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Williamson L.,University of Chicago | Kim J.,EMD Performance Materials Corporation | Cao Y.,Merck Performance Materials | Lin G.,EMD Performance Materials Corporation | And 2 more authors.
Proceedings of SPIE - The International Society for Optical Engineering | Year: 2015

Directed self-assembly (DSA) of lamellae-forming block copolymers (BCP) via chemo-epitaxy is a potential lithographic solution to achieve patterns of dense features. Progress to date demonstrates encouraging results, but in order to better understand the role of all parameters, systematic analysis of each factor needs to be assessed. Small changes in the volume fraction of a lamellae-forming BCP have been shown to change the connectivity of unguided domains. When an asymmetric lamellae-forming BCP is assembled on chemical patterns generated with the LiNe flow, the patterning performance and defect modes change depending on whether the majority or minority volume fraction phase is guided by the chemical pattern. Asymmetric BCP formulations were generated by blending homopolymer with a symmetric BCP. The patterning performance of the BCP formulations was assessed for different pattern pitches, guide stripe widths, backfill materials and annealing times. Optical defect inspection and SEM review are used to track the majority defect mode for each formulation. Formulation-dependent trends in defect modes show the importance of optimizing the BCP formulation in order to minimize the defectivity. © 2015 SPIE.


Dimiev A.M.,Rice University | Dimiev A.M.,EMD Performance Materials Corporation | Dimiev A.M.,Merck KGaA | Ceriotti G.,Rice University | And 3 more authors.
ACS Nano | Year: 2016

Successful application of graphene is hampered by the lack of cost-effective methods for its production. Here, we demonstrate a method of mass production of graphene nanoplatelets (GNPs) by exfoliation of flake graphite in the tricomponent system made by a combination of ammonium persulfate ((NH4)2S2O8), concentrated sulfuric acid, and fuming sulfuric acid. The resulting GNPs are tens of microns in diameter and 10-35 nm in thickness. When in the liquid phase of the tricomponent media, graphite completely loses its interlayer registry. This provides a ∼100% yield of GNPs from graphite in 3-4 h at room temperature or in 10 min at 120 °C. © 2015 American Chemical Society.


Kim Y.S.,Cornell University | Shoorideh G.,Cornell University | Zhmayev Y.,Cornell University | Lee J.,Cornell University | And 6 more authors.
Nano Energy | Year: 2015

We have incorporated graphene nanoribbons (GNRs) which are unzipped from multi-wall carbon nanotubes (MWCNT) into silicon-carbon (Si/C) nanofibers, not only to reinforce hybrid Si/C fibers, but also to increase the electrical conductivity and charge transport capability of fibers. We demonstrated that GNRs are promising components for improving the rechargeable Li-ion battery performance due to their unique nanostructures and properties. Water based electrospinning, an easily scalable and environmentally benign process, was utilized to fabricate GNR/Si/C fibers. The resulting fibers exhibited a high reversible capacity of more than 1800mAh/g at 0.5C, and an excellent performance of 1400mAh/g with no capacity fading at a charge/discharge rate of 1C. This outstanding performance should be attributed to the enhanced charge and mass transfer ability of fibers by incorporation of ultrathin, flexible, conductive, and high aspect ratio GNRs. Electrodes made with GNR/Si/C fibers are more durable than ones with Si/C fibers, and do not exhibit dramatic volume and morphology changes after cycling. Moreover, GNR/Si/C fiber anodes were tested in a full-cell configuration where they displayed a steady gravimetric capacity of ca. 1400mAh/ganode for 25 cycles. © 2015.


Singh A.,IMEC | Singh A.,Catholic University of Leuven | Nam J.,Samsung | Lee J.,SK hynix | And 5 more authors.
Proceedings of SPIE - The International Society for Optical Engineering | Year: 2016

Directed self-Assembly (DSA) of block copolymers (BCP) has attracted significant interest as a patterning technique over the past few years. We have previously reported the development of a new process flow, the CHIPS flow (Chemo-epitaxy Induced by Pillar Structures), where we use ArFi lithography and plasma etch to print guiding pillar patterns for the DSA of cylindrical phase BCPs into dense hexagonal hole arrays of 22.5 nm half-pitch and 15 nm half-pitch [1]. The ability of this DSA process to generate dense regular patterns makes it an excellent candidate for patterning memory devices. Thus, in this paper we study the applicability of the CHIPS flow to patterning for DRAM storage layers. We report the impact of various process conditions on defect density, defect types and pattern variability. We also perform detailed analysis of the DSA patterns, quantify pattern placement accuracy and demonstrate a route towards excellent LCDU after pattern transfer into a hard mask layer. © 2016 COPYRIGHT SPIE. Downloading of the abstract is permitted for personal use only.


Noya G.,Merck Performance Materials Manufacturing G.K. | Hama Y.,Merck Performance Materials Manufacturing G.K. | Ishii M.,Merck Performance Materials Manufacturing G.K. | Nakasugi S.,Merck Performance Materials Manufacturing G.K. | And 2 more authors.
Proceedings of SPIE - The International Society for Optical Engineering | Year: 2016

Spin-on-carbon hard mask (SOC HM) has been used in semiconductor manufacturing since 45nm node as an alternative carbon hard mask process to chemical vapor deposition (CVD). As advancement of semiconductor to 2X nm nodes and beyond, multiple patterning technology is used and planarization of topography become more important and challenging ever before. In order to develop next generation SOC, one of focuses is planarization of topography. SOC with different concepts for improved planarization and the influence of thermal flow temperature, crosslink, film shrinkage, baking conditions on planarization and filling performance are described in this paper. © 2016 SPIE.


Doise J.,Catholic University of Leuven | Doise J.,IMEC | Bekaert J.,IMEC | Chan B.T.,IMEC | And 3 more authors.
Proceedings of SPIE - The International Society for Optical Engineering | Year: 2016

Directed self-assembly (DSA) of block copolymers (BCP) is considered a promising patterning approach for the 7 nm node and beyond. Specifically, a grapho-epitaxy process using a cylindrical phase BCP may offer an efficient solution for patterning randomly distributed contact holes with sub-resolution pitches, such as found in via and cut mask levels. In any grapho-epitaxy process, the pattern density impacts the template fill (local BCP thickness inside the template) and may cause defects due to respectively over- or underfilling of the template. In order to tackle this issue thoroughly, the parameters that determine template fill and the influence of template fill on the resulting pattern should be investigated. In this work, using three process flow variations (with different template surface energy), template fill is experimentally characterized as a function of pattern density and film thickness. The impact of these parameters on template fill is highly dependent on the process flow, and thus pre-pattern surface energy. Template fill has a considerable effect on the pattern transfer of the DSA contact holes into the underlying layer. Higher fill levels give rise to smaller contact holes and worse critical dimension uniformity. These results are important towards DSA-aware design and show that fill is a crucial parameter in grapho-epitaxy DSA. © 2016 SPIE.


Miyamoto Y.,Merck Performance Materials Manufacturing G.K. | Sekito T.,Merck Performance Materials Manufacturing G.K. | Sagan J.,EMD Performance Materials Corporation | Horiba Y.,Merck Performance Materials Manufacturing G.K. | And 3 more authors.
Proceedings of SPIE - The International Society for Optical Engineering | Year: 2015

Negative tone shrink materials (NSM) suitable for resolution enhancement of negative tone development (NTD) 193nm immersion resists have been developed. While this technology is being expanded to integrated circuits (IC) manufacturing, there still have two major problems to apply various processes. One of them is shrink ID bias which means shrink differences between isolated (I) and dense (D) CDs, and the other one is Y/X shrinkage bias which means shrinkage differences between major axis (Y) and minor axis (X) of the elongated or oval shape pattern. While we have presented the improvement of shrink ID bias at SPIE2014 [1], the reduction of Y/X shrinkage bias was the examination theme for quite some time. In this paper, we present Y/X shrinkage bias of current NTD shrink material, new concept material for Y/X bias reduction and the result of new shrink material. Current NTD shrink model has Y/X bias of 1.6 (Y shrink=16nm) at a mixing bake (MB) of 150°C on AZ AX2110P NTD elongated pattern of X=70nm and Y=210nm ADI. This means shrinkage of Y has larger shrinkage than X and that makes difficult to apply shrink material. We expected that the characteristic shape of elongated pattern was one of the root-cause for Y/X bias, and then simulated how to achieve equivalent shrinkage at Y and X. We concluded that available resist volume per each Y and X unit was not equivalent and need new shrink concept to solve Y/X bias. Based on our new concept, we prepared new shrink material which has lower Y/X bias and larger shrink amount compared with current NTD shrink material. Finally we have achieved lower Y/X bias from 1.6 to 1.1 at MB150°C and moreover got higher shrinkage than current NTD shrink material from 10.1nm to 16.7nm. © 2015 SPIE.


Wan L.,HGST Inc | Ruiz R.,HGST Inc | Gao H.,HGST Inc | Patel K.C.,HGST Inc | And 5 more authors.
ACS Nano | Year: 2015

We explore the lithographic limits of lamellae-forming PS-b-PMMA block copolymers by performing directed self-assembly and pattern transfer on a range of PS-b-PMMA materials having a full pitch from 27 to 18.5 nm. While directed self-assembly on chemical contrast patterns was successful with all the materials used in this study, clean removal of PMMA domains and subsequent pattern transfer could only be sustained down to 22 nm full pitch. We attribute this limitation to the width of the interface, which may represent more than half of the domain width for materials with a critical dimension below 10 nm. With the limit of pattern transfer for PS-b-PMMA set at 11 nm, we propose an integration scheme suitable for bit patterned media for densities above 1.6 Tdot/in2, which require features below this limit. Directed self-assembly was carried out on chemical contrast patterns made by a rotary e-beam lithography system, and pattern transfer was carried out to demonstrate fabrication of large area (up to 25 mm-wide annular band of circular tracks) nanoimprint templates for bit patterned media. We also demonstrate compatibility with hard disk drive architecture by fabricating patterns with skewed radial lines with constant angular pitch and with servo patterns that are needed in hard disk drives to generate a radial positional error signal (PES). © 2015 American Chemical Society.


Doise J.,Catholic University of Leuven | Doise J.,IMEC | Bekaert J.,IMEC | Chan B.T.,IMEC | And 3 more authors.
Journal of Micro/ Nanolithography, MEMS, and MOEMS | Year: 2016

Directed self-assembly (DSA) of block copolymers (BCP) is considered a promising patterning approach for the 7-nm node and beyond. Specifically, a graphoepitaxy process using a cylindrical phase BCP may offer an efficient solution for patterning randomly distributed contact holes with subresolution pitches, such as found in via and cut mask levels. In any graphoepitaxy process, the pattern density impacts the template fill (local BCP thickness inside the template) and may cause defects due to over- or underfilling of the template. In order to tackle this issue thoroughly, the parameters that determine template fill and the influence of template fill on the resulting pattern should be investigated. Using three process flow variations (with different template surface energy), template fill is experimentally characterized as a function of pattern density and film thickness. The impact of these parameters on template fill is highly dependent on the process flow, and thus prepattern surface energy. Template fill has a considerable effect on the pattern transfer of the DSA contact holes into the underlying layer. Higher fill levels give rise to smaller contact holes and worse critical dimension uniformity. These results are important for DSA-aware design and show that fill is a crucial parameter in graphoepitaxy DSA. © 2016 Society of Photo-Optical Instrumentation Engineers (SPIE).


PubMed | EMD Performance Materials Corporation and HGST Inc
Type: Journal Article | Journal: ACS nano | Year: 2015

We explore the lithographic limits of lamellae-forming PS-b-PMMA block copolymers by performing directed self-assembly and pattern transfer on a range of PS-b-PMMA materials having a full pitch from 27 to 18.5 nm. While directed self-assembly on chemical contrast patterns was successful with all the materials used in this study, clean removal of PMMA domains and subsequent pattern transfer could only be sustained down to 22 nm full pitch. We attribute this limitation to the width of the interface, which may represent more than half of the domain width for materials with a critical dimension below 10 nm. With the limit of pattern transfer for PS-b-PMMA set at 11 nm, we propose an integration scheme suitable for bit patterned media for densities above 1.6 Tdot/in(2), which require features below this limit. Directed self-assembly was carried out on chemical contrast patterns made by a rotary e-beam lithography system, and pattern transfer was carried out to demonstrate fabrication of large area (up to 25 mm-wide annular band of circular tracks) nanoimprint templates for bit patterned media. We also demonstrate compatibility with hard disk drive architecture by fabricating patterns with skewed radial lines with constant angular pitch and with servo patterns that are needed in hard disk drives to generate a radial positional error signal (PES).

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