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Solid-state bulk lead halide perovskite thin films have recently shown progress as triplet sensitizers in infrared-to-visible photon upconversion (UC) schemes. Common systems pair lead halide perov...

Summary We investigate the rubrene triplet sensitization by perovskite thin films based on methylammonium formamidinium lead triiodide (MAFA) of varying thicknesses. The power-law dependence of both the MAFA photoluminescence (PL) intensity and upconverted emission is tracked as a function of the incident power density. Bimolecular triplet-triplet annihilation (TTA) exhibits a unique power-law dependence with a slope change from quadratic-to-linear at the threshold Ith. The underlying MAFA PL power-law dependence dictates the power law of the upconverted PL: (1) below Ith, the slope of the upconverted PL is twice the value of the MAFA PL; (2) above Ith, it follows the same power law as the underlying recombination of mobile electrons and holes in the MAFA films. We find that the Ith shifts to subsolar incident laser powers when increasing the MAFA thickness above 30 nm. For the thickest MAFA film of 380 nm we find an upconversion threshold of Ith = 7.1 mW/cm2.

High capital expenditures associated with manufacturing thin silicon wafers make it difficult for the industry to scale up and prevent novel technologies from entering the market. Thin wafers fail largely due to breakage during solar cell processing and handling. One of the root causes for breakage is sub-mm edge cracks in the silicon wafer, and these cracks cannot be reliably detected by most commercially-available crack detection tools. In this work, we first investigate the correlation between wafer thickness and critical crack length, and explain the importance of detecting sub-500-μm edge cracks as the wafer thickness is reduced. Secondly, we extend our previous work of micro-crack detection to demonstrate an edge illumination technique using a near-infrared laser to image edge cracks less than 500 μm in length in multicrystalline silicon. Thirdly, we investigate two fundamental edge illumination mechanisms based on dark-field imaging; namely, direct and vicinal illumination. We will then compare these methods to a state-of-the-art rear illumination method. The advantages and disadvantages of both illumination methods are presented and provide an in-depth analysis of light-crack interaction. In particular, we find that the robustness of vicinal illumination is due to diffuse reflectance. The diffuse reflectance has less dependence on crack configurations, while direct illumination has more dependence on the crack configurations because it utilizes specular reflectance. Our results show that our proposed prototype can detect sub-mm edge cracks in multicrystalline silicon wafers, which is an important step in enabling thin silicon wafer manufacturing.

The role electron-transport layers (ETLs) play in perovskite solar cells (PSCs) is still widely debated. Conduction band alignment at the perovskite/ETL interface has been suggested to be an import...

Triplet-triplet annihilation-based photon upconversion (UC) using bulk perovskite sensitizers has been previously shown to facilitate efficient UC at low fluences. However, the fabrication of the UC devices has not been fully optimized; thus, there is room for improvement. Here, we apply techniques that have been successful in enhancing the performance of perovskite solar cells in order to also improve perovskite-sensitized UC devices. In particular, we investigate the use of a post-fabrication thermal annealing step, overstoichiometric vs stoichiometric addition of PbI2 to the perovskite precursors, methylammonium vs formamidinium cation-rich lead halide perovskite compositions, and the use of different solvents for the annihilator molecules on the perovskite/annihilator interface. We find that excess PbI2 does not significantly affect the UC process, while the perovskite composition is crucial for the yield of extracted carriers across the interface. Comparing toluene and chlorobenzene, we find that the solvent used to deposit the annihilator is also a key factor in the overall device performance. Moreover, we find that thermal annealing of the whole device architecture significantly improves the UC performance by a factor of three.

Silicon dominates contemporary solar cell technologies1. But when absorbing photons, silicon (like other semiconductors) wastes energy in excess of its bandgap2. Reducing these thermalization losses and enabling better sensitivity to light is possible by sensitizing the silicon solar cell using singlet exciton fission, in which two excited states with triplet spin character (triplet excitons) are generated from a photoexcited state of higher energy with singlet spin character (a singlet exciton)3–5. Singlet exciton fission in the molecular semiconductor tetracene is known to generate triplet excitons that are energetically matched to the silicon bandgap6–8. When the triplet excitons are transferred to silicon they create additional electron–hole pairs, promising to increase cell efficiencies from the single-junction limit of 29 per cent to as high as 35 per cent9. Here we reduce the thickness of the protective hafnium oxynitride layer at the surface of a silicon solar cell to just eight angstroms, using electric-field-effect passivation to enable the efficient energy transfer of the triplet excitons formed in the tetracene. The maximum combined yield of the fission in tetracene and the energy transfer to silicon is around 133 per cent, establishing the potential of singlet exciton fission to increase the efficiencies of silicon solar cells and reduce the cost of the energy that they generate. A silicon and tetracene solar cell employing singlet fission uses an eight-angstrom-thick hafnium oxynitride interlayer to promote efficient triplet transfer, increasing the efficiency of the cell.

In this review, we highlight the current advancements in the field of triplet sensitization by three-dimensional (3D) perovskite nanocrystals and bulk films. First introduced in 2017, 3D perovskite sensitized upconversion (UC) is a young fast-evolving field due to the tunability of the underlying perovskite material. By tuning the perovskite bandgap, visible-to-ultraviolet, near-infrared-to-visible or green-to-blue UC has been realized, which depicts the broad applicability of this material. As this research field is still in its infancy, we hope to stimulate the field by highlighting the advantages of these perovskite nanocrystals and bulk films, as well as shedding light onto the current drawbacks. In particular, the keywords toxicity, reproducibility and stability must be addressed prior to commercialization of the technology. If successful, photon interconversion is a means to increase the achievable efficiency of photovoltaic cells beyond its current limits by increasing the window of useable wavelengths.

Microcracks in silicon solar cells reduce the mechanical strength of the wafer and cause breakage during manufacturing, transportation, and field operation. Therefore, there is a need to trace where microcracks initiate in the manufacturing line. As wafers become thinner, the critical crack length required for fracture significantly decreases for the same loading conditions. Currently, very few industry-standard tools can reliably detect submillimeter cracks, which will become more critical for thinner wafers. In this work, we demonstrate a technique to detect submillimeter cracks located at the edges of various multicrystalline silicon wafers and solar cells. The proposed technique, which is based on near-infrared dark-field imaging with vicinal laser illumination from the wafer edge, has several advantages over state-of-the-art optical transmission imaging and dark-field scattering techniques. Moreover, we adapt this technique to achieve the high-throughput requirement of inline metrology; hence, it can be used to detect submillimeter cracks in a manufacturing line. With a high-frame-rate line-scan camera, this proposed crack technique is designed to theoretically achieve a scanning throughput of less than 1 s per wafer.

Photon upconversion, particularly via triplet–triplet annihilation (TTA), could prove beneficial in expanding the efficiencies and overall impacts of optoelectronic devices across a multitude of technologies. The recent development of bulk metal halide perovskites as triplet sensitizers is one potential step toward the industrialization of upconversion-enabled devices. Here, we investigate the impact of varying additions of bromide into a lead iodide perovskite thin film on the TTA upconversion process in the annihilator molecule rubrene. We find an interplay between the bromide content and the overall device efficiency. In particular, a higher bromide content results in higher internal upconversion efficiencies enabled by more efficient charge extraction at the interface likely due to a more favorable band alignment. However, the external upconversion efficiency decreases as the absorption cross section in the near infrared is reduced. The highest upconversion performance is found in our study for a bromide content of 5%. This result can be traced back to a high absorption cross section in the near infrared and higher photoluminescence quantum yield in comparison to the iodide-only perovskite and an increased driving force for charge transfer.

Bismuth-based materials have been studied as alternatives to lead-based perovskite materials for photovoltaic applications. However, poor film quality has limited device performance. In this work, we developed a solvent-engineering method and show that it is applicable to several bismuth-based compounds. Through this method, we obtained compact films of methylammonium bismuth iodide (MBI), cesium bismuth iodide (CBI), and formamidinium bismuth iodide (FBI). On the basis of film growth theory and experimental analyses, we propose a possible mechanism of film formation. Additionally, we demonstrate that the resultant compact MBI film is more suitable to fabricate efficient and stable photovoltaic devices compared to baseline MBI films with pinholes. We further employed a new hole-transporting material to reduce the valence-band offset with the MBI. The best-performing photovoltaic device exhibits an open-circuit voltage of 0.85 V, fill factor of 73%, and a power conversion efficiency of 0.71%, the highest r...

Light- and elevated temperature-induced degradation (LeTID) is a detrimental effect observed under operating conditions in p-type multicrystalline silicon (mc-Si) solar cells. In this contribution, we employ synchrotron-based techniques to study the dissolution of precipitates due to different firing processes at grain boundaries in LeTID-affected mc-Si. The synchrotron measurements show clear dissolution of collocated metal precipitates during firing. We compare our observations with degradation behavior in the same wafers. The experimental results are complemented with process simulations to provide insight into the change in bulk point defect concentration due to firing. Several studies have proposed that LeTID is caused by metal-rich precipitate dissolution during contact firing, and we find that the solubility and diffusivity are promising screening metrics to identify metals that are compatible with this hypothesis. While slower and less soluble elements (e.g., Fe and Cr) are not compatible according to our simulations, the point defect concentrations of faster and more soluble elements (e.g., Cu and Ni) increase after a high-temperature firing process, primarily due to emitter segregation rather than precipitate dissolution. These results are a useful complement to lifetime spectroscopy techniques, and can be used to evaluate additional candidates in the search for the root cause of LeTID.

Recent advances in perovskite-sensitized photon upconversion via triplet-triplet annihilation (TTA) in rubrene have yielded several unanswered questions about the underlying mechanism and processes occurring at the interface. In particular, the near-infrared perovskite emission is not significantly quenched and a rapid reversible photobleach of the upconverted emission can be observed under fairly low excitation densities of 3.2 mW/cm2. In this contribution, we investigate the perovskite/organic interface in more detail and conclude that non-covalent interactions between the organic layer and perovskite result in surface trap passivation. In addition, band bending results in a charge space region at the perovskite/rubrene interface, which precharges the rubrene interface with holes. Upon initial illumination, electrons can rapidly transfer to the excited triplet state of rubrene, followed by efficient TTA upconversion. As the device is continuously illuminated, the precharged holes are consumed and a new equilibrium is reached, resulting in the previously investigated steady-state upconversion efficiency.

Crystalline silicon comprises 90% of the global photovoltaics (PV) market and has sustained a nearly 30% cumulative annual growth rate, yet comprises less than 2% of electricity capacity. To sustain this growth trajectory, continued cost and capital expenditure (capex) reductions are needed. Thinning the silicon wafer well below the industry-standard 160 μm, in principle reduces both manufacturing cost and capex, and accelerates economically-sustainable expansion of PV manufacturing. In this analysis piece, we explore two questions surrounding adoption of thin silicon wafers: (a) What are the market benefits of thin wafers? (b) What are the technological challenges to adopt thin wafers? In this analysis, we re-evaluate the benefits and challenges of thin Si for current and future PV modules using a comprehensive technoeconomic framework that couples device simulation, bottom-up cost modeling, and a sustainable cash-flow growth model. When adopting an advanced technology concept that features sufficiently good surface passivation, the comparable efficiencies are achievable for both 50 μm wafers and 160 μm ones. We then quantify the economic benefits for thin Si wafers in terms of poly-Si-to-module manufacturing capex, module cost, and levelized cost of electricity (LCOE) for utility PV systems. Particularly, LCOE favors thinner wafers for all investigated device architectures, and can potentially be reduced by more than 5% from the value of 160 μm wafers. With further improvements in module efficiency, an advanced device concept with 50 μm wafers could potentially reduce manufacturing capex by 48%, module cost by 28%, and LCOE by 24%. Furthermore, we apply a sustainable growth model to investigate PV deployment scenarios in 2030. It is found that the state-of-the-art industry concept could not achieve the climate targets even with very aggressive financial scenarios, therefore the capex reduction benefit of thin wafers is advantageous to facilitate faster PV adoption. Lastly, we discuss the remaining technological challenges and areas for innovation to enable high-yield manufacturing of high-efficiency PV modules with thin Si wafers., U.S. Department of Energy (DOE) (Award DE-EE0007535)

Reducing silicon usage by adopting thinner wafers can significantly reduce capital expenditure (capex) and cost, and thus accelerate the growth of manufacturing capacity and deployment. In this work, we evaluated potential benefits of thin Si wafers for current and future PV modules. We apply a technoeconomic framework that couples bottom-up cost model, and a cash-flow growth model to analyze PV modules with thin wafers. First, we show that, comparing the current PERC with 160 µm thick wafers to the high-efficiency concept with 50 µm thin wafers, the capex is reduced from 0.39 to 0.2 $/(W/year) while the cost is from 0.32 to 0.2 $/W. Second, the potential of accelerated deployment is analyzed for the high-efficiency thin wafer concept. We found the significant advantages of higher growth rate (~20% relative) and higher deployment plateau (~3 times) than the current PERC modules.

Photon upconversion via triplet–triplet annihilation could allow for the existing efficiency limit of single junction solar cells to be surpassed. Indeed, efficient upconversion at subsolar fluences has been realized in bulk perovskite-sensitized systems. Many questions have remained unanswered, in particular, regarding their behavior under photovoltaic operating conditions. Here, we investigate the impact of repeated and continuous illumination on bilayer perovskite/rubrene upconversion devices. We find that variations of the underlying perovskite carrier recombination dynamics greatly impact the upconversion process. Trap filling and triplet sensitization are in direct competition: more saturated trap states in the perovskite and, thus, longer underlying perovskite photoluminescence lifetimes allow for an increased number of carriers to diffuse to the perovskite/rubrene interface and undergo charge extraction to the triplet state of rubrene. As a result, the upconversion efficiency is greatly influenced by the underlying trap density: the upconverted photoluminescence intensity increases by two orders of magnitude under continuous illumination for 4 h. This shows that the upconversion efficiency is difficult to define for this system. Importantly, these results indicate that perovskite-sensitized upconversion devices exhibit peak performance under continuous illumination, which is a requirement for their successful integration into photovoltaics to help overcome the Shockley–Queisser limit in single junction solar cells.

The recent spotlight on supported nanoparticles (NPs) has attracted attention in the field of catalysis and fuel cell technology. Supported NPs can be used as model catalysts to gain a fundamental understanding of the catalytic properties at the interface. Here, especially the wet-chemical preparation of platinum NPs in alkaline ethylene glycol is a powerful approach to synthesize stable particles with a narrow size distribution in the nanometer regime. We combine high resolution imaging by scanning tunneling microscopy with electrochemical characterization by cyclic voltammetry to gain insights into the underlying degradation mechanism of supported platinum NPs, paving the way toward a rational design of supported catalysts with controlled activity and stability.

Nanometer-sized metal clusters are prime candidates for photoactivated catalysis, based on their unique tunable optical and electronic properties, combined with a large surface-to-volume ratio. Due to the very small optical cross sections of such nanoclusters, support-mediated plasmonic activation could potentially make activation more efficient. Our support is a semi-transparent gold film, optimized to work in a back-illumination geometry. It has a surface plasmon resonance excitable in the 510–540 nm wavelength range. Ptn clusters (size distribution peaked at n = 46 atoms) have been deposited onto this support and investigated for photoactivated catalytic performance in the oxidative decomposition of methylene blue. The Pt cluster catalytic activity under illumination exceeds that of the gold support by more than an order of magnitude per active surface area. To further investigate the underlying mechanism of plasmon-induced catalysis, the clusters have been imaged with optically-assisted scanning tunneling microscopy under illumination. The photoactivation of the Pt clusters via plasmonic excitation of the support and subsequential electronic excitation of the clusters can be imaged with nanometer resolution. The light-induced tunneling current on the clusters is enhanced relative to the gold film support.

Correction for ‘Revisiting thin silicon for photovoltaics: a technoeconomic perspective’ by Zhe Liu et al., Energy Environ. Sci., 2020, 13, 12–23, DOI: 10.1039/C9EE02452B.

Lead halide-based perovskite thin films have attracted great attention due to the explosive increase in perovskite solar cell efficiencies. The same optoelectronic properties that make perovskites ideal absorber materials in solar cells are also beneficial in other light-harvesting applications and make them prime candidates as triplet sensitizers in upconversion via triplet-triplet annihilation in rubrene. In this contribution, we take advantage of long carrier lifetimes and carrier diffusion lengths in perovskite thin films, their high absorption cross sections throughout the visible spectrum, as well as the strong spin-orbit coupling owing to the abundance of heavy atoms to sensitize the upconverter rubrene. Employing bulk perovskite thin films as the absorber layer and spin-mixer in inorganic/organic heterojunction upconversion devices allows us to forego the additional tunneling barrier owing from the passivating ligands required for colloidal sensitizers. Our bilayer device exhibits an upconversion efficiency in excess of 3% under 785 nm illumination.

The same optical and electronic properties that make perovskite thin films ideal absorber materials in photovoltaic applications are also beneficial in photon upconversion devices. In this contribution, we investigate the rubrene-triplet sensitization by perovskite thin films based on methylammonium formamidinium lead triiodide (MAFA). To elucidate the role of trap states which affect the free carrier lifetimes, we fabricate MAFA perovskite thin films with three different thicknesses. By measuring the change in the photoluminescence properties under different excitation fluences, we find that the prevalent recombination mechanism shifts from monomolecular for thinner films to bimolecular recombination for thicker MAFA films, indicating a reduction in shallow trap-assisted recombination. The addition of rubrene shows a passivating effect on the MAFA surface, but adds an additional quenching pathway due to charge transfer to the triplet state of rubrene. We observe that the threshold for efficient triplet-triplet annihilation shifts to lower incident powers with increasing MAFA thickness, which suggests that the charge transfer to the triplet state competes with non-radiative trap filling. Hence, injection of free electrons and holes into the upconverting organic semiconductor can provide a new avenue for sensitization of rubrene, and may allow us to move away from the necessity of efficient excitonic singlet-to-triplet converters.

By harvesting sub-bandgap photons, we have a path to overcome the Shockley-Queisser limit in photovoltaics (PVs). We investigate semiconductor nanocrystal (NC) sensitized upconversion via triplet-triplet annihilation (TTA) in organic semiconductors (OSCs). Since this process relies on optically inactive triplet states in the OSCs, we utilize PbS NCs to directly sensitize the triplet state via energy transfer. This is possible due to the strong spin-orbit coupling in PbS NCs, resulting in rapid spin-dephasing of the exciton. Current technology allows for upconversion of light with a photon energy above $\sim 1.1$ eV. However, while internal efficiencies are rapidly improving, the low external device efficiencies render them impractical for applications, as devices are based on a single monolayer of NCs. Our results show simply increasing the PbS NC film thickness does not show improvement in the efficiency due to poor exciton transport between PbS NCs. Here, we present a new strategy to increase the external upconversion efficiency by utilizing thin tinbased halide perovskites as the absorbing layer. Resonant energy transfer from the perovskite to the PbS NCs allows for subsequent sensitization of the triplet state in rubrene.

The high capital expenditure (capex) necessary to manufacture crystalline silicon PV modules negatively affects the levelized cost of electricity (¢/kWh) and critically impacts the rate at which the PV industry can scale up. Wafer, cell, and module fabrication with thin free-standing silicon wafers is one key to reduce capex. Thin wafers reduce capex associated with silicon refining and wafer fabrication, which together sum to 58% of the total capex of silicon module manufacturing. In addition, thin wafers directly and significantly reduce variable costs. However, introducing 50 μm thin free-standing wafers into today's manufacturing lines result in cracking, creating a yield-based disincentive. Due to the brittle nature of silicon, wafer breakage is the major concern due to the high stress that is induced during processes in manufacturing lines. In this paper, we describe an improved method for edge micro-crack detection that can help enable low-capex, thin free-standing Si wafers. We present a method of detecting and measuring cracks along wafer edges by using a dark-field IR scattering imaging technique which enables detection of edge cracks at the micron scale. Keywords: Capex; polysilicon; thin free-standing wafer; edge crack detection; IR scattering; dark-field imaging, United States. Department of Energy (Grant DE-EE0007535)

The root cause of light- and elevated temperature-induced degradation (LeTID) in multicrystalline silicon p-type passivated emitter and rear cell (PERC) devices is still unknown. Some researchers hypothesize that high temperature firing processes dissolve metal-rich precipitates which can then participate in LeTID. To address this hypothesis, synchrotron-based X-ray techniques, including fluorescence and absorption near-edge spectroscopy, are employed. In as-grown industrial material, we observe collocated copper- and nickel-rich precipitates, which persist after firing and are below the detection limit after phosphorous diffusion. We conclude that precipitates decrease in size due to the firing process and that this may result in an increase in bulk interstitial metal concentration. We further employ microphotoluminescence at a grain versus grain boundary to highlight similarities and possible differences in degradation and regeneration behavior.

Atomically flat, conductive, and transparent noble metal films are produced to extend the wavelength range of room-temperature single-molecule optical absorption detected by scanning tunneling microscopy (SMA-STM). Gold films grown on a platinum underlayer to 15 nm total thickness, deposited by electron beam evaporation onto c-plane sapphire substrates, show sufficient light transmission for backside illumination for laser-assisted STM experiments. Low resistance, transparency, and the atomically flat island surfaces make these good substrates for SMA-STM studies. Monte Carlo lattice kinetics were simulated to allow for a better understanding of the growth modes of the Pt–Au films and of the achieved morphologies. SMA-STM is detected for a quantum dot deposited by aerosol spraying onto Pt–Au films, demonstrating the suitability of such films for single-molecule absorption spectroscopy studies.

Nature employs self-assembly to fabricate the most complex molecularly precise machinery known to man. Heteromolecular, two-dimensional self-assembled networks provide a route to spatially organize different building blocks relative to each other, enabling synthetic molecularly precise fabrication. Here we demonstrate optoelectronic function in a near-to-monolayer molecular architecture approaching atomically defined spatial disposition of all components. The active layer consists of a self-assembled terrylene-based dye, forming a bicomponent supramolecular network with melamine. The assembly at the graphene-diamond interface shows an absorption maximum at 740 nm whereby the photoresponse can be measured with a gallium counter electrode. We find photocurrents of 0.5 nA and open-circuit voltages of 270 mV employing 19 mW cm−2 irradiation intensities at 710 nm. With an ex situ calculated contact area of 9.9 × 102 μm2, an incident photon to current efficiency of 0.6% at 710 nm is estimated, opening up intriguing possibilities in bottom-up optoelectronic device fabrication with molecular resolution., Two-dimensional, self-assembled heteromolecular networks often lack functionality. Here the authors study the photoresponse of self-assembled heteromolecular networks, while controlling their positions and interfaces at an atomic level, suggesting bottom-up assembly of optoelectronics devices.