Intramolecular Chloro-Sulfur Interaction and Asymmetric Side-Chain Isomerization to Balance Crystallinity and Miscibility in All-Small-Molecule Solar Cells.

Intramolecular Cl-S non-covalent interaction is introduced to modify molecular backbone of a benzodithiophene terthiophene rhodamine (BTR) benchmark structure, helping planarize and rigidify the molecular framework for improving charge transport. Theoretical simulations and temperature-variable NMR experiments clearly validate the existence of Cl-S non-covalent interaction in two designed chlorinated donors and explain its important role in enhancing planarity and rigidity of the molecules for enhancing their crystallinity. The asymmetric isomerization of side-chains further optimizes the molecular orientation and surface energy to strike a balance between its crystallinity and miscibility. This carefully manipulated molecular design helps result in increased carrier mobility and suppressed charge recombination to obtain simultaneously enhanced short-circuit current (Jsc ) and fill factor (FF) and a very high efficiency of 15.73 % in binary all-small-molecule organic solar cells.

Graphene electrodes for electric poling of electro-optic polymer films.

We propose electric poling of electro-optic (EO) polymer films with graphene electrodes. The use of graphene electrodes can waive the use of buffer layers and minimize the poling voltage. To demonstrate the idea, we prepared EO polymer thin-film waveguides for poling with traditional Au/ITO electrodes and graphene electrodes, where the EO polymer is a guest-host system formed by doping 15 wt% of dipolar polyene chromophore AJLZ53 into the random copolymer P(S-co-MMA). Our experiments confirm that the use of graphene electrodes can significantly reduce the poling voltage. For a 3.8-µm-thick EO polymer film, we achieve high EO coefficients of 82 pm/V at 1541 nm and 110 pm/V at 1300 nm with a poling voltage of 420 V. In addition, the use of graphene electrodes allows more flexible waveguide designs and can potentially simplify the fabrication of devices based on EO polymer.

Development of a molecular K+ probe for colorimetric/fluorescent/photoacoustic detection of K.

The potassium ion (K+) plays significant roles in many biological processes. To date, great efforts have been devoted to the development of K+ sensors for colorimetric, fluorescent, and photoacoustic detection of K+ separately. However, the development of molecular K+ probes for colorimetric detection of urinary K+, monitoring K+ fluxes in living cells by fluorescence imaging, and photoacoustic imaging of K+ dynamics in deep tissues still remains an open challenge. Herein, we report the first molecular K+ probe (NK2) for colorimetric, fluorescent, and photoacoustic detection of K+. NK2 is composed of 2-dicyanomethylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran (TCF) as the chromophore and phenylazacrown-6-lariat ether (ACLE) as the K+ recognition unit. Predominate features of NK2 include a short synthetic procedure, high K+ selectivity, large detection range (5-200 mM), and triple-channel detection manner. NK2 shows good response to K+ with obvious color changes, fluorescence enhancements (about threefold), and photoacoustic intensity changes. The existence of other metal ions (including Na+, Mg2+, Ca2+, Fe2+) and pH changes (6.5-9.0) have no obvious influence on K+ sensing of NK2. Portable test strips stained by NK2 can be used to qualitatively detect urinary K+ by color changes for self-diagnosis of diseases induced by high levels of K+. NK2 can be utilized to monitor K+ fluxes in living cells by fluorescent imaging. We also find its excellent performance in photoacoustic imaging of different K+ concentrations in the mouse ear. NK2 is the first molecular K+ probe for colorimetric, fluorescent, and photoacoustic detection of K+ in urine, in living cells, and in the mouse ear. The development of NK2 will broaden K+ probes' design and extend their applications to different fields. Graphical abstract.

RF photonic downconversion of vector modulated signals based on a millimeter-wave coupled electrooptic nonlinear polymer phase-modulator.

We report the RF photonic reception and downconversion of vector modulated RF signals using a millimeter-wave coupled electrooptic phase modulator with in-plane slotted patch antennas based on SEO125 nonlinear polymer. We demonstrate experimental results with QPSK, 8-PSK, 16-QAM, 32-QAM, and 64-QAM millimeter-wave signals centered at 36 GHz. After downconversion to intermediate frequencies between 0.5 GHz and 2 GHz, the vector encoded signals are demodulated using an electrical signal analyzer and found to have measured error vector magnitudes below 8%. Design, simulation, fabrication, and experimental results are presented and discussed.

Silicon-organic hybrid (SOH) modulators for intensity-modulation / direct-detection links with line rates of up to 120 Gbit/s.

High-speed interconnects in data-center and campus-area networks crucially rely on efficient and technically simple transmission techniques that use intensity modulation and direct detection (IM/DD) to bridge distances of up to a few kilometers. This requires electro-optic modulators that combine low operation voltages with large modulation bandwidth and that can be operated at high symbol rates using integrated drive circuits. Here we explore the potential of silicon-organic hybrid (SOH) Mach-Zehnder modulators (MZM) for generating high-speed IM/DD signals at line rates of up to 120 Gbit/s. Using a SiGe BiCMOS signal-conditioning chip, we demonstrate that intensity-modulated duobinary (IDB) signaling allows to efficiently use the electrical bandwidth, thereby enabling line rates of up to 100 Gbit/s at bit error ratios (BER) of 8.5 × 10-5. This is the highest data rate achieved so far using a silicon-based MZM in combination with a dedicated signal-conditioning integrated circuit (IC). We further show four-level pulse-amplitude modulation (PAM4) at lines rates of up to 120 Gbit/s (BER = 3.2 × 10-3) using a high-speed arbitrary-waveform generator and a 0.5 mm long MZM. This is the highest data rate hitherto achieved with a sub-millimeter MZM on the silicon photonic platform.

Rational Design of Dipolar Chromophore as an Efficient Dopant-Free Hole-Transporting Material for Perovskite Solar Cells.

In this paper, an electron donor-acceptor (D-A) substituted dipolar chromophore (BTPA-TCNE) is developed to serve as an efficient dopant-free hole-transporting material (HTM) for perovskite solar cells (PVSCs). BTPA-TCNE is synthesized via a simple reaction between a triphenylamine-based Michler's base and tetracyanoethylene. This chromophore possesses a zwitterionic resonance structure in the ground state, as evidenced by X-ray crystallography and transient absorption spectroscopies. Moreover, BTPA-TCNE shows an antiparallel molecular packing (i.e., centrosymmetric dimers) in its crystalline state, which cancels out its overall molecular dipole moment to facilitate charge transport. As a result, BTPA-TCNE can be employed as an effective dopant-free HTM to realize an efficient (PCE ≈ 17.0%) PVSC in the conventional n-i-p configuration, outperforming the control device with doped spiro-OMeTAD HTM.

Enhanced conductivity of sol-gel silica cladding for efficient poling in electro-optic polymer/TiO2 vertical slot waveguide modulators.

We report the enhanced conductivity of sol-gel silica under-cladding for efficient poling of electro-optic (EO) polymer in a hybrid EO polymer/TiO2 vertical slot waveguide modulator. The electrical volume conductivity of sol-gel silica cladding increases approximately 30 times when the calcining time of the cladding layer is critically reduced to 45 minutes, which increases the in-device EO coefficient of the 600-nm-thick EO polymer film in modulators and reduces the lower halfwave voltage (Vπ) of the modulators. The lowest driving voltage (Vπ) of the TiO2 slot waveguide modulator is 2.0 V for an electrode length (Le) of 10 mm and wavelength of 1550 nm (VπLe = 2.0 V·cm) for the low-index guest-host EO polymer SEO125. The optical propagation loss is reduced to 7 dB/cm.

Mesoporous sol-gel silica cladding for hybrid TiO2/electro-optic polymer waveguide modulators.

We report the efficient poling of an electro-optic (EO) polymer in a hybrid TiO(2)/electro-optic polymer multilayer waveguide modulator on mesoporous sol-gel silica cladding. The mesoporous sol-gel silica has nanometer-sized pores and a low refractive index of 1.24, which improves mode confinement in the 400-nm-thick EO polymer film in the modulators and prevents optical absorption from the lower Au electrode, thereby resulting in a lower half-wave voltage of the modulators. The half-wave voltage (Vπ) of the hybrid modulator fabricated on the mesoporous sol-gel silica cladding is 6.0 V for an electrode length (Le) of 5 mm at a wavelength of 1550 nm (VπLe product of 3.0 V·cm) using a low-index guest-host EO polymer (in-device EO coefficient of 75 pm/V).

Enhanced third harmonic generation by organic materials on high-Q plasmonic photonic crystals.

The enhanced optical nonlinearity enabled by localized plasmonic fields has been well studied for all-optical switching processing (AOSP) devices for future optical communication systems. In this work, plasmonic photonic crystals with a nonlinear polycarbonate/polymethine blend cladding layer are designed to enhance the third harmonic generation (THG) at the telecom wavelengths (~1550 nm). Due to the presence of he two-dimensional (2-D) gold nano-patch arrays with improved Q-factor and high local fields, more than 20 × of enhanced THG signals in the hybrid organic-plasmonic nanostructure are experimentally observed. The enhanced THG in the hybrid organic-plasmonic materials suggested that such extraordinary nonlinear effects can be used for AOSP devices and wavelength conversion.

A Full-Scale Analysis of Absorption Edges in Dye-Doped Nonlinear Optical Polymers.

A full-scale analysis of the absorption edges by modified Tauc-Lorentz models is essential in determining the optical bandgap and Urbach energy of semiconductors, transparent conductors, ionic compounds, and dielectric materials. This technique has not yet been applied to analyzing organic nonlinear optical (NLO) materials. This problem is tackled by preparing high-quality films of guest-host NLO polymers with a wide thickness range from sub-micron to 200 microns, allowing accurate measurement of full-spectral absorption coefficients of NLO materials over four orders of magnitude by the UV-VIS-NIR spectroscopy. The Tauc model and a new Monolog-Lorentz model are used to study the optical absorption edge of guest-host NLO polymers containing various push-pull chromophores and the dependence of optical bandgap and Urbach edge on the structure and composition of materials is analyzed. The results reveal the critical transition of the Urbach exponential tail to a low energy tail that overlaps with vibrational overtones of materials at the telecom wavelengths. Determining the fundamental absorption region of organic NLO films in this study provides quantitative insight into the research to harness the resonance-enhanced nonlinear coefficients of materials by operating at the wavelengths near the band edge with the control of optical loss.

Exploring Favorable Supramolecular Interactions of Multifluorinated Aromatics in Dendronized Push-Pull Chromophores for Electro-Optics.

Multifluorinated aromatics serve as supramolecular synthons in the research of organic electro-optic (EO) materials by exploiting π-π stacking interaction between the aromatic hydrocarbon and multifluorinated aromatic groups for performance improvement. However, non-classical hydrogen bonding remains largely unexplored in fluorinated EO dendrimers. In this study, three Fréchet-type generation 1 benzyl ether co-dendrons were synthesized by replacing one benzyl group with 2,3,5,6-tetrafluorobenzyl (p-HF4Bz), pentafluorobenzyl (C6F5Bz), and 2,3,4,5-tetrafluorobenzyl (o-HF4Bz) groups, to afford the benzoic acid derivatives D1, D2, and D3, which were further bonded to the donor and π-bridge moieties to afford three co-dendronized push-pull phenyltetraene chromophores EOD1, EOD2, and EOD3, respectively. The weak C-H⋅⋅⋅X (X=O, F) interactions in the crystal structure of D1 cumulatively add to the benzoic acid dimers to form an extended hydrogen-bonded network, while D2 is crystallized into a centric one-dimensional chain with strong intermolecular interactions. The poled films of EOD1 with PMMA exhibited the largest and most stable EO activity with optical homogeneity among the series. The results identify the effectiveness of weak but favorable hydrogen bonds enabled by the enhanced carbon acidity of p-HF4Bz synthon in D1, over the interactions in D2 and D3, for the rational design of supramolecular EO dendrimers.

Neutral Cyanine: Ultra-Stable NIR-II Merocyanines for Highly Efficient Bioimaging and Tumor-Targeted Phototheranostics.

Fluorescence imaging (FLI)-guided phototheranostics using emission from the second near-infrared (NIR-II) window show significant potential for cancer diagnosis and treatment. Clinical imaging-used polymethine ionic indocyanine green (ICG) dye is widely adopted for NIR fluorescence imaging-guided photothermal therapy (PTT) research due to its exceptional photophysical properties. However, ICG has limitations such as poor photostability, low photothermal conversion efficiency (PCE), short-wavelength emission peak, and liver-targeting issues, which restrict its wider use. In this study, two ionic ICG derivatives are transformed into neutral merocyanines (mCy) to achieve much-enhanced performance for NIR-II cancer phototheranostics. Initial designs of two ionic dyes show similar drawbacks as ICG in terms of poor photostability and low photothermal performance. One of the modified neutral molecules, mCy890, shows significantly improved stability, an emission peak over 1000 nm, and a high photothermal PCE of 51%, all considerably outperform ICG. In vivo studies demonstrate that nanoparticles of the mCy890 can effectively accumulate at the tumor sites for cancer photothermal therapy guided by NIR-II fluorescence imaging. This research provides valuable insights into the development of neutral merocyanines for enhanced cancer phototheranostics.

Wide optical spectrum range, subvolt, compact modulator based on an electro-optic polymer refilled silicon slot photonic crystal waveguide.

We design and demonstrate a compact and low-power, band-engineered, electro-optic (EO) polymer refilled silicon slot photonic crystal waveguide (PCW) modulator. The EO polymer is engineered for large EO activity and near-infrared transparency. A PCW step coupler is used for optimum coupling to the slow-light mode of the band-engineered PCW. The half-wave switching voltage is measured to be Vπ = 0.97 ± 0.02 V over an optical spectrum range of 8 nm, corresponding to the effective in-device r(33) of 1199 pm/V and V(π) × L = 0.291 ± 0.006 V × mm in a push-pull configuration. Excluding the slow-light effect, we estimate that the EO polymer is poled with an efficiency of 89 pm/V in the slot.

High-Performance Supramolecular Organogel Adhesives for Antimicrobial Applications in Diverse Conditions.

Supramolecular organogel coatings that can disinfect the deposited microbial pathogens are emerging as an effective vehicle to prevent pathogen transmission. However, the development of anti-pathogen supramolecular adhesives with mechanical robustness and controlled oil inclusion is technically challenging. Here, we report supramolecular adhesives with mechanical integrity and robust interfacial adhesion over a wide range of biogenic antimicrobial oil. Bifunctional monomers are synthesized and assembled into linear polymers with semicrystalline stackings through hierarchical hydrogen bonds, where incorporated bioactive oil could regulate the semicrystalline stackings into nanosized crystalline domains through intermolecular hydrogen bonds. The abundant bonding motifs provided by the supramolecular cross-linked networks could accommodate oil molecules with high inclusion capability and provide more interfacial binding sites with high adhesion strength, and the nanosized crystalline domains could stabilize the organogel network and compensate for the interactions with oil molecules to enhance structural and mechanical stability. In addition, rapid healing, robust adhesion, and antimicrobial and antiviral properties of the resultant organogel coatings are demonstrated. This study paves the way for the development of high-performance antimicrobial supramolecular adhesives with controlled oil inclusion, showing potential applications in soft robotics, tissue engineering, and biomedical devices.

Push-Pull Heptamethines Near the Cyanine Limit Exhibiting Large Quadratic Electro-Optic Effect.

Harnessing the quadratic electro-optic (QEO) of near-infrared polymethine chromophores over broad telecom wavelength bands is a subject of immense potential but remains largely under-investigated. Herein a series of push-pull heptamethines containing the tricyanofuran (TCF) acceptors and indoline or benzo[e]indoline donors are reported. These dipolar chromophores can attain a highly delocalized "cyanine-like" electronic ground state in solvents spanning a wide range of polarities, in some cases even closer to the ideal polymethine state than symmetrical cyanines. A transmission-mode electromodulation spectroscopy is used to study the electric-field-induced changes in optical absorption and refraction of polymer films doped with heptamethine chromophores, and large and thermally stable QEO effect with high efficiency-loss figure-of-merits that compare favorably to those from dipolar polyenes in poled or unpoled polymers and III-V semiconductors is obtained. The study opens a path for developing organic materials based on cyanine-like merocyanines for complementary metal oxide semiconductor -compatible, fast, efficient, and low-loss electro-optic modulation.

Trimming of high-Q-factor silicon ring resonators by electron beam bleaching.

We demonstrate a novel position-resolved resonance trimming strategy for silicon ring resonators. Ring resonators are covered with a chromophore-doped guest host polymer cladding. Illumination of the polymer cladding with high-energy electrons causes a bleaching of the chromophore molecules. Bleaching of the chromophores induces a reduction of the polymer refractive index, which can be used to trim the resonance frequency of the ring resonators. A maximum refractive index change of 0.06 and a TM polarization resonance shift of 16.4 nm have been measured. A Q factor of 20,000 before bleaching remains unaltered after the electron beam exposure process.

Silicon-polymer hybrid slot waveguide ring-resonator modulator.

We demonstrate a ring-resonator modulator based on a silicon-polymer hybrid slot waveguide with a tunability of 12.7 pm/V at RF speeds and a bandwidth of 1 GHz, for optical wavelengths near 1550 nm. Our slot waveguides were fabricated with 193 nm optical lithography, as opposed to the electron beam lithography used for previous results. The tunability is comparable to some of the best ring-based modulators making use of the plasma dispersion effect. The speed is likely limited only by resistance in the strip-loading section, and it should be possible to realize significant improvement with improved processing.

Effective in-device r33 of 735 pm/V on electro-optic polymer infiltrated silicon photonic crystal slot waveguides.

We design and fabricate a 320 nm slot for an electro-optic (E-O) polymer infiltrated silicon photonic crystal waveguide. Because of the large slot width, the poling efficiency of the infiltrated E-O polymer (AJCKL1/amorphous polycarbonate) is significantly improved. When coupled with the slow light effect from the silicon photonic crystal waveguide, an effective in-device r(33) of 735 pm/V, which to our knowledge is a record high, is demonstrated, which is ten times higher than the E-O coefficient achieved in thin film material. Because of this ultrahigh E-O efficiency, the V(π)L of the device is only 0.44 V mm, which is to our knowledge the best result of all E-O polymer modulators.

Electric-field sensors utilizing coupling between a D-fiber and an electro-optic polymer slab.

This paper provides a detailed analysis of electric field sensing using a slab-coupled optical fiber sensor (SCOS). This analysis explains that the best material for the slab waveguide is an inorganic material because of the low RF permittivity combined with the high electro-optic coefficient. The paper also describes the fabrication and testing of a SCOS using an AJL chromophore in amorphous polycarbonate. The high uniform polymer slab waveguide is fabricated using a hot embossing process to create a slab with a thickness of 50 µm. The fabricated polymer SCOS was characterized to have a resonance slope of ΔP/Δλ=6.83E5 W/m and a resonance shift of Δλ/E=1.47E-16 m(2)/V.

Ultrastretchable conductive liquid metal composites enabled by adaptive interfacial polarization.

Gallium-based liquid metals (LMs) are emerging candidates for the development of metal/polymer-based flexible circuits in wearable electronics. However, the high surface energies of LMs make them easily depleted from the polymer matrix and therefore substantially suppress the stretchability of the conductive composites. Here, we reveal that a dynamic interplay between the LM and the polyvinylidene fluoride (PVDF) copolymer can help to address these issues. Weak and abundant interfacial polarization interactions between the PVDF copolymer and the oxide layer allow continuous and adaptive configuration of the compartmented LM channels, enabling ultra-stretchability of the composites. The conductive LM-polymer composites can maintain their structural integrity with a high surface conductivity and small resistance changes under large strains from 1000% to 10 000%. Taking advantage of their flexible processability under mild conditions and exceptional performance, our design strategy allows the scalable fabrication of conductive LM-polymer composites for a range of applications in wearable devices and sensors.