This study is based on a latent ruthenium catalyst that includes a Schiff base moiety. This catalyst was formulated with a photoacid generator and a ring-opening metathesis polymerization (ROMP) active monomer such as cyclooctadiene or dicyclopentadiene. Exposure of this mixture to ultraviolet light generates acid that protonates the Schiff base and thereby renders the latent catalyst active leading to ROMP of the monomer. A resist system based on new photoinitiated ROMP chemistry has been developed. This sort of formulation has been used to produce high-resolution replicas of a transparent mold by imprint lithography.

We introduce a preclinical imaging platform - a 3D photoacoustic/fluorescence tomography (PAFT) instrument augmented with an environmentally responsive dual-contrast biocompatible nanoprobe. The PAFT instrument was designed for simultaneous acquisition of photoacoustic and fluorescence orthogonal projections at each rotational position of a biological object, enabling direct co-registration of the two imaging modalities. The nanoprobe was based on liposomes loaded with J-aggregates of indocyanine green (PAtrace). Once PAtrace interacts with the environment, a transition from J-aggregate to monomeric ICG is induced. The subsequent recovery of monomeric ICG is characterized by dramatic changes in the optical absorption spectrum and reinstated fluorescence. In the activated state, PAtrace can be simultaneously detected by both imaging modes of the PAFT instrument using 780 nm excitation and fluorescence detection at 810 nm. The fluorescence imaging component is used to boost detection sensitivity by providing low resolution map of activated nanoprobes, which are then more precisely mapped in 3D by the photoacoustic imaging component. Activated vs non-activated particles can be distinguished based on their different optical absorption peaks, removing the requirements for complex image registration between reference and detection scans. Preliminary phantom and in vivo animal imaging results showed successful activation and visualization of PAtrace with high sensitivity and resolution. The proposed PAFT-PAtrace imaging platform could be used in various functional and molecular imaging applications including multi-point in vivo assessment of early metastasis.

A process for 3D programmed self-assembly of lithographically printable microscale polymer particles using ssDNA hybridization as the associative force is described. We report our progress in establishing the unit processes required for 3D programmed self-assembly and demonstrate the successful fabrication and sequence-specific self-assembly of covalent ssDNA-functionalized parallelepipeds with dimensions in the sub 10 μm regime characterized by optical microscopy and imaging flow cytometry. This technology has the potential to produce parallelepiped particles with different ssDNA on each facet.

A strong adhesion force between resist and underlayer materials was employed to reduce resist pattern peeling generated from de-molding in step-and-flash imprint lithography (SFIL), while simultaneously minimizing the adhesion force between resist material and the template surface with fluorinated surfactants. The reduction in resist pattern peeling by the interaction between the fluorinated SiO2 resist with epoxy groups and UV reactive underlayer materials with epoxy groups during UV irradiation was investigated. An optimized resist material formulation and high adhesion strength between resist and underlayer materials led to the well-patterned 80 nm resist lines on an underlayer for 100 imprints. The underlayer material was modified by a thermal crosslinking reaction of the aminoplast at 130 degrees C before nanoimprinting and, in conjunction with a cationic epoxy chemical reaction between the resist and the underlayer during UV irradiation before de-molding, proved to be quite effective for SFIL defect reduction. (C) 2013 Elsevier B.V. All rights reserved.

Reverse-tone Step and Flash Imprint Lithography (S-FIL/R) requires materials that can be spin coated onto patterned substrates with significant topography and that are highly-planarizing. Ideally, these planarizing materials must contain silicon for etch selectivity, be UV or thermally curable, have low viscosity, and low volatility. One such novel material in particular, a branched and functionalized siloxane (Si-12), is able to adequately satisfy the above requirements. This paper describes a study of the properties of epoxy functionalized Si-12 (epoxy-Si-12) as a planarizing layer. An efficient synthetic route to epoxy-Si-12 was successfully developed, which is suitable and scalable for an industrial process. Epoxy-Si-12 has a high silicon content (30.0 %), low viscosity (29 cP @ 25 °C), and low vapor pressure (0.65 Torr @ 25 °C). A planarizing study was carried out using epoxy-Si-12 on trench patterned test substrates. The material showed excellent planarizing properties and met the calculated critical degree of planarization (critical DOP), which is a requirement for a successful etch process. An S-FIL/R process using epoxy-Si-12 was demonstrated using, an ImprioR 100 (Molecular Imprints Inc., USA) imprint tool. The results indicate that epoxy-Si-12 works very well as a planarizing layer for S-FIL/R.

A new method facilitates high-throughput sequencing of the repertoire of immunoglobulin heavy-light chain pairs in human B cells. Each B-cell receptor consists of a pair of heavy and light chains. High-throughput sequencing can identify large numbers of heavy- and light-chain variable regions (VH and VL) in a given B-cell repertoire, but information about endogenous pairing of heavy and light chains is lost after bulk lysis of B-cell populations. Here we describe a way to retain this pairing information. In our approach, single B cells (>5 × 104 capacity per experiment) are deposited in a high-density microwell plate (125 pl/well) and lysed in situ. mRNA is then captured on magnetic beads, reverse transcribed and amplified by emulsion VH:VL linkage PCR. The linked transcripts are analyzed by Illumina high-throughput sequencing. We validated the fidelity of VH:VL pairs identified by this approach and used the method to sequence the repertoire of three human cell subsets—peripheral blood IgG+ B cells, peripheral plasmablasts isolated after tetanus toxoid immunization and memory B cells isolated after seasonal influenza vaccination.

Imaging flow cytometry was used to analyze the self-assembly of DNA-conjugated polystyrene microspheres. This technique enables quantitative analysis of the assembly process and thereby enables detailed analysis of the effect of structural and process variables on the assembly yield. In a demonstration of the potential of this technique, the influence of DNA strand base pair (bp) length was examined, and it was found that 50 bp was sufficient to drive the assembly of microspheres efficiently, forming not only dimers but also chainlike structures. The effect of stoichiometry on the yield was also examined. The analysis demonstrated that self-assembly of 50 bp microspheres can be driven nearly to completion by stoichiometric excess in a manner similar to Le Chatelier's principle in common chemical equilibrium.

Nanoimprint lithography is a newly developed patterning method that employs a hard template for the patterning of structures at micron and nanometerscales. This technique has many advantages such as cost reduction, high resolution, low line edge roughness (LER), and easy operation. However, resist peeling, defects, low degree of planarization, and low throughput issues present challenges that must be resolved in order to mass produce advanced nanometer-scale devices. In this study, the new approach of using spin-on hard mask materials under the resist to modify its adhesion during a UV irradiation process in nano imprint lithography was proposed to increase process latitudes. The performance of this process is evaluated by using step and flash imprint lithography. We expect that these spin-on hard mask materials (NCI-NIL-U series) under organic resist will be one of the most promising materials in the next generation of nano imprint lithography.

We discuss the lithographic qualification of a new type of binary mask blank consisting of an opaque layer of MoSi on a glass substrate, referred to simply as OMOG. First, OMOG lithographic performance will be compared to a previous chrome/MoSi/glass binary intensity mask (BIM) blank. Standard 70-nm chrome on class (COG) was not considered, as it failed to meet mask-making requirements. Theory and a series of simulation and experimental studies show OMOG to outperform BIM, particularly due to electromagnetic effects and optical proximity correction (OPC) predictability concerns, as OMOG behaves very similarly to the ideal thin mask approximation (TMA). A new TMA-predictability metric is defined as a means to compare mask blanks. We weigh the relative advantages and disadvantages of OMOG compared to 6% attenuated phase shifting. Although both mask blanks are likely sufficient for the 32-nm and 22-nm nodes, some differences exist and are described. Overall, however, of the blanks considered, it is concluded that OMOG provides the most robust and extendable imaging solution available for 32-nm and beyond.

Nanoimprint lithography is a newly developed patterning method that employs a hard template for the patterning of structures at micro- and nanometer scales. This technique has many advantages such as cost reduction, high resolution, low line edge roughness (LER), and easy operation. However, resist peeling, defects, low degree of planarization, and low throughput issues present challenges that must be resolved in order to mass produce advanced nanometer-scale devices. In this study, the new approach of using a silicon-containing spin-on hard mask underlayer material with high adhesion by reacting methacrylate groups of the underlayer to the acrylate groups of resist material during ultraviolet irradiation was demonstrated to obtain the excellent patterning dimensional accuracy and increase the process latitudes. The performance of this process is evaluated by using step and flash imprint lithography. The obtained high adhesion between the underlayer and resist material was found to lead a silicon-containing underlayer material to excellent patterning dimensional accuracy and 80 nm straight profiles. We expect that the silicon-containing a spin-on hard mask material under organic resist will be one of the most promising materials in the next generation of nanoimprint lithography.

Scaling of designs to the 45nm and future nodes presents challenges for block level lithography. Shrinking distances between devices drive aggressive resist placement tolerances, challenging the ability to control critical dimension (CD). In particular, the potential variation in shallow trench isolation oxide may result in variation of resist profile and CD, thereby affecting edge placement accuracy. Potential sources of this include wafer-to-wafer or within-wafer STI trench depth variations, and STI CMP variations that may be induced by active area pattern density fluctuations. Some other potential sources of CD fluctuation include oxide sidewall variation, and implant level overlay or CD errors modulating the proximity to the oxide sidewall. Depending on the actual variation of isolation oxide and the exposure latitude of the resist, the CD variations simply from oxide variation may consume a large portion of the CD budget.Several examples are given of variations in resist profile and CD arising from these substrate effects. The CD uniformity of a test structure was shown to decrease dramatically with the addition of a BARC to the resist stack, most likely due to the suppression of substrate reflectivity variations. Simulations performed using Panoramic Technologies software demonstrated the potential sensitivity of the factors outlined above on CD and profile errors. A comparison of simulated vs. experimental results is made for a case of intentional overlay error, showing the failure mode of the resist profile as the mask edge passes from STI to the active area. The simulations using a full physical model provided with the simulation software predict a resist foot forming over the active area, which was confirmed experimentally.

Presented here is an analysis of photoresist profile and feature control performance for high-energy well implant lithography as it is implemented in microelectronic devices, specifically SRAMs, at the 45 and 65nm nodes. As device designs become increasingly smaller to the tune of Moore's Law, deep well implant lithography specifications become more and more stringent, and issues related to lateral implant scattering that were more trivial for more relaxed designs begin to make significant contributions to photoresist feature uniformity and implant profile control. Simplified process assumptions that overlook such non-ideal implant phenomena can result in an overestimation of process latitude. Undesirable variability derived from the implantation, lithography, and substrate associated with a deep well formation process can degrade implantation profiles and have adverse effects on device electrical performance. Mechanisms for these adverse effects such as implant scattering and implant straggle will be explored followed by their relationships to process tolerance and electrical performance. Emphasis will be placed on evaluating the optimum photoresist feature profile for a given process and determining its true process latitude as opposed to "centering" a feature in a device layout during design. Finally, challenges confronting process control methods for high-aspect ratio implant mask features will be discussed followed by some proposed process improvement suggestions.

We present a systematic analysis of the imaging performance for a 0.93 numerical aperture (NA) state-of-the-art immersion lithography scanner and we compare this performance to its dry NA=0.93 counterpart. The increased depth of focus (DOF) enabled by immersion lithography presents a set of advantages for semiconductor manufacturing which we explore in this article. First, we show that 0.93 NA immersion prevents, for a 65nm gate-level process, the need for imposing pitch restrictions with an attenuated-PSM solution; something not possible with an equivalent "dry" process. Second, we demonstrate the superior critical dimension uniformity (CDU) of an immersion process in the presence of realistic focus variations typically encountered in semiconductor manufacturing. Third, we confirm that the through-pitch behavior of "wet" and "dry" scanners is well matched, enabling the possibility of transferring optical proximity corrections (OPC) between the two types of lithography scanners. The transferability of OPC is key to enabling a fast insertion of immersion lithography into the manufacturing process for the 65nm and 45nm nodes. Finally, we conclude that, from an imaging perspective, immersion is ready for high-volume manufacturing.