TW385620B - An organic light emitting device containing a protection layer - Google Patents

Abstract

The present invention is directed to organic light emitting devices comprised of a heterostructure for producing electroluminescence, wherein the heterostructure includes a protection layer between a hole transporting layer and an indium tin oxide anode layer. The hole injection enhancement layer may be comprised of 3, 4, 9, 10-perylenetetracarboxylic dianhydride (PTCDA), bis(1, 2, 5-thiadiazolo)-p-quinobis (1, 3-dithiole) (BTQBT), or other suitable, rigid organic materials. The present invention is further directed to methods of fabricating such devices, wherein the devices may include alternative combinations of materials for each of the layers included in the devices.

Description

A7 B7 V. Description of the invention. (1) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The present invention relates to an organic light emitting device including a protective layer between the hole transport layer and the ITO anode layer. Bright background organic light emitting devices (OLEDs) are light emitting devices that include several layers, one of which includes an organic material that can electrically excite light by applying a voltage across the device 'c. W. Tang et al., Applied Physics Letter (Appi. Phys. Lett) 51, 913 (1987). It has been confirmed that certain LEDs have sufficient brightness, color range, and operating life (SR Forrest, PE Burrows and M.E. Thompson), which are used as an alternative to LCD-based full-color plane display technology. Laser Focus World, February 1995). In addition, since many organic thin films used in these devices are transparent in the visible spectral region, they can obtain entirely new types of display pixels, among which red (R), green (G), and blue (B) emissions The layers are arranged in a vertically stacked shape to provide a simple manufacturing method, a small RGB pixel size, and a large fill factor. Transparent OLEDs (TOLEDs), which represent important steps towards achieving high-resolution, independently addressable stacking pixels, have been published in International Patent Applications PCT / US95 / 15790 and PCT / US97 / 02681. It is reported that these TOLEDs can have a transparency of greater than 71% when turned off, and can emit light with high probability (close to 1% quantum efficiency) from both the top and bottom device surfaces when the device is turned on. This TOLED uses hand-transparent indium tin oxide (ITO) as a hole injection electrode, and uses Mg-Ag-ITO layer for power supply (for sub-injection. It published a method using Mg-Ag-ITO electrode for stacking on top of TOLED- 4- This paper scale is applicable to China D house standard rate (CNS) A rule ^ (21〇χ297 seam) (Please read the precautions on the back before filling this page) Γ Binding-Order V. Description of the invention (2) A7 B7 Device of the second different-color emitting OLED hole injection contact printed on the staff consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. Each of a stack of 40 LEDs (S0 ^ ED) including a plurality of vertically stacked layers The device can be addressed independently and emit its own characteristic color through the transparent organic layer, transparent contacts, and glass substrate, so that the device can emit any color that can be produced by changing the relative output of the red and blue emitting layers. The PCT / US95 / 15790 announcement provides the disclosure of an overall OLED that can use external power supplied in a color-adjustable display device to independently change and control the intensity and color. In this way, the PCT / US95 / 15790 description was obtained by close Pixel size Principles of Feasibility of Providing Overall, Full-Color Pixels with High Image Resolution "In addition, this device can be manufactured using relatively low-cost manufacturing techniques compared to previous techniques. Its structure is based on the use of layers of organic optoelectronic materials The device generally relies on a common mechanism that causes light emission. The typical mechanism of this mechanism is based on the recombination of centrally charged radiation. Specifically, the organic light emitting device includes a thin organic layer of at least two anodes and cathodes of the separation device. The material of one of these layers is selected specifically based on the energy addition of the material transport hole ("hole transport layer" or "HTL"), and the material of one of the other layers is specifically based on its The ability to transport electrons is selected ("electron transport layer" or METL "). With this structure, when the potential energy applied to the anode is higher than the potential energy applied to the cathode, can the device be regarded as having a forward bias? Diode. Under these bias conditions, impotence injects holes (positive charge) into the hole transport layer, and at the same time injects electrons into the electron sample layer. " Therefore, the light-emitting medium adjacent to the anode forms a hole injection and transportation area, and the light-emitting medium adjacent to the cathode forms a hole injection and transportation area. The injected holes and electrons-·----- Packing-* t (Please read the note on the back before filling in this page) The silver scale of the paper is applicable to the Chinese National Sample (CNS) A4 specification (21〇 > < 297 mm) A7 B7 ---- --- V. Description of the invention (3) Each initial move to an electrode with opposite charge. When the electron public electricity _ is on the molecule, 'Frenkel e? Ccit ^ || ^ ^ short-lived state recombination It is conceived that the electrons will relax from their conduction potential. In some cases, it will be preferentially passed through photoelectricity. From the viewpoint of the operating mechanism of this typical thin-layer organic device, electricity is taught. Including the light-emitting area that receives the flow of charge carriers (electrons and holes) from each electrode ^ The materials that generate the electrically excited light emission are often the same materials used as the electron carousel transport layer. Such a device is referred to as having a single-heterogeneous $. Alternatively, the electro-optically excited material family may exist in a separate emitting layer in the hole transport layer and the electron casting room, which is called a double-poor heterogeneous structure. In addition to making the emission material the main material in the electric transport layer or the electric temple embankment, the emission material can also be included in the main material section. ^ Although fee I 〇 exists as the main pair and dopant The materials are selected so that there is sufficient energy transmission between the main materials department and the dopant materials department of the Central Bureau of Standard Vehicles of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives. It is hoped that OLEDs are made of materials that provide electrically excited light emission in a relatively narrow energy band 2 centered near the selected spectral region. This spectral region is equivalent to the need to color and postscript-one of them-so that π: Colored layer in OLED or SOLED. It is particularly desirable that these compounds = basic generations. The types of compounds emitted can be changed by selectively changing substituents or by modifying the structure of the emitting emissive compounds. In addition, the emitter must be able to produce acceptable electrical properties for the OLED. In addition, these materials and androgen-doped materials may be easily incorporated into the hole transport layer or the electron transport layer by using a convenient manufacturing technique. It may be preferable to use them in an OLED. 6 This paper is suitable for financial standards A7 B7 V. Description of the invention (4) The display of the effective electro-excitation light from the airborne molecular organic light emitting device printed by the Office of the Central Bureau of Standards, Ministry of Economic Affairs, and the Consumer Cooperatives has inspired it as an emission plane Potential applications shown. In order to be effectively used for low-cost active arrays, it is necessary to show a device structure capable of integrating pixel electronics. Conventional OLEDs are grown on transparent electrodes such as ITO, and the emitted light is viewed through the substrate, which complicates the integration of electronic components such as silicon-based display drivers. It is therefore desirable to develop an OLED that emits light via transparent contacts on the top. Surface-emitting polymer-based OLEDs grown on silicon with transparent ΊΤ 半 and translucent Au or A1 top anodes have been shown, DR Baigent et al., Applied Physics Letters, 65, 2636 (1994); HH Kim et al., Journal of Lightwave Technology ( J. Lightwave Technol.), 12, 2107 (1994) Similar integration of molecular OLED capture was achieved using the Turner Si02 interface, Kim et al. However, the Turner interface will increase the operating power of the device and can be avoided in structures such as the recently published transparent TOLEDs, V. Bulovic et al., Nature 380, 29 (1996); G. Gu et al., Applications Physical Letter, 68, 2606 (1996), which can be grown mainly on silicon substrates. However, TOLED anodes form electrode contacts that directly contact the substrate, "bottom contacts". However, for display drivers using n-channel field effect transistors (NFETs), such as amorphous silicon NFETs, OLEDs The bottom contact is the cathode. This will require the fabrication of inverting OLEDs (IOLEDs), which reverse the order of the layers on the substrate. For example, for OLEDs with a single heterogeneous structure, electrons are injected into the cathode layer and deposited on the substrate Above, the electric pre-transport layer is deposited on the cathode (electrode transport layer is deposited on the electron transport layer, and the hole injection anode layer is deposited on the hole »—, J C. (Please read the precautions on the back before filling in this Page) Order-1 />.-rv This paper size applies to China's national standard (CNS > A4 specification (2 丨 0X297)) A7 B7 V. Description of the invention (5) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Therefore, the fabrication of such IOLEDs will require direct or indirect sputtering deposition of the IT0 anode layer on a rather fragile alkali-based film. Since the ITO layer is typically deposited by conventional sputtering or method To produce with about 5 The thickness of 00 Angstroms is as high as 4000 Angstroms, so it is desirable that these layers be deposited at the highest possible deposition rate and the time required to prepare these layers. For example, it has been found that when 1 is on an exposed substrate, the ιτο layer can The deposition rate of β is more than 50-100 angstroms. However, if IT0 is directly deposited on the machine layer or the Mg: Ag surface that is typically deposited on several organic layers, the deposition rate may only be about 2- 5 Angstroms / minute. Because the organic layer is highly vulnerable to damage when subjected to high energy particle beams used at higher ITO deposition rates, higher deposition rates can surprise the underlying organic layer and cause substantial damage. The OLED's overall performance caused an unacceptably large deterioration. When the ITO layer of the OLED is deposited on such a fragile organic surface, the ITO layer can be deposited at a substantially higher deposition rate than what has been feasible so far. "It will be better" In addition, if the hole injection characteristics of the hole injection layer can be improved, it will be proved that CuPc can be used as an effective hole injection layer in conventional OLEDs, SA VanSlyke et al. , Applied Physics No. 69, 216〇 (1996) and U.S. Patent No. 4,720,432, and 3,4,9,10-chitratetracarboxylic dianhydride (? 1 ^ 08) has been previously established as a hole transporting layer, PE Burrows Correspondence of Applied Materials, 64, 2285 (1994), V. Bulovic et al., Chemical Physics (Chem. Phys.) Il0, 1 (1996) •, and V. Bulovic et al., Chemical Physics, 210, 13 (1996). In addition, this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm).

Order 1 * A7 __B7 V. Description of the invention (6) Printed by Fangong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs, it has been previously verified that PTCDA, FF So, etc. are used in the structure of the photodetector with ITO electrodes deposited on the film surface Human, IEEE. Trans. Electron. Devices 36,% 6 (1989). This material can withstand the spray deposition of ITO with minimal degradation of its conductive properties. Conventional displays, including LCD (liquid crystal) and conventional OLED (organic light emitting device) displays, have additional disadvantages that are not well suited for viewing under bright ambient light. As explained in 圏 21, from a bright light source L, such as the sun, the light R is emitted from one or more layers (mainly metal layers) of the display D. The reflected light R interferes with the viewer's ability to view the message with light I produced by display D, thereby reducing the perceptual comparison of the image produced by display D. Therefore, there is a need for OLED cheek displays with improved contrast that can be viewed in bright ambient light conditions. SUMMARY OF THE INVENTION The present invention relates to OLEDs including a heterogeneous structure for generating electrical excitation light, and a method for manufacturing such OLEDs, in which the heterogeneous structure is included between the cable transport layer and the ITO anode layer to protect the underlying layer. The organic layer is a layer that is protected from damage during the ITO sputtering deposition process. One of the characteristics of the present invention is that the protective layer in the OLEDs can not only be used to protect the undercut layer, but also the protective layer can be provided as a hole injection implantation layer. For example, the protective layer in U.S. Serial No. 08 / 865,491, filed on May 29, 1997, can also be used as a hole injection enhancement layer. Examples of preferred embodiments of the present invention include PTCDA or Nobuyuki Ayaka Based compounds. '' The present invention is more about the improved method of ITO layer for OLED, in which the national paper (CNS) A4 specification (210X297 mm) is applied at -9- this paper size (please read the note on the back of the ® before filling in This page). Binding V. Description of the invention (7) A7 B7 In the process of preparing the ITO layer by the seal of the Shell Industry Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, the capture rate of self-service meals was deposited at 1τ0 layer after the degree To a sufficiently thick rate so that Shou Shimonoseki can prevent the damage of a single suction / infant. S layer. Β is more specific & the present invention (another aspect is about 50 to about 200 angstroms to about 200 angstroms) After the thickness of the layer, the initial f product rate is increased by 纟 "to 1. The doubling rate of the prostitute product method. To be more specific (the transfer sample of the present invention is about 2-5 at the initial deposition rate). Angstroms / minute 'and a final deposition rate of at least about 5060 Angstroms / minute. The present invention is more about a high-contrast, transparent organic light-emitting device (TOLED) display, wherein the contrast shown on the cheek is determined by Improved by minimizing the amount of reflected light. This is based on the TOLEDE structure and after the TOLED display The configuration of the low reflectance absorber is completed. TOLED has a substantially transparent conductive layer, so it will not reflect light like the conventional metal conductive layer of OLEDs. Set a low reflectance absorber behind kT〇led display It can absorb light displayed by TOLEE). Most of the light incident on the TOLEDil display is absorbed by a low reflectance absorber, and only a small amount of incident light is reflected back to the viewer. This form provides the image shown by the display The improved life ratio. The display of the present invention also shows the improved surprise ratio of different color images. The present invention is more about an OLED including a main compound and a dopant compound. The saturation wavelength of the color generates emission in a rather narrow energy band centered on the person. Those skilled in the art will know the further objects and advantages of the present invention by revealing the detailed description of the invention. 0 '-10- Guan Jia in the paper scale system _ (210X297 ^ · (Please read the note of back ig *-matter before filling out this page) Binding Α7 Β7 V. Description of the invention (8) Attached brief description Circle 1 shows the generation of a single heterogeneous structure device Exemplary IOLED »Shoulder 2 shows the forward bias current of 0.05mm IOLED with PTCD Α and Cu Pc protective capping layer (PCLs: Protective cap Uyer) as a hole penetration enhancement layer and devices without PCL- Voltage (IV) characteristics. 蹰 3 shows the relationship between the luminous intensity and current (LI) of IOLEDs in ® 2. Circle 4 shows that IOLEDs with a hole injection enhancement layer are compared to the conventional Alq without a hole injection enhancement layer. ^ OLED ^ EL characteristics of the shape of the emission spectrum. ’-Circle 5 shows the current versus voltage of the OLED with and without the 60 angstrom PTDCA layer between the ITO anode layer and the NPDf hole transport layer. Circle 6 shows a cross section of an OLED comprising an ITO layer prepared in two stages. The first stage is prepared using a low ITO deposition rate, and the second stage is prepared using a substantially higher ITO deposition rate. Circle 7 shows the resistance of a layer of 200 (" standard "cubic centimeters per minute) of Ar and a 1000 Angstrom layer deposited on glass at 5 milliseconds, a force of 5 millivolts, and +5 watts of RF power. The rate is a function of the flux as a function of flux. B 8 shows the change in the function of watt flux absorbed as a function of wavelength for a 1000 Å thick ITO layer deposited at 45 watts of RF power (for 200). Printed by scctn Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs

Ar flow rate, 5 mTorr pressure, .0.8 Angstrom / second rate on glass substrate). , Circle 9 shows the IV characteristics of to LEDs manufactured using higher ITO deposition rates (as shown by small hollow circles) and the ITO layer ’s IV characteristics (virtual Line). II 11- This paper size applies to Chinese National Standard (CNS) A4 specifications (V. Description of invention (9) A7 B7 Seal circle of the Military Industry Cooperative Cooperative of the Central Standards Bureau of the Ministry of Economy 10 Representative OLED showing a single heterogeneous structure device »躅11 shows the first spectrum of the photon's excitation light (PL) of ginseng (5-hydroxy-quinoline) aluminum, ginseng (5-hydroxy-quinoline) aluminum, and (5-hydroxy-quinoline) gallium. Fig. 12 shows the emission layer containing para- (5-hydroxy-quinoxaline) aluminum, with and without the biphenyl square acid squiliutn compound of formula III, which is the electro-excitation light of the dopant OLED Spectral_. 'Circle 13 shows the ι_ν characteristics of the ginseng (5-Wilky-Junlin) with and without bis-phenyl square acid hydrazone compound of formula VI with and without chemical formula. 14 shows the main compound The photon excitation light spectra of Alq3 and Alx3 are compared with the winter absorption spectrum of dopants. Among them, the dopant: the internal salt of bisphenyl square acid radium dye (" BIS-OH "), indigo dye compound and fullerene ) Compound, C60. Circle 15 蒴 shows the photon excitation spectrum of the dopant compound in solution, bisphenyl &Quot; BIS-OH "(in CH2CI2), indigo dye compound (in DMSO), and C60 (in methylbenzyl) of square acid dysprosium dye. 躏 16 _shows electrical excitation of TPD-Alq3 / C6 () device The light spectrum is a function of increasing the C60 concentration in the main material of Alq3. Circle 17 shows the TPD-Alq3 / (bisphenol square acid drill "material of chemical formula XI") equipped with a lack of electroluminescence. The light emission spectrum becomes the bisphenol square in the Alq3 main material A function of the dopant concentration of the honeycomb medium. 'Circle I.8 # shows the electric excitation spectrum of the TPD-A 丨 x3 / (Bisphenol square acid dysprosium dye of the chemical formula XI) device into the bismuth in the ΑΓχ3 main material Function of square acid laser doping concentration. ≪ Figure 19 shows TPD-Alx.3 / Ind-12 with 1.7% indigo dye and compound concentration. The paper size is applicable to Chinese National Standard (CNS) A4 specification (2丨 0X297 rye) (Please read back the note of Qin before || fill this page) Γ Pack. Order A7 ____B7 V. Description of invention (10) Printed blue &dye; The compound is charged with the electrical excitation light spectrum. Circle 20 shows a representative compilation based on chemical formula XIII.-Circle 21 shows the line of bright ambient light The conventional display device under the conditions of the display. S 22 shows the root of the high-contrast TOLED display of the present invention under bright ambient light conditions. Circle 23 is a cross-sectional circle of the first specific example of the high-contrast TOLED display according to the present invention. The circle / 24 is the cross section B of the second specific example of the high-contrast TOLED display according to the present invention. The circle 25 is a cross-sectional circle of the first stacked example light emitting device according to the present invention. " The circle 26 is a cross-section circle of a stack light emitting device according to a second embodiment of the present invention. The circle 27 is a cross-section circle of a stack of light emitting devices according to the first main embodiment of the present invention. Circle 28 is an inverted stacked light emitting device according to a specific example of the present invention. Cross Section ® »Circle 29 shows an LED with a split Bragg reflector structure. Detailed description of specific examples of school calibration The present invention will now describe in detail specific specific examples of the invention. It should be understood that these specific examples are merely illustrative examples, and the present invention is not limited thereto. The OLEDs of the present invention include a heterogeneous structure for generating electricity, which can be manufactured into a single heterogeneous structure and a double heterogeneous structure. For preparing -13- This paper size is applicable to Laijia CNS) A4 specification (2 丨 GX297 mm.-(Please read the note of the back nail *-Matters before filling this page) 'Binding A7 B7 V. Description of the invention (11) The materials, methods and devices of Yuyi or double heterogeneous organic thin film, for example, published in US Patent No. 5,554,220, the entire contents of which are incorporated herein by reference. The terms used herein are The heterogeneous structure guaranteeing the generation of electro-excitation light refers to the heterogeneous structure of a single heterogeneous structure including a hole injection layer, a hole transport layer, an electron transport layer, and a cathode layer in order. One or more of these There may be one or more additional layers between successive pairs of equal layers. For example, for a double heterogeneous structure, a separate emission layer is included between the hole rotation layer and the electron transport layer. The anode or depolarization layer Either can be contacted with the substrate, and each electrode can be transported through the device, so that it can generate electrical contacts that generate electrical excitation light from the electron order transport layer, hole transport layer or individual emission layer. The cathode layer is deposited on the substrate. The device is said to have an inverted 0LED (ILED) structure. The inverted structure can also be called " OILED " structure " such as the heterogeneous structure used to generate electrical excitation light includes part of a stacked OLED (SOLED) Then, one or both of the electrodes of the individual heterogeneous structure can be contacted with each other. Or, according to the electrical circuit used to drive the SOLED, an insulating layer can be provided between the electrodes of the OLEDs in the stack. 》 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs; -1 Pack --- -C (Please read. Read the notes on the back before filling this page) The single or double heterogeneous structure mentioned here is only As an illustration of how an OLED that can specifically implement the present invention can be manufactured, it does not mean that the present invention is limited by the specific materials or order in which the layers shown are manufactured. Soft, and / or plastic, metal or glass substrate; the first electrode, which is typically a high work function hole injection anode layer, such as an indium tin salt (ITO) anode layer; hole transport layer; electronics Transport layer ; And the second electrode layer, such as • 14- This paper size is applicable to Chinese National Standard (CNS) A4 (21 〇χ 297 mm) A7 B7 V. Description of the invention (η)

--I 'Metal-cathode layer with low work function electron injection of slow-silver alloy (Mg: Ag) or lithium-ming alloy (Li: Al). In a preferred embodiment of the present invention, the order of these layers can be reversed or reversed, so that the cathode layer directly contacts the substrate. Preferred materials that can be used as substrates in representative embodiments of the invention include, inter alia, glass, transparent polymers such as polyester, sapphire, or quartz, or virtually any other material that can be used as a substrate for OLEDs. Preferred materials that can be used as a hole injection anode layer in a representative specific example of the present invention include, in particular, ITO, Zn-In-Sn02 or Sb02, or the essence of a hole injection anode layer that can be used as an OLED Any other materials on it. Preferred materials families that can be used in the hole transport layer in the representative specific examples of the present invention include, in particular, N, N, -diphenyl-N, N, · bis (3-fluorenylphenyl) 1-1 " Toluene, 4,4'diamine (TPD), 4,4, -bis [N- (l-theyl) -N-phenyl-amino] bibenzyl (or-NPD) or 4,4 '· Bis [N- (2-fanyl) -N-phenyl-amino] biphenyl (dot · NPD). Preferred materials that can be used as the electron transporting layer include, in particular, ginseng (8 • hydroxylingoline) aluminum ( Alq3) and carbene. If there is an individual emission layer, the preferred materials that can be used as the individual emission layer include, in particular, Alq3 doped with dyes, or virtually any other material that can be used as the individual emission layer of the OLED. Where an insulating layer is present, it may include an insulating material such as SiO2, SiNx or ai2o3, or virtually any other material that may be used as an insulating material for OLEDs, which may be deposited by various methods, such as plasma to promote chemical vapor deposition ( PECVD), electron beam, etc. 'The OLEDs of the present invention may also include, for example, published in SA • 15- This paper size applies the Chinese National Standard (CNS) Α4 ^ ΤΤ ^: κ297 mm --- L ----__ ^ r equipment I- -C (Please read the * 'Note *-Matters before filling out this page) Order LI. The Central Standards Bureau of the Ministry of Economic Affairs and the Consumer Cooperatives printed and printed 5. The Invention Description (13) Α7 Β7 The Central Bureau of Standards of the Ministry of Economic Affairs Producer of Applied Labor Cooperatives, 'Applied Physics Letters' 70, UMd " 7) and Tang et al., Doped layers in Journal of Applied Physics (J. Appl. Phys.) 64, 3610 (1989) and incorporated them This article is for reference. The OLEDs of the present invention have 'different' organic materials that can completely self-deposit molecular molecules, for example, OLEDs in which some layers include polymeric materials. Polymeric materials typically require solvent-based methods, such as spin coating. The hollow deposition method, rather than the solvent-based deposition of polymeric materials, is particularly suitable for manufacturing the OLED of the present invention. Since this method can integrate all the hollow deposition steps into a single monolithic step sequence for manufacturing OLEDs, therefore, this type of The method does not require the use of solvents or the removal of air-sensitive layers from the hollow chamber, so that each layer will be exposed to environmental conditions. The hollow deposition material is preferably at about 10.5 to about 10 · 11 Tor below 1 atm. Back Material deposited in the air by pressure. Although not limited to the thickness range cited here, if the substrate is a soft plastic or metal foil substrate, such as aluminum foil, it can be as thin as 10 microns (# m), Or if the substrate is a rigid, transparent or opaque substrate or if the substrate includes a silicon-based display driver, it may be substantially thicker; the ITO anode layer may be from about 500 angstroms (1 angstrom = 10.8 cm) to Greater than about 4000 Angstroms thick; hole transport layer from about 50 Angstroms to greater than about 1000 Angstroms thick; individual emission layers of a double heterogeneous structure, if present, from about 50 Angstroms to about 200 Angstroms thick; electron transport layer from About 50 angstroms to about 1000 angstroms thick; and the metal cathode layer is from about 50 angstroms to more than about 100 angstroms thick, or if the cathode layer includes a protective silver layer and is opaque, it is substantially thicker. ^ Therefore, according to whether the package contains a single heterogeneous structure or a double heterogeneity -16- This paper size is applicable to the Chinese family standard (CNS) A4 specification (210X297 mm) (please read the note on the back before filling in this (Page). Binding. II-m 1- »5. Description of the invention (Η) A7 B7 structure, whether the device is SOLED or single OLED, whether the device is TOLED or IOLED, whether 0L £ D intends to generate emission in a better spectral region , Or whether to use other design variations, but there are substantial changes in the type, number, thickness, and order of the layers present. However, the present invention is particularly related to virtually any type of OLED structure having a protective layer between the electrical transport layer and the anode layer. More specifically, the present invention relates to an OLED including a protective layer as a protective capping layer (PCL) to reduce ITO spray damage to the underlying organic layer during the manufacturing process of the OLEDs. The invention further relates to OLEDs with enhanced hole injection efficiency properties observed for OLEDs containing such a protective layer. Improving hole injection efficiency is characterized by a higher injection current under a certain forward bias, and / or a higher maximum current before the device fails. Therefore, the "hole injection layer" is characterized by a layer with a current of at least about 10% higher than that of a similar device lacking this additional layer, typically about 50-100% or higher. Such layers are believed to provide improved coordination of the capabilities of the associated layers in a manner that results in enhanced hole injection. It can also be used as a protective layer for hole injection enhancement layer. For example, it can be formed by depositing the following compounds: * phthalocyanine compound or 3,4,9,10-Cyclotetracarboxylic dianhydride (PTCDA): ----- -· — 一: Γ 装 ——--C (#Read the notes on the back first, and then fill out this page)

• II Printed by the Central Bureau of Standards of the Ministry of Economy

乂 Double (1,2,5- 喽 Di 嗖) · Double 醗 (ι, 3-Dithiopyrene) (BTQBT), or other fast organic materials, such as the following compounds: -17- 本Paper size applies to China National Standards (CNS) A4 specifications (210X297 mm) A7 B7 5. Invention description (15)

1,4,5,8-fluorene tetracarboxylic dianhydride (1 ^ 1 ^ 0 eight):

Where R = H, fluorenyl or aryl; (Please read the precautions on the back before filling this page)

C Pack

Order 11 = 111 (1,4,5,8-fluorenetetracarbonyldiimide);

Where ruler = 0113, (] ^ ,: ^ -dimethyl-1,4,5,8-tetrakischimine); < J. Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

Where R = H, alkyl or aryl; ^ NR > > -18-This paper size applies Chinese National Standard (CNS) Λ4 specification (210X297 mm) A7 B7 V. Description of the invention (l6) where R = H , (3,4,9,10-Cyclotamidine)

Where R = CH3, (N, N, -dimethyl-3,4,9,10-endotetracarboximidine)

With the CA index name, bisbenzimidazole [2, la: l ', 2'-b ·] anthracene [2,1,9-clef.6,5, ΙΟ-dVr] bisisoquinoline-10,21- Diketone

Please read t. Ί%-Things before filling in this page

Consumers' Cooperatives, Central Standards Bureau, Ministry of Economic Affairs, India

With the CA index name, Shuangzhai [2 ·, 3 ·: 4,5] imidazole [2, la: 2 ', l'-a'] anthracene [2,1,9- and &amp; 6,5,10- 4'61,] diisoquinoline-10,21-dione; 〇 0 ^ N- has the CA index name, bisbenzimidazole [2, la: l ', 2', li] phenylhydrazone [lmn] [ 3,8] morpholine-8,1-dione; .N Λ ~ Λ .〇-Ν &gt; = &lt; Ν-〇Ν 19 This paper size applies Chinese National Standards (CNS) M specifications (210X297 mm) A7 __________ ^ __ B7 V. Description of the invention (l7) Printed by the Central Laboratories of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, with the CA index name, stupid [lmn] stilbene [2,, 3,: 4,5] imidazole [2,1 -You can also use these chicory, articles :, Yijun, Lin, Shehuayin, or * # lymphoid compounds, or substituted derivatives of any of the compound family, while still remaining within the scope and spirit of the present invention . In one of the preferred conceivable examples, the cathode is deposited as a bottom layer on the substrate deposited by the inverted OLED. This inversion OLED has the advantage that it can be made entirely from hollow-deposited molecular organic materials, unlike, for example, OLEDs in which some layers include polymeric materials that cannot be easily deposited using hollow-deposition techniques. Although a protective layer is typically not required in polymer-containing inversion OLEDs, since the glass transition temperature (Tg) of polymer materials is typically much higher than the Tg of molecular (non-polymeric) organic materials, it is more resistant to Damage caused by IT0 spraying, but such polymer-containing inverted OLEDs cannot be easily manufactured using a hollow deposition technique that can be easily used to prepare OLEDs. Protective capping layers typically include a crystalline organic layer that protects the underlying hole-conducting material from damage suffered during the spray deposition of the ITO anode. Therefore, the present invention relates to an OLED having an organic layer which can be completely made from a hollow deposition material. In addition, this OLED includes a hollow deposition molecule containing a crystalline organic layer. The crystalline organic layer can not only be used to protect the underlying hole transport material from the ITO anode spray deposition process. This organic layer can also be injected into the layer as a hole. The forward bias current and voltage (IV) characteristics of PTCDA and CuPc PCLs shown in circle 2 are shown in the figure below. These characteristics are similar to -20- This paper applies China National Standards (CNS) Α4 Specifications (2 丨 0 × 297g) (谙 Read the notes on the back * 'before filling out this page) 五 τ V. Description of the invention (18) A7 B7 The Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs printed on the observation trap Previously published conventional IOLEDs with limited conduction, Z. Shen et al., Jpn. J. Appl. Phys. 3 5 'M01 (1996), PE Burrows, Journal of Applied Physics, 79, 7991 ( 1996), (Iar V (m + 1 &gt;). For IOLEDs, m = 8, regardless of the details of the specific device structure or PCL thickness. For all devices, EL brightness at a current density of 10 mA / cm² It is between 40 and 100 candelas per square meter, and has nothing to do with the details of the HTL, PCL or anode structure. The characteristics of the IOLED shown in circle 2 are representative samples of devices with different thicknesses of PTCDA or CuPc. Use CuPc as- The operating voltage for the IOLED of PCL is between 40 Egypt and 170 Angstroms and that of CuPc. It has nothing to do with it. In contrast, when the operating voltage of POLEDA-protected IOLEDs increases from 40 Angstroms to 60 Angstroms, it suddenly decreases by 1.5 volts. The voltage drop across the PCL is compared to the voltage across the remaining devices. The drop is typically small because PTCDA and CuPc are thinner and more conductive. Therefore, sudden changes in IV characteristics reflect changes in hole injection efficiency from ITO contacts. Although not intended to be affected by holes in OLEDs with PCL The precise theoretical limit on how the implantation efficiency can be improved, but it is believed that this enhancement is partly due to the reduced damage of the hollow-deposited hole transporting layer during the deposition of the ITO layer, and partly due to the hole from the ITO to the hole injection enhancement layer The lowered barrier caused by the injection. IX Q "Dongji select product typically causes thin film damage to the topmost organic layer. Compared to 100% production of devices with PTCDA or CuPc PCL, this damage caused by 15 The device with PCL has only 30% of the output. The operating voltage of IOLEDs with a PTCDA layer of <40 Angstroms (a sudden increase in pressure occurs when the thickness of the damaged area is equal to the thickness of the PCL. In this case,- 21- (锖 先Read the notes on the back of the book and fill in this book) Γ Pack. The paper size of the book is standard DU home sample (CNS) M specification (2! () &Gt; &lt; 297 male A7 ______B7 V. Description of the invention (l9) Ministry of Economy Further deposits of ITO by the Central Bureau of Standards, Shellfish Consumer Cooperatives, India will degrade TPD that is directly exposed to plasma spray. The presence of PCL also affects the maximum sonic current da) before the device collapses, where the Imax of IOLED without PCL is only 10 obtained from IOLED with PTCDA or CuPc PCL. / 〇. The difference in Imax can be clearly seen in Figures 2 and 3, in which all IOLEDs are driven at the high current level until a device breakdown occurs. Therefore, PCL is here to protect the organic materials underneath, reduce the IOLED operating voltage, and increase the Imax of the IOLED containing PCL. A similar reduction in the operation of the electric exhibition was previously observed on OLEDs with a CuPc-coated ITO anode, as previously observed, 'S.A. VanSlyke et al., Applied Physics Letters, 69' 2160 (1996). It is believed that this is due to a decrease in the energy barrier of the hole injected from Cuτ to CuPc compared to the energy barrier between ITO and HTL. The lowest transition voltage (that is, the voltage equal to the ohmic conduction trap and the finite conduction) is obtained for IOLEDs with> 100 Angstroms of PTCDA PCLs. These results show improved hole injection efficiency compared to IOLED devices that do not include PCL. S3 shows the light intensity of the IOLEDs in Figure 2 as a function of current (L-I). The external EL quantum efficiency of protected IOLEDs is 7; = (0.15 ± 0.01)% compared to 7 of unprotected devices = (0.30 ± 0.02). /. . This difference is believed to be due to the absorption of PCL, as both CuPc and PTCDA exhibit strong absorption at the Alq3 peak emission wavelength of 530 nm. For example, when CuPc PCL thickness increases from 40 to 170 angstroms, 7; 25% reduction. Similarly, for POLEDA-protected IOLEDs, as the PTCDA film thickness increases from 10 angstroms to 120 angstroms, 77 decreases by 25 ° /. 'Is consistent with the absorption of PTCDA. I do n’t know the reason for the remaining 7 differences between IOLED with and without PCL „: -1 Pack-1-» (please read the note on the back and front—the matter before filling out this page) Order-22- This paper The scale applies to the Chinese national standard (0 milk) 6 (2 丨 0 \ 297 mm) B7 V. Description of the invention (20), although it is believed that the flaws in the PTCDA / ITO interface will scatter part of the emitted light. To PTCDA, it can be further absorbed here. Therefore, it is expected that the different PCL materials for Alq3 emission are bright, some of which are explained above, which can slightly increase the IOLED efficiency. The shape of the EL emission spectrum of IOLED with PCLs is similar to Conventional Alq3-based OLED (Figure 4). The IOLED spectrum of PTCDA PCL with a thickness of 60 Angstroms is slightly broadened due to PCL absorption. The results shown in ®5 show that the cathode is the bottom contact, and the use of organic hole injection is included. The surface emission of a novel anode of PCL and transparent spray-deposited ITO film, or inverted organic LED (IOLED) can produce improved hole injection efficiency compared to an IOLED lacking this PCL. "IOLED can grow on the cathode Any smooth substrate including materials such as Si and The top of the opaque substrate of metal foil. IOLED IV characteristics and EL spectrum are similar to conventional OLEDs. Although the operating voltage is higher and the efficiency is slightly reduced, it indicates that the device contacts need to be further optimized. Another aspect of the invention printed by the Industrial and Commercial Cooperative is related to another method for reducing or preventing ITO spraying and exposing. This method can be used instead of or in addition to using a protective layer. In this method, the ITO layer begins It is deposited at a relatively low IT0 deposition rate to avoid damage to the underlying organic layer, and then the 170 layer is deposited at a relatively high rate to reduce the time required to fabricate the OLED. In particular, 'on the OLED surface may occur In the initial dark segment of the substantially damaged ITO deposition process, the ITO deposition rate is preferably only about 2-5 Angstroms / minute. However, when the growing ITO layer reaches a certain level that is sufficient to protect one or more layers below it, After each threshold thickness, the deposition rate can be increased several times / to increase the deposition rate to at least 5 to 10 times higher than the initial deposition rate. Although the improved -23- this paper size is applicable National CNS) A4 ^^ x 297 male A7 _B7 V. Description of the invention (21) The ITO deposition method is better used in combination with public protection but it can be improved without the use of a protective layer in a certain sinking state. For the RF power used to prepare the ITO layer according to the subject method is an Advanced Energy ATX-600RF power supply (Fort Collins, Colorado, USA), the power setting can be set from about 1 watt at a low lT0 deposition rate. -7 watts and higher ITO deposition rates vary from about 20 watts to 40 watts. Therefore, when the deposition rate from a low ιτο towards a higher IT0 deposition rate, the power setting of the RF power source can be increased from an increase of about 3 times to an increase of about 40 times. It is better to increase from about 5 times to about 10 times. Whenever an IOLED is manufactured, the one or more layers below may be, for example, a thin and quite fragile Mg: Ag cathode layer, an organic layer below the Mg: Ag cathode layer, and / or an ITO layer is deposited directly thereon Organic layers, such as hole transport layers. As explained herein, a low ITO deposition rate is a rate at which fragile layers cannot be detected with virtually identifiable damage, and a high ITO deposition rate can be detected at a rate that can detect identifiable damage to the fragile layers. The Consumer Cooperative of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs of India is called “• Protective ITO layer”, which is sufficient to protect one or more layers below from the threshold thickness of ΙΤΟ in the process of ITO deposition. Among the IV characteristics of OLEDs prepared using higher ITO deposition rates, compared to the ITO prepared with only a low, non-destructive ιτο deposition rate, no identifiable differences were observed. There is no substantially identifiable difference in the characteristics of the voltage system required to obtain a specific current within the voltage range applied across the specific OLED structure. At any time, ITO is deposited only at low, non-destructive ΙΤΟ. Specificity of deposition under the rate • 24 · This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 Gongchu &gt; A7 _____B7 V. Description of the invention (22) The Central Ministry of Economic Affairs, Central Bureau of the Ministry of Economic Affairs, Printed OLED Structure Institute The observed thickness is within 20/0. Although the threshold thickness of the growing IT0 layer required to protect the underlying layer may vary depending on the actual materials used below, it is substantially improved. Prior to high deposition rates, this threshold thickness is preferably about 50 to 200 Angstroms, and about 50 to 100 Angstroms. Fortunately, although the maximum rate that can be used without causing damage can also be within the physical range. Depending on the actual coating material, the deposition rate can be increased from about 25 Angstroms / minute to at least about 50 to about 60 Angstroms per minute. The deposition procedure is programmed to gradually and continuously increase the ITO deposition rate throughout the process. Or, the continuous increase of the ITO deposition rate only after reaching a certain threshold ITO thickness is also completely within the scope and spirit of the present invention. In this case, when the ITO deposition rate increases gradually and continuously, it should be understood The threshold thickness sufficient as a protective ITO layer can be slightly thinner than that required when the ITO deposition rate suddenly increases to a substantially higher ITO deposition rate. The performance of the LEDs prepared by the present invention can be determined by Compared with the 1- ¥ characteristics of OLEDs made with accelerated ITO deposition rate compared to 〇1 ^ 1) prepared with a single ITO deposition rate during the entire ITO deposition process, it was found that this accelerated deposition was used The LED prepared by the rate method can be made into an IV characteristic, and the IV characteristic of an OLED that maintains the deposition rate at a low deposition rate throughout the ITO deposition process has no practically identifiable difference. In a preferred specific example of the present invention, The ITO layer is the actual oxygen flux selected by RF power spraying on the target in the presence of an oxygen flux selected to provide a desired combination of transparency and resistivity for a certain ITO layer thickness. The characteristics of the specific manufacturing system used can vary, too, and can be evaluated for the visible radiation absorption of the ITO layer. In particular, in the visible spectrum -25- this paper is suitable for financial institutions 5 standards (CNS) M Specifications (2 丨 0 &gt; &lt; 297 public meals) ------ -Pei ·, 1T V. Description of the invention (23) The absorption and visible absorption of visible radiation in the area as a function of wavelength is obtained by accelerating the deposition rate The ιτο layer is equivalent to the total light transmittance of the ITO coating prepared at a lower ITO deposition rate. For higher ITO deposition rates, the oxygen flux can vary within a range from about 0.35 sccm (&quot; standard cubic centimeter / splitter &quot;); and for very low ιτο deposition rates The oxygen flux can be from nothing to about 02sccnj, preferably about 0-1sccm. Using these criteria to evaluate the performance of the ιτο layer made using the subject method, it has been found that it is possible to use at least a 10-fold increase in ITo deposition rate to produce coatings prepared with only the lowest use; buto deposition rate ITO coating with almost the same IV characteristics. This increase is typically caused by a 10-fold increase using the RF power setting. In another aspect of the present invention, the electron-transporting layer of the LED prepared according to the present invention may include an organic radical, which may be prepared in a manner compatible with the method of manufacturing the electron-transporting layer of the LED. In a representative specific example, the electron transport material is represented by the chemical structure CpAr. Of the chemical formula (I):

^ ------ Order (I) The Central Samples Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative Co., Ltd. This is called a cyclopentadienyl radical substituted by a polyaryl group. , Ar2, Ar3, Ay4, and Ar5 are hydrogen, an alkyl group, or an unsubstituted or substituted aromatic group. Although the term "Ar-based" may typically be used only to refer to aryl groups, this term is used here to include hydrogen or alkyl groups. At most only one of the Ar-groups is alkyl or argon. , While the rest are better aromatic groups, and all Ar- groups are the best aromatic groups. Aromatic groups can be 26- This paper size applies to China National Standards (CNS) A4 specifications (210X297) Chu A7 B7 V. Description of the invention (25) The organic free radical, which is a combination of the electron transport and electron emission properties of the electron transport layer, is more specific. In a more specific example, the organic radical is of formula (II) Pentaphenylcyclofluorene dienyl radical, Cp® ·:

Wherein, each aryl group of the chemical formula (I) is defined in the chemical formula (π) as a single phenyl group which may be unsubstituted or substituted by the substituents R !, R2, R3, R4 and R5, respectively, wherein each R- group Independent of other R-groups, it represents one or more of an electron donor group, an electron acceptor group, or an alkyl group. Regarding a specific example of the present invention, the organic radical may be an unsubstituted Cp4 represented by the chemical formula (III): (m) „.-1 Pack-(谙 Read the precautions on the back-side first, then (Fill in this page) Ordered by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

Regarding yet another specific specific example of the present invention, the organic radical may be a tetrabenzylcyclofluoradienyl radical of the chemical formula (IV), -28- This paper size is applicable to the Chinese National Standard (CNS) A4 specification ( 210X 297 mm) 5. Description of the invention (26) A7 B7

Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Shellfish Consumer Cooperative and its further substituted variants, for example, 氲 shown in Chemical Formula (IV) may be replaced by an alkyl group. Although not intended to be limited by the inventive theory of a representative example of a specific organic radical as published herein, the properties of CpAr. Radicals believed to be used as electron transport materials in the ETL of OLEDs The combination is based on β, which includes a central cyclopentadienyl ring with steric protection, which can form a generally stable organic radical due to the substantially complete rilip protection of the cyclopentadienyl ring; cyclopentadienyl The ability of free radicals to easily form anions. This anion acts as an electron carrier together with the free radicals; and the strong aromatic characteristics of the cycloadienyl anion, which results in the 7T-orbital domain of the anion, the dragon-orbital domain The strong overlap of electrons thus promotes the electron mobility that promotes the utility of the material as an electron carrier. The present invention has a substituent which can be selected to be included in an organic radical to change the emission spectrum and reduction potential of a radical in a manner that can produce a perfect combination of electron transport and electron emission properties that are particularly suitable for use as an electron transport layer. Further features. The present invention relates to an electron-transporting material suitable for use in an electron-transporting layer of an OLED. The electron-transporting material includes a stable organic free radical and an anion formed by a free radical. __ ·,. .------. Quark radicals, for example, pentaphenylcyclopentadiene of chemical formula (ΠΙ) -29- This paper is suitable for gil home transfer (CNS) Α4 specifications (21 ( ) &gt; &lt; 297 male thin) --- (Please read the Qin matters on the back before filling this page) Γ. Order A7 B7 V. Description of Invention (24) Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs The total number of compounds selected by the formulae to be the same or different from each other, which have been covered by Chemical Formula I, has so far been limited to those that can be applied to the preparation of the electron transport layer, and that these compounds have actually been chemically prepared to date. If the carrier mobility of the electron-transporting layer has a value of at least 10.6 cm 2 / volt-second, the organic radical compound is defined herein as being suitable for use as an electron-transporting material. An unsubstituted or substituted aromatic group may be, for example, a phenyl group; a radical diagram having a fused benzene ring, such as a fluorenyl group; or an aromatic heterocyclic ring such as a pyridyl group or a thiophenyl group. Each aromatic group may be unsubstituted or substituted by one or more substituents independently of the other aromatic groups. The substituent may be an electron donor group, an electron acceptor group, or a polyl group. For their compounds not only as electron transport materials, but also as emissive materials, unsubstituted or substituted aromatic groups are selected to adjust the spectral emission characteristics in such a way as to produce the desired color, for example, using the CIE ratio The characteristics determined by the χ_γ chromaticity coordinates of the color system. For example, it is known that a substantial change in the emission spectrum of a benzyl-containing compound can be generated depending on whether the phenyl group is unsubstituted or instead is ortho or para-substituted by an electron donor group or an electron acceptor group. In addition to being selected to adjust the emission characteristics, the donor and acceptor groups can also be selected to affect the extent of intermolecular interactions and therefore the carrier mobility. In addition, these substituents can also be selected to adjust the in situ energy of the organic radical, that is, the energy required to transport the original radical, and thus convert the radical to the anion of the radical. By choosing substituents to produce easily available reduction potentials, it is possible to favorably change the hip-bearing mobility and / or load depth, so that it can be produced with a particularly suitable -27 _ First read the note on the back of the page and fill in this page) Γ Binding B7 V. Description of the invention (27) radicals, Cp * and fluorene phenylcyclopentadienyl anion of chemical formula (V):

1 The (V) easily available reduction site can cause the proper electron conduction through the electron transport layer, wherein the confused electron conduction is defined herein as meaning to have a voltage of at least about 10-6 cm 2 / volt second. Electron mobility is the basis for electron conduction. Including Cp. · The free radical electron transport layer provides further advantages in some cases where the electronic carousel material can also be used as the emitting material in OLEDs ^ When the electron transport material is also provided as the emitting material, 〇LED can be manufactured with a single heterogeneous structure. If the electron transport material is not also provided as an emission material, the OLED can be manufactured from a single heterogeneous structure, where the hole transport layer is an emission layer, or from a double heterogeneous structure. This invention is more about a novel method for preparing Cp * radicals into a thin layer of an electron transporting material with high electron mobility and high carrier density in the form of orthomorphism, which is printed by the Shelley Consumer Cooperative of the Ministry of Economic Affairs The layer system is included in a multilayer structure, and particularly in a heterogeneous structure for generating electrical excitation light. It is believed that no prior art electron transport materials have been published that contain organic free radicals. Therefore, although the present invention relates to the use of a cyclopentadienyl group substituted with a polyaryl group, it is a cyclopentadienyl radical group substituted with a polyphenyl group, or a pentaphenylcyclofluorenyl diphenyl group. Free radicals, as a representative species', but it should be understood that the present invention is generally coaxed to be included in the electron transport layer. -30- This paper size applies to China National Standard (CNS) A4 specifications (210X 297 male A7 B7. 28) Any organic radical that has an electron mobility of at least 10_ <5 square centimeters per volt as the electron transport material family. Cp # • radicals are different from pentaphenylcyclopentane except that they are free radicals Ene itself, Cp * H:

---C- (Please read the note on the back of the ife-item before filling out this page) The Central Printing Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, printed it when published in OLEDs, it is a blue emitting material , C. Adachi et al., Applied Physics Letters, Volume 56, 799-801 (1990), and films of pentaphenylcyclopentadienyl radicals have been observed and published with a purple color, MJ Heeg et al., Organometallic Chemistry Journal (J. Organometallic Chem.), Vol. 346, 321-332 (1988) ○ In addition, &lt;: ρΦ • radicals are different from 0: ι &gt; ΦΗ || The origin of Cp # H will have to be followed by the loss of Η + to obtain a stable anion form, which is not feasible in energy. In particular, although based on these differences, there is absolutely no reason to expect that 0ρΦΗ will have good cross-body transport properties, Cp *. Radicals are particularly suitable for this use. Another characteristic of the present invention is that although it is typically difficult to prepare and store Cp *. Through conventional methods, the Cp *. Radical material of the present invention is easy to mix with precursors that are stable in air. Ground truth. f Cyclopentadiene metal dicyclopentadiene complex, such as (〇ρΦ) 2M 'f square M = Fe, Ru, Sn, Ge or Pb' can be published in Heeg et al. -31- Applicable to China National Standard (CNS) A4 specification (210X297 mm) Order A7 ________ B7 V. Invention description (29) These materials can be represented by the following equation: MX2 + 2 Cp * Li- &gt; (Cp *) 2M + 2LiX »(1) Self-Metal and Cp * Anions, [CpY,

(Please read the above-mentioned precautions before filling out this page.) Packing. Prepared by the printing policy of the Central Coopers Consumer Cooperative of the Ministry of Economic Affairs, where M = Fe, Ru, Sn, G * e, or Pb; and X = halogenated Or ground acid. Each of these complexes is an air-stable complex. However, Ge and Pb complexes are not Redetin. It is reported that the attempted sublimation of Ge and Pb complexes at 250 ° C and about 10_4 Torr will cause the formation of metal mirrors and gaseous sublimation of 0ρΦ • radical species, as shown in the following equation: (Cp *) 2M — Μ · (solid) +2 Cp * (gas phase) (2) 250 ° C, 10_4 Torr According to Heeg et al., Organic free radicals Cp * from the gas phase deposited purple films only include Cp * · free Base Materials "The present invention is directed to the use of such precursor materials and such methods in the preparation of electron transport layers that can be used in virtually any type of multilayer structure including electron transport layers. In particular, the electron-transporting layer containing a radical may be included, for example, in a multilayer structure of a light-emitting device, that is, in a heterogeneous structure for generating electrical excitation light. Accordingly, the present invention relates to incorporating an electron transport layer on the subject into a multilayer structure, wherein the electron transport layer is an electrical hole transport layer having electrical contact. , ιτ d -32- This paper is suitable for 011 transfers (CNS) A4 specifications (21Qx 297 Gongchu) A7 __B7 V. Description of the invention (30) Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs When free radical materials are incorporated in multilayer junctions as electron transporting layers, materials containing stable organic free radicals are intended to provide benefits and advantages that are particularly suitable for use as electron transporting materials. Although in the more preferred embodiment of the present invention, the electron transport layer is intended to include mainly organic radicals, or even in some cases, an electron rotation layer consisting essentially of organic radicals, but also Considering that a layer containing a radical material that has undergone dimerization, or even substantial dimerization, can also be provided as an effective electron transport material, it is therefore considered to be thin within the scope of the present invention. In essence, although the electron transport layer, if it does not include organic radical materials, it mainly contains organic radical materials, but the present invention can cover the electron transport of the electron transport layer by including the existence of proven organic radicals. Characteristics of any electron transport layer of organic radical materials. For example, this layer may include an organic radical material that is buried in a non-radical but still the parent of the electron transport material. Here, an electron transporting layer mainly containing organic radicals is defined as a layer in which an organic radical is a main component of the electron transporting layer. "In a preferred embodiment of the present invention, a pentaphenylcyclopentadienyl-based Ge (ten Benzylic dicyclopentadiene germanium) or? 1) The (decylphenylbicyclofluorenediene lead) complex is used as a source for preparing a thin layer of C〆 in a hollow deposition system. The present invention is more about OLEDs that can include a dopant compound in the emission layer. A dopant that can move the emission wavelength of the emission layer containing only the main compound is added to the main compound in an amount that can shift the emission wavelength for any reason. , So that the LED device emits light that can be perceived by the human eye as being close to one of them-one of the main colors is better. "Although it is generally considered that the characteristics describing color perception are subjective behaviors," the National Commission for Lighting Inspection (International Commission (Please Read the back-to-side note * -item before filling out this page). Loading ------ Order ----! -33- The paper button and towel ^ A 7 B7 __-- --- V. Invention It shows that (3!) Of mum—) has developed a quantitative chromaticity scale, also known as 准 rubbing criterion. According to this notation, a saturated color may have a single point representation with a quantitative basis based on the ratio of the definition axis of the chromaticity scale. Those skilled in the art should clearly see that this single point on the CIE scale will be difficult in practice, but fortunately, it does not need to meet the standards or specifications ^ In the more specific embodiment of the present invention, 〇LED produces the main color, The dopant is added to the host compound so that the OLED emits light that is perceived by the human eye as close to the main color. Through the implementation of the present invention, 'the intention is to construct the 0LED so that it can approximate the emission description characteristics of absolute (or saturated) chromaticity, as defined by the CIE standard. In addition, it is also expected that LEDs using the material of the present invention may exceed the frequency light. Gu Shi Luminance per square meter's ball is slightly lower in some moods, maybe as low as 10 turbidity per square meter is acceptable ° Printed here by the Central Government Bureau of the Ministry of Economic Affairs The compound is a compound that can be doped with a dopant to emit light with desired spectral characteristics. The term "M host" is used to refer to a compound in an emission layer that accepts hole / electron recombination energy and then transfers this excitation energy to a dopant compound via an emission / absorption energy transfer process, which typically exists Very low concentration. The dopant can then relax to a slightly lower energy It state, which emits all of its energy into a luminescence emission in the desired spectral region. 100% dopant excited state excitation will be emitted Energy-doped spines are described as having 100% quantum efficiency. For the host compound / dopant concentration to be used in SOLEDs with adjustable colors, if not all of the host compounds' hair rinses are transferred to androgen-doped, Most of them are better transferred to the dopant, which in turn may emit from lower energy levels, but have high quantum efficiency and produce visible radiation with the desired chromaticity. -34- Material (CNS) A4 specification (21GX297 Gongchu) Μ _____B7 V. Description of the invention (32) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, on the terms used here. An electron transport / emission layer of a heterogeneous structure OLED device, or an individual emission layer of a dual heterogeneous structure device. As known to those skilled in the art, the use of dopant species such as those published herein makes it not only possible Expand the range of colors emitted by OLEDs, and expand the range of possible choices of host and / or heterogeneous compounds. Therefore, for an effective host compound / dopant system, although the host compound can be doped Agent species have strong emission in the spectral region where light is strongly absorbed by the species, but it is better for the host to have no emission band in the region where the dopant also emits strongly. In the structure where the host compound is also used as electricity, it is extra Standards such as oxidative transport in situ energy of a species have also become a consideration. However, in general, the spectral characteristics of the host and dopant species are the most important criteria. The amount of dopant present is sufficient to make the main material The emission wavelength of the branch is shifted as close as possible to the amount that will saturate the main color as defined by the CIE scale. Typically, the effective amount is from about 0.01 to 10.0 in terms of the emission layer. Ear percentage. The preferred amount is from about 0.1 to 1.0 mole percentage. The main criterion for determining the proper doping level is the extent to which emission with appropriate spectral characteristics can be effectively obtained. For example, without limitation, such as doping The amount of the dopant species is too low, so the emission from the device will also include the light component from the host compound itself, which will be at a shorter wavelength than the expected emission from the dopant species. Conversely, the If the amount is too high, the emission efficiency may be adversely affected by self-quenching-a net non-emissive mechanism. Or, too high amounts of dopant species may adversely affect the hole or electron transport of the host material. Properties. Another specific example of the present invention relates to the paper containing (5-hydroxy) quinol-35-. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 ^ &lt; 297 * ^^ ~ y (Please read first Note on the back, please fill out this page)

, 1T Α7 Β7 five,

Description of the invention (33) Lin) The launch of the main material of the metal complex, (V) η where M is A1, Ga, In, Zη or Mg, if M is A1, Ga or In, then η ~ 3 If μ is Zn or Mg, then π = 2. Yet another specific example of the present invention relates to a dopant material including an internal salt having a chemical structure of Chemical Formula VI:---- L ---.- _, '1itch—I 一 &quot; I / (Please read #-* 面 之 Notet before filling out this page)

, / 1 CVI) R2

, 1T where Ri, R2, 1 and 114 are unsubstituted or substituted alkyl, aryl or heterocyclic ring (such as pyrrole), and 115 and 116 are unsubstituted or substituted alkyl group, respectively. Aryl, OH or NH2. Such compounds are referred to herein as bisphenyl square acid sulfonium compounds. To be more specific, one of the specific examples of the present invention relates to a dopant material including a compound having a chemical structure of Chemical Formula VII: (VE) where R = alkyl. Such compounds are referred to herein as square acid fluorene dyes. Yet another specific example of the present invention relates to a dopant material including an indigo dye compound having a chemical structure of Chemical Formula VIII: 36 Ruchilang towel household material (CNS) A side M 210X 297 mm

U Printed by the Consumer Cooperatives of the Central Government Bureau of the Ministry of Economic Affairs

V. Description of the invention (34 A7 B7

(Vffl) where X = NH, NR9, S, Se, Te, or O, where is an aryl group or a phenyl group, and 117 and 118 are each an unsubstituted or substituted alkyl or aryl group, or? An r-electron-donating group such as -OR, -Br, -NR2, etc. or a π-electron acceptor group such as -CN, -NO2, etc. To be more specific, another specific example of the present invention relates to an erbium-doped material family including an indigo dye &lt; compound having a chemical structure of Chemical Formula IX: (IX) 闰 Read Back. 面 5- S- 亊 ^ Copybook., Page

Where X = NΗ. Another specific example of the present invention is a dopant material containing an olefin compound, for example, an "associated compound. 6 Illustrative examples of the present invention. The main compound preferably includes a compound of formula V , Where M = Α1 and η = 3, see (5 · Hydroxy- ♦ 喏 喏 (, 'Α1χ3 &quot;):) ^ (X: -sr · Printed by the Consumer Standards Cooperative of the Central Standardization Bureau of the Ministry of Economic Affairs ¾

As the dopant compound, a square acid chromophore compound including chemical sXI is preferred, 1,3-bis [4- (dimethylamino) -2-hydroxyphenylbenzene 2,4, 2 and 2 dihydroxide Acquired 37 paper standards Gu Zhongguan Jiaxian (CNS) ⑽ (21GX297 A7 B7 V. Description of the invention (35) Cyclopentinyl k, double (internal swing) [63842-83-ip

Printed by the Central Government Bureau of the Ministry of Economic Affairs and Consumer Cooperatives, it is possible to manufacture hollow-deposited OLEDs with a single heterogeneous structure into an electron transport layer with a main compound of formula X and a dopant compound of formula XI, where OLEDs have a Combined with the current-voltage (IV) characteristics, UV-visible light, photon excitation light, and electrical excitation light properties of OLED. It is believed that the effect of this special host compound / dopant combination is based on the high energy transfer from the autonomous compound to the dopant. Β is the paired host compound and dopant, a high amount of plutonium energy. Compared with the use of the main compound alone, the transfer can obtain more exciting electrical excitation light. Although not intending to be limited by the present invention's theory of representative examples published herein, it is to explain how such combinations of host compounds and dopant compounds can be selected and paired to provide the old electrical excitation light (EL) In this way, the light pre-excitation light (PL) of the Alx3 main compound with and without the dopant dye compound can be compared with Al also prepared with and without the dopant compound:

The PL of these compounds can be measured using standard techniques, for example, 'immersing the compound in a solvent, exposing it to a photon excitation source, and using such materials as purchased from the United States -38-A7 ___B7 in this paper scale 5. Description of the invention ( 36) Printed by Photon Technology International, Somerville, NJ, Equipment for Testing of Light as a Function of Wavelength as a Function of Wavelength by Alcohol Consumer Cooperative of Central Bureau of Standards and Quarantine of the Ministry of Economic Affairs Alq3, Alx3, and PL of Gax3 The spectrum is shown in circle 11 »Alx3 produces an orange photonic light emission with a maximum chirp at about 620 nm, which is shifted toward red with respect to an Alq3 class having a PL maximum at about 515 nm. It is believed that this large red shift is significant for achieving a high energy transfer from the Alx3 host compound to the red fluorescent dye erbium dopant. The EL spectrum of an OLED prepared with undoped and doped Alx3 layers is shown in "12» Although the undoped host material has a slightly red-shifted EL spectrum compared to the PL spectrum of the host material, for example, The accurate CIE colorimetric system describes the characteristics, and the largest occurrence occurs in the wavelength region that still has an orange appearance (x = 0-565, y = 0.426). However, when this host material is doped with a dysprosium dye of chemical formula XI, the EL spectrum has the largest chain in a wavelength region significantly shifted toward red (x = 0.561, y = 0.403). Other specific examples of the present invention relate to an OLED having an emission layer including a dopant including an indigo dye compound or an olefin compound of Chemical Formula VIII. These kinds of compound species are represented by the indigo dye compound of the chemical formula IX and the olefinic compound C60, and there is no limit to the range of these kinds of compounds. These compounds as shown in circle 14 and the bisphenol square acid sulfonium compound of Chemical Formula XI and the absorption spectrum show that these compounds have an absorption width that is properly coordinated to accept photon-excitation light from the main compounds Alx3 &amp; Alq3. The photon excitation light spectrum of this particular dopant as shown in circle 15 shows that each of these compounds emit light in the red region of the visible spectrum or toward the red region &lt; domain. In addition, if dopene or square acid dysprosium dopant is added to use Alx3 or Alq3 ---- „----- i ^--Γ, (Please read the precautions on the back before filling in this 萸)

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U -39- This paper size is in accordance with Chinese National Standard (cSJS) A4 (210X297 mm) A7 B7 printed by the Central Government Bureau of Shellfish Consumer Cooperatives V. Description of the invention (37) A single heterogeneous structure as the main material The electrical excitation light spectrum of the 0LED in the device shows that each of these compounds has been proven to have full transfer of the excitation energy of the autonomous compound under the dopant roll of the dog, see countries 16, 17, and 18. Partial energy The dopant is then radiated into electrically excited light. The dopant replaces substantially all of the emission capacity of the main compound with the dopant. For example, it is particularly advantageous in SOLEDs with adjustable box colors. In having more than one color In these devices of the emissive layer, each layer is expected to have its own custom-defined chromaticity and spectral emission that does not overlap with the spectral emission of any other layer. The electrically excited light emission of an OLED containing a representative indigo dye compound has been confirmed to be close to 650 nm (with CIE 値, x = 0.693 and y = 0.305) maximum erbium emission band, which produces a saturated red appearance. (5-hydroxy) quinoline Zn and Mg derivatives are also The preparation and discovery produced almost the same PL spectrum as observed for Alx3 #. In view of the use of Bahua 3 as the main material of the red emitting dopant, which also has good energy coordination, this PL spectrum shows Zn and Mg Derivatives can also be effectively used as the main material of appropriately selected red emitting dopants "(5-Hydroxy) Jun Zhilin's Ga derivative has also been prepared and found to have a PL emission spectrum as shown in B11" These results are shown Ga analogs are not only effective as dopant emitting materials, but also as technical doping materials. Examples of other main compounds or containment compounds include the demonstration and explanation of Meigu in the joint application of applicants who filed applications on August 6, 1996 Emission compound and / or host compound of the type described in Patent Application No. 08 / 693,359. Further representative examples of the present invention include emissive compounds including radicalized XII: + &amp; 40 (# 先 读 背(Note the matter t fill in this page)

V Γ ____15. Description of the invention (38) A7 B7 (χπ &gt; 3 where M is a trivalent metal ion such as A1 or Ga; and R is an alkyl group, a phenyl group, a substituted alkyl group, a substituted Phenyl, trimethylsilyl, or substituted trimethylsilyl; and wherein X, Y, and 2 are each independently C or N, so that at least two of X, Y, and Z are N; and chemical formula XIII · (view) • J 3 are provided in ® 20 according to specific examples of compounds of formula I, which are all species available on the market (Aldrich Chemical Co "Inc. )). As published in many U.S. patents assigned to Kodak (see, e.g., U.S. Patent No. 5,5 52,678 to Tang et al.), Used in their green-emitting OLEDs The commonly used emissive compound is a borne compound with the general formula

(Please read the precautions on the back before filling out this page)-Binding

J 3 where M is a trivalent ion of a metal such as aluminum and gallium. An example of a green emitting compound according to this general formula would be wheat (S-hydroxyxanthroline) aluminum, also known as Alq3. The compounds of the present invention represented by the chemical formulae XII and XIII have red shifted emissions due to the changed ligand structure. Compound of Chemical Formula XII-41- This paper size applies to Chinese National Standard (CNS) A4 specification (210X297). 5. Description of the invention (39) The choice of A7 B7 is to add two nitrogen atoms to the quinoline salt ligand. The observation that the pyridine side caused a shift of 100 nanometers with respect to the emission wavelength from the emission of octamon is based. With this method of shifting the emission red color of OLEDs, the compound of formula XII is designed and synthesized to have a specific purpose of shifting the emission from the / Uq3 containing compound material towards shorter wavelengths. The ligand of chemical formula XII is an example of a fused ring, multi-heteroatom structure that provides many of the same structural characteristics of quinoline-based ligands but has buccal shift emission to Alq3. -The compound 雎 represented by the chemical formula XIII is not a metal complex, but it can be prepared as a hole-conducting material for the HTL layer in an OLED. In addition to being a hole-transporting material, compounds of formula XIII also exhibit desirable emission characteristics. Please read the precautions on the back of this compound and the compound of formula XII before filling this page). Order Table 1 • Compound absorption Λ Emission A Alq3 380nm 540nm XII 280nm 390nm XIII 35 5nm 402nm ο I Central Standard of the Ministry of Economy Another specific example of the fundamental invention of the printed packaging of the local co-operative consumer cooperative, the Min 22 cheek is shown in bright ambient light conditions, such as a high-contrast TOLED display under low light. The high-contrast TOLED display of the present invention includes a TOLED display TD and a low reflectance absorber, such as a black absorber BA disposed behind the display TD. The TOLED display TD can be manufactured as U.S. Patent Application No. 08/354 674 and 42 The scale of the application is applicable to the US county (CNS) A sight (21 () &gt; &lt; 297 Gong 4 A7 _________B7 V. Invention Description (40) published in 08 / 613,207, the entire content of which is incorporated herein as References. As explained in circle 22, 'from the bright light source L, such as the sun, the light r emitted by the TOLED cheek shows the layers of the TD and is absorbed by the black absorber ba. As a result, it is emitted by the inverted TD and is The light seen by the viewer V is not washed away by the ambient light reflected by the display as in the conventional case. A cross-sectional view of a specific example of the high contrast display according to the present invention is shown in circle 23. The TOLED 1 is arranged on a transparent substrate 2, and the transparent substrate 2 is arranged on the absorber 3 with a low reflection ratio. The light I emitted by the price 1 goes toward the viewer. For simplicity, it will include several layers of different materials TOLED 1 is shown as a layer. Transparent The substrate 2 may include a crack or a plastic mold, which may be soft or hard. The absorption with a low reflectance || 3 may include, for example, a layer of paper or a thick layer of paint or printed on at least the side facing the substrate 2 Cardboard. It is also possible to deposit the absorber 3 with low reflectance directly on the bottom surface of the substrate 2, such as by matting the base of the substrate with black paint to extinction paint. The absorber 3 with low reflectance is also This can be achieved by spin-coating carbon black on the polymer base material or by evaporative deposition. The cross-section threshold of the second specific example of the high-contrast indication of the present invention by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs is shown in Circle 24 »In this specific example, the low reflectance absorber 3 is disposed between TOLED 1 and the substrate 2. In the specific example of circle 24, the low reflectance absorber 3 is deposited on the substrate 2 The base material 2 does not need to be transparent. The absorber 3 and the base material 2 with low reflectance can also be made into one layer. Since it is desirable to make the absorber 3 with low reflectance facing the surface of the potato as absorbent as possible, This surface can be quite rough, so you may not want to use it on this paper. Use China National Standard (CNS) A4 specification (2) 0297 mm) Central Consumers Bureau of Ministry of Economic Affairs, Consumer Cooperatives, India and India A7 __ _ __ _ B7 V. Description of Invention (41) Manufacturing TOLED 1 β So, if necessary A planarization layer 4 may be deposited on the reflectance absorber 3 to provide a smooth surface on which TOLEpi is deposited. The planarization layer 4 may include, for example, a polymer or plastic, and may be applied via spin coating. Although, as previously mentioned, a low-reflectance absorber can be realized as a "black absorber," the present invention also covers the use of low-reflection having a color different from the color emitted by Ding. Than the absorber. For example, within the scope of the present invention, a dark green absorber behind a red emitting TOLED, or another selected color combination may be used to provide a high color contrast display. Therefore, a surface with a low reflectance may have a high light absorption over the entire visible region of the spectrum to produce a gray to black surface, or it may be only in the spectral region corresponding to a portion of the wavelength region generated by the light emitting device Medium has high absorption. For a black absorber, the light absorption is preferably at least about 50%, and about 80-90% or more higher. To extract even more el light in a direction perpendicular to the OLED, an anti-reflection (AR) coating can be deposited on the transparent ITO anode. For the conventional Oled, this requires the AR coating to be deposited over the transparent substrate before the ITO layer and the remaining OLED layers are deposited. In this type, care must be taken to reflect in transparent substrates. For IOLED, EL light does not pass through the substrate, which simplifies the design of the AR coating. And, with IOLED, the AR coating can be directly deposited on the impotence, so it can also be used as a passivation layer to protect ^)! ^ :!) from atmospheric degradation. The IOLED structure of the present invention can also be manufactured to have one or more calender structures to control the spectral width of the emitted light.圏 29 颍 Made in 44 Prague. ^ Paper size is applicable to China National Standard 1 &quot; CNS &gt; A4 size (210X297mm) '---- (Please read the precautions on the back before filling this page) V. Description of the invention (42) A7 B7 Printed reflector (DBR) structure 60 on the consumer cooperative of the Ministry of Economic Affairs, Central Government Bureau, printed on top 50, this structure 60 is remanufactured on the substrate 70. The DBR structure is also It can be called a multilayer stack (MLS), such as taught by H.A. MacLeo.d, Thin Film Optical Filters 94-110 (1969). The DBR structure 60 is a 1 / 4-wavelength stack 62 of a highly reflective layer of a dielectric material. The stack 62 can be made to have 2 to 10 alternating layers of titanium dioxide Ti02 and silicon dioxide Si02. A layer of ITO 61 is deposited on the stack 62. A cathode 55 of the OLED 50 is deposited on the ITO layer 61, which is formed as a thin translucent layer of a Mg: Ag alloy. ETL / EL layer 54, HTL 53, protective layer 52 and ITO anode 51 »ITO anode 51 and 60 DBR structure at the bottom can be sequentially deposited to provide good cavities and microcavities. In particular, if the thickness of the ETL / EL layer 54 is substantially equal to λ / 2n, where I is the wavelength of the emitted light and η is the reflectance of the ITO anode layer 51 (which is about 2.0 with respect to air), the spectrum is narrowed Achieved with the temporal increase of the effective rate of OLED. To further narrow the spectrum of light emitted by the OLED of FIG. 29, another DBR structure may be placed above the OLED 50. However, this will require an electrical path from the reverse side of the combined structure to the anode 51 of the OLED. "Another way is that the top-side DBR can be replaced by a color filter layer composed of, for example, an organic dye film. The present invention further provides a monochromatic and multi-color light emitting device using a phosphorescent colonization layer to make the color of light emitted from the organic light emitting material low-frequency and at least different colors. In one example of the present invention, a blue light bowl emitted from an organic light emitting layer is turned into red light in a stacked OLED using a low-frequency conversion layer. In another example of the present invention, using a low-frequency conversion layer to emit organic light -45- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) U3. ---- · C-. (Please read the notes on the back before filling this page)

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I A7 _________B7 V. Description of the invention (43) The blue light emitted from the vomiting layer of the Central Consumers' Bureau of the Ministry of Economic Affairs of the Consumer Cooperatives is converted into green and / or red light. The light emitting device history of the present invention is used in a variety of monochrome and multicolor applications to provide high-brightness and high-efficiency displays. The present invention can also provide an organic light emitting device using a low-direction frequency conversion phosphorescent phosphor layer to provide high-efficiency and high-level display. A light emitting device according to the present invention includes a plurality of organic light emitting layers arranged in a stack, and a low-frequency variable frequency shattering body layer disposed between any of the plurality of organic light emitting layers. In the first specific example of the present invention with respect to the low-frequency conversion phosphor, the light emitting device 100 is set as shown by a circle 25. In this stacked arrangement of organic light emitting layers, the first blue light emitting layer 1 丨 2 is disposed on the substrate 111, the edge light emitting layer 113 is disposed on the first blue light emitting layer 112, and the red color is low. The variable frequency light-breaking body layer 114 is disposed on the green light emitting layer 113, and the second blue light emitting layer 115 is disposed on the low-direction variable frequency phosphorescent cross layer 114. The transparent conductive layers 120, 121, 122, and 123 are disposed between the light emitting layers. The metal contact layer 130 is disposed on the second blue light emitting layer 115. Disposed between the green light emitting layer 113 and the red low-frequency conversion phosphorescent chirped layer 114 is a mirror structure 125, which is preferably a multilayer stack of a dielectric material. The mirror structure 125 shown in circle 25 is characterized by red dreams and blue and marginal color blocking bands to prevent the red low-directional frequency conversion race light layer 114 from being affected by the green and beneficial light emission layers 113 and 112, respectively. Pumping. By reflecting green and blue light, the mirror structure 125 can also increase the efficiency of the device by at least a factor of two. In addition, the mirror structure 125 caused the red low-direction variable-frequency phosphorescent phosphor layer 114 to be secondly lifted by the second blue light-emitting layer 115, and the red low-d variable-frequency phosphorescent cross-layer layer 114 was hoisted by the second blue-light emitting layer 115 for some reason, so that the layer Π4 Thick-46- This paper size is applicable to China National Standard (CNS) A4 specification (210X297mm) _—I (Please read the precautions on the back before filling this page) Order

-U A7 ------- B7 V. Description of the invention (44) The printability of the Shellfish Consumer Cooperative of the Central Sample Bureau of the Ministry of Economic Affairs is much lower than the thickness required for the single pass device (smgle_pass device). For example, the 'red low-direction changing light fil layer 114 is as thin as 1000_. Mirror structure 125 is known in the art to allow red light to pass but prevent green and blue light from passing through any suitable material. For example, the mirror structure 125 includes at least two dielectric materials having different dielectric constants arranged in the multilayer stack 4. The thickness of | in the stack is defined by the wavelength range g of the structure. Typical inorganic stylus materials used to form the mirror structure 125 include SiO2 / Ti〇2 and SiO2 / SiNx. Although such inorganic materials are within the scope of the present invention, the use of organic dielectric materials such as 3,5,7,8-tea tetradine acid (&quot; NTCDA &quot;) and polytetrafluoroethylene (TEFLON) good. The use of organic dielectric materials minimizes the risk of damaging the organic light-emitting materials during the deposition of the dielectric materials used for the mirror structure 125. As is known in the art, 'Light Emissions 112, 113, and 115 are used by Dangdang The organic material that emits light when excited by current is made "Therefore, when an electric chirp is applied to both ends of the conductive layers 120 and 121, the light emitting device shown in circle 25 will emit chirped light, and when conductive layers 121 and 122 are applied, When hail pressure is applied between them, it will glow green. In order to emit red light, a voltage is applied between the conductive layer I23 and the metal contact layer 130, so that the second blue light emitting layer U5 emits blue light, which then changes from red low to the variable frequency phosphor layer 114 to red light. The chirped light emitted from the second blue light emitting layer cannot pass through the mirror structure 125, and therefore resonates between the layers 125 and 130, which causes the red low-direction frequency conversion phosphorescent male layer 114 to be hoisted for some reason. The resulting red light emission enters the substrate through the light emitting layers 113 and U2. The form shown in Ming 25 enables red light to emit more light than is possible with red (color organic light emitting layers). • 47- This paper size applies to the Chinese national standard (CN'S 丨 A4 specification (2IOX297 mm) {Please Read the ^ -Notes on Private Matters before filling out this page)-Binding and ordering J. Gram, Description of Inventions (45) Α7 Β7 The Central Consumer Bureau of the Ministry of Economic Affairs, Consumer Cooperatives printed in the heroic example of circle 25 Substrate 1U is a substantially transparent base such as soil, quartz, stone, or plastic. For simplicity, light is emitted in circles; | 112, 113, and 115 are shown as a single layer "&gt; As is well known in the art, when it is not a single-wide polymer device, these layers actually include multiple sub-wide (such as HTL, EL, and ETL) sub-layer configurations and it is easy to see whether the device is DH ( Double heterogeneous structure) or SH (single heterogeneous structure) morphology. When the transparent conductive layer simultaneously serves as the cathode of one first emitting layer and the impotence of the other, such as layer 121, it includes marriage _ 录 _ Oxide („IT〇 ··) is better than #. When the transparent conductive layer is different, it acts as a cathode and anode, such as 122 pray 'It is provided as the cathode of the green light emitting layer 113, but separated by a mirror structure 125 and a second cover light emitting layer 115, which includes a compound electrode, such as a translucent low work function metal and 17 〇. However, it is not the same as the anode layer of the cathode and the anode. The 17 β β metal contact layer 130 includes any material such as magnesium, Syria, aluminum, silver, gold, and alloys thereof. In another specific example of the invention, the green low-direction variable-frequency phosphorescent chirped layer 126 is inserted between the red low-directional variable-frequency phosphorescent cross-section layer 114 and the second blue light-emitting layer 115, as shown by circle 26. The layer 126 reaches to In the green light, the thorium is transformed, resulting in a more obscure transition from dust to red light. In another example of the present invention, a blue light emitting layer is used to make both red and green low-frequency variable-frequency phosphorescent chirped layers surge. "As shown in circle 27" In the device 200, the first blue light emitting layer 112 is provided on the substrate 1 &lt; 11, and the green low-frequency conversion phosphor body layer 126 is provided on the first blue light emitting layer U2. ， -48- This paper size applies Chinese National Standard (CNS) Α 4 Specifications (210 X 297 mm) ---- ^ ----- Γί ^ .— (Please read the note on the back *-Matters before filling this page) Order

U A7 __ B7 V. Description of the invention (46) The second blue light emission layer 115 printed by the staff of the Central Standards Bureau of the Ministry of Economic Affairs and the cooperative is printed on the green low-frequency conversion layer 126, and the red low-frequency conversion phosphor layer 114 is set Above the second blue light emitting layer 115, and the second blue light emitting layer 127 is disposed on the red low-frequency conversion phosphor layer 114. Disposed between the light emitting layers are transparent conductive layers 120, 121, 122, 1:23, and 125. The metal contact layer 130 is disposed on the third blue light emission layer 127. In addition, the first and second mirror structures 128 and 125 are respectively disposed between the first blue light emission layer 112 and the green low-frequency conversion layer 126. And between the second blue light-emitting layer 115 and the red low-directional metamorphic phosphorescent cross-layer 114. The first mirror structure 128 allows red and green light to pass, and prevents cover light from passing. The second mirror structure 125 allows red light to pass through, but prevents green light and white light from passing through. Regarding the representative specific example of the present invention in which the OLED further includes a low-direction variable-frequency phosphor layer, the OLED may include: a transparent substrate; a first blue organic light-emitting layer on the substrate; A green organic light emitting layer on each of the blue organic light emitting layers; and a mirror structure on the green organic light emitting layer, the mirror structure including at least one multilayer stack of dielectric materials, the mirror structure allows red light to pass through And prevent the passage of blue and green light; a red low-direction variable-frequency phosphor layer on the mirror structure; and a second magenta organic light-emitting layer β on the red low-direction variable-frequency phosphor layer, or, this one contains The OLED of the low-direction pseudo-phosphor layer may include: a fangming substrate; a first ocher-colored light-emitting layer on the substrate; and a first specular structure on the first blue organic light-emitting layer The mirror structure includes a multilayer stack of at least one dielectric material, and the mirror structure 1 allows red and green light to pass, and prevents blue light from passing; -49- on the first mirror structure, this paper size applies Chinese country Associate (CNS) A4 size (210X297 mm) (Please read the back of the note term ί then fill out this page) stapling IIJ / Β__ν ^

V. Description of the invention (47) The low-level change of the edge color of Gu Siguang It layer printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs; the second blue organic light-emitting layer on the green low-frequency variable-frequency light-breaking layer; The clock face structure of the second blue organic light emitting layer, the broken face structure includes at least one dielectric stack of a multilayer stack #, the mirror structure allows red light to pass, and prevents blue and green light from passing through A red low frequency conversion phosphor layer on the mirror structure; and a third ocher organic light emitting layer on the red low frequency conversion phosphor male layer. The light emitting device of the present invention may include a low-loss, high-reflectivity dielectric material between the transparent conductive layer 120 and the substrate 111 as needed, such as a layer 14 of dioxide (Ti02). When the transparent conductive layer n0 is made of ITO, which is a high-consumption material, the layer 140 is particularly preferable. The reflectances of 1402 and 1.0 are about 2.6 and 2.2, respectively. The layer 140 thus substantially eliminates guided waves and absorption in the ITO, and light emitted from the light emitting layers 112, 113, and 115 is now easily transmitted through the layer 140 and the substrate iu. The present invention will now be described in detail by showing some specific representative specific examples of manufacturing methods, and the materials, devices, and method steps which are understood as examples are for illustration purposes only. In particular, the invention is not intended to be limited to the methods, materials, conditions, program parameters, devices, etc., explicitly cited herein. EXAMPLES Before depositing an organic thin film of a representative OLED of the present invention, a (100) Si substrate can be cleaned by rapid ultrasonic cleaning in a detergent solution and deionized water, and then cleaned at 1, 1, 1, 3 Boil in gaseous ethane, wash in ketone, and finally boil in 2-propanol. Between cleaning steps, the substrate can be dried in high purity nitrogen. The background pressure before deposition is generally &gt; &lt; 10 · 7 Torr or less &lt; &apos; &gt; and the force during the deposition process is about 5X10'7 to 1.1X10 Torr. -50 · II .1-— I · 1 I ......... 1-! 1 I I --- --C, (Please read the note on the back before filling this page) Order This paper size is applicable to China Garden Standard (CNS &gt; A4 size (210x297 mm) V. Description of invention (48) A7 B7 Printed by I. I Protected IOLED in the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 丨 丨An IOLED structure (Loop 1) was grown by depolarizing a 25: 1 Mg-Ag alloy by thermally evaporating 1,000 Angstroms thick in the air, and then 500 Angstroms of wheat (8-hydroxyquinoline) aluminum (Alq3) was deposited. ) Electron transport and electro-excitation light (EL) layer, and 250 Angstroms of N, N, -diphenyl-N, N · -bis (3-methylphenyl) -BuΓ-linbenzene-4,4 Hole transport layer (HTL) of '-diamine (TPD). Alternatively, 4,4'-bis [N- (l-fluorenyl) -N-phenyl-amino] biphenyl ("τ -NPD) as the IOLED of HTL, the result is similar to the IOLED obtained by using TPD », in order to protect the fragile HTL from the deposition of the top ITO anode contact, and make 3,4,9,10- Carboxic dianhydride (PTCDA) or phthalocyanine bronze (CuPc) films β Typical organic deposition rates range from 1 angstrom / second to 5 Angstroms / second, the substrate is kept at room temperature. Finally, under the environment of 2000: 1 Ar: 02, and 5 mTorr, the top ITO layer is deposited by spraying ITO wiper with RF magnetron. The RF power is 5 watts, which results in a deposition rate of 200 Angstroms / hour. 0.05 mm2 IOLEDs with PTCDA and CuPc PCLs, and forward bias current-voltage (IV) characteristics for devices without PCL are shown in circle 2. Circle 3 shows the light intensity of IOLEDs in Circle 2 as a function of current (LI). An OLED including a layer structure with the following sequence is also prepared: ITO layer / 60 Angstrom PTDCA / 500 Angstrom NPD / 500 Angstrom Alq3 / 1000 Angstrom 1 ^ Balu / 500 Ang Ag, and similar OLEDs without a PTCDA layer. The current versus voltage of this device is shown in circle 5. Π. OLEDs were fabricated using the improved ιτο deposition method. In the representative embodiment, the paper standard is -51-. This paper standard is in accordance with China National Standards (CNS) A4 specification (210X297 mm). (Xu Xun 闰 read the precautions on the back before filling in this page) '&Binding; A7 ___B7 V. Invention Note (49) Used from South Wall Technology Company, Palo Alto, California, USA (Southwall Technologies, Inc.), a commercially available glass substrate coated with ITO. A hole transporting layer including about 300 Angstrom TPD was deposited on the ITO anode layer, and an electron transporting layer including about 500 Angstrom (8-hydroxyquinoline) aluminum (Alq3) was deposited on the TPD hole transporting layer, and about A cathode layer of 120 angstrom Mg-Ag was deposited on the Alq3 electron transport layer. An ITO layer according to the present invention is then prepared by depositing about 150 Angstroms of ITO on the Mg-Ag cathode layer using only 5 watts of RF power in the presence of about 200 sccm Ar and 0.1 seem 02, and then at about 200 In the presence of seem Ar and 0.42 seem 02, an additional 400 Angstroms of ITO was deposited using 45 watts of RF power. Circle 7 shows the current-voltage (i-v) characteristics of this heterogeneous structure. The I-V characteristics of this device have no practically discernable difference between OLEDs that deposit all of the ITO layers at a lower deposition rate. While the special OLED structure of circle 6 has been described, it should be understood that any OLED structure having an ITO layer deposited using a low initial deposition rate and then deposited using a substantially higher deposition rate would be in accordance with the present invention.

Ijl. EELE with an organic free radical containing electric transport layer 1. A single heterogeneous structure containing organic free radicals Printed by the Ministry of Economic Affairs Central Standards Bureau Shellfisher Consumer Cooperative Co., Ltd. The transparent substrate is pre-coated with about 15 ohms / Square sheet resistance indium tin sulphide (ITO) layer. The substrate can be ultrasonically washed in a detergent, then washed in deionized water, 1,13-trifluoroethane, acetone, and formazan, and dried in pure nitrogen between steps. . The clean, dry substrate is then transferred to the aerial deposition system. Then it can be used at high altitude (<2xl0'6 Thor) -52- This paper size applies Chinese national standard f (CNS (210X297 mm) A7 -------- B7 V. Description of invention (% ) All organic and metal depositions are performed under the policy of the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The deposition is performed at a nominal deposition rate of 2-4 Angstroms per second via thermal evaporation from a Ta crucible equipped with a baffle. Layer vapor deposition of approximately 350 angstroms of N, N, -diphenyl-N, N'-bis (3-methylphenyl) 1-1 · amidine-4,4'-diamine (TPD) On a clean ITO substrate. A sample of M (C5Ph5) 2 (where M can be Ge or Pb) can then be heated to about 250eC to release Cp *. It can be deposited in layers above the TPd film. The final thickness can be about 400 Angstroms. ”Then, it can be co-evaporated from individual Ta boat m (b0at) to deposit a national array of about 250: 1 Mg: Ag atomic ratio. .Ag layer can be deposited with a thickness of 50 angstroms and oxidized by the atmosphere of _ # pole. The double heterogeneous structure of the base j -V »·;; The double inhomogeneity can be made by including an individual emitting layer, this individual emitting layer can Become a hetero- or undoped para- (8-hydroxyquinoline) aluminum Alq3. The double heterogeneous structure can be prepared essentially as described for a single heterogeneous structure, except after depositing the TPD layer and after depositing organic Individual emissive layers of Alq3 are deposited before the radical layer. OLEDs that select the host material and / or doped materials are used in the preparation of the present invention to select the host and / or dopant materials and add them to the OLE). The hole transporting layer includes N, N, -dibenzyl-N, N'-bis (3-methylphenyl), toluene-44, _diamine (TpD), and the electron transporting layer includes doping. Or un-doped para- (5-hydroxyquinoxaline) aluminum (Alx3) or doped or un-doped Alq3. The hole transporting material TPD and the electron transporting material 4343 and ^ 1 ～ are synthesized according to the literature steps, and are sublimated before use. -53- Chinese paper standard (CNS) Α4 specification (21〇X 297 cm) is applicable for unpaper size (Please read the precautions on the back before filling this page)

A7 B7 V. Description of the invention (51) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs The cone blender C60 was purchased from Southern Chemical Group, LLC, and was used in the received state. The bisphenol square acid osmium dopant and the indigo dye compound dopant of chemical formula XI were purchased from Ai Ju Chemical Co., Ltd. and were treated twice to obtain pure green and purple crystalline materials. Phenyl- (5-hydroxyquinoline) aluminum (Alx3) is prepared by reacting aluminum paraisopropoxide with 5-hydroxyquinoline in isopropylhydrazone under argon. Isopropanol was dried on CaH2 before use. The amount of ligand used for the reaction is slightly excessive. The isopropanol mixture was refluxed under argon for one and a half hours, and the orange product was isolated via rotary evaporation. A mixture of 0.2 g of Ga (N03) 3 · χΗ20 in 200 ml of water-containing solution and an excess of 1% alcohol solution at 60eC was added, and then 10% ammonium argon oxide was added to make the solution slightly alkaline to form Ginseng (5-hydroxyquinoline) gallium (Gax3). An orange sinker was obtained, and after cooling, it was filtered off. The preparation of Gax3 is similar to that described in Spectrochimica Acta, 1956, Vol. 8, pp. 1-8. Regarding reagents, 5-hydroxyxanthroline was prepared in accordance with SK Freeman, PE Spoerri, Journal of Organic Chemistry (J. Org. Chem.), 1951, 16, 438; reference isopropionate aluminum (99.99% purity), (: ^ 〇3) 0112〇 (99.999% purity) was purchased from Aiju Chemical Company; and isopropyl alcohol was purchased from Fisher Scientific. The ITO / rhenium borosilicate substrate (100 ohms / square) was obtained using a precision step sampler. All chemicals are resistant to heating in various boats and vessels. TPD is first deposited at a rate of from 1 to 4 Angstroms per second. The thickness is typically controlled at about 300 Angstroms. ί Λ1 ^-. · C,: (Please read the notes on the back before filling this page) Order

C • 54- This paper size is applicable to the Chinese National Standard (CMS) A4 (210X297 mm) A7 B7 Printed by the Central Government Bureau of the Ministry of Economic Affairs Shellfish Consumer Cooperatives V. Description of the invention (52) The electronic transport layer (Alq3, Alx3) is doped with various dyes (c6 &lt;), bisphenol square acid fluorene dye and indigo fluorene dye compound of chemical formula IX). Typically, the dopant is first evaporated under the condition that the substrate is covered. After the dopant rate stabilizes, the main material is evaporated at the specified rate. The cover on the substrate is then opened, and the rate of deposition of the β-dopants of the main material family and the guest material family at the desired concentration is generally 0.1-0.2 angstroms / second. The total thickness of this layer is controlled to about 45 Angstroms. The substrate was then released into the air and the light army was placed directly on the substrate. The Light Army Department is made of indeterminate panels and includes holes with diameters of 0.25, 0.5, 0.75, and 1.0 mm. The substrate is then placed back into the air for further coating. Magnesium and silver are co-deposited at a generally 2.6 Angstrom / second rate. Mg: Agi ratio varies from 7: 1 to 12: 1 »The thickness of this layer is typically about 500 Angstroms. Finally, 1000 Angstroms Ag was deposited at a rate between 1 and 4 Angstroms / second. The I-V characteristics of these OLEDs were measured, and they are shown in circle 13 for the doped and future doped A1χ3. The close similarity of the results with and without the dopant shows that the dopant does not disturb the electrical properties of the device. For OLEDs containing Alqs (as the main material, with and without the same material dopant, where the energy coordination of the main material and the dopant is poor), almost all of this emission is obtained from. Among the compounds, M = Ga dissolves a 25-gram sample of 4 · hydroxypyrazolidine [3,4-d] pyrimidine in a 1.1 M NaOH aqueous solution in a 25-milliwell well. A solution prepared by dissolving 114 g of gallium nitrate in 1.5 ml of water was slowly added to the NaOH solution, and the gallium was formed when the gallium acid was added. The white and precipitates were separated, ^ 5 ml aliquots of 6 Turn the wash twice and air dry. Separated products ^ 55 Zhongguan "_ (⑽) A4 size (17〇 ^ 297 ^^ ~ (please read the precautions on the back before filling out this page). Packing. Order 5. Description of the invention (53 ) A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs has an emission maximum at 390 nm when excited at 250 nm. VI. Preparation of compounds of formula XIII 1. Ref. (4-Ethylbenzyl Amine was prepared by dissolving 1.26 g (0.0225 mole) in formazan to obtain an aqueous solution of 〇11. The KOH solution was added to 100 ml of 2.00 g (0.038 mole) by adding In a solution of ginseng (4 · trimethylalkylidenephenylphenyl) amine prepared in argon furan (THF), a color detection solution was generated, which was stirred at room temperature for 3 hours. The mixture was filtered through Cebonite to remove a small amount of orange precipitate. The diatomaceous earth was washed with two 10 ml portions of THF. The solvent was removed from the combined filtrate in the air while leaving Sticky gray-sweep-color check residue. Triturate the residue with 50 ml of nail polish and stir for an additional 1 hour at room temperature. An orange powder equivalent to the chemical product was prepared, collected, washed in 25 ml portions of pentamidine, and dried in the air. Two portions of the external product were prepared from the filtrate in a similar manner to provide 0.746 g ( 63%) of the total yield. The emission characteristics of the compound at a wavelength of 346 nanometers are as follows: Emission (solution): 430nm Emission (solid): 517nm 2-Methyl (4-trimethylsilylethylbenzyl) ) Amidine [N (C6H4CCSi (CH3) 3] 100 ml of Schenk) was charged with 1.8 g of trimethylmenthyl acetylene, 15 ml of diethylamine, 2.0 g of ginseng (4- Bromophenyl) amine, 0.059 grams of PdCl :, 75 grams of triphenylphosphine, and 0.032 of copper (I). The reaction mixture was heated to avoid flowing for 24 hours. The solvent was removed in the air, and 7〇-56- This paper size applies to China National Standard (CNS) A4 (210X297 cm) m · in ^ — fluff I * * c:-(Please read the precautions on the back before filling this page}

• 1T

J V. Description of the invention (54) A7 B7 The benzene was printed by the Consumer Cooperative of the Central Government Bureau of the Ministry of Economic Affairs, and then the residue was extracted with 70 ml of ether. The two organic extracts were filtered through alumina, combined, and the solvent was removed in the air. The resulting skull has a melting point of 155-158eC and has a blue-like fluorescence. Excitation at 255 or 350 nm produces a luminescence centered at 402 nm. VII. Preparation of OLEDs containing an emissive material of the radical formula I A transparent substrate (such as a chip or plastic) is pre-coated with a molybdenum oxide (ITO) layer having a sheet resistance of about 15 ohms / square. The substrate can be cleaned by thorough scrubbing in deionized water, 1,1,1-trifluoroethane, acetone, and methanol, and dried in degassing nitrogen between steps. Then-transfer the clean, dry substrate to the aerial deposition system. All organic and metal depositions can then be performed at high altitude (&lt; 2 X 10'6 Tor). The deposition system is thermally evaporated at a nominal deposition rate of 2-4 Angstroms / second via a Ta crucible with baffles. First, about 350 angstroms of N, N, -diphenyl-N, N · -bis (3-methylphenyl) 1, Γ-methylbenzene-4,4 * -diamine (TPD A layer of vapor is deposited on the cleaned ITO substrate. A sample of the compound according to chemical formula XII and the selected fluorescent dyeing family are then cooked in individual Ta boats to deposit a thin film on top of the TPD film, which is 0.1-10 mol% of the dye. A mixture of compounds. The emission color of the OLED will be indicated by the luminescent properties of the dye department itself, and can be selected across the entire visible spectrum through the selection of dyes. This hybrid thin film of the present invention is deposited to a thickness of about 400 Angstroms, and then can be co-evaporated from individual Ta boats to deposit about 100: 1 Mg: Ag ratio of a circular 0.25 mm diameter 1000 Angstrom electrode. Queue β can then add a 500 Angstrom Ag layer to suppress atmospheric oxidation of the electrode. '. iL ~~. · --- T ilί; c ί Jing first read and read the notes on the back one p and then fill in two pages) Order — ^ l·L. -57- This paper size applies the Chinese National Standard (CNS ) A4 specification (210X297 mm) ____B7 V. Description of the invention (55) VIII. Preparation of OLEDs with the chemical formula XIII of Scion Gen. Printing of transparent substrates (such as glass or plastic) ) Pre-coated indium oxide (ITO) layer with a sheet resistance of about 15 ohms / square. The substrate can be thoroughly washed in deionized water, 1,1,1-three gas ethane, acetone, and formic acid. Wash and clean, and dry under pure nitrogen between steps. The clean, dry substrate is then transferred to an airborne deposition system. All organic and metal depositions can then be performed at high altitude (&lt; 2 X 10'6 Tor). The deposition system is cooked through a Ta crucible with a baffle at a nominal deposition rate of 2-4 Angstroms / second. The first step is to heat a sample of the compound according to formula XIII and a selected fluorene fluorescent dye in an individual Ta boat to deposit a thin film over the cleaned substrate, which is 0.1-10 mole percent. Based on the mixture in compound π. The emission color of the OLED will be indicated by the luminescent properties of the dye itself, and can be spanned across the entire visible spectrum through proper selection of the dye. The hybrid film invented by this sample was deposited to a thickness of about 400 Angstroms. Secondly, deposit a thin film of a hole-blocking material, such as 100 angstroms of bimorphs (for example, 2 · (4 · 硪 phenyl) -5- (4-second butylbenzyl) _1,3,4- Oxadiazole), followed by the deposition of an electron-transporting material, such as a thin film (about 300 angstroms) of aluminum (8-kiloyl) aluminum. Then it can be co-evaporated from individual Ta boats to deposit approximately 10: 1 Mg.Ag than a circular 0.25 mm diameter array of 1000 angstroms. Then an 500 Å thick Ag layer can be added to suppress the Atmospheric oxidation of the electrode. Those skilled in the art will be aware of certain modifications to various courtesy examples of the present invention. These modifications are intended to be covered by the spirit and scope of the accompanying patent application park. , • 58- ^ Paper Newcastle® Financial Materials (CNS) Α4ί ^ 7_2Ϊ0χ297mm7

Claims (1)

A8 B8 C8 D8 1. Application for a patent application 1. An organic light emitting device comprising an electrically excited light layer between a pair of electrodes, wherein a protective layer is provided between the electrically excited light layer and at least one of the electrodes. 2. The organic light emitting device according to claim 1 in the scope of patent application, wherein the electro-excitation light layer is included in the heterogeneous structure for generating electro-excitation light, and the protective layer is in the hole transport layer and the anode layer between. 3. The organic light emitting device according to item 2 of the patent application park, wherein the heterogeneous structure is a single heterogeneous structure. 4. The organic light emitting device according to item 2 of the applied patent, wherein the heterogeneous structure is a double non-uniform structure. 5. The organic light emitting device according to item 1 of the patent application, wherein the protective layer includes tritium, stubble, iso-edge forest, phthalocyanine, or brown # based compound. 6. The organic light emitting device according to item 5 of the applied patent, wherein the compound is 3,4,9,10-tetracarboxylic dianhydride; phthalocyanine compound; 3,4,7,8 -Benzenetetracarboxylic dianhydride; 3,4,9,10 · anhydrotetracarboxylic dianhydride; bis (1,2,5-thiadiazole) -p-bis (1,3-thiosulfan); 1,4 , 5,8-benzenetetracarboxylic dianhydride; (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Where R = H, alkyl or aryl; 〇-f &gt; RN &gt; &gt; = \ &quot; NR A &gt; &gt; -59- This paper size is applicable to China National Standard (CNS) 8-4 specification ( 210X297 mm) A8 BS C8 D8 6. Application scope of patents where R = H, alkyl or aryl; with CA index name, bisbenzimidazole [2, la: r, 2'-b ·] anthracene [2, 1,9- &lt; ^ [: 6,5,104'6 '; ^] Diisoquinoline-10,21-dione compound; CA index name, double crop [2 ·, 3 ·: 4,5] Imidazole [2, la: 2 ', ra ·] anthracene [2., l, 9-def: 6,5,10-d, e'f] diisoquinoline-10,21-dione compound; f Compounds with CA index names, bisbenzimidazole [2,1 &lt; deca, 2 ', 1 "] benzophenone [Ιπιη] [3,8] morpholine-8, I-diones;. CA index names, Benzo [lmxi] bisbenzo [2 \ 3 ': 4,5] imido [2,1-1 &gt;: 2'1'-11 [3,8] morpholine-9,20-difluorene compound; or Substituted derivative of one of the compounds. 7. V The organic light emitting device according to item 6 of the scope of patent application, wherein the protective layer includes the 3,4,9,10-tetracarboxylic dianhydride. 8. According to Number 5 of the scope of patent application Organic light emitting device, wherein the protective layer includes phthalocyanine bronze. 9. The organic light emitting device according to item &amp; scope of the applied patent, wherein the heterogeneous structure includes an electron transporting layer containing an organic radical. Central Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperative (please read the precautions on the back before filling out this page) 10. According to the organic light emitting device in the scope of patent application, the heterogeneous structure used to generate electrical excitation light includes the main material And dopant emission layer, the main material is (5-liquid) * Chazlin's metal complex with the following chemical structure: -60- This paper uses Chinese National Standard (CNS ) A4 specification (210 X 297 mm) A8 B8 C8 D8 6. Application scope Where M is A1, Ga or In, then n = 3, and if M is Zn or Mg, then n = 2 0 11. According to the organic light emitting device of claim 10, the dopant includes a chemical formula The following bisphenyl square acid europium (sq'uarili.um) compounds: (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs where Ri, R2, R3 &amp; R4 are unsubstituted or substituted alkyl, aryl or heterocyclic rings, and 5 and 6 are unsubstituted Or substituted alkyl, aryl, OH or NH2. 12. The organic washing and emitting device according to claim 10, wherein the dopant includes an indigo dye compound having a chemical structure of the following chemical formula: Where X = NH, NR9, S, Se, Te, or O, where 9 is pit or phenyl, and 7 and 118 are unsubstituted or substituted alkyl or aryl groups 囷, 7Γ- Electron donor group 囷 or 7Γ-electron acceptor group. '-61-This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) A8 Βδ C8 D8 VI. Application scope of patent 13. According to the organic light emitting device of the scope of patent application No. 10, where, Dopants include fullerene compounds. 14. The organic light emitting device according to Item 2 of the patent application: a radiation device, wherein the non-r-substance structure includes an emission layer containing a main material and a dopant, and the dopant &lt; includes a compound of the following chemical formula: Wherein I, R2, Chi 3 and Chi 4 are each unsubstituted or substituted pit group, aryl or heterocyclic ring, and R5 and R6 are each unsubstituted or substituted fluorenyl, aryl, OH Or NH2. 15. According to the organic light emitting device of the scope of patent application No. 2, wherein the heterogeneous structure includes an emission layer containing a main material and a dopant, the dopant includes an indigo dye compound having the chemical formula as follows: (Notes for filling in this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs where X =: NH, NR9, S, Se, Te, or 0, where the ruler 9 is an alkyl group or a phenyl group, and R7 and anion 8 are unsubstituted or substituted respectively. Alkyl or aryl group, 7T-electron donor group or electron acceptor group. 16. The organic light emitting device according to item 2 of the scope of patent application, wherein the heterogeneous structure includes an emitting layer containing a main material and a dopant, the dopant including an olefin compound. -62- This paper is fully compliant with Chinese National Standards (CNS) A4 specifications (210X 297 mm) A8 BS C8 D8 Sixth, the scope of patent application 17. Organic light emitting device according to the second paragraph of the patent application, which should not The homogeneous structure includes an emission layer containing a main compound represented by the following chemical formula: The Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs prints ions where M is a divalent or trivalent metal atom; where η is 3 when M is trivalent, and η = 2 when M is divalent. , Wherein the metal atom is selected from the group consisting of aluminum, gallium, indium, and pyrene, and X, ytterbium, and z are each independently or exclusively C or N, so that at least two of X, ytterbium, and Z are Ν〇18 According to the patent application, the organic light emitting device of item 2, wherein the heterogeneous structure includes an emission layer containing a main compound having a structure _ represented by the following formula: NfO ~ ^ ~ RL J 3 where R It is an alkyl group, a phenyl group, a substituted alkyl group, a substituted phenyl ', a trimethylsilyl group, or a substituted trimethylsilyl group. 19. $ The organic light emitting device according to Item 1 of the patent application, wherein the organic light emitting device includes a plurality of organic light emitting devices in a well-stacked configuration and one of them; and The frequency conversion phosphor layer is disposed between any two of the plurality of organic light emitting layers. 20. The organic light emitting device according to item 1 of the patent application park, wherein the organic light emitting device is substantially transparent and has an absorber with a low reflection ratio. -63- This paper standard applies to Chinese National Standard (CNS) Α4 Specifications (210 X 297 mm) (Please read the precautions on the back before filling out this page) -3 A8 B8 C8 D8 々. The scope of patent application is set next to the organic light emitting device that is substantially transparent to form a high contrast Light emission display. 21. —A kind of organic light emitting device according to item 1 of the application for flat display, transportation, theater, television, printer, wall screen, cinema screen, sports field, electronic device, lighting device , Screen advertising boards or tricks. 22. —A kind of organic light emitting @, which includes: a substrate;: Tim 4 丨 cathode layer;-m · »electron transport layer; hole transport layer; protective layer; and anode. 23. The organic light emitting device according to item 22 of the scope of patent application, wherein the * protective layer includes chicory, tea, isoquinine, phthalocyanine, or morpholino compounds. 0 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please (Please read the notes on the back before filling this page) 24. The organic light-emitting device according to item 23 of the scope of patent application, in which the compound is 3,4,9,10-chicotechidic acid anhydride; 3,4,7 , 8-pyridinetetracarboxylic diacid * liver; 3,4,9,10-acoustetracarboxylic di-anhydride; bis (1,2,5-pyridadiazole) -p-bis (1,3-disulfide) Azole); 1,4,5,8- ¥ tetracarboxylic dianhydride; Among them R ^ H, alkyl or aryl; -64- This paper size applies to Chinese national standards (CNS> A4 specification (210X297 cm)> A8 B8 C8 D8 々, patent application scope V RN iy \ yy -i〇 where R = H, alkyl or aryl has a CA index name, bisbenzimidazole {2, la: r, 2i-b ·] shallot [2, l; 9-def: 6,5,10-d'e'f '] Diisoquinoline-10,21-dione compound; CA index name, double crop [2 ·, 3 ·; 4,5] imidazole [2, l-a__2, ra *] shallot [2, l , 9-def: 6,5,10-d, e, f,] di-isoquinolin-10,21-dione compound; with the CA index name, bisbenzimidazole [2, la: l ' , 2 ', Ji] benzo [lmn] [3,8] morphine, a compound of -8,1-dione; with the CA index name, benzo [lmn] 双 朵 ί 2, · 3': 4,5] A compound of imidazole [2, lb: 2'rI] [_ 3,8] morphine, lin-9,20-dione; or a substituted derivative of one of the compounds. 25. According to item 24 of the scope of patent application An organic first emitting device, wherein the protective layer includes the 3,4,9,10-chirotetracarboxylic dianhydride. 26. The organic light emitting device according to item 23 of the patent application scope, wherein the protective layer includes Huayin Copper. Printed by Shelley Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) 27. — A method of manufacturing an organic light emitting device for generating electrical excitation light, including: Manufacturing a heterogeneous structure for generating electrical excitation light, wherein the manufacturing method includes the step of depositing a protective layer on the electrical transport layer, and then depositing a tin oxide oxide anode layer on the protective layer. Paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) AS B8 CS D8 VI. Patent application scope 28. According to the 27th method of patent application scope, the protective layer includes tritium, poly, isoquine Fluoroline, phthalocyanine, or morphine # -based compound. 29. The method according to item 28 of the applied patent, wherein the compound is 3,4,9,10-anhydride; acid anhydride; 3,4,7, 8-Tetratetracarboxylic dianhydride; 3,4,9,10-pyridinetetracarboxylic dianhydride; bis (_1,2,5-pyrimidiazole) -p-bisbis (1,3-dithiazolyl); 1, 4,5,8-benzenetetracarboxylic dianhydride; Where R = H 'alkyl or aryl; (Please read the notes on the back before filling in this page) , π Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs where R = H, alkyl or aryl, with CA index name, bisbenzimidazole [2, lcl ,, 2'-b,] anthracene [2,1 , 9-Heart [: 6,5,10-Shi 61 '] diisoquinoline-10,21-dione compound; with CA index name, bisphosphonium [2 ", 3': 4,5] imidazole [ 2, la: 2,, l, -a ·] anthracene [2, l, 9-def: 6,5,10-d, e, f] diisoxoline-10,21-dirim compound; has CA index name, bisbenzimidazole [2, la: l, 2, 2, lri] ,. [lmn] [3,8] morpholine-8,1-dione compound;) CA index name, benzene Benzo [1πιη] bisbenzene [2,, 3,: 4,5] midot [2, lb: 2'rI] [3,8] Compounds of morpholine-9,20-dione; -66-Paper Standards apply to China National Standards (CNS) A4 specifications (210 x 297 at public expense) A8 B8 C8 DS ^ ----------------, scope of patent application, or substitution of one of the compounds The method of claim 3, wherein the protective layer comprises the 3,4,9,10-tetracarboxic anhydride. 31. The method according to item 28 of the patent application park, wherein the protective layer includes phthalocyanine bronze. 3 2 · Method according to the scope of application for patent No. 27, wherein the manufacturing method includes the following steps: (a &gt; Deposition of indium tin oxide at a low deposition rate to form a protective indium tin oxide layer; and then. (b) Depositing oxides at a substantially higher deposition rate. 33. The method according to item 27 of the patent application, wherein the manufacturing method includes heating the organometallic complex under sufficient conditions to sufficiently The temperature at which the organometallic complex forms organic radicals from the gas phase to form an electron transport layer. 37. The method according to item 27 of the patent application, wherein the manufacturing method includes depositing a main material and doping. Step of the dopant layer, the dopant includes the following compounds of the North School formula: (Please read the precautions on the back before filling out this page) Equipment, printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Wherein R2, R3, and R · 4 are each an unsubstituted or substituted alkyl, aryl, or heterocyclic ring, and Re are each an unsubstituted or substituted alkyl, aryl, OH, or NH2, respectively. . 3 5. The method according to item η of the scope of patent application, wherein the manufacturing method package -67- this paper M is suitable for nnjia county (CNS) Α4 · (2 丨 G χ 297 public race) AS BS C8 D8 VI. Application The scope of the patent includes the step of depositing a layer comprising a host material and a dopant, the dopant including an indigo dye compound of the following formula: \ * Where * X = NH, NR9., S, Se, Te, or Q, where 9 is an alkyl or phenyl group, and 117 and 118 are each an unsubstituted or substituted alkyl or aryl group, π -An electron donor group or a π-electron acceptor group. 36. The method according to item 27 of the scope of the patent application, wherein the manufacturing method includes the step of distantly containing a layer containing a main material and a dopant, the dopant including a dilute compound. 37. An electron transporting layer of a multilayer structure, wherein the multilayer structure includes a hole transporting layer, comprising: an electron transporting layer containing a radical, the electron transporting layer being: (a) in direct contact with a layer of emitting material, The winter layer of the emitting material is in direct contact with the hole detection layer of the multilayer structure; or (b) is in contact with the hole transportation layer cover of the multilayer structure. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) 38.-A type of organic light emitting device that includes a heterogeneous structure for generating electrical excitation light Including an electron transporting layer containing an organic radical. 3 9. A high-contrast light emission display, comprising: a substantially transparent organic light emitting device; and an absorber with a low reflectance ratio disposed adjacent to the substantially transparent organic light emitting device. r- -68-This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 40.-, an organic light emitting device for generating electroluminescence, which includes: a heterogeneous structure for generating electrical luminescence, _ the heterogeneous structure means the emission layer of the material containing winter king and dopant, the main material The system includes a metal complex with the following chemical formula ((5_carboxy 隹 4): Wherein: when fM is A and G ^ In, n = 3, and when μ is zn or Mg, n = 2. 41. An organic light emitting device for generating electric light emission, comprising: a heterogeneous structure for generating electrical excitation light, the heterogeneous structure having an emission layer including a king material and a dopant, the dopant comprising Compound 42 having a chemical formula as follows: An organic light emitting device for generating electric number light emission, comprising: a heterogeneous structure for generating electric excitation light, the heterogeneous structure having an emission comprising a main material and a dopant Layer, the doping agent includes: (Please read the precautions on the back before filling out this page)-Packing. Order printed by the Ministry of Economic Affairs, Central Bureau of Standards and Consumers Cooperatives Among them, I, R2, Chi 3 and Han 4 are unsubstituted or substituted tigeryl, aryl or heterocyclic ring, and R5 and R <$ are unsubstituted or substituted alkyl, Radical, OH or NH2. 43. An organic light emitting device for generating electrical excitation light, comprising: -69- — (CNS) A4 ^ (210X297 ^ *) A8 Βδ C8 D8 Homogeneous structure, the heterogeneous structure has an emission layer including a main material and a dopant, and the dopant includes an indigo dye compound having the chemical formula: Where X = NH, NR9, S, Se, Te, or 0, where R9 is a C: yl or phenyl group, and 117 and 118 are unsubstituted or substituted alkyl or aromatic groups, Electron donor bases &gt; or dragon-electron acceptor base maps. 44. An organic light emitting device for generating electroluminescence, comprising: a heterogeneous structure for generating electrical excitation light, the heterogeneous structure having an emission layer including a main material and a dopant, the dopant comprising Ethylene compound 45. An organic light emitting device for generating and generating electrical excitation light, comprising: a heterogeneous structure for generating electrical excitation light, the heterogeneous structure having an emission layer including a main material and a dopant The main compound is represented by the following chemical formula: Printed by the Central Standards Bureau, Ministry of Economic Affairs, Consumer Cooperatives (please read the notes on the back before filling out this page) where M is the ion of a divalent or trivalent metal atom; where M is trivalent, η = 3, and When M is divalent I, then η = 2, where the metal atom is selected from the group consisting of aluminum, gallium, indium, and zinc, and X, ytterbium, and Zn are each independently and independently C or N, so At least two of Y, Y, and Z are N. -70- This paper size applies to Chinese National Standard (CNS) A4 specification (2 丨 0 × 297 mm) A8 B8 〇 D8 46. Patent application scope An organic light emitting device for generating electrical excitation light, which includes: Generates a heterogeneous structure of electroluminescence, the heterogeneous structure has an emission layer containing a main material and a dopant, and the main compound is represented by the following chemical formula: -R wherein R is an alkyl group, a phenyl group, and a substituted alkyl group , Substituted phenyl, substituted silyl, or substituted m-methylsilyl. 47. A light emitting device comprising: a substrate; a plurality of organic light emitting layers arranged in a stack above the substrate; and a low-frequency variable-frequency phosphorescence disposed between any two of the plurality of light emitting layers Body layer. 48. A light emitting device comprising: a substrate; a filter structure above the substrate; a low-direction variable-frequency phosphorescent susceptor layer above the filter structure; and a low-frequency variable-frequency phosphorescent layer above the low-frequency variable-frequency phosphor layer Organic light emitting layer. ~ (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs -71- This paper size applies to China National Standard (CNS) A4 (210X297 mm)