Atomic Layer Deposition of Platinum Oxide and Metallic Platinum Thin Films from Pt(acac)<sub>2</sub> and Ozone

Hämäläinen, Jani; Munnik, F.; Ritala, Mikko; Leskelä, Markku

doi:10.1021/cm801187t

Cited by 96 publications

(54 citation statements)

References 52 publications

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“…These prior studies use as the metal precursor either (Pt(acac) 2 ) or (methylcyclopentadienyl)trimethylplatinum (MeCpPtMe 3 ), and as the oxidant, either O 2 , oxygen plasma, or O 3 (ozone). [10,11] Here we select MeCpPtMe 3 and ozone for Pt deposition on CDP because growth temperatures as low as 100 °C with growth rates on the order of 0.45 Å/cycle have been demonstrated for this combination. [11] These conditions are compatible with CDP, which unless held under high steam partial pressures, undergoes a slow and highly detrimental dehydration/decomposition reaction at temperatures above ~150 °C.…”

Section: A C C E P T E D Accepted Manuscriptmentioning

confidence: 99%

Atomic layer deposition of Pt@CsH2PO4 for the cathodes of solid acid fuel cells

Lim

Liu

Pandey

et al. 2018

Electrochimica Acta

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Atomic layer deposition (ALD) has been used to apply continuous Pt films on powders of the solid acid CsH 2 PO 4 (CDP), in turn, used in the preparation of cathodes in solid acid fuel cells (SAFCs).The film deposition was carried out at 150 °C using trimethyl(methylcyclopentadienyl)platinum (MeCpPtMe 3 ) as the Pt source and ozone as the reactant for ligand removal. Chemical analysis showed a Pt growth rate of 0.09 ± 0.01 wt%/cycle subsequent to an initial nucleation delay of 84 ± 20 cycles. Electron microscopy revealed the contiguous nature of the films prepared using 200 or more cycles. The cathode overpotential (0.48 ± 0.02 V at a current density of 200 mA/cm 2 ) was independent of Pt deposition amount beyond the minimum required to achieve these continuous films. The cell electrochemical characteristics were moreover extremely stable with time, with the cathode overpotentials increasing by no more than 10 mV over a 100 h period of measurement. Thus, ALD holds promise as an effective tool in the preparation of SAFC cathodes with high activity and excellent stability.

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Section: A C C E P T E D Accepted Manuscriptmentioning

confidence: 99%

Atomic layer deposition of Pt@CsH2PO4 for the cathodes of solid acid fuel cells

Lim

Liu

Pandey

et al. 2018

Electrochimica Acta

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“…The surface reactions during plasma Pt ALD are believed to be fairly similar to the surface reactions during thermal Pt ALD. 37 Amorphous PtO x films were deposited at lower temperatures of 120 and 130 C and metallic Pt films were grown at !140 C. 37 The low density Pt film could also be rationalized by a corrugated and wormlike structure similar to the structure observed by the SEM images in Figs. Nucleation is difficult because the initial substrate may not supply oxygen to initiate the reaction.…”

Section: B Mechanism Of Pt Ald Nucleation and Growth On Al 2 O 3 Submentioning

confidence: 99%

Nucleation and growth of Pt atomic layer deposition on Al2O3 substrates using (methylcyclopentadienyl)-trimethyl platinum and O2 plasma

Baker¹,

Cavanagh²,

Seghete³

et al. 2011

Journal of Applied Physics

104

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The nucleation and growth of Pt atomic layer deposition (ALD) on Al 2 O 3 substrates was studied using (methylcyclopentadienyl)-trimethyl platinum (MeCpPtMe 3 ) and O 2 plasma as the reactants. The nucleation of Pt ALD was examined on Al 2 O 3 ALD substrates at 300 C using a variety of techniques including spectroscopic ellipsometry, x-ray reflectivity, x-ray photoelectron spectroscopy, and scanning electron microscopy. These techniques revealed that Pt ALD does not nucleate and grow immediately on the Al 2 O 3 ALD substrates. There was negligible Pt ALD during the first 38 ALD cycles. The Pt ALD growth rate then increased substantially during the next 12 ALD cycles. Subsequently, the Pt ALD growth rate reached a steady state linear growth regime for >50 ALD cycles. These measurements suggest that the Pt ALD first forms a number of nanoclusters that grow slowly during the first 38 ALD cycles. These islands then merge during the next 12 cycles and yield a steady state Pt ALD growth rate of $0.05 nm/cycle for >50 ALD cycles. The Pt ALD film at the onset of the steady state linear growth regime was approximately 2-3 nm in thickness. However, the SEM images of these Pt ALD films appeared corrugated and wormlike. These films also had a density that was only 50-70% of bulk Pt. Film densities that were consistent with bulk Pt were not observed until after >100 ALD cycles when the Pt ALD films appeared much smoother and were 4-5 nm in thickness. The Pt ALD nucleation rate could be enhanced somewhat using different O 2 plasma parameters.

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“…However, in the case of metal ALD, since temperatures as high as 300°C are generally required to achieve successful deposition with the thermal energy of the precursor reactions, it is difficult to deposit conformal metal films onto thermally weak substrates using ALD, causing difficulties in a wide range of applications, including textile electronics. 14,15 To ensure successful metal ALD at low temperatures, ALD in which the precursor is combined with a plasma-generated radical as highly reactive counter reactants has been investigated; however, the high energy of the plasma causes degradation of substrates that do not have a high thermal stability and robustness under plasma conditions. [16][17][18][19] In addition, Dendooven et al 20 investigated Pt ALD at low temperatures around 100°C by using O 3 as a reactant with a (methylcyclopentadienyl)trimethylplatinum (MeCpPtMe 3 ) precursor.…”

Section: Introductionmentioning

confidence: 99%

Highly conductive and flexible fiber for textile electronics obtained by extremely low-temperature atomic layer deposition of Pt

et al. 2016

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Thermal atomic layer deposition (ALD) of metal has generally been achieved at high temperatures of around 300°C or at relatively low temperatures with highly reactive counter reactants, including plasma radicals and O 3 , which can induce severe damage to substrates. Here, the growth of metallic Pt layers by ALD at a low temperature of 80°C is achieved by using [(1,2,5,6-η)-1,5-hexadiene]-dimethyl-platinum(II) (HDMP) and O 2 as the Pt precursor and counter reactant, respectively. ALD results in the successful growth of continuous Pt layers at the low temperature without any reactive reactants owing to the low activation energy of the HDMP precursor for surface reactions. Because of the high reactivity of the precursor, the growth of a pure Pt layer is achieved on various thermally weak substrates, leading to the fabrication of high-performance conductive cotton fibers by ALD. A capacitive-type textile pressure sensor is successfully demonstrated by stacking elastomeric rubber-coated conductive cotton fibers perpendicularly and integrating them onto a fabric with a 7 × 8 array configuration to identify the features of the applied pressure, which can be effectively utilized as a new platform for future wearable and textile electronics. INTRODUCTIONAtomic layer deposition (ALD) has widely attracted considerable interest for various high technologies, such as semiconductor devices and display devices, 1-3 because of its superb ability to deposit ultrathin films with excellent controllability and conformality even on complex three-dimensional (3D) structures. 1-8 Based on these superior properties, ALD has been intensively studied for several applications. In particular, textile electronics using the ALD is one of the promising fields since several materials can be readily deposited at temperatures lower than 150°C by ALD, leading to the effective functionalization of thermally fragile substrates such as plastics, cellulose papers and polymeric textiles. [9][10][11][12] Chen et al. 13 demonstrated hydrophobic silk fabrics with a high laundering durability and robustness due to a TiO 2 coating deposited by ALD. However, in the case of metal ALD, since temperatures as high as 300°C are generally required to achieve successful deposition with the thermal energy of the precursor reactions, it is difficult to deposit conformal metal films onto thermally weak substrates using ALD, causing difficulties in a wide range of applications, including textile electronics. 14,15 To ensure successful metal ALD at low temperatures, ALD in which the

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Atomic Layer Deposition of Platinum Oxide and Metallic Platinum Thin Films from Pt(acac)₂ and Ozone

Cited by 96 publications

References 52 publications

Atomic layer deposition of Pt@CsH2PO4 for the cathodes of solid acid fuel cells

Atomic layer deposition of Pt@CsH2PO4 for the cathodes of solid acid fuel cells

Nucleation and growth of Pt atomic layer deposition on Al2O3 substrates using (methylcyclopentadienyl)-trimethyl platinum and O2 plasma

Highly conductive and flexible fiber for textile electronics obtained by extremely low-temperature atomic layer deposition of Pt

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Atomic Layer Deposition of Platinum Oxide and Metallic Platinum Thin Films from Pt(acac)2 and Ozone

Cited by 96 publications

References 52 publications

Atomic layer deposition of Pt@CsH2PO4 for the cathodes of solid acid fuel cells

Atomic layer deposition of Pt@CsH2PO4 for the cathodes of solid acid fuel cells

Nucleation and growth of Pt atomic layer deposition on Al2O3 substrates using (methylcyclopentadienyl)-trimethyl platinum and O2 plasma

Highly conductive and flexible fiber for textile electronics obtained by extremely low-temperature atomic layer deposition of Pt

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Atomic Layer Deposition of Platinum Oxide and Metallic Platinum Thin Films from Pt(acac)₂ and Ozone