Minimization of the Rayleigh-Doppler error of differential absorption lidar by frequency tuning: a simulation study.

We present simulations suggesting that it is possible to minimize the systematic errors of differential absorption lidar (DIAL) measurements caused by the Rayleigh-Doppler effect by selecting an online frequency close to one of the inflection points on either side of the absorption line. Thus, it seems advantageous to select an absorption line of suitable cross section at these points on the line slopes rather than at the peak. First, we extend the classical simulation study of Ansmann (1985) for another water vapor absorption line but again with the online frequency at the line peak. As expected, we also found large systematic errors of more than 40% at the edges of aerosol layers and clouds. Second, we simulate the systematic errors for other online frequencies away from the peak for the same input profile. The results demonstrate that the errors vanish close to the inflection points. Since both the shape of the absorption lines and the width of the broadened backscatter signal depend on the atmospheric conditions, these optimum frequencies vary slightly with height and climatology. Third, we calculate the errors for a typical aerosol profile of the planetary boundary layer obtained from lidar measurements. With this case, we discuss how to select practically the online frequency so that the errors are minimized for all heights of interest. We found that the error reduces from 20 to < 1% at the top of the planetary boundary layer while, at the same time, the error reduces from 6 to 2% in 5 km.

Space-borne profiling of atmospheric thermodynamic variables with Raman lidar: performance simulations.

The performance of a space-borne water vapour and temperature lidar exploiting the vibrational and pure rotational Raman techniques in the ultraviolet is simulated. This paper discusses simulations under a variety of environmental and climate scenarios. Simulations demonstrate the capability of Raman lidars deployed on-board low-Earth-orbit satellites to provide global-scale water vapour mixing ratio and temperature measurements in the lower to middle troposphere, with accuracies exceeding most observational requirements for numerical weather prediction (NWP) and climate research applications. These performances are especially attractive for measurements in the low troposphere in order to close the most critical gaps in the current earth observation system. In all climate zones, considering vertical and horizontal resolutions of 200 m and 50 km, respectively, mean water vapour mixing ratio profiling precision from the surface up to an altitude of 4 km is simulated to be 10%, while temperature profiling precision is simulated to be 0.40-0.75 K in the altitude interval up to 15 km. Performances in the presence of clouds are also simulated. Measurements are found to be possible above and below cirrus clouds with an optical thickness of 0.3. This combination of accuracy and vertical resolution cannot be achieved with any other space borne remote sensing technique and will provide a breakthrough in our knowledge of global and regional water and energy cycles, as well as in the quality of short- to medium-range weather forecasts. Besides providing a comprehensive set of simulations, this paper also provides an insight into specific possible technological solutions that are proposed for the implementation of a space-borne Raman lidar system. These solutions refer to technological breakthroughs gained during the last decade in the design and development of specific lidar devices and sub-systems, primarily in high-power, high-efficiency solid-state laser sources, low-weight large aperture telescopes, and high-gain, high-quantum efficiency detectors.

Adsorption Behavior of Lysozyme at Titanium Oxide-Water Interfaces.

We present an in situ X-ray reflectivity study of the adsorption behavior of the protein lysozyme on titanium oxide layers under variation of different thermodynamic parameters, such as temperature, hydrostatic pressure, and pH value. Moreover, by varying the layer thickness of the titanium oxide layer on a silicon wafer, changes in the adsorption behavior of lysozyme were studied. In total, we determined less adsorption on titanium oxide compared with silicon dioxide, while increasing the titanium oxide layer thickness causes stronger adsorption. Furthermore, the variation of temperature from 20 to 80 °C yields an increase in the amount of adsorbed lysozyme at the interface. Additional measurements with variation of the pH value of the system in a region between pH 2 and 12 show that the surface charge of both protein and titanium oxide has a crucial role in the adsorption process. Further pressure-dependent experiments between 50 and 5000 bar show a reduction of the amount of adsorbed lysozyme with increasing pressure.

Feature issue introduction: Light, Energy and the Environment, 2016.

This feature issue highlights contributions from authors who presented their research at the OSA Light, Energy and the Environment Congress, held in Leipzig, Germany from November 14 to 17, 2016.

Stress Management in Thin-Film Gas-Permeation Barriers.

Gas diffusion barriers (GDB) are essential building blocks for the protection of sensitive materials or devices against ambient gases, like oxygen and moisture. In this work, we study the mechanics of GDBs processed by atomic layer deposition (ALD). We demonstrate that a wide range of ALD grown barrier layers carry intrinsic mechanical tensile stress in the range of 400-500 MPa. In the application of these GDBs on top of organic electronic devices, we derive a critical membrane force (σ · h)crit = 1200 GPaÅ (corresponding to a layer thickness of about 300 nm) for the onset of cracking and delamination. At the same time, we evidence that thicker GDBs would be more favorable for the efficient encapsulation of statistically occurring particle defects. Thus, to reduce the overall membrane force in this case to levels below (σ · h)crit, we introduce additional compressively strained layers, e.g., metals or SiNx. Thereby, highly robust GDBs are prepared on top of organic light emitting diodes, which do not crack/delaminate even under damp heat conditions 85 °C/85% rh.

Modification Pathways for Copoly(2-oxazoline)s Enabling Their Application as Antireflective Coatings in Photolithography.

Chromophore-functionalized copoly(2-oxazoline)s are successfully evaluated as bottom antireflective coatings (BARCs) in high-resolution photolithography. With respect to UV light sources used in photolithographic production routines, anthracene is chosen as a chromophore. For application as polymer in BARCs, the copolymer poly(2-ethyl-2-oxazolin)45 -stat-poly(2-dec-9'-enyl-2-oxazolin)20 -stat-poly(2-(3'-(1"-(anthracen-9-ylmethyl)-1",2",3"-triazol-4-yl)propyl)-2-oxazolin)35 can be synthesized by the Huisgen cycloaddition click reaction of the copolymer poly(2-ethyl-2-oxazolin)45 -stat-poly(2-dec-9'-enyl-2-oxazolin)20 -stat-poly(2-pent-4'-inyl-2-oxazolin)35 and the corresponding azide-functionalized anthracenes. These copolymers can be crosslinked by the thermally induced thiol-ene reaction involving the unsaturated C=C bonds of the poly(2-dec-9'-enyl-2-oxazoline) repetition units and a multifunctional thiol as crosslinker. Tests of this BARC in a clean room under production conditions reveal a significant decrease of the swing-curve of a chemically amplified positive photoresist by more than 50%, hence significantly increasing the resolution of the photoresist.

Parametrization of optimum filter passbands for rotational Raman temperature measurements.

We revisit the methodology of rotational Raman temperature measurements covering both lidar and non-range-resolved measurements, e.g., for aircraft control. The results of detailed optimization calculations are presented for the commonly used extraction of signals from the anti-Stokes branch. Different background conditions and realistic shapes of the filter transmission curves are taken into account. Practical uncertainties of the central passbands and widths are discussed. We found a simple parametrization for the optimum filter passband shifts depending on the atmospheric temperature range of interest and the background. The approximation errors of this parametrization are smaller than 2% for temperatures between 200 and 300 K and smaller than 4% between 180 and 200 K.

Highly robust transparent and conductive gas diffusion barriers based on tin oxide.

Transparent and electrically conductive gas diffusion barriers are reported. Tin oxide (SnOx ) thin films grown by atomic layer deposition afford extremely low water vapor transmission rates (WVTR) on the order of 10(-6) g (m(2) day)(-1) , six orders of magnitude better than that established with ITO layers. The electrical conductivity of SnOx remains high under damp heat conditions (85 °C/85% relative humidity (RH)), while that of ZnO quickly degrades by more than five orders of magnitude.

Conformal and highly luminescent monolayers of Alq3 prepared by gas-phase molecular layer deposition.

The gas-phase molecular layer deposition (MLD) of conformal and highly luminescent monolayers of tris(8-hydroxyquinolinato)aluminum (Alq3) is reported. The controlled formation of Alq3 monolayers is achieved for the first time by functionalization of the substrate with amino groups, which serve as initial docking sites for trimethyl aluminum (TMA) molecules binding datively to the amine. Thereby, upon exposure to 8-hydroxyquinoline (8-HQ), the self-limiting formation of highly luminescent Alq3 monolayers is afforded. The growth process and monolayer formation were studied and verified by in situ quartz crystal monitoring, optical emission and absorption spectroscopy, and X-ray photoelectron spectroscopy. The nature of the MLD process provides an avenue to coat arbitrarily shaped 3D surfaces and porous structures with high surface areas, as demonstrated in this work for silica aerogels. The concept presented here paves the way to highly sensitive luminescent sensors and dye-sensitized metal oxides for future applications (e.g., in photocatalysis and solar cells).

Short-range optical air data measurements for aircraft control using rotational Raman backscatter.

A first laboratory prototype of a novel concept for a short-range optical air data system for aircraft control and safety was built. The measurement methodology was introduced in [Appl. Opt. 51, 148 (2012)] and is based on techniques known from lidar detecting elastic and Raman backscatter from air. A wide range of flight-critical parameters, such as air temperature, molecular number density and pressure can be measured as well as data on atmospheric particles and humidity can be collected. In this paper, the experimental measurement performance achieved with the first laboratory prototype using 532 nm laser radiation of a pulse energy of 118 mJ is presented. Systematic measurement errors and statistical measurement uncertainties are quantified separately. The typical systematic temperature, density and pressure measurement errors obtained from the mean of 1000 averaged signal pulses are small amounting to < 0.22 K, < 0.36% and < 0.31%, respectively, for measurements at air pressures varying from 200 hPa to 950 hPa but constant air temperature of 298.95 K. The systematic measurement errors at air temperatures varying from 238 K to 308 K but constant air pressure of 946 hPa are even smaller and < 0.05 K, < 0.07% and < 0.06%, respectively. A focus is put on the system performance at different virtual flight altitudes as a function of the laser pulse energy. The virtual flight altitudes are precisely generated with a custom-made atmospheric simulation chamber system. In this context, minimum laser pulse energies and pulse numbers are experimentally determined, which are required using the measurement system, in order to meet measurement error demands for temperature and pressure specified in aviation standards. The aviation error margins limit the allowable temperature errors to 1.5 K for all measurement altitudes and the pressure errors to 0.1% for 0 m and 0.5% for 13000 m. With regard to 100-pulse-averaged temperature measurements, the pulse energy using 532 nm laser radiation has to be larger than 11 mJ (35 mJ), regarding 1-σ (3-σ) uncertainties at all measurement altitudes. For 100-pulse-averaged pressure measurements, the laser pulse energy has to be larger than 95 mJ (355 mJ), respectively. Based on these experimental results, the laser pulse energy requirements are extrapolated to the ultraviolet wavelength region as well, resulting in significantly lower pulse energy demand of 1.5 - 3 mJ (4-10 mJ) and 12-27 mJ (45-110 mJ) for 1-σ (3-σ) 100-pulse-averaged temperature and pressure measurements, respectively.

High-power Ti:sapphire laser at 820 nm for scanning ground-based water-vapor differential absorption lidar.

The Ti:sapphire (TISA) laser transmitter of the mobile, three-dimensional-scanning water-vapor differential absorption lidar (DIAL) of the University of Hohenheim is described in detail. The dynamically-stable, unidirectional ring resonator contains a single Brewster-cut TISA crystal, which is pumped from both sides with 250 Hz using a diode-pumped frequency-doubled Nd:YAG laser. The resonator is injection seeded and actively frequency-stabilized using a phase-sensitive technique. The TISA laser is operating near 820 nm, which is optimum for ground-based water-vapor DIAL measurements. An average output power of up to 6.75 W with a beam quality factor of M2<2 is reached. The pointing stability is <13 µrad (rms), the depolarization <1%. The overall optical-optical conversion efficiency is up to 19%. The pulse length is 40 ns with a pulse linewidth of <157 MHz. The short- and long-term frequency stabilities are 10 MHz (rms). A spectral purity of 99.9% was determined by pointing to a stratus cloud in low-elevation scanning mode with a cloud bottom height of ≈2.4 km.

Facile encapsulation of oxide based thin film transistors by atomic layer deposition based on ozone.

A simplified encapsulation strategy for metal-oxide based TFTs, using ozone instead of water as an oxygen source in a low-temperature ALD process is demonstrated. Thereby, the threshold voltage remains unaltered and the hysteresis is permanently reduced. Costly energy- and time-consuming post-treatment processes can be avoided. This concept is widely applicable to various encapsulation materials (e.g., Al2 O3 , TiO2 , ZrO2 ) and metal-oxide channel semiconductors (e.g., zinc-tin-oxide (ZTO), indium-gallium-zinc-oxide (IGZO)).

Low-temperature, solution-processed MoO(x) for efficient and stable organic solar cells.

Sol-gel processed MoO(x) (sMoO(x)) hole-extraction layers for organic solar cells are reported. A Bis(2,4-pentanedionato)molybdenum(VI)dioxide/isopropanol solution is used and only a moderate thermal post deposition treatment at 150 °C in N(2) ambient is required to achieve sMoO(x) layers with a high work-function of 5.3 eV. We demonstrate that in P3HT:PC(60)BM organic solar cells (OSCs) our sMoO(x) layers lead to a high filling factor of about 65% and an efficiency of 3.3% comparable to that of reference devices with thermally evaporated MoO(3) layers (eMoO(3)). At the same time, a substantially improved stability of the OSCs compared to devices using a PEDOT:PSS hole extraction layer is evidenced.

Laser-based air data system for aircraft control using Raman and elastic backscatter for the measurement of temperature, density, pressure, moisture, and particle backscatter coefficient.

Flight safety in all weather conditions demands exact and reliable determination of flight-critical air parameters. Air speed, temperature, density, and pressure are essential for aircraft control. Conventional air data systems can be impacted by probe failure caused by mechanical damage from hail, volcanic ash, and icing. While optical air speed measurement methods have been discussed elsewhere, in this paper, a new concept for optically measuring the air temperature, density, pressure, moisture, and particle backscatter is presented, being independent on assumptions on the atmospheric state and eliminating the drawbacks of conventional aircraft probes by providing a different measurement principle. The concept is based on a laser emitting laser pulses into the atmosphere through a window and detecting the signals backscattered from a fixed region just outside the disturbed area of the fuselage flows. With four receiver channels, different spectral portions of the backscattered light are extracted. The measurement principle of air temperature and density is based on extracting two signals out of the rotational Raman (RR) backscatter signal of air molecules. For measuring the water vapor mixing ratio-and thus the density of the moist air-a water vapor Raman channel is included. The fourth channel serves to detect the elastic backscatter signal, which is essential for extending the measurements into clouds. This channel contributes to the detection of aerosols, which is interesting for developing a future volcanic ash warning system for aircraft. Detailed and realistic optimization and performance calculations have been performed based on the parameters of a first prototype of such a measurement system. The impact and correction of systematic error sources, such as solar background at daytime and elastic signal cross talk appearing in optically dense clouds, have been investigated. The results of the simulations show the high potential of the proposed system for reliable operation in different atmospheric conditions. Based on a laser emitting pulses at a wavelength of 532 nm with 200 mJ pulse energy, the expected measurement precisions (1-σ statistical uncertainty) are <0.6 K for temperature, <0.3% for density, and <0.4% for pressure for the detection of a single laser pulse at a flight altitude of 13,000 m at daytime. The errors will be smaller during nighttime or at lower altitudes. Even in optically very dense clouds with backscatter ratios of 10,000 and RR filters suppressing the elastic backscatter by 6 orders of magnitude, total errors of <1.4 K, <0.4%, and <0.9%, are expected, respectively. The calculations show that aerospace accuracy standards will be met with even lower pulse energies of 75 mJ for pressure and 18 mJ for temperature measurements when the backscatter signals of 10 laser pulses are averaged. Using laser sources at 355 nm will lead to a further reduction of the necessary pulse energies by more than a factor of 3.

Detailed performance modeling of a pulsed high-power single-frequency Ti:sapphire laser.

Differential absorption lidar (DIAL) is a unique technique for profiling water vapor from the ground up to the lower stratosphere. For accurate measurements, the DIAL laser transmitter has to meet stringent requirements. These include high average power (up to 10 W) and high single-shot pulse energy, a spectral purity >99.9%, a frequency instability <60 MHz rms, and narrow spectral bandwidth (single-mode, <160 MHz). We describe extensive modeling efforts to optimize the resonator design of a Ti:sapphire ring laser in these respects. The simulations were made for the wavelength range of 820 nm, which is optimum for ground-based observations, and for both stable and unstable resonator configurations. The simulator consists of four modules: (1) a thermal module for determining the thermal lensing of the Brewster-cut Ti:sapphire crystal collinear pumped from both ends with a high-power, frequency-doubled Nd:YAG laser; (2) a module for calculating the in-cavity beam propagations for stable and unstable resonators; (3) a performance module for simulating the pumping efficiency and the laser pulse energy; and (4) a spectral module for simulating injection seeding and the spectral properties of the laser radiation including spectral impurity. Both a stable and an unstable Ti:sapphire laser resonator were designed for delivering an average power of 10 W at a pulse repetition frequency of 250 Hz with a pulse length of approximately 40 ns, satisfying all spectral requirements. Although the unstable resonator design is more complex to align and has a higher lasing threshold, it yields similar efficiency and higher spectral purity at higher overall mode volume, which is promising for long-term routine operations.

Spaceborne profiling of atmospheric temperature and particle extinction with pure rotational Raman lidar and of relative humidity in combination with differential absorption lidar: performance simulations.

The performance of a spaceborne temperature lidar based on the pure rotational Raman (RR) technique in the UV has been simulated. Results show that such a system deployed onboard a low-Earth-orbit satellite would provide global-scale clear-sky temperature measurements in the troposphere and lower stratosphere with precisions that satisfy World Meteorological Organization (WMO) threshold observational requirements for numerical weather prediction and climate research applications. Furthermore, nighttime temperature measurements would still be within the WMO threshold observational requirements in the presence of several cloud structures. The performance of aerosol extinction measurements from space, which can be carried out simultaneously with temperature measurements by RR lidar, is also assessed. Furthermore, we discuss simulations of relative humidity measurements from space obtained from RR temperature measurements and water-vapor data measured with the differential absorption lidar (DIAL) technique.

Electro- and magnetocommunication in [5,5]ditrovacenyls, [(eta7-C7H7)V(eta5-C5H4-X-eta5-C5H4)V(eta7-C7H7)], mediated by the spacers X = (Z)-CH=CH-, (E)-CH=CH-, > C=CH2, -CH2CH2-, and -CH2-.

Five new paramagnetic dinuclear complexes containing [5]trovacenyl groups, (eta7-C7H7)V(eta5-C5H4-), have been prepared and characterized, including by single-crystal X-ray diffraction. As intervening spacers, ethenediyl units in the geminal and vicinal (Z)- and (E)-bridging modes as well as methanediyl and ethanediyl units have been included with the aim of studying their propensity to transmit electric and magnetic information. It is found that redox splitting of consecutive electron-transfer steps is resolved for reduction (0-->1- -->2-) only, unsaturation of the C2 bridge not being requisite, since the -CH2CH2- spacer also gives rise to a small redox splitting. Magnetic communication is quantified in terms of the exchange coupling constant J, accessible from the EPR hyperfine pattern in solution and from magnetic susceptometry in the solid state. The results obtained from these methods generally differ; this fact is not surprising in view of conformational differences in the respective states of aggregation. It is concluded that orientation-dependent mechanisms of spin-spin interactions (pi-orbital overlap, hyperconjugation) contribute extensively although, as implied by sizeable J values for -CH2- and -C2H4- linked di[5]trovacenyl groups, coupling mediated by the sigma-orbital chain must also be considered.

Combined temperature lidar for measurements in the troposphere, stratosphere, and mesosphere.

We describe the performance of a combined Raman lidar. The temperature is measured with the rotational Raman technique and with the integration technique simultaneously. Additionally measured parameters are particle extinction and backscatter coefficients and water vapor mixing ratio. In a previous stage of the system, instrumental problems restricted the performance. We describe how we rebuilt the instrument and overcame these restrictions. As a result, the measurement time for the same spatial resolution and accuracy of the rotational Raman temperature measurements is reduced by a factor of approximately 4.3, and their range could be extended for the first time to the upper stratosphere.

Calculation of the calibration constant of polarization lidar and its dependency on atmospheric temperature.

The volume depolarization ratio of the molecular backscatter signal detected with polarization lidar varies by a factor of nearly 4 depending on whether the rotational Raman bands are included in the detected signals of the individual system or not. If the rotational Raman spectrum is included partially in the signals, this calibration factor depends on the temperature of the atmosphere. This dependency is studied for different spectral widths of the receiving channels. In addition, the sensitivity to differences between the laser wavelength and the center wavelength of the receiver are discussed.

Combined Raman lidar for the measurement of atmospheric temperature, water vapor, particle extinction coefficient, and particle backscatter coefficient.

The lidar of the Radio Science Center for Space and Atmosphere (RASC; Kyoto, Japan) make use of two pure rotational Raman (MR) signals for both the measurement of the atmospheric temperature profile and the derivation of a temperature-independent Raman reference signal. The latter technique is new and leads to significant smaller measurement uncertainties compared with the commonly used vibrational Raman lidar technique. For the measurement of temperature, particle extinction coefficient, particle backscatter coefficient, and humidity simultaneously, only four lidar signal are needed the elastic Cabannes backscatter signal, two RR signals, and the vibrational Raman water vapor signal. The RASC lidar provides RR signals of unprecedented intensity. Although only 25% of the RR signal intensities can be used with the present data-acquisition electronics, the 1-s -statistical uncertainty of nighttime temperature measurements is lower than for previous systems and is < 1K up to 11-km height for, e.g., a resolution of 500 m and 9 min. In addition, RR measurements in daytime also have become feasible.