Exchange Interactions Mediated by Nonmagnetic Cations in Double Perovskites.

Establishing the physical mechanism governing exchange interactions is fundamental for exploring exotic phases such as quantum spin liquids in real materials. In this Letter, we address exchange interactions in Sr_{2}CuTe_{x}W_{1-x}O_{6}, a series of double perovskites that realize a spin-1/2 square lattice and are suggested to harbor a quantum spin liquid ground state arising from the random distribution of nonmagnetic ions. Our ab initio multireference configuration interaction calculations show that replacing Te atoms with W atoms changes the dominant couplings from nearest to next-nearest neighbor due to the crucial role of unoccupied states of the nonmagnetic ions in the super-superexchange mechanism. Combined with spin-wave theory simulations, our calculated exchange couplings provide an excellent description of the inelastic neutron scattering spectra of the parent compounds, as well as explaining that the magnetic excitations in Sr_{2}CuTe_{0.5}W_{0.5}O_{6} emerge from bond-disordered exchange couplings. Our results demonstrate the crucial role of the nonmagnetic cations in exchange interactions paving the way to further explore quantum spin liquid phases in bond-disordered materials.

Atomic/molecular layer deposition of Cu-organic thin films.

The gas-phase atomic/molecular layer deposition (ALD/MLD) technique is strongly emerging as a viable approach to fabricate new exciting inorganic-organic hybrid thin-film materials. However, much less effort has been made to develop new precursors specifically intended for ALD/MLD; this applies to both the organic and inorganic precursors, and in the latter case in particular to transition metal precursors. Here we introduce copper bisdimethylaminopropoxide (Cu(dmap)2) as a promising transition metal precursor for ALD/MLD to be combined with a variety of organic precursors with different backbones and functional groups, i.e. hydroquinone (HQ), terephthalic acid (TPA), 4,4'-oxydianiline (ODA), p-phenylenediamine (PPDA) and 1,4-benzenedithiol (BDT). Hybrid Cu-organic thin films were obtained from all five organic precursors with appreciably high growth rates ranging from 1.0 to 2.6 Å per cycle. However, the Cu(dmap)2 + HQ process was found to yield hybrid Cu-organic films only at temperatures below 120 °C, while at higher temperatures metallic Cu films were obtained. The films were characterized by XRR, GIXRD, FTIR, Raman, XPS and UV-Vis spectroscopy.

Iron-Terephthalate Coordination Network Thin Films Through In-Situ Atomic/Molecular Layer Deposition.

Iron terephthalate coordination network thin films can be fabricated using the state-of-the-art gas-phase atomic/molecular layer deposition (ALD/MLD) technique in a highly controlled manner. Iron is an Earth-abundant and nonhazardous transition metal, and with its rich variety of potential applications an interesting metal constituent for the inorganic-organic coordination network films. Our work underlines the role of the metal precursor used when aiming at in-situ ALD/MLD growth of crystalline inorganic-organic thin films. We obtain crystalline iron terephthalate films when FeCl3 is employed as the iron source whereas depositions based on the bulkier Fe(acac)3 precursor yield amorphous films. The chemical composition and structure of the films are investigated with GIXRD, XRR, FTIR and XPS.

Spin-liquid-like state in a spin-1/2 square-lattice antiferromagnet perovskite induced by d10-d0 cation mixing.

A quantum spin liquid state has long been predicted to arise in spin-1/2 Heisenberg square-lattice antiferromagnets at the boundary region between Néel (nearest-neighbor interaction dominates) and columnar (next-nearest-neighbor interaction dominates) antiferromagnetic order. However, there are no known compounds in this region. Here we use d10-d0 cation mixing to tune the magnetic interactions on the square lattice while simultaneously introducing disorder. We find spin-liquid-like behavior in the double perovskite Sr2Cu(Te0.5W0.5)O6, where the isostructural end phases Sr2CuTeO6 and Sr2CuWO6 are Néel and columnar type antiferromagnets, respectively. We show that magnetism in Sr2Cu(Te0.5W0.5)O6 is entirely dynamic down to 19 mK. Additionally, we observe at low temperatures for Sr2Cu(Te0.5W0.5)O6-similar to several spin liquid candidates-a plateau in muon spin relaxation rate and a strong T-linear dependence in specific heat. Our observations for Sr2Cu(Te0.5W0.5)O6 highlight the role of disorder in addition to magnetic frustration in spin liquid physics.

Atomic layer deposition of nickel-cobalt spinel thin films.

We report the atomic layer deposition (ALD) of high-quality crystalline thin films of the spinel-oxide system (Co1-xNix)3O4. These spinel oxides are ferrimagnetic p-type semiconductors, and promising material candidates for several applications ranging from photovoltaics and spintronics to thermoelectrics. The spinel phase is obtained for Ni contents exceeding the x = 0.33 limit for bulk samples. It is observed that the electrical resistivity decreases continuously with x while the magnetic moment increases up to x = 0.5. This is in contrast to bulk samples where a decrease of resistivity is not observed for x > 0.33 due to the formation of a rock-salt phase. From UV-VIS-NIR absorption measurements, a change from distinct absorption edges for the parent oxide Co3O4 to a continuous absorption band ranging deep into the near infrared for 0 < x ≤ 0.5 was observed. The conformal deposition of dense films on high-aspect-ratio patterns is demonstrated.

Thermoelectric and Structural Characterization of Al-Doped ZnO/Y2O3 Multilayers.

The influence of Y2O3 nanolayers on thermoelectric performance and structure of 2% Al-doped ZnO (AZO) thin films has been studied. Multilayers based on five 50 nm thick AZO layers alternated with few nanometers thick Y2O3 layers were prepared by pulsed laser deposition on Al2O3 single crystals by alternate ablation of AZO target and Y2O3 target. The number of laser shots on Y2O3 target was maintained very low (5, 10 and 15 pulses in three separate experiments. The main phase (AZO) presents polycrystalline orientation and typical columnar growth not affected by the presence of Y2O3 nanolayers. The multilayer with 15 laser shots of Y2O3 showed best thermoelectric performance with electrical conductivity σ 48 S/cm and Seebeck coefficient S = −82 µV/K, which estimate power factor (S2·σ) about 0.03 × 10−3 W m−1 K−2 at 600 K. The value of thermal conductivity (κ) was found 10.03 W m−1 K−1 at 300 K, which is one third of typical value previously reported for bulk AZO. The figure of merit, ZT = S2·σ·T/κ, is calculated 9.6 × 10−4 at 600 K. These results demonstrated the feasibility of nanoengineered defects insertion for the depression of thermal conductivity.

Anomalous thickness-dependent optical energy gap of ALD-grown ultra-thin CuO films.

Usually an inverse square relation between the optical energy gap and the size of crystallites is observed for semiconducting materials due to the strong quantum localization effect. Coulomb attraction that may lead to a proportional dependence is often ignored or considered less important to the optical energy gap when the crystallite size or the thickness of a thin film changes. Here we report a proportional dependence between the optical energy gap and the thickness of ALD-grown CuO thin films due to a strong Coulomb attraction. The ultrathin films deposited in the thickness range of 9-81 nm show a p-type semiconducting behavior when analyzed by Seebeck coefficient and electrical resistivity measurements. The indirect optical energy gap nature of the films is verified from UV-vis spectrophotometric measurements. A progressive increase in the indirect optical energy gap from 1.06 to 1.24 eV is observed with the increase in the thickness of the films. The data are analyzed in the presence of Coulomb attractions using the Brus model. The optical energy gap when plotted against the cubic root of the thickness of the films shows a linear dependence.

ALD/MLD processes for Mn and Co based hybrid thin films.

Here we report the growth of novel transition metal-organic thin-film materials consisting of manganese or cobalt as the metal component and terephthalate as the rigid organic backbone. The hybrid thin films are deposited by the currently strongly emerging atomic/molecular layer deposition (ALD/MLD) technique using the combination of a metal ß-diketonate, i.e. Mn(thd)3, Co(acac)3 or Co(thd)2, and terephthalic acid (1,4-benzenedicarboxylic acid) as precursors. All the processes yield homogeneous and notably smooth amorphous metal-terephthalate hybrid thin films with growth rates of 1-2 Å per cycle. The films are stable towards humidity and withstand high temperatures up to 300 or 400 °C under an oxidative or a reductive atmosphere. The films are characterized with XRR, AFM, GIXRD, XPS and FTIR techniques.

Atomic/molecular layer deposition: a direct gas-phase route to crystalline metal-organic framework thin films.

Atomic/molecular layer deposition offers us an elegant way of fabricating crystalline copper(ii)terephthalate metal-organic framework (MOF) thin films on various substrate surfaces. The films are grown from two gaseous precursors with a digital atomic/molecular level control for the film thickness under relatively mild conditions in a simple and fast one-step process.

Isovalent Ca and Ba substitutions in thermoelectric layer-structured oxyselenide Sr2CoO2Cu2Se2.

Multilayered compounds typically present exotic functionalities, and some of them have been suggested as potential materials for thermoelectric conversion owing to their unique capability to decouple electronic and heat transport. Here we report new [CoO2] and [Cu2Se2] layered A2CoO2Cu2Se2 compounds in which Sr at the intervening alkaline-earth A site is partially replaced with Ca or Ba. The parent Sr2CoO2Cu2Se2 phase is a direct gap p-type semiconductor, and density functional theory (DFT) calculations indicate its topmost valence band consists of Cu 3d-Se 4p states. Upon the isovalent cation substitution the lattice modification in the ab plane is constrained by the stiff [CoO2] layer such that the lattice shrinkage/expansion mainly happens along the c axis. Substitution of Sr with the heavier and larger Ba significantly enhances the thermopower but more hole states would be required to optimize the thermoelectric performance. Thermal stability is related to the inter-oxide-selenide-layer interaction, and our thermogravimetric measurement data reveal that the A2CoO2Cu2Se2 materials could operate in the intermediate temperature region.

Iron-based inorganic-organic hybrid and superlattice thin films by ALD/MLD.

Here we present novel layer-by-layer deposition processes for the fabrication of inorganic-organic hybrid thin films of the (-Fe-O-C6H4-O-)n type and also superlattices where thicker iron oxide layers alternate with monomolecular-thin organic layers. The processes are based on a combination of atomic layer deposition (ALD) and molecular layer deposition (MLD) techniques where the cyclopentadienyl iron dicarbonyl dimer (Cp2Fe2(CO)4) is used as the iron source and hydroquinone (HQ) as the organic precursor. For the (-Fe-O-C6H4-O-)n hybrid films a growth rate value as high as 3.7 Å per cycle was achieved at 180 °C. Superlattices where thin crystalline iron oxide layers of the magnetite structure alternate with single organic layers consisting of benzene rings were moreover successfully fabricated from the same precursors at 160 °C using water as the source of oxygen in the ALD cycles for the magnetite layers. We foresee that our new ALD/MLD processes offer a valuable novel tool to modify the properties of magnetite thin films and even more widely possess the potential to boost the ALD/MLD research frontier on functional transition metal oxide based thin films.

Atomic layer deposition of quaternary oxide (La,Sr)CoO3-δ thin films.

A novel atomic layer deposition (ALD) process was developed for fabricating quaternary cobalt oxide (La1-xSrx)CoO3-δ thin films having the eye on future applications of such films in e.g. solid oxide fuel cell cathodes, oxygen separation membranes or thermocouples. The deposition parameters and the conditions of a subsequent annealing step were systematically investigated, and using the thus optimized parameters the cation stoichiometry in the films could be accurately tuned. The most detailed study was conducted for x = 0.7, i.e. the composition with the highest application potential within the (La1-xSrx)CoO3-δ system.

Magnetic structure of Sr2CuWO6.

Magnetic structure of the double perovskite Sr2CuWO6 was determined from neutron powder diffraction data. At 3 K the material is magnetically long-range ordered into a collinear antiferromagnetic structure described by a propagation vector k = (0, 1/2, 1/2) with the Cu(II) moments of 0.57(1) µB parallel to the a-axis. The result is in agreement with our previous prediction (Vasala et al 2014 Phys. Rev. B 89 134419) based on electronic structure calculations, showing that the three-dimensional magnetic long-range order is caused by relatively strong antiferromagnetic next-nearest-neighbor interactions.

Measurement of local magnetic fields in the CuO2 planes of CuBa2YCu2O7-delta superconductors.

A fully oxygenated Cu(1)Ba2YCu(2)2O7-delta sample having 0.167 at % of the Cu atoms replaced by enriched 57Fe was synthesized. As confirmed by 57Fe Mössbauer spectroscopy approximately 16% of the Fe atoms entered the superconducting Cu(2)O2 planes. Mössbauer spectra recorded at various temperatures between 77 and 373 K exhibited the presence of a weak magnetic hyperfine interaction in the Fe atoms entering the CuO2 planes. The nonzero internal field obtained from the Mössbauer data increased following a Brillouin-type behavior, from the estimated Néel-like temperature of approximately 400 K down to 96 K where it reached approximately 1.5 T. Upon further cooling below T_{c} the internal field decreased fast down to approximately 0.4 T at 77 K. The presence of the internal field is believed to be related to magnetic correlations among the CuO2-plane atoms, i.e., to reflect local antiferromagnetic coupling between the Cu atoms.

Validity and reproducibility of a food frequency questionnaire for pregnant Finnish women.

The authors developed a self-administered 181-item food frequency questionnaire (FFQ) to assess dietary intake during pregnancy for Finnish women from August 1995 to July 1996. In the validation study (n = 113), the data that were collected by using two 5-day food records completed during the eighth month of pregnancy were compared with FFQ data. The intake of foods and nutrients was higher as determined by FFQ than that assessed using food records. Pearson correlation coefficients for nutrients, after adjustment for energy, ranged from 0.19 (vitamin E) to 0.70 (thiamin) and, for foods, from 0.03 (high-fat milk) to 0.84 (low-fat milk). Energy adjustment improved the correlations for nutrients. Correction for attenuation improved correlations for both foods and nutrients. On average, 70% of the foods and 69% of the nutrients fell into the same or adjacent quintiles, according to the FFQ and the food record. In the reproducibility study, 111 women completed the FFQs twice at a 1-month interval. The intraclass correlation coefficients for nutrients ranged from 0.42 (ethanol) to 0.72 (sucrose, riboflavin, and calcium), and for foods, they ranged from 0.44 (ice cream) to 0.91 (coffee). The authors conclude that the FFQ has an acceptable reproducibility and represents a useful tool for categorizing pregnant women according to their dietary intake.

Folate, vitamin D, and iron intakes are low among pregnant Finnish women.

OBJECTIVE: To evaluate dietary habits and nutrient intake of Finnish pregnant women, to relate these to the use of dietary supplements, and to explore possible dietary variations according to age and education. DESIGN: A random dietary survey using two five day estimated food records. SETTING: Pregnant women from 13 maternity clinics in the city of Oulu, Finland. SUBJECTS: One hundred and eighteen pregnant women in their third trimester. MAIN RESULTS: The main sources of energy were cereal products and milk products. The consumption of fish and poultry was low. Women with a higher educational level consumed more vegetables, fruit, fruit juices, and tea and less sausages, inner organs and coffee than women with a lower educational level. Younger women (< 25 y) consumed more sugar and pork and less berries, butter and inner organs than older women. On average 15% of the total energy was supplied by protein, 33% by fats, 52% by carbohydrates, and 12% by sucrose. Compared to the Nordic nutrition recommendations, the proportion of polyunsaturated fatty acids and the intake of dietary fibre were low and the intake of sugar high. The intakes of vitamins and minerals met or exceeded the recommended allowances, except for vitamin D, folate, and iron. Of the subjects 70% used dietary supplements. With the exception of vitamin D, folate, and iron, both the supplement users and non-users had an adequate nutrient intake from their diet. CONCLUSIONS: A balanced diet covers the increased nutrient requirements during pregnancy, with the exception for vitamin D, folate, and iron. The use of dietary supplements during pregnancy is excessive and partly focused on the wrong nutrients. Young and less educated, and smoking pregnant women need more nutritional guidance.

Significance of cow's milk protein antibodies as risk factor for childhood IDDM: interactions with dietary cow's milk intake and HLA-DQB1 genotype. Childhood Diabetes in Finland Study Group.

Dietary factors are suspected to play an aetiological role in the development of insulin-dependent diabetes mellitus (IDDM). We analysed cow's milk formula, betalactoglobulin, and bovine serum albumin antibodies by an enzyme-linked immunoassay in unselected children with newly diagnosed IDDM and in their non-diabetic siblings and inquired about infant feeding practices by questionnaire. Among 410 diabetic sibling pairs matched for age and sex, by logistic regression analysis - including overall duration of breast-feeding, age at introduction of dairy products, recent consumption of cow's milk and HLA-DQB1 genotype ("high/moderate" vs "low/decreased" risk of IDDM) - bovine serum albumin IgG antibody levels (OR 2.12, 95% CI 1.25-3.57) and genetic risk (OR 3.81, 95% CI 2.43-5.17) were positively associated with IDDM; cow's milk formula IgM antibodies were inversely associated with the risk of IDDM (OR 0.50, 95% CI 0.29-0.87). Of the diabetic sibling pairs, 42 were identical for HLA-DQB1 alleles associated with IDDM risk or protection (DQB1*0201, *0301, *0302 and *0602/03). In these 42 pairs, children with IDDM had higher median levels of bovine serum albumin IgG, of betalactoglobulin IgG, and of cow's milk formula IgG and IgA antibodies than the non-diabetic siblings (p < 0.05). In conclusion, children with IDDM have higher levels of cow's milk protein antibodies than their HLA-DQB1-matched sibling controls, and these high levels of antibodies are independent risk markers for IDDM.