Circular economy priorities for photovoltaics in the energy transition.

Among the many ambitious decarbonization goals globally, the US intends grid decarbonization by 2035, requiring 1 TW of installed photovoltaics (PV), up from ~110 GW in 2021. This unprecedented global scale-up will stress existing PV supply chains with increased material and energy demands. By 2050, 1.75 TW of PV in the US cumulatively demands 97 million metric tonnes of virgin material and creates 8 million metric tonnes of life cycle waste. This analysis leverages the PV in Circular Economy tool (PV ICE) to evaluate two circular economy approaches, lifetime extension and closed-loop recycling, on their ability to reduce virgin material demands and life cycle wastes while meeting capacity goals. Modules with 50-year lifetimes can reduce virgin material demand by 3% through reduced deployment. Modules with 15-year lifetimes require an additional 1.2 TW of replacement modules to maintain capacity, increasing virgin material demand and waste unless >90% of module mass is closed-loop recycled. Currently, no PV technology is more than 90% closed-loop recycled. Glass, the majority of mass in all PV technologies and an energy intensive component with a problematic supply chain, should be targeted for a circular redesign. Our work contributes data-backed insights prioritizing circular PV strategies for a sustainable energy transition.

Thermomechanical Lift-Off and Recontacting of CdTe Solar Cells.

Controlled delamination of thin-film photovoltaics (PV) post-growth can reveal interfaces that are critical to device performance yet are poorly understood because of their inaccessibility within the device stack. In this work, we demonstrate a technique to lift off thin-film solar cells from their glass substrates in a clean, reproducible manner by first laminating a polymeric backsheet to the device and then thermally shocking the system at low temperatures ( T ≤ -30 °C). To enable clean delamination of diverse thin-film architectures, a theoretical framework is developed and key process control parameters are identified. Focusing on cadmium telluride (CdTe) devices, we show that the lamination temperature and device architecture control the quality of lift-off, while the rate at which the film stack is removed is controlled by the delamination temperature. Crack-free CdTe devices are removed and successfully recontacted, recovering up to 80% of the original device efficiency. The areal density of these devices is ∼0.4 kg m-2, a reduction of over an order of magnitude relative to their initial weight on glass. The framework developed here provides a pathway toward both the development of inexpensive, flexible PV with high specific power and the study of previously buried interfaces in thin-film architectures.

Self-compensation in arsenic doping of CdTe.

Efficient p-type doping in CdTe has remained a critical challenge for decades, limiting the performance of CdTe-based semiconductor devices. Arsenic is a promising p-type dopant; however, reproducible doping with high concentration is difficult and carrier lifetime is low. We systematically studied defect structures in As-doped CdTe using high-purity single crystal wafers to investigate the mechanisms that limit p-type doping. Two As-doped CdTe with varying acceptor density and two undoped CdTe were grown in Cd-rich and Te-rich environments. The defect structures were investigated by thermoelectric-effect spectroscopy (TEES), and first-principles calculations were used for identifying and assigning the experimentally observed defects. Measurements revealed activation of As is very low in both As-doped samples with very short lifetimes indicating strong compensation and the presence of significant carrier trapping defects. Defect studies suggest two acceptors and one donor level were introduced by As doping with activation energies at ~88 meV, ~293 meV and ~377 meV. In particular, the peak shown at ~162 K in the TEES spectra is very prominent in both As-doped samples, indicating a signature of AX-center donors. The AX-centers are believed to be responsible for most of the compensation because of their low formation energy and very prominent peak intensity in TEES spectra.

Two-Dimensional Cadmium Chloride Nanosheets in Cadmium Telluride Solar Cells.

In this study we make use of a liquid nitrogen-based thermomechanical cleavage technique and a surface analysis cluster tool to probe in detail the tin oxide/emitter interface at the front of completed CdTe solar cells. We show that this thermomechanical cleavage occurs within a few angstroms of the SnO2/emitter interface. An unexpectedly high concentration of chlorine at this interface, ∼20%, was determined from a calculation that assumed a uniform chlorine distribution. Angle-resolved X-ray photoelectron spectroscopy was used to further probe the structure of the chlorine-containing layer, revealing that both sides of the cleave location are covered by one-third of a unit cell of pure CdCl2, a thickness corresponding to about one Cl-Cd-Cl molecular layer. We interpret this result in the context of CdCl2 being a true layered material similar to transition-metal dichalcogenides. Exposing cleaved surfaces to water shows that this Cl-Cd-Cl trilayer is soluble, raising questions pertinent to cell reliability. Our work provides new and unanticipated details about the structure and chemistry of front surface interfaces and should prove important to improving materials, processes, and reliability of next-generation CdTe-based solar cells.

n-Type transparent conducting films of small molecule and polymer amine doped single-walled carbon nanotubes.

In this report, we investigate the electrical and optical properties of thin conducting films of SWNTs after treatment with small molecule and polymeric amines. Among those tested, we find hydrazine to be the most effective n-type dopant. We use absorbance, Raman, X-ray photoelectron, and nuclear magnetic resonance spectroscopies on thin conducting films and opaque buckypapers treated with hydrazine to study fundamental properties and spectroscopic signatures of n-type SWNTs and compare them to SWNTs treated with nitric acid, a well-characterized p-type dopant. We find that hydrazine physisorbs to the surface of semiconducting and metallic SWNTs and injects large electron concentrations, raising the Fermi level as much as 0.7 eV above that of intrinsic SWNTs. Hydrazine-treated transparent SWNT films display sheet resistances nearly as low as p-type nitric-acid-treated films at similar optical transmittances, demonstrating their potential for use in photovoltaic devices as low work function transparent electron-collecting electrodes.

Controlling the optical properties of plasmonic disordered nanohole silver films.

Disordered nanohole arrays were formed in silver films by colloidal lithography techniques and characterized for their surface-plasmon activity. Careful control of the reagent concentration, deposition solution ionic strength, and assembly time allowed generation of a wide variety of nanohole densities. The fractional coverage of the nanospheres across the surface was varied from 0.05-0.36. Electrical sheet resistance measurements as a function of nanohole coverage fit well to percolation theory indicating that the electrical behavior of the films is determined by bulk silver characteristics. The transmission and reflection spectra were measured as a function of coverage and the results indicate that the optical behavior of the films is dominated by surface plasmon phenomena. Angle-resolved transmission and reflection spectra were measured, yielding insight into the nature of the excitations taking place on the metal films. The tunability of the colloidal lithography assembly method holds much promise as a means to generate customized transparent electrodes with high surface plasmon activity throughout the visible and NIR spectrum over large surface areas.

Transparent conductive single-walled carbon nanotube networks with precisely tunable ratios of semiconducting and metallic nanotubes.

We present a comprehensive study of the optical and electrical properties of transparent conductive films made from precisely tuned ratios of metallic and semiconducting single-wall carbon nanotubes. The conductivity and transparency of the SWNT films are controlled by an interplay between localized and delocalized carriers, as determined by the SWNT electronic structure, tube-tube junctions, and intentional and unintentional redox dopants. The results suggest that the main resistance in the SWNT thin films is the resistance associated with tube-tube junctions. Redox dopants are found to increase the delocalized carrier density and transmission probability through intertube junctions more effectively for semiconductor-enriched films than for metal-enriched films. As a result, redox-doped semiconductor-enriched films are more conductive than either intrinsic or redox-doped metal-enriched films.

Reversibility, dopant desorption, and tunneling in the temperature-dependent conductivity of type-separated, conductive carbon nanotube networks.

We present a comprehensive study of the effects of doping and temperature on the conductivity of single-walled carbon nanotube (SWNT) networks. We investigated nearly type-pure networks as well as networks comprising precisely tuned mixtures of metallic and semiconducting tubes. Networks were studied in their as-produced state and after treatments with nitric acid, thionyl chloride, and hydrazine to explore the effects of both intentional and adventitious doping. For intentionally and adventitiously doped networks, the sheet resistance (R(s)) exhibits an irreversible increase with temperature above approximately 350 K. Dopant desorption is shown to be the main cause of this increase and the observed hysteresis in the temperature-dependent resistivity. Both thermal and chemical dedoping produced networks free of hysteresis. Temperature-programmed desorption data showed that dopants are most strongly bound to the metallic tubes and that networks consisting of metallic tubes exhibit the best thermal stability. At temperatures below the dopant desorption threshold, conductivity in the networks is primarily controlled by thermally assisted tunneling through barriers at the intertube or interbundle junctions.