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Table of contents
- Woodhead Publishing Series in Electronic and Optical Materials | Tanum nettbokhandel
- Nanolithography and Patterning Techniques in Microelectronics (Woodhead Publishing in Materials)
- ISBN 13: 9781855739314
- Knovel offers following tools to help you find materials and properties data
- Alexandre Martha
Chan V. Foucher D. Lammertink R.
Woodhead Publishing Series in Electronic and Optical Materials | Tanum nettbokhandel
Zehner R. Spatz J. Morkved T. Chou S. IEEE, 85 4 — Shin K. Jeong U. Park C. Lazzari M. Angelescu D. Thesis, Princeton University, Kim S. Block copolymer nanolithography 37 Rockford L. Trawick M. Segalman R. Amundson K. De Rosa C. Keller A. Sundrani D.
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Kimura M. Morrison F. Hadziioannou G. Almdal K. Chen Z. Zhuang L. Because these components are typically incompatible and confined between surfaces, phase growth is hindered and the wetting behavior at surfaces grows in importance due to the high surface to volume ratio. The complex interplay between wetting and phase separation in thin film polymer blends provides an opportunity to vary the morphology in a systematic fashion over length scales ranging from tens of nanometers to tens of microns. Although these features are larger than those possible with conventional lithographic methods, manipulating wetting and phase separation to control feature size is more facile, requiring only one or two steps to make well-defined, complex structures, and much less expensive.
Moreover, combining polymer film technology with soft-lithographic methods provides a simple route for pattern replication.
Nanolithography and Patterning Techniques in Microelectronics (Woodhead Publishing in Materials)
Thus, patterning of thin film polymer blends has the potential to replace conventional lithographic methods to create meso-scale structures. The greatest hurdle to control pattern formation in thin film polymer blends is in understanding the dynamic interplay between phase separation, wetting and dewetting. Because of the slow dynamics of polymers, nonequilibrium patterns can be frozen during morphology evolution leading to unstable structures. Thus, the dynamics of phase separation and wetting will be considered in this chapter.
For example, after quenching into a thermodynamically unstable regime of temperature-composition, a homogeneous polymer mixture will undergo a spontaneous demixing process, which is called a spinodal decomposition1. This process leads to isotropic pattern development in bulk with a periodicity that follows dynamic scaling analysis2.
ISBN 13: 9781855739314
However, if the mixture is confined to a film, preferential wetting 39 40 Nanolithography and patterning techniques in microelectronics of one component at the surface is dynamically coupled with phase separation, causing the formation of alternating layers with oscillating concentrations, i. When the phase size approaches the film thickness, domain growth changes from 3D to pseudo-2D, followed by the growth of a well defined lateral pattern4,5,6.
As an additional complication, films can rupture by dewetting leading to roughened surfaces7,8. In summary, pattern formation in thin film polymer blends requires an understanding of the complex dynamic interplay between phase separation, wetting and dewetting.
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The purpose of this chapter is to consolidate in one place the most recent developments in the area of surface-induced pattern formations in thin film polymer blends. Because it is the technologically most useful geometry, the chapter will be limited to films deposited on a substrate with a free surface i. Because of its practical use, phase morphologies occurring at deep quenches will be considered rather than those near criticality, such as wetting transitions.
We limit our scope to the studies of lateral pattern formation, which have the potential to compete with conventional lithography. Consequently, experimental studies of wetting and dewetting will receive limited attention in this chapter. Pattern evolution in blends containing one or more crystallizing components9,10,11,12,13 is also beyond the scope of this chapter. The content of this chapter is related to other chapters including Chapter 1 which describes how copolymer ordering produces patterns and Chapter 5 where dewetting of confined polymer films is used to create topographic features.
Several reviews related to the subject of this chapter fill in several of the topics not covered. For example, the dynamic properties of phase separation are reviewed by Gunton et al. A recent review by Binder14 covers the theory describing the interplay between surface and finite size effects, the key topics underpinning thin film phase behavior.
Surface segregation and wetting phenomena are extensively covered in the review by Budkowski This work includes an extensive review of experimental studies along with related theories. A comparison with an earlier review by Krausch16 shows how rapidly this field developed. Theories of phase transitions in polymer blends under confinement are reviewed by Binder This review is particularly interesting because it compares theories and experiments from the point of view of a theorist; we note that the theories are limited to planar boundaries i.
A recent review by Geoghegan and Krausch18 summarizes developments in thin film polymer blends, including wetting, phase separation, and dewetting. This review also presents studies of lateral pattern formation in polymer blends. Finally, the role of hydrodynamics in pattern evolution of polymer solutions and melts are reviewed by Tanaka4. Because hydrodynamics Surface-induced structure formation of polymer blends 41 has been found to play a role even in the demixing of viscous polymer melts, this review is particularly relevant.
This chapter is organized as follows. Section 2. Techniques are classified as either depth profiling or lateral imaging; an introduction to the next generation of techniques such as those that provide 3D information is provided. In section 2. First, pattern evolutions under symmetric wetting conditions ABA are discussed. Here, the dynamic interplay between wetting and phase separation plays a crucial role and eventually thin films rupture by dewetting.
Secondly, pattern evolutions under asymmetric wetting conditions AB are discussed. Here, growing wetting layers eventually form a bilayer structure, and eventually dewetting may occur.
Thirdly, morphology evolutions on chemically or structurally patterned substrates are discussed. Alternating boundary conditions cause a phase confinement, resulting in pattern replication. Finally, solvent-induced structure formation is discussed.
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Although the resulting structures are difficult to control and are unstable, this method of structure formation deserves attention because cosolvents that equally solubilize all polymer components are difficult to achieve in practice. Thus, this method may have the broadest practical application of all previously mentioned processing routes. In this case, thermodynamics determines whether the mixture develops co-existing phases whereas kinetics predicts time-dependent phase development. Thermodynamically, phase behaviors can be defined from the free energy density of mixing, F c.
However, recent theoretical development points out that the linear theory is incorrect due to the nonlinear coupling between waves and thus lm increases with time When the compositional fluctuation develops to fully co-existing phases, interfaces between phases become sharp. Correspondingly, well-defined phase domains continue to grow, characterizing the late stage of spinodal decomposition. Kinetics of the late stage of spinodal decomposition is described using a dynamic scaling hypothesis, which proposes that a dominant length scale characterizes domain growth at the late stage1.
Scaling arguments predict that the growth exponent a indicates the mechanisms of domain growth. In this case, molecular diffusion of the minority component in the majority phase controls the growth. Alternatively, Binder and Stauffer23 predicted that domains migrate as a Brownian motion and occasional coalescence drives domain growth. In polymer mixtures, however, inphase material flow becomes important when minority phases are percolated i.
For thin film polymer blends, however, confinement induces many complications in phase separation. For example, the phase diagram of a confined system differs from the bulk In addition, thickness confinement induces a dimensional change of phase separation from 3D to pseudo-2D, causing a change in the growth mechanism4,5,6. Most importantly, morphology development is greatly perturbed by wetting phenomena because of a large surface to volume ratio in thin film geometry.
A dramatic example is the surface-directed spinodal decomposition SDSD 3 , where spinodal decomposition acquires anisotropy due to the surface effect, resulting in a formation of layered structure parallel to the surface. Naturally, transient and final morphology cannot be interpreted without understanding wetting phenomena. Surface-induced structure formation of polymer blends 2.