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The development of new resist materials is vital to fabrication techniques for next-generation microelectronics. Inorganic resists are promising candidates because they have higher etch resistance, are more impervious to pattern collapse, and are more absorbing of extreme ultraviolet (EUV) radiation than organic resists. However, there is limited understanding about how they behave under irradiation. In this work, a Hf-based hybrid thin film resist, known as "hafnicone", is deposited from the vapor-phase via molecular layer deposition (MLD), and its electron-beam and deep-ultraviolet (DUV)-induced patterning mechanism is explored. The hafnicone thin films are deposited at 100 °C by using the Hf precursor tetrakis(dimethylamido)hafnium(IV) and the organic precursor ethylene glycol. E-beam lithography, scanning electron microscopy, and profilometry are used to investigate the resist performance of hafnicone. With 3 M HCl as the developer, hafnicone behaves as a negative tone resist which exhibits a sensitivity of 400 μC/cm

Coordination polymers deposited by hybrid molecular layer deposition (MLD) techniques are of interest as highly conformal, functional materials. Incorporation of a second metal into these coordination polymers can result in additional functionality or fine tuning of the materials properties. Here, we investigate the deposition of multi-metal coordination polymers using hybrid MLD of Zn-Al and Zn-Hf with ethylene glycol as the organic linker. It is found that facile transmetalation occurs for the Zn-Al films, which results in Al-rich films, but does not take place for the Zn-Hf films. Additionally, the Zn-Hf films are found to be more resilient to ambient conditions than the pure Zn-based coordination polymer.

WS(S2)(S2CNEt2)2 has been successfully employed in the aerosol-assisted chemical vapor deposition of WS2 at temperatures above 350 °C. This precursor was found to decompose primarily through the loss of H2S, CS2, and SCNEt. The WS2 deposits were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, and X-ray diffraction. The deposits exhibited plate-like structures growing vertically from the substrate.

Thermal atomic layer deposition (ALD) of metals on metal oxide surfaces typically suffers from nucleation delays that result in poor-quality films. The poor nucleation may be caused by a lack of suitable chemisorption sites on the oxide surface which are needed for metal nucleation to occur. In this work, we demonstrate that pre-functionalizing the surface with a sub-monolayer of small organometallic molecules from the vapor phase can lead to a significant increase in surface coverage of the metal deposited by ALD. This process is demonstrated for Pt ALD from (methylcyclopentadienyl)trimethylplatinum (MeCpPtMe3) and O2, with nucleation enhanced almost three-fold at 100 ALD cycles after the pre-treatment, and even more significantly at lower ALD cycle numbers. We hypothesize that the high coverage of the organometallic molecule provides an alternative chemisorption mechanism for the platinum precursor and thus leads to an increase in nucleation sites. The growth of the platinum deposits was investigated in depth though scanning electron microscopy (SEM) and grazing incidence small angle x-ray scattering (GISAXS). These studies show that the pre-treatment results in the growth of larger and more highly ordered Pt nanoparticles at early cycle numbers, which subsequently coalesce into continuous and pinhole free films. Surface pretreatment by organometallic molecules therefore introduces a potential route to achieve improved nucleation and growth of ultrathin films.

Tungsten nitrido amido guanidinato complexes of the type WN(NR(2))[(NR′)(2)C(NR(2))](2) (R = Me, Et(;) R’ = (i)Pr, Cy) were synthesized as precursors for aerosol-assisted chemical vapor deposition (AACVD) of WN(x)C(y) thin films. The reaction of tungsten nitrido amido complexes of the type WN(NR(2))(3) (R = Me, Et) with two equivalents of a carbodiimide R′N=C=NR′ (R′ = (i)Pr, Cy) resulted in two insertions of a carbodiimide into W–N(amido) bonds, affording bis(guanidinato) amido nitrido tungsten complexes. These compounds were characterized by (14)N NMR, indicating distinctive chemical shifts for each type of N-bound ligand. Crystallographic structure determination of WN(NMe(2))[(N(i)Pr)(2)C(NMe(2))](2) showed the guanidinato ligands to be non-equivalent. The complex WN(NMe(2))[(N(i)Pr)(2)C(NMe(2))](2) was demonstrated to serve as a precursor for AACVD of WN(x)C(y) thin films, resulting in featureless, X-ray amorphous thin films for growth temperatures 200 – 400 °C.

As one of the most attractive transition metal dichalcogenides (TMDs), the growth of molybdenum disulfide (MoS2) with industrial compatibility is of great importance. Atomic layer deposition (ALD) has been shown to be a promising method to achieve the growth of high-quality TMD materials. However, MoS2 films deposited by ALD often are amorphous with nonideal stoichiometry and require high-temperature post-deposition annealing. In this study, we introduce a modified ALD recipe using Mo(CO)6 and H2S, resulting in controllable linear growth behavior, a S-to-Mo ratio of 2:1, and crystalline films at a temperature as low as 190 °C. The growth mechanisms and key factors leading to this improvement are proposed and complemented by kinetics calculations. This newly developed methodology relies on aligning the process time with the reaction kinetics of carbonyl disassociation. The MoS2 films prepared herein were shown to be active hydrogen evolution reaction catalysts.

The photothermal heating of plasmonic metal nanostructures can be exploited for bottom-up nanofabrication via surface plasmon-mediated chemical solution deposition (SPMCSD). Herein, we demonstrate the versatility of this plasmon-mediated strategy with a rapid deposition (t ≈ 5 min) of metallic copper nanoparticles (Cu NPs) on a silver (Ag) film on nanosphere (AgFON) substrate under low-power, visible-light irradiation (I0 = 2.0 W/cm2, λ > 435 nm). The resultant plasmonic nanostructures exhibit significant optical extinction and enriched chemical affinity for Raman probe molecules, rendering the hybrid AgFON/Cu substrate a suitable plasmonic platform for chemical sensing via surface-enhanced Raman scattering (SERS).

Atomic layer deposition (ALD) is a powerful tool for achieving atomic level control in the deposition of thin films. However, several physical and chemical phenomena can occur which cause deviation from "ideal" film growth during ALD. Understanding the underlying mechanisms that cause these deviations is important to achieving even better control over the growth of the deposited material. Herein, we review several precursor chemisorption mechanisms and the effect of chemisorption on ALD growth. We then follow with a discussion on diffusion and its impact on film growth during ALD. Together, these two fundamental processes of chemisorption and diffusion underlie the majority of mechanisms which contribute to material growth during a given ALD process, and the recognition of their role allows for more rational design of ALD parameters.

First row transition metal complexes (Ni, Co, Cu, Zn) with N,N-disubstituted-N′-acylthiourea ligands have been synthesized and characterized. Bis(N,N-diisopropyl-N′-cinnamoylthiourea)nickel was found to have the lowest onset temperature for thermal decomposition. Thin film deposition of Ni, Co, and Zn sulfides by aerosol assisted chemical vapor deposition from their respective N,N-diisopropyl-N′-cinnamoylthiourea complexes at 350 °C has been demonstrated.

A critical step involved in many applications of one-dimensional seeded CdSe@CdS nanorods, such as luminescent solar concentrators, optical gains, and photocatalysis, is the localization of excitons from the light-harvesting CdS nanorod antenna into the light-emitting CdSe quantum dot seed. We report that the rod-to-seed exciton localization efficiency decreases with the rod length but is independent of band alignment between the CdSe seed and CdS rod. This universal dependence can be well modeled by the competition between exciton one-dimensional diffusion to the CdSe seed and trapping on the CdS rod. This finding provides a rational approach for optimizing these materials for their various device applications.

The synthesis of a modular colloidal polymer system based on the dipolar assembly of CdSe@CdS nanorods functionalized with a single cobalt nanoparticle "tip" (CoNP-tip) is reported. These heterostructured nanorods spontaneously self-assembled via magnetic dipolar associations of the cobalt domains. In these assemblies, CdSe@CdS nanorods were carried as densely grafted side chain groups along the dipolar NP chain to form bottlebrush-type colloidal polymers. Nanorod side chains strongly affected the conformation of individual colloidal polymer bottlebrush chains and the morphology of thin films. Dipolar CoNP-tipped nanorods were then used as "colloidal monomers" to form mesoscopic assemblies reminiscent of traditional copolymers possessing segmented and statistical compositions. Investigation of the phase behavior of colloidal polymer blends revealed the formation of mesoscopic phase separated morphologies from segmented colloidal copolymers. These studies demonstrated the ability to control colloidal polymer composition and morphology in a manner observed for classical polymer systems by synthetic control of heterostructured nanorod structure and harnessing interparticle dipolar associations.

The synthesis of a ferromagnetic heterostructured material consisting of a CdSe@CdS nanorod attached to a single dipolar cobalt nanoparticle (CoNP) into a “matchstick” morphology is reported. CdSe@CdS nanorods were modified by an activation reaction with Pt(acac)2 which enabled selective one-sided deposition of a dipolar metallic CoNP-tip via the thermolysis of Co2(CO)8 in the presence of polystyrene ligands. Small (

A methodology providing access to dumbbell-tipped, metal-semiconductor and metal oxide-semiconductor heterostructured nanorods has been developed. The synthesis and characterization of CdSe@CdS nanorods incorporating ferromagnetic cobalt nanoinclusions at both nanorod termini (i.e., dumbbell morphology) are presented. The key step in the synthesis of these heterostructured nanorods was the decoration of CdSe@CdS nanorods with platinum nanoparticle tips, which promoted the deposition of metallic CoNPs onto Pt-tipped CdSe@CdS nanorods. Cobalt nanoparticle tips were then selectively oxidized to afford CdSe@CdS nanorods with cobalt oxide domains at both termini. In the case of longer cobalt-tipped nanorods, heterostructured nanorods were observed to self-organize into complex dipolar assemblies, which formed as a consequence of magnetic associations of terminal CoNP tips. Colloidal polymerization of these cobalt-tipped nanorods afforded fused nanorod assemblies from the oxidation of cobalt nanoparticle tips at the ends of nanorods via the nanoscale Kirkendall effect. Wurtzite CdS nanorods survived both the deposition of metallic CoNP tips and conversion into cobalt oxide phases, as confirmed by both XRD and HRTEM analysis. A series of CdSe@CdS nanorods of four different lengths ranging from 40 to 174 nm and comparable diameters (6-7 nm) were prepared and modified with both cobalt and cobalt oxide tips. The total synthesis of these heterostructured nanorods required five steps from commercially available reagents. Key synthetic considerations are discussed, with particular emphasis on reporting isolated yields of all intermediates and products from scale up of intermediate precursors.