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. The review is concluded with an outlook on the challenges in the field of STE PL emission and the most promising venues for future research.

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

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

Highly Luminescent Transparent Cs2Ag x Na1-x Bi y In1-y Cl6 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 Cs2Ag x Na1-x Bi y In1-y Cl6 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 x = 0.40 and y = 0.01 revealed a photoluminescence quantum yield of 85%, highlighting thermal evaporation as a promising approach to functional perovskite-based optical materials.

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. We discuss the factors determining the efficiency and spectral parameters of the broadband PL of doped LFPs depending on the dopant and host matrix, both in micro- and nanocrystalline states, address the most relevant challenges this rapidly developing research area is facing, and outline the most promising concepts for further progress in this field.

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 NEt4OH upon ambient drying of the water solvent. These effects include (i) formation of stage-1 intercalates of NEt4OH 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 in situ X-ray diffraction allowing different stages to be identified, including the deposition of a primary "wet" intercalate of hydrated NEt4OH and the gradual elimination of excessive water during its ambient drying. The intercalated NEt4+ cations show a specific "flattened" conformation allowing the dynamics of formation and structure of the intercalate to be probed by vibrational spectroscopies. The two-dimensional self-assembly on mica is assumed to be driven both by the internal hexagonal symmetry of heptazine units and by a templating effect of the mica surface.

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. The Ag-Zn-S phase, having its bandgap in near infrared range, is the reason for the non-monotonous dependence of the absorption edge of CAZTS NCs on the Ag content, with a trend to redshift even below the bandgaps of bulk AZTS and CZTS. The work function, electron affinity, and ionization potential of the AZTS NCs are derived using photoelectron spectroscopy measurements.

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. The alloying effect is expected to be of a general character for different In-based ternary chalcogenides.

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. Here, we report on the manifestations of photo-induced enhancement of photoluminescence (PL) of aqueous colloidal NCs embedded in water-soluble polymers. Based on the comparison of results obtained on bare and core/shell NCs, NCs of different compounds (CdSe, CdTe, ZnO) as well as different embedding polymers, we conclude on the most probable mechanism of the photoenhancement for these sorts of systems. Contrary to photoenhancement observed earlier as a result of surface photocorrosion, we do not observe any change in peak position and width of the excitonic PL. Therefore, we suggest that the saturation of trap states by accumulated photo-excited charges plays a key role in the observed enhancement of the radiative recombination. This suggestion is supported by the unique temperature dependence of the trap PL band as well as by power-dependent PL measurement.

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 Na2SeSO3 is used as a stable Se2- 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 1.65 eV (750 nm) to 1.90 eV (650 nm) depending on the average QD size and composition. The PL quantum yield varies strongly with basic synthesis parameters (ratios of constituents, Zn addition, duration of thermal treatment, etc.) reaching 4% for "core" AISe and 12% for "core/shell" AISe/ZnS QDs. The shape and position of PL bands is interpreted in terms of the model of radiative recombination of a self-trapped exciton. The AISe-GSH QDs reveal phonon Raman spectra characteristic for small and Ag-deficient tetragonal Ag-In-Se QDs. The ability of ultra-small AISe QDs to support such "bulk-like" vibrations can be used for future deeper insights into structural and optical properties of this relatively new sort of QDs.

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. The unique geometric GCNT structure and versatility of possible chemical modifications allow new photocatalytic applications of GCNTs to be envisaged including selective photocatalysts of multi-electron processes as well as light-induced and light-directed motion of GCNT-based microswimmers. Closely-packed arrays of aligned GCNTs show great promise as multifunctional membrane materials for the light energy conversion and storage, light-driven pumping of liquids, selective adsorption, and electrochemical applications. These emerging applications require synthetic routes to GCNTs with highly controlled morphological parameters and composition to be available. We recognize three major strategies for the GCNT synthesis including templating, supramolecular assembling of precursors, and scrolling of nano-/microsheets, and outline promising routes for further progress of these approaches in the light of the most important emerging applications of GCNTs.

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. All these observations are similar to those reported earlier for Ag-In-S and Ag-In-S/ZnS NCs and allowed us to assume a general photoluminescence mechanism for all three ternary compounds, based on the model of radiative self-trapped exciton recombination.

Temperature-Dependent Photoluminescence of Silver-Indium-Sulfide Nanocrystals in Aqueous Colloidal Solutions.

The temperature dependence of the photoluminescence (PL) intensity of colloidal semiconductor nanocrystals (NCs) makes them an appealing option in bio-sensing applications. Here, we probed the temperature-dependent PL behavior of aqueous glutathione (GSH)-capped Ag-In-S (AIS) NCs and their core/shell AIS/ZnS heterostructures. We show that both core and core-shell materials reveal strong PL quenching upon heating from 10 to 80 °C, which is completely reversible upon cooling. The PL quenching is assigned to the thermally activated dissociation of complexes formed by ligands with the metal cations on the NC surface and the introduction of water into the NC coordination sphere. This unique mechanism of the thermal PL quenching results in a much higher temperature sensitivity of the aqueous colloidal AIS (AIS/ZnS) NCs as compared with previously reported analogs capped by covalently bound ligands. Our results are expected to stimulate further studies on aqueous ternary NCs as colloidal luminescent nano-thermometers applicable for ratiometric temperature sensing.

Raman study of flash-lamp annealed aqueous Cu2ZnSnS4 nanocrystals.

The effect of flash-lamp annealing (FLA) on the re-crystallization of thin films made of colloidal Cu2ZnSnS4 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. The formation of secondary phases at higher FLA power densities, as well as the dependence of the formation on the film thickness are also investigated. Importantly, no inert atmosphere for the FLA treatment of the NCs is required, which makes this technology even more suitable for mass production, in particular for printed thin films on flexible substrates.

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 Sn2+ and other metal(II) ions, perovskite materials formed on the basis of M3+ cations (Sb3+, Bi3+) as well as on combinations of M+/M3+ ions aliovalent to 2Pb2+ (Ag+/Bi3+, Ag+/Sb3+, etc.). The survey is concluded with an outlook highlighting the most promising strategies for future progress of photovoltaic systems based on lead-free perovskite compounds.

"Green" Aqueous Synthesis and Advanced Spectral Characterization of Size-Selected Cu2ZnSnS4 Nanocrystal Inks.

Structure, composition, and optical properties of colloidal mercaptoacetate-stabilized Cu2ZnSnS4 (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 (2.04 eV). The size-selected CZTS nanocrystals revealed also phonon confinement, with the main phonon mode frequency varying by about 4 cm-1 between 2 nm and 3 nm NCs.

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. The review is concluded by an outlook with a critical discussion of the most promising ways and challenging aspects of further progress in the metal chalcogenide NC-based solar photovoltaics and photochemistry.

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. In the present work, the copper-doping of aqueous non-stoichiometric AIS QDs was found to result in a red shift of the PL band maximum from around 630 nm to ∼780 nm and PL quenching. The deposition of a ZnS shell results in PL intensity recovery with the highest quantum yield of 15%, with almost not change in the PL band position, opposite to the undoped AIS QDs. Size-selective precipitation using 2-propanol as a non-solvent allows discrimination of up to 9 fractions of Cu-doped AIS/ZnS QDs with the average sizes in the fractions varying from around 3 to 2 nm and smaller and with reasonably the same composition irrespective of the QD size. The decrease of the average QD size results in a blue PL shift yielding a series of bright luminophors with the emission color varies from deep-red to bluish-green and the PL efficiency increases from 11% for the first fraction to up to 58% for the smallest Cu-doped AIS/ZnS QDs. The rate constant of the radiative recombination of the size-selected Cu-doped AIS/ZnS QDs revealed a steady growth with the QD size decrease as a result of the size-dependent enhancement of the spatial exciton confinement. The copper doping was found to result in an enhancement of the photoelectrochemical activity of CAIS/ZnS QDs introduced as spectral sensitizers of mesoporous titania photoanodes of liquid-junction solar cells.

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. The dominant peaks in the SERS spectra are assigned to surface optical phonon modes.

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 = 1.3-1.4. A model cell with a FTO/ZnO/CdS photoanode produced by SILAR and FTO/ZnO/CuxS films as counter-electrode showed a light conversion efficiency, η = 1.73%, which is 25% higher than a similar cell where copper sulfide was deposited onto ZnO in "dark" conditions. Varying the conditions of the photocatalytic deposition of the starting copper nanoparticles slightly affects the electrocatalytic properties of the final FTO/ZnO/CuxS heterostructures.