Pseudopeptidic ligands: exploring the self-assembly of isopthaloylbisglycine (H2IBG) and divalent metal ions

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Thermal Atomic Layer Etching of Aluminum Oxide (Al2O3) Using Sequential Exposures of Niobium Pentafluoride (NbF5) and Carbon Tetrachloride (CCl4) : A Combined Experimental and Density Functional Theory Study of the Etch Mechanism

Thermal atomic layer etching (ALEt) of amorphous Al2O3 was performed by alternate exposures of niobium pentafluoride (NbF5) and carbon tetrachloride (CCl4). The ALEt of Al2O3 is observed at temperatures from 380 to 460 degrees C. The etched thickness and the etch rate were determined using spectroscopic ellipsometry and verified by X-ray reflectivity. The maximum etch rate of about 1.4 A/cycle and a linear increase of the removed film thickness with the number of etch cycles were obtained at a temperature of 460 degrees C. With the help of density functional theory calculations, an etch mechanism is proposed where NbF5 converts part of the Al2O3 surface into an AlF3 or aluminum oxyfluoride layer, which upon reacting with CCl4 is converted into volatile halide-containing byproducts, thus etching away the converted portion of the material. Consistent with this, a significant surface fluorine content of about 55 at. % was revealed when the elemental depth profile analysis of a thick NbF5-treated Al2O3 layer was performed by X-ray photoelectron spectroscopy. The surface morphology of the reference, pre-, and postetch Al2O3 surfaces was analyzed using atomic force microscopy and brightfield transmission electron microscopy. Moreover, it is found that this process chemistry is able to etch Al2O3 selectively over silicon dioxide (SiO2) and silicon nitride (Si3N4).Peer reviewe

Thermal gas-phase etching of titanium nitride (TiN) by thionyl chloride (SOCl2)

In this work, thermal based gas-phase etching of titanium nitride (TiN) is demonstrated using thionyl chloride (SOCl2) as a novel etchant. A single etchant is utilised in a pulsed fashion to etch TiN. This type of etching technique may also be considered as a chemical gas-phase or dry etching. The removed TiN amount was measured by various techniques like spectroscopic ellipsometry (SE), weighing balance and in some cases X-ray reflectometry (XRR). Additionally, the post-etch surfaces were analysed with X-ray photoelectron spectroscopy (XPS) and bright field transmission electron microscopy (BF-TEM). The surface roughness and morphology of before and after etching TiN films were measured using atomic force microscopy (AFM). The etch per cycle (EPC) was calculated and is plotted as a function of SOCl2 pulse time, purge time after SOCl2 exposure, number of etch cycles and etch temperature (T-etch). An increase in EPC with an increase in SOCl2 pulse time as well as etch temperature was observed. SOCl2 is able to etch TiN starting from 270 degrees C with an EPC of about 0.03 angstrom to almost 1.2 angstrom at 370 degrees C. Arrhenius plot determined the activation energy (E-a) of about 25 kcal/mol for TiN etching by SOCl2. In addition, the etch selectivity between different substrates such as silicon dioxide (SiO2), silicon nitride (Si3N4) and aluminum oxide (Al2O3) was investigated on blanket as well as 3D structures. Moreover, thermodynamic calculations were performed for various possible etch reactions. Titanium from TiN is proposed to be etched in the form of either titanium trichloride (TiCl3) or titanium tetrachloride (TiCl4). Nitrogen from TiN films may form volatile by-products such as diatomic nitrogen (N-2), nitrous oxide (N2O) and nitrogen dioxide (NO2).Peer reviewe

Combining Experimental and DFT Investigation of the Mechanism Involved in Thermal Etching of Titanium Nitride Using Alternate Exposures of NbF5 and CCl4, or CCl4 Only

Thermally activated chemical vapor-phase etching of titanium nitride (TiN) is studied by utilizing either alternate exposures of niobium pentafluoride (NbF5) and carbon tetrachloride (CCl4) or by using CCl4 alone. Nitrogen (N-2) gas purge steps are carried out in between every reactant exposure. Titanium nitride is etched in a non-self-limiting way by NbF5-CCl4 based binary chemistry or by CCl4 at temperatures between 370 and 460 degrees C. Spectroscopic ellipsometry and a weight balance are used to calculate the etch per cycle. For the binary chemistry, an etch per cycle of approximate to 0.8 angstrom is obtained for 0.5 and 3 s long exposures of NbF5 and CCl4, respectively at 460 degrees C. On the contrary, under the same conditions, the etch process with CCl4 alone gives an etch per cycle of about 0.5 angstrom. In the CCl4-only etch process, the thickness of TiN films removed at 460 degrees C varies linearly with the number of etch cycles. Furthermore, CCl4 alone is able to etch TiN selectively over other materials such as Al2O3, SiO2, and Si3N4. X-ray photoelectron spectroscopy and bright field transmission electron microscopy are used for studying the post-etch surfaces. To understand possible reaction products and energetics, first-principles calculations are carried out with density functional theory. From thermochemical analysis of possible reaction models, it is found that NbF5 alone cannot etch TiN while CCl4 alone can etch it at high temperatures. The predicted byproducts of the reaction between the CCl4 gas molecules and TiN surface are TiCl3 and ClCN. Similarly, TiF4, NbFCl3, and ClCN are predicted to be the likely products when TiN is exposed to both NbF5 and CCl4. A more favorable etch reaction is predicted when TiN is exposed to both NbF5 and CCl4 (Delta G = -2.7 eV at 640 K) as compared to exposure to CCl4 only (Delta G = -2 eV at 640 K) process. This indicates that an enhanced etch rate is possible when TiN is exposed alternately to both NbF5 and CCl4, which is in close agreement with the experimental results.Peer reviewe

Multisite musculoskeletal pain predicts medically certified disability retirement among Finns

BackgroundMusculoskeletal pain at several sites (multisite pain) is more common than single-site pain. Little is known on its effects on disability pension (DP) retirement. MethodsA nationally representative sample comprised 4071 Finns in the workforce aged 30 to 63. Data (questionnaire, interview, clinical examination) were gathered in 2000-2001 and linked with national DP registers for 2000-2011. Pain during the preceding month in 18 locations was combined into four sites (neck, upper limbs, low back, lower limbs). Hazard ratios (HR) of DP were estimated by Cox regression. ResultsThe HR of any DP (n=477) was 1.6 (95% confidence interval 1.2-2.1) for one, 2.5 (1.9-3.3) for two, 3.1 (2.3-4.3) for three and 5.6 (4.0-7.8) for four pain sites, when adjusted for age and gender. When additionally adjusted for clinically assessed chronic diseases, the HRs varied from 1.4 (1.0-1.8) to 3.5 (2.5-4.9), respectively. When further adjusted for physical and psychosocial workload, education, body mass index, smoking, exercise and sleep disorders, the HRs were 1.3 (0.9-1.7), 1.6 (1.2-2.2), 1.8 (1.3-2.5) and 2.5 (1.8-3.6). The number of pain sites was especially strong in predicting DPs due to musculoskeletal diseases (HRs in the full model; 3.1 to 4.3), but it also predicted DPs due to other somatic diseases (respective HRs 1.3 to 2.3); pain in all four sites was also predictive of DPs due to mental disorders (full model HR 2.2). ConclusionsThe number of pain sites independently predicted DP retirement. Employees with multisite pain may need specific support to maintain their work ability.Peer reviewe

Mental Health Conditions and Nonpersistence of Direct Oral Anticoagulant Use in Patients With Incident Atrial Fibrillation : A Nationwide Cohort Study

BACKGROUND: Mental health conditions (MHCs) are associated with poor outcomes in patients with atrial fibrillation. However, persistence of oral anticoagulation therapy in patients with atrial fibrillation and MHCs is unknown. We aimed to evaluate the effect of MHCs on the persistence of direct oral anticoagulant (DOAC) use in patients with atrial fibrillation based on a nationwide cohort. METHODS AND RESULTS: The nationwide registry-based FinACAF (Finnish Anticoagulation in Atrial Fibrillation) cohort included 67 503 patients with incident atrial fibrillation and indication for permanent oral anticoagulation (CHA(2)DS(2)-VASc score >1 in men and >2 in women) starting DOAC therapy between 2011 and 2018. MHCs of interest were depression, bipolar disorder, anxiety disorder, schizophrenia, and composite of any MHC. The main outcome was nonpersistence of DOAC use, defined as the first 120-day period without DOAC purchases after drug initiation. The mean age of the patients was 75.3 +/- 8.9 years, 53.6% were women, and the prevalence of any MHC was 17.8%. Persistence after 1 year from DOAC initiation was 79.3% in patients without MHCs and 77.2% in patients with any MHC, and after 2 years were 64.4% and 60.6%, respectively (P CONCLUSIONS: MHCs are associated with nonpersistence of DOAC use.Peer reviewe

Mental health conditions and adherence to direct oral anticoagulants in patients with incident atrial fibrillation : A nationwide cohort study

Objective: Medication adherence is essential for effective stroke prevention in patients with atrial fibrillation (AF). We aimed to assess whether adherence to direct oral anticoagulants (DOACs) in AF patients is affected by the presence of mental health conditions (MHCs). Methods: The nationwide FinACAF cohort covered 74,222 AF patients from all levels of care receiving DOACs during 2011-2018 in Finland. Medication possession ratio (MPR) was used to quantify adherence. Patients with MPR >= 0.90 were defined adherent. MHCs of interest were depression, bipolar disorder, anxiety disorder and schizophrenia. Results: The patients' (mean age 75.4 +/- 9.5 years, 50.8% female) mean MPR was 0.84 (SD 0.22), and 59.5% had MPR >= 0.90. Compared to patients without MHC, the adjusted ORs (95% CI) for adherent DOAC use emerged slightly lower in patients with depression (0.92 (0.84-0.99)) and bipolar disorder (0.77 (0.61-0.97)) and unsignificant in patients with anxiety disorder (1.08 (0.96-1.21)) and schizophrenia (1.13 (0.90-1.43)). However, when only persistent DOAC therapy was analyzed, no MHC was associated with poor adherence, and instead anxiety disorder was associated with adherent DOAC use (1.18 (1.04-1.34)). Conclusion: Adherence to DOACs in AF patients in Finland was relatively high, and no meaningful differences between patients with and without MHCs were observed.Peer reviewe

All-Cause and Cause-Specific Mortality among Users of Basal Insulins NPH, Detemir, and Glargine

Background Insulin therapy in type 2 diabetes may increase mortality and cancer incidence, but the impact of different types of basal insulins on these endpoints is unclear. Compared to the traditional NPH insulin, the newer, longer-acting insulin analogues detemir and glargine have shown benefits in randomized controlled trials. Whether these advantages translate into lower mortality among users in real life is unknown. Objective To estimate the differences in all-cause and cause-specific mortality rates between new users of basal insulins in a population-based study in Finland. Methods 23 751 individuals aged >= 40 with type 2 diabetes, who initiated basal insulin therapy in 2006-2009 were identified from national registers, with comprehensive data for mortality, causes of death, and background variables. Propensity score matching was performed on characteristics. Follow-up time was up to 4 years (median 1.7 years). Results 2078 deaths incurred. With NPH as reference, the adjusted HRs for all-cause mortality were 0.39 (95% CI, 0.30-0.50) for detemir, and 0.55 (95% CI, 0.44-0.69) for glargine. As compared to glargine, the HR was 0.71 (95% CI, 0.54-0.93) among detemir users. Compared to NPH, the mortality risk for both cardiovascular causes as well as cancer were also significantly lower for glargine, and especially for detemir in adjusted analysis. Furthermore, the results were robust in various sensitivity analyses. Conclusion In real clinical practice, mortality was substantially higher among users of NPH insulin as compared to insulins detemir or glargine. Considering the large number of patients who require insulin therapy, this difference in risk may have major clinical and public health implications. Due to limitations of the observational study design, further investigation using an interventional study design is warranted.Peer reviewe

The effect of mental health conditions on the use of oral anticoagulation therapy in patients with atrial fibrillation : the FinACAF study

Aims Little is known about the effects of mental health conditions (MHCs) on the utilization of oral anticoagulation (OAC) therapy in atrial fibrillation (AF) patients. We aimed to assess whether MHCs affect initiation of OAC therapy among AF patients with special focus on non-vitamin K antagonist oral anticoagulants (NOACs). Methods and results The Finnish AntiCoagulation in Atrial Fibrillation (FinACAF) registry included all 239 222 patients diagnosed with incident AF during 2007-18 in Finland identified from national registries covering primary to tertiary care and drug purchases. Patients with previous depression, bipolar disorder, anxiety disorder, or schizophrenia diagnosis or a fulfilled psychiatric medication prescription within the year preceding the AF diagnosis were classified to have any MHC. The main outcome was OAC initiation, defined as first fulfilled OAC prescription after AF diagnosis. The patients' mean age was 72.7 years and 49.8% were female. The prevalence of any MHC was 19.9%. A lower proportion of patients with any MHC compared with those without MHCs were initiated on OAC therapy (64.9% vs. 73.3%, P < 0.001). Any MHC was associated with lower incidence of OAC initiation [adjusted subdistribution hazard ratio (aSHR) 0.867; 95% confidence interval (CI) 0.856-0.880], as were depression (aSHR 0.868; 95% CI 0.856-0.880), bipolar disorder (aSHR 0.838; 95% CI 0.824-0.852), anxiety disorder (aSHR 0.840; 95% CI 0.827-0.854), and schizophrenia (aSHR 0.838; 95% CI 0.824-0.851), during the entire follow-up. Any MHC remained associated with impaired incidence of OAC initiation also in the NOAC era during 2015-18 (aSHR 0.821; 95% CI 0.805-0.837). Conclusion MHCs are common among AF patients, and they are associated with a lower rate of OAC initiation even during the NOAC era.Peer reviewe