Pralay K. Santra

Mn-Doped Quantum Dot Sensitized Solar Cells: A Strategy to Boost Efficiency over 5%

To make Quantum Dot Sensitized Solar Cells (QDSC) competitive, it is necessary to achieve power conversion efficiencies comparable to other emerging solar cell technologies. By employing Mn(2+) doping of CdS, we have now succeeded in significantly improving QDSC performance. QDSC constructed with Mn-doped-CdS/CdSe deposited on mesoscopic TiO(2) film as photoanode, Cu(2)S/Graphene Oxide composite electrode, and sulfide/polysulfide electrolyte deliver power conversion efficiency of 5.4%.

Tandem-Layered Quantum Dot Solar Cells: Tuning the Photovoltaic Response with Luminescent Ternary Cadmium Chalcogenides

Photon management in solar cells is an important criterion as it enables the capture of incident visible and infrared photons in an efficient way. Highly luminescent CdSeS quantum dots (QDs) with a diameter of 4.5 nm were prepared with a gradient structure that allows tuning of absorption and emission bands over the entire visible region without varying the particle size. These crystalline ternary cadmium chalcogenides were deposited within a mesoscopic TiO(2) film by electrophoretic deposition with a sequentially-layered architecture. This approach enabled us to design tandem layers of CdSeS QDs of varying band gap within the photoactive anode of a QD solar cell (QDSC). An increase in power conversion efficiency of 1.97-2.81% with decreasing band gap was observed for single-layer CdSeS, thus indicating varying degrees of photon harvesting. In two- and three-layered tandem QDSCs, we observed maximum power conversion efficiencies of 3.2 and 3.0%, respectively. These efficiencies are greater than the values obtained for the three individually layered photoanodes. The synergy of using tandem layers of the ternary semiconductor CdSeS in QDSCs was systematically evaluated using transient spectroscopy and photoelectrochemistry.

CuInS2-Sensitized Quantum Dot Solar Cell. Electrophoretic Deposition, Excited-State Dynamics, and Photovoltaic Performance

Ternary metal chalcogenides such as CuInS2 offer new opportunities to design quantum dot solar cells (QDSC). Chemically synthesized CuInS2 quantum dots (particle diameter, 2.6 nm) have been successfully deposited within the mesoscopic TiO2 film using electrophoretic deposition (150 V cm(-1) dc field). The primary photoinduced process of electron injection from excited CuInS2 into TiO2 occurs with a rate constant of 5.75 × 10(11) s(-1). The TiO2/CuInS2 films are photoactive and produce anodic photocurrent with a power conversion efficiency of 1.14%. Capping the TiO2/CuInS2 film with a CdS layer decreases the interfacial charge recombination and thus offers further improvement in the power conversion efficiency (3.91%). The synergy of using CdS as a passivation layer in the composite film is also evident from the increased external quantum efficiency of the electrode in the red region where only CuInS2 absorbs the incident light.

Earth-Abundant Cobalt Pyrite (CoS2) Thin Film on Glass as a Robust, High-Performance Counter Electrode for Quantum Dot-Sensitized Solar Cells

We report a cobalt pyrite (cobalt disulfide, CoS2) thin film on glass as a robust, high-performance, low-cost, earth-abundant counter electrode for liquid-junction quantum dot-sensitized solar cells (QDSSCs) that employ the aqueous sulfide/polysulfide (S(2-)/Sn(2-)) redox electrolyte as the hole-transporting medium. The metallic CoS2 thin film electrode is prepared via thermal sulfidation of a cobalt film deposited on glass and has been characterized by powder X-ray diffraction and electron microscopy. Using the CoS2 counter electrode, CdS/CdSe-sensitized QDSSCs display improved short-circuit photocurrent density and fill factor, achieving solar light-to-electricity conversion efficiencies as high as 4.16%, with an average efficiency improvement of 54 (±14)% over equivalent devices assembled with a traditional platinum counter electrode. Electrochemical measurements verify that CoS2 shows high electrocatalytic activity toward polysulfide reduction, rationalizing the improved QDSSC performance. CoS2 is also less susceptible to poisoning by the sulfide/polysulfide electrolyte, a problem that plagues platinum electrodes in this application; furthermore, CoS2 exhibits excellent stability in sulfide/polysulfide electrolyte, resulting in highly reproducible performance.

Growth mechanism of nanocrystals in solution: ZnO, a case study.

We investigate the mechanism of growth of nanocrystals from solution using the case of ZnO. Spanning a wide range of values of the parameters, such as the temperature and the reactant concentration that control the growth, our results establish a qualitative departure from the widely accepted diffusion controlled coarsening (Ostwald ripening) process quantified in terms of the Lifshitz-Slyozov-Wagner theory. Further, we show that these experimental observations can be qualitatively and quantitatively understood within a growth mechanism that is intermediate between the two well-defined limits of diffusion control and kinetic control.

Synchronized Energy and Electron Transfer Processes in Covalently Linked CdSe–Squaraine Dye–TiO2 Light Harvesting Assembly

Manipulation of energy and electron transfer processes in a light harvesting assembly is an important criterion to mimic natural photosynthesis. We have now succeeded in sequentially assembling CdSe quantum dot (QD) and squaraine dye (SQSH) on TiO(2) film and couple energy and electron transfer processes to generate photocurrent in a hybrid solar cell. When attached separately, both CdSe QDs and SQSH inject electrons into TiO(2) under visible-near-IR irradiation. However, CdSe QD if linked to TiO(2) with SQSH linker participates in an energy transfer process. The hybrid solar cells prepared with squaraine dye as a linker between CdSe QD and TiO(2) exhibited power conversion efficiency of 3.65% and good stability during illumination with global AM 1.5 solar condition. Transient absorption spectroscopy measurements provided further insight into the energy transfer between excited CdSe QD and SQSH (rate constant of 6.7 × 10(10) s(-1)) and interfacial electron transfer between excited SQSH and TiO(2) (rate constant of 1.2 × 10(11) s(-1)). The synergy of covalently linked semiconductor quantum dots and near-IR absorbing squaraine dye provides new opportunities to harvest photons from selective regions of the solar spectrum in an efficient manner.

Prevention of photooxidation in blue-green emitting Cu doped ZnSe nanocrystals

This communication highlights unstable blue-green emitting Cu doped ZnSe nanocrystals stabilized by diluting the surface Se with a calculated amount of S.

Origin of the Substitution Mechanism for the Binding of Organic Ligands on the Surface of CsPbBr3 Perovskite Nanocubes

Optoelectronic properties of CsPbBr3 perovskite nanocubes (NCs) depend strongly on the interaction of the organic passivating molecules with the inorganic crystal. To understand this interaction, we employed a combination of synchrotron-based X-ray photoelectron spectroscopy (XPS), nuclear magnetic resonance (NMR) spectroscopy, and first-principles density functional theory (DFT)-based calculations. Variable energy XPS elucidated the internal structure of the inorganic part in a layer-by-layer fashion, whereas NMR characterized the organic ligands. Our experimental results confirm that oleylammonium ions act as capping ligands by substituting Cs+ ions from the surface of CsPbBr3 NCs. DFT calculations shows that the substitution mechanism does not require much energy for surface reconstruction and, in contrast, stabilizes the nanocrystal by the formation of three hydrogen bonds between the -NH3+ moiety of oleylammonium and surrounding Br- on the surface of NCs. This substitution mechanism and its origin are in stark contrast to the usual adsorption of organic ligands on the surface of typical NCs.

Highly Efficient Flexible Quantum Dot Solar Cells with Improved Electron Extraction Using MgZnO Nanocrystals

Colloidal quantum dot (CQD) solar cells have high potential for realizing an efficient and lightweight energy supply for flexible or wearable electronic devices. To achieve highly efficient and flexible CQD solar cells, the electron transport layer (ETL), extracting electrons from the CQD solid layer, needs to be processed at a low-temperature and should also suppress interfacial recombination. Herein, a highly stable MgZnO nanocrystal (MZO-NC) layer is reported for efficient flexible PbS CQD solar cells. Solar cells fabricated with MZO-NC ETL give a high power conversion efficiency (PCE) of 10.4% and 9.4%, on glass and flexible plastic substrates, respectively. The reported flexible CQD solar cell has the record efficiency to date of flexible CQD solar cells. Detailed theoretical simulations and extensive characterizations reveal that the MZO-NCs significantly enhance charge extraction from CQD solids and diminish the charge accumulation at the ETL/CQD interface, suppressing charge interfacial recombination. These important results suggest that the low-temperature processed MZO-NCs are very promising for use in efficient flexible solar cells or other flexible optoelectronic devices.

Beyond the “Coffee Ring”: Re-entrant Ordering in an Evaporation-Driven Self-Assembly in a Colloidal Suspension on a Substrate

We study the phenomenon of evaporation-driven self-assembly of a colloid suspension of silica microspheres in the interior region and away from the rim of the droplet on a glass plate. In view of the importance of achieving a large-area, monolayer assembly, we first realize a suitable choice of experimental conditions, minimizing the influence of many other competing phenomena that usually complicate the understanding of fundamental concepts of such self-assembly processes in the interior region of a drying droplet. Under these simplifying conditions to bring out essential aspects, our experiments unveil an interesting competition between ordering and compaction in such drying systems in analogy to an impending glass transition. We establish a re-entrant behavior in the order-disorder phase diagram as a function of the particle density, such that there is an optimal range of the particle density to realize the long-range ordering. The results are explained with the help of simulations and phenomenological theory.