Chemical vapor deposition of (in)organic layers : in situ film growth studies, nano-porosity and moisture permeation barrier properties

Although polymers represent the substrate of choice for flexible devices such as solar cells and OLEDs because they are lightweight, flexible, transparent, inexpensive, and compatible with roll-to-roll processing, they have the drawback to be highly permeable to moisture and oxygen. This poses severe limitations to the performance of the flexible device. This drawback is presently addressed by depositing inorganic (Al2O3, SiO2, Si3N4) thin film barrier layers on the polymer substrate. Despite their impermeable bulk counterpart, the (water vapor) permeation through single barrier layers is driven by several paths, which include nm-sized pores as well as substrate/process induced macro-defects. It is, therefore, of paramount importance to determine and control the density of the macro-defects, as well as to control the inorganic barrier layer microstructure, defined by its (open) nano-porosity. The state-of-the art in barrier layer technology applied to polymer substrates as well as to the direct encapsulation of the (flexible) device is a µm-thick multilayer consisting of inorganic barrier layers decoupled by organic interlayers. This encapsulation solution against water permeation into the device can virtually guarantee a device lifetime of ten years. Although several approaches have been followed in engineering the multilayer, there is still a debate on the effective role of the organic interlayer in affecting the multilayer barrier properties. It is generally considered that the organic interlayer acts as smoothening layer allowing the decoupling between macro-defects either present on the polymer substrate or in the inorganic barrier layer. It is also hypothesized that the organic interlayer infiltrates into the nano-pores present in the barrier layer, therefore affecting the barrier itself at microstructure level. However, this hypothesis has neither been followed by any experimental evidence, nor it has been investigated in the case of organic interlayer deposition methods other than polymerization from its liquid phase. This thesis work aimed to gain insight into the role of the organic interlayer in affecting the multilayer barrier properties. A model system, based on a siloxane chemistry, has been adopted in which the multi-layer is developed by means of two vacuum deposition techniques, i.e. PECVD for the inorganic SiO2-like barrier layer and initiated-chemical vapor deposition (i-CVD) for the poly(V3D3) organic interlayer. This latter allows the polymerization process to develop organic films with full retention of the monomer chemistry. A novel deposition setup has been, therefore, developed to implement both deposition processes in a vacuum chamber, equipped with in situ real time diagnostic tools, such as spectroscopic ellipsometry (SE). As first research step, the i-CVD polymer growth has been studied in situ by means of SE which allowed following all stages of the deposition process from the initial monomer adsorption to the linear film growth and to the thickness losses due to the presence of unreacted monomer units at the end of the deposition process. Moreover, in situ SE measurements allowed characterizing the thickness losses as bulk- related phenomenon and brought new information on the polymerization process which propagate not only at the surface of the growing layer but also in the bulk. Furthermore, a correlation has been made between specific process parameters (i.e. the monomer surface concentration) and the deposition of stable, highly cross-linked polymer layers (i.e. exhibiting no thickness loss upon evacuation). This has allowed to define a process parameter window, i.e. PM/Psat, followed in situ by SE, which controls the deposition of high quality poly(V3D3) layers. The follow-up studies of the i-CVD polymer growth on SiO2-like moisture permeation barrier layers, performed by means i-CVD monomer (V3D3) adsorption/desorption isothermal studies, have highlighted the filling/infiltration of the i-CVD monomer into the open nano-defects/porosity of the SiO2-like layer underneath. This result has, therefore, provided support to the above-mentioned hypothesis on the infiltration of the organic interlayer into the nano-porosity of the SiO2-like barrier layer underneath. Finally, the contribution to the improvement of the barrier performance of the PE-CVD/i-CVD deposited multilayer due the filling of the PE-CVD deposited SiO2-like layer nano-pores has been studied with respect to the smoothening/decoupling effect of the SiO2-like layers macro-defects. Ca test measurements allowed discerning between the water permeation through the macro-defects/pinholes and the permeation through the matrix. The effect of the filling/infiltration of the SiO2-like layer nano-defects has been studied as function of intrinsic porosity of the SiO2-like layer (i.e. as function of the intrinsic WVTR values). It is concluded that the effect of the SiO2-like nano-defect filling by the poly(V3D3) is effective only for SiO2-like layers initially exhibiting an intrinsic WVTR value > 10-3 g m-2 day-1. The above-mentioned results, in combination with an evaluation of the local macro-defects prior and upon deposition of the organic interlayer, and a comparison with parallel studies reported in literature, allow to conclude that the main contribution of the i-CVD layer in improving the multilayer barrier properties is given by the smoothening/decoupling of the macro-defects. The SiO2-like layer microstructure characterization has been carried out on layers deposited on a silicon substrate by means of ellipsometric porosimetry measurements which allowed discerning between the different residual open porosity of the deposited SiO2-like layers. The same characterization in terms of refractive index and residual open porosity, however, should be also carried out in case of polymers as substrates, for example for barrier-on-foil applications. However, polymeric substrates often show optical anisotropy and the proper determination of the barrier layer optical constants can be achieved only by a proper optical characterization of the substrate. In order to perform the microstructure characterization of barrier layers deposited on polymers, the polymer (poly(ethylenenaphtalate), PEN) anisotropy has been characterized by means of the Generalized and Spectroscopic Ellipsometry combined approach. This approach has allowed defining the optical constants of a SiO2-like barrier layer deposited on PEN

Initiated-chemical vapor deposition of organosilicon layers: Monomer adsorption, bulk growth, and process window definition

Organosilicon layers have been deposited from 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane (V3D3) by means of the initiated-chemical vapor deposition (i-CVD) technique in a deposition setup, ad hoc designed for the engineering of multilayer moisture permeation barriers. The application of Fourier transform infrared (FTIR) spectroscopy shows that the polymerization proceeds through the scission of the vinyl bond and allows quantifying the degree of conversion of vinyl groups, which is found to be larger than 80% for all the deposited layers. In situ real-time spectroscopic ellipsometry (SE) allows following all the i-CVD growth stages, i.e., from the initial monomer adsorption to the layer bulk growth. Finally, the combination of SE and FTIR has allowed defining the process window for the deposition of stable and highly cross-linked poly(V3D3) layers by tuning a key process parameter, i.e. the surface monomer adsorption. (C) 2012 American Vacuum Society. [http://dx.doi.org/10.1116/1.4711762

The impact of the nano-pore filling on the performance of organosilicon-based moisture barriers

Promising results in terms of moisture and oxygen permeation barrier properties have been reported for organic/inorganic multilayers, but the impact of the organic interlayer on the overall barrier performance is still under discussion. It is generally accepted that the organic interlayer acts as a smoothening layer, allowing for the decoupling between defects/pinholes present in the polymer substrate and the inorganic layer. It is, however, also hypothesized that the organic interlayer infiltrates into the nano-pores present in the inorganic barrier layer, therefore affecting the barrier properties at microstructural level. In the present work, the moisture permeation barrier performance of SiO2/organosilicon multilayers deposited by means of initiated- and plasma enhanced-chemical vapor deposition is investigated. Calcium test measurements were used to discriminate between the overall water permeation (effective water vapor transmission rate, WVTR) through the layer and the permeation through the matrix porosity (intrinsic WVTR). The improvement in terms of intrinsic barrier performance was found to correlate with the residual nano-porosity content, due to the filling/infiltration of the organosilicon monomer in the SiO2 nano-pores. However, such improvement upon the deposition of the organosilicon interlayer is limited to a factor four. These results, in combination with the analysis of the local defects present in the multilayer structure, lead to the conclusion that the main contribution of the organosilicon interlayer to the overall barrier performance is the decoupling of the above-mentioned local defects/pinholes

Vitamin D and COVID-19 severity and related mortality: a prospective study in Italy

Abstract Background Vitamin D deficiency has been suggested to favor a poorer outcome of Coronavirus disease-19 (COVID-19). We aimed to assess if 25-hydroxyvitamin-D (25OHD) levels are associated with interleukin 6 (IL-6) levels and with disease severity and mortality in COVID-19. Methods We prospectively studied 103 in-patients admitted to a Northern-Italian hospital (age 66.1 ± 14.1 years, 70 males) for severely-symptomatic COVID-19. Fifty-two subjects with SARS-CoV-2 infection but mild COVID-19 symptoms (mildly-symptomatic COVID-19 patients) and 206 subjects without SARS-CoV-2 infection were controls. We measured 25OHD and IL-6 levels at admission and focused on respiratory outcome during hospitalization. Results Severely-symptomatic COVID-19 patients had lower 25OHD levels (18.2 ± 11.4 ng/mL) than mildly-symptomatic COVID-19 patients and non-SARS-CoV-2-infected controls (30.3 ± 8.5 ng/mL and 25.4 ± 9.4 ng/mL, respectively, p < 0.0001 for both comparisons). 25OHD and IL-6 levels were respectively lower and higher in severely-symptomatic COVID-19 patients admitted to intensive care Unit [(ICU), 14.4 ± 8.6 ng/mL and 43.0 (19.0–56.0) pg/mL, respectively], than in those not requiring ICU admission [22.4 ± 1.4 ng/mL, p = 0.0001 and 16.0 (8.0–32.0) pg/mL, p = 0.0002, respectively]. Similar differences were found when comparing COVID-19 patients who died in hospital [13.2 ± 6.4 ng/mL and 45.0 (28.0–99.0) pg/mL] with survivors [19.3 ± 12.0 ng/mL, p = 0.035 and 21.0 (10.5–45.9) pg/mL, p = 0.018, respectively). 25OHD levels inversely correlated with: i) IL-6 levels (ρ − 0.284, p = 0.004); ii) the subsequent need of the ICU admission [relative risk, RR 0.99, 95% confidence interval (95%CI) 0.98–1.00, p = 0.011] regardless of age, gender, presence of at least 1 comorbidity among obesity, diabetes, arterial hypertension, creatinine, IL-6 and lactate dehydrogenase levels, neutrophil cells, lymphocytes and platelets count; iii) mortality (RR 0.97, 95%CI, 0.95–0.99, p = 0.011) regardless of age, gender, presence of diabetes, IL-6 and C-reactive protein and lactate dehydrogenase levels, neutrophil cells, lymphocytes and platelets count. Conclusion In our COVID-19 patients, low 25OHD levels were inversely correlated with high IL-6 levels and were independent predictors of COVID-19 severity and mortality