skip to main content


Title: Expanding the molecular-ruler process through vapor deposition of hexadecanethiol
The development of methods to produce nanoscale features with tailored chemical functionalities is fundamental for applications such as nanoelectronics and sensor fabrication. The molecular-ruler process shows great utility for this purpose as it combines top-down lithography for the creation of complex architectures over large areas in conjunction with molecular self-assembly, which enables precise control over the physical and chemical properties of small local features. The molecular-ruler process, which most commonly uses mercaptoalkanoic acids and metal ions to generate metal-ligated multilayers, can be employed to produce registered nanogaps between metal features. Expansion of this methodology to include molecules with other chemical functionalities could greatly expand the overall versatility, and thus the utility, of this process. Herein, we explore the use of alkanethiol molecules as the terminating layer of metal-ligated multilayers. During this study, it was discovered that the solution deposition of alkanethiol molecules resulted in low overall surface coverage with features that varied in height. Because features with varied heights are not conducive to the production of uniform nanogaps via the molecular-ruler process, the vapor-phase deposition of alkanethiol molecules was explored. Unlike the solution-phase deposition, alkanethiol islands produced by vapor-phase deposition exhibited markedly higher surface coverages of uniform heights. To illustrate the applicability of this method, metal-ligated multilayers, both with and without an alkanethiol capping layer, were utilized to create nanogaps between Au features using the molecular-ruler process.  more » « less
Award ID(s):
1536528
NSF-PAR ID:
10478911
Author(s) / Creator(s):
; ; ; ;
Publisher / Repository:
Beilstein Institute
Date Published:
Journal Name:
Beilstein Journal of Nanotechnology
Volume:
8
ISSN:
2190-4286
Page Range / eLocation ID:
2339 to 2344
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Chemical self-assembly has garnered tremendous interest as a tool for generating nanometer-scale structures and devices. Organosilane self-assembled monolayers (SAMs) are of particular interest due to their ability to assemble on a wide range of substrates with varied chemical functionalities. Nanoshaving, an atomic force lithographic technique, has been demonstrated as a method to generate nanopatterns of organosilane SAMs. However, this method requires extremely high force setpoints, which rapidly dulls atomic force microscopy tips and degrades the resolution of the resulting nanopattern. In this work, we utilize Cu-ligated mercaptohexadecanoic acid (MHDA) multilayers to circumvent this limitation. Initially, a 10-undecenyltrichlorosilane (UTS) SAM is assembled onto a Si substrate, and the terminal olefin groups of the UTS SAM are oxidized to carboxyl groups. Subsequently, a Cu-ligated MHDA multilayer is assembled via the sequential deposition of Cu2+ ions and MHDA molecules. The interface between the oxidized UTS SAM and Cu-ligated MHDA multilayer serves as a natural low force breakpoint for nanoshaving. We demonstrate that the resulting nanopatterns can function as a chemical resist to fabricate metal nanostructures. 
    more » « less
  2. Heterogeneous bonding between metals and ceramics is of significant relevance to a wide range of applications in the fields of industry, defense, and aerospace. Metal/ceramic bonding can be used in various specific part applications such as vacuum tubes, automotive use of ceramic rotors, and rocket igniter bodies. However, the bonding of ceramic to metal has been challenging mainly due to (1) the low wettability of ceramics, on which the adhesion of molten adhesive bonders is limited and (2) the large difference between the coefficients of thermal expansion (CTE) of the two dissimilar bonded materials, which develops significant mechanical stresses at the interface and potentially leads to mechanical failures. Vapor-phase deposition is a widely used thin film processing technique in both academic research laboratories and manufacturing industries. Since vapor phase coatings do not require wettability or hydrophobicity, a uniform and strongly adherent layer is deposited over virtually any substrate, including ceramics. In this presentation, we report on the effect of vapor phase-deposited interfacial metal layers on the mechanical properties of bonding between stainless steel and Zerodur (lithium aluminosilicate-based glass ceramic). Direct-current magnetron sputtering was utilized to deposit various thin interfacial layers containing Ti, Cu, or Sn. In addition, to minimize the unfavorable stress at the bonded interface due to the large CTE difference, a low temperature allow solder, that can be chemically and mechanically activated at temperatures of approximately 200 °C, was used. The solder is made from a composite of Ti-Sn-Ce-In. A custom-built fixture and universal testing machine were used to evaluate the bonding strength in shear, which was monitored in-situ with LabView throughout the measurement. The shear strength of the bonding between stainless steel and Zerodur was systematically characterized as a function of interfacial metal and metal processing temperature during sputter depositions. Maximum shear strength of the bonding of 4.36 MPa was obtained with Cu interfacial layers, compared to 3.53 MPa from Sn and 3.42 MPa from Ti adhesion promoting layers. These bonding strengths are significantly higher than those (~0.05 MPa) of contacts without interfacial reactive thin metals. The fracture surface microstructures are presented as well. It was found that the point of failure, when Cu interfacial layers were used, was between the coated Cu film and alloy bonder. This varied from the Sn and Ti interfacial layers where the main point of failure was between the interfacial film and Zerodur interface. The findings of the effect of thin adhesion promoting metal layers and failure behaviors may be of importance to some metal/ceramic heterogeneous bonding studies that require high bonding strength and low residual stresses at the bonding interface. The authors gratefully acknowledge the financial support of the Improvement of Measurement Standards and Technology for Mechanical Metrology (Grant No. 20011028) by KRISS. 
    more » « less
  3. null (Ed.)
    Abstract

    Harnessing the exotic properties of molecular level nanostructures to produce novel sensors, metamaterials, and futuristic computer devices can be technologically transformative. In addition, connecting the molecular nanostructures to ferromagnetic electrodes bring the unprecedented opportunity of making spin property based molecular devices. We have demonstrated that magnetic tunnel junction based molecular spintronics device (MTJMSD) approach to address numerous technological hurdles that have been inhibiting this field for decades (P. Tyagi, J. Mater. Chem., Vol. 21, 4733). MTJMSD approach is based on producing a capacitor like a testbed where two metal electrodes are separated by an ultrathin insulator and subsequently bridging the molecule nanostructure across the insulator to transform a capacitor into a molecular device. Our prior work showed that MTJMSDs produced extremely intriguing phenomenon such as room temperature current suppression by six orders, spin photovoltaic effect, and evolution of new forms of magnetic metamaterials arising due to the interaction of the magnetic a molecule with two ferromagnetic thin films. However, making robust and reproducible electrical connections with exotic molecules with ferromagnetic electrodes is full of challenges and requires attention to MTJMSD structural stability. This paper focuses on MTJMSD stability by describing the overall fabrication protocol and the associated potential threat to reliability. MTJMSD is based on microfabrication methods such as (a) photolithography for patterning the ferromagnetic electrodes, (b) sputtering of metallic thin films and insulator, and (c) at the end electrochemical process for bridging the molecules between two ferromagnetic films separated by ∼ 2nm insulating gap. For the successful MTJMSD fabrication, the selection of ferromagnetic metal electrodes and thickness was found to be a deterministic factor in designing the photolithography, thin film deposition strategy, and molecular bridging process. We mainly used isotropic NiFe soft magnetic material and anisotropic Cobalt (Co) with significant magnetic hardness. We found Co was susceptible to chemical etching when directly exposed to photoresist developer and aged molecular solution. However, NiFe was very stable against the chemicals we used in the MTJMSD fabrication. As compared to NiFe, the Co films with > 10nm thickness were susceptible to mechanical stress-induced nanoscale deformities. However, cobalt was essential to produce (a) low leakage current before transforming the capacitor from the magnetic tunnel junction into molecular devices and (b) tailoring the magnetic properties of the ferromagnetic electrodes. This paper describes our overall MTJMSD fabrication scheme and process optimization to overcome various challenges to produce stable and reliable MTJMSDs. We also discuss the role of mechanical stresses arising during the sputtering of the ultrathin insulator and how to overcome that challenge by optimizing the insulator growth process. This paper will benefit researchers striving to make nanoscale spintronics devices for solving grand challenges in developing advanced sensors, magnetic metamaterials, and computer devices.

     
    more » « less
  4. Abstract

    The incorporation of metal-organic frameworks into advanced devices remains a desirable goal, but progress is hindered by difficulties in preparing large crystalline metal-organic framework films with suitable electronic performance. We demonstrate the direct growth of large-area, high quality, and phase pure single metal-organic framework crystals through chemical vapor deposition of a dimolybdenum paddlewheel precursor, Mo2(INA)4. These exceptionally uniform, high quality crystals cover areas up to 8600 µm2and can be grown down to thicknesses of 30 nm. Moreover, scanning tunneling microscopy indicates that the Mo2(INA)4clusters assemble into a two-dimensional, single-layer framework. Devices are readily fabricated from single vapor-phase grown crystals and exhibit reversible 8-fold changes in conductivity upon illumination at modest powers. Moreover, we identify vapor-induced single crystal transitions that are reversible and responsible for 30-fold changes in conductivity of the metal-organic framework as monitored by in situ device measurements. Gas-phase methods, including chemical vapor deposition, show broader promise for the preparation of high-quality molecular frameworks, and may enable their integration into devices, including detectors and actuators.

     
    more » « less
  5. Molybdenum disulfide (MoS2) transistors are a promising alternative for the semiconductor industry due to their large on/off current ratio (>1010), immunity to short-channel effects, and unique switching characteristics. MoS2 has drawn considerable interest due to its intriguing electrical, optical, sensing, and catalytic properties. Monolayer MoS2 is a semiconducting material with a direct band gap of ~1.9 eV, which can be tuned. Commercially, the aim of synthesizing a novel material is to grow high-quality samples over a large area and at a low cost. Although chemical vapor deposition (CVD) growth techniques are associated with a low-cost pathway and large-area material growth, a drawback concerns meeting the high crystalline quality required for nanoelectronic and optoelectronic applications. This research presents a lower-temperature CVD for the repeatable synthesis of large-size mono- or few-layer MoS2 using the direct vapor phase sulfurization of MoO3. The samples grown on Si/SiO2 substrates demonstrate a uniform single-crystalline quality in Raman spectroscopy, photoluminescence (PL), scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and scanning transmission electron microscopy. These characterization techniques were targeted to confirm the uniform thickness, stoichiometry, and lattice spacing of the MoS2 layers. The MoS2 crystals were deposited over the entire surface of the sample substrate. With a detailed discussion of the CVD setup and an explanation of the process parameters that influence nucleation and growth, this work opens a new platform for the repeatable synthesis of highly crystalline mono- or few-layer MoS2 suitable for optoelectronic application.

     
    more » « less