Lanthanide <i>N</i>,<i>N</i>-Dimethylaminodiboranates as a New Class of Highly Volatile Chemical Vapor Deposition Precursors

Daly, Scott R.; Kim, Do Young; Girolami, Gregory S.

doi:10.1021/ic201852j

Cited by 40 publications

(55 citation statements)

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“…S12 †), which may reect the presence of trace actinide uoride contamination or incomplete elimination of uorinated byproducts. Fluorine contamination is known to occur during the preparation of lanthanide oxide lms by chemical vapor deposition of uorinated precursors, [116][117][118][119][120][121] although this effect has been mitigated by incorporating H 2 O gas. 116 Under anhydrous conditions, complexes similar to Th(hfa) 4 and U(hfa) 4 also function as single-source precursors for the preparation of lanthanide uorides.…”

Section: So X-ray Spectromicroscopymentioning

confidence: 99%

Structural properties of ultra-small thorium and uranium dioxide nanoparticles embedded in a covalent organic framework

et al. 2020

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Section: So X-ray Spectromicroscopymentioning

confidence: 99%

Structural properties of ultra-small thorium and uranium dioxide nanoparticles embedded in a covalent organic framework

et al. 2020

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“…31 Consequently, lanthanide complexes containing DMADB ligands are among the most volatile compounds known for these elements. 32,33 Several M(DMADB) 3 complexes with trivalent lanthanides (all except promethium) and an actinide (uranium) have been reported. 31−33 Because the DMADB ligand can chelate to or bridge between two metal centers, a variety of solid-state structures have been observed depending on the size of the M 3+ ion: the coordination number increases from 12 to 14 as the ionic radius of the metal center becomes larger.…”

Section: ■ Introductionmentioning

confidence: 99%

Volatilities of Actinide and Lanthanide N,N-Dimethylaminodiboranate Chemical Vapor Deposition Precursors: A DFT Study

et al. 2012

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N,N-Dimethylaminodiboranate complexes with praseodymium, samarium, erbium, and uranium, which are potential chemical vapor deposition precursors for the deposition of metal boride and oxide thin films, have been investigated by DFT guided by field-ionization mass spectroscopy experiments. The calculations indicate that the volatilities of these complexes are correlated with the M−H bond strengths as determined by Mayer bond order analysis. The geometries of the gas-phase monomeric, dimeric, and trimeric species seen in field-ionization mass spectroscopy experiments were identified using DFT calculations, and the relative stabilities of these oligomers were assessed to understand how the lanthanide aminodiboranates depolymerize to their respective volatile forms during sublimation. ■ INTRODUCTIONLanthanide-containing materials, such as lanthanide oxides and borides, have interesting optical, 1−3 magnetic, 4−6 and electrical 4,7,8 properties that make them useful for technological applications such as capacitors, field effect transistors, displays, thermoelectric devices, light-emitting diodes, and lasers. For many of these applications, defect-free thin films are necessary, and in some cases it is crucial to deposit the films uniformly onto substrates with high aspect ratios. 9 To achieve these results, there is much interest in developing better precursors for the chemical vapor deposition (CVD) and atomic layer deposition (ALD) of lanthanide-containing thin films. 10,11 For transition metals, some of the most volatile compounds known are homoleptic compounds containing the borohydride ligand, BH 4 − , and these have been shown to be useful CVD precursors. 12−20 Homoleptic borohydride compounds of the lanthanides are known but they are not particularly volatile 21−25 because their solid state structures are polymeric. 26−28 By comparison, actinide borohydrides in the +4 oxidation state such as U(BH 4 ) 4 are reasonably volatile despite the fact that some of them are also polymeric in the solid state. 29 Recently, a new class of metal borohydrides has been described that contain the N,N-dimethylaminodiboranate anion, H 3 BNMe 2 BH 3 − (DMADB) (Figure 1). 30−32 DMADB is a polydentate ligand capable of chelating a single metal center or bridging between two metal centers. Compared to the smaller BH 4 − ligand, the DMADB ligand better saturates the coordination sphere of large metals in lower oxidation states. 31 Consequently, lanthanide complexes containing DMADB ligands are among the most volatile compounds known for these elements. 32,33 Figure 1. Ball and stick (left) and schematic (right) structure of the N,N-dimethylaminodiboranate (DMADB) ligand. Color code: Nitrogen in blue, carbon in gray, boron in bronze, and hydrogen in white. Article pubs.acs.org/JPCC

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“…> 9) Ln(III) complexes coordination number 10 is the most commonly observed (see Figure 4) [27]. The second commonly observed high coordination numbers are 11 and 12 [28] whereas the coordination numbers 13 and 14 are extremely rare [29]. Due to the inter-ligand repulsions (''firstorder'' effects), monodentate ligands could lead to coordination numbers of only up to 8 and 9.…”

Section: High-coordinate Ln(iii) Complexesmentioning

confidence: 99%

High-Coordinate Mononuclear Ln(III) Complexes: Synthetic Strategies and Magnetic Properties

2020

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Single-molecule magnets involving monometallic 4f complexes have been investigated extensively in last two decades to understand the factors that govern the slow magnetization relaxation behavior in these complexes and to establish a magneto-structural correlation. The prime goal in this direction is to suppress the temperature independent quantum tunneling of magnetization (QTM) effect via fine-tuning the coordination geometry/microenvironment. Among the various coordination geometries that have been pursued, complexes containing high coordination number around Ln(III) are sparse. Herein, we present a summary of the various synthetic strategies that were used for the assembly of 10- and 12-coordinated Ln(III) complexes. The magnetic properties of such complexes are also described.

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Lanthanide N,N-Dimethylaminodiboranates as a New Class of Highly Volatile Chemical Vapor Deposition Precursors

Cited by 40 publications

References 144 publications

Structural properties of ultra-small thorium and uranium dioxide nanoparticles embedded in a covalent organic framework

Structural properties of ultra-small thorium and uranium dioxide nanoparticles embedded in a covalent organic framework

Volatilities of Actinide and Lanthanide N,N-Dimethylaminodiboranate Chemical Vapor Deposition Precursors: A DFT Study

High-Coordinate Mononuclear Ln(III) Complexes: Synthetic Strategies and Magnetic Properties

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