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At least 127 records · Page 7

Patterned dielectric back contact design for GaAs thermophotovoltaic devices

-Patterned-dielectric back contact structures in optoelectronic devices are designed to boost the reflectance of light from the device back surface while retaining a low-resistance pathway for electrical conductance. Their reduced light absorption at near- and sub-bandgap photon energies leads to improved luminescence in light-emitting diodes, greater photon recycling, voltage, and efficiency in photovoltaic cells, and greater recuperation of unabsorbed sub-bandgap light in thermophotovoltaic (TPV) systems. However, diffraction from the patterned features can deflect incident light in propagation directions that lead to light trapping and parasitic absorption in the cell. Here, in this article, we use rigorous coupled-wave analysis (RCWA) to study three-dimensional diffractive scattering of electromagnetic waves by periodic metal point-contact gratings on 1.42-eV GaAs TPV cells, to analyze their effect on unwanted sub-bandgap absorption in order to achieve higher TPV system efficiency. Solutions of Maxwell's equations calculated using RCWA are compared to measured sub-bandgap reflectance in experimental GaAs TPV devices with varying metal point-contact diameters and spacing. Modeling and experiments indicate decreased total reflectance due to these diffractive effects for a small point contact diameter of 1 μm, and this effect is much stronger at higher contact coverage fractions.

14 SOLAR ENERGY↗

Changes in SSL Device Efficiency and Optical Performance Under Accelerated Aging Conditions

Lighting application efficiency (LAE) describes the efficient delivery of light from the light source to the lighted task and is viewed as a new frontier—increasing energy savings with solid-state lighting (SSL) technologies. The framework for LAE that is proposed by the U.S. Department of Energy (DOE) consists of four major elements: light source efficiency, optical delivery efficiency, spectral efficiency, and intensity effectiveness. This report focuses on a sampling of the available SSL products that can be broadly defined as having modified spectral output because the method of spectra modification has a significant impact on light source efficiency and long-term optical delivery and spectral efficiencies. This report focused on the changes in light source, optical delivery, and spectral efficiencies that occur during aging of SSL devices. An accelerated stress test (AST) regiment was developed for the devices under test (DUTs) examined in this report to provide insights into how the performance of SSL devices change with aging. The AST protocols demonstrate that the SSL products discussed in this report often reduce light source efficiency to achieve different spectral characteristics. In addition, aging of the optical components (e.g., lenses, solder masks) in SSL devices can produce increased light absorption, which negatively impacts optical delivery efficiency and light source efficiency. The modified spectral outputs of the selected SSL products discussed in this report come in a variety of form factors and achieve enhanced optical performance by using a variety of methods. All of the products examined in this study use mid-power light-emitting diodes (MP-LEDs), although the number, configuration, phosphor content, and light-emitting diode (LED) pump of the MP-LEDs differ. Product MS-1 is a 60-watt (W) replacement A19 lamp with a hermetically sealed glass globe, which contains an embedded optical filter to absorb green and yellow emissions, thereby creating a “sunlike” modified spectrum. Product MS-2 is a 60-W replacement A19 lamp with 30 MP-LEDs, and it uses a violet LED pump, along with green and red phosphor emissions, to produce a “healthy” spectrum. This spectrum omits blue emissions in an effort to reduce melanopic lux. Product MS-3 is an LED module consisting of 21 MP-LEDs that use a violet LED pump, along with blue, green, and red phosphors, to produce a “sunlike” spectrum. Products MS-4 and MS-5 are both 6-inch (in) downlights that use a manual switching mechanism so that users can select application-specific correlated color temperatures before installation. Products MS-4 and MS-5 both contain two LED primaries (2,700 Kelvin [K] and 5,000 K) for spectral tuning. Product MS-4 contains 12 MP-LEDs for each LED primary, and Product MS-5 contains 10 MP-LEDs for each LED primary. This report summarizes the overall findings from up to 8,000 hours (hrs) of AST on the lamp DUTs (Products MS-1 and MS-2); up to 5,000 hrs of AST on the LED light engine DUTs (Product MS-3); and up to 7,000 hrs of AST on the downlight DUTs (Products MS-4 and MS-5). The AST procedures used in this study included a room temperature operational life (RTOL) test, an operational life test conducted at 45 degrees Celsius (°C; 45OL) test, an operational life test conducted at 75°C (75OL), a wet high-temperature operational life test performed at 65°C and 90% relative humidity (6590), and a wet high-temperature operational life test performed at 75°C and 75% relative humidity (7575). The AST procedures used for Products MS-1 and MS-2 were RTOL, 45OL, and 6590. The AST procedures used for Products MS-3, MS-4, and MS-5 were RTOL, 75OL, and 7575. During the ASTs described herein, separate populations of each product (three DUTs in each population for Products MS-1, MS-2, MS-4, and MS-5; four DUTs in each population for Product MS-3) were subjected to power cycling of 1 hr on and 1 hr off. The key findings from this study include the following. Enhanced optical performance came at the cost of reduced light source efficiency for the lamps and light engines examined in this study. The optical filter used to produce a “sunlike” spectrum for Product MS-1 reduced light source efficiency by 26%, from 113 lumens per watt (lm/W) to 85 lm/W. Products MS-2 and MS-3 that used a violet-pumped LED to achieve “healthy” and “sunlike” enhanced optical performance, respectively, suffered the largest reduction in initial light source efficiency (49 lm/W for Product MS-2 and 68 lm/W for Products MS-3) perhaps because of the use of violet LED as the optical pump. Product MS-2 also had the poorest color fidelity because of undersaturation of blues and oversaturation of greens and yellows. Chromaticity maintenance of the products in this study was generally good, with parametric failure only occurring for one product at one AST condition (i.e., Product MS-3 at 7575). The chromaticity shift for Product MS-3 in 7575 test conditions resulted from reduced emissions of the broad green and red phosphors used to mimic sunlight in the 500–750 nanometer (nm) range. As a result of these phosphor emission losses, chromaticity shifted toward the more stable violet-pumped LED and blue phosphor. Although chromaticity maintenance was acceptable for most products tested, different chromaticity shift mechanisms were observed for temperature and humidity tests compared with temperature alone for Products MS-1, MS-2, and MS-3. For Product MS-1, a relative increase in green emissions was observed with humidity, which may indicate humidity-accelerated degradation of the optical filter at green wavelengths (optical delivery efficiency reduction) or degradation of the emitters in the red region (spectral efficiency reduction). The violet-pumped products (i.e., MS-2 and MS-3) exhibited different chromaticity shift behavior in the temperature-humidity environments, with Product MS-2 shifting generally yellow because of photo-induced oxidation of the plastic globe (i.e., a reduction of optical delivery efficiency) and Product MS-3 shifting toward violet and blue emitters because of faster loss of emission from green and red phosphors (i.e., a reduction in spectral efficiency). Because of an initial drop in power consumption, the light source efficiency of downlights (Products MS-4 and MS-5) increased at RTOL throughout the test duration. The light source efficiency initially increased during 75OL until a decay in luminous flux maintenance (LFM) dominated light source efficiency, whereas the light source efficiency decreased for the entire 7575 test duration. It was found that increasing the ambient environment of an SSL device from 25°C to 75°C decreases the LFM by 2.7 to 5.5, depending on design of the SSL device. Adding humidity to the system (75OL to 7575) was found to decrease LFM by another factor of approximately 3.0. A common location of failure was identified for the downlights (Products MS-4 and MS-5) operated in the 7575 environment. This failure abruptly occurred between 3,000 to 5,000 hrs of testing on the film capacitor of the electromagnetic interference (EMI) filter near the diode bridge for 11 of the 12 downlights. It is likely that this failure was caused by a combination of the high electrical voltage across the capacitor, the location of the capacitor near the heat sources (e.g., transformers, diode bridges, power resistors), and the high stress environment of 7575. Longer test times are needed to fully understand the LFM, luminous efficacy changes, and chromaticity shifts for some of the products. Because of the high reliability, light source efficiency, and spectral tuning capabilities of LEDs, the expectations of LAE for SSL products are greatly increased over traditional lighting products. The data gathered in this report begin to provide an understanding of the tradeoffs that current SSL products undergo when optimizing the different efficiency elements of LAE. As discussed in this report, the findings from the tests conducted show that the optimization of spectral efficiency can come at the cost of initial light source efficiency. Furthermore, the introduction of violet LEDs can promote long-term optical delivery efficiency degradation, and the introduction of optical filters or new phosphors can lead to unwanted spectral efficiency changes because the ratio of phosphor emitters changes with aging. The data presented in this report also identified a common failure location in 6-in downlights. The results regarding long-term behavior of the modified spectra devices studied provide valuable information about changes to the light source, spectral, and optical delivery efficiencies as the devices age. This information can be used to improve future SSL designs.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Shining a Light on Some Fundamental Research Opportunities in Semiconductor Photoelectrochemistry

Decades of research in semiconductor photoelectrochemistry have yielded a deep understanding of charge transfer, energetics, and stability at solid−liquid interfaces. Theoretical frameworks developed by Gerischer and contemporaries, together with extensive experimental validation, have clarified the key principles affecting the interfacial kinetics and energetics of semiconductor photoelectrodes. Nevertheless, significant opportunities remain for advances in fundamental understanding of semiconductor photoelectrochemistry. Exciting opportunities include exploiting advances in theory, synthesis, and instrumentation to determine the chemical identity and reactivity of surface states; exerting control of band-edge energetics through molecular-level surface modification processes; and systematically improving emerging photoelectrode protection strategies to enable long-term photoelectrode operation under both oxidative and reductive conditions. Advanced morphologies, such as nanowire and microwire arrays, present new pathways to combine efficient light absorption with effective charge collection and catalyst integration. Unique light−matter interactions during photoelectrochemical deposition of p-type semiconductors readily allow preparation at scale of complex 3D morphologies that are difficult, if not impossible, to access by other methods. Continued exploration of these avenues will expand the fundamental understanding of semiconductor−liquid interfaces and could additionally advance the realization of efficient, stable, and scalable systems for solar fuel generation and other emerging photoelectrochemical applications.

Bean, Paul J. L. [California Institute of Technolo↗

Deciphering between enhanced light emission and absorption in multi-mode porphyrin cavity polariton samples

Abstract It remains unclear how the collective strong coupling of cavity-confined photons to the electronic transitions of molecular chromophore leverages the distinct properties of the polaritonic constituents for future technologies. In this study, we design, fabricate, and characterize multiple types of Fabry-Pérot (FP) mirco-resonators containing copper(II) tetraphenyl porphyrin (CuTPP) to show how cavity polariton formation affects radiative relaxation processes in the presence of substantial non-Condon vibronic coupling between two of this molecule’s excited electronic states. Unlike the prototypical enhancement of Q state radiative relaxation of CuTPP in a FP resonator incapable of forming polaritons, we find the light emission processes in multimode cavity polariton samples become enhanced for cavity-exciton energy differences near those of vibrations known to mediate non-Condon vibronic coupling. We propose the value of this detuning is consistent with radiative relaxation of Herzberg-Teller polaritons into collective molecular states coupled to the cavity photon coherently. We contrast the feature stemming from light emission from the HT polariton state with those that occur due to polariton-enhanced light absorption. Our results demonstrate the landscape of molecular and photonic interactions enabled by cavity polariton formation using complex chromophores and how researchers can design resonators to leverage these interactions to characterize and control polaritonic properties.

Odewale, Elizabeth O.↗

Determination of the major groups of phytoplankton pigments from the absorption spectra of total particulate matter

The contributions of detrital particles and phytoplankton to total light absorption are retrieved by nonlinear regression on the absorption spectra of total particles from various oceanic regions. The model used explains more than 96% of the variance in the observed particle absorption spectra. The resulting absorption spectra of phytoplankton are then decomposed into several Gaussian bands reflecting absorption by phytoplankton pigments. Such a decomposition, combined with high-performance liquid chromatography data on phytoplankton pigment concentrations, allows the computation of specific absorption coefficients for chlorophylls a, b, and c and carotenoids. The spectral values of these in vivo absorption coefficients are then discussed, considering the effects of secondary pigments which were not measured quantitatively. We show that these coefficients can be used to reconstruct the absorption spectra of phytoplankton at various locations and depths. Discrepancies that do occur at some stations are explained in terms of particle size effect. These coefficients can be used to determine the concentrations of phytoplankton pigments in the water, given the absorption spectrum of total particles.

Hoepffner, Nicolas↗

Atmospheric Aerosols

Aerosols, defined as particles and droplets suspended in air, are always present in the atmosphere. They are part of the earth-atmosphere climate system, because they interact with both incoming solar and outgoing terrestrial radiation. They do this directly through scattering and absorption, and indirectly through effects on clouds. Submicrometer aerosols usually predominate in terms of number of particles per unit volume of air. They have dimensions close to the wavelengths of visible light, and thus scatter radiation from the sun very effectively. They are produced in the atmosphere by chemical reactions of sulfur-, nitrogen- and carbon-containing gases of both natural and anthropogenic origins. Light absorption is dominated by particles containing elemental carbon (soot), produced by incomplete combustion of fossil fuels and by biomass burning. Light-scattering dominates globally, although absorption can be significant at high latitudes, particularly over highly reflective snow- or ice-covered surfaces. Other aerosol substances that may be locally important are those from volcanic eruptions, wildfires and windblown dust.

Pueschel, R. F.↗

Tailored Persistent Radical‐containing Heterotrimetal‐Organic Framework for Boosting Efficiency of Visible/NIR Light‐driven Photocatalytic CO 2 Reduction

Abstract Promoting light absorption range of photocatalysts is of great significance to improve solar light‐driven photocatalytic CO 2 reduction efficiency. Herein, a new viologen‐based multicomponent heterotrimetallic metal–organic framework (MOF) [Cu 3 Th 6 ( µ 3 ‐O) 4 ( µ 3 ‐OH) 4 (cpb) 12 ][Fe III (CN) 6 ] 6 (IHEP‐14) with an unprecedented (6, 18)‐connected she ‐ d topology is presented. Upon UV irradiation, this MOF undergoes ligand and iron photoreduction, and a single‐crystal‐to‐single‐crystal transformation to generate persistent radical‐containing MOF [Cu 3 Th 6 ( µ 3 ‐O) 4 ( µ 3 ‐OH) 4 (cpb • ) 12 ][Fe II (CN) 6 ] 6 (IHEP‐15). This radical‐containing MOF shows excellent stability without fading after at least 2 months in air. Besides extending the photoabsorption to a wider wavelength range covering from 200 to 2,500 nm, the generation of persistent radical in IHEP‐15 also largely enhances its CO 2 adsorption capacity by a factor of three due to the strong affinity between π orbital of the radical and the π system of CO 2 . These attributes endow IHEP‐15 with excellent visible/NIR light‐driven CO 2 photoreduction activity, with CO production rates under visible and NIR irradiation of 570.3 and 209.3 µmol h −1 g −1 , respectively. Notably, the latter is a record high for NIR‐induced CO production among all MOFs reported so far.

Hu, Kong‐Qiu↗

Chemical Imaging of Atmospheric Biomass Burning Particles from North American Wildfires

The effects of biomass burning aerosols (BBA) on radiative forcing and cloud formation depend on chemical composition and the internal structures of individual particles within smoke plumes. To improve our understanding of the chemical and physical properties of BBA emitted at different times of the day and their evolution during atmospheric aging, we conducted a study as a part of the Fire Influence on Regional to Global Environments and Air Quality field campaign. Particle samples were collected onboard a research aircraft from smoke plumes from a wildfire in eastern Oregon during late afternoon and nighttime flights on August 28, 2019. A time-resolved aerosol collector was used to collect samples on substrates for offline spectromicroscopic imaging to investigate the single-particle characteristics of BBA particles. Approximately 20,400 individual particles from 10 selected samples were analyzed using computer-controlled scanning electron microscopy coupled with energy-dispersive X-ray microanalysis, revealing their elemental composition, morphology, and viscosity. Elemental microanalysis indicated that aged potassium is likely found in the form of K 2 SO 4 , KNO 3 , and possible K-organic salts. Further chemical speciation and carbon bonding mapping within individual particles were conducted using synchrotron-based scanning transmission X-ray microscopy (STXM) coupled with near edge X-ray absorption fine structure (NEXAFS) spectroscopy. Real-time, water-soluble light absorption measurements were acquired using a particle-into-liquid sampler instrument coupled to a liquid waveguide capillary cell and total organic analyzer. In the late afternoon samples, 65% of the total particle number population consisted entirely of organic components, compared to 46% in the nighttime particles. These differences were attributed to discrepancies in composition at the time of emission and to the daytime condensation and accumulation of photochemically formed secondary organic material on existing BBA particles, a process that halts at night. Microscopy images indicated that particle viscosity was lower in the nighttime particles (<10 1 Pa·s), likely due to increased relative humidity and a higher contribution from hygroscopic inorganic components. The chemical heterogeneity of individual particles was quantified using STXM-derived mixing state parameters. The nature of carbon bonding within individual particles was inferred from the extent of carbon sp 2 hybridization derived from NEXAFS spectra. Average percentages of sp 2 hybridization range between 40% and 60%, with no noticeable differences between late afternoon and nighttime flights. These findings were compared with the online optical properties of both late afternoon and nighttime smoke plumes, providing valuable insights into the complex relationship between chemical composition and optical properties of BBA particles at different times of the day.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Laser activated MTOS microwave device

A light-activated semiconductor device usable as an optoelectronic switch, pulse generator or optical detector is provided. A semiconductor device is disclosed which provides back-to-back metal-thin oxide-silicon (MTOS) capacitors. Each capacitor includes a thin, light-absorptive aluminum electrode which overlies a thin oxide layer and a lightly doped region implanted in an intrinsic silicon substrate.

Maserjian, J.↗

Algal culture studies for CELSS

Microalgae are well-suited as a component of a Closed Environmental Life Support System (CELSS), since they can couple the closely related functions of food production and atmospheric regeneration. The objective was to provide a basis for predicting the response of CELSS algal cultures, and thus the food supply and air regeneration system, to changes in the culture parameters. Scenedesmus growth was measured as a function of light intensity, and the spectral dependence of light absorption by the algae as well as algal respiration in the light were determined as a function of cell concentration. These results were used to test and confirm a mathematical model that describes the productivity of an algal culture in terms of the competing processes of photosynthesis and respiration. The relationship of algal productivity to cell concentration was determined at different carbon dioxide concentrations, temperatures, and light intensities. The maximum productivity achieved by an air-grown culture was found to be within 10% of the computed maximum productivity, indicating that CO2 was very efficiently removed from the gas stream by the algal culture. Measurements of biomass productivity as a function of cell concentration at different light intensities indicated that both the productivity and efficiency of light utilization were greater at higher light intensities.

Radmer, R.↗

Improvement in Suppression of Pulsed Nd:YAG Laser Light With Iodine Absorption Cells for Filtered Rayleigh Scattering Measurements

Filtered Rayleigh scattering using iodine absorption cells is an effective technique for obtaining density, temperature, and velocity measurements in high speed confined flows. By tuning a single frequency laser to a strong iodine absorption line, stray scattered laser light can be greatly suppressed. For example, the minimum transmission predicted by an iodine absorption model calculation is less than 10(exp -5) at the 18788.44/cm line using a 200 mm absorption cell containing iodine vapor at 0.46 T. Measurements obtained by other researches using a CW Nd:YAG laser agree with the model calculations. However, measurements made by us and by others using Q-switched, injection-seeded, frequency doubled Nd:YAG lasers only show minimum transmission of about 3 x 10(exp -3). This greatly reduces the applicability of the filtered Rayleigh scattering technique using these lasers in experiments having large amounts of stray scattered laser light. The purposes of the present study are to characterize the spectrum of the excess light transmitted by the iodine cell and to make changes to the laser to reduce the transmitted laser light. Transmission data as a function of laser frequency for the iodine absorption line at 18788.44/cm are presented. A planar mirror Fabry-Perot interferometer was used to characterize the frequency spectrum of the light passed through the cell. Measurements taken with the laser tuned to the center of the iodine absorption line show the light transmitted through the iodine cell to have a component with a bandwidth of about 40 GHz. This is probably caused by other modes in the laser that exist in spite of the single frequency injection beam. A second broadband component was also observed, possibly caused by the laser flash lamps or by fluorescence. An intracavity etalon was installed in the laser oscillator cavity to suppress the 40 GHz component. Measurements taken with the etalon tuned to the injection frequency showed a reduction in the transmitted laser light. This improvement allows the iodine cell to block significantly more of the stray laser light in filtered Rayleigh scattering experiments. Examples are given of filtered Rayleigh scattering measurements showing the effect of the etalon on measurements taken in a Mach 3 flow in the NASA Lewis 4 inch by 10 inch supersonic wind tunnel.

Seasholtz, Richard G.↗

Reflectance differences between Target and Torch rape cultivars

Spectroradiometric reflectance measurements were made on Target and Torch plants (four and five leaves, respectively) that were growing in 0.09 m2 soil-containing flats. Torch's spectrophotometric single leaf reflectance was consistently lower than Target's at the 650-nm chlorophyll absorption band because Torch's chlorophyll concentration was larger than Target's, which caused more red light absorption. Spectroradiometric measurements indicate that: wet soil strongly absorbs visible light (500 to 700 nm) so that Target's soil-containing flat with 60% plant cover has less reflectance than Torch's soil-containing flat with 75% plant cover; Torch (most foiliage) has higher near-infrared (750 to 1,350 nm) reflectance than Target (least foliage); and the 2,200-nm wavelength is a candidate band to distinguish Target from Torch. The difference in chlorophyll concentrations between Target and Torch, compared with leaf structural differences, is apparently the most important factor that would affect the infrared color film's tonal response to vegetation in the photographic sensitive region (500 to 900 nm).

Gausman, H. W.↗

Extinction of Laser Light Due to Arctic Haze Final Campaign Report

Recent changes in emission patterns may have altered the historical stability of light attenuation strengths within the Arctic and, more specifically, the polar dome. While there have been decades of past and ongoing research on how atmospheric constituents, such as aerosols, affect light absorption, the bulk of this work is focused on the visible region. In recent years, there has been renewed interest in understanding laser light propagation at wavelengths such as 1 and 2 µm in this area. There is a need to evaluate how specific environmental parameters affect the propagation of light in this wavelength region, in particular: the extinction, scattering, and absorption coefficients, and how they relate to particle concentration; cn 2 and refractive index variations. Seasonally dependent variations in particle concentrations and compositions introduce different absorption and scattering characteristics that, in conjunction with varying temperatures, index-of-refraction variations, and wind, can result in laser beam focus and irradiance degradation. Understanding the fundamental influence of these parameters with respect to the propagation of light across a wide spectral band could lead to new insights about the minimal required datastreams required to provide accurate light propagation forecasting.

54 ENVIRONMENTAL SCIENCES↗

Oxygen detection using the laser diode absorption technique

Accurate measurement of the concentration and flow rate of gaseous oxygen is becoming of greater importance. The detection technique presented is based on the principal of light absorption by the Oxygen A-Band. Oxygen molecules have characteristics which attenuate radiation in the 759-770 nm wavelength range. With an ability to measure changes in the relative light transmission to less than 0.01 percent, a sensitive optical gas detection system was configured. This system is smaller in size and light in weight, has low energy requirements and has a rapid response time. In this research program, the application of temperature tuning laser diodes and their ability to be wavelength shifted to a selected absorption spectral peak has allowed concentrations as low as 1300 ppm to be detected.

Disimile, P. J.↗

Silver nanoparticle enhanced metal-organic matrix with interface-engineering for efficient photocatalytic hydrogen evolution

Integrating plasmonic nanoparticles into the photoactive metal-organic matrix is highly desirable due to the plasmonic near field enhancement, complementary light absorption, and accelerated separation of photogenerated charge carriers at the junction interface. The construction of a well-defined, intimate interface is vital for efficient charge carrier separation, however, it remains a challenge in synthesis. Here we synthesize a junction bearing intimate interface, composed of plasmonic Ag nanoparticles and matrix with silver node via a facile one-step approach. The plasmonic effect of Ag nanoparticles on the matrix is visualized through electron energy loss mapping. Moreover, charge carrier transfer from the plasmonic nanoparticles to the matrix is verified through ultrafast transient absorption spectroscopy and in-situ photoelectron spectroscopy. The system delivers highly efficient visible-light photocatalytic H 2 generation, surpassing most reported metal-organic framework-based photocatalytic systems. This work sheds light on effective electronic and energy bridging between plasmonic nanoparticles and organic semiconductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Scalable Manufacturing of Efficient Perovskite/Silicon Tandem Modules

Crystalline-Si (c-Si) technology produces excellent solar cells with conversion efficiencies of up to 26.7%—nearly their practical limit of 27%—and has been commercialized extensively to produce panels below $\$0.40$/W. Techno-economic analysis shows that module efficiency will continue to be a primary cost driver because of high balance-ofsystems costs, and there is no path to higher efficiencies with single-junction silicon cells. In this project, three research teams from University of North Carolina, Arizona State University and National Renewable National Laboratory worked together to develop perovskite-silicon tandem cells with a high throughput process which can handle 5000 wafers per hour, enabled by very low added CAPEX of ~$20k for a doctor-blade coater. This can potentially increase the module efficiency to 30% (with grid) with small increase of cost, which will drive down the cost of silicon modules to be at least 16% cheaper than present silicon PERC modules. We also explored the alternative narrow bandgap perovskites as silicon replacement for all perovskite tandem cells. This project has substantially advanced the progress of solution-process perovskitessilicon tandem solar cells and perovskite-perovskite tandem solar cells with many inventions and discoveries, evidenced by 18 publications and 6 invention disclosures. Several notable examples include 1) we developed the new idea of small pyramid in combination with solution grown perovskites and demonstrated record-efficiency of 28.5% for 1 cm2 on textured silicon bottom cells and 25.2% for 24 cm2 on chemically etched silicon bottom cells for perovskite-silicon tandem cells. 2) We developed perovskite ink that can coat perovskites onto texture silicon without voids;, and new device structure to enhance the yield of fabrication by reducing shunting 3) We identified the origin of open circuit voltage on mixed halide wide bandgap perovskites, and came with a solution for this problem, reducing the voltage loss to a record small value, which can potentially push the perovskite-silicon tandem cell efficiency to over 31%; 4) We have developed efficient alternative low bandgap semiconductors, i.e. gradient-doped Sn based perovskites by Ba ions, new oxide hole transport layers which increase the efficiency of perovskite/perovskite tandem cells reached record efficiency of 26.3%; 5) We developed bifacial perovskite/perovskite tandem cells by overcoming contacts issues and regaining light absorption, further boosting the equivalent efficiency to 29.3% under 1 sun illumination with 30% albedo light; 6) We developed the first all perovskite tandem module fabricated in air by discovery a combination of oxidization and reduction couples, yield an aperture efficiency of 21.6% for all perovskite mininodules, exceeding that of single junction perovskite minimodules. These discoveries not only accelerate the commercialization of perovskite-silicon tandem solar cells, but also provide guidance in designing other type of perovskite solar cell technologies.

14 SOLAR ENERGY↗

Accessing the triplet manifold of naphthalene benzimidazole–phenanthroline in rhenium(i) bichromophores

In this work, the steady-state and ultrafast to supra-nanosecond excited state dynamics of fac-[Re(NBI-phen)(CO) 3 (L)](PF 6 ) (NBI-phen = 16H-benzo[4',5']isoquinolino[2',1':1,2]imidazo[4,5-f][1,10]phenanthrolin-16-one) as well as their respective models of the general molecular formula [Re(phen)(CO) 3 (L)](PF 6 ) (L = PPh 3 and CH 3 CN) has been investigated using transient absorption and time-gated photoluminescence spectroscopy. The NBI-phen containing molecules exhibited enhanced visible light absorption with respect to their models and a rapid formation (<6 ns) of the triplet ligand-centred (LC) excited state of the organic ligand, NBI-phen. These triplet states exhibit an extended excited state lifetime that enable the energized molecules to readily engage in triplet–triplet annihilation photochemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanism of cyanoacetylene photochemistry at 185 and 254 nm

The role of cyanoacetylene (HC3N) in the atmospheric photochemistry of Titan and its relevance to polymer formation are discussed. Investigation of the relative light absorption of HC3N, acetylene (C2H2), and diacetylene (C4H2) revealed that HC3N is an important absorber of UV light in the 205- to 225-nanometer wavelength region in Titan's polar regions. Laboratory studies established that photolysis of C2H2 initiates the polymerization of HC3N even though the HC3N is not absorbing the UV light. Quantum yield measurements establish that HC3N is 2-5 times as reactive as C2H2 for polymer formation. Photolysis of HC3N with 185-nanometer light in the presence of N2, H2, Ar, or CF4 results in a decrease in the yield of 1,3,5-tricyanobenzene (1,3,5-tcb), while photolysis in the presence of CH4, C2H6, or n-C4H10 results in an increase in 1,3,5-tcb. The rate of loss of HC3N is increased by all gases except H2, where it is unchanged. It was not possible to detect 1,3,5-tcb as a photoproduct when the partial pressure of HC3N was decreased to 1 torr. Photolysis of HC3N with 254-nanometer light in the presence of H2 or N2 results in the formation of 1,2,4-tcb, while photolysis in the presence of CH4, C2H6, or n-C4H10 results in the formation of increasing amounts of 1,3,5-tcb. Mechanisms for the formation of polymers are presented.

Non-NASA Center↗