MOCVD of Aluminum Nitride Thin Films with a New Type of Single-Source Precursor: AlCl3:tBuNH2

Joo, Oh‐Shim; Jung, Kwang‐Deog; Cho, Sunghoon; Kyoung, Je‐Hong; Ahn, Chang‐Kyu; Choi, Sung Chul; Dong, Yongkwan; Yun, Hoseop; Han, Sung‐Hwan

doi:10.1002/1521-3862(20021203)8:6<273::aid-cvde273>3.0.co;2-o

Cited by 10 publications

(6 citation statements)

References 9 publications

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“…The structure of 6 shows that the aluminum atom adopts a distorted-tetrahedral geometry. The Al−N bond distance of 1.9641(15) Å is shorter than the corresponding bond distance in 1 but longer than in the related complex [AlCl 3 {NH 2 ( t Bu)}] (Al−N = 1.939(2) Å). , There are no other packing interactions of note. The formation of compound 6 was surprising, as the expected product was either the 1:1 adduct [MeAlCl 2 {NH( t Bu)(SiMe 3 )}] or the dimeric complex [MeAlCl{NH( t Bu)] 2 .…”

Section: Resultsmentioning

confidence: 81%

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Organoaluminum Silylamido Complexes

et al. 2004

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The reaction between [Et2AlCl] and 1 equiv of HN(SiMe3)2 in CH2Cl2 afforded colorless crystals of [Et2AlCl{NH(SiMe3)2}] (1). In contrast, reaction of [Et2AlCl] with 1 equiv of HN(SiMe2H)2 or HN t Bu(SiMe3) resulted in the isolation of dimers, of the type [EtAlCl{NH(R‘)}]2 (2, R‘ = SiMe2H; 3, R‘ = t Bu). Reaction of [Et3Al] with 1 equiv of HN(SiMe2H)2 or HN(SiMe3)2 yielded the expected dimeric complexes, [Et2Al{N(SiMe2H)2}]2 (4) and [Et2Al{N(SiMe3)2}]2 (5), via ethane elimination. The related reaction between [MeAlCl2] and HN t Bu(SiMe3) in CH2Cl2 solution resulted in the formation of the 1:1 adduct [MeAlCl2{NH2( t Bu)}] (6). The structures of compounds 1 and 6 have been determined by X-ray crystallography. In addition, the decomposition of 1 and 6 has been studied by thermal gravimetric analysis.

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Section: Resultsmentioning

confidence: 81%

“…Recently the 1:1 adduct [AlCl 3 {NH 2 ( t Bu)}] was successfully used as a precursor to AlN thin films, with little carbon contamination incorporated . Therefore, to study the decomposition pathways of some of the complexes described herein, thermal gravimetric analyses (TGA) were carried out.…”

Section: Resultsmentioning

confidence: 99%

Organoaluminum Silylamido Complexes

et al. 2004

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“…[1][2][3] Volatile group 13-15 donor-acceptor complexes are prospective single-source precursors (SSP) for the chemical vapor deposition (CVD) of binary and composite nitrides. 4,5 Volatility and the strength of the donor-acceptor bond are the two key characteristics of a successful SSP. Volatility of the solid adduct is determined by its sublimation enthalpy, which in turn depends on the structural properties of the compounds.…”

Section: Introductionmentioning

confidence: 99%

“…2 Complexes with large donor-acceptor bond energies and sufficient volatility, such as the pyridine adducts MX 3 ·Py, reveal a significant concentration in vapors even at elevated (600-800 K) temperatures. 2,6 Usually, complexes with monodentate donors, for example AlCl 3 ·NH 2 t Bu, 5 are used as SSP for the synthesis of binary 13-15 compounds. For generating ternary and composite nitrides SSP should have different group 13 elements in the same molecule.…”

Section: Introductionmentioning

confidence: 99%

Structural and thermodynamic properties of molecular complexes of aluminum and gallium trihalides with bifunctional donor pyrazine: decisive role of Lewis acidity in 1D polymer formation

et al. 2013

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Solid state structures of group 13 metal halide complexes with pyrazine ( pyz) of 2 : 1 and 1 : 1 composition have been established by X-ray structural analysis. Complexes of 2 : 1 composition adopt molecular structures MX 3 ·pyz·MX 3 with tetrahedral geometry of group 13 metals. Complexes of AlBr 3 and GaCl 3 of 1 : 1 composition are 1D polymers (MX 3 ·pyz) ∞ with trigonal bipyramidal geometry of the group 13 metal, while the weaker Lewis acid GaI 3 forms the monomeric molecular complex GaI 3 ·pyz, which is isostructural to its pyridine analog GaI 3 ·py. Tensimetry studies of vaporization and thermal dissociation of AlBr 3 ·pyz and AlBr 3 ·pyz·AlBr 3 complexes have been carried out using the static method with a glass membrane null-manometer. Thermodynamic characteristics of vaporization and equilibrium gas phase dissociation of the AlBr 3 ·pyz complex have been determined. Comprehensive theoretical studies of (MX 3 ) n ·( pyz) m complexes (M = Al, Ga; X = Cl, Br, I; n = 1, 2; m = 1-3) have been carried out at the B3LYP/ TZVP level of theory. Donor-acceptor bond energies were obtained taking into account reorganization energies of the fragments. Computational data indicate that the formation of (MX 3 ·pyz) ∞ polymers with coordination number 5 is only slightly more energetically favorable than the formation of molecular complexes of type MX 3 ·pyz for X = Cl, Br. It is expected that on melting (MX 3 ·pyz) ∞ polymers dissociate into individual MX 3 ·pyz molecules. This dovetails with low melting enthalpies of the (MX 3 ·pyz) ∞ complexes.Polymer stability decreases in the order AlCl 3 > AlBr 3 > GaCl 3 > AlI 3 > GaBr 3 > GaI 3 . For MI 3 ·pyz complexes computations predict that the monomeric structure motif is more energetically favorable compared to the catena polymer. These theoretical predictions agree well with the experimentally observed monomeric complex GaI 3 ·pyz in the solid state. Thus, the Lewis acidity of the group 13 halides may play a decisive role in the formation of 1D polymeric networks.

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“…Molecular rings and cage‐compounds with an Al‐N skeleton have been extensively studied in view of their structural diversity and the application to obtain the semi‐conductor AlN . If an alane X 3 Al is allowed to react with an amine N Y 3 , the chemical nature and partial charge of the substituent plays the key role for the formation of the final product.…”

Section: Introductionmentioning

confidence: 99%

Aluminum/Nitrogen Cycles and an Open Cage with Al–H and N–H Functions

Veith

Walgenbach

Hüch

et al. 2017

Zeitschrift anorg allge chemie

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The cyclic tert‐butyl‐amino alane dimer [tBu–N(H)AlH2]2 (1) was obtained from reaction between alane with tert‐butylamine and its boranate derivative [tBu–N(H)–Al(BH4)2)]2 (2) subsequently from 1 by hydride/chloride exchange using PbCl2 followed by reaction with LiBH4. Both compounds form four‐membered Al2N2 cycles with typical Al–N bond lengths of 1.940(5) Å (1) and 1.945(5) Å (2) as found from X‐ray diffraction analysis. The tert‐butyl substituents at the nitrogen atoms may be situated at the same side of the ring (cis) or at opposite sides (trans). For compound 1 both isomers are present in solution, showing particular temperature dependent NMR shifts. In the solid both compounds 1 and 2 adopt the trans arrangement. When 1 is reacted with PbCl2 in half of the molarity ratio used for 2, surprisingly the novel compound 3, a zwitterion, can be obtained: [(tBu–N)(Al–H)3(tBu–N(H))3Cl((H)N–tBu)3(Al–H)2(Al–Cl)(N–tBu)]+[(tBu–N)(tBu–N(H))(AlCl2)2]–. X‐ray structure analysis reveals that the anion is made of a tert‐butyl amino aluminum dichloride dimer (central Al2N2 ring) with one of the two nitrogen atoms being deprotonated. The cationic counterpart consists of three entities: (i) There is a first seco‐norcubane like Al3N4 basket with tert‐butyl groups at the nitrogen atoms, two hydride and one chloride ligand at the aluminum atoms and three hydrogen atoms on the open side of the basket, all pointing in the same direction; (ii) There is a second similar Al3N4 basket with the same substituent pattern except that all aluminum atoms have exclusively hydrogen ligands; (iii) Both baskets coordinate a central chloride through the six protons at the open nitrogen face of the baskets in such a way that the chloride lies in the center of a H6 trigonal anti‐prism [mean H–Cl–H = 56.1(9)°]. As each of the open cages has a positive charge the overall charge by combination with the chloride adds to +1. The structure of the cationic part of 3 is unprecedented in AlN polycycles.

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MOCVD of Aluminum Nitride Thin Films with a New Type of Single-Source Precursor: AlCl3:tBuNH2

Cited by 10 publications

References 9 publications

Organoaluminum Silylamido Complexes

Organoaluminum Silylamido Complexes

Structural and thermodynamic properties of molecular complexes of aluminum and gallium trihalides with bifunctional donor pyrazine: decisive role of Lewis acidity in 1D polymer formation

Aluminum/Nitrogen Cycles and an Open Cage with Al–H and N–H Functions

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