Advances in the deposition chemistry of metal-containing thin films using gas phase processes

Bahlawane, Naoufal; Kohse‐Höinghaus, Katharina; Premkumar, Peter Antony; Lenoble, D.

doi:10.1039/c1sc00522g

Cited by 29 publications

(28 citation statements)

References 117 publications

(146 reference statements)

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“…Soft wet‐chemical synthesis in organic solvents from metal–organic complexes is an important method to obtain metal or metal alloy nanoparticles . Metal amidinates are important precursors for metal nanoparticles for thin metal films from low‐pressure chemical vapor deposition (CVD) and atomic layer deposition (ALD) …”

Section: Introductionmentioning

confidence: 99%

Synthesis of Metal Nanoparticles and Metal Fluoride Nanoparticles from Metal Amidinate Precursors in 1-Butyl-3-Methylimidazolium Ionic Liquids and Propylene Carbonate

et al. 2016

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Decomposition of transition‐metal amidinates [M{MeC(NiPr)2}n] [M(AMD)n; M=MnII, FeII, CoII, NiII, n=2; CuI, n=1) induced by microwave heating in the ionic liquids (ILs) 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([BMIm][BF4]), 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([BMIm][PF6]), 1‐butyl‐3‐methylimidazolium trifluoromethanesulfonate (triflate) ([BMIm][TfO]), and 1‐butyl‐3‐methylimidazolium tosylate ([BMIm][Tos]) or in propylene carbonate (PC) gives transition‐metal nanoparticles (M‐NPs) in non‐fluorous media (e.g. [BMIm][Tos] and PC) or metal fluoride nanoparticles (MF2‐NPs) for M=Mn, Fe, and Co in [BMIm][BF4]. FeF2‐NPs can be prepared upon Fe(AMD)2 decomposition in [BMIm][BF4], [BMIm][PF6], and [BMIm][TfO]. The nanoparticles are stable in the absence of capping ligands (surfactants) for more than 6 weeks. The crystalline phases of the metal or metal fluoride synthesized in [BMIm][BF4] were identified by powder X‐ray diffraction (PXRD) to exclusively Ni‐ and Cu‐NPs or to solely MF2‐NPs for M=Mn, Fe, and Co. The size and size dispersion of the nanoparticles were determined by transmission electron microscopy (TEM) to an average diameter of 2(±2) to 14(±4) nm for the M‐NPs, except for the Cu‐NPs in PC, which were 51(±8) nm. The MF2‐NPs from [BMIm][BF4] were 15(±4) to 65(±18) nm. The average diameter from TEM is in fair agreement with the size evaluated from PXRD with the Scherrer equation. The characterization was complemented by energy‐dispersive X‐ray spectroscopy (EDX). Electrochemical investigations of the CoF2‐NPs as cathode materials for lithium‐ion batteries were simply evaluated by galvanostatic charge/discharge profiles, and the results indicated that the reversible capacity of the CoF2‐NPs was much lower than the theoretical value, which may have originated from the complex conversion reaction mechanism and residue on the surface of the nanoparticles.

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Section: Introductionmentioning

confidence: 99%

Synthesis of Metal Nanoparticles and Metal Fluoride Nanoparticles from Metal Amidinate Precursors in 1-Butyl-3-Methylimidazolium Ionic Liquids and Propylene Carbonate

et al. 2016

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“…The deposition parameters are: temperature substrate = 450 °C; oxygen flow = 2000 standard cubic centimetres (sccm); nitrogen flow = 850 sccm; total process pressure = 12 mbar. A detailed description of the deposition approach fabrication can be found elsewhere 35 . The annealing processes were performed in a Rapid Thermal Annealing reactor (Annealsys) under Argon, under vacuum or at high oxygen partial pressure (in same conditions as during the deposition) and the changes in conductivity were not significantly depending on the annealing atmosphere.…”

Section: Methodsmentioning

confidence: 99%

Tuning the electrical properties of the p-type transparent conducting oxide Cu1−xCr1+xO2 by controlled annealing

Popa

Afonso

Grysan

et al. 2018

Sci Rep

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Off-stoichiometric copper chromium oxide delafossite received lately a great interest due to its high p-type electrical conductivity and adequate optical transmittance in the visible range. However, for a suitable integration in active devices such as p-n junctions, transistors or optoelectronic devices, the electronic properties must be efficiently tailored. Here, post-deposition thermal treatment is proven as an adequate approach for finely controlling the electrical properties of this former degenerate semiconducting material. The energetics of the annealing process are investigated using two different approaches, as a function of the annealing temperature and as a function of the annealing time, allowing the accurate determination of the activation energy of the annealing of defects. By using this method, the electrical carrier concentration was varied in the 1021 – 1017 cm−3 range while the recorded changes in the drift mobility covered three orders of magnitude. Moreover, we demonstrate the ability to accurately manipulate the Fermi level of such materials, which is of great importance in controlling the carrier injection and extraction in optoelectronic active layers.

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“…Soft, wet‐chemical synthesis in organic solvents from metal–organic complexes is an important route to nanometals and allows the preparation of metals and alloys in the nanometer scale regime . Metal amidinates (Scheme ) have been investigated and widely used as precursors for metal nanoparticles and thin metal films in low‐pressure chemical vapor deposition (CVD) or atomic layer deposition (ALD) …”

Section: Introductionmentioning

confidence: 99%

Soft, Wet‐Chemical Synthesis of Metastable Superparamagnetic Hexagonal Close‐Packed Nickel Nanoparticles in Different Ionic Liquids

Wegner

Rutz

Schütte

et al. 2017

Chemistry A European J

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The microwave-induced decomposition of bis{N,N'-diisopropylacetamidinate}nickel(II) [Ni{MeC(NiPr) } ] or bis(1,5-cyclooctadiene)nickel(0) [Ni(COD) ] in imidazolium-, pyridinium-, or thiophenium-based ionic liquids (ILs) with different anions (tetrafluoroborate, [BF ] , hexafluorophosphate, [PF ] , and bis(trifluoromethylsulfonyl)imide, [NTf ] ) yields small, uniform nickel nanoparticles (Ni NPs), which are stable in the absence of capping ligands (surfactants) for more than eight weeks. The soft, wet-chemical synthesis yields the metastable Ni hexagonal close-packed (hcp) and not the stable Ni face-centered cubic (fcc) phase. The size of the nickel nanoparticles increases with the molecular volume of the used anions from about 5 nm for [BF ] to ≈10 nm for [NTf ] (with 1-alkyl-3-methyl-imidazolium cations). The n-butyl-pyridinium, [BPy] , cation ILs reproducibly yield very small nickel nanoparticles of 2(±1) nm average diameter. The Ni NPs were characterized by high-resolution transmission electron microscopy (HR-TEM) and powder X-ray diffraction. An X-ray photoelectron spectroscopic (XPS) analysis shows an increase of the binding energy (E ) of the electron from the Ni 2p orbital of the very small 2(±1) nm diameter Ni particles by about 0.3 eV to E =853.2 eV compared with bulk Ni , which is traced to the small cluster size. The Ni nanoparticles show superparamagnetic behavior from 150 K up to room temperature. The saturation magnetization of a Ni (2±1 nm) sample from [BPy][NTf ] is 2.08 A m kg and of a Ni (10±4 nm) sample from [LMIm][NTf ] it is 0.99 A m kg , ([LMIm]=1-lauryl-3-methyl- imidazolium). The Ni NPs were active catalysts in IL dispersions for 1-hexene or benzene hydrogenation. Over 90 % conversion was reached under 5 bar H in 1 h at 100 °C for 1-hexene and a turnover frequency (TOF) up to 1330 mol (mol ) h or in 60 h at 100 °C for benzene hydrogenation and TOF=23 mol (mol ) h .

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Advances in the deposition chemistry of metal-containing thin films using gas phase processes

Cited by 29 publications

References 117 publications

Synthesis of Metal Nanoparticles and Metal Fluoride Nanoparticles from Metal Amidinate Precursors in 1-Butyl-3-Methylimidazolium Ionic Liquids and Propylene Carbonate

Synthesis of Metal Nanoparticles and Metal Fluoride Nanoparticles from Metal Amidinate Precursors in 1-Butyl-3-Methylimidazolium Ionic Liquids and Propylene Carbonate

Tuning the electrical properties of the p-type transparent conducting oxide Cu1−xCr1+xO2 by controlled annealing

Soft, Wet‐Chemical Synthesis of Metastable Superparamagnetic Hexagonal Close‐Packed Nickel Nanoparticles in Different Ionic Liquids

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