Positron Annihilation Spectroscopy PAL

Furthermore, in addition to the bulk thermal properties of polymers and resists, determination of Tg of film interfaces and of ultrathin films has become an important issue in thin film imaging (bilayer, 157 nm, and EUV). Various techniques have been employed, which include ellipsometry [481,482], positron annihilation spectroscopy (PALS) [483], QCM [484], scanning viscoelasticity microscope (SVM) [485],x-ray reflectivity [486,487], and thermal probe [488]. 

Figure 4.6 (a, b) Pore size distributions can be measured through a variety of techniques—including eUipsometric porosimetry (EP) and Positron Annihilation Spectroscopy (PALS) (Reprinted with permission from Gates et al., 2007a, 2009a). 

Positron Annihilation Spectroscopy (PALS) can investigate the free volume existing between polymer chains. The lifetime of particles (positrons) injected into a sample can thus provide information on the void structure existing in polymers and polymer blends. For immiscible polymers, free volume existing at the interface due to poor adhesion can be detected by PALS. In miscible polymers, densification due to favorable interactions may be capable of determination. This technique involves the injection of positrons into a polymeric system from a radioisotope capable of emitting positrons, such as Na. The positrons (positively charged electrons) combine with electrons to annihilate or to form a bound state called a positronium (Ps). If the spins of the positron and electron are antiparaUel, para-positroniums (pPS) with a lifetime of 0.125 ns are formed. If the spins of the positron and electrons are parallel, an orthopositronium (oPs) is formed with a lifetime of 1-5 ns. The oPs hfetime, Ts, is related to the free volume cavity in which the oPs is formed [388,389]. 

Positron annihilation spectroscopy (PALS) is a technique of free volume determination in polymers that involves the injection of subatomic particles and the measurement of their decay times. This technique can be very sensitive to the degree of miscibihty and free volume behavior of polymer blends. The concept of free volume is important to understand polymer characteristics in the glassy state. For instance, PALS was used to evaluate the free volume sites of thermotropic hquid crystalline polymer blends. These blends presented smaller and fewer free volume sites than expected from a weighted average due to their intrinsic affinity. This is interesting because in contrast to thermoplastic blend results, the degree of blend miscibility alters free volume behavior as a function of blend composition [106]. In addition, the order and the dynamics in the mesophase can be accessed by nuclear magnetic resonance [107]. 

Spectroscopy, 490. See also 13C NMR spectroscopy FT Raman spectroscopy Fourier transform infrared (FTIR) spectrometry H NMR spectroscopy Infrared (IR) spectroscopy Nuclear magnetic resonance (NMR) spectroscopy Positron annihilation lifetime spectroscopy (PALS) Positron annihilation spectroscopy (PAS) Raman spectroscopy Small-angle x-ray spectroscopy (SAXS) Ultraviolet spectroscopy Wide-angle x-ray spectroscopy (WAXS)... 

For future high-speed microelectronic devices, copper interconnection with low dielectric constant (low-k) interlayer films is required to decrease RC (R interconnect resistance, C interlayer dielectric capacitance) delay. Recently, porous Si02 and silica-based films, developed for low-k films, have been extensively studied by positron annihilation spectroscopy [28], [29], [19]. Since Ps formation occurs with high probability, and the o-Ps annihilate via pick-off process in Si02-based materials, positron annihilation spectroscopy (especially PALS) gives useful information on the size of the pores. 

In recent years, positron annihilation lifetime (PAL) spectroscopy has been demonstrated to be a special sub-nanometer probe to determine the free-volume hole size, fraction and distribution in a variety of polymers (4-9). In this technique, measured lifetimes and relative intensities of the positron and positronium, Ps (a bound atom which consists of an electron and a positron), are related to the size and fraction of sub-nanometer holes in polymeric materials. Because of the positive-charge nature, the positron and Ps are repelled by the ion core of polymer molecules and trapped in open spaces, such as holes, free volumes, and voids. The observed... 

Positron annihilation lifetime spectroscopy (PALS) can be used to measure the free volume in various materials. Jean et al. discussed the application of positron annihilation spectroscopy (PAS) in the detailed study of polymers and polymers with fillers. The primary experimental PAS technique used in this research is PALS, one of the three techniques in the PAS family and a powerful tool for measuring the free volume in various materials. The free volume has a great role in polymer research and is widely used to explain the behaviour of physical properties such as glass transition temperature, viscosity and physical ageing. Free volume is affected by the blending of polymers, ageing and addition... 

The free volume (FV) in polymer systems is of great interest because the size and concentration of its elements (holes) affect numerous transport and other physicochemical properties of polymers. Positron annihilation lifetime (PAL) spectroscopy is now one of the most efficient approaches for investigations of FV. The foundations of this method for probing polymers were based in particular on Walker-Brandt-Berko s free volume model (7). According to this model, Positronium, Ps, (a bound atomic system, which consists of an electron and the positron) tends to be localized or trapped before its annihilation in FV or, in other words, in areas with reduced electron density. Accordingly, annihilation characteristics (lifetimes and intensities of longer lifetime components of annihilation radiation) provide information regarding the concentration and sizes of FV elements. (2-5)... 

In this work positron annihilation lifetime spectroscopy (PALS) was used to investigate structural diversity inside zeolite precursor matrix caused by the presence of alkali cations Na, K, Rb and Cs. PALS is an established and well-proven method for structural investigations of various materials, extensively used for metals and alloys, semiconductors and porous materials [3, 4]. In the investigations of zeolites PALS has been mostly used for their void structure and size study [5, 6, 7, 8], also in correlation to... 

Positron annihilation lifetime spectroscopy (PALS) provides a method for studying changes in free volume and defect concentration in polymers and other materials [1,2]. A positron can either annihilate as a free positron with an electron in the material or capture an electron from the material and form a bound state, called a positronium atom. Pnra-positroniums (p-Ps), in which the spins of the positron and the electron are anti-parallel, have a mean lifetime of 0.125 ns. Ortho-positroniums (o-Ps), in which the spins of the two particles are parallel, have a mean lifteime of 142 ns in vacuum. In polymers find other condensed matter, the lifetime of o-Ps is shortened to 1-5 ns because of pick-off of the positron by electrons of antiparallel spin in the surrounding medium. 

Lozano-Castello D, Cazorla-Amoros D, Linares-Solano A, Hall PJ, and Fernandez JJ. Characterization of activated carbon fibers by positron annihilation lifetime spectroscopy (PALS). In Unger KK, et al., eds. Studies in Surface Science and Catalysis, Characterisation of Porous Solids V, vol. 128, the Netherlands Elsevier Science. 2000 523-532. 

Independent of whether or not a well-defined crossover temperature can be observed in NS data above Tg, it has been well known for a considerable time that on heating a glass from low temperatures a strong decrease of the Debye-Waller factor, respectively Mossbauer-Lamb factor, is observed close to Tg [360,361], and more recent studies have confirmed this observation [147,148,233]. Thus, in addition to contributions from harmonic dynamics, an anomalously strong delocalization of the molecules sets in around Tg due to some very fast precursor of the a-process and increases the mean square displacement. Regarding the free volume as probed by positron annihilation lifetime spectroscopy (PALS), for example, qualitatively similar results were reported [362-364]. 

The main techniques used are positron annihilation lifetime spectroscopy (PALS) and the Doppler broadening (DB) or angular correlation (AC) techniques. The PALS parameters are the relative intensities (I j) and the... 

The aim of this chapter is to introduce the reader to the application of positron annihilation techniques to polymers. An extensive review of the large volume of publications related to positron studies in polymers will not be presented. Rather it is intented to introduce the reader to the theory and techniques used in polymer studies and indicate the types of information that can be obtained about different polymer systems. The main focus of this chapter will be on the use of positron annihilation lifetime spectroscopy (PAL) in polymer studies. Chapter 11 discusses the use of monoenergetic slow positron beams used to study polymers surfaces. One of the interesting new developments in the application of positron annihilation techniques in polymers is the positron age-momentum correlation technique (AMOC). This technique promises to shed new light on the mechanisms of positronium formation and annihilation in polymer systems. A more detailed discussion of this technique can be found elswhere in this text. 

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