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1. Cascade synthesis and optoelectronic applications of intermediate bandgap Cu3VSe4 nanosheets

   https://doi.org/10.1038/s41598-020-78649-9  

   Liu, Mimi ; Lai, Cheng-Yu ; Zhang, Meng ; Radu, Daniela R. ( December 2020 , Scientific Reports)

   Two-dimensional (2D) ternary materials recently generated interest in optoelectronics and energy-related applications, alongside their binary counterparts. To date, only a few naturally occurring layered 2D ternary materials have been explored. The plethora of benefits owed to reduced dimensionality prompted exploration of expanding non-layered ternary chalcogenides into the 2D realm. This work presents a templating method that uses 2D transition metal dichalcogenides as initiators to be converted into the corresponding ternary chalcogenide upon addition of copper, via a solution-phase synthesis, conducted in high boiling point solvents. The process starts with preparation of VSe₂nanosheets, which are next converted into Cu₃VSe₄sulvanite nanosheets (NSs) which retain the 2D geometry while presenting an X-ray diffraction pattern identical with the one for the bulk Cu₃VSe₄. Both the scanning electron microscopy and transmission microscopy electron microscopy show the presence of quasi-2D morphology. Recent studies of the sulfur-containing sulvanite Cu₃VS₄highlight the presence of an intermediate bandgap, associated with enhanced photovoltaic (PV) performance. The Cu₃VSe₄nanosheets reported herein exhibit multiple UV–Vis absorption peaks, related to the intermediate bandgaps similar to Cu₃VS₄and Cu₃VSe₄nanocrystals. To test the potential of Cu₃VSe₄NSs as an absorber for solar photovoltaic devices, Cu₃VSe₄NSs thin-films deposited on FTO were subjected to photoelectrochemical testing, showing p-type behavior andmore »stable photocurrents of up to ~ 0.036 mA/cm². The photocurrent shows a ninefold increase in comparison to reported performance of Cu₃VSe₄nanocrystals. This proves that quasi-2D sulvanite nanosheets are amenable to thin-film deposition and could show superior PV performance in comparison to nanocrystal thin-films. The obtained electrical impedance spectroscopy signal of the Cu₃VSe₄ NSs-FTO based electrochemical cell fits an equivalent circuit with the circuit elements of solution resistance (R_s), charge-transfer resistance (R_ct), double-layer capacitance (C_dl), and Warburg impedance (W). The estimated charge transfer resistance value of 300 Ω cm²obtained from the Nyquist plot provides an insight into the rate of charge transfer on the electrode/electrolyte interface.

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2. The new oxide paradigm for solid state ultraviolet photodetectors

   https://doi.org/10.1117/12.2319505  

   Sandana, Vinod E. ; McClintock, Ryan ; Razeghi, Manijeh ; Harel, Shlomo ; Arrateig, X. ; Rogers, David J. ; Bove, Philippe ; Teherani, Ferechteh H. ; Frisch, Eran ; Teherani, Ferechteh H. ; et al ( March 2018 , Oxide-based Materials and Devices IX)

   The bandgap of wurzite ZnO layers grown on 2 inch diameter c-Al2O3 substrates by pulsed laser deposition was engineered from 3.7 to 4.8 eV by alloying with Mg. Above this Mg content the layers transformed from single phase hcp to mixed hcp/fcc phase before becoming single phase fcc above a bandgap of about 5.5 eV. Metal-Semiconductor-Metal (MSM) photodetectors based on gold Inter-Digitated-Transducer structures were fabricated from the single phase hcp layers by single step negative photolithography and then packaged in TO5 cans. The devices gave over 6 orders of magnitude of separation between dark and light signal with solar rejection ratios (I270 : I350) of over 3 x 105 and dark signals of 300 pA (at a bias of -5V). Spectral responsivities were engineered to fit the “Deutscher Verein des Gas- und Wasserfaches” industry standard form and gave over two decade higher responsivities (14 A/W, peaked at 270 nm) than commercial SiC based devices. Homogeneous Ga2O3 layers were also grown on 2 inch diameter c-Al2O3 substrates by PLD. Optical transmission spectra were coherent with a bandgap that increased from 4.9 to 5.4 eV when film thickness was decreased from 825 to 145 nm. X-ray diffraction revealed that the films weremore »of the β-Ga2O3 (monoclinic) polytype with strong (-201) orientation. β-Ga2O3 MSM photodetectors gave over 4 orders of magnitude of separation between dark and light signal (at -5V bias) with dark currents of 250 pA and spectral responsivities of up to 40 A/W (at -0.75V bias). It was found that the spectral responsivity peak position could be decreased from 250 to 230 nm by reducing film thickness from 825 to 145 nm. This shift in peak responsivity wavelength with film thickness (a) was coherent with the apparent bandgap shift that was observed in transmission spectroscopy for the same layers and (b) conveniently provides a coverage of the spectral region in which MgZnO layers show fcc/hcp phase mixing.« less
3. Optical Properties of Magnesium-Zinc Oxide for Thin Film Photovoltaics

   https://doi.org/10.3390/ma14195649  

   Alaani, Mohammed A. ; Koirala, Prakash ; Phillips, Adam B. ; Liyanage, Geethika K. ; Awni, Rasha A. ; Sapkota, Dhurba R. ; Ramanujam, Balaji ; Heben, Michael J. ; O’Leary, Stephen K. ; Podraza, Nikolas J. ; et al ( October 2021 , Materials)

   Motivated by their utility in CdTe-based thin film photovoltaics (PV) devices, an investigation of thin films of the magnesium-zinc oxide (MgxZn1−xO or MZO) alloy system was undertaken applying spectroscopic ellipsometry (SE). Dominant wurtzite phase MZO thin films with Mg contents in the range 0 ≤ x ≤ 0.42 were deposited on room temperature soda lime glass (SLG) substrates by magnetron co-sputtering of MgO and ZnO targets followed by annealing. The complex dielectric functions ε of these films were determined and parameterized over the photon energy range from 0.73 to 6.5 eV using an analytical model consisting of two critical point (CP) oscillators. The CP parameters in this model are expressed as polynomial functions of the best fitting lowest CP energy or bandgap E0 = Eg, which in turn is a quadratic function of x. As functions of x, both the lowest energy CP broadening and the Urbach parameter show minima for x ~ 0.3, which corresponds to a bandgap of 3.65 eV. As a result, it is concluded that for this composition and bandgap, the MZO exhibits either a minimum concentration of defects in the bulk of the crystallites or a maximum in the grain size, an observation consistent withmore »measured X-ray diffraction line broadenings. The parametric expression for ε developed here is expected to be useful in future mapping and through-the-glass SE analyses of partial and complete PV device structures incorporating MZO.« less
4. Near full light absorption and full charge collection in 1-micron thick quantum dot photodetector using intercalated graphene monolayer electrodes

   https://doi.org/10.1039/c9nr09901h  

   Chen, Wenjun ; Ahn, Seungbae ; Balingit, Marquez ; Wang, Jiaying ; Lockett, Malcolm ; Vazquez-Mena, Oscar ( February 2020 , Nanoscale)

   Quantum dots (QDs) offer several advantages in optoelectronics such as easy solution processing, strong light absorption and size tunable direct bandgap. However, their major limitation is their poor film mobility and short diffusion length (<250 nm). This has restricted the thickness of QD film to ∼200–300 nm due to the restriction that the diffusion length imposes on film thickness in order to keep efficient charge collection. Such thin films result in a significant decrease in quantum efficiency for λ > 700 nm in QDs photodetector and photovoltaic devices, causing a reduced photoresponsivity and a poor absorption towards the near-infrared part of the sunlight spectrum. Herein, we demonstrate 1 μm thick QDs photodetectors with intercalated graphene charge collectors that avoid the significant drop of quantum efficiency towards λ > 700 nm observed in most QD optoelectronic devices. The 1 μm thick intercalated QD films ensure strong light absorption while keeping efficient charge extraction with a quantum efficiency of 90%–70% from λ = 600 nm to 950 nm using intercalated graphene layers as charge collectors with interspacing distance of 100 nm. We demonstrate that the effect of graphene on light absorption is minimal. We achieve a time-modulation response of <1 s. Wemore »demonstrate that this technology can be implemented on flexible PET substrates, showing 70% of the original performance after 1000 times bending test. This system provides a novel approach towards high-performance photodetection and high conversion photovoltaic efficiency with quantum dots and on flexible substrates.« less
5. Transient Lattice Response Upon Photoexcitation in CuInSe2 Nanocrystals with Organic or Inorganic Surface Passivation

   https://doi.org/https://doi.org/10.1021/acsnano.0c05553  

   S. M. Harvey, D. W. ( September 2020 , ACS nano)

   CuInSe2 nanocrystals offer promise for optoelectronics including thin-film photovoltaics and printed electronics. Additive manufacturing methods such as photonic curing controllably sinter particles into quasi-continuous films and offer improved device performance. To gain understanding of nanocrystal response under such processing conditions, we investigate impacts of photoexcitation on colloidal nanocrystal lattices via time-resolved X-ray diffraction. We probe three sizes of particles and two capping ligands (oleylamine and inorganic S2–) to evaluate resultant crystal lattice temperature, phase stability, and thermal dissipation. Elevated fluences produce heating and loss of crystallinity, the onset of which exhibits particle size dependence. We find size-dependent recrystallization and cooling lifetimes ranging from 90 to 200 ps with additional slower cooling on the nanosecond time scale. Sulfide-capped nanocrystals show faster recrystallization and cooling compared to oleylamine-capped nanocrystals. Using these lifetimes, we find interfacial thermal conductivities from 3 to 28 MW/(m2 K), demonstrating that ligand identity strongly influences thermal dissipation.