Growth and Properties of Hybrid Organic‐Inorganic Metalcone Films Using Molecular Layer Deposition Techniques

Lee, Byoung H.; Yoon, Byunghoon; Абдулагатов, А. И.; Hall, Robert A.; George, Steven M.

doi:10.1002/adfm.201200370

Cited by 135 publications

(146 citation statements)

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“…36 Combining ALD and MLD can also produce organic-inorganic alloys or nanolaminates, where the properties are tunable between pure inorganic and organic-inorganic. 37,38 The number of materials is nearly endless considering the metals and types of organic linkages available.…”

Section: B Molecular Layer Depositionmentioning

confidence: 99%

History of atomic layer deposition and its relationship with the American Vacuum Society

Parsons¹,

Elam²,

George³

et al. 2013

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

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Document VersionPublisher's PDF, also known as Version of Record (includes final page, issue and volume numbers) Please check the document version of this publication:• A submitted manuscript is the author's version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. People interested in the research are advised to contact the author for the final version of the publication, or visit the DOI to the publisher's website.• The final author version and the galley proof are versions of the publication after peer review.• The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication General rightsCopyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.• Users may download and print one copy of any publication from the public portal for the purpose of private study or research.• You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal ? Take down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. This article explores the history of atomic layer deposition (ALD) and its relationship with the American Vacuum Society (AVS). The authors describe the origin and history of ALD science in the 1960s and 1970s. They also report on how the science and technology of ALD progressed through the 1990s and 2000s and continues today. This article focuses on how ALD developed within the AVS and continues to evolve through interactions made possible by the AVS, in particular, the annual International AVS ALD Conference. This conference benefits students, academics, researchers, and industry practitioners alike who seek to understand the fundamentals of self-limiting, alternating binary surface reactions, and how they can be applied to form functional (and sometimes profitable) thin film materials. The flexible structure of the AVS allowed the AVS to quickly organize the ALD community and create a primary conference home. Many new research areas have grown out of the original concepts of "Atomic Layer Epitaxy" and "Molecular Layering," and some of them are described in this article. The people and research in the ALD field continue to evolve, and the AVS ALD Conference is a primary example of how the AVS can help a field expand and flourish.

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Section: B Molecular Layer Depositionmentioning

confidence: 99%

History of atomic layer deposition and its relationship with the American Vacuum Society

Parsons¹,

Elam²,

George³

et al. 2013

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

Self Cite

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“…The precursors for ALD and MLD can be combined to grow hybrid organic−inorganic metal alkoxide polymers known as "metalcones". 5,6 These hybrid MLD films can possess interesting mechanical and electrical properties. 7,8 ALD and MLD can also be combined to form ALD/MLD alloys and nanolaminates that can be fine-tuned by varying the composition of the alloy.…”

Section: Introductionmentioning

confidence: 99%

Pyrolysis of Alucone Molecular Layer Deposition Films Studied Using In Situ Transmission Fourier Transform Infrared Spectroscopy

DuMont

George

2015

J. Phys. Chem. C

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The pyrolysis of alucone molecular layer deposition (MLD) films was studied in vacuum using in situ transmission Fourier transform infrared spectroscopy. The initial alucone MLD films were grown using trimethylaluminum (TMA) and either ethylene glycol (EG) (HO−(CH 2 ) 2 − OH) or hydroquinone (HQ) (HO−C 6 H 4 −OH) at 150°C. The alucone MLD films were then pyrolyzed in vacuum at temperatures ranging from 400 to 750°C. The absorbance features for the C−H, C−C, and C−O stretching vibrations were observed to be lost at pyrolysis temperatures from 350 to 500°C. For the alucone films grown using TMA and EG, the loss of these absorbance features was coupled to an increase in carboxylate (R-COO − ) absorbance features. The carboxylate absorbance features reached their peak at a pyrolysis temperature of 450°C and then decreased slowly with higher pyrolysis temperatures. The carboxylate absorbance features are consistent with an Al 2 O 3 /carbon composite material with Al 3+ /COO − species at the interface. In addition, the presence of carbon in the Al 2 O 3 /carbon composite led to an increase in the background infrared absorbance for the pyrolyzed alucone films grown using HQ containing six carbons. This background infrared absorbance is linked to electrical conductance in a network of carbon domains in the pyrolyzed alucone films, as described by Drude−Zener theory. In contrast, the alucone films grown using EG containing two carbons did not display an increase in the background infrared absorbance. This absence of background infrared absorbance is consistent with less carbon in the Al 2 O 3 /carbon composite grown using EG. The pyrolysis of the alucone films on ZrO 2 particles led to very conformal Al 2 O 3 /carbon composite films, as observed by transmission electron microscopy images. I. INTRODUCTIONAtomic layer deposition (ALD) and molecular layer deposition (MLD) are ideal techniques to deposit ultrathin inorganic and organic films. 1−4 Both ALD and MLD are based on sequential, self-limiting surface reactions that allow conformal film growth on high aspect ratio structures with precise thickness control. The precursors for ALD and MLD can be combined to grow hybrid organic−inorganic metal alkoxide polymers known as "metalcones". 5,6 These hybrid MLD films can possess interesting mechanical and electrical properties. 7,8 ALD and MLD can also be combined to form ALD/MLD alloys and nanolaminates that can be fine-tuned by varying the composition of the alloy. 6,9,10 Metalcone MLD films can also serve as a precursor to a new set of ceramic materials. Hybrid organic−inorganic MLD films can be annealed in air to burn out the carbon and yield porous metal oxide films. 11−14 These porous metal oxide films have been shown to contain micropores and mesopores. 11 Hybrid organic−inorganic MLD films can also be pyrolyzed under vacuum or inert atmosphere to yield electrically conducting metal oxide/carbon composite films. 15 This strategy is similar to the fabrication of ceramics from polymers in polymerderived ceramic processing....

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“…[24,25] In combination with the ALD fabrication of inorganic materials, a very convenient and highly controllable route to nanostructuring is molecular layer deposition (MLD) to produce hybrid inorganic-organic materials (Figure 1d). [26][27][28][29][30][31][32] The combined ALD/MLD technique has been used to fabricate various nanoscale oxide-organic superlattices in a highly controllable fashion [33] and crystalline ZnO-organic superlattices fabricated using hydroquinone (HQ, benzene-1,4-diol, HOC 6 H 4 OH) as the organic precursor indeed show orderof-magnitude reduction of thermal conductivity. [34] The orderof-magnitude reduction of thermal conductivity has also been proven for analogous hybrid TiO 2 -organic superlattices fabricated by ALD/MLD, highlighting the wider applicability of the oxide-organic superlattice approach for the thermal engineering of metal oxides.…”

Section: Wileyonlinelibrarycommentioning

confidence: 99%

Flexible Thermoelectric ZnO–Organic Superlattices on Cotton Textile Substrates by ALD/MLD

Karttunen

Sarnes

Townsend

et al. 2017

Adv Elect Materials

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we focus on small-scale energy harvesting based on the thermoelectric effect.Thermoelectric materials can be used to convert waste heat to electric energy via Seebeck effect. They are characterized by a dimensionless figure-of-merit ZT = S 2 σT/(κ e + κ L ), where S is the Seebeck coefficient (thermopower), σ the electrical conductivity, T the temperature, and κ e and κ L the electronic and lattice contributions to the thermal conductivity κ. [12] Figure 1 illustrates the basic principle of a conventional thermoelectric (TE) energy conversion device and the concept of a TE generator device combined with a flexible substrate. Furthermore, Figure 1c shows how the ZT value arises from the abovementioned individual components. Alloys of bismuth telluride (Bi 2 Te 3 ) and antimony telluride (Sb 2 Te 3 ) are by far the most widely used TE materials. They show high ZT values for near-room-temperature applications and have been utilized for decades in solid-state refrigeration applications. A major obstacle for the widespread utilization of Bi-Sb-Te based thermoelectrics is the low abundance of tellurium: it is among the rarest elements in the Earth's crust. Furthermore, current thermoelectric generators based on conventional TE materials such as Bi 2 Te 3 are typically inflexible solid-state devices, which would not be convenient for mobile small-scale applications. [12] Consequently, there is a significant interest in producing flexible and efficient TE generator solutions. In particular, a mechanically flexible TE generator solution integrated with light-weight and comfortable textile substrates could be an enabling platform for body-heat-based energy harvesting.Recently Lee et al. fabricated woven-yarn thermoelectric textiles by coating electrospun polyacrylonitrile nanofiber cores with n-type Bi 2 Te 3 and p-type Sb 2 Te 3 and twisting them into flexible yarns. [13] By weaving the TE-coated yarns into textiles, they were able to obtain an output power of up to 8.56 W m −2 for a temperature difference of 200 K in the textile thickness direction. Another recent study on thermoelectric fabrics utilized a completely different type of material solution, where thermoelectric PEDOT:PSS (poly(3,4-ethylenedioxythiophene) polystyrene sulfonate) polymer was used to coat a polyester fabric with a solution-based method. [14] This fabric-TE device was based on p-type PEDOT:PSS only, resulting in a so-called unileg-type device that produced an output power of about 260 µW m −2 for a temperature difference of 75 K.The thermoelectric properties of both pristine ZnO and ZnO-organic superlattice thin films deposited on a cotton textile are investigated. The thin films are fabricated by atomic layer deposition/molecular layer deposition, using hydroquinone as the organic precursor for the superlattices. The resulting thin-film coatings are crystalline, in particular when deposited on a textile substrate with a thin predeposited Al 2 O 3 seed layer. The thermoelectric properties of the ZnO and ZnO-organic superlattice coatings are comp...

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Growth and Properties of Hybrid Organic‐Inorganic Metalcone Films Using Molecular Layer Deposition Techniques

Cited by 135 publications

References 93 publications

History of atomic layer deposition and its relationship with the American Vacuum Society

History of atomic layer deposition and its relationship with the American Vacuum Society

Pyrolysis of Alucone Molecular Layer Deposition Films Studied Using In Situ Transmission Fourier Transform Infrared Spectroscopy

Flexible Thermoelectric ZnO–Organic Superlattices on Cotton Textile Substrates by ALD/MLD

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