Optical waveguides at micro/nanoscale based on functional small organic molecules

Optical waveguides synthesized at the micro/nanoscale have drawn great interest for their potential applications in high speed miniaturized photonic integrations. In this Perspective article, we mainly focus on the related works on active optical waveguides based on functional small organic molecules in micro/nano regime. We begin with a general overview of recent progress in sub-wavelength optical waveguides, including the development of waveguide materials of inorganic semiconductors, polymers, and small organic molecules. Then brief highlights are put on the recently reported organic optical waveguides with various unique optical properties induced by the ordered molecular aggregations in the micro/nano-sized solid-state structures, such as polarized emission, lasing, aggregation-induced enhanced emission, etc. This article concludes with a summary and our personal view about the direction of future development in organic opto-functional waveguides as photonic devices.     

Analysis of corrosion processes at the surface of diamond-like carbon protected zinc selenide waveguides

A detailed surface analytical study on the corrosion behavior of unprotected and diamond-like carbon (DLC)-coated mid-infrared (MIR) waveguides used in remote sensing applications at strongly oxidizing conditions is presented. High-quality DLC films, with a thickness of 100 nm serving as MIR-transparent corrosion barrier, have been produced at the surface of zinc selenide (ZnSe) attenuated total reflection waveguides via pulsed laser deposition techniques. IR microscopy and atomic force microscopy are applied to investigate the chemical inertness of DLC-based membranes against aqueous solutions of hydrogen peroxide. These stability studies show that uncoated ZnSe waveguides are subject to severe chemical surface modifications, while DLC-protected waveguides maintain their optical properties and chemical integrity. In situ studies on the corrosion behavior by a recently developed approach combining scanning electrochemical microscopy (SECM) with Au/Hg amalgam ultramicroelectrodes in a scanning stripping voltammetry experiment provides additional insight into the mechanisms of the corrosion process. It is demonstrated that the combination of surface analytical techniques and, in particular, the innovative application of SECM with amalgam electrodes provides superior information on corrosion processes at the surface of optical waveguides. This detailed study confirms the efficiency of protective DLC coatings deposited onto IR-transparent optical waveguides, rendering this novel concept ideal for sensing applications in harsh environments.     

Sol-gel processed barium titanate waveguides

Monolayer monomode and multilayer multimode BaTiO₃ waveguides have been prepared on amorphous silica substrates by using the dip-coating technique and the sol-gel process. After heat treatment, these waveguides were hard and of good optical quality (losses as low as 2.6 dB/cm were measured) but, their structure was found to depend strongly on the number of layers. Monolayer waveguides were totally amorphous even when heated at 1000°C, while multilayer ones exhibited the tetragonal BaTiO₃ structure at an annealing temperature of 600°C.     

A compact optofluidic cytometer with integrated liquid-core/PDMS-cladding waveguides

We developed a simple method to construct liquid-core/PDMS-cladding optical waveguides through pressurized filling of dead-ended micro-channels with optical fluids. The waveguides are in the same layer as microfluidic channels which greatly simplifies device fabrication. With proper contrast between the refractive index of the core and cladding, the transmission loss of the waveguides is less than 5 dB cm(-1). We also developed a method to create flat and optically clear surfaces on the sides of PDMS devices in order to couple light between free-space and the waveguides embedded inside the chip. With these newly developed techniques, we make a compact flow cytometer and demonstrate the fluorescence counting of single cells at a rate of up to ～50 cell s(-1) and total sample requirement of a few microlitres. This method of making liquid-core optical waveguides and flat surfaces has great potential to be integrated into many PDMS-based microsystems.     

Rapid Prototyping of Low‐Loss IR Chalcogenide‐Glass Waveguides by Controlled Remelting

A method for fabricating infrared‐transmitting waveguides that yields low optical losses and strong confinement of light is presented. The method minimises the number of fabrication steps by exploiting the photosensitivity of arsenic trisulfide glass, using it both as a photoresist and as a waveguiding material. Controlled annealing/remelting of the waveguides minimises scattering due to fluctuations in refractive index at the interface between the waveguide and the surrounding medium, allowing low losses to be realised. Bends and Y‐splitter structures have been realised, as well as the longest As₂S₃ serpentine planar waveguides yet reported.     

Color-tunable persistent luminescence in 1D zinc–organic halide microcrystals for single-component white light and temperature-gating optical waveguides

Information security of photonic communications has become an important societal issue and can be greatly improved when photonic signals are propagated through active waveguides with tunable wavelengths in different time and space domains. Moreover, the development of active waveguides that can work efficiently at extreme temperatures is highly desirable but remains a challenge. Herein, we report new types of low-dimensional Zn(ii)–organic halide microcrystals with fluorescence and room-temperature phosphorescence (RTP) dual emission for use as 1D color-tunable active waveguides. Benefiting from strong intermolecular interactions (i.e., hydrogen bonds and π–π interactions), these robust waveguide systems exhibit colorful photonic signals and structural stability at a wide range of extreme simulated temperatures (>300 K), that covers natural conditions on Earth, Mars, and the Moon. Both experimental and theoretical studies demonstrate that the molecular self-assembly can regulate the singlet and triplet excitons to allow thermally assisted spectral separation of fluorescence and RTP, in combination with the single-component standard white-light emission. Therefore, this work demonstrates the first use of metal–organic halide microcrystals as temperature-gating active waveguides with promising implications for high-security information communications and high-resolution micro/nanophotonics.

1D zinc–organic halide microcrystals exhibiting thermally assisted spectral separation of fluorescence and phosphorescence could be used as single-component standard white-light and temperature-gating active waveguides.     

Fluorene‐based rib waveguides with optimized geometry for long‐term amplified spontaneous emission stability

Amongst the different optoelectronic applications of conjugated polymers, waveguide amplifiers and optically pumped lasers are those requiring larger photochemical stability, owing to the large irradiation conditions under operation. In this context, suitable waveguide optimization enabling the reduction of amplified spontaneous emission (ASE) threshold values appears as important as synthetic chemistry protocols to promote polymer robustness against photo‐oxidation. In this work, we develop rib waveguides with different geometries based on four different fluorene‐based compounds and assess the influence of rib confinement on ASE properties. We observe ASE threshold values as low as 8.9 × 10^?4 mJ cm^?2, being among the lowest threshold values reported so far on blue emitting polymer/oligomer waveguides. We demonstrate that the enhanced ASE efficiency on some of these rib waveguides leads to a fivefold increase in operation lifetime respect to spin‐coated slab waveguides, thus confirming the impact of waveguide geometry on ASE operation stability. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1040–1045     

Planar ZrO2 Waveguides Prepared by the Sol-Gel Process: Structural and Optical Properties

ZrO₂ waveguides are prepared by the sol-gel process from a solution containing zirconiumn-propoxide and acetylacetone in propanol-2. Structural characterizations are investigated for different annealing temperatures using suitable techniques including Waveguide Raman Spectroscopy, Electron Microscopy and Atomic Force Microscopy. Films are amorphous at 300°C and the pure ZrO₂ tetragonal crystalline phase appears beyond 400°C. Crystallized films present a dense, uniform and polycrystalline structure made up by randomly oriented nanocrystallites, the diameter of which increases from 38 Å at 400°C to 53 Å at 600°C. Waveguides are at least monomode TE₀ at 632.8 nm. At this wavelength, optical losses are about, 0.8±0.2dB/cm for amorphous layers and increase up to 2.5±0.4 dB/cm for 600°C heat-treated waveguides.     

Er3+-doped Multicomponent Silicate Glass Planar Waveguides Prepared by Sol-Gel Processing

Erbium doped silica-titania planar waveguides, co-doped with ytterbium and aluminum, have been prepared by sol-gel processing, using multilayer spin-coating deposition on silicon or silica glass substrates. The Er3+ doping level varied between 0 and 2 at.%, while Yb3+ varied from 0 to 3 at.%. Aluminum was incorporated up to 15 at.% Al and it was found to have no significant effect on the refractive index of the silica-titania (80 : 20 mol%) matrix. The Er3+ fluorescence emission was flat within ±0.5 dB, between 1520 and 1560 nm. The corresponding 4I13/2 metastable level lifetime was found to decrease from 6.1 to 3.5 ms, as the Er concentration increased from 0.1 to 0.5 at.%, for films co-doped with 0.5 at.% Yb and 10 at.% Al and the fluorescence decay was essentially single exponential below a Er quenching concentration of 0.5 at.% (1.1 × 1020 ions/cm3). The lifetime appears to be limited by Er-Er interactions at higher rare-earth ion concentrations and by residual OH species in the sol-gel derived waveguides. Vacuum heat treatment at a temperature near 570°C was somewhat effective in increasing the Er fluorescence lifetime, whereas reactive atmosphere processing in CCl4 or Cl2 at a similar temperature appeared to be less effective.     

Ultra-sensitive mid-infrared evanescent field sensors combining thin-film strip waveguides with quantum cascade lasers

We demonstrate ultra-sensitive chemical sensing in the mid-infrared spectral regime with a combination of quantum cascade lasers (QCLs) with GaAs/Al(0.2)Ga(0.8)As strip waveguides fabricated via metal-organic vapor-phase epitaxy (MOVPE) and reactive ion etching (RIE) using evanescent field absorption spectroscopy. These strip waveguides have been designed with a width of 200 μm, thereby facilitating 2-D confinement and mode-matched propagation of mid-infrared radiation emitted from a distributed feedback (DFB) QCL at a wavelength of 10.3 μm. Acetic anhydride was detected with a limit of detection (LOD) of 18 pL (19.4 ng) deposited at the waveguide surface by overlapping of the vibrational absorption of the methyl group with the emission frequency of the QCL. The obtained results indicate a remarkable enhancement in sensitivity by three orders of magnitude compared to previously reported multimode planar silver halide waveguides. Further reduction of the waveguide strip width to 50 μm resulted in an additional sensitivity enhancement yielding a calculated LOD of 0.05 pL for the exemplary analyte acetic anhydride, which is among the most sensitive evanescent field absorption measurements with a miniaturized mid-infrared sensor system reported to date.     

Lab-on-a-chip with integrated optical transducers

Taking the next step from individual functional components to higher integrated devices, we present a feasibility study of a lab-on-a-chip system with five different components monolithically integrated on one substrate. These five components represent three main domains of microchip technology: optics, fluidics and electronics. In particular, this device includes an on-chip optically pumped liquid dye laser, waveguides and fluidic channels with passive diffusive mixers, all defined in one layer of SU-8 polymer, as well as embedded photodiodes in the silicon substrate. The dye laser emits light at 576 nm, which is directly coupled into five waveguides that bring the light to five different locations along a fluidic channel for absorbance measurements. The transmitted portion of the light is collected at the other side of this cuvette, again by waveguides, and finally detected by the photodiodes. Electrical read-out is accomplished by integrated metal connectors. To our knowledge, this is the first time that integration of all these components has been demonstrated.     

Photoluminescence of Erbium-Doped Silicate Sol-Gel Planar Waveguides

Er³⁺-doped silica-titania planar waveguides, prepared by sol-gel processing, have a tendency to exhibit a reversible photoluminescence (PL) quenching phenomenon at 1.5 μm, when they are not fully densified. In the present paper, the presence of porosity and OH species associated with a simultaneous decrease in the Er³⁺ PL intensity and lifetime are followed in detail by infrared and m-line spectroscopies. Different chemical compositions and EtOH/precursor ratios, as well as optimized heat treatments, have been used in order to ensure the preparation of fully densified waveguides with enhanced spectroscopic properties. Both the Er³⁺ PL spectra and the fluorescence lifetimes at 1.5 μm have been determined in the SiO₂-TiO₂-AlO_1.5-ErO_1.5, SiO₂-HfO₂-AlO_1.5-ErO_1.5 and SiO₂-HfO₂-TiO₂-AlO_1.5-ErO_1.5 systems, as a function of the matrix composition and Er³⁺ ion concentration. These waveguides, densified at 900°C, appear to offer the best performance in terms of stability and strength of the PL signal.     

Laser densification of channel waveguides in gel-silica substrates

Channel waveguides are important components in optical signal processing. A new method is described for producing such waveguides with high design flexibility. The channel waveguides are produced using CO₂ laser densification of partially densified gel-silica matrices (Type VI optical silica). Critical processing conditions include pore size and initial density of the matrix, laser power, translational speed of the sample, distance between sample and focusing lens, and ambient humidity.Channel waveguides less than 500 µm wide were produced in gel-silica substrates of different pore sizes and bulk densities throgh laser densification. Optically transparent waveguides were obtained for speeds of the sample over 1.4 cm/s and laser power settings ranging between 12 and 16 mA. Substrates with three different pore sizes were analyzed, i.e, 12, 30 and 45 Å, with densities varying from 1.1 g/cc to 2.1 g/cc. Fourier transform infrared microspectrometry of the densified regions showed that IR shifts ranging from 1 to 38 cm^–1 in the peak position of the Si-O-Si stretching vibrational mode were achieved. This corresponds to changes of index of refraction ranging from 0.01 to 0.20. The experiments show also that the larger the pore size the wider is the range of parameters for producing effective waveguides.     

Integrated wavelength-selective optical waveguides for microfluidic-based laser-induced fluorescence detection

We demonstrate the fabrication and characterization of a novel, inexpensive microchip capable of laser induced fluorescence (LIF) detection using integrated waveguides with built-in optical filters. Integrated wavelength-selective optical waveguides are fabricated by doping poly(dimethysiloxane) (PDMS) with dye molecules. Liquid-core waveguides are created within dye-doped PDMS microfluidic chips by filling channels with high refractive index liquids. Dye molecules are allowed to diffuse into the liquid core from the surrounding dye-doped PDMS. The amount of diffusion is controlled by choosing either polar (low diffusion) or apolar (high diffusion) liquid waveguide cores. The doping dye is chosen to absorb excitation light and to transmit fluorescence emitted by the sample under test. After 24 h, apolar waveguides demonstrate propagation losses of 120 dB cm(-1) (532 nm) and 4.4 dB cm(-1) (633 nm) while polar waveguides experience losses of 8.2 dB cm(-1) (532 nm) and 1.1 dB cm(-1) (633 nm) where 532 and 633 nm light represent the excitation and fluorescence wavelengths, respectively. We demonstrate the separation and detection of end-labelled DNA fragments using polar waveguides for excitation light delivery and apolar waveguides for fluorescence collection. We demonstrate that the dye-doped waveguides can provide performance comparable to a commercial dielectric filter; however, for the present choice of dye, their ultimate performance is limited by autofluorescence from the dye. Through the detection of a BK virus polymerase chain reaction (PCR) product, we demonstrate that the dye-doped PDMS system is an order of magnitude more sensitive than a similar undoped system (SNR: 138 vs. 9) without the use of any external optical filters at the detector.     

Polymer waveguide backplanes for optical sensor interfaces in microfluidics

A polymer optical backplane capable of generic luminescence detection within microfluidic chips is demonstrated using large core polymer waveguides and vertical couplers. The waveguides are fabricated through a new process combining mechanical machining and vapor polishing with elastomer microtransfer molding. A backplane approach enables general optical integration with planar array microfluidics since optical backplanes can be independently designed but still integrated with planar fluidic circuits. Fabricated large core waveguides exhibit a loss of 0.1 dB cm(-1) at 626 nm, a measured numerical aperture of 0.50, and a collection efficiency of 2.86% in an n = 1.459 medium, comparable to a 0.50 NA microscope objective. In addition to vertical couplers for out-of-plane collection and excitation, polymer waveguides are doped with organic dyes to provide wavelength selective filtering within waveguides, further improving optical device integration. With large core low loss waveguides, luminescence collection is improved and measurements can be performed with simple LEDs and photodetectors. Fluorescein detection via fluorescence intensity with a limit of detection (3sigma) of 200 nM in a 1 microL volume is demonstrated. Phosphorescence lifetime based oxygen detection in water in an oxygen controllable microbial cell culture chip with a limit of detection (3sigma) of 0.08% or 35 ppb is also demonstrated utilizing the waveguide backplane. Single waveguide luminescence collection performance is equivalent to a back collection geometry fiber bundle consisting of nine 500 microm diameter collection fibers.     

Vapour‐Phase Epitaxial Growth of Dual‐Colour‐Emitting DCM‐Perylene Micro‐Heterostructure Optical Waveguides

Organic micro‐heterostructures (MHS) with dual optical emissions are essential to produce miniaturized optical waveguides for wavelength division multiplexing technologies. The bimolecular MHS produced by solution‐based bottom‐up self‐assembly technique often leads to poor surface smoothness, edge imperfection, defects, and unwanted thin films deposits. Conversely, sequential sublimation technique at ambient pressure facilitates effective integration of α‐perylene micro‐square with dicyanomethylene‐2‐methyl‐6‐(p‐dimethylaminostyryl) 4H‐pyran (DCM) microrods in an epitaxial manner to produce MHS. The obtained DCM/perylene MHS act as optical waveguides to produce red (λ_max≈670 nm) or/and yellow (λ_max≈607 nm) dual optical outputs via an energy transfer mechanism depending upon the heterostructures geometry and optical excitation positions. The presented dual‐color emitting MHS optical waveguides are essential for the integrated nano‐photonic and optoelectronic device structures.     

Improved Composition for Sol-Gel Rare-Earth Doped Planar Waveguides

A multilayer sol-gel process has been developed in order to make highly doped rare-earth planar waveguides on silica or silicon substrates.Starting with a small range of constituents, such as SiO₂, TiO₂, P₂O₅ and Al₂O₃, we show that a large variety of gel compositions, with different spectroscopic behaviour, can be made when doped with rare-earths.We have doped the sol-gel films with neodymium and we have optimized their compositions by measuring the neodymium fluorescence lifetime. For a composition with 10 atom% of phosphorous, the lifetime evolution with neodymium concentration was studied and a quenching concentration was found at 1% of neodymium. We have also shown the strong influence of phosphorous or aluminium in the sol composition on the fluorescence lifetime, for a given neodymium concentration. First results on similar planar waveguides, doped with erbium, are also presented.The stability of the fluorescence lifetime over a long period of time is an other important point to be checked for these new materials: the lifetime evolution over a 9 months measurement period is presented.     

Fiber-free coupling between bulk laser beams and on-chip polymer-based multimode waveguides

In this paper, we demonstrate the design of a virtually alignment-free optical setup for use with microfluidic applications involving a layered glass/SU-8/PDMS (polydimethylsiloxane) chip. We show how inexpensive external lenses combined with carefully designed on-chip lenses can be used to couple light from a bulk beam to on-chip waveguides and back into a bulk beam again. Using this setup, as much as 20% of the light coming from the source can be retrieved after passing through the on-chip waveguides. The proposed setup is based on a pin-aided alignment system that makes it possible to change chips in the optical train in only a few seconds with a standard deviation of about 2% in the transmitted power. Furthermore, we demonstrate how these optical setups can be combined with microfluidics to create an on-chip flow cytometer enabling detection and counting of polystyrene particles down to 1 μm at a rate of 100 Hz.     

Pure-silica optical waveguides, fiber couplers, and high-aspect ratio submicrometer channels for electrokinetic separation devices

A new fabrication procedure for integration of ultraviolet transparent pure-silica planar waveguides, fiber couplers and high-aspect ratio submicrometer channels is presented. Only a single photolithographic mask step is required. The channels are 80-90 microm deep and the width can be reduced to about 0.5 microm, corresponding to a height-to-width ratio of more than 150. The core of the waveguides consists of pure silicon dioxide, which is favorable over doped silica, due to the absence of absorption centers associated with the dopants. This furthermore improves the long-term stability of the waveguides, because of an increased radiation resistance of the glass. The propagation loss decreases from 1.0 dB/cm at 200 nm to 0.2 dB/cm at 800 nm, which, to our knowledge, is the lowest propagation loss reported for integrated planar waveguides in the ultraviolet wavelength region to date. The effective optical path length is 1.2 mm for an absorbance cell with a nominal length of 1.0 mm, indicating effective suppression of stray light. The limit of detection for paracetamol when present in the entire channel network was determined to 3 microg/mL. Finally, the applicability of the fabricated devices for capillary electrophoresis was evaluated by separation of caffein, paracetamol and ketoprofone using absorbance detection at 254 nm.     

A biomimetic mass-flow transducer utilizing all-optofluidic generation of self-digitized, pulse code-modulated optical pulse trains

We present a new mass-flow transducer producing responses in the form of optical pulse trains that are encoded with information on the strength and position of the stimulus. We implemented the self-digitization and encoding capabilities all-optofluidically, without involving external electronics, by integrating one optical fiber cantilever with multiple polymer optical waveguides on a microfluidic platform. The transducer can also be configured to respond only to transitional stimuli. These features closely mimic the rate-coding, action potential labeling, and rapid adaptation processes observed in biological mechanoreceptors and allow multiple transducers to transmit signals over a single, shared channel. We fabricated the transducer using polymer-based soft-lithography techniques. Its characterization confirmed the stimulus strength-dependent generation of optical pulses and the feasibility of multiplexing 2(n-1) to 2(n) transducers using n waveguides.