Towards Optical Information Recording: A Robust Visible-Light-Driven Molecular Photoswitch with the Ring-Closure Reaction Yield Exceeding 96.3 .

Diarylethene molecular photoswitches hold great fascination as optical information materials due to their unique bistability and exceptional reversible photoswitching properties. Conventional diarylethenes, however, rely on UV light for ring-closure reactions, typically with modest yields. For practical application, diarylethenes driven by visible lights are preferred but achieving high ring-closure reaction yield remains a significant challenge. Herein, we synthesized a novel all-visible-light-driven photoswitch, TPAP-DTE, by facilely endcapping the dithienylethene (DTE) core with triphenylamine phenyl (TPAP) groups. Owing to the electron-donating conjugation effect of TPAP, the open-form TPAP-DTE responds strongly to short-wavelength visible lights with considerable photocyclization quantum yields and molar absorption coefficient. Upon 405 nm visible-light irradiation, TPAP-DTE achieves a ring-closure reaction yield exceeding 96.3 % (confirmed by both nuclear magnetic resonance spectroscopy and high-performance liquid chromatography). Its ring-opening reaction yield is 100 % upon irradiation with long-wavelength visible light. TPAP-DTE could be regarded as a bidirectional "quasi"-quantitative conversion molecular switch. Furthermore, TPAP-DTE exhibits robust fatigue resistance over 100 full photoswitching cycles and great anti-aging property under 85 °C and 85 % humidity for at least 1000 h. Consequently, its rewritable QR-code, multilevel data storage, and anti-counterfeiting/encryption applications are successfully demonstrated exclusively using visible lights, positioning TPAP-DTE as a highly promising medium for information recording.

Simultaneous synthesis and integration of nanoscale silicon by three-photon laser direct writing.

Typical fabrication processes of compact silicon quantum dot (Si QD) devices or components entail several synthesis, processing and stabilization steps, leading to manufacture and cost inefficiency. Here we report a single step strategy through which nanoscale architectures based on Si QDs can be simultaneously synthesized and integrated in designated positions by using a femtosecond laser (532 nm wavelength and 200 fs pulse duration) direct writing technique. The extreme environments of a femtosecond laser focal spot can result in millisecond synthesis and integration of Si architectures stacked by Si QDs with a unique crystal structure (central hexagonal). This approach involves a three-photon absorption process that can obtain nanoscale Si architecture units with a narrow line width of 450 nm. These Si architectures exhibited bright luminescence peaked at 712 nm. Our strategy can fabricate Si micro/nano-architectures to tightly attach to a designated position in one step, which demonstrates great potential for fabricating active layers of integrated circuit components or other compact devices based on Si QDs.

Direct Laser Writing of Functional QD-Polymer Structure with High Resolution.

Promising direct laser writing (DLW) technology has been introduced to process functional quantum dot (QD)-polymer nanocomposites. The results reveal that after surface modification, the QDs are compatible with the SR399 monomer, and the homogeneous incorporation of QDs is accordingly obtained owing to the copolymerization and resultant cross-linking of QDs into SR399 resin under DLW processing with a laser wavelength (λ) of 532 nm. Moreover, compared with other scholars, we have proved that the surface modified QDs incorporated into the nanocomposites that can be successfully processed via DLW can reach a concentration of up to 150 mg/mL. Owing to the threshold behavior and nonlinear nature of the DLW process, it is feasible to modify the attendant exposure kinetics and design lines of any small size by selecting an appropriate laser power (P) and scan speed (v). The superfine feature size of 65 nm (λ/8) of the red QD-polymer suspended line can be tailored by applying the optimized P of 15 mW and v of 700 µm/s, and the finest green QD-polymer suspended line also reaches 65 nm (λ/8) with the optimized P of 14 mW and v of 250 µm/s used. Moreover, DLW processed QD-polymer structures present strong and homogeneous photoluminescence emission, which shows great potential for application in high-resolution displays, anti-counterfeit technology, and optical encryption. Additionally, the two types of long pass QD-polymer absorptive filters prepared by DLW exhibit superior optical performance with a considerably high transmittance of more than 90% for red QD-polymer block filter, and over 70% for green QD-polymer block filter in the transmittance region, which means that different filters with specific performance can be easily customized to meet the demand of various microdevices. Therefore, the DLW process can be applied to produce geometrically complex micro- and nanoscale functional structures, which will contribute to the development of advanced optoelectronic devices.

Three-Dimensional Nanolithography with Visible Continuous Wave Laser through Triplet Up-Conversion.

Direct laser writing (DLW) technology usually fabricates micronanostructures based on the principle of two-photon polymerization. However, two-photon polymerization requires high laser intensity which can be achieved by expensive femtosecond lasers. To address the issue, a direct laser writing method has been proposed in this work; it is based on triplet up-conversion which is characterized by its low cost, high precision, multidimensional property, and rapid processing. The feasibility of this method is jointly verified by applying both dynamic modeling and experiments. Based on the obtained results, the low laser intensity fabrication of multidimensional nanostructures is achieved. The minimum line width (∼50 nm) of micronanostructures is reached when the laser intensity is set at 2.5 × 105 W/cm2 along with a processing speed of 150 µm/s. As a result, the direct laser writing method, based on triplet up-conversion, offers a new route to achieve low-intensity and high-precision micronanostructure fabrication.

Measurement of Interfacial Adhesion Force with a 3D-Printed Fiber-Tip Microforce Sensor.

With the current trend of device miniaturization, the measurement and control of interfacial adhesion forces are increasingly important in fields such as biomechanics and cell biology. However, conventional fiber optic force sensors with high Young's modulus (>70 GPa) are usually unable to measure adhesion forces on the micro- or nano-Newton level on the surface of micro/nanoscale structures. Here, we demonstrate a method for interfacial adhesion force measurement in micro/nanoscale structures using a fiber-tip microforce sensor (FTMS). The FTMS, with microforce sensitivity of 1.05 nm/µN and force resolution of up to 19 nN, is fabricated using femtosecond laser two-photon polymerization nanolithography to program a clamped-beam probe on the end face of a single-mode fiber. As a typical verification test, the micronewton-level contact and noncontact adhesion forces on the surfaces of hydrogels were measured by FTMS. In addition, the noncontact adhesion of human hair was successfully measured with the sensor.

Cluster-enabled patterning of copper nanostructures from aqueous solution using a femtosecond laser.

A one-step method for patterning low-resistivity nanoscale copper wire is proposed herein to solve the challenging issues of using common metals rather than noble metal nanostructures fabricated by direct laser writing in solution. A complexing and a reducing agent were introduced for the single-photon absorption of copper solution in the visible range and to enable two-photon absorption with a femtosecond laser. Copper clusters were generated prior to direct laser writing to decrease induced laser energy during two-photon absorption and accelerate copper nanowire patterning to avoid the boiling of copper solution. A surfactant was used to restrain the overgrowth of copper clusters to obtain written nanowires with high uniformity. By controlling the laser writing parameters, the obtained copper wire had a minimum width of 230 nm and a resistivity of 1.22 × 10-5Ω·m. Our method paves the way for the fabrication of common metal nanodevices by direct laser writing.

Femtosecond laser induced in-situ crystallization of Tb-based luminescent metal organic framework.

Luminescent metal-organic frameworks (LMOFs) are a class of interesting and well-investigated MOF materials, which have shown remarkable prospects in the past and have been widely applied in different fields. However, due to their organic hybrid aspect, micro-/nano-patterning LMOFs in devices via a conventional semiconductor process is very challenging. In this work, we have introduced an elegant technique via nonlinear photon-chemical effect to induce the synthesis and growth of LMOFs. A facile technique for local synthesis and micro-pattering Tb-based luminescent metal organic frameworks (Tb(BTC)·G) from a solution of precursors is achieved. A single step approach micro-patterning for device integration with simultaneous chemical synthesis was proposed. Micro-devices with excellent fluorescence performance based on Tb(BTC)·G have been demonstrated. This work first suggested a high resolution bottom-up micro-patterning technique for MOF device fabrication using femtosecond laser direct writing, showing great potential on MOF based micro/nano-devices integration, especially promising for patterning high resolution luminescent MOF devices.

Fiber-tip polymer clamped-beam probe for high-sensitivity nanoforce measurements.

Micromanipulation and biological, material science, and medical applications often require to control or measure the forces asserted on small objects. Here, we demonstrate for the first time the microprinting of a novel fiber-tip-polymer clamped-beam probe micro-force sensor for the examination of biological samples. The proposed sensor consists of two bases, a clamped beam, and a force-sensing probe, which were developed using a femtosecond-laser-induced two-photon polymerization (TPP) technique. Based on the finite element method (FEM), the static performance of the structure was simulated to provide the basis for the structural design. A miniature all-fiber micro-force sensor of this type exhibited an ultrahigh force sensitivity of 1.51 nm µN-1, a detection limit of 54.9 nN, and an unambiguous sensor measurement range of ~2.9 mN. The Young's modulus of polydimethylsiloxane, a butterfly feeler, and human hair were successfully measured with the proposed sensor. To the best of our knowledge, this fiber sensor has the smallest force-detection limit in direct contact mode reported to date, comparable to that of an atomic force microscope (AFM). This approach opens new avenues towards the realization of small-footprint AFMs that could be easily adapted for use in outside specialized laboratories. As such, we believe that this device will be beneficial for high-precision biomedical and material science examination, and the proposed fabrication method provides a new route for the next generation of research on complex fiber-integrated polymer devices.

Direct Imaging of Integrated Circuits in CPU with 60 nm Super-Resolution Optical Microscope.

Far-field super-resolution optical microscopies have achieved incredible success in life science for visualization of vital nanostructures organized in single cells. However, such resolution power has been much less extended to material science for inspection of human-made ultrafine nanostructures, simply because the current super-resolution optical microscopies modalities are rarely applicable to nonfluorescent samples or unlabeled systems. Here, we report an antiphase demodulation pump-probe (DPP) super-resolution microscope for direct optical inspection of integrated circuits (ICs) with a lateral resolution down to 60 nm. Because of the strong pump-probe (PP) signal from copper, we performed label-free super-resolution imaging of multilayered copper interconnects on a small central processing unit (CPU) chip. The label-free super-resolution DPP optical microscopy opens possibilities for easy, fast, and large-scale electronic inspection in the whole pipeline chain for designing and manufacturing ICs.

Fiber-Tip Polymer Microcantilever for Fast and Highly Sensitive Hydrogen Measurement.

Hydrogen as an antioxidant gas has been widely used in the medical and biological fields for preventing cancer or treating inflammation. However, controlling the hydrogen concentration is crucial for practical use due to its explosive property when its volume concentration in air reaches the explosive limit (4%). In this work, a polymer-based microcantilever (µ-cantilever) hydrogen sensor located at the end of a fiber tip is proposed to detect the hydrogen concentration in medical and biological applications. The proposed sensor was developed using femtosecond laser-induced two-photon polymerization (TPP) to print the polymer µ-cantilever and magnetron sputtering to coat a palladium (Pd) film on the upper surface of the µ-cantilever. Such a device exhibits a high sensitivity, roughly -2 nm %-1 when the hydrogen concentration rises from 0% to 4.5% (v/v) and a short response time, around 13.5 s at 4% (v/v), making it suitable for medical and environmental applications. In addition to providing an ultracompact optical solution for fast and highly sensitive hydrogen measurement, the polymer µ-cantilever fiber sensor can be used for diverse medical and biological sensing applications by replacing Pd with other functional materials.

Ultra-high capacity for three-dimensional optical data storage inside transparent fluorescent tape: erratum.

In Opt. Lett.45, 1535 (2020)OPLEDP0146-959210.1364/OL.387278, there was an error regarding the corresponding author assignment. That error is corrected here.

Zn2+ responsive fluorescence enhancement for optical data storage.

In this paper, we put forward a new application in optical data storage (ODS) of tetraphenylethene (TPE)-doped photopolymer, which has an aggregation-induced emission attribute. The photopolymer host reacted with the excitation light at the focal point of a high numerical-aperture lens to enhance the fluorescence intensity mainly because of the function of the ${{\rm Zn}^{2 + }}$Zn2+ ion. We recorded data inside the photopolymer matrix by using this property and had distinct fluorescence intensity contrast between the photochemical regions and other regions. This attribute paves a new way for superresolution ODS and opens the way to exploring the possibility of utilizing TPE-doped photopolymers as chemical sensors in the future.

Ultra-high capacity for three-dimensional optical data storage inside transparent fluorescent tape.

In this Letter, we show an ultralarge capacity for three-dimensional optical data storage inside transparent fluorescent tape using the two-photon absorption photo-bleaching method. We can obtain transparent fluorescent tape by means of the simple dip method. We successfully demonstrate recording and reading of six layers of binary data bits with lateral separation of 2 µm and longitudinal layer separation of 3 µm. Thus, this result leads to a storage density of approximately ${80}\;{{\rm Gbits/cm}^3}$80Gbits/cm3. Therefore, we can realize authentic ultrahigh capacity optical data storage using long transparent fluorescent tape in the future, like magnetic tape, and fundamentally solve the data explosion disaster.

Direct laser writing of nanoscale undoped conductive polymer.

The fabrication of poly 3,4-ethylene dioxythiophene (PEDOT) devices generally requires a separated strategy for EDOT polymerization and PEDOT coating, thus increasing th difficulty of their integration. With the goal of insolubility of PEDOT in a common solution, material modifications including grafting vinyl moiety groups on the side chain of the PEDOT can increase its solubility, but also markedly reduce the conductivity. Here, we report direct laser writing of pure EDOT monomer into PEDOT with a feature size of 140 nm. The PEDOT nanowire possesses the high conductivity of 1.28 × 105 S m-1 and can be patterned on solid and flexible substrates with various structures, thus paving the way towards organic highly conductive device fabrication and integration.

High-Speed All-Optical Modulator Based on a Polymer Nanofiber Bragg Grating Printed by Femtosecond Laser.

On-chip optical modulator for high-speed information processing system has been widely investigated by many researchers, but the connection with the fiber system is difficult. The fiber-based optical modulator is a good solution to this problem. Fiber Bragg Grating has good potential to be used as an optical modulator because of its linear temperature response, narrow bandwidth, and compact structure. In this paper, a new fiber-integrated all-optical modulator has been realized based on a polymer nanofiber Bragg grating printed by a femtosecond laser. This device exhibits a fast temporal response of 176 ns and a good linear modulation of -45.43 pm/mW. Moreover, its stability has also been studied. This work first employs Bragg resonance to realize a fiber-integrated all-optical modulator and paves the way toward realization of multifunctional lab-in-fiber devices.

Bragg resonance in microfiber realized by two-photon polymerization.

A new method for microfiber Bragg gratings (µ-FBGs) fabrication by means of two-photon polymerization in photosensitive resin is reported. Such polymerized µ-FBGs were cured along with the surface of microfibers without any damage or distortion to the substrate. The laser intensity was optimized to improve the spectral properties of the polymerized gratings. The refractive index measurement was performed and the maximum sensitivity obtained is ~207 nm/RIU at the refractive index value of 1.440 with the fiber diameter being 1.7 µm. This work opens a new idea for optical structure integration and further optical functionality integration.

Femtosecond Laser Microprinting of a Polymer Optical Fiber Interferometer for High-Sensitivity Temperature Measurement.

Femtosecond laser induced multi-photon polymerization technique can be applied to fabricate an ultracompact polymer optical fiber interferometer which was embedded in a section of hollow core fiber. The production of the photoresin, used in this work, is described. Such a device has been used for temperature measurement, due to its excellent thermal properties. Transmission spectrum, structural morphology, and temperature response of the polymer optical fiber interferometer are experimentally investigated. A high wavelength sensitivity of 6.5 nm/°C is achieved over a temperature range from 25 °C to 30 °C. The proposed polymer optical fiber interferometer exhibits high temperature sensitivity, excellent mechanical strength, and ultra-high integration. More complex fiber-integrated polymer function micro/nano structures produced by this technique may result in more applications in optical fiber communication and optical fiber sensors.

Biomimetic gyroid nanostructures exceeding their natural origins.

Using optical two-beam lithography with improved resolution and enhanced mechanical strength, we demonstrate the replication of gyroid photonic nanostructures found in the butterfly Callophrys rubi. These artificial structures are shown to have size, controllability, and uniformity that are superior to those of their biological counterparts. In particular, the elastic Young's modulus of fabricated nanowires is enhanced by up to 20%. As such, the circular dichroism enabled by the gyroid nanostructures can operate in the near-ultraviolet wavelength region, shorter than that supported by the natural butterfly wings of C. rubi. This fabrication technique provides a unique tool for extracting three-dimensional photonic designs from nature and will aid the investigation of biomimetic nanostructures.

Anomalous Fluorescence Enhancement from Double Heterostructure 3D Colloidal Photonic Crystals--A Multifunctional Fluorescence-Based Sensor Platform.

Augmenting fluorescence intensity is of vital importance to the development of chemical and biochemical sensing, imaging and miniature light sources. Here we report an unprecedented fluorescence enhancement with a novel architecture of multilayer three-dimensional colloidal photonic crystals self-assembled from polystyrene spheres. The new technique uses a double heterostructure, which comprises a top and a bottom layer with a periodicity overlapping the excitation wavelength (E) of the emitters, and a middle layer with a periodicity matching the fluorescence wavelength (F) and a thickness that supports constructive interference for the excitation wavelength. This E-F-E double heterostructure displays direction-dependent light trapping for both excitation and fluorescence, coupling the modes of photonic crystal with multiple-beam interference. The E-F-E double heterostructure renders an additional 5-fold enhancement to the extraordinary FL amplification of Rhodamine B in monolithic E CPhCs, and 4.3-fold acceleration of emission dynamics. Such a self-assembled double heterostructure CPhCs may find significant applications in illumination, laser, chemical/biochemical sensing, and solar energy harvesting. We further demonstrate the multi-functionality of the E-F-E double heterostructure CPhCs in Hg (II) sensing.

Three-dimensional deep sub-diffraction optical beam lithography with 9 nm feature size.

The current nanofabrication techniques including electron beam lithography provide fabrication resolution in the nanometre range. The major limitation of these techniques is their incapability of arbitrary three-dimensional nanofabrication. This has stimulated the rapid development of far-field three-dimensional optical beam lithography where a laser beam is focused for maskless direct writing. However, the diffraction nature of light is a barrier for achieving nanometre feature and resolution in optical beam lithography. Here we report on three-dimensional optical beam lithography with 9 nm feature size and 52 nm two-line resolution in a newly developed two-photon absorption resin with high mechanical strength. The revealed dependence of the feature size and the two-line resolution confirms that they can reach deep sub-diffraction scale but are limited by the mechanical strength of the new resin. Our result has paved the way towards portable three-dimensional maskless laser direct writing with resolution fully comparable to electron beam lithography.