Spie Press Book • newChemistry and Lithography, Second Edition, Vol. 1: The Chemical History of Lithography
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This book is the first in a series of three volumes that make up the second edition of Chemistry and Lithography (2010). Although it is continued in Vol. 2, Chemistry in Lithography , and Vol. 3, The Practice of Lithography, each volume stands on its own. Volume 1 of the second edition weaves together threads of a narrative on the history of optical and molecular physics, optical technology, chemistry, and lithography, with the aim to give readers new insight into an aspect of the relationships between these fields that is often not fully appreciated: how the marriage of chemistry and optics led to the development and evolution of lithography. The book shows how major developments in chemistry, physics, and the technology of light have influenced the invention and development of lithography well beyond what its inventor envisioned. It also shows how developments in lithography have not only influenced the development of optics and chemistry, but also have played a critical role in the large-scale manufacture of integrated circuits that run the computers and machineries on which our modern electronic and information age depend. Finally, this book provides an analysis of the emerging trends in lithographic patterning, along with the current and potential applications of the resulting patterned structures and surfaces.
Table of Contents
- General Preface to the Second Edition
- Acronyms and Abbreviations
- 1 Introduction to Lithography
- 2 Invention of Lithography and Photolithography
- 2.1 Introduction
- 2.2 Invention of Lithography
- 2.3 Invention of Photolithography
- 2.4 Pioneers of Photolithography
- 2.4.1 Joseph Nicéphore Niépce: the inventor of photography and photolithography
- 2.4.2 Louis Jacques Mandé Daguerre
- 2.4.3 William Henry Fox Talbot
- 3 Physical Origins of Lithography
- 3.1 Introduction
- 3.2 Key Developments in Optical Physics that Enabled the Invention and Development of Lithography
- 3.2.1 Tactile and emission theories of light
- 3.2.2 Early studies in optics and catoptrics
- 3.2.3 The nature of light
- 3.2.4 Light and color
- 3.2.5 Light as a wave or particle
- 3.2.6 Electromagnetic theory
- 3.2.7 Electromagnetic spectrum
- 3.3 Key Developments in Optical Instruments and Glassmaking Technologies that Enabled the Development of Lithography
- 3.4 Key Developments in Atomic and Molecular Physics that Enabled the Invention and Development of Lithography
- 3.4.1 The nature of matter
- 3.4.2 Molecular theory of matter
- 3.4.3 Electrons
- 3.4.4 X-rays
- 3.4.5 Radioactivity
- 3.4.6 The beginnings of quantum theory
- 3.4.7 Blackbody radiation
- 3.4.8 Planck's quantum hypothesis for the blackbody radiation law
- 3.4.9 Einstein's quantum hypothesis for the photoelectric effect
- 3.4.10 Bright and dark line spectra
- 3.4.11 Atomic structure
- 3.4.12 Nuclear model of the atom
- 3.4.13 Bohr's model of the hydrogen atom
- 3.4.14 Implications of Bohr's theory
- 3.4.15 Quantum theory of light
- 4 Chemical Origins of Lithography
- 4.1 Introduction
- 4.2 Key Developments in Chemistry that Enabled the Invention and Development of Lithography
- 4.2.1 The four-element theory
- 4.2.2 Chemistry as a distinct discipline
- 4.2.3 Alchemy
- 4.2.4 Early theories on the nature of fire and combustion
- 4.2.5 Phlogiston theory
- 4.2.6 Beginnings of modern chemistry
- 4.2.7 Discovery of simple gases in common air
- 4.2.8 Absorption of light
- 4.2.9 Chemical effects of light
- 4.2.10 Foundation of modern chemistry
- 4.2.11 Post-Lavoisian evolution of chemistry
- 4.3 Laws and Theories of Chemical Reactions
- 4.3.1 Atomic theory
- 4.3.2 The law of constant or definite proportions
- 4.3.3 The law of multiple proportions
- 4.3.4 The law of reciprocal proportions or the law of equivalents
- 4.3.5 Electrochemical theory
- 4.3.6 Laws of electrolysis
- 4.3.7 Law of combining volumes
- 4.3.8 Avogadro's hypothesis
- 4.3.9 Law of mass action
- 4.3.10 Thermochemical laws
- 4.3.11 The phase rule
- 4.3.12 Theory of solutions
- 4.3.13 Theory of electrolytic dissociation
- 4.3.14 Le Chatelier's law of reactions
- 4.3.15 The periodic table and the periodic law
- 4.3.16 Electronic theory of valency
- 4.3.17 Theory of the periodic table
- 4.3.18 Theory of directed valencies
- 4.3.19 Theory of substitution
- 4.4 Rational Synthesis of Chemical Substances
- 4.5 The Structure of Chemical Compounds and Phenomena Deriving from Them
- 4.5.1 The structural formula of benzene
- 4.5.2 Optical activity
- 5 Evolution of Lithography
- 5.1 Introduction
- 5.2 Offset Lithography
- 5.3 The Printed Circuit Board and the Development of the Electronics Industry
- 5.4 The Transistor and Microelectronics Revolution
- 5.4.1 The invention of the transistor
- 5.4.2 Limits of discrete transistors
- 5.4.3 The integrated circuit
- 5.4.4 Other notable developments in transistor technology
- 5.4.5 Overall device technology trends
- 5.5 Semiconductor Lithography
- 5.6 Advanced Lithographic Patterning Techniques and Imaging Mechanisms
- 5.6.1 Optical lithography
- 5.6.2 X-ray lithography
- 5.6.3 Electron-beam lithography
- 5.6.4 Ion-beam lithography
- 5.6.5 Extreme-ultraviolet lithography
- 5.6.6 Soft lithography
- 5.6.7 Nano-imprint lithography
- 5.6.8 Proximal probe lithography
- 5.6.9 Atom lithography
- 5.6.10 Self-assembly lithography
- 5.6.11 Stereolithography
- 5.7 Outlook on the Evolution of Lithography
General Preface to the Second Edition
A second edition of a text has a number of advantages over the first edition: in addition to representing the accumulated wisdom of the readers who have suggested ideas for improving the previous edition, it also incorporates developments in the field that have taken place since the publication of the first edition. From their familiarity with the previous edition and in keeping with the general aim to make the text accessible, readers will be aware that I have provided not a slight tinkering with the text in this edition, but a wholesale rewriting of some chapters, while introducing entirely many new ones.
This present edition is a series of three volumes, namely, The Chemical History of Lithography (volume 1), Chemistry in Lithography (volume 2), and The Practice of Lithography (volume 3). Each volume is a unit in itself and can stand alone, which is fortunate in view of their different subject matters.
My motivation for splitting the second edition of Chemistry and Lithography into the above three volumes is because the subject matter of these three books is very broad and lends itself nicely to multiple angles of analysis and interpretation. Lithographically fabricated structures appear in an increasing wide range of scientific and technical fields, beyond their traditional niches in fine arts, paper printing, and electronics. In particular, the last ten years since the publication of the first edition of Chemistry and Lithography have witnessed a phenomenal pace of development in advanced lithography, perhaps the fastest pace of development in any decade over the 222-year history of the field. The transistor count of the leading-edge integrated circuit when the first edition was published was around 2.5 billion, and a short five years later that count rose to 10 billion. By the time the present edition is published, the transistor count of an equivalent device may well be over 20 billion, representing a nearly ten-fold increase within a decade in the ability to process, communicate, and store electronic information, made possible in no small part by advances in lithography. Such is the pace of the development in this field that the analysis I make in these three volumes is a sufficiently different and significantly expanded version of the treatment of the subject I rendered in the first edition. As such, there are a considerable number of changes within the text of the present edition.
The first edition covered some brief historical material in Part I, and in volume 1 of the present edition these historical aspects are extended. It seems reasonable to me that with the rapid advances being made in advanced lithography it is very important to realize that some of the concepts that we now take for granted in chemistry and physics that enervate lithography are by no means self-evident and often were developed only after much struggle and controversy. Improvements are still being made in all of these fields and can all the more be clearly understood by those who appreciate how our present understanding of the fields were attained.
In developing volume 1 of the present edition, I drew considerably from Part I of the first edition. Relative to Part I of the first edition, volume 1 of the present edition comprises five significantly expanded chapters: Chapters 1 and 2 of first edition with slight tinkering; an expanded version of Chapter 4 of the first edition; and two new chapters derived from expanding and splitting up Chapter 3 of the first edition. The object of volume 1 of the present edition is to weave together threads of a narrative on the history of optical and molecular physics, optical technology, chemistry, and lithography, with a view to creating a rich tapestry that gives the reader new insights into an aspect of the relationships between these fields that are often not fully appreciated: how the marriage between chemistry and optics led to the development and evolution of lithography. I show how major developments in the chemistry, physics, and technology of light influenced the invention and development of lithography, well beyond what its inventor envisioned. I also show how developments in lithography have not only influenced the development of optics and chemistry, but also played a critical role in the large-scale manufacture of integrated circuits that run the computers and machineries on which our modern electronic and information age depend.
Part of the analysis in volume 1 of the present edition is necessarily skewed toward the underlying science and technologies of advanced lithographic patterning techniques, in terms of materials, processes, and imaging, along with their unique features, strengths, and limitations. This book also provides an analysis of the emerging trends in lithographic patterning, as well as the current and potential applications of the resulting patterned structures and surfaces.
The object of volume 2 of the present edition is to deconstruct lithography into its essential chemical principles and to situate its various aspects in specific fields of chemistry. It comprises 16 chapters developed around a rewriting of Chapters 5 through 8 of Part II of the first edition and parts of Chapters 13 and 14 of Part III of the first edition. It also includes eight entirely new chapters that explore in a fundamental manner the role of chemistry in mediating specific aspects of the lithographic process.
Volume 2 of the present edition is in fact an outgrowth of the SPIE Advanced Lithography Short course Chemistry and Lithography (SC1099) that I have taught at the SPIE Advanced Lithography Symposium over the past six years. In this volume, I develop a chemistry and lithography interaction matrix, and use it as a device to illustrate how various aspects and practices of advanced lithography derive from established principles and phenomena of chemistry. For instance, lithographic unit operations involving principally the resist fall within the realm of process chemistry. Photochemistry is involved in the generation of photons from the exposure sources of optical, extreme ultraviolet, and x-ray lithographic exposure tools; the interaction of O2, H2O, NH3, SOx, and hydrocarbons with photons within the optical lithographic tool exposure chamber, as well as their roles in the oxidation, carbon deposition and growth, and formation of inorganic salt crystals (also called haze crystals) on masks and optical elements; cleaning of contaminated optics and masks with UV photons; clear defect repair of masks via photo-induced decomposition of organometallic precursors and deposition of metals on defective areas of the mask; and UV curing and photooxidative degradations of resists during exposure. Photochemistry is also the basis of the exposure action of photoacids and photobases in resists, as well as resist poisoning by airborne molecular bases. It is also the basis of laserproduced and discharge produced plasmas—the radiation sources for extreme-ultraviolet (EUV) lithographic patterning. Finally, photochemistry is the basis of the plasma (dry) stripping of resists and other hydrocarbon contaminants from wafers and masks.
Similarly, radiation chemistry is involved in the generation of electrons and ions from the exposure sources of electron-beam and ion-beam lithographic exposure tools, respectively; cleaning of contaminated optics and masks, and repair of defective masks with electrons and ions; the electronand ion-mediated exposure process as well as electron-beam and ion-beam curing, and crosslinking of resists. The manufacture of lithographic exposure sources, optical elements, masks, and resist materials involves materials chemistry. Polymer chemistry is the basis of the synthesis of polymeric resist resins used in optical, charged particle, and imprint lithography, as well as block copolymers used in directed block copolymer self-assembly lithography.
Surface chemistry is the basis of priming of relevant mask and wafer substrates, and their subsequent coating with resists and associated layers used in the fabrication of masks and semiconductor device wafers. Colloid chemistry is the basis of the cleaning of masks and wafers, and development process of exposed resists. It also explains the basis for the stability of resist, developer, and wet cleaning solutions. Electrochemistry is the basis of the corrosion and electromigration processes of Cr and Mo mask or reticle absorber features, as well as electrostatic damage of the same objects. It is also the basis of electrochemical imprint lithography. Organometallic chemistry is the basis for the precursor materials used in clear defect repair of masks, as well as EUV metal-oxide resists.
The Practice of Lithography (volume 3) comprises 12 chapters, made up of Chapters 9 through 17 of the first edition, in addition to three new chapters covering full treatment of EUV lithography, as well as imprint lithography, directed block copolymer self-assembly lithography, and proximal probe lithography. The object of this volume is to present how the more important lithographic patterning techniques are used to print images on appropriately prepared flat substrate surfaces using radiations as varied as photons, electrons, and ions, as well as mechanical force, thermodynamically driven directed self-assembly of block copolymers, and even electron tunneling phenomena. In particular, I cover photolithography (or optical lithography), electron-beam lithography, ion-beam lithography, EUV lithography, imprint lithography, directed block copolymer self-assembly lithography, and proximal probe lithography.
Immersion ArF laser optical lithography is currently used in high-volume manufacture of integrated circuits at 22-, 15-, and 10-nm nodes, using doublepatterning techniques to decrease feature pitch, where appropriate. EUV lithography is now entering high-volume production at the 7-nm node in some of the leading-edge semiconductor companies. Imprint lithography, especially in its roll-to-roll format, is increasingly being used in the fabrication of flexible and wearable electronic devices, diffractive optical elements, and large-area electronics. Directed block copolymer self-assembly is increasingly being used in the fabrication of functional nanostructures used in applications ranging from photonics to biomimetics, and from electrochemical energy storage to patterned electronic media. Now is an auspicious moment to provide an in-depth look into the chemistry that underpins these most advanced of lithographies.
Along with the introduction of EUV lithography into device manufacturing at single-digit-nanometer technology nodes, we enter a regime where the resist suffers from increased stochastic variation and the attendant effects of shot noise—a consequence of the discrete nature of photons, which, at very low number per exposure pixel, show increased variability in the response of the resist relative to its mean. Examples of resist response that may experience shot noise effects under very low-photon-count-per-pixel conditions within small exposure volumes, such as in EUV lithographic patterning, include photon absorption by the resist, and chemical conversion of light sensitive components in the resist, as well as the chemical changes that make a resist molecule soluble in the developer. We will examine in this volume of the present edition the role of stochastics in EUV lithography in far greater detail than we did in the first edition.
As in the first edition, I have made an attempt throughout the three books of the present edition to provide examples illustrating the diversity of chemical phenomena in lithography across the breadth of scientific spectrum, from fundamental research to technological applications. The format of this book is not necessarily chronological, but it is such that related aspects of lithography are thematically organized and presented with a view to conveying a unified view of the developments in the field over time, spanning many centuries, from the very first recorded reflections on the nature of matter to the latest developments currently at the frontiers of lithography science and technology. The emphasis is mostly placed on applications that have relevance to the semiconductor industry.
A great many of the pioneers of chemistry and lithography are not represented at all in the three books of the present edition. I can only record my immense debt to them and all who have contributed to the development of the two fields to the state in which I have reported it.
I am most grateful for suggestions from a number of experts, particularly the following: Andreas Erdman of Fraunhofer IISB, Manuel Thesen of micro resist technology GmbH, and Folarin Latinwo of Synopsys. Special thanks go to SPIE Senior Editor, Dara Burrows, for her editorial assistance in producing this book, which is much improved because of her efforts.
I am also grateful to my colleagues in the Department of Polymer Science and Engineering of University of Massachusetts at Amherst and, in particular, Prof. Jim Watkins, for lively scientific and technical discussions on polymers and flexible electronics. The opportunity to work in this department has not only helped me to broaden and deepen my scientific research interests, but also, in a direct way, has made it possible for me to write this book.
Lastly, I acknowledge the informal assistance I have received from my family members, in particular, from my wife Anett and daughter Sophie, who created a conducive atmosphere to work on this book at home.
Florence Village, Northampton, Massachusetts