Chittaranjan Das

Room‐Temperature Atomic Layer Deposition of Al2O3: Impact on Efficiency, Stability and Surface Properties in Perovskite Solar Cells

In this work, solar cells with a freshly made CH3 NH3 PbI3 perovskite film showed a power conversion efficiency (PCE) of 15.4 % whereas the one with 50 days aged perovskite film only 6.1 %. However, when the aged perovskite was covered with a layer of Al2 O3 deposited by atomic layer deposition (ALD) at room temperature (RT), the PCE value was clearly enhanced. X-ray photoelectron spectroscopy study showed that the ALD precursors are chemically active only at the perovskite surface and passivate it. Moreover, the RT-ALD-Al2 O3 -covered perovskite films showed enhanced ambient air stability.

A facile corrosion approach to the synthesis of highly active CoOx water oxidation catalysts

Ultra-small rock salt cobalt monoxide (CoO) nanoparticles were synthesized and subjected to partial oxidation (‘corrosion’) with ceric ammonium nitrate (CAN) to form mixed-valence CoOx (1 < x < 2) water oxidation catalysts. Spectroscopic, microscopic and analytical methods evidenced a structural reformation of cubic CoO to active CoOx with a spinel structure. The superior water oxidation activity of CoOx has been established in electrochemical water oxidation under alkaline conditions. Electrochemical water oxidation with CoOx was recorded at a considerably low overpotential of merely 325 mV at a current density of 10 mA cm−2 in comparison to 370 mV for CoO. Transformation of both octahedral CoII and CoIII sites into amorphous Co(OH)2–CoOOH is the key to high electrochemical activity while the presence of a higher amount of octahedral CoIII sites in CoOx is imperative for an efficient oxygen evolution process.

Modification of Hematite Electronic Properties with Trimethyl Aluminum to Enhance the Efficiency of Photoelectrodes

The electronic properties of hematite were investigated by means of synchrotron radiation photoemission (SR-PES) and X-ray absorption spectroscopy (XAS). Hematite samples were exposed to trimethyl aluminum (TMA) pulses, a widely used Al-precursor for the atomic layer deposition (ALD) of Al2O3. SR-PES and XAS showed that the electronic properties of hematite were modified by the interaction with TMA. In particular, the hybridization of O 2p states with Fe 3d and Fe 4s4p changed upon TMA pulses due to electron inclusion as polarons. The change of hybridization correlates with an enhancement of the photocurrent density due to water oxidation for the hematite electrodes. Such an enhancement has been associated with an improvement in charge carrier transport. Our findings open new perspectives for the understanding and utilization of electrode modifications by very thin ALD films and show that the interactions between metal precursors and substrates seem to be important factors in defining their electronic and photoelectrocatalytic properties.

Thermal and plasma enhanced atomic layer deposition of TiO2: Comparison of spectroscopic and electric properties

Titanium oxide (TiO2) deposited by atomic layer deposition (ALD) is used as a protective layer in photocatalytic water splitting system as well as a dielectric in resistive memory switching. The way ALD is performed (thermally or plasma-assisted) may change the growth rate as well as the electronic properties of the deposited films. In the present work, the authors verify the influence of the ALD mode on functional parameters, by comparing the growth rate and electronic properties of TiO2 films deposited by thermal (T-) and plasma-enhanced (PE-) ALD. The authors complete the study with the electrical characterization of selected samples by means of capacitance–voltage and current–voltage measurements. In all samples, the authors found a significant presence of Ti3+ states, with the lowest content in the PE-ALD grown TiO2 films. The observation of Ti3+ states was accompanied by the presence of in-gap states above the valence band maximum. For films thinner than 10 nm, the authors found also a strong leakag...

Engineering of Sub-Nanometer SiOx Thickness in Si Photocathodes for Optimized Open Circuit Potential.

Silicon is one of the most promising materials to be used for tandem-cell water-splitting devices. However, the electrochemical instability of bare Si makes it difficult to be used for stable devices. Besides that, the photovoltage loss in Si, caused by several factors (e.g., metal oxide protection layer and/or SiO2 /Si or catalyst/Si interface), limits its use in these devices. In this work, we present that an optimized open circuit potential (OCP) of Si can be obtained by controlling the SiOx thickness in sub-nanometer range. It can be done by means of a simple and cost-effective way using the combination of a wet chemical etching and the low temperature atomic layer deposition (ALD) of TiO2 . We have found that a certain thickness of the native SiOx is necessary to prevent further oxidation of the Si photocathode during the ALD growth of TiO2 . Moreover, covering the Si photocathode with an ALD TiO2 layer enhances its stability.

Quantum size effects in TiO2 thin films grown by atomic layer deposition

Summary We study the atomic layer deposition of TiO2 by means of X-ray absorption spectroscopy. The Ti precursor, titanium isopropoxide, was used in combination with H2O on Si/SiO2 substrates that were heated at 200 °C. The low growth rate (0.15 Å/cycle) and the in situ characterization permitted to follow changes in the electronic structure of TiO2 in the sub-nanometer range, which are influenced by quantum size effects. The modified electronic properties may play an important role in charge carrier transport and separation, and increase the efficiency of energy conversion systems.

A four stranded beta-sheet structure in a designed, synthetic polypeptide

A designed four stranded beta-sheet peptide has been constructed using three internal d-proline residues to nucleate beta-hairpin formation.

In-gap states in titanium dioxide and oxynitride atomic layer deposited films

Valence band (VB) spectra of titanium dioxide (TiO2) and oxynitride (TiOxNy) films prepared by different atomic layer deposition (ALD) processes are compared and related to electrical characterization [current–voltage (JV) and capacitance–voltage (CV)] results. By increasing the nitrogen amount in the TiO2 film, band-gap narrowing is observed. The band-gap decrease is related to the contribution of the nitrogen density of states, which induces defects within the band-gap and thus reduces its optical band-gap. In-gap states are found in the VB spectra at 1 eV below the Fermi energy in all investigated ALD samples, i.e., in TiO2 as well as in TiOxNy films. An exponential correlation between leakage current density and in-gap state intensity is derived by the combination of JV measurements and VB spectra, whereas the in-gap states seem to have no influence on hysteresis and fixed oxide charges found in the CV data. It is argued that the in-gap states in TiO2 and TiOxNy have an excitonic or polaronic origin. ...

Selective Deposition of an Ultrathin Pt Layer on a Au-Nanoisland-Modified Si Photocathode for Hydrogen Generation

Platinum, being the most efficient and stable catalyst, is used in photoelectrochemical (PEC) devices. However, a minimal amount of Pt with maximum catalytic activity is required to be used to minimize the cost of production. In this work, we use an environmentally friendly, cost-effective, and less Pt-consuming method to prepare PEC devices for the hydrogen evolution reaction (HER). The Pt monolayer catalyst is selectively deposited on a Au-nanoisland-supported boron-doped p-type Si (100) photocathode. The PEC device based on the Si photocathode with an ultralow loading of the Pt catalyst exhibits a comparable performance for the HER to that of devices with a thick Pt layer. In addition, we demonstrate that by using a thin TiO2 layer deposited by atomic layer deposition photo-oxidation of the Si photocathode can be blocked resulting in a stable PEC performance.

Room-Temperature Atomic-Layer-Deposited Al2O3 Improves the Efficiency of Perovskite Solar Cells over Time

Electrical characterisation of perovskite solar cells consisting of room-temperature atomic-layer-deposited aluminium oxide (RT-ALD-Al2 O3 ) film on top of a methyl ammonium lead triiodide (CH3 NH3 PbI3 ) absorber showed excellent stability of the power conversion efficiency (PCE) over a long time. Under the same environmental conditions (for 355 d), the average PCE of solar cells without the ALD layer decreased from 13.6 to 9.6 %, whereas that of solar cells containing 9 ALD cycles of depositing RT-ALD-Al2 O3 on top of CH3 NH3 PbI3 increased from 9.4 to 10.8 %. Spectromicroscopic investigations of the ALD/perovskite interface revealed that the maximum PCE with the ALD layer is obtained when the so-called perovskite cleaning process induced by ALD precursors is complete. The PCE enhancement over time is probably related to a self-healing process induced by the RT-ALD-Al2 O3 film. This work may provide a new direction for further improving the long-term stability and performance of perovskite solar cells.