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Phosphor handbook Luminescent and applied materials
Third Edition Xiaojun Wang Digital Instant Download
Author(s): Xiaojun Wang, Ru-Shi Liu, (eds.)
ISBN(s): 9780367555122, 0367555123
Edition: Third
File Details: PDF, 36.77 MB
Year: 2022
Language: english
Phosphor Handbook
Phosphor Handbook
Fundamentals of Luminescence
Edited by
Ru-Shi Liu
Xiao-Jun Wang
Third Edition
Third edition published 2022
by CRC Press
6000 Broken Sound Parkway NW, Suite 300, Boca Raton, FL 33487-2742
Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot assume
responsibility for the validity of all materials or the consequences of their use. The authors and publishers have attempted
to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission
to publish in this form has not been obtained. If any copyright material has not been acknowledged please write and let us
know so we may rectify in any future reprint.
Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or uti-
lized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopy-
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fication and explanation without intent to infringe.
DOI: 10.1201/9781003098690
vii
Foreword to the Third Edition
of the Phosphor Handbook
The field of luminescence and phosphors has a long history, starting from early observations of light
in the dark from afterglow materials. Centuries of extensive research followed aimed at providing
insight into optical phenomena, now resulting in an increasing role of phosphors in our daily lives.
Applications of luminescence grow more diverse and include, for example, phosphors in the color
displays that our eyes seem to be glued to, energy-efficient LED lighting, data communication,
luminescent probes in medical imaging and sensing, gadgets relying on afterglow phosphors and
even luminescent lanthanides in our banknotes. It is interesting to note the central role that Asia has
played in the discovery and development of new luminescent materials. Early applications involved
afterglow paints in China, creating alternative images in the dark. While fundamental lumines-
cence research was carried out in the 20th century at all continents, there has been a remarkably
strong role of Japan and China in research, development and discovery of new luminescence pro-
cesses and phosphors. It is, therefore, not surprising that the first edition of the Phosphor Handbook
(Keikotai Handobukku) was initiated by the Phosphor Research Society in Japan in the 1980s.
The first Phosphor Handbook was a great book but with an impact limited to those speaking
Japanese. Fortunately, about ten years later, the book was translated into English and edited by
two giants in the field of luminescence: Shigeo Shionoya and William Yen. It is this version of the
book that I acquired soon after it was released, and it has been a source of information ever since.
All aspects of luminescent materials were covered: phosphor synthesis, optical measuring tech-
niques, fundamentals of luminescence processes, operation principles of light emitting devices,
light and color perception and of course an almost complete overview of all luminescent materials
known, indexed by host material and activator ion. I cannot count how often I consulted this book,
to quickly look up the optical properties of an ion-host combination, find a suitable material with
specific luminescence characteristics, understand the operation principles of phosphors in vari-
ous applications and learn about careful measurements and analysis of phosphor properties. The
authors, except for one, were Japanese, underpinning the central role of Japan in phosphor research.
As the field of luminescence continued to evolve and expand, it became clear that a second edi-
tion of the Phosphor Handbook was needed. Sadly Shigeo Shionoya has passed away, and in 2006,
William Yen together with Hajime Yamamoto edited the second edition of the Phosphor Handbook.
The new edition was updated mostly by asking the original authors to adapt the various chapters
to include recent developments. The Phosphor Handbook continued to play a prominent role in
the luminescence community as a source of information on any topic related to phosphors. Almost
15 years later, it was again time to adapt the Handbook to cover important new developments in the
rapidly changing phosphor field where new applications and new materials emerge, and also mea-
suring techniques have changed with the introduction of, for example, cheap (pulsed) diode lasers,
fiber optics and compact CCD-based spectrometers. Our great colleagues William Yen and Hajime
Yamamoto are unfortunately no longer with us and also many of the authors of the various chapters
of the first and second edition of the Phosphor Handbook have passed away. This made it far from
trivial to realize a third edition. We can be extremely grateful that Ru-Shi Liu and Xiao-Jun Wang
have taken the initiative to edit and write this third edition of the Phosphor Handbook. It is very
appropriate that the book is dedicated to the three founders, Shigeo Shionoya, William Yen and
Hajime Yamamoto. At the same time, it is appropriate to sincerely thank Ru-Shi Liu and Xiao-Jun
Wang for their strong commitment and time invested to organize, write and edit this third edition.
The third edition of the Phosphor Handbook is in some aspects different from the two previous
editions. The authors are not the same, and it is wonderful to see that so many highly respected
ix
x Foreword to the Third Edition of the Phosphor Handbook
colleagues in the field have taken the time to contribute their expertise and knowledge to this third
edition. Interestingly, again almost all of the authors of this third edition are Asian (with well over
100 contributing authors, you can count the non-Asian authors on the fingers of one hand). This
illustrates the continued strong position of Asia in phosphor research. Just as in the previous edi-
tions, all aspects and the broad scope of phosphor research are covered, which makes this Handbook
a worthy successor of the previous editions. It will serve as a comprehensive resource describing
a wide variety of topics that were also included in the previous editions. It will educate newcom-
ers and help everyone in the field to quickly access all relevant knowledge in the exciting field of
phosphor research. In addition to the “classic” topics that continue to be relevant (but sometimes for-
gotten), many new topics are included, in Theory (e.g., first principle calculations), Materials (e.g.,
recent developments in quantum dots and upconversion nanocrystals) and Applications (e.g., LED
phosphors for NIR sensing and agriculture). All this information no longer fits in a single volume,
and this third edition is, therefore, divided into three volumes.
At the time of writing this foreword, I have not read the new edition of the Handbook but did
receive an overview of all the chapters and contributing authors. Based on this information, it is
clear that the full phosphor community, from students to professors, can benefit from this new com-
prehensive source of everything you always wanted to know about phosphors – and more. The third
edition of the Phosphor Handbook will be a classic and continue to promote progress and develop-
ment of phosphors, in the spirit of the first edition. I look forward to reading it and hope that you as
a reader will enjoy exploring this great book and be inspired by it in your research on luminescent
materials.
Andries Meijerink
Utrecht, June 2021
Preface to the Third Edition
The last version of the Phosphor Handbook was well received by the phosphor research community
since its publication in 2007. However, in last 14 years, many notable advances have occurred. The
success of the blue LED (Nobel Prize in Physics, 2014) and its phosphor-converted solid illumination
greatly advanced the traditional phosphor research. New phosphorescent materials such as quantum
dots, nanoparticles and efficient upconversion, quantum cutting phosphors and infrared broadband
emission phosphors have been quickly developed to find themselves in ever-broader applications,
from phototherapy to bioimaging, optics in agriculture to solar cell coating. These applications have
all expanded beyond the traditional use in lighting and display. All of these developments should
be included in the popular Handbook, making it necessary to publish a new version that reflects the
most recent developments in phosphor research. Unfortunately, all the three well-respected editors
of the previous version have passed away. As their former students and colleagues, we, the editors,
feel a strong sense of responsibility to carry on the legacy of the Handbook and to update accord-
ingly to continue serving the phosphor community. The aim of the third edition of the Handbook is
to continue to provide an initial and comprehensive source of knowledge for researchers interested
in synthesis, characterization, properties and applications of phosphor materials.
The third edition of the Handbook consists of three separate volumes. Volume 1 covers the theoreti-
cal background and fundamental properties of luminescence as applied to solid-state phosphor materi-
als. New sections include the rapid developments in principal phosphors in nitrides, perovskite and
silicon carbide. Volume 2 provides the descriptions of synthesis and optical properties of phosphors
used in different applications, including the novel phosphors for some newly developed applications.
New sections include Chapters 5 – Smart Phosphors, 6 – Quantum Dots for Display Applications,
7 – Colloidal Quantum Dots and Their Applications, 8 – Lanthanide-Doped Upconversion
Nanoparticles for Super-Resolution Imaging, 9 – Upconversion Nanophosphors for Photonic
Application, 16 – Single-Crystal Phosphors, 19 – Phosphors-Converting LED for Agriculture,
20 – AC-Driven LED Phosphors and 21 – Phosphors for Solar Cells. Volume 3 addresses the experi-
mental methods for phosphor evaluation and characterization and the contents are widely expanded
from the Second Edition, including the theoretical and experimental designs for new phosphors as well
as the phosphor analysis through high pressure and synchrotron studies. Almost all the chapters in
the third edition, except for some sections in the Fundamentals of Luminescence, have been prepared
by the new faces who are actively and productively working in phosphor research and applications.
We commemorate the memory of the three mentors and editors of the previous editions –
Professors Shigeo Shionoya, Hajime Yamamoto and William M. Yen. It was their efforts that com-
pleted the original Handbook that guided and inspired numerous graduate students and researchers
in phosphor studies and applications. We wish to dedicate this new edition to them.
As the editors, we sincerely appreciate all the contributors from across the world who overcame
various difficulties through such an unprecedented pandemic year to finish their chapters on time.
We are grateful to Professor Andries Meijerink of Utrecht University for writing the foreword to
the Handbook. We also highly appreciate the help from Nora Konopka, Prachi Mishra, and Jennifer
Stair of CRC Press/Taylor & Francis Group and perfect editing work done by Garima Poddar of
KGL. Finally, we hope that this third edition continues the legacy of the Handbook to serve as a
robust reference for current and future researchers in this field.
Co-editors:
Ru-Shi Liu
Taipei, Taiwan
Xiao-Jun Wang
Statesboro, GA, USA
May, 2021
xi
Preface to the Second Edition
We, the editors as well as the contributors, have been gratefully pleased by the reception accorded
to the Phosphor Handbook by the technical community since its publication in 1998. This has
resulted in the decision to reissue an updated version of the Handbook. As we had predicted, the
development and the deployment of phosphor materials in an ever increasing range of applications
in lighting and display have continued its explosive growth in the past decade. It is our hope that an
updated version of the Handbook will continue to serve as the initial and preferred reference source
for all those interested in the properties and applications of phosphor materials.
For this new edition, we have asked all the authors we could contact to provide corrections and
updates to their original contributions. The majority of them responded, and their revisions have
been properly incorporated in the present volume. It is fortunate that the great majority of the mate-
rial appearing in the first edition, particularly those sections summarizing the fundamentals of
luminescence and describing the principal classes of lightemitting solids, maintains its currency
and, hence, its utility as a reference source.
Several notable advances have occurred in the past decade, which necessitated their inclusion
in the second edition. For example, the wide dissemination of nitride-based LEDs opens the pos-
sibility of white light solid-state lighting sources that have economic advantages. New phosphors
showing the property of “quantum cutting” have been intensively investigated in the past decade
and the properties of nanophosphors have also attracted considerable attention. We have made an
effort, in this new edition, to incorporate tutorial reviews in all of these emerging areas of phosphor
development.
As noted in the preface of the first edition, the Handbook traces its origin to one first compiled by
the Phosphor Research Society (Japan). The society membership supported the idea of translating
the contents and provided considerable assistance in bringing the first edition to fruition. We con-
tinue to enjoy the cooperation of the Phosphor Research Society and value the advice and counsel
of the membership in seeking improvements in this second edition.
We have been, however, permanently saddened by the demise of one of the principals of the
society and the driving force behind the Handbook itself. Professor Shigeo Shionoya was a teacher,
a mentor and a valued colleague who will be sorely missed. We wish to dedicate this edition to his
memory as a small and inadequate expression of our joint appreciation.
We also wish to express our thanks and appreciation of the editorial work carried out flawlessly
by Helena Redshaw of Taylor & Francis.
William M. Yen
Athens, GA, USA
Hajime Yamamoto
Tokyo, Japan
December, 2006
xiii
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These two covers are beforehand prepared for the trick by filling
the two compartments of each, one with wine, and the other with
water. The air-holes are stopped with pellets of wax, but for the sake
of distinction the “wine” compartment of each is plugged with red
wax, and the “water” compartment with white wax. Any other
distinguishing mark is, of course, equally good. So long as the air-
holes are thus stopped, there is no fear of the liquid running out.
The performer, having filled the glasses as already described, mixes
the contents in the decanter, and in placing the latter on the stand,
removes the wax plug from the bottom, thus allowing the wine to
run out, and to percolate through the above-mentioned holes into
the stand, where it remains. He next places the empty glasses on
their respective stands, and places the covers over them. He then
asks the audience into which of the glasses they desire that the wine
shall travel, and into which the water. When they have made their
decision, he has only to remove the red pellet from the cover which
is over the glass into which the wine is to pass, and the white pellet
from the opposite cover. The tying of the tape from cover to cover is
merely designed to give time for the liquids to reach their respective
destinations, and is, indeed, altogether dispensed with by many
performers. The air-holes may be stopped by means of tinfoil pasted
over them, instead of the wax, if preferred. The foil is instantly
removeable by scraping with the nail.
To Fire Borrowed Rings from a Pistol, and make them Pass into a
Goblet filled with Bran and covered with a Handkerchief, the Bran
Disappearing, and being found
elsewhere.—The glass used in
this instance is of ordinary
tumbler size. It is not brought
forward as above, with the
bran shape already in place, Fig. 217.
but empty, and may therefore
be freely offered for inspection. With it is brought forward a wooden
box, of any size and shape, filled with bran, and in this, ready to
hand, is concealed the bran shape. We have already had occasion to
describe the magic pistol, or rather pistol tube; but the tube used in
this instance (see Fig. 217) has an additional peculiarity. It is of
comparatively small size, being about two inches wide at the mouth.
Within this mouth fits easily a tin cup, a, about an inch and three-
quarters in depth, and having its edge turned over outwards all
round, so as to afford a ready grip to the palm when it may be
necessary to remove it. The pistol is beforehand loaded with powder,
and the cup above described is placed in the mouth of the tube.
The performer begins by asking the loan of three rings, to be
fired from his magic pistol. To preclude the possibility of their being
exchanged, he requests the owners to drop them into the pistol
themselves. First, however, by way of wad, he takes a small piece of
white paper, and presses its centre portion into the mouth of the
pistol tube, its edges projecting all round, and forming a sort of cup
to receive the rings. Three rings having been offered, and dropped
into the pistol, the performer closes over the edges of the paper, and
presses them down with his wand, the effect being as if the rings
were fairly rammed down into the pistol, though they really remain
in the cup, just within the mouth. He now hands the pistol to one of
the spectators, requesting him to hold it muzzle upwards above his
head. In handing it to him, he places for a moment his own right
hand over the mouth of the tube, his palm being flat upon it, and in
again removing the hand lifts out and palms the cup (which the
projecting edge enables him to do with perfect ease). He has thus
obtained possession of the rings. (As the holder of the pistol has
been instructed to hold it above his head, he is not very likely to look
into it; but lest he should do so, and discover that the rings are
already removed, it is well to place in the tube beforehand a piece of
crumpled white paper, to represent that which contained the rings.)
The performer now hands round the glass for examination, and
subsequently draws attention to the box of bran. While doing this he
has little difficulty in getting the rings out of the cup and paper into
his right hand. He then, holding the glass in his left hand, dips it into
the box, and fills it with bran, which he forthwith pours slowly back
again to prove its genuineness. Meanwhile, his right hand is
engaged in fishing up the bran shape among the bran, placing it
mouth upwards in the box, and dropping the rings into it. When he
again dips the glass into the box, he slips it mouth downwards over
the shape, immediately turning it into the natural position, and
bringing it up, to all appearance, full of bran. As the rings were in
the shape, they are, of course, now in the glass. He brushes the
loose bran off the top, and then covers the glass with a borrowed
handkerchief, taking particular notice on which side hangs the loop
of thread. The person holding the pistol is now requested to take
good aim, and fire at the glass. He does so, and the performer,
lifting the handkerchief with the shape within it, lets the latter drop
on the servante, and advancing with the glass, requests the owners
to identify their rings.
The trick may either end here, upon the supposition that the
bran has been blown away altogether by the explosion, or the bran
may be shown to have passed to some other place. There are
numerous methods of effecting this latter transposition. For instance,
the pea vase (see page 351), first shown empty, may be used, or
the bran may be made to fall out of a second borrowed
handkerchief, by means of the bag shown at page 248, or may be
found in the apparatus next described.
The Coffee Trick. (Coffee Berries changed to Hot Coffee, White Beans
to Sugar, and Bran to Hot Milk).—The pieces of apparatus used in this
trick are of brass or japanned tin, and
are three in number, two being tall
cylindrical vases, standing eighteen to
twenty inches in height, the third a
goblet-shaped vase, of about half that
height. The latter is made upon the
principle of the “bran glass,” above
described, consisting of three portions
Fig. 221. (see Fig. 221), the goblet a, the cover
c, and a shallow tray b, which fits into
the goblet, and which, if the cover is pressed down smartly, and
again removed, is lifted off with it. It differs, however, from the
“bran shape” in the fact that b is open at top instead of at bottom,
and is only about one-fifth the depth of the goblet, leaving therefore
considerable space below it. This portion of the apparatus is
prepared for use by placing in the goblet a quantity of hot milk,
putting b in position above it, and finally filling b with loose bran.
The construction of the other two vases will be quickly
understood upon an inspection of Figs. 222, 223. a is the vase, and
c the cover fitting loosely over it, but between these two is a well, b,
made double, so as to fit at once into and outside of a, after a mode
of construction which we have more than once had occasion to
notice. There is a bayonet-catch at the lower edge of c,
corresponding with a pin or stud at the lower edge of b, so that c
may be lifted off either with or without b. There is a similar catch at
the lower edge of b, corresponding with a stud at the bottom of a,
but cut in the opposite direction to the other catch, so that the
action of unlocking a from b locks b to c, and vice versâ.
The vase a requires a
special description. A shallow
saucer of tin, d, just fits the
interior of the vase, working
up and down therein piston-
fashion, but prevented from
coming out altogether by the
fact that the upper edge of a
is slightly turned inwards all
round. Below d is a spiral
spring, whose action tends
to force d to the top of the
vase, as shown in Fig. 222.
Fig. 222.
From the centre of d, however,
there extends downwards
through the spiral spring a
piece of stiff wire e, with a
crook, f, at the end. The foot
of the vase is hollow
throughout. If the saucer d is
forced down by pressure from
within, this wire, as soon as it
reaches the position shown in
Fig. 223, will hook itself within
the foot of the vase, and so
keep down d, until the crook is
Fig. 223. again released, when the
whole will instantly return to the condition shown in Fig. 222. The
bottom of the foot is open, so that the fingers can without difficulty
find and release the crook when necessary.
The vases are prepared by pressing down d in each as shown by
the dotted lines in Fig. 223, and filling the well of the one with hot
coffee, and that of the other with loaf-sugar. Their respective covers
are then placed over them. The attention of the audience is first
directed to a couple of wooden boxes, each about half as long again
as the vases, and ten or twelve inches in depth, one of which is filled
with coffee-berries, and the other with white haricot beans. The
performer now uncovers the vase which contains the coffee, first
turning the bayonet-catch so as to lift off the well b with the cover,
and shows, by holding the vase upside down and rattling his wand
within it, that it is perfectly empty. He now fills it with coffee-berries,
laying it down in the box to do so, and holding it by the foot with
one hand while he shovels the berries into it with the other. Having
completely filled it with the berries, he holds it aloft, and, to show
that there is “no deception,” tilts it, and lets them run back again
into the box. Again he dips it into the box, but, as he does so,
releases the crook (which the fingers of the hand holding the vase
are just in position to do), and thus lets d fly up to the top of the
vase. Again he brings up the vase, apparently full as before, but
really having only a mere layer of berries, of the depth of d, at the
top. He now puts on the cover, the well in which again forces d and
the superposed layer of coffee-berries down to make way for it, and
causes the crook again to catch beneath the hollow of the foot. The
same operation is now gone through with the vase whose well
contains the sugar, and the box of white beans. The performer lastly
takes from the third vase a handful of bran, which he scatters to
show its genuineness, and then places the cover over it. The trick is
now really completed. On removing the respective covers (taking
care of course, first to turn the bayonet-catches in the right
direction), the wells are released from the covers and locked to the
vases, which are thus found full respectively of hot coffee and sugar,
and, on removing the cover of the third vase, the bran is lifted off
with it, and the milk is revealed.
Some coffee vases, and more particularly those of French make,
dispense with the bayonet-catch, replacing it by a peculiar
arrangement inside the top of the cover. The upper edge of the well
is slightly turned in all round, and the turning of the knob at the top
of the cover causes three flat bolts or catches to shoot out circularly
from the edges of a hollow disc, soldered to the top of the cover
inside, and insert themselves
under this projecting edge. (See
Figs. 224, 225.) The mechanical
arrangement by which this is
effected is almost impossible to
explain in writing, though it
becomes readily intelligible upon
an actual inspection of the Fig. 224. Fig. 225.
apparatus, and will be understood
without much difficulty after a slight study of the above diagrams,
the arrow in each case indicating the direction in which the knob
must be turned, in order to bring the bolts into the condition shown
in the opposite diagram.
The Wizard’s Omelet. (Borrowed Rings and Live Doves produced from
an Omelet.)—This is a trick which always produces a great sensation,
whether performed upon the stage or in the drawing-room. Its effect
is as follows: The performer produces either naturally or magically
(e.g., from the egg-bag, or from the mouth of his assistant, as
described at page 329) three eggs, which he hands round for
examination. His assistant next borrows from the audience three
ladies’ rings, receiving them, in order to prove that he does not
tamper with them in any way, on the performer’s wand instead of in
his hands. The wand, with the rings still upon it, is laid upon the
table. The assistant next brings in an omelet pan, and places it, with
its lid beside it, on the table. The performer breaks the eggs into it,
dropping in shells and all—then pours some spirits over it, to which
he sets fire, and while it is still blazing drops the rings from the wand
into it. He brings it forward to show that the rings are really in the
flames; and on returning to his table, claps the cover on the pan,
and fires a pistol (any ordinary pistol) over it. Without a moment’s
interval, he again removes the cover. All traces of the omelet and
egg-shells have vanished, but in their place are found three live
doves, each with a ribbon round its neck, to which is attached one of
the borrowed rings.
The explanation of this surprising result is simplicity itself. The
reader, with his present knowledge, will readily conjecture that, as to
the rings, a substitution is effected; but he may not so easily guess
the manner of such substitution. It will be remembered that the
rings were collected by the assistant on the performer’s wand. This
arrangement, which is ostensibly adopted to prevent, in reality
facilitates an exchange. The assistant makes his collection with three
dummy rings placed beforehand on the lower end of the wand, and
concealed by the hand in which he holds it; which, we will suppose,
is the right hand. In returning to the stage, he takes hold with the
left hand of the opposite end of the wand, and allows the borrowed
rings to run down into that hand, at the same moment releasing the
dummy rings from the right hand, and allowing them to run upon
the middle of the wand in place of the others. He now has the
borrowed rings in his left hand, and (laying the wand with the
substitutes on the table) carries them off with him to prepare for the
dénouement of the trick.
The only other matter
which will require explanation
is the construction of the
omelet pan. This is a shallow
pan of brass or tin, about ten
inches in diameter, by two and
a half in depth. Within this is
an inner pan, also of brass or
tin, fitting tightly within it, but
about half an inch less in
depth. The lid is made with a
very deep rim or shoulder all
round, and just fits within the
lining, though less tightly than
the latter fits within the pan. Fig. 233.
(See Fig. 233, in which a represents the pan, b the lining, and c the
lid.) The assistant, as soon as he gets behind the scenes, loops the
borrowed rings to the ribbons, which are already tied round the
necks of the three doves, and places the latter in b, immediately
putting on c (the two together having the appearance of a simple
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