Synthesis and Complexation Study of New Aminoalkynyl−amidinate Ligands

Abstract The current library of amidinate ligands has been extended by the synthesis of two novel dimethylamino‐substituted alkynylamidinate anions of the composition [Me 2 N−CH 2 −C≡C−C(NR) 2 ] − (R = i Pr, cyclohexyl (Cy)). The unsolvated lithium derivatives Li[Me 2 N−CH 2 −C≡C−C(NR) 2 ] ( 1 : R = i Pr, 2 : R = Cy) were obtained in good yields by treatment of in situ‐ prepared Me 2 N−CH 2 −C≡C−Li with the respective carbodiimides, R−N=C=N−R. Recrystallization of 1 and 2 from THF afforded the crystalline THF adducts Li[Me 2 N−CH 2 −C≡C−C(NR) 2 ] ⋅  n THF ( 1 a : R = i Pr, n =1; 2 a : R = Cy, n =1.5). Precursor 2 was subsequently used to study initial complexation reactions with selected di‐ and trivalent transition metals. The dark red homoleptic vanadium(III) tris(alkynylamidinate) complex V[Me 2 N−CH 2 −C≡C−C(NCy) 2 ] 3 ( 3 ) was prepared by reaction of VCl 3 (THF) 3 with 3 equiv. of 2 (75 % yield). A salt‐metathesis reaction of 2 with anhydrous FeCl 2 in a molar ratio of 2 : 1 afforded the dinuclear homoleptic iron(II) alkynylamidinate complex Fe 2 [Me 2 N−CH 2 −C≡C−C(NCy) 2 ] 4 ( 4 ) in 69 % isolated yield. Similarly, treatment of Mo 2 (OAc) 4 with 3 or 4 equiv. of 2 provided the dinuclear, heteroleptic molybdenum(II) amidinate complex Mo 2 (OAc)[Me 2 N−CH 2 −C≡C−C(NCy) 2 ] 3 ( 5 ; yellow crystals, 50 % isolated yield). The cyclohexyl‐substituted title compounds 2 a , 4 , and 5 were structurally characterized through single‐crystal X‐ray diffraction studies.imag

Optical properties of In2O3 from experiment and first-principles theory: influence of lattice screening

The framework of many-body perturbation theory led to deep insight into electronic structure and optical properties of diverse systems and, in particular, many semiconductors. It relies on an accurate approximation of the screened Coulomb electron–electron interaction W, that in current implementations is usually achieved by describing electronic interband transitions. However, our results for several oxide semiconductors indicate that for polar materials it is necessary to also account for lattice contributions to dielectric screening. To clarify this question in this work, we combine highly accurate experimentation and cutting-edge theoretical spectroscopy to elucidate the interplay of quasiparticle and excitonic effects for cubic bixbyite In2O3 across an unprecedentedly large photon energy range. We then show that the agreement between experiment and theory is excellent and, thus, validate that the physics of quasiparticle and excitonic effects is described accurately by these first-principles techniques, except for the immediate vicinity of the absorption onset. Finally, our combination of experimental and computational data clearly establishes the need for including a lattice contribution to dielectric screening in the screened electron–electron interaction, in order to improve the description of excitonic effects near the absorption edge

In-situ study and modeling of the reaction kinetics during molecular beam epitaxy of GeO2 and its etching by Ge

Rutile GeO2 has been predicted to be an ultra-wide bandgap semiconductor suitable for future power electronics devices while quartz-like GeO2 shows piezoelectric properties. To explore these crystalline phases for application and fundamental materials investigations, molecular beam epitaxy (MBE) is a well-suited thin film growth technique. In this study, we investigate the reaction kinetics of GeO2 during plasma-assisted MBE using elemental Ge and plasma-activated oxygen fluxes. The growth rate as a function of oxygen flux is measured in-situ by laser reflectometry at different growth temperatures. A flux of the suboxide GeO desorbing off the growth surface is identified and quantified in-situ by the line-of-sight quadrupole mass spectrometry. Our measurements reveal that the suboxide formation and desorption limits the growth rate under metal-rich or high temperature growth conditions, and leads to etching of the grown GeO2 layer under Ge flux in the absence of oxygen. The quantitative results fit the sub-compound mediated reaction model, indicating the intermediate formation of the suboxide at the growth front. This model is further utilized to delineate the GeO2-growth window in terms of oxygen-flux and substrate temperature. Our study can serve as a guidance for the thin film synthesis of GeO2 and defect-free mesa etching in future GeO2-device processing

Epitaxial synthesis of unintentionally doped p-type SnO (001) via suboxide molecular beam epitaxy

By employing a mixed SnO$_2$+Sn source, we demonstrate suboxide molecular beam epitaxy growth of phase-pure single crystalline metastable SnO(001) thin films at a growth rate of ~1.0nm/min without the need for additional oxygen. These films grow epitaxially across a wide substrate temperature range from 150 to 450{\deg}C. Hence, we present an alternative pathway to overcome the limitations of high Sn or SnO$_2$ cell temperatures and narrow growth windows encountered in previous MBE growth of metastable SnO. In-situ laser reflectometry and line-of-sight quadrupole mass spectrometry were used to investigate the rate of SnO desorption as a function of substrate temperature. While SnO ad-molecules desorption at Ts = 450{\deg}C was growth-rate limiting,the SnO films did not desorb at this temperature after growth in vacuum. The SnO (001) thin films are transparent and unintentionally p-type doped, with hole concentrations and mobilities in the range of 0.9 to 6.0x10$^{18}$cm$^{-3}$ and 2.0 to 5.5 cm$^2$/V.s, respectively. These p-type SnO films obtained at low temperatures are promising for back-end-of-line (BEOL) compatible applications and for integration with n-type oxides in p-n heterojunction and field-effect transistorsComment: 18 pages, 10 figure

Epitaxial synthesis of unintentionally doped p-type SnO (001) via suboxide molecular beam epitaxy

By employing a mixed SnO2 + Sn source, we demonstrate suboxide molecular beam epitaxy (S-MBE) growth of phase-pure single-crystalline metastable SnO (001) thin films on Y-stabilized ZrO2 (001) substrates at a growth rate of ∼1.0 nm/min without the need for additional oxygen. These films grow epitaxially across a wide substrate temperature range from 150 to 450 °C. Hence, we present an alternative pathway to overcome the limitations of high Sn or SnO2 cell temperatures and narrow growth windows encountered in previous MBE growth of metastable SnO. In situ laser reflectometry and line-of-sight quadrupole mass spectrometry were used to investigate the rate of SnO desorption as a function of substrate temperature. While SnO ad-molecule desorption at TS = 450 °C was growth-rate limiting, the SnO films did not desorb at this temperature after growth in vacuum. The SnO (001) thin films are transparent and unintentionally p-type doped, with hole concentrations and mobilities in the range of 0.9-6.0 × 1018 cm-3 and 2.0-5.5 cm2 V-1 s-1, respectively. These p-type SnO films obtained at low substrate temperatures are promising for back-end-of-line (BEOL) compatible applications and for integration with n-type oxides in pn heterojunctions and field-effect transistors