Mo Nanowires Research Articles

Nanoscale Wet Etching of Molybdenum Interconnects with Organic Solutions.

Molybdenum (Mo) has emerged as a promising material for advanced semiconductor devices, especially in the design and fabrication of interconnects requiring sub-10nm metal nanostructures. However, current wet etching methods for Mo using aqueous solutions struggle to achieve smooth etching profiles at such scales. To address this problem, we explore wet chemical etching of patterned Mo nanowires (NWs) using an organic solution: ceric ammonium nitrate (CAN) dissolved in acetonitrile (ACN). In this study, we demonstrate two distinct etching pathways by controlling the reaction temperature: i) digital cyclic scheme at room temperature, with a self-limiting Mo recess per cycle of ≈1.6nm, and ii) direct etching at elevated temperature (60°C), with a time-controlled Mo recess of ≈2nm min-1. These methods not only offer a highly controllable nanoscale Mo etching but also ensure smooth and uniform etching profiles independent of the crystal grain orientation of the metal.

Free-space direct nanoscale 3D printing of metals and alloys enabled by two-photon decomposition and ultrafast optical trapping.

Nanoscale three-dimensional (3D) printing of metals and alloys has faced challenges in speed, miniaturization and deficiency in material properties. Traditional nanomanufacturing relies on lithographic methods with material constraints, limited resolution and slow layer-by-layer processing. This work introduces polymer-free techniques using two-photon decomposition and optical force trapping for free-space direct 3D printing of metals, metal oxides and multimetallic alloys with resolutions beyond optical limits. This method involves the two-photon decomposition of metal atoms from precursors, rapid assembly into nanoclusters via optical forces and ultrafast laser sintering, yielding dense, smooth nanostructures. Enhanced near-field optical forces from laser-induced localized surface plasmon resonance facilitate nanocluster aggregation. Our approach eliminates the need for organic materials, layer-by-layer printing and complex post-processing. Printed Mo nanowires show an excellent mechanical performance, closely resembling the behaviour of single crystals, while Mo-Co-W alloy nanowires outperform Mo nanowires. This innovation promises the customizable 3D nanoprinting of high-quality metals and metal oxides, impacting nanoelectronics, nanorobotics and advanced chip manufacturing.

Solving the Annealing of Mo Interconnects for Next‐Gen Integrated Circuits

AbstractRecent surge in demand for computational power combined with strict constraints on energy consumption requires persistent increase in the density of transistors and memory cells in integrated circuits. Metal interconnects in their current form struggle to follow the size downscaling due to materials limitations at the nanoscale, causing severe performance losses. Next‐generation interconnects need new materials, and molybdenum (Mo) is considered the best choice, offering low resistivity, good scalability, and barrierless integration at a low cost. However, it requires annealing at temperatures far exceeding the currently accepted limit. In this work, the challenges of high‐temperature annealing of patterned Mo nanowires are looked into, and a new approach is presented to overcome them. It is demonstrated that while a conventional annealing process improves the average grain size, it can also reduce the cross‐section area, thus increasing the resistivity. Using high‐resolution transmission electron microscopy (TEM) with in situ heating, the evolution of structural features in real time is directly observed. Using insights from these experiments, a cyclic pulsed annealing method is developed, and it is shown that the desired grain structure is achieved in only a few seconds, without forming the surface grooves. These findings can radically facilitate Mo integration, boosting the efficiency of future integrated circuits.

Controlled Stepwise Wet Etching of Polycrystalline Mo Nanowires

AbstractWith the persistent downscaling of integrated circuits, molybdenum (Mo) is currently considered a potential replacement for copper (Cu) as a material for metal interconnects. However, fabricating metal nanostructures with critical dimensions of the order of 10 nm and below is challenging. This is because the very high density of grain boundaries (GBs) results in highly non‐uniform surface profiles during direct wet etching. Moreover, wet etching of Mo with conventional aqueous solutions is problematic, as products of Mo oxidation have different solubility in water, which leads to increased surface roughness. Here, a process is shown for achieving a stable and uniform soluble surface layer of Mo oxide by wet oxidation with H2O2 dissolved in IPA at −20 °C. The oxide layer is then selectively dissolved, and by repeating the oxidation and dissolution multiple times, a uniform etch profile is demonstrated with a fine control over the metal recess. Ultimately, this presents a method of precise and uniform wet etching for Mo and other metals needed to fabricate complex nanostructures that are critical in developing next‐generation electronic devices.

Electrical Resistivity Modification of Electrodeposited Mo and Mo–Co Nanowires for Interconnect Applications

Achieving historically anticipated improvement in the performance of integrated circuits is challenging, due to the increasing cost and complexity of the required technologies with each new generation. To overcome this limitation, the exploration and development of novel interconnect materials and processes are highly desirable in the microelectronics field. Molybdenum (Mo) is attracting attention as an advanced interconnect material due to its small resistivity size effect and high cohesive energy; however, effective processing methods for such materials have not been widely investigated. Here, we investigate the electrochemical behavior of ions in the confined nanopores that affect the electrical properties and microstructures of nanoscale Mo and Mo–Co alloys prepared via template-assisted electrodeposition. Additives in an electrolyte allow the deposition of extremely pure metal materials, due to their interaction with metal ions and nanopores. In this study, boric acid and tetrabutylammonium bisulfate (TBA) were added to an acetate bath to inhibit the hydrogen evolution reaction. TBA accelerated the reduction of Mo at the surface by inducing surface conduction on the nanopores. Metallic Mo nanowires with a 130 nm diameter synthesized through high-aspect-ratio nanopore engineering exhibited a resistivity of (63.0 ± 17.9) μΩ·cm. We also evaluated the resistivities of Mo–Co alloy nanowires at various compositions toward replacing irreducible conventional barrier/liner layers. An intermetallic compound formed at a Mo composition of 28.6 at%, the resistivity of the Mo–Co nanowire was (58.0 ± 10.6) μΩ·cm, indicating its superior electrical and adhesive properties in comparison with those of conventional barriers such as TaN and TiN. Furthermore, density functional theory and non-equilibrium Green’s function calculations confirmed that the vertical resistance of the via structure constructed from Mo-based materials was 21% lower than that of a conventional Cu/Ta/TaN structure.

Controlled and Uniform Wet Etching of Molybdenum Nanowires

We achieved the controlled recess of molybdenum (Mo), which is alternative interconnect material for copper (Cu), by wet chemical etching. This wet etching process includes two main steps which are chemical oxidation of Mo and its subsequent dissolution, respectively. Firstly, Mo nanowires (NWs) are uniformly oxidized with potassium permanganate (KMnO4) solution in acetone. Secondly, the Mo oxide is dissolved using an aqueous solution of HCl. Mo NWs are characterized through transmission electron microscopy (TEM) imaging after each of the above steps. Cyclic etching experiments including oxidation and dissolution of Mo showed that Mo recess is linear and can be controlled for each cycle, where the etching produced the smooth Mo surface. This controlled Mo recess is crucial for the fabrication of next-generation metal interconnects.

Plasma Oxidation of Patterned Mo Nanowires for Precise and Uniform Dry Etching

We demonstrate that a uniform recess of polycrystalline Mo can be achieved using a two-step method: metal oxidation with isotropic oxygen plasma that forms a layer of MoO3 and selective etching of this oxide layer. The oxidation step fully defines the recess depth, and its uniformity is ensured by the low facet dependence of plasma oxidation. We have extensively studied the oxidation of patterned Mo nanowires (30 nm width) in isotropic oxygen plasma and achieved uniform oxide layers of predefined thickness by controlling radio-frequency (RF) power, gas pressure, and exposure time. We showed that using highly selective oxide etching, we can perform multiple etching cycles with a typical etch rate of 1-2 nm per cycle, depending on the RF power. Due to plasma isotropy, this approach can be implemented for a controlled uniform etching of large vertical stacks of metal nanostructures.

Dislocation "Bubble-Like-Effect" and the Ambient Temperature Super-plastic Elongation of Body-centred Cubic Single Crystalline Molybdenum.

With our recently developed deformation device, the in situ tensile tests of single crystal molybdenum nanowires with various size and aspect ratio were conducted inside a transmission electron microscope (TEM). We report an unusual ambient temperature (close to room temperature) super-plastic elongation above 127% on single crystal body-centred cubic (bcc) molybdenum nanowires with an optimized aspect ratio and size. A novel dislocation “bubble-like-effect” was uncovered for leading to the homogeneous, large and super-plastic elongation strain in the bcc Mo nanowires. The dislocation bubble-like-effect refers to the process of dislocation nucleation and annihilation, which likes the nucleation and annihilation process of the water bubbles. A significant plastic deformation dependence on the sample’s aspect ratio and size was revealed. The atomic scale TEM observations also demonstrated that a single crystal to poly-crystal transition and a bcc to face-centred cubic phase transformation took place, which assisted the plastic deformation of Mo in small scale.

Fabrication and Characterization of Ni–Mo Nanowires by Electrodeposition

Fabrication and Characterization of Ni–Mo Nanowires by Electrodeposition

Template Effects of Microstructure and Property of Sol–Gel-Deposited ZnO:Al:Mo Films

Four types of organic template were used to induce the nanowire microstructure of a sol–gel-deposited ZnO:Al:Mo films. Dip coating in one constant positive and one reverse direction was used to control the array of the ZnO:Al:Mo nanowires thus formed. Long and parallel arrayed nanowires were observed for the films deposited with the templates and showed obvious blueshifts and enhanced UV–visible transmittance. Polyethylene glycol-1000 and -2000 have a better effect than polyethylene glycol-4000 and polylevulinic pyrrolidone-k30. The films showed strong ultraviolet, violet, and bluish violet emissions. The templates also led to thicker films and more native defects, thereby enhancing photoluminescence to different degrees.

Microstructural and Optical Properties of Transparent Conductive ZnO : Al : Mo Films Deposited by Template-Assisted Sol–Gel Method

Transparent conductive ZnO : Al : Mo films with a molar ratio of Zn : Al : Mo = 99 : 0·99 : 0·01 were deposited on quartz glass substrate by a template-assisted sol-gel process and characterized by X-ray diffraction, atomic force microscopy, scanning electron microscopy, and UV–Vis and luminescent spectrophotometries. The four types of organic template have induced nanowire morphology with varying aspect ratio. Dip coating in one constant positive and reverse direction causes the parallel array of ZnO : Al : Mo nanowires on the quartz glass substrate. Long and parallel arrayed nanowire films show obviously blue shifts and enhanced transmittances in the UV-Vis light range. The PEG-1000 and PEG-2000 have optimal effects among four templates as constant weight content is used. The films show strong ultraviolet, violet and bluish violet emissions. The templates also lead to overall thicker film and more native defect and thereby remarkably enhancing photoluminescence of the films. Long chain organic template can be used to optimize the optical properties of the doped ZnO film.

A novel facile synthesis and characterization of molybdenum nanowires

We describe a straightforward technique to synthesize pure Mo nanowires (NWs) from Mo6SyIz (8,2 <y + z ≤ 10) NWs as precursor templates. The structural transformations occur when Mo6SyIz NWs are annealed in Ar/H2 mixture leading to the formation of pure Mo NWs with similar structures as initial morphologies. Detailed microscopic characterizations show that large diameters (>15 nm) Mo NWs are highly porous, while small diameters (<7 nm) are made of solid nanocrystalline grains. We find NW of diameter 4 nm can carry up to 30 μA current without suffering structural degradation. Moreover, NWs can be elastically deformed over several cycles without signs of plastic deformation.

Synthesis of hybrid polymethacrylate–noble metal (M = Au, Pd) nanoparticles for the growth of metal-oxide semiconductor nanowires

Metal-oxide semiconductor nanowires (NWs) such as ZnO, β-Ga2O3 and SnO2 with diameters of tens of nanometres and lengths of many micrometres have been grown using micellar nanohybrids consisting of methacrylate-based diblock copolymers and noble metal nanoparticles (MNPs). Micellar Au and Pd MNPs with diameters as small as 2.3 ± 0.3 nm were deposited on Si(001) by spin coating or drop casting and metal-oxide NWs were grown by reactive vapor transport. A high yield of β-Ga2O3 NWs with diameters of approximately 40 nm, lengths > 10 μm and a monoclinic crystal structure were obtained at 900 °C with the largest MNPs. These exhibited a broad, symmetric photoluminescence (PL) spectrum centred at 2.3 eV attributed to defect states situated energetically in the energy band gap of β-Ga2O3. We find that a reduction in the size of the MNPs below 10 nm leads to the formation of necklace like β-Ga2O3 NWs via the encapsulation of the MNPs which act as catalytic centres for the formation of branched nanostructures along the length of the β-Ga2O3 NWs that are also responsible for a blue shift in the PL at 2.8 eV as a result of quantum confinement. This was not observed upon reducing the density of MNPs or in the case of ZnO or SnO2 NWs grown with the smallest of MNPs probably due to differences in surface energy. We show that polymethacrylate-noble MNPs may be patterned directly by electron beam lithography and may be exploited for the selective location growth of semiconductor NWs while we also discuss the difference between the sizes of the hybrid polymer-MNPs and MO NWs which is attributed to agglomeration.

Stress-induced phase transformation and strain rate effect in polycrystalline Mo nanowires

Using molecular dynamics and modified analytic embedded atom methods, the stress-induced phase transformation and strain rate effect on deformation characteristics of polycrystalline molybdenum nanowires are studied at room temperature under uniaxial tensile strain. The results show the tensile ductility of the nanowires increases with increasing strain rate. The surface rupture occurs at one position as the strain is bigger than 6% at a strain rate of 0.01% ps −1, but it does at multiple positions in the range of larger strain at higher strain rate. Moreover, an increased strain rate delays the appearance of “face-centered cubic (fcc)” atoms, but increases the peak fraction of “fcc” atoms. During the deformation process, two kinds of structure transformation are observed: (1) the “body-centered cubic (bcc)” configuration transforms into “other” configurations, and subsequently the “other” configurations transform into the “fcc” or “hexagonal close-packed (hcp)” configuration and (2) the “fcc” configuration converts into “other” configurations, and then into “bcc” or “hcp” configuration. In addition, the mechanical properties of the polycrystalline nanowires are compared with those of single-crystalline nanowires.

Nanowire transformation and annealing by Joule heating

Joule heating of bundles of Mo6S3I6 nanowires, in real time, was studied using in situ TEM probing. TEM imaging, electrondiffraction, and conductivity measurements showed a complete transformation ofMo6S3I6 into Mo via thermal decomposition. The resulting Mo nanowires had a conductivity that was2–3 orders higher than the starting material. The conductivity increased even further, up to1.8 × 106 S m − 1, when the Mo nanowires went through annealing phases. These results suggest that Jouleheating might be a general way to transform or anneal nanowires, pointing to applicationssuch as metal nanowire fabrication, novel memory elements based on materialtransformation, or in situ improvement of field emitters.

Theoretical studies on electronic and magnetic properties of ultrathin Mo nanowires

We present a detailed theoretical study on electronic and magnetic properties of Mo nanowires with different structures. The ultrathin nanowires of this 4d transition metal show a unique behavior for the stability. We notice that zigzag structure is stable at the lower values of nearest neighbor distance. On slightly stretching the nanowire, the ladder structure is preferred while the dimerized structure, with the highest value of cohesive energy, is the most stable structure at larger nearest neighbor distances. This work suggests that magnetic ordering of Mo nanowires can be tuned with structure. The linear and ladder structures of Mo nanowires show antiferromagnetic ordering. Equilateral zigzag structure prefers a nonmagnetic state whereas the planar zigzag structure is ferromagnetic. The dimerized structure stands out showing degenerate nonmagnetic and ferromagnetic states. The highest value of magnetic moment (∼1.16 μB/atom) is predicted for linear chains. Relative break force values suggest that these nanowires would be difficult to be realized. The density of states and band structure shine light on engineering the electronic properties with structural tailoring. We notice that dimerized structure is the only one which can be used in semiconducting applications with a band gap of 1.1 eV. Interestingly, all these Mo nanowires show a signature of covalent bonding coexisting with metallic charge sharing, the former getting enhanced with the stretching of the wire.

Single Crystalline Molybdenum Nanowires, Nanowire Arrays and Nanopore Arrays in Nickel-Aluminium

This work describes a novel fabrication method of single crystalline Mo nanowires and nanowire arrays. The method utilizes directional solidification (ds) of a NiAl-Mo eutectic alloy and its subsequent electrochemical processing. In the first step, a self-organized array of Mo nanowires embedded in a NiAl matrix is obtained. By combining the Pourbaix diagrams of the three elements involved, a strategy for selective removal of either of the two phases is derived. An oxidizing acidic solution of pH 0.2 dissolved the matrix and released an array of long and uniform Mo wires. Even a complete extraction of the wires is possible through entire dissolution of the matrix. On the other hand, electrodissolution of the Mo with a simultaneous passivation of the NiAl matrix at the pH 6 and the potential of 200 mV SHE yielded nanopore arrays with rectangular pores. This method has several advantages. First of all, it is one of the few top-down methods that allow the production of large amounts of nanostructures. In addition, both the wires and the matrix are single crystalline which makes them favorable for various applications. Further, the obtained nanostructures exhibit extremely high aspect ratios (> 1000), unreachable by most other techniques. This technique has the potential for the production of nanowire arrays either for employment in sensors or in field emission.

Nanostructuring of NiAl–Mo eutectic alloys by selective phase dissolution

A technique for the electrochemical structuring of directionally solidified NiAl–Mo eutectic by selective phase dissolution is presented. Local matrix dissolution at 200 mV SHE in 1 M HCl of pH 1 yielded the grid of Mo nanowires spanning along the central part of the sample. On the other hand, the dissolution of the fibrous minor phase while passivating the continuous NiAl matrix resulted in continuous nanopore arrays. Initially, mechanical polishing and electropolishing were employed to thin the samples. Etching time was optimized by plotting the etch time until hole formation as a function of initial sample thickness, along with plotting sample thickness versus etching time. As a next step, an investigation into the passivation behaviour of the NiAl was performed in order to determine the optimal potential for wire dissolution. A potential scan from 0 to 2500 mV SHE on a bulk sample of pure NiAl in an electrolyte of 0.1 M acetate buffer pH 6.0 indicated that a potential of 500 mV SHE, just below the breakdown potential would provide maximum driving force for wire dissolution process. Different parameters within the electrochemical system are varied in order to optimize the wire dissolution. The extent of wire dissolution is measured both quantitatively (total charge transfer) and qualitatively (optical and SEM imaging).

Growth of Large-Area Aligned Molybdenum Nanowires by High Temperature Chemical Vapor Deposition: Synthesis, Growth Mechanism, and Device Application

Large-area aligned Mo nanowires have been grown on stainless steel substrates by high-temperature chemical vapor deposition with the use of Mo metal. The detailed physical and chemical growth processes regarding the formation of the nanowires have been investigated using mass spectroscopy, thermogravimetry, and differential scanning calorimetry analysis, as well as structure analysis by electron microscopy. In reference to Gibbs energy calculation, our study reveals that the growth relies on the decomposition of MoO2 vapors through condensation of its vapor at high substrate temperatures. The aligned growth is a result of competing growth with the nanowires normal to the substrate surface reaching the final growth front. The field emission measurement and the vacuum luminescent tube study show that the Mo nanowires have potential application as electron emitters.