Organic luminescence device

[0001] This is a continuation of PCT/JP 02/08803, filed Aug. 30, 2002.

[0002] The present invention relates to an organic (electro-)luminescence device and particularly to an organic luminescence device for emitting light by applying an electric field to a film of an organic compound (organic compound layer).

[0003] An organic luminescence device generally comprises a pair of electrodes (comprising an anode and a cathode) and a film comprising a fluorescent organic compound disposed between the electrodes. Into the organic compound layer (film), holes and electrons are injected from the anode and the cathode, respectively, thus forming excitons of the fluorescent organic compound. When the excitons are returned to ground state, the organic luminescence device emits light or causes luminescence.

[0004] According to a study by Eastman Kodak Co. (“Appl. Phys. Lett.”, vol. 51, pp. 913- (1987)), it has been reported that a function-separation type organic luminescence layer comprising mutually laminated two layers including a layer of an aluminum quinolinol complex (as an electron transporting and luminescent material) and a layer of a triphenylamine derivative (as a hole transporting material) causes luminescence at a luminance (brightness) of ca. 1,000 cd/m² under application of a voltage of ca. 10 volts. This is also reported in, e.g., U.S. Pat. Nos. 4,539,507; 4,720,432 and 4,885,211.

[0005] Further, by changing species of the fluorescent organic compound, it is possible to effect luminescence over broad wavelength regions ranging from an ultraviolet region to an infrared region. In this regard, various compounds have been extensively studied in recent years. Such compounds have been proposed in, e.g., U.S. Pat. Nos. 5,151,629, 5,409,783 and 5,382,477, and Japanese Laid-Open Patent Applications (JP-A) 2-247278 (corr. to U.S. Pat. Nos. 5,130,603 and 6,093,864), JP-A 3-255190 (corr. to U.S. Pat. No. 5,227,252), JP-A 5-202356, JP-A 9-202878 and JP-A 9-227576.

[0006] In addition to the above-mentioned organic luminescence devices using low-molecular weight materials, an organic luminescence device using a conjugated polymer has been reported by a research group of Cambridge University (“Nature”, vol. 347, pp. 539- (1990)). According to this report, a signal layer of polyphenylenevinylene (PPV) is formed through a wet-coating process and luminescence from the single layer is confirmed. Such an organic luminescence device using a conjugated polymer has also been proposed by, e.g., U.S. Pat. Nos. 5,247,190, 5,514,878 and 5,672,678, JP-A 4-145192 (corr. to U.S. Pat. Nos. 5,317,169 and 5,726,457), and JP-A 5-247460.

[0007] As described above, recent progress in organic luminescence device is noticeable, and the resultant organic luminescence devices are characterized by high luminance (brightness) under application of a low voltage, various (light-)emission wavelengths, high-speed responsiveness, small thickness and light weight, thus suggesting possibility of wide applications.

[0008] However, the above-described organic luminescence devices are still required to effect light output (emission) at a higher luminance and/or a higher conversion efficiency in the present state. These organic luminescence devices are also still insufficient in terms of durability such that the devices are liable to be changed in their properties with time when used for a long period or liable to be deteriorated by the influence of ambient air containing oxygen or of humidity. Further, in the case of using the organic luminescence devices for full-color display, it is necessary to effect luminescences of blue, green and red with good color purities. However, a satisfactory solution to the problem has not been realized yet, and particularly a red luminescence with a good color purity has not been satisfactorily provided.

[0009] On the other hand, spiro compounds having a unique three-dimensional structure and unique material properties have been noted as an organic functional material (J. Am. Chem. Soc. 110, p. 5687- (1988)). A proposal of using a spiro compound in an organic luminescence device has been reported (JP-A 7-278537) but has failed to provide an electron-transporting layer or a luminescence layer exhibiting sufficient luminescence performance.

[0010] A generic object of the present invention is to provide improvements to problems an mentioned above encountered in organic luminescence devices proposed heretofore.

[0011] A more specific object of the present invention is to provide an organic (electro-) luminescence device capable of effecting light output (emission) at high efficiency and luminance while realizing a prolonged life.

[0012] Another object of the present invention is to provide an organic luminescence device capable of providing a wide variety of emission wavelengths and emission hues, inclusive of particularly orange and red hues, and a good durability.

[0013] A further object of the present invention is to provide an organic luminescence device which can be produced easily and relatively inexpensively.

[0014] According to the present invention, there is provided an organic luminescence device, comprising:

[0015] a pair of an anode and a cathode, and

[0016] at least one organic layer disposed between the anode and the cathode, wherein

[0017] the above-mentioned at least one organic layer comprises a layer comprising at least one species of a compound represented by the following formula (I-a):
wherein K₁, K₂, K₃ and K₄ independently denote a substituted or unsubstituted aromatic ring or a substituted or unsubstituted heterocyclic ring, at least one of K₁, K₂, K₃ and K₄ being a heterocyclic ring containing at least one nitrogen atom; and

[0018] L₁, L₂, L₃ and L₄ independently denote a hydrogen atom, an alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, an alkoxy group, a nitro group, a substituted or unsubstituted amino group, or a group represented by any one of the following formulas (X), (XI) and (XII):
wherein R₅ to R₁₅ independently denote a hydrogen atom, an alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a nitro group;

[0019] X₁ to X₃ and Y₁ to Y₃ independently denote a nitrogen atom or C—R₁₆ where R₁₆ denotes a hydrogen atom, an alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group;

[0020] Z₁ to Z₃ independently denote —O—, —S—, —NR₁₇—, —Si(R₁₈)R₁₉—, —C(R₂₀)R₂₁—, —CH═CH— or —CH═N—, in which R₁₇, R₂₀ and R₂₁ independently denote a hydrogen atom, an alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group; and R₁₈ and R₁₉ independently denote an alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group;

[0021] l and p are respectively 0 or 1;

[0022] m and n are respectively 0 or an integer of 1-30, with the proviso that m+n is an integer of 1-30; and

[0023] q and r are respectively an integer of 2-30.

[0025] The organic luminescence device according to the present invention is characterized in that at least one organic (compound) layer disposed between the pair of electrodes (anode and cathode) includes a layer comprising at least one species of a spiro compound represented by the above-mentioned formula (I-a) or (I-b).

[0026] In the case of using the spiro compound of the formula (I-a) having a carbon atom as a spiro atom, the spiro compound may preferably be a compound represented by any one of the following formulas (II-a) to (IX-a):
wherein R₁ to R₄ independently denote a hydrogen atom, an alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, an alkoxy group, a nitro group, or a substituted or unsubstituted amino group.

[0027] In the case of using the spiro compound of the formula (I-b) having a silicon atom as a spiro atom, the spiro compound may preferably be a compound represented by any one of the following formulas (II-b) to (IX-b):
wherein R₁ to R₄ independently denote a hydrogen atom, an alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, an alkoxy group, a nitro group, or a substituted or unsubstituted amino group.

[0028] In the organic luminescence device of the present invention at least one of L₁ to L₄ in the formula (I-a) or (I-b) may preferably be the above-mentioned group represented by any one of the formulas (X), (XI) and (XII) since the resultant spiro compound has a high glass transition point to improve a stability of the organic luminescence device and the resultant emission wavelength is shifted to a longer wavelength side. Further, in the organic luminescence device of the present invention, the layer comprising at least one species of the spiro-compound of the formula (I-a) or (I-b) may preferably be used as electron injection layer, an electron-transporting or a luminescence layer.

[0029] Specific examples of the groups represented by K₁ to K₄, L₁ to L₄ and R₁ to R₂₁ in the above-mentioned formula (I-a) to (IX-a), (I-b) to (IX-b) and (X) to (XII) are enumerated hereinbelow.

[0030] Specific examples of the alkyl group may include: methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, and octyl.

[0031] Specific examples of the aralkyl group may include: benzyl and phenethyl.

[0032] Specific examples of the aryl group may include: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, and fluorenyl.

[0033] Specific examples of heterocyclic group may include: thienyl, pyrrolyl, imidazolyl, furyl, pyridyl, indolyl, quinolinyl, and carbazolyl.

[0034] Specific examples of the alkoxyl group may include: methoxyl, ethoxyl, propoxyl, and phenoxyl.

[0035] Specific examples of the amino group may include: dimethylamino, diethylamino, dibenzylamino, and diphenylamino.

[0036] Specific examples of the substituents which may be possessed by the above-mentioned groups may include: alkyl groups, such as methyl, ethyl and propyl; aralkyl groups, such as benzyl and phenethyl; aryl groups, such as phenyl, nephthyl and anthryl; heterocyclic groups, such as thienyl, pyrrolyl, pyridyl and quinolinyl; and amino groups, such as dimethylamino, diethylamino, dibenzylamino and diphenylamino.

[0037] Further, specific examples of the preferred groups represented by the above-mentioned formulas (X), (XI) and (XII) as the groups L₁ to L₄ in the formula (I-a) or (I-b) may include those (A-1 to A-15) shown below.

[0038] Other specific examples of the groups L₁ to L₄ may include those (B-1 to B-16) shown below.

[0039] Specific examples (Example Compound Nos. a-1 to a-43 and b-1 to b-39) of the Spiro compounds of the formulas (I-a) and (I-b) are enumerated in Tables 1-16 hereinafter separately for the respective preferred formulas (II-a) to (IX-a) and (II-b) to (IX-b) wherein some representative structures for the groups L₁ and L₄ are identified by symbols A-1 to A-15 and B-1 to B-16 shown above, and “Ph” represents a phenyl group.

[0040] Further, the respective numerals in parentheses for the groups R₁ to R₄ represent their substitution positions, respectively, specifically indicated in the formulas (II-a) to (IX-a) and (II-b) to (IX-b).

[0041] Incidentally, the spiro compounds according to the present invention inclusive of those enumerated below are synthesized by, e.g., methods as reported by James M, Tour et al; Journal of Organic Chemistry, Vol. 61, pp. 6906- (1996) and R. West et al.; J. Am. Chem. Soc., 124, pp. 49- (2002).

[0042]

TABLE 1
	Formula (II-a)
No.	R1	R2	R3	R4	L1	L2	L3	L4
a-1	H	H	H	H	A-1	A-1	A-1	A-1
a-2	H	H	H	H	A-5	A-5	A-5	A-5
a-3	H	H	H	H	A-11	A-11	A-11	A-11
a-4	H	H	H	H	A-14	A-14	A-14	A-14
a-5	CH3	CH3	H	H	H	H	B-1	B-1
	(3)	(6)
a-6	H	H	H	H	B-2	B-2	B-2	B-2
a-7	H	H	H	H	B-3	B-3	B-3	B-3

[0043]

TABLE 2
	Formula (III-a)
No.	R1	R2	R3	R4	L1	L2	L3	L4
a-8	H	H	H	H	A-4	A-4	A-4	A-4
a-9	H	H	H	H	A-7	A-7	A-7	A-7
a-10	H	H	H	H	A-12	A-12	A-12	A-12
a-11	H	H	H	H	CH2CH3	CH2CH3	B-4	B-4
a-12	H	H	H	H	B-5	B-5	B-5	B-5
a-13	H	H	H	H	B-6	B-6	ph	ph

[0044]

TABLE 3
	Formula (IV-a)
No.	R1	R2	R3	R4	L1	L2	L3	L4
a-14	H	H	H	H	A-2	A-2	A-2	A-2
a-15	H	H	H	H	A-8	A-8	A-8	A-8
a-16	H	H	H	H	A-13	A-13	A-13	A-13
a-17	H	ph(6)	H	ph(6)	B-7	H	B-7	H
a-18	H	H	H	H	NO2	B-8	NO2	B-8
a-19	H	H	H	H	B-9	B-9	B-9	B-9

[0045]

TABLE 4
	Formula (V-a)
No.	R1	R2	R3	R4	L1	L2	L3	L4
a-20	H	H	H	H	A-1	A-1	A-1	A-1
a-21	H	H	H	H	A-3	A-3	A-3	A-3
a-22	H	H	H	H	A-6	A-6	A-6	A-6
a-23	H	H	H	H	A-10	A-10	A-10	A-10
a-24	H	H	H	H	A-15	A-15	A-15	A-15
a-25	H	H	H	H	B-10	B-10	B-10	B-10
a-26	H	H	H	H	B-11	B-11	OCH3	OCH3

[0046]

TABLE 5
	Formula (VI-a)
No.	R1	R2	R3	R4	L1	L2	L3	L4
a-27	H	H	H	H	A-3	A-3	A-3	A-3
a-28	H	H	H	H	A-7	A-7	A-7	A-7
a-29	H	H	H	H	A-15	A-15	A-15	A-15
a-30	CH3 (3)	CH3 (6)	CH3 (3′)	CH3 (6′)	(CH2)3CH3	(CH2)3CH3	B-12	B-12
a-31	H	H	H	H	B-13	B-13	B-13	B-13
a-32	H	H	H	H	B-14	B-14	H	H

[0047]

TABLE 6
	Formula (VII-a)
No.	R1	R2	R3	R4	L1	L2	L3	L4
a-33	H	H	H	H	A-2	A-2	A-2	A-2
a-34	H	H	H	H	A-5	A-5	A-5	A-5
a-35	H	H	H	H	A-13	A-13	A-13	A-13
a-36	CH3	CH3	H	H	H	H	B-15	B-15
	(1)	(8)
a-37	H	H	H	H	B-16	B-16	H	H

[0048]

TABLE 7
	Formula (VIII-a)
No.	R1	R2	R3	R4	L1	L2	L3	L4
a-38	H	H	H	H	A-1	A-1	A-1	A-1
a-39	H	H	H	H	A-4	A-4	A-4	A-4
a-40	H	H	H	H	B-1	B-1	B-1	B-1

[0049]

TABLE 8
	Formula (IX-a)
No.	R1	R2	R3	R4	L1	L2	L3	L4
a-41	H	H	H	H	A-2	A-2	A-2	A-2
a-42	H	H	H	H	A-6	A-6	A-6	A-6
a-43	H	H	H	H	A-12	A-12	A-12	A-12

[0050]

TABLE 9
	Formula (II-b)
No.	R1	R2	R3	R4	L1	L2	L3	L4
b-1	H	H	H	H	A-1	A-1	A-1	A-1
b-2	H	H	H	H	A-4	A-4	A-4	A-4
b-3	H	H	H	H	A-11	A-11	A-11	A-11
b-4	CH3	CH3	CH3	CH3	B-1	B-1	B-1	B-1
	(3)	(6)	(3′)	(6′)
b-5	H	H	H	H	B-2	B-2	B-2	B-2
b-6	H	H	H	H	B-3	B-3	B-3	B-3

[0051]

TABLE 10
	Formula (III-b)
No.	R1	R2	R3	R4	L1	L2	L3	L4
b-8	H	H	H	H	A-5	A-5	A-5	A-5
b-9	H	H	H	H	A-6	A-6	A-6	A-6
b-10	H	H	H	H	A-12	A-12	A-12	A-12
b-11	H	H	H	H	CH2CH3	CH2CH3	B-4	B-4
b-12	H	H	H	H	B-5	B-5	B-5	B-5
b-13	H	H	H	H	B-6	B-6	ph	ph

[0052]

TABLE 11
	Formula (IV-b)
No.	R1	R2	R3	R4	L1	L2	L3	L4
b-14	H	H	H	H	A-2	A-2	A-2	A-2
b-15	H	H	H	H	A-8	A-8	A-8	A-8
b-16	H	H	H	H	A-13	A-13	A-13	A-13
b-17	H	H	H	H	B-7	B-7	B-7	B-7
b-18	H	H	H	H	NO2	NO2	NO2	NO2
b-19	H	H	H	H	B-8	B-8	B-8	B-8

[0053]

TABLE 12
	Formula (V-b)
No.	R1	R2	R3	R4	L1	L2	L3	L4
b-20	H	H	H	H	A-1	A-1	A-1	A-1
b-21	H	H	H	H	A-3	A-3	A-3	A-3
b-22	H	H	H	H	A-10	A-10	A-10	A-10
b-23	H	H	H	H	B-9	B-9	B-9	B-9
b-24	H	H	H	H	B-10	B-10	OCH3	OCH3

[0054]

TABLE 13
	Formula (VI-b)
No.	R1	R2	R3	R4	L1	L2	L3	L4
b-25	H	H	H	H	A-3	A-3	A-3	A-3
b-26	H	H	H	H	A-7	A-7	A-7	A-7
b-27	H	H	H	H	A-15	A-15	A-15	A-15
b-28	H	H	H	H	B-11	B-11	B-11	B-11
b-29	H	H	H	H	B-12	B-12	H	H

[0055]

TABLE 14
	Formula (VII-b)
No.	R1	R2	R3	R4	L1	L2	L3	L4
b-30	H	H	H	H	A-2	A-2	A-2	A-2
b-31	H	H	H	H	A-5	A-5	A-5	A-5
b-32	H	H	H	H	A-13	A-13	A-13	A-13
b-33	CH3	CH3	H	H	H	H	B-13	B-13
	(1)	(8)

[0056]

TABLE 15
	Formula (VIII-b)
No.	R1	R2	R3	R4	L1	L2	L3	L4
b-34	H	H	H	H	A-1	A-1	A-1	A-1
b-35	H	H	H	H	A-4	A-4	A-4	A-4
b-36	H	H	H	H	B-14	B-14	B-14	B-14

[0057]

TABLE 16
	Formula (IX-b)
No.	R1	R2	R3	R4	L1	L2	L3	L4
b-37	H	H	H	H	A-2	A-2	A-2	A-2
b-38	H	H	H	H	A-7	A-7	A-7	A-7
b-39	H	H	H	H	A-12	A-12	A-12	A-12

[0058] In the organic luminescence device of the present invention, the organic compound layer(s) comprising the above-mentioned spiro compound of the formula (I-a) or (I-b) may be formed between the pair of anode and cathode (electrodes) by vacuum deposition or wet-coating process. The organic compound layer(s) may preferably be formed in a (total) thickness of at most 10 μm, more preferably at most 0.5 μm, further preferably 0.01-0.5 μm.

[0059] The organic compound layer(s) constituting the organic luminescence device of the present invention may have a single-layer structure as shown in FIG. 1 or a laminate structure of two or more layers as shown in FIGS. 2, 3 and 4.

[0060] More specifically, FIG. 1 is a schematic sectional view illustrating an embodiment of the organic luminescence device of the present invention. Referring to FIG. 1, the organic luminescence device includes a substrate 1, and an anode 2, a luminescence layer 3 and a cathode disposed in this order on the substrate 1 so as to form a laminate structure. The luminescence layer 3 may comprise a single species of luminescent material exhibiting a hole-transporting function, an electron-transporting function and a luminescence function in combination or a mixture of plural compounds exhibiting these functions, respectively. The luminescence layer 3 may have a thickness of 5 nm to 1 μm, preferably 10-500 nm.

[0061] FIG. 2 is a sectional view showing a laminate structure of another embodiment of the organic luminescence device. Referring to FIG. 2, the organic luminescence device includes a substrate 1, and an anode 2, a hole-transporting layer 5, an electron-transporting layer 6 and a cathode 4 disposed successively in this order on the substrate 1 so as to form a laminate structure. In this case, either one or both of the hole-transporting layer 5 and the electron-transporting layer 6 may contain a luminescent material also having a hole-transporting function and/or an electron-transporting function, respectively, for constituting a luminescence layer 3 in combination. One of the layers 6 and 5 may contain a material having no luminescent function but having a good electron-transporting or hole-transporting function. Each of the hole-transporting layer 5 and the electron-transporting layer 6 may have a thickness of 5 nm to 1 μm, preferably 10-500 nm.

[0062] FIG. 3 is a sectional view showing still another embodiment of the organic luminescence device of the present invention. Referring to FIG. 3, the organic luminescence device includes a substrate 1, and an anode 2, a hole-transporting layer 5, a luminescence layer 3, an electron-transporting layer 6 and a cathode 4 disposed successively in this order on the substrate 1 to form a laminate structure. In this embodiment, the carrier transporting functions and the luminescent function of the organic compound layer are separated and assigned to the respective layers. Each of the hole-transporting layer 5, the luminescence layer 3 and the electron-transporting layer 6 may contain a single species or plural species of compounds showing respectively expected functions so as to exhibit desired performances. More specifically, in the case of using plural species of compounds in combination, a lot of latitude is provided in selection of materials for each layer, and various compounds having different emission wavelengths can be used to provide a variety of luminescence hues.

[0063] Further, as the carriers and excitons are effectively confined in the central luminescence layer 3, it is possible to increase the luminescence efficiency.

[0064] In the embodiment of FIG. 3, each of the hole-transporting layer 5, the luminescence layer 3 and the electron-transporting layer 6 may have a thickness of 5 nm-1 μm, preferably 10-500 nm.

[0065] FIG. 4 is a sectional view showing another embodiment of the organic luminescence device. Referring to FIG. 4, the organic luminescence device includes a substrate 1, and an anode 2, a hole-transporting layer 5, an electron-transporting layer 6, an electron injection layer 7 and a cathode 4 disposed successively in this order on the substrate 1 so as to form a laminate structure. The electron injection layer 7 is disposed in order to efficiently inject electrons from the cathode 4 into the electron-transporting layer 6, thus functionally separating an electron injection performance and an electron-transporting performance, respectively, rom the cathode 4. Each of the hole-transporting layer 5, the electron-transporting layer 6 and the electron injection layer 7 may have a thickness of 5 nm to 1 μm, preferably 10-500 nm.

[0066] It is to be understood however that FIGS. 1-4 described above merely show basic structures of the organic luminescence device according to the present invention, and various modifications thereof are possible. For example, between the organic compound layer(s) and the electrodes (anode and cathode), it is possible to dispose an insulating layer, an adhesive layer, or an interference layer. Further, the hole-transporting layer 5 can be divided into two layers with different ionization potentials.

[0067] The spiro compound represented by the formula (I-a) or (I-b) have better electron injection performance, electron-transporting performance, luminescence performance and durability than conventional compounds and can be adopted in any of the device structures shown in FIGS. 1 to 4.

[0068] The organic compound layer containing the spiro compound of the formula (I-a) or (I-b) is particularly useful as an electron injection layer, an electron-transporting layer and/or a luminescence layer. A layer thereof may be formed by vacuum deposition or solution coating in a form which is not liable to crystallize and is excellent in stability with time.

[0069] In the present invention, the Spiro compound of the formula (I-a) or (I-b) can be used to constitute an electron injection layer, an electron-transporting layer and/or a luminescence layer, as desired, in combination with a known hole-transporting compound, luminescent compound or electron-transporting compound, examples of which are enumerated hereinbelow.

[0070] As mentioned above, the organic compound layer(s) containing the spiro compound of the formula (I-a) or (I-b) or other organic compound layers may be formed into film by vacuum deposition or coating of a solution of the relevant compound in an appropriate solvent. In the case of the solution coating, the organic compound can be used in mixture with an appropriate binder resin to form a film.

[0071] The binder resin used for the above purpose may be selected from a wide variety of scope. Examples thereof may include: polyvinyl carbazole resin, polycarbonate resin, polyester resin, polyarylate resin, polystyrene resin, acrylic resin, methacrylic resin, butyral resin, polyvinyl acetal resin, diallyl phthalate resin, phenolic resin, epoxy resin, silicone resin, polysulfone resin, and urea resin. These resins may be used singly or in combination of two or more species or in the form of copolymers.

[0072] As a material for the anode (2 shown in FIGS. 1-4), it is preferred to use one having as large a work function as possible, examples of which may include: metals, such as gold, platinum, nickel, palladium, cobalt, selenium and vanadium, and their alloys; metal oxides, such as tin oxide, zinc oxide, indium tin oxide (ITO), and indium zinc oxide; and electroconductive polymers, such as polyaniline, polypyrrole, polythiophene, and polyphenylene sulfide. These compounds may be used singly or in combination of two or more species.

[0073] On the other hand, as a material for the cathode 4 shown in FIGS. 1-4, it is preferred to use one having a small work function, examples of which may include: metals, such as lithium, sodium, potassium, calcium, magnesium, aluminum, indium, silver, lead, tin and chromium, and their alloys. It is also possible to use metal oxide, such as indium tin oxide (ITO). The cathode may be formed in a single layer or a lamination of plural layers.

[0074] The substrate 1 shown in FIGS. 1-4 for the organic luminescence device of the present invention may include an opaque substrate of metal, ceramics, etc., and a transparent substrate of glass, quartz, plastics, etc. It is possible to form the substrate with a color filter film, a fluorescent color conversion film, a dielectric reflection film, etc., thus controlling emitted luminescent light.

[0075] In order to prevent contact with oxygen and/or moisture, the organic luminescence device of the present invention may further include a protective layer or a sealing layer. Examples of the protective layer may include: an inorganic film of diamond, metal oxide, metal nitride, etc.; a polymer film of fluorine-containing resin, polyparaxylene, polyethylene, silicone resin, polystyrene, etc., and a film of light-curable resin. It is also possible to effect packaging of the organic luminescence device per se with a sealing resin while covering the organic luminescence device with glass, gas-impermeable film, metal, etc.

[0076] Hereinbelow, the present invention will be described more specifically based on Examples.

[0077] An electroluminescence device of a structure as shown in FIG. 2 was prepared in the following manner.

[0078] A 0.7 mm-thick glass substrate (substrate 1) coated with a 120 nm-thick film of ITO (indium tin oxide) (anode 2) formed by sputtering was successively washed with acetone and isopropyl alcohol (IPA) under application of ultrasonic wave and then washed with IPA under boiling, followed by cleaning by UV/ozone (i.e., irradiation with ultraviolet rays in the ozone-containing atmosphere), to obtain a transparent conductive substrate (including the substrate 1 and the ITO anode 2 formed thereon).

[0079] The transparent conductive substrate was coated by vacuum deposition of a compound (TPD) represented by a structural formula shown below:
to form a 70 nm-thick hole-transporting layer 5 and then by vacuum deposition of a spiro compound (Example Compound No. a-1 listed in Table 1) to form a 70 nm-thick electron-transporting layer 6. The vacuum deposition was respectively performed in a vacuum of 1.0×10⁻⁴ Pa and at a film thickness growth rate of 0.2-0.3 nm/sec.

[0080] Then, the electron-transporting layer 6 was further coated by vacuum deposition of Al—Li alloy (Li content: 1 atom %) to form a 150 nm-thick metal film (cathode 4) under a vacuum of 1.0×10⁻⁴ Pa and at a film thickness growth rate of 1.0-1.2 nm/sec, thereby forming an organic luminescence device of a structure shown in FIG. 2.

[0081] The thus-obtained device was then supplied with a DC voltage of 8 volts between the ITO electrode 2 as an anode and the Al—Li alloy electrode 4 as a cathode, whereby a current flowed at a density of 8.5 mA/cm² and red luminescence was observed at a luminance of 600 cd/m². The device was further subjected to 100 hours of continuous voltage application at a constant current density of 7.0 mA/cm² in a nitrogen atmosphere, whereby the device initially exhibited a luminance of 520 cd/m², which was lowered to 490 cd/m² after 100 hours, thus showing only a small luminance deterioration.

[0082] The results are shown in Table 17 set forth hereinafter.

[0083] Organic luminescence devices were prepared and evaluated in the same manner as in Example A-1 except for replacing the Spiro compound (Ex. Comp. No. a-1) with those shown in Table 17, respectively.

[0084] The results are inclusively shown in Table 17 set forth hereinafter.

[0085] Comparative organic luminescence devices were prepared and evaluated in the same manner as in Example A-1 except for using Comparative Compound Nos. 1-3, respectively, shown below, instead of the spiro compound (Ex. Comp. No. a-1). The results are also shown in Table 17.

[0086]

TABLE 17
			Luminance
		Initial	(at 7.0 mA/cm2)
Exam-		Voltage	Luminance	Initial	After 100
ple		(V)	(cd/m2)	(cd/m2)	hrs. (cd/m2)
	Example
	Compound
	No.
A-1	a-1	8	600	520	490
2	a-4	8	540	500	460
3	a-7	8	340	290	240
4	a-9	8	440	400	360
5	a-10	8	530	495	460
6	a-13	8	200	165	135
7	a-14	8	565	510	475
8	a-17	8	180	150	120
9	a-21	8	420	385	335
10	a-22	8	470	430	385
11	a-26	8	190	140	115
12	a-27	8	515	475	440
13	a-29	8	530	495	460
14	a-32	8	195	160	135
15	a-33	8	560	485	445
16	a-36	8	160	140	115
17	a-38	8	530	480	440
18	a-40	8	170	145	105
19	a-42	8	450	415	380
20	a-43	8	525	480	450
	Compound
	No.
Comp.	Comp.	8	20	15	**
A-1	No. 1
Comp.	Comp.	8	60	40	10
A-2	No. 2
Comp.	Comp.	8	15	10	**
A-3	No. 3
**: No luminescence

[0087] The procedure of Example A-1 was repeated up to the formation of the hole-transporting layer 5.

[0088] Then, the hole-transporting layer 5 was further coated by vacuum deposition of a mixture of spiro compound (Ex. Compound No. a-2) and aluminum tris(quinolinol) in a weight ratio of 1:20 to form a 70 nm-thick electron-transporting layer 6 under a vacuum of 1.0×10⁻⁴ Pa and at a film thickness growth rate of 0.2-0.3 nm/sec.

[0089] Then, the electron-transporting layer 6 was further coated by vacuum deposition of Al—Li alloy (Li content: 1 atom. %) to form a 150 nm-thick metal film 4 under a vacuum of 1.0×10⁻⁴ Pa and at a film thickness growth rate of 1.0-1.2 nm/sec, thereby forming an organic luminescence device of a structure shown in FIG. 2.

[0090] The thus-obtained device was then supplied with a DC voltage of 8 volts between the ITO electrode 2 as an anode and the Al—Li alloy electrode 4 as a cathode, whereby a current flowed at a density of 9.0 mA/cm² and orange luminescence was observed at a luminance of 830 cd/m². The device was further subjected to 100 hours of continuous voltage application at a constant current density of 7.0 mA/cm² in a nitrogen atmosphere, whereby the device initially exhibited a luminance of 640 cd/m², which was lowered to 590 cd/m² after 100 hours, thus showing only a small luminance deterioration.

[0091] The results are shown in Table 18 set forth hereinafter.

[0092] Organic luminescence devices were prepared and evaluated in the same manner as in Example A-21 except for replacing the spiro compound (Ex. Comp. No. a-2) with those shown in Table 18, respectively.

[0093] The results are inclusively shown in Table 18 set forth hereinafter.

[0094] Comparative organic compound devices were prepared and evaluated in the same manner as in Example A-21 except for using Comparative Compound Nos. 1-3, respectively, shown above, instead of the spiro compound (Ex. Comp. No. a-2). The results are also shown in Table 18.

[0095]

	TABLE 18
		Luminance
	Initial	(at 7.0 mA/cm2)
Exam-	Compound	Voltage	Luminance	Initial	After 100
ple	No.	(V)	(cd/m2)	(cd/m2)	hrs. (cd/m2)
A-21	a-2	8	830	640	590
22	a-5	8	540	480	435
23	a-11	8	505	460	430
24	a-15	8	590	520	475
25	a-18	8	490	455	405
26	a-20	8	1020	810	750
27	a-23	8	800	610	570
28	a-25	8	530	480	440
29	a-30	8	480	445	400
30	a-34	8	780	600	565
31	a-37	8	530	500	455
32	a-39	8	680	580	540
Comp.	Comp.	8	240	200	110
A-4	No. 1
Comp.	Comp.	8	300	240	95
A-5	No. 2
Comp.	Comp.	8	245	200	40
A-6	No. 3

[0096] The procedure of Example A-1 was repeated up to the formation of the hole-transporting layer 5.

[0097] Then, the hole-transporting layer 5 was further coated by vacuum deposition of aluminum tris(quinolinol) to form a 30 nm-thick luminescence layer 3 and then by vacuum deposition of a spiro compound (Ex. Compound No. a-8) to form a 50 nm-thick electron-transporting layer 6, respectively under a vacuum of 1.0×10⁻⁴ Pa and at a film thickness growth rate of 0.2-0.3 nm/sec.

[0098] Then, the electron-transporting layer 6 was further coated by vacuum deposition of Al—Li alloy (Li content: 1 atom. %) to form a 150 nm-thick metal film 4 under a vacuum of 1.0×10⁻⁴ Pa and at a film thickness growth rate of 1.0-1.2 nm/sec, thereby forming an organic luminescence device of a structure shown in FIG. 3.

[0099] The thus-obtained device was then supplied with a DC voltage of 10 volts between the ITO electrode 2 as an anode and the Al—Li alloy electrode 4 as a cathode, whereby a current flowed at a density of 12.0 mA/cm² and yellow luminescence was observed at a luminance of 1270 cd/m². The device was further subjected to 100 hours of continuous voltage application at a constant current density of 10.0 mA/cm² in a nitrogen atmosphere, whereby the device initially exhibited a luminance of 1080 cd/m², which was lowered to 990 cd/m² after 100 hours, thus showing only a small luminance deterioration.

[0100] The results are shown in Table 19 set forth hereinafter.

[0101] Organic luminescence devices were prepared and evaluated in the same manner as in Example A-33 except for replacing the spiro compound of (Ex. Comp. No. a-8) with those show in Table 19, respectively.

[0102] The results are inclusively shown in Table 19 set forth hereinafter.

[0103] Comparative organic luminescence devices were prepared and evaluated in the same manner as in Example A-33 except for using Comparative Compound Nos. 1-3, respectively, shown above, instead of the spiro compound Ex. Comp. No. a-8. The results are also shown in Table 19.

[0104]

	TABLE 19
		Luminance
	Initial	(at 10.0 mA/cm2)
Exam-	Compound	Voltage	Luminance	Initial	After 100
ple	No.	(V)	(cd/m2)	(cd/m2)	hrs. (cd/m2)
A-33	a-8	10	1270	1080	990
34	a-3	10	1100	930	860
35	a-6	10	860	720	640
36	a-12	10	870	730	660
37	a-16	10	1030	900	820
38	a-19	10	830	690	650
39	a-24	10	1280	1120	1010
40	a-28	10	1070	920	860
41	a-31	10	900	760	700
42	a-35	10	1150	970	910
43	a-41	10	1440	1230	1130
Comp.	Comp.	10	120	100	30
A-7	No. 1
Comp.	Comp.	10	160	130	45
A-8	No. 2
Comp.	Comp.	10	50	35	**
A-9	No. 3
**: No luminescence.

[0105] A transparent conductive substrate prepared and treated for cleaning in the same manner as in Example A-1 was coated with a solution of 0.050 g of a spiro compound (Ex. Comp. No. a-1) and 1.00 g of poly-N-vinylcarbazole (weight-average molecular weight=63,000) in 80 ml of chloroform by spin coating at a rate of 2000 rpm, followed by drying, to form a 120 nm-thick luminescence layer 3.

[0106] Then, the luminescence layer 3 was further coated by vacuum deposition of Al—Li alloy (Li content: 1 atom %) to form a 150 nm-thick metal film 4 under a vacuum of 1.0×10⁻⁴ Pa and at a film thickness growth rate of 1.0-1.2 nm/sec, thereby forming an organic luminescence device of a structure shown in FIG. 1.

[0107] The thus-obtained device was then supplied with a DC voltage of 10 volts between the ITO electrode 2 as an anode and the Al—Li alloy electrode 4 as a cathode, whereby a current flowed at a density of 9.5 mA/cm² and red luminescence was observed at a luminance of 450 cd/m².

[0108] An organic luminescence device was prepared in the same manner as in Example A-44 except for using Comparative Compound No. 2 instead of the spiro compound Ex. Comp. No. a-1.

[0109] The resultant device was similarly supplied with a DC voltage of 10 volts, whereby a current followed at a density of 9.0 mA/cm² and yellow-green luminescence was observed at a luminance of 30 cd/m².

[0110] An electroluminescence device of a structure as shown in FIG. 2 was prepared in the following manner.

[0111] A 0.7 mm-thick glass substrate (substrate 1) coated with a 120 nm-thick film of ITO (indium tin oxide) (anode 2) formed by sputtering was successively washed with acetone and isopropyl alcohol (IPA) under application of ultrasonic wave and then washed with IPA under boiling, followed by cleaning by UV/ozone (i.e., irradiation with ultraviolet rays in the ozone-containing atmosphere), to obtain a transparent conductive substrate (including the substrate 1 and the ITO anode 2 formed thereon).

[0112] The transparent conductive substrate was coated by vacuum deposition of a compound (TPD) represented by a structural formula shown below:
to form a 70 nm-thick hole-transporting layer 5 and then by vacuum deposition of a spiro compound (Example Compound No. b-1 listed in Table 9) to form a 70 nm-thick electron-transporting layer 6. The vacuum deposition was respectively performed in a vacuum of 1.0×10⁻⁴ Pa and at a film thickness growth rate of 0.2-0.3 nm/sec.

[0113] Then, the electron-transporting layer 6 was further coated by vacuum deposition of Al—Li alloy (Li content: 1 atom %) to form a 150 nm-thick metal film (cathode 4) under a vacuum of 1.0×10⁻⁴ Pa and at a film thickness growth rate of 1.0-1.2 nm/sec, thereby forming an organic luminescence device of a structure shown in FIG. 2.

[0114] The thus-obtained device was then supplied with a DC voltage of 8 volts between the ITO electrode 2 as an anode and the Al—Li alloy electrode 4 as a cathode, whereby a current flowed at a density of 8.0 mA/cm² and red luminescence was observed at a luminance of 560 cd/m². The device was further subjected to 100 hours of continuous voltage application at a constant current density of 7.0 mA/cm² in a nitrogen atmosphere, whereby the device initially exhibited a luminance of 510 cd/m², which was lowered to 485 cd/m² after 100 hours, thus showing only a small luminance deterioration.

[0115] The results are shown in Table 20 set forth hereinafter.

[0116] Organic luminescence devices were prepared and evaluated in the same manner as in Example B-1 except for replacing the spiro compound (Ex. Comp. No. b-1) with those shown in Table 20, respectively.

[0117] The results are inclusively shown in Table 20 set forth hereinafter.

[0118] Comparative organic luminescence devices were prepared and evaluated in the same manner as in Example B-1 except for using Comparative Compound Nos. 1 and 2, respectively, shown below, instead of the spiro compound (Ex. Comp. No. b-1). The results are also shown in Table 20.

[0119]

TABLE 20
			Luminance
	Example	Initial	(at 7.0 mA/cm2)
Exam-	Compound	Voltage	Luminance	Initial	After 100
ple	No.	(V)	(cd/m2)	(cd/m2)	hrs. (cd/m2)
B-1	b-1	8	560	510	485
2	b-3	8	540	500	470
3	b-7	8	350	310	245
4	b-9	8	530	480	455
5	b-10	8	535	495	460
6	b-12	8	230	210	190
7	b-14	8	590	540	495
8	b-17	8	190	160	140
9	b-21	8	490	470	435
10	b-23	8	370	330	285
11	b-26	8	490	460	415
12	b-27	8	510	475	440
13	b-29	8	230	195	160
14	b-31	8	500	460	430
15	b-33	8	260	230	200
16	b-35	8	490	460	420
17	b-38	8	530	490	445
Comp.	Comp.	8	20	15	**
B-1	No. 1
Comp.	Comp.	8	60	40	10
B-2	No. 2
**: No luminescence

[0120] The procedure of Example B-1 was repeated up to the formation of the hole-transporting layer 5.

[0121] Then, the hole-transporting layer 5 was further coated by vacuum deposition of a mixture of spiro compound (Ex. Compound No. b-2) and aluminum tris(quinolinol) in a weight ratio of 1:20 to form a 70 nm-thick electron-transporting layer 6 under a vacuum of 1.0×10⁻⁴ Pa and at a film thickness growth rate of 0.2-0.3 nm/sec.

[0122] Then, the electron-transporting layer 6 was further coated by vacuum deposition of Al—Li alloy (Li content: 1 atom. %) to form a 150 nm-thick metal film 4 under a vacuum of 1.0×10⁻⁴ Pa and at a film thickness growth rate of 1.0-1.2 nm/sec, thereby forming an organic luminescence device of a structure shown in FIG. 2.

[0123] The thus-obtained device was then supplied with a DC voltage of 8 volts between the ITO electrode 2 as an anode and the Al—Li alloy electrode 4 as a cathode, whereby a current flowed at a density of 8.5 mA/cm² and orange luminescence was observed at a luminance of 800 cd/m². The device was further subjected to 100 hours of continuous voltage application at a constant current density of 7.0 mA/cm² in a nitrogen atmosphere, whereby the device initially exhibited a luminance of 620 cd/m², which was lowered to 590 cd/m² after 100 hours, thus showing only a small luminance deterioration.

[0124] The results are shown in Table 21 set forth hereinafter.

[0125] Organic luminescence devices were prepared and evaluated in the same manner as in Example B-18 except for replacing the spiro compound (Ex. Comp. No. b-2) with those shown in Table 21, respectively.

[0126] The results are inclusively shown in Table 21 set forth hereinafter.

[0127] Comparative organic compound devices were prepared and evaluated in the same manner as in Example B-18 except for using Comparative Compound Nos. 1 and 2, respectively, shown above, instead of the spiro compound (Ex. Comp. No. b-2). The results are also shown in Table 21.

[0128]

	TABLE 21
		Luminance
	Initial	(at 7.0 mA/cm2)
Exam-	Compound	Voltage	Luminance	Initial	After 100
ple	No.	(V)	(cd/m2)	(cd/m2)	hrs. (cd/m2)
B-18	b-2	8	800	620	590
19	b-5	8	530	470	430
20	b-8	8	780	600	560
21	b-11	8	490	455	405
22	b-15	8	790	630	595
23	b-20	8	980	800	750
24	b-25	8	830	630	600
25	b-30	8	800	600	540
26	b-34	8	780	600	565
27	b-37	8	770	600	560
28	b-39	8	810	610	555
Comp.	Comp.	8	240	200	110
B-3	No. 1
Comp.	Comp.	8	300	240	95
B-4	No. 2

[0129] The procedure of Example B-1 was repeated up to the formation of the hole-transporting layer 5.

[0130] Then, the hole-transporting layer 5 was further coated by vacuum deposition of aluminum tris(quinolinol) to form a 30 nm-thick luminescence layer 3 and then by vacuum deposition of a spiro compound (Ex. Compound No. b-4) to form a 50 nm-thick electron-transporting layer 6, respectively under a vacuum of 1.0×10⁻⁴ Pa and at a film thickness growth rate of 0.2-0.3 nm/sec.

[0131] Then, the electron-transporting layer 6 was further coated by vacuum deposition of Al—Li alloy (Li content: 1 atom. %) to form a 150 nm-thick metal film 4 under a vacuum of 1.0×10⁻⁴ Pa and at a film thickness growth rate of 1.0-1.2 nm/sec, thereby forming an organic luminescence device of a structure shown in FIG. 3.

[0132] The thus-obtained device was then supplied with a DC voltage of 10 volts between the ITO electrode 2 as an anode and the Al—Li alloy electrode 4 as a cathode, whereby a current flowed at a density of 11.0 mA/cm² and yellow luminescence was observed at a luminance of 1050 cd/m². The device was further subjected to 100 hours of continuous voltage application at a constant current density of 10.0 mA/cm² in a nitrogen atmosphere, whereby the device initially exhibited a luminance of 980 cd/m², which was lowered to 930 cd/m² after 100 hours, thus showing only a small luminance deterioration.

[0133] The results are shown in Table 22 set forth hereinafter.

[0134] Organic luminescence devices were prepared and evaluated in the same manner as in Example B-29 except for replacing the spiro compound of (Ex. Comp. No. b-4) with those show in Table 22, respectively.

[0135] The results are inclusively shown in Table 22 set forth hereinafter.

[0136] Comparative organic luminescence devices were prepared and evaluated in the same manner as in Example B-29 except for using Comparative Compound Nos. 1 and 2, respectively, shown above, instead of the spiro compound Ex. Comp. No. b-4. The results are also shown in Table 22.

[0137]

	TABLE 22
		Luminance
	Initial	(at 10.0 mA/cm2)
Exam-	Compound	Voltage	Luminance	Initial	After 100
ple	No.	(V)	(cd/m2)	(cd/m2)	hrs. (cd/m2)
B-29	b-4	10	1050	990	930
30	b-6	10	830	700	640
31	b-13	10	870	730	660
32	b-16	10	1010	930	860
33	b-18	10	850	710	630
34	b-19	10	820	690	640
35	b-22	10	1120	1040	950
36	b-28	10	790	700	630
37	b-32	10	1000	960	920
38	b-34	10	1050	960	910
39	b-36	10	800	710	640
Comp.	Comp.	10	120	100	30
B-5	No. 1
Comp.	Comp.	10	160	130	45
B-6	No. 2

[0138] A transparent conductive substrate prepared and treated for cleaning in the same manner as in Example B-1 was coated with a solution of 0.050 g of a spiro compound (Ex. Comp. No. b-1) and 1.00 g of poly-N-vinylcarbazole (weight-average molecular weight=63,000) in 80 ml of chloroform by spin coating at a rate of 2000 rpm, followed by drying, to form a 120 nm-thick luminescence layer 3.

[0139] Then, the luminescence layer 3 was further coated by vacuum deposition of Al—Li alloy (Li content: 1 atom %) to form a 150 nm-thick metal film 4 under a vacuum of 1.0×10⁻⁴ Pa and at a film thickness growth rate of 1.0-1.2 nm/sec, thereby forming an organic luminescence device of a structure shown in FIG. 1.

[0140] The thus-obtained device was then supplied with a DC voltage of 10 volts between the ITO electrode 2 as an anode and the Al—Li alloy electrode 4 as a cathode, whereby a current flowed at a density of 9.0 mA/cm² and orange luminescence was observed at a luminance of 410 cd/m².

[0141] An organic luminescence device was prepared in the same manner as in Example B-40 except for using Comparative Compound No. 2 instead of the spiro compound Ex. Comp. No. b-1.

[0142] The resultant device was similarly supplied with a DC voltage of 10 volts, whereby a current followed at a density of 9.0 mA/cm² and yellow-green luminescence was observed at a luminance of 30 cd/m².

[0143] As described above, the organic luminescence device according to the present invention using a spiro compound represented by the above-mentioned formula (I-a) or (I-b) produces high-luminance luminescence at a low applied voltage and is excellent in durability. Particularly, an organic layer using the spiro compound of formula (I-a) or (I-b) is suitable for an electron-transporting layer or a luminescence layer constituting an organic luminescence device. Further, it is possible to produce the organic luminescence device through vacuum deposition, casting, wet-coating (e.g., spin coating), etc., thus readily realizing a large-size organic luminescence device relatively inexpensively.