<i>In situ</i> analysis of nucleation reactions during TiCl4/H2O atomic layer deposition on SiO2 and H-terminated Si surfaces treated with a silane small molecule inhibitor

Clerix, Jan-Willem J.; Dianat, Golnaz; Delabie, Annelies; Parsons, Gregory N.

doi:10.1116/6.0002493

Cited by 3 publications

(2 citation statements)

References 55 publications

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“…Step 4A then produces a slight increase in hydrophobicity, with the WCA ≈ 75°. This small change may be due to DMATMS reacting with a small number of Si–OH sites or due to some physisorption of DMATMS on the Si–H surface …”

Section: Resultsmentioning

confidence: 99%

“…This small change may be due to DMATMS reacting with a small number of Si−OH sites or due to some physisorption of DMATMS on the Si−H surface. 30 The changes in the WCA for both surfaces during sequence B are shown in Figure 2c,d promote more rapid silicon hydroxylation during the subsequent liquid DI H 2 O exposure.…”

Section: Selectivity Inversion On Blanket Substratesmentioning

confidence: 93%

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“Dual-Tone” Area-Selective Deposition: Selectivity Inversion of Polymer on Patterned Si/SiO₂ Starting Surfaces

Carroll,

Margavio,

Parsons

2024

Chem. Mater.

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Area-selective deposition (ASD) has recently emerged as a promising augmentation of lithographic patterning of small device features. However, current ASD processes are restricted to predefined growth and nongrowth surfaces, limiting their flexibility in industrial processing. In this work, we define the concept of "dual-tone ASD," where a patterned surface is tuned to enable ASD on one of two adjacent surfaces while avoiding growth on the other surface. For the example case in this work, starting with ASD of the poly(3,4-ethylenedioxythipohene) (PEDOT) conjugated polymer on SiO 2 vs on hydrogen-terminated silicon (Si−H), we demonstrate a method to modify a patterned Si−H/SiO 2 surface to invert the selectivity, enabling PEDOT to grow selectively on the modified Si region and not on the modified SiO 2 . The selectivity inversion was achieved by selective modification of the substrate surface energy via treatments with dilute hydrofluoric acid (DHF), (dimethylamino)trimethylsilane (DMATMS), and water. Versatile control over selectivity configurations during ASD has implications for deposition of lateral control layers to reduce overgrowth defects, blocking layers for nonselective deposition steps, and sacrificial layers for recently reported simultaneous deposition and etching processes. Through this study, we identify generalized requirements for selectivity inversion as a patterning strategy in the ASD toolbox and show how this strategy is consistent with previous reports of ASD on metal−dielectric patterned surfaces. Extension of these surface energy treatment strategies to other materials will provide additional opportunities for selectivity inversion, leading to flexible applications of ASD in manufacturing settings.

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Section: Resultsmentioning

confidence: 99%

Section: Selectivity Inversion On Blanket Substratesmentioning

confidence: 93%

“Dual-Tone” Area-Selective Deposition: Selectivity Inversion of Polymer on Patterned Si/SiO₂ Starting Surfaces

Carroll,

Margavio,

Parsons

2024

Chem. Mater.

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Low‐Temperature Dual‐Material Area‐Selective Deposition: Molybdenum Hexafluoride‐Mediated SiO₂ Fluorination/Passivation for Self‐Aligned Molybdenum/Metal Oxide Nanoribbons

Oh,

Thelven,

Margavio

et al. 2024

Adv Funct Materials

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Area‐selective deposition (ASD) is a forefront nanopatterning technique gaining substantial attention in the semiconductor industry. While current research primarily addresses single‐material ASD, exploring multi‐material ASD is essential for mitigating complexity in advanced nanopatterning. This study describes molybdenum hexafluoride (MoF6)‐mediated fluorination/passivation of the hydroxylated SiO2 (SiO2‒OH) at 250 °C as a new method to pacify nucleation during subsequent ZnO and TiO2 atomic layer deposition (ALD). In contrast, Al2O3 ALD is not passivated on the fluorinated SiO2 (SiO2‒F). The study further shows that Mo ALD using MoF6 and silane (1 wt% SiH4 in Ar) selectively proceeds on hydrogen‐terminated Si (Si‒H), whereas SiO2‒OH becomes fluorine‐passivated without observable Mo deposition. This enables subsequent ZnO and TiO2 ASD on Mo versus SiO2‒F, as confirmed by X‐ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and scanning transmission electron microscopy (STEM). Proposed growth and inhibition mechanisms highlight the importance of the metal oxide precursor in achieving selectivity. Taken together, self‐aligned Mo/ZnO and Mo/TiO2 nanoribbons are demonstrated on coplanar nanoscale Si‒H/SiO2‒OH patterns by sequentially integrating two individual ASD processes: 1) Mo ASD on Si‒H versus SiO2‒OH; and 2) ZnO or TiO2 ASD on Mo versus SiO2‒F. This work highlights the potential for this approach in new ASD systems.

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Inhibition of atomic layer deposition of TiO2 by functionalizing silicon surface with 4-fluorophenylboronic acid

Silva-Quinones,

Mason,

Norden

et al. 2024

Journal of Vacuum Science &Amp; Technology A

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As the size of the components in electronic devices decreases, new approaches and chemical modification schemes are needed to produce nanometer-size features with bottom-up manufacturing. Organic monolayers can be used as effective resists to block the growth of materials on non-growth substrates in area-selective deposition methods. However, choosing the appropriate surface modification requires knowledge of the corresponding chemistry and also a detailed investigation of the behavior of the functionalized surface in realistic deposition schemes. This study aims to investigate the chemistry of boronic acids that can be used to prepare such non-growth areas on elemental semiconductors. 4-Fluorophenylboronic acid is used as a model to investigate the possibility to utilize the Si(100) surface functionalized with this compound as a non-growth substrate in a titanium dioxide (TiO2) deposition scheme based on sequential doses of tetrakis(dimethylamido)titanium and water. A combination of X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry allows for a better understanding of the process. The resulting surface is shown to be an effective non-growth area to TiO2 deposition when compared to currently used H-terminated silicon surfaces but to exhibit much higher stability in ambient conditions.

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In situ analysis of nucleation reactions during TiCl4/H2O atomic layer deposition on SiO2 and H-terminated Si surfaces treated with a silane small molecule inhibitor

Cited by 3 publications

References 55 publications

“Dual-Tone” Area-Selective Deposition: Selectivity Inversion of Polymer on Patterned Si/SiO₂ Starting Surfaces

“Dual-Tone” Area-Selective Deposition: Selectivity Inversion of Polymer on Patterned Si/SiO₂ Starting Surfaces

Low‐Temperature Dual‐Material Area‐Selective Deposition: Molybdenum Hexafluoride‐Mediated SiO₂ Fluorination/Passivation for Self‐Aligned Molybdenum/Metal Oxide Nanoribbons

Inhibition of atomic layer deposition of TiO2 by functionalizing silicon surface with 4-fluorophenylboronic acid

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In situ analysis of nucleation reactions during TiCl4/H2O atomic layer deposition on SiO2 and H-terminated Si surfaces treated with a silane small molecule inhibitor

Cited by 3 publications

References 55 publications

“Dual-Tone” Area-Selective Deposition: Selectivity Inversion of Polymer on Patterned Si/SiO2 Starting Surfaces

“Dual-Tone” Area-Selective Deposition: Selectivity Inversion of Polymer on Patterned Si/SiO2 Starting Surfaces

Low‐Temperature Dual‐Material Area‐Selective Deposition: Molybdenum Hexafluoride‐Mediated SiO2 Fluorination/Passivation for Self‐Aligned Molybdenum/Metal Oxide Nanoribbons

Inhibition of atomic layer deposition of TiO2 by functionalizing silicon surface with 4-fluorophenylboronic acid

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Product

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“Dual-Tone” Area-Selective Deposition: Selectivity Inversion of Polymer on Patterned Si/SiO₂ Starting Surfaces

“Dual-Tone” Area-Selective Deposition: Selectivity Inversion of Polymer on Patterned Si/SiO₂ Starting Surfaces

Low‐Temperature Dual‐Material Area‐Selective Deposition: Molybdenum Hexafluoride‐Mediated SiO₂ Fluorination/Passivation for Self‐Aligned Molybdenum/Metal Oxide Nanoribbons