Planar Polymer Research Articles

Sensitivity enhancement by using adlayer of MoS2 heterostructure in a common path Mach-Zehnder interferometer method for biochemical sensor

The heterostructure of two-dimensional MoS2 material are promising and useful in the field of biochemical sensors. In present communication, the sensitivity of a four-layer planar polymer optical waveguide having an ad-layer of MoS2 material is presented. A common path Mach-Zehnder interferometric method is used for biological sensing applications. The effective refractive indexes of fundamental modes (TE0, TM0) are obtained at considered wavelength range and the difference of their propagation constant is calculated. The output interference signal in presence of different cover medium shows maxima shift which are considered as sensing signal. The phase sensitivity is calculated by using this output interference signal which is 200/RIU.

From spherical compartments to polymer films: exploiting vesicle fusion to generate solid supported thin polymer membranes.

Solid supported polymer membranes as scaffold for the insertion of functional biomolecules provide the basis for mimicking natural membranes. They also provide the means for unraveling biomolecule-membrane interactions and engineering platforms for biosensing. Vesicle fusion is an established procedure to obtain solid supported lipid bilayers but the more robust polymer vesicles tend to resist fusion and planar membranes rarely form. Here, we build on vesicle fusion to develop a refined and efficient way to produce solid supported membranes based on poly(dimethylsiloxane)-poly(2-methyl-2-oxazoline) (PMOXA-b-PDMS-b-PMOXA) amphiphilic triblock copolymers. We first create thiol-bearing polymer vesicles (polymersomes) and anchor them on a gold substrate. An osmotic shock then provokes polymersome rupture and drives planar film formation. Prerequisite for a uniform amphiphilic planar membrane is the proper combination of immobilized polymersomes and osmotic shock conditions. Thus, we explored the impact of the hydrophobic PDMS block length of the polymersome on the formation and the characteristics of the resulting solid supported polymer assemblies by quarz crystal microbalance with dissipation monitoring (QCM-D), atomic force microscopy (AFM) and spectroscopic ellipsometry (SE). When the PDMS block is short enough, attached polymersomes restructure in response to osmotic shock, resulting in a uniform planar membrane. Our approach to rapidly form planar polymer membranes by vesicle fusion brings many advantages to the development of synthetic planar membranes for bio-sensing and biotechnological applications.

Stress in a Stimuli-Responsive Polymer Brush

The application of a polymer brush in sensing, actuation, self-folding, among others acutely depends on the tuneable bending of a brush-grafted substrate caused by the stress in the brush. However, the stress in a stimuli-responsive brush has not been investigated. In this work, we study the stress in the stimuli-responsive planar polymer brushes of neutral water-soluble polymers with low to very high graft densities using strong stretching theory (SST). First, SST with the Langevin force-extension relation for a polymer chain is extended to the study of stimuli-responsive brushes. Stress profile and other properties of a Poly(N-isopropylacrylamide) (PNIPAm) brush are then obtained using the extended SST and an empirical Flory-Huggins parameter. The model predicts that the stress in a PNIPAm brush is inhomogeneous and compressive at all temperatures and graft densities. The resultant stress is predicted to increase in magnitude with increasing graft density. Moreover, it decreases in magnitude with an increase in temperature before plateauing in low graft density brushes. In contrast, its magnitude increases weakly with increasing temperature in high density brushes. This contrasting behavior is traced to the minimum in interaction free energy density \emph{vs} polymer volume fraction curve for PNIPAm solution at a large volume fraction, and stiffening of chains due to finite extensibility. Furthermore, our results indicate that the ability to tune the resultant stress by changing temperature diminishes with increasing graft density.

All-Optical Planar Polymer Waveguide-Based Biosensor Chip Designed for Smartphone-Assisted Detection of Vitamin D.

An all-optical plasmonic sensor platform designed for smartphones based on planar-optical waveguide structures integrated in a polymer chip is reported for the first time. To demonstrate the applicability of the sensor system for biosensing purposes, the detection of 25-hydroxyvitamin D (25OHD) in human serum samples using an AuNP-enhanced aptamer-based assay was demonstrated. With the aid of the developed assay sensitivity of 0.752 pixel/nM was achieved for 25OHD concentrations ranging from 0–100 nM. The waveguide structure of the sensor enables miniaturisation and parallelisation, thus, demonstrates the potential for simultaneous detection of various analytes including biomarkers. The entire optical arrangement can be integrated into a single polymer chip which allows for large scale and cost-efficient sensor fabrication. The broad utilization and access of smartphone electronics make the proposed design most attractive for its wider use in lab-on-chip applications.

Combined thermomechanical and optical simulations of planar-optical polymer waveguides

In this work, we describe a theoretical approach for combined thermal, mechanical and optical simulation and analysis of planar polymer waveguides. We consider a finite element approach for thermal and stress/deformation simulation. Also, a Crank-Nicholson finite difference beam propagation method (CN-BPM) is implemented to perform the optical simulation. The results of the finite element (thermo-mechanical) analysis are coupled with the CN-BPM results to carry out the optical simulation of poly(methyl methacrylate) (PMMA) waveguides as function of temperature. For thermal simulation, a model was designed where a polysilicon microheater was added to the upper cladding of the PMMA waveguides to vary the temperature between 20 °C and 200 °C. Thus, the impact of the induced temperature gradients on the refractive index modulation of the PMMA waveguides and the corresponding change in numerical aperture are obtained. In addition, the temperature gradients influence the beam intensity profiles and the movement of the primary eyes within the optical waveguides, thus, impacting the optical properties. Furthermore, the thermally induced mechanical stress and deformation were calculated for transverse and axial directions. In the next step, validation of the model by systematic experimental studies will be performed. In general, our approach provides a toolbox for more comprehensive multi-physics theoretical analysis of polymer-optical waveguides which, in future, can be extended to more complex and functional structures as required for flexible sensor networks, as example.

Multi-Channel Single-Mode Polymer Waveguide Fabricated Using the Mosquito Method

We experimentally demonstrate that the Mosquito method is capable of fabricating polymer optical waveguides with single-mode cores. The Mosquito method we developed is a technique to form planar polymer waveguides using a commercially available microdispenser. In this article, the flow of the core monomer dispensed from the tip of the needle is simulated using fluid analysis software. The results show that the shape of the needle periphery significantly affects the fabrication of perfectly circular cross-sectional cores. In addition, we demonstrate that the Mosquito method is capable of reducing the MFD variation to 0.4 μm. We find such a small MFD fluctuation is comparable to that of typical single-mode optical fibers.

Refractive Index Sensor Based on Metal-Clad Planar Polymer Waveguide Operating at 850 nm

A metal-clad planar polymer waveguide refractive index sensor based on epoxy (EPO) polymer materials by using light intensity interrogation at 850 nm is designed. The polymethyl methacrylate (PMMA) material is deployed as the low refractive index (RI) buffer layer in order to better couple the optical guided mode and the surface plasmon polaritons (SPP) mode for working in water environment. The effects of the gold film thickness, PMMA buffer layer thickness, waveguide layer thickness, waveguide width, and gold length on the sensor sensing characteristics have been comprehensively studied. Simulation results demonstrate that the normalized transmission increases quasi-linearly with the increment of RI of the analyte from 1.33 to 1.46. The sensitivity is 491.5 dB/RIU, corresponding to a high RI resolution of 2.6×10−9 RIU. The designed SPP-based optical waveguide sensor is low-cost, wide-range, and high-precision, and has a broad application prospect in biochemical sensing with merits of miniaturization, flexibility, and multiplexing.

Microstructure-Based Fiber-To-Chip Coupling of Polymer Planar Bragg Gratings for Harsh Environment Applications.

This article proposes and demonstrates a robust microstructure-based fiber-to-chip coupling scheme for planar Bragg grating devices. A polymer planar Bragg grating substrate is manufactured and microstructured by means of a micromilling process, while the respective photonic structures are generated by employing a sophisticated single-writing UV-exposure method. A stripped standard single-mode fiber is inserted into the microstructure, which is filled with a UV-curable adhesive, and aligned with the integrated waveguide. After curing, final sensor assembly and thermal treatment, the proposed coupling scheme is capable of withstanding pressures up to 10 bar, at room temperature, and pressures up to 7.5 bar at an elevated temperature of 120 °C. Additionally, the coupling scheme is exceedingly robust towards tensile forces, limited only by the tensile strength of the employed single-mode fiber. Due to its outstanding robustness, the coupling scheme enables the application of planar Bragg grating devices in harsh environments. This fact is underlined by integrating a microstructure-coupled photonic device into the center of a commercial-grade carbon fiber reinforced polymer specimen. After its integration, the polymer-based Bragg grating sensor still exhibits a reflection peak with a dynamic range of 24 dB, and can thus be employed for sensing purposes.

Understanding the role of Nanomorphology on Resistance Evolution in the Hybrid Form-Fuse Process for Conformal Electronics

Manufacturing conformal electrically conductive circuits on rigid freeform surfaces currently require compromises between process scalability, cost, and thermal tolerance and geometric complexity of the object material. The Form-Fuse process operates by printing silver nanoparticle interconnects on planar polymer sheets followed by sequential vacuum forming and Flash Light Sintering (FLS) and can overcome the above issues. We investigate the role of nanoparticle morphology on this process by using nanowires (NW) in combination with nanoflakes (NF) and nanospheres (NS) as the printed nanoparticles. The characterization of FLS temperature, electrical resistance, morphology, and optical absorption along with electromagnetic and molecular dynamics modeling yields the following insights. The forming-induced resistivity rise is greater for higher NS and NF content due to localized embedding of NWs into the polymer. This embedding also reduces blowoff defects during FLS to create an expanded defect-free FLS window. The resistance reduction due to FLS is also greater for the mixed NW-NF and NW-NS cases, thanks to the change in localized optical absorption and interparticle fusion kinetics upon the introduction of NFs and NSs into a NW ensemble. The change in fusion kinetics is driven by enhanced dislocation growth between nanoparticles, despite surface and grain boundary diffusion trends contrary to the neck growth trends. We show that Form-Fuse can achieve similar or lesser electrical resistivity than state-of-the-art conformal 3D printing while enabling greater scalability and structural material capability and retaining the capability to handle complex shapes. We discuss the impact of our findings on the nanoparticle material cost and capabilities of Form-Fuse compared to other conformal electronics manufacturing processes.

Fs-laser based hybrid micromachining for polymer micro-opto electrical systems

We report on femtosecond laser direct writing of electrically conductive copper structures on transparent cyclic olefin copolymer based planar optical chips. The process is based on a laser-induced reduction of CuO nanoparticles dissolved in a water-soluble resin. Thus generated conductive copper structures are characterized with respect to their chemical composition and electrical resistivity. In addition, the application of ultrashort laser pulses enables a hybrid micromachining approach comprising ablation of polymer substrates and the fabrication of copper patterns in a single laser processing setup. A possible electro-optical application of this approach is demonstrated by employing the copper structures as an electro-thermal microheater in combination with a polymer planar optical Bragg grating sensor. This, in turn, highlights the potential of generating copious micro-opto-electro-mechanical polymer structures for numerous sensing applications ranging from Lab-on-Chip to environmental applications using the presented hybrid micromachining approach.

Hypersensitive H2 sensor based on polymer planar Bragg gratings coated with Pt-loaded WO3-SiO2: erratum.

We present an erratum to our Letter [Opt. Lett.45, 3601 (2020)OPLEDP0146-959210.1364/OL.395341]. Labeling errors in two figures and an incorrect sentence are revised. The corrections have no influence on the conclusions of the original Letter.

Planar and Twisted Molecular Structure Leads to the High Brightness of Semiconducting Polymer Nanoparticles for NIR-IIa Fluorescence Imaging.

Semiconducting polymer nanoparticles (SPNs) emitting in the second near-infrared window (NIR-II, 1000-1700 nm) are promising materials for deep-tissue optical imaging in mammals, but the brightness is far from satisfactory. Herein, we developed a molecular design strategy to boost the brightness of NIR-II SPNs: structure planarization and twisting. By integration of the strong absorption coefficient inherited from planar π-conjugated units and high solid-state quantum yield (ΦPL) from twisted motifs into one polymer, a rise in brightness was obtained. The resulting pNIR-4 with both twisted and planar structure displayed improved ΦPL and absorption when compared to the planar polymer pNIR-1 and the twisted polymer pNIR-2. Given the emission tail extending into the NIR-IIa region (1300-1400 nm) of the pNIR-4 nanoparticles, NIR-IIa fluorescence imaging of blood vessels with enhanced clarity was observed. Moreover, a pH-responsive poly(β-amino ester) made pNIR-4 specifically accumulate at tumor sites, allowing NIR-IIa fluorescence image-guided cancer precision resection. This study provides a molecular design strategy for developing highly bright fluorophores.

Multiple conformation locks gift polymer donor high efficiency

Abstract The mechanism that how noncovalent conformation locks (NCLs) to improve the photovoltaic performance of polymer donors was investigated. By developing a model system with three structure-related copolymers W1, W2 and W3, a clear correlation was found between the locking strength in polymer backbone and the photovoltaic performance. W1 with the strongest S⋅⋅⋅O and F⋅⋅⋅H double-side locking gave the highest power conversion efficiency (PCE) of 16.23%, while W2 with a S⋅⋅⋅O single-side locking and W3 with a weakened S⋅⋅⋅O locking caused by Cl–H steric repulsion gave lower PCEs of 11.73% and 0.92%, respectively. With the aid of single crystal X-ray diffraction analysis, density functional theory calculation, grazing-incidence wide-angle X-ray scattering analysis, atomic force microscope study and device characterization, the functions of NCLs in improving the planarity, packing, crystallinity and hole mobility of polymers, as well as the morphology of blend films, were illuminated in detail.

Hypersensitive H2 sensor based on polymer planar Bragg gratings coated with Pt-loaded WO3-SiO2.

This Letter demonstrates a novel, to the best of our knowledge, hydrogen sensor based on a polymer planar Bragg grating coated with Pt-loaded WO3-SiO2. The reflected Bragg signal shows a distinct peak splitting correlated to substrate anisotropies originating from the injection molding process. Especially at low H2 concentrations, both sensing peaks exhibit an outstanding response to the heat generated by the exothermic reaction between hydrogen molecules and coating. Thereby, a hydrogen volume ratio of 50 ppm leads to a Bragg wavelength shift of -37pm, which yields an outstandingly low detection limit of only 5 ppm H2 in air. Thus, functionalized polymer planar Bragg gratings are eminently suitable for H2 leak detection applications.

Quantitative Analysis of Doping-Induced Polarons and Charge-Transfer Complexes of Poly(3-hexylthiophene) in Solution.

The mechanism and the nature of the species formed by molecular doping of the model polymer poly(3-hexylthiophene) (P3HT) in its regioregular (rre-) and regiorandom (rra-) forms in solution are investigated for three different dopants: the prototypical π-electron acceptor 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), the strong Lewis acid tris(pentafluorophenyl)borane (BCF), and the strongly oxidizing complex molybdenum tris[1-(methoxycarbonyl)-2-(trifluoromethyl)ethane-1,2-dithiolene] (Mo(tfd-CO2Me)3). In a combined optical and electron paramagnetic resonance study, we show that the doping of rreP3HT in solution occurs by integer charge transfer, resulting in formation of P3HT radical cations (polarons) for all of the dopants considered here. Remarkably, despite the different chemical nature of the dopants and dopant-polymer interaction, the formed polarons exhibit essentially identical optical absorption spectra. The situation is very different for the doping of rraP3HT, where we observe formation of a charge-transfer complex with F4TCNQ and of a "localized" P3HT polaron on nonaggregated chains upon doping with BCF, while there is no indication of dopant-induced species in the case of Mo(tfd-CO2Me)3. We estimate the ionization efficiency of the respective dopants for the two polymers in solution and report the molar extinction coefficient spectra of the three different species. Finally, we observe increased spin delocalization in regioregular compared to regiorandom P3HT by electron nuclear double resonance, suggesting that the ability of the charge to delocalize on aggregates of planarized polymer backbones plays a significant role in determining the doping mechanism.

Epoxy polymer optical waveguide for micro-opto-electro-mechanical systems

The paper reports on the fabrication and characterisation of E3135 epoxy polymer planar waveguides fabricated onto allyl diglycol carbonate substrate. We measured transmission spectra from the visible to near-infrared region and studied waveguiding properties by the m-line spectroscopy using six lasers (532.0, 654.2, 846.4, 1308.2, 1549.1 and 1652.1 nm). Optical scattering losses of the planar waveguides were measured by the fibre scanning method. The lowest values of the optical losses were 0.33 dB/cm at 632.8 nm and 0.35 dB/cm at 850 nm. Our research showed that the epoxy polymer E3135 is a promising material for the implementation into the MOEMS structures with higher integration density, thus it allows for realisation low-cost and feasibly elaborated MOEMS components.

Sodium Alginate Cross-Linkable Planar 1D Photonic Crystals as a Promising Tool for Pb2+ Detection in Water

Due to its high toxicity, Pb2+ pollution is a serious threat for human health and environments. However, in situ real-time detection of Pb2+ pollution is difficult and laboratory instruments are usually required. Then, the possibility to monitor water quality without laboratory instruments could lead to the extensive assessment of polluted water sources, especially in rural environments and developing countries where large lead concentrations are often found in surface water. Consequently, new simple colorimetric sensors are highly interesting in the field. In this work we report for the first time disposable polymer planar 1D photonic crystals made of poly (N-vinylcarbazole) as high refractive index medium and sodium alginate as low refractive index and active medium for the detection of Pb2+ in water. The detection relies on the ionic exchange occurring into the alginate matrix. This process effectively induces a physical cross-linking phenomenon, which inhibits water solubilization of the polymer. In turn, this affects the spectral response of the planar 1D photonic crystals modifying its color.

Estimation of cover sensitivity of a planar polymer waveguide through double path broadband difference interferometeric analysis

Broadband difference interferometeric analysis of a double path planar polymer optical waveguide is presented for bio-sensing applications. Mathematical formulation of intensity of output signal is obtained using interferometeric analysis. Further, the dispersion equation is obtained by matching the field at core cladding interface that gives the cutoff film thickness for TE0 and TM0 modes in considered spectral range. The waveguide is analyzed by propagating either same polarized (TETE or TMTM) modes or unlike polarized (TETM) modes in the reference arm and sensing arm. It is observed that difference of propagation constant for same polarized mode increases with increase of wavelength while for unlike polarized modes it first increases up to a maximum value and then decreases in the considered wavelength range. The maxima of output interference signal shifted prominently with the cover refractive index for the wavelength range near the maximum value of propagation constant difference. The obtained sensitivity 9.226 for unlike polarized modes in arms is much larger than the sensitivity 0.071 of same polarized modes in arms.

Effects of Intra- and Interchain Interactions on Exciton Dynamics of PTB7 Revealed by Model Oligomers.

Recent studies have shown that molecular aggregation structures in precursor solutions of organic photovoltaic (OPV) polymers have substantial influence on polymer film morphology, exciton and charge carrier transport dynamics, and hence, the resultant device performance. To distinguish photophysical impacts due to increasing π-conjugation from chain lengthening and π–π stacking from single/multi chain aggregation in solution and film, we used oligomers of a well-studied charge transfer polymer PTB7 with different lengths as models to reveal intrinsic photophysical properties of a conjugated segment in the absence of inter-segment aggregation. In comparison with previously studied photophysical properties in polymeric PTB7, we found that oligomer dynamics are dominated by a process of planarization of the conjugated backbone into a quinoidal structure that resembles the self-folded polymer and that, when its emission is isolated, this quinoidal excited state resembling the planar polymer chain exhibits substantial charge transfer character via solvent-dependent emission shifts. Furthermore, the oligomers distinctly lack the long-lived charge separated species characteristic of PTB7, suggesting that the progression from charge transfer character in isolated chains to exciton splitting in neat polymer solution is modulated by the interchain interactions enabled by self-folding.

Thermoforming of planar polymer optical waveguides for integrated optics in smart packaging materials

Abstract The innovations in smart packaging will open up a wide range of opportunities in the future. This work describes the processing of additive manufactured and planar integrated polymer optical waveguides for use in smart packaging products. The previously published combination of flexographic and Aerosol Jet printing is complemented by thermoforming and thus creates three-dimensional integrated multimode waveguides with optical attenuation of 1.9 dB/cm ± 0.1 dB/cm @ 638 nm. These properties will be the basis to develop smart applications in packaging materials.