Two-photon polymerization with diode lasers emitting ultrashort pulses with high repetition rate.

In this Letter, we investigate the resolution of two-photon polymerization (2PP) with an amplified mode-locked external cavity diode laser with adjustable pulse length and a high repetition rate. The experimental results are analyzed with a newly developed 2PP model. Even with low pulse peak intensity, the produced structural dimensions are comparable to those generated by traditional 2PP laser sources. Thus, we show that a compact monolithic picosecond laser diode without amplification and with a repetition rate in the GHz regime can also be applied for 2PP. These results show the high application potential of compact mode-locked diode lasers for low-cost and compact 2PP systems.

Time and Mechanism of Nanoparticle Functionalization by Macromolecular Ligands during Pulsed Laser Ablation in Liquids.

Laser ablation of gold in liquids with nanosecond laser pulses in aqueous solutions of inorganic electrolytes and macromolecular ligands for gold nanoparticle size quenching is probed inside the laser-induced cavitation bubble by in situ X-ray multicontrast imaging with a Hartmann mask (XHI). It is found that (i) the in situ size quenching power of sodium chloride (NaCl) in comparison to the ablation in pure water can be observed by the scattering contrast from XHI already inside the cavitation bubble, while (ii) for polyvinylpyrrolidone (PVP) as a macromolecular model ligand an in situ size quenching cannot be observed. Complementary ex situ characterization confirms the overall size quenching ability of both additive types NaCl and PVP. The macromolecular ligand as well as its monomer N-vinylpyrrolidone (NVP) are mainly effective for growth quenching of larger nanoparticles on later time scales, leading to the conclusion of an alternative interaction mechanism with ablated nanoparticles compared to the electrolyte NaCl, probably outside of the cavitation bubble, in the surrounding liquid phase. While monomer and polymer have similar effects on the particle properties, with the polymer being slightly more efficient, only the polymer is effective against hydrodynamic aggregation.

Monitoring of photochemically induced changes in phase-modulating samples with digital holographic microscopy.

This paper analyzes the performance of single-shot digital holographic microscopy for rapid characterization of static step-index structures in transparent polymer materials and for online monitoring of the photoinduced polymerization dynamics. The experiments are performed with a modified Mach-Zehnder transmission digital holographic microscope of high stability (phase accuracy of 0.69°) and of high magnification (of ≈90×). Use of near-infrared illumination allows both nondestructive examination of the manufactured samples and monitoring of optically induced processes in a photosensitive material concurrently with its excitation. The accuracy of the method for a precise sample's topography evaluation is studied on an example of microchannel sets fabricated via two-photon polymerization and is supported by reference measurements with an atomic force microscope. The applicability of the approach for dynamic measurements is proved via online monitoring of the refractive index evolution in a photoresin layer illuminated with a focused laser beam at 405 nm. High correlation between the experimental results and a kinetics model for the photopolymerization process is achieved.

Investigation of multiple laser shock peening on the mechanical property and corrosion resistance of shipbuilding 5083Al alloy under a simulated seawater environment: publisher's note.

This publisher's note corrects the labeling of Figs. 10-13 in Appl. Opt.57, 6300 (2018)APOPAI0003-693510.1364/AO.57.006300.

Investigation of multiple laser shock peening on the mechanical property and corrosion resistance of shipbuilding 5083Al alloy under a simulated seawater environment.

To investigate the effect of laser shock peening (LSP) with different LSP impacts on the mechanical properties in artificial seawater and corrosion resistance of shipbuilding 5083Al alloy in 3.5% NaCl solution, wear property and electrochemical corrosion resistance tests were performed by a ball-on-disk sliding wear tester and electrochemical workstation. The wear mass losses of the samples treated by 1 and 3 LSP impacts are much lower, by 55.22% and 65.94%, respectively, than those of untreated specimens in artificial seawater. Compared with the untreated sample, the electrochemical corrosion rate of the treated samples decreased by 74.91% and 95.03% after being treated by 1 and 3 LSP impacts, respectively. The reasons for the enhancement of the wear properties and electrochemical corrosion behavior were caused by the increased residual stress and microhardness after the LSP treatment.

Optimized expression-based microdissection of formalin-fixed lung cancer tissue.

Analysis of specific DNA alterations in precision medicine of tumors is crucially important for molecular targeted treatments. Lung cancer is a prototypic example and one of the leading causes of cancer-related deaths worldwide. One major technical problem of detecting DNA alterations in tissue samples is cellular heterogeneity, that is, mixture of tumor and normal cells. Microdissection is an important tool to enrich tumor cells from heterogeneous tissue samples. However, conventional laser capture microdissection has several disadvantages like user-dependent selection of regions of interest (ROI), high costs for dissection systems and long processing times. ROI selection in expression-based microdissection (xMD) directly relies on cancer cell-specific immunostaining. Whole-slide irradiation leads to localized energy absorption at the sites of most intensive staining and melting of a membrane covering the slide, so that tumor cells can be isolated by removing the complete membrane. In this study, we optimized xMD of lung cancer tissue by enhancing staining intensity of tumor cell-specific immunostaining and processing of the stained samples. This optimized procedure did not alter DNA quality and resulted in enrichment of mutated EGFR DNA from lung adenocarcinoma specimens after xMD. We here also introduce a quality control protocol based on digital whole-slide scanning and image analysis before and after xMD to quantify selectivity and efficiency of the procedure. In summary, this study provides a workflow for xMD, adapted and tested for lung cancer tissue that can be used for lung tumor cell dissection before diagnostic or investigatory analyses.

Synthesis of Magnetic Nanoparticles by Ultrashort Pulsed Laser Ablation of Iron in Different Liquids.

Magnetic nanoparticles were generated by ultrashort pulsed laser ablation of an iron target in water, methanol, ethanol, acetone and toluene. The relationship between ablation rate, liquid properties and the physical and chemical properties of the nanoparticles was studied. Composition, morphology and magnetic properties were investigated by TEM, XPS and vibrating-sample (VSM) and SQUID magnetometry. The properties of the generated nanoparticle ensembles reflected the influence of the liquid environment on the particle formation process. For example, the composition was strongly dependent on the carbon to oxygen ratio within the molecules of the liquid. In contrast to short pulsed laser ablation in liquids, the nanoparticles generated by ultrashort pulses had a higher level of polycrystallinity.

Plasma-Enhanced Atomic Layer Deposition of Molybdenum Oxide Thin Films at Low Temperatures for Hydrogen Gas Sensing.

Molybdenum oxide thin films are very appealing for gas sensing applications due to their tunable material characteristics. Particularly, the growing demand for developing hydrogen sensors has triggered the exploration of functional materials such as molybdenum oxides (MoOx). Strategies to enhance the performance of MoOx-based gas sensors include nanostructured growth accompanied by precise control of composition and crystallinity. These features can be delivered by using atomic layer deposition (ALD) processing of thin films, where precursor chemistry plays an important role. Herein, we report a new plasma-enhanced ALD process for molybdenum oxide employing the molybdenum precursor [Mo(NtBu)2(tBu2DAD)] (DAD = diazadienyl) and oxygen plasma. Analysis of the film thickness reveals typical ALD characteristics such as linearity and surface saturation with a growth rate of 0.75 Å/cycle in a broad temperature window between 100 and 240 °C. While the films are amorphous at 100 °C, crystalline ß-MoO3 is obtained at 240 °C. Compositional analysis reveals nearly stoichiometric and pure MoO3 films with oxygen vacancies present at the surface. Subsequently, hydrogen gas sensitivity of the molybdenum oxide thin films is demonstrated in a laboratory-scale chemiresistive hydrogen sensor setup at an operation temperature of 120 °C. Sensitivities of up to 18% are achieved for the film deposited at 240 °C, showing a strong correlation between crystallinity, oxygen vacancies at the surface, and hydrogen gas sensitivity.

A new metalorganic chemical vapor deposition process for MoS2 with a 1,4-diazabutadienyl stabilized molybdenum precursor and elemental sulfur.

Molybdenum disulfide (MoS2) is known for its versatile properties and hence is promising for a wide range of applications. The fabrication of high quality MoS2 either as homogeneous films or as two-dimensional layers on large areas is thus the objective of intense research. Since industry requirements on MoS2 thin films can hardly be matched by established exfoliation fabrication methods, there is an enhanced need for developing new chemical vapor deposition (CVD) and atomic layer deposition (ALD) processes where a rational precursor selection is a crucial step. In this study, a new molybdenum precursor, namely 1,4-di-tert-butyl-1,4-diazabutadienyl-bis(tert-butylimido)molybdenum(vi) [Mo(NtBu)2(tBu2DAD)], is identified as a potential candidate. The combination of imido and chelating 1,4-diazadieneyl ligand moieties around the molybdenum metal center results in a monomeric compound possessing adequate thermal characteristics relevant for vapor phase deposition applications. Hexagonal MoS2 layers are fabricated in a metalorganic CVD (MOCVD) process with elemental sulfur as the co-reactant at temperatures between 600 °C and 800 °C. The structure and composition of the films are investigated by X-ray diffraction, high resolution transmission electron microscopy, synchrotron X-ray photoelectron spectroscopy and Raman spectroscopy revealing crystalline and stoichiometric MoS2 films. The new MOCVD process developed for MoS2 is highly promising due to its moderate process conditions, scalability and controlled targeted composition.

Investigation of albumin-derived perfluorocarbon-based capsules by holographic optical trapping.

Albumin-derived perfluorocarbon-based capsules are promising as artificial oxygen carriers with high solubility. However, these capsules have to be studied further to allow initial human clinical tests. The aim of this paper is to provide and characterize a holographic optical tweezer to enable contactless trapping and moving of individual capsules in an environment that mimics physiological (in vivo) conditions most effectively in order to learn more about the artificial oxygen carrier behavior in blood plasma without recourse to animal experiments. Therefore, the motion behavior of capsules in a ring shaped or vortex beam is analyzed and optimized on account of determination of the optical forces in radial and axial direction. In addition, due to the customization and generation of dynamic phase holograms, the optical tweezer is used for first investigations on the aggregation behavior of the capsules and a statistical evaluation of the bonding in dependency of different capsule sizes is performed. The results show that the optical tweezer is sufficient for studying individual perfluorocarbon-based capsules and provide information about the interaction of these capsules for future use as artificial oxygen carriers.

Optical screw-wrench for microassembly.

For future micro- and nanotechnologies, the manufacturing of miniaturized, functionalized, and integrated devices is indispensable. In this paper, an assembly technique based on a bottom-up strategy that enables the manufacturing of complex microsystems using only optical methods is presented. A screw connection is transferred to the micrometer range and used to assemble screw- and nut-shaped microcomponents. Micro-stereolithography is performed by means of two-photon polymerization, and microstructures are fabricated and subsequently trapped, moved, and screwed together using optical forces in a holographic optical tweezer set-up. The design and construction of interlocking microcomponents and the verification of a stable and releasable joint form the main focus of this paper. The assembly technique is also applied to a microfluidic system to enable the pumping or intermixing of fluids on a microfluidic chip. This strategy not only enables the assembly of microcomponents but also the combination of different materials and features to form complex hybrid microsystems.

Synthesis and evaluation of new copper ketoiminate precursors for a facile and additive-free solution-based approach to nanoscale copper oxide thin films.

Novel copper ketoiminate compounds were synthesized and for the first time applied for additive-free solution-based deposition of nanoscale copper oxide thin films. The two closely related compounds, namely the bis[4-(2-ethoxyethyl-imino)-3-pentanonato]copper, [Cu(EEKI)2], and bis[4-(3-methoxypropylimino)-3-pentanonato]copper, [Cu(MPKI)2], were characterized by means of elemental and thermogravimetric analysis (TGA), as well as electron impact mass spectrometry (EI-MS). The advantages of these compounds are that they are liquid and possess excellent solubility in common organic solvents in addition to an optimum reactivity towards ambient moisture that enables a facile solution-based approach to nanoscale copper oxide thin films. Moreover, no additives or aging is needed to stabilize the solution processing of the copper oxide layers. [Cu(MPKI)2] was tested in detail for the deposition of copper oxide thin films by spin coating. Upon one-step annealing, high-quality, uniform, crystalline copper oxide thin films were deposited on Si, SiO2, as well as on quartz substrates. Structural, morphological and compositional characteristics of the copper oxide nanostructures were investigated in detail by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and a combined analysis using Rutherford backscattering spectroscopy (RBS) and nuclear reaction analysis (NRA). It was possible to control the copper oxide phases (CuO and Cu2O) by systematic tuning of the post-deposition annealing conditions. The functional properties in terms of optical band gap were investigated using UV/Vis spectroscopy, while the transport properties, such as resistivity, mobility and carrier concentration were analyzed employing Hall measurements, which confirmed the p-type conductivity of the copper oxide layers.

Generation of bioinspired structural colors via two-photon polymerization.

Colors of crystals, pigments, metals, salt solutions and bioluminescence occur in nature due to the optical properties of electrons in atoms and molecules. However, colors can also result from interference effects on nanostructures. In contrast to artificial coloration, which are caused by well-defined regular structures, the structural colors of living organisms are often more intense and almost angle-independent. In this paper, we report the successful manufacturing of a lamellar nanostructure that mimics the ridge shape of the Morpho butterfly using a 3d-direct laser writing technique. The viewing angle dependency of the color was analyzed via a spectrometer and the structure was visualized using a scanning electron microscope. The generated nano- and micro-structures and their optical properties were comparable to those observed in the Morpho butterfly.

Pollen characterization and identification by elastically scattered light.

The authors recorded the elastic light-scattering pattern of pollen over a large spatial angle range to investigate the potential light scattering for pollen identification. The scattering from elm, hazel, birch, chestnut, willow, sunflower, ragweed and pine was measured. The scattering patterns show distinct differences that can be used for the classification of pollen with simple algorithms.

Analysis of the particle stability in a new designed ultrasonic levitation device.

The use of acoustic levitation in the fields of analytical chemistry and in the containerless processing of materials requires a good stability of the levitated particle. However, spontaneous oscillations and rotation of the levitated particle have been reported in literature, which can reduce the applicability of the acoustic levitation technique. Aiming to reduce the particle oscillations, this paper presents the analysis of the particle stability in a new acoustic levitator device. The new acoustic levitator consists of a piezoelectric transducer with a concave radiating surface and a concave reflector. The analysis is conducted by determining numerically the axial and lateral forces that act on the levitated object and by measuring the oscillations of a sphere particle by a laser Doppler vibrometer. It is shown that the new levitator design allows to increase the lateral forces and reduce significantly the lateral oscillations of the levitated object.