M. Creatore

Plasma-assisted atomic layer deposition of Al2O3 moisture permeation barriers on polymers

Thin Al2O3 films of different thicknesses (10–40nm) were deposited by plasma-assisted atomic layer deposition on substrates of poly(2,6-ethylenenaphthalate) (PEN), and the water vapor transmission rate (WVTR) values were measured by means of the calcium test. The permeation barrier properties improved with decreasing substrate temperature and a good WVTR of 5×10−3gm−2day−1 (WVTRPEN=0.5gm−2day−1) was measured for a 20nm thick Al2O3 film deposited at room temperature using short purging times. Such ultrathin, low-temperature deposited, high-quality moisture permeation barriers are an essential requirement for the implementation of polymeric substrates in flexible electronic and display applications.

Evolution of the electrical and structural properties during the growth of Al doped ZnO films by remote plasma-enhanced metalorganic chemical vapor deposition

Al-doped zinc oxide (AZO) films were deposited by means of remote plasma-enhanced metalorganic chemical vapor deposition from oxygen/diethylzinc/trimethylaluminum mixtures. The electrical, structural (crystallinity and morphology), and chemical properties of the deposited films were investigated using Hall, four point probe, x-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), electron recoil detection (ERD), Rutherford backscattering (RBS), and time of flight secondary ion mass spectrometry (TOF-SIMS), respectively. We found that the working pressure plays an important role in controlling the sheet resistance Rs and roughness development during film growth. At 1.5 mbar the AZO films are highly conductive (Rs 4% of the film thickness), however, they are characterized by a large sheet resistance gradient with increasing film thickness. By decreasing the pressure from 1.5 to 0.38 mbar, the gradient is significa...

Rf plasma deposition of SiO2-like films : plasma phase diagnostics and gas barrier film properties optimisation

Hexamethyldisiloxane/oxygen fed radiofrequency glow discharges have been utilised for the deposition onto polyethyleneterephtalate of transparent silicon dioxide-like films with barrier properties to oxygen. The complexity of such plasma phases and the increasing interest shown for the industrial deposition process of barrier films have led the authors to investigate Fourier transform infrared absorption spectroscopy as a plasma technique for better understanding of the deposition mechanism and the development of a process control useful for scaling up. The above mentioned technique has shown its potential in the correlation of plasma phase chemistry with the barrier properties of the SiOx coated polymer, especially when very good performances are required (OTR≤3 cm3/m2 day atm).

In situ spectroscopic ellipsometry growth studies on the Al-doped ZnO films deposited by remote plasma-enhanced metalorganic chemical vapor deposition

In situ spectroscopic ellipsometry (SE) was applied to study the pyramidlike and pillarlike growth of Al doped ZnO (AZO) films deposited by means of remote plasma-enhanced metalorganic chemical vapor deposition for transparent conductive oxide applications. Real time SE studies in the visible region allowed discerning between the two growth modes by addressing the time evolution of the bulk and surface roughness layer thickness. While the pillarlike mode is characterized by a constant growth rate, a slower rate in the initial stage (up to 150–200 nm film thickness), compared to the bulk, is observed for the growth of pyramidlike AZO films. The two modes differ also in terms of surface roughness development: a saturation behavior is observed for film thickness above 150–200 nm in the case of the pyramidlike films, while a slow linear increase with film thickness characterizes the pillarlike mode. By extending the SE analysis of the AZO films to the near infrared region, valuable information about the in gr...

Deposition of SiOx : films from hexamehtyldisiloxane/oxygen radiofrequency glow discharges: process optimization by plasma diagnostics

Optical emission and Fourier transform infrared absorption diagnostics have been carried out in hexamethyldisiloxane/oxygen RF discharges for studying the effects of the feed composition and the power on the deposition of SiO2—like thin films. Ex situ FTIR absorption has been utilized to monitor organic moieties and silanol groups in the film. It is shown that carbon-free films can be obtained by highly diluting the monomer in oxygen, while medium-to-high power is necessary to abate silanol groups. These two conditions represent the optimization criterion to obtain excellent barrier films for food packaging applications.

High-efficiency humidity-stable planar perovskite solar cells based on atomic layer architecture

Perovskite materials are drawing tremendous interest for photovoltaic solar cell applications, but are hampered by intrinsic material and device instability issues. Such issues can arise from environmental influences as well as from the chemical incompatibility of the perovskite layer with charge transport layers and electrodes used in the device stack. Several attempts have been made to address the instability issue, mostly concentrating on the substitution of the organic cations in the perovskite lattice, and on alternatives for the organic charge extraction layers, without laying much emphasis on stabilising the existing, conventional high efficiency methylammonium lead iodide/spiro-OMeTAD based devices. To address the latter issue, we utilized atomic layer deposition (ALD) as a straightforward and soft deposition process to conformally deposit Al2O3 on top of the perovskite absorber. An ultra-thin ALD Al2O3 film effectively protects the perovskite layer while it is sufficiently thin enough to provide a tunnel contact. The fabricated perovskite solar cells (PSCs) exhibit superior device performance with a stabilised power conversion efficiency (PCE) of 18%, a significant reduction in hysteresis loss, and enhanced long-term stability (beyond 60 days) as a function of the unencapsulated storage time in ambient air, under humidity conditions ranging from 40 to 70% at room temperature. PCE measurements after 70 days of humidity exposure show that the devices incorporating 10 cycles of ALD Al2O3 could significantly retard the humidity-induced degradation thereby retaining about 60–70% of its initial PCE, while that of the reference devices drops to a remaining 12% of their initial PCE. This work successfully addresses and tackles the problem of the hybrid organic–inorganic IV-halide perovskite solar cell’s instability in a humid environment, and the key findings pave the way to the upscaling of these devices.

Process control for plasma processing of polymers

Abstract PE-CVD processes of a variety of coatings — fluoropolymers, SiO x , PEO- and Ag-PEO-like, COOH functional layers — are described, as well as plasma treatments aimed to selectively graft NH 2 groups on polymers, with the use of spectroscopic plasma- and surface-diagnostics parameters of potential use for process transfer and control in industrial applications.

High current diffuse dielectric barrier discharge in atmospheric pressure air for the deposition of thin silica-like films

The diffuse dielectric barrier discharge in atmospheric pressure air was applied for the thin film deposition on polymeric web in industrially relevant roll-to-roll configuration. The silica-like film deposition was performed using the admixture of hexamethyldisiloxane precursor to air flow. Fast discharge imaging at 2 μs exposure time confirms plasma uniformity in a single current pulse time scale. Morphology and composition analyses indicate that the process results in ultrasmooth films (roughness comparable to initial substrate roughness) and shows the possibility to synthesize carbon-free layers.

High-rate plasma-deposited SiO2 films for surface passivation of crystalline silicon

SiO2 films were deposited by means of the expanding thermal plasma technique at rates in the range of 0.4–1.4μm∕min using an argon∕oxygen∕octamethylcyclotetrasiloxane (OMCTS) gas mixture. The film composition was studied by means of various optical and nuclear profiling techniques. The films deposited with a low OMCTS to oxygen ratio showed no residual carbon and a low hydrogen content of ∼2% with a refractive index close to thermal oxide. For a higher OMCTS to oxygen ratio a carbon content of ∼4% was detected in the films and the refractive index increased to 1.67. The surface passivation of the SiO2 films was tested on high quality crystalline silicon. The films yielded an excellent level of surface passivation for plasma-deposited SiO2 films with an effective surface recombination velocity of 54cm∕s on 1.3Ωcm n-type float zone crystalline silicon substrates after a 15min forming gas anneal at 600°C.

On the formation mechanisms of the diffuse atmospheric pressure dielectric barrier discharge in CVD processes of thin silica-like films

Pathways of formation and temporal evolution of the diffuse dielectric barrier discharge at atmospheric pressure were experimentally studied in this work by means of optical (fast imaging camera) and electrical diagnostics. The chosen model system is relevant for applications of plasma-enhanced chemical vapor deposition of thin silica-like film on the polymeric substrate, from cost-efficient gas mixtures of Ar/N2/O2/hexamethyldisiloxane. It was found that the discharge can gradually experience the phases of homogeneous low current Townsend-like mode, local Townsend to glow transition and expanding high current density (?0.7Acm?2) glow-like mode. While the glow-like current spot occupies momentarily only a small part of the electrode area, its expanding behavior provides uniform treatment of the whole substrate surface. Alternatively, it was observed that a visually uniform discharge can be formed by the numerous microdischarges overlapping over the large electrode area.