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Organic Electronics for Electrochromic Materials and Devices
Organic Electronics for Electrochromic
Materials and Devices
Hong Meng
Author All books published by Wiley-VCH
are carefully produced. Nevertheless,
Prof. Hong Meng authors, editors, and publisher do not
Peking University warrant the information contained in
Shenzhen Graduate School these books, including this book, to
Building G 306 be free of errors. Readers are advised
Lishui Road, Nanshan Disctrict to keep in mind that statements, data,
518055 Shenzhen illustrations, procedural details or other
China items may inadvertently be inaccurate.
10 9 8 7 6 5 4 3 2 1
v
Contents
Preface xiii
About the Author xiv
1 Introduction 1
1.1 General Introduction 1
1.2 The History of Electrochromic Materials 3
1.3 The Key Parameters of Electrochromism 5
1.3.1 Electrochromic Contrast 5
1.3.2 Switching Time 8
1.3.3 Coloration Efficiency 9
1.3.4 Optical Memory 11
1.3.5 Stability 12
1.4 Conclusion 14
References 14
5 Metallohexacyanates 143
5.1 Background 143
5.2 Technology Development of PB 144
5.3 Crystal Structure 144
5.4 Electrochromic Mechanism 145
5.5 Synthesis 147
5.6 Electrochromic Devices (ECDs) 150
5.7 Nanocomposites 154
5.8 PB Analogs 160
5.9 Multifunctional Applications 170
References 175
Index 505
xiii
Preface
In recent years, with the development of artificial intelligence, more and more
industries strive to be “smart.” As a new generation of display technology, organic
electrochromic (OEC) devices offer numerous advantages such as flexibility, full
colors, wide origins of materials, fast switching time, low driving voltage, and
simple configuration. In addition, these devices possess “smart” characteristics of
multi-stimulation and multi-response. Therefore, the OEC industry is emerging as
a potential display competitor in the field of electronic information.
This book covers major topics related to the phenomenon of electrochromism,
including the history of organic electrochromism, fundamental principles, different
types of electrochromic materials, development of device structures, multifunctional
devices, their characterizations and applications, and future prospects of OEC tech-
nology. It also spotlights recent research progress reported by academic institutes
and enterprises, and discusses the existing challenges in further development of this
area.
This book provides a comprehensive review of OEC materials and devices, and
can be used as a teaching reference for undergraduate and graduate students as well
as teachers in the fields of organic chemistry and polymer science etc. Also, this
book can be adopted as a comprehensive reference for researchers engaged in the
development of OEC technology enterprise in the field of electrochromism.
Introduction
2.5
UV Visible Infrared
2
Irradiance W/(m2 nm)
1.5
5778 K blackbody
1
Sunlight at sea level
H2 O
Atmospheric
0.5 H2O
absorption bands
O2
H2O CO
O3 H2O 2 H2O
0
250 500 750 1000 1250 1500 1750 2000 2250 2500
Wavelength (nm)
Figure 1.1 Solar irradiance spectrum above atmosphere and at the surface of the Earth.
Source: Nick84: https://commons.wikimedia.org/wiki/File:Solar_spectrum_en.svg, Licensed
under CC BY-SA 3.0.
current, and ions are conducted by the electrolyte solution. Then the EC materials
undergo electrochemical oxidation and/or reduction, which results in changes in
the optical bandgap and colors. As shown in Figure 1.2, a typical ECD has five layers:
two transparent conducting oxide (TCO) layers, EC layer, ion-conducting layer
(electrolyte solution), ion storage layer. Particularly, the ion storage layer acts as the
“counter electrode” to store ions and keep electric charge balance. And according to
the exact state of EC materials, there are three types of ECD: film type (I), solution
type (II), and hybrid type (III). The Type I ECD is the most common; many kinds of
EC materials are suitable for this type including TMOs, conjugated/non-conjugated
polymers, metallo-supermolecular polymers, and MOF/covalent organic frame-
work (COF) materials, which using spin-coating, spray-coating, and dip-coating
processes to form uniform films; these films won’t dissolute in electrolyte solutions.
Type II ECD requires that the EC materials have good solubility in electrolyte
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pauperism, arranged by nationality, he is impressed by the immense
preponderance of the Germans and Irish among those listed. His
first conclusion is likely to be that the popular idea of the greater
desirability of these races over the newer immigrants is an error; but
as soon as he recalls how much longer these races have been in this
country, on the average, than the southeastern Europeans, he
realizes that these tables, taken by themselves, are wholly unreliable
as indicating relative tendencies among races. The following table
will serve as an illustration:
PER CENT OF FOREIGN-BORN PAUPERS IN ALMSHOUSES BY COUNTRY OF BIRTH[289]
294. The total of per cents adds up to more than 100 as more than one cause is
often reported for the same case.
There is no great difference in the proportions of the different
causes in the different general groups. It may be significant to note
that the per cent of cases due to the neglect or bad habits of the
breadwinner is a little larger for the native-born white of native
father than for the foreign-born, and larger for the native-born white
of foreign father than for either. If we take persons instead of cases,
the showing of the native-born of foreign father is even worse. The
relatively small number of cases due to this cause—the only one
which may be charged directly to the “fault” of the breadwinner—
indicates that the difficulty lies rather with the industrial system of
the United States than with the culpability of the individual.
That assimilation, in so far as it is represented by ability to speak
English, will not remedy the situation is indicated by some suggestive
figures given in the report on Charity Seekers above quoted. It is
shown (p. 70) that of the total number of persons assisted, six years
of age or over, belonging to non-English speaking races, 76.3 per cent
were able to speak English. Now in the report on Manufactures and
Mining it appears that only 53.2 per cent of the foreign-born
employees studied, belonging to non-English speaking races, could
speak English. That is, the percentage of dependents, who are so far
“assimilated” as to be able to speak English, is much greater than the
percentage of those who are at work, in spite of the fact that the
former class includes younger children than the latter. This
harmonizes with the fact already demonstrated, that dependent
foreigners have been in this country much longer than the average of
their group. It also lends color to the suggestion made by a charity
worker, that one reason why the newer immigrants do not appear in
larger numbers on the books of philanthropic organizations is that
they are not yet “on to the ropes,” and that as they become
familiarized with American methods, they will seek relief in
increasing numbers.
The subject of crime is customarily linked with that of pauperism
in the discussions of immigration, and the same claim is frequently
made, viz. that immigration has increased the amount of crime in
this country. The attempts at proof of this assertion generally follow
the same method adopted in the case of pauperism, that is, they
consist in an examination of the relative tendency toward criminality
of the general groups of native-born and foreign-born. In other
words, the line of argument is, if the foreign-born manifest a larger
proportion of criminals among their number than do the native-
born, all increases in the foreign-born population will mean a more
than proportional increase in crime for the country as a whole. There
is, however, another way in which immigration might operate to
increase crime. That is, by interfering with the natural adjustment of
economic relations between different classes, it may so alter the
condition of the native-born as to lead to an increase in crime in this
class. For instance, it has been claimed that a large proportion of the
“hobo” class (who are, to be sure, not necessarily criminal) are native
Americans who have been forced out of employment by foreign
competition. In a similar way, other individuals may have been
driven into active crime. This proposition, whatever the incidental
evidence for or against it, is manifestly incapable of statistical proof,
and for any semi-mathematical demonstration we must rely on the
other method of approach.
In the matter of crime the effort to make generalizations is
complicated by the fact that it is necessary to take into account, not
only the number of crimes, but the nature and severity of the
criminal act. Tests of criminality, to be accurate, should include
quality as well as quantity. This is obviously very difficult to do. We
are accustomed in everyday phraseology to speak of one crime as
being worse than another. Presumably crimes against the person are
more serious than crimes against property. In the case of crimes
against property, we might naturally consider it “worse” to steal
$1000 than $5, but it would not necessarily be so.
These conditions frequently result in an injustice to the immigrant.
The police and court records of our great cities show an amazing
proportion of crimes chargeable to the foreign population. For
instance, out of 71,253 persons held for trial or summarily tried and
convicted in the Magistrates’ Courts of New York City in 1907, only
30,261, or considerably less than half, were born in the United
States. But when these records are studied more closely it becomes
apparent that a large share of the offenses of the foreign-born are
violations of the city ordinances,—offenses which are comparatively
trivial in themselves do not indicate any special tendency toward
criminality, and are in many cases intimately associated with a low
station in life. The moral character of alien groups may in this way be
seriously misrepresented.
Nevertheless, if comparisons are to be made at all, they must rest
upon such records as these, and such allowances as are possible be
made afterwards. Figures of this kind are available in the
publications of the Census Bureau, the Commissioner General of
Immigration, and the Immigration Commission. In the census report
on Prisoners we find that of the prisoners enumerated in the United
States on June 30, 1904, 76.83 per cent were native-born, and 23.7
per cent foreign-born. In the general white population, ten years of
age or over, in 1900, 80.5 per cent were native-born and 19.5 per
cent foreign-born. If a due allowance is made for a disproportionate
growth of the foreign-born population between 1900 and 1904, the
relative proportions of prisoners among the two groups would be
approximately equal. Of the white prisoners of known nativity
committed during 1904 the percentages were as follows:
Nativity Total Major Offenders Minor Offenders
Native-born 71.2 per cent 78.3 per cent 69.9 per cent
Foreign-born 28.8 per cent 21.7 per cent 30.1 per cent
The somewhat less favorable showing made by the foreign-born in
the case of those committed than of those enumerated, is accounted
for by the large proportion of minor offenses among the foreign-
born. Many minor offenders, serving short sentences, would not be
included at all in the enumeration. Over half the major offenders
among the foreign-born had been in the United States ten years or
more, and about two thirds of the minor offenders.
According to the Report of the Commissioner General of
Immigration for 1908 (p. 98), there were in the penal institutions of
the United States, including Alaska, Hawaii, and Porto Rico (in
which the figures are not large enough to affect the conclusions
materially), in 1908, 149,897 inmates, of whom 15,323 were aliens,
8102 naturalized, and 126,562 native-born. Thus the percentage of
native-born was 84.4 and of foreign-born 15.6.
The Immigration Commission made a careful study of the matter
of crime among the immigrants, reviewing the foregoing data, and
collecting some original data of its own, covering 2206 convictions in
the New York City Court of General Sessions from October 1, 1908, to
June 30, 1909. This is, so far as known to the Commission, the first
time that any court in the United States had made a record of the
race of persons convicted in it. This fact illustrates the utter
inadequacy of the data for making any deductions as to the influence
of immigration upon crime in the United States. Not only courts, but
police departments and penal institutions, are very lax in their
keeping of records in this respect.
In response to the questions, “Is the volume of crime in the United
States augmented by the presence among us of the immigrant and
his offspring?” and “If immigration increases crime, what races are
responsible for such increase?” the Commission says that no
satisfactory answer has ever been made, or can ever be made,
without much more complete data than have ever been collected or
are available. Certain general conclusions, however, have been
reached by the Commission, which harmonize with those reached by
other students, and are worthy of acceptance as far as they go. First,
“No satisfactory evidence has yet been produced to show that
immigration has resulted in an increase in crime disproportionate to
the increase in adult population. Such comparable statistics of crime
and population as it has been possible to obtain indicate that the
immigrants are less prone to commit crime than are native
Americans.”[295] Second, “Immigration has, however, made changes
in the character of crime in the United States.”[296] These changes
have been in the direction of an increase in offenses of personal
violence, and offenses against public policy (disorderly conduct,
drunkenness, violation of corporation ordinances, etc.), some of
which are incident to city life, and probably in offenses against
chastity. There does not appear to have been any increase in the
majority of offenses against property, or, as they may be better
called, gainful offenses.[297]
Comparing the different races as regards criminality, it appears
that the Irish stand at the head as regards the total number of
offenses and the Germans next. In respect to major offenses,
however, the Germans stand first, while the Irish again take first
place in the minor offenses.[298] The Germans are much addicted to
crimes against property, the Irish and Scotch to drunkenness, Greeks
and natives of Russia to violations of corporation ordinances, and
immigrants from France, Russia, Poland, and Canada to crimes
against chastity. The Italians are preëminent in crimes of violence or
crimes against the person.[299]
It is even more difficult to postulate the causes of crime than of
pauperism. Until the criminologists have furnished us with a more
efficient means of determining the causes of crime in general, there
can be no profit in the attempt to classify the causes of crime among
a particular group of the population. In respect to the nature of crime
committed by different races, there seems to be something in the
racial character of some of our immigrants which predisposes them
in a certain direction, as exemplified in the preceding paragraph.
There is also evidence that among some of the newer immigrants,
crime is largely a matter of economic position. This is well illustrated
by the case of the Greeks. Among the members of this very recent
immigrant group, there has been a noteworthy decline in the average
of criminality within the last few years, and the explanation appears
to be that the crimes of the Greeks are such as correspond with a low
economic situation—violations of corporation ordinances, of the
sanitary code, etc. As a larger and larger proportion of the
individuals of this nationality rise above this lowly estate, the
percentage of crime among them falls off correspondingly.[300] This
emphasizes once more the responsibility of the United States for
some of the evil conditions for which we habitually blame the
immigrants.
There are two particular forms of crime which are closely
associated with foreign groups in the United States. These are the
Black Hand outrages and the white slave traffic. The former of these
is confined almost wholly to persons of the Italian race. In some of its
features it recalls the Molly Maguire occurrences of a generation
earlier. In fact, the resemblance between the Irish societies and the
Mafia of southern Italy was noted in a contemporary magazine
article at the time of the disturbances in the anthracite region of
Pennsylvania.[301] In both cases no organic connection between the
societies in the new world and the old is manifest. In fact, the best
judgment in regard to the Black Hand appears to be that there is no
real organization in existence in America, but that individuals of
Italian race use the power of the dreaded name to accomplish their
own ends. Like the Molly Maguires, the Black Hand operators utilize
warning letters, but they differ from them in that their purpose is
often, if not usually, blackmail, which was seldom the case with the
Irish society.
The white slave traffic has aroused tremendous public interest
during the last few years, and has been thoroughly exploited in the
daily and periodical press. Only the essential features, particularly in
their bearing on immigration, need to be reviewed in the present
connection. Not all of the girls concerned in this business are
immigrants, nor are all the persons who draw a revenue from it
foreigners; yet the various investigations of the subject have
demonstrated that the whole trade is fundamentally an affair of our
foreign population.
One surprising thing about this traffic is that essentially it is an
economic phenomenon. It is not a perverted sex passion which
demands the perpetuation of the inhuman system; it is the desire for
large and easy profits, and the life of indolence that goes with them,
which actuates the promoters of the traffic, while on the part of the
alien women it is frequently the desire for larger earnings which
brings them to our shores. The demand has to be stimulated.
There are two classes of these alien girls who are brought over.
One consists of innocent girls who are brought over under a false
understanding. The incentive is usually a false promise of
employment or of marriage. Sometimes false marriages, and
occasionally actual marriages, are resorted to. With this class of
subjects, the male importer is naturally the most successful. All kinds
of inducements are offered by the procurer, including an apparently
sincere love-making. About the only inducements which female
importers can offer to such girls are easier or more lucrative
employment. The other class, probably constituting a large majority,
are women who have already been leading an immoral life on the
other side, and come in the hope of bettering their prospects,
although they recognize the power of the importer.
These women and girls are usually brought over second class, and
every conceivable artifice is employed to deceive the inspectors.
When a girl has been safely introduced into the country, she is
completely in the power of the man who controls her. The
supposition is that the man furnishes protection and care to the girl
in return for her earnings. She is sometimes kept in a disorderly
house, sometimes in a hotel or other resort, but always where the
man can keep control of her. She is thoroughly frightened, and every
device is employed to keep her from communicating with any outside
sources of relief, or escaping. She is often deprived of street clothing,
so as to make escape impossible. She is kept heavily in debt, so that
there may be a legal claim over her. Only a very small part of her
earnings is given to her, and she is charged outrageous prices for all
the supplies which are furnished her. Her life is one of hopeless and
terrible degradation, and she has nothing to look forward to except a
wretched and continually descending existence, and an early death.
Alien women are particularly desirable to the promoters of this
traffic because their lack of connections in this country, and their
ignorance of the language and customs of the country make it more
difficult for them to escape or to make trouble for their men than in
the case of native girls. In addition to the terrible wrongs wrought
upon the women themselves, this practice has resulted in an increase
in the number of prostitutes in the United States, in the introduction
and dissemination of dangerous diseases, and in the introduction of
various forms of unnatural vice, more degrading and terrible than
even prostitution itself in its ordinary form.
The great majority of the alien women found by the Immigration
Commission engaged in these pursuits, as well as the men who
prosecute the traffic, are French and Hebrews. Belgians are largely
engaged in it, according to Commissioner Bingham. Germans are
numerous, and there are a few Irish and Italians, with of course a
scattering of individuals of other races.
A number of these women are detected at the port of entry and
returned, and a good many are deported. But it is a practice very
difficult of detection, and it is not easy to get at the facts in regard to
its extent in this country. It is certain that the class of abandoned
women in this country is largely recruited in this way. Commissioner
Bingham estimated in 1908 that there were more than 100,000 such
women on the Pacific coast and in Mexico, who had come in through
New York.
No evidence has been found to justify the suspicion that there was
an organization controlling this traffic in this country. But those
engaged in the trade naturally are acquainted with each other, and
are always ready to help each other against a common enemy. They
have various meeting places where they get together for gambling,
conference, and divers forms of recreation.
It has been proven that this traffic is slavery in more than name, as
girls are sometimes sold directly by one person to another. The new
federal law is designed to put a check to all practices of this sort, by
making it illegal to transport women or girls from one state to
another for immoral purposes. The efforts of the Immigration
Commission and other governmental agencies within the last two or
three years have accomplished a good deal in breaking up some of
the resorts, and deporting or imprisoning the culprits. But while the
traffic has received a serious setback, it is by no means killed. This is
emphatically one of the things where eternal vigilance is the price of
safety. Nothing short of a sweeping change in public opinion and
practice will ever put it out of the way beyond the possibility of
resurrection.[302]
In respect to juvenile delinquency the most unenviable place is
held by the native-born children of immigrants. They not only
manifest two or three times as great a tendency toward crime as the
native-born children of native parents, but they are much more
criminal than foreign-born children. Of the juvenile delinquents
committed during 1904, according to the census report, 76.7 per cent
were native white. This percentage was made up as follows: native
parentage, 37.6 per cent; foreign parentage, 24.9 per cent; mixed
parentage, 9.7 percent; parentage unknown, 4.5 per cent. An exact
comparison of the children of native parents and of foreign parents
in this respect would require information as to the total number of
the two classes in the country in the year in question, which is not
available. But it cannot be supposed that the number of native-born
children of foreign parents compared with the number of native-born
children of native parents is anything like the ratio shown in the
above figures. This high degree of criminality is attributed by
Professor Commons and by the Immigration Commission largely to
concentration in the cities. Whatever the cause, this tendency toward
lawlessness among the second generation of immigrants is
indisputable, and is one of the most disturbing elements in the whole
situation.[303]
Still another way in which the immigrant becomes a burden upon
the American public is through insanity. The laws are very strict in
regard to the admission of aliens who are liable to be subject to this
misfortune. Yet it is impossible to prevent the entrance of large
numbers who ultimately appear in the category of the insane. The
maladaptation of the immigrant to his environment shows itself in
this way perhaps as clearly as in any other.
In the institutions for the insane, both public and private, in the
United States, including Alaska, Hawaii, and Porto Rico, in 1908,
there were, according to the Report of the Commissioner General of
Immigration, 172,185 inmates. Of these 25,066 were aliens, 25,128
naturalized citizens, and 121,451 native-born. Thus the percentages
were 70.5 per cent native-born and 29.5 per cent—nearly one third—
foreign-born.[304]
An even larger percentage of foreign-born appears among the
insane persons enumerated in hospitals in continental United States
on December 31, 1903—34.3 per cent of the white insane of known
nativity[305]—while of the persons received at Bellevue and Allied
Hospitals for treatment for insanity during the period of the
investigation of the Immigration Commission, 63.4 per cent were
foreign-born, and 36.6 per cent native-born. Moreover, among the
native-born, more than half (20.6 per cent of the total) were native-
born of foreign father.
Summing up the matter of insanity, the Commission speaks as
follows: “For the high ratio of insanity among the foreign-born,
several causes have been assigned, and while it is difficult to
determine the values of the various factors it is probably true that
racial traits or tendencies have a more or less important influence. A
further cause of mental disease is probably to be found in the total
change in climate, occupation, and habits of life which the majority
of immigrants experience after arrival in the United States.”
The efficiency of the inspection in regard to feeble-mindedness is
shown by the very small proportion of foreign-born of that class
appearing in the statistics. This is an affliction which can more easily
be detected than the liability to insanity, of which there may be no
observable indication at the time of admission.[306]
CHAPTER XVI
INDUSTRIAL EFFECTS. CRISES. SOCIAL
STRATIFICATION. POLITICAL EFFECTS