Advanced Light Management for Encapsulated Silicon Solar Cells: An Antireflective Textured Film with a Down-Shifting Lead-free Perovskite CsAgNaBiInCl Phosphor.

Light management (LM) is the key to the encapsulation of high-performance silicon (Si) photovoltaic devices (PVs). In this work, simulation analyses provide meaningful insights into optical losses and guide the improvement of the PV performance of the encapsulated silicon solar cells (Encap-Si SCs). An antireflective layer, textured polydimethylsiloxane (PDMS), is designed to reduce reflection losses, especially at a lower illumination intensity, thereby achieving an improvement of 10.

Correction: Luminescence and photoelectrochemical properties of size-selected aqueous copper-doped Ag-In-S quantum dots.

[This corrects the article DOI: 10.1039/C8RA00257F.].

Exploring Highly Efficient Broadband Self-Trapped-Exciton Luminophors: from 0D to 3D Materials.

The review summarizes our recent reports on brightly-emitting materials with varied dimensionality (3D, 2D, 0D) synthesized using "green" chemistry and exhibiting highly efficient photoluminescence (PL) originating from self-trapped exciton (STE) states. The discussion starts with 0D emitters, in particular, ternary indium-based colloidal quantum dots, continues with 2D materials, focusing on single-layer polyheptazine carbon nitride, and further evolves to 3D luminophores, the latter exemplified by lead-free double halide perovskites. The review shows the broadband STE PL to be an inherent feature of many materials produced in mild conditions by "green" chemistry, outlining PL features general for these STE emitters and differences in their photophysical properties.

Highly Luminescent Transparent CsAg Na Bi In Cl Perovskite Films Produced by Single-Source Vacuum Deposition.

Thermal deposition of halide perovskites as a universal and scalable route to transparent thin films becomes highly challenging in the case of lead-free double perovskites, requiring the evaporation dynamics of multiple metal halide sources to be balanced or a single-phase precursor preliminary synthesized to achieve a reliable control over the composition and the phase of the final films. In the present Letter, the feasibility of the single-source vacuum deposition of microcrystalline CsAg Na Bi In Cl double perovskites into corresponding transparent nanocrystalline films while preserving the bulk spectral and structural properties is shown. The perovskite films produced from the most emissive powders with = 0.

Doping/Alloying Pathways to Lead-Free Halide Perovskites with Ultimate Photoluminescence Quantum Yields.

Tailored modifications of halide lead-free perovskites (LFPs) via doping/alloying with metal cations have been recognized as a promising pathway to highly efficient inorganic phosphors with photoluminescence (PL) quantum yields of up to 100 %. Such materials typically display selective sensitivity to UV light, a broad PL range, and long PL lifetimes as well as a unique compositional variability and stability-an ideal combination for many light-harvesting applications. This Minireview presents the state-of-the-art in doped LFPs, focusing on the reports published mostly in the last two to three years.

Self-assembly of colloidal single-layer carbon nitride.

We introduce a new concept of a "bottom-to-top" design of intercalate carbon nitride compounds based on the effects of self-assembly of colloidal single-layer carbon nitride (SLCN) sheets stabilized by tetraethylammonium hydroxide NEtOH upon ambient drying of the water solvent. These effects include (i) formation of stage-1 intercalates of NEtOH during the ambient drying of SLCN colloids on glass substrates and (ii) the spontaneous formation of layered hexagonally-shaped networks of SLCN sheets on freshly-cleaved mica surfaces. The dynamics of the intercalate formation was followed by X-ray diffraction allowing different stages to be identified, including the deposition of a primary "wet" intercalate of hydrated NEtOH and the gradual elimination of excessive water during its ambient drying.

Spontaneous alloying of ultrasmall non-stoichiometric Ag-In-S and Cu-In-S quantum dots in aqueous colloidal solutions.

The effect of spontaneous alloying of non-stoichiometric aqueous Ag-In-S (AIS) and Cu-In-S (CIS) quantum dots (QDs) stabilized by surface glutathione (GSH) complexes was observed spectroscopically due to the phenomenon of band bowing typical for the solid-solution Cu(Ag)-In-S (CAIS) QDs. The alloying was found to occur even at room temperature and can be accelerated by a thermal treatment of colloidal mixtures at around 90 °C with no appreciable differences in the average size observed between alloyed and original individual QDs. An equilibrium between QDs and molecular and clustered metal-GSH complexes, which can serve as "building material" for the new mixed CAIS QDs, during the spontaneous alloying is assumed to be responsible for this behavior of GSH-capped ternary QDs.

Single-layer carbon nitride: synthesis, structure, photophysical/photochemical properties, and applications.

This Perspective provides a critical summary of the current state of the art in the synthesis and properties of polyheptazine single-layer carbon nitride (SLCN). The summary combines the authors' research and literature reports on SLCN concerning the synthesis of single-layer polyheptazine sheets, light absorption and emission by SLCN, photochemical and photocatalytic properties of SLCN as well as examples of applications of SLCN sheets as "building blocks" in heterostructures with nanocrystalline semiconductors and metals. The Perspective is concluded with an outlook discussing the most promising directions for further studies and applications of SLCN and related composites.

Raman and X-ray Photoelectron Spectroscopic Study of Aqueous Thiol-Capped Ag-Zn-Sn-S Nanocrystals.

The synthesis of (Cu,Ag)-Zn-Sn-S (CAZTS) and Ag-Zn-Sn-S (AZTS) nanocrystals (NCs) by means of "green" chemistry in aqueous solution and their detailed characterization by Raman spectroscopy and several complementary techniques are reported. Through a systematic variation of the nominal composition and quantification of the constituent elements in CAZTS and AZTS NCs by X-ray photoemission spectroscopy (XPS), we identified the vibrational Raman and IR fingerprints of both the main AZTS phase and secondary phases of Ag-Zn-S and Ag-Sn-S compounds. The formation of the secondary phases of Ag-S and Ag-Zn-S cannot be avoided entirely for this type of synthesis.

Photoinduced Enhancement of Photoluminescence of Colloidal II-VI Nanocrystals in Polymer Matrices.

The environment strongly affects both the fundamental physical properties of semiconductor nanocrystals (NCs) and their functionality. Embedding NCs in polymer matrices is an efficient way to create a desirable NC environment needed for tailoring the NC properties and protecting NCs from adverse environmental factors. Luminescent NCs in optically transparent polymers have been investigated due to their perspective applications in photonics and bio-imaging.

Ultra-small aqueous glutathione-capped Ag-In-Se quantum dots: luminescence and vibrational properties.

We introduce a direct aqueous synthesis of luminescent 2-3 nm Ag-In-Se (AISe) quantum dots (QDs) capped by glutathione (GSH) complexes, where sodium selenosulfate NaSeSO is used as a stable Se precursor. A series of size-selected AISe QDs with distinctly different positions of absorption and PL bands can be separated from the original QD ensembles by using anti-solvent-induced size-selective precipitation. The AISe-GSH QDs emit broadband PL with the band maximum varying from 1.

Graphitic carbon nitride nanotubes: a new material for emerging applications.

We provide a critical review of the current state of the synthesis and applications of nano- and micro-tubes of layered graphitic carbon nitride. This emerging material has a huge potential for light-harvesting applications, including light sensing, artificial photosynthesis, selective photocatalysis, hydrogen storage, light-induced motion, membrane technologies, and can become a major competitor for such established materials as carbon and titania dioxide nanotubes. Graphitic carbon nitride tubes (GCNTs) combine visible-light sensitivity, high charge carrier mobility, and exceptional chemical/photochemical stability, imparting this material with unrivaled photocatalytic activities in photosynthetic processes, such as water splitting and carbon dioxide reduction.

Mercury-indium-sulfide nanocrystals: A new member of the family of ternary in based chalcogenides.

A general synthesis approach of aqueous glutathione-capped ternary Ag-In-S, Cu-In-S, and Hg-In-S nanocrystals (NCs) is introduced, allowing the NC composition to be varied in a broad range. Ternary Hg-In-S (HIS) NCs are reported for the first time and found to have the same tetragonal chalcopyrite motif as Cu-In-S and Ag-In-S NCs, corroborated by phonon spectra, while X-ray photoelectron spectroscopic data indicate mercury to be present as Hg in the Hg-In-S NCs. Colloidal HIS and Hg-In-S/ZnS NCs showed little or no variations of the spectral width of the photoluminescence band upon NC size selection, temperature variation in a broad range of 10-350 K, deposition of a ZnS shell, or postsynthesis annealing.

Raman study of flash-lamp annealed aqueous CuZnSnS nanocrystals.

The effect of flash-lamp annealing (FLA) on the re-crystallization of thin films made of colloidal CuZnSnS nanocrystals (NCs) is investigated by Raman spectroscopy. Unlike similar previous studies of NCs synthesized at high temperatures in organic solvents, NCs in this work, which have diameters as small as 2-6 nm, were synthesized under environmentally friendly conditions in aqueous solution using small molecules as stabilizers. We establish the range of FLA conditions providing an efficient re-crystallization in the thin film of NCs, while preserving their kesterite structure and improving their crystallinity remarkably.

"Green" Aqueous Synthesis and Advanced Spectral Characterization of Size-Selected CuZnSnS Nanocrystal Inks.

Structure, composition, and optical properties of colloidal mercaptoacetate-stabilized CuZnSnS (CZTS) nanocrystal inks produced by a "green" method directly in aqueous solutions were characterized. A size-selective precipitation procedure using 2-propanol as a non-solvent allows separating a series of fractions of CZTS nanocrystals with an average size (bandgap) varying from 3 nm (1.72 eV) to 2 nm (2.

Lead-free hybrid perovskites for photovoltaics.

This review covers the state-of-the-art in organo-inorganic lead-free hybrid perovskites (HPs) and applications of these exciting materials as light harvesters in photovoltaic systems. Special emphasis is placed on the influence of the spatial organization of HP materials both on the micro- and nanometer scale on the performance and stability of perovskite-based solar light converters. This review also discusses HP materials produced by isovalent lead(II) substitution with Sn and other metal(II) ions, perovskite materials formed on the basis of M cations (Sb, Bi) as well as on combinations of M/M ions aliovalent to 2Pb (Ag/Bi, Ag/Sb, etc.

Solar light harvesting with multinary metal chalcogenide nanocrystals.

The paper reviews the state of the art in the synthesis of multinary (ternary, quaternary and more complex) metal chalcogenide nanocrystals (NCs) and their applications as a light absorbing or an auxiliary component of light-harvesting systems. This includes solid-state and liquid-junction solar cells and photocatalytic/photoelectrochemical systems designed for the conversion of solar light into the electric current or the accumulation of solar energy in the form of products of various chemical reactions. The review discusses general aspects of the light absorption and photophysical properties of multinary metal chalcogenide NCs, the modern state of the synthetic strategies applied to produce the multinary metal chalcogenide NCs and related nanoheterostructures, and recent achievements in the metal chalcogenide NC-based solar cells and the photocatalytic/photoelectrochemical systems.

Luminescence and photoelectrochemical properties of size-selected aqueous copper-doped Ag-In-S quantum dots.

Ternary luminescent copper and silver indium sulfide quantum dots (QDs) can be an attractive alternative to cadmium and lead chalcogenide QDs. The optical properties of Cu-In-S and Ag-In-S (AIS) QDs vary over a broad range depending on the QD composition and size. The implementation of ternary QDs as emitters in bio-sensing applications can be boosted by the development of mild and reproducible syntheses directly in aqueous solutions as well as the methods of shifting the photoluminescence (PL) bands of such QDs as far as possible into the near IR spectral range.

Enhanced Raman scattering of ZnO nanocrystals in the vicinity of gold and silver nanostructured surfaces.

nonresonant surface enhanced Raman scattering by optical phonons of ZnO nanocrystals on and beneath silver and gold island films is reported. For both configurations comparable SERS efficiency is observed, proving their potential utility. Variations in peak intensities can be attributed to difference in the morphology of island films on and beneath nanocrystals as well as to variation of the interface between semiconductor and metal.

Photoassisted formation of Cu(x)S-based cathodes for CdS-sensitized solar cells with S(2-)/S(x)(2-) electrolyte.

The sulfidation of copper nanoparticles deposited onto ZnO surface by the photocatalytic reduction of Cu(II) results in the formation of ZnO/CuxS films that can be used as efficient counter electrodes in solar cells based on sulfide/polysulfide electrolytes. The films are formed by the spherical copper sulfide nano/micro-aggregates of tabulate CuxS nanoparticles with x = 1.3-1.

Size-dependent photoinduced interactions between ZnO nanocrystals and a nitronyl nitroxide radical Nit(o-OH)Ph.

Spectral and photochemical properties of ZnO nanocrystal solutions containing free nitronyl nitroxide radical 2-(o-hydroxyphenyl)-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl (Nit(o-OH)Ph) were studied. The ZnO photoluminescence quenching by Nit(o-OH)Ph was observed and analysis of the dependences of ZnO photoluminescence intensity on radical concentrations revealed the prevalence of a static mechanism for this process. The changes in spectral properties of colloidal ZnO nanocrystal solutions in the presence of a Nit(o-OH)Ph radical under illumination were studied.

Gelatin-templated mesoporous titania for photocatalytic air treatment and application in metal chalcogenide nanoparticle-sensitized solar cells.

Mesoporous titania as powders and thin films on ITO were prepared using gelatin as an available and non-expensive pore-forming agent. The mesoporous TiO2 manifested a much higher photocatalytic activity in the gas-phase air oxidation of ethanol and acetaldehyde than the commercial nanocrystalline TiO2 P25 (Degussa Corp.).

A spectroscopic and photochemical study of Ag(+)-, Cu(2+)-, Hg(2+)-, and Bi(3+)-doped Cd(x)Zn(1-x)S nanoparticles.

A combination of stationary and time-resolved absorption and photoluminescence spectroscopy with flash and steady-state photolysis of Ag(+), Cu(2+), Hg(2+), or Bi(3+)-doped Cd(x)Zn(1-)(x)S nanoparticles was used to assess the nature of the doping influence upon the optical properties of Cd(x)Zn(1-x)S nanoparticles. The relationships between the type and the concentration of a dopant and the dynamics of the photoinduced processes in the doped nanoparticles are derived and discussed. A correlation is found between the magnitude of doping-induced changes in the intensity and decay dynamics of the deep trap photoluminescence and an enhancement of the transient bleaching recovery and acceleration of the photocorrosive degradation of the doped Cd(x)Zn(1-x)S NPs compared to the undoped ones.