Self-reducing precursors for aluminium metal thin films: evaluation of stable aluminium hydrides for vapor phase aluminium deposition.

Thin films of Al as interconnect materials and those of AlN as wide bandgap semiconductor and piezoelectric material are of great interest for microelectronic applications. For the fabrication of these thin films via chemical vapor deposition (CVD) based routes, the available precursor library is rather limited, mostly comprising aluminium alkyls, chlorides, and few small amine-stabilized aluminium hydrides. Herein, we focused on rational precursor development for Al, their characterization and comparison to existing precursors comprising stabilized aluminium hydrides. We present and compare a series of potentially new and reported aluminium hydride precursors divided into three main groups with respect to their stabilization motive, and their systematic structural variation to evaluate the physicochemical properties. All compounds were comprehensively characterized by means of nuclear magnetic resonance spectroscopy (NMR), Fourier-transform infrared spectroscopy (FTIR), elemental analysis (EA), electron-impact ionization mass spectrometry (EI-MS) and thermogravimetric analysis (TGA). Promising representatives were further evaluated as potential single source precursors for aluminium metal formation in proof-of-concept experiments. Structure and reaction enthalpies with NH3 or H2 as co-reactants were calculated via first principles density functional theory simulations and show the great potential as atomic layer deposition (ALD) precursors for Al and AlN thin films.

SnO deposition via water based ALD employing tin(II) formamidinate: precursor characterization and process development.

Tin monoxide (SnO) is a promising oxide semiconductor which is appealing for a wide range of applications from channel materials in p-type field effect transistors (FET) to electrode materials searched for next-generation batteries. For the controlled growth of SnO films at low temperatures, atomic layer deposition (ALD) is employed in this study, where the choice of the precursor plays a significant role. A comparative thermal evaluation of four different amidinate-based tin(II) precursors and the influence of the ligand sphere on their physicochemical properties revealed that bis(N,N'-diisopropylformamidinato tin(II) (1) possesses the required volatility, good thermal stability and sufficient reactivity towards water, to be implemented as the ALD precursor. The water-assisted ALD process resulted in crystalline SnO films on Si substrates with a growth per cycle (GPC) of 0.82 Å at temperatures as low as 140 °C. By employing complementary analytical tools, namely, X-ray diffraction (XRD), atomic force microscopy (AFM), X-ray reflectivity (XRR), Rutherford backscattering spectrometry/nuclear reaction analysis (RBS/NRA) and X-ray photoelectron spectroscopy (XPS), the formation of tin monoxide was confirmed. Finally, the optical properties of the as-deposited films were analyzed via UV-Vis spectroscopy, exhibiting a band gap of 2.74 eV, which further confirms the formation of the targeted SnO phase.

Additive-free spin coating of tin oxide thin films: synthesis, characterization and evaluation of tin ß-ketoiminates as a new precursor class for solution deposition processes.

The fabrication of SnOx in thin film form via chemical solution deposition (CSD) processes is favored over vacuum based techniques as it is cost effective and simpler. The precursor employed plays a central role in defining the process conditions for CSD. Particularly for processing SnO2 layers that are appealing for sensor or electronic applications, there are limited precursors available for CSD. Thus the focus of this work was to develop metalorganic precursors for tin, based on the ketoiminate ligand class. By systematic molecular engineering of the ligand periphery, a series of new homoleptic Sn(ii) ß-ketoiminate complexes was synthesized, namely bis[4-(2-methoxyethylimino)-3-pentanonato] tin, [Sn(MEKI)2] (1), bis[4-(2-ethoxyethylimino)-2-pentanonato] tin, [Sn(EEKI)2] (2), bis[4-(3-methoxypropylimino)-2-pentanonato] tin, [Sn(MPKI)2] (3), bis[4-(3-ethoxypropylimino)-2-pentanonato] tin, [Sn(EPKI)2] (4) and bis[4-(3-isopropoxypropylimino)-2-pentanonato] tin, [Sn(iPPKI)2] (5). All these N-side-chain ether functionalized compounds were analyzed by nuclear magnetic resonance (NMR) spectroscopy, electron impact mass spectrometry (EI-MS), elemental analysis (EA) and thermogravimetric analysis (TGA). The solid state molecular structure of [Sn(MPKI)2] (3) was eludicated by means of single crystal X-ray diffraction (SCXRD). Interestingly, this class of compounds features excellent solubility and stability in common organic solvents alongside good reactivity towards H2O and low decomposition temperatures, thus fulfilling the desired requirements for CSD of tin oxides. With compound 3 as a representative example, we have demonstrated the possibility to directly deposit SnOx layers via hydrolysis upon exposure to air followed by heat treatment under oxygen at moderate temperatures and most importantly without the need for any additive that is generally used in CSD. A range of complementary analytical methods were employed, namely X-ray diffraction (XRD), Rutherford backscattering spectrometry (RBS), nuclear reaction analysis (NRA), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) to analyse the structure, morphology and composition of the SnOx layers.

PEALD of HfO2 Thin Films: Precursor Tuning and a New Near-Ambient-Pressure XPS Approach to in Situ Examination of Thin-Film Surfaces Exposed to Reactive Gases.

A bottom-up approach starting with the development of new Hf precursors for plasma-enhanced atomic layer deposition (PEALD) processes for HfO2 followed by in situ thin-film surface characterization of HfO2 upon exposure to reactive gases via near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) is reported. The stability of thin films under simulated operational conditions is assessed, and the successful implementation of HfO2 dielectric layers in metal-insulator-semiconductor (MIS) capacitors is demonstrated. Among the series of newly synthesized mono-guanidinato-tris-dialkyl-amido class of Hf precursors, one of them, namely, [Hf{η2-(iPrN)2CNEtMe}(NEtMe)3], was representatively utilized with oxygen plasma, resulting in a highly promising low-temperature PEALD process at 60 °C. The new precursors were synthesized in the multigram scale and thoroughly characterized by thermogravimetric analyses, revealing high and tunable volatility reflected by appreciable vapor pressures and accompanied by thermal stability. Typical ALD growth characteristics in terms of linearity, saturation, and a broad ALD window with constant growth of 1.06 Å cycle-1 in the temperature range of 60-240 °C render this process very promising for fabricating high-purity smooth HfO2 layers. For the first time, NAP-XPS surface studies on selected HfO2 layers are reported upon exposure to reactive H2, O2, and H2O atmospheres at temperatures of up to 500 °C revealing remarkable stability against degradation. This can be attributed to the absence of surface defects and vacancies. On the basis of these promising results, PEALD-grown HfO2 films were used as dielectric layers in the MIS capacitor device fabrication exhibiting leakage current densities less than 10-7 A cm-2 at 2 MV cm-1 and permittivities of up to 13.9 without postannealing.