ABSTRACT
There are very few p-type semiconductors available compared to n-type semiconductors for positive sensing response for oxidizing gases and other important electronic applications. Cupric oxide (CuO) is one of the few oxides that show p-type conductivity, useful for sensing oxidizing gases. Many researchers obtained CuO using the chemical and solid-state routes, but uniformity and large-area deposition have been the main issues. Chemical vapor deposition is one such technique that provides control on several deposition parameters, which allow obtaining thin films having crystallinity and uniformity over a large area for the desired application. However, CuO-chemical vapor deposition (CVD) is still unfathomed due to the lack of suitability of copper precursors based on vapor pressure, contamination, and toxicity. Here, to address these issues, we have taken four Cu complexes (copper(II) acetylacetonate, copper(II) bis(2,2,6,6-tetramethyl-3,5-heptanedionato), copper(II) ethylacetoacetate, and copper(II) tert-butylacetoacetate), which are evaluated using thermogravimetry for suitability as a CVD precursor. The decomposition behavior of the complexes was also experimentally confirmed by depositing CuO thin films via CVD. Phase purity, decomposition, volatility, growth rate, and morphological characteristics of the films are investigated in detail. Analysis suggests that copper(II) tert-butylacetoacetate has the highest vapor pressure and growth rate at a low temperature, making it the most suitable precursor for high-throughput CVD. Further, to investigate the role of these precursors, films deposited using Cu complexes were subjected to gas sensing. The CuO gas sensor fabricated on glass shows pronounced NO2 sensing. The sensing results of CuO films have been explained from the standpoint of roughness, morphology, and unpassivated bonds present on the surface of films and vapor pressure of precursors. The higher density of surface state and the lower resistivity of the Cu(tbaoac)2 film lead to a sensor with higher responsivity and sensitivity (down to 1 ppm). These precursors can probably be utilized to improve the performance of other metal oxide gas sensors, especially Cu2O and Cu-III-O2.
ABSTRACT
A detailed thermodynamic analysis of the solid and gas phases of the Mo-S-C-O-H system used for large area chemical vapor deposition (CVD) of MoS2 is presented and compared with experimental results. Given the multivariable nature of the problem, excellent agreement is observed. Deviations, observed from thermodynamic predictions, mainly at low temperatures and high flow rates have been highlighted and discussed. CVD phase diagrams which predict parameter windows in which pure MoS2 can be synthesized have been provided for important gas phase chemistries. Pure H2 as a carrier gas is shown to facilitate the largest contamination free process window. CO presence is shown to significantly reduce the nucleation rate and enable large island sizes but at the cost of carbon contamination. Oxygen leaks are shown to result in sulphur contamination. The absence of H2S during cooling is shown to yield Mo due to the reduction of MoS2 by hydrogen. Oxidation of Mo causes oxide contamination.
ABSTRACT
Layered transition metal dichalcogenides (TMDs), such as MoS2, are candidate materials for next generation 2-D electronic and optoelectronic devices. The ability to grow uniform, crystalline, atomic layers over large areas is the key to developing such technology. We report a chemical vapor deposition (CVD) technique which yields n-layered MoS2 on a variety of substrates. A generic approach suitable to all TMDs, involving thermodynamic modeling to identify the appropriate CVD process window, and quantitative control of the vapor phase supersaturation, is demonstrated. All reactant sources in our method are outside the growth chamber, a significant improvement over vapor-based methods for atomic layers reported to date. The as-deposited layers are p-type, due to Mo deficiency, with field effect and Hall hole mobilities of up to 2.4 cm(2) V(-1) s(-1) and 44 cm(2) V(-1) s(-1) respectively. These are among the best reported yet for CVD MoS2.
ABSTRACT
Ultra-small crystals of undoped and Eu-doped gadolinium oxide (Gd2O3) were synthesised by a simple, rapid microwave-assisted route, using benzyl alcohol as the reaction solvent. XRD, XPS and TEM analysis reveal that the as-prepared powder material consists of nearly monodisperse Gd2O3 nanocrystals with an average diameter of 5.2 nm. The nanocrystals show good magnetic behaviour and exhibit a larger reduction in relaxation time of water protons than the standard Gd-DTPA complex currently used in MRI imaging. Cytotoxicity studies (both concentration- and time-dependent) of the Gd2O3 nanocrystals show no adverse effect on cell viability, evidencing their high biological compatibility. Finally, Eu:Gd2O3 nanocrystals were prepared by a similar route and the red luminescence of Eu3+ activator ions was used to study the cell permeability of the nanocrystals. Red fluorescence from Eu3+ ions observed by fluorescence microscopy shows that the nanocrystals (Gd2O3 and Eu:Gd2O3) can permeate not only the cell membrane but can also enter the cell nucleus, rendering them candidate materials not only for MRI imaging but also for drug delivery when tagged or functionalized with specific drug molecules.
ABSTRACT
In the title compound, [Zn(C(5)H(7)O(2))(2)(C(5)H(5)N)], the metal atom has square-pyramidal coordination geometry with the basal plane defined by the four O atoms of the chelating acetyl-acetonate ligands and with the axial position occupied by the pyridine N atom. The crystal packing is characterized by a C-Hâ¯O hydrogen-bonded ribbon structure approximately parallel to [10[Formula: see text]].
ABSTRACT
In the title compound, [Al(C(5)H(7)O(3))(3)], three acac-type ligands (methyl 3-oxobutanoate anions) chelate to the aluminium(III) cation in a slightly distorted AlO(6) octa-hedral coordination geometry. Electron delocalization occurs within the chelating rings.
ABSTRACT
In each of the zinc(II) complexes bis(acetylacetonato-kappa(2)O,O')(1,10-phenanthroline-kappa(2)N,N')zinc(II), [Zn(C(5)H(7)O(2))(2)(C(12)H(8)N(2))], (I), and bis(acetylacetonato-kappa(2)O,O')(2,2'-bipyridine-kappa(2)N,N')zinc(II), [Zn(C(5)H(7)O(2))(2)(C(10)H(8)N(2))], (II), the metal center has a distorted octahedral coordination geometry. Compound (I) has crystallographically imposed twofold symmetry, with Z' = 0.5. The presence of a rigid phenanthroline group precludes intramolecular hydrogen bonding, whereas the rather flexible bipyridyl ligand is twisted to form an intramolecular C-H...O interaction [the chelated bipyridyl ligand is nonplanar, with the pyridyl rings inclined at an angle of 13.4 (1) degrees]. The two metal complexes are linked by dissimilar C-H...O interactions into one-dimensional chains. The present study demonstrates the distinct effects of two commonly used ligands, viz. 1,10-phenanthroline and 2,2'-bipyridine, on the structures of metal complexes and their assembly.
Subject(s)
2,2'-Dipyridyl/chemistry , Organometallic Compounds/chemistry , Phenanthrolines/chemistry , Crystallography, X-Ray , Hydrogen Bonding , Models, Molecular , Molecular StructureABSTRACT
Novel mixed amido-malonato complexes of titanium are reported. The complexes were synthesized by partially replacing the amido groups from the complexes [Ti(NMe2)4] and [Ti(NEt2)4] via Brønstedt acid/base reactions, using the malonate-ligands di-isopropylmalonate (Hdpml) and di-tert-butylmalonate (Hdbml). Four representative complexes were synthesized and fully characterised by 1H NMR, 13C NMR, CHN analysis and mass spectrometry. The crystal structures of the six-coordinated complexes [Ti(NMe2)2(dbml)2] (3) and [Ti(NEt2)2(dbml)2] (4) are presented and discussed. The complexes are solids and the chemical and thermal characteristics of the complexes strongly depend on the substitution at the malonate ligand. While dpml containing complexes show a promising behaviour for classical MOCVD, dbml containing complexes seem to be more suitable for liquid injection-metal-organic chemical vapour deposition (LI-MOCVD). Based on its thermal characteristics, the most promising complex for thermal CVD, [Ti(NEt2)2(dpml)2] (2) was selected for preliminary MOCVD experiments, which indicate a good suitability for the deposition of TiO2 thin films.
