Synthesis and Characterization of Fluorinated β‐Ketoiminate Zinc Precursors and Their Utility in the AP‐MOCVD Growth of ZnO:F

Cosham, Samuel D.; Kociok‐Köhn, Gabriele; Johnson, Andrew L.; Hamilton, Jeff; Hill, Michael S.; Molloy, Kieran C.; Castaing, R

doi:10.1002/ejic.201500536

Cited by 16 publications

(12 citation statements)

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“…38 On the other hand, the F dopant also serves to narrow the optical band gap by stabilisation of Ti 3+ and V O sites, producing a donor level at the CBM and limiting electron-hole recombination. 107 As such, the TiO 2 :F films have been found to perform significantly better than pure anatase in a photocatalytic test (photoinduced degradation of methylene blue dye).…”

Section: Halide Dopantsmentioning

confidence: 93%

n-Type doped transparent conducting binary oxides: an overview

et al. 2016

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This article focuses on n-type doped transparent conducting binary oxides -namely, those with the general formula M x O y :D, where M x O y is the host oxide material and D is the dopant element. Such materials are of great industrial importance in modern materials chemistry. In particular, there is a focus on the search for alternatives to indium-based materials, prompted by indium's problematic supply risk as well as a number of functional factors. The important relationship between computational study and experimental observation is explored, and an extensive comparison is made between the electrical properties of a number of the most interesting experimentally-prepared materials. In writing this article, we aim to provide both an accessible tutorial of the physical descriptions of transparent conducting oxides, and an up-to-date overview of the field, with a brief history, some key accomplishments from the past few decades, the current state of the field as well as postulation on some likely future developments.

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Section: Halide Dopantsmentioning

confidence: 93%

n-Type doped transparent conducting binary oxides: an overview

et al. 2016

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“…6 More recently Cosham et al have synthesised a series of fluorinated Zn-ketoiminates for atmospheric pressure MOCVD. 7 Besides their favourable stability and reactivity, in contrast to β-diketonates and β-diketiminates, β-ketoiminates offer the opportunity to vary the side chain at the R-position easily. β-ketoimines are easily synthesized in high yields, and are therefore available with countless variations.…”

Section: Introductionmentioning

confidence: 99%

Systematic molecular engineering of Zn-ketoiminates for application as precursors in atomic layer depositions of zinc oxide

et al. 2016

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Molecular engineering of seven closely related zinc ketoiminates, namely, [Zn(dapki)], [Zn(daeki)], [Zn(epki)], [Zn(eeki)], [Zn(mpki)], [Zn(meki)], and [Zn(pki)], leads to the optimisation of precursor thermal properties in terms of volatilisation rate, onset of volatilisation, reactivity and thermal stability. The influence of functional groups at the imine side chain of the ligands on the precursor properties is studied with regard to their viability as precursors for atomic layer deposition (ALD) of ZnO. The synthesis of [Zn(eeki)], [Zn(epki)] and [Zn(dapki)] and the crystal structures of [Zn(mpki)], [Zn(eeki)], [Zn(dapki)] and [Zn(pki)] are presented. From the investigation of the physico-chemical characteristics, it was inferred that all compounds are monomeric, volatile and exhibit high thermal stability, all of which make them promising ALD precursors. Compound [Zn(eeki)] is in terms of thermal properties the most promising Zn-ketoiminate. It is reactive towards water, possesses a melting point of 39 °C, is stable up to 24 days at 220 °C and has an extended volatilisation rate compared to the literature known Zn-ketoiminates. It demonstrated self-saturated, water assisted growth of zinc oxide (ZnO) with growth rates in the order of 1.3 Å per cycle. Moreover, it displayed a broad temperature window from T = 175-300 °C and is the first report of a stable high temperature (>200 °C) ALD process for ZnO returning highly promising growth rates.

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“…To compare the volatility of 7 with literature known systems, zinc chelate complexes such as the uorinated zinc acetylacetonate [Zn{CF 3 C(O)CHC(O)CH 3 } 2 ] 57 and the zinc b-ketoiminate 58 have been used as reference compounds. It should be noticed that there is a lack of vapor pressure measurements for the zinc chelate compounds, despite of their wide use in the numerous applications for deposition of ZnO.…”

Section: Vapor Pressure Measurementsmentioning

confidence: 99%

“…This value is comparable with the one for [Zn{CF 3 C(O)CHC(O)CH 3 } 2 ] (140 C of 11.1 mbar) 57 but signicantly higher than the vapor pressure for [Zn{CF 3 C(O) CHC(NH(CH 2 ) 2 OMe)Me} 2 ] (0.53 mbar at 160 C). 58 Hence, complex 7 was investigated for its applicability in the low pressure CVD process (see below).…”

Section: Vapor Pressure Measurementsmentioning

confidence: 99%

“…The vapor pressure of 7 was determined to 10.4 mbar at 160 C, which is comparable with the one of [Zn{CF 3 C(O)CHC(O)CH 3 } 2 ] (11.1 mbar at 140 C), 57 but signicantly higher than for [Zn{CF 3 C(O)CHC(N(CH 2 ) 2 -OMe)Me} 2 ] (0.53 mbar at 160 C). 58 Hence, 7 was used as CVD precursor for the deposition of ZnO. Deposition parameters have been varied to investigate their inuence on the morphology of the metal oxide thin lms.…”

Section: Layer Characterizationmentioning

confidence: 99%

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