Radiation chemistry development

Masahiro Irie received his B.S. and M.S. degrees from Kyoto University and his Ph.D. in radiation chemistry from Osaka University. He joined Hokkaido University as a research associate in 1968 and started his research on photochemistry. In 1973 he moved to Osaka University and developed various types of photoresponsive polymers. In 1988 he was appointed Professor at Kyushu University. In the middle of the 1980 s he invented a new class of photochromic molecules - diaryl-ethenes - which undergo thermally irreversible and fatigue resistant photochromic reactions. He is currently interested in developing singlecrystalline photochromism of the diarylethene derivatives. 

In studies of this kind, methods developed in radiation chemistry and photochemistry are often applied The methods of pulse radiolysis and flash photolysis allow one to investigate the mechanism of reactions in which free radicals, electrons and positive holes are the intermediates. In order to understand the mechanisms of processes that occur on colloidal particles it is important to know how free radicals... 

Chemical effects from the absorption of charged-particle irradiation were observed almost immediately following the discoveries of X-rays and the electron in the last decade of the nineteenth century. The field, though, remained unnamed until 1942, when Milton Burton christened it radiation chemistry. At present, it has developed into a vigorous discipline embracing radiation physics on one hand and radiation biology on the other. The purpose of this book is to give a coherent account of the development of this field with stress on the fundamental aspects. 

Development of new applications of radiation modifications of the properties of polymers in high technology industries such as electronics and the exposure of polymer materials to radiation environments as diverse as medical sterilization and the Van Allen belts of space have resulted in a renewed interest in fundamental radiation chemistry of polymers. 

The interaction of neutrons with organic molecules occurs mainly through knock-on of protons. Thus, the radiation chemistry is similar to proton irradiation. Radiation chemistry by positive ions is of increasing importance on account of ion implantation technology, plasma development and deposition processes, and cosmic irradiation. 

Polymer chemistry and polymer radiation chemistry in particular are key elements of the electronics industry. Polymer materials that undergo radiation induced changes in solubility are used to define the individual elements of integrated circuits. As the demands placed on these materials increases due to increased circuit density and complexity, new materials and chemistry will be required. Many of the new chemistries that are being developed are described in this article. 

Optimization of both resist sensitivity and contrast requires a fundamental appreciation of the radiation chemistry in addition to appreciation how polymer molecular parameters affect the lithographic behavior of the resist. The intent of this chapter is to further the readers understanding of the polymer and radiation chemistry that is associated with a large part of the microelectronics industry, and provide some of the necessary background to effect future developments. 

C The Epoxy Resists. The first negative tone electron beam resist materials with useful sensitivity were based on utilizing the radiation chemistry of the oxirane or epoxy moiety. The most widely used of these materials, COP (Figure 32) is a copolymer of glycidyl methacrylate and ethyl acrylate and was developed at Bell Laboratories (43,44). COP has found wide applicability in the manufacturing of photomasks. The active element... 

A number of different techniques have been developed for studying nonhomogeneous radiolysis kinetics, and they can be broken down into two groups, deterministic and stochastic. The former used conventional macroscopic treatments of concentration, diffusion, and reaction to describe the chemistry of a typical cluster or track of reactants. In contrast, the latter approach considers the chemistry of simulated tracks of realistic clusters using probabilistic methods to model the kinetics. Each treatment has advantages and limitations, and at present, both treatments have a valuable role to play in modeling radiation chemistry. 

The IRT model has been developed in detail in a series of papers of Green, Pimblott and coworkers and has been validated by comparison with full random flight simulations [47,49,51]. The IRT treatment of the radiation chemistry relies upon the generation of random reaction times from initial coordinate positions from pair reaction time distribution functions. A simulation, such as a random flight calculation, starts with the initial spatial distribution of the reactants. The separations between all the pairs of particles are evaluated... 

Shortly after the discovery of the hydrated electron. Hart and Boag [7] developed the method of pulse radiolysis, which enabled them to make the first direct observation of this species by optical spectroscopy. In the 1960s, pulse radiolysis facilities became quite widely available and attention was focussed on the measurement of the rate constants of reactions that were expected to take place in the spurs. Armed with this information, Schwarz [8] reported in 1969 the first detailed spur-diffusion model for water to make the link between the yields of the products in reaction (7) at ca. 10 sec and those present initially in the spurs at ca. 10 sec. This time scale was then only partially accessible experimentally, down to ca. 10 ° sec, by using high concentrations of scavengers (up to ca. 1 mol dm ) to capture the radicals in the spurs. From then on, advancements were made in the time resolution of pulse radiolysis equipment from microseconds (10 sec) to picoseconds (10 sec), which permitted spur processes to be measured by direct observation. Simultaneously, the increase in computational power has enabled more sophisticated models of the radiation chemistry of water to be developed and tested against the experimental data. 

Allen, A.O. The story of the radiation chemistry of water. In Early Developments in Radiation Chemistry, Kroh, J., Ed. Royal Society of Chemistry London, 1989 p 1. 

Photochemistry and radiation chemistry of biomolecules in vacuo and in water. Radiolytic products from Auger cascade are interesting from the viewpoint of radiotherapy. The development of irradiation systems is required in which liquid samples can be irradiated with vacuum UV or ultrasoft x-rays of high intensity. 

It is clear that the development of nuclear technology is impossible without the support of radiation chemistry. Thus the radiation chemistry is important not only in basic science, but also in technology. 

This book is not intended to give a complete survey of polymer irradiation. For this, we have to refer to such excellent texts as Atomic Radiation of Polymers by Charlesby and Radiation Chemistry of Polymeric Systems by Chapiro. Since these books were issued in 1961 and 1962, more experimental research has been done and more theories have been developed by these authors, who are also the authors of the first two chapters of this volume. New trends have been discovered, and more light has been shed on polymer irradiation by the authors of the following 18 chapters. Thanks to their work and efforts, polymer irradiation is making inroads into the plastic and related industries. 

Three extensive introductory chapters by Everhart, Broers, and Bowden provide a solid foundation in the physics and chemistry of the lithographic process together with an overview of current resist systems. These 3 chapters, coupled with 20 chapters from outstanding radiation polymer chemists throughout the world, provide a firm basis for understanding the important fundamental concepts in radiation chemistry as applied to design, development, and application of resist materials. 

ESR Spectroscopy. Electron Spin Resonance spectroscopy is an important technique for investigating the role of radical intermediates in radiation chemistry. The technique has been used widely for many years in the study of radicals occurring in irradiated solid polymers (.6,7). However, by their very nature, such species are reactive and may only exist in low concentration. The identification of these species can also be a problem since in the majority of polymers the environment of the radicals leads to broad, unresolved ESR spectra, which makes detailed spectral analysis difficult. In recent years, many of these problems of sensitivity and resolution have been reduced by more sensitive and stable ESR spectrometers and by development of new methods of data handling and manipulation. 

From this result on MRS, we expected that a combination of phenolic-resin-based resist and aqueous alkaline developer would lead to etching-type dissolution and non-swelling resist patterns. In this paper, we report on a new non-swelling negative electron beam resist consisting of an epoxy novolac, azide compound and phenolic resin matrix (EAP) and discuss the radiation chemistry of this resist. 

Okamura S (1989) A short history of applied radiation polymer chemistry in Japan. In Kroh J (ed) Early developments in radiation chemistry. Royal Soc. Chem., London, 321... 

The scientific development of radiation chemistry is reviewed from the discovery in 1895 of x-rays and radioactivity by Roentgen and Becquerel through to the present. 

The purpose of this article is to review the development of radiation chemistry which began with the discovery of x-rays by Roentgen(l) in 1895 and shortly afterwards of radioactivity by Becquerel(2), which in both cases Involved the observation of chemical change in photographic plates and luminescence in certain phosphors. Clearly, in the space available, the review will be restricted and subjective, but will, it is hoped, give the general framework in which the subject has developed. 

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