Optical Tomography of Polymeric Microsphere Layers Using Confocal Raman Microscopy.

In confocal Raman microscopy, depth profiling is a key application that enables analysis of the structural and chemical composition and size of three-dimensional (3D) transparent objects. However, the precise interpretation of a probed sample's Raman depth profile measurement can be significantly affected by both its size and surrounding objects. This study provides a more comprehensive understanding of the observed optical effects at the interface between polymer spheres and different substrates. Ray- and wave-optical simulations support our results. We derive a correction factor that, depending on the instrumental configuration, allows us to determine the nominal dimensions of the scanned objects more accurately from Raman depth profiles. Our studies support the need for careful consideration when employing depth profiling in confocal Raman microscopy for nondestructive, quantitative tomography of 3D objects.

Ablation threshold of GaN films for ultrashort laser pulses and the role of threading dislocations as damage precursors.

The laser-induced ablation threshold of c-plane GaN films upon exposure to ultrashort laser pulses was investigated for different wavelengths from the IR to the UV range and pulse widths between 0.34 and 10 ps. The one-pulse ablation threshold ranges between 0.15 and 3 J/cm2 and shows an increase with the wavelength and the pulse width, except for deep UV pulses. Based on a rate equation model, we attribute this behavior to the efficiency of seed carrier generation by interband absorption. In addition, the multi-pulse ablation threshold was analyzed. Accumulation effects are more prominent in case of IR than with UV pulses and are closely linked to damage precursors. By a thorough structural investigation, we demonstrate that threading dislocations, especially those with a screw component, significantly contribute to laser damage, since they provide a variety of dispersed states within the band gap.

Confocal Raman Microscopy for the Analysis of the Three-Dimensional Shape of Polymeric Microsphere Layers.

The reconstruction of the three-dimensional (3D) morphology of polymeric microsphere layers based on confocal Raman microscopy was studied. Refraction of the Raman laser beam at the curved surface of the spheres broadens the focus volume inside the sphere. Compared to planar layers, the focus gets trapped inside the spheres such that the measured depth profiles are shifted and broadened. Additionally, the Raman signal of the underlying substrate is already observed for nominal focus positions above the microsphere layer. The results are successfully modeled with ray-optical simulations that allow for a clear understanding of the relevant mechanisms that lead to the generation of the Raman signals in the complex three-dimensional structures.

Versatilely tuned vertical silicon nanowire arrays by cryogenic reactive ion etching as a lithium-ion battery anode.

Production of high-aspect-ratio silicon (Si) nanowire-based anode for lithium ion batteries is challenging particularly in terms of controlling wire property and geometry to improve the battery performance. This report demonstrates tunable optimization of inductively coupled plasma reactive ion etching (ICP-RIE) at cryogenic temperature to fabricate vertically-aligned silicon nanowire array anodes with high verticality, controllable morphology, and good homogeneity. Three different materials [i.e., photoresist, chromium (Cr), and silicon dioxide (SiO2)] were employed as masks during the subsequent photolithography and cryogenic ICP-RIE processes to investigate their effects on the resulting nanowire structures. Silicon nanowire arrays with a high aspect ratio of up to 22 can be achieved by tuning several etching parameters [i.e., temperature, oxygen/sulfur hexafluoride (O2/SF6) gas mixture ratio, chamber pressure, plasma density, and ion energy]. Higher compressive stress was revealed for longer Si wires by means of Raman spectroscopy. Moreover, an anisotropy of lattice stress was found at the top and sidewall of Si nanowire, indicating compressive and tensile stresses, respectively. From electrochemical characterization, half-cell battery integrating ICP-RIE-based silicon nanowire anode exhibits a capacity of 0.25 mAh cm-2 with 16.67% capacity fading until 20 cycles, which has to be improved for application in future energy storage devices.

Wafer-scale transfer route for top-down III-nitride nanowire LED arrays based on the femtosecond laser lift-off technique.

The integration of gallium nitride (GaN) nanowire light-emitting diodes (nanoLEDs) on flexible substrates offers opportunities for applications beyond rigid solid-state lighting (e.g., for wearable optoelectronics and bendable inorganic displays). Here, we report on a fast physical transfer route based on femtosecond laser lift-off (fs-LLO) to realize wafer-scale top-down GaN nanoLED arrays on unconventional platforms. Combined with photolithography and hybrid etching processes, we successfully transferred GaN blue nanoLEDs from a full two-inch sapphire substrate onto a flexible copper (Cu) foil with a high nanowire density (~107 wires/cm2), transfer yield (~99.5%), and reproducibility. Various nanoanalytical measurements were conducted to evaluate the performance and limitations of the fs-LLO technique as well as to gain insights into physical material properties such as strain relaxation and assess the maturity of the transfer process. This work could enable the easy recycling of native growth substrates and inspire the development of large-scale hybrid GaN nanowire optoelectronic devices by solely employing standard epitaxial LED wafers (i.e., customized LED wafers with additional embedded sacrificial materials and a complicated growth process are not required).

Toward three-dimensional hybrid inorganic/organic optoelectronics based on GaN/oCVD-PEDOT structures.

The combination of inorganic semiconductors with organic thin films promises new strategies for the realization of complex hybrid optoelectronic devices. Oxidative chemical vapor deposition (oCVD) of conductive polymers offers a flexible and scalable path towards high-quality three-dimensional inorganic/organic optoelectronic structures. Here, hole-conductive poly(3,4-ethylenedioxythiophene) (PEDOT) grown by oxidative chemical vapor deposition is used to fabricate transparent and conformal wrap-around p-type contacts on three-dimensional microLEDs with large aspect ratios, a yet unsolved challenge in three-dimensional gallium nitride technology. The electrical characteristics of two-dimensional reference structures confirm the quasi-metallic state of the polymer, show high rectification ratios, and exhibit excellent thermal and temporal stability. We analyze the electroluminescence from a three-dimensional hybrid microrod/polymer LED array and demonstrate its improved optical properties compared with a purely inorganic microrod LED. The findings highlight a way towards the fabrication of hybrid three-dimensional optoelectronics on the sub-micron scale.

Photoluminescence of planar and 3D InGaN/GaN LED structures excited with femtosecond laser pulses close to the damage threshold.

We study the photoluminescence emission from planar and 3D InGaN/GaN LED structures, excited using a femtosecond laser with fluences close to sample's damage threshold. For a typical laser system consisting of a titanium-sapphire regenerative amplifier, which is pumping an optical parametric amplifier delivering output pulses of a few tens of MW pulse power with ∼100 fs pulse duration, 1 kHz repetition rate and a wavelength of 325 nm, we determine the damage threshold of the InGaN/GaN LEDs to be about 0.05 J/cm2. We find that the relative intensity of the GaN photoluminescence (PL) and InGaN PL changes significantly close to the damage threshold. The changes are irreversible once the damage threshold is exceeded. As the damage threshold is approached, the InGaN luminescence band blue-shifts by several tens of meV, which is attributed to band filling effects. The PL decay time reduces substantially, by about 30%, when the excitation energy density is increased by approximately two orders of magnitude. The results are comparable for 2D and 3D LED structures, where in the latter case m-plane QWs exhibit different recombination dynamics because of the absence of the quantum confined Stark effect.

Intense intrashell luminescence of Eu-doped single ZnO nanowires at room temperature by implantation created Eu-Oi complexes.

Successful doping and excellent optical activation of Eu(3+) ions in ZnO nanowires were achieved by ion implantation. We identified and assigned the origin of the intra-4f luminescence of Eu(3+) ions in ZnO by first-principles calculations to Eu-Oi complexes, which are formed during the nonequilibrium ion implantation process and subsequent annealing at 700 °C in air. Our targeted defect engineering resulted in intense intrashell luminescence of single ZnO:Eu nanowires dominating the photoluminescence spectrum even at room temperature. The high intensity enabled us to study the luminescence of single ZnO nanowires in detail, their behavior as a function of excitation power, waveguiding properties, and the decay time of the transition.

Electrochemical reduction of O2 in 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ionic liquid containing Zn2+ cations: deposition of non-polar oriented ZnO nanocrystalline films.

The influence of the Zn(2+) concentration and temperature on the electrochemical reduction of O(2) in a solution of zinc bis(trifluoromethanesulfonyl)imide (Zn(TFSI)(2)) salt in 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR(14)TFSI) ionic liquid is presented. ZnO nanocrystalline films were then electrodeposited, under enhanced O(2) reduction, at temperatures in the 75-150 °C range. Their morphology, chemical composition, structural and optical properties were analyzed. In contrast to the polar-oriented ZnO usually obtained from aqueous and conventional solvent based electrolytes, nanocrystalline films oriented along non-polar directions, (11 ̅10) and (11 ̅20), were obtained from this ionic liquid electrolyte. A significant content of carbon was detected in the films, pointing to the active participation and crucial effect of pyrrolidinium cation (and/or byproducts) during the electrodeposition. The films showed semiconducting behavior with an optical gap between 3.43 and 3.53 eV as measured by optical transmittance. Their room temperature photoluminescence spectra exhibited two different bands centered at ∼3.4 and ∼2.2 eV. The intensity ratio between both bands was found to depend on the deposition temperature. This work demonstrates the great potential of ionic liquids based electrolytes for the electrodeposition of ZnO nanocrystalline thin films with innovative microstructural and optoelectronic properties.

The influence of local heating by nonlinear pulsed laser excitation on the transmission characteristics of a ZnO nanowire waveguide.

We perform a transmission experiment on a ZnO nanowire waveguide to study its transmission characteristics under nonlinear femtosecond-pulse excitation. We find that both the second harmonic and the photoluminescence couple into low-order waveguide modes of the nanowires but with distinctly different efficiencies. We measure the transmission spectrum of a single ZnO nanowire waveguide for near-UV light generated by interband recombination processes. The transmission spectrum allows us to determine the absorption edge of the excited nanowire and to study the temperature profile of the nanowire under femtosecond-pulse excitation.

Recombination dynamics of surface-related excitonic states in single ZnO nanowires.

With decreasing diameter the influence of surface-related effects becomes increasingly important for an understanding of the optical properties of semiconductor nanowires. We present time integrated and time resolved photoluminescence studies of single zincoxide nanowires with different diameters. We analyze the changes in the optical spectra for wires with different surface-to-volume ratios, present optical spectra of single wires at different excitation densities, and study the time-resolved dynamics of the surface related and donor-bound exciton related emission lines for a single nanowire at low temperatures.

Scalable fabrication of nanowire photonic and electronic circuits using spin-on glass.

We present a method which can be used for the mass-fabrication of nanowire photonic and electronic devices based on spin-on glass technology and on the photolithographic definition of independent electrical contacts to the top and the bottom of a nanowire. This method allows for the fabrication of nanowire devices in a reliable, fast, and low cost way, and it can be applied to nanowires with arbitrary cross section and doping type (p and n). We demonstrate this technique by fabricating single-nanowire p-Si(substrate)-n-ZnO(nanowire) heterojunction diodes, which show good rectification properties and, furthermore, which function as ultraviolet light-emitting diodes.

High-order waveguide modes in ZnO nanowires.

We use tapered silica fibers to inject laser light into ZnO nanowires with diameters around 250 nm to study their waveguiding properties. We find that high-order waveguide modes are frequently excited and carry significant intensity at the wire surface. Numerical simulations reproduce the experimental observations and indicate a coupling efficiency between silica and ZnO nanowires of 50%. Experimentally, we find an emission angle from the ZnO nanowires of about 90 degrees , which is in agreement with the simulations.