Holographic Patterning Research Articles

Formation of diffraction gratings in optically patternable hydrogel films

AbstractLocal light‐induced material response forms the basis for volume holographic patterning of light‐responsive materials. This enables applications as multifunctional biomedical materials capable of integrating optical functions, such as for advanced intraocular lens (IOL) implants. Therefore, hydrogel films based on 8‐arm PEG and azobenzene‐functionalized acrylates are prepared. A local change in optical properties is induced by UV exposure: a decrease in refractive index is detected by ellipsometric examination. One‐dimensional diffractive surface gratings, generated using a photomask, show optical functionality and are visualized in the atomic force microscope. The results show that a local change in optical properties can be induced in functionalized hydrogel films by photochemical crosslinking, making them suitable for volume holographic patterning.

Characterisation of Holographic Recording in Environmentally Stable Photopolymerisable Glass

Photopolymerisable glasses are holographic recording materials which provide good recording capability, improved dimensional stability, and negligible shrinkage. Recently, a novel photopolymerisable hybrid sol-gel (PHSG) for holographic recording of volume gratings has been reported. The PHSG has significantly improved gelation time and high water resistance, both of which make it an attractive material for mass production of holographic optical elements (HOEs) with no sensitivity to ambient humidity. In order to achieve full control over the performance of the material and further improve its properties, a study of grating formation under holographic patterning is essential. This paper reports characterisation of the grating recording in PHSG. The approach is based on the analysis of grating parameters during exposure and post-recording dark processes. The obtained results suggest that photopolymerisation of the methacrylate groups is the main contributor to the creation of refractive index modulation during exposure. During the dark process, the enhancement of the refractive index modulation is observed, probably due to further polycondensation. The observations made facilitate controlled and predictable diffraction efficiency of gratings recorded on the PHSG, thereby furthering the prospect of the development of HOEs with customisable specification.

Multi-Wavelength Optical Patterning for Multiscale Materials Design

Laser interferometry is a consolidated technique for materials structuring, enabling single step and large area patterning. Here we report the investigation of the morphological modification encoded on a thin film of a photosensitive material by the light interference pattern obtained from a laser operating in multiline mode. Four lines with equal intensity are retained, with the same p linear polarization. An azopolymer is exploited as medium for the holographic recording. Optical microscopy and profilometer measurements analyze the modification induced in the bulk and on the surface of the irradiated area. We show that the intensity profile of the interference patterns of two laser beams is the one obtained assuming each line of the laser as an independent oscillator of given intensity and wavelength, and how these light structures are faithfully replicated in the material bulk and on the topography of the free surface. Patterns at different length scales are achievable in a single step, that can be traced back to both interference fringes and wave envelopes. The proposed multi-wavelength holographic patterning provides a simple tool to generate complex light structures, able to perform multiscale modifications of photoresponsive materials

High-quality micropattern printing by interlacing-pattern holographic femtosecond pulses

Abstract To improve the efficiency of femtosecond laser direct writing, holographic femtosecond laser patterning using spatial light modulators has been widely used for the processing of micro/nanopatterns. However, the speckle noise of modulated optical fields severely limits the quality of fabricated patterns. We present a simple and effective method which involves interlacing a target pattern into a series of target subpatterns that consist of spaced spots to solve this problem. The separation of spots weakens the random interference between adjacent spots of optical fields, so the speckle noise reduces effectively, which improves the uniformity of the modulated optical fields and makes the fabricated patterns with high quality. With optimal interlacing numbers, complex micropattern arrays containing curved edges and sophisticated structures can be fabricated with superior quality and high efficiency. Binary holograms with improved optical characterization are realized by using the interlacing-pattern method, revealing the extensive potential of this method in micropattern processing and functional device fabrication with high quality and efficiency.

Single-wall carbon nanotube promoted allylic homopolymerization for holographic patterning

This article interrogates the mechanism for the incorporation of single-wall carbon nanotubes in the photo-initiated thiol-ene polymerization process and its application in holographic patterning. We find that single-wall carbon nanotube is able to turn on the allylic homopolymerization, which is not involved in the conventional thiol-ene photopolymerization process because of the autoinhibition of allyl monomer. This also leads to an enhancement of conversion for both thiol and allyl monomers. For the first time, the ability of single-wall carbon nanotube that promotes an autoinhibition monomer to homopolymerize is revealed. By applying this new mechanism, a flexible single-wall carbon nanotube-polymer composite film for the use of holographic patterning is demonstrated. The effects of the incorporation of single-wall carbon nanotubes on refractive index modulation and mechanical properties of a volume grating recorded are examined. It is shown that a substantial increase in refractive index modulation and diffraction efficiency is realized by small loading of single-wall carbon nanotubes (0.0015 wt%). This validate the proposed mechanisms provide a simple way to control the photopolymerization and therefore to tailor polymers for optical application uses.

Effect of ketyl radical on the structure and performance of holographic polymer/liquid-crystal composites

Holographic polymer/liquid-crystal composites, which are periodically ordered materials with alternative polymer-rich and liquid-crystal-rich phases, have drawn increasing interest due to their unique capabilities of reconstructing colored three-dimensional (3D) images and enabling the electro-optic response. They are formed via photopolymerization induced phase separation upon exposure to laser interference patterns, where a fast photopolymerization is required to facilitate the holographic patterning. Yet, the fast photopolymerization generally leads to depressed phase separation and it remains challenging to boost the holographic performance via kinetics control. Herein, we disclose that the ketyl radical inhibition is able to significantly boost the phase separation and holographic performance by preventing the proliferated diffusion of initiating radicals from the constructive to the destructive regions. Dramatically depressed phase separation is caused when converting the inhibiting ketyl radical to a new initiating radical, indicating the significance of ketyl radical inhibition when designing high performance holographic polymer composites.

Conformable Holographic Photonic Ink Sensors Based on Adhesive Tapes for Strain Measurements.

Buildings, bridges, and aircrafts are frequently exposed to fluctuation loads, which could start with a fine crack that instantly leads to unpredictable structure failures. The stationary strain sensors can be utilized, but they are costly and only detect limited deformation forms and sizes. Here, we fabricated photonic strain sensors on adhesive tapes, which can provide real-time monitoring of irregular surfaces. Holographic interference patterning was used to produce nonlinear curved nanostructures of one dimensional (1D) (900 nm × 880 nm) and two dimensional (2D) from a black dye film on a robust uniform adhesive layer and heat resistance tape. The patterned structure of the black dye was stable in broad pH environments. Diffracted light from the curved nanostructure detected the signal during structural damage, a shift or material tear of 5 με at less than 1.3 N cm-2. Additionally, the 2D nanostructure detected a surface change from x or y axis. Tilting the 1D structure within a range of 0.3° to 14.2° provided visible wavelength changes under broadband light to reveal early deflection signs. The curved nanopatterns could be also used for transferable holographic symbol design. Photonic nanopatterns on an adhesive tape could be used as a rapid response, conformable, lightweight, and low-cost dynamic strain sensor.

Direct Laser Writing of Nanophotonic Structures on Contact Lenses.

Contact lenses are ubiquitous biomedical devices used for vision correction and cosmetic purposes. Their application as quantitative analytical devices is highly promising for point-of-care diagnostics. However, it is a challenge to integrate nanoscale features into commercial contact lenses for application in low-cost biosensors. A neodymium-doped yttrium aluminum garnet (Nd:YAG) laser (1064 nm, 3 ns pulse, 240 mJ) in holographic interference patterning mode was utilized to produce optical nanostructures over the surface of a hydrogel contact lens. One-dimensional (925 nm) and two-dimensional (925 nm × 925 nm) nanostructures were produced on contact lenses and analyzed by spectroscopy and angle-resolve measurements. The holographic properties of these nanostructures were tested in ambient moisture, fully hydrated, and artificial tear conditions. The measurements showed a rapid tuning of optical diffraction from these nanostructures from 41 to 48°. The nanostructures were patterned near the edges of the contact lens to avoid any interference and obstruction to the human vision. The formation of 2D nanostructures on lenses increased the diffraction efficiency by more than 10%. The versatility of the holographic laser ablation method was demonstrated by producing four different 2D nanopattern geometries on contact lenses. Hydrophobicity of the contact lens was characterized by contact angle measurements, which increased from 59.0° at pristine condition to 62.5° at post-nanofabrication. The holographic nanostructures on the contact lens were used to sense the concentration of Na+ ions. Artificial tear solution was used to simulate the conditions in dry eye syndrome, and nanostructures on the contact lenses were used to detect the electrolyte concentration changes (±47 mmol L–1). Nanopatterns on a contact lens may be used to sense other ocular diseases in early stages at point-of-care settings.

Fabrication and performance of efficient thin circular polarization gratings with Bragg properties using bulk photo-alignment of a liquid crystalline polymer

Thin circular polarization gratings, characterized by high diffraction efficiency and large, up to 42°, diffraction angles were created by polarization holography for the first time. The high efficiency of the gratings is the result of the specific properties of a photo-crosslinkable liquid crystalline polymer and a two-step photochemical/thermal processing procedure. A diffraction efficiency of up to 98% at 532 nm has been achieved for gratings with periods of 700 nm. In contrast to polarization gratings with larger periods these gratings exhibit Bragg properties. So one beam is either transmitted or diffracted depending on the direction of the circular polarization of the incident light, whereas the maximal diffraction efficiency is achieved only at the proper incident angle. The fabrication procedure consists of holographic exposure of the film at room temperature which provides the photo-selective cycloaddition of cinnamic ester groups. Upon subsequent thermal annealing above Tg bulk photo-alignment of the LC polymer film occurs enhancing the optical anisotropy within the grating. The holographic patterning provides high spatial resolution, the arbitrary orientation of the LC director as well as high optical quality, thermal and chemical stability of the final gratings. Highly efficient symmetric and slanted circular polarization gratings were fabricated with the proposed technique.

Computer Generated Holography with Intensity-Graded Patterns.

Computer Generated Holography achieves patterned illumination at the sample plane through phase modulation of the laser beam at the objective back aperture. This is obtained by using liquid crystal-based spatial light modulators (LC-SLMs), which modulate the spatial phase of the incident laser beam. A variety of algorithms is employed to calculate the phase modulation masks addressed to the LC-SLM. These algorithms range from simple gratings-and-lenses to generate multiple diffraction-limited spots, to iterative Fourier-transform algorithms capable of generating arbitrary illumination shapes perfectly tailored on the base of the target contour. Applications for holographic light patterning include multi-trap optical tweezers, patterned voltage imaging and optical control of neuronal excitation using uncaging or optogenetics. These past implementations of computer generated holography used binary input profile to generate binary light distribution at the sample plane. Here we demonstrate that using graded input sources, enables generating intensity graded light patterns and extend the range of application of holographic light illumination. At first, we use intensity-graded holograms to compensate for LC-SLM position dependent diffraction efficiency or sample fluorescence inhomogeneity. Finally we show that intensity-graded holography can be used to equalize photo evoked currents from cells expressing different levels of chanelrhodopsin2 (ChR2), one of the most commonly used optogenetics light gated channels, taking into account the non-linear dependence of channel opening on incident light.

Optimized holographic femtosecond laser patterning method towards rapid integration of high-quality functional devices in microchannels.

Rapid integration of high-quality functional devices in microchannels is in highly demand for miniature lab-on-a-chip applications. This paper demonstrates the embellishment of existing microfluidic devices with integrated micropatterns via femtosecond laser MRAF-based holographic patterning (MHP) microfabrication, which proves two-photon polymerization (TPP) based on spatial light modulator (SLM) to be a rapid and powerful technology for chip functionalization. Optimized mixed region amplitude freedom (MRAF) algorithm has been used to generate high-quality shaped focus field. Base on the optimized parameters, a single-exposure approach is developed to fabricate 200 × 200 μm microstructure arrays in less than 240 ms. Moreover, microtraps, QR code and letters are integrated into a microdevice by the advanced method for particles capture and device identification. These results indicate that such a holographic laser embellishment of microfluidic devices is simple, flexible and easy to access, which has great potential in lab-on-a-chip applications of biological culture, chemical analyses and optofluidic devices.

Holographic patterning of fluorescent microstructures comprising silver nanoclusters

Metal nanoclusters, which exhibit extraordinary physical and chemical properties that are different from their bulk counterparts, are highly promising nanomaterials for photonics. Recently, the use of two-photon excitation to fabricate silver nanoclusters in polymers was reported but still lacks speed and flexibility which are imperative for applications such as labeling and spectroscopy. Here, we demonstrate the fabrication of fluorescent nanocluster microstructures using spatially phase-shaped laser beams. Using an incident power of 60 mW and exposure time of 8 s, we found that the smallest line-width of the fluorescent microstructures is 478 nm, which is comparable to the line-width achieved with a two-photon laser scanning approach. As a proof-of-principle demonstration, the technique is used to fabricate fluorescent micro-labels that could be used in anti-counterfeiting applications.

Direct Holographic Patterning of ZnO

Zinc oxide thin films are holographically patterned on submicronic scale by direct photodissolution method. The photodissolution process in solution is highly sensitive in the UV range (355 nm). 1D and 2D nanostructures are successfully obtained by this photoresist‐free process. The kinetic of the reaction is studied by recording the transmitted intensity through the evolution of the ZnO film thickness along the reaction time. Application of an electrical potential strongly increases the dissolution rate (1.5 μm min−1) and decreases the pattern formation time. As a first demonstration of the potential of all‐in liquid direct ZnO heterostructuring, selective growth of ZnO nanorods is performed by chemical bath deposition using holographically patterned ZnO films as a substrate.

Hybrid Sensors Fabricated by Inkjet Printing and Holographic Patterning

Inkjet printing and patterning strategies have been developed for fabrication of hybrid holographic sensors using zeolite nanocrystals on glass-supported photopolymers. The flexibility of the proposed techniques was demonstrated by fabrication and characterization of two types of holographic sensors. The first type, which is a reversible sensor, is based on a transmission hologram recorded in a hydrophobic MFI-type zeolite doped layer with high sensitivity toward alcohols. In this type of sensor the patterning of the zeolite nanocrystals in the volume of the polymer layer is achieved by holographic recording; the pattern periodicity is in the submicrometer range. The second type of sensor is based on a reflection hologram, and it is produced by inkjet printing of zeolite nanocrystals on photopolymer layer before holographic recording. The resulting localized presence of zeolite nanocrystals in the layer is key for the performance of the sensor. Irreversible humidity sensors based on photopolymer layers do...

Holographic patterning of high-performance on-chip 3D lithium-ion microbatteries

As sensors, wireless communication devices, personal health monitoring systems, and autonomous microelectromechanical systems (MEMS) become distributed and smaller, there is an increasing demand for miniaturized integrated power sources. Although thin-film batteries are well-suited for on-chip integration, their energy and power per unit area are limited. Three-dimensional electrode designs have potential to offer much greater power and energy per unit area; however, efforts to date to realize 3D microbatteries have led to prototypes with solid electrodes (and therefore low power) or mesostructured electrodes not compatible with manufacturing or on-chip integration. Here, we demonstrate an on-chip compatible method to fabricate high energy density (6.5 μWh cm(-2)⋅μm(-1)) 3D mesostructured Li-ion microbatteries based on LiMnO2 cathodes, and NiSn anodes that possess supercapacitor-like power (3,600 μW cm(-2)⋅μm(-1) peak). The mesostructured electrodes are fabricated by combining 3D holographic lithography with conventional photolithography, enabling deterministic control of both the internal electrode mesostructure and the spatial distribution of the electrodes on the substrate. The resultant full cells exhibit impressive performances, for example a conventional light-emitting diode (LED) is driven with a 500-μA peak current (600-C discharge) from a 10-μm-thick microbattery with an area of 4 mm(2) for 200 cycles with only 12% capacity fade. A combined experimental and modeling study where the structural parameters of the battery are modulated illustrates the unique design flexibility enabled by 3D holographic lithography and provides guidance for optimization for a given application.

An improved multi-exposure approach for high quality holographic femtosecond laser patterning

High efficiency two photon polymerization through single exposure via spatial light modulator (SLM) has been used to decrease the fabrication time and rapidly realize various micro/nanostructures, but the surface quality remains a big problem due to the speckle noise of optical intensity distribution at the defocused plane. Here, a multi-exposure approach which used tens of computer generate holograms successively loaded on SLM is presented to significantly improve the optical uniformity without losing efficiency. By applying multi-exposure, we found that the uniformity at the defocused plane was increased from ∼0.02 to ∼0.6 according to our simulation. The fabricated two series of letters “HELLO” and “USTC” under single-and multi-exposure in our experiment also verified that the surface quality was greatly improved. Moreover, by this method, several kinds of beam splitters with high quality, e.g., 2 × 2, 5 × 5 Daman, and complex nonseperate 5 × 5, gratings were fabricated with both of high quality and short time (<1 min, 95% time-saving). This multi-exposure SLM-two-photon polymerization method showed the promising prospect in rapidly fabricating and integrating various binary optical devices and their systems.

Facile Image Patterning via Sequential Thiol–Michael/Thiol–Yne Click Reactions

Freestanding substrates with high refractive index modulation, good oxygen resistance, and low volume shrinkage are critical in photolithography for the purpose of high density data storage, image patterning and anticounterfeiting. Herein, we demonstrate a novel paradigm of direct holographic image patterning via the radical-mediated thiol–yne click reaction subsequent to the base-catalyzed thiol-Michael addition reaction. With the benefit of a newly synthesized alkyne monomer, 9-(2-((2-(prop-2-yn-1-yloxy)ethyl)thio)ethyl)-9H-carbazole (POETEC), holograms with as high as 96% diffraction efficiency, refractive index modulation of 0.0036, dynamic range of 5.6 per 200 μm and volume shrinkage of 1.1%, are successfully patterned in an aerobic environment. Uniquely and distinctly, an inhibitor is unnecessary to prevent the initiation of the sequential reaction in this framework.

Holographic patterning of graphene-oxide films by light-driven reduction.

We report on the patterning and reduction of graphene-oxide films by holographic lithography. Light reduction can be used to engineer low-cost graphene-based devices by performing a local conversion of insulating oxide into the conductive graphene. In this work, computer-generated holograms have been exploited to realize complex graphene patterns in a single shot, different from serial laser writing or mask-based photolithographic processes. The technique has been further improved by achieving speckle noise reduction: submicron and diffraction-limited features have been obtained. In addition we have also demonstrated that the gray-scale lithography capability can be used to obtain different reduction levels in a single exposure.

Molecularly Imprinted Silver‐Halide Reflection Holograms for Label‐Free Opto‐Chemical Sensing

Hierarchical structuring of materials offers exciting opportunities to construct functional devices that exploit the ordering at different length scales to impart key functional properties. Herein, multiple processes are combined to create complex materials organized at the molecular, nano, and microscales for selective detection of testosterone by label‐free opto‐chemical sensing. Molecular imprinting is used to construct molecular scale analyte‐selective cavities. Microphase separation produces a porous polymer film within which sensitized silver halide nanocolloids are dispersed by a process of infusion and controled precipitation, then converted to periodic layers of silver nanoparticles by holographic patterning followed by chemical development. Testosterone binding is followed via wavelength changes of the holographic reflection peak as a function of testosterone concentration and incubation time. Polymer cross‐linking and film porosity are optimized with respect to the needs of both molecular recognition and hologram quality. The silver halide infusion step does not destroy the molecular selectivity of the molecularly imprinted polymers (MIP). Selective, label‐free sensing of testosterone is possible at concentrations down to 1 μm. The approach is generic and should be applicable to many types of molecules and conventional MIP formulations, individually or in multiplexed arrays.

Single-step holographic fabrication of large-area periodically corrugated metal films

We have developed a simple, high-throughput, and cost-effective method to fabricate one-dimensional and two-dimensional periodically corrugated silver films over centimeter scale areas. This fabrication uses a single-step holographic patterning technique with laser intensities as low as 88.8 mW/cm(2) to deposit silver nanoparticles directly from solution to create gratings with periodicities of 570 nm. A dip in the transmission spectrum for these samples is observed due to certain visible wavelengths coupling to surface plasmon polaritons (SPPs) and the peak wavelength of this dip has a linear relationship with the surrounding material's refractive index (RI) with a sensitivity of 553.4 nm/RIU. The figure of merit (the ratio of refractive index sensitivity to the full width at half maximum (FWHM)) is typically in the range of 12-23. Our technique enables single-step fabrication of uniform, sub-wavelength periodic metal structures over a large area with low cost. Such sub-wavelength periodic metal structures are promising candidates as disposable sensors in applications such as affordable environmental monitoring systems and point-of-care diagnostics.