Sc2O3, Er2O3, and Y2O3 thin films by MOCVD from volatile guanidinate class of rare-earth precursors.

Alternative novel precursor chemistries for the vapor phase deposition of rare-earth (RE) oxide thin films were developed by synthesising the homoleptic guanidinate compounds tris(N,N'-diisopropyl-2-dimethylamidoguanidinato)-scandium(III) [Sc(DPDMG)(3)] (1), tris(N,N'-diisopropyl-2-dimethylamidoguanidinato)-erbium(III), [Er(DPDMG)(3)] (2) and tris(N,N'-diisopropyl-2-dimethylamidoguanidinato)-yttrium(III), [Y(DPDMG)(3)] (3). All three compounds are monomeric as revealed by single crystal X-ray diffraction (XRD) analysis, nuclear magnetic resonance (NMR) and electron impact mass spectrometry (EI-MS). The thermal analysis revealed that the compounds are volatile and very stable under evaporation conditions. Therefore the complexes were evaluated as precursors for the growth of Sc(2)O(3), Er(2)O(3) and Y(2)O(3) thin films, respectively, by metal-organic chemical vapor deposition (MOCVD). Uniform Sc(2)O(3), Er(2)O(3) and Y(2)O(3) films on Si(100) substrates with reproducible quality were grown by MOCVD by the combination of the respective guanidinate precursors and oxygen in the temperature range 350-700 °C. The structural, morphological, compositional and electrical properties of the films were investigated in detail. The most relevant film properties are highlighted in relation to the distinct advantages of the novel precursor chemistries in comparison to the commonly used literature known RE precursors. This study shows that compounds 1-3 are very good precursors for MOCVD yielding Sc(2)O(3), Er(2)O(3) and Y(2)O(3) thin films which are stoichiometric and display suitable electrical properties for their potential use as high dielectric constant (high-k) materials.

Malonate complexes of dysprosium: synthesis, characterization and application for LI-MOCVD of dysprosium containing thin films.

A series of malonate complexes of dysprosium were synthesized as potential metalorganic precursors for Dy containing oxide thin films using chemical vapor deposition (CVD) related techniques. The steric bulkiness of the dialkylmalonato ligand employed was systematically varied and its influence on the resulting structural and physico-chemical properties that is relevant for MOCVD was studied. Single crystal X-ray diffraction analysis revealed that the five homoleptic tris-malonato Dy complexes (1-5) are dimers with distorted square-face bicapped trigonal-prismatic geometry and a coordination number of eight. In an attempt to decrease the nuclearity and increase the solubility of the complexes in various solvents, the focus was to react these dimeric complexes with Lewis bases such as 2,2'-biypridyl and pyridine (6-9). This resulted in monomeric tris-malonato mono Lewis base adduct complexes with improved thermal properties. Finally considering the ease of synthesis, the monomeric nature and promising thermal characteristics, the silymalonate adduct complex [Dy(dsml)(3)bipy] (8) was selected as single source precursor for growing DySi(x)O(y) thin films by liquid injection metalorganic chemical vapor deposition (LI-MOCVD) process. The as-deposited films were analyzed for their morphology and composition by scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analysis, Rutherford backscattering (RBS) analysis and X-ray photoelectron spectroscopy.

Growth of crystalline Gd2O3 thin films with a high-quality interface on Si(100) by low-temperature H2O-assisted atomic layer deposition.

This work documents the first example of deposition of high-quality Gd(2)O(3) thin films in a surface-controlled, self-limiting manner by a water-based atomic layer deposition (ALD) process using the engineered homoleptic gadolinium guanidinate precursor [Gd(DPDMG)(3)]. The potential of this class of compound is demonstrated in terms of a true ALD process, exhibiting pronounced growth rates, a high-quality interface between the film and the substrate without the need for any additional surface treatment prior to the film deposition, and most importantly, encouraging electrical properties.

Homoleptic gadolinium guanidinate: a single source precursor for metal-organic chemical vapor deposition of gadolinium nitride thin films.

Deposition of a rare earth nitride thin film using a chemical gas phase deposition technique is reported for the first time. The gadolinium tris-guanidinate complex [Gd{((i)PrN)(2)CNMe(2)}(3)] is found to be an effective single source precursor for the MOCVD growth of gadolinium nitride (GdN) thin films.

Hafnium carbamates and ureates: new class of precursors for low-temperature growth of HfO2 thin films.

Novel volatile compounds of hafnium, namely tetrakis-N,O-dialkylcarbamato hafnium(iv) [Hf((i)PrNC(O)O(i)Pr)(4)] () and tetrakis-N,N,N'-trialkylureato hafnium(iv) [Hf((i)PrNC(O)N-(Me)Et)(4)] (), have been synthesized through the simple insertion reaction of isopropyl isocyanate into hafnium isopropoxide and hafnium ethylmethylamide, respectively; based on the promising thermal properties, compound has been evaluated as a precursor for metalorganic chemical vapor deposition (MOCVD) of HfO(2) thin films, which resulted in the growth of stoichiometric and crystalline layers with a uniform morphology at temperature as low as 250 degrees C.

Synthesis, characterization, and thermal properties of homoleptic rare-earth guanidinates: promising precursors for MOCVD and ALD of rare-earth oxide thin films.

Eight novel homoleptic tris-guanidinato complexes M[(N(i)Pr)(2)CNR(2)](3) [M = Y (a), Gd (b), Dy (c) and R = Me (1), Et (2), (i)Pr (3)] have been synthesized and characterized by NMR, CHN-analysis, mass spectrometry and infrared spectroscopy. Single crystal structure analysis revealed that all the compounds are monomers with the rare-earth metal center coordinated to six nitrogen atoms of the three chelating guanidinato ligands in a distorted trigonal prism geometry. With the use of TGA/DTA and isothermal TGA analysis, the thermal characteristics of all the complexes were studied in detail to evaluate their suitability as precursors for thin film deposition by MOCVD and ALD. The (i)Pr-Me(2)N-guanidinates of Y, Gd and Dy (1a-c) showed excellent thermal characteristics in terms of thermal stability and volatility. Additionally, the thermal stability of the (i)Pr-Me(2)N-guanidinates of Y and Dy (1a, c) in solution was investigated by carrying out NMR decomposition experiments and both the compounds were found to be remarkably stable. All these studies indicate that (i)Pr-Me(2)N-guanidinates of Y, Gd and Dy (1a-c) have the prerequisites for MOCVD and ALD applications which were confirmed by the successful deposition of Gd(2)O(3) and Dy(2)O(3) thin films on Si(100) substrates. The MOCVD grown films of Gd(2)O(3) and Dy(2)O(3) were highly oriented in the cubic phase, while the ALD grown films were amorphous.

Bis(2-butyl-N,N'-diisopropylamidinato)dichlorohafnium(IV).

The title compound, [Hf(C11H23N2)2Cl(2)], is a monomeric hafnium(IV) complex containing two bidentate amidinate ligands and two cis Cl atoms. The crystals are triclinic (space group P-1) and there is one independent six-coordinate monomer with a highly distorted octahedral geometry in the asymmetric unit. The reported structure is the first hafnium-amidinate complex to be characterized successfully by single-crystal X-ray diffraction.