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Diffractive Multiplexing for High-Throughput Roll-to-Roll Laser Patterning of Flexible Organic Photovoltaic Modules (Final Report)
The purpose of this project is to demonstrate a cost-effective, high-throughput roll-to-roll (R2R) process for patterning of flexible, semitransparent organic photovoltaic (OPV) modules by developing diffractive optics-based laser multiplexing (DOL Multiplexing). DOL Multiplexing allows a single, high-powered laser source to perform parallel scribing across the R2R web width in a manner compatible with high process speeds. Such a process could have enormous benefits in terms of increased process speeds and reduced costs, both up-front capital costs, and long-term operational costs, over galvanometer-based step and scan methods or many-laser systems.
Rapid Open-Air Processing of Low-Cost Perovskite Solar Modules
We report an industrially relevant approach to both scalable and fast open-air perovskite photovoltaic (PV) module production. This work resolves some of the most formidable barriers to module-level scaling that the perovskite community has been facing. Key advances include scalable large-area spray deposition, new monolithic integration scribing techniques, advanced photoluminescence characterization, and reproducible high-throughput manufacturability. Our rapid spray processing techniques enabled the highest perovskite PV efficiency produced in open-air. Innovations in scribing techniques enabled the first single-source laser process to achieve perovskite module monolithic integration and technoeconomic analysis led to a comprehensive cost model for perovskite module manufacturing. We report significant progress in reducing perovskite manufacturing costs necessary to potentially compete with incumbent Si-based PV for utility-scale power generation.
Crystalline Si Surface Passivation with Nafion for Bulk Defects Detection with Electron Paramagnetic Resonance
Here, in monocrystalline Si (c-Si) solar cells, identification and mitigation of bulk defects are crucial to achieving a high photoconversion efficiency. To spectroscopically detect defects in the c-Si bulk, it is desirable to passivate the surface defects. Passivation of the c-Si surface with dielectrics such as Al 2 O 3 and SiNx requires deposition at elevated temperatures, which can influence defects in the bulk. Herein, we report on the passivation of different Czochralski (Cz) Si wafer surfaces by an organic copolymer, Nafion. We test the efficacy of the surface passivation at temperatures ranging from 6 to 473 K to detect bulk defects using electron paramagnetic resonance (EPR) spectroscopy. By comparing with state-of-the-art passivation layers, including Al 2 O 3 and liquid HF/HCl, we found that at room temperature, Nafion can provide comparable passivation of n-type Cz Si with an implied open-circuit voltage (iV oc ) of 713 mV and a recombination current prefactor J o of 5 fA/cm 2 . For p-type Cz Si, we obtained an iV oc of 682 mV with a J o of 22.4 fA/cm 2 . Scanning electron microscopy and photoluminescence reveal that Nafion can also be used to passivate the surface of c-Si solar cell fragments scribed from a solar cell module by using a laser. Consistent with previous studies, analysis of the EPR spectroscopy data confirms that the H-terminated surface is necessary, and fixed negative charge in Nafion is responsible for the field-effect passivation. While the surface passivation quality was maintained for almost 24 h, which is sufficient for spectroscopic measurements, the passivation degraded over longer durations, which can be attributed to surface SiO x growth. These results show that Nafion is a promising room-temperature surface passivation technique to study bulk defects in c-Si.
LeTID-Affected Cells from a Utility-Scale Photovoltaic System Characterized by Deep Level Transient Spectroscopy
Photovoltaic modules from a utility-scale field experienced power loss by light- and elevated temperature-induced degradation (LeTID). Samples of one of the affected monocrystalline silicon cells were cored and extracted from the module packaging and encapsulation. One of the cell fragments was processed using a regeneration cycle of applying short-circuit-rated current in forward bias at 85 degrees C for 2 weeks, while the other fragment was kept in its outdoor-degraded LeTID state. Both samples were scribed to form 2-mm diameter isolated areas using a femtosecond-pulse-width laser micromachining system. Both isolated areas contained front grid line segments which were wire bonded to larger contact pads, and the samples were probed in a cryostat linked to a deep-level transient spectroscopy (DLTS) system. Using DLTS, a majority-carrier, hole-trap defect was detected on each sample with an activation energy of 0.42 eV. The LeTID-degraded sample, however, had a larger signal corresponding to a trap density of 1.1x10^13 cm-3, which was about five times larger than the 2.1x10^12 cm-3 trap density of the regenerated sample.
Laser-Interference Surface Preparation for Enhanced Coating Adhesion and Adhesive Joining of Multi-Materials (Final Project Report)
This report investigates a laser-interference surface treatment as a non-contact, i.e., without major solid/liquid medium application or abrasion, and non-chemical surface preparation method for aerospace coating systems. It was proposed to use the laser-interference technique to structure surfaces of Al and/or Ti, creating "rough" surfaces with pre-engineered series of ridges and valleys at submicron scale. The science goal of this study was to develop an understanding of the surface microstructure, topology, and physical mechanisms that would improve adhesion and corrosion protection of Al2024-T3. Microstructure analysis indicates that the laser-interference structuring (LIS) was found to reduce the formation of CuMn-rich precipitates in Al 2024-T3 over a 500-800 nm depth from top surface. The X-cut and cross-hatch coating adhesion ratings indicate that the LIS specimens meet the performance requirements in the coating adhesion specifications by having a higher or identical ranking to those specimens prepared with current state-of-the-art chemical conversion or sulfuric acid anodizing. After the ASTM B117 corrosion exposure, it was found that the laser processed specimens exhibited only few blisters. It was found that the corrosion damage was minimized at a laser rastering speed of 4 mm/s, for which only 33% of specimens developed very minor corrosion damage. The ASTM D1654 creepage ratings, used to evaluate corrosion damage along the scribe lines, were found to be at least nine for all coated panels. These results indicate that the laser-interference technique with the additional acetone wiping has the potential to be further developed as a minor chemical surface preparation technique for chromate-containing epoxy primers coatings.
Field‐Relevant Degradation Mechanisms in Metal Halide Perovskite Modules
Field testing, failure analysis, and understanding of degradation mechanisms are essential to advancing metal halide perovskite (MHP) photovoltaic (PV) technology toward commercialization. Here, we present performance data from up to 1 year of outdoor testing of MHP modules in Golden, Colorado. The module encapsulation architecture and encapsulant materials have a significant impact on module reliability, with modules containing a polyolefin elastomer (POE) in addition to a desiccated polyisobutylene (PIB) edge seal outlasting modules with only a PIB edge seal or PIB blanket. Nondestructive and destructive characterization of the field-tested modules points to module scribes and interfaces as areas of potential mechanical weakness and chemical migration, resulting in shunt pathways and increased series resistance. Finally, indoor accelerated stress testing with light and elevated temperatures is performed, demonstrating failure with similar scribe degradation signatures as compared to the field-tested modules. In conclusion, under both outdoor testing and light and elevated temperature conditions, electrochemical corrosion between the copper electrode and the mobile iodine ions appeared dominant, with a significant progression at the scribes that is speculated to result from an interplay between the initial laser damage and joule heating from enhanced ion diffusion under bias.
Corrosion Behavior of Laser-Interference Structured AA2024 Coated with a Chromate-Containing Epoxy Primer
In this study, the corrosion behavior of laser-interference treated AA2024-T3 specimens, which are coated with a primer, is presented. The surface of as-received AA2024-T3 specimens were laser-interference structured by splitting the primary beam of a Q-switched Nd:YAG pulsed nanosecond laser into two beams and focusing them to the same spot on the specimen surface. After being stored in plastic cases for up to 70 d, without any additional cleaning, the specimens were spray painted with a chromate-containing epoxy primer, CA7233, compliant to MIL-PRF-23377 Type I Class C2 specification. The corrosion behavior of laser-interference specimens was assessed against that of specimens prepared by chromated conversion coating and sulfuric acid anodizing treatments. After the ASTM B117 corrosion exposure, it was found that the laser processed specimens exhibited only few blisters. On one hand, most specimens prepared at a laser fluence of 1.78 J/cm 2 , without any additional chemical cleaning, were found to develop one very small blister after only 96 h of exposure. However, the growth of these blisters was not significant even after 1,000 h of salt spray exposure. On the other hand, only a fraction of the specimens prepared at a laser fluence of 1.24 J/cm 2 and acetone wiped right after the laser structuring were found to develop several tiny blisters after 790 h and longer exposure. Overall, it was found that the corrosion damage was minimized at a laser rastering speed of 4 mm/s, a condition for which only 33% of specimens developed very minor corrosion damage. Furthermore, the ASTM D1654 creepage ratings, which was used to evaluate the corrosion damage along the scribe lines, were found to be at least nine for all coated panels. These results indicate that the laser-interference technique with the additional acetone wiping has the potential to be further developed as a nonchemical surface preparation technique for chromate-containing epoxy primers coating systems.
Direct laser writing of volumetric gradient index lenses and waveguides
Abstract Direct laser writing (DLW) has been shown to render 3D polymeric optical components, including lenses, beam expanders, and mirrors, with submicrometer precision. However, these printed structures are limited to the refractive index and dispersive properties of the photopolymer. Here, we present the subsurface controllable refractive index via beam exposure (SCRIBE) method, a lithographic approach that enables the tuning of the refractive index over a range of greater than 0.3 by performing DLW inside photoresist-filled nanoporous silicon and silica scaffolds. Adjusting the laser exposure during printing enables 3D submicron control of the polymer infilling and thus the refractive index and chromatic dispersion. Combining SCRIBE’s unprecedented index range and 3D writing accuracy has realized the world’s smallest (15 µm diameter) spherical Luneburg lens operating at visible wavelengths. SCRIBE’s ability to tune the chromatic dispersion alongside the refractive index was leveraged to render achromatic doublets in a single printing step, eliminating the need for multiple photoresins and writing sequences. SCRIBE also has the potential to form multicomponent optics by cascading optical elements within a scaffold. As a demonstration, stacked focusing structures that generate photonic nanojets were fabricated inside porous silicon. Finally, an all-pass ring resonator was coupled to a subsurface 3D waveguide. The measured quality factor of 4600 at 1550 nm suggests the possibility of compact photonic systems with optical interconnects that traverse multiple planes. SCRIBE is uniquely suited for constructing such photonic integrated circuits due to its ability to integrate multiple optical components, including lenses and waveguides, without additional printed supports.
Low loss fiber-coupled volumetric interconnects fabricated via direct laser writing
Photonic integrated circuits (PICs) are vital for high-speed data transmission. However, optical routing is limited in PICs composed of only one or a few stacked planes. Further, coupling losses must be low in deployed systems. Previously, we developed the subsurface controllable refractive index via beam exposure (SCRIBE) technique to write accurate 3D gradient refractive index (GRIN) profiles within a mesoporous silica scaffold. Here, we apply SCRIBE to fabricate low loss, broadband, polarization insensitive, fiber-coupled, single-mode volumetric interconnects that include waveguides traversing arbitrary 3D paths. By seamlessly integrating mode-matching subsurface lenses and GRIN waveguide tapers, calibrating for positional writing errors, implementing multipass exposure, automating alignment, and switching to antireflection coated fibers, we reduced the insertion loss for a fiber-PIC-fiber interconnect from 50 to 2.14 dB, or 1.47 dB, excluding the fiber array’s loss. Further, we establish an upper bound of 0.45 dB loss per coupler. We report quality factors of 27,000 and 77,000 and bending losses of 6 and 3 dB/cm for 15 and 30 µm radii microrings, respectively. We also demonstrate Bézier escalators, polarization-rotating and polarization-splitting interconnects, and a seven-channel 25 µm pitch volumetric interconnect. The SCRIBE platform presents a clear path toward realizing 3D PICs with unique functionality.
Evaluating Interconnection Schemes for Semi-Transparent Perovskite Mini-Modules
This work evaluates the critical issues surrounding P1, P2, and P3 scribing for semi-transparent perovskite module integration. We find that P1 scribing procedures are well-translated from other thin-film technologies. P2 scribing is best performed with a mechanical scribe, but remains a source of series resistance. P3 scribing is found to cause an increase in scribing dead area and a potential degradation source.
UV-Enabled Defect Engineering in Multilayer GaSe and InSe and UV Writing of the Grating Pattern
III–VI post-transition-metal chalcogenides are layered semiconductor materials that exhibit direct band gaps in multilayers. Defect engineering is essential in 2D layered semiconductors for functional devices. Here, in this work, we report defect engineering in multilayer gallium selenide (GaSe) and indium selenide (InSe), where defects generated by ultraviolet (UV, 325 nm) laser irradiation result in an additional photoluminescence (PL) line. The additional PL line is due to defect-bound excitons. Characteristics of the defect emission are similar in GaSe and InSe samples subjected to UV irradiation, air annealing, and hydrostatic pressure. Two-beam UV interference was applied to create grating patterns with a periodic array of low and high densities of defects in GaSe. Density functional theory has identified the defect type in GaSe. The results provide valuable insights into defect generation and UV scribing of photonic circuits in 2D Se-based multilayers for optical integration in a 2D platform.