Benzethonium chloride as a tungsten corrosion inhibitor in neutral and alkaline media for the post-chemical mechanical planarization application.

The cleaning solution for the post-chemical mechanical planarization (post-CMP) process of tungsten in neutral-alkaline media requires corrosion inhibitors as an additive, especially for advanced devices where the device node size shrinks below 10 nm. In the present study, the corrosion inhibition performance of benzethonium chloride (BTC) is evaluated in neutral-alkaline conditions. The electrochemical impedance spectroscopy (EIS) analysis showed âˆ¼ 90 % of corrosion inhibition efficiency with an optimum concentration of 0.01 wt% BTC at both pH 7 and 11. Langmuir adsorption isotherm, frontier molecular orbital theory, molecular simulation, contact angle, precipitation study, and X-ray photoelectron spectroscopy analysis were performed to identify the inhibition mechanism of the BTC molecule on the W surface. Based on the proposed mechanism, the electrostatic attraction between the positively charged N atom in the BTC molecule and the negatively charged W surface initiates the adsorption of the molecule. The high dipole moment and large molecular size enhance the physical adsorption of the molecule to the surface. In addition to this, the adsorption isotherm analysis shows that possible chemical interaction with a moderate value of Gibbs free energy change of adsorption exists between the W and BTC molecule. The excellent corrosion inhibition efficiency of BTC on W is confirmed by the frontier molecular orbital theory and molecular dynamic simulation analysis.

Chemically controlled megasonic cleaning of patterned structures using solutions with dissolved gas and surfactant.

Acoustic cavitation is used for megasonic cleaning in the semiconductor industry, especially of wafers with fragile pattern structures. Control of transient cavitation is necessary to achieve high particle removal efficiency (PRE) and low pattern damage (PD). In this study, the cleaning performance of solutions with different concentrations of dissolved gas (H2) and anionic surfactant (sodium dodecyl sulfate, SDS) in DIW (DI water) on silicon (Si) wafers was evaluated in terms of PRE and PD. When only DIW was used, PRE was low and PD was high. An increase in dissolved H2 gas concentration in DIW increased PRE; however, PD also increased accordingly. Thus, we investigated the megasonic cleaning performance of DIW and H2-DIW solutions with various concentrations of the anionic surfactant, SDS. At 20 ppm SDS in DIW, PRE reached a maximum value and then decreased with increasing concentration of SDS. PRE decreased slightly with increasing concentrations of SDS surfactant when dissolved in H2-DIW. Furthermore, PD decreased significantly with increasing concentrations of SDS surfactant in both DIW and H2-DIW cases. A high-speed camera setup was introduced to analyze bubble dynamics under a 0.96 MHz ultrasonic field. Coalescence, agglomeration, and the population of multi-bubbles affected the PRE and PD of silicon wafers differently in the presence of SDS surfactant. We developed a hypothesis to explain the change in bubble characteristics under different chemical environmental conditions.

Large-scale plasma patterning of transparent graphene electrode on flexible substrates.

Graphene, a two-dimensional carbon material, has attracted significant interest for applications in flexible electronics as an alternative transparent electrode to indium tin oxide. However, it still remains a challenge to develop a simple, reproducible, and controllable fabrication technique for producing homogeneous large-scale graphene films and creating uniform patterns with desired shapes at defined positions. Here, we present a simple route to scalable fabrication of flexible transparent graphene electrodes using an oxygen plasma etching technique in a capacitively coupled plasma (CCP) system. Ascorbic acid-assisted chemical reduction enables the large-scale production of graphene with solution-based processability. Oxygen plasma in the CCP system facilitates the reproducible patterning of graphene electrodes, which allows controllable feature sizes and shapes on flexible plastic substrates. The resulting graphene electrode exhibits a high conductivity of 80 S cm(-1) and a transparency of 76% and retains excellent flexibility upon hard bending at an angle of ±175° and after repeated bending cycles. A simple LED circuit integrated on the patterned graphene film demonstrates the feasibility of graphene electrodes for use in flexible transparent electrodes.

Effect of dissolved gases in water on acoustic cavitation and bubble growth rate in 0.83 MHz megasonic of interest to wafer cleaning.

Changes in the cavitation intensity of gases dissolved in water, including H2, N2, and Ar, have been established in studies of acoustic bubble growth rates under ultrasonic fields. Variations in the acoustic properties of dissolved gases in water affect the cavitation intensity at a high frequency (0.83 MHz) due to changes in the rectified diffusion and bubble coalescence rate. It has been proposed that acoustic bubble growth rates rapidly increase when water contains a gas, such as hydrogen faster single bubble growth due to rectified diffusion, and a higher rate of coalescence under Bjerknes forces. The change of acoustic bubble growth rate in rectified diffusion has an effect on the damping constant and diffusivity of gas at the acoustic bubble and liquid interface. It has been suggested that the coalescence reaction of bubbles under Bjerknes forces is a reaction determined by the compressibility and density of dissolved gas in water associated with sound velocity and density in acoustic bubbles. High acoustic bubble growth rates also contribute to enhanced cavitation effects in terms of dissolved gas in water. On the other hand, when Ar gas dissolves into water under ultrasound field, cavitation behavior was reduced remarkably due to its lower acoustic bubble growth rate. It is shown that change of cavitation intensity in various dissolved gases were verified through cleaning experiments in the single type of cleaning tool such as particle removal and pattern damage based on numerically calculated acoustic bubble growth rates.

Wafer-scale nanowell array patterning based electrochemical impedimetric immunosensor.

We have reported that nanowell array (NWA) can enhance electrochemical detection of molecular binding events by controlling the binding sites of the captured molecules. Using NWA biosensor based amperometric analysis, we have detected biological macromolecules such as DNA, protein or aptamers at low concentrations. In this research, we developed an impedimetric immunosensor based on wafer-scale NWA for electrochemical detection of stress-induced-phosphoprotein-1 (STIP-1). In order to develop NWA sensor through the cost-effective combination of high-throughput nanopattern, the NWA electrode was fabricated on Si wafer by krypton-fluoride (KrF) stepper semiconductor process. Finally, 12,500,000 ea nanowell with a 500 nm diameter was fabricated on 4 mm × 2 mm substrate. Next, by using these electrodes, we measured impedance to quantify antigen binding to the immunoaffinity layer. The limit of detection (LOD) of the NWA was improved about 100-fold compared to milli-sized electrodes (4 mm × 2 mm) without an NWA. These results suggest that wafer-scale NWA immunosensor will be useful for biosensing applications because their interface response is appropriate for detecting molecular binding events.

Detection of single nucleotide polymorphisms using a biosensor-containing titanium-well array.

The rapid identification and verification of single nucleotide polymorphisms (SNPs) were demonstrated using a well array sensor containing anti-biofouling titanium (Ti). Probe single-stranded DNA (ssDNA) was immobilized inside a titanium-well array on amine-modified glass surfaces with anti-biofouling behavior via a streptavidin-biotin interaction. Fluorescence intensity changes originating from the hybridization of nucleic acids to protein-bound nucleic acids linked to Alexa Fluor (FL) 647 were observed. The protocol was highly sensitive and reproducible for the detection of DNA hybridization. Significant changes in fluorescence signals were observed when using target DNA with a single base mismatch, indicating that this method is applicable to SNP detection. The microarray technology for the detection of SNPs using anti-biofouling Ti and other methods can be used as a highly sensitive in vitro medical sensor, as highlighted by an increase in genotyping accuracy.

A self-assembled monolayer-based micropatterned array for controlling cell adhesion and protein adsorption.

We developed a surface micropatterning technique to control the cell adhesion and protein adsorption. This micropatterned array system was fabricated by a photolithography technique and self-assembled monolayer (SAM) deposition. It was hypothesized that the wettability and functional terminal group would regulate cell adhesion and protein adsorption. To demonstrate this hypothesis, glass-based micropatterned arrays with various functional terminal groups, such as amine (NH(2)) group (3-aminopropyl-triethoxysilane, APT), methyl (CH(3)) group (trichlorovinylsilane, TVS), and fluorocarbon (CF(3)) group (trichloro(1H, 1H, 2H, 2H-perfluorooctyl)silane, FOTS), were used. The contact angle was measured to determine the hydrophilic and hydrophobic properties of materials, demonstrating that TVS and FOTS were hydrophobic, whereas APTs were relatively hydrophilic. The cell adhesion was significantly affected by the wettability, showing that the cells were not adhered to hydrophobic surfaces, such as TVS and FOTS. Thus, the cells were selectively adhered to glass substrates within TVS- and FOTS-based micropatterned arrays. However, the cells were randomly adhered to APTs-based micropatterned arrays due to hydrophilic property of APTs. Furthermore, the protein adsorption of the SAM-based micropatterned array was analyzed, showing that the protein was more absorbed to the TVS surface. The surface functional terminal group enabled the control of protein adsorption. Therefore, this SAM-based micropatterned array system enabled the control of cell adhesion and protein adsorption and could be a potentially powerful tool for regulating the cell-cell interactions in a well-defined microenvironment.

Synthesis of Fe metal precipitated colloidal silica and its application to W chemical mechanical polishing (CMP) slurry.

The objective of this paper is to develop a new method of Fe (metal) precipitation on colloidal silica to overcome the stability problem, which would be responsible in producing defects, with commercially available fumed silica slurry containing Fe ions. The slurry was developed by using sodium silicate (Na(2)SiO(3)) as a raw material and the concentration of precipitation of metal was controlled by addition of Fe salt (Fe(NO(3))(3)). To compare the concentration of precipitated Fe with directly added Fe ions in slurry solutions, static electrochemical and peroxide decomposition experiments were performed. Although the performance of the Fe precipitation appeared to be lower than Fe ion addition during these experiments, nearly equal removal rate was observed due to the dynamic condition during polishing. The Fe precipitated colloidal silica particles at the concentration of 52ppm showed the similar W removal rate and selectivity of W to TEOS (tetraethylorthosilicate) to commercially available fumed silica slurry containing externally added Fe ions. The introduction of Fe particle precipitation on colloidal silica particles would result in a longer shelf life time and hence lower defect level in W CMP.

Collapse behavior and forces of multistack nanolines.

Two types of multistack nanolines (MNLs), Si-substrate (Si)/siliconoxynitride (SiON)/amorphous Si (a-Si)/ SiO(2) and Si/ SiO(2) /polycrystalline Si (poly-Si)/ SiO(2) were used to measure the collapse force and to investigate their collapse behavior by an atomic force microscope (AFM). The Si/SiON/a-Si/ SiO(2) MNL showed a larger length of fragment in the collapse patterns at a smaller collapse force. The Si/ SiO(2) /poly-Si/ SiO(2) MNL, however, demonstrated a smaller length of fragment at a higher applied collapse force. The collapse forces increased by the square of the linewidth in both Si/SiON/a-Si/ SiO(2) and Si/SiO(2) /poly-Si/ SiO(2) MNLs. Once an AFM tip touches an Si/SiON/a-Si/ SiO(2) line, which is a softer MNL, it was delaminated first at the Si/SiON interface. One end of the delaminated line was first broken and then the other end was bent until it was broken. A harder MNL, Si/ SiO(2) /poly-Si/ SiO(2), however, was broken at two ends simultaneously after the delamination occurred at the Si/ SiO(2) /poly-Si interface. The different collapse behaviors were attributed to the magnitude of adhesion forces at the stack material interfaces and the mechanical strength of MNLs.

Convective assembly and dry transfer of nanoparticles using hydrophobic/hydrophilic monolayer templates.

A convective directed-assembly process on a flat substrate that does not require motion and is followed by a dry-transfer process of nanoparticles is presented. The convective assembly process was achieved using Au nanoparticles on hydrophobic/hydrophilic-surface-patterned Si substrates as functions of temperature, gap height, and particle size. An investigation of the particle assembly mechanism showed that the effects of temperature, gap height, and particle size were responsible for controlling the evaporation time, the evaporation length, and the assembly speed, respectively. To ensure conformal contact during the dry-transfer process, chemically patterned hybrid templates with elastic and flexible properties were fabricated and used. The hybrid templates provided conformal contact with a target silicon substrate coated with MPTMS (3-mercaptopropyltrimethoxysilane) and successfully transferred Au particles to the target substrates.

Development of inlaid electrodes for whole column electrochemical detection in HPLC.

An electrochemical microfluidic device has been fabricated on PET (polyethylene terephthalate) substrate using an imprinting method. The imprinting transfers patterns from a stamp into a substrate mechanically. However, a blanket mould imprinting process has been introduced to embed the photolithographically produced gold metal electrode lines into the PET substrate resulting in an individually addressable array flush to better than 100 nm. The device formed one wall of a packed chromatography column. The array was electrochemically characterised using standard redox probes in both stagnant conditions and under flow. Both numerical modelling and experimental data show improved sensitivity under flow and a limiting current which scaled linearly with the cube root of the volume flow rate. A chromatographic separation of the bioanalytical significant neurotransmitter dopamine (DA) and its metabolite DOPAC was achieved and electrochemically detected at multiple locations within the column. The PET device was stable and robust to leaks to pressures well in excess of those required for chromatographic separations.

Nanoparticle scanning and detection on flat and structured surfaces using fluorescence microscopy.

A new technique is proposed for the scanning and detection of nanoparticles on flat substrates and three-dimensional structures using fluorescence microscopy. This technique is utilized for particle removal measurements especially in semiconductor and hard disk manufacturing. This fluorescent particle scanning technique enables nanoscale particle detection. The technique shows that single particles down to 63 nm could be detected and counted. The technique is also capable of detecting particles in trenches that are as deep as 500 microm.

Fabrication of nano- and micro-scale UV imprint stamp using diamond-like carbon coating technology.

Two-dimensional (2-D) and three-dimensional (3-D) diamond-like carbon (DLC) stamps for ultraviolet nanoimprint lithography were fabricated with two methods: namely, a DLC coating process, followed by focused ion beam lithography; and two-photon polymerization patterning, followed by nanoscale-thick DLC coating. We used focused ion beam lithography to fabricate 70 nm deep lines with a width of 100 nm, as well as 70 nm deep lines with a width of 150 nm, on 100 nm thick DLC layers coated on quartz substrates. We also used two-photon polymerization patterning and a DLC coating process to successfully fabricate 200 nm wide lines, as well as 3-D rings with a diameter of 1.35 microm and a height of 1.97 microm, and a 3-D cone with a bottom diameter of 2.88 microm and a height of 1.97 microm. The wafers were successfully printed on an UV-NIL using the DLC stamps without an anti-adhesive layer. The correlation between the dimensions of the stamp's features and the corresponding imprinted features was excellent.