KCN Chemical Etching of van der Waals Sb2Se3 Thin Films Synthesized at Low Temperature Leads to Inverted Surface Polarity and Improved Solar Cell Efficiency.

Recent developments in Sb2Se3 van der Waals material as an absorber candidate for thin film photovoltaic applications have demonstrated the importance of surface management for improving the conversion efficiency of this technology. Sb2Se3 thin films' versatility in delivering good efficiencies in both superstrate and substrate configurations, coupled with a compatibility with various low-temperature deposition techniques (below 500 °C and often below 350 °C), makes them highly attractive for advanced photovoltaic applications. This study presents a comparative analysis of the most effective chemical etchings developed for related thin film chalcogenide technologies to identify and understand the most appropriate surface chemical treatments for Sb2Se3 in substrate configuration, synthesized using a sequential process at very low temperatures (320 °C). Eight different chemical etchings were tested and investigated, and the results show that only KCN-based solutions lead to an improvement in the solar cell's performance, primarily due to an increase in the fill factor. Surface analysis of the samples shows that KCN etching produces very Sb-rich surfaces that do not affect the properties of the bulk. It is proposed that this Sb-rich interface inverts the surface polarity, creating a "buried junction" with CdS, thereby explaining the improvement of the fill factor of the devices, as confirmed by device modeling. The results of this study underscore the importance of surface management in low-temperature synthesized Sb2Se3 absorbers, where Sb-rich interfaces are crucial for achieving high-efficiency devices. This research contributes to ongoing efforts to improve the performance of Sb2Se3 thin film photovoltaic technology and could pave the way for the development of more efficient solar cells with optimized interfaces.

SbSeI and SbSeBr micro-columnar solar cells by a novel high pressure-based synthesis process.

Van der Waals chalcogenides and chalcohalides have the potential to become the next thin film PV breakthrough, owing to the earth-abundancy and non-toxicity of their components, and their stability, high absorption coefficient and quasi-1D structure, which leads to enhanced electrical anisotropic properties when the material is oriented in a specific crystalline direction. However, quasi-1D semiconductors beyond Sb2(S,Se)3, such as SbSeX chalcohalides, have been scarcely investigated for energy generation applications, and rarely synthesised by physical vapor deposition methodologies, despite holding the promise of widening the bandgap range (opening the door to tandem or semi-transparent devices), and showing enticing new properties such as ferroelectric behaviour and defect-tolerant nature. In this work, SbSeI and SbSeBr micro-columnar solar cells have been obtained for the first time by an innovative methodology based on the selective halogenation of Sb2Se3 thin films at pressure above 1 atm. It is shown that by increasing the annealing temperature and pressure, the height and density of the micro-columnar structures grows monotonically, resulting in SbSeI single-crystal columns up to 30 µm, and tuneable morphology. In addition, solar cell prototypes with substrate configuration have shown remarkable Voc values above 550 mV and 1.8 eV bandgap.

Two-Dimensional Synergistic Interfacial Orientation on Tin Oxide-Reinforced Cobalt Carbonate Hydroxide Heterostructures for High-Performance Energy Storage.

A hierarchical cobalt carbonate hydroxide (CCH) nanostructure with outstanding electrochemical kinetics and structural stability for energy storage is largely unknown. Herein, we report tin oxide-functionalized CCH surface-enabled unique two-dimensional (2D) interlayered heterostructures that promote high conductivity with more electroactive sites to maximize redox reactions. A simple electrodeposition technique was utilized to construct the hierarchical 2D CCH electrode, while a surface-reinforced method was employed to fabricate the 2D interlayered SnO on CCH. The fabricated SnO@CCH-8 electrode showed a maximum areal capacity of 720 mC cm-2 (specific capacitance of 515 F g-1) at a current density of 1 mA cm-2 in 3 M KOH electrolyte. The obtained results indicate that the synergetic effect of SnO in the CCH network delivers an efficient charge transfer pathway to achieve high-performance energy storage. Moreover, SnO@CCH-8//AC was devised as a hybrid supercapacitor (HSC), ensuring a maximum specific capacitance of 129 F g-1 and maximum specific energy and power of 40.25 W h kg-1 and 9000 W kg-1, respectively, with better capacitance retention (94%) even beyond 10,000 cycles. To highlight the excellent performance in real-time studies, the HSC was constructed using a coin cell and displayed to power 21 light-emitting diodes (LEDs).

Poly(amidoamine) Dendrimer as an Interfacial Dipole Modification in Crystalline Silicon Solar Cells.

Poly(amidoamine) (PAMAM) dendrimers are used to modify the interface of metal-semiconductor junctions. The large number of protonated amines contributes to the formation of a dipole layer, which finally serves to form electron-selective contacts in silicon heterojunction solar cells. By modification of the work function of the contacts, the addition of the PAMAM dendrimer interlayer quenches Fermi level pinning, thus creating an ohmic contact between the metal and the semiconductor. This is supported by the observation of a low contact resistivity of 4.5 mΩ cm2, the shift in work function, and the n-type behavior of PAMAM dendrimer films on the surface of crystalline silicon. A silicon heterojunction solar cell containing the PAMAM dendrimer interlayer is presented, which achieved a power conversion efficiency of 14.5%, an increase of 8.3% over the reference device without the dipole interlayer.

Polymeric Interlayer in CdS-Free Electron-Selective Contact for Sb2Se3 Thin-Film Solar Cells.

High open-circuit voltage in Sb2Se3 thin-film solar cells is a key challenge in the development of earth-abundant photovoltaic devices. CdS selective layers have been used as the standard electron contact in this technology. Long-term scalability issues due to cadmium toxicity and environmental impact are of great concern. In this study, we propose a ZnO-based buffer layer with a polymer-film-modified top interface to replace CdS in Sb2Se3 photovoltaic devices. The branched polyethylenimine layer at the ZnO and transparent electrode interface enhanced the performance of Sb2Se3 solar cells. An important increase in open-circuit voltage from 243 mV to 344 mV and a maximum efficiency of 2.4% was achieved. This study attempts to establish a relation between the use of conjugated polyelectrolyte thin films in chalcogenide photovoltaics and the resulting device improvements.

Does Sb2Se3 Admit Nonstoichiometric Conditions? How Modifying the Overall Se Content Affects the Structural, Optical, and Optoelectronic Properties of Sb2Se3 Thin Films.

Sb2Se3 is a quasi-one-dimensional (1D) semiconductor, which has shown great promise in photovoltaics. However, its performance is currently limited by a high Voc deficit. Therefore, it is necessary to explore new strategies to minimize the formation of intrinsic defects and thus unlock the absorber's whole potential. It has been reported that tuning the Se/Sb relative content could enable a selective control of the defects. Furthermore, recent experimental evidence has shown that moderate Se excess enhances the photovoltaic performance; however, it is not yet clear whether this excess has been incorporated into the structure. In this work, a series of Sb2Se3 thin films have been prepared imposing different nominal compositions (from Sb-rich to Se-rich) and then have been thoroughly characterized using compositional, structural, and optical analysis techniques. Hence, it is shown that Sb2Se3 does not allow an extended range of nonstoichiometric conditions. Instead, any Sb or Se excesses are compensated in the form of secondary phases. Also, a correlation has been found between operating under Se-rich conditions and an improvement in the crystalline orientation, which is likely related to the formation of a MoSe2 phase in the back interface. Finally, this study shows new utilities of Raman, X-ray diffraction, and photothermal deflection spectroscopy combination techniques to examine the structural properties of Sb2Se3, especially how well-oriented the material is.

Atomic layer deposition of vanadium oxide films for crystalline silicon solar cells.

Transition metal oxides (TMOs) are promising materials to develop selective contacts on high-efficiency crystalline silicon solar cells. Nevertheless, the standard deposition technique used for TMOs is thermal evaporation, which could add potential scalability problems to industrial photovoltaic fabrication processes. As an alternative, atomic layer deposition (ALD) is a thin film deposition technique already used for dielectric deposition in the semiconductor device industry that has a straightforward up scalable design. This work reports the results of vanadium oxide (V2O5) films deposited by ALD acting as a hole-selective contact for n-type crystalline silicon (c-Si) solar cell frontal transparent contact without the additional PECVD passivating layer. A reasonable specific contact resistance of 100 mΩ cm2 was measured by the transfer length method. In addition, measurements suggest the presence of an inversion layer at the c-Si/V2O5 interface with a sheet resistance of 15 kΩ sq-1. The strong band bending induced at the c-Si surface was confirmed through capacitance-voltage measurements with a built-in voltage value of 683 mV. Besides low contact resistance, vanadium oxide films provide excellent surface passivation with effective lifetime values of up to 800 µs. Finally, proof-of-concept both-side contacted solar cells exhibit efficiencies beyond 18%, shedding light on the possibilities of TMOs deposited by the atomic layer deposition technique.

Towards the Bisbenzothienocarbazole Core: A Route of Sulfurated Carbazole Derivatives with Assorted Optoelectronic Properties and Applications.

Ladder-type molecules, which possess an extended aromatic backbone, are particularly sought within the optoelectronic field. In view of the potential of the 14H-bis[1]benzothieno[3,2-b:2',3'-h]carbazole core as a p-type semiconductor, herein we studied a set of two derivatives featuring a different alkylation patterning. The followed synthetic route, involving various sulfurated carbazole-based molecules, also resulted in a source of fluorophores with different emitting behaviors. Surprisingly, the sulfoxide-containing fluorophores substantially increased their blue fluorescence with respect to the nearly non-emitting sulfur counterparts. On this basis, we could shed light on the relationship between their chemical structure and their emission as an approach for future applications. Considering the performance in organic thin-film transistors, both bisbenzothienocarbazole derivatives displayed p-type characteristics, with hole mobility values up to 1.1 × 10-3 cm2 V-1 s-1 and considerable air stability. Moreover, the role of the structural design has been correlated with the device performance by means of X-ray analysis and the elucidation of the corresponding single crystal structures.

Influence of Co-Sputtered Ag:Al Ultra-Thin Layers in Transparent V2O5/Ag:Al/AZO Hole-Selective Electrodes for Silicon Solar Cells.

As optoelectronic devices continue to improve, control over film thickness has become crucial, especially in applications that require ultra-thin films. A variety of undesired effects may arise depending on the specific growth mechanism of each material, for instance a percolation threshold thickness is present in Volmer-Webber growth of materials such as silver. In this paper, we explore the introduction of aluminum in silver films as a mechanism to grow ultrathin metallic films of high transparency and low sheet resistance, suitable for many optoelectronic applications. Furthermore, we implemented such ultra-thin metallic films in Dielectric/Metal/Dielectric (DMD) structures based on Aluminum-doped Zinc Oxide (AZO) as the dielectric with an ultra-thin silver aluminum (Ag:Al) metallic interlayer. The multilayer structures were deposited by magnetron sputtering, which offers an industrial advantage and superior reliability over thermally evaporated DMDs. Finally, we tested the optimized DMD structures as a front contact for n-type silicon solar cells by introducing a hole-selective vanadium pentoxide (V2O5) dielectric layer.

Transition-Metal Oxides for Kesterite Solar Cells Developed on Transparent Substrates.

Fabrication on transparent soda-lime glass/fluorine-doped tin oxide (FTO) substrates opens the way to advanced applications for kesterite solar cells such as semitransparent, bifacial, and tandem devices, which are key to the future of the PV market. However, the complex behavior of the p-kesterite/n-FTO back-interface potentially limits the power conversion efficiency of such devices. Overcoming this issue requires careful interface engineering. This work empirically explores the use of transition-metal oxides (TMOs) and Mo-based nanolayers to improve the back-interface of Cu2ZnSnSe4, Cu2ZnSnS4, and Cu2ZnSn(S,Se)4 solar cells fabricated on transparent glass/FTO substrates. Although the use of TMOs alone is found to be highly detrimental to the devices inducing complex current-blocking behaviors, the use of Mo:Na nanolayers and their combination with n-type TMOs TiO2 and V2O5 are shown to be a very promising strategy to improve the limited performance of kesterite devices fabricated on transparent substrates. The optoelectronic, morphological, structural, and in-depth compositional characterization performed on the devices suggests that the improvements observed are related to a combination of shunt insulation and recombination reduction. This way, record efficiencies of 6.1, 6.2, and 7.9% are obtained for Cu2ZnSnSe4, Cu2ZnSnS4, and Cu2ZnSn(S,Se)4 devices, respectively, giving proof of the potential of TMOs for the development of kesterite solar cells on transparent substrates.

Enhanced Chiral Sensing with Dielectric Nanoresonators.

Chiro-sensitive molecular detection is highly relevant as many biochemical compounds, the building blocks of life, are chiral. Optical chirality is conventionally detected through circular dichroism (CD) in the UV range, where molecules naturally absorb. Recently, plasmonics has been proposed as a way to boost the otherwise very weak CD signal and translate it to the visible/NIR range, where technology is friendlier. Here, we explore how dielectric nanoresonators can contribute to efficiently differentiate molecular enantiomers. We study the influence of the detuning between electric (ED) and magnetic dipole (MD) resonances in silicon nanocylinders on the quality of the CD signal. While our experimental data, supported by numerical simulations, demonstrate that dielectric nanoresonators can perform even better than their plasmonic counterpart, exhibiting larger CD enhancements, we do not observe any significant influence of the optical chirality.

Enantiomer-Selective Molecular Sensing Using Racemic Nanoplasmonic Arrays.

Building blocks of life show well-defined chiral symmetry which has a direct influence on their properties and role in Nature. Chiral molecules are typically characterized by optical techniques such as circular dichroism (CD) where they exhibit signatures in the ultraviolet frequency region. Plasmonic nanostructures have the potential to enhance the sensitivity of chiral detection and translate the molecular chirality to the visible spectral range. Despite recent progress, to date, it remains unclear which properties plasmonic sensors should exhibit to maximize this effect and apply it to reliable enantiomer discrimination. Here, we bring further insight into this complex problem and present a chiral plasmonic sensor composed of a racemic mixture of gammadions with no intrinsic CD, but high optical chirality and electric field enhancements in the near-fields. Owing to its unique set of properties, this configuration enables us to directly differentiate phenylalanine enantiomers in the visible frequency range.

Interface engineering and solid-state organization for triindole-based p-type organic thin-film transistors.

Inspired by the excellent device performance of triindole-based semiconductors in electronic and optoelectronic devices, the relationship between the solid-state organization and the charge-transporting properties of an easily accessible series of triindole derivatives is reported herein. The vacuum-evaporated organic thin-film transistors (OTFTs) exhibited a non ideal behaviour with a double slope in the saturation curves. Moreover, the treatment of the gate insulator of the OTFT device with either a self-assembled monolayer (SAM) or a polymer controls the molecular growth and the film morphology of the semiconducting layer, as shown by X-ray diffraction (XRD) analyses, atomic force microscopy (AFM) and theoretical calculations. N-Trihexyltriindole exhibited the best device performance with hole mobilities up to 0.1 cm2 V-1 s-1 at the low VG range and up to 0.01 cm2 V-1 s-1 at high VG, as well as enhanced Ion/Ioff ratios of around 106. The results suggest that the non-ideal behaviour of the here studied OTFT devices could be related to the higher interfacial disorder in comparison to that in the bulk.

Reduction of Charge Traps and Stability Enhancement in Solution-Processed Organic Field-Effect Transistors Based on a Blended n-Type Semiconductor.

Solution-processed n-type organic field-effect transistors (OFETs) are essential elements for developing large-area, low-cost, and all organic logic/complementary circuits. Nonetheless, the development of air-stable n-type organic semiconductors (OSCs) lags behind their p-type counterparts. The trapping of electrons at the semiconductor-dielectric interface leads to a lower performance and operational stability. Herein, we report printed small-molecule n-type OFETs based on a blend with a binder polymer, which enhances the device stability due to the improvement of the semiconductor-dielectric interface quality and a self-encapsulation. Both combined effects prevent the fast deterioration of the OSC. Additionally, a complementary metal-oxide semiconductor-like inverter is fabricated depositing p-type and n-type OSCs simultaneously.

Solid-state organization of n-type carbazole-based semiconductors for organic thin-film transistors.

The development of new organic semiconductors has been mainly led by the search for new π-conjugated cores, but recently the use of flexible side chains is attracting more and more attention to control the molecular packing and order in the solid state to improve the charge-transporting properties. In this work, the charge transport properties of a series of tricyanovinyl-substituted carbazole-based materials with different alkyl chain lengths have been investigated and correlated with the respective intermolecular interactions and molecular packings via X-ray diffraction (XRD) studies.

Intermittent chaos for ergodic light trapping in a photonic fiber plate.

Extracting the light trapped in a waveguide, or the opposite effect of trapping light in a thin region and guiding it perpendicular to its incident propagation direction, is essential for optimal energetic performance in illumination, display or light harvesting devices. Here we demonstrate that the paradoxical goal of letting as much light in or out while maintaining the wave effectively trapped can be achieved with a periodic array of interpenetrated fibers forming a photonic fiber plate. Photons entering perpendicular to that plate may be trapped in an intermittent chaotic trajectory, leading to an optically ergodic system. We fabricated such a photonic fiber plate and showed that for a solar cell incorporated on one of the plate surfaces, light absorption is greatly enhanced. Confirming this, we found the unexpected result that a more chaotic photon trajectory reduces the production of photon scattering entropy.

HOMO stabilisation in π-extended dibenzotetrathiafulvalene derivatives for their application in organic field-effect transistors.

Three new organic semiconductors, in which either two methoxy units are directly linked to a dibenzotetrathiafulvalene (DB-TTF) central core and a 2,1,3-chalcogendiazole is fused on the one side, or four methoxy groups are linked to the DB-TTF, have been synthesised as active materials for organic field-effect transistors (OFETs). Their electrochemical behaviour, electronic absorption and fluorescence emission as well as photoinduced intramolecular charge transfer were studied. The electron-withdrawing 2,1,3-chalcogendiazole unit significantly affects the electronic properties of these semiconductors, lowering both the HOMO and LUMO energy levels and hence increasing the stability of the semiconducting material. The solution-processed single-crystal transistors exhibit high performance with a hole mobility up to 0.04 cm(2) V(-1) s(-1) as well as good ambient stability.

A compact tetrathiafulvalene-benzothiadiazole dyad and its highly symmetrical charge-transfer salt: ordered donor π-stacks closely bound to their acceptors.

A compact and planar donor-acceptor molecule 1 comprising tetrathiafulvalene (TTF) and benzothiadiazole (BTD) units has been synthesised and experimentally characterised by structural, optical, and electrochemical methods. Solution-processed and thermally evaporated thin films of 1 have also been explored as active materials in organic field-effect transistors (OFETs). For these devices, hole field-effect mobilities of µFE = (1.3±0.5)×10(-3) and (2.7±0.4)×10(-3)  cm(2) V s(-1) were determined for the solution-processed and thermally evaporated thin films, respectively. An intense intramolecular charge-transfer (ICT) transition at around 495 nm dominates the optical absorption spectrum of the neutral dyad, which also shows a weak emission from its ICT state. The iodine-induced oxidation of 1 leads to a partially oxidised crystalline charge-transfer (CT) salt {(1)2I3}, and eventually also to a fully oxidised compound {1I3}⋅1/2I2. Single crystals of the former CT compound, exhibiting a highly symmetrical crystal structure, reveal a fairly good room temperature electrical conductivity of the order of 2 S cm(-1). The one-dimensional spin system bears compactly bonded BTD acceptors (spatial localisation of the LUMO) along its ridge.