Real-Time Observation of Atomic Layer Deposition Inhibition: Metal Oxide Growth on Self-Assembled Alkanethiols

Avila, Jason R.; DeMarco, Erica J.; Emery, Jonathan D.; Farha, Omar K.; Pellin, Michael J.; Hupp, Joseph T.; Martinson, Alex B. F.

doi:10.1021/am503008j

Cited by 65 publications

(105 citation statements)

References 39 publications

(96 reference statements)

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“…Despite the successful demonstrations of AS‐ALD using SAMs, there are limitations associated with conventional methods of preparing the SAMs. First, depending on the type of SAM and the desired substrate, formation of the monolayer may require dipping the substrate into a solution containing the SAM‐forming molecules for several hours to a few days . The need for long SAM exposure in solution adds significant time to the overall AS‐ALD process.…”

Section: Introductionmentioning

confidence: 99%

“…It has been shown that the thermal stability of some well known SAMs such as thiols on metal surfaces is limited to a temperature of only ≈100 °C, which is below the growth temperature for many ALD processes. As a result, we hypothesize that after a number of ALD cycles, desorption or degradation of organic molecules from the SAM layer generates defects such as pinholes that serve as nucleation sites for ALD . Different approaches have been proposed to circumvent this problem, such as performing ALD at lower temperatures or using longer initial deposition times for the SAMs.…”

Section: Introductionmentioning

confidence: 99%

“…Since the onset of ALD that signals loss of selectivity is thought to originate from degradation or loss of the SAM from the substrate, we expect to see a significant enhancement in selectivity if the SAM can be regenerated or redeposited from the vapor without altering the properties of the deposited film on the silicon (Si) surface. Moreover, due to the different kinetics of molecular adsorption onto a surface from the vapor phase, and the fact that vapor dosing of dodecanethiol (DDT) provides an undiluted exposure of the surface to SAM molecules compared to ethanolic solution of DDT, the deposition time may be significantly reduced if carried out from the vapor phase . Vapor deposition also could provide better SAM coverage on porous or 3D structures, and could allow the SAM passivation step to be integrated with the rest of the ALD process.…”

Section: Introductionmentioning

confidence: 99%

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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%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

Hashemi¹,

Bent

2016

Adv Materials Inter

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“…Compared with Al 2 O 3 ALD, there have been far fewer studies of TiO 2 ALD on metal surfaces. In one study, Martinson et al reported "island growth" of TiO 2 ALD on Au using tetrakis(dimethylamido)titanium and water at 150 °C, where a lower growth rate was observed by in situ QCM measurements during the first 30 cycles[339]. They commented that surface oxygen contamination of the nominally bare Au might have nucleated the TiO 2 ALD.…”

mentioning

confidence: 99%

Atomic layer deposition—Sequential self-limiting surface reactions for advanced catalyst “bottom-up” synthesis

Elam

Stair

2016

Surface Science Reports

270

215

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Catalyst synthesis with precise control over the structure of catalytic active sites at the atomic level is of essential importance for the scientific understanding of reaction mechanisms and for rational design of advanced catalysts with high performance. Such precise control is achievable using atomic layer deposition (ALD). ALD is similar to chemical vapor deposition (CVD), except that the deposition is split into a sequence of two self-limiting surface reactions between gaseous precursor molecules and a substrate. The unique self-limiting feature of ALD allows conformal deposition of catalytic materials on a high surface area catalyst support at the atomic level. The deposited catalytic materials can be precisely constructed on the support by varying the number and type of ALD cycles. As an alternative to the wet-chemistry based conventional methods, ALD provides a cycle-by-cycle "bottom-up" approach for nanostructuring supported catalysts with near atomic precision. In this review, we summarize recent attempts to synthesize supported catalysts with ALD. Nucleation and growth of metals by ALD on oxides and carbon materials for precise synthesis of supported monometallic catalyst are reviewed. The capability of achieving precise control over the particle size of monometallic nanoparticles by ALD is emphasized. The resulting metal catalysts with high dispersions and uniformity often show comparable or remarkably higher activity than those prepared by conventional methods. For supported bimetallic catalyst synthesis, we summarize the strategies for controlling the deposition of the secondary metal selectively on the primary metal nanoparticle but not on the support to exclude monometallic formation. As a review of the surface chemistry and growth behavior of metal ALD on metal surfaces, we demonstrate the ways to precisely tune size, composition and structure of bimetallic metal nanoparticles. The cycle-by-cycle "bottom up" construction of bimetallic (or multiple components) nanoparticles with near atomic precision on supports by ALD is illustrated. Applying metal oxide ALD over metal nanoparticles can be used to precisely synthesize nanostructured metal catalysts. In this part, the surface chemistry of Al 2 O 3 ALD on metals is specifically reviewed. Next, we discuss the methods of tailoring the catalytic performance of metal catalysts including activity, selectivity and stability, through selective blocking of the low-coordination sites of metal nanoparticles, the confinement effect, and the formation of new metal-oxide interfaces. Synthesis of supported metal oxide catalysts with high dispersions and "bottom up" nanostructured photocatalytic architectures are also included. Therein, the surface chemistry and morphology of oxide ALD on oxides and carbon materials as well as their catalytic performance are summarized.

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“…This growth rate is more than 0.2 Å/cycle higher than that reported by Lim and co-workers 24 likely due to the lower reactor temperatures used here, which has been observed for other ALD processes. 21,27,28 Figure 2a also shows the importance of using a long purge time (30 s) in order to sufficiently clear the reactor of precursor and to avoid undesirable CVD reactions, with 15 s showing a higher average growth rate and more variations between runs. In contrast, variations in pulse time and reactor temperature have negligible effect on the growth rate with the exception of a slight profile observed for 0.1 s pulse and 130°C reactor temperature as shown in Figure 2b, c. The wall-mounted QCM used in this study was equipped with 2 ports, one near the reactor inlet and outlet to observe if any growth profile was observed during the ALD process.…”

mentioning

confidence: 99%

Fabrication of Thin Films of α-Fe₂O₃ via Atomic Layer Deposition Using Iron Bisamidinate and Water under Mild Growth Conditions

Avila

Kim

Rimoldi

et al. 2015

ACS Appl. Mater. Interfaces

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Atomic layer deposition (ALD) has been shown to be an excellent method for depositing thin films of iron oxide. With limited iron precursors available, the methods widely used require harsh conditions such as high temperatures and/or the use of oxidants such as ozone or peroxide. This letter aims to show that bis(N,N'-di-t-butylacetamidinato) iron(II) (iron bisamidinate or FeAMD) is an ideal ALD precursor because of its reactivity with water and relative volatility. Using in situ QCM analysis, we show outstanding conformal self-limiting growth of FeOx using FeAMD and water at temperatures lower than 200 °C. By annealing thin films of FeOx at 500 °C, we observe the formation of α-Fe2O3, confirming that we can use FeAMD to fabricate thin films of catalytically promising iron oxide materials using moderate growth conditions.

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Real-Time Observation of Atomic Layer Deposition Inhibition: Metal Oxide Growth on Self-Assembled Alkanethiols

Cited by 65 publications

References 39 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

Atomic layer deposition—Sequential self-limiting surface reactions for advanced catalyst “bottom-up” synthesis

Fabrication of Thin Films of α-Fe₂O₃ via Atomic Layer Deposition Using Iron Bisamidinate and Water under Mild Growth Conditions

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Real-Time Observation of Atomic Layer Deposition Inhibition: Metal Oxide Growth on Self-Assembled Alkanethiols

Cited by 65 publications

References 39 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

Atomic layer deposition—Sequential self-limiting surface reactions for advanced catalyst “bottom-up” synthesis

Fabrication of Thin Films of α-Fe2O3 via Atomic Layer Deposition Using Iron Bisamidinate and Water under Mild Growth Conditions

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Fabrication of Thin Films of α-Fe₂O₃ via Atomic Layer Deposition Using Iron Bisamidinate and Water under Mild Growth Conditions