Directed Self-assembly Process Research Articles

Calculating the acoustic radiation force on spherical particles in a standing ultrasound wave field considering single and multiple scattering

Ultrasound directed self-assembly (DSA) utilizes the acoustic radiation force (ARF) associated with a standing ultrasound wave to organize particles dispersed in a fluid medium into specific patterns. The ARF is a superposition of the primary acoustic radiation force, which results from the incident standing ultrasound wave, and the acoustic interaction force, which originates from single and multiple scattering between neighboring particles. In contrast with most reports in the literature that neglect multiple scattering when calculating the ARF, we demonstrate that the deviation between considering single or multiple scattering may reach up to 100%, depending on the ultrasound DSA process parameters and material properties. We evaluate a theoretical case with three spherical particles in a viscous medium and derive operating maps that quantify the deviation between both scattering approaches as a function of the ultrasound DSA process parameters. Then, we study a realistic system with hundreds of particles dispersed in a viscous medium, and show that the deviation between the ARF resulting from single and multiple scattering increases with decreasing particle size and increasing medium viscosity, density ratio, compressibility ratio, and particle volume fraction. This work provides a quantitative basis for determining whether to consider single or multiple scattering in ultrasound DSA simulations.

Enhanced and Efficient Guiding Template Design for Lamellar DSA With Graph Monomorphism

Lamellar directed self-assembly (DSA) technology in combination with the self-aligned via (SAV) process has emerged as a novel and promising choice for via/contact layer fabrication, where a via between Metal-x and Metal-(x+1) is generated at the intersection of a wire segment on Metal-(x+1) and a rectangular and perpendicular guiding template. Compared to the highly investigated cylindrical DSA, lamellar DSA does not suffer from the overlay error of generated holes and thus can have better yield, and it also benefits from the better flexibility of various via pitches a single template can produce. A state-of-the-art work has addressed the guiding template design problem for the new process, and an integer linear programming (ILP) formulation that can optimally solve the problem as well as a simple heuristic approach are proposed. However, solving the ILP formulation is time-consuming, and the heuristic method suffers from unignorable degradation in solution quality due to several algorithm deficiencies. In this paper, we propose an enhanced and efficient template design algorithm flow for the lamellar DSA and SAV process by using graph monomorphism for pattern conflict check in multiple patterning lithography. Experimental results show that the proposed flow can greatly reduce the numbers of conflicts and short templates and is almost as efficient as the existing heuristic approach.

Self-Aligned Assembly of a Poly(2-vinylpyridine)-b-Polystyrene-b-Poly(2-vinylpyridine) Triblock Copolymer on Graphene Nanoribbons.

Directed self-assembly (DSA) of block copolymers is one of the most promising patterning techniques for patterning sub-10 nm features. However, at such small feature sizes, it is becoming increasingly difficult to fabricate the guiding pattern for the DSA process, and it is necessary to explore alternative guiding methods for DSA to achieve long-range ordered alignment. Here, we report the self-aligned assembly of a triblock copolymer, poly(2-vinylpyridine)-b-polystyrene-b-poly(2-vinylpyridine) (P2VP-b-PS-b-P2VP) on neutral graphene nanoribbons with the gap consisting of a P2VP-preferential silicon oxide (SiO2) substrate via solvent vapor annealing. The assembled P2VP-b-PS-b-P2VP demonstrated long-range, one-dimensional alignment on the graphene substrate in a direction perpendicular to the boundary of the graphene and substrate with a half-pitch size of 8 nm, which greatly alleviates the lithography resolution required for traditional chemoepitaxy DSA. A wide processing window is demonstrated with the gap between graphene stripes varying from 10 to 100 nm, overcoming the restriction on widths of guiding patterns to have commensurate domain spacing. When the gap was reduced to 10 nm, P2VP-b-PS-b-P2VP formed a straight-line pattern on both the graphene and the substrate. Monte Carlo simulations showed that the self-aligned assembly of the triblock copolymer on the graphene nanoribbons is guided at the boundary of parallel and perpendicular lamellae on graphene and SiO2, respectively. Simulations also indicate that the swelling of a system allows for rapid rearrangement of chains and quickly anneal any misaligned grains and defects. The effect of the interaction strength between SiO2 and P2VP on the self-assembly is systematically investigated in simulations.

Block copolymer directed self-assembly defect modes induced by localized errors in chemoepitaxial guiding underlayers: A molecular simulation study

Block copolymer (BCP) directed self-assembly (DSA) has been presented as a potential economically attractive enhancement to extend the capabilities of optical lithography for semiconductor manufacturing. One concern in DSA is the level of defectivity that can be achieved in such a process. Although entropic effects will always lead to some degree of defectivity, highly ordered structures with a low theoretical equilibrium defect density can be produced by guiding the ordering and placement of the BCP domains using a patterned underlayer. Recent experimental studies have shown that while DSA processes can significantly reduce the observed defect density, defectivity levels are generally still higher than allowable for high-volume manufacturing and higher than what would be anticipated from free energy estimates of the observed defect modes. In particular, bridge defects are one of the most commonly observed defect modes in experimental DSA studies. A number of hypotheses have been proposed to explain the origins of these defects. One hypothesis is that so-called affinity defects present in the underlayer can spawn bridge defects in the overlying BCP film. The goal of the work reported here was to investigate the extent to which bridge defects can be generated or further reinforced in lamellae-forming block copolymer films due to affinity defects in the underlayer pattern. Coarse-grained molecular dynamics simulations were used to simulate the chemoepitaxial DSA of monodisperse block copolymer films atop underlayers with varying affinity defect sizes. Affinity defects were simulated by creating circular regions of a single polymer block type (which is the opposite block type of that used to pattern the underlayer guiding stripes) in the nominally neutral background region of the underlayer. These affinity defects were positioned in regions of the underlayer where they were the incorrect type to match the overlying block copolymer pattern. It was observed that the presence of an affinity defect in the neutral region of the underlayer caused the energetically preferential polymer block to wet the affinity defect, thus creating the nucleus of what could potentially become a bridge defect—even when the affinity defects were very small. As the radius of the underlayer affinity defect (RoD) increased, the amount of block copolymer of incorrect type (with respect to a perfectly assembled copolymer pattern) that assembled above the affinity defect increased; but, in general, the thickness of the wetting layer in contact with the affinity defect was only roughly one polymer chain thick. These data suggest that an affinity defect in the underlayer alone is unlikely to be noticeably enhanced by significant bridge defect formation in a monodisperse block copolymer film.

Lamellar Orientation of a Block Copolymer via an Electron-Beam Induced Polarity Switch in a Nitrophenyl Self-Assembled Monolayer or Si Etching Treatments

Directed self-assembly (DSA) was investigated on self-assembled monolayers (SAMs) chemically modified by electron beam (EB) irradiation, which is composed of 6-(4-nitrophenoxy) hexane-1-thiol (NPHT). Irradiating a NPHT by EB could successfully induce the orientation and selective patterning of block copolymer domains. We clarified that spatially-selective lamellar orientations of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) could be achieved by a change of an underlying SAM. The change of an underlying SAM is composed of the transition of an NO2 group to an NH2 group, which is induced by EB. The modification in the polarity of different regions of the SAM with EB lithography controlled the lamellar orientation of PS-b-PMMA. The reduction of the NPHT SAM plays an important role in the orientation of block copolymer. This method might significantly simplify block copolymer DSA processes when it is compared to the conventional DSA process. By investigating the lamellae orientation with EB, it is clarified that only suitable annealing temperatures and irradiation doses lead to the vertical orientation. We also fabricated pre-patterned Si substrates by EB lithographic patterning and reactive ion etching (RIE). DSA onto such pre-patterned Si substrates was proven to be successful for subdivision of the lithographic patterns into line and space patterns.

Directed Self‐Assembly of Patchy Microgels into Anisotropic Nanostructures

Multi-geometry nanostructures with high-order, complex, and controllable geometries have attracted extensive attention in the development of functional nanomaterials. A simple and versatile strategy is proposed to construct various anisotropic nanostructures through the directed self-assembly (DSA) of patchy microgels. A general criterion for interaction parameters is developed by the variance analysis method to achieve the formation of 1D nanorods by the single directional DSA process, and 2D or 3D polymorphs including V/T/h/cross shapes, multiple arms, multi-directional bending, single/multiple rings, nanocages, etc., by the multi-directional DSA process of binary microgel blends. At the optimum interaction parameters, the nanorods exhibit the quickest formation process and the most thermodynamically stable geometry, while the various 2D or 3D assemblies exhibit controlled jointing behaviors for versatile assembly geometries. The number of recognition sites on the patchy microgel surface guides the aggregation modes of microgels during the DSA process. These assemblies can bear large curvature variance with the increase of shear rates due to the high flexibility and the ability of adjusting orientation spontaneously. The DSA behavior of patchy microgels differs from the traditional self-assembly process of block copolymers, which may open a new route for guiding the formation of controllable nanoparticle architectures.

Universal perpendicular orientation of block copolymer microdomains using a filtered plasma

Sub-10 nm patterns prepared by directed self-assembly (DSA) of block copolymer (BCP) thin films offer a breakthrough method to overcome the limitations of photolithography. Perpendicular orientation of the BCP nanostructures is essential for lithographic applications, but dissimilar surface/interfacial energies of two blocks generally favour parallel orientations, so that the perpendicular orientation could only be obtained under very limited conditions. Here, we introduce a generalized method for creating perpendicular orientations by filtered plasma treatment of the BCP films. By cross-linking the surface of disordered BCP films using only physical collisions of neutral species without ion bombardment or UV irradiation, neutral layers consistent with the BCP volume fraction are produced that promote the perpendicular orientations. This method works with BCPs of various types, volume fractions, and molecular weights individually at the top and bottom interfaces, so it was applied to orientation-controlled 3D multilayer structures and DSA processes for sub-10 nm line-spacing patterns.

X-ray characterization of contact holes for block copolymer lithography

The directed self-assembly (DSA) of block copolymers (BCPs) is a promising low-cost approach to patterning structures with critical dimensions (CDs) which are smaller than can be achieved by traditional photolithography. The CD of contact holes can be reduced by assembling a cylindrical BCP inside a patterned template and utilizing the native size of the cylinder to dictate the reduced dimensions of the hole. This is a particularly promising application of the DSA technique, but in order for this technology to be realized there is a need for three-dimensional metrology of the internal structure of the patterned BCP in order to understand how template properties and processing conditions impact BCP assembly. This is a particularly challenging problem for traditional metrologies owing to the three-dimensional nature of the structure and the buried features. By utilizing small-angle X-ray scattering and changing the angle between the incident beam and sample we can reconstruct the three-dimensional shape profile of the empty template and the residual polymer after self-assembly and removal of one of the phases. A two-dimensional square grid pattern of the holes results in scattering in both in-plane directions, which is simplified by converting to a radial geometry. The shape is then determined by simulating the scattering from a model and iterating that model until the simulated and experimental scattering profiles show a satisfactory match. Samples with two different processing conditions are characterized in order to demonstrate the ability of the technique to evaluate critical features such as residual layer thickness and sidewall height. It was found that the samples had residual layer thicknesses of 15.9 ± 3.2 nm and 4.5 ± 2.2 nm, which were clearly distinguished between the two different DSA processes and in good agreement with focused ion beam scanning transmission electron microscopy (FIBSTEM) observations. The advantage of the X-ray measurements is that FIBSTEM characterizes around ten holes, while there are of the order of 800 000 holes illuminated by the X-ray beam.

DSA-Compliant Routing for 2-D Patterns Using Block Copolymer Lithography

2-D directed self-assembly (DSA) is an emerging lithography for the 5-nm process node and beyond that can substantially increase design flexibility in critical routing layers and reduce the number of cuts for better yield. The state-of-the-art 2-D DSA process manipulates the orientation of double posts inside guiding templates to guide block copolymers (BCPs) to form 2-D patterns. However, a key challenge arises on how to correctly assign double post orientations and place cut patterns to make desired net connections for a given routing instance. In this paper, we propose a novel 2-D DSA-compliant routing (2-D-DCR) framework to systematically derive feasible orientation assignments for double posts to maximize routability. Specifically, 2-D-DCR features a complete set of new routing rules which transform the underlying physical BCP growth principles for large-scale routing, adopts a network-flow-based double-post assignment routing algorithm, and leverages a 2-D DSA line-end creation property to maximally reduce line-end cuts. Experimental results show that our 2-D-DCR can effectively generate a 2-D-DCR solution with zero double post conflicts, maximized routability, and minimized the number of cuts.

Engineering the Kinetics of Directed Self-Assembly of Block Copolymers toward Fast and Defect-Free Assembly.

Directed self-assembly (DSA) of block copolymers (BCPs) can achieve perfectly aligned structures at thermodynamic equilibrium, but the self-assembling morphology can become kinetically trapped in defective states. Understanding and optimizing the kinetic pathway toward domain alignment is crucial for enhancing process throughput and lowering defectivity to levels required for semiconductor manufacturing, but there is a dearth of experimental, three-dimensional studies of the kinetic pathways in DSA. Here, we combined arrested annealing and TEM tomography to probe the kinetics and structural evolution in the chemoepitaxy DSA of PS- b-PMMA with density multiplication. During the initial stages of annealing, BCP domains developed independently at first, with aligned structures at the template interface and randomly oriented domains at the top surface. As the grains coarsened, the assembly became cooperative throughout the film thickness, and a metastable stitch morphology was formed, representing a kinetic barrier. The stitch morphology had a three-dimensional structure consisting of both perpendicular and parallel lamellae. On the basis of the mechanistic information, we studied the effect of key design parameters on the kinetics and evolution of structures in DSA. Three types of structural evolutions were observed at different film thicknesses: (1) immediate alignment and fast assembly when thickness < L0 ( L0 = BCP natural periodicity); (2) formation of stitch morphology for 1.25-1.45 L0; (3) fingerprint formation when thickness >1.64 L0. We found that the DSA kinetics can be significantly improved by avoiding the formation of the metastable stitch morphology. Increasing template topography also enhanced the kinetics by increasing the PMMA guiding surface area. A combination of 0.75 L0 BCP thickness and 0.50 L0 template topography achieved perfect alignment over 100 times faster than the baseline process. This research demonstrates that an improved understanding of the evolution of structures during DSA can significantly improve the DSA process.

Vapor Phase Exchange of Self-Assembled Monolayers for Engineering of Biofunctional Surfaces.

We show that 4'-nitro-1,1'-biphenyl-4-thiol self-assembled monolayers (NBPT SAMs) on gold can be exchanged with 11-(mercaptoundecyl)triethylene glycol (C11EG3OH) SAMs via vapor deposition (VD). The pristine and the exchanged SAMs obtained by VD as well as solution method (SM) were characterized by X-ray photoelectron spectroscopy (XPS) and polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS). Using surface plasmon resonance (SPR), it is shown that C11EG3OH SAMs on gold obtained by vapor deposition exchange (VDEx) have the same protein resistivity as SAMs obtained by the direct self-assembly process. As expected, the cross-linked NBPT SAM are found to be resistive to both exchange processes, VDEx and solution method exchange (SMEx). In this way, VDEx opens up an elegant and new approach of patterning SAM surfaces in situ at vacuum conditions without using any solvents. By combining electron irradiation-induced chemical lithography of NBPT SAMs with VDEx, biofunctional patterned substrates were engineered and used for immobilization of protein arrays.

Design technology co-optimization assessment for directed self-assembly-based lithography: design for directed self-assembly or directed self-assembly for design?

We report a systematic study of the feasibility of using directed self-assembly (DSA) in real product design for 7-nm fin field effect transistor (FinFET) technology. We illustrate a design technology co-optimization (DTCO) methodology and two test cases applying both line/space type and via/cut type DSA processes. We cover the parts of DSA process flow and critical design constructs as well as a full chip capable computational lithography framework for DSA. By co-optimizing all process flow and product design constructs in a holistic way using a computational DTCO flow, we point out the feasibility of manufacturing using DSA in an advanced FinFET technology node and highlight the issues in the whole DSA ecosystem before we insert DSA into manufacturing.

Quantitative Three-Dimensional Characterization of Block Copolymer Directed Self-Assembly on Combined Chemical and Topographical Prepatterned Templates.

Characterization of the three-dimensional (3D) structure in directed self-assembly (DSA) of block copolymers is crucial for understanding the complex relationships between the guiding template and the resulting polymer structure so DSA could be successfully implemented for advanced lithography applications. Here, we combined scanning transmission electron microscopy (STEM) tomography and coarse-grain simulations to probe the 3D structure of P2VP-b-PS-b-P2VP assembled on prepatterned templates using solvent vapor annealing. The templates consisted of nonpreferential background and raised guiding stripes that had PS-preferential top surfaces and P2VP-preferential sidewalls. The full 3D characterization allowed us to quantify the shape of the polymer domains and the interface between domains as a function of depth in the film and template geometry and offered important insights that were not accessible with 2D metrology. Sidewall guiding was advantageous in promoting the alignment and lowering the roughness of the P2VP domains over the sidewalls, but incommensurate confinement from the increased topography could cause roughness and intermittent dislocations in domains over the background region at the bottom of the film. The 3D characterization of bridge structures between domains over the background and breaks within domains on guiding lines sheds light on possible origins of common DSA defects. The positional fluctuations of the PS/P2VP interface between domains showed a depth-dependent behavior, with high levels of fluctuations near both the free surface of the film and the substrate and lower fluctuation levels in the middle of the film. This research demonstrates how 3D characterization offers a better understanding of DSA processes, leading to better design and fabrication of directing templates.

Process highlights to enhance directed self-assembly contact patterning performances

We focus on the directed self-assembly (DSA) for contact hole (CH) patterning application using polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA) block copolymers (BCPs). By employing the DSA planarization process, we highlight the DSA advantages for CH shrink, repair, and multiplication, which are extremely needed to push forward the limits of currently used lithography. Meanwhile, we overcome the issue of pattern density-related defects that are encountered with the commonly used graphoepitaxy process flow. Our study also aims to evaluate the DSA performances as functions of material properties and process conditions by monitoring main key manufacturing process parameters: CD uniformity (CDU), placement error (PE), and defectivity [hole open yield (HOY)]. Concerning process, it is shown that the control of surface affinity and the optimization of self-assembly annealing conditions enable significant enhancement of CDU and PE. Regarding material properties, we show that the best BCP composition for CH patterning should be set at 70/30 of PS/PMMA total weight ratio. Moreover, it is found that increasing the PS homopolymer content from 0.2% to 1% has no impact on DSA performances. Using a C35 BCP (cylinder-forming BCP of natural period L0=35 nm), good DSA performances are achieved: CDU-3σ=1.2 nm, PE-3σ=1.2 nm, and HOY=100%. Finally, the stability of DSA process is also demonstrated through the process follow-up on both patterned and unpatterned surfaces over several weeks.

Controlling and tracking of colloidal nanostructures through two-photon fluorescence

Multiphoton absorbing dye-coated trapped spherical bead at the focal plane of femtosecond optical tweezers shows nonlinear optical (NLO) phenomena. One such NLO process of two-photon fluorescence (TPF) has been used for the background-free imaging of a femtosecond laser-trapping event. Due to the high peak powers of femtosecond laser pulses with low average powers, it is possible to not only trap single nanospheres, but encourage optically directed self-assembly. The TPF signatures of trapped particles show evidence of such a directed self-assembly process which, in turn, can provide information about the structural dynamics during the process of cluster formation. We are able to trap and characterize structure and dynamics in 3D until pentamer formation from the decay characteristics of trapping at the focal plane.

Virtual fabrication using directed self-assembly for process optimization in a 14-nm dynamic random access memory

For directed self-assembly (DSA) to be deployed in advanced semiconductor technologies, it must reliably integrate into a full process flow. We present a methodology for using virtual fabrication software, including predictive DSA process models, to develop and analyze the replacement of self-aligned quadruple patterning with Liu–Nealey chemoepitaxy on a 14-nm dynamic random access memory (DRAM) process. To quantify the impact of this module replacement, we investigated a key process yield metric for DRAM, interface area between the capacitor contacts and transistor source/drain. Additionally, we demonstrate virtual fabrication of the DRAM cell’s hexagonally packed capacitors patterned with an array of diblock copolymer cylinders in place of fourfold litho-etch (LE4) patterning.

Topochemical polymerization for preparing polymer crystals

It has been challenging for preparing large-size polymer crystals from direct solution self-assembly process because of their high molecular weight, polydispersity, complex and strong intermolecular interactions. Topochemical polymerization is an important tool for synthesizing polymers in solid state, which exhibit advantages of free-solvent, environment-friendly, high yield in stereo and regional reaction as well as possibly realizing the crystal-to-crystal transformation, and would be a promising solution. In this review, we systematically summarized the molecule systems that could achieve corresponding polymer crystals through topochemical polymerization, including olefins, diacetylenes, azide-alkynes, fullerene and their derivatives, and discussed their reaction characteristics and requirements. Finally, we briefly discussed the basic characterization techniques and promising application fields of polymer crystals, and also the existing challenges and opportunities in the field of topochemical polymerization.

Directed Self-Assembly of Triblock Copolymer on Chemical Patterns for Sub-10-nm Nanofabrication via Solvent Annealing.

Directed self-assembly (DSA) of block copolymers (BCPs) is a leading strategy to pattern at sublithographic resolution in the technology roadmap for semiconductors and is the only known solution to fabricate nanoimprint templates for the production of bit pattern media. While great progress has been made to implement block copolymer lithography with features in the range of 10-20 nm, patterning solutions below 10 nm are still not mature. Many BCP systems self-assemble at this length scale, but challenges remain in simultaneously tuning the interfacial energy atop the film to control the orientation of BCP domains, designing materials, templates, and processes for ultra-high-density DSA, and establishing a robust pattern transfer strategy. Among the various solutions to achieve domains that are perpendicular to the substrate, solvent annealing is advantageous because it is a versatile method that can be applied to a diversity of materials. Here we report a DSA process based on chemical contrast templates and solvent annealing to fabricate 8 nm features on a 16 nm pitch. To make this possible, a number of innovations were brought in concert with a common platform: (1) assembling the BCP in the phase-separated, solvated state, (2) identifying a larger process window for solvated triblock vs diblock BCPs as a function of solvent volume fraction, (3) employing templates for sub-10-nm BCP systems accessible by lithography, and (4) integrating a robust pattern transfer strategy by vapor infiltration of organometallic precursors for selective metal oxide synthesis to prepare an inorganic hard mask.

Placement error in directed self-assembly of block copolymers for contact hole application

Directed self-assembly (DSA) of block copolymers has shown interesting results for contact hole application, as a vertical interconnection access for CMOS sub-10 nm technology. The control of critical dimension uniformity (CDU), defectivity, and placement error (PE) is challenging and depends on multiple processes and material parameters. This paper reports the work done using the 300-mm pilot line available in materials to integrate the DSA process on contact and via level patterning. In the first part, a reliable methodology for PE measurement is defined. By tuning intrinsic edge detection parameters on standard reference images, the working window is determined. The methodology is then implemented to analyze the experimental data. The impact of the planarization process on PE and the importance of PE as a complement of CDU and hole open yield for process window determination are discussed.

Contact Hole Shrinking of Directed Self-Assembly and Its Application Based on Simulation Approach.

Directed self-assembly (DSA) of block copolymers (BCPs) has become an intense field of study as a complementary technique to conventional lithography for 1×-nm semiconductor patterning. DSA contact hole (C/H) shrinking is a possible implemental technique in the DSA process. In this paper, a DSA C/H shrinking is fully modeled and simulated by using a self-consistent field theory (SCFT). Simulation results show good agreement with experiment results. In terms of this simulation, the potential of DSA C/H shrinking with thermal reflow is integrated into the conventional CMOS lithography process in order to achieve high resolution and pattern density multiplication at a low cost. The optical proximity correction (OPC) of DSA C/H shrinking due to prepattern C/H and pitch can increase process window for DSA C/H shrinking.