ORGANIC MATERIAL AND ORGANIC OPTOELECTRONIC DEVICE USING THE SAME

Abstract

An organic material comprises a structure such as Formula I:

##STR00001##

The structure contains polycyclic fused rings, diene groups, and naphthalene rings, which can effectively enhance the thermal stability of the material. The invention also provides an organic optoelectronic device comprising a first electrode, an active layer, and a second electrode. The active layer comprises the aforementioned organic material. This organic optoelectronic device exhibits great dark current density, detectivity, and photoelectric conversion efficiency in the near-infrared wavelength range, as well as superior thermal stability.

Claims

1. An organic material comprises a structure such as Formula I: ##STR00049## wherein Ar1 is a monocyclic ring or polycyclic ring comprising at least one five-membered heterocycle or six-membered heterocycle with one or more heteroatoms, and the heteroatoms are independently selected from at least one of S, N, O, and Se; R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are independently selected from the following groups and their derivatives: C1-C30 alkyl, C1-C30 silyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 haloalkyl, C2-C30 ester, C1-C30 alkylaryl, C1-C30 alkyl heteroaryl, C1-C30 silyl aryl, C1-C30 silyl heteroaryl, C1-C30 alkoxyaryl, C1-C30 alkoxy heteroaryl, C1-C30 alkylthioaryl, C1-C30 alkylthio heteroaryl, C1-C30 haloalkyl aryl, C1-C30 haloalkyl heteroaryl, C2-C30 esteryl aryl, and C2-C30 esteryl heteroaryl; and R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13, R.sub.14, R.sub.15 and R.sub.16 are independently selected from the following groups and their derivatives: C1-C30 alkyl, C1-C30 silyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 haloalkyl, halogen, hydrogen, deuterium, tritium, and cyano group.

2. The organic material of claim 1, wherein an optical band gap of the organic material is <1.25 eV.

3. The organic material of claim 1, wherein Ar1 is selected from the following structures: ##STR00050## wherein each structure is connected by *, and R.sub.17 and R.sub.18 are independent single groups or connected to each other by covalent bonds to form a combined group.

4. The organic material of claim 3, wherein R.sub.17 and R.sub.18 are selected from the following groups and their derivatives: halogen, hydrogen, cyano, C1-C30 alkyl, C2-C30 alkenyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 halogenated alkyl, C2-C30 ester, C1-C30 alkylaryl, C1-C30 alkyl heteroaryl, C1-C30 silyl aryl, C1-C30 silyl heteroaryl, C1-C30 alkoxyaryl, C1-C30 alkoxy heteroaryl, C1-C30 alkylthioaryl, C1-C30 alkylthioheteroaryl, C1-C30 halogenated alkylaryl, C1-C30 halogenated alkyl heteroaryl, C2-C30 esteryl aryl and C2-C30 esteryl heteroaryl.

5. The organic material of claim 1, wherein R.sub.1 and R.sub.2 are further independently selected from the following groups and their derivatives: C1-C30 alkyl, C1-C30 alkylaryl and C1-C30 alkyl heteroaryl; and R.sub.3 and R.sub.4 are further independently selected from the following groups and their derivatives: C1-C30 alkyl, C1-C30 silyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 alkylaryl, C1-C30 alkyl heteroaryl, C1-C30 alkoxyaryl, C1-C30 alkoxy heteroaryl, C1-C30 alkylthioaryl, C1-C30 alkylthio heteroaryl, C1-C30 haloalkyl aryl and C1-C30 haloalkyl heteroaryl.

6. The organic material of claim 1, wherein R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13, R.sub.14, R.sub.15 and R.sub.16 are independently selected from the following groups: halogen, hydrogen, deuterium, and cyano group, and R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13, R.sub.14, R.sub.15 and R.sub.16 are not hydrogen atoms at same time.

7. The organic material of claim 1, wherein R.sub.5, R.sub.10, R.sub.11 and R.sub.16 are further selected from hydrogen; and R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.12, R.sub.13, R.sub.14 and R.sub.15 are further independently selected from the following groups and their derivatives: halogen, hydrogen, C1-C5 haloalkyl, C1-C5 alkoxy, and cyano group.

8. An organic composition comprising at least one P-type organic semiconductor material and at least one N-type organic semiconductor material, wherein the P-type organic semiconductor material comprises at least one of organic conjugated polymer or organic conjugated small molecule; and the N-type organic semiconductor material comprises at least one organic material of claim 1.

9. An organic optoelectronic device comprising: a first electrode; an active layer which at least comprises the organic material of claim 1; and a second electrode, wherein the active layer is disposed between the first electrode and the second electrode, and at least one of the first electrode and the second electrode is a transparent or semi-transparent electrode.

10. An organic optoelectronic device comprising: a first electrode; an active layer which at least comprises the organic composition of claim 8; and a second electrode, wherein the active layer is disposed between the first electrode and the second electrode, and at least one of the first electrode and the second electrode is a transparent or semi-transparent electrode.

Description

BRIEF DESCRIPTION OF THE APPENDED DRAWINGS

[0019] Some of the embodiments will be described in detail, with reference to the following figures, wherein like designations denote like members, wherein:

[0020] FIG. 1 shows a schematic structural diagram of one embodiment of an organic optoelectronic device of the present invention.

[0021] FIG. 2 shows absorption spectra in thin-film state of Comparative Example 1, Example 1, Example 2, Example 3, and Example 6 of the organic materials.

[0022] FIG. 3 shows the thin-film absorption spectra of Comparative Example 1 of the organic materials with and without annealing.

[0023] FIG. 4 shows the thin-film absorption spectra of Example 1 of the organic materials with and without annealing.

[0024] FIG. 5 shows the thin-film absorption spectra of Example 2 of the organic materials with and without annealing.

[0025] FIG. 6 shows the thin-film absorption spectra of Example 3 of the organic materials with and without annealing.

[0026] FIG. 7 shows the thin-film absorption spectra of Example 6 of the organic materials with and without annealing.

DETAILED DESCRIPTION OF THE INVENTION

[0027] In order to make the advantages, spirit and features of the present invention easier and clearer, it will be detailed and discussed in the following with reference to the embodiments and the accompanying drawings. It is worth noting that the specific embodiments are merely representatives of the embodiments of the present invention, but it can be implemented in many different forms and is not limited to the embodiments described in this specification. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

[0028] The terminology used in the various embodiments disclosed in the present invention is only for the purpose of describing specific embodiments, and is not intended to limit the various embodiments disclosed in the present invention. As used herein, singular forms also include plural forms unless the context clearly indicates otherwise. Unless otherwise defined, all terms (including technical and scientific terms) used in this specification have the same meanings as commonly understood by one of ordinary skill in the art to which the various embodiments disclosed herein belong. The above terms (such as those defined in commonly used dictionaries) will be interpreted as having the same meaning as the contextual meaning in the same technical field, and will not be interpreted as having an idealized or overly formal meaning, unless explicitly defined in the various embodiments disclosed herein.

[0029] In the description of this specification, the description of the reference terms an embodiment, a specific embodiment and the like means that specific features, structures, materials, or characteristics described in connection with the embodiment are included in at least one embodiment of the present invention. In this specification, the schematic expressions of the above terms do not necessarily refer to the same embodiment. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments.

Definition

[0030] As used herein, donor material and p-type (P-type) material refer to a semiconductor material, such as an organic semiconductor material, having holes as a primary current or charge carrier. In some embodiments, when a p-type semiconductor material is deposited on a substrate, it can provide the hole mobility greater than about 10.sup.5 cm.sup.2/Vs.

[0031] As used herein, acceptor material and n-type (N-type) material refer to the semiconductor material, such as the organic semiconductor material, having electrons as the primary current or the charge carrier. In some embodiments, when an n-type semiconductor material is deposited on a substrate, it can provide the electron mobility of more than about 10.sup.5 cm.sup.2/Vs.

[0032] * or * in the structures listed herein represents the available bonding positions of this structure, but not limited thereto.

[0033] As used herein, solution process refers to a process in which a compound (e.g., a polymer), material, or composition can be used in a solution state, such as spin coating, printing (e.g., inkjet printing, gravure printing, and lithography printing), spray coating, slit coating, drop casting, dip coating, and blade coating.

[0034] As used herein, annealing refers to a post-deposition thermal treatment to a semi-crystalline polymer film for certain duration in the environment or under decompressed or pressurized environment. Annealing temperature refers to the temperature at which the polymer film or the mixed film of the polymer and other molecules can perform small-scale molecular movement and rearrangement during the annealing process. Without being limited by any particular theory, it is believed that annealing can lead to an increase in crystallinity in the polymer film and enhance the carrier mobility of the polymer film or a mixed film formed by the polymer and other molecules, and the molecules are arranged alternately to achieve the effect of independent transporting paths of effective electrons and holes.

[0035] The external quantum efficiency (EQE) as used herein is the spectral response Amp/Watt unit, which Amp is converted to the number of electrons per unit time (electron/sec) and Watt is converted to the number of photons per unit time (Photons/sec), and insert the quantum efficiency obtained by the above formula. Generally speaking, quantum efficiency (QE) refers to external quantum efficiency (EQE), also known as incident photon-electron conversion efficiency (IPCE).

[0036] Dark current density (J.sub.d or J.sub.dark) as used herein, also known as no-illumination current, refers to the current flows in an optoelectronic device in the absence of light irradiation.

[0037] The responsibility (R) and the detectivity (D*) as used herein are based on measuring the dark current and external quantum efficiency (EQE) of the organic photodetector, and are calculated by the following formula:

[00001]$R\left(\right)=\mathrm{EQE}\frac{{}_q}{\mathrm{hc}},D^{*}=\frac{\left(/1240\right)\left(EQE\right)}{\sqrt{2e{J}_{dark}}}$

Wherein, is the wavelength, e is the elementary charge (1.60210.sup.19 Coulombs), h is Planck's constant (6.62610.sup.34 m.sup.2 kg/s), c is the speed of light (310.sup.8 m/sec), and J.sub.dark is the dark current.

[0038] In an embodiment, an organic material comprises a structure such as Formula I:

##STR00004##

Wherein, Ar1 is a monocyclic ring or polycyclic ring comprising at least one five-membered heterocycle with or without substituents or six-membered heterocycle with or without substituents with one or more heteroatoms. The heteroatoms are independently selected from at least one of S, N, O, and Se. R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are independently selected from the following groups: C1-C30 alkyl with or without substituents, C1-C30 silyl with or without substituents, C1-C30 alkoxy with or without substituents, C1-C30 alkylthio with or without substituents, C1-C30 haloalkyl with or without substituents, C2-C30 ester with or without substituents, C1-C30 alkylaryl with or without substituents, C1-C30 alkyl heteroaryl with or without substituents, C1-C30 silyl aryl with or without substituents, C1-C30 silyl heteroaryl with or without substituents, C1-C30 alkoxyaryl with or without substituents, C1-C30 alkoxy heteroaryl with or without substituents, C1-C30 alkylthioaryl with or without substituents, C1-C30 alkylthio heteroaryl with or without substituents, C1-C30 haloalkyl aryl with or without substituents, C1-C30 haloalkyl heteroaryl with or without substituents, C2-C30 ester aryl with or without substituents, and C2-C30 ester heteroaryl with or without substituents. R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13, R.sub.14, R.sub.15 and R.sub.16 are independently selected from the following groups: C1-C30 alkyl with or without substituents, C1-C30 silyl with or without substituents, C1-C30 alkoxy with or without substituents, C1-C30 alkylthio with or without substituents, C1-C30 haloalkyl with or without substituents, halogen, hydrogen, deuterium, tritium, and cyano group. This structure has good optical properties and an appropriate energy gap, and can be used with suitable p-type materials to make organic optoelectronic devices. Wherein, this structure has polycyclic condensed rings, diene groups and naphthalene rings. The structure of the present invention includes the following characteristics: 1. the optical band gap is lower than 1.25 eV; and 2. it has good thermal stability.

[0039] In a preferred embodiment, Ar1 is selected from one of the following structures:

##STR00005##

Wherein, each structure is connected by *, and R.sub.17 and R.sub.18 are independent single groups or connected to each other by covalent bonds to form a combined group. In practice, R.sub.17 and R.sub.18 are selected from the following groups: halogen, hydrogen, cyano, C1-C30 alkyl with or without substituents, C2-C30 alkenyl with or without substituents, C1-C30 alkoxy with or without substituents, C1-C30 alkylthio with or without substituents, C1-C30 haloalkyl with or without substituents, C2-C30 ester with or without substituents, C1-C30 alkylaryl with or without substituents, C1-C30 alkyl heteroaryl with or without substituents, C1-C30 silyl aryl with or without substituents, C1-C30 silyl heteroaryl with or without substituents, C1-C30 alkoxyaryl with or without substituents, C1-C30 alkoxy heteroaryl with or without substituents, C1-C30 alkylthioaryl with or without substituents, C1-C30 alkylthio heteroaryl with or without substituents, C1-C30 haloalkyl aryl with or without substituents, C1-C30 haloalkyl heteroaryl with or without substituents, C2-C30 esteryl aryl with or without substituents and C2-C30 esteryl heteroaryl with or without substituents.

[0040] In practice, R.sub.1 and R.sub.2 are further independently selected from the following groups: C1-C30 alkyl with or without substituents, C1-C30 alkylaryl with or without substituents and C1-C30 alkyl heteroaryl with or without substituents. R.sub.3 and R.sub.4 are further independently selected from the following groups: C1-C30 alkyl with or without substituents, C1-C30 silyl with or without substituents, C1-C30 alkoxy with or without substituents, C1-C30 alkylthio with or without substituents, C1-C30 alkylaryl with or without substituents, C1-C30 alkyl heteroaryl with or without substituents, C1-C30 alkoxyaryl with or without substituents, C1-C30 alkoxy heteroaryl with or without substituents, C1-C30 alkylthioaryl with or without substituents, C1-C30 alkylthio heteroaryl with or without substituents, C1-C30 haloalkyl aryl with or without substituents and C1-C30 haloalkyl heteroaryl with or without substituents.

[0041] In practice, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13, R.sub.14, R.sub.15 and R.sub.16 are independently selected from the following groups: halogen, hydrogen, deuterium, and cyano group, and R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13, R.sub.14, R.sub.15 and R.sub.16 are not hydrogen atoms at same time. In a preferred embodiment, R.sub.5, R.sub.10, R.sub.11 and R.sub.16 are further selected from hydrogen. R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.12, R.sub.13, R.sub.14 and R.sub.15 are further independently selected from the following groups: halogen, hydrogen, C1-C5 haloalkyl with or without substituents, C1-C5 alkoxy with or without substituents, and cyano group.

[0042] In details, the organic material could comprise the following example 1 to example 22:

##STR00006## ##STR00007## ##STR00008## ##STR00009## ##STR00010## ##STR00011## ##STR00012## ##STR00013## ##STR00014## ##STR00015## ##STR00016##

It should be understood that the above-listed embodiments are only intended to allow the person skilled in the art to understand the structure and composition of the present invention more clearly, and are not limited thereto.

[0043] In an embodiment, an organic composition of the present invention comprising at least one P-type organic semiconductor material and at least one N-type organic semiconductor material. The P-type organic semiconductor material comprises at least one of organic conjugated polymer or organic conjugated small molecule. The N-type organic semiconductor material comprises at least one organic material aforementioned.

[0044] Wherein, the P-type organic semiconductor material is further selected from at least one organic conjugated polymer. The conjugated polymer is composed of a plurality of monomers, and the monomers include one selected from the following structures and combinations thereof:

##STR00017##

wherein Ar2, Ar3, Ar4 and Ar5 are independently selected from a monocyclic or polycyclic structure.

[0045] The conjugated polymer further comprises the following structures:

##STR00018##

Wherein, Ar2, Ar3, Ar4 and Ar5 are monocyclic or polycyclic structures containing C4-C30 ring atoms respectively. n is a positive integer from 1 to 1000. x and y are molar fractions, where 0<x<1, 0<y<1 and x+y=1. In a preferred embodiment, at least one of the ring atoms included in Ar2, Ar3, Ar4 and Ar5 is a heteroatom, wherein the heteroatom is independently selected from at least one of S, O, Se, N, F, Cl and Si.

[0046] In one embodiment, Ar2 and Ar4 are independently selected from the following structures:

##STR00019##

Wherein, each structure is connected by *. A.sub.1, A.sub.2, A.sub.3 and A.sub.4 are independently selected from O, S and Se. R.sub.a, R.sub.b, R.sub.c, R.sub.d, R.sub.e and R.sub.f are independently selected from the following groups: hydrogen, halogen, cyano group, C1-C30 alkyl with or without substituents, C1-C30 alkoxy with or without substituents, C1-C30 alkylthio with or without substituents, C1-C30 haloalkyl with or without substituents, C2-C30 ester with or without substituents, C1-C30 alkylaryl with or without substituents, C1-C30 alkyl heteroaryl with or without substituents, C1-C30 silyl aryl with or without substituents, C1-C30 silyl heteroaryl with or without substituents, C1-C30 alkoxyaryl with or without substituents, C1-C30 alkyloxy heteroaryl with or without substituents, C1-C30 alkylthioaryl with or without substituents, C1-C30 alkylthio heteroaryl with or without substituents, C1-C30 haloalkyl aryl with or without substituents, C1-C30 haloalkyl heteroaryl with or without substituents, C2-C30 esteryl aryl with or without substituents and C2-C30 esteryl heteroaryl with or without substituents.

[0047] In a preferred embodiment, Ar2 and Ar4 are independently selected from one of the following structures:

##STR00020##

[0048] From the above embodiments, Ar2 and Ar4 are independently and preferably selected from one of the following structures:

##STR00021##

[0049] In one embodiment, Ar3 and Ar5 are independently selected from the following structures:

##STR00022## ##STR00023## ##STR00024##

[0050] Wherein, each structure is connected by *. A.sub.5, A.sub.6, A.sub.7 and A.sub.8 are independently selected from O, S and Se. R.sub.g, R.sub.h, R.sub.i, R.sub.j, R.sub.k and R.sub.l are independently selected from the following groups: hydrogen, halogen, cyano group, C1-C30 alkyl with or without substituents, C1-C30 alkoxy with or without substituents, C1-C30 alkylthio with or without substituents, C1-C30 haloalkyl with or without substituents, C2-C30 ester with or without substituents, C1-C30 alkylaryl with or without substituents, C1-C30 alkyl heteroaryl with or without substituents, C1-C30 silyl aryl with or without substituents, C1-C30 silyl heteroaryl with or without substituents, C1-C30 alkoxyaryl with or without substituents, C1-C30 alkyloxy heteroaryl with or without substituents, C1-C30 alkylthioaryl with or without substituents, C1-C30 alkylthio heteroaryl with or without substituents, C1-C30 haloalkyl aryl with or without substituents, C1-C30 haloalkyl heteroaryl with or without substituents, C2-C30 esteryl aryl with or without substituents and C2-C30 esteryl heteroaryl with or without substituents. Wherein, * and * are bonded by a single band.

[0051] In a preferred embodiment, Ar3 and Ar5 are independently selected from one of the following structures:

##STR00025## ##STR00026## ##STR00027##

[0052] From the above embodiments, Ar3 and Ar5 are independently and preferably selected from one of the following structures:

##STR00028## ##STR00029##

[0053] The substituents mentioned above can be independently selected from the following groups and their derivatives: C1-C30 alkyl, C3-C30 branched alkyl, C1-C30 silyl, C2-C30 ester, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 haloalkyl, C2-C30 olefin, C2-C30 alkyne, C2-C30 carbon chains containing cyano group, C1-C30 carbon chains containing nitro groups, C1-C30 carbon chains containing hydroxy groups, C3-C30 carbon chains containing keto groups, halogens, cyano groups, hydrogen, deuterium and tritium. The above-mentioned aryl group and heteroaryl group may have a monocyclic or polycyclic structure.

[0054] In practice, the conjugated polymer further comprises the following embodiments P-1P-39 and PBDB-T:

##STR00030## ##STR00031## ##STR00032## ##STR00033## ##STR00034## ##STR00035## ##STR00036##

##STR00037## ##STR00038## ##STR00039## ##STR00040##

It should be understood that the above-listed embodiments are only intended to allow the person skilled in the art to understand the structure and composition of the present invention more clearly, and are not limited thereto.

[0055] Please refer to FIG. 1. FIG. 1 shows a schematic structural diagram of one embodiment of an organic optoelectronic device of the present invention. As shown in FIG. 1, in another embodiment, the present invention further provides an organic optoelectronic device 1, which comprises a first electrode 11, a second electrode 15 and an active layer 13. The active layer 13, which comprises at least one of the aforementioned organic material comprising Formula I and the aforementioned organic composition, is disposed between the first electrode 11 and the second electrode 15. The organic optoelectronic device 1 further comprises a first carrier transporting layer 12 and a second carrier transporting layer 14. The organic optoelectronic device 1 may have a stacked structure, which sequentially includes a substrate 10, the first electrode 11 (transparent or semi-transparent electrode), the first carrier transporting layer 12, the active layer 13, the second carrier transporting layer 14 and the second electrode 15. The first carrier transporting layer 12 is configured to transport carriers in the first electrode 11 and the active layer 13, and the second carrier transporting layer 14 is configured to transport carriers in the active layer 13 and the second electrode 15. Specifically, the first carrier transporting layer 12 is one of an electron transporting layer and a hole transporting layer, and the second carrier transporting layer 14 is the other one. In detail, when the first carrier transporting layer 12 is the electron transporting layer, the second carrier transporting layer 14 is the hole transporting layer, which is an inverted stacked structure; when the first carrier transporting layer 12 is the hole transporting layer, the second carrier transporting layer 14 is an electron transporting layer, which is a conventional stacked structure. In practice, the organic optoelectronic device 1 may comprise an organic photovoltaic device, an organic photodetector device, or an organic light emitting diode.

[0056] In order to illustrate the organic composition of the present invention more clearly, the following experiments will be conducted using Comparative Example 1 and organic material Examples 1-3 and Example 6 of the invention to illustrate the differences in efficacy. These materials will then be further utilized as N-type organic semiconductor materials combined with at least one P-type organic semiconductor material to prepare the organic composition. The active layers comprising the aforementioned organic materials or organic compositions will be fabricated into organic optoelectronic devices for material testing and device performance evaluation.

[0057] For the optical physical quality testing part of material testing and device testing, the UV absorption spectrum measurement instrument model is Hitachi UH5700, and the oxidation potential is measured by using cyclic voltammetry with CH Instrument 611E.

Synthesis of Example 1

Synthesis of M2

##STR00041##

[0058] Tributyl(1,3-dioxolan-2-ylmethyl)phosphonium bromide (0.66 g, 1.80 mmol), M1 (0.70 g, 0.45 mmol) and sodium hydride (60%, 0.10 g, 2.70 mmol) were placed sequentially into a 100 mL two necked flask. Under argon atmosphere, anhydrous tetrahydrofuran was added and stirred with a magnet, and the mixture was reacted at room temperature for 6 hours. 10% dilute hydrochloric acid (3.5 mL) was added, and the mixture was stirred at room temperature for 30 minutes. The mixture was extracted three times with heptane/water, the organic layers were collected, magnesium sulfate was added to remove water, and the solvent was removed. The crude product was purified by silica gel column chromatography (the eluent was heptane/dichloromethane=1/3) to obtain a red oil M2 (700 mg, yield 97%). .sup.1H NMR (600 MHz, CDCl.sub.3): 9.70 (d, J=7.8 Hz, 2H), 8.09 (d, J=15.0 Hz, 2H), 7.31 (d, J=4.2 Hz, 2H), 6.94 (d, J=3.6 Hz, 2H), 6.60 (dd, J=15.0 Hz, J=7.8 Hz, 2H) 4.62 (d, J=4.2, 4H), 2.89 (t, J=7.8, 4H), 2.06 (m, 2H), 2.78 (m, 2H), 1.37-0.67 (m, 120H).

Synthesis of Example 1

##STR00042##

M2 (350 mg, 0.22 mmol), M3 (183 mg, 0.65 mmol) and chloroform (10.5 mL) were placed in a 100 mL two necked flask and stirred with a magnet under argon for 30 minutes. Pyridine (0.18 mL) was added in an ice bath and the reaction was allowed to react for 24 hours. Methanol was added to precipitate the product, and the solid was collected by suction filtration. The crude product was purified by silica gel column chromatography (the eluent was heptane/dichloromethane=1/5) to obtain Example 1 (320 mg, yield 69%) as a blue-black solid. .sup.1H NMR (600 MHz, CDCl.sub.3): 9.11 (s, 2H), 8.89 (dd, J=14.4 Hz, J=12.0 Hz, 2H), 8.60 (d, J=11.4, 2H), 8.30 (s, 2H), 8.08 (d, J=14.4 Hz, 2H), 7.87-7.80 (m, 4H), 7.36 (d, J=3.6 Hz, 2H), 6.98 (d, J=3.6 Hz, 2H), 4.69 (d, J=7.2 Hz, 4H), 2.90 (d, J=6.6 Hz, 4H), 2.13-2.11 (m, 2H), 1.78 (m, 2H), 1.38-0.70 (m, 120H).

Synthesis of Example 2

Synthesis of M5

##STR00043##

Tributyl(1,3-dioxolan-2-ylmethyl)phosphonium bromide (0.58 g, 1.56 mmol), M4 (0.66 g, 0.39 mmol) and sodium hydride (60%, 0.06 g, 2.34 mmol) were placed sequentially into a 100 mL two necked flask. Under argon atmosphere, anhydrous tetrahydrofuran was added and stirred with a magnet, and the mixture was reacted at room temperature for 6 hours. 10% dilute hydrochloric acid (3.3 mL) was added, and the mixture was stirred at room temperature for 30 minutes. The mixture was extracted three times with heptane/water, the organic layers were collected, magnesium sulfate was added to remove water, and the solvent was removed. The crude product was purified by silica gel column chromatography (the eluent was heptane/dichloromethane=1/1) to obtain a red oil M5 (475 mg, yield 69%). .sup.1H NMR (600 MHz, CDCl.sub.3): 9.70 (d, J=7.8 Hz, 2H), 7.78 (d, J=15.0 Hz, 2H), 7.33 (s, 2H), 6.53 (dd, J=15.3 Hz, J=7.5 Hz, 2H), 4.63 (d, J=6.6 Hz, 4H), 3.02 (t, J=7.8, 4H), 2.88 (m, 4H), 2.07 (m, 2H), 1.78 (m, 2H), 1.71 (m, 2H), 1.47-0.69 (m, 128H).

Synthesis of Example 2

##STR00044##

M4 (100 mg, 0.06 mmol), M3 (48 mg, 0.17 mmol) and chloroform (5 mL) were placed in a 100 mL two necked flask and stirred with a magnet under argon for 30 minutes. Pyridine (0.1 mL) was added in an ice bath and the reaction was allowed to react for 24 hours. Methanol was added to precipitate the product, and the solid was collected by suction filtration. The crude product was purified by silica gel column chromatography (the eluent was heptane/dichloromethane=1/10) to obtain Example 2 (60 mg, yield 45%) as a blue-black solid. .sup.1H NMR (600 MHZ, CDCl.sub.3): 9.09 (s, 2H), 8.81-8.77 (m, 2H), 8.60 (d, J=11.4 Hz, 2H), 8.27 (s, 2H), 7.84-7.77 (m, 6H), 7.35 (s, 2H), 4.69 (m, 4H), 3.08 (t, J=7.8, 4H), 2.89 (m, 4H), 2.18 (m, 2H), 1.89 (m, 4H), 1.82 (m, 2H), 1.43-0.72 (m, 126H).

Synthesis of Example 3

##STR00045##

M6 (200 mg, 0.15 mmol), M3 (130 mg, 0.45 mmol) and chloroform (5 mL) were placed in a 100 mL two necked flask and stirred with a magnet under argon for 30 minutes. Pyridine (0.1 mL) was added in an ice bath and the reaction was allowed to react for 20 hours. Methanol was added to precipitate the product, and the solid was collected by suction filtration. The crude product was purified by silica gel column chromatography (the eluent was heptane/dichloromethane=1/10) to obtain Example 3 (270 mg, yield 99%) as a blue-black solid. .sup.1H NMR (500 MHz, CDCl.sub.3): 9.12 (s, 2H), 8.83-8.78 (m, 2H), 8.62 (d, J=12.0 Hz, 2H), 8.30 (s, 2H), 7.87-7.81 (m, 4H), 7.78 (d, J=14.0 Hz, 2H), 4.66 (d, J=8.0 Hz, 4H), 3.05 (t, J=7.8 Hz, 4H), 2.12-2.11 (m, 2H), 1.90-1.85 (m, 4H), 1.30-0.71 (m, 98H)

Synthesis of Example 6

Synthesis of M14

##STR00046##

Tributyl(1,3-dioxolan-2-ylmethyl)phosphonium bromide (0.34 g, 0.92 mmol), M13 (0.30 g, 0.23 mmol) and sodium hydride (60%, 0.03 g, 1.39 mmol) were placed sequentially into a 100 mL two necked flask. Under argon atmosphere, anhydrous tetrahydrofuran was added and stirred with a magnet, and the mixture was reacted at room temperature for 6 hours. 10% dilute hydrochloric acid (1.5 mL) was added, and the mixture was stirred at room temperature for 30 minutes. The mixture was extracted three times with heptane/water, the organic layers were collected, magnesium sulfate was added to remove water, and the solvent was removed. The crude product was purified by silica gel column chromatography (the eluent was heptane/dichloromethane=1/1.5) to obtain a red oil M14 (260 mg, yield 83%). .sup.1H NMR (600 MHz, CDCl.sub.3): 9.70 (d, J=7.5 Hz, 2H), 7.77 (d, J=15.0 Hz, 2H), 6.51 (dd, J=7.5 Hz, J=15.0 Hz, 2H), 4.55 (d, J=8.0 Hz, 4H), 2.98 (t, J=7.5 Hz, 4H), 2.04 (m, 2H), 1.86-1.83 (m, 4H), 1.28-0.67 (m, 98H).

Synthesis of Example 6

##STR00047##

M14 (260 mg, 0.19 mmol), M3 (161 mg, 0.58 mmol) and chloroform (8 mL) were placed in a 100 mL two necked flask and stirred with a magnet under argon for 30 minutes. Pyridine (0.26 mL) was added in an ice bath and the reaction was allowed to react for 24 hours. Methanol was added to precipitate the product, and the solid was collected by suction filtration. The crude product was purified by silica gel column chromatography (the eluent was heptane/dichloromethane=1/9) to obtain Example 6 (227 mg, yield 63%) as a blue-black solid. .sup.1H NMR (600 MHz, CDCl.sub.3): 9.12 (s, 2H), 8.82-8.78 (m, 2H), 8.62 (d, J=12.0 Hz, 2H), 8.29 (s, 2H), 7.87-7.77 (m, 6H), 4.61 (d, J=7.2 Hz, 4H), 3.04 (t, J=7.8 Hz, 4H), 2.12 (m, 2H), 1.87 (quint, J=7.2 Hz, 4H), 1.52-0.71 (m, 98H).

[0059] Material testing of organic material Examples 1 to 3 and Example 6 and Comparative Example 1 includes material optical property testing:

The structure of Comparative Example 1 is as follows:

##STR00048##

[0060] Please refer to FIG. 2 and Table 1. FIG. 2 shows absorption spectra in thin-film state of Comparative Example 1, Example 1, Example 2, Example 3, and Example 6 of the organic materials. Table 1 shows the material test of organic material Comparative Example 1, Example 1, Example 2, Example 3, and Example 6 (including the data results of FIG. 2).

TABLE-US-00001 TABLE 1 the material test of organic material Comparative Example 1, Example 1, Example 2, Example 3, and Example 6 (including the data results of FIG. 2). organic .sub.soln.sup.max .sub.film.sup.max .sub.film.sup.onset (10.sup.5 E.sub.g.sup.opt HOMO LUMO material (nm) (nm) (nm) cm.sup.1M.sup.1) (eV) (eV) (eV) Comparative 801 918 1025 1.19 1.21 5.51 4.30 Example 1 Example 1 841 939 1069 1.35 1.16 5.44 4.28 Example 2 847 900 1014 1.16 1.22 5.52 4.37 Example 3 835 922 1058 1.38 1.17 5.54 4.37 Example 6 844 943 1080 1.54 1.15 5.43 4.28
As shown in FIG. 2 and Table 1, the organic material Example 1, Example 2, Example 3 and Example 6 have good performance in absorption spectra. The maximum absorption values of the organic materials in thin-film state, as shown in Table 1, fall within the range of 900-943 nm, and the onset absorption values range from 1014-1080 nm. In FIG. 2, the thin film absorption spectrum of the organic material shows good absorption properties in the range of 300-1100 nm, with an extinction coefficient of 1.16-1.5410.sup.5 cm.sup.1M.sup.1. The application range of the above-mentioned Comparative Example 1, Example 1, Example 2, Example 3, and Example 6 can be from visible light to infrared light.

[0061] Thermal stability performance test of single material absorbance:

[0062] Please refer to FIG. 3 to FIG. 7. FIG. 3 shows the thin-film absorption spectra of Comparative Example 1 of the organic materials with and without annealing. FIG. 4 shows the thin-film absorption spectra of Example 1 of the organic materials with and without annealing. FIG. 5 shows the thin-film absorption spectra of Example 2 of the organic materials with and without annealing. FIG. 6 shows the thin-film absorption spectra of Example 3 of the organic materials with and without annealing. FIG. 7 shows the thin-film absorption spectra of Example 6 of the organic materials with and without annealing. In order to test the stability of the material after annealing, the thin film organic material was heated at 220 C. for 30 minutes in the atmosphere, and the absorption spectrum was used to observe the changes in its absorption intensity and waveform before and after annealing. As shown in FIG. 3, the absorption intensity of the organic material Comparative Example 1 decreases significantly after annealing, and the absorption spectrum undergoes a blue shift. As shown in FIG. 4 to FIG. 7, in contrast, the absorption intensity of organic material Example 1, Example 2, Example 3, and Example 6 does not decrease significantly after annealing, and maintains a certain onset absorption value. It can be seen that the organic materials of the present invention have good thermal stability and can maintain good device performance under device manufacturing and device operation requiring high temperature operation.

[0063] Preparation and performance testing of organic photodetectors of organic optoelectronic devices:

[0064] A glass coated by a pre-patterned indium tin oxides (ITO) with a sheet resistance of 15 /sq is used as a substrate. The substrate is ultrasonically oscillated in soap deionized water, deionized water, acetone, and isopropanol in sequence, and washed in each step for 15 minutes. The washed substrate is further treated with a UV-ozone cleaner for 15 minutes. The top coat of AZO (Aluminum-doped zinc oxide) solution is spin coated on the ITO substrate with a spin rate of 2000 rpm for 40 seconds, and then baked at 120 C. in air for 5 minutes to form an electron transporting layer (ETL). The active layer solution comprises the aforementioned organic composition, wherein at least one P-type organic semiconductor material is used as a donor material, and at least one N-type organic semiconductor material is used as an acceptor material (the weight ratio of donor material to acceptor material is 1:12). The concentration of the donor material was 1020 mg/mL. In order to completely dissolve the active layer material, the active layer solution needs to be stirred on a hot plate at 100 C. for at least 3 hours. After completely dissolving the active layer material, the active layer solution is filtered with PTFE filter membrane (pore size 0.451.2 m) and heated for 1 hour. Then, the active layer solution is cooled to the room temperature for spin coating, and the spin rate was used to control the film thickness in the range of 100-800 nm. Finally, the thin film formed by the coated active layer is annealed at 100 C. for 5 minutes, and then transferred to a thermal evaporation machine. A thin layer (8 nm) of MoO.sub.3 is deposited as a hole transporting layer (HTL) under a vacuum of 310.sup.6 Torr. In this experiment, a Keithley 2400 source meter was used to record the dark current density (J.sub.dark, at a bias of 08 V) in the absence of light. External quantum efficiency system was used to measure external quantum efficiency (EQE) with a range of 300-1100 nm (bias voltage 08 V), and silicon (300-1100 nm) is used for light source calibration.

[0065] It should be noted here that, in practical applications, the first electrode preferably has good light transmittance. The first electrode is usually made of the transparent conductive material, preferably selected from one of the following conductive material groups: indium oxide, tin oxide, fluorine-doped tin oxide (FTO) derivative, or composite metal oxides such as indium tin oxide (ITO) and indium zinc oxide (IZO). The material of the second electrode is a conductive metal, preferably silver or aluminum, more preferably silver. Suitable and preferred materials for electron transporting layer include, but are not limited to, metal oxides such as ZnO.sub.x, aluminum doped ZnO (AZO), TiO.sub.x or nanoparticles thereof, salts (such as LiF, NaF, CsF, Cs.sub.2CO.sub.3), amines (such as primary amines, secondary or tertiary amines), conjugated polymer electrolytes (such as polyethyleneimine), conjugated polymers (such as poly[3-(6-trimethylammoniumhexyl)thiophene], poly(9,9)-bis(2-ethylhexyl-fluorene)-b-poly[3-(6-trimethylammoniumhexyl)thiophene] or poly[(9,9-bis(3-(N,N-dimethylamino)) propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)], and organic compounds such as tris(8-quinolinyl)-aluminum (III) (Alq.sub.3), 4,7-diphenyl-1,10-phenanthroline, or a combination of one or more of the foregoing. Suitable and preferred materials for hole transporting layer include, but are not limited to metal oxides such as ZTO (Zinc Tin Oxide), MoO.sub.x, WO.sub.x, NiO.sub.x, SnO.sub.x or nanoparticles thereof, metal-containing salts, such as copper sulfide, copper thiocyanate, copper iodide, copper indium sulfide, lead sulfide, cobalt acetate, tungsten disulfide, etc., conjugated polymer electrolytes such as PEDOT:PSS, polymeric acids such as polyacrylates, conjugated polymers such as polytriarylamine (PTAA), insulating polymers such as Nafion films, polyethyleneimine or polystyrene sulfonates, organic compounds such as N,N-diphenyl-N,N-bis(1-naphthyl) (1,1-biphenyl)-4,4-diamine (NPB), N,N-diphenyl-N,N-(3-methylbenzene base)-1,1-biphenyl-4,4-diamine (TPD), or a combination of one or more of the above.

[0066] Please refer to Table 2. Table 2 shows the dark current density test results of the organic optoelectronic devices of Example 1, Example 3, Example 6 and Comparative Example 1 in the annealing test.

TABLE-US-00002 TABLE 2 the dark current density test results of the organic optoelectronic devices of Example 1, Example 3, Example 6 and Comparative Example 1 in the annealing test. PBDB-T:N-type J.sub.dark (A/cm.sup.2) @ 4 V (1:1) Initial 1 hr 2 hr Example 1 1.96E07 3.82E08 2.11E08 Example 3 4.15E08 2.17E08 2.25E08 Example 6 4.50E08 3.28E08 2.21E08 Comparative 1.20E08 3.64E08 3.33E08 example 1
In the preparation of organic optoelectronic devices, organic material Example 1, Example 3, Example 6 and Comparative Example 1 are used as N-type organic semiconductor materials, and organic optoelectronic devices Example 1, Example 3, Example 6 and Comparative Example 1 are prepared with PBDB-T as a P-type organic semiconductor material. The organic optoelectronic devices are subjected to device testing to investigate its initial performance of dark current density and the device performance after annealing at 160 C. for 1 hour and 2 hours. As shown in Table 2, in terms of initial device performance, Example 1, Example 3 and Example 6 have higher dark current density at 4V. After annealing at 160 C., in the trend of dark current density at 4V, Example 1, Example 3 and Example 6 all showed a decreasing trend, while Comparative Example 1 showed an increasing trend. In the application of organic photodetectors, a lower dark current density is highly desirable, as it improves the signal-to-noise ratio and enhances detectivity. As shown in Table 2, the dark current density of Comparative Example 1 increases due to annealing. In particular, after two hours of annealing, the dark current densities of Example 1, Example 3, and Example 6 are 2.1110.sup.8, 2.2510.sup.8 and 2.2110.sup.8 A/cm.sup.2, while Comparative Example 1 is 3.3310.sup.8 A/cm.sup.2. The dark current density of Comparative Example 1 changes from the originally lowest to the highest. It can be seen that, compared with Comparative Example 1, the organic optoelectronic devices of Example 1, Example 3 and Example 6 of the present invention have better device thermal stability.

[0067] Furthermore, the performance test of the organic photodetectors was carried out using the organic optoelectronic devices Example 1 and the Comparative Example 1.

Please refer to Table 3. Table 3 shows the performance test of the organic optoelectronic devices Example 1 and Comparative Example 1.

TABLE-US-00003 TABLE 3 the performance test of the organic optoelectronic devices Example 1 and Comparative Example 1. Retention D* J.sub.dark EQE at 940 at 940 nm PBDB-T:Acceptor (A/cm.sup.2) @ 4 V nm (%) @ 4 V (%) @ 4 V (1:1) Initial 1 hr 2 hr Initial 1 hr 2 hr Initial 1 hr 2 hr Example 1 1.96E07 3.82E08 2.11E08 54.1 56.3 51.8 100% 236% 292% Comparative 1.20E08 3.64E08 3.33E08 48.1 29.2 29.0 100% 35% 36% example 1
In the preparation of organic optoelectronic devices, organic material Example 1 and Comparative Example 1 are used as N-type organic semiconductor materials, and organic optoelectronic devices Example 1 and Comparative Example 1 are prepared with PBDB-T as a P-type organic semiconductor material. As shown in Table 3, in terms of initial device performance, Example 1 has a higher external quantum efficiency (EQE) performance and a higher dark current density. After annealing at 160 C., in the trend of dark current density at 4V, Example 1 gradually decreases from 1.9610.sup.7 A/cm.sup.2 to 2.1110.sup.8 A/cm.sup.2, while the dark current density of Comparative Example 1 is gradually increased from 1.2010.sup.8 A/cm.sup.2 to 3.3310.sup.8 A/cm.sup.2. As for the trend of EQE, Example 1 slightly decreased from 54.1% to 51.8%, while Comparative Example 1 significantly decreased from 48.1% to 29.0%. After calculating the detectivity of the organic optoelectronic devices, we set the initial value as 100%. After annealing at 160 C., Example 1 increased to 292%, while Comparative Example 1 decreased to only 36%. It can be seen from this that the organic optoelectronic devices of the present invention have good device thermal stability.

[0068] Based on the above experimental results, the organic material, organic composition and organic optoelectronic devices using the organic material containing the formula I of the present invention as organic photodetectors have the following characteristics: (1) the device manufacturing process does not require the use of toxic halogenated solvents; (2) it has low dark current density and good EQE and detection performance in the near-infrared light band; and (3) the materials and devices have good thermal stability.

[0069] With the detailed description of the above embodiments, it is hoped that the features and spirit of the present invention can be more clearly described, and the scoped of the present invention is not limited by the embodiments disclosed above. On the contrary, the intention is to cover various changes and equivalent arrangements within the scope of the patents to be applied for in the present invention.