Inherent substrate-dependent growth initiation and selective-area atomic layer deposition of TiO2 using “water-free” metal-halide/metal alkoxide reactants

Atanasov, Sarah E.; Kalanyan, Berç; Parsons, Gregory N.

doi:10.1116/1.4938481

Cited by 74 publications

(100 citation statements)

References 29 publications

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“…Previous studies have achieved area selective deposition of thin films using methods such as relying on inherent selectivity differences between different surface materials, choosing precursors that enhance or delay the growth on one surface versus another, using an unreactive polymer film as a blocking layer in the regions where ALD is not desired or precursor infiltration in polymers . However, more commonly, the surface of the substrate is chemically modified with self‐assembled monolayers (SAMs) .…”

Section: Introductionmentioning

confidence: 99%

Sequential Regeneration of Self‐Assembled Monolayers for Highly Selective Atomic Layer Deposition

Hashemi¹,

Bent

2016

Adv Materials Inter

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Next generation 3D electronic devices will require novel processing methods. Area selective atomic layer deposition (ALD) of robust films has the opportunity to play an important role in significantly reducing complexities associated with current top‐down fabrication processes of patterned structures. An all‐vapor process is demonstrated for depositing and regenerating thiol self‐assembled monolayers (SAMs) on copper between ALD cycles. It is shown that by redosing SAM precursors, the SAM quality can be restored after it begins to degrade. It is also shown that this approach is effective in improving the blocking properties of the SAMs against ZnO ALD. This process allows selective deposition of dielectric films on dielectric regions of patterned Cu/SiO2 substrates more than three times thicker than approaches that do not regenerate the SAM. In addition, this all‐vapor strategy provides the ability to integrate the selective deposition process into the ALD reactor, reduces artifacts associated with depositing the SAMs on porous or 3D structures, and decreases the required deposition time for the passivation layer, opening up the possibility for new applications in next generation electronic devices.

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Section: Introductionmentioning

confidence: 99%

Sequential Regeneration of Self‐Assembled Monolayers for Highly Selective Atomic Layer Deposition

Hashemi¹,

Bent

2016

Adv Materials Inter

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“…TiO 2 and WO 3 have been widely reported in ALD growth 35,[42][43][44][45][46][47][48][49][50] . Recipes involve the sequential use of a metal precursor (metal-halide, or metal-organic), a purging mechanism using an inert gas, and an oxygen source (often H 2 O, O 3 , or plasma excited O 2 ) [51][52][53] . Use of plasma results in improved material properties such as high density as well as low-impurity content at lower deposition temperatures, while the growth per cycle is still comparable with non-plasma ALD processes 54 .…”

mentioning

confidence: 99%

Precursor-surface interactions revealed during plasma-enhanced atomic layer deposition of metal oxide thin films by in-situ spectroscopic ellipsometry

Kılıç

Mock

Sekora

et al. 2020

Sci Rep

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We find that a five-phase (substrate, mixed native oxide and roughness interface layer, metal oxide thin film layer, surface ligand layer, ambient) model with two-dynamic (metal oxide thin film layer thickness and surface ligand layer void fraction) parameters (dynamic dual box model) is sufficient to explain in-situ spectroscopic ellipsometry data measured within and across multiple cycles during plasma-enhanced atomic layer deposition of metal oxide thin films. We demonstrate our dynamic dual box model for analysis of in-situ spectroscopic ellipsometry data in the photon energy range of 0.7-3.4 eV measured with time resolution of few seconds over large numbers of cycles during the growth of titanium oxide (TiO 2) and tungsten oxide (WO 3) thin films, as examples. We observe cyclic surface roughening with fast kinetics and subsequent roughness reduction with slow kinetics, upon cyclic exposure to precursor materials, leading to oscillations of the metal thin film thickness with small but positive growth per cycle. We explain the cyclic surface roughening by precursor-surface interactions leading to defect creation, and subsequent surface restructuring. Atomic force microscopic images before and after growth, x-ray photoelectron spectroscopy, and x-ray diffraction investigations confirm structural and chemical properties of our thin films. Our proposed dynamic dual box model may be generally applicable to monitor and control metal oxide growth in atomic layer deposition, and we include data for Sio 2 and Al 2 o 3 as further examples. Transition metal oxides (TMOs) are subject of contemporary interest for many applications. A wide range of interesting electrical, optical, electrochromic, and photocatalytic properties make TMOs attractive for device applications 1-6. TMOs are being exploited, for example, as efficient light absorber materials in photo-voltaic devices 7,8 , as ion-transport, and/or ion-storage materials in rechargeable batteries 9 , as active materials in switchable electrochromic optical windows 10-12 , in low-earth-orbit protective coatings for all-solid-state electrochromic surface heat radiation control devices 13,14 , in gas sensing devices 15,16 , and in photo-catalysis devices 6. TMOs are often fabricated as thin films, where fabrication conditions critically influence the resulting thin film properties 17-19. Various growth processes for the fabrication of TMO thin films have been developed by utilizing physical vapor deposition (PVD) such as magnetron sputtering 20-22 , thermal evaporation 23,24 , and chemical vapor deposition (CVD) 25-27. Thin films deposited by PVD processes are often affected by thickness and composition non-uniformity. Adhesion failure and non-homogeneous coverage across highly-faceted surfaces are often reported 28-30. CVD processes enable deposition of highly uniform thin films in the thickness range of nanometers to many micrometers 31-33. However, CVD growth processes critically depend on reaction conditions such as

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“…Finally, one can also want different properties for a unique material (resistivity, transparency), or varying chemical and/or structural composition (crystallinity, density, roughness, doping level) as a function of a surface or a space direction. Selective deposition by ALD can be obtained using: inherent selectivity of the process [66][67][68][69][70] , surface activation 71 , surface deactivation [72][73][74][75][76][77][78][79][80] , and super-cycles ABC type 81 or with alternate deposition and etching steps 58,[82][83][84][85] . As in PECVD and PEALD processes, ions from the plasma can be used in any of these steps and therefore help to promote a selective deposition.…”

Section: Selective Deposition Process: Ions Versus Radicalsmentioning

confidence: 99%

Plasma deposition—Impact of ions in plasma enhanced chemical vapor deposition, plasma enhanced atomic layer deposition, and applications to area selective deposition

Vallée

Bonvalot

Belahcen

et al. 2020

Journal of Vacuum Science &Amp; Technology A: Vacuum, Surfaces, and Films

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In this paper, the emerging role of ionic species in plasma assisted chemical deposition processes is discussed in details for commemorating the Career of John Coburn who studied the role of ionic species in plasma etching processes forty years ago. It is shown that in both Plasma Enhanced Chemical Vapor Deposition (PECVD) and Plasma Enhanced Atomic Layer Deposition (PEALD) processes, plasma ions can play a major role in tuning a wide range of physical properties of thin films. In both processes, the possibility of extracting plasma ions with a tunable incident kinetic energy driven on the substrate surface is shown to provide a valuable additional degree of freedom in plasma processing. While a too large incident kinetic energy of plasma ions may have damaging effects linked to surface sputtering and atomic peening, a relatively low energy ion bombardment ensures a substantial improvement of thin film purity and the effective tuning of its microstructural properties. This phenomenon is attributed to the synergetic effect boosting momentum transfer and chemical reactivity among radicals and ionic plasma species which in turn modulates plasma-surface interactions. Taking advantage of these tunable physical properties opens up the way to a large array of pathways for selective deposition processes in both 2D and 3D nanoscale microstructures.

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Inherent substrate-dependent growth initiation and selective-area atomic layer deposition of TiO2 using “water-free” metal-halide/metal alkoxide reactants

Cited by 74 publications

References 29 publications

Sequential Regeneration of Self‐Assembled Monolayers for Highly Selective Atomic Layer Deposition

Sequential Regeneration of Self‐Assembled Monolayers for Highly Selective Atomic Layer Deposition

Precursor-surface interactions revealed during plasma-enhanced atomic layer deposition of metal oxide thin films by in-situ spectroscopic ellipsometry

Plasma deposition—Impact of ions in plasma enhanced chemical vapor deposition, plasma enhanced atomic layer deposition, and applications to area selective deposition

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