scales. Although the antennas' electric near-field distributions are commonly understood to determine the spatial resolution, recent experiments showing subnanometer-resolved optical images put this understanding into question. This is because such images enter a regime in which classical electrodynamical descriptions might no longer be applicable and quantum plasmonic and atomistic effects could become relevant. After summarizing the current understanding of plasmonic phenomena at extremely short length scales, we discuss the different mechanisms contributing to the signal enhancement. In addition to the known contributions from electric-field and chemical enhancement, several new models have been proposed very recently that could provide important guidelines for the optimization of TERS experiments. We then review recent developments in the areas of antenna design, fabrication, and characterization. Finally, we briefly highlight recent applications to illustrate future directions of tip-enhanced near-field Raman microscopy and TERS.

From Highly Crystalline to Outer Surface-Functionalized Covalent Organic Frameworks--A Modulation Approach.

Crystallinity and porosity are of central importance for many properties of covalent organic frameworks (COFs), including adsorption, diffusion, and electronic transport. We have developed a new method for strongly enhancing both aspects through the introduction of a modulating agent in the synthesis. This modulator competes with one of the building blocks during the solvothermal COF growth, resulting in highly crystalline frameworks with greatly increased domain sizes reaching several hundreds of nanometers. The obtained materials feature fully accessible pores with an internal surface area of over 2000 m(2) g(-1). Compositional analysis via NMR spectroscopy revealed that the COF-5 structure can form over a wide range of boronic acid-to-catechol ratios, thus producing frameworks with compositions ranging from highly boronic acid-deficient to networks with catechol voids. Visualization of an -SH-functionalized modulating agent via iridium staining revealed that the COF domains are terminated by the modulator. Using functionalized modulators, this synthetic approach thus also provides a new and facile method for the external surface functionalization of COF domains, providing accessible sites for post-synthetic modification reactions. We demonstrate the feasibility of this concept by covalently attaching fluorescent dyes and hydrophilic polymers to the COF surface. We anticipate that the realization of highly crystalline COFs with the option of additional surface functionality will render the modulation concept beneficial for a range of applications, including gas separations, catalysis, and optoelectronics.

Phase retrieval of ultrashort laser pulses using a MIIPS algorithm.

We developed a new method for retrieving the group delay dispersion of a laser from Multiphoton Intra-pulse Interference Phase Scan (MIIPS) data. The method takes into account the spectral amplitude of the laser pulse and provides a direct feedback on the accuracy of the retrieval. The main advantage of the method derives from providing sufficiently high accuracy to avoid the need for multiple experimental iterations. Another advantage is that the new method can discriminate among pulses with different spectral phase and amplitude profiles, in which MIIPS traces occupy the same position in the phase-frequency MIIPS map.

Microscopic view on the ultrafast photoluminescence from photoexcited graphene.

We present a joint theory-experiment study on ultrafast photoluminescence from photoexcited graphene. On the basis of a microscopic theory, we reveal two distinct mechanisms behind the occurring photoluminescence: besides the well-known incoherent contribution driven by nonequilibrium carrier occupations, we found a coherent part that spectrally shifts with the excitation energy. In our experiments, we demonstrate for the first time the predicted appearance and spectral shift of the coherent photoluminescence.

Graphene Near-Degenerate Four-Wave Mixing for Phase Characterization of Broadband Pulses in Ultrafast Microscopy.

We investigate near-degenerate four-wave mixing in graphene using femtosecond laser pulse shaping microscopy. Intense near-degenerate four-wave mixing signals on either side of the exciting laser spectrum are controlled by amplitude and phase shaping. Quantitative signal modeling for the input pulse parameters shows a spectrally flat phase response of the near-degenerate four-wave mixing due to the linear dispersion of the massless Dirac Fermions in graphene. Exploiting these properties we demonstrate that graphene is uniquely suited for the intrafocus phase characterization and compression of broadband laser pulses, circumventing disadvantages of common methods utilizing second or third harmonic light.

Tip-enhanced near-field optical microscopy.

Tip-enhanced near-field optical microscopy (TENOM) is a scanning probe technique capable of providing a broad range of spectroscopic information on single objects and structured surfaces at nanometer spatial resolution and with highest detection sensitivity. In this review, we first illustrate the physical principle of TENOM that utilizes the antenna function of a sharp probe to efficiently couple light to excitations on nanometer length scales. We then discuss the antenna-induced enhancement of different optical sample responses including Raman scattering, fluorescence, generation of photocurrent and electroluminescence. Different experimental realizations are presented and several recent examples that demonstrate the capabilities of the technique are reviewed.

Antenna-enhanced optoelectronic probing of carbon nanotubes.

We report on the first antenna-enhanced optoelectronic microscopy studies on nanoscale devices. By coupling the emission and excitation to a scanning optical antenna, we are able to locally enhance the electroluminescence and photocurrent along a carbon nanotube device. We show that the emission source of the electroluminescence can be pointlike with a spatial extension below 20 nm. Topographic and antenna-enhanced photocurrent measurements reveal that the emission takes place at the location of highest local electric field indicating that the mechanism behind the emission is the radiative decay of excitons created via impact excitation.

Extraction of photogenerated electrons and holes from a covalent organic framework integrated heterojunction.

Covalent organic frameworks (COFs) offer a strategy to position molecular semiconductors within a rigid network in a highly controlled and predictable manner. The π-stacked columns of layered two-dimensional COFs enable electronic interactions between the COF sheets, thereby providing a path for exciton and charge carrier migration. Frameworks comprising two electronically separated subunits can form highly defined interdigitated donor-acceptor heterojunctions, which can drive the photogeneration of free charge carriers. Here we report the first example of a photovoltaic device that utilizes exclusively a crystalline organic framework with an inherent type II heterojunction as the active layer. The newly developed triphenylene-porphyrin COF was grown as an oriented thin film with the donor and acceptor units forming one-dimensional stacks that extend along the substrate normal, thus providing an optimal geometry for charge carrier transport. As a result of the degree of morphological precision that can be achieved with COFs and the enormous diversity of functional molecular building blocks that can be used to construct the frameworks, these materials show great potential as model systems for organic heterojunctions and might ultimately provide an alternative to the current disordered bulk heterojunctions.

The balancing act between high electronic and low ionic transport influenced by perovskite grain boundaries.

A better understanding of the materials' fundamental physical processes is necessary to push hybrid perovskite photovoltaic devices towards their theoretical limits. The role of the perovskite grain boundaries is essential to optimise the system thoroughly. The influence of the perovskite grain size and crystal orientation on physical properties and their resulting photovoltaic performance is examined. We develop a novel, straightforward synthesis approach that yields crystals of a similar size but allows the tuning of their orientation to either the (200) or (002) facet alignment parallel to the substrate by manipulating dimethyl sulfoxide (DMSO) and tetrahydrothiophene-1-oxide (THTO) ratios. This decouples crystal orientation from grain size, allowing the study of charge carrier mobility, found to be improved with larger grain sizes, highlighting the importance of minimising crystal disorder to achieve efficient devices. However, devices incorporating crystals with the (200) facet exhibit an s-shape in the current density-voltage curve when standard scan rates are used, which typically signals an energetic interfacial barrier. Using the drift-diffusion simulations, we attribute this to slower-moving ions (mobility of 0.37 × 10-10 cm2 V-1 s-1) in combination with a lower density of mobile ions. This counterintuitive result highlights that reducing ion migration does not necessarily minimise hysteresis.

Launching propagating surface plasmon polaritons by a single carbon nanotube dipolar emitter.

We report on the excitation of propagating surface plasmon polaritons in thin metal films by a single emitter. Upon excitation in the visible regime, individual semiconducting single-walled carbon nanotubes are shown to act as directional near-infrared point dipole sources launching propagating surface plasmons mainly along the direction of the nanotube axis. Plasmon excitation and propagation is monitored in Fourier and real space by leakage radiation microscopy and is modeled by rigorous theoretical calculations. Coupling to plasmons almost completely reshapes the emission of nanotubes both spatially and with respect to polarization as compared to photoluminescence on a dielectric substrate.

Microfluidic mixing as platform technology for production of chitosan nanoparticles loaded with different macromolecules.

In recent decades, biotechnological drugs have emerged as relevant therapeutic tools. However, therapeutic molecules can exert their activity only if properly formulated and delivered into the body. In this regard, nano-sized drug delivery systems have been shown to provide protection, stability, and controlled release of payloads, increasing their therapeutic efficacy. In this work, a microfluidic mixing technique for the preparation of chitosan-based nanoparticles was established with the capability of easily exchanging macromolecular biological cargos such as the model protein ß-Galactosidase, mRNA, and siRNA. The nanoparticles obtained showed hydrodynamic diameters ranging from 75 nm to 105 nm, low polydispersity of 0.15 to 0.22 and positive zeta potentials of 6 mV to 17 mV. All payloads were efficiently encapsulated (>80 %) and the well-known cytocompatibility of chitosan-based nanoparticles was confirmed. Cell culture studies demonstrated increased cellular internalization of loaded nano-formulations compared to free molecules as well as successful gene silencing with nano-formulated siRNA, suggesting the ability of these nanoparticles to escape the endosome.

Ultrafast hot electron-hole plasma photoluminescence in two-dimensional semiconductors.

The transition metal dichalcogenide family of semiconducting two-dimensional materials has recently shown a prominent potential to be an ideal platform to study the exciton Mott transition into electron-hole plasma and liquid phases due to their strong Coulomb interactions. Here, we show that pulsed laser excitation at high pump fluences can induce this exciton Mott transition to an electron-hole plasma in mono and few-layer transition metal dichalcogenides at room temperature. The formation of an electron-hole plasma leads to a broadband light emission spanning from the near infrared to the visible region. In agreement with our theoretical calculations, the photoluminescence emission at high energies displays an exponential decay that directly reflects the electronic temperature - a characteristic fingerprint of unbound electron-hole pair recombination. Furthermore, two-pulse excitation correlation measurements were performed to study the dynamics of electronic cooling, which shows two decay time components, one of less than 100 fs and a slower component of few ps associated with the electron-phonon and phonon-lattice bath thermalizations, respectively. Our work may shed light on further studies of the exciton Mott transition into other two-dimensional materials and their heterostructures and its applications in nanolasers and other optoelectronic devices.

In-plane remote photoluminescence excitation of carbon nanotube by propagating surface plasmon.

In this work, we demonstrate propagating surface plasmon polariton (SPP) coupled photoluminescence (PL) excitation of single-walled carbon nanotube (SWNT). SPPs were launched at a few micrometers from individually marked SWNT, and plasmon-coupled PL was recorded to determine the efficiency of this remote in-plane addressing scheme. The efficiency depends upon the following factors: (i) longitudinal and transverse distances between the SPP launching site and the location of the SWNT and (ii) orientation of the SWNT with respect to the plasmon propagation wave vector (k(SPP)). Our experiment explores the possible integration of carbon nanotubes as a plasmon sensor in plasmonic and nanophotonic devices.

Tip-enhanced near-field optical microscopy of quasi-1 D nanostructures.

High-resolution imaging and spectroscopy of single CdSe nanowires and carbon nanotubes using tip-enhanced near-field optical microscopy increases the optical excitation and emission rates within a nanoscale sample volume. The resulting signal enhancement for Raman scattering and photoluminescence as well as the tip-sample-distance dependence are investigated.

Probing the ultrafast dynamics of excitons in single semiconducting carbon nanotubes.

Excitonic states govern the optical spectra of low-dimensional semiconductor nanomaterials and their dynamics are key for a wide range of applications, such as in solar energy harvesting and lighting. Semiconducting single-walled carbon nanotubes emerged as particularly rich model systems for one-dimensional nanomaterials and as such have been investigated intensively in the past. The exciton decay dynamics in nanotubes has been studied mainly by transient absorption and time-resolved photoluminescence spectroscopy. Since different transitions are monitored with these two techniques, developing a comprehensive model to reconcile different data sets, however, turned out to be a challenge and remarkably, a uniform description seems to remain elusive. In this work, we investigate the exciton decay dynamics in single carbon nanotubes using transient interferometric scattering and time-resolved photoluminescence microscopy with few-exciton detection sensitivity and formulate a unified microscopic model by combining unimolecular exciton decay and ultrafast exciton-exciton annihilation on a time-scale down to 200 fs.

1,10-Phenanthroline as an Efficient Bifunctional Passivating Agent for MAPbI3 Perovskite Solar Cells.

Passivation is one of the most promising concepts to heal defects created at the surface and grain boundaries of polycrystalline perovskite thin films, which significantly deteriorate the photovoltaic performance and stability of corresponding devices. Here, 1,10-phenanthroline, known as a bidentate chelating ligand, is implemented between the methylammonium lead iodide (MAPbI3) film and the hole-transport layer for both passivating the lead-based surface defects (undercoordinated lead ions) and converting the excess/unreacted lead iodide (PbI2) buried at interfaces, which is problematic for the long-term stability, into "neutralized" and beneficial species (PbI2(1,10-phen)x, x = 1, 2) for efficient hole transfer at the modified interface. The defect healing ability of 1,10-phenanthroline is verified with a set of complementary techniques including photoluminescence (steady-state and time-resolved), space-charge-limited current (SCLC) measurements, light intensity dependent JV measurements, and Fourier-transform photocurrent spectroscopy (FTPS). In addition to these analytical methods, we employ advanced X-ray scattering techniques, nano-Fourier transform infrared (nano-FTIR) spectroscopy, and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) to further analyze the structure and chemical composition at the perovskite surface after treatment at nanoscale spatial resolution. On the basis of our experimental results, we conclude that 1,10-phenanthroline treatment induces the formation of different morphologies with distinct chemical compositions on the surface of the perovskite film such that surface defects are effectively passivated, and excess/unreacted PbI2 is converted into beneficial complex species at the modified interface. As a result, an improved power conversion efficiency (20.16%) and significantly more stable unencapsulated perovskite solar cells are obtained with the 1,10-phenanthroline treatment compared to the MAPbI3 reference device (18.03%).

Enhancing and redirecting carbon nanotube photoluminescence by an optical antenna.

We observe the angular radiation pattern of single carbon nanotubes' photoluminescence in the back focal plane of a microscope objective and show that the emitting nanotube can be described by a single in-plane point dipole. The near-field interaction between a nanotube and an optical antenna modifies the radiation pattern that is now dominated by the antenna characteristics. We quantify the antenna induced excitation and radiation enhancement and show that the radiative rate enhancement is connected to a directional redistribution of the emission.