Han-Hao Cheng

Control of the orientation of symmetric poly(styrene)-block-poly(D,L-lactide) block copolymers using statistical copolymers of dissimilar composition

The interactions of block copolymers with surfaces can be controlled by coating those surfaces with appropriate statistical copolymers. Usually, a statistical copolymer comprised of monomer units identical to those of the block copolymer is used; that is, typically a poly(styrene)-stat-poly(methyl methacrylate) (PS-stat-PMMA) is used to direct the alignment of poly(styrene)-block-poly(methyl methacrylate) (PS-block-PMMA), and poly(styrene)-stat-poly(2-vinylpyridine) (PS-stat-P2VP) has been used for poly(styrene)-block-poly(2-vinylpyridine) (PS-block-P2VP). Reports of controlling the orientation of block copolymers with statistical copolymers with a dissimilar composition are limited. Here, we demonstrate that this method can be further extended to show that PS-stat-PMMA can be used to control the wetting properties of poly(styrene)-block-poly(D,L-lactide) (PS-block-PDLA). Surfaces were modified with a series of cross-linked PS-stat-PMMA-stat-glycidyl methacrylate terpolymers, and the surface chemistries and energies were assessed using angle-dependent X-ray photoelectron spectroscopy and the two-liquid harmonic method, respectively. From these experiments, an expected neutral compositional window was identified for symmetrical PS-block-PDLA. Moreover, high-resolution SEM, AD-XPS, and grazing-incidence SAXS measurements were used to evaluate the morphology of PS-block-PDLA as a function of the surface composition of the underlying cross-linked copolymer films, and the neutral composition was found to range from 32 to 38 mol % of PS, in the bulk polymer. Ultimately, we demonstrated the determination of nonpreferential surface compositions that allow the self-assembly of lamellae with sizes in the sub-10 nm regime that are oriented perpendicular to the substrate. These findings have important implications for the use of PS-block-PDLA block copolymers in directed self-assembly, most specifically in advanced lithographic processes.

EUVL compatible LER solutions using functional block copolymers

Directed self assembly (DSA) of block copolymers is an emerging technology for achieving sub-lithographic resolution. We investigate the directed self assembly of two systems, polystyrene-block-poly-DL-lactic acid (PS-b-PDLA) and PSb- poly(methyl methacrylate). For the PS-b-PDLA system we use an open source EUVL resist and a commerciallyavailable underlayer to prepare templates for DSA. We investigate the morphology of the phase separated domains and compare the LER of the resist and the PS-PDLA interface. For the PS-b-PMMA system we again use an open source resist, but the annealing conditions in this case require crosslinking of the resist prior to deposition of the block copolymer. For this system we also investigate the morphology of the phase separated domains and compare the LER of the resist and the PS-PMMA interface.

Chain scission resists for extreme ultraviolet lithography based on high performance polysulfone-containing polymers

A series of polymers with a comb architecture were prepared where the poly(olefin sulfone) backbone was designed to be highly sensitive to extreme ultraviolet (EUV) radiation, while the well-defined poly(methyl methacrylate) (PMMA) arms were incorporated with the aim of increasing structural stability. It is hypothesized that upon EUV radiation rapid degradation of the polysulfone backbone will occur leaving behind the well-defined PMMA arms. The synthesized polymers were characterised and have had their performance as chain-scission EUV photoresists evaluated. It was found that all materials possess high sensitivity towards degradation by EUV radiation (E0 in the range 4–6 mJ cm−2). Selective degradation of the poly(1-pentene sulfone) backbone relative to the PMMA arms was demonstrated by mass spectrometry headspace analysis during EUV irradiation and by grazing-angle ATR-FTIR. EUV interference patterning has shown that materials are capable of resolving 30 nm 1 : 1 line : space features. The incorporation of PMMA was found to increase the structural integrity of the patterned features. Thus, it has been shown that terpolymer materials possessing a highly sensitive poly(olefin sulfone) backbone and PMMA arms are able to provide a tuneable materials platform for chain scission EUV resists. These materials have the potential to benefit applications that require nanopattering, such as computer chip manufacture and nano-MEMS.

Single-Crystalline 3C-SiC anodically Bonded onto Glass: An Excellent Platform for High-Temperature Electronics and Bioapplications

Single-crystal cubic silicon carbide has attracted great attention for MEMS and electronic devices. However, current leakage at the SiC/Si junction at high temperatures and visible-light absorption of the Si substrate are main obstacles hindering the use of the platform in a broad range of applications. To solve these bottlenecks, we present a new platform of single crystal SiC on an electrically insulating and transparent substrate using an anodic bonding process. The SiC thin film was prepared on a 150 mm Si with a surface roughness of 7 nm using LPCVD. The SiC/Si wafer was bonded to a glass substrate and then the Si layer was completely removed through wafer polishing and wet etching. The bonded SiC/glass samples show a sharp bonding interface of less than 15 nm characterized using deep profile X-ray photoelectron spectroscopy, a strong bonding strength of approximately 20 MPa measured from the pulling test, and relatively high optical transparency in the visible range. The transferred SiC film also exhibited good conductivity and a relatively high temperature coefficient of resistance varying from -12 000 to -20 000 ppm/K, which is desirable for thermal sensors. The biocompatibility of SiC/glass was also confirmed through mouse 3T3 fibroblasts cell-culturing experiments. Taking advantage of the superior electrical properties and biocompatibility of SiC, the developed SiC-on-glass platform offers unprecedented potentials for high-temperature electronics as well as bioapplications.

Can ionic liquid additives be used to extend the scope of poly(styrene)-block-poly(methyl methacrylate) for directed self-assembly?

Abstract. Directed self-assembly (DSA) is a promising approach for extending conventional lithographic techniques by being able to print features with critical dimensions under 10 nm. The most widely studied block copolymer system is polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA). This system is well understood in terms of its synthesis, properties, and performance in DSA. However, PS-b-PMMA also has a number of limitations that impact on its performance and hence scope of application. The primary limitation is the low Flory-Huggins polymer-polymer interaction parameter (χ), which limits the size of features that can be printed. Another issue with block copolymers in general is that specific molecular weights need to be synthesized to achieve desired morphologies and feature sizes. Here we explore blending ionic liquid (IL) additives with PS-b-PMMA to increase the χ parameter. ILs have a number of useful properties that include negligible vapor pressure, tunable solvent strength, thermal stability, and chemical stability. The blends of PS-b-PMMA with an IL selective for the PMMA block allowed the resolution of the block copolymer to be improved. Depending on the amount of additive, it is also possible to tune the domain size and the morphology of the systems. These findings may expand the scope of PS-b-PMMA for DSA.

Healing LER using directed self assembly: treatment of EUVL resists with aqueous solutions of block copolymers

Overcoming the resolution-LER-sensitivity trade-off is a key challenge for the development of novel resists and processes that are able to achieve the ITRS targets for future lithography nodes. Here, we describe a process that treats lithographic patterns with aqueous solutions of block copolymers to facilitate a reduction in LER. A detailed understanding of parameters affecting adhesion and smoothing is gained by first investigating the behavior of the polymers on planar smooth and rough surfaces. Once healing was established in these model systems the methodology is tested on lithographically printed features where significant healing is observed, making this a promising technology for LER remediation.

Electron-Beam-Induced Freezing of an Aromatic-Based EUV Resist: A Robust Template for Directed Self-Assembly of Block Copolymers

Resist freezing is routinely used in lithography applications to facilitate double patterning and the directed self-assembly (DSA) of block copolymers. Previous reports of graphoepitaxy within patterned positive-tone resists used chemical freezing agents which are known to cause significant shrinkage of critical dimensions (CD). We report the “freezing” of an aromatic-based extreme ultraviolet resist by exposure to an electron beam, so did not require the use of chemical agents. Crucially, the process did not lead to significant changes in CD and line edge roughness, where the “frozen” patterns were resistant to treatment with solvents and annealing to temperatures well above the glass transition temperature of the uncrosslinked resist. Finally, we take advantage of these properties and demonstrate the utility of this process for applications in the DSA of block copolymers leading to pattern multiplication.

Electron beam induced freezing of positive tone, EUV resists for directed self assembly applications

The commercialization of 32 nm lithography has been made possible by using double patterning, a technique that allows for an increased pattern density, potentially, through resist freezing and high precision pattern registration. Recent developments in directed self assembly (DSA) also uses resist freezing for stabilizing positive tone resists used in graphoepitaxy. We have developed a method of patterning an open source, positive tone EUV resist using electron beam lithography (EBL), and studied a novel way of freezing a positive tone EUV photoresists through electron beam induced crosslinking. Through metrological analysis, crosslinked pattern was observed to retain consistent critical dimensions (CD) and line-edge roughness (LER) after they were annealed at temperatures higher than the glass transition of the photoresist. This process has been used to freeze patterned EUV photoresists, which have been subsequently used for directed self assembly of PS-b-PMMA and has potential applications in double patterning in an LFLE scenario.

Extending the scope of poly(styrene)-block-poly(methyl methacrylate) for directed self assembly

Directed self-assembly (DSA) is a promising technique for extending conventional lithographic techniques by being able to print features with critical dimensions under 10 nm. The most widely studied block copolymer system is polystyreneblock- polymethyl methacrylate (PS-b-PMMA). The system is well understood in terms of its synthesis, properties and performance in DSA. However, PS-b-PMMA also has a number of limitations that impact on its performance and hence scope of application. The primary limitation is the low Flory-Huggins polymer-polymer interaction parameter (χ), which limits the size of features that can be printed by DSA. Another issue with block copolymers in general is that specific molecular weights need to be synthesized to achieve desired morphologies and feature sizes. We are exploring blending ionic liquid additiveswithPS-b-PMMAto increase the χ parameter. This allows smaller feature sizes to be accessed by PS-b-PMMA. Depending on the amount of additive it is also possible to tune the domain size and the morphology of the systems. These findings may expand the scope of PS-b-PMMA for DSA.

Fabrication of bismuth nanowire devices using focused ion beam milling

In this work, a focused ion beam (FIB) milling process has been developed to fabricate 50 nm Bi nanowire and transistor structures using FEI‐200 dual beam FIB system. For the fabrication, 50 nm bismuth film was thermally evaporated through EBL patterned PMMA windows onto SiO2 substrates with pre‐defined contact pads. Bi nanowire widths ranging from 30 nm to 100 nm have been successfully fabricated by milling out unwanted areas using 30 KeV Ga+ ion beam. A single‐pixel‐line ion beam blanking technique has been utilised to fabricate Bi nanowire as small as 30 nm in diameter and few micrometers long. In order to form good ohmic contacts for sub 50 nm bismuth nanowires, a drill‐and‐fill process has been developed using FIB to sputter away the surface oxide of bismuth after the in‐situ platinum nanowire contacts deposition. To our knowledge, this is the first time a focused ion beam process has been used to fabricate bismuth nanowire. The fabricated Bi nanowires were electrically characterised using a semicond...