PONDICHERRY UNIVERSITY

Department of Nanoscience & Technology ASSIGNMENT ON:

NANOLITHOGRAPHY

Submitted toDr. A. Vadivel Murugan Reader

Submitted byMohammad Rameez 1st Yr. M.Tech

Table of Contents
Introduction ........................................................................................................................................... 2 Scanning Probe lithography................................................................................................................. 3 Soft lithography and nanoimprint lithography .................................................................................. 5 Dip-pen nanolithography (DPN).......................................................................................................... 8 Nanosphere lithography (NSL) ............................................................................................................ 9 Nanostensil Lithography .................................................................................................................... 11 Summary.............................................................................................................................................. 12 References ............................................................................................................................................ 13

Introduction
Nanolithography is the branch of nanotechnology concerned with the study and application of fabricating nanometre-scale structures, meaning patterns with at least one lateral dimension between the size of an individual atom and approximately 100 nm. Nanolithography is used during the fabrication of leading-edge semiconductor integrated circuits (Nano circuitry) or nanoelectromechanical systems (NEMS). As of 2012, nanolithography is a very active area of research in academia and in industry.

Scanning Probe lithography

AFM nanolithography has shown itself to be a unique tool for materials structuring and patterning with nanometer precision. AFM was invented in 1986 for use as a microscope to directly image the surface morphology with atomic and molecular resolution. The morphological image of a surface is obtained by recording and regulating the forces felt by a probe as it scans the surface. AFM can be used to study both insulating and conducting materials, and can be operated in liquid, air or vacuum. The working principle of AFM nanolithography is based on the interaction between the probe and substrate. The typical radius of curvature of the probe is 2060 nm, and the probesubstrate separation in close contact condition is <1 nm. When suitable forces are exerted, and/or external fields applied, the probe can induce various physical and chemical processes on the substrate surface. Consequently, localized nanostructures are generated through physical modifications and/or chemical reactions of the surface materials. AFM nanolithography possesses the versatility to pattern a wide range of materials including metals, semiconductors, polymers and biological molecules in different media. Due to its nanoscale positioning and imaging capability, AFM nanolithography is uniquely able to create site-specific and localized functional structures. Moreover, the morphological and physical properties of patterns formed can be immediately characterized with AFM by integrating additional measurement modules. This combined fabrication and characterization function in AFM nanolithography allows convenient in situ and in-line pattern creation and characterization. Numerous AFM-based lithographic techniques have been developed in the last two decades. Generally, these techniques can be classified into two groups in terms of their operational principles: (i) force-assisted AFM nanolithography; (ii) bias-assisted AFM nanolithography (see Fig). In force-assisted AFM nanolithography, a large force is applied to the tip for pattern fabrication, and the tipsurface interaction is mainly mechanical. Typical methods in this category include mechanical indentation and plowing, thermomechanical writing, nanomanipulation, and dippen nanolithography (DPN). During force-assisted nanolithography, forces larger than those used for AFM imaging are loaded onto the tip. The initially featureless surface is then patterned by mechanically scratching, pulling, or pushing the surface atoms and molecules with the probe. In DPN, instead of manipulating the existing molecules on the surfaces, the tip is used as a nanoscale pen to directly deposit collections of ink materials onto the substrate to define a functional structure. As for bias-assisted AFM nanolithography, the AFM tip is biased to create a localized electric field in the regime of 108 V/m to 1010 V/m, and the

tip acts as a nanoscale electrode for current injection or collection. Under such a high localized field, electrostatic, electrochemical, field emission, dielectric breakdown and explosive gas discharge processes can be initiated to facilitate pattern formation. Depending on the magnitude of tip bias and substrate materials, the application of tip voltage can lead to anodic oxidation, (a) Forceassisted and (b) bias-assisted AFM nanolithography.electrochemical deposition, electrostatic attraction, and nanoscale explosion and shock wave propagation. In anodic oxidation, the tip is negatively biased, and the local field induces the ionic dissociation of a water meniscus formed between the tip and sample surface. The oxidative OHanions migrate along the field and react with the substrates to form oxide structures. Electrochemical deposition is capable of generating positive structures with distinct physio-chemical properties from the precursor materials through bias- induced local chemical reactions.
(a) Force-assisted and (b) bias-assisted AFM nanolithography

Soft lithography and nanoimprint lithography

Soft lithography arose from the innovation of using a relatively soft polymer stamp to imprint a solution of molecules (ink) onto a substrate for pattern transferring. This technique requires inexpensive materials and employs nonspecialized equipment. It was first introduced by Bain and Whitesides in1989.This process can be separated into two main steps: the fabrication of a patterned polymer stamp, and the use of this stamp to transfer molecules in geometries defined by the elements relief structure. Figure depicts the schematic illustration of soft lithography. The uniqueness of this technique is on the utilization of a soft stamp for pattern transferring, thus it allows a conformal contact between the stamp and the substrate resulting in a patterning capability on flexible or curved substrates. Similar to soft lithography, nanoimprint lithography utilizes a hard mold to imprint into a polymer film for nanoscale patterning. Nanoimprint lithography has emerged as a candidate for nextgeneration manufacturing methods as it has great potential to circumvent the issues in photolithography, thereby, promising a high-throughput and highresolution method with a relatively low cost. Nanoimprint lithography was first introduced by S.Y. Chou ashot embossing technique enabling the definition of features with lateral sizes down to sub-10 nm.The procedure of imprinting lithography is shown in Fig. The technique heats thermoplastic polymer above its glass transition temperature enables material flow, filling the structures of a mold. After that, its temperature is lowered and the replicated patterns are solidified in place, after which the mold is removed. The most commonly used materials for mold have been quartz and silicon that are kinds of hard material. Typically, mold features are patterned by using conventional lithography techniques such as photolithography and electron beam lithography. A hard material offers a number of advantages for nanofabrication. The rigidity retains nanoscale features with minimal local deformation.Moreover, a hard mold is thermally stable at high temperature. Although nanoimprint lithography has made a great progress in a relatively short time, there are few issues to be resolved. One of them is life time of the mold. Heating/cooling cycles and high pressure, applied during embossing, cause stress and wear on molds. This stress also presents a problem of alignment for multi-layer fabrication. Viscosity of embossed material is also an important issue. It appears to be a limiting factor for minimizing pattern size and increasing feature density. In 1996, nanoimprint lithography was devised through the introduction of a low-viscosity UV-curable monomer as compliant polymer layer in order to enhance fluidity of the embossed material. The process is called UV-nanoimprint as schematically

shown in Fig.(right). After imprinting on a UV-curable monomer layer, broadband UV light radiation directly through the backside of the transparent mold causes the monomer crosslink, forming a rigid polymer. It can reduce imprint pressures significantly and avoid time consuming as well as stress induced during high temperature cycle. UV-curable monomers are very important factor for a success of UV-nanoimprint technique. For this technique, the UVcurable Amonil polymer (AMO GmbH, Germany) with a viscosity of about 50 mPas was used in many works, while a novel low-viscosity polymer with a viscosity of about one third that of Amonil and spin ability down to 150 nm thick has been recently developed.

Fig. Schematic illustration of soft lithography

Schematic illustrations of hot-embossing imprint nanolithography

UV-imprint nanolithography

Dip-pen nanolithography (DPN)

In 1999, Mirkins group invented the DPN technique to deliver collections of molecules in a positive printing mode. DPN is an AFM-based direct-write lithographic technique in which the AFM probe is used as a pen to directly deliver materials (inks) to a nanoscopic region on a target substrate. In most cases, the transport of ink molecules from the tip to the substrate is mediated by a water meniscus which is formed through capillary condensation. Depending on the selection of ink molecules, DPN is capable of creating structures made of various materials such as metal, inorganic compounds, organic molecules, and biological species. The fabrication of a wide range of functional structures by DPN has been demonstrated, and some of the typical structures include high resolution organic features, metallic and magnetic patterns, polymer brush arrays, and biological devices. Acomprehensive and dedicated description on the evolution of DPN can be found in a recent review article by Mirkin and coworkers. The resolution of DPN depends on several parameters: The grain size of the substrate the texture of paper controls the resolution of conventional writing.chemisorptions and self assembly can be used to limit the diffusion of the molecules after deposition. The tip-substrate contact time and thus the scan speed influence DPN resolution.by controlling the rate of ODT transport from the tip to the substrate. Relative humidity seems to affect the resolution of the lithographic process The size of the water meniscus that bridges the tip and substrate depends on relative humidity

Nanosphere lithography (NSL)

Nanosphere lithography (NSL), the subject of this project, is an inexpensive, material specific and high-output nanostructure fabrication process which can systematically produce a 2-D array of periodic structures. It makes use of placing nanospheres in a tightly packed pattern on a substrate in order to create a mask for pattern transfer. By removing the spheres after thin film deposition or etching, the remaining 2-D array on the substrate has triangular shaped nanostructures in a hexagonal pattern, often called a Fischer pattern. Nanosphere Lithography can be performed using several techniques, each with different variables that will affect the overall size, shape, and uniformity of the nanostructures. In order to minimize the feature size, a mask more complicated than a single layer of nanospheres is required. As the mask increases in complexity, the parameters that need to be adjusted in order to create a uniform pattern also increase. Previous groups who attempted to create nanostructures using a double layer mask ran into difficulties. Due to this fact, it was believed that understanding the method for creating a uniform single layer must first be explored in order to create a more complex mask. To create a single layer of nanospheres, cover slips were initially cleaned with a strong acid and then rinsed with deionized water. Half the cover slips were treated with 3Aminopropyltriethoxysilane (APTES) to alter the surface charge of the cover slips for better adhesion. Polystyrene spheres with a 1um diameter were then diluted into five different concentrations ranging from 107 to 1010 particles/ml. The solutions were drop-coated onto the cover slips, which had been dried with nitrogen. Each concentration was dropped onto two slips, one treated and the other untreated with APTES. The samples were covered and allowed to dry overnight before being viewed with the optical microscope. Samples that had the largest region of a uniform hexagonal close pack were coated in a thermal evaporator with thin films of approximately 10 nm of titanium followed by 100 nm of gold. Using scotch tape, the spheres were removed from the cover slips. While complete removal of the spheres was desired, some were left attached to the cover slips by this method. The samples were viewed by scanning electron microscopy(SEM) and Fischer Patterns were observed over large areas. The concentration which resulted in the largest single layer uniform close pack was 5x109 particles/ml on a cover slip not treated with APTES, which can be seen in Figure 1a. Samples with lower concentrations displayed sparse areas of tightly packed spheres, while higher concentrations produced multilayers. The resulting Fischer Pattern after the removal of the spheres can be seen in Figure 1c. The APTES treated cover slips did not significantly enhance the uniformity of patterns, which could be explained as below. First, this could be due to the limited

sample size of our experiments. Second, given that the spheres were dropcoated onto the cover slips, if the surface charge condition was not optimized, the spontaneous spreading of the spheres could be hindered hence the uniformity of the patterns was weakened.

Nanostensil Lithography
The Nanostensil technique is a patterning method based on shadow mask

evaporation A thin membrane is used as a solid mask to transfer the patterns from

the membrane to the substrate during the evaporation.

Summary
Lithography technology has contributed to the advance in the semiconductor and IC industry as well as the success of commercial MEMS devices. For the past decades, photolithography has been the key technology in manufacturing of ICs, microchips and MEMS devices including micro accelerometers, DMDs, MEMS pressure sensors, micropumps, microvalves, optical switches, inkjet heads, microgrippers, and microactuators. Alternative lithography techniques have been extensively developed for specific applications: electron beam and focused ion beam lithographies for nanoscale patterning in R&D, photo-mask fabrication and ICs production, soft lithography for a wide range of LOC applications, nanoimprint lithography for bio-sensors, bio-electronics, nano channels, and nano wires, dip-pen lithography for bio-electronics, bio-sensors, and gas sensors. Among them, nanoimprint lithography has sturdily emerged as it is able to circumvent the issues in conventional lithography technology, thereby, allowing a high-throughput and high-resolution method with a relatively low cost. Nanolithography technology is also shaping the future of nanoscience and technology. This emerging discipline provides alternative routes to overcome current technical barriers in many areas including nanoelectronics, nanomedicine, nanoelectromechanical systems, and nanobiosensors. Such a dramatic advancement in nanoscience and technology is leading to technology revolutions in a broad range from next-generation electronic devices to healthcare systems, from cosmetics to textiles, and from agriculture to high-tech businesses.

References
[1] R. F. Pease and S. Y. Chou, Lithography and other patterning techniques for future electronics, Proc. IEEE, vol. 96, pp. 248-270, 2008. [2] B. D. Gates, Q. Xu, M. Stewart, D. Ryan, C. G. Willson, and G. M. Whitesides, New approaches to nanofabrication: Molding, printing, and other techniques, Chem. Rev., vol. 105, pp. 1171-96, 2005. [3] R. Menon, A. Patel, D. Gil, and H. I. Smith, Maskless lithography, Mater. Today, vol. 8, pp. 26-33, 2005. [4] G. L. T. Chiu and J. M. Shaw, Optical lithography: introduction, IBM J. Res. Develop., vol. 41, pp. 3-6, 1997. [5] W. M. Moreau, Semiconductor lithography: Principles, Practices and Materials. Plenum Publishing, 1988. [6] D. J. Elliott, Integrated circuit fabrication technology, 2nd ed. McGraw-Hill Book, 1989. [7] A. R. Neureuther, J. Rubinstein J, E. Chin, L. Wang, M. Miller, C. Clifford, and K. Yamazoe, Modeling Optical Lithography Physics, Jpn.. J. Appl. Phys., vol. 49, 06GA01, 2010. [8] D. P. Sanders, Advances in patterning materials for 193 nm immersion lithography, Chem. Rev., vol. 110, pp. 321-360, 2010.