The extensive benefits of the new generation of nanostructured surfaces is very promising for enhancing light absorption efficiency in photonic devices. However, the low throughput and the high cost of available technologies such as lithography for fabrication of nanostructures has proved to be a difficult technological hurdle for advanced manufacturing. In this research we present a solution based process based on high molecular weight block copolymer (BCP) nanolithography for fabrication of periodic structures on large areas of optical surfaces. Block copolymer self- assembly technique is a solution based process that offers an alternative route to produce highly ordered photonic crystal structures. BCPs forms nanodomains (5-10 nm) due to microphase separation of incompatible constitute blocks. The size and shape of the nanostructure can be customised by the molecular weight and volume fraction of the polymer blocks. However, the major challenge is BCPs do not phase separate into their signature ordered pattern above 100 nm, whereas for nanofeatures to be used as photonic gratings, they must be greater than 100 nm (typically ¼ wavelength). This is due to significant kinetic penalty arising from higher entanglement in high molecular weight polymers. In this work we present the results of exploiting commercially available block copolymers to phase separate into periodic domains greater than 100 nm. The process do not include any blending with homopolymers, or adding colloidal particles, and to our best knowledge, has not been yet achieved or reported in the literatures. We have pattern transferred the BCP mask to silicon substrate by reactive ion etch (ICP-RIE). The final product is black silicon, consists of hexagonally packed conic Si nanofeatures with diameter above 100nm and periodicity of 200 nm. The height of the Si nanopillars varies from 100 nm to 1 micron. We have characterized the angle dependent optical reflectance properties of the black silicon. The antireflective properties of the Si nanofeatures were probed in the 400 nm – 2500 nm wavelength range and compared to an Au reflectance standard. As the subwavelength grating is made from the same material as the substrate (Si), the index matching at the substrate interfaces has lead to highly improved antireflecting performance. The reflectivity of the silicon substrate shows one order of magnitude reduction in a broad range of wavelength from NIR to UV-visible, below 1%. The simplicity of the solution based large block copolymer nanolithography and the capability of integration to existing fabrication process, makes this novel technique a very attractive alternative for manufacturing photonic crystals on large, arbitrary shaped and curved objects such as photovoltaics and IR camera lenses for medical imaging.
Bottom-up alternative lithographic masks from directed self-assembly systems have been extending the limits of critical
dimensions in a cost-effective manner although great challenges in controlling defectivity remain open. Particularly,
defectivity and dimensional metrology are two main challenges in lithography due to the increasing miniaturisation of
circuits. To gain insights about the percentage of alignment, defectivity and order quantification, directed self-assembly
block copolymer fingerprints were investigated via an image analysis methodology. Here we present the analysis of
hexagonal phase of polystyrene-b-polydimethylsiloxane (PS-b-PDMS) forming linear patterns in topological substrates.
From our methodology, we have performed dimensional metrology estimating pitch size and error, and the linewidth of
the lines was estimated. In parallel, the methodology allowed us identification and quantification of typical defects
observable in self-assembly, such as turning points, disclination or branching points, break or lone points and end points.
The methodology presented here yields high volume statistical data useful for advancing dimensional metrology and
defect analysis of self- and directed assembly systems.
Helium ion microscopy (HIM) has been used to study nanopatterns formed in block copolymer (BCP) thin films. Owing to its’ small spot size, minimal forward scattering of the incident ion and reduced velocity compared to electrons of comparable energy, HIM has considerable advantages and provides pattern information and resolution not attainable with other commercial microscopic techniques.
In order to realize the full potential of BCP nanolithography in producing high density ultra-small features, the dimensions and geometry of these BCP materials will need to be accurately characterized through pattern formation, development and pattern transfer processes. The preferred BCP pattern inspection techniques (to date) are principally atomic force microscopy (AFM) and secondary electron microscopy (SEM) but suffer disadvantages in poor lateral resolution (AFM) and the ability to discriminate individual polymer domains (SEM). SEM suffers from reduced resolution when a more surface sensitive low accelerating voltage is used and low surface signal when a high accelerating voltage is used. In addition to these drawbacks, SEM can require the use of a conductive coating on these insulating materials and this reduces surface detail as well as increasing the dimensions of coated features. AFM is limited by the dimensions of the probe tip and a skewing of lateral dimension results. This can be eliminated through basic geometry for large sparse features, but when dense small features need to be characterized AFM lacks reliability. With this in mind, BCP inspection by HIM can offer greater insight into block ordering, critical dimensions and, critically, line edge roughness (LER) a critical parameter whose measurement is well suited to HIM because of its’ enhanced edge contrast.
In this work we demonstrate the resolution capabilities of HIM using various BCP systems (lamellar and cylinder structures). Imaging of BCP patterns of low molecular weight (MW)/low feature size which challenges the resolution of HIM technique. Further, studies of BCP patterns with domains of similar chemistry will be presented demonstrating the superior chemical contrast compared to SEM. From the data, HIM excels as a BCP inspection tool in four distinct areas. Firstly, HIM offers higher resolution at standard imaging conditions than SEM. Secondly, the signal generated from He+ is more surface sensitive and enables visualization of features that cannot be resolved using SEM. Thirdly; superior chemical contrast enables the imaging of un etched samples with almost identical chemical composition. Finally, dimensional measurement accuracy is high and consistent with requirements for advanced lithographic masks.
Multilevel controllable nanoimprint driven molecular orientation has been obtained in thin films of block copolymer polystyrene-b-polyethylene oxide( PS-b-PEO) by means of solvent vapours assisted nanoimprint lithography (SAIL). The NIL setup using solvent vapours was capable of imprinting nanoscale features over a large area and simultaneously annealing PS-b-PEO thin films. A line pattern stamp was replicated in the BCP film in over a large area with a high resolution registry, and was also observed that the PS-b-PEO film exhibited microphase segregation in the residual layer exhibits a nanodot array from showing hexagonally packed PEO dots in the PS matrix, with a diameter of 20 nm with 40 nm pitch. The order of the hexagonally arranged nanodot lattice seen in the nanodots array was quantified from SEM images using by the opposite partner method from SEM images analysis and compared with to conventionally solvent annealed BCP films, demonstrating an improvement of the ordering of up to 50%. Grazing-incidence small-angle X-ray scattering (GISAXS) study demonstrates the excellent fidelity of the pattern transfer and confirms the periodicity of the BCP in the mesas. In addition, applying the SAIL methodology to BCP thin films in nanopatterned silsequioxane substrates, it was possible to obtain multilevel structures decorated with the BCP microphase segregation. The SAIL technique is a versatile and robust platform to obtain complex high density periodic nanostructures, particularly for second generation block copolymers directed self-assembly.
This paper outlines alternative uses of block copolymer (BCP) patterning compared to their well-researched exploitation in defining silicon circuitry and interconnects. The challenge in these alternative applications is usually to define ‘active’ patterns of materials other than silicon and instead of using the self-assembled block copolymer pattern as a means to form an on-chip etch mask, to use it as a template for deposition of functional components. In this paper we briefly discuss progress in the field of block copolymer patterning and some potential applications. The paper will then outline two examples in the area of sensing and antimicrobial surfaces. Here, polystyrene-b-polyethylene oxide (PS-b-PEO) is used as a suitable template as it forms well-ordered arrangements on several substrate types. The PEO block can then be used as a host block towards precursor inclusion from solution because of its’ selective chemistry. Onward processing then creates a pattern of included materials that mimics the original BCP arrangement. To demonstrate the potential of these methods we illustrate examples as sensors and antimicrobial surfaces which both take advantage of the small feature size, high surface area and coverage that can be attained by these techniques.
The line patterns obtained by the self-assembly of the block copolymer (BCP) polystyrene-b-polyethylene oxide (PS-b-PEO)
was investigated. The hexagonal PS-b-PEO 42k-11.5k in a thin film was solvent annealed in a chlorophorm saturated
atmosphere for three different annealing times. The microphase segregation of this BCP returned 18nm cylinders of PEO
through the PS matrix, with an approximately 40 n periodicity, as expected. Under chlorophorm vapours, the PEO cylinders
oriented perpendicular to the silicon substrate while increasing the annealing time. These cylinders formed linear patterns
with different alignment. To achieve insights about the percentage of alignment, defect type pareto and density, and order
quantification to compare the three annealing recipes, the samples were analysed with innovative image analysis software
specifically developed in our laboratory to identify elements and defects of line arrays from block copolymer self-assembly.
From this technique, it was extracted dimensional metrology estimating pitch size and placement error, and the line-width of
the lines was estimated. Secondly, the methodology allows identification and quantification of typical defects observable in
BCP systems, such as turning points, disclination or branching points, break or lone points and end points. The defect density
and the quantification of the alignment were estimated using our technique. The methodology presented here represents a
step forward in dimensional metrology and defect analysis of BCP DSA systems and can be readily used to analyze other
lithographic or non-lithographic patterns.
Different linear patterns obtained from the directed self-assembly of the block copolymer (BCP) polystyrene-b-polyethylene oxide (PS-b-PEO) were analysed and compared. The hexagonal phase PS-b-PEO in a thin film exhibits linear pattern morphology, by conventional solvent annealing in an atmosphere saturated in chloroform. The surface energy of the silicon substrates was varied using surface functionalization of a self-assembly monolayer (SAM) and a polymer brush, chosen to investigate the influence of the surface energy on the self-assembly of the BCP. The linear patterns formed were analyzed with innovative image analysis software specifically developed in our laboratory to identify elements and defects of line arrays from block copolymer self-assembly. The technique starts by performing dimensional metrology to calculate the pitch size and estimate the linewidth of the lines. Secondly, the methodology allows identification and quantification of typical defects observable in BCP systems, such as turning points, disclination or branching points, break or lone points and end points. The defect density and the quantification of the alignment were estimated using our technique. The methodology presented here represents a step forward in dimensional metrology and defect analysis of BCP DSA systems and can be readily used to analyze other lithographic or non-lithographic patterns.
The nanometer range structure produced by thin films of diblock copolymers makes them a great of interest as templates
for the microelectronics industry. We investigated the effect of annealing solvents and/or mixture of the solvents in case
of symmetric Poly (styrene-block-4vinylpyridine) (PS-b-P4VP) diblock copolymer to get the desired line patterns. In this
paper, we used different molecular weights PS-b-P4VP to demonstrate the scalability of such high χ BCP system which
requires precise fine-tuning of interfacial energies achieved by surface treatment and that improves the wetting property,
ordering, and minimizes defect densities. Bare Silicon Substrates were also modified with polystyrene brush and ethylene
glycol self-assembled monolayer in a simple quick reproducible way. Also, a novel and simple in situ hard mask technique
was used to generate sub-7nm Iron oxide nanowires with a high aspect ratio on Silicon substrate, which can be used to
develop silicon nanowires post pattern transfer.
We report a simple technique to fabricate horizontal, uniform Si nanowire arrays with controlled orientation and density
at spatially well defined locations on substrate based on insitu hard mask pattern formation approach by microphase
separated polystyrene-b-poly(ethylene oxide) (PS-b-PEO) block copolymer (BCP) thin films. The methodology may be
applicable to large scale production. Ordered microphase separated patterns of the BCP were defined by solvent
annealing and the orientation was controlled by film thickness and annealing time. Films of PEO cylinders with parallel
orientation (to the surface plane) were applied to create ‘frames’ for the generation of inorganic oxide nanowire arrays.
These PEO cylinders were subject to selective metal ion inclusion and subsequent processing was used to create iron
oxide nanowire arrays. The oxide nanowires were isolated, of uniform diameter and their structure a mimic of the
original BCP nanopatterns. The phase purity, crystallinity and thermal stability of the nanowires coupled to the ease of
large scale production may make them useful in technological applications. Here, we demonstrate that the oxide
nanowire arrays could be used as a resist mask to fabricate densely packed, identical ordered, good fidelity silicon
nanowire arrays on the substrate. The techniques may have significant application in the manufacture of transistor
circuitry.
Tailored pore size mesoporous silica, incorporating different concentrations of transition metal-based catalysts, has been used as platforms for the growth of carbon nanotubes by the catalytic chemical vapor deposition method. Both compositional surface analysis by EDX/SEM combinatory techniques and thermo gravimetric analysis were employed to characterize the samples prior to CNT growth. The CNTs produced were characterized using Raman Spectroscopy, high resolution SEM and TEM. Raman spectroscopy showed good quality highly graphitic CNTs and indicated the presence of crystalline graphitic carbon, microcrystalline graphite as well as amorphous carbon in the carbon nanotube layer. TEM and HI RES SEM images matched diameters of the carbon nanotubes to the corresponding pores of the matrices. Comparison of the carbon nanotube diameters to porous properties of the mesoporous silica confirmed probable growth from within the pores. The density of the carbon nanotubes was found to be high for higher metal concentrations for the same pore diameters. Fe and Co were confirmed to be better catalysts, compared to Ni, for growth of carbon nanotubes by the catalytic chemical vapour method.
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