Unusual defect properties of the one-dimensional photovoltaic semiconductor selenium.

Defect tolerance is crucial in photovoltaic absorbers. Here we report that trigonal selenium (t-Se) exhibits a perovskite-like antibonding valence band maximum arising from Se p-p coupling. This results in the shallow nature of dominant Se vacancy defects. We further reveal the unique defect self-healing characteristic of Se intrinsic point defects.

Lanthanide-Like Contraction Enables the Fabrication of High-Purity Selenium Films for Efficient Indoor Photovoltaics.

The lanthanide contraction involves a reduction in atomic radius among f-block elements below the expected level. A similar contraction is observed in group-16 elements. The atomic radius of Se (117 pm) is slightly larger than that of S (104 pm) arising from the presence of d electrons, compared to the significant increase in atomic radius from O (73 pm) to S. This lanthanide-like contraction contributes to Se's robust oxidative resistance. Here we report a selective oxidation strategy utilizing Se's strong antioxidative property to remove coexisting narrow-bandgap Te impurities from Se feedstocks. This strategy selectively oxidizes volatile Te impurities into involatile TeO2 that remains in the evaporation source, while only volatile Se deposits onto the substrate during the thermal-evaporation deposition process. This enables the fabrication of high-purity Se films possessing a wide bandgap of 1.88 eV, ideally suited to the optimal bandgap for indoor photovoltaics (IPVs). The resulting Se photovoltaics exhibit an efficiency of 20.1% under 1000-lux indoor illumination, outperforming market-dominant amorphous silicon and all types of lead-free perovskite IPVs. Unencapsulated Se devices show no efficiency degradation after 20,000 hours of storage in ambient atmosphere.

Template Selection Strategy for Synthesis of One-Dimensional CrSbSe3 Ferromagnetic Semiconductor Nanoribbons.

CrSbSe3─the only experimentally validated one-dimensional (1D) ferromagnetic semiconductor─has recently attracted significant attention. However, all reported synthesis methods for CrSbSe3 nanocrystals are based on top-down methods. Here we report a template selection strategy for the bottom-up synthesis of CrSbSe3 nanoribbons. This strategy relies on comparing the formation energies of potential binary templates to the ternary target product. It enables us to select Sb2Se3 with the highest formation energy, along with its 1D crystal structure, as the template instead of Cr2Se3 with the lowest formation energy, thereby facilitating the transformation from Sb2Se3 to CrSbSe3 by replacing half of the Sb atoms in Sb2Se3 with Cr atoms. The as-prepared CrSbSe3 nanoribbons exhibit a length of approximately 5 µm, a width ranging from 80 to 120 nm, and a thickness of about 5 nm. The single CrSbSe3 nanoribbon presents typical semiconductor behavior and ferromagnetism, confirming the intrinsic ferromagnetism in the 1D CrSbSe3 semiconductor.

Adhesion-Controlled Heterogeneous Nucleation of Tin Halide Perovskites for Eco-Friendly Indoor Photovoltaics.

The rapid development of the Internet of Things (IoT) has accelerated the advancement of indoor photovoltaics (IPVs) that directly power wireless IoT devices. The interest in lead-free perovskites for IPVs stems from their similar optoelectronic properties to high-performance lead halide perovskites, but without concerns about toxic lead leakage in indoor environments. However, currently prevalent lead-free perovskite IPVs, especially tin halide perovskites (THPs), still exhibit inferior performance, arising from their uncontrollable crystallization. Here, a novel adhesive bonding strategy is proposed for precisely regulating heterogeneous nucleation kinetics of THPs by introducing alkali metal fluorides. These ionic adhesives boost the work of adhesion at the buried interface between substrates and perovskite film, subsequently reducing the contact angle and energy barrier for heterogeneous nucleation, resulting in high-quality THP films. The resulting THP solar cells achieve an efficiency of 20.12% under indoor illumination at 1000 lux, exceeding all types of lead-free perovskite IPVs and successfully powering radio frequency identification-based sensors.

Sustainable Recycling of Selenium-Based Optoelectronic Devices.

Selenium (Se), the world's oldest optoelectronic material, has been widely applied in various optoelectronic devices such as commercial X-ray flat-panel detectors and photovoltaics. However, despite the rare and widely-dispersed nature of Se element, a sustainable recycling of Se and other valuable materials from spent Se-based devices has not been developed so far. Here a sustainable strategy is reported that makes use of the significantly higher vapor pressure of volatile Se compared to other functional layers to recycle all of them from end-of-life Se-based devices through a closed-space evaporation process, utilizing Se photovoltaic devices as a case study. This strategy results in high recycling yields of ≈ 98% for Se and 100% for other functional materials including valuable gold electrodes and glass/FTO/TiO2 substrates. The refabricated photovoltaic devices based on these recycled materials achieve an efficiency of 12.33% under 1000-lux indoor illumination, comparable to devices fabricated using commercially sourced materials and surpassing the current indoor photovoltaic industry standard of amorphous silicon cells.

Structure of Amorphous Selenium: Small Ring, Big Controversy.

Selenium (Se) discovered in 1817 belongs to the family of chalcogens. Surprisingly, despite the long history of over two centuries and the chemical simplicity of Se, the structure of amorphous Se (a-Se) remains controversial to date regarding the dominance of chains versus rings. Here, we find that vapor-deposited a-Se is composed of disordered rings rather than chains in melt-quenched a-Se. We further reveal that the main origin of this controversy is the facile transition of rings to chains arising from the inherent instability of rings. This transition can be inadvertently triggered by certain characterization techniques themselves containing above-bandgap illumination (above 2.1 eV) or heating (above 50 °C). We finally build a roadmap for obtaining accurate Raman spectra by using above-bandgap excitation lasers with low photon flux (below 1017 phs m-2 s-1) and below-bandgap excitation lasers measured at low temperatures (below -40 °C) to minimize the photoexcitation- and heat-induced ring-to-chain transitions.

Regioselective Multisite Atomic-Chlorine Passivation Enables Efficient and Stable Perovskite Solar Cells.

Passivating defects using organic halide salts, especially chlorides, is an effective method to improve power conversion efficiencies (PCEs) of perovskite solar cells (PSCs) arising from the stronger Pb-Cl bonding than Pb-I and Pb-Br bonding. However, Cl- anions with a small radius are prone to incorporation into the perovskite lattice that distorts the lead halide octahedron, degrading the photovoltaic performance. Here, we substitute atomic-Cl-containing organic molecules for widely used ionic-Cl salts, which not only retain the efficient passivation by Cl but also prevent the incorporation of Cl into the bulk lattice, benefiting from the strong covalent bonding between Cl atoms and organic frameworks. We find that only when the distance of Cl atoms in single molecules matches well with the distance of halide ions in perovskites can such a configuration maximize the defect passivation. We thereby optimize the molecular configuration to enable multiple Cl atoms in an optimal spatial position to maximize their binding with surface defects. The resulting PSCs achieve a certified PCE of 25.02%, among the highest PCEs for PSCs, and retain 90% of their initial PCE after 500 h of continuous operation.

Tex Se1-x Photodiode Shortwave Infrared Detection and Imaging.

Short-wave infrared detectors are increasingly important in the fields of autonomous driving, food safety, disease diagnosis, and scientific research. However, mature short-wave infrared cameras such as InGaAs have the disadvantage of complex heterogeneous integration with complementary metal-oxide-semiconductor (CMOS) readout circuits, leading to high cost and low imaging resolution. Herein, a low-cost, high-performance, and high-stability Tex Se1- x short-wave infrared photodiode detector is reported. The Tex Se1- x thin film is fabricated through CMOS-compatible low-temperature evaporation and post-annealing process, showcasing the potential of direct integration on the readout circuit. The device demonstrates a broad-spectrum response of 300-1600 nm, a room-temperature specific detectivity of 1.0 × 1010 Jones, a -3 dB bandwidth up to 116 kHz, and a linear dynamic range of over 55 dB, achieving the fastest response among Te-based photodiode devices and a dark current density 7 orders of magnitude smaller than Te-based photoconductive and field-effect transistor devices. With a simple Si3 N4 packaging, the detector shows high electric stability and thermal stability, meeting the requirements for vehicular applications. Based on the optimized Tex Se1- x photodiode detector, the applications in material identification and masking imaging is demonstrated. This work paves a new way for CMOS-compatible infrared imaging chips.

Mitigating Electron Leakage of Solid Electrolyte Interface for Stable Sodium-Ion Batteries.

The interfacial stability is highly responsible for the longevity and safety of sodium ion batteries (SIBs). However, the continuous solid-electrolyte interphase(SEI) growth would deteriorate its stability. Essentially, the SEI growth is associated with the electron leakage behavior, yet few efforts have tried to suppress the SEI growth, from the perspective of mitigating electron leakage. Herein, we built two kinds of SEI layers with distinct growth behaviors, via the additive strategy. The SEI physicochemical features (morphology and componential information) and SEI electronic properties (LUMO level, band gap, electron work function) were investigated elaborately. Experimental and calculational analyses showed that, the SEI layer with suppressed growth delivers both the low electron driving force and the high electron insulation ability. Thus, the electron leakage is mitigated, which restrains the continuous SEI growth, and favors the interface stability with enhanced electrochemical performance.

Indoor photovoltaics awaken the world's first solar cells.

Selenium (Se) solar cells were the world's first solid-state photovoltaics reported in 1883, opening the modern photovoltaics. However, its wide bandgap (~1.9 eV) limits sunlight harvesting. Here, we revisit the world's oldest but long-ignored photovoltaic material with the emergence of indoor photovoltaics (IPVs); the absorption spectrum of Se perfectly matches the emission spectra of commonly used indoor light sources in the 400 to 700 nm range. We find that the widely used Te adhesion layer also passivates defects at the nonbonded Se/TiO2 interface. By optimizing the Te coverage from 6.9 to 70.4%, the resulting Se cells exhibit an efficiency of 15.1% under 1000 lux indoor illumination and show no efficiency loss after 1000 hours of continuous indoor illumination without encapsulation, outperforming the present IPV industry standard of amorphous silicon cells in both efficiency and stability. We further fabricate Se modules (6.75 cm2) that produce 232.6 µW output power under indoor illumination, powering a radio-frequency identification-based localization tag.

Solution-processed Ge(ii)-based chalcogenide thin films with tunable bandgaps for photovoltaics.

Solution processes have been widely used to construct chalcogenide-based thin-film optoelectronic and electronic devices that combine high performance with low-cost manufacturing. However, Ge(ii)-based chalcogenide thin films possessing great potential for optoelectronic devices have not been reported using solution-based processes; this is mainly attributed to the easy oxidation of intermediate Ge(ii) to Ge(iv) in the precursor solution. Here we report solution-processed deposition of Ge(ii)-based chalcogenide thin films in the case of GeSe and GeS films by introducing hypophosphorous acid as a suitable reducing agent and strong acid. This enables the generation of Ge(ii) from low-cost and stable GeO2 powders while suppressing the oxidation of Ge(ii) to Ge(iv) in the precursor solution. We further show that such solution processes can also be used to deposit GeSe1-x S x alloy films with continuously tunable bandgaps ranging from 1.71 eV (GeS) to 1.14 eV (GeSe) by adjusting the atomic ratio of S- to Se-precursors in solution, thus allowing the realization of optimal-bandgap single-junction photovoltaic devices and multi-junction devices.

Robust Self-Assembled Molecular Passivation for High-Performance Perovskite Solar Cells.

Defect passivation via post-treatment of perovskite films is an effective method to fabricate high-performance perovskite solar cells (PSCs). However, the passivation durability is still an issue due to the weak and vulnerable bonding between passivating functional groups and perovskite defect sites. Here we propose a cholesterol derivative self-assembly strategy to construct crosslinked and compact membranes throughout perovskite films. These supramolecular membranes act as a robust protection layer against harsh operational conditions while providing effective passivation of defects from surface toward inner grain boundaries. The resultant PSCs exhibit a power conversion efficiency of 23.34 % with an impressive open-circuit voltage of 1.164 eV. The unencapsulated devices retain 92 % of their initial efficiencies after 1600 h of storage under ambient conditions, and remain almost unchanged after heating at 85 °C for 500 h in a nitrogen atmosphere, showing significantly improved stability.

Strain in perovskite solar cells: origins, impacts and regulation.

Metal halide perovskite solar cells (PSCs) have seen an extremely rapid rise in power conversion efficiencies in the past few years. However, the commercialization of this class of emerging materials still faces serious challenges, one of which is the instability against external stimuli such as moisture, heat and irradiation. Much focus has deservedly been placed on understanding the different origins of intrinsic instability and thereby enhancing their stability. Among these, tensile strain in perovskite films is an important source of instability that cannot be overcome using conventionally extrinsic stabilization approaches such as encapsulation. Here we review recent progress in the understanding of the origin of strain in perovskites as well as its corresponding characterization methods, and their impacts on the physical properties of perovskites and the performance of PSCs including efficiency and stability. We then summarize the latest advances in strain-regulation strategies that improve the intrinsic stability of perovskites and photovoltaic devices. Finally, we provide a perspective on how to make further progress in stable and high-efficiency PSCs via strain engineering.

Surface-Defect States in Photovoltaic Absorber GeSe.

GeSe is an emerging promising light-harvesting material for photovoltaics due to its excellent optoelectronic properties, nontoxic and earth-abundant constituents, and high stability. In particular, perovskite-like antibonding states at the valence band maximum arising from Ge-4s and Se-4p coupling enable the bulk-defect-tolerant properties in GeSe. However, a fundamental understanding of surface-defect states in GeSe, another important factor for high-performance photovoltaics, is still lacking. Here, we investigate the surface-defect properties of GeSe through first-principle calculations. We find that different from common semiconductors possessing numerous surface dangling bonds, some GeSe surfaces are prone to reconstruction, thus eliminating the dangling bonds. The rearranged armchair edges exhibit unexpected benign defect properties, similar to those of bulk GeSe, arising from the formation of bulk-like [GeSe3] tetrahedrons. We further show that the stable exposed (111) surfaces are hard to reconstruct due to the stiff structure but are effectively passivated by the addition of H.

Investigation of the sublimation mechanism of GeSe and GeS.

GeSe and GeS have emerged as promising light-harvesting materials for photovoltaics due to their attractive optoelectronic properties, non-toxic and earth-abundant constituents, and excellent stability. Here we unveil the diatomic molecule sublimation mechanism of GeSe and GeS that directly guides the optimization of GeSe and GeS solar-cell fabricated via the close-space sublimation method.

One-Pot Synthesis Enables Magnetic Coupled Cr2Te3/MnTe/Cr2Te3 Integrated Heterojunction Nanorods.

Magnetic heterostructures offer great promise in spintronic devices due to their unique magnetic properties, such as exchange bias effect, topological superconductivity, and magneto-resistance. Although various magnetic heterostructures including core/shell, multilayer, and van der Waals systems have been fabricated recently, the construction of perfect heterointerfaces usually rely on complicated and high-cost fabrication methods such as molecular-beam epitaxy; surprisingly, few one-dimensional (1D) bimagnetic heterojunctions, which provide multidegrees of freedom to modulate magnetic properties via magnetic anisotropy and interface coupling, have been fabricated to date. Here we report a one-pot solution-based method for the synthesis of ferromagnetic/antiferromagnetic/ferromagnetic heterojunction nanorods with excellent heterointerfaces in the case of Cr2Te3/MnTe/Cr2Te3. The precise control of homogeneous nucleation of MnTe and heterogeneous nucleation of Cr2Te3 is a key factor in synthesizing this heterostructure. The resulting 1D bimagnetic heterojunction nanorods exhibit high coercivity of 5.8 kOe and exchange bias of 892.5 Oe achieved by the magnetic MnTe/Cr2Te3 interface coupling.

Interfacial Strain Engineering in Wide-Bandgap GeS Thin Films for Photovoltaics.

Wide-bandgap semiconductors exhibiting a bandgap of ∼1.7-1.9 eV have generated great interest recently due to their important applications in tandem solar cells as top cells and emerging indoor photovoltaics. However, concerns about the stability and toxicity especially in indoor application limit the choice of these materials. Here we report a new member of this family, germanium monosulfide (GeS); this material displays a wide bandgap of 1.7 eV, nontoxic and earth-abundant constituents, and high stability. We find that the little success of GeS solar cells to date is primarily attributed to the challenge in fabricating high-quality polycrystalline GeS films, wherein the high thermal expansion coefficient (α = 3.1 × 10-5 K-1) combined with high crystallization temperature (375 °C) of GeS induces large tensile strain in the GeS film that peels off GeS from the substrate. By introducing a high-α buffer layer between GeS and substrate, we achieve a high-quality polycrystalline GeS thin film that compactly adheres to substrate with no voids. Solar cells fabricated by these GeS films show a power conversion efficiency of 1.36% under AM 1.5G illumination (100 mW cm-2). The unencapsulated devices are stable when stored in ambient atmosphere for 1500 h. Their efficiencies further increase to 3.6% under indoor illumination of 1000 lux.

An antibonding valence band maximum enables defect-tolerant and stable GeSe photovoltaics.

In lead-halide perovskites, antibonding states at the valence band maximum (VBM)-the result of Pb 6s-I 5p coupling-enable defect-tolerant properties; however, questions surrounding stability, and a reliance on lead, remain challenges for perovskite solar cells. Here, we report that binary GeSe has a perovskite-like antibonding VBM arising from Ge 4s-Se 4p coupling; and that it exhibits similarly shallow bulk defects combined with high stability. We find that the deep defect density in bulk GeSe is ~1012 cm-3. We devise therefore a surface passivation strategy, and find that the resulting GeSe solar cells achieve a certified power conversion efficiency of 5.2%, 3.7 times higher than the best previously-reported GeSe photovoltaics. Unencapsulated devices show no efficiency loss after 12 months of storage in ambient conditions; 1100 hours under maximum power point tracking; a total ultraviolet irradiation dosage of 15 kWh m-2; and 60 thermal cycles from -40 to 85 °C.

Crystallization Kinetics Modulation of FASnI3 Films with Pre-nucleation Clusters for Efficient Lead-Free Perovskite Solar Cells.

Tin halide perovskites are rising as promising materials for lead-free perovskite solar cells (PSCs). However, the crystallization rate of tin halide perovskites is much faster than the lead-based analogs, leading to more rampant trap states and lower efficiency. Here, we disclose a key finding to modulate the crystallization kinetics of FASnI3 through a non-classical nucleation mechanism based on pre-nucleation clusters (PNCs). By introducing piperazine dihydriodide to tune the colloidal chemistry of the FASnI3 perovskite precursor solution, stable clusters could be readily formed in the solution before nucleation. These pre-nucleation clusters act as intermediate phase and thus can reduce the energy barrier for the perovskite nucleation, resulting in a high-quality perovskite film with lower defect density. This PNCs-based method has led to a conspicuous photovoltaic performance improvement for FASnI3 -based PSCs, delivering an impressive efficiency of 11.39 % plus improved stability.