Evaluation of Sn(<scp>ii</scp>) aminoalkoxide precursors for atomic layer deposition of SnO thin films

Parish, James D.; Snook, Michael W.; Johnson, Andrew L.

doi:10.1039/d1dt02480a

Cited by 3 publications

(3 citation statements)

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“…SSPs have been reported for a variety of metal oxide thin films, often using alkoxide-based ligands to ensure low decomposition temperature and high compositional purity. 205,270–275 BaTiO 3 , BaZrO 3 , and BaTi 0.5 Zr 0.5 O 3 were developed by Veith et al via a sol–gel technique using [BaM(OH)(O i Pr) 5 (HO i Pr) 3 ] 2 (M = Ti, Zr) and [BaTi 0.5 Zr 0.5 (O i Pr) 6 ] 2 SSPs. 245 BaTiO 3 thin films were reported to be pure state at 600 °C using these precursors, whereas the equivalent films using dual-source precursors still contained many impurities at 1200 °C including BaCO 3 and Ba 2 TiO 4 .…”

Section: Precursor Design and Growth Criteria For Semiconductor Mater...mentioning

confidence: 99%

“…SSPs have been reported for a variety of metal oxide thin films, often using alkoxidebased ligands to ensure low decomposition temperature and high compositional purity. 205,[270][271][272][273][274][275] SSPs. 245 BaTiO 3 thin films were reported to be pure state at 600 1C using these precursors, whereas the equivalent films using dual-source precursors still contained many impurities at 1200 1C including BaCO 3 and Ba 2 TiO 4 .…”

Section: Metal Oxides and Chalcogenidesmentioning

confidence: 99%

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A chemist's guide to photoelectrode development for water splitting – the importance of molecular precursor design

Harris-Lee,

Marken,

Bentley

et al. 2023

EES. Catal.

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Section: Precursor Design and Growth Criteria For Semiconductor Mater...mentioning

confidence: 99%

Section: Metal Oxides and Chalcogenidesmentioning

confidence: 99%

A chemist's guide to photoelectrode development for water splitting – the importance of molecular precursor design

Harris-Lee,

Marken,

Bentley

et al. 2023

EES. Catal.

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“…Tetrylenes [3][4][5][6][7]-heavier carbene analogs-have recently attracted significant attention [8][9][10][11][12][13][14][15][16][17][18][19][20]), primarily due to their possible application as analogs of transition metals in catalysis [21][22][23], in activation of small molecules [24][25][26][27][28][29][30], as ligands [31,32], in possible synthesis of derivatives with E-E bonds [33][34][35], reagents for synthesis [36][37][38][39] or precursors [40][41][42] in material chemistry. These species are reactive and unstable; to stabilize them, the introduction of bulky groups (kinetic stabilization) or polydentate ligands (thermodynamic stabilization) is used.…”

Section: Introductionmentioning

confidence: 99%

Germanium Complexes with ONO Tridentate Ligands: O-H Bond Activation Control According to DFT Calculations

Zaitsev

Trubachev

Полещук

2023

IJMS

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Polydentate ligands are used for thermodynamic stabilization of tetrylenes—low-valent derivatives of Group 14 elements (E = Si, Ge, Sn, Pb). This work shows by DFT calculations how the structure (the presence or absence of substituents) and type (alcoholic, Alk, or phenolic, Ar) of tridentate ligands 2,6-pyridinobis(1,2-ethanols) [AlkONOR]H2 and 2,6-pyridinobis(1,2-phenols) [ArONOR]H2 (R = H, Me) may affect the reactivity or stabilization of tetrylene, indicating the unprecedented behavior of Main Group elements. This enables the unique control of the type of the occurring reaction. We found that unhindered [ONOH]H2 ligands predominantly led to hypercoordinated bis-liganded {[ONOH]}2Ge complexes, where an E(+2) intermediate was inserted into the ArO-H bond with subsequent H2 evolution. In contrast, substituted [ONOMe]H2 ligands gave [ONOMe]Ge: germylenes, which may be regarded as kinetic stabilized products; their transformation into E(+4) species is also thermodynamically favorable. The latter reaction is more probable for phenolic [ArONO]H2 ligands than for alcoholic [AlkONO]H2. The thermodynamics and possible intermediates of the reactions were also investigated.

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Heteroallene Insertions into Tin(II) Alkoxide Bonds

Ryan,

Brookes,

Straiton

et al. 2024

Inorg. Chem.

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A series of iso-carbamate complexes have been synthesized by the reaction of [Sn II (O i Pr) 2 ] or [Sn II (O t Bu) 2 ] with either aryl or alkyl isocyanates, ONC-R (R = 2,4,6-trimethylphenyl (Mes), 2,6-diisopropylphenyl (Dipp), isopropyl ( i Pr), cyclohexyl (Cy) and tert-butyl ( t Bu)). In the case of aryl isocyanates, mono-insertion occurs to form structurally characterized complexesPr)] 2 (1: R = Mes, 2: R = Dipp) and [Sn{κ 2 -N,O-R-NC(O t Bu)O}(μ-O t Bu)] 2 (3: R = Mes, 4: R = Dipp). The complicated solution-state chemistry of these species has been explored using 1 H DOSY experiments. In contrast, reactions of tin(II) alkoxides with alkyl isocyanates result in the formation of bis-insertion products [Sn{κ 2 -N,O-R-NC(O i Pr)O} 2 ] (5: R = i Pr, and 6: R = Cy) and [Sn{κ 2 -N,O-R-NC(O t Bu)O} 2 ] (7: R = i Pr, 8: R = Cy), of which complexes 6−8 have also been structurally characterized. 1 H NMR studies show that the reaction of t Bu-NCO with either [Sn(O i Pr) 2 ] or [Sn(O t Bu) 2] results in a reversible mono-insertion. Variable-temperature 2D 1 H− 1 H exchange spectroscopy (VT-2D-EXSY) was used to determine the rate of exchange between free t Bu-NCO and the coordinated t Bu-iso-carbamate ligand for the {O i Pr} alkoxide complex, as well as the activation energy (E a = 92.2 ± 0.8 kJ mol −1 ), enthalpy (ΔH ‡ = 89.4 ± 0.8 kJ mol −1 ), and entropy (ΔS ‡ = 12.6 ± 2.9 J mol −1 K −1 ) for the process [Sn(O i Pr) 2 ] + t Bu-NCO ↔ [Sn{κ 2 -N,O-t Bu-NC(O i Pr)O}(O i Pr)]. Attempts to form Sn(II) alkyl carbonates by the insertion of CO 2 into either [Sn(O i Pr) 2 ] or [Sn(O t Bu) 2 ] proved unsuccessful. However, 119 Sn{ 1 H} NMR spectroscopy of the reaction of excess CO 2 with [Sn(O i Pr) 2 ] reveals the presence of a new Sn(II) species, i.e., [( i PrO)Sn(O 2 CO i Pr)], VT-2D-EXSY ( 1 H) of which confirms the reversible alkyl carbonate formation (E a = 70.3 ± 13.0 kJ mol −1 ; ΔH ‡ = 68.0 ± 1.3 kJ mol −1 and ΔS ‡ = −8.07 ± 2.8 J mol −1 K −1 ).

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Evaluation of Sn(ii) aminoalkoxide precursors for atomic layer deposition of SnO thin films

Abstract: A series of amino alcohols and fluorinated aminoalcohols (H{ON}) having a different number of methyl/trifluoromethyl substituents at the α-carbon atom, [HOC(R1)(R2)CH2NMe2] (R1 = R2 = H (H{dmae}) (a); R1 =...

Cited by 3 publications

References 63 publications

A chemist's guide to photoelectrode development for water splitting – the importance of molecular precursor design

A chemist's guide to photoelectrode development for water splitting – the importance of molecular precursor design

Germanium Complexes with ONO Tridentate Ligands: O-H Bond Activation Control According to DFT Calculations

Heteroallene Insertions into Tin(II) Alkoxide Bonds

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