Chemical vapour deposition of In2O3 thin films from a tris-guanidinate indium precursor

Barry, Seán T.; Gordon, Peter G.; Ward, Matthew J.; Heikkilä, Mikko; Monillas, Wesley H.; Yap, Glenn P. A.; Ritala, Mikko; Leskelä, Markku

doi:10.1039/c1dt10877h

Cited by 35 publications

(31 citation statements)

References 25 publications

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“…Homoleptic tricoordinated M-N bonded compounds have been reported [12][13][14][15][16] , but these often require bulky ligands to stabilise the In centre, reducing their volatility and thermal stability. Instead, formation of homoleptic hexacoordinated M-N bonded compounds, through the implementation of chelating bidentate ligands, has given the volatile and thermal stable In tris-amidinate (In[iPr-N-C(CH3)-N-iPr]3) 17 , formamidinate (In[iPr-N-C(H)-N-iPr]3) 18 and guanidinate (In[iPr-N-C(NMe2)-N-iPr]3) 19,20 precursors, which were used for the deposition of In2O3 18,20 and InS 21 by ALD. We recently investigated these precursors in combination with NH3 plasma for the deposition of crystalline InN.…”

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confidence: 99%

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In-situ Activation of a Highly Volatile and Thermally Stable Indium(III) Triazenide Precursor for Epitaxial Growth of Indium Nitride by Atomic Layer Deposition

O'Brien¹,

Rouf²,

Samii³

et al. 2019

Preprint

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Indium nitride (InN) is characterised by its superb electron mobility making it a ground-breaking material for high frequency electronics. The difficulty of depositing highquality crystalline InN currently impedes its broad implementation in electronic devices. Herein, we report a new highly volatile and thermally stable In(III) triazenide precursor and demonstrate its ability to deposit high-quality epitaxial hexagonal InN by atomic layer deposition (ALD). The new triazenide precursor was found to sublime at 80 °C and thermogravimetric analysis showed single step volatilisation with an onset temperature of 145 °C and negligible residual mass. Strikingly, two temperature intervals were observed when depositing InN films. In the high temperature interval, the precursor underwent thermal decomposition inside the ALD reaction chamber to produce a more reactive indium compound whilst retaining self-limiting growth behaviour. Stochiometric InN films with very low levels of impurities were grown epitaxially on 4H-SiC. This new triazenide precursor now enables ALD of InN for semi-conductor applications.<br>

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confidence: 99%

“…2.252(13) Å) 18 and guanidinate (av. 2.260(4) Å) 19,20 . This result shows the electron withdrawing effect of the triazenide ligand has little effect on the In-N bond distances.…”

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confidence: 99%

In-situ Activation of a Highly Volatile and Thermally Stable Indium(III) Triazenide Precursor for Epitaxial Growth of Indium Nitride by Atomic Layer Deposition

O'Brien¹,

Rouf²,

Samii³

et al. 2019

Preprint

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“…Al-back contact c-Si Zr(NEtMe)2(guan)2 O2 500 -600 8.74 NR 2009 [12] ZrO2 Glass Zr(CpMe)(η 1 -guan)2Cl Air 500 -600 NR 5-18% 2009 [32] In2O3 Si (100) Glass In(guan)3 Air 275 - 350 43 In(0): < 2% 2011 [4] HfO2…”

Section: Contribution Of Guanidinates To Precursor Developmentmentioning

confidence: 99%

“…CVD grown indium oxide films deposited at 275 -350ºC with humid air as a co-reagent achieved a growth rate of 43 nm/min. [4] Very recently, the same precursor has demonstrated self-limited growth of indium oxide in a waterassisted process between 160 -320ºC at a rate of 0.4 -0.45Å/cycle. [21] No In(0) impurities were reported in either example, although low carbon impurities were noted.…”

Section: Versatility Of Metal Guanidinate Precursorsmentioning

confidence: 99%

“…In recent years, the nanoscale thin film deposition methods of chemical vapour deposition (CVD) and atomic layer deposition (ALD) have become common for growing nano-thin coatings to keep pace with industrial demand for smaller, more sophisticated microelectronic devices. [1][2][3][4][5][6] New precursor compounds for vapour deposition are uncommon, as they must delicately balance thermal stability and reactivity, amongst other criteria. Some of the earliest volatile precursors employed halide ligands, which can enable volatility of relatively heavy metals (e.g., lead, tungsten).…”

Section: Introductionmentioning

confidence: 99%

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Development of Volatile Inorganic Compounds and Their Application for Chemical Vapour Deposition of Metal and Metal Oxide Thin Films

Kurek¹

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Chemical vapour deposition is a necessary and important technology for the manufacture of nano-thin metal films. The reactivity and thermal stability of the metal complexes used in this process are key to the deposition process.Through logical design, guanidinate ligands have evolved into iminopyrrolidinates to prevent decomposition pathways. These ligands were first tested on aluminum metal centres. Iminopyrrolidinates have been further stabilized with additional methyl moieties and have led to promising new copper precursors. Copper metal is desirable for interconnecting material in electronics due to its high conductivity.The reactivity of 1,3-diisopropyl-imidazolin-2-ylidene copper hexamethyl disilazide has been explored and yielded three new copper metal compounds.Sputtered thin films of gold have been used in metal assisted chemical etching to produce high aspect ratio structures on the surface of silicon substrates. PrefaceHere are the full bibliographical details for all reproduced publications included in this thesis. The supervisor, Seán T. Barry, and the student, Agnieszka Kurek, confirm that the student was fully involved in setting up and conducting the research, obtaining data and analyzing results, as well as preparing and writing the material presented in the co-authored articles integrated in this thesis. Additionally, the supervisor confirms the information provided by the student in this preface.To cite material from this thesis, please cite both this thesis and the relevant article from the chapter, if the chapter is based on a published work. Kurek, A.; Gordon, P.G.; Karle, S.; Devi, A.; Barry, S.T. Recent Advances Using Guanidinate Ligands for Chemical Vapour Deposition (CVD) and Atomic Layer Deposition (ALD) Applications, Aust. J. Chem. 2014, 67, 989-996. Wasslen, Y.A.; Kurek, A.; Johnson, P.A.; Pigeon, T.C.; Monillas, W.H.; Yap, G.P.A.; Barry, S.T. Coyle, J.P.; Pallister, P.J.; Kurek, A.; Sirianni, E.R.; Yap, G.P.A.; Barry, S.T. Copper Iminopyrrolidinates: A Study of Thermal and Surface Chemistry, Inorg. Chem. 2013, 52, 910.

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Metallic Materials Deposition: Metal‐Organic PrecursorsUpdate based on the original article by Charles H. Winter, Wenjun Zheng and Hani M. El‐Kaderi,Encyclopedia of Inorganic ChemistrySecond Edition, © 2005, John Wiley & Sons, Ltd.

Winter

Knisley

Kalutarage

et al. 2012

Encyclopedia of Inorganic and Bioinorganic Chemistry

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This review describes metal‐organic precursors for the growth of metal‐containing thin films by chemical vapor deposition (CVD)‐based methods. The major emphasis is on precursors that have been reported since 2004, which corresponds to a time of major growth in this field. Progress in the development of metal‐organic precursors is documented for the main group, lanthanide, and group 4– 11 elements. In the main group elements, there has been considerable research activity directed toward the identification of strontium and barium precursors, due both to the technological importance of mixed oxide phases and the inherent difficulties in obtaining volatile, stable thermally complexes of these large metal ions. Aluminum, gallium, and indium have also been the subject of intense investigation because of the importance of many phases containing these elements. The group 4 and 5 elements titanium, zirconium, hafnium, niobium, and tantalum have been the subject of considerable precursor development activity because of the importance of several mixed oxide phases and the applications of zirconium oxide and hafnium oxide as high‐permittivity gate materials in microelectronic devices. Growth of metal nitride films of these elements has also been an active area of research for use as barrier materials in microelectronic devices. The deposition of copper and other first‐row transition‐metal films from metal‐organic precursors is driven by the urgent need for copper metalization procedures in microelectronics device manufacturing. The atomic layer deposition (ALD) growth of the noble metals ruthenium, rhodium, iridium, palladium, and platinum has been a very active research area. The current state of metal‐organic precursor development is presented for each of these metallic elements.

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Chemical vapour deposition of In2O3 thin films from a tris-guanidinate indium precursor

Cited by 35 publications

References 25 publications

In-situ Activation of a Highly Volatile and Thermally Stable Indium(III) Triazenide Precursor for Epitaxial Growth of Indium Nitride by Atomic Layer Deposition

In-situ Activation of a Highly Volatile and Thermally Stable Indium(III) Triazenide Precursor for Epitaxial Growth of Indium Nitride by Atomic Layer Deposition

Development of Volatile Inorganic Compounds and Their Application for Chemical Vapour Deposition of Metal and Metal Oxide Thin Films

Metallic Materials Deposition: Metal‐Organic PrecursorsUpdate based on the original article by Charles H. Winter, Wenjun Zheng and Hani M. El‐Kaderi,Encyclopedia of Inorganic ChemistrySecond Edition, © 2005, John Wiley & Sons, Ltd.

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