2022 Optical Interference Coatings Conference: Manufacturing Problem Contest [Invited].

Participants in the 2022 Manufacturing Problem Contest were challenged to fabricate an optical filter with a specified stepped transmittance spanning three orders of magnitude from 400 to 1100 nm. The problem required that contestants be versed in the design, deposition, and measurement of optical filters to achieve good results. Nine samples from five institutions were submitted with total thicknesses between 5.9 and 53.5 µm with between 68 and 1743 layers. The filter spectra were measured by three independent laboratories. The results were presented in June 2022 at the Optical Interference Coatings Conference in Whistler, B.C., Canada.

Pyroelectric detector-based method for low uncertainty spectral irradiance and radiance responsivity calibrations in the infrared using tunable lasers.

The standard uncertainty of detector-based radiance and irradiance responsivity calibrations in the short-wave infrared (SWIR) traditionally has been limited to around 1% or higher by the poor spatial uniformity of detectors used to transfer the scale from radiant power. Pyroelectric detectors offer a solution that avoids the spatial uniformity uncertainty but also introduces additional complications due to alternating current (AC) measurement techniques. Herein, a new, to the best of our knowledge, method for low uncertainty irradiance responsivity calibrations in the SWIR is presented. An absolute spectral irradiance responsivity scale was placed on two pyroelectric detectors (PED) at wavelengths λ from 500 to 3400 nm. The total combined uncertainty (k=1) was ≈0.28% (>1000nm), 0.44% (900 nm), and 0.36% (≈950nm and <900nm) for PED #1 and 0.34% (>1000nm), 0.48% (900 nm), and 0.42% (≈950nm and <900nm) for PED #2. This was done by utilizing a demodulation technique to digitally analyze the time-dependent AC waveforms, which obviates the use of lock-in amplifiers and avoids associated additional uncertainty components.

Bidirectional reflectance capabilities of the NIST Robotic Optical Scattering Instrument.

The National Institute of Standards and Technology (NIST) Robotic Optical Scattering Instrument (ROSI) serves as the national reference instrument for specular and diffuse bidirectional reflectance measurements in the ultraviolet to short-wave infrared wavelength regions. This paper gives a comprehensive overview of the design, operation, and capabilities of ROSI. We describe measurement methods for diffuse and specular reflectance, identify and quantify the elements of the uncertainty budget, and validate the reflectance scale through comparison with NIST's previous reference instrument, the Spectral Tri-function Automated Reference Reflectometer. Examples of the range of ROSI's capabilities, including the limits for low-reflectance measurements and a research application using out-of-plane measurements of bidirectional reflectance for remote sensing reference reflectors, are also covered.

2019 Topical Meeting on Optical Interference Coatings: Manufacturing Problem Contest [invited].

For the seventh Manufacturing Problem Contest, participants were challenged to fabricate an optical filter with transmittance specified for s-polarization at two incident angles: 10° and 50° from 400 nm to 1100 nm. The problem required that contestants be equally versed in the design, deposition, and measurement of optical filters in order to achieve good results. Eight teams from five different countries participated in the contest using various deposition techniques. The fabricated filters had a total thickness between 8.2 µm and 17.6 µm and a total number of layers from 74 to 255, which were deposited onto one or both sides of the substrate. The performances of the filters were measured by two independent laboratories. The evaluation results were presented at the Topical Meeting on Optical Interference Coatings conference held in Santa Ana Pueblo, New Mexico, in June 2019.

Exposure study on UV-induced degradation of PTFE and ceramic optical diffusers.

We report on a study of the ultraviolet (UV)-induced degradation on optical grade polytetrafluoroethylene (PTFE) and ceramic diffuser samples. Long-term UV exposure may significantly alter the reflectance and lead to an error in the calibration of optical instruments. A large integrating sphere was used to irradiate the samples for 334.7 days at an irradiance level of 194.9 W/m2. Samples were qualified and measured for reflectance factor, bidirectional reflectance distribution function, and fluorescence, before and after the exposure, and at 12-week intervals during the exposure. This study revealed significant differences between the aging behavior of ceramic and PTFE samples.

Comparison of Bidirectional Transmittance Distribution Function (BTDF) Measurements on Fused Silica and Sintered Polytetrafluoroethylene Diffusers.

Accurate determination of the bidirectional transmittance distribution function (BTDF) of transmissive diffusers is critical for the on-orbit spectral radiance calibration of several satellite-based, Earth remote sensing instruments. This study presents the results of the comparison of BTDF measurements by NASA Goddard Space Flight Center's Diffuser Calibration Laboratory and the National Institute of Standards and Technology's Spectral Tri-function Automated Reference Reflectometer facility on two transmissive diffusers: HOD-500, a synthetic fused silica sample manufactured by Hereaus Quarzglas and Spectralon-250, a sintered polytetrafluoroethylene sample manufactured by Labsphere, Incorporated. BTDF measurements were acquired at seven wavelengths from 290 nm to 740 nm, at incident elevation angles of 0° and 30°, and at scatter elevation angles from 1° to 15°. Comparison of the measurements made by the two facilities revealed excellent agreement within their combined standard uncertainties. NASA chose the parameters for the BTDF measurements to be identical to those NASA used when measuring the BTDF of the flight diffusers to be flown onboard the Tropospheric Monitoring of Pollution (TEMPO) and the Geostationary Environment Monitoring Spectrometer (GEMS) satellite instruments. Successful agreement between NASA and NIST of BTDF results, therefore, effectively validates the BTDF measurements NASA made for these satellite flight programs.

Correction of an adding-doubling inversion algorithm for the measurement of the optical parameters of turbid media.

We present broadband measurements of the optical properties of tissue-mimicking solid phantoms using a single integrating sphere to measure the hemispherical reflectance and transmittance under a direct illumination at the normal incident angle. These measurements are traceable to reflectance and transmittance scales. An inversion routine using the output of the adding-doubling algorithm restricted to the reflectance and transmittance under a direct illumination was developed to produce the optical parameters of the sample along with an uncertainty budget at each wavelength. The results for two types of phantoms are compared to measurements by time-resolved approaches. The results between our method and these independent measurements agree within the estimated measurement uncertainties.

Algorithm for rapid determination of optical scattering parameters.

Preliminary experiments at the NIST Spectral Tri-function Automated Reference Reflectometer (STARR) facility have been conducted with the goal of providing the diffuse optical properties of a solid reference standard with optical properties similar to human skin. Here, we describe an algorithm for determining the best-fit parameters and the statistical uncertainty associated with the measurement. The objective function is determined from the profile log likelihood, including both experimental and Monte Carlo uncertainties. Initially, the log likelihood is determined over a large parameter search box using a relatively small number of Monte Carlo samples such as 2·104. The search area is iteratively reduced to include the 99.9999% confidence region, while doubling the number of samples at each iteration until the experimental uncertainty dominates over the Monte Carlo uncertainty. Typically this occurs by 1.28·106 samples. The log likelihood is then fit to determine a 95% confidence ellipse. The inverse problem requires the values of the log likelihood on many points. Our implementation uses importance sampling to calculate these points on a grid in an efficient manner. Ultimately, the time-to-solution is approximately six times the cost of a Monte Carlo simulation of the radiation transport problem for a single set of parameters with the largest number of photons required. The results are found to be 64 times faster than our implementation of Particle Swarm Optimization.

Optical reflectance of pyrheliometer absorption cavities: progress toward SI-traceable measurements of solar irradiance.

We have accurately determined the absorptance of three pyrheliometer cavities at 532 nm by measuring the residual reflectance using an angle-resolved bidirectional reflectometer. Measurements were performed at a normal incidence as a function of the viewing angle and position on the cavity cone. By numerically integrating the measured angle-resolved scatter over both the direction and position and accounting for an obstructed view of the cavity, we determined that the effective cavity reflectance was between 8×10-4 and 9×10-4. Thus, the absorptance of the three cavities ranged from 0.99909±0.00014 to 0.99922±0.00012 (k=2 combined expanded uncertainties). These measurements, when extended over the spectral range of operation of the pyrheliometer, are required to establish SI traceability for absolute solar irradiance measurements.

National Institute of Standards and Technology measurement service of the optical properties of biomedical phantoms: Current status.

The National Institute of Standards and Technology (NIST) has maintained scales for reflectance and transmittance over several decades. The scales are primarily intended for regular transmittance, mirrors, and solid surface scattering diffusers. The rapidly growing area of optical medical imaging needs a scale for volume scattering of diffuse materials that are used to mimic the optical properties of tissue. Such materials are used as phantoms to evaluate and validate instruments under development intended for clinical use. To address this need, a double-integrating sphere based instrument has been installed to measure the optical properties of tissue-mimicking phantoms. The basic system and methods have been described in previous papers. An important attribute in establishing a viable calibration service is the estimation of measurement uncertainties. The use of custom models and comparisons with other established scales enabled uncertainty measurements. Here, we describe the continuation of those efforts to advance the understanding of the uncertainties through two independent measurements: the bidirectional reflectance distribution function and the bidirectional transmittance distribution function of a commercially available solid biomedical phantom. A Monte Carlo-based model is used and the resulting optical properties are compared to the values provided by the phantom manufacturer.

Establishment and application of the 0/45 reflectance factor scale over the shortwave infrared.

This paper describes the establishment and application of the 0/45 reflectance factor scale in the shortwave infrared (SWIR) from 1100 to 2500 nm. Design, characterization, and the demonstration of a four-stage, extended indium-gallium-arsenide radiometer to perform reflectance measurements in the SWIR have been previously discussed. Here, we focus on the incorporation of the radiometer into the national reference reflectometer, its validation through comparison measurements, and the uncertainty budget. Next, this capability is applied to the measurement of three different diffuser materials. The 0/45 spectral reflectance factors for these materials are reported and compared to their respective 6/di spectral reflectance factors.

Femtosecond pump-probe studies of nitrosyl chloride photochemistry in solution.

We present a femtosecond pump-probe study of the primary events of nitrosyl chloride (ClNO) photochemistry in solution. Following 266 nm photolysis, the resulting evolution in optical density is measured for ClNO dissolved in acetonitrile, chloroform, and dichloromethane. The results demonstrate that photolysis results in the production of a photoproduct that has an absorption band maximum at 295 nm in acetonitrile and 330 nm in chloroform and dichloromethane. To determine the extent of Cl production, comparative photochemical studies of methyl hypochlorite (MeOCl) and ClNO are performed. Photolysis of MeOCl in solution results in the production of the Cl:solvent charge-transfer complex; therefore, a comparison of the spectral evolution observed following MeOCl and ClNO photolysis under identical photolysis conditions is performed to determine the extent of Cl production following ClNO photolysis. We find that similar to the gas-phase photochemistry, Cl and NO formation is the dominant photochemical channel in acetonitrile. However, the photochemistry in chloroform and dichloromethane is more complex, with a second product formed in addition to Cl and NO. It is proposed that in these solvents photoisomerization also occurs, resulting in the production of ClON. The results presented here represent the first detailed examination of the solution phase photochemistry of ClNO.

The phase-dependent photochemical reaction dynamics of halooxides and nitrosyl halides.

Recent progress in understanding the phase-dependent reactivity of halooxides and nitrosyl halides is outlined. Halooxide reactivity is represented by the photochemistry of chlorine dioxide (OClO) and dichlorine monoxide (ClOCl). The gas phase photochemical dynamics of OClO are contrasted with the dynamics in condensed environments. The role of excited-state symmetry in defining the reaction dynamics and the observation of photoisomerization resulting in the production of ClOO are discussed. The current understanding of the excited-state reaction dynamics of ClOCl and evidence for photoisomerization of this species resulting in the production of ClClO are outlined. Finally, the photochemical reaction dynamics of the nitrosyl halide ClNO are presented. The main difference between the gas and condensed phase reaction dynamics of this species is that whereas photodissociation to form Cl and NO dominates the gas phase reaction dynamics, photoisomerization resulting in ClON production occurs to an appreciable extent in condensed environments. The observation of photoisomerization for OClO, ClOCl and ClNO suggests that this process is a general feature of the condensed phase reaction dynamics for smaller halooxides and nitrosyl halides. Finally, future areas for study in both halooxide and nitrosyl halide photoreactivity are outlined.