A size-selected series of water-soluble luminescent Ag–In–S (AIS) and core/shell AIS/ZnS quantum dots (QDs) were produced by a precipitation technique. Up to 10–11 fractions of size-selected AIS (AIS/ZnS) QDs emitting in a broad color range from deep-red to bluish-green were isolated with the photoluminescence (PL) quantum yield reaching 47% for intermediate fractions. The size of the isolated AIS (AIS/ZnS) QDs varied from ∼2 to ∼3.5 nm at a roughly constant chemical composition of the particles throughout the fractions as shown by the X-ray photoelectron spectroscopy. The decrease of the mean AIS QD size in consecutive fractions was accompanied by an increase of the structural QD imperfection/disorder as deduced from a notable Urbach absorption “tail” below the fundamental absorption edge. The Urbach energy increased from 90–100 meV for the largest QDs up to 350 meV for the smallest QDs, indicating a broadening of the distribution of sub-bandgap states. Both the Urbach energy and the PL bandwidth of the size-selected AIS QDs increased with QD size reduction from 3–4 to ∼2 nm, and a distinct correlation was observed between these parameters. A study of size-selected AIS and AIS/ZnS QDs by UV photoelectron spectroscopy on Au and FTO substrates revealed their valence band level E VB at ∼6.6 eV (on Au) and ∼7 eV (on FTO) pinned to the Fermi level of conductive substrates resulting in a masking of any possible size-dependence of the valence band edge position.

The 2–3 nm size-selected glutathione-capped Ag–In–S (AIS) and core/shell AIS/ZnS quantum dots (QDs) were produced by precipitation/redissolution from an aqueous colloidal ensemble. The QDs reveal broadband photoluminescence (PL) with a quantum yield of up to 60% for the most populated fraction of the core/shell AIS/ZnS QDs. The PL band shape can be described by a self-trapped exciton model implying the PL band being a sequence of phonon replica of a zero-phonon line resulting from strong electron–phonon interaction and a partial conversion of the electron excitation energy into lattice vibrations. It can be concluded that the position and shape of the PL bands of AIS QDs originate not from energy factors (depth and distribution of trap states) but rather from the dynamics of the electron–phonon interaction and the vibrational relaxation in the QDs. The rate of vibrational relaxation of the electron excitation energy in AIS QDs is found to be size-dependent, increasing almost twice from the largest to the smallest QDs.

We report unusual spectral features in the resonant Raman scattering spectra of colloidal CdSe nanoparticles as small as 2–3 nm. High-frequency shoulders of the longitudinal optical phonon peak and its overtones were observed and their dependence on the excitation wavelength, temperature, nanoparticle size, and surface passivation with ZnS shell studied. As the probable origin of the uncommon spectral feature the participation of acoustic phonons and manifestation of the density of surface-related vibrational states is discussed.

The engineering of acetylenic carbon-rich nanostructures has great potential in many applications, such as nanoelectronics, chemical sensors, energy storage, and conversion, etc. Here we show the synthesis of acetylenic carbon-rich nanofibers via copper-surface-mediated Glaser polycondensation of 1,3,5-triethynylbenzene on a variety of conducting (e.g., copper, graphite, fluorine-doped tin oxide, and titanium) and non-conducting (e.g., Kapton, glass, and silicon dioxide) substrates. The obtained nanofibers (with optical bandgap of 2.51 eV) exhibit photocatalytic activity in photoelectrochemical cells, yielding saturated cathodic photocurrent of ca. 10 µA cm−2 (0.3–0 V vs. reversible hydrogen electrode). By incorporating thieno[3,2-b]thiophene units into the nanofibers, a redshift (ca. 100 nm) of light absorption edge and twofold of the photocurrent are achieved, rivalling those of state-of-the-art metal-free photocathodes (e.g., graphitic carbon nitride of 0.1–1 µA cm−2). This work highlights the promise of utilizing acetylenic carbon-rich materials as efficient and sustainable photocathodes for water reduction

A review of recent applications of Raman spectroscopy as a fast, sensitive, and non-destructive technique for exploring II–VI semiconductor nanocrystals fabricated by various methods (colloidal chemistry, Langmuir–Blodgett method, diffusion-limited growth) is presented. Specific size-related features revealed in the nanocrystal Raman spectra (phonon confinement, surface phonons) are analysed, as well as more complicated size effects for ultrasmall nanocrystals (NCs) related to the activation of the phonon density of states modified by surface reconstruction. Similarities and differences of the Raman scattering in II–VI and III–V or elemental (Si) semiconductor NCs are briefly analysed. Implementation of resonant conditions and application of infrared absorption analysis, complementary to the Raman spectroscopy—resulting in the observation of phonon modes ‘silent’ in conventional Raman scattering processes—are discussed. Furthermore, Raman spectroscopy is employed for fast and efficient assessment of the composition of matrix-embedded ternary II–VI nanocrystals, as well as more complicated multimode quaternary II–VI systems. Selective probing of electronic and vibrational spectra of different parts of heterogeneous NCs (such as core–shell systems) by tuning the excitation wavelength in resonant Raman scattering is considered. The analysis of phonon spectra is applied to the quantitative estimation of strain in the core and shell, and degree of interface intermixing, as well as to checking the surface oxidation. The above approaches and phenomena are further explored in more complex compound NCs beyond II–VI, such as CuInS2/ZnS. Recent results in the field of surface- and tip-enhanced Raman spectroscopy and surface-enhanced infrared absorption are analysed showing the perspectives of Raman spectroscopy as a tool for investigation of single-nanocrystal phonon spectra.

Semiconductor core–shell nanocrystals (NCs) have greatly improved luminescent properties including better resistance to photobleaching and ligand exchange. It was suggested that compound alloying at the core/shell interface could play an important role in obtaining bright and stable NCs. Here, we investigate the interface composition and strain evolution in spherical and dot-in-plate CdSe/CdS nanocrystals with shell thickness ranging from 1 to 3 nm, using a combination of Raman and infrared spectroscopy. A slower rate of strain accumulation in the core is observed for dot-in-plate nanocrystals and is linked to the anisotropic shape of the plate-like shell. We resolved the respective contributions of the core, shell, and alloyed interface and observed a drastic change of the shell-related Raman feature with the appearance of the bulk-like optical phonon in the shell thicker than 1 nm. The average composition of the alloy interface is estimated using the frequencies of the alloy modes. Because of the high crystallinity of the samples, up to fourth-order optical phonon processes are observed and analyzed. This work confirms the presence of an alloyed interface in core/shell CdSe/CdS structures of different geometries and establishes a precise roadmap for its quantitative analysis using vibrational spectroscopy.

CdSe nanocrystals (NCs) were obtained from cadmium sulfate and sodium selenosulfate in aqueous gelatin solutions. A near-bandgap emission of CdSe NCs was noticeably enhanced after passivation with CdS or ZnS. Resonant Raman scattering spectra of the passivated NCs revealed new peaks attributed to the formation of the sulfide shells around CdSe cores. The peaks observed for the CdSe/CdS core-shell NCs near 280 cm −1 were attributed to LO vibrations within a thin CdS passivating layer. Observation of the peak in the same frequency range for CdSe/ZnS is discussed within an assumption of alloying at the core-shell interface. Notable changes in the Raman spectra at different excitation wavelengths and shell parameters were attributed to the resonant and size-selective nature of the Raman process.

The results of a resonant Raman scattering (RRS) study of polymer-stabilized colloidal CdSe nanoparticles (NPs) are reported. The size-selective nature of the RRS is demonstrated by analysing the NP ensembles with different average size [Formula: see text] and size distribution Δd using a set of excitation wavelengths. The effect of size selection on the estimation of [Formula: see text] and Δd values from the RRS spectra is discussed, as well as some peculiarities of RRS on surface optical phonons. From the experimentally observed small variation of the I(2LO)/I(LO) ratio for 2-5 nm NPs a minor effect of [Formula: see text] on the electron-phonon coupling strength in this [Formula: see text] range is supposed.