New method for studying the pyrolysis of VPE/CVD precursors under vacuum conditions. Application to trimethylantimony and tetramethyltin

Svoboda, G. D.; Gleaves, John; Mills, Patrick L.

doi:10.1021/ie00001a004

Cited by 37 publications

(18 citation statements)

References 11 publications

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“…In fact, SbMe 3 was reported to significantly decompose at a temperature of 400°C [23,24], with an activation energy of 171 kJ/mol [25]. The decomposition products of Sb 2 Me 4 -SbMe and SbMe 3 -are already observed at 300°C, which is in agreement with the early investigation by Dickson et al [11], who reported on the growth of Sb films at 300°C from this precursor in the presence of hydrogen.…”

Section: Methodssupporting

confidence: 86%

Low-temperature thermolysis behavior of tetramethyl- and tetraethyldistibines

Bahlawane

Reilmann

Schulz

et al. 2008

J. Am. Soc. Mass Spectrom.

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The thermolysis behavior of tetramethyl-and tetraethyldistibine (Sb2Me4 and Sb 2Et4) was investigated using a mass spectrometer coupled to a tubular flow reactor under near-chemical vapor deposition (CVD) conditions. Sb 2Me4 undergoes a gas-phase disproportionation with an estimated activation energy of 163 kJlmo1. This reaction leads to the formation of methylstibinidine, SbMe, that reacts on the surface to produce antimony film and SbMe 3 . Unfortunately, this clean decomposition pathway is limited to a narrow temperature range of 300-350 "C. At temperatures exceeding 400°C, SbMe 3 decomposes following a radical route with a consequent risk of carbon contamination. In contrast, Sb 2Et 4 disproportionates at the hot wall of the reactor. According to mass-spectrometric data, this reaction is significant starting at a temperature of 100°C, with an apparent activation energy of 104 kJ/mol. Within the temperature range of 100-250°C, the precursor decomposition leads to the formation of antimony films and SbEt 3 , whereas different molecular reaction pathways are significantly activated above 250°C. The use of Sb 2Et 4 lowers the risk of carbon contamination compared to Sb 2Me4 at high temperature. Therefore, Sb 2Et 4 is a promising CVD precursor for the growth of antimony films in the absence of hydrogen atmosphere in a wide temperature range. [5,6], and transparent electrode [7] materials for a wide range of applications. Most of the antimony-containing materials possess metastable compositions that impose low processing temperatures. Chemical vapor deposition (CVD) is considered as a nearly ideal, low-cost, and high throughput approach for device manufacturing; however, its application here is hindered by the lack of suitable, low-temperature antimony precursors [8]. Standard antimony precursors including SbMe 3 and SbEt 3 exhibit high thermal stability, which complicates the growth of materials such as InSb [9,10].These precursors were therefore judged not suitable as controllable antimony sources because of their strong Sb--C bond [11,12]. The strength of the Sb-C bond was found to decrease with increasing ligand size [13], although the extremely low volatility of the resulting molecules represents a significant drawback [14]. Deuterated stibine (SbD 3 ) was proposed by Todd et a1.[8] as a suitable carbon-free antimony source that allows deposition of antimony films at temperatures as low as 200°C. SbD 3 shows an enhanced stability compared to that of SbH 3 at 23°C, which allows its implementation as a CVD Address reprint requests to Dr. Naoufal

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Section: Methodssupporting

confidence: 86%

Low-temperature thermolysis behavior of tetramethyl- and tetraethyldistibines

Bahlawane

Reilmann

Schulz

et al. 2008

J. Am. Soc. Mass Spectrom.

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show abstract

“…Knudsen flow has been experimentally verified in the TAP reactor by several groups [28,29,32,46] and an excellent agreement was found between the experimental data and Eq. (6) in all studies, which included a variation of the temperature, mass of the gas, reactor packing and reactor dimensions.…”

Section: Transport and Reaction In The Tap Reactormentioning

confidence: 56%

“…Two different approaches have been used. One is based on solving the partial differential equations by a Laplace transformation and then calculating the exit flow by a numerical Fast Fourier Transform algorithm [58,59,29,30]. This approach is only possible for linear equations (first order kinetics and low surface coverages).…”

Section: Sticking Coefficientmentioning

confidence: 99%

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Assessment of kinetic modeling procedures of TAP experiments

Schuurman

2007

Catalysis Today

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“…The elucidation of the kinetics of the reactions that produce solid films from Sill4, Si2H 6 and SiaH s on polysilicon substrates was achieved by monitoring the transient responses of the above silanes after introduction of pulses into a specially designed silicon-wafer stacked reactor. Only one similar TAP study on CVD precursors is known in the literature [10]. In the latter, the pyrolysis of trimethylantimony and tetramethyltin is investigated.…”

Section: Introductionmentioning

confidence: 99%