Photoactivated Molecular Layer Deposition through Iodo−Ene Coupling Chemistry

Lillethorup, Mie; Bergsman, David S.; Sandoval, Tania E.; Bent, Stacey F.

doi:10.1021/acs.chemmater.7b01780

Cited by 10 publications

(25 citation statements)

References 47 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…New organic components have also been developed for the purely organic MLD processes; the MLD material library already includes, besides the initially introduced polyimides [ 15,17–22,137–143 ] and polyamides, [ 15,23–28,144–149 ] many other polymers: polyurea, [ 29,30,37,38,51,150–164 ] polythiourea, [ 52 ] polyurethane, [ 165,166 ] polyazomethine, [ 167–172 ] poly(3,4‐ethylenedioxy‐thiophene), [ 173–177 ] polyimide–polyamide, [ 141 ] poly(ethylene terephthalate) (PET), [ 50,178–180 ] and others. [ 31,32,39–44,176,181–200 ] In recent years, the organic precursor library has been rapidly expanding. We have collected in Table 1 the organic precursors so far used in ALD/MLD processes, together with the heating temperatures employed for their evaporation in the corresponding process conditions; [ …”

Section: Organic Precursors In Ald/mldmentioning

confidence: 99%

Atomic/Molecular Layer Deposition for Designer's Functional Metal–Organic Materials

Multia

Karppinen

2022

Adv Materials Inter

View full text Add to dashboard Cite

organic ligands act as bridges between the metal centers to form infinite 1D, 2D, or 3D structures. These materials are often referred to as coordination polymer (CP) [1] or metal-organic framework (MOF) [2] materials; the latter term is used when the metal-organic material is crystalline and highly porous. [3] The research field of CP-and MOF-type materials has grown tremendously over the last two decades. The structural and chemical diversity of these materials has served as a continuous source of scientific excitement; the same diversity has also triggered huge technological interest as these materials possess enormous potential to be tailored for a wide variety of applications ranging from gas capture, storage, and separation to sensing, catalysis, optics, electronics, and energy storage. [4][5][6][7] Most of the targeted application breakthroughs of metal-organics require that these materials can be produced as highquality thin films and coatings, which can be integrated with the other components in the actual device configuration. The possibility to deposit such thin films in an industry-feasible manner on the substrate types needed, would be a major step forward in the field. [8] Traditionally, solvent-based processes such as liquid-phase epitaxy, Langmuir-Blodgett, layer-by-layer, and electrochemical deposition techniques have been used for metal-organic thin films. [9][10][11] These are, however, incompatible with the requirements set by the possible integration of the materials in microelectronics. This is due to corrosion and contamination risks, and the problems in patterning and precise deposition on high-aspect-ratio features. Hence, it is vital to develop solventfree thin-film deposition routes for the metal-organic material family. In the optimal case, these deposition methods should allow conformal coatings on large-area and high-aspect-ratio substrates.The currently strongly emerging ALD/MLD technique is uniquely suited to address the challenge in a scientifically elegant yet industrially feasible way. This technique is derived from the two parent gas-phase thin-film techniques: ALD for inorganic materials (mostly binary metal oxides, sulfides, and nitrides), [12][13][14] and its counterpart MLD for purely organic thin films (e.g., polyimides and polyamides). [15] In both cases, the attractive film growth characteristics are derived from the unique way of separating the different precursor gas pulses. Currently, ALD is the standard thin-film technology in many Atomic layer deposition (ALD) for high-quality conformal inorganic thin films is one of the cornerstones of modern microelectronics, while molecular layer deposition (MLD) is its less-exploited counterpart for purely organic thin films. Currently, the hybrid of these two techniques, i.e., ALD/MLD, is strongly emerging as a state-of-the-art gas-phase route for designer's metal-organic thin films, e.g., for the next-generation energy technologies. The ALD/MLD literature comprises nearly 300 original journal papers covering most of the alkali...

show abstract

Section: Organic Precursors In Ald/mldmentioning

confidence: 99%

Atomic/Molecular Layer Deposition for Designer's Functional Metal–Organic Materials

Multia

Karppinen

2022

Adv Materials Inter

View full text Add to dashboard Cite

show abstract

“…8,11 In earlier work by our group, a photoactivated MLD process (pMLD) was described which uses UV light to enable an iodo-ene polymerization chemistry, forming new C−C bonds in the process. 11 This exciting development toward MLD polymer synthesis via UV activation enables new MLD chemistries to be introduced. However, the final polymer film in the previous work still contained ester groups within the backbone.…”

Section: ■ Introductionmentioning

confidence: 99%

“…However, the final polymer film in the previous work still contained ester groups within the backbone. 11 In the current work, we introduce a C−C bond forming pMLD chemistry resulting in a heteroatom-free, all-carbon backbone. Thin film polymers with carbon backbones possess important properties such as conductivity, 12 photoresistance, 13 and high stability, 14 though they have not yet been developed via MLD.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Previous work on pMLD films also shows very long soaking times to reach saturation. 11 The longer time required for the DIOFB monomer to reach saturation is potentially due to the lower vapor pressure of DIOFB than that of HD (∼8 vs 223 Torr at room temperature), resulting in a lower exposure of monomer to the surface. 35,36 Additionally, since the reaction rate is related to the surface concentration of C−I groups, we expect the reaction to be completed more quickly when the surface is presaturated with the DIOFB precursor, which is the case during the HD dosing.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Previous work on pure organic MLD polymers has shown that degradation occurs between 250 and 300 °C, tested under low-vacuum nitrogen-flow conditions, with one exception being a polyester film grown using a similar pMLD method, which has shown stability up to 350 °C. 11 Hybrid ALD-MLD films tend to decompose at even lower temperatures, 4,61,62 although there are examples of silicon oxycarbide hybrid films with stabilities up to 600 °C. 9,63 Generally, MLD polymers exhibit good stabilities to solvents, acids, and bases tested by sonication.…”

Section: ■ Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Growth of a Surface-Tethered, All-Carbon Backboned Fluoropolymer by Photoactivated Molecular Layer Deposition

Closser

Lillethorup²,

Bergsman

et al. 2019

ACS Appl. Mater. Interfaces

Self Cite

View full text Add to dashboard Cite

The synthesis of an all-carbon backboned fluoropolymer using photoactivated molecular layer deposition (pMLD) is developed. pMLD is a vapor-phase, layer-by-layer, organic thin film synthesis method utilizing UV light, allowing for the creation of materials previously unavailable via thermal MLD. The carbon backbone is achieved by reacting an iodine-containing fluorocarbon monomer (1,4-diiodooctafluorobutane) and a diene monomer (1,5-hexadiene) under UV irradiation in a step-growth polymerization sequence. The polymerization occurs with a growth rate of 1.3 Å/cycle, forming a copolymer containing hydrocarbon and fluorocarbon segments. X-ray photoelectron spectroscopy (XPS) was used to confirm the formation of new carbon–carbon bonds and quantify the final film composition. In situ XPS thermal annealing experiments confirm the film stability up to 400 °C. The ability to pattern the fluoropolymer on a surface is demonstrated using a photomask, suggesting that these films could be incorporated into photolithographic processes. Together, these results demonstrate that pMLD can be used to synthesize carbon backboned films with photopatterning ability, expanding the available chemistries and potential applications of MLD polymers.

show abstract

Molecular layer deposition (MLD) for lightwave control and extended applications

Yoshimura

2024

Nano-Structures & Nano-Objects

View full text Add to dashboard Cite

Photoactivated Molecular Layer Deposition through Iodo−Ene Coupling Chemistry

Cited by 10 publications

References 47 publications

Atomic/Molecular Layer Deposition for Designer's Functional Metal–Organic Materials

Atomic/Molecular Layer Deposition for Designer's Functional Metal–Organic Materials

Growth of a Surface-Tethered, All-Carbon Backboned Fluoropolymer by Photoactivated Molecular Layer Deposition

Molecular layer deposition (MLD) for lightwave control and extended applications

Contact Info

Product

Resources

About