Shining Light on Poly(ethylene glycol): From Polymer Modification to 3D Laser Printing of Water Erasable Microstructures

The implementation of stimuli-responsive bonds into 3D network assemblies is a key concept to design adaptive materials that can reshape and degrade. Here, a straightforward but unique photoresist is introduced for the tailored fabrication of poly(ethylene glycol) (PEG) materials that can be readily erased by water, even without the need for acidic or basic additives. Specifically, a new class of photoresist is developed that operates through the backbone crosslinking of PEG when irradiated in the presence of a bivalent triazolinedione. Hence, macroscopic gels are obtained upon visible light-emitting diode irradiation (λ > 515 nm) that are stable in organic media but rapidly degrade upon the addition of water. Photoinduced curing is also applicable to multiphoton laser lithography (λ > 700 nm), hence providing access to 3D printed microstructures that vanish when immersed in water at 37 °C. Materials with varying crosslinking densities are accessed by adapting the applied laser writing power, thereby allowing for tunable hydrolytic erasing timescales. A new platform technology is thus presented that enables the crosslinking and 3D laser printing of PEG-based materials, which can be cleaved and erased in water, and additionally holds potential for the facile modification and backbone degradation of polyether-containing materials in general.     

Nanostructured imaging of biological specimens in vivo with laser plasma X-ray contact microscopy

Soft X-ray contact microscopy (SXCM) enables the study of the ultrastructure of living hydrated specimens, without the need of dehydration or any other chemical pretreatment, by using suitable pulsed X-ray sources such as laser plasmas. The successful imaging of biological specimen requires the development of sensitive photoresist materials for image recording; these should have capabilities of high-resolution lithography and an extended grey scale. A very sensitive photoresist, used for the first time in SXCM, enabled the biological imaging with the specific source in single-pulse experiments in the water window spectral range. This photoresist is an epoxy novolac-based chemically amplified photoresist (EPR), which has been proven capable of resolving subtenth-micron features. The photoresist response was at least two orders of magnitude “faster” than polymethyl methacrylate (PMMA), which is the standard resist used so far in SXCM. Atomic force microscopy (AFM) and scanning electron microscopy of the biological specimen images recorded in the resist clearly showed the flagella of the motile green alga, suggesting a lateral resolution better than 100 nm. The resist was also capable of providing height features, as small as 20 nm, in AFM depth profiles and discriminating the flagella intersection areas.     

3D Two-Photon Microprinting of Nanoporous Architectures

A photoresist system for 3D two-photon microprinting is presented, which enables the printing of inherently nanoporous structures with mean pore sizes around 50 nm by means of self-organization on the nanoscale. A phase separation between polymerizable and chemically inert photoresist components leads to the formation of 3D co-continuous structures. Subsequent washing-out of the unpolymerized phase reveals the porous polymer structures. To characterize the volume properties of the printed structures, scanning electron microscopy images are recorded from ultramicrotome sections. In addition, the light-scattering properties of the 3D-printed material are analyzed. By adjusting the printing parameters, the porosity can be controlled during 3D printing. As an application example, a functioning miniaturized Ulbricht light-collection sphere is 3D printed and tested.     

Fabrication of three-dimensional photonic crystals by interference lithography with low light absorption

We report on the fabrication of polymer templates of photonic crystals by means of holographic (or interference) lithography. The grating is written in a SU-8 photoresist using a He-Cd laser of wavelength 442 nm. The use of the wavelength found within the photoresist low absorption band enables fabricating structures that are uniform in depth. Parameters of the photoresist exposure and development for obtaining a porous structure corresponding to an orthorhombic lattice are determined.     

4D Direct Laser Writing of Submerged Structural Colors at the Microscale

Biomimetic stimuli-responsive structure colors (SCs) can improve the visualization and identification in the micro functional structure field such as information encryption/decryption and smart actuators. However, it is still challenging to develop the ability to 4D print arbitrary submerged colorful patterns with stimuli-responsive materials at the microscale. Herein, a hydrogel photoresist with feature resolution (98 nm) for the fabrication of 4D microscopic SCs by the femtosecond direct laser writing method is developed. The 4D printed woodpile SCs are grouped as pixel palettes with various laser parameters and they spanned almost the entire color space. The coloring mechanism of diffraction gratings is not only investigated by optics microscopy and spectroscopy but also supported by simulation. Moreover, the 4D printed hydrogel-integrated amphichromatic fish constructions and pixelated painting can visually discolor reversibly by regulating the solution pH. This finding promises an ideal coloring method for sensors, anti-counterfeiting labels, and transformable photonic devices.     

Tailoring the Mechanical Properties of 3D Microstructures Using Visible Light Post‐Manufacturing

The photochemistry of anthracene, a new class of photoresist for direct laser writing, is used to enable visible‐light‐gated control over the mechanical properties of 3D microstructures post‐manufacturing. The mechanical and viscoelastic properties (hardness, complex elastic modulus, and loss factor) of the microstructures are measured over the course of irradiation via dynamic mechanical analysis on the nanoscale. Irradiation of the microstructures leads to a strong hardening and stiffening effect due to the generation of additional crosslinks through the photodimerization of the anthracene functionalities. A relationship between the loss of fluorescence—a consequence of the photodimerization—and changes in the mechanical properties is established. The fluorescence thus serves as a proxy read‐out for the mechanical properties. These photoresponsive microstructures can potentially be used as “mechanical blank slates”: their mechanical properties can be readily adjusted using visible light to serve the demands of different applications and read out using their fluorescence.     

Micro-patternable nanoporous polymer integrated with microstructures for molecular filtration

This paper proposes a facile method to fabricate nanoporous microstructures by a photo-patternable SU-8 photoresist, to serve as a molecular filter in microfluidic systems. The fabrication process involves solvent-controlled nanoporous structure formation combined with standard photolithography steps for microstructure fabrication. The self-formed nanoporous morphology embedded inside the microstructure exhibits a sufficient mechanical strength and eliminates complex processes or protocols for integration/assembly of nano-?and microstructures. Field emission gun scanning electronic microscopy (FEGSEM) images showed the fabricated nanoporous morphologies with embedded nanogaps of about 6-10?nm. Atomic force microscopy (AFM) images also depicted a clear difference on the degree of porosity between the solvent-controlled SU-8 and the standard resist. Fluorescent dyes, namely Rhodamine-B and Rhodamine-6G, were employed to estimate the diffusivity of the fabricated SU-8 based nanofilter and demonstrated that the Rhodamine based fluorescent molecules can penetrate these nanosized filtration structures. The fabricated nanofilter was capable of providing a molecular weight cut-off range up to 70?kDa, estimated roughly for a molecule with a diameter of 6-10?nm. This simple process provides a novel way to integrate the nanofiltration capability into microstructures while maintaining a sufficient mechanical strength for molecular level filtration in lab-on-chip (LOC) systems.     

Additive Manufacturing of SiOC,SiC, and Si3N4 Ceramic 3D Microstructures

Herein, the fabrication of hard ceramic SiOC 3D microstructures by precursor synthesis, laser lithography, and pyrolysis combination is proposed. Precursors are hybrid organosilicon materials prepared via sol–gel method using trimethoxymethylsilane and 3-(trimethoxysilyl)propyl methacrylate, which has an acrylate functional group enabling laser photopolymerization process. Hard 3D ceramic structures (hardness up to ≈15 GPa, reduced elastic modulus ≈105 GPa) from soft organometallic derivatives are obtained after high-temperature pyrolysis under nitrogen atmosphere. The advantage of the proposed method is the absence of shrinkage defects leading to a uniform repetitive decrease in the volume of printed microstructures. In contrast to slurry-based printing technology, the proposed method is focused on homogeneous monolithic molecular resins resulting in visual smooth surfaces of prepared microstructures. Moreover, the printing resolution of the proposed method is substantially improved through the absence of predispersed ceramic microparticles in mixtures, which is a necessary element in a slurry-based technology.     

Shape‐Shifting 3D Protein Microstructures with Programmable Directionality via Quantitative Nanoscale Stiffness Modulation

The ability to shape‐shift in response to a stimulus increases an organism's survivability in nature. Similarly, man‐made dynamic and responsive “smart” microtechnology is crucial for the advancement of human technology. Here, 10–30 μm shape‐changing 3D BSA protein hydrogel microstructures are fabricated with dynamic, quantitative, directional, and angle‐resolved bending via two‐photon photolithography. The controlled directional responsiveness is achieved by spatially controlling the cross‐linking density of BSA at a nanometer lengthscale. Atomic force microscopy measurements of Young's moduli of structures indicate that increasing the laser writing distance at the z‐axis from 100–500 nm decreases the modulus of the structure. Hence, through nanoscale modulation of the laser writing z‐layer distance at the nanoscale, control over the cross‐linking density is possible, allowing for the swelling extent of the microstructures to be quantified and controlled with high precision. This method of segmented moduli is applied within a single microstructure for the design of shape‐shifting microstructures that exhibit stimulus‐induced chirality, as well as for the fabrication of a free‐standing 3D microtrap which is able to open and close in response to a pH change.     

Analysis of femtosecond laser surface patterning on bulk single-crystalline diamond

Preliminary work is reported on 2-D and 3-D microstructures written directly with a Yb:YAG 1026?nm femtosecond (fs) laser on bulk chemical vapour deposition (CVD) single-crystalline diamond. Smooth graphitic lines and other structures were written on the surface of a CVD diamond sample with a thickness of 0.7?mm under low laser fluences. This capability opens up the opportunity for making electronic devices and micro-electromechanical structures on diamond substrates. The fabrication process was optimised through testing a range of laser energies at a 100?kHz repetition rate with sub-500?fs pulses. These graphitic lines and structures have been characterised using optical microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and atomic force microscopy. Using these analysis techniques, the formation of sp² and sp³ bonds is explored and the ratio between sp² and sp³ bonds after fs laser patterning is quantified. We present the early findings from this study and characterise the relationship between the graphitic line formation and the different fs laser exposure conditions.     

Two‐Photon Polymerization of Biocompatible Photopolymers for Microstructured 3D Biointerfaces

Three‐dimensional microstructured scaffolds provide a means for cells to be cultured in vitro in a way that resembles natural conditions more closely than flat tissue culture polystyrene. In the presented work, two‐photon polymerization (2PP) is applied as a tool for the engineering of high‐resolution 3D scaffold structures with a well defined microarchitecture made of biocompatible photo resins. 2PP is a novel photolithographic technique using femtosecond laser pulses which enables free 3D microstructuring of liquid photo resins due to the relationship of the axial and lateral spatial confinement of the photoreaction to the focal volume of a focused laser beam. A set of photo resins were tested with regard to 2PP processability and three different classes of methacrylated photopolymerizable monomers (methacrylated oligolactones, urethane dimethacrylate, poly(ethylene glycol diacrylate)) were found to be efficient 2PP materials. 3D microstructures based on computer models were produced and tested for biocompatibility. The initial cell adhesion and the viability of bovine chondrocytes on the polymeric scaffolds were evaluated morphologically by confocal laser scanning microscopy (CLSM) after three‐day culture on 2PP derived microstructures. 2PP derived scaffolds were fabricated in different sizes and geometries, starting from the 100 µm‐range reaching out to the cm‐range showing the actual possibilities to produce large volume scaffolds even for implantation purposes.     

Characterization of bidimensional gratings by spectroscopic ellipsometry and angle-resolved Mueller polarimetry

We studied two bidimensional square gratings of square holes formed in photoresist layers deposited on silicon wafers, both by classical spectroscopic ellipsometry (1.5-4.5-eV spectral range) at a constant incidence angle (70.7 degrees) and by angle-resolved Mueller polarimetry at a constant wavelength (532 nm). The grating period was 1 microm in both directions, and the nominal hole sizes were 250 and 500 nm, respectively. The ellipsometric spectra were fitted by rigorous coupled-wave analysis simulations with two adjustable parameters, the resist layer thickness and the hole size. These parameters were found to be in good agreement with independent scanning electron microscopy measurements. The experimental angle-resolved Mueller spectra were remarkably well reproduced by the simulations, showing that angle-resolved Mueller polarimetry has a great potential for grating metrology applications.     

飞秒激光玻璃微加工技术

为了研究飞秒激光作用下光学玻璃内部发生的改性过程,利用重复频率为1kHz、中心波长为775am、脉宽为130fs的飞秒激光对光学玻璃进行微加工．结果表明,激光辐照区发生永久性折射率改变,并且玻璃的改性线宽随着激光功率的增加而增加,随激光扫描速度的降低而增加．根据飞秒激光致使光学玻璃发生改性的特点,利用飞秒激光在光学玻璃内部直接刻写了相位光栅和二维图案,研究了相位光栅的衍射特性．     

All-plastic organic dye laser with distributed feedback resonator structure

We demonstrated an all-plastic waveguide organic dye laser with distributed feedback (DFB) resonator. We fabricated DFB structure on a surface of SU-8 2002 photoresist polymer using the interference of two beams of a frequency-tripled Nd:YAG pulse laser at 355 nm. The typical grating pitch of fabricated DFB structure was 190, 380 and 570 nm, corresponding to the number of mode m, and each corresponding grating amplitude was ca. 1, 4-5, and 25 nm, respectively. Shallow amplitude of 1 or 4-5 nm is ascribed to the wide incidence angle of the interference beams. Threshold of lasing for m = 3 is lower than that for m = 1 or m = 2 depending on the emission wavelength. DFB structure with the smaller amplitude of gratings at m = 1 and 2 is required for the higher threshold of laser emission. By controlling the grating pitch with nanometer scale, we can tune the wavelength of laser emission with 40 to 60 nm tunability. Effective energy transfer via nonradiative Förster transfer mechanism assists in lowering the threshold of laser emission.     

3D‐Printed Biomimetic Super‐Hydrophobic Structure for Microdroplet Manipulation and Oil/Water Separation

Biomimetic functional surfaces are attracting increasing attention for various technological applications, especially the superhydrophobic surfaces inspired by plant leaves. However, the replication of the complex hierarchical microstructures is limited by the traditional fabrication techniques. In this paper, superhydrophobic micro‐scale artificial hairs with eggbeater heads inspired by Salvinia molesta leaf was fabricated by the Immersed surface accumulation three dimensional (3D) printing process. Multi‐walled carbon nanotubes were added to the photocurable resins to enhance the surface roughness and mechanical strength of the microstructures. The 3D printed eggbeater surface reveals interesting properties in terms of superhydrophobilicity and petal effect. The results show that a hydrophilic material can macroscopically behave as hydrophobic if a surface has proper microstructured features. The controllable adhesive force (from 23 μN to 55 μN) can be easily tuned with different number of eggbeater arms for potential applications such as micro hand for droplet manipulation. Furthermore, a new energy‐efficient oil/water separation solution based on our biomimetic structures was demonstrated. The results show that the 3D‐printed eggbeater structure could have numerous applications, including water droplet manipulation, 3D cell culture, micro reactor, oil spill clean‐up, and oil/water separation.     

Multifunctional Au@mSiO2/Rhodamine B Isothiocyanate Nanocomposites: Cell Imaging,Photocontrolled Drug Release,and Photothermal Therapy for Cancer Cells

The synthesis of Au@mesoporous SiO₂/rhodamine B isothiocyanate (Au@mSiO₂/RBITC) composite nanoparticles (NPs) is presented and their unique biofunctional properties are studied. The structure and morphology of the NPs are characterized by X‐ray powder diffraction, transmission electron microscopy, and Fourier transform infrared spectroscopy. These NPs can not only be functionalized for fluorescence imaging, but also possess well‐defined mesopore structures for drug loading and strong infrared surface plasmon absorption for light‐controlled drug release and photothermal therapy for cancer cells. In the biological experiments, one 808 nm laser is coupled to a confocal laser scanning microscopy (CLSM) system to monitor the photothermal therapy, drug release, and cell position and viability in real time by using the multichannel function of CLSM for the first time. Such novel nanomaterials offer a new chemotherapeutic route for cancer treatment by combining cell imaging and hyperthermia in a synergistic way.     

Micro‐ and Nanopatterning of Functional Organic Monolayers on Oxide‐Free Silicon by Laser‐Induced Photothermal Desorption

The photothermal laser patterning of functional organic monolayers, prepared on oxide‐free hydrogen‐terminated silicon, and subsequent backfilling of the laser‐written lines with a second organic monolayer that differs in its terminal functionality, is described. Since the thermal monolayer decomposition process is highly nonlinear in the applied laser power density, subwavelength patterning of the organic monolayers is feasible. After photothermal laser patterning of hexadecenyl monolayers, the lines freed up by the laser are backfilled with functional acid fluoride monolayers. Coupling of cysteamine to the acid fluoride groups and subsequent attachment of Au nanoparticles allows easy characterization of the functional lines by atomic force microscopy (AFM) and scanning electron microscopy (SEM). Depending on the laser power and writing speed, functional lines with widths between 1.1 μm and 250 nm can be created. In addition, trifluoroethyl‐terminated (TFE) monolayers are also patterned. Subsequently, the decomposed lines are backfilled with a nonfunctional hexadecenyl monolayer, the TFE stripes are converted into thiol stripes, and then finally covered with Au nanoparticles. By reducing the lateral distance between the laser lines, Au‐nanoparticle stripes with widths close to 100 nm are obtained. Finally, in view of the great potential of this type of monolayer in the field of biosensing, the ease of fabricating biofunctional patterns is demonstrated by covalent binding of fluorescently labeled oligo‐DNA to acid‐fluoride‐backfilled laser lines, which—as shown by fluorescence microscopy—is accessible for hybridization.     

Periodic microstructures produced by femtosecond laser irradiation on titanium plate

The periodic microstructures on titanium plate were formed by the irradiation of the femtosecond laser with the laser wavelength of 800 nm and the pulse length of 100 fs. They were oriented to the direction parallel to the laser polarization vector and their (parallel periodic microstructures) period was 1.5–2.4 μm. The periodic nanostructures were also produced by the femtosecond laser ablation, which were oriented to the direction perpendicular to the laser polarization vector and whose period was about 700 nm. Our results indicated that the laser fluence required for the parallel periodic microstructures was higher than that for the periodic nanostructures. The parallel periodic microstructures and the periodic nanostructures might be formed by an intensity modulation, which arose from the interaction of the laser and its scattered wave with a surface wave. The number of laser pulses to irradiate Ti plate was increased from 10 to 110. From 50 pulses, microdots were generated on the hills of the parallel periodic microstructures. From 70 pulses, the parallel periodic microstructures were varied to those with spatial modulation on the hills and the period of them was increased due to the bonding of the hills.     

透明导电InSnGaMo氧化物薄膜光电性能研究

利用脉冲激光沉积法在石英衬底上制备出了可见光透过率高、电阻率极低的Ga,Mo共掺杂ITO基InSnGaMo复合氧化物薄膜。研究了衬底温度对薄膜结构、表面形貌、光电性能的影响。实验结果表明:衬底温度对InSnGaMo复合氧化物薄膜形貌、光电性能均有很大影响。X射线衍射、扫描电镜和霍尔测试结果表明,随着衬底温度的升高,薄膜晶粒度增大,电阻率快速下降,可见光平均透过率明显提高。当衬底温度为450℃时,InSnGaMo复合氧化物薄膜的电阻率最低为4.15×10-4Ω.cm,载流子浓度和迁移率最大分别为3×1020cm-3,45 cm2V-1s-1,在可见及近红外区平均透过率达92%,特别地,波长为362 nm时,最高透射率可达99%。     

Spectral resolution analysis of resonant grating waveguides

A high spectral resolution analysis of narrowband reflection filters based on resonant grating waveguide structures is presented. A tunable high‐performance dye laser with ～0.15 cm^‐1 line width and a beam analyzing system consisting of three simultaneously controlled CCD cameras were used to investigate grating waveguide resonances at wavelengths ～694 nm and ～633 nm. A reflectivity of 91 % and a line width of ～0.3 nm were measured and theoretically modeled for a resonant reflection filter specifically designed for the ruby laser wavelength 694.2 nm. A resonance shift of several nanometers was observed for a second grating waveguide structure in the region of the helium‐neon laser emission wavelength 632.8 nm by changing the sample temperature. We discuss the potential of grating waveguide devices combining the narrow line width and the tunability of the resonant response as promising candidates for implementation in innovative concepts for reflection filter and sensor applications.