Oleksandr L. Stroyuk

Preparation and optical properties of highly luminescent colloidal single-layer carbon nitride

Thermal treatment of graphitic carbon nitride (g-CN) in aqueous solutions of tetraethyl ammonium hydroxide at ∼100 °C yields transparent colloidal solutions retaining stability at a CN concentration of up to 50 g L−1 and upon dilution by a factor of 103. Atomic force microscopy showed that the major part of the CN particles in diluted colloidal solutions are characterized by a lateral size of around 30–50 nm and a thickness of 0.3–0.4 nm typical of a single CN layer. Besides, a small fraction of multi-layer 2–5 nm thick g-CN particles with a size of ∼60 nm is present in the solutions. Photoexcitation of the colloidal CN near the edge of the absorption band results in emission of strong broad-band photoluminescence with a maximum at 460–470 nm and a quantum yield of 45–50%.

Non-stoichiometric Cu–In–S@ZnS nanoparticles produced in aqueous solutions as light harvesters for liquid-junction photoelectrochemical solar cells

A direct “green” aqueous synthesis of mercapto acetate-stabilized copper indium sulfide (CIS) nanoparticles (NPs) and core/shell CIS@ZnS NPs of a varied composition under ambient conditions and a temperature lower than 100 °C is reported. The CIS@ZnS NPs can be anchored to the surface of nanocrystalline FTO/TiO2 films without additional purification or ligand exchange steps yielding visible-light-sensitive heterostructures ready for using as photoanodes in the liquid-junction solar cells. The highest photoelectrochemical activity in a three-electrode cell was demonstrated by a TiO2/CIS@ZnS heterostructure with atomic Cu : In : S and Zn : Cu ratios of 1 : 5 : 10 and 1 : 1. The optimized TiO2/CIS@ZnS photoanodes were tested in two-electrode solar cells with aqueous polysulfide electrolyte and TiO2/Cu2S heterostructures produced by a photo-assisted method as counter-electrodes. Under illumination by a 30 mW cm−2 xenon lamp, the optimized cells showed the average light conversion efficiency of 8.15%, the average open-circuit voltage of −0.6 V and the average fill factor of 0.42. The cells revealed excellent stability and reproducibility of photoelectrochemical parameters with around one percent variation of the light conversion efficiency around an average value for six identical solar cells.

A spectroscopic and photochemical study of Ag+-, Cu2+-, Hg2+-, and Bi3+-doped CdxZn1−xS 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. The impact of the dopant upon the intensity of the luminescence and microsecond transient bleaching bands was found to grow substantially from Ag(+) to Cu(2+), Hg(2+) and Bi(3+). The same trend was found to hold for the acceleration of the steady-state photochemical corrosion of doped Cd(x)Zn(1-x)S nanoparticles. The differences among the effect of the dopant ions studied were interpreted in terms of the depth and charge of surface states created by Cd(2+) (Zn(2+)) substitution by a dopant.

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.

“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.

Photoelectrochemical Properties of Nanoheterostructures Based on Titanium Dioxide and Ag-In-S Quantum Dots Produced by Size-Selective Precipitation

The photoelectrochemical properties of FTO/TiO2/AIS nanoheterostructures containing Ag-In-S (AIS) nanoparticles (NPs) produced by the size-selective precipitation were investigated. It was found that the photocurrent of such composites increases by almost twice with decrease of the average AIS NP size from 3.5-4 to ~2 nm. The dependence of the rate constant of photoinduced electron transfer between AIS NPs and TiO2 on the average size of the NPs is similar in nature and agrees with the size dependence of the photoelectrochemical activity of TiO2/AIS nanoheterostructures.