Ellipsometric Porosimetry for the Microstructure Characterization of Plasma-Deposited SiO2-Like Films

SiO2 layers have been deposited from Ar/O2/hexamethyldisiloxane mixtures in a remote expanding thermal plasma setup enabling a good control of both the ion flux (by changing the deposition chemistry and the arc plasma parameters) as well as the ion energy. This latter is achieved by an additional rf substrate biasing or a tailored ion biasing technique, i.e. a low frequency pulse-shaped bias. The role of the ion energy and ion-to-growth flux ratio on the film microstructure and densification at low substrate temperature (100ºC) has been investigated by means of ellipsometric porosimetry. This technique monitors the refractive index change due to the adsorption (and desorption) of ethanol vapors in the volume of macro-meso-micro pores in the SiO2 layer. From the analysis of the adsorption isotherm and the presence of hysteresis during the desorption step as a function of the equilibrium partial pressure, the open porosity in the layer can be determined. It is found that both biasing techniques lead to densification of the deposited layer, which experiences a transition from micro-/ mesoporosity to microporosity and eventually non-porosity, as function of the increasing ion energy. Although both biasing techniques lead to a comparable critical ion energy value per deposited SiO2 unit (about 100 eV), the ion-to-growth flux ratio and ion energy are not found to be interchangeable parameters. In fact, in the case of the rf bias, the meso- and large micropores are first affected leading to a quantitative decrease of porosity, i.e. from 11% to 3% at an ion energy less than 20 eV. A further increase in ion energy eventually reduces the presence of smaller micropores leading to non porous films at energy of 45 eV. When the pulse-shaped biasing technique is adopted, the micro- and mesopores are simultaneously affected over the whole range of available ion energy, leading to a non porous layer only at very high energy values, i.e. 240 eV. This difference is attributed to the increasing ion-to-growth flux ratio accompanying the rf biasing, as a consequence of the rf plasma generation in front of the substrate

Improved conductivity of aluminum-doped ZnO : the effect of hydrogen diffusion from a hydrogenated amorphous silicon capping layer

Plasma-deposited aluminum-doped ZnO (ZnO:Al) demonstrated a resistivity gradient as function of the film thickness, extending up to about 600¿nm. This gradient decreased sharply when the ZnO:Al was capped by a hydrogenated amorphous silicon layer (a-Si:H) and subsequently treated according to the solid phase crystallization (SPC) procedure at 600¿°C. The resistivity reduced from 1.2¿·¿10-1 to 2.6¿·¿10-3 O¿·¿cm for a film thickness of 130¿nm, while for thicker films the decrease in resistivity was less pronounced, i.e., a factor of 2 for a film thickness of 810¿nm. While the carrier concentration was not affected, the mobility significantly increased from 7 to 30 cm2/V¿·¿s for the thick ZnO:Al layers. This increase was ascribed to the passivation of grain boundary defects by hydrogen, which diffused from the a-Si:H toward the ZnO:Al during the SPC procedure. The passivation effect was more pronounced in thinner ZnO:Al layers, characterized by a smaller grain size, due to the presence of large grain boundaries. For thicker films with grain sizes up to 200–300¿nm the mobility became progressively less affected by the presence of grain boundaries. Therefore, the hydrogen-induced improvement in conductivity was less significant for the thick ZnO:Al film

Control by atomic layer deposition over the chemical composition of nickel cobalt oxide for the oxygen evolution reaction

Anion exchange membrane water electrolysis (AEMWE) is a promising technology for renewable electricity-driven water splitting toward hydrogen production. However, application of AEMWE at industrial scale requires the development of oxygen evolution reaction (OER) electrocatalysts showing long-term stability under mild alkaline conditions. Among these, nickel cobalt oxide thin films are considered promising candidates. The ideal chemical composition of these oxides remains debatable, with recent literature indicating that rock-salt NiCoO2 may exhibit similar OER activity as the traditional spinel NiCo2O4. In this work, we present the development of a plasma-enhanced atomic layer deposition (ALD) process of nickel cobalt oxide thin films (∼20 nm) with focus on the role of their chemical composition and crystal structure on the OER activity. The film composition is tuned using a supercycle approach built upon CoOx cycles with CoCp2 as a precursor and O2 plasma as a co-reactant and NiOx cycles with Ni(MeCp)2 as a precursor and O2 plasma as a co-reactant. The films exhibit a change in the crystallographic phase from the rock-salt to spinel structure for increasing cobalt at. %. This change is accompanied by an increase in the Ni3+-to-Ni2+ ratio. Interestingly, an increase in electrical conductivity is observed for mixed oxides, with an optimum of (2.4 ± 0.2) × 102 S/cm at 64 at. % Co, outperforming both NiO and Co3O4 by several orders of magnitude. An optimal electrocatalytic performance is observed for 80 at. % Co films. Cyclic voltammetry measurements simultaneously show a strong dependence of the OER-catalytic performance on the electrical conductivity. The present study highlights the merit of ALD in controlling the nickel cobalt oxide chemical composition and crystal structure to gain insight into its electrocatalytic performance. Moreover, these results suggest that it is important to disentangle conductivity effects from the electrocatalytic activity in future work

Supported polysilsesquioxane membrane and production thereof

Membranes of the invention comprise a hybrid silica film on a organic polymer support. The silica comprises organic bridging groups bound to two or more silicon atoms, in particular at least 1 of said organic bridging groups per 10 silicon atoms. The membranes can be produced by dry chemistry processes, in particular plasma-enhanced vapour deposition of bridged silane precursors, or by wet chemistry involving hydrolysis of the bridged silane precursors. The membranes are inexpensive and efficient for separation of small molecules and filtration processes

Efficient light harvesting from flexible perovskite solar cells under indoor white light-emitting diode illumination

This is the first report of an investigation on flexible perovskite solar cells for artificial light harvesting by using a white light-emitting diode (LED) lamp as a light source at 200 and 400 lx, values typically found in indoor environments. Flexible cells were developed using either low-temperature sol–gel or atomic-layer-deposited compact layers over conducting polyethylene terephthalate (PET) substrates, together with ultraviolet (UV)-irradiated nanoparticle TiO2 scaffolds, a CH3NH3PbI3–xClx perovskite semiconductor, and a spiro-MeOTAD hole transport layer. By guaranteeing high-quality carrier blocking (via the 10–40 nm-thick compact layer) and injection (via the nanocrystalline scaffold and perovskite layers) behavior, maximum power conversion efficiencies (PCE) and power densities of 10.8% and 7.2 μW·cm–2, respectively, at 200 lx, and 12.1% and 16.0 μW·cm–2, respectively, at 400 lx were achieved. These values are the state-of-the-art, comparable to and even exceeding those of flexible dye-sensitized solar cells under LED lighting, and significantly greater than those for flexible amorphous silicon, which are currently the main flexible photovoltaic technologies commercially considered for indoor applications. Furthermore, there are significant margins of improvement for reaching the best levels of efficiency for rigid glass-based counterparts, which we found was a high of PCE ~24% at 400 lx. With respect to rigid devices, flexibility brings the advantages of being low cost, lightweight, very thin, and conformal, which is especially important for seamless integration in indoor environments.</p

Strong and weak coupling limits in optics of quantum well excitons

A transition between the strong (coherent) and weak (incoherent) coupling limits of resonant interaction between quantum well (QW) excitons and bulk photons is analyzed and quantified as a function of the incoherent damping rate caused by exciton-phonon and exciton-exciton scattering. For confined QW polaritons, a second, anomalous, damping-induced dispersion branch arises and develops with increasing damping. In this case, the strong-weak coupling transition is attributed to a critical damping rate, when the intersection of the normal and damping-induced dispersion branches occurs. For the radiative states of QW excitons, i.e., for radiative QW polaritons, the transition is described as a qualitative change of the photoluminescence spectrum at grazing angles along the QW structure. Furthermore, we show that the radiative corrections to the QW exciton states with in-plane wavevector approaching the photon cone are universally scaled by an energy parameter rather than diverge. The strong-weak coupling transition rates are also proportional to the same energy parameter. The numerical evaluations are given for a GaAs single quantum well with realistic parameters.Comment: Published in Physical Review B. 29 pages, 12 figure

Expanding Thermal Plasma Deposition of a-Si:H Thin Films for Surface Passivation of c-Si Wafers,

We investigated the material properties of expanding thermal plasma deposited a-Si:H thin films, providing a record-low surface recombination velocity of 1.6 cm/s (at injection level of 1 1015 cm-3). a-Si:H thin films with different thicknesses have been deposited at a high deposition rate (1.2 nm/s) on both sides of low resistivity (1-5 Ohm cm), 260µm thick, n- and ptype c-Si FZ wafers. The material properties of a -Si:H films have been characterized by Fourier Transform Infrared diagnostic and Spectroscopic Ellipsometry. The surface passivation of the wafers has been determined by photoconductivity decay measurements of the effective carrier lifetime. The investigation points out that the growth of ETP a-Si:H films begins with the formation of a thin porous layer (&lt;10 nm) with a refractive index of 3.9 (at 2 eV) and a microstructure parameter (R*) of 0.50. Despite the open network formation at the a-Si/c-Si interface, a 7 nm a-Si:H film achieves a recombination velocity as low as 12 cm/s (at 1·1015 cm-3 injection level on ntype wafers). The good passivation is probably due to the large hydrogen content of the a-Si:H film, which terminates dangling bonds present on the c-Si surface. After this initial growth, a dense a-Si:H network develops with a refractive index of 4.3 (at 2 eV) and R* = 0.03. The surface recombination velocity decresses linearly with the a-Si:H thickness, achieving a record value of 1.6 cm/s (at 1·1015 cm-3 injection level) for 90 nm thick a-Si film on n-type wafers. As compared to hot wire CVD and radiofrequency PECVD techniques, ETP is capable to deposit thin a-Si:H films with outstanding surface passivation at higher temperature (250° C) and higher deposition rate (1.2 nm/s). The stability in time of surface passivation has been investigated. Effective carrier lifetime is found to decrease following a stretched exponential. Photo-electronic properties of a-Si:H are know to relax in time in a similar fashion. These results therefore suggest a correlation between the photo-electronic roperties of the a-Si:H/c-Si interface and a-Si:H bulk material

Nitrogen incorporation during metal organic chemical vapor deposition of ZnO films using a remote Ar/N2 plasma

Nitrogen-contg. zinc oxide films were deposited by the metal org. CVD technique from oxygen/diethylzinc mixts. injected in an argon/nitrogen expanding thermal plasma. IR spectroscopy and mass spectrometry measurements suggest that nitrogen is incorporated mostly as -C.tplbond.N and segregated at grain boundaries. The correlation between the presence of nitrile bonds and the formation of HCN in the plasma phase points towards an inherent limitation during such deposition process, i.e., when using carbon-rich precursors in a highly reactive nitrogen environment, such as an Ar/N2 expanding thermal plasma. [on SciFinder (R)

Application of atmospheric pressure glow discharge (APGD) for deposition of thin silica like films on polymeric webs

Silica-like films were deposited on PEN and PET polymeric foils in atmospheric pressure glow discharge (APGD) in a roll-to-roll reactor open to ambient air. APGD was ignited in a mixture of inexpensive carrying gas argon and nitrogen with oxygen and hexamethyldisiloxane (HMDSO) precursor. The uniform diffuse glow in various gas mixtures was sustained by utilizing electronic stabilization network. APGD operation in air for a present setup was demonstrated. The contribution of different deposition mechanisms to the resulting silica-like film is discussed. The dependence of film structure and chemical composition on the conditions during deposition process was studied by means of SEM, ATR-FTIR and XPS analysis. The influence of oxidant concentration on the deposited film properties is analyzed and discussed