Amorphous organic thin-film device, amorphous organic polymer composition, and amorphous inorganic composition

An amorphous organic thin-film device comprising an organic thin-film containing a dye molecules represented by the following formula (1) or (2): EQU R-X-Y!.sub.n (1) EQU R'-X'-Y!.sub.n (2) wherein R represents an aromatic skeleton, R' represents a heterocyclic aromatic skeleton, X represents a linkage group containing a chemical bond formed by a condensation reaction, X' represents a member selected from the group consisting of a single bond, --O--, --NH--, --NR"CO-- and --CH.sub.2 --, Y represents a dye skeleton with or without a substituent; and n is an integer of 3 or more, in which n members of X, X' and Y may be the same or different.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to an amorphous organic thin-film device, an 
amorphous organic polymer composition, and an amorphous inorganic 
composition for use in various applications. 
2. Description of the Related Art 
Recently, various types of electronic devices using thin films of organic 
materials have been extensively researched. Among the films of organic 
materials, an amorphous thin film is particularly important in view of 
transparency, homogeneity, and stability since the amorphous thin film has 
no grain boundary. For example, as an organic photosensitive thin film 
used in electrophotography according to the Carlson process, an amorphous 
thin film consisting of an amorphous polymer in which a charge-generation 
agent or a charge-transport agent is dispersed or dissolved homogeneously. 
As for an ultra thin film of organic materials, typically such as 
Langmuir-Blodgett film (LB film), an amorphous LB film consisting of a 
polymer or a dye is more homogeneous than the crystalline LB film formed 
of an aliphatic acid. The amorphous LB film has excellent properties as an 
ultra thin insulating film (e.g., Jpn. Pat. Appln. KOKAI Publication No. 
63-166261). In recent years, electroluminescence (EL) devices using 
vapor-deposited films of organic materials have been developed (e.g., Jpn. 
Pat. Appln. KOKAI Publication Nos. 57-51781, 59-194393, and 63-295695). In 
the EL devices, to decrease an applied voltage, a thin film of several 
tens of nanometers in thickness is required. In order to obtain a device 
which is durable against the vapor deposition process for an upper 
electrode and which has no electrical short circuit and high operational 
stability, amorphous thin films are used. Further, an organic thin film 
which efficiently transports electrons or holes is required not only for 
the aforementioned organic photosensitive bodies and the organic E1 
devices, but also for organic photovoltaic cells, organic rectifying 
devices, and the like. Hence, a stable amorphous thin film is strongly 
desired in these electronic devices. 
Further, an amorphous organic polymer composition consisting of an 
amorphous polymer containing a dye molecule, is employed not only as a 
thin film in the aforementioned organic photosensitive bodies, but also as 
a bulk material used in photoresist thin films, optical switching devices 
using optical waveguides, optical disks, and the like. In addition, the 
amorphous organic polymer composition is widely used as various coating 
thin films. Furthermore, an amorphous inorganic composition consisting of 
an inorganic glass containing a functional dye molecule, is used as 
various optical functional materials (e.g., Jpn. Pat. Appln. KOKAI 
Publication Nos. 2-302329 and 61-74638). 
Hitherto, however, with the exception of thin films comprising a polymer, 
amorphous thin films consisting of a low molecular-weight dye molecule 
have rarely been realized in electronic devices. The major reason for this 
is that due to low glass transition temperatures (Tg) of most amorphous 
thin films consisting of low molecular-weight materials, the 
crystallization is facilitated by heat generated when devices are driven, 
and degradation of amorphous thin films easily develops. In addition, a 
composition consisting of a polymer containing a low molecular-weight dye 
molecule carries a drawback in that when a dye having low Tg in a bulk 
state is used in such a composition, the Tg of the entire composition 
decreases, leading to a decrease in heat resistance. Note that in such a 
composition, if a crystalline dye is added to the polymer, the decrease in 
Tg can be prevented. However, in such a composition, it is impossible to 
raise the concentration of the dye since it is difficult to attain a 
homogeneous dispersion. Although the heat resistance can be improved if 
the dye molecules are chemically bound to the polymer, a difficulty in 
synthesis accompanies that. The same problems as those of the 
above-mentioned polymer composition arise in the case where the dye is 
contained in an inorganic glass by means of e.g., a sol-gel method. 
Particularly, since the highly ionic inorganic glass is generally poor in 
compatibility with various hydrophobic dyes, it is difficult to raise the 
concentration of the dye. 
From the foregoing, the demand has been increased to develop a low 
molecular-weight dye available for amorphous thin films which can be used 
in various types of electronic devices. However, amorphous thin films 
obtained from conventional low molecular-weight dyes have problems in that 
the films fail to have sufficient heat resistance due to low Tg and also 
it is difficult to raise the concentration of the dye. 
SUMMARY OF THE INVENTION 
It is an object of the present invention to develop a dye molecule from 
which a thin film or a bulk having high Tg can be obtained, thereby 
providing an amorphous organic thin-film device, an amorphous organic 
polymer composition, and an amorphous inorganic composition which have 
excellent heat resistance, a long life time, and satisfactory optical or 
electronic characteristics. 
The amorphous organic thin-film device of the present invention comprises 
an organic thin film containing a dye molecule, wherein the dye molecule 
has a molecular structure containing an aromatic skeleton and three or 
more dye skeletons which respectively bond to the aromatic skeleton via a 
chemical bond formed by a condensation reaction. 
Examples of the chemical bonds formed by a condensation reaction include an 
ester linkage, an amide linkage, a urethane linkage, a carbonate linkage, 
a thioester linkage, a urea linkage, a thiourea linkage, an ether linkage, 
a hydrazone linkage, a carbamate linkage and thioether linkage. It is 
preferable that at least one of three or more dye skeletons possess a 
substituent which can generate a hydrogen bond. 
The other amorphous organic thin-film device of the present invention 
comprises an organic thin film containing a dye molecule, wherein the dye 
molecule has a molecular structure containing a heterocyclic aromatic 
skeleton and three or more dye skeletons which bind to the heterocyclic 
aromatic skeleton so as to form a .pi. electron conjugated system. 
It is preferable that at least one of three or more dye skeletons possess a 
substituent which can generate a hydrogen bond, and that the heterocyclic 
aromatic skeleton contains an sp.sup.2 nitrogen atom. 
In the present invention, a composition can be prepared from an amorphous 
organic polymer in which one of the aforementioned two types of dye 
molecules is contained, and a composition prepared from an inorganic 
material in which one of the aforementioned two types of dye molecules is 
contained.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
Hereinbelow, the present invention will be described in detail. 
Generally, in an organic thin film, the heat resistance thereof can be 
increased by raising a glass transition temperature (Tg) of an organic 
material to be used. The present inventor has investigated various dye 
molecules with respect to the relationship between a thermodynamic 
parameter (.SIGMA..DELTA.aStr,m/Mw) and Tg. Where, Mw is a dye molecular 
weight, .SIGMA..DELTA.Str,m is the sum total of an entropy change of 
melting and entropy changes of transition from a glass transition point to 
a melting point in a dye crystal. In this study, the glass transition 
temperatures (Tg) of individual dyes were measured by means of a 
commercially available differential scanning calorimeter (DSC) under the 
same conditions: a sample weight of 10 to 20 mg, a heating rate of 
0.08.degree. C./s. Note that the sum total of an entropy change of melting 
and entropy changes of transition from a glass transition point to a 
melting point, is a physical value inherent in a substance. The results 
are shown in FIG. 1. 
Judging from FIG. 1, it is necessary to decrease .SIGMA..DELTA.Str,m/Mw to 
raise a value of Tg. It is expected that Tg of a dye can be increased if a 
value of .SIGMA..DELTA.Str,m/Mw is reduced by synthesizing a dye molecule 
having a large Mw. However, in general, with Mw is raised, 
.SIGMA..DELTA.Str,m also increases. Hence, to increase Tg, it is necessary 
to increase Mw without increasing .SIGMA..DELTA.Str,m. The present 
inventor carried investigation farther with respect to the relationship 
between .SIGMA..DELTA.Str,m and Mw pertaining to individual dyes. As a 
result, he found that Mw can be increased without providing a significant 
increase in .SIGMA..DELTA.Str,m if a dye molecule has a good symmetrical 
molecular structure of a spherical form with high density. 
Important properties of the amorphous thin film other than Tg include a 
maximum crystal growth velocity, MCV (mm/min) and Tc,max which is a 
temperature at which a maximum crystal growth is attained. With MCV 
decreases, crystallization becomes difficult to be induced. This property 
facilitates the formation of an amorphous thin film and the resultant 
amorphous thin film acquires stability. The higher Tc,max becomes, the 
harder the crystallization of the amorphous thin film is induced by heat 
generated when a device is driven. 
The present inventor found that the smaller .SIGMA..DELTA.Str,m/Mw, the 
larger Tc,max, and that MCV has a correlation with an enthalpy change of 
melting .DELTA.Hm(kJ/mol) and the melting point Tm(K), and further found 
that the larger Mw/(Tm/.DELTA.Hm) becomes, the smaller MCV becomes. Note 
that AHm corresponds to the intensity of cohesive force between molecules. 
Hence, to decrease MCV, it is necessary to weaken the cohesive force and 
is effective to make the molecule nearly spherical with good symmetriy. 
In view of the findings, the present inventor paid attention to a dye 
molecule having a molecular structure which has three or more dye 
skeletons bound around an aromatic skeleton thereof. Up until now, a 
device comprising an amorphous thin film with high Tg containing a dye 
molecule having aforementioned molecular structure, for example, 
represented by the following formula (23) has been proposed in Pat. Appln. 
KOKAI Publication No.5-152072. However, in the dye molecule, since dye 
skeletons bind directly to the aromatic skeleton located at the center, 
.pi. electrons conjugate each other, with the result that an absorption 
wavelength and a fluorescence wavelength shift to the longer wavelength 
side, compared to the inherent wavelength of the dye. Therefore, in this 
device, even if a dye molecule is designed in accordance with requisitive 
characteristics of the device, a shift of the absorption wavelength and 
fluorescence wavelength inevitably occurs, causing a problem in that the 
optical and electronic characteristics of the device changes due to the 
shift of wavelength. Besides this, the aforementioned dye molecule is 
difficult to synthesize since the synthesis requires many steps. 
##STR1## 
wherein R1, R2, and R3 are selected from the group consisting of 
--NH.sub.2, --N(CH3).sub.2 and --N(C.sub.2 H.sub.5).sub.2. 
In the present invention, use is made of a dye molecule consisting of an 
aromatic skeleton and three or more dye skeletons which are introduced 
into the aromatic skeleton via chemical bonds formed by a condensation 
reaction so as to exhibit high heat resistance, satisfactory optical and 
electronic characteristics. The dye molecule to be used in the present 
invention has chemical bonds formed by a condensation reaction between the 
aromatic skeleton and dye skeletons. For this reason, the dye molecule of 
the present invention differs from the dye molecule represented by the 
formula (23). To be more specific, the dye molecule used in the present 
invention can be represented by the following formula (1): 
EQU R-X-Y!.sub.n (1) 
wherein R represents an aromatic skeleton; X represents a linkage group 
containing a chemical bond formed by a condensation reaction such as-an 
ester linkage, an amide linkage, a urethane linkage, a carbonate linkage, 
a thioester linkage, a urea linkage, a thiourea linkage, an ether linkage, 
a hydrazone linkage, a carbamate linkage or a thioether linkage; Y 
represents a dye skeleton with or without a substituent; and n is an 
integer of 3 or more, in which n members of X and Y may be the same or 
different. 
In the present invention, a dye molecule is used, which has a nearly 
spherical form consisting of an aromatic skeleton typically such as a 
benzene ring, a biphenyl ring, and a condensed ring, around of which three 
or more dye skeletons are introduced via chemical bonds formed by a 
condensation reaction. It is preferable that the dye skeletons be 
introduced into an aromatic skeleton in such a way that the resultant dye 
molecule is not a linear nor an asymmetrical structure but a structure as 
symmetrical spherical as possible. An example of such a dye molecule is a 
dye molecule having a molecular structure containing the dye skeletons 
which are symmetrically introduced into 1-,3-, and 5-positions of a 
benzene ring, or 3-, 3'-, 5-, and 5'-positions of a biphenyl ring. 
The aromatic skeleton is not particularly restricted as long as it is 
trivalent or more. For example, the following skeletons (A-1) to (A-41) 
may be used. 
##STR2## 
wherein R represents hydrogen or an alkyl group. 
##STR3## 
Three or more dye skeletons may be the same or different and can be 
selected in accordance with its usage. For example, the following 
skeletons (B-1) to (B-79) may be used. However, the skeleton is not 
restricted to them. 
Fulvalenes 
##STR4## 
Heterocyclic compounds containing an ion 
##STR5## 
wherein .phi. represents an aryl group. 
##STR6## 
wherein R represents hydrogen or an alkyl group. 
##STR7## 
wherein M represents a metal ion capable of forming a complex compound 
##STR8## 
wherein Me represents a methyl group and R represents an alkyl group. 
##STR9## 
wherein Me represents a methyl group. 
##STR10## 
Others 
##STR11## 
wherein .phi. represents an aryl group. 
Such a dye skeleton may have an appropriate substitutent. Particularly, 
when the dye molecule has a substituent which can generate a hydrogen bond 
such as a hydroxyl group, a carboxyl group, an amido group, an amino 
group, a urethane group, or urea group is used, Tg of the resultant film 
can be improved by virtue of a hydrogen bond generated between molecules. 
On the other hand, when an alkyl group is used as a substituent, Tg and 
film-forming properties can be further adjusted by varying the type of 
alkyl group to be used. 
Linkage groups containing a chemical bond formed by a condensation reaction 
may contain other linkage as long as it contains a chemical linkage such 
as an ester linkage, an amido linkage, a urethane linkage, a carbonate 
linkage, a thioester linkage, a urea linkage, a thiourea linkage, an ether 
linkage, a hydrazone linkage, a carbamate linkage or thioether linkage 
represented by the formula below. Since Tg of the resultant film increases 
when the hydrogen bond generates between dye molecules, it is preferred to 
use a chemical linkage which can generate the hydrogen bond between 
molecules, such as an amido linkage, a urethane linkage, a urea linkage, 
or a thiourea linkage. 
##STR12## 
wherein R is hydrogen atom, an alkyl group or an aryl group. 
In the dye molecule represented by the formula (1), since a central 
aromatic skeleton thereof binds to an outer dye skeletons via chemical 
bonds formed by a condensation reaction, a .pi. electron conjugated system 
of the dye skeletons hardly expands over the chemical bond. Hence, 
compared to the wavelength inherent in the dye skeleton, the absorption 
wavelength and fluorescence wavelength of the dye molecule represented by 
the formula (1) do not shift to the long wavelength side, thereby 
successfully suppressing the change in the optical and electronic 
characteristics. The dye molecule represented by the formula (1) can be 
synthesized by a condensation reaction between a polyfunctional aromatic 
skeleton and monofunctional dye skeletons. Since such a condensation 
reaction is generally performed under mild conditions and provides a high 
yield, a desired dye molecule can be readily obtained. Further, when a 
thin film or a bulk is formed using a dye molecule consisting of an 
aromatic skeleton in which three or more dye skeletons are introduced as 
shown in the formula (1), it generally has a higher Tg value by 10.degree. 
to 200.degree. C. than that formed of a dye molecule consisting of an 
aromatic skeleton to which only two similar dye skeletons are introduced. 
As a method of forming the amorphous organic thin film according to the 
present invention, common methods can be used, which include a cast 
method, a vapor-deposition method, an LB method, a water-surface 
development method, an electrodeposition method, and the like. Among them, 
the vapor-deposition method is simple and advantageous particularly in 
forming a multi-layered film. 
In the present invention, a film having further higher heat resistance can 
be obtained by generating a chemical bonding between dye molecules, on or 
after the film forming process. For the purpose of generation of the 
chemical bond, there is a method of polymerizing unsaturated bonds by 
ultraviolet rays or x-rays radiation, on or after the film forming 
process, using a dye molecule containing a group having a polymerizable 
unsaturated bond, such as a vinyl group, a diacethylene group, or an allyl 
group. Alternatively, in order to obtain such a chemical bond, an organic 
thin film is formed of a cross-linking agent and a dye molecule having a 
condensable substituent such as a hydroxyl group, an amino group, a 
carboxyl group, a thiol group, or an aldehyde group, and the cross linking 
agent and the dye molecule may be allowed to react each other, on and 
after the film forming process. As an cross-linking agent to be used with 
a dye molecule containing a hydroxyl group and an amino group, for 
example, a diisocyanate compound can be used. 
In the present invention, an amorphous organic polymer composition can be 
provided by adding a dye molecule represented by the formula (1) to an 
amorphous organic polymer. In this case, the content of the dye molecule 
in the amorphous organic polymer composition is, desirably, 5 wt % or 
more, and 80 wt % or less. If the content is less than 5 wt %, the 
properties of the dye molecule may not be sufficiently available. On the 
contrary, if the content exceeds 80 wt%, the polymer properties may not 
sufficiently appear. 
The polymer constituting the amorphous organic polymer composition is not 
particularly restricted as long as it is an amorphous polymer. However, it 
is preferable that the molecular weight of the polymer be 3000 or more. 
More preferably, the molecular weight is 50,000 or more and 500,000 or 
less, taking properties as a polymer and formability thereof into 
consideration. 
Further, in the present invention, an amorphous inorganic composition can 
be provided by adding a dye molecule represented by the formula (1) to an 
amorphous inorganic material. In this case, the content of the dye 
molecule in the amorphous inorganic composition is desirably 5 wt % or 
more, and 80 wt % or less. If the content is less than 5 wt %, the 
properties of the dye molecule may not be sufficiently available. On the 
contrary, if the content exceeds 80 wt %, the properties as the inorganic 
material may not sufficiently appear. 
The inorganic material constituting the amorphous inorganic composition is 
not particularly restricted as long as it is an amorphous inorganic 
material. For example, an inorganic glass such as a silica glass, or a 
borate glass can be used. Particularly, in order to mix the dye molecule 
in a simple manner, an inorganic glass is preferable which is prepared by 
a sol-gel method using an organic solvent. In the sol-gel method, it is 
necessary that a temperature of heat treatment for obtaining a glass be 
less than the decomposing or denaturing temperature of the dye molecule. A 
practical heat treatment temperature varies depending on the dye molecule 
to be used; however, a temperature of 200.degree. C. or less is 
preferable. 
Since an inorganic glass, particularly, an oxide glass has a strong 
polarity of metal--oxygen bond, the inorganic glass and a non-polarized 
dye molecule are poor in compatibility each other. Particularly, when the 
concentration of the dye molecule is high, it is very difficult to 
homogeneously disperse the dye molecule in the inorganic glass by a 
conventional method. However, since the dye molecule according to the 
present invention contains three or more chemical bonds having a polarity, 
it can be homogeneously dispersed in the inorganic glass by virtue of 
interaction with the inorganic glass, even if the dye molecule present in 
a high concentration. In addition, by virtue of the interaction, even in 
higher temperatures, diffusion of the dye molecule rarely occurs, 
resulting in an increase in heat resistance. In particular, the dye 
molecule having chemical bonds which can generate a hydrogen bond can bind 
to a constitutional atom (mostly an oxygen atom) of the inorganic glass 
with a hydrogen bond, thereby improving compatibility and heat resistance. 
To return to the conventional dye molecules, their properties are not of a 
satisfactory level since they generally have poor heat resistance as 
described above and their charge transporting ability, in particular, 
electron-transport ability is not sufficient for use as a functional dye 
molecule. Taking the aforementioned dye molecule represented by the 
structure (23) as an example, its electron-transport ability has been 
improved but its function is still insufficient. 
In the present invention, to improve the charge-transport ability, the dye 
molecule is used having a heterocyclic aromatic skeleton and three or more 
dye skeletons bound to the heterocyclic aromatic skeleton in such a way 
that .pi. electrons conjugate. To be more specific, such a dye molecule 
can be represented by the following formula (2): 
EQU R'-X'- Y!.sub.n (2) 
wherein R' represents a heterocyclic aromatic skeleton, X' represents a 
member selected from the group consisting of a single linkage --O--, 
--NH--, --NR"CO--, where R" represents a hydrogen atom, an alkyl group or 
an aryl group, and Y and n are the same as those in the formula (1). 
In the dye molecule represented by the formula (2), by appropriately 
choosing a heterocyclic aromatic skeleton having the highest occupied 
molecular orbital level or the lowest unoccupied molecular orbital level 
(referred to as "HOMO level", "LUMO level", respectively), and then, by 
binding three or more dye skeletons to the heterocyclic aromatic skeleton 
so as to generate .pi. electron conjugated system, the HOMO level or the 
LUMO level of the entire dye molecule can be controlled, improving of the 
charge-transport ability. 
The heterocyclic aromatic skeleton of the dye molecule represented by the 
formula (2) is not particularly restricted. Examples of the heterocyclic 
aromatic skeletons include the aforementioned (A-19), (A-20), (A-24) to 
(A-41), and the like. Three or more dye skeletons may be the same or 
different, and may be chosen in accordance with their respective usages. 
Examples of the dye skeletons include the aforementioned (B-1) to (B-79), 
and the like. The dye skeleton may have a substituent. When the dye 
skeleton has a substituent such as a hydroxyl group, an amido group, an 
amino group, a urethane group, or a urea group, Tg of the resultant film 
can be improved more by virtue of a hydrogen bond generated between 
molecules. On the other hand, in the case where an alkyl group can be used 
as a substituent, Tg and film forming property can be adjusted by varying 
the type of alkyl group to be employed. For the aforementioned reasons, it 
is preferable that the dye molecule has the dye skeletons introduced so as 
to be made in a nearly spherical form. 
In the dye molecule represented by the formula (2), the HOMO level and the 
LUMO level can be controlled by choosing the type and the number of hetero 
atoms present in the heterocyclic aromatic skeleton. To be more specific, 
the heterocyclic aromatic skeleton having an sp.sup.2 nitrogen atom or 
phosphorus atom is superior in the acceptor property and lower in the LUMO 
level, to the corresponding carbocyclic aromatic skeleton. In particular, 
the dye molecule having an sp.sup.2 nitrogen atom in the heterocyclic 
aromatic skeleton increases in the acceptor property. This is considered 
effective in view of the present circumstance in which the dye molecule 
having a strong acceptor property is desired. On the other hand, the 
heterocyclic aromatic skeleton having oxygen, sulfur, selenium, sp.sup.3 
nitrogen, and the like, increases in donor property and the HOMO level. 
Therefore, as described above, the HOMO level and the LUMO level of an 
entire dye molecule can be controlled by the conjugation between the 
heterocyclic aromatic skeleton and the dye skeletons. The HOMO level and 
the LUMO level of the dye molecule can be controlled in a broader range if 
the most suitable heterocyclic aromatic skeleton is chosen, compared to 
the case in which the control is performed depending on only a molecular 
design of the dye skeleton. 
In the dye molecule represented by the formula (2), in the case where the 
dye skeletons and the heterocyclic aromatic skeleton are directly bound to 
each other on their sp.sup.2 or sp carbons, the degree of conjugation is 
the highest. However, in the case where the dye skeletons are indirectly 
bound to the heterocyclic aromatic skeleton via an appropriate linkage 
group, .pi. conjugation occurs to some extent. To be more specific, when 
they bind to each other via an oxygen atom or an nitrogen atom having a 
lone pair of electrons, .pi. electron conjugation occurs although the 
degree of the conjugation is smaller, compared to the case in which the 
binding is effected between sp.sup.2 or sp carbons. When they bind each 
other via an amido bond or an sp.sup.3 carbon, the .pi. conjugation occurs 
although the degree of the conjugation is significantly small. When the 
.pi. conjugation occurs between the heterocyclic aromatic skeleton and the 
dye skeletons, even if its degree is small, the HOMO level and the LUMO 
level can be effectively controlled. 
In the case where an amorphous organic thin film is formed using a dye 
molecule represented by the formula (2), the aforementioned common method 
can be applied. Among them, the vapor-deposition method is simple and 
advantageous particularly in forming a multi-layered film. In an attempt 
to attaining higher heat resistance, it is an effective method to generate 
a chemical bond between dye molecules, on or after the film forming 
process. 
In the present invention, an amorphous organic polymer composition can be 
provided by adding a dye molecule represented by the formula (2) to an 
amorphous organic polymer. In this case, the content of the dye molecule 
in the composition and the molecular weight of the polymer are the same as 
those described above. Alternatively, an amorphous inorganic composition 
can be provided by adding a dye molecule represented by the formula (2) to 
an amorphous inorganic material. In this case, the content of the dye 
molecule and the inorganic compound to be used are the same as above. 
Hereinbelow, application examples can be briefly explained. 
(Organic electroluminescence device) 
FIG. 2 is a elevational sectional view of an example of an organic 
electroluminescence device (EL device). As shown in FIG. 2, the EL device 
has a structure in which an organic thin film is sandwiched between two 
electrodes 1 and 5. The organic thin film sandwiched has a three-layered 
structure in which luminescent layer 3 containing fluorescent dye 
molecules is placed between a hole-transport layer 2 and an 
electron-transport layer 4. At least one of the two electrodes 1 and 5 
(e.g., electrode 1) is a transparent electrode. The organic thin film 
layer may be a multi-layered structure of four layers or more, or a 
two-layered structure consisting of a luminescent layer and the 
hole-transport layer or the electron-transport layer. In the organic EL 
device of either structure, electrons and holes are injected into the 
luminescent layer and recombined each other, thereby emitting light. The 
electron-transport layer and the hole-transport layer have a function to 
increase an injection probability of carriers. 
(Organic solar cell) 
An organic solar cell has a structure in which an organic thin film is 
sandwiched between two electrodes. The organic thin film may have a 
two-layered structure consisting of a charge-generation layer containing 
dye molecules which absorb visible light and generate electrons and holes, 
or multi-layered structure constituted by three or more layers having a 
charge-generation layer placed between a hole-transport layer and an 
electron-transport layer. At least one of the two electrode is a 
transparent electrode. In the cell of either structure, charges can be 
efficiently separated so that generated electrons and holes are prevented 
from recombining with each other, increasing the photoelectric conversion 
efficiency. 
(Organic photosensitive body for electrophotography) 
A photosensitive body has a structure on metal formed by stacking a 
charge-generation layer and either a hole transport agent or an electron 
transport agent in sequential order. The charge generation layer contains 
dye molecules which adsorb visible light and generate electrons and holes. 
In the case where the hole-transport layer is employed in the 
photosensitive body, the surface of the photosensitive body is negatively 
charged with corona discharge or the like. In the case of 
electron-transport layer, the surface of the photosensitive body is 
positively charged. Thereafter, when recording light is irradiated on the 
photosensitive body, electrons and holes are generated only in the 
irradiated portion. In the hole transport layer, the holes can be 
efficiently transported to the surface of the film of the photosensitive 
body and cancels the negative charges. When the film is developed using 
toner which has been positively charged, toner adheres onto the 
non-irradiated portion, thereby printing the obtained toner image on 
paper. On the other hand, in the electron-transport layer, electrons are 
efficiently transported to the surface of the film of the photosensitive 
body and cancels the positive charges. When the film is developed using 
toner which has been negatively charged, toner adheres onto the 
non-irradiated portion. As a result, the obtained toner image can be 
printed on paper. 
(Organic rectifying device) 
An rectifying device has a structure in which an organic thin film is 
sandwiched between two electrodes. The organic thin film sandwiched 
contains a hole-transport layer (P-type semiconductor) and an 
electron-transport layer (N-type semiconductor). In this device, 
rectification occurs in the same manner as in a P-N junction of an 
inorganic semiconductor. Further, as is the same manner as in the case of 
the inorganic semiconductor, when a small amount of acceptors and donors 
are doped into the hole-transport layer and the electron-transport layer, 
respectively, the current density can be increased. 
(Optical switching device) 
A switching device has a structure constituted of an organic thin film in 
which an optical path (waveguide) having a different refractive index from 
the surrounding region, is formed so as to be branched. In this device, 
when electric voltage is applied to one of branches of the waveguide, the 
refractive index thereof changes, causing a shift of the phases of the 
light components with different optical path lengths by exactly half a 
wavelength. This shift induces interference of light at the confluent 
point of the branched waveguide. An output light is therefore switched on 
and off in accordance with the presence and absence of the voltage 
application. 
(Optical disk) 
As an optical disk, use is made of a thin film consisting of dye molecules 
which absorb semiconductor laser beams, or the thin film consisting of an 
amorphous polymer in which dye molecules are homogeneously mixed/ Writing 
is performed by radiating a laser light to the film. The temperature of 
the irradiated spots increases and the crystallization of the dye molecule 
occurs. In this way, the writing is completed. Since the crystallized 
spots scatter the light, reading of the data is carried out. To erase the 
data, the disk film is melted by further raising temperature and returned 
to a homogeneous amorphous state. 
(Photochemical hole burning (PHB) optical memory) 
An amorphous organic polymer composition or an amorphous inorganic 
composition in which dye molecules are dispersed, are cooled with liquid 
nitrogen. To this composition, laser beams are irradiated having very 
narrow wavelength width which falls in the range of the absorption band of 
the dye molecules having a wide wavelength width. The dye molecules 
absorbing the laser beams are then subjected to a photochemical reaction, 
thereby recording sharp holes having a reduced absorption strength, on the 
original wide absorption band corresponding to the wavelength of the laser 
beams. When the wavelength of the laser is varied, a plurality of holes 
can be generated in a spot, thereby achieving multiple recording. 
(Color filter) 
A resist consisting of an amorphous organic polymer composition in which 
dye molecules are dispersed, is coated on a glass substrate, followed by 
patterning by light to cure a light-exposed portion. The unexposed portion 
is removed with a solvent, and then another resist consisting of an 
amorphous organic polymer composition in which another dye molecules are 
dispersed, is coated on the glass, and exposed to light to form a pattern. 
By repeating this procedure using the three primary colors, red, green, 
and blue, a color filter to be used in a liquid crystal display can be 
manufactured. 
It is a matter of course that the present invention is not restricted to 
the aforementioned thin film devices or bulk materials and can be applied 
to a wide range of usages requiring heat resistance, such as a surface 
coating material. 
EXAMPLES 
Synthesis example 1 
Synthesis of oxadiazole derivative 1 
1.5 g of 1,3,5-benzenetricarboxylic trichloride and 5.5 g of 
5-(2-aminophenyl)-2-(3-methoxyphenyl)-1,3,4-oxadiazole were reacted in dry 
pyridine for 5 hours at 80.degree. C. The reaction mixture was added to 
1000 ml of water. Then the generated precipitate was filtrated, and 
further washed well with acetone and warmed ethanol, thereby obtaining 4.5 
g of the oxadiazole derivative represented by the following formula (3) in 
a white powder form. 
______________________________________ 
Elemental analysis: C.sub.54 H.sub.39 N.sub.9 O.sub.9 
Carbon Hydrogen Nitrogen 
______________________________________ 
(Theoretical value) 
67.7% 4.1% 13.2% 
(Determined value) 
67.7% 4.1% 13.4% 
______________________________________ 
The infrared absorption spectrum of this oxadiazole derivative according to 
the KBr disk method is shown in FIG. 3. It was found that the glass 
transition temperature (Tg) of this oxadiazole derivative was 130.degree. 
C. as measured by the differential scanning calorimetry. In 
visible-ultraviolet absorption spectrum, the wavelength of the absorption 
edge of this compound in 1,4-dioxane coincides with that of the starting 
material, 5-(2-aminophenyl)-2-(3-methoxyphenyl)-1,3,4-oxadiazole. No shift 
toward the longer wavelength side was observed. 
##STR13## 
Synthesis example 2 
Synthesis of Oxadiazole Derivative 2 
1.0 g of cyanuric chloride and 5.0 g of 
4-aminophenyl-phenyl-1,3,4-oxadiazole were reacted in DMSO for a week at 
80.degree. C. The reaction mixture was added to water, and then the 
generated precipitate was washed with water and methanol, and further 
recrystallized in ethanol, thereby obtaining 1.0 g of the oxadiazole 
derivative represented by the formula (4) in a pale yellowish powder form. 
__________________________________________________________________________ 
Elemental analysis: C.sub.45 H.sub.30 N.sub.12 O.sub.3 
Carbon Hydrogen 
Nitrogen 
__________________________________________________________________________ 
(Theoretical value) 
68.7% 3.8% 21.4% 
(Determined value) 
67.5% 3.4% 20.8% 
##STR14## (4) 
__________________________________________________________________________ 
Synthesis example 3 
Synthesis of a Carbazole Derivative 
1.0 g of 1,3,5-benzenetricarboxylic trichloride and 2.2 g of 
N-aminocarbazole were reacted in dry pyridine for 5 hours at 80.degree. C. 
The reaction mixture was added to 1000 ml of water, and then the generated 
precipitate was flitrated, and further washed well with methanol and 
warmed ethanol, thereby obtaining 1.3 g of the carbazole derivative 
represented by the following formula (5) in a yellowish powder form. 
______________________________________ 
Elemental analysis: C.sub.45 H.sub.30 N.sub.6 O.sub.3 
Carbon Hydrogen Nitrogen 
______________________________________ 
(Theoretical value) 
76.7% 4.3% 11.9% 
(Determined value) 
76.0% 4.0% 11.0% 
______________________________________ 
The infrared absorption spectrum of this carbazole derivative according to 
the KBr disk method is shown in FIG. 4. It was found that the glass 
transition temperature (Tg) of this carbazole derivative was 230.degree. 
C. as measured by the differential scanning calorimetry. In 
visible-ultraviolet absorption spectrum, the wavelength of the absorption 
edge of this compound in 1,4-dioxane almost coincides with that of the 
starting material, N-aminocarbazole. No shift toward the longer wavelength 
side was observed. 
##STR15## 
Synthesis example 4 
Synthesis of a Naphthalene Derivative 1 
1.0 g of cyanuric chloride and 4.0 g of 1,3-dimethylnaphthalene were 
reacted in the presence of aluminum chloride in carbon tetrachloride for a 
week at 80.degree. C. The reaction mixture was added to cold diluted 
hydrochloric acid, and then the generated precipitate was washed with 
water and methanol, and further recrystallized in ethanol, thereby 
obtaining 1.0 g of the naphthalene derivative represented by the following 
formula (6) in a pale yellowish powder form. 
______________________________________ 
Elemental amlysis: C.sub.39 H.sub.33 N.sub.3 
Carbon Hydrogen Nitrogen 
______________________________________ 
(Theoretical value) 
86.2% 6.1% 7.7% 
(Determined value) 
85.0% 5.8% 7.6% 
##STR16## (6) 
______________________________________ 
Synthesis example 5 
Synthesis of a Naphthalene Derivative 2 
1.0 g cyanuric chloride and 5.0 g of potassium salt of 2-hydroxynaphthalene 
were reacted in the presence of 18-crown-6 in DMSO for two days at 
80.degree. C. The reaction mixture was added to water, and then the 
generated precipitate was washed with water and methanol, and further 
recrystallized in ethanol, thereby obtaining 1.0 g of the naphthalene 
derivative represented by the formula (7) in a pale yellowish powder form. 
______________________________________ 
Elemental amlysis: C.sub.33 H.sub.21 N.sub.3 O.sub.3 
Carbon Hydrogen Nitrogen 
______________________________________ 
(Theoretical value) 
78.1% 4.2% 8.3% 
(Determined value) 
78.0% 3.9% 7.8% 
##STR17## (7) 
______________________________________ 
Example 1 
Organic Electroluminescence Device 
A carbazole derivative represented by the aforementioned formula (5) was 
vapor-deposited onto a glass substrate/ITO electrode at a thickness of 50 
nm, thereby forming a hole-transport layer. On the hole-transport layer, 
pentaphenylcyclobutadiene was vapor-deposited at a thickness of 30 nm, 
thereby forming a luminescent layer. Further, on the luminescent layer, an 
oxadiazole derivative represented by the aforementioned formula (3) was 
vapor-deposited at a thickness of 50 nm, thereby forming an 
electron-transport layer. In this manner, an organic thin film layer 
having of a three layered structure was prepared. Finally, an aluminum 
electrode having an area of 1 cm.sup.2 was formed on the obtained organic 
thin film layer, thereby manufacturing an organic electroluminescence 
device. 
The initial luminance of the device was measured at a DC voltage of 10 V 
under a vacuum immediately after it was manufactured. The device exhibited 
a luminance of 500 cd/m.sup.2. When the device was continuously driven 
until the initial luminance decreased by half, it required 10 days. 
Example 2 
Organic Electroluminescence Device 
An organic electroluminescence device was manufacutred in the same manner 
as in Example 1 except that a triphenylamine derivative represented by the 
following formula (8) was used instead of a carbazole derivative 
represented by the aforementioned formula (5). Immediately after the 
device was manufactured, the initial luminance of the device was measured 
at a DC voltage of 10 V under a vacuum. The device exhibited a luminance 
of 700 cd/m.sup.2. when the device was continuously driven until the 
initial luminance decreased by half, it required 9 days. 
##STR18## 
Example 3 
Organic Solar Cell 
A carbazole derivative represented by the aforementioned formula (5) was 
vapor-deposited onto a glass substrate/ITO electrode at a thickness of 50 
nm, thereby forming a hole-transport layer. On this hole-transport layer, 
copper phthalocyanine was vapor-deposited at a thickness of 50 nm, thereby 
forming a charge-generation layer. Further, on the charge-generation 
layer, an oxadiazole derivate represented by the following formula (9) was 
vapor-deposited at a thickness of 50 nm, thereby forming an 
electron-tansport layer. In this manner, an organic thin film layer 
consisting of three-layered structure was prepared. Finally, three 
aluminum electrodes having an area of 1 cm.sup.2 were formed on the 
obtained organic thin film layer, thereby manufacturing an organic solar 
cell. 
Immediately after the cell was manufactured, the initial photoelectric 
conversion efficiency was measured by radiating light, from the glass 
substrate side, of a tungsten lamp from which ultraviolet rays of 400 nm 
or less were eliminated. As a result, each of three electrodes indicated a 
value in a range of 1.2 to 1.5%. When, the cell was continuously driven 
until the photoelectric conversion efficiency decreased by half, it 
required a half year. 
##STR19## 
Example 4 
Organic Photosensitive Body for Electrophotography 
Onto an aluminum vapor-deposited film formed on the glass, a polycarbonate 
film was casted in which copper naphthalocyanine was dispersed in an 
amount of 30 wt %, thereby forming a coating film (charge-generation 
layer) of 2 .mu.m in thickness. On this polycarbonate film, the coating 
film (hole-transport layer) of a polycarbonate having 2 .mu.m in thickness 
was formed in which a triphenylamine derivative represented by the 
following formula (10) was dissolved in an amount of 30 wt %. 
Immediately after the film was prepared, the film was charged to a surface 
potential of 700 V by means of corona discharge. Subsequently, attenuation 
of the surface charge potential of the resultant film was measured by 
radiating a monochromatic light having a wavelength of 630 nm and a power 
of 0.4 .mu.W/cm.sup.2. As a result, the film exhibited a high sensitivity 
of approximately 2 cm.sup.2 /.mu.J. Thereafter, the organic photosensitive 
body was left to stand for a half year at room temperature and subjected 
to the same measurement. As a result, no degradation caused by the storage 
was observed in the properties of the photosensitive body. 
##STR20## 
Example 5 
Organic Rectifying Device 
Onto an aluminum vapor-deposited electrode formed on the glass, the 
triphenylamine derivative represented by the aforementioned formula (8) 
was vapor-deposited, thereby forming a hole-transport layer. On this 
hole-transport layer, an oxadiazole derivative represented by the 
aforementioned formula (3) was vapor-deposited at a thickness of 20 nm, 
thereby forming an electron-transport layer. In this manner, organic thin 
film layer consisting of two-layered structure was prepared. Finally, an 
aluminum upper electrode having an area of 1 cm.sup.2 was formed on the 
organic thin-film layer. 
Immediately after the device was manufactured, the current-voltage 
characteristics of the resultant device were determined under a vacuum 
while light was being shielded. The device showed the rectification 
characteristics that a current was observed if the upper electrode was 
negative charged. Thereafter, the rectifying device was left to stand for 
a half year at room temperature and subjected to the same measurement. As 
a result, no degradation caused by the storage was observed in the 
properties. 
Example 6 
Optical Switching Device 
Onto the aluminum substrate, a polycarbonate thin film of 10 .mu.m in 
thickness was formed, containing a pyrene derivative represented by the 
following formula (11) in an amount of 30 wt %. To this thin film, 
ultraviolet rays were pattern-radiated to photo-oxidize the pyrene 
skeleton in air, thereby forming a branched optical path (waveguide) 
having a different refractive index from that of the surrounding region. 
In the thus-obtained device, when a voltage was applied to one of branches 
of the aforementioned waveguide and change the refractive index thereof, 
it is possible to shift the length of the optical path by exactly half a 
wavelength and switch an output light on and off in accordance with the 
presence and absence of the voltage application. Thereafter, the optical 
switching device was left to stand for a half year at room temperature and 
subjected to the same measurement. As a result, no degradation caused by 
the storage was observed in the properties of the optical switching 
device. 
##STR21## 
Example 7 
Optical Disk 
Onto a polycarbonate substrate, a chloroform solution of a pentacene 
derivative represented by the following formula (12) was spin-coated, 
thereby forming a thin film of 0.5 .mu.m in thickness. The produced thin 
film had an amorphous structure. To this thin film, semiconductor laser 
beams having a wavelength of 630 nm and a power of 0.4 .mu.W/cm.sup.2 were 
radiated, in order to heat to crystallize very small spots, thereby 
effecting writing. As a reading out light, semiconductor laser beams of 
630 nm in wavelength and 1 mW/cm.sup.2 in power were radiated to the disk 
film, and the reflection light was measured. Since the intensity of the 
reflection light was increased 10 times or more by virtue of the 
crystallization, the record was able to be read out with a high 
sensitivity. After such a writing was repeated for 10.sup.4 times, no 
change was observed. 
##STR22## 
Example 8 
Heat-resistant Transparent Organic-glass Film 
An oxadiazole derivative (ultraviolet absorbing dye) represented by the 
aforementioned formula (3) was mixed in polycarbonate in an amount of 10 
wt % based on the polycarbonate, and then, melt-molded to provide a 
transparent polycarbonate plate of 3 mm in thickness. The ultraviolet 
absorbing dye absorbs ultraviolet rays and converts the rays to heat or 
fluorescence of a long wavelength, thereby preventing degradation of a 
polymer caused by ultraviolet rays. 
This polycarbonate plate was left to stand for a half year in air. As a 
result, no color staining was observed and degradation of the properties 
of the polycarbonate plate was rarely occurred. 
Example 9 
Color Filter 
As red dye, a compound represented by the following formula (13) was mixed 
with a positive-working photoresist (manufactured by Tokyo Ohka Kogyo Co., 
Ltd.) in an amount of 50 wt % based on the positive-type photoresist. The 
mixture was spin-coated onto a glass substrate to form a coating layer of 
5 .mu.m in thickness. After ultraviolet rays were irradiated onto the 
coated glass substrate through a mask and the irradiated portion of the 
substrate was cured, non-exposed portion was washed off with a solvent. 
Second, as blue dye, a compound represented by the following formula (14) 
was mixed with the positive-working photoresist (manufactured by Tokyo 
Ohka Kogyo Co., Ltd.) in an amount of 50 wt % in a similar manner. This 
mixture was spin-coated onto the glass substrate. After ultraviolet rays 
were irradiated onto the coated glass substrate through a mask and the 
irradiated portion of the substrate was cured, non-exposed portion was 
washed off with a solvent. Subsequently, as a green dye, a compound 
represented by the following formula (15) was mixed with the 
positive-working photoresist (manufactured by Tokyo Ohka Kogyo Co., Ltd.) 
in an amount of 50 wt % in a similar manner. The mixture was spin-coated 
onto the glass substrate. After ultraviolet rays were inradiated onto the 
coated glass substrate through a mask, the irradiated portion of the 
substrate was cured, non-exposed portion was washed off with a solvent. 
Finally, a transparent thermosetting resin containing no dyes was coated 
on the resultant glass substrate and heated it up, thereby manufacturing a 
color filter. When this color filter was left to stand for two hours in 
air at 200.degree. C., no degradation such as color-fading was observed. 
##STR23## 
Example 10 
PHB Optical Memory 
A porphyrin derivative represented by the following formula (16) and 
triethoxysilane having an amount 100 times as high as that of the 
porphyrin derivative were dissolved in a mixed solvent of chloroform and 
ethanol. To the mixture, a small amount of diluted hydrochloric acid was 
added and the mixture was heated, thereby obtaining a sol. This mixture 
was casted onto a quartz substrate to form a film of 10 .mu.m in 
thickness. The obtained thin film was heated under a vacuum at 150.degree. 
C., thereby obtaining an amorphous inorganic composition. 
To this thin film, dye laser beams of 645 nm in wavelength were radiated 
for 30 seconds with a power of 30 .mu.W/cm.sup.2 in a liquid nitrogen. As 
a result, holes were generated in a Q1 band of porphyrin. The half life of 
the generated holes was a half year. 
##STR24## 
Example 11 
Organic Electroluminescence Device 
An organic electroluminescence device was manufactured in the same manner 
as in Example 1 except that electron-transport layer was formed using a 
naphthalene derivative represented by the aforementioned formula (6) 
instead of an oxadiazole derivative represented by the aforementioned 
formula (3). Further, the same measurement as in Example 1 was carried 
out. The device exhibited an initial luminance of 800 cd/m.sup.2. It took 
10 days to decrease the luminance by half. 
Example 12 
Organic Electroluminescence Device 
An organic electroluminescence device was manufactured in the same manner 
as in Example 11 except that a naphthalene derivative represented by the 
aforementioned formula (7) was used instead of a naphthalene derivative 
represented by the aforementioned formula (6). Further, the same 
measurement as in Example 1 was carried out. The device exhibited an 
initial luminance of 500 cd/m.sup.2. It took 9 days to reduce the 
luminance by half. 
Example 13 
Organic Electroluminescence Device 
An organic electroluminescence device was manufactured in the same manner 
as in Example 11 except that an oxadiazole derivative represented by the 
aforementioned formula (4) was used instead of a naphthalene derivative 
represented by the aforementioned formula (6). Further, the same 
measurement as in Example 1 was carried out. The device exhibited an 
initial luminance of 700 cd/m.sup.2. It took 10 days to decrease the 
luminance by half. 
Example 14 
Organic Electroluminescence Device 
An organic electroluminescence device was manufactured in the same manner 
as in Example 1 except that a triphenylamine derivative represented by the 
following formula (17) was used instead of a carbazole derivative 
represented by the aforementioned formula (5). Further, the same 
measurement as in Example 1 was carried out. The device exhibited an 
initial luminance of 600 cd/m.sup.2. It took 10 days to reduce the 
luminance by half. 
##STR25## 
Example 15 
Organic Solar Cell 
An organic solar cell was prepared in the same manner as in Example 3 
except that a naphthalene derivative represented by the aforementioned 
formula (6) was used instead of an oxadiazole derivative represented by 
the aforementioned formula (9). Further the same measurement as Example 3 
was carried out. The cell exhibits an initial photoelectric conversion 
efficiency of 1.2 to 1.5%. It took a half year to decrease the 
photoelectric conversion efficiency by half. 
Example 16 
Organic Photosensitive Body for Electrophotography 
Onto aluminum vapor-deposited electrode formed on the glass, a 
polycarbonate film in which copper phthalocyanine was dispersed in an 
amount of 30 wt %, was casted to form a coating film of 2 .mu.m in 
thickness, thereby forming a charge-generation layer. On the 
charge-generation layer, a polycarbonate coating film of 2 .mu.m in 
thickness was formed in which a triphenylamine derivative represented by 
the aforementioned formula (17) was dissolved in an amount of 30 wt %, 
thereby forming a hole-transport layer. 
Immediately after the film was prepared, the film was charged to 500 V of a 
surface potential by means of corona discharge. Subsequently, attenuation 
of the surface charge potential of the resultant film was measured by 
radiating a monochromatic light having a wavelength of 630 nm and a power 
of 0.4 .mu.W/cm.sup.2. As a result, the film exhibited approximately 2 
cm.sup.2 /.mu.J. From this result, it was found that organic 
photosensitive body was obtained whose sensitivity was higher than that 
obtained in Example 4. Thereafter, the organic photosensitive body was 
left to stand for a half year at romm temperature and subjected to the 
same measurement. As a result, no degradation caused by the storage was 
observed in the properties of the photosensitive body. 
Example 17 
Organic Rectifying Device 
An organic rectifying device was prepared in the same manner as in Example 
5 except that a triphenylamine derivative represented by the 
aforementioned formula (17) was used instead of that represented by the 
aforementioned formula (8) and an oxadizole derivative represented by the 
aforementioned formula (4) was used instead of that represented by 
aforementioned formula (3). 
Immediately after the device was manufactured, the current-voltage 
characteristics of the resultant device were determined under a vacuum 
while light was being shielded. The device showed the rectification 
characteristics that a current was observed if the upper electrode was 
negatively charge. Thereafter, the organic rectifying device was left to 
stand for a half year at room temperature and subjected to the same 
measurement. As a result, no degradation caused by storage was observed in 
its properties. 
Example 18 
Heat-resistant Transparent Organic-glass Film 
A transparent polycarbonate plate was prepared in the same manner as in 
Example 8 except that the oxadiazole derivative represented by the 
aforementioned formula (4) was used instead of that represented by the 
aforementioned formula (3). In this case, the ultraviolet absorbing dye 
absorbs ultraviolet rays and converts the rays to heat or fluorescence of 
long wavelength, thereby preventing degradation of a polymer caused by 
ultraviolet rays. 
The oxadiazole derivative represented by the formula (4) can reduce the 
LUMO level and is expected to suppress the electron transport in the 
polymer, thereby further preventing its degradation. This polycarbonate 
plate was left to stand for a year in air. As a result, no color staining 
was observed and degradation of the properties of the polycarbonate plate 
rarely occurred. 
Example 19 
PHB Optical Memory 
An amorphous inorganic composition was prepared in the same manner as in 
Example 9 except that a porphyrin derivative represented by the following 
formula (18) was used instead of that represented by a formula (16). 
To this film, dye laser beams were radiated. As a result, holes were 
efficiently generated in a Q1 band of porphyrin. The half life of the 
generated holes was a half year. 
##STR26## 
wherein R is the same as (13) 
Comparative Example 1 
The wavelength of the absorption edge of the compound whose oxadiazole 
skeleton was directly bound to a central benzene skeleton represented by 
the following formula (19), was 325 nm. A shift to the longer wavelength 
side was observed in this compound, compared to 310 nm of the wavelength 
of the absorption edge of a monomer represented by the following formula 
(20). In the wavelength of the absorption peak, the shift to the longer 
wavelength side by 25 nm was observed. 
##STR27## 
Comparative Example 2 
Organic Electroluminescence Device 
An organic electroluminescence device was manufactred prepared in the same 
manner as in Example 11 except that a naphthalene derivative represented 
by the following formula (21) was used instead of that represented by the 
aforementioned formula (6). The same measurement as in Example 1 was 
carried out. As a result, an initial luminance of this device was only 300 
cd/m.sup.2. 
##STR28## 
Comparative Example 3 
Heat Resistant Transparent Organic Glass Film 
A transparent polycarbonate plate was prepared in the same manner as in 
Example 18 except that an oxadiazole derivative represented by the 
following formula (22) was used instead of that represented by the 
aforementioned formula (4). This polycarbonate plate was left to stand for 
a year in air. As a result, color staining due to degradation was 
observed. 
##STR29##