PHOSPHOR
`. .
`HANDBOOK
`
`I
`
`•.
`
`Edited under the Auspices of
`.Phosphor Research Society
`
`Editorial Committee Co-chairs
`Shigeo Shionoya
`William M. Yen
`
`Members
`Takashi Hase
`Shigeru Kamiya
`Eiichiro Nakazawa
`Kazuo Narita
`Katsutoshi Ohno
`Masaaki Tamatani
`Marvin J. Weber
`Hajime Yamamoto
`
`CRC Press
`Boca Raton Boston London New York Washington, D.C.
`
`,
`
`VIZIO 1011
`
`

`
`Acquiring Editor:
`Project Editor:
`Cover design:
`
`Robert Stem
`Albert W. Starkweather, Jr.
`Dawn Boyd
`
`QC'' f
`, 7
`. pq~
`\ ~ ~'\
`Cot Z
`
`Library of Congress Cataloging-in-Publication Data
`
`Phosphor handbook I edited under the auspices of the Phosphor Research Society ; editorial committee co(cid:173)
`chairs Shigeo Shionoya, William M. Yen ; members Takashi Hase ... [et al.]
`p. em.
`Includes bibliographical references and index.
`ISBN 0-8493-7560-6 (alk. paper)
`1. Phosphors-Handbooks, manuals, etc. 2. Phosphors-Industrial applications-Handbooks, manuals,
`etc. I. Phosphor Research Society.
`QC476.7.P48 1998
`620.1'1295-dc21
`
`98-15663
`CIP
`
`This book contain information obtained from authentic and highly regarded sourtes. Reprinted material is
`quoted with permission, and sources are indicated. A wide variety of references are listed. Reasonable efforts
`have been made to publish reliable data and information, but the author and the publisher cannot assume
`responsibility for the validity of aU materials or for the consequences of their use.
`Neither th.is book nor any part may be reproduced or transmitted in any form or by any mean , electronic
`or mechan.ica"l, including photocopying, microfilming, and recording, or by any information sto rage or retrieval
`system, without prior permission in writing from the publi her.
`The consent of CRC Press LLC does not extend to copying for general distribution, for promotion, for creating
`new works, or for resale. Specific permission must be obtained in writing from CRC Press LLC for such copying.
`Direct all inquiries to CRC Press LLC, 2000 Corporate Blvd., N.W., Boca Raton, FL 33431.
`
`Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are only
`used for identification and explanation, without intent to infringe.
`
`© 1999 by CRC Press LLC (English language version)
`© 1987 by the Phosphor Research Society (Keikotai Dogakkai) Uapanese language version)
`
`Originally published in Japanese by Ohmsha, Ltd. under the title Keikotai Handobukku.
`
`No claim to original U.S. Government works
`International Standard Book Number 0-8493-7560-6
`Library of Congress Card Number 98-15663
`Printed in the United States of America 1 2 3 4 5 6 7 8 9 0
`Printed on acid-free paper
`
`VIZIO 1011
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`Preface
`
`TI1is volume is the English version of a revised edition of the Phosphor Handbook (Keikotai
`J-Jandobukktt) which was first published .in Japanese in December, 1987. The original Handbook
`was organized and edited tmder the auspices of the Phosphor Research Society (in Japan.) and
`issued to celebrate the 20011' Scientific Meeting of the Society whiCh occurred in April, 1984.
`The Phosphor Research Society is an organization of scientists and engineers engaged
`in the research and development of phosphors in Japan which was established in 1941.
`For more than half a century, the Society has promoted interaction between those interested
`in phosphor research and has served as a forum for discussion of the most recent devel(cid:173)
`opments. The Society sponsors five annual meet.ings; in each meeting four or live papers
`are presented reflecting new cutting edge developments in phosphor research in Japan
`and elsewhere. A technical digest with extended abstracts of the presentations is ctistrib(cid:173)
`uted during these meetings and sexve as a record of the proceedings of these meetings.
`This Handbook is designed to serve as a general reference for aU those who might
`have an intexest in the properties and/ ox applications of phosphors. This volume begins
`with a concise summary of the fundamentals of luminescence and then summarizes the
`principal classes of phosphors and their light emitting properties. Detailed descriptions
`of the procedures for synthesis and manufacture of practical phosphors appear in later
`chapters and in the manner in which these materials are used in technical applications.
`The majority of the authors of the various chapters are important members of the Phosphor
`Research Society and they have all made significant contributions to the advancement of
`the phosphor field. Many of the contributors have played central roles in the evolution
`and remarkable development of lighting and display industries of Japan. The contributors
`to the original Japanese version of the Handbook have provided English translations of
`their articles; in addition, they have all updated their contributions by including the newest
`developments in their respective fields. A number of new sections have been added in
`this volume to reflect the most recent advances in phosphor technology.
`As we approach the new millennium and the dawning of a radical new era of display
`and information exchange, we believe that the need for more efficient and targeted phos(cid:173)
`phors will continue to increase and that these materials will continue to play a central
`role in technological developments. We, the co-editors, are pleased to have engaged in
`this effoit. It is our earnest hope that this Handbook becomes a useful tool to all scientists
`and engineers engaged in researcl\ in phosphors and related fields and that the community
`will use this volume as a daily and routine reference, so that the aims of the Phosphor
`Research Society in promoting progress and development in phosphors is fully attained.
`Co-Editors:
`Shigeo Shionoya
`Tokyo, Japan
`William M. Yen
`Athens, GA, USA
`May, 1998
`
`VIZIO 1011
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`chapter one
`
`Introduction to the handbook
`
`Shigeo Shionoya
`
`Contents
`
`1.1 Terminology ............................................................................................................................ 3
`1.2 Past and present phosphor research .................................................................................. .4
`1.3 Applications of phosphors ................................................................................................... 5
`1.4 Contents of the handbook .................................................................................................... 6
`References ......................................................................................................................................... 8
`
`This Handbook is a comprehensive description of phosphors with an emphasis on prac(cid:173)
`tical phosphors and their uses in various kinds of technological applications. Following
`this introduction, Part II deals with the fundamentals of phosphors: namely, the basic
`principles of luminescence and the principal phosphor materials and their optical prop(cid:173)
`erties. Part III describes practical phosphors: phosphors used in lamps, cathode-ray tubes,
`X-ray and ionizing radiation detection, etc. Part IV describes the common measurement
`methodology used to characterize phosphor properties, while Part V discusses a number
`of related important items. Finally, Part VI details some of the history of phosphor tech(cid:173)
`nology and industry.
`
`1.1 Terminology
`The origin and meaning of the terminology related to phosphors must first be explained.
`The wmd phosphor was invented in the early 17th century and its meaning remains
`unchanged. It is said that an alchemist, Vincentinus Casciarolo of Bologna, Italy, found a
`heavy crystalline stone with a gloss at the foot of a volcano, and fired it in a charcoal oven
`intending to convert it to a noble metal. Casciarolo obtained no metals but found that the
`sintered stone emitted red light in the dark after exposure to sunlight. This stone was
`called the "Bolognian stone." From the knowledge now known, the stone found appears
`to have been barite (BaS04), with the fired product being BaS, which is now known to be
`a host for phosphor materials.
`After this discovery, similar findings were reported from many places in Europe, and
`these light-emitting stones were named phosphors. This word means "light bearer" in
`Greek, and appears in Greek myths as the personification of the morning star Venus. The
`
`3
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`4
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`Phosphor Handbook
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`word phosphorescence, which means per isting light emission from a substance after the
`exciting radiation has ceased, was derived from the word phosphor.
`Prior to the discovery of Bolognian stone, the Japanese were reported to have prepared
`phosphorescent paint from seashells. This fact is described in a lOth century O'linese
`document (Song dynasty) (see 18.7 for details). It is very intere:sting to learn that the credit
`for preparing phosphors for the first time should fall to the Japanese.
`TI1e wordfluorescmce was .introduced to denote the imperceptible short after-glow of
`the mineral fluorite (CaF2) following excitation. This is to distinguish the emission from
`phosphorescence, which is used to denote a 1ong after-glow of a few hours.
`The word lllntinescence, which includes both fluorescence and phosphorescence, was
`first used by Eilhardt Wiedemann, a German physicist, in 1888. This word originates from
`the Latin word lumen, which means light.
`Presently, the word luminescence is defined as a phenomenon in which the electronic
`state of a substance is excited by some kind of external energy and the excitation energy
`is given off as light. Here, the word light includes not 011ly electromagnetic waves in the
`visible region of 400 to 700 nm, but also those in the neighboring regions on both ends,
`i.e., the near-ultraviolet and the near-infrared regions.
`During the first half of this century, the difference between fluorescence and phos(cid:173)
`phorescence was a subject actively discussed. Conu·oversy centered on the duration of the
`after-glow after excitation ceased and on the temperature dependence of the after-glow.
`However, according to present knowledge, these discussions are now meaningle-Ss.
`In modem usage, light emission from a substance during the time when it is exposed
`to exciting radiation is called fluorescence, while the after-glow if detectable by the human
`eye after the cessation of excitation is called phosphorescence. However, it should be noted
`that these definitions are applied only to inorganic materials; for organic molecul s, dif(cid:173)
`ferent terminology is used. For organics, light emission from a singlet excited state is called
`fluorescence, while that from a triplet excited state is defined as p1wsplzorescence (see 2.5 for
`details).
`The definition of the word phosphor itself is not clearly defined and is dependent on the
`user. In a narrow sense, the word is used to mean inorganic phosphors, usually those in
`powder form and synthesized for the purpose of practical applications. Single crystals, thin
`ulms, and organic molecules that exhibit luminescence are rarely called phosphors. In a
`broader sense, the word phosphor is equivalent to "solid luminescent material."
`
`1.2 Past and present phosphor research
`The scientific research on phosphors has a Long history going back more than 100 years.
`A prototype of the ZnS-type phosphors, an important class of phosphors for television
`tubes, was first prepared by Theodore Sidot, a young French chemist, in 1866 rather
`accidentally (see 3.7.1 for details). It seems U1at this marked the beginning of scientific
`research and synthesis of phosphors.
`From the late 19th century to the early 20th centu~ Philip E.A. Lenard and co-workers
`in Germany perf01med active and extensive research on phosphors, and achieved impressive
`results. They prepared various kinds of phosphors based on alkaline earti'l chalcogenides
`(sulfides and selenides) and zinc sulfide, and investigated the luminescence pwperties.
`They established the principle that phosphors of these compounds are synthe ized
`by .introducing metallic impurities into ti'le materials by firing. The metallic impurities,
`called luminescence activators, form luminescence centers in the host. Lenard and co(cid:173)
`workers tested not only heavy metal ions but various rare-earth ions as potential activators.
`Alkaline cl1alcogenide phosphors developed by this research group are called Lenard
`phosphors, and their achievements are summarized in their book.1
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`VIZIO 1011