TW476227B - Optoelectronic devices containing highly transparent non-metallic cathodes - Google Patents

Abstract

A novel class of low reflectivity, high transparency, non-metallic cathodes useful for a wide range of electrically active, transparent organic devices are disclosed. As a representative embodiment, the highly transparent non-metallic cathode of an OLED employs a thin film of copper phthalocyanine (CuPc) capped with a film of low-power, radio-frequency sputtered indium-tin-oxide (ITO). The CuPc prevents damage to the underlying organic layers during the ITO sputtering process. Due to the low reflectivity of the non-metallic cathode, a non-antireflection-coated, non-metallic-cathode-containing TOLED is disclosed that is 85% transmissive in the visible, emitting nearly identical amounts of light in the forward and back-scattered directions. The performance of the non-metallic-cathode-containing TOLED is found to be comparable to that of TOLEDs employing a more reflective and absorptive cathode consisting of a semi-transparent thin film of Mg:Ag capped with ITO. The present invention is further directed toward novel OLEDs in which the highly transparent non-metallic cathodes may be used in OLEDs comprised of a charge carrier layer containing a compound having molecules that have at least one electron transporting moiety and at least one hole transporting moiety, OLEDs comprised of an emissive layer containing an azlactone-related dopant, OLEDs comprised of an emissive layer containing a phosphorescent dopant compound, or OLEDs comprised of a hole transporting layer containing a glassy organic hole transporting material comprised of a compound having a symmetric molecular structure.

Description

476227 5. Description of the invention (i) Scope of the invention The present invention relates to a non-metallic cathode, especially a transparent non-metallic cathode, which can be used in optoelectronic devices. Specifically, the present invention relates to an organic light emitting device (0LED§) including a bi-degree transparent non-metal cathode. The present invention further relates to a novel organic light emitting device ... An organic light emitting device including a charge carrier layer 'The charge carrier layer contains a compound having at least one electron transporting portion and at least one hole transporting portion in its molecule; a An organic light-emitting device including an emission layer, the emission layer containing a dopant related to azlactone; an organic light-emitting device including an emission layer, the emission layer containing a phosphorescent doped compound; or an organic device including a hole transport layer In a light-emitting device, the hole-transporting layer contains a glassy organic hole-transporting material, which includes a compound having a symmetrical molecular structure. BACKGROUND OF THE INVENTION Optoelectronic devices include devices that convert electrical energy into light energy or vice versa, and devices that detect light signals electronically. The device includes a photodetector, a photoelectrode body, a solar cell, a light emitting diode, and a laser. The device generally includes a pair of electrodes, and J4 of this electrode has at least one layer of charge carrier heat. Depending on the function of the device, the or the plutonium charge-carrying sub-layer may include rods that can electroluminescence when an electrical duration is applied to both ends of the watch, or can form a photovoltaic effect when illuminated. Heterogeneous material layer. In particular, 'organic light-emitting diodes include several organic layers, one of which contains organic materials that can be electroluminescent by applying a voltage across the device, c ° Tang et al.' Appl. Phys. Lett 51, 913 (1987 ). Certain organic light-emitting devices obviously have sufficient brightness and proper color range

C: \ Prograni Files \ Patent \ 55293. Ptd Page 9 476227 Jade, description of the invention (2) Destiny 'S.R. Burrows and M · Practical management technology for full-color flat-panel displays mainly based on liquid crystal display devices E. Thompson, Last Focus World, February 1995. Because many organic thin films used in this device are transparent in the visible light region, they can obtain a new type of display pixel, in which organic light-emitting devices that emit red (R), green (G), and blue (B) are placed Form a vertical stack geometry to provide a simple manufacturing method, smaller RGB pixel size, and larger slot fill ratio. US Patent No. 5,707,745. This patent discloses a laminated organic light emitting device (SOLED), whose intensity and color can be individually changed and controlled by an external power source located in a color adjustable display device. Each layer in the SOLED can be individually addressed and emit its own unique color. This color emission can be transmitted through adjacent laminated, transparent, individually addressable organic layers 'transparent contacts and glass substrates' so that the device can emit any color by changing the relative output of the chromophore. U.S. Patent No. 5,707,745 thus describes a principle of achieving a combined full-color pixel that provides high image resolution, which can be achieved by small pixels. In addition, the device can be manufactured using a relatively low-cost technique compared to the prior art method. Witness Organic Light-Emitting Device (TOLED), V. Bulovic, G.Gu. P.E. Burrows, M.E. Thompson, and S.R. Forrest, Nature 3 8 0 '2 9 (1 9 9 6), Show another important step to obtain a high-resolution individually addressable stacked R-G-B pixel, which is recorded in US Patent No. 5,703,436, where T0LED has a higher than 71% when off Transparency 'and when the device is connected, it emits light from the top and bottom of the device with high efficiency (about 1% of the quantum efficiency). The T0LED uses transparent indium tin oxide (I TO)

C: \ Prograni Fi les \ Patent \ 55293.ptd page 10

Aim4 months • 87116739 amended as a hole injection electrode ’and the Mg-Ag-I TO electrode layer is used for electron beam injection. A device is disclosed in which the side of the Mg-Ag-IT0 electrode layer iIT〇 is used as a hole injection contact for a second different-color organic light-emitting device stacked on top of the TO LED. The cathode injects electrons into the lightning charge carriers) into the hole transport layer, thereby forming a hole injection and sub-transport layer. The adjacent part of the luminescent medium and the anode forms an electron injection rotation area, and the adjacent part of the luminescent medium and the cathode faces an opposite charge electrode transfer area. When the injected holes and electrons are directed upwards, Freun ^ is formed. For example, when the electrons and holes are located in the same molecule, the molecules are captured to have a Frenkel exciton of 5 $ f. These excitations can be caused by materials from the conduction band energy of electrons. The reorganization of these transient states is given priority in the form of valence electron bands, and it is the structure of the device. In the operation of a typical thin-layer organic light-emitting region from each electrode, the device receiving the structure mainly using an organic optoelectronic material layer is usually a general mechanism that causes light emission. This institution is generally reorganized by the injected electrons and electricity. In a word, the organic light emitting device includes at least two organic thin layers separated by ΐί m ϊ ξ 3 ϊ. Among these thin layers, the material-hole transport layer ("HTL") is selected for the ability to transmit holes, and "the ability to transport electrons is selected" The material of the layer is specifically based on its help in injection and Under the structure, when applied to the anode, the electron transport layer (ETL). At this junction, the device can be regarded as having a potential of 33, which is higher than the potential applied to the cathode. Next, the anode will have holes (positive and negative biased diodes. Under these bias conditions

O: \ 55 \ 55293.ptc _1_ Page 11 2001.04.10.011 476227 V. Description of the invention (4) The materials used as the electron transport layer or hole transport layer of the organic light emitting device are often materials, which are stored in the organic light emitting device To produce electroluminescence. A device in which an electron transport layer or a hole transport layer is used as an emission layer is referred to as having a single heterostructure " (SH). Or the electroluminescent material may exist in an individual emitting layer located between the hole transporting layer and the electron transporting layer, and is referred to as "dual heterostructure" (DH). In a single heterostructure organic light emitting device, an electric hole The electron transport layer is injected from the hole transport layer, where it is combined with the electrons to form an exciton, or the electron is injected from the electron wheel layer into the hole transport layer, and is combined with the hole to form an exciton. Because the exciton Captured in the material with the lowest energy gap, and the commonly used electron transport layer material usually has a smaller energy gap than the hole transport layer f 一般, so the early-heterostructure device's emission layer is generally electrical :: Transfer layer. The material used in the organic light-emitting device of Yu Zhi is used for the electron transport layer and the electric Tfli transport layer. The material should be selected by the worker to effectively transfer the hole from the hole. Note: In the electron transport layer And 1. It is believed that the best conductivity of the hole transport layer and the electron transport layer of the best organic light-emitting device is A / gg, which has a good energy level correction between the energy levels of the occupants (Η Ο Μ Ο). Yu Yutian And τ _ & Zhi heterostructure organic light emitting device In the center, the hole is injected from the hole transporting layer, and the electron transporting layer of the son's eye is injected into the individual emitting layer, and the hole and the electron are combined here to form excitons. The ba-mu-a — layer of materials still contains metals with low work functions such as M g · A g. The gold sp,, r, 'S ^ skin provides a current for the electrical path of Zhou Zhisi, and A package that shoots electrons and shi ^ ^ ^ ^ ^ ^ + mainly on the adjacent electron transport layer. However, the metal layer is also visible.

LiL sees high reflectivity and light absorption in the light area 0 ιΗ 476227 V. Description of the invention (5) means that if a transparent organic light-emitting device is needed, such as a single organic light-emitting device with a stack of full-color SOLEDs or a monochrome TOLED A balance needs to be struck between metals that are thick enough to serve as a cathode, but not thick enough to cause a substantial loss of light transmission or reflectivity. Therefore, the conventional TOLEI) uses a thick layer of 75-100 angstroms of Mg: Ag encapsulated with flood deposited steel tin oxide; the Mg: Ag layer simultaneously injects electrons into A 1 qs and prevents it from being indium tin oxide By sputtering. Therefore, although a device with a light transmittance of about 7% can be obtained, the composite cathode still reflects significantly. In addition, among SOLEDs containing at least one coloring layer between the metal cathodes of adjacent color-emitting organic light-emitting devices, Microporous effect, leading to color tuning problems. 1 Shen, PE Burrows, V. Bulovic, SR Forrest, and M.E. Thompson, Science 276, 2009 (1997). This microporous effect can also lead to undesired emission Dependence on light angle. In addition, the thin Mg: Ag layer is easily degraded in the atmosphere, so special design and processing steps are needed to maintain its efficacy as the cathode of organic light-emitting devices. A solar energy, pool, which is highly transparent has been disclosed for years An indium tin oxide layer can be used as a cathode under certain conditions, but the indium tin oxide cathode is said to be made by depositing a charge-carrying organic layer on indium tin oxide, N. Karl, A. Bauer, J. Holzaofel, J. Marktanner, M. Mobus > F. Stolzlé, " Effective Organic Photovoltaic Cells: The Role of Laser Collection, Exciton Diffusion at the Interface, and Used to Separate Electric Fields within Charges And highly charged carrier mobility ", molecular crystals and liquid crystals (molecu) [ar Crysta 1 sand L iquid Crysta 1 s], 2 5 2 research, 2 4 3-2 5 8 ( Karl et al.) And ffhitlock, J.B., panay〇tatos, p.,

C: \ Prograni Files \ Patent \ 55293. Ptd Page 13 476227 V. Description of the invention (6) f: rma: GD, CoX, MD, SaVers, RR •, and Blrd, • ·, f organic "Study on Materials and Device Structures of Semiconductor Solar Cells", P ^ ical Eng ·, Vol. 32, No. 8, 1921_ 1 934 (1989 ^ 8 (Whlt 10Ck Temple)). The organic layer has been deposited on the upper layer. The indium tin oxide layer is not expected to form a low-resistance contact with the adjacent organic layer, so it cannot be used as a cathode. The cathode of this article is confirmed as follows for organic light-emitting devices. It is expected to use a highly transparent cathode such as a highly transparent indium tin oxide anode = k optoelectronic device. In addition, it is desirable that the highly transparent cathode still has the electron injection characteristics equivalent to a translucent low work function metal thin layer such as Mg: Ag in the organic I light coat 1, which is a commonly used cathode ^ Layers. Various compounds have been used as hole transport layer materials or snow transport layer materials. Most of the hole transport layer materials are composed of various materials that exhibit high hole mobility (10 cm2 / volt second). Consisting of triarylamine. The electron transport layer used in organic light-emitting devices varies slightly. Tris (8-hydroxyquinolinium) aluminum (A 1) is the most common electron transport layer material. Others include oxadiazole, triazole, and trioxane. ... For example, generally a single heterostructure device can be made of ITO / TPD / Alq3 / Mg-Ag '. Steel tin oxide is used as the anode, and diphenyl-n, N'-bis (3-fluorene basic group) -1,1' -Biphenyl-4, 4'-diamine (TPD) as the hole transport layer, A lqs as the electron transport layer 'and Mg-Ag as the cathode. When the bias voltage is applied across the device, the hole is indium tin oxide Injected into TPD, and moved towards the interface between TPD and A Us, 'electron is injected from Mg-Ag alloy to A 1 q3, and moved to the same interface. Holes are injected from TPD to A 1 q3', which is combined with electron An exciton is formed. The exciton diffuses arbitrarily through the A 1 q3 layer until it recombines and passes through light.

476227

The maximum distance of a child moving in the Aiq3 layer of the device is about 300 Angstroms in Alq3. ^ :: Most of the emissive materials in organic light emitting devices have low: one: ΐ ΐ mobility. As a result, exciton formation is generally caused by the charge carriers that are extremely close to m! Being injected into the interface of the emission layer. For example, most electron transport layer materials have extremely poor hole transmission. At the point where the emissive electron transport 3: is very close to the hole transport layer / electronic rotation layer v: the structure life is very short, so it will not move far away before the reorganization. The Li group only uses the emission material, -4 Generate exciton = layer, μ "= view" and the color of radical -1- extension L C: \ Program Files \ Patent \ 55293.

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V. Description of the invention (8) days: National Patent No. 5 9 q "Hydroxypentine coordination complex", No. δ70 reveals a series of Alq, 2 ((Hr) f with two 8-hydroxy-2- (ΠΙ) complexes, and electronic input derived from complex salt complexes. These objects f are blue emitters and are reasonable devices. This structure is lost due to 2 (〇Ar). It is necessary to manufacture between TPD and AU3. In addition, these strong Mg-Ag electrodes have poor electron injection efficiency and color emission, which is almost the same as their electroluminescence (EL) spectrum. Heterogeneous: The PL spectrum is the same. These compounds are also of the same quality, such as used for Yansheng *, have the same material properties, and show good properties- & Μ, the second monitor color emission. The transport layer material is a relatively poor hole transport. "At the molecular level, the disclosed t-electron transport has M < ergosine as an electron transport agent: column, the emitting material, its agent Tam 〇t 〇 et al.,]] Q ″ 叩 diphenylamine as a hole to transport 1, d, 4 _______ trxL; jj electroluminescence in multilayer light-emitting diodes ^ and three stupid The molecule of amine is organic-1.85⑴97). These emissive materials; ^ e'Mater. 9, 1077 The agent forms a low ionization potential of the excitable dislocation. When the wave layer is easy to transport compounds with holes, the external quantum efficiency and energy conversion are found. The luminescence lifetime of devices made of materials is often higher than: South '. However, the tendency of these materials to transport electrons is higher than that of holes. It has also been found that, in addition to being used as the electron emitting material in the electron transport layer as the main emitting material and emitting material, > and the same as the electron transporting agent in the form of a relatively low concentration in the electron emitting material itself can be mixed The main material in the electron transport layer is the second layer. When the material exists in the form of a dopant or dopant, it is said to be the host material. Transform it from the subject

C: \ Prograiii Fi ies \ Patent \ 55293. Ptd brother page 16 f / DZZ / 5. Description of the invention (9) When this dopant material is formed,

褛 烟 φ In addition, these materials need to be able to manufacture light emitting equipment and can be connected to X's Lei Fang ^, L materials can be incorporated into the organic light-emitting wear +2 ball body and # heterogeneous material manufacturing skills- Especially the use of straight two for two uses: by the easy-to-use device. -The organic luminescence is expected to be used in the center close to the selected grip area p p ^, 丄 cutting, appraising, and relatively narrow frequency-frequency power-emitting luminescence materials, this spectral region corresponds to the three primary colors red, period ^ One of them makes it available in organic light-emitting devices or SOLEDs as colored and shame. It is particularly desirable that these compounds can be selected from a class of compounds in which the emission is' ~ The substituents are selectively modified or modified by modifying the structure of the basic compound produced by the charge transfer transition. In addition, it is expected that the compound can also be easily deposited into a thin film by using a vacuum deposition technology, so that it can be easily incorporated into an organic light-emitting device prepared by using vacuum-deposited organic materials. '" A document by Yuan Jinzhi revealed a sea surface buoy transponder (Aequorea victoria), which produces extremely narrow green fluorescence, R. Heim, Α. β

CuMtt 'and R.Y. TSien' natural 0 9 95) 3 73 ′ 6 6 3- 6 64. The center of the recorded spectrum is about 5 10 nanometers, and the half-width is 4 mm. The active chromophores that can be generated by this emission are: ~ 〇

The p-hydroxyimididimidazolidinone chromophore is based on the

476227 V. Description of the invention (10) The Ser-Tyr-Gly sequence is cyclized and oxidized, and is bonded to two positions of the protein, labeled "pr 〇tπ. According to records, the mutant form of this protein produces a large blue color The emission of displacement. The blue displacement is said to be due to changes in the protein matrix of the bonding dye, not the dye itself, R. Heim, DCPrasher, and RYTsien, Pr oc. Nat. Acad. Sci · (1 9 94) 9 1, 1 2 5 0 1-1 2 50 4. The fluorescence in these dyes comes from the donor / acceptor network, including phenate ion donors and carbonyl acceptors. This Hexm publication describes a hair color The purpose of the group is to use fluorescent tags to label proteins to detect their position or configuration changes in vitro and in intact cells. However, these publications do not disclose the isolated chromophore molecule itself. Preparation or use. The present invention also relates to a compound related to gamma lactone, which can be used as a dopant in the emission layer of an organic light-emitting device, wherein the emission of the dopant can be changed by selectively changing a substituent. Or by modifying the substrate used to produce the emission The structure of the compound is changed. The compound can be easily deposited into a thin film using vacuum deposition technology so that it can be easily incorporated into organic light-emitting devices made entirely of vacuum-deposited organic materials. The review literature discussing azlactone does not reveal the fluorescent properties And the use of these compounds, YS Rao and R. Fi Her, synthesis (1 9 75) 7 4 9-76 4. On February 23, 196, 1 f pending review US 0 8/774 , 3 3 3 relates to an organic light emitting device containing an emissive compound that generates saturated red emission. The emissive layer includes an emissive compound having a chemical structure of the following formula I ...

C: \ Prograni Fi les \ Patent \ 55293. Ptd page 18 476227 V. Description of the invention (11)

Where X is C or N; R3, R9, and Ri () are each selected from hydrogen, alkyl, substituted alkyl, aryl, and substituted aryl; wherein R9 and R1Q can be combined to form a fused ring; M丨 is a divalent, trivalent, or tetravalent metal; and a, b, and c are each 0 or 1; wherein, when X is C, a is 1; when X is N, a is 0 When c is 1, b is 0; and when b is 1, c is 0. The examples disclosed under serial number 08 / 774,087 include a compound of formula I, where X = C; R8 dibenzyl; R9 di R10 = Η; c di 0; and b = 1 = the chemical name of this compound is 5 , 10,15,20 -tetrabenzyl-21H, 23H -pyrene (TPP). An organic light-emitting device including an emission layer containing TPP generates an emission spectrum including two narrow-band frequencies centered at about 6 50 and about 7 1 3 nm

C: \ Program Files \ Patem \ 55293. Ptd 苐 Page 19 476227 V. Description of the invention (12) Band ′ is shown in Figure 1. The emission of this device includes Fen light from a Tpp dopant. One question of using TPP-doped devices is out of the 713 milliseconds & laughter band, which occupies about 40% of the emissions, and is not available in a narrow range. The first problem is that the organic light-emitting device doped with TPP is extremely unsettled. Second, the useful life of the device is relatively short. Expect Dreams with TPP = two improvements. The present invention refers to the clothing of the previous art. Another aspect of the present invention is based on the spin statistics. It is generally known that most of the excitons generated by the floor-light device are in the state of non-emissive triplet. The formation of the triplet state can greatly lose the excitation energy of the organic light emitting device through non-radiative transition to the ground state. It is expected that the quantum efficiency of the overall organic light-emitting device can be increased by this kind of energy via the exciton triplet transport path: for example, the exciton triplet energy is transferred to the emitting material. Unfortunately, zinc has known that the energy from the excited triplet can effectively transport the triplet of the phosphorescent molecule under specific conditions, but it is generally expected that the rate of phosphorescent decay will not be fast enough to make the display device more readable. The present invention also relates to an organic light emitting device 'which also addresses these problems of prior art devices. Organic light-emitting device damage has been proven to be caused by thermally induced deformation of the organic layer (such as melting, crystal formation, thermal expansion, etc.) ^ This damage mode can be referred to the study using hole transport # material K. Naito and A. Mmra , Journal of Physical Chemistry (1 99 3), 97 '6240 -62 48; S. Toloto, T. Tanaka, A. Okada, and T. Taga should correspond to Physics Letters (1996), 69, (7), 878-8 80; Y. Shirota, T Kobata, and N.

Noma, Chemical Letters (1 989), 1 1 45-1 1 48; T. Noda, I. Imae N · Moma and Υ Shirota, Advanced Materials Science (1 997), 9, No. 3;

C: \ Program Files \ Patent \ 55293. Ptd Page 20 476227 V. Description of the invention (13) E. Han, L. Do, M. Fujihira, H. Inada and Y. Shirota Journal of Applied Physics (1 99 6) , 80, (6) 3 297-701; 1 \ 1 \ 〇 (13, 11 · Ogawa, N · Noma, and Y · Shirota Applied Physics Letters; S. Van Slyke, C. Chen, and C · Tang Applied Physics Letters (1 99 6), 69, 15, 2 1 60-2 1 62; and U.S. Patent No. 5,061,569. In contrast to crystalline or polycrystalline forms, it is desirable to use glass in the organic layer of an organic light emitting device. Organic materials, because glass can provide higher transparency and produce superior charge carrier characteristics compared with polycrystalline materials that are generally produced when preparing crystalline thin films of materials. However, if glassy organic When the layer is heated to touch its Tg, the thermally-induced deformation of the organic layer causes catastrophic and irreversible damage to the organic light-emitting device. In addition, the thermally-induced deformation of the glassy organic layer may occur at a temperature lower than \ The speed of deformation may be related to the difference between the temperature and the temperature at which the deformation occurs. Even if the device is not heated above Tg, the lifetime of the organic light emitting device may still be related to the organic layer 1. As a result, there is a need for a high organic material that can be used in the organic layer of the organic light emitting device. The most commonly used hole transport material in the hole transport layer is biphenyl bridged diamine, which has the following chemical structure of N, N, -diphenyl-N, N -bis (3-fluorenylphenyl)- 1,1-bibenzyl ~ 4,4, -diamine (TPD):

C: \ Program Files \ Patent \ 55293. Ptd page 21 476227 5. Description of the invention (14)

TPD This material has good hole mobility, and effectively transports holes to aluminum tris (8-hydroxy_phosphonate) in a single heterostructure organic # light device. However, the melting point of TPD is 167 ° and the glass transition temperature is 65 °. If a device made using TPD is heated to 65 ° C --- this glass transition temperature--above, it will cause catastrophic and irreversible damage. In order to increase the glass transition temperature of the hole transport layer, different modifications were made on several groups of the basic structure of TPD, Naito et al .; Tokito et al .; Shirota et al .; Noda et al. (Advanced Material Science); Han et al .; Noda et al. (Applied Physics Academic Express); Van S 1 yke et al .; and US Patent No. 5,061,559. Although these studies have produced substances with values up to 150 ° C, it is not clear why specific structural modifications increase Tg, while other modifications may not affect or even possibly reduce them at all. Other modifications may result in a substance that does not have a glass transition temperature at all or does not have a combination of properties suitable for a hole transport layer. For example, the amine group of TPD is replaced with a carbazolyl group to produce 4, 4′-bis (N-carbazolyl) bibenzyl (CBP), which has the following chemical structure:

C: \ Prograin Files \ Patent \ 55293. Ptd page 22 476227 V. Description of the invention (15)

CBP increases its melting point to 2 8 5 ° C. However, the substance does not have a glass transition temperature. Other changes in the basic structure of Ding PD can increase the value even more, but this substance often has poor hole transportability compared to TPD, that is, the device properties of organic light-emitting devices produced by such high-temperature substances Worse than TPD. U.S. Patent No. 5,0 6,1,59,9 discloses a hole transporting substance including at least two tertiary amine moieties and additionally an aromatic moiety containing at least two argon atoms bonded to tertiary amine Of fused aromatic rings. Among the large number of compounds included in the broad categories listed, U.S. Patent No. 5,0 6,1,59,9 does not disclose a method for selecting a compound having a high glass transition temperature. For example, naphthalene derivatives do make stable glass. One of them is 4, 4′-bis [(1-naphthyl) -N-benzyl-amino] bibenzyl (a-NPD), which has a chemical structure:

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a-NPD The inventor's measurement showed that the Tg of a-NPD was 100-105 C ′, which was significantly lower than that of TPD at 65 ° C. This substance has superior hole conductivity, Tg 1 0 0- 1 0 5 ° C is higher than TPD about 65 ° C. Organic light-emitting devices prepared using NPD have electrical properties very similar to those of organic light-emitting devices prepared using peripheral TPD. However, 4,4'-bis [(2-Cequiyl)-[^-phenyl-amino] biphenyl (/ 3-NPD) having the following structure:

C: XProgram Fi lesXPatenr ', 55293. ptd p. 24 476227 5. Description of the invention (17)

β-NPD is well known to have significantly lower α-derivatives!;. Obviously, due to the low and irregular differences between α- / 3-derivatives, the known records do not use the / 3-derivatives as hole transport materials for organic light-emitting devices. If the organic light-emitting device can be manufactured from a glass-like charge carrier material having improved temperature stability, it is desirable to provide a light-emitting characteristic equivalent to that of the prior art compound. The "π electric charge carrier layer" used in the present invention means a thunder hole transporting layer, an electron transporting layer, or an individual emitting layer of an organic light emitting device having a double heterostructure. In addition, a glass can be selected and prepared using The method of the charge carrier substance has improved temperature stability, especially the glassy charge carrier substance with high glass transition temperature. In addition, the Tg of the substance and the hole transporting property usually have an inverse ratio. Relationship. The use of hole transporting layers with good hole transporting properties can make organic light-emitting devices have desired properties, such as higher quantum efficiency and lower span.

C: \ Prograni Files \ Patent \ 55293. Ptd 苐 Page 25, 476227 V. Description of the invention (18) Organic electricity is issued first. ¾-Wu Gu needs it-a species with high thunder words: state quantum efficiency, and Higher illumination. Send layers. The advantages and summary of the hole hole workability and high glass transition temperature of the invention of the hole are summarized in the present invention. A low-resistance contact of a semiconductor organic layer includes a conductive non-metal layer. Shi Bin chooses any type of photoelectric edge bright non-metal cathode, which can be used in practical detail. In particular, the present invention is applicable to, for example, organic light-emitting and bright non-metal cathodes, which can make electron injection properties The invention of a transparent gold layer cathode is particularly relevant-Explained: about 85 percent less or higher. Includes non-metallic cathodes. ‘Π-degree transparent organic light-emitting device (OLED), in another specific example, is an inorganic rich conductor material such as oxygen = organic light-emitting device. Λ-Cu Sn as a non-metallic cathode In another specific example, the present invention is related-including non-metallic cathodes. Modal plate + V limb shooting, in another aspect of the present invention, it is very ancient, extremely polar, and it can be contacted organically f ::, the device includes a non-metallic cathode injection and the organic hair is sent to the organic hair Let's install = electric ... male skin layer in order to prevent the cathode layer from being deposited ^ _ Two connected to the snow in the light-emitting area of the device ^: Beside the machine, the edge protection layer can be provided with another-additional electron transport layer This: Between the layers: 乂 Help to send electrons to the C: \ Program Files \ Patent \ 55293. Pid 可 26. 5. Description of the invention (19) Luminous area of the machine light-emitting device. In another aspect of the present invention, the present invention relates to a method for manufacturing a cathode, which includes preparing a cathode, the cathode includes a conductive non-metallic layer that is resistive to a semiconductor organic layer, and wherein 1 # is included in Conductivity: A region is formed between the metal layer and the organic conductor of the abundance of conductors, and the conductive metal layer is in electrical contact with the absorptive layer of the isolator. 9 In addition, the present invention relates to a method for manufacturing an organic light-emitting device. Non-metallic cathode ... The current generates an electric current sub-layer with holes in the 11th bit. The amine portion can be specifically used as electricity, including the heterojunction compound of the carousel, and the enthalpy is placed on the substrate. Another related organic light emitting device (OLED) includes a heterostructure which can have an electric / charged electron transport portion and at least one The electron-transporting moiety is a heteroluminous structure of coordinated luminescence, where the 'comprising a compound having at least one transporting moiety in the molecule, wherein the amine-transmitting moiety. This hole turns on the phenolate. The derivatization of triarylamine based on the acyl-8 ~ chilinate complex of this compound is based on the group I metal such as 2-fluorenyl-8-quinolinate complex of Al, Ga or In. The hole transport part can be An example of hole transport is via a triarylamine, for example, two ligands with A 1 2-曱 as the electron transporting part, and a hole transporting part. The transmitting part and at least < holes may be individual emitting layers of the emitting layer ' This electron injection promoting layer is between the US series and the cathode, and the hole promotion injection layer is an electron transporting layer with a charge carrier structure of a compound having at least one electron transport in the molecule, or double denier It can also be used as the main emission promoting layer, such as the electron transport layer of an organic light-emitting device, which is injected into the f-rotation layer; or

C: \ Prograni Fi les \ Patent \ 55293. Ptd Page 27 — 476227

Promoting the placement of electricity in the field electrode with holes is the reason for this invention. It is believed that the hole-transmitting layer and anode of the anode that generate sock luminous tf in the belt related to the ester of the machine-emitting device of the present invention are detailed: in the hole wheel layer Λ == mention:-an electron with high hole mobility In the transport layer, in most of the volume of the sub-transport layer, the electricity and sound are transmitted by the three holes; in the ... This kind of property can increase the lifetime of the organic light emitting device. Also related-a compound related to azlactone, which can be used as a doping toughness in a certain emission layer. The present invention relates to a heterogeneous compound, which is selected from the group consisting of azine compounds, and is based on the electroluminescence of Ping in the center of a range of primary colors. In addition, the present invention relates to an organic light-emitting device and a method for manufacturing the organic light-emitting device, including a heterostructure for generating electroluminescence ', wherein the heterostructure may include an emission layer containing a compound related to γ-lactone. . The present invention also relates to an organic light emitting device and a method for manufacturing a light emitting device, wherein the emission from the device can be scraped through the phosphorescence decay = process 41, wherein the phosphorescence decay rate is fast enough to meet the requirements of the display system. . In detail, the present invention also relates to an organic light-emitting device, which includes a substance that can receive energy from the singlet or triplet state of the exciton, and emits energy by means of phosphorescent radiation. ^ < 7 < Heavy form One of the advantages of the present invention is that the phosphorescent decay cake uses nourishment ^ ^ Stateful energy 'This kind of energy is used for non-radiative energy transmission and relaxation.

476227 V. Description of the invention (21) Machine lighting devices are generally wasted. The present invention is also related to a kind of organic hairdressing device, which may include materials that can produce high two: laterite emission. _In other words, the organic light-emitting device of the present invention may include PtOEP, a compound that generates a narrow emission, and has a large peak when it is mixed in an electron transport layer containing aluminum tris (8-quinolinate) Close to 640 μm. This emission is found to be a highly saturated red emission. Another advantage of the s elaboration of organic light-emitting devices doped with PtOET is that when the organic ^ 9 裒 1 is exposed to the surrounding% environment for several days, it should be: when the previous technology Jt! Zhi'an; r ， #. It is the stability of the application period with a clear and larger application ratio than a. The present invention also relates to a method for manufacturing an organic light-emitting device, wherein the phosphorescent dopant compound generates a highly saturated red circuit, which has a light response function to the human eye. In order to expose < \ youyi and points, in other words, the present invention also relates to a method and method for selecting a phosphorescent dopant compound that can be used in organic hairpins i, where the phosphorescent compound ^ = is a button compound , Its symmetry is lower than that of pt0ET = companion, and the sex is low, so the radiation spike is induced toward the naked eye and the milk is sensed, but it remains in the spectral region that feels saturated red. Zhihua :: Another kind of organic light-emitting device, which includes a heterogeneous structure, and a hole-transporting layer with a broken glass structure. The two-layered layer may contain a compound having a symmetrical molecular structure. = 子 的 端端 系 系Transport the amine part for the hole, between the two aromatic meridians with or without ::

C.XPrograiTi Fi les \ Patent \ 55293. Ptd page 29 f3

87116739 > Year + Month SJai bond. — Other objects and advantages of the present invention can be clarified by those skilled in the art from the present invention. Brief Description of the Drawings Figure 1A shows a schematic illustration of a standard prior art organic light emitting device. FIG. 1 B1 shows a representative organic light emitting device of the present invention. 1B 2 show another representative organic light emitting device of the present invention. Fig. 1C shows light output with respect to the current of the organic light emitting device shown in Fig. 1 B1. The organic light emitting device has an indium tin oxide cathode and a Cupc electron injection interface layer. The lowest value set shown in this figure was obtained at 180 hours. Figure 1D shows the light output of a current with respect to a standard prior art TOLED with a Mg: Ag cathode layer. The lowest value set in this figure was measured at 80 hours. FIG. 1E shows the I-V curves of the Zn Pc electron injection interface layer and the Cu Pc electron injection interface layer. Fig. 1F shows the light output relative to the ZnPc electron injection interface layer. Compared with the CuPc electron injection interface layer, the efficiency β of the CuPc device is 0.23%, and the ZnPc device is 0.15%. Figure 1G shows the transmittance (τ), reflectance (R), and absorbance (A) of an organic light-emitting device with an indium tin oxide cathode and a cu pc electron injection interface layer as a function of wavelength (nm). Figure 1 (a) shows the I-V characteristics of a standard prior art organic light-emitting device with a Mg: Ag cathode layer. The higher value group is at 0 hours, and the lower value group is at 180 hours. ’

O: \ 55 \ 55293.ptc Page 30, 2001.04.10.030 _ Supplementary Birds, January 16th, 17116739 Rev. 5 Description of Inventions (23) Figure II shows an organic light emitting device with an indium tin oxide cathode and CuPc electron injection interface layer I- V characteristics, the higher value group is located at 0 hours, and the lower value group is located at 60 and 180 hours. Figure 1 J shows the light output with respect to the current. The thickness of the injection layer of the device c u p c ranges from about 30 angstroms to about 120 angstroms. These devices show a quantum efficiency of about 0.1%. Figure 1K shows the I-v characteristics of the device of Figure 1J. FIG. 1L shows the current-voltage characteristics of a TOLED (nMF-TOLEDn) containing a non-metal cathode with a diameter of 0.4 mm and a reference TOLD that was grown in the same vacuum cycle. FIG. 1M is a schematic diagram of a TOLED structure including a non-metallic cathode. FIG. 1N is the sum of the light energy output of the top and bottom surfaces of the TOLED_ (nMF_TOLEDn) and the reference TOLED shown in FIG. 1L with the non-metal cathode. The measured brightness at the maximum current density corresponds to 20000 candle / m2. Figure 10 shows the electroluminescence spectra from both the top and bottom surfaces of the device. A fitting curve (solid line) is placed on the top emission spectrum using the calculation method described in the present invention. FIG. 1P shows a proposed simplified energy level diagram for a TOLED containing a non-metal cathode. Dss represents the density of the surface state. Figure 1Q shows a digitally reproduced photo taken from a TOLED with a non-metallic cathode and a conventional TOLED. Conventional TOLEDs display small gray areas, while TOLEDs with non-metallic cathodes cannot be visually observed in digitally reproduced photos. Figure 2A shows ai-pnP, A1-pCb, and Al-mCb in (: 112 (: 12

O: \ 55 \ 55293.ptc Page 31 2001.04.10. 031 4; 6Ih j Phase number 87116739_ > Year of the day correction __ 5. Description of the invention (24) Absorption and fluorescence spectrum. -Figure 2B shows the electroluminescence (EL) and photoluminescence (PL) spectra of an organic light emitting device with an Al-pNP layer. FIG. 2C shows the ι_ν characteristics of an organic light emitting device having an Al-pNP layer. FIG. 2D shows the I-v characteristics of an organic light-emitting device having an Al-pCb layer. FIG. 2E shows an EL & PL spectrum of an organic light emitting device having an Al_pCb layer. Fig. 2F shows el and PL spectra of an organic light emitting device having an Al-pCb / chico layer. -Fig. 26 shows the characteristics of an organic light-emitting device having an Al-pCb / Etc layer. Figure 3 A shows the electroluminescence spectra of a device doped with 0.8% compound 3 as a dopant and an undoped A 1 q3 device (π 0%,,), which is related to the presence in CH2C12 Comparison of the photoluminescence spectra of the dopants. Figure 3B shows the I-v characteristics of a doped or undoped device. Figure 4A shows the photoluminescence (EL) spectrum of an organic light emitting device doped with TPP. FIG. 4B shows the EL spectrum as a function of wavelength at different voltages (6, 9, 12, and 15 volts), which is an organic light-emitting device with an Alq3 layer doped with 0.6 mole percent PtOEP, and is doped with TPP The EL spectrum (π TPP… ELn) of the device is compared. Figure 4C shows the EL spectrum as a function of wavelength at different voltages, which is an organic light-emitting device doped with about 0.6 mole percent PtOEP. Fig. 4D shows photoluminescence (PL) optical readings of PtOEP-doped Alq3 devices as a function of wavelength at different PtOEP concentrations. Figure 4E shows the PtOEP solution as a function of wavelength at different laser wavelengths.

O: \ 55 \ 55293.ptc Page 32 2001.04.10.032 476227 ~ _ Amendment Γ- ~~ -MMr Case Shen 87116739_ 6] Year ^ Month and Day Amendment _ 1 ^ 1 ~ > PL of Invention Note (25) The spectrum is compared with the EL spectrum of an organic light-emitting device having an A1q3 layer doped with 0.6 mole percentage pt0] Ep. Fig. 5A shows a representative platinum perylene and four other perylenes which can be used to prepare platinum perylenes which can be used as platinum-substituted phosphorescent dopant compounds in organic light emitting devices. Figure 5B shows the electroluminescence (EL) spectrum of a polymer organic light-emitting device doped with ptDPP, the photoluminescence (pL) spectrum of ptDDp in polyvinylene, and the EL spectrum of PtOEP doped in Alq3 device. Comparison. FIG. 5C1 shows a ptDpp ^ EL spectrum expressed as a function of an applied voltage, which is doped in an A1q3 layer of an organic light emitting device including (11〇 // 〇 / ^ 1 (13 / ^ 勿 人 2)). Fig. 5C2 shows the doped PtDPP 2M (el spectrum of ΐ3 organic light-emitting device, compared with A lq3 organic light-emitting device doped with PtOEP (each device operates at 9 volts). Fig. 5D shows the organic light-emitting device doped with PtDpp Comparison of the CIE coordination and emission wheel with other red light-emitting organic light-emitting devices. Figure 5E shows the light response curve standardized by c 丨 e for the sensitivity of the human eye and the specifications for compounds that produce saturated red emission The emission spectra overlap. Figure 6A shows a current versus voltage diagram of a specific example of the present invention. Figure 6B shows a current versus voltage diagram of a specific example of the present invention with a CuPu hole injection promotion layer. A detailed description of a preferred specific example is now directed to The present invention has been described in detail with specific preferred specific examples.

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476227 V. Description of the invention (26) The four specific a examples are provided as § particularly explicit examples, without limiting the present invention. The present invention is particularly related to a novel cathode, which includes a conductive layer = f layer, which is related to semiconductor organic The layer forms a low resistance contact. The cathode can be used in a variety of electrical devices. In particular, because the cathode of the present invention can be manufactured from high-yield materials, the cathode can be particularly used in organic optoelectronic devices, light-emitting devices, solar cells, photodetectors, lasers, and optical crystals. s. R. Forrest, Chemistry Review (Chem. Rev.) 97, 1 7 9 3. Every day. (1 9 9 7). In a lightning device having at least one electron transport layer (ETL) (including electron transport materials) and at least one hole transport layer (HTL) (including hole transport materials), the cathode and the electron transport layer located in the device The snow on the side is the same, and the anode is the same as the electrode on the side of the hole transport layer of the device. For example, in an organic light-emitting device, the cathode may mean an electrode that injects electrons into the electron transport layer, and the anode is an electrode that injects holes into the lightning hole transport layer. Injecting holes into the hole transport layer is equivalent to extracting electrons from the hole transport layer. 4: Each electrode of the organic light-emitting device can generally be a layer that directly contacts the muon transport layer of the adjacent hole carousel layer & 'Look at this electrode as a positive "cathode. Dare to co-examine the serial number 0 8 It was revealed in / 8 65,49 1 that an additional organic I may be included between the anode hole transport layers. This additional layer is called f ::. Electricity? Injection f, and it was revealed that the protective layer was used during the electrode layer deposition. The protective layer and / or the hole injection efficiency used to promote the anode = 2 Erguang. For example, the sequence of 0/8 6 5, 49 丨 reveals, for example, cyanine compounds such as: J ^ znpG) _m (cupe) or PTM. The protective layer can be deposited on the top layer of the same layer as the transport layer for subsequent subsequent low-level precipitation of the tin anode layer on the oxide surface.

°! 〇Λ_ April 476227-: ϋ 87116739

] 90. 4 、. 1 6 / Last year ί \ ^

-4 < " · Protect organic layer during V product. The serial number 0 8/8 6 5, 4 9 1 also reveals that the protective layer can promote the hole injection rate of the hole injection anode in some cases. θ; Because the specific metal combines a South conductivity and a low work function, even if the performance of the electronic device is susceptible to the negative influence of the high reflectivity of the metal cathode layer, it is particularly useful for optoelectronic devices, such as those containing a cathode / organic layer boundary surface 9 Organic light-emitting devices still include inherently highly reflective and suitable absorbing cathode materials. In optoelectronic devices such as organic light-emitting devices where high transparency is desired, a very thin metal layer is generally used to prepare a semi-transparent metal layer. But even so, the high reflectivity of the metal associated with the high conductivity of the metal cathode material and the bipolarity still results in the overall performance of the device. For example, for the overall device, the quantum efficiency is reduced. s damage the hair, one of the unexpected discoveries is that the conductive f /: / right machine / think has formed a low-resistance contact, where the conductive non-gold] 1 m interface (hereinafter referred to as " cathode / Organic layer interface ^ ί ί ϊ = iβ " ΐ ΐ is a cathode layer that injects electrons and passes it through the cathode The snoring sound is thus in the Γ transport layer. The semiconducting organic layer at the cathode / organic layer interface is thus the electron injection interface layer in the core conductor 8 7 Γ in the present invention. Electricity when the organic optoelectronic layer interface is actually used; the voltage across the organic layer [of: ;; at the cathode / organic layer interface, the electricity, and the total voltage drop of the positive electrode is 40,000, The voltage drop across the interface is very sharp. 7 It is better to pass the cathode / organic drop to approximately 30% of the total voltage drop.

476227 V. Description of the invention (28) The conductive non-metallic layer may be selected from a variety of non-metallic materials. It is intended to cover all kinds of materials, such as the material of the bar ^ ... metal. ^ Is the 忒 material formula—or A 罝. It belongs to the chemical uncombined form ^ 4 for early alone or with one or more other metals. It can be used in a process-the metal can be in the form of a metal or is, the free metal belongs to: = = gold: the invention-or more Inventors sometimes call Ben] Ben, Ben_, 'where " metal-free, including ... chemical two = materials belonging to the genus ^. The "not all genus, 戋 " helm this genus " shaking w +, gold a in the form of mouth σ" ^ ^ π genus or metal-free material can also refer to "metal substitutes. Used in the invention, Metal substitution means that g is a metal in the general definition, but where appropriate, it has metal-like properties, and metal substitutions that are widely used for electrodes include materials with wide bandgap semiconductors, such as bright conductive Sexual oxides such as indium tin oxide (IT0), tin oxide (τ〇), and indium tin germanium oxide (GITO). Indium tin oxide is a highly doped degraded η + semiconductor, and its optical energy band gap is about 3 · 2 Electron volts, making it transparent at wavelengths greater than about 320 nm. Another electrode material is the transparent conductive polymer polyanal ine and its chemical related substances. Known the present invention Non-metallic cathode materials that do not contain metals or metal alloys in the form of metals or their chemical uncombined forms (ie metal-free). Special cathode materials that contain free metals in the form of low-concentration metals can fall into this disclosure. Scope and spirit. So 'though not expected Or it is not expected that the preferred negative S sealant contains free metal in any metal form, but intentionally adding low-concentration metal only to bypass the scope of the present invention or even to provide advantages that are not yet known, still completely fall within the scope of the present invention and Within the spirit. The non-metallic material of the present invention therefore has the characteristics of the inclusion material to effectively exclude free metals.

苐 Page 36 C: \ Prograni Fi les \ Patent \ 55293. Ptd 476227- 丨 90 · 4 · ί 6

'mwM m 87116739 said that the material that effectively excludes free metals in the correction corresponds to a decrease in the conductivity value as its temperature decreases toward absolute zero. The concomitant nature of non-metallic materials is that due to the lack of the electron conduction band occupied by the part contained in the free metal, the reflectivity cannot be measured in practice. Another surprising finding of the present invention is that when a representative specific example of the applied cathode is used in, for example, an organic light emitting device, the cathode can effectively inject electrons into adjacent organic layers, even if the non-metallic cathode material is not The same is true for Fermi energy levels (fermi energy 1 eve 1) provided by metals with general low work function. Although the electron injection barrier between the conductive non-metallic layer and the semiconductor organic layer at the cathode / organic layer interface is expected to be large, electrons are still injected efficiently. The present invention therefore further relates to a method for effectively reducing the barrier to electron injection. — In detail, in a representative specific example of the present invention, the method of the present invention for generating a low resistance to the flow of electrons at the cathode / organic layer interface includes on or near the surface of the semiconductor organic layer at the cathode / organic interface. Tie between non-metallic cathode material and semiconductor organic material body to provide damage area. The damaged area is prepared in such a manner that a high-density surface state or a defect state is used to transport electrons. Although these surface states or defect states have not been directly measured, but are actually not easy to observe directly, low-resistance contact across the cathode / organic layer interface indirectly proves that the existence of these surface states is believed to substantially reduce the Necessary for transport barriers. In particular, it is believed that the surface state energy level is between the energy level of the conductive electrons in the non-metallic cathode material and the energy level of the conductive electrons in the semiconductor organic layer body of the cathode / organic interface. In addition, it is believed that the distribution of surface states

O: \ 55 \ 55293.ptc Page 37 2001.04.10.037 476227 V. Description of the invention (30) ί i: ϊ ΐ are dense enough in the interval to be used in semiconductor organic materials and inefficiently: In the presence of a large barrier, gas can be transported through the cathode / organic layer interface. It has been found that non-metallic cathodes with an iH machine layer boundary have a high efficiency when injecting electrons into adjacent electron-transporting layers with and without s. As a specific example of the replaceability of the present invention, in which the steel tin oxide c interface is used, and only when the tin oxide is deposited on the impurity-containing low-resistance contact, the organic layer is deposited on the indium tin oxide layer No. Therefore, another aspect of the present invention is that when a better indium tin oxide and / or Cu.cPc compound is used to form the cathode / organic layer interface, the present invention is particularly related to an L anion, in which a non-metallic indium tin oxide layer is deposited on On the phthalocyanine layer, the deposition rate of indium tin and the thickness of the phthalocyanine are low-resistance contacts. By controlling indium tin oxide sputter deposition methods to control the degree of surface damage, the cathode / organic layer interface with the required low resistance can be produced, as described in the present invention. The decrease in t-wall of the electron transport 1 is due to the surface-like fc having a high density on or near the surface of the organic layer. Another method including the step of waiting into a high-density surface state to form a cathode having a low-resistance contact between the snow-conducting non-metal layer and the semiconductor organic layer is also fully included in the scope and spirit of the present invention. / I believe that the feature of the present invention, that is, the ability to form a high-efficiency electron transport cathode / organic layer boundary (equivalent to a low work function metal material, but not highly reflective of metal materials) is previously known for use in organic A unique combination of properties not found in materials used in photoelectric equipment. Therefore, miscellaneous needles ^^ generation

476227 ——_ V. Description of the invention (31) The body example describes the present invention, but it is believed that the scope of the present invention can form any cathode with a low-resistance conductivity of two T f with a semiconductor organic layer. In addition, it is believed that the methods include the preparation of non-metallic materials with sufficient density = properties to reduce conductivity and semiconductor organic: two = barriers, all of which are fully covered by the present invention "Secondary ~ the substantial reduction of movable barriers) The present invention refers to the present invention: The formation of the low-resistance interface between the conductive non-metallic layer of the organic interface and the semiconductor organic layer is reduced. Therefore, the present invention is related to a method _, _ which includes a preparation-interface, and one of the interfaces is provided on one side. 5 Non-metallic materials with a semi-release on the other side of the interface: material, where the preparation step includes the step of forming any intermediate region between the conductive non-generic material: the organic material and the organic material. Semiconducting: the material can be used as a cathode 'to form a semiconductor organic material. The use of non-reflective conductive cathode materials that do not have the inherent inherent properties of metal materials usually provides specific advantages, that is, a device that expects high light transmission. As a cathode, the organic light-emitting device i. Other features of the present invention-so that, for example, organic light-emitting devices can use a highly transparent non-metallic cathode Equivalent to the electron injectability of a semi-transparent metal cathode, and the actual translucent metal cathode (which generally provides an overall device of about 10 ° ^ = the thinnest maximum light transmittance) is compared with the 'use of the non-metallic cathode of the present invention Can be made with a device with a strict light transmittance of at least about 8 5 percent. The conductive non-metallic material that can be used to prepare the cathode of the present invention can be selected as page 39 C: \ Program Files \ Patenix55293. Ptd 476227 5 'Description of the invention (32) For example, see edge bandgap semiconductors that are transparent, such as wide bandgap semiconductors with an energy gap of at least 1 electron volt and a light transmittance of at least 50% in terms of incident and received radiation. A wide bandgap semiconductor is preferred. Semiconductors include conductive oxides such as indium tin oxide, tin oxide, or indium tin germanium oxide (GIT⑻). The abundant conductive organic materials that can be effectively used in combination with an indium tin oxide layer to produce effective electron injection have the following properties: 1 、 化 # And structural stability, which is sufficient to limit the damage caused by sputtering during the indium tin oxide layer deposition as described below. Large planar molecules such as phthalocyanine, naphthalocyanine and Is a representative example. Compounds such as dagger or other compounds with other extended conjugated structures (such as other fused benzene box-, · ', Cai, en-, phenanthrene-, and PolyaCene) can also be used. Derivatives. Polymer materials can also be used in specific cases. 2. Electron mobility, which is sufficient only as a layer for electrical early transport; the electron transport material 'its carrier movement of at least 10-6 cm2 / volt seconds The property value is generally believed to be sufficient for the material to be used as an electron transport layer, and the only one with a substantially higher value is preferred; larger planar molecules such as phthalocyanine and specific fluorene are still representative examples. Ionization potential (IP) and HOMO / LUMO band gap difference (energy band gap between the highest occupied molecular orbital and the lowest occupied molecular transport), that is, " ip —H〇M〇 / LUM〇 gap energy, 'approximately Equal to or better than the p-H0M0 / LUM0 gap energy of the film to be injected with electrons. This introduction is not a restriction that must be strictly adhered to, but only needs to be followed approximately. For example, 'for a specific material composition, it can deviate slightly. The introduction about 0 · 5 son Fu . Use this introduction to help prevent formation of impeding electrons into contact

No. 476? 27—90 ^ 4 ·.; 1: 87116739 Description of the invention (free film (for example, A 1 q3) barrier. The method of the present invention may especially include the use of indium tin oxide as a layer and cyanine such as CuPc or ZnPc as Electronic injection industry: under the electric non-metals, the conductive non-metallic indium tin oxide layer system ... upper, electronic injection including CuPc or ZnPc only spreads.

^ 'Indium tin oxide is equivalent to about 丄 to ㈣ Angstroms per minute: the next sputtering on the organic layer' until about 100 Angstroms to about 3 JJ 5 is deposited. As detailed below, the conductive non-metallic layer / half 0 angstrom thickness can provide low-resistance contact for organic light-emitting devices and other types of layer boundaries. The invention in an electric device is therefore particularly concerned with a novel highly transparent organic hair (EDs) which uses a non-metallic cathode. With non-metallic cathode X, the calendering device has extremely low reflectivity and high transparency, which is close to the theoretical maximum that can be achieved by multiple layers. The low reflectivity of the organic light-emitting device is advantageous for comparative display applications, and it is used to eliminate the micro-porous effect unique to laminated organic light-emitting devices (SOLEDs). It is predicted that the use of these low-resistance non-metallic organic light-emitting devices can be particularly useful for reliable high-resolution full-color = displays, "head-up" displays, and organic-based lasers. In the representative specific example of the present invention shown in the box, TOLED is deposited on a glass substrate of indium tin oxide (ITO) film, and the indium tin oxide and film are used as transparent hole injection anodes. The TOLED includes, for example, a non-metallic electron injection interface layer 6, an electron transport layer 2, a hole transport layer 3, a cathode layer 4, and a substrate 5. After the hole transport layer and the electron transport layer are deposited, the product can be added to the cuPc film and the electron injection interface layer is added.

I. Supplementary Benefits 5. The package of invention description (34) has a low amount of RF money to shoot indium tin oxide. — Is the cathode of the device. & in some =: layer of indium tin oxide layer system to prevent the organic bottom layer on indium tin oxide: over: outside the protective layer 'or even the adjacent electron transport layer. The first: S: i area 'is used to transport electrons uT ^ ^ Ά ® ^ 〇a ^ ^ ^ said that there may be another intermediate electron rotation layer between the electron transport layer and the CUPC layer, such as 4, 4,-( CBP), as shown in Figure 1B2. The middle thunder; the final 1 Ό—click all) the electron injection of the low-resistance contact of the cathode layer $ = ^ The layer is located with the non-gold. The organic light-emitting device of ^ s ^ ^ 0 1 βZ specifically includes = metal layer The electron injection interface layer 6, the intermediate electron transport layer 7, the electron transport layer 2, the hole transport layer 3, the cathode layer 4, and the substrate 5. Because the metal cathode layer is not included, the representative TOLEDs of the present invention, which are mainly based on A 丨, then emit almost the same light in the direction of astigmatism, and the overall external quantum efficiency is about 0.3%. These devices are in the visible light region. The light transmittance exceeds 80%. The reflectivity and absorbance characteristics, current-voltage, brightness-current, and electroluminescence spectrum of the organic light-emitting device of the present invention prove that its performance is at least equivalent to that of a conventional TOLED, and some aspects are even superior. The conventional TOLED system uses a highly reflective cathode including Mg: Ag and encapsulated with indium tin oxide.

For example, as shown in the comparison of the TOLED results in FIG. 1C and FIG. 1D, the light output of the TOLED of the present invention is reduced by only two times at 180 hours, while the light output of the prior art TOLED is reduced by about 4 times at the same time interval. The results in Fig. 1E show that both Cu (CuPc) and Zn (ZnPc) phthalocyanines can be used as the electron injection interface layer. The results in Fig. 1F show that the CuPc device has much higher quantum efficiency. Figure 1H

O: \ 55 \ 55293.ptc Page 42 2001.04.10.042

V. Description of the invention The comparison of the result of (35) mm with the result of FIG. 1I shows that the I-V characteristics of the organic light-emitting device manufactured by the present invention have the same degree of stability as the prior art devices. The results of FIG. 1G show that the total light transmittance of the organic light-emitting device manufactured by the present invention is close to the theoretical maximum value that can be achieved by the organic light-emitting device. The difference is that part of the spectrum shows the Q-frequency absorption structure characteristics of C U P C. The reflection spectrum of this device is close to the theoretical minimum, as limited by the glass / air and indium tin oxide / air interfaces. The anti-reflection layer can further reduce the reflectivity to a negligible value. The electron injection interface layer in contact with the tin oxide layer may have a thickness of about 15-120 Angstroms. For example, Figures 1J and 1K show that when CuPc is used as the electron injection interface layer, a device having a CuPc injection layer having a thickness of 30 angstroms to about 20 angstroms produces comparable performance characteristics. The device used to collect data as shown in Figures 1 j and 1 K also includes a 50 Angstrom 2CuPc layer sandwiched between an indium tin oxide cathode layer and a hole transport layer. This Cupc layer is in contact with the indium tin oxide cathode layer as a hole injection promotion layer, as disclosed in co-pending application serial number 08/865, 491, filed on May 29, 1997. The current-voltage (I-V) characteristics of another typical example of the scope of the present invention, another typical transparent organic light-emitting device with a non-metal cathode, and a conventional TOLED grown in the same process are shown in Fig. U. The TO LED system used to obtain 1L is shown in Figure 1M, where the non-metallic cathode! ^ Indium tin, the electron injection interface layer 6 is Cupc, the electron transport 2 and 2 are All, the hole transport layer 3 is a_NpD, the anode layer 4 is, ΪΪ ::, and the substrate 5. The device includes another CuPc layer 8, which is lost between the indium tin oxide electrode and the hole transport layer. Two different operations, domains, were found to be below and below the "connection voltage". Below VT, no trapping space

Inspection: Amendment 丨 _ Case No. YYYY_V. V. INTRODUCTION TO THE INVENTION (36) The charge-limiting transport follows I Vra-1. Above VT, the current is limited by the trapped charge in accordance with I oc— V m-1. Ρ Burrows, SR Forrest, Letters in Applied Physics 64, 2285 (1994), PEBurrows, Z. Shem, Bulovic, DM McCarty, SR · Forrest, JA Cronin and Μ E · Thompson, Journal of Applied Physics 79, 7 9 9 1 (1 9 9 6). The injectability of this indium tin oxide / CuPc is slightly lower than the result of indium tin oxide / Mg: Ag contact. This is due to the general difference in VT reflected by TOLED (4.2 volts) and TOLED (5.2 volts) with nonmetallic cathode. When CuPc in the cathode is replaced with ZnPc, it has similar I-V characteristics, showing that it also forms a good electron injection contact point. However, when CuPc was replaced by PTCDA, its VT increased significantly to 20 volts. The total output light energy emitted from the top and bottom surfaces of the device as a function of current is shown in Figure 1N. The device is the same as Figure 丨 L. The total efficiency of this device is the same when == (0 · 38 ± 0 · 05). The brightness at 10 mA / m 2 ~ 2000 candelas / m2, increased to 2 燔, / m2 at 10 mA / cm2, corresponding to the maximum driving current in Figure 1N. The ratio of the energy emitted from the top surface and the bottom surface of the non-metallic 'T0LED is r = 1.05. · The difference between the combined refractive index of CuPc and other organic pine M in TO LEDs with non-metallic cathodes is quite large for U soil. Compared with the low surface of the device, the amplitude of the output electroluminescence spectrum that is not measured is slightly wider, such as The known composite refractive index of each layer on the top surface shown in Fig. 丨 is assumed, and assuming that the radiating diode is uniformly distributed in the emitting layer, r is measured as a function of wavelength (gray). The fitted curve of the blade light is obtained by multiplying the emission of the substrate by r (again). ,table

3¾ Features 87116739 V. Description of the Invention (37)

The combined curve is very close to the normalized measured output spectrum (Figure 丨 N. Other differences between experimental values ignore the dispersion value of ^ and the difference value. Although the characteristics of the device using CuPc or ZnPc cathodes are the same, but ^ f Set it 30% lower. However, in the sharp comparison of the CuPc and ZnPc cathodes, the j rate of the pTCDA2 device in the cathode is only about 1% of the CuPc device. Shows that pTC]) A cathode injects electrons into the electron transport layer The effect is extremely poor, which is consistent with 丨 -v data. The removal of the translucent metal film from TOLED significantly increases the overall transmittance. This point can be easily known from the digitized reproduction photos obtained from the TOLE] array with a non-metallic cathode and the conventional TOLED array, as shown in Figure 丨 Q. The array was placed on a white background with a black dot screen for comparison. The device illuminates from the bottom. The conventional TO LED array consists of an arrow of about 0.2-0.4 cm. The TO LED array containing a non-metallic cathode is an arrow of about 丨 · 3 — 丨 6 cm. Means. The photo in Fig. 1Q shows that the nonmetal cathode of the present invention is not damaged because the electrode does not contain any metal, and the conventional TOLE [) has a light gray appearance because of the metal cathode. The TO LED array containing a non-metallic cathode is only available when the non-reflective coated device shown in FIG. 1 G has a digital measurement of transparency and the transmittance is shown as 0.85 ± 0.005. Detection corresponds to a 35% increase over conventional organic light emitting devices. The reflectivity and absorbance of TOLEDs with non-metal cathodes are also plotted in Figure 1G. The main source of light absorption is the CuPc Q band, β · Η · Schechtman and WESpicer, J. of Mol. Spec · 33, 28 (1970 ), Its peaks are located; l = 620 nm and 665 nm. Without being limited to the theory of operation of the present invention, believe in indium tin oxide

O: \ 55 \ 55293.ptc Page 45 2001.04.10. 045 476227 Case No. b 87116739 > Year + Month Day Amendment 夂 Description of invention (39) = In the original stage of deposition, a state of induced damage occurs, which is in This invention is called a damaged layer at the cathode / organic film interface. Contrary to previous knowledge of high-efficiency electron injection electrodes (C · W · Tang and S. A. VanS i Ike, Applied Physics Letters 5 1 '9 1 3 (1 9 8 7)), The lowest occupied molecular orbital (LUMO) needs to be aligned with the Fermi energy of the low work function metal. It is believed that the damaged layer here is used to provide improved electron injection properties for non-metallic cathodes. Fermi level materials provided by functional metals are not compatible. The improved electron injection properties of highly transparent non-metallic cathodes can be understood from the band diagrams provided in Figure 丨 p. Ionization potential (I p) (defined as the degree of vacuum to reach the HOMO distance) and light energy gap (Eg) are taken from A. Ra jag〇pal, CIWu and A. Kahn, 1997 Fall Mtg. Of Mat · Res · Soc. Thesis J1.9; and K. Seki, Mol. Cryst. Liq. Cryst. 171, 255 (19 9 9). Because the ionization potential (ip) of CuP falls between the work functions of indium tin oxide, CuPc reduces the barrier to the injection of holes into the hole transport layer. In contrast, although the present invention discloses that an electrode can effectively inject electrons when an electrode is prepared according to the present invention, the barrier to electron injection at the indium tin oxide / CuPc interface is still high (6 · electron volts). This apparent contradiction is consistent with the prior records, SR · Forrest, LY · Leu, FF So, and W · Υ · Y〇〇n, Applied Physics 6 6, 59 08 (1 9 8 9). The anode made of PTCDA and encapsulated with indium tin oxide effectively injected holes. In this case, although the barrier system from indium tin oxide to pTCDA was 2.1 electron volts, it still reached hole injection. The value of the ionization energy (defined as the degree of vacuum reaching the distance of H0M〇) is from A · Ra jagopal, C. I. Wu and A. Kahn applications

O: \ 55 \ 55293.ptc Page 46 2001.04.10. 047

No. 87116739 V. Description of the invention (41) ^ year ¥ month _ revision Physics Journal 83, 2649 (1998) and K. Seki, Mol.

Li q. Cryst · 1 71, 2 5 5 (1 9 8 9). Although the author group revealed that the vacuum is non-planar between organic heterojunctions, as shown in Figure 1D, this situation will not change our conclusions, so it is omitted for simplicity. Effective electron injection in the presence of a high energy barrier shows that the barrier is effectively reduced due to the electrode deposition / formation process. When the indium tin oxide is sputtered on the CuPc surface, the Cu can form a Cu-0 bond through an exothermic reaction (FF So and SR Forrest, Journal of Applied Physics, 63, 442 (1988)), resulting in high density Medium gap (midgap) or surface state]) ss, as shown in Figure 1P. These states, whose density decreases as they move away from the indium tin oxide interface, provide a small energy π step " so that the injected electricity can be easily climbed. These data and patterns of formation are different from previous disclosures that require low work function metals to provide efficient electron injection. Compared with the TOLED without the non-metallic cathode of the present invention, the residual energy barrier can slightly increase the VT of the TOLED with the non-metallic cathode. Only when the damage is limited to the CuPc layer can the damage effectively produce the non-metallic cathode of the present invention, which is proved by reducing the thickness of the CuPc layer from 60 to 30 angstroms. The reduction in thickness also reduced the manufacturing yield of TO LEDs containing non-metallic cathodes from about 90 percent to 40 percent. Manufacturing yield is defined as the ratio of active devices that are not short-circuited to the total number of devices manufactured and tested. The yield rate is based on a test group of 10 to 20 test devices. These results show that only the first few single-layer CuPc are damaged in the low-resistance cathode / organic layer interface, as shown by indium tin oxide / PTCDA. It is speculated that when the CuPc is too thin, the sputtered indium tin oxide can "break through" and damage the lower layer A 1 q3. actual

O: \ 55 \ 55293.ptc Page 47 2001.04.10. 049 _I 87116739 Price {year_a_correction_ on the indium tin oxide directly sputtered on a-NPD or Alq3, where the indium tin oxide layer Individually used as the cathode or anode, so that the yield is close to zero. The present invention believes that the limited damage of CuPc and PTCDA may be due to the extension of conjugated electron orbitals in such large planar molecules. When an active metal or oxygen atom is incident on one of these surface molecules during sputtering, the impact can be efficiently distributed on a large number of bonds in the molecular 7Γ electronic system. In contrast, there is no corresponding large redundant electronic system in A i q3 or a-NPD. For these molecules, the collision energy is more concentrated on a few atomic sites, increasing the possibility of molecular bond rupture. The planar or near-planar stacked arrangement of such crystalline molecular systems such as CuPc and PTCDA also facilitates the energy dispersal between several adjacent molecules of the crystal lattice. — Based on the theory that defects induced by active atoms play a role in assisting carrier injection, they are tested by manufacturing TOLEDs with transparent non-metal cathodes, such as shown in Figure 1L. The differences are Alq3 and a-NPD The order of the layers is reversed. For devices in which the order of the electron transport layer and hole transport layer are reversed, it is found that the VT increase factor is 2 (~ 10 volts), and even though it is known that the indium tin oxide / CuPc interface injects holes at 0: — NPD The ability is superior, and the quantum efficiency 77 is still measured beyond about 10-3%. The low efficiency of this device therefore provides evidence for the fact that the CuPc / Indium Tin Oxide interface without a damaged layer cannot inject electrons into Alq3. Therefore, it is concluded that the low-energy deposition of CuPc on the top surface of indium tin oxide does not produce the intermediate interstitial state required for electron injection. Therefore, because the indium tin oxide layer prepared by Karl et al. And Whitlock et al. Is also manufactured by depositing an organic layer on the indium tin oxide layer, rather than depositing the indium tin oxide layer on the organic layer to produce a damaged layer , So when Karl waited

O: \ 55 \ 55293.ptc Page 48 2001.04.10. 051 476227 V. Description of the invention (41) When the electrode of the person and Whitlock, etc. is used as the cathode of the solar cell, it is expected to be prepared by Karl inch person and Whitlock person The oxidized tin layer also cannot sonicate the properties of the present invention to promote electron injection. _ The asymmetry of the characteristics of the device is also consistent with the extremely low current and lack of electroluminescence when the T0 JJ with a non-metallic cathode is reverse biased. In this case, 4% of the electrons cannot cross the electron volt energy barrier from the tin oxide and enter the undamaged CuPc at the anode. Once electrons are injected into the CuPc, they are transported to the Aiq3 * due to a lack of electron transport energy in this direction. In contrast, a high electronic energy barrier of 0.9 electron volts exists from PTCDA to Alqs. This energy barrier combined with the poor electron mobility of PTCDA makes the oxidation in contact with PTCDA; the device with indium tin cathode and mainly A 1 qs has high ντ and low π ^ However, this low efficiency does not mean that PTCDA is useless To make a good low-resistance cathode / organic interface. In particular, these crusts only show that the energy barrier between PTCDA and A1q3 is 0.9 electron volts too high. According to the introduction of the present invention for correcting the LUM0 / H0M0 energy level ', the PTCDA and the appropriate adjacent charge carrier layer are appropriately matched, so that an effective indium tin oxide / PTCDA interface can be manufactured. In another example of the organic light-emitting device of the present invention, the non-metallic cathode can be used in a double heterostructure, in which a light-emitting thin layer exists between the electron transport layer and the hole transport layer. In another specific example of an organic light emitting device, one of the electron transporting layers is an emission layer, and the indium tin oxide layer may be in contact with an electron injection interface layer for generating electroluminescence, and in addition, it may be in direct contact with the hole transporting layer. . In this case, the IP-HOMO / LUM0 gap energy of the material used in the electron injection interface layer is approximately equal to or preferably smaller than that of the material of the adjacent hole transport layer.

C: \ Prograni Files \ Patent \ 55293.ptd Page 49 U 厶 厶 / V. Description of the invention (42) :: 0ji0: L: M〇 Interstitial energy, in addition, the ionization of the hole transport layer material representative of the present invention The property is == the ionized electricity of the material used is: Su layer, the indium oxide kick layer can be ::: 'where the hole transport layer: for emission and contact with the electroluminescent injection interface layer, the interface layer Department is also approximately equal to or less than :: Dagger: Material =: _ / 通. The material of the gap energy gap energy layer ^ P—Η_ is just smaller than the electron ionization layer and the electron injection interface layer of the hole transport layer material. The two pairs are ::; = /: / 'Light :) Second, for any organic light-emitting device including a structure including a non-golden body == structure, wherein the heterogeneous / inventive organic light-emitting device specifically includes a device for generating electric fields, the structure :, which is manufactured into a single-heterostructure or Double heterostructure. ′ :: Heterogeneous material of organic thin film with early- 异 double heterostructure: method and: preparation of this = US, Patent No. 5,5 54,22 0, which is mentioned in its entirety; ^ is shown herein. This Luming Institute you θ — 丨, m, is combined into the meaning means the single two heterogeneous ;: ^ ^ heterogeneous structure of electroluminescence " hole transport layer, electric = including hole injection anode layer, Other layers may exist between one or more of the child transport layer and the p-layer of the p-diode layer. : Like: Second: In terms of thin structure, the hole transporting layer and the electron transporting layer may include a heterogeneous emission layer. The individual emitting layer can be defined as "light-emitting thin layer". The anode: :: Page 50 C: \ Program Files \ Patent \ 55293. Ptd 476227

There may be a replacement or additional hole injection between the hole transport layers. The hole injection promotion layer may, in some cases, include an electron advance layer. CuPc is the same material as the layer. In each case, the indium tin oxide electrode of the emitting interface is in direct contact. The difference between the two CuPc layers is that the j layer is in contact with the indium tin oxide layer as the anode, while in the other case, it is the indium oxide of the UPc layer. Tin layer. In each case, the CuPc layer functions as a cathode layer and an interface layer. On the one hand, when it comes into contact with the indium tin oxide anode, the rabbit = Cu • CuPc layer helps the hole to be transported from the anode to the hole transport layer. On the other hand, when the ball indium tin oxide cathode is in contact, the CuPc layer helps Child transport layer. In each case, the CuPc layer can also be used as: a thin organic layer (if present) to prevent damage during the deposition process. Indium tin oxide is used as an electrode in the SOLED structure. 3 ^ When used individually as anode and cathode. X times The anode or cathode layer can be in contact with the substrate, and each electrode is connected to a snow point. This contact can transmit voltage across the device to cause electroluminescence from the electron-drying or hole-transporting layer. If the cathode layer is deposited on the substrate 3, the device can be said to have an opposite or 10L ED structure. If a heterostructure for generating electroluminescence is included as part of a laminated organic light emitting device (S0jEy), one or both electrodes of the individual heterostructure may be in contact with adjacent heterojunction electrodes. Regardless of the circuit used to move the soLED, the double layer can provide an insulating layer between adjacent electrodes of two stacked organic light emitting devices. Although the present invention relates to an organic light-emitting device including a non-metallic cathode layer instead of a metal cathode layer, the organic light-emitting device of the present invention may

C: \ Prograni Fi les \ Patent \ 55293.ptd page 51

V. Invention Description (44)

Used in combination with the top or bottom organic hair of organic hair dryers containing metal layers; for example, as soLED

Mg: Ag metal cathode layer, ^: Second, in this case, if the cathode layer is made of a thin layer to prevent the Mg: A; =: protective layer, for example, the fabrication of an organic light-emitting device made of an Ag layer. Used to illustrate the implementation of the present invention in a specific material or sequence. For example & while, the non-limiting manufacturing of the thin layer shown may be opaque or transparent, rigidly heterogeneous structure-generally including-substrate, ^ ^ θ times flexible, and / or plastic, 厶 η gold, type ^ 7 objects such as polysilicon, glass, sapphire or τ, too 1 ribe ·, can be used as other substrates of organic light-emitting devices and also related to an organic light-emitting device (0LE π electroluminescence heterojunction hibiscus, Gan Shi G is used to produce a sub-layer, which is covered with two layers. Heterogeneity has a special charge carrier. The 6-knife armor has at least one electron-transporting part, one hole-transporting part, and two or one compound. y ΙΠ group metals such as A1, Ga, and the formula τ ^ are 2 hydrazino-8-quinolinate complexes coordinated to ^^ _ or 11. The 祢 迗 part of the tortoise hole can transport the amine part of the hole. The "charge carrier layer" used in the present invention may mean a "hole transport layer (HTL), an electron transport layer" (ETL), or an organic light-emitting device having a double heterostructure 9 (_ Device), the individual emission layer " The charge carrier layer (including at least one electron transport in the molecule The part and at least one hole transporting part of the compound) may be an emission layer such as an electron transport layer of a single heterostructure (sH), or an individual emission layer of a double heterostructure. The charge carrier layer (including molecules having at least An electron-transporting part and at least one hole-transporting part) can also be a non-emissive layer such as an organic light emitting device placed on the cathode

C: \ Program Files \ Patent \ 55293. Ptd page 52 476227 V. Description of the invention (45) Electron injection promotion layer between electron transport layer. The "hole transporting part" used in the present invention means a group, when present in a layered material of an organic light-emitting device, when a voltage is applied, the material has a hole penetrating through the layer due to conduction of the hole. Electrical conductivity. The "electron transporting part" used in the present invention means a group. When present in a layered material of an organic light-emitting device, when a voltage is applied, the material has through The conductivity of the layer. The "hole transporting amine moiety π" used in the present invention means an amine group as a hole transporting moiety. The hole-transporting amine portion generally contains a nitrogen atom, which is directly bonded to two phenyl groups (except for a phenyl group which forms a coordination bond with a Group III metal), wherein the two phenyl groups are combined to form a nitrogen-containing group. Heterocyclic groups, such as carbazolyl, or the two phenyl groups may be bonded to each other. Each benzene can be condensed with another phenyl group and bonded to a nitrogen atom, such as 1-naphthyl or 2-naphthyl. In particular, the present invention relates to a compound having the following chemical structure:

(Where Ai and% each include one or more stupid groups, which produce an overall hole transport function; and -R- is a calcined group or an aryl group, preferably an aryl group), which can form a compound other than a Group III metal Bit bond. The bases of A i and A9 can be bonded to form a gas containing

C: \ Program Files \ Patent \ 55293. Ptd 页 page 53 476227

476227

C: XProgram Files \ Patent \ 55293. Ptd page 55 476227 5. Description of the invention (48) About 100 times. This difference can be explained by the different structures of the two molecules. In particular, A 1 -pCb is more rigid due to its carbazole portion, which prevents non-radiative self-extinguishment of solid molecules, and makes the photoluminescence emission efficiency of Al-pCb hundreds of times higher than that of Al-pNP. The invention further relates to an organic light-emitting device, which includes an emitting layer containing a dopant compound, the compound being selected from compounds related to azlactone having a chemical structure of formula F-I: (F-!)

Wherein R is hydrogen or a donor or acceptor group relative to hydrogen; R 'is an alkyl group or a substituted or unsubstituted aryl group; I and D are hydrogen or a bond to form a condensation Aryl ring; X is 0; NR5, where R5 is hydrogen or substituted or unsubstituted alkyl; alkyl or substituted or unsubstituted aryl; and 22 are each a carbon or nitrogen atom And Y is M (—metal atom), and at this time, Zi and Z2 are both nitrogen atoms; Y is 0; NRS, where R6 is hydrogen or substituted or unsubstituted alkyl; or S ; At this time, Zi and redundant 2 are both carbon atoms; or Y is absent. Substitutive donor groups include 7Γ electron donor groups such as -0 R, -Br, -NR3R4, where R3 and 1-4 are each hydrogen or substituted or unsubstituted

C: \ Prograin Files \ Pateni \ 55293. Ptd page 56 476227 5. Description of the invention (49) Alkyl. Representative acceptor groups include 7 'electron acceptor groups such as -CN, -N02 or carbonyl-containing groups. For a more detailed representative specific example, the present invention relates to an organic light emitting device, which includes an emitting layer including a dopant compound having a chemical structure of Formula C-1 I and using azlactone as a substrate:

Wherein R, R ', Xin and 1-2 have the aforementioned definitions. As for other more detailed representative specific examples, the present invention relates to an organic light-emitting device, which includes an emitting layer including a dopant compound having a chemical structure of formula C-II I and using azlactone as a substrate ...

Wherein R and R 'have the aforementioned definitions. In detail, the dopant compound with lactone as the substrate has a chemical structure of the formula C-1 I I, where R = H and R '= C6H5 (compound 1); R = OOCCH3

C: \ Program Files \ Patent \ 55293.ptd 苐 Page 57 476227 5. Description of the invention (50) and R '= C6H5 (compound 2); 1 ^ = ^ ((:) 13) 2 and 1?' CSH5 ( Compound 3); and R = C (CH3) and R ′ = C6H5 (Compound 4). In another detailed embodiment of the present invention, the dopant compound having azlactone as a substrate may have the formula C-IV Chemical structure:

Where R '= C6H5 (compound 5). In another detailed embodiment of the present invention, the dopant compound having azlactone as a substrate has a chemical structure of the formula C-V (compound 6):

Chemical structure of (C-V) or formula C-VI (compound 7):

C: \ Program Files \ Patent \ 55293. Ptd 苐 Page 58 476227 V. Description of the invention (51) 0 (C-VI)

These compounds with azlactone as a substrate can be prepared from para-substituted formaldehyde and a maleic acid derivative. By changing the para-substituted donor base, the emission can be adjusted from the green to the blue part of the spectrum 'as shown in the results shown in Table c 1 below.

C: \ Prograni Files \ Patent \ 55293. Ptd 页 Page 59 476227 V. Description of the invention (52) Table C1 · Fluorescence data showing the maximum absorbance and photoluminescence (PL) of compounds 1-7. Absorbance maximum (in nanometers) PL maximum (in nanometers) Compound 1 364 (dichloromethane) 367 (dichloromethylene) 416 (dichloromethane) Compound 2 368 (dichloromethane) 422 ( Dichloromethane) Compound 3 471 (dichloromethane) 481 (difluorenyl sulfene) 464 (hexane) 467 (fluorene benzene) 522 (dichloromethane) 552 (dichloromethane)-: 464 (hexane Alkane) 500 (Benzene) Compound 4 373 (Digasmethane) 374 (Dimethylmethane) 428 (Dichloromethane) Compound 5 368 (methylene chloride) 471 (Shoulder type, dichloromethane) 518 (dichloromethane, excitation = 360 nm) 582 (dichloromethane, excitation = 470 nm) Compound 6 513 (dichloromethane) 518 (dichloromethylene) 498 (hexane) 499 ( Toluene) 734 (dichloromethane, excitation = 320 nanometers) 752 (dichloromethane, excitation = 520 nanometers) 406 (difluorenylfluorene) 524 (hexane) 6〇2 (xylene) compound 7 438 (Dimethyl fluorene) Very weak emission The fluorescence color prediction of the materials shown in Table C1 is due to the charge transport transition

C: \ Program Files \ Patent \ 55293. Ptd Page 60 476227 5. Launch of Invention Note (53). Other detailed examples of dopant compounds using azlactone as a substrate in the present invention include: a chemical structure of formula C-III (where R = OH, and R '= C6H5) and a chemical structure of formula C-III where R = C (CH3) 3 and R '= CH3. Compound 6 is an example of a compound having a charge transport network different from the derivative of Compound 1. The emission in this case is from an amine donor and a sungyl acceptor. This dye can be excited in blue or green to get a red emission, as shown by compound 6 in dichloromethane. Compound 6 demonstrates that these dyes have different emission wavelengths that cause red and color emission. Although the PL efficiency of this dye is extremely poor, derivatives of other receptors are expected to increase this efficiency. The line width found in the doped organic light-emitting device of the representative compound of the formula C-I I or C-I I I (Compound 3) is narrower than when using A 1 q3 alone, but wider than the solution. It is believed that the reason is that the molecules in the solution do not have the planar structure shown by the formula C-1 I, and in the solid state, the dihedral angle around the bond of the benzene ring having a diamido group to the carbonyl moiety Easy to distribute. This dispersion gives the absorbance and fluorescence a certain energy range and increases the observed line width. This dispersion also reduces the overall fluorescent quantum efficiency. To prevent such broadening of the solid state, materials with a localized chemical configuration can be used, including rigid or localized molecules as shown in Formula C-I. In these compounds, the cyclic group remains coplanar with the azyl group. Therefore, although the present invention is directed to a representative specific example of the formula CI I or C-II I with azlactone as the substrate, the compounds related to azlactone of the formula C-I are also fully included in the present invention Within spirit and scope. Compounds related to azlactone covered by formula C-I include, but are not limited to, compounds of formula C-I I and C-I I I with azlactone as substrate

C: \ Program Files \ Patent \ 55293.ptd 苐 Page 61 476227 V. Description of Invention (54). The invention further relates to a compound of the formula C-I related to azlactone:

Where R is hydrogen or a donor or acceptor group relative to hydrogen; R'dialkyl or substituted or unsubstituted aryl; heart and dipper are hydrogen or bonded to form a fused aromatic Basic ring; X is 0; NR5, where: R5 is hydrogen or substituted or unsubstituted alkyl; alkyl or substituted or unsubstituted aryl; Zi and redundant 2 are each a carbon atom Or nitrogen atom; and Y is M (—metal atom), and at this time Zi and Z2 are both nitrogen atom; Y is 0; N R6, where R6 is hydrogen or substituted or unsubstituted alkane Or S; at this time, Zi and 4 are both carbon atoms; or Y is absent; the prerequisite is that when Y is absent, Zi is a carbon atom and z2 is a nitrogen atom, R is relative to hydrogen A group that is a donor or acceptor group. In another more specific representative embodiment of the present invention, the present invention relates to a compound having a chemical structure of the formula C-I I with azlactone as a substrate:

C: \ Prograin Files \ Patent \ 55293. Ptd Page 62 476227 5. Description of the invention (¾) Where R is a group that is a donor or stylistic group relative to the hydrogen system, R, = alkyl or substituted Or unsubstituted aryl; and h and R2 are hydrogen or bonded to form a fused aryl ring. In another more detailed representative specific example of the compound of the present invention, the present invention relates to a compound having a chemical structure of formula C-II

Wherein R is a group which is a donor or acceptor group with respect to the hydrogen system; and R '= an alkyl group or a substituted or unsubstituted aryl group. The amount of the dopant that can shift the emission wavelength of the emission layer containing only the host compound to the host compound is shifted in emission wavelength, so that the LLD device emits light that can be recognized by the human eye and approaches a primary color. Although the color identification system has been confirmed, Commissi on intern at ionale de Γ Eclairage (International Commission on Illumination) has developed a quantitative chroma scale, also known as the C IE standard. According to this standard, the saturated color is represented by a single point, and a specific quantitative coordinate is determined according to the axis defined by the chroma scale. Those skilled in the art know that the pregnancy point on the CI scale indicates a standard or a goal, which is actually different, but fortunately it is not necessary to achieve it. In a preferred embodiment of the present invention (in which the organic light-emitting device mainly generates primary colors), the dopant is dreamed into the host compound, so that the organic light-emitting device emits light that can be recognized by human eyes and is close to the saturated primary color. Via the invention

C: \ PrograniFiies \ Patent \ 55293.ptd Page 63 V. Description of the invention (56) Ling Shi 'expects that the organic light-emitting device formed can have an emission close to absolute (or saturated β degree value, such as c I Ε scale In addition, the LED using the holding material of the present invention can also have display brightness, which can exceed 100 candelas / m2, only a lower value is acceptable under certain conditions, perhaps as low as 10 haze / m. 2. The host compound as defined in the present invention is a compound that can be doped with a dopant to emit light with a desired spectral characteristic. The compound includes, but is not limited to, an emission compound and a host compound, such as August 6, 1996 The U.S. patent application serial number 0 8/6 93, 3 5 9 described in the application is incorporated herein by reference. The π host π used herein means a compound in the emission layer, which is used to receive 1 The hole / electron recombination energy transports the excitation energy to the components of the dopant compound generally present at extremely low concentrations through the emission / absorption energy transport process. The dopant then relaxes to an excited state with a slightly lower energy level, To radiate all the energy with the luminescence of the desired spectral region It is better. The dopant that radiates a 100% dopant exciter is said to have a quantum efficiency of 100%. In terms of the host / dopant concentration of a color-tunable SOLED, If not all, most of Jiaojia ’s main energy is lost. It is sent to the food supplement, and then its light shot (perhaps from a lower energy level but with high quantum efficiency) generates visible light radiation with the desired color. The invention relates to a compound related to azlactone, which serves as a dopant that meets these energy transport requirements. 'As far as the host compound used in the present invention is concerned, the compound can be used in organic light-emitting devices with a single heterostructure. Electronic rotation / emission layer or individual emission layer of heterogeneous structure. As known to those skilled in the art, using replacements such as those disclosed in the present invention can not only extend the range of the emission color θ of organic 'light-emitting devices, but also expand Possible species of host and / or dopant compound "chapter

476227 V. Description of the invention (57). Therefore, as far as an effective host / dopant system is concerned, although the host erbium compound can have an intensity emission in the spectral region where the dopant substance strongly absorbs light, the host substance also emits light at the intensity of the dopant It is better to have a transmission band within the range. In the structure where the host compound also functions as a charge carrier, other criteria such as the redox potential of the substance are also considered. However, the spectral characteristics of the host and dopant species are usually the most important criteria. The dopant content is sufficient to bring the bulk dry material emission wavelength as close to the saturated primary color as possible, as defined by the CI E scale. The effective amount is about 0.01 to 100.0 mol% based on the emitting layer. A preferred amount is from about 0.1 to 0 percent real. The main criterion for determining an appropriate doping concentration is the concentration at which an emission with appropriate spectral characteristics can be achieved. It is mentioned before exemplifying, but not limiting, that if the dopant substance concentration is too low, the emission of the device also includes the component from the host compound itself, which has a shorter wavelength than the required emission from the dopant substance. On the contrary, if the dopant concentration is too high, the emission efficiency is negatively affected by the self-decreasing net non-emission mechanism. Or the concentration of the dopant substance is too high, which has a negative impact on the electron transport or electron transport properties of the host material. The present invention further relates to an organic light-emitting device, wherein the emission from the device is obtained through a phosphorescence decay process, and the phosphorescence decay rate is fast enough to meet the requirements of the display device. In a representative specific example of the present invention, the emitting layer comprises an emitting compound having a structure represented by the formula D_ί:

476227 V. Description of the invention (58)

Where M = Pt; a 2 1; b 2 0; c 2 1; X = C; and 1? 8 2} 1; and R9 = R1Q = Ε ΐ (ethyl). This compound in particular has a chemical structure of the formula D-I I

Et Et

C: \ Program Files \ Patent \ 55293.ptcl p.66

O: \ 55 \ 55293.ptc Page 67 2001.04.10.071 Date of revision 87116739 Amendment V. Description of the invention (64) 1.3 Molar percentage The shape of the spectrum of PtOEP is about the same as the device of 0.6 Molar percentage. The spectral shape of the organic light-emitting device prepared using 6 mole percent pPOEP is shown in Fig. 4C. As the voltage increased, the intensity of the red radiation increased significantly, but no distribution from A 1 q3 was found, even at high voltages. Although the present invention is not limited to its theory of operation, it is believed that the explanation of the increase in Aq3 emission as the voltage increases is related to the three different lifetimes of the photoluminescence of Alq3 and pTOEP. The PL lifetime of Alq3 is about 13 nsec (nanoseconds) in both solid and solution, while the PL lifetime of PtOEP varies from about 10 microseconds to about 100 microseconds (microseconds) depending on the medium. If the voltage applied to the device doped with pt0EP remains low, then the number of excitons delivered to PtOEP is as small as the exciton ptOEP molecule can relax at a sufficient rate relative to the rate of production of the A1 exciton, with the result always There are sufficient dopant molecules to deliver energy from A 1 q3. As the voltage increases, the effective p t o e P dopant molecules become saturated and cannot relax rapidly to match the rate of exciton generation from A 1 q3. At this higher voltage value, some Alqs excitons relax due to radiation before the excitation energy is delivered to the PtoEp molecule. At 6 mole percent pt0EP, there is a dopant sufficient to trap all excitons, but the higher doping concentration reduces the overall efficiency. The results shown in Fig. 4D support these results, which are the PL spectra of a1q3 doped pt0EP devices as a function of wavelength at different doping concentrations. At the lowest doping concentration of 0.6 mol%, it is found that the large emission band of a 1 is particularly high at the high doping concentration of 6 mol% PtOEp. It is clear that there is a sufficient amount of PtOEP to capture all sources from A1q3 exciton energy. The emission from organic light-emitting devices using PtOEP as the substrate is extremely narrow.

O: \ 55 \ 55293.ptc Page 68 2001 · 04 · 10. 〇72 Correction

87116739 Year, month, and year of the year Amendment 5. Description of invention (66) The center is located at 6 4 5 nm. The narrow band (corresponding to saturated red emission) at half-maximum half-width is about 30 nm. Comparison of the PL spectrum of a pt〇EP in solution as a function of wavelength at different laser wavelengths (Figure 4E) with the EL spectrum of an Alqs organic light-emitting device doped with PtOEP, showing that the organic light-emitting device doped with pt〇Ep selectively produces From the narrow band of PtOEP, the center spike is located at about 645 nm. This narrow high-saturation red emission is generated, and almost no other PtOEP spikes are included, even when the PL emission spectrum of pt〇EP is compared with the wide emission band from A 1 h, which makes us expect that the other center is located at about 6 This is also true for the frequency bands of 20 and about 6 8 5 nm, as shown by the PL spectrum of PtOEP in solution. The conclusion is that the emission from a device doped with PtOEP is far superior to a saturated red emission compared to a device doped with TPP because it does not have a long wavelength tail or a high peak of 700 nm. The quantum efficiency (external quantum efficiency) of these devices is shown in Table D1. In each case, the efficiency is listed based on a reference device (Indium Tin Oxide / TPD / Alth / Mg-Ag) prepared simultaneously with the doped device. At low driving voltages, the efficiency of the doped device is better, and at higher voltages, the efficiency of the undoped device is higher. These results show that PtOEP-doped devices can be performed at an efficiency equivalent to that of prior art devices doped with Alqs. It has been found that the service life of the PtOEP device (predicted for several days under environmental conditions) is equivalent to an undoped Alqs device, and it is determined to be superior to a device using τρρ as a doping agent. _ >

Page 69 2001.04.1〇, 〇74 V. Description of the invention (62) # A1q3 organic light-emitting device of hetero-PtO £ T relative to the undoped organic light-emitting device reference quantum efficiency 7 / (doped by Miscellaneous) V (Reference) 〇6 Molar percent low voltage (6-7 volts) 0.2 percent 0.15 percent high voltage (11-12 volts) 0.07 percent 0.18 percent L3 Moire percent low voltage (6-7 volts) 0.2 percent 0.11% still voltage (11-12 volts) 0.11% 0.24% 6 mol% low voltage (6-7 volts) 0.14% 0.17% high voltage (1M2 volts) 0.07% 0.2% This organic light emitting device can be used for example switching time In passive array flat displays not faster than about 10 microseconds, in active array displays where switching time only takes about 10 milliseconds, or in low-resolution display applications. The phosphorescent compound can generally be selected from phosphorescent compounds having a chemical structure of formula D-I: C: \ Prograni Files \ Patent \ 55293. Ptd page 70 476227 5. Description of the invention (63)

4 \ ^ where X is C or N; R8, R9, and 'are selected from hydrogen, alkyl, substituted alkyl, aryl, and substituted aryl; R9 and' can be combined to form a fused ring; Are divalent, trivalent, or tetravalent metals; and 8, 13, and (: each is 0 or 1; where, when X is C, a is 1; when X is N, a is 0; When the c system is 1, the 'b system is 0, and when the b system is 1, the c system is 0. The phosphorescent compound may also be selected from (another example) a phosphorescent phospholine compound, which may be partially or completely hydrogenated. Depending on its phosphorescence lifetime, in addition to phosphorescent compounds (in some cases, compounds with a phosphorescent lifetime not longer than about 10 microseconds), it can also effectively trap triplet energy of exciton from the charge carrier material, and then Corresponds to

C: \ Program Files \ Patent \ 55293.ptd Page 71 476227 V. Description of the invention (64) '' The ability to emit the excitation energy in the form of phosphorescence in a narrow band of high saturation colors, and select the phosphorescent compound, such as in Alq3 It is proved by PtOEP in the organic light-emitting device of the substrate. Although PtOEP itself has been proven to have the most suitable combination of properties as a phosphorescent compound in organic light-emitting devices, this compound has the disadvantages of producing a red emission near the edge of the sensitive western line of the eye, and the central system of the standard human eye's light response function Located at about 550 nm. Especially at the blue and red ends of the spectrum, eye sensitivity decreases sharply as a function of wavelength. It is expected that when the phosphorescent compound produces perceptually saturated red emission at a high external quantum efficiency, it will have narrow peaks at shorter wavelengths with higher eye sensitivity. For example, if the emission band width remains substantially constant and the peak emission is shifted to a shorter wavelength by about 20 nanometers, for organic light-emitting devices that generate the same number of photons, such as organic light-emitting devices with the same current and quantum efficiency The device can sense a brightness increase factor of about 2. That is to say, the number of photons from the interrogation is the same, but the same observer will feel that the height of the device with the central peak of the known wavelength is increased by about two times. However, the emission system is located in an area that is still sensed as red and thus can be used in an organic light emitting device. The present invention also relates to an organic light emitting device, wherein the plutonium emission system is obtained through a phosphorescence decay process, wherein the luminescence decay =; 22 in order to meet the needs of the display device ', and wherein the phosphorescent dopant compound contains symmetry The sex is lower than the symmetry of the 4-fold fold of P10 EP. The advantages of selecting a phosphorescent dopant compound such as #oxoline as the emitting material for an organic well device are based on two particular facts. "The amount of light + efficiency of this compound can be much higher than that of compound II such as TPI.

L; \ Prograni Files \ Patent \ 55293. Ptd Page 72 476227 V. Description of the invention (65) For example, the phosphorescent quantum efficiency of PtOEP is higher than 50%, and it is as high as 90% in solid state, while the phosphorescent quantum efficiency of TPP is only About 10 percent. The improved phosphorescent quantum efficiency provides the possibility of fabricating organic light emitting devices at higher efficiency. The second advantage is provided by the choice of a phosphorescent compound such as a perylene compound, since the emission from the compound is generally from the triplet state. Molecules that can be taught to the triplet state provide the possibility of transferring energy from the non-emissive triplet state to the triplet state of the energy in the form of phosphorescent radiation. Although the rate of dish light (meaning radiation from the triplet state) is generally much lower than that of fluorescence (meaning radiation from the singlet state), the carbon light from preparations such as platinum perylene compounds can be fast enough to meet specific requirements Display device requirements. In particular, compounds such as PtOEP (with a lifetime of about 7 microseconds when used as a dopant in the A 1Q3 layer) can make passive arrays with switching times no faster than about 10 microseconds or only need about 10 seconds to switch between h Active barrier display The particular advantage of the present invention is that it is a teasing ~ itch scale light flipping compound, transmitted to the eye peak sensitivity to the west line tip government office # π 岭 亿 σ 籾 便 ^ in the red spectral region . Youdou, by ^ 7, it is still kept at the sensory saturation and chemically modified compound. The 4-fold symmetry of the 噗 1forest ligand is symmetrical to PtOEP towards the shorter wave county EP. It is found that the emission spike is particularly relevant to the present invention One has 槔 H about: lb — 30 nm. The structure of the phosphorescent dopant compound ^ ... i, which contains the formula E — 1 1

476227

C: \ Prograni Files \ Patent \ 55293. Ptd page 74 4th post Amendment I_ 龙 _ No. 87116739 said Amendment V. Description of the invention (73)

Rs

(E-IN) wherein R5 and 1-6 can be electron donors or electron acceptor groups, such as -F, -CN or -OCH3, and R5 and 1-6 can be the same or different. As a representative compound used in an organic light-emitting device, the phosphorescent platinum compound can be selectively substituted at the 5,15 position of the phosphonium ring by selecting a phenyl group to obtain 5,15-memo-diphenyl Tan Lin # (11) compound (shown in Figure 5A) was selected. Or the platinum compound can be prepared from any other 5, 15-substituted perylene compounds (also shown in Figure 5A). In particular, in a representative specific example of the present invention, the squamatozoline compound can be selected from 5,15-memo-diphenylphosphonium (H2DPP); (H2BPFPP);

O: \ 55 \ 55293.ptc Page 75 2001.04.10.081 476227 Amendment Supplement V. Description of the invention (74) 5,15-memo-bis (cyanophenyl) antholin (H2BCPP); or 5,15-mem〇- Bis (methoxyphenyl) phosphonium (H2BAp). This compound can be prepared using methods such as those described below. In a representative specific example of the present invention, an organic light-emitting device is manufactured, in which PtOEP is doped as a phosphorescent platinum jelly compound. As shown in FIG. 5B, P t 0 EP is substituted with a polymer mixture of polyethylene (referred to as π-substituted p 丨 J) pp polymer organic light-emitting device ") in close to polystyrene PtDPP produces emission spikes at the photoluminescence spikes. These peaks are shifted toward the lower wavelength by about 20 nm with respect to the electroluminescence spectrum of the organic light-emitting device having the A lq3 layer doped with PtDPP. As shown in FIG. 5C1, for an organic light-emitting device including an indium tin oxide / NPD / Alq3-PtDPP / MgAg layer (PtDPP is doped in the A lq3 layer), an electroluminescence spectrum is generated, at 9 volts, 1 5 Organic light-emitting devices operating at volts, or 24 volts, have a narrow emission band at about 630 nanometers. The device with A 1 q3 as the substrate produced a small blue shift with increasing voltage, apparently because the Alq3 emission spectral region increased from 500 to 5500 nm. As shown in FIG. 5C2, for an organic light-emitting device having an A lq3 layer doped with PtDPP, the emission peak is shifted toward a shorter wavelength relative to an emission peak generated by an organic light-emitting device having an Alq3 layer doped with PtOEP. About 15 nm. These results show that for an organic light-emitting device having equal quantum efficiency, an organic light-emitting device having an Alq3 layer doped with PtDPP is 1.4 times brighter than an organic light-emitting device having an Alq3 layer doped with PtOEP. The practical significance of manufacturing an organic light-emitting device with an emission spike with a 15-20 nm blue shift can be shown in the right-hand side of the CIE chromaticity diagram (as shown in Figure 5D).

O: \ 55 \ 55293.ptc Page 76 2001.04.10. 082 426221 Amendment on the 6th of Nana > No. 87116739_ and I / month / year correction_ Data proof. The C I E chroma curve is listed in this figure, which includes the (X, y) coordinates of individual saturated monochromatic lines at 600, 650, and 700 nm. The (X'y) coordinate of the emission produced by an organic light emitting device having an Alq3 layer doped with PtDPP is compared with an organic light emitting device containing other red emitting dopants such as DCM2, indigo, and PtOEP. Using the CIE standardized light response curve (indicated by the dashed line in Figure 5E) for human eye sensitivity, the relative brightness under a specific light output standard can be determined by calculating the overlap of the normalized emission spectrum and the light response curve. As shown in the following formula, I lumens 0 ^ (light response) (EL spectrum) cU, where I is the intensity of the sensed lumens. This function can be called the luminescence integral. As shown in the representative data of FIG. 5E, the light emission overlap integral of p t DPP emissive organic light-emitting device 0 · 17 (relative unit) is much larger than that of PtOEP emissive organic light-emitting device 0 · 13. The net result is that for a PtDPP emissive organic light-emitting device, the CIE coordinate is maintained in the saturated red area of the chromaticity diagram, and the PtOEP emissive organic light-emitting device has a detectable brightness of up to 40% or higher. Although the DC M 2 emissive organic light-emitting device has a light emission overlap integral that is much higher than PtDPP or PtOEP (individuals are ΐ9 versus 0.17 or 0.13), that is, if the same light output standard is performed, the DCM2 emissive organic light-emitting device is actually It is less bright because the quantum efficiency of DCM2 emissive organic light-emitting devices is substantially lower than that of organic light-emitting devices manufactured using phosphorescent Pt-containing compounds. DCM2 has the structure shown in the following formula:

O: \ 55 \ 55293.ptc Page 77 2001.04.10.084 476227 V. Description of the invention (70)

It is described as a red emitting chromophore that can be used in organic light emitting devices. C. W. Tang et al., Electroluminescence of Doped Organic Thin Films, Journal of Applied Physics, 65, 3 6 1 0 (19 8 9). The present invention also relates to an organic light emitting device comprising: Produces electroluminescence heterostructure with hole transporting layer of glass structure. The hole transporting layer contains a compound having a symmetrical molecular structure. The end of the symmetric molecule is a hole-transporting amine moiety with an unsaturated bond between the two aliphatic aromatic hydrocarbons. The "unsaturated bond π" used in the present invention means a bond having at least one double bond. Π The "aliphatic hydrocarbon" used in the present invention means a hydrocarbon containing at least one aromatic. "Symmetry" means a molecule having a point around which the molecule is symmetrical. "The charge carrier layer" used in the present invention means π hole transport layer n (HTL), π electron transport layer " ETL) or "individual emission layer π (in the case of an organic light emitting device having a double heterostructure). The “hole transport part π” used in the present invention means a group, which exists when

C: \ Program Files \ Patent \ 55293. Ptd Page 78 476227 V. Description of the invention (71) When the machine light-emitting device is in a layered material, the conduction of the 而 hole makes the material consistent-knowing the pressure of the child's main It is used for electricity, and the electron transport part means "two or two layers = conductivity." In the layered material made by the present invention, in the second embodiment, when f is in an organic light-emitting device, the material has a lightning guide that runs through the layer and mainly hunts the conduction of electrons to make the amine transport part: means an amine group. The "hole hole amine delivery part" used in this month generally includes a direct bond ^: hole delivery part. The hole can be combined to form a nitrogen atom of the phenyl group, two of which are two Benzo groups may not be bonded to each other. Each: 3 T 'for example, carbazolyl' or the group, and bonded to a nitrogen atom, such as: i group; = may = Yu another -benzene Although not intended to be limited to any theory Or the method is based on the conductivity of the hole or the original method, but the present invention is based on the results of the release of the electronic structure shows that the terminal beauty ρ Α male, sensible method explained: bonding hole transport Some of the molecules have unlocalized at the j-terminus ::: ^. One molecule is 4,4, — (N'N, -bisimino-stilbene) dibenzide (ISB). In contrast, Among the amines such as TPD and NPD, the positive and nitrogen unshared electron pairs are conjugated via biphenyl, so that the holes are mainly localized on the y-linkage. Unsaturation The importance of bonding can be proved by the exemplified 4 4, — (n Ν′-iminodifluorenyl) biben (IDB), which has the same structure as iSB, except that IDB is between the aminophenyl group. It has a saturated bond, while iSB is unsaturated. Analysis by the inventors shows that I 0β has a two-electron pair that is conjugated to a biphenyl group, and ISB has a coupling to a homostilbyl group (instead of Nitrogen) nitrogen does not share electron pairs. To the extent that the hole is unlocalized, it is decorated on the homostilbyl group. This unlocalized helps the hole to stay awake____ ^ 1

C: \ Program Files \ Patent \ 55293.ptd Page 9 of 476227 V. Description of the invention (2) It is outside the I SB molecule and not on the biphenyl group. It will be screened here and adjacent to it. Molecular isolation. Keeping the hole on the outside of the molecule makes it more in contact with neighboring molecules and increases the rate at which the hole is transported to the neighboring molecules, resulting in good hole conduction properties. Moreover, the analysis by the present inventors shows that the substitution can be performed on a molecule having an unsaturated bond between two aliphatic aromatic hydrocarbons in the terminal group, and the hole is still not localized at the end or the periphery of the molecule instead of the center. The present invention specifically includes a symmetrical compound having a biphenyl bridge group represented by the following formula F-I: (F-I)

Among them, R is the hole-transporting amine moiety, with rhyme and bond between the two meridians. The molecule shown by the formula F-I is symmetrical, because the center of the biphenyl group located between the two R groups has a point, and the molecule is symmetrical around this point. The "symmetric π" used in the present invention needs to be that the atoms on either side of the symmetry point have the same bonding order between the atoms, that is, the R group needs to have the same atoms bonded in the same order, but it is allowed to twist due to the bonding The atomic positions are different. The present invention also includes a symmetric compound represented by formula F-II and having a phenyl group bridge bond:

C: \ Prograin Files \ Patent \ 55293. Pid 苐 page 80 476227 V. Description of the invention (73)

R wherein R has the same definition as above. An example of transporting the R group of an amine moiety in a hole having an unsaturated bond between two aliphatic arenes is represented by the formula F-11 I: (F-HI)

Wherein the two phenyl · system is an aliphatic aromatic hydrocarbon, and the vinyl system is an unsaturated bond located between the two aliphatic aromatic hydrocarbons. The R group of formula F-III is thrown into the molecule of formula F-I, and the present invention therefore includes I S B shown by formula F-I V

C: \ Program Files \ Patent \ 55293. Ptd Page 81 476227 V. Description of the invention (74) The vinyl group of SB can be substituted, while the unsaturated bond between the two aliphatic aromatic hydrocarbons remains. For example, the unsaturated bond may actually be provided by a phenylene group, resulting in a molecule having a structure as shown by the formula F-V: (F-V)

Or the vinyl group of the ISB may be substituted to produce a molecule having the structure shown by Formula F-VI:

Where & and {? 2 are selected from the group consisting of: alkyl, phenyl, substituted alkyl, and substituted phenyl. I may be the same as R2 or may be different. The displacement of the molecules leading to formulas F-V and F-VI is expected to contribute to the unlocalization of the holes-

C: \ Prograoi Files \ Patent \ 55293. Ptd 苐 Page 82 476227 5. The description of the invention (75) is at the end of the molecule. In addition, this substitution increases the molecular weight of the molecule, resulting in a higher Tg. In conventional organic light-emitting devices with a single heterostructure, the emissive material is an electron transporting layer, and the hole transporting part needs to have a higher absorption energy than the electron transporting layer. In conclusion, if the formed molecule is to be used in a single heterostructure organic light-emitting device having an emissive electron-transporting layer, the replacement is preferably to not cause the electron spectrum of I SB to have a large shift. To provide an alignment group for ISB, a compound having an R group can be used, which transports the amine moiety for the hole, with a saturated bond between two aliphatic aromatic hydrocarbons. The R basis is represented by the formula F-VI I:

Using the R group of formula F-II in a molecule of formula F-I to produce 4,4 '-(N, N'-aminodifluorenyl) biphenyl (IDB) as shown in formula F-VIII:

C: \ Program Files \ Patent \ 55293.ptd Page 83 476227 V. Description of the invention (76) Table 1 lists the thermal properties and other physical properties of irilSB and IDB and its phenylene bridge homogeneity: Table F 1: ISB And physical data of IDB and its phenyl bridge homogeneity. Compound melting point: (° C) Tg (° C) into max abs. (Nm) Amax PL (nm) ISB 317 110 300, 340 530 IDB-117 320 402 73 315 368-.- 310 110 290, 340 444,488 I SB (11 0 ° C) and IDB (11 7 ° C) are far higher than some materials used for hole transport in organic light-emitting devices, such as TPD (65 ° C) and NPD (105 ° C) ), Which is a material commonly used in organic light-emitting devices. As a result, an organic light emitting device that uses 闬 s B or I DB as a hole transporting part can be operated at a higher temperature than that using TPD or N P D, and it is predicted that it will have a longer lifetime when operated at the same temperature. As discussed in detail below, two different organic light-emitting devices are fabricated using I SB and I D B as hole transporting layer materials. TPD and NPD are also used for hole transmission

C: \ ProgramFiles \ Patent \ 55293.ptd 苐 Page 84 476227 V. Description of the invention (7) = The same organic light-emitting device is made of materials. Two types of organic two-coated steel tin oxide substrates are used as anodes: Wide: The simplest organic light-emitting device structure for Tohoku is indium tin oxide / = k a Alq ^ Mg-Ag. A slightly more complex structure uses copper phthalate * CuPc, an electron-emitting agent, namely indium tin oxide / CuPc / hole hole layer / Alq3 / Mg-Ag. The use of two CuPc hole injections (such as those disclosed in co-pending applications No. 08/8 65, 49) can improve quantum efficiency. As shown in Table j? 2, it was found that among the two organic light emitting devices, the organic light emitting device using ISB as the hole transporting layer has superior performance than the organic light emitting device using IDB, and the organic light emitting device using ISB has Performance of organic light emitting devices using N p D:

C: \ Program Files \ Patent \ 55293. Ptd 85th i 476227 V. Description of the invention (78) TPD 1 a-NDP 1 a 1 0.78% 0.85% 0.30% 0.58% Beihe ΐφ oblique 屮 0.93% 0.88% 0.15% 0.62 % Quantum efficiency without CuPc layer 8.25 volts 7.3 volts 9.5 volts 1 1 7.5 volts V @ 0.1mA with CuPc layer 9.29 volts 8.65 volts 12,9 volts! 9.0 volts V@0.1 mA without CuPc layers 0.230 0.285 0.071 0.174 9 PP Λ ^ ^ ^ σι \ ^ ° ^ ^ 〇y 1 fO and Ιίφ-rj base 0.250 0.251 1 0.025 i | 0.156 $ 5 π, y _ > _ 屮 violation 11280 12550 1510 @ 1mA 8460 ί at 1 mm Luminous intensity @ 5γπΛ with CuPc layer 13865 12925 925: S —〇 彐> 8930 Luminous intensity at 1 mm point @ 5mA without CuPc layer

C: \ Prograii] Files \ Patent \ 55293. The efficiency is very good, and the higher Tg shows that the lifetime of the organic light-emitting device using I SB as the substrate is greatly improved, and can be operated at a lower temperature than the organic light-emitting device using NPD and TPD as the substrate. The similarities in the properties of TPD, NPD and I BS organic light emitting devices are also shown in Figs. 2A and 2B. The current-voltage diagrams of organic light-emitting devices made of TPD, NPD, and ISB are almost indistinguishable, and IDB is poor. Table 2 also shows that organic light-emitting devices using I S B as a hole-transporting layer are superior in several respects to organic light-emitting devices using I DB as a hole-transporting layer. Organic light-emitting devices using I SB as the substrate have higher quantum efficiency, lower voltage required to achieve the same current, and higher light emission intensity at the same current. Both I S B and I D B are symmetrical molecules with high Tg. The only structural difference between I SB and IDB is that I SB has-

The IDB is saturated. This difference in the nature of the use of ISBs versus organic light-emitting devices using IDBs is consistent with the superior conductivity of ISBs over IDBs. Although the value of I DB is slightly higher than that of SB, it is predicted that only Tg cannot change the properties of the organic light-emitting device by an amount as observed in the present invention. '、 Representative materials that can be used as hole injection anodes in the representative specific examples of the present invention include indium tin oxide, Zn-In-Sn02 or Sb02, or essentially any other hole injection anodes that can be used as organic light emitting devices Layer of material. The hole transporting layer of organic light-emitting devices is expected to use a representative material in the form of glass, rather than crystalline or polycrystalline materials, because glass can provide higher transparency. Excellent overall charge carrier characteristics of the material.

Page 87 2001.04.10.095 4 / OZZ / V. Description of the invention (80) The representative plant used in the hole transporting layer in the example is Benzy-N, r-bis (3-fluorenylphenyl), -fa 22 Two include Ν, Ν '~ (TPD), 4,4, -bis [N_ (1_naphthyl) _N, 4'-bis saddle, pyrene, or 4,4, -bisU_ (2_naphthyl_benzene "-NPD ). Benminamino] biphenyl (Zhao can be used as a representative of the electron transport layer) Ming (AW or 4,4, _ di (N_ yesterday)) can be used as an individual emission layer (if present) AlQ3 of the dye or substantially any other material of the 'emission layer'. Let the individual Qiwei Yizhi be issued in the organic light-emitting device of the present invention: to form sou: D containing the metal cathode layer as the first Combined with the use of clothing, the material of the metal cathode layer can be used in the month. It can be used as an electron beam or a metal oxide. It is a material of the metal cathode layer of an extremely light-emitting device. Α 〇Bar 1 is present) can include-insulation materials such as 1 09, si Ν 戋 au can be any other material that can be used as a device. It can be used in a variety of ways, such as γ bamboo, PECVD, electron beam, etc. quot; Water promotes chemical vapor, and the invention of the organic light-emitting device has the advantage that the molecules can be completely self-deposited and have the advantages of K. Vacuum deposition materials are materials that can be deposited in a vacuum of two atm. 〇_5 to about 10 π ^ ear; vacuum deposition is preferred, or about 50 Torr to about 5-5 Torr vacuum deposition. ', Iridium is not limited to the range of thickness, but if it is a flexible plastic substrate Such as M, the substrate can be as thin as a meter, * is rigid

C: \ Program Files \ Patent \ 55293. Ptd

476223 _-_ correction 丨 correction

_Μ 嗉 号 87116739 ~ Jade, description of the invention (90) Opaque substrate or right This substrate includes a display driver with Shi Xi as the substrate, which is relatively thick; the indium tin oxide anode layer is composed of about 500 Angstroms丨 〇 ° _8 > 1 m) to more than about 400 angstroms thick; the hole transport layer is from about 50 angstroms to li, about 100 angstroms thick; the individual emission layers of the double heterostructure (if (Existing) system is 1 angstrom to about 2000 angstroms thick; the electron transport layer is from about 500 angstroms to about 1,000 / thickness, and the non-metallic cathode layer is from about 4,000 angstroms to more than about 15,000 The thickness is about 400-1000 angstroms, and about 500 angstroms is more preferable. Therefore, although the device includes a single heterostructure or a double heterostructure, the device is a SOLE or a single organic light emitting device, the device hurts: T0LED or I0LED, whether the organic light emitting device is used to generate emission in a better spectral region, Or whether other design changes are used to substantially change the type, thickness, and order of the thin layer, but the present invention relates to a device in which an organic light emitting device includes a heterostructure for generating electroluminescence, wherein the heterostructure It includes a cathode, which contains a conductive non-metallic layer, and the disc semiconductor organic layer is in low-resistance contact. " " Various specific examples of the present invention can be incorporated into optoelectronic devices, including cars, computers, televisions, printers, large-area walls, theater or stadium curtains, billboards or signboards. In addition, although specific examples have been used to illustrate the high-transparency non-metallic cathode of the present invention, 'wherein the highly transparent non-metallic cathode is housed in an organic light-emitting device', virtually any type of optoelectronic device having an anode and a cathode can include the present invention. Manufactured highly transparent non-metallic cathode. The non-metallic cathode of the present invention may be particularly included in an organic light emitting device, a solar cell, a photovoltaic crystal, a laser, or a photodetector.

Page 89: 2001.04.10.098 mm Tomorrow f no supplementary case number 87116739 V. Description of the invention (92) The present invention will now be described in detail with regard to a method for showing a specific representative specific example, but it is known that the material, device and method are only for Illustrative rather than limiting. The invention is not particularly limited to the methods, materials, conditions, method parameters, devices, etc. described herein. Embodiment A of the present invention, an embodiment of an organic light-emitting device containing a non-metallic cathode. Example A1 An organic light-emitting device is prepared using a known method. The organic light-emitting device includes a non-metallic indium tin oxide cathode layer instead of a metal cathode. Floor. In addition, the 'electron injection interface layer is located between the indium tin oxide cathode and the human q3 electron transport layer. The commercially available indium tin oxide / borosilicate has an indium tin oxide thickness of about 150 angstroms. The organic layer was thermally deposited in a standard bell-shaped evaporator at a pressure of 1x0-0 Torr. The α-NPD layer is deposited to a thickness of about 350 Angstroms, the Ald3 electrical transport layer is deposited to a thickness of about 450 Angstroms, and the copper phthalocyanine (CuPc) or zinc phthalocyanine (ZnPc) is deposited to a thickness of about 60 Angstroms. The top indium tin oxide cathode layer is RF deposited by sputtering at low energy and has a thickness of about 65 Angstroms. An organic light emitting device containing a CBP layer between a CuPc layer and A leu is also prepared. This organic light-emitting device exhibits properties equivalent to those of an organic light-emitting device without a CBP layer. One such device is qualitatively determined by measuring current-voltage, luminous intensity-current, electroluminescence spectrum and transmission, reflection and absorption spectrum. Representative numbers ^ are shown in Figures 1C-1K. ^ ^ The results are compared with a standard organic light emitting device. For example, as shown in FIG. 1A, 1 includes metal Mg: Ag cathode layer}, electron transport layer 2, hole transport layer '/ cathode layer 4 and substrate 5. The a-NPD hole transport layer has about 350 angstroms.

Amendment ^ 3 ^ No. 871187 卯 V. Description of the invention (94) degrees' The thickness of the AU3 electron transport layer is about 450 Angstroms, and the thickness of the Mg: Ag cathode layer is about 150 Angstroms. Example A2 An example of a TOLED containing a non-metallic cathode according to the present invention is illustrated in FIG. 1M. The device is shown, for example, in GV Bulovic, PE Burrows, SR Forrest, and M.E. Thompson, Letters in Applied Physics, 68, 2 06 (196), as shown below, at a basic pressure < 1. The vacuum system of -7 Torr is formed on a pre-cleaned glass substrate coated with a thin film resistor of 20 ohm / □ •. A copper phthalocyanine (CuPc) thick film of 30 angstroms to 60 angstroms was deposited on the indium tin oxide to improve hole injection properties, and then a hole transporting layer film of "ο angstrom to 40 angstroms": 4,4, -bis [N- (1-naphthyl) -N-phenylamino] -biphenyl (α-NPD). Secondly, an electron-transporting layer having a thickness of 400 to 500 angstroms is grown. (8-hydroxyquinoline) aluminum (Alq3), followed by a second layer of 30 angstroms to 60 angstroms

CuPc thick film, S.A. Van, Slyke C.H. Chem, and C.W.Tang. Letters in Applied Physics 69, 2 1 60 (19 9 6). The first layer of 200 Angstroms A lq3 was doped with 1% (by mass) coumarin (cm6). The substrate is transported to an indium tin oxide sputtering bath, where 400 angstroms to 600 angstroms are placed in an Ar (2 0 seem) and 02 (0.10 seem) environment at a pressure of 5 mTorr and 5 watts of energy. RF sputtering of indium tin oxide on top of CuPC. The control group was manufacturing a conventional T0LED without a highly transparent non-metallic cathode while manufacturing the test device. The conventional T0LED has the same structure in particular. The difference is that the indium tin oxide / CuPc top electrode is replaced by a thickness of 100 angstroms and deposited on the Alqs surface A Mg: Ag (30: 1 mass ratio) translucent film is deposited on the surface of A1q3, and encapsulated with a low-indium tin oxide. The second group of T0LEDs with non-metallic cathodes uses phthalocyanine (ZnPc) instead of oxygen.

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Page 91 2001.04.10.102 476227 V. Description of the invention (84) Manufactured by CuPc of indium bilayer interlayer. Finally, in the third group of devices, 'the electron injectable CuPc layer is a 60 angstrom thick 3, 4, 9, 10-pyridine tetraacid dianhydride (PTCDA) layer, which has been shown to protect the underlying organic film to Prevent possible damage during sputtering. V. Bu 1 ov i c, P · Ti an, P. E.

Burrows, MR Gokhale and SR Forrest Letters in Applied Physics 70, 2954 (1997). B. An example of an organic light-emitting device containing a charge carrier layer containing a compound having at least one electron transporting part and at least one hole transporting part in the molecule. Experiment: UV-visible light spectrum is stripped on Aviv spectrophotometer model 14DS. the amount. H NMR was recorded on a Bruker 2 50 spectrometer. Photo- and electro-luminescence spectra were measured using a Photon Technology International fluorometer. Current-voltage characteristic measurements are recorded on EG & G Instruments Potentiostat Model 283. Melting point was measured on an uncalibrated Me e-T e m p I I device. Elemental analysis was performed at A11 an t i c M i c r 1 a b, I n c ·. Mass spectrometric analysis was performed on a solid probe with a Hew 1 e 11-P a c k a r d G C / M S spectrophotometer with a mass selective detector (M s s Se 1 e c t i ν e De t e c t 〇 r). Gradient sublimation is performed in a Lindberg three-zone furnace with a basic vacuum of 10-3 Torr. Chemicals: Compounds that include a series of derivatives with a fluorenyldiamine moiety (known to have good hole transport properties) are present in two equivalents of 8-hydroxyfluorenyl_line

苐 Page 92 C: \ Program Files \ Patent \ 55293. Ptd z / 5. In the description of the invention (85), it reacts with A1 (OPr) 3 to form part of the compound. The resulting compound A 1 -mCb 〇 has an electron transporting part and a hole transporting compound called Al-pNP. Al-pCb, T P D and A 1 qs are sublimated according to the literature formula. Ligand 4- (N-benzyl-'both compounds are treated with ^ ν, nylamino) phenol, 3-carbazole, 4-and iminyl dibenzyl phenol before use. U1 lman Coupling the iodine & aryl ether with the corresponding amine, and 'synthesized by deprotection of the methoxy group using version 3', it is assigned under the serial number 08/929, 〇29 of September 8, 1997. An organic light-emitting device of a sex-specific asymmetric electric charge carrier substance, said publication is incorporated herein by reference. 8-hydroxymethylquinoline was purchased from -A 1 drich as a standard . Bis (2-fluorenyl-8-quinolinate) [p- (N_phenyl_2-Ceenylamino) phenol radical] Ming (III), Al-pNP: Al (OPr) 3 ( A mixture of 0.63 g, 3.1 mmoles and 8-hydroxymethylquinoline (0.51 g, 3.2 mmoles) was added with 40 ml of ethanol under argon. The mixture was refluxed for 3 hours to give a yellow-green solution. Subsequently, 8-hydroxyfluorenylquinoline (0.51 g, 3.2 mmol) and p- (N-benzyl-2-naphthylamino) were added to the air (1.45 g, 4.68 mmol). Ear) Orange solution in 40 ml of ethanol. The mixture was refluxed. The night solvent was removed from the yellow glassy material was sublimed in yellow above the 3 0 0 ° C was collected via sublimation yellow crystalline material is formed and re-sublimation substance divided pray the following results.:

Yield: 60%. Melting point: 1 3 6-1 4 2 ° C Elemental composition (calculated value): C, 77_ 2; H, 4.93; N, 6. 43

C: \ Prograni Files \ Patent \ 55293. Ptd page 93 476227 V. Description of the invention (86) Elemental composition (measured value): C, 77.0; H, 5.00 ;, 6.31 Mass spectrum: 6 5 3 (p) , 34 2 (p-p- (N-phenyl-2-naphthylamino) phenol), 2 5 9 (p- (N-benzyl-2-zeinylamino) phenol), 1 59 (8-hydroxyl Amidinoquinoline). Bis (2-fluorenyl-8-quinolinate complex) (p-carbazole phenol complex) aluminum (I 11), A pCb · AK〇Pr) 3 (0.63 g, 3.1 mmol Ear) and 8-hydroxyfluorenylquinoline (0.51 g, 3.2 mmol) were added to 40 ml of ethanol under argon. The mixture was refluxed for 3 hours to give a yellow-green solution. A lamp of 8-hydroxyamidoquinoline (0.51 g, 3.2 mmol) and p-carbazole (1.2 g, 4.6 mmol) in 40 ml of ethanol was then added to the air. Yellow solution. Cereal mixes return overnight. The solvent was removed from the yellow solution, and the yellow glassy substance sublimed above 300 ° C. The sublimed yellow crystalline material was collected and sublimed again. Analysis of the formed substances produced the following crusts: Yield: 63% Percent melting point: 2 8 3 ° C Elemental composition (calculated): C, 75 · 9; H, 4 · 69; N, 6.98 Elemental composition (measured Value): C, 75. 6; H, 4. 79; N, 6. 96 Mass spectrum: 601 (p), 343 (ρ-pair (yesterday salivary root network), 259 (pair-yesterday sigma root network) ), 159 (8-hydroxyfluorenylquinoline). Bis (2-fluorenyl-8- _ phosphonate complex) (m-carbazolol complex) aluminum (III): AlOPr * 3 (0.28 G, 1.37 mmoles) and 8-hydroxymethylquinoline (0.22 g, 1.38 mmoles) in ethanol (65 ml) under argon. The mixture was refluxed under argon for 2 hours to form The yellow-green solution transits through the plastic in the air to produce a clear solution. Add 2-fluorenyl-8-_line (0.22 g,

C: \ Program Files \ Patent \ 55293.ptd Page 94 476227 V. Description of the invention

Mol) and savory saliva (0.54 g, 2.1 mol) in ethanol solution (30 liters), the combined yellow-green solution was refluxed for 3 hours. The volatile matter was removed under reduced pressure and vacuum. The glass-like substance was sublimated twice through a 3-section sublimator at 2800 to produce a pale yellow microcrystalline solid. Analysis of the formed substances produced the following crusts: Yield: 0 · 29 grams (35 percent) Melting point: 2 8 (ΓC Elemental composition (calculated value): C, 75.9; H, 4.69; N, 6.98 Elemental composition (measured value ): C3 7 5. 1; Pyrene, 4. 72; N, 6. 90 Mass spectrum: 601 (p), 34 3 (p-m-carbazole phenol complex), 25 9 (m-carbazole phenol), 159 (8-hydroxymethylquinoline). Device manufacturing and characterization: Indium tin oxide (1000 ohm / □) borosilicate substrate is coated with ultrasonic cleaner for 5 minutes, and then deionized water is used. Rinse. Processed in boiling 1,1,1-dichloroethane for two minutes for two minutes. The substrate was washed twice with Acrylic Ultrasonic for two minutes, and washed twice with methanol for two minutes. Dry under flow. ^ The background pressure in the deposition system before the device is generally 7 X 1 0-7 Torr or lower, while the pressure during film deposition is between 5 X 1 0_7 Torr and 2 X 1 (Γ6 Between the ears. The compound that constitutes the organic light-emitting device is evaporated from a hot-button boat that is difficult to control on a substrate that is kept close to room temperature. The TPD precedes the distance from 1 to 4 Angstroms per second. Deposition to produce a 300 angstrom thin film, followed by the deposition of an electron transport layer (A1q3, Alx3) at a rate of 1 to 40 angstroms per second to a thickness of 4500 angstroms. For dye-doped organic light-emitting devices, the Electronic conveying material

C: \ Prograiii Files \ Patent \ 5529; 3. ptd page 95 476227 'rubber correction iiSS_87116739 f, invention H101) materials and dyes are co-deposited at the required ratio. This slot opens to air and places a baffle directly on the substrate. Lock and silver are then co-deposited at a typical rate of 3 angstroms / second. The Mg: Ag ratio is from 7: 1 to 12: 1. This layer is typically 500 angstroms thick. Finally, the device encapsulates 1000 angstroms at a deposition rate of 1 to 4 angstroms per second. Ag ° manufactures three types of organic light-emitting devices with at least one electron transporting part and at least one hole transporting part in the molecule: SH-A type: oxidation Indium tin \ 1 ^]) (30 0 Angstroms) \ 11 £ ding \ 1 ^ —Ag (500 Angstroms) \ Ag (1 0 0 0 Angstroms) SH-B type: Indium tin oxide \ HET \ A1q3 (45 〇Angles) \ Mg-Ag (500 Angstroms) \ Ag (100 Angstroms). DH type: Indium tin oxide \ TPD (300 Angstroms) \ HET \ A1q3 \ Mg_Ag (500 Angstroms) \ Ag ( 1 0 0 0 Angstrom) wherein HET represents a charge carrier layer, which includes a compound having at least one electron transporting part and at least one hole transporting part in the molecule, such as A1-pNP or Al-pCb. In addition, TPD / Alq3 organic light-emitting devices are generally manufactured at the same time as SH-A type, SH-B type, and D Η type, for reference. The device is qualitative in air within five hours of manufacture. Experimental results: Each of the organic light-emitting devices manufactured has a heterostructure and a charge carrier layer, including a compound having at least one electron transporting part and at least one hole transporting part in the molecule, which is also used as an emissive material.

The absorption and photoluminescence (PL) spectra of Al-pNP, Al-pCb and Al-mCb in a solution in methylene chloride are shown in Fig. 2A. All three compounds are

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P.96 2001.04.10.109 476227 ____________ 90.4.16 _; A ^ number 87116739_ ^ April, April, 2005 Revision _ V. Description of the invention (103) The absorbance point is displayed between 280 and 380 nm. The carbazole derivatives A1-pCb and Al-mCb show an intense blue emission at about 360 nm, while Al-pCb has a lower energy emission at 480 nm. Al-pNP was shown to show a single intensity blue emission at about 4400 nm, indicating the potential application of this substance as a blue emitter. In order to detect the properties of these novel substances, Al-pNP and Al-pCb are used to fabricate different types of organic light-emitting devices. As mentioned above, three types of organic light-emitting devices are manufactured for each material (SH-A, SH-B, and DH types). Thin films of TPD and AI-pCb are also deposited on the substrate. These films are stimulated with ultraviolet light and the absorption and PL emission are measured. Figure 2B shows the electroluminescence (EL) spectra of SH-A, SH-B, and DH-type organic light-emitting devices manufactured using ABNP, and SH_A-type organic light-emitting devices, PNP in dichloromethane, and the TPD film. PL spectrum. Fig. 2C shows the I-V characteristics of SH-A, SH-B, and DH-type organic light-emitting devices manufactured using Al-pNP and a reference organic light-emitting device having a TPD hole transport portion and an Alq3 electron transport layer. Table B1 shows the yield, PL, and EL data of organic light-emitting devices manufactured using Al-pNP. In FIGS. 2B and 2C and Table B1, “SH-A” means a single heterostructure organic light emitting device having a TPD hole transporting part and an Al-pNP electron transporting layer (300 Angstrom TPD / 1000 Angstrom Al-pNP) ° nSH-B " means a single heterostructure organic light-emitting device with an Al-pNP hole transport layer and an Alq3 electron transport layer (300 Angstrom Al-pNP / 45 0 Angstrom Alq3). n DH1 'means a TPD electrode Hole-transporting layer, Al-pNP individual emission layer, and Alq3 electron-transporting layer of dual heterostructure organic light-emitting device (300 Angstrom TPD / 200 Angstrom Al-pNP / 450 Angstrom Alq3). Π reference yield in Table B1 Means at the same time as the organic light-emitting device at the top of the column

O: \ 55 \ 55293.ptc Page 97 2001.04.10.111 Supplementary information 871167 Evil ___ such as winter, moon and sun, τ _____ V. Description of the invention (105) '-Manufactured with TPD hole transport layer and AU3 electrons The reference of the transport layer is the yield of the organic light emitting device (300 Angstrom TPD / 45 Angstrom A U3). The maximum value recorded in Table B1 is the maximum value in the visible light region, and may be a generalized maximum value that does not correspond to the southernmost spike of β. As shown in Table B1, 511_A organic light-emitting device with A1-1) rating has no effect, and the yield is as low as 0.0005%. Only a part of the low yield can be explained by pollution. It is shown in the reference organic light-emitting device. Reference yield. The SH-A organic light-emitting device having Al-pNP emits white light. The organic light-emitting device with A1-pNp ^ SH_B has a better yield of 0.02%. The organic light-emitting device with A1-pNP2DH has a better yield of 0.05%, and improved i-v characteristics' are shown in Fig. 2C. These results show that A1_pNp has certain hole transport properties' but is a poor propellant in the solid state system. Table 1 Structure SH-A SH-B DH Yield (percent) 0.0005 0.02 0.05 Yield (percent) (reference) 0.02 0.1 0.1 PL (nm) 565 519 518 EL (nano) 525 514 520 Figure 2D shows the use Reference of SH-A, SH-B and DH (2) organic light-emitting devices manufactured by Al-PNP and having TPD hole transport layer and Alq3 electron transport layer

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87116739 V. Description of the invention (106) + month a_ I-V characteristics of organic light-emitting device. Fig. 2E shows EL spectra of a DH (2) type organic light-emitting device and a reference organic light-emitting device, and PL spectra of a DH (2) type organic light-emitting device and an Al-pCb thin film. Table B2 lists the yield, PL, and EL of organic light-emitting devices manufactured using Al-pCb. In FIGS. 2D and 2E and Table B2, nSH-Απ represents a single heterostructure organic light emitting device having a TPD hole transport layer and an Al-pCb electron transport layer (300 Angstrom TPD / 500 Angstrom Al-pCb). It means a single heterostructure organic light emitting device with an Al-pCb hole transport layer and an Alq3 electron transport layer (300 Angstrom Al-pCb / 450 Angstrom AU3). “n DH (1)” means a double heterostructure organic light emitting device having a TPD hole transport layer, an A1-pCb individual emission layer, and an Alq3 electron transport layer (300 Angstrom TPD / 450 Angstrom Al-pCb / 450 Angstrom Alq3). `` n DH (2) '' means a double heterostructure organic light-emitting device (300 Angstrom TPD / 410 Angstrom Al-pCb / 40 Angstrom Alq3) with the same material as DH (1) but different deposition thickness. Table B2 "Reference yield" column refers to the goodness of a reference SH organic light-emitting device (300 Angstrom TPD / 4 50 Angstrom Alq3) with a TPD hole transport layer and an Alq3 electron transport layer manufactured at the same time as the organic light-emitting device located at the top of the column. rate. The application of A1-pCb in SH-A, SH-B and DH type organic light-emitting devices makes their color and yield higher than those of Al-pNP. The PL spectrum of the A1-pCb thin film shown in Fig. 2E is the same as that of Al-pCb in a dichloromethane solution (as shown in Fig. 2A), has the same blue emission, and has an intensity equivalent to A lq3. As shown in FIG. 2E and Table B2, the DH (2) organic light-emitting device having Al-pCb has a blue emission with a peak at about 500 nm.

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| 9% 4. I 87116739 Revised five tables B2 structure SH-A SH-B Qing) DH (2) Yield (percent) 0.03 0.001 0.11 0.02 Yield (percent) (Reference) 0.14 0.14 0.14 0.14 PL (nm) 480 509 495 480 EL (亳 micron) 500 518 518 500 The efficiency and color purity of DH (2) organic light-emitting devices with Al-pCb are further improved due to the technique of doping dyes. Fig. 2F shows a PL spectrum of a DH (2) organic light-emitting device which is immersed in a two-methane solution and has Al-pCb uniformly doped with 1% lettuce, and an EL spectrum of the same organic light-emitting device. Fig. 2G shows the I-V characteristics of a DH (2) organic light-emitting device having Al-pCb uniformly doped with 1% 笸 and a TPD / Alq3 organic light-emitting device in which Alq3 is doped with 1% 笸. Table B3 shows PL and EL data of an organic light-emitting device manufactured using Al-pCb. In Figs. 2F and 2G and Table B3, n DH (2) n means an A pCb layer with a TPD hole transport layer, uniformly doped 1%, as an individual emission layer, and an Alq3 electron transport layer (300 angstroms). TPD / 400 Angstrom 1% Al-pCb / 50 Angstrom Alq3) dual heterostructure organic light emitting device. The “Reference, Yield” column in Table B3 means the reference SH organic light-emitting device (30 0 Angstrom TPD / with a TPD hole transport layer and an Alq3 electron transport layer manufactured at the same time as the organic light-emitting device on the top of the barrier). 45 0 Angstrom Alq3).

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t 87116739 V. Description of the invention (109) Correction table B3 Structure DH (2) Yield (percent) 0.05 Yield (percent) (reference) 0.12 PL (nanometer) 445 EL (nanometer) 455 m ratio 100% H weight PC weight 1-1 A. The dopant has a uniform cb spectrum in the layer -P light ---- LAE. The spectrum of the doped dopant layer is strong when the color is strong. The miscellaneous solution in the PL device was mixed with this mash. F 2 is as strong as the long wave of the Ze system. The figure shows the installation of κβ, the warp, and the warp, and the warp, and the warp. 05 does not emit the body owner should be the spectral light ο body owner. The rate of self-efficacy is the indication of this inefficiency. In the end of a certain process, there are some sub-components and sub-components mixed with the color of the green to the spectrum to send light to the sub-components mixed with mixed color / (\ mixed color green and blue as they are, use the agent to make miscellaneous Blended with bright-colored hair, other hair, or 1 × vegetarian bean incense, such as bean curd, or color, that is, oxobutylamino, fluorenyl, phenylhydroxy, ring, W, and photo-based hydroxyl. -2's / — \ layer emitting agent is mixed with a diester γ inside 4. Acridine \ —f} and difluorene-based > > 3 >

O: \ 55 \ 55293.ptc Page 101 2001.04.10.117 476227 V. Description of the invention (94) The method for manufacturing an organic light-emitting device is as follows: · A hole transport material TPD and an electronic material Aiq3 are synthesized according to known methods, And sublimate before use. Compound 1 · Mixed hippuric acid (4.0 g, 0.22 mol), formaldehyde (25 g, 0.24 mol), sodium acetate (16.0 g, 0.24 mol), and anhydrous acetic acid ( 120 ml, 1.2 mol), stir well for 3 days. The resulting yellow mixture was added to cold deionized water (1 liter) and the yellow solid was collected by filtration. Yellow needles (48 g) were collected after crystallization from acetone (2 liters). Yield: 88 percent. Melting point: 1 6 2- 1 63 ° C. Analytical calculated values: C, 77.1; H, 4.45; N, 5.62. Experimental values: 76.2, H, 4.47; N, 5.55. Mass spectrum: 249 (P), 105 (PhCO), 77 (Ph). Nuclear magnetic resonance spectrum (25 ° C, CDC13): 8.15-8 · 3 0 (m), 7, 47-7 · 6 5 (m). Compound 2: mixed with uric acid (5.0 g, 27.9 mmol), p-hydroxyacetaldehyde (3.70 g, 30.3 mmol), sodium acetate (2.0 g, 30 mmol) and anhydrous Acetic acid (20 ml, 212 mmol) was stirred well for 1 day. The resulting yellow mixture was added to cold deionized water (0.2 l) and the yellow solid was collected by filtration. Yellow crystals were collected after crystallization from acetone. Mass spectrum: 3 0 7 (P), 2 6 5 (P-CH3COO + H), 105 (PhCO), 77 (Ph). Nuclear magnetic resonance spectrum (25 ° C, CDC13): 8.25 (d, 8 · 8Ηζ), 8.18 (d, 8.0 Hz), 7.50-7 · 66 (π), 7.20-7 · 26 (πι), 2.34 (s, Me). Compound 3: mixed with uric acid (5.0 g, 27.9 mmol), p-dioxaloxal (4.38 g, 29.4 mmol), sodium acetate (2.0 g, 30 mmol) And anhydrous acetic acid (20 ml, 21 2 mmol), stir well for 1 day. Add the dark red mixture of Caicheng Zhi to cold deionized water (200ml).

C: \ Prograni Fi lss \ Patent \ 55293. Ptd page 102 476227 5. Description of the invention (95) Collect the red solid. Red crystals (1.0 g) were collected after crystallization from acetone and sublimation (200 ° C). Yield: 12 percent. Melting point: 2 11 -2 1 3 ° C. Analytical calculated values: C, 74. 0; H, 5. 52; N, 9. 58. Experimental values: 73.9, H, 5, 51; N, 9. 54. Mass spectrum: 2 92 (P), 15 9 (P-PhCOCO), 105 (PhCO), 77 (Ph). NMR spectrum (25 ° C, CDC13): 8.15 (dd, 8.3Hz, 1.8Hz), 7. 46 -7. 56 (m), 7.22 (s), 6. 82 (d, 8. 75Hz), 3 . 12 (s, Me). Compound 4: mixed with uric acid (8.57 g, 47.8 mmol), p-tert-butylacetaldehyde (8.0 ml, 47.8 mmol), sodium acetate (3.2 g, 48.5 mmol) and anhydrous Acetic acid (35 ml, 317 mmol) was stirred thoroughly for 2 ^ days. The resulting yellow mixture was added to cold deionized water (150 ml), and the yellow solid was collected by filtration. The yellow crystals were collected after crystallization from acetone and purification by sublimation (160 ° C). Yield 88%. Melting point: 142 ° C. Analytical calculated values: C, 78 · 7; H, 6.27; N, 4.58. Experimental values: 77.7, H, 6.25; N, 4.58. Mass spectrum: 3 0 5 (P), 10 5 (PhCO), 77 (Ph). Nuclear magnetic resonance spectrum (25t, CDC13): 8.13-8. 20 (m), 7.50-7.64 (π0, 1.36 (s, Me). Compound 5: mixed uric acid (0.45 g, 2. · 5 millimoles), 4-diamidoamino-1-naphthaldehyde (0.50 milliliters, 2.5 millimoles), sodium acetate (0.26 g, 3.9 millimoles), and anhydrous acetic acid (10 milliliters, 106 millimoles) Mol), stir well for 2 days. The resulting red mixture is added to cold deionized water (100 ml) to form a red oil. Diethyl ether is used to extract the red product. The solvent is removed, and the red liquid is used as a red liquid. After passing through the Shixi gel column, the dark red eluate was collected and the solvent was removed to obtain a red liquid (0.52 g).

C: \ Progran] Files \ Patent \ 55293. Ptd 苐 103 p. 476227 V. Description of the invention (96) Compound 6: Mixed 4-nitroequuric acid (2.25 g, 100 mmol), Methylamine = aldehyde (1.53 ml, 10.2 mmol), sodium acetate (0.75 g, 11.4 ¾ mole) and anhydrous acetic acid (40 ml, 424 mmol), and stirred well for 2 days. The formed dark red mixture was added to cold deionized water (150 mL), and a black solid was collected by filtration. Crystals were collected from acetone and purified by sublimation (190 ° C), and color crystals were collected. Mass spectrum: 3 3 7 (P), 1 5 9 (p-n0-PhCOCO). Nuclear magnetic resonance spectrum (25 it, CDC 1 3): 8. 229 q 8 · 5Ηζ), 8.12 (d, 8 · 0ΗZ), 7.26 (d, 11ΗZ) β J4 8 · 5Hz), 3.12 (s, Me ). '.' Compound 7: Mixed N-Ethylglycerol (2.02 g, 17.3 mmol) p-dimethylaminocarbaldehyde (2.49 g, 16.7 mmol), sodium acetate ^ 0.91 g, 13.8 millimoles) and anhydrous acetic acid (10 milliliters, 106 millimoles) and stir well for two days. The formed dark red mixture was added to cold deionized water (150 mL), and the reddish solid was collected by filtration, and crystallized from propane snapper for purification. The organic light-emitting device was prepared using the following method: ′ The indium tin oxide / borosilicate substrate (100 ohm / square) was cleaned with a cleaner for five minutes, and then rinsed with deionized water. It boils on the boiling moon; it is processed twice in two minutes for two minutes. The substrate was washed twice with acetone ultrasound for two minutes and twice with ethanol for two minutes. Background pressure before deposition—generally 7 × 10-7 Torr or lower, and the pressure during deposition is about χ10-10 Torr. All Huasi mouth is compared to resistive heating in a tantalum boat. TPD precedes deposition from i to 4 Angstroms / sec ^^; The thickness is generally controlled at 300 angstroms. '' This electron transport layer A 1 Q3 is doped with compound 3. The dopant is generally light

1___ ill C: \ ProgramFiles \ Patent \ 55293.ptd 苐 Page 104 4-h.c: Xiugua r-Κ! Ϊ ^ ϊ M \ m

10-year Yiyue No. _i ± JE No. 87116739 Also drink it, Α 切士. ‘· ΤΛΤ3ββκ-Γ-: .-- '. II. V. V. Description of the invention (114) Evaporation under the cover substrate. After the dopant rate is stabilized, the host material evaporates to a specific rate. Then, the covering on the substrate starts, and the subject and object of the required concentration are deposited. The dopant rate is generally between 0.1 and 0.2 angstroms / second. The total thickness of this layer is controlled at 450 angstroms. The substrate is then released from the air and a mask is placed directly on the substrate. The mask is made of a stainless steel plate and contains holes having a diameter of 0.25, 0.5, 0.75 and 1 mm. The substrate is placed back into the vacuum for further coating. The town and silver are co-deposited at a typical rate of 2.6 Angstroms / second. The μ g: a g ratio ranges from 7: 1 to 12: 1. The thickness of this layer is generally 500 Angstroms. Finally, 1000 angstroms of Ag were deposited at a rate of 1 to 4 angstroms / second. The device is qualitative within five hours of manufacture. Generally, the electroluminescence spectrum, I-V curve, and quantum efficiency are measured from previous measurements. The spectrum of a doped device and an undoped A 1 device containing a compound as a dopant is shown in FIG. 3A. The emission of this device is from compound 3 dopant. ′, ° The I-V characteristics of the device shown in FIG. 3B show that the compound can be used not only in organic light-emitting devices, but also that the compound can provide a higher current standard for a specific voltage. D. Example of an organic light-emitting device containing an emission layer containing a phosphorescent dopant compound The method for manufacturing an organic light-emitting device (OLED) is as follows: The hole transport material TPD and the electron transport material A1 (h are formed according to the literature method t, Sublimation before use. The dopant pt〇ET was purchased from Porphyrin Products, Inc., Logan, υτ and considered as the standard.

O: \ 55 \ 55293.ptc Page 105 2001.04.10.122

The following method was used to prepare the organic light-emitting device: 忒 Indium tin oxide / borosilicate substrate (100 ohm /: wave cleaning for five minutes, followed by rinsing with deionized water and cleaning agent. The substrate is made of two acrylics and two swords and washed with methanol for two minutes. The background pressure before the two depositions is generally 7 x 10_7 Torr or the pressure between the two is about 5 X 1 (P to 1 · 1 x 1 Torr. D,-, "All chemicals are resistively heated in various buttons m during the accumulation period. Deposition at a rate of τρ to t Angstroms per second. The thickness is generally controlled At 300 angstroms, PtOEp is doped in the Al "electron transport layer Alq3. The dopant is generally evaporated *. After the dopant rate is stabilized, the main Ί = ^ rate i follows The coverage that starts on the substrate, ^ product = also the host and the object. The dopant rate-generally is 0.20 ^ 丨 and the total thickness of this layer is controlled at 450 angstroms. The substrate was taken out from the deposition system, and the mask was directly placed on the substrate. The mask was made of a stainless steel plate, and contained a diameter of 0.25, 0.5, 5 and 7 耄. Holes. The substrate is put back into the vacuum for further coating. · And 1 Magnesium and silver are co-deposited at a typical rate of 2.6 Angstroms per second. Mg ·· 7: 1 to 12 · 1. 1. Thickness of this layer Generally, it is 500 angstroms. Finally, 100 angstroms of Ag are deposited at a rate of 糸 angstroms / second. 丄 丄 Main 4 The device is characterized within five hours of manufacture. Generally, it is related to the front electroluminescence spectrum, IV Curve, and quantum efficiency. Electron E, containing an emitting layer containing a phosphorescent dopant compound with less symmetry.

4/6227 5. Description of the invention (99) '------- Examples of organic light-emitting devices Electrode hole transport material TPD and electronic rotation material AlQ3 are synthesized according to literature methods and sublimated before use. The dopant PtDPP compound and other peroxoline compounds are synthesized as follows. The organic light-emitting device was prepared using the following method: The oxidized steel substrate was tuned / tuned; the oxalate substrate (1 Q Q ohm / square) was ultrasonically cleaned with a detergent for five minutes, and then rinsed with deionized water. It is treated twice in two minutes in boiling 丨, 丨, j — three gas ethane. The substrate was washed twice with acetone for two minutes and was washed twice with methanol for two minutes. The background pressure before deposition is generally 7 X 1 (Γ7 Torr or lower, and the pressure between the deposition vehicles is about 5 X 1 0-7 to 1 · 1 X 1 (Γ6 Torr. All chemicals are in various groups Resistive heating in the boat. T p J) is deposited before the rate of 1 to 4 angstroms per second. The thickness is generally controlled at 300 angstroms. The electron transport layer A 1 q3 series #heterocompounds, such as pt D pp The exchange sword is generally evaporated under the cover substrate. After the dopant rate is stabilized, the host material evaporates to a specific rate. Then, the substrate and the object on the substrate are deposited to deposit the required concentration. The dopant rate is generally 0 · 1-0.2 Angstroms / second. The total thickness of this layer is controlled at 450 Angstroms. Then the substrate is taken out from the deposition system and a mask is placed directly on the substrate. The mask system Manufactured from stainless pin plates and containing holes with diameters of 0.25, 0.5, 0.75, and 1 millisecond. The substrate is placed back into the vacuum for further coating. Magnesium and silver are co-deposited at a typical rate of 2. 6 Angstroms / second. The ratio of Mg: Ag is from 7: 1 to 1 2 ·· 1. The thickness of this layer is generally 50 Angstroms. Finally, it is between 1 and 4 Angstroms / second. An A g of 1000 Angstroms was deposited under the hand.

C: \ PrografnFiles \ Patent \ 55293.ptd Brother 107 Page 476227 Five 'Description of Invention (100) --- The device is qualitative within five hours of manufacture. It is generally measured from the previous emission spectrum, I-V curve, and quantum efficiency. Synthesis and characterization of pediatric compounds: 2, 2-Disallocyl pinane was prepared from a modified literature method in August Chemical Journal, 2 2, 2 2 9-2 4 9): Yi 2, 2 '- Dipyrrolylthione. A vigorously stirred solution of 7.0 ml (90 mmol) of thiophosgene in 150 ml of anhydrous tetrahydrofuran was added dropwise 12.5 g (186¾ mole) of biloxol. After 30 minutes, methanol (20 'ml) was added and the mixture was stirred at room temperature for 30 minutes. The resulting mixture was evaporated to dryness. This crude material was used in the next step without purification. 2, 2'-dipyrrolidone. The aforementioned crude thioketone was added in 200 ml of 95% ethanol containing 10 g of hydrogen hydroxide), and 17 liters of hydrogen peroxide (30 knives) was slowly added at 0 °. This mixture was allowed to incubate at 0 ° C for 2 hours, then at 60 ° C for 30 minutes, and then concentrated to 1/5 of the original volume. Add OOml of H ?, pass over the sink, wash with cold ethanol, and dry to produce the product (5.6 g: 39% starting from sulfur phosgene). Its purity is sufficient for subsequent steps. 2,2 ' -Disallocyloxane. A solution of 3.3 g (20.1 mmol) of 2,2, -dipyrrole in 200 ml of 95% ethanol containing 3.3 ml of morphine was refluxed under reflux, and IB1.7 g X6 was added in portions. 3 ml of H9-0 were added 10 minutes after each addition. The mixture was refluxed for another two hours after the last addition. 30 Q ml of H? 0 was added and the mixture was extracted several times with Et20. The combined extracts were dried with sulfuric acid and concentrated 'to produce a thick oil, which was then extracted by sintering, until the content of the product was measured by T L C in the remote extraction method. The combined dreams partially collapsed to produce 2.3 g (78%) of a pale yellow crystalline product.

476227 V. Description of the invention (101) General method for synthesizing 5, 15-median-dibenzylopyridin: 2, 2-dipyrrolidine (0.5 g, 3.42 moles) and isomolar amount The aldehyde was dissolved in 500 liters of anhydrous dichloromethane. The solution was purged with gas for 15 minutes. Difluoroacetic acid (154 microliters, 2.6 millimoles) was added via k via a syringe, and the mixture was stirred at 1 for 3 hours in the absence of light. Add 2,3-dichloro-5,6-dicyano (1.04 g, 4.6 mmol) and continue stirring for 30 minutes. The resulting dark solution was concentrated to 3/3 of its original volume and poured into a column of silica gel packed with hexane. Elution with dichloromethane produces a purple band, which is concentrated to produce a color-blocked solid 'which is filtered and washed with ethanol, followed by hexane. The solid purity is sufficient for the measurement of ambient photoluminescence. 5, 15-memo-diphenylphosphonium (h2DPP): Yield: 0.63 g, 80 percent, mass spectrum (EI) m / z (relative intensity) 4 62 (M +, 100), 3 8 6 (50), 368 (30), 313 (25), 231 (50). 5,15-memo-bis (pentafluorophenyl) phosphonium (H2BPFpp): yield 0.05 g, 5 percent, mass spectrum (ΕΙ) ιη / ζ (relative intensity) 642 (M \ 100), 623 (8) 602 (8), 368 (45), 321 (35), 236 (40). 5, 15-memo-bis (4-cyanophenyl) phosphonium (H2BCPP): Yield: 0.09 g, 10 percent, mass spectrum (El), m / z (relative intensity) 512 (Γ, 100), 411 (50), 368 (35), 355 (40), 294 (45), 281 (50). 5, 15-memo-bis (4-anisyl) pyridoline (H2BAP) ·· Yield: 0.09 g, 10%, mass spectrum (El) m / z (relative intensity) 522 (M +, 8), 4 1 6 (1 0 0), 4 0 1 (2 0), 3 7 2 (2 3). 5,15-memo -Diphenylphosphonium platinum (II) (PtDPP) ° H2DPP (0.05

C: \ Program Files \ Patent \ 55293.ptd 页 Page 109 476227 V. Description of the invention (102) grams, 0.1 millimoles) and Pt (PhCN) 2Cl2 (0.1 grams, 0.1 milliliter, 1.0 milliliter The mixture in anhydrous water was refluxed at 24 hours under I) and completely dried under vacuum to remove trace phCN. 'The formation of dissolved methyl chloride, using hexane: dichloromethane (1: 1, Zhao; ^ The solid was dissolved in the second extraction agent and subjected to chromatography to produce a red solid product (0.04 ^ product) as a washing 1H _: 510.15 (S '2H), 9.20 7 (dd' 4H J, fractional ratio). K.5HZ ) '8.93 (dd' 4H, J1 = 12Hz, J? = 7,5 Factory 'Z;? .77 (m'6H).%' Mass ⑻) m / z (relatively strong 幺 65 5 (r F / include Hole-transporting layer of organic light-emitting device n This layer contains a package .... :: A glassy organic hole-transporting material of a compound of symmetrical molecular structure Suitable for organic light-emitting devices (OLED): Chemicals: According to the following method Preparation of ISB: Place a third sodium butanolate in a round bottom flask

= Grams), PMba3 (0.22 grams), DPPF (dibenzyl iron complex: two grams) and 50 ml of anhydrous methylbenzyl. The reaction mixture was placed under argon for 3 minutes. Dimobiben (3.12 g) and imine stilbene (4.25 g) were added for 8 hours, and the amine was no longer measured by u mass spectrometry. The solvent was removed from the reaction mixture, and the crude residue was dried under vacuum. The dried reeds were subjected to gradient aspiration under reduced pressure (104 Torr). Sublimation yielded 2.06 grams of pure material, 36% of theoretical reaction yield. T IDB was prepared according to the following method: 51 millimolars (1,000 g) of imine dibenzyl reacted with 17¾ moles (6.94 g) of 4, 4'-diiodine dibenzyl. The reaction product with 34 t 旲 (2.16 g) of copper powder, 68 mM (9.398 g) potassium carbonate, 2 毫 Ϊ ® 1 * 1 _window__ page 110 C: \ Program Files \ Patent \ 55293. ptd 476227 5. Description of the invention (103) Ear (0.530 g) 18-crown-6-ether and 20 ml o-dichlorobenzene in a round bottom flask equipped with a condenser. The flask was heated to 185 t and refluxed under argon for 24 hours. The reaction, the mixture was filtered while hot, and after the liquid reduction class, it was recognized at the beginning — one, one, ..., one > 丄, one ~ 于 in a vacuum to filter thirst to remove the solvent. The residue was passed through a short tube of silica gel in toluene to remove the solvent, and the residual solid was purified at 0.02 ° C at 2 20 ° C; purification. The electronic transport materials AU3 and TPD and NPD of the bucket sublimation sublimation institute are based on the literature method. All organic materials are sublimated before use. ,synthesis. Method: The indium tin oxide / borosilicate substrate (100 ohm / square) r * was cleaned by sonication for five minutes, and then rinsed with deionized water. Take: Detergent Ultra · Three gas ethane treatment twice in two minutes. The substrate uses propane super 1,2,1, 1 ~ 2 minutes twice, and is washed with methanol for two minutes and two ^ 7 waves are washed. The background pressure before the two depositions is generally 8 X 10-7 Torr. "= . The pressure is about 5 X10-7 to 2 X1 (Γ6 Torr. The next 1 is low, all the chemicals are deposited in the resistive heating of the button-boat pho -1 at the rate of 1 to 3.6 Angstroms per second. The thickness-general control is then controlled by: electricity = transmission layer UU3) at a rate of m and 3 angstroms / second. The total thickness of this layer is controlled at 450 angstroms. After removing the substrate from the air, a mask is directly placed on the substrate. The yoke is made of a stainless steel plate and contains a hole with a diameter of 0.25 ', 5.0'7_π 1 mm. The substrate was then put back into the vacuum and co-deposited at a rate of .3 Hans. Mg: The second line is 9: 丨.

This / t and degree are generally 50 angstroms. Finally, it sinks at a rate of 2 7 I ^ &

"V Π Π ... r_ 结 / 案 k 87116739_ As amended by the year of the month _ V. Description of the invention (123) Ag of 1000 Angstroms. Device Qualification: The device is qualitative within one day of manufacture. Measurement I -V curve, quantum efficiency and luminous intensity. The data of the organic light-emitting device derived from these measurements are listed in Table F2. The current-voltage (IV) characteristics of the device are shown in Figures 6 A and 6B. Figure 6A Shows the current-voltage characteristics of an organic light-emitting device with a single heterostructure. The device includes an indium tin oxide anode, a hole transport layer, an A 1 q3 electron transport layer, and a Mg-A g cathode, in the order described above. Deposited on the substrate. Four different diagrams are shown for four different hole transport layer materials: TPD, NPD, ISB and IDB ° The current-voltage diagrams of TPD, NPD and ISB are very similar, showing that regardless of the hole transport layer system For TPD, NPD or ISB, the current-voltage characteristics of the organic light-emitting device have not changed significantly. The current-voltage chart of I DB shows that the current is lower than that of TPD, NPD and ISB, showing that in terms of current-voltage characteristics, the IDB system Is a less desirable hole transport layer. Figure 6B Shows the current-voltage characteristics of an organic light-emitting device with a single heterostructure, which has a hole injection promotion layer, including: indium tin oxide anode, CuPc hole injection promotion layer, hole transport layer, Alq3 electron transport layer, and M g _ A g cathode, which is sequentially deposited on the substrate as described above. Four different diagrams are shown for four different hole transport layer materials: TPD, NPD, ISB, and IDB. Currents for TPD, NPD, and ISB -The voltage diagram is very similar, showing that whether the hole transport layer is TPD, NPD or ISB, the current-voltage characteristics of the organic light-emitting device have not changed significantly. The current-voltage diagram of IDB shows that the current is lower than that of TPD, NPD and I SB Graph showing the current-voltage characteristics,

O: \ 55 \ 55293.ptc Page 112 2001.04 · 10.131 A Case No. 87116739% Vi: Month Day Amendment V. Description of the Invention (125) I D B is a less desirable hole transport layer. Figures 6 A and 6 B show that for two different organic light emitting device structures, an organic light emitting device using I SB as a hole transporting layer has a current-voltage characteristic similar to an organic light emitting device using TPD or NPD as a hole transporting layer. . This similarity, as well as the higher Tg of I SB and the longer predicted lifetime of organic light-emitting devices using I SB, show that IS B is a superior hole transport layer.

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Claims (1)

476227 ψ \ Correction No. 87116739 \ | Month or day of the year Modification THiTll 1. A cathode, which is characterized by including a conductive non-metallic layer with low-resistance contact with a semiconductor organic layer. 2. The cathode according to item 1 of the patent application scope, wherein the conductive non-metallic layer comprises a wide bandgap semiconductor having a bandgap of at least 1 electron volt. 3. The cathode according to item 1 of the patent application range, wherein the wide band gap semiconductor has a transmittance of at least 50% for incident and containing irradiation. 4. The cathode according to item 1 of the patent application scope, wherein the semiconductor organic layer comprises a polymer (ρ ο 1 y a c e n e) compound. 5. The cathode system as described in item 1 of the patent application scope includes dedication. 6. The cathode system as in item 1 of the patent application scope includes copper Gengjing. 7. The cathode system according to item 1 of the patent application scope includes zinc phthalocyanine. 8. An optoelectronic device, characterized in that it includes a device that converts electrical energy into light energy or converts light energy into electrical energy. The device includes, for example, patent application scopes 1, 2, 3, 4, 5, 6, and / or 7 The cathode of the item. 9. An organic light emitting device, characterized by comprising a heterostructure for generating electroluminescence, wherein the heterostructure includes a cathode such as those in the scope of patent applications 1, 2, 3, 4, 5, 6, and / or 7. 1 0. An organic laser, characterized in that it includes an organic laser as described in the scope of patent applications No. 1, 2, 3, 4, 5, 6, and / or 7. 1 1. A method for manufacturing an optoelectronic device, comprising: manufacturing an optoelectronic device, wherein the manufacturing method includes the steps of: wherein the semiconductor organic layer is in which the semiconductor organic layer is in which the semiconductor organic layer is O: \ 55 \ 55293.ptc Page 115 476227 Case No. 87116739 0 In the following year, the special layer is revised. In the main month, the ft area, the plane with six planes, and the two planes should form a warp-shaped plane across the lower plane and lower plane. Table, the timing of the layer is extremely negative, so the layer is an electric light, which is used as the electrical layer guide. The product that should sink to the top and the voltage to conduct the tr conductivity is the method of its method. 1 × 1 Eyebrow 1 Fan Wei Li, please apply as little as possible to the gap zone to include the 3 layers. Gap body band conduction energy, half-gap wideband, the energy should be wide and wide, the children of Fattefang Vol., _ 1 1 1 Fan Wei Li, please apply for as little as possible light transmission and acceptance In the body guide semi-percentage machine, the body guide has the method of its method IX τ-< Di Wei Fanli specially requested to apply the system if the system has a body guide. The law, the object, and the combination of terms \) y τ— * 0 1i en C round a y Fan Polley. cThe province's green-small-ti polygphthalic acid enveloping the U-bracketing charter has a body guide. Among its legal methods, IX T-H. Fan Li specially requested to apply the Ru-phthalocyanine copper-cladding laminating machine with a body guide. Half: The envelopment includes its special features in the law, the 11th law of the Fangwei Fan Jieli (Yin-Jing-I, please make the two-in-one package • 7 series 8 layers of extremely Yin Layered gold J ± L ¥ The electrical conductance package includes a preparation of the semi-conductor half-layer in the shape of the square body. The machine and the material body are made of semi-gold and non-layered fi-metallic electrical conductors. The realm is in this step: the middle step, including the enveloping method, the boundary layer machine 9 has a contact resistance that is lower than the gold non-sense conductance, and the legal method of the item. 8 Fan Li, please apply as the first day [卩"Nap tolerance" and bb XV please enter the # Shen ☆ package. For the children of the Fattfang Volt that leads to as little as 20 layers of electricity, 8 light-transmitting bands. , Degree. Half-gap width ratio of conduction energy of gap body band is 100% O: \ 55 \ 55293.ptc Page 116 47622 7 _ Case No. 87116739 ^ 0 year (丨 Monthly Amendment_) VI. Patent application scope 2 1. The method of claim 18, wherein the semiconductor organic layer includes a polyacene compound. 2 2. For example, the method of claim 18, wherein the semiconductor organic layer system includes phthalocyanine. 2 3. The method of the claim 18, wherein the semiconductor organic layer system includes copper cyanine. 2 4. The method of claim 18, wherein the semiconductor organic layer system includes zinc phthalocyanine. 25. A laminated organic light-emitting device including a first heterostructure to generate electroluminescence, and a second A heterostructure is used to generate electroluminescence, and the second heterostructure is laminated on the first heterostructure; at least one heterostructure includes, for example, patent application scopes 1, 2, 3, 4, 5, and 6 And / or the cathode of item 7. 2 6. A method for manufacturing an organic light-emitting device, which is characterized by including preparing a heterostructure for generating electroluminescence, wherein the preparation method includes forming a # 1, 2 , 3 The steps of the cathode of items 4, 5, 6, and / or 7. 2 7. The organic light-emitting device according to item 9 of the patent application scope, wherein the heterostructure further includes a charge carrier layer, wherein the charge carrier layer includes A compound having a molecule having at least one electron-transporting moiety and at least one hole-transporting moiety. The electron-transporting moiety is a 2-fluorenyl-8-quinolinate complex ligand coordinated to a metal selected from A1, Ga, and In. . 28. The organic light-emitting device according to item 27 of the patent application scope, wherein the gold O: \ 55 \ 55293.ptc Page 117 476227 _ Case No. 87116739 丨 丨 Month Revision _6. The scope of patent application belongs to A 1. 29. The organic light-emitting device according to item 27 of the patent application scope, wherein the hole transporting portion is an hole transporting amine portion. 30. The organic light-emitting device according to item 27 of the patent application scope, wherein the hole transporting part is a triarylamine-derived phenate. 31. The organic light-emitting device according to item 27 of the scope of patent application, wherein the compound has two 2-methyl-8-quinolinate complex ligands coordinated to A 1 as an electron transporting moiety, and one The triarylamine is derivatized with a phenate as a hole transporting moiety. 32. The organic light-emitting device according to item 27 of the application for a patent, wherein the compound is bis (2-fluorenyl-8-phosphonium acid complex) [p- (N-phenyl-2-mercaptoamino) ) Phenolate complex] aluminum (II I). 3 3. The organic light-emitting device according to item 27 of the application, wherein the compound is bis (2-methyl-8-quinolinate complex) (p-carbazole phenolate complex) aluminum (III). 3 4. The organic light-emitting device according to item 27 of the scope of patent application, wherein the compound is bis (2-methyl-8-quinolinate complex) (m-carbazole phenolate complex) aluminum (Π I) . 35. The organic light-emitting device according to item 27 in the scope of patent application, wherein the charge carrier layer is an emission layer. 36. The organic light-emitting device according to item 27 of the scope of patent application, wherein the charge carrier layer is an individual emitting layer with a double heterostructure. 37. The organic light-emitting device according to item 27 of the scope of patent application, wherein the charge carrier layer is a single-structured electron transport layer. O: \ 55 \ 55293.ptc Page 118 476227 _ Case No. 87116739 Gas c > Modification of year M month _ 6. Application for patent scope 3 8. For the organic light-emitting device with the scope of patent application No. 27, wherein the charge is The carrier layer is an electron injection layer sandwiched between the cathode and an electron transport layer. 39. The organic light-emitting device according to item 27 of the patent application, wherein the charge carrier layer comprises the compound doped with a dye. 40. The method according to item 26 of the patent application scope, wherein the preparation method further comprises a step of forming a charge carrier layer, wherein the charge carrier layer includes at least one electron transporting portion and at least one hole in the molecule. A compound of a transporting moiety, the electron transporting moiety is a 2-fluorenyl-8-quinolinate complex ligand coordinated to a metal selected from A1, Ga, and In. 41. The organic light-emitting device according to item 9 of the scope of patent application, wherein the heterostructure further includes an emission layer containing a dopant compound having a chemical structure of the formula C-I: Wherein R is hydrogen or a donor or acceptor group relative to the hydrogen system, R 'is an alkyl group or a substituted or unsubstituted aryl group; R1 and R2 are hydrogen or a bond to form a condensation Aryl ring; X is 0; NR5, where R5 is hydrogen or substituted or unsubstituted alkyl; alkyl or substituted or unsubstituted aryl; O: \ 55 \ 55293.ptc Page 119 476227 _ Case No. 87116739 4 Leap Year 丨 丨 Month Amendment _ 6. The scope of patent application Z 1 and Z 2 are each a carbon atom or a nitrogen atom; and the ammonium system is M ( —Metal atom), and at this time both Z1 and Z2 are nitrogen atoms; the actinide is 0; NR 6, where R 6 is hydrogen or a substituted or unsubstituted alkyl group; or S; at this time Z 1 And Z 2 are both carbon atoms; or actinide does not exist. 42. The organic light-emitting device according to item 41 of the scope of patent application, wherein Z 1 is a carbon atom, Z 2 is a nitrogen atom, X is an oxygen atom, and thallium is absent, wherein the dopant compound has Chemical structure of formula C-II: (C-II) 4 3. The organic light-emitting device according to item 42 of the patent application range, wherein the dopant compound has a chemical structure of the formula C-II, wherein R1 and R2 are hydrogen, R is difluorene, and R '= C6H5. 4 4. The organic light-emitting device according to item 42 of the application, wherein the dopant compound has a chemical structure of formula C-I I, wherein R1 and R2 are hydrogen, R = 00CCH3 and R '= C6H5. 4 5. The organic light-emitting device according to item 42 of the application, wherein the dopant compound has a chemical structure of formula C-II, wherein R1 and R2 are hydrogen, R = N (CH3) 2 and R '= C6H5. O: \ 55 \ 55293.ptc Page 120 476227 Amendment No. 87116739 6. Application for patent scope 46. For the organic light-emitting device with the scope of patent application No. 42, wherein the dopant compound has a chemical structure of formula CI I Where R1 and R2 are hydrogen, R = C (CH3) and R '= C6H5. 47. The organic light-emitting device according to item 41 of the scope of patent application, wherein the dopant compound has a chemical structure of the formula C-I V: (C- / V) where R '= C6H5. Wherein, the dopant is 48. The organic light-emitting device such as the item 41 of the patent application range has a chemical structure of the formula C_V: (C-V) (CH3 > 2N Wherein, the dopant is 49. The organic light-emitting device according to item 41 of the patent application has a compound structure of the formula C-V I: O: \ 55 \ 55293.ptc Page 121 476227 Case No. 87116739 6. Scope of Patent Application Amendment (ch3) 2n (C-VI) Wherein, the cathode layer and the electricity are used. For example, the organic light-emitting device of item 41 of the patent application to generate electroluminescence heterogeneous structure sequentially includes a substrate sub-transport layer, a hole transport layer and an anode. Floor. Among them, the anode layer and the electricity 51. The heterogeneous structure for generating electroluminescence, such as the organic light-emitting device of item 41 of the patent application, sequentially includes a substrate hole transport layer, an electron transport layer, and a cathode layer. 5 2. The method according to item 26 of the patent application range, wherein the preparation method further comprises a step of forming an emission layer, the emission layer containing a dopant of the formula C _ I Compound: R R · wherein R is hydrogen or a group relative to the hydrogen system as a donor or acceptor R 'is an alkyl group or a substituted or unsubstituted aryl group; R 1 and R 2 are hydrogen or a bond Form a fused aryl ring; X is 0; NR5, where R5 is hydrogen or substituted or unsubstituted alkyl; alkyl or O: \ 55 \ 55293.ptc Page 122 476227 _ Case No. 87Π6739 I January 1st amendment_ VI. A substituted or unsubstituted aryl group in the scope of patent application; Z 1 and Z 2 are each a carbon atom or nitrogen Atom; and Y is M (-metal atom), and at this time both Z1 and Z2 are nitrogen atoms; Υ is 0; NR 6, wherein R 6 is hydrogen or substituted or unsubstituted alkyl Or S; at this time, Z 1 and Z 2 are both carbon atoms; or actinide does not exist. 5 3. — A compound having a chemical structure of formula C-I: Where R is hydrogen or a donor or acceptor group relative to hydrogen; R 'is an alkyl or substituted or unsubstituted aryl; R1 and R2 are hydrogen or bonded to form a thick Aryl ring; X is 0; NR5, where R5 is hydrogen or substituted or unsubstituted alkyl; alkyl or substituted or unsubstituted aryl; ZA 1 and ZA 2 are each carbon Atom or nitrogen atom; and Υ is M (-metal atom), and at this time both Z1 and Z2 are nitrogen atoms; Υ is 0; NR 6, where R 6 is hydrogen or substituted or unsubstituted Alkyl group; or S; at this time, Z 1 and Z 2 are both carbon atoms; or actinide does not exist; the prerequisite is that when actinide does not exist, Z 1 is a carbon atom O: \ 55 \ 55293.ptc Page 123 476227 _ Case No. 87116739 Amendment_ VI. When the scope of patent application and Z 2 system is nitrogen atom, R system is donor or acceptor group relative to hydrogen system Group of groups. 54. The compound according to item 53 of the scope of patent application, wherein Z 1 is a carbon atom, Z 2 is a nitrogen atom, X is an oxygen atom, and Y is absent, wherein the compound has the formula C-II Chemical structure: 55. The compound according to item 54 of the scope of patent application, wherein the compound has a chemical structure of formula C-II, wherein R1 and R2 are hydrogen, R = 00CCH3 and R 'di C6H5. 56. The compound according to item 54 of the scope of patent application, wherein the compound has a chemical structure of formula C-II, wherein R1 and R2 are hydrogen, R = N (CH3) 2 and R, = C6H5. 57. The compound according to item 54 of the scope of patent application, wherein the compound has a chemical structure of formula C-II, wherein R1 and R2 are hydrogen, R = C (CH3) and R'-C6H5. 58. The organic light-emitting device according to item 9 of the application, wherein the heterostructure further includes an emission layer containing a phosphorescent dopant compound. 59. The organic light-emitting device according to item 58 of the application, wherein the emitting layer is an electron transporting layer. 60. The organic light emitting device according to item 58 of the scope of patent application, wherein the light emitting device O: \ 55 \ 55293.ptc Page 124 476227 _Case No. 87116739 Modified U_Year _ Amendment_ VI. Scope of patent application The radioactive layer is a hole transporting layer. 61. The organic light-emitting device according to item 58 of the scope of patent application, wherein the phosphorescent dopant compound has a phosphorescent activity of not more than about 10 microseconds. 62. The organic light-emitting device according to item 58 of the application, wherein the phosphorescent dopant compound has a chemical structure of formula D-I: ·· Wherein X is C or N; R8, R9 and R10 are each selected from hydrogen, alkyl, substituted alkyl, aryl and substituted aryl; R9 and R10 can be combined to form a fused ring; M1 is a divalent, trivalent, or tetravalent metal; and a, b, and c are each 0 or 1; wherein, when X is C, a is 1; when When X is N, a is O: \ 55 \ 55293.ptc Page 125 476227 _ Case No. 87116739 ^ 0 year 1 \ Month day amendment_ VI. Patent application scope 0; when c is 1, b is 0; and when b is 1 In this case, c is 0. 63. The organic light-emitting device according to item 58 of the scope of patent application, wherein the phosphorescent dopant compound is octaethylpyrene platinum and has a chemical structure of the following formula: Et Et 64. The organic light emitting device according to claim 63, wherein the phosphorescent dopant compound is doped in an electron transporting layer containing tri- (8-hydroxyquinoline) aluminum. 65. The organic light-emitting device according to item 64 of the patent application scope, wherein the heterostructure for generating electroluminescence includes a hole transport layer including N, N'-diphenyl-N, N'-bis ( 3-methylphenyl) -1,1'-biphenyl-4,4'-diamine. 6 6. The organic light emitting device according to item 64 of the patent application scope, wherein the phosphorescent dopant compound generates a saturated red emission having a peak at about 640 nm. 6 7. The organic light-emitting device according to item 58 of the patent application scope, wherein O: \ 55 \ 55293.ptc Page 126 476227 _ Case No. 87116739 B ^ year \ 丨 month day__ VI. Heterostructures that apply for patents to generate electroluminescence sequentially include a substrate, a cathode layer, and an electron transport layer , Hole transport layer and anode layer. 6 8. The organic light-emitting device according to item 58 of the scope of patent application, wherein the heterostructure for generating electroluminescence includes a substrate, an anode layer, a hole transport layer, an electron transport layer, and a cathode layer in order. 69. The laminated organic light-emitting device according to item 25 of the patent application scope, which includes at least one heterogeneous structure of a conductive non-metal layer in low-resistance contact with the semiconductor organic layer, and further includes an emission layer containing phosphorescent doping剂 组合 物。 Agent compounds. 70. The method of claim 26, wherein the preparation method further includes a step of forming an emission layer, the emission layer containing a phosphorescent dopant compound. 71. The organic light-emitting device according to item 58 of the application, wherein the phosphorescent dopant compound has a chemical structure of the formula E-1 I: O: \ 55 \ 55293.ptc Page 127 476227 Amendment No. 87116739 丨 Month and Sixth, the scope of patent application where R-group R1, R2, R3 and R4 are individually alkyl, aryl or argon, prerequisites Is at least one R group different from at least one other R group. 7 2. The organic light emitting device according to item 71 of the scope of patent application, wherein the phosphorescent dopant compound has a structure of the formula E-I I I: (ill) where R5 and R6 can be electron donors or electron acceptor groups, and R5 and R6 can be the same or different. 73. The organic light-emitting device according to item 71 of the scope of patent application, wherein the phosphorescent dopant compound has a structure of formula E-I I, wherein R 1 and R 3 are O: \ 55 \ 55293.ptc Page 128 476227 _ Case No. 87116739 (丨 Monthly Amendment _) VI. Patent application scope for hydrogen, and R2 and R4 are unsubstituted phenyl groups. 7 4. As for patent application scope The organic light-emitting device according to item 71, wherein the emission layer is an electron transport layer. 7 5. The organic light-emitting device according to item 71 of the patent application scope, wherein the emission layer is an hole transport layer. 7 6. The organic light-emitting device according to item 71 of the patent application, wherein the phosphorescent dopant compound has a phosphorescence activity of not more than about 10 microseconds. 7 7. The organic light-emitting device according to item 71 of the patent application, wherein the phosphorescence The dopant compound is doped in an electron transporting layer containing tri- (8-hydroxyquinoline) aluminum. 7 8. The organic light-emitting device according to item 71 of the patent application scope, wherein the light-emitting device is used to generate electroluminescence. The heterostructure includes a hole transporting layer containing N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine. 79. The organic light-emitting device according to item 73 of the application, wherein the phosphorescent dopant compound is doped. In the electron-transporting layer containing tri- (8-hydroxyquinoline) aluminum. 80. The organic light-emitting device according to item 79 of the patent application scope, wherein the heterostructure for generating electroluminescence includes a hole-transporting layer, Contains N, N'-diphenyl-1'-bis (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine. 8 1. As claimed in the scope of patent application No. 7 3 Item of the organic light emitting device, wherein the phosphorescent dopant compound generates saturated red emission having a peak at about 630 nm. 8 2. The organic light emitting device according to item 71 of the patent application range, wherein the device is used to generate electricity. The heterogeneous structure of photoluminescence includes a substrate, a cathode layer, O: \ 55 \ 55293.ptc Page 129 476227 Case No. 87116739 said Amendment 6. Scope of patent application Sub-transport layer, hole transport layer and anode layer. 8 3. The organic light-emitting device according to item 71 of the scope of patent application, wherein the heterostructure for generating electroluminescence includes a substrate, an anode layer, a hole transport layer, an electron transport layer, and a cathode layer in order. 8 4. The laminated organic light-emitting device according to item 69 of the application, wherein the phosphorescent dopant compound has a chemical structure of the formula E-1 I: Rb (II) wherein R-groups R1, R2, R3 and R4 are each alkyl, aryl or hydrogen, a prerequisite is that at least one R group is different from at least one other R group. 85. The laminated organic light-emitting device according to item 69 of the patent application scope, wherein the phosphorescent dopant compound has a structure of the formula E-I I I: O: \ 55 \ 55293.ptc page 130 476227 case number 87116739 c7 year I \ month said amendment VI. Scope of patent application Rs (III) wherein R 5 and R 6 may be electron donors or electron acceptor groups, and R 5 and R 6 may be the same or different. 86. The laminated organic light-emitting device according to item 84 of the application, wherein the phosphorescent dopant compound has a structure of formula E-II, wherein R1 and R3 are hydrogen, and R2 and R4 are Substituted phenyl. 8 7. The method according to item 70 of the scope of patent application, wherein the phosphorescent dopant compound has a chemical structure of the formula E-I I: O: \ 55 \ 55293.ptc Page 131 476227 O: \ 55 \ 55293.ptc Page 132 476227 Amendment No. 87116739 Hum 〇 丨 | Month Sixth, scope of patent application r5 (IN) where R5 and R6 can be electron donors or electron acceptor groups, and R5 and R6 can be the same or different. 89. The method according to item 87 of the scope of patent application, wherein the phosphorescent dopant compound has a structure of the formula EI I, wherein R1 and R3 are hydrogen, and R2 and R4 are unsubstituted phenyl groups. . 90. The organic light-emitting device according to item 9 of the application, wherein the heterostructure further includes a hole transporting layer having a glass structure, wherein the hole transporting layer includes a compound having a symmetrical molecular structure, and the molecular terminal group is O: \ 55 \ 55293.ptc Page 133 476227 _ Case No. 87116739 丨 丨 Month Revision _ 6. Application for Patent Scope The amine moiety is transported in the hole with unsaturated bond between two aliphatic aromatic hydrocarbons. 91. The organic light-emitting device according to claim 90, wherein the compound has the following formula: Where A includes mono or diphenyl, R1 and R2 are each selected from hydrogen, alkyl, phenyl, substituted alkyl, and substituted phenyl, and R1 and R2 can be bridged 0 9 2. If applied The organic light-emitting device according to item 91 of the patent, wherein the compound has the following formula: O: \ 55 \ 55293.ptc Page 134 476227 _ Case No. 87Π6739 ^ C7 I I Month Day Amendment 6. Scope of patent application The compound has the following formula: 9 4. The organic light-emitting device according to item 91 of the application, wherein the compound has the following formula: 95. The organic light-emitting device according to item 91 of the application, wherein R 1 and R 2 are the same. 96. The organic light-emitting device according to item 91 of the application, wherein R 1 and R 2 are different. 9 7. The organic light-emitting device according to item 90 of the patent application scope, wherein O: \ 55 \ 55293.ptc Page 135 476227 _ Case No. 87116739_ Year ^ Month Day Amendment 6. Scope of Patent Application The compound has the following formula: 98. The organic light-emitting device according to item 90 of the patent application scope, wherein the compound is a main component of the hole transport layer. 99. The organic light-emitting device according to item 90 of the application, wherein the compound is a dopant for a hole transport layer. 100. The organic light-emitting device according to item 90 of the scope of patent application, wherein the heterostructure used to generate electroluminescence sequentially includes a substrate, a cathode layer, an electron transport layer, a hole transport layer, and an anode layer. 101. The organic light-emitting device according to item 90 of the scope of patent application, wherein the heterostructure used to generate electroluminescence includes a substrate, a cathode layer, an electron transport layer, a hole transport layer, and a hole injection layer. And anode layer. 102. The organic light-emitting device according to item 90 of the scope of patent application, wherein the heterostructure used to generate electroluminescence includes a substrate, a cathode layer, an electron transport layer, an emission layer, a hole transport layer, and an anode. Floor. 103. The organic light-emitting device according to item 90 of the scope of patent application, wherein the heterostructure for generating electroluminescence includes a substrate, a cathode layer, O: \ 55 \ 55293.ptc Page 136 476227 _ Case No. 87116739 丨 January Day Amendment_ VI. Scope of patent application Sub-transport layer, hole transport layer, emission layer, hole injection layer and anode layer. 104. The organic light-emitting device according to item 90 of the patent application scope, wherein the heterostructure for generating electroluminescence includes a substrate, an anode layer, a hole transport layer, an electron transport layer, and a cathode layer in order. 105. The method of claim 26, wherein the preparation method further comprises the step of forming a hole transporting layer having a glass structure, wherein the hole transporting layer includes a compound having a symmetric molecular structure, and its molecular ends The base system transports an amine moiety through an electric hole having an unsaturated bond between two aliphatic aromatic hydrocarbons. 1 06. The organic light-emitting device according to item 9 of the application, wherein the heterostructure further includes a hole transporting layer having a glass structure, and the hole transporting layer includes a compound having the following molecular formula: 1 0 7. The organic light-emitting device according to item 9 of the application, wherein the heterostructure further includes a hole transporting layer having a glass structure, and wherein the hole transporting layer includes a compound having the following molecular formula: O: \ 55 \ 55293.ptc Page 137