Patent Grant
7112674
This application is a national stage of PCT/DE02/03110 filed Aug. 21, 2002, and based upon DE 101 41 266.5 filed Aug. 21, 2001 under the International Convention.
The present invention relates to a new organic electroluminescent device based on 2,5-diaminoterephthalic acid derivatives. Said derivatives are emitter substances for organic light-emitting diodes (OLED).
Organic light-emitting diodes, which have long been known, use the electroluminescence of certain organic compounds. An OLED's structure and the tasks of its individual layers are exemplified in
A layer sequence of organic substances is arranged between two electrodes, of which at least one must be translucent, each organic substance having a specific function within the device.
An arrangement of the type described above emits green light generated due to the excitation of Alq3 by the excitons formed from the holes and electrons.
However, such a simple arrangement has several drawbacks:
Said drawbacks can in part be eliminated by doping. This means that one or more substances are co-evaporated during the diode's production process. In general, these substances are contained in the Alq3 layer in an amount ranging up to a few percent. Said co-evaporation process is difficult to control.
The invention relates to new emitter substances which eliminate the known drawbacks of Alq3 both as an emitter substance and a host material for dopants. As a consequence, Alq3 is generally required as an electron conductor only. The new emitter substances are characterized by:
For the purposes of the invention, the term “device” relates to an arrangement in which the substrate and layers are arranged on top of one another according to
The object of the invention is to provide new organic electroluminescent devices using improved emitter substances.
According to the invention, the organic electroluminescent device contains 2,5-diaminoterephthalic acid derivatives of the following formula 1a in one or several emitter layers in a pure or doped form in a device
wherein the ring A is a triply unsaturated benzene ring wherein R4′ and R8′ are omitted, or the ring A is a doubly unsaturated ring having a double bond in the 1,2-position and in the 4,5-position, and
wherein R10 represents a nitrile radical —CN or a radical —C(═X1)—X2R1,
R11 is a nitrile radical —CN or a radical —C(═X3)—X4R5,
wherein
X1 and X3 can be the same or different atoms or groups, such as oxygen, sulphur, imino, preferably oxygen;
X2 and X4 can be the same or different atoms or groups, such as oxygen, sulphur, amino, wherein the amino nitrogen can be substituted with alkyl having 1 to 20 C-atoms, preferably C1 to C8, or with aryl, e.g. phenyl, naphthyl, or with heteroaryl, e.g. cumaryl, pyridyl, chinolyl, indolyl, carbazolyl, imidazolyl, thienyl, thiazolyl, furyl, oxazolyl;
R1 to R8, R4′ and R8′ can be the same or different substituents, such as hydrogen, alkyl having 1 to 20 atoms, preferably C1 to C8; aryl, e.g. phenyl, naphthyl, as well as heteroaryl, e.g. cumaryl, pyridyl, chinolyl, indolyl, carbazolyl, imidazolyl, thienyl, thiazolyl, furyl, oxazolyl, and the aforesaid radicals can be substituted singly or doubly with atoms or groups, e.g. di-C1–C3-amino or alkoxy with alkyl radicals C1 to C10, preferably C1–C4; C1–C4 alkyl, cyano, fluorine, chlorine, bromine or iodine as well as phenyl;
R4 and R8 can also be the same or different substituents, such as halogen, nitro, cyano or amino;
R2 to R4, R6 to R8, R4′ and R8′ can also be trifluoromethyl or pentafluorophenyl,
and wherein the following radicals can form a saturated or unsaturated ring
X1 and X2, R1 and R2, R2 and X2, R2 and R3, R3 and R4, R4 and X3, X3 and X4, R5 and X4, R6 and X4, R6 and R7, R7 and R8, R8 and X1, R3 and R4′, R7 and R8 ′, R4 and R4′, and R8 and R8′, to which rings further rings can be fused.
It is preferred that R2, R3, R6 and R7 be trifluoromethyl or pentafluorophenyl, R4 and R8 be halogen, nitro, cyano or amino, and the other substituents have the meaning indicated above.
It is particularly preferred that R4 and R8 be trifluoromethyl or pentafluorophenyl, and the other substituents have the meaning indicated above.
As regards spelling in the following text, R1-8 means R1 to R8; X2,4 means X2 and X4; R4′,8′ means R4′ and R8′.
The invention also relates to new 2,5-diaminoterephthalic acid derivatives of the formula 19
wherein X1 is O and X2 is O or N; R2 and R6 are methylene (—CH2—) which can be substituted with trifluoromethyl, R3 and R7 are the same or different, H, C1–C8 alkyl, aryl or heteroaryl, and R4 and R8 are the same or different, H, alkyl, aryl or trifluoromethyl. It is particularly preferred that alkyl be C1–C4 alkyl, aryl be phenyl or naphthyl, and heteroaryl be pyridyl, thienyl or furyl.
In general, it is preferred that substituents arranged opposite one another, such as X1 and X3, X2 and X4, R1 and R5, R2 and R6, R3 and R7, R4 and R8, R4′ and R8′, and R10 and R11, are the same, i.e. not different, in all structures according to the invention.
The electroluminescent devices according to the invention preferably contain 2 to 3 different substances which are mixed with one another in one device.
Now, preferred structures will be listed, wherein in the structures 1
R7 and R8 can be members of a ring;
wherein symmetric combinations of the aforesaid structural types are preferred
R3 and R4 as well as R7 and R8 can be members of a ring;
and wherein in the structure 2
X1 and X2 can be members of a ring provided X1=N and there is no substituent R1 in case X2≠N;
X2 and R1 can be members of a ring provided X2=N;
X2 and R2 can be members of a ring provided X2=N;
X4 and R5 can be members of a ring provided X4=N;
wherein symmetric combinations of the aforesaid structural types are preferred
and wherein in the structures 3
and wherein in the structures 4
The emitter substances of formula 1, i.e. derivatives of 2,5-diaminoterephthalic acid, can be obtained by reacting esters of cyclohexane-2,5-dione-1,4-dicarboxylic acid with primary anilines or amines, subsequent oxidation and, optionally, further modification. Said derivatives can be processed into cyclized derivatives in a manner known per se, as shown e.g. in Formula Diagrams I and II.
The compounds of formula 3 can be produced by reacting the respective 2,5-diaminoterephthalic acid amides with dehydrating agents.
In order to produce the compounds of formula 4, wherein R4 and R8 as well as R4′ and R8′ are not H, the esters of 2,5-diaminocyclohexane-1,4-dicarboxylic acid are converted into hydrazides and reacted with potassium hexacyanoferrate(III) in order to obtain aldehydes. These 2,5-diaminocyclohexane-1,4-dicarbaldehydes can be converted into oximes which are reacted with formic acid in order to obtain the compounds of formula 4.
Examples of the new emitters according to formula 1 are listed in Table 1:
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
1.10
1.11
1.12
1.13
1.14
1.15
1.16
1.17
1.18
1.19
1.20
1.21
1.22
1.23
1.24
1.25
1.26
1.27
1.28
1.29
1.30
1.31
1.32
1.33
1.34
1.35
1.36
1.37
1.38
1.39
1.40
1.41
1.42
1.43
17.0
5.0
11.0
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
1.10
1.11
1.12
1.13
1.14
1.15
1.16
1.17
1.18
1.19
1.20
1.21
1.22
1.23
1.24
1.25
1.26
1.27
1.28
1.29
1.30
1.31
1.32
1.33
1.34
1.35
1.36
1.37
1.38
1.39
1.40
1.41
1.42
1.43
17.0
5.0
11.0
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
1.10
1.11
1.12
1.13
1.14
1.15
1.16
1.17
1.18
1.19
1.20
1.21
1.22
1.23
1.24
1.25
1.26
1.27
1.28
1.29
1.30
1.31
1.32
1.33
1.34
1.35
1.36
1.37
1.38
1.39
1.40
1.41
1.42
1.43
17.0
5.0
11.0
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
1.10
1.11
1.12
1.13
1.14
1.15
1.16
1.17
1.18
1.19
1.20
1.21
1.22
1.23
1.24
1.25
1.26
1.27
1.28
1.29
1.30
1.31
1.32
1.33
1.34
1.35
1.36
1.37
1.38
1.39
1.40
1.41
1.42
1.43
17.0
5.0
11.0
19.0
19.1
19.2
19.3
19.4
19.5
19.6
19.7
19.8
19.9
19.10
19.11
19.12
7.0
13.0
19.0
19.1
19.2
19.3
19.4
19.5
19.6
19.7
19.8
19.9
19.10
19.11
19.12
7.0
13.0
19.0
19.1
19.2
19.3
19.4
19.5
19.6
19.7
19.8
19.9
19.10
19.11
19.12
7.0
13.0
20.0
8.0
20.0
8.0
14.0
18.0
6.0
12.0
21.0
9.0
15.0
18.0
6.0
12.0
21.0
9.0
15.0
22.0
10.0
16.0
22.0
10.0
16.0
2.0
2.1
2.2
2.3
2.4
2.5
2.6
2.7
2.8
2.9
2.10
2.11
2.12
2.13
2.14
2.15
2.16
2.17
2.18
2.19
2.20
2.21
2.22
2.24
2.25
2.26
2.27
2.28
2.29
2.30
2.31
2.32
2.33
2.34
2.35
2.36
2.37
2.38
2.39
2.40
2.41
2.42
2.43
2.0
2.1
2.2
2.3
2.4
2.5
2.6
2.7
2.8
2.9
2.10
2.11
2.12
2.13
2.14
2.15
2.16
2.17
2.18
2.19
2.20
2.21
2.22
2.24
2.25
2.26
2.27
2.28
2.29
2.30
2.31
2.32
2.33
2.34
2.35
2.36
2.37
2.38
2.39
2.40
2.41
2.42
2.43
2.0
2.1
2.2
2.3
2.4
2.5
2.6
2.7
2.8
2.9
2.10
2.11
2.12
2.13
2.14
2.15
2.16
2.17
2.18
2.19
2.20
2.21
2.22
2.24
2.25
2.26
2.27
2.28
2.29
2.30
2.31
2.32
2.33
2.34
2.35
2.36
2.37
2.38
2.39
2.40
2.41
2.42
2.43
37.0
23.0
30.0
37.0
23.0
30.0
39.0
39.1
39.2
39.3
39.4
39.5
39.6
39.7
39.8
39.9
39.10
39.11
39.12
25.0
32.0
39.0
39.1
39.2
39.3
39.4
39.5
39.6
39.7
39.8
39.9
39.10
39.11
39.12
25.0
32.0
40.0
26.0
40.0
26.0
33.0
38.0
24.0
31.0
41.0
27.0
34.0
43.0
29.0
36.0
43.0
29.0
36.0
The new emitters are used in a device comprising or not comprising an electron transport layer, wherein the layers in a device can be arranged as shown in
Typically, the emitter layers are 3–10 nm thick, preferably 4–6 nm. The emission wavelengths depend on the chemical structure in a characteristic manner, i.e. electronic and steric factors of the molecules obviously influence the wavelength of the emitted light and the performance achieved. The wavelengths of the examples listed in Table 2 range between 538 nm and 618 nm.
In order to achieve mixed colours, the new emitters of formulas 1.0–58.0 can be arranged on top of one another, either in the form of several layers each of which consists of an emitter material in its pure form (
The layers comprising the new emitters of formulas 1.0–58.0 can be doped with known emitter materials, as shown in
The new emitters of formulas 1.0–58.0 can be used in devices comprising hole conductors known per se (59 and 60) and other components. Typical examples are shown in
4,4′,4″-tris(N-(α-naphthyl)-N-phenylamino)-triphenylamine (1-NAPHDATA)
N,N′-di(α-naphthyl)-N,N′-diphenylbenzidine (α-NPD)
The devices based on the new emitters can be produced in a manner known per se, i.e. by vacuum deposition at between 1 and 10−9 torrs.
Alternatively, the devices can be produced by solution coating, e.g. web coating or spin coating. Here, the new emitters of formulas 1.0–58.0 can be applied either as the pure substance or as a dopant contained in a suitable polymer.
Surprisingly, it has been found that particularly efficient devices can be produced using substances of the formula 1.0 which have been substituted with fluorine. A remarkably high photometric efficiency is observed in these cases. Using the substance 1.2, a device emitting a spectrally nearly pure green is obtained.
The following examples are intended to illustrate the invention in more detail, but do by no means limit the same.
0.06 mol cyclohexane-2,5-dione-1,4-dicarboxylic acid diester is suspended in a mixture of 200 ml glacial acetic acid and 200 ml alcohol (corresponding to the ester component). In a nitrogen atmosphere, 0.135 mol of a primary amine or aniline is speedily added. The reaction mixture is refluxed for 5–8 hours while stirring thoroughly. Anilines which have been substituted with an acceptor require longer reaction times.
In the case of anilines, the crude product can be isolated by sucking off the cooled-down reaction mixture, thoroughly washing it with methanol and drying.
Aliphatic amines form highly soluble products, i.e. the solvent must be separated almost completely using a rotary evaporator. The crude product is added into methanol, thoroughly cooled, sucked off and dried.
The esters of dihydroterephthalic acid obtained in Example 1 are oxidized. Yields of up to 95% are achieved during isolation. In order to purify the separated crude product, it can be recrystallized from DMF, toluene, chloroform or methanol. The substances obtained are sublimable.
The esters obtained according to Example 2 are saponified in mixtures of n-propanol and water. 0.01 mol terephthalic acid diester is suspended in approx. 50 ml n-propanol, and 50 ml water containing 0.03 mol potassium hydroxide is added. The suspension is refluxed until a clear solution is obtained. Once another 2 hours have passed, the liquid is sucked off. In order to neutralize the solution, approx. 5 ml glacial acetic acid is added dropwise. The acid obtained is washed with methanol and dried.
In order to produce the substances 19.1–19.4, 0.01 mol of the terephthalic acid obtained is refluxed for 2 hours in 100 ml glacial acetic acid to which 15 ml formaldehyde solution (37%) has been added.
The reaction products are separated and washed with methanol. They are recrystallized from acetonitrile or chloroform. The substances obtained can be purified by sublimation.
In order to obtain compounds of this type, the respective terephthalic acid ester (Example 2) can be alkylated. 0.05 mol terephthalic acid ester is suspended in 350 ml anhydrous DMSO, and 18.63 g (0.131 mol) methyl iodide is added. 6.1 g (0.152 mol) 60% sodium hydride in paraffin is added in portions at a temperature ranging between 20 and 23° C. and while stirring throrougly. Once a reaction time of approx. 5 hours has passed, the colour of the solid constitutents has changed from orange to pure yellow. Now, approx. 200 ml methanol is added to the mixture, thereby considerably improving filterability.
The separated yellow reaction product is thoroughly washed with methanol and dried. A pure product is obtained by recrystallization from toluene.
A 55 nm thick layer of 4,4′,4″-tris(N-(α-naphthyl)-N-phenylamino)-triphenylamine and another 5 nm thick layer of N,N′-di(α-naphthyl)-N,N′-diphenylbenzidine were deposited onto a structured ITO glass substrate measuring 50×50 mm2. Onto these hole transport layers, 5 nm 1,6-bis(2,4-dimethoxyphenyl)-benzo[1,2-d;4,5-d′]-1,2,6,7-tetrahydro-bis[1,3]oxazine-4,9-dione (19.4) is deposited.
In addition, a 30 nm thick layer of tris-(8-hydroxychinolinato)-aluminium is now applied onto this emitter layer, followed by a very thin buffer layer (0.5 nm) of lithium fluoride and finally aluminium.
The arrangement was tested applying an adjustable voltage between 0 and 15 V. The device emits a wavelength of 578 nm (yellow). A luminance (emission intensity) of 100 cd/m2 was achieved at 5.0 V. The maximum luminance (emission intensity) achieved was 11,400 cd/m2.
A device was produced according to Example 5, into which a 5 nm thick layer of 2,5-bis-(N-(2,4-dimethoxyphenyl)amino)terephthalic acid diethyl ester was incorporated as emitter substance between the hole conductor and the electron conductor.
The device was also tested applying an adjustable voltage between 0 and 15 V. The device emits a wavelength of 618 nm (red). A luminance (emission intensity) of 100 cd/m2 was achieved at 9.5 V. The maximum luminance (emission intensity) achieved was 644 cd/m2.
The device has the same structure as those of Examples 5 and 6. The emitter substance used was 2,5-bis-(N-phenylamino)-terephthalic acid diethyl ester.
Once again, the device was tested applying an adjustable voltage between 0 and 15 V. The device emits a yellow light (578 mm). A luminance (emission intensity) of 100 cd/m2 was achieved at 5.6 V. The maximum luminance (emission intensity) recorded was 5,300 cd/m2.
Analogously to Examples 5–7 and according to the same structural principle, a 5 nm thick layer of N,N′-dimethyl-2,5-bis-(N-(2-fluorophenyl)-amino)terephthalic acid dimethyl ester was deposited onto the hole transport layers.
The arrangement (
Typically, the emitter layers are 3–10 nm thick, preferably 4–6 nm.
Photometric Parameters of Selected Emitter Substances
1)V
2)nm
3)cd/m2
4)cd/A
5)lm/W
1)voltage at 100 cd/m2
2)λmax of electroluminescence
3)max. luminance (emission intensity)
4)max. photometric efficiency
5)max. performance efficiency
Preparation and Measuring Conditions
a) Substrate: 125 nm ITO, approx. 13 Ω/sq and 85% tranmission, 50×50 mm2 glass substrate (1.1 mm thick polished soda-lime float glass with SiO2 layer and 8 individual ITO anodes (active surface area: 2×2 mm2))
Purified 2×20 min in an ultrasonic bath with Aceton selectopur and Methanol selectopur,
b) Pressure (2–4)×10−5 mbar during deposition
Change of mask and intermediate aeration of the deposition chamber, first with nitrogen and then with air
c) The device according to
Programmable voltage supply (SMU) and digital multimeter for recording and processing the OLED curve in a PC via GPIB-BUS and LabView program
Voltage pulse operation (pulses lasting 1 s) between −10 V and +15 V (0.5 V increments): current density-voltage curve and luminance (emission intensity)-voltage curve as well as the calculated photometric efficiency values (in cd/A) and performance efficiency values (in 1 m/W) as a function of U
d) Wavelength of maximum by recording the electroluminescence spectrum using an Xdap diode array spectrometer
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| 101 41 266 | Aug 2001 | DE | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/DE02/03110 | 8/21/2002 | WO | 00 | 2/20/2004 |
| Publishing Document | Publishing Date | Country | Kind |
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| WO03/019697 | 3/6/2003 | WO | A |
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