TW518908B - Organic electroluminescent element, and method for manufacturing the same - Google Patents

Abstract

To provide an organic electroluminescent element reducing leakage currents and a method for manufacturing an EL panel using the element. This method for manufacturing an organic electroluminescent element at least includes (A) the process of depositing a first electrode on a substrate, (B) the process of layering one or more organic compound thin-film layers including a luminescent layer on the first electrode, and (C) the process of depositing a second electrode on the organic compound thin-film layers. The substrate temperature is 70 DEG C or less during the processes (B), (C), between the processes (B), (C), and during the period from the end of the process (C) to the time when the substrate temperature attains room temperature, and the absolute value of rate of variation in temperature is within 1.5 DEG C/sec. The invented process can produce an electroluminescent element having excellent rectifying characteristics.

Description

518908 V. Description of the invention (1) [Field of the invention] The present invention relates to an organic electroluminescence device and a manufacturing method thereof that can be used for a flat light source or a display device; an organic electroluminescence panel And a vacuum deposition apparatus for manufacturing the organic electro-laser element. [Known Technology] The best application of organic electric laser elements is in flat display devices. Unlike inorganic electro-laser elements, organic electro-laser elements do not require Ac or high voltage 'and because of the diversity of organic compounds, it is quite easy to provide different colors. Therefore, it is expected in the application of full color, and its related research and development are still ongoing, and a structure with high light emission at low voltage has been developed. When an inorganic electric laser device emits light by being excited by an electric field, an organic electric laser device emits light by carrier injection, and carrier injection occurs when holes and electrons are injected from the anode and the cathode, respectively. The positive carriers injected from the two electrodes (anode and cathode) migrate to the opposite electrode, and their recombination generates an exciton. When the energy of these excitons is released, light is emitted, and this emitted light is the light emitted by the organic X-electron laser element. In the past, the research of organic electro-optical laser devices mainly used a single crystal of thorium purity (anthracene). However, its luminance, iuminescence efficiency, and luminescence stability were all relatively low.

Kodak's Tang et al. Reported in 987 a structure comprising two laminated organic thin layers, which can provide quite high luminosity and stability at low voltages.

518908 V. Description of the invention (2) Nature. This is a turning point, which makes the research and development of organic electric laser devices very popular. In the structure reported by Tang et al., Two laminated organic thin layers including a luminescent layer and a hole transporation layer are inserted between a pair of electrodes. At a voltage of 10V, it exhibits the superior characteristics of 丨, 00cd / m2, which cannot be reached on the base of the moon, see Ding ang et al., Appl. Phys.

Lett., 51 (12), 9 1 3 (1 987). Recently, a structure has been developed which provides an electron transport layer between the cathode and the light emitting layer in the above structure, and another structure provided between the hole transport layer and the anode in the above structure. The structure of a hole injection layer. Furthermore, many researches have focused on various layered materials, which have resulted in many improvements in luminous efficiency and lifetime. The application of organic electro-laser elements in flat displays (where organic electro-laser elements are arranged on the XY plane) is highly regarded. Expected; and passive matrix actuated 256 X 64 dot monochrome displays have been developed [for example, h. Nakata, Display and Imaging Vol. 5, pp. 273-277 (1997); H. Nakata, Basics and Application of Organic EL Devices, Organic Molecular Electronics and

Article of the sixth session of Bioelectronics, the Hapan Society of Applied Physics, pp. 147 ~ 154 (1997)]. In the passive matrix actuation type 256x64 point organic electro-optical laser device, the scanning of the column electrode (cathode) is usually 1/64 power, and the edge electrode (anode) is actuated in parallel; that is, linear continuous actuation is used. In this case, unless the organic electric laser panel uses an organic electric laser element with excellent rectification

Page 5 518908 V. Description of the invention (3) Otherwise, it will cause even non-selected pixels to emit light, and interference phenomena can be seen ', and the display has a very low-quality image. [For example, the pixels around each selected pixel (pixel) will emit a + shape. For a detailed description, see S. Ohtsuki, " Basics and Application of Organic EL Devices 丨, Organic Molecular

Article of the sixth session of Electronics and Bioelectronics, the Hapan Society of Applied Physics, ρρ · 1 39-1 46 (1 997)] The organic electro-optical laser element is a kind of cold light device with a positive carrier injection type. Under the application of voltage, that is, when a negative voltage is applied to the electrode on the side of the hole transport layer and a positive voltage is applied to the electrode on the side of the electron transport layer, 'no current will pass through this device. However, in its practical application, in some cases, when a reverse voltage is applied, a very small amount of leakage current occurs. This leakage current may come from, for example, (1) the nature determined by the materials constituting the organic layer and the electrode, and (2) physical changes of the organic layer and the metal layer, such as inconsistent structure of each layer. However, the mechanism of 'leakage current' is still unclear. Incidentally, it has been reported that the use of a special substance as a cathode can improve rectification [N · Asai et al ·, Display and Paging, Vol · 5, pp · 279 ~ 283 (1 997)]. However, it only reported a small part of the research on the conditions for manufacturing organic electric laser elements, and found that there is no condition that can effectively manufacture organic electric laser elements with superior rectification. As described above, when the organic electro-optical laser element is arranged on the X-Y plane to manufacture a panel, and the panel is subjected to a simple matrix motion, when the element is at low rectification,

518908 V. Description of the invention (4) The leakage current mentioned above will be generated, so a cross-talk phenomenon is seen, and the image quality of this display is very low. [Objective of the invention] ^ The object of the present invention is to provide an organic electric laser element which has high rectification without changing the characteristics of the traditional organic electric laser element, and to provide a method for using such a device. Electromechanical laser panel. The present invention provides a method for manufacturing an organic electric laser device. The bean includes at least: (A) forming a first electrode on a substrate; (B) forming more than one layer of an organic compound film on the first electrode, and the organic compound film includes A light emitting layer; and (C) forming a second electrode on the organic compound thin film layer, wherein the temperature of the substrate is maintained at 70 or lower, and the rate of temperature change of the substrate is maintained at 1.5 ° C / second or lower The absolute value is between step (β) and (C), between steps (B) and (c), and when step (c) is completed, the temperature of the substrate becomes room temperature at one time. In order to control the temperature of the substrate, the present invention further provides a vacuum deposition device, which at least: (1) a substrate support having a smooth surface to support the substrate; and (2) a substrate temperature control device for controlling the The temperature substrate of the substrate on the layer film forming surface, and the structure of the substrate temperature control device includes at least: (2 -1) a temperature sensor;

Page 7 518908 __—— V. Description of the invention (5) (2-2) Computing device; (2-3) Heat release and absorption device. By using the steps of the present invention, it is possible to manufacture an organic electro-optical laser panel having, for example, a tendency, which avoids interference, has a high display quality, and has a significant change in the properties of the display element. [Brief description of the drawings] FIG. 1 is a schematic diagram showing a general organic electric laser device. Fig. 2 shows the structure of a vacuum reaction chamber of a vacuum deposition apparatus of the present invention, which can control the temperature of a substrate. Fig. 3 is a graph showing the current-voltage characteristics of the organic electric laser device manufactured in Example 丨 and Comparative Example 1. The vertical axis represents current, but is expressed as an absolute value after taking the logarithm to show the current flowing in the negative direction. _Symbol description】 Substrate: 11, 2 4 Transparent electrodes: 1 2 Hole transport layer: 1 3 Light emitting layer: 14 Electron transport layer: 1 5 Cathode: 16 Calculation unit: 21 Heat release and absorber: 2 2 Thermocouple : 2 3 Main window plate: 2 5 Vapor source window plate: 2 6 Evaporation source: 2 7 [Detailed description of the invention] The present invention has done some research in order to solve the above-mentioned problems of the traditional organic electro-excitation light element. As a result, it was found that when the organic layer and the electrode are formed, the above problems can be reduced by maintaining the temperature change rate and the substrate temperature on the molding surface of the organic layer. surface

Page 8 518908

The invention provides a method for manufacturing an organic electric laser device, which at least comprises: (A) forming a first electrode on a substrate; (B) forming one or more organic compound films on the first electrode, the organic compound film including a light-emitting layer , And (C) forming a second electrode on the organic compound thin film layer, wherein the temperature of the substrate is maintained at 70 r or lower, and the rate of the base is maintained at 1.5 T; / sec or lower than this absolute value, in step (㈦ And VC), between steps (B) and (c), and when step (c) is completed, the temperature of the substrate becomes room temperature.

First, in the present invention, the substrate of the organic electro-optic light-emitting element may be selected from various materials having characteristics such as flatness, resistance to stress generated when manufacturing the organic electro-laser element, and low light loss rate. It is a glass substrate. ^ In order to obtain the effect of the present invention, the temperature of the substrate on the molding surface of the organic layer is preferably 'maintained' at 1 · 5 it / s or lower; more preferably at 0.75 ° C / s or Below this absolute value. It is desirable that the substrate temperature be maintained constant. · The maximum temperature of the substrate to be formed on the organic layer molding surface is 80. "0 or lower" can certainly achieve the effect of the present invention. In order to ensure that the effect of the present invention is obtained, the maximum temperature is set to 700 ° C or lower, preferably t or lower. In order to implement the manufacturing process of the present invention, the minimum temperature of the substrate is as low as possible. (: However, in the practical application of the process of the present invention, the substrate temperature is usually maintained at about room temperature. The temperature of the substrate on the molding surface of the organic layer (hereinafter this temperature is referred to as

518908 V. Description of the invention (referred to as the temperature of the substrate) The temperature sensor can be placed on the substrate on which the organic layer will be formed, or on the first electrode when the first electrode has been formed thereon, and Measure its temperature. ▲ When the organic compound thin film layer includes a luminescent layer consisting of two or more hole transport layers, electron transport layers, etc., step (B) refers to not only the formation time of individual organic compound thin film layers' There is also the time between when the substrate is formed on the evaporative deposition device and the next layer.

In the present invention, the time period during which the temperature of the substrate and the rate of temperature change are controlled is expected to be from the time when at least the main window plate of the evaporation deposition device is opened to start forming the first organic compound thin film layer to the second electrode, and the substrate is cooled to room temperature And it can be taken out of the evaporative deposition device for the entire time. In the above, when the temperature control of the substrate is started, it is the time to open the evaporative deposition I and set the window plate. However, in the implementation of such a process, it may be easier to control the substrate temperature than to control the timing of the evaporation source heating. By using the process of the present invention, when a reverse bias voltage is applied, it is already possible to obtain an organic electro-optic light element with a lower leakage current.

In the present invention, the reason for the improvement in the rectification of the organic electric laser element is' presumably that the microdisorder of the heterointerface can be reduced by reducing the change in the substrate temperature, thereby reducing the organic electric laser. Component leakage current. The micro-disturbance of the interface is caused by thermal stress, which is caused by the difference in thermal properties between the individual substances constituting the different layers. In the present invention, the steps (B) and (C) are desirably processed by vacuum deposition,

518908 V. Description of the invention (8)-Vacuum deposition is a technology that uses an evaporation source to heat under vacuum to produce steam or clusters and deposits it on a substrate. In terms of heating, electron beam heating (which is a technique for heating an electron beam directly on a substance), resistance heating, and the like can be used. In the present invention, the vacuum deposition device has at least: a) a substrate support having a smooth surface to support the substrate; and (2) a substrate temperature control device to control the substrate temperature of the film forming surface; the substrate temperature control The composition of the device is at least: (2 -1) temperature sensor; (2-2) computing device; (2-3) heat release and absorption device. The temperature change of the substrate can be known from the evaluation temperature sensor of the computing device. A signal is sent from the device to the heat release and absorption device to eliminate the substrate temperature change ', and the substrate temperature and change rate can be determined in advance. By using such a substrate temperature control device, the temperature of the substrate can be slightly changed during the formation of the film layer, and it can also be maintained at 70 t or lower, thereby generating a higher-quality organic electroluminescent device. . Ideally, the heat release and absorption devices can be combined into one. It is also expected that the substrate temperature controller in the vacuum deposition apparatus can control the substrate temperature of the film forming surface to 70 or lower, and maintain the substrate temperature changing rate of the film forming ^ at 1 · 5 ° C / sec or low. Here the absolute value. The ideal substrate support requires a smooth surface, as measured by JIS B 060 1 -1 994. The surface roughness is: (1) arithmetic average roughness

518908

= 200 nm or less, and (2) Maximum height (Ry) = 800 nm or less. If the surface rough chain degree of the substrate support satisfies the above two conditions, then the contact area between the substrate and the support is large, and can be released by heat release and storage (which is integrated with the substrate support into one ) Improve control of substrate temperature. The smooth surface of the substrate support and the substrate can be filled with a soft metal without leaving any gap. By filling the metal between the substrate and the support, the temperature control of the substrate is further improved. In general, such soft metals can be indium and aluminum. Commercially available flakes of indium or other metals that meet these criteria.

The vacuum deposition apparatus of the present invention is suitable for steps (B) & (C). "In the present invention, there is further provided an organic electric laser element manufactured by these processes for manufacturing an organic electric laser element. The organic electric laser element of the present invention is suitable for an organic electric laser panel, and most of the elements are A matrix arrangement. A display manufactured by using the organic electric laser device of the present invention has low leakage current when applied with a reverse bias, and has low interference and high development quality. The first figure shows an organic electric laser device Structure diagram. A transparent electrode 12 is formed on the substrate; a hole transport layer is sequentially formed on the transparent electrode 12.

i3, the light emitting layer 14 and the electron transport layer 15; and a cathode 16 is formed on the electron transport layer 15. There is no particular limitation on the structure of the organic electro-optical laser device produced by the process of the present invention; therefore, the results of past research and development can be used. That is, a known substrate, a known anode, various known

518908 V. Description of the invention (10) Mechanical materials, known cathodes, etc. In this case, the organic electric laser element in the three-layer organic layer 13 is not used. / In the first figure, the two hairs can be planted into one. The carrier is combined with H carrier transport layers, and the carrier layer of the wheel layer becomes four or more layers. Yes, σ σ or change the three layers. It is also possible to use two materials in each organic layer that can be used on the cathode and light more than 16 ^ times. On the substrate sequence, two / one of the elements H in the i-th figure are transmitted. The manufacturing sequence of the components in the forward direction, the hole transfer layer, and the light-emitting / electrical process is Yang Dangjian [However, the special ::: 传;: 板:; The second order is the more negotiable order is the cathode , Electron transmission ;: light-emitting yin;:; lose the layer and anode. There is no specific restriction on this order. σtwo Figure 2 shows a vacuum deposition device (with a substrate temperature controller) according to the present invention. In Fig. 2, the substrate 24 (on which an existing film layer is formed) is fixed to a substrate support integrated with a heat release and absorber. A thermocouple 23 is provided on the substrate 24 to measure the / jul degree of the substrate. g When the first electrode is formed on the substrate μ, the thermocouple 23 is provided on the first electrode. ... W '. The temperature of the substrate is controlled by the following method. The temperature of the substrate and its changing rate measured by the thermocouple 23 are obtained by a computing unit 21 (computation uni t). The computing unit 21 sends a signal to the heat release and absorber 22 integrated with the substrate support (the heat release and absorber mentioned hereinafter are all heat release and absorber with a substrate support), so it can be eliminated on the substrate. Temperature changes that occur on the substrate

Page 13 518908 V. Description of the invention (11) The change rate and substrate temperature fall within a predetermined range, namely 1.5 ° C / sec or lower and 70 ° C or lower respectively; according to this signal, there is a substrate support The heat release and absorption will be exchanged with the substrate. An individual substance for forming a film layer is placed in an individual evaporation source 27 and is heated by a resistance heating device or an electron beam device. The formation of a film layer is started by opening the vapor source window plate 26 and the main window plate 25, and is completed after closing the main window plate 25.

The heat release absorber 22 and the thermocouple 23 having the substrate support are exposed to a vacuum environment, and therefore, they must be composed of a substance or structure that does not adversely affect the vacuum system. The thermocouple 23 is used to monitor the temperature of the substrate surface, and one thermocouple is used as shown in Fig. 2; however, two thermocouples may be used. When the size of the substrate is large enough, or when only a few evaporation sources are used, it is preferable to use multiple thermocouples. In such cases, the position and size of each thermocouple should be determined so as not to obstruct the flow of vapors moving on the substrate. The heat release absorber with the substrate support will exchange heat with the substrate and can eliminate the temperature change of the substrate.

In the present invention, the surface roughness of the surface of the heat release absorber 22 having a substrate support in contact with the substrate 24 is measured in accordance with JIS b 060 1 -1994, preferably (1) the arithmetic average roughness (Ra ) Is 200 nm or less, and (2) the maximum height (Ry) is 800 nm or less. The heat-releasing absorption with the substrate support Gong 22 provides such a smooth surface that a high adhesion force can be obtained between the substrate and the heat-releasing absorber 22 with the substrate support, and even in a vacuum environment Fast heat transfer is still possible. Be aware of radon, unless with a heat release absorber with substrate support

Page 14 518908

V. Description of the invention (12) The roughness of the surface of the substrate on the side contacted by 22 is the same grade as that of the surface of the heat release absorber 22 with the substrate support, or is less than, otherwise it cannot be obtained as described above. Good heat conduction. When the adhesion between the two surfaces is insufficient, the thermal energy transmission is not smooth, and the control force of the substrate temperature is reduced. (Example: Time delay of temperature control rises). Between the smooth surface of the substrate support and the substrate, it can be filled with a soft metal so that there is no gap in between. By filling the metal between the substrate and the support, the temperature control of the substrate can be further improved. By filling a relatively soft metal (such as indium) flakes or other similar properties between the two surfaces, and by pressing the two surfaces (press_bond), you can get higher adhesion, so you can The heat conduction between the substrate 24 and the heat release absorber 22 having a substrate support is made smoother. This type of metal sheet does not allow higher temperature control between the two surfaces with poor adhesion, and also has the function between the two surfaces with higher adhesion. The calculation unit 21 may calculate a temperature change of the thermocouple and transmit a signal to the heat release absorber 22 having a substrate support to eliminate the temperature change. The heat release absorber 22 having a substrate support changes the surface temperature of the substrate based on the signal transmitted therefrom. By the above-mentioned mechanism, during the formation of the film layer, the temperature change rate (expressed in absolute value) of the substrate can be controlled to 丨 5 it / s or lower, preferably 0. 75 ° C or lower, The optimum is zero (ie, the temperature of the solid substrate), and the temperature of the substrate can be controlled at 70 t or lower. Incidentally, the heat release absorption 2 2 may have a structure having a heater and a cooling member inside the structure, or an inert Hquid inside the structure or

518908 V. Description of the invention (13) ---- A cycle similar to this nature. The vacuum reaction chamber of the vacuum deposition device further provides the required number of other required components (not shown in Figure 2), such as a device for monitoring the evaporation rate, a photomask for patterning the film layer, and other. In Figure 2 there are three evaporation sources, but more evaporation sources may be used, depending on the number of film layers formed by vacuum deposition. ^ Usually, when the film layer is formed by vacuum deposition, the temperature of the substrate gradually rises as the heating of the sacrificial source starts. At the same time, with the opening of the main window, the temperature of the substrate will rise rapidly until the main window is closed. The first important point of the present invention is that the temperature of the substrate will gradually increase from the time when the evaporation source starts to heat until the film layer is formed; further, the substrate temperature is maintained at 70 ° C or lower. The rate at which the substrate temperature increases is preferably 5 ·. 〇 / s or lower, more preferably 疋 0 · 7 5 C / s or lower 'is optimally zero (ie, fixed substrate temperature), even after the main window has been opened. When the formation of the film layer is completed, the main window panel is closed, and the heating evaporation source is stopped (the heat supply becomes zero), and the substrate temperature is rapidly decreased. The second important point of the present invention is that the substrate temperature drops gently. The substrate temperature decreasing rate is preferably 1.5 ° C / sec or lower, and more preferably 0.75 ° C / sec or lower. The rise and fall of the substrate temperature is noticeable, especially the vacuum vapor deposition of high-boiling materials, and the formation of electrode layers from metal materials in the manufacturing process of ordinary organic electric laser devices has become a problem. The temperature change rate of the substrate may become larger, and the formation of the organic compound & thin film layer depends on the characteristics of each organic substance used, the stability of the deposition rate, the thickness of each layer, and so on. Therefore, according to this

518908 'Consistently in the production of organic electro-laser elements with low leakage current, the steps of continuously forming all film layers in a vacuum deposition device are before and after the steps of forming these film layers (outside the steps before descending the tarmac layer) In the case of multiple substrates, as long as the above temperature change rate and subsequent evaporation steps are maintained, it may not be necessary to wait for the evaporation source to reach the required one. When the evaporation source is also a thermal output, the thickness of the substrate and the degree of control are also described. A large number of rises in the film-shaped process, so the temperature of the 4 materials can increase the temperature of the vacuum sink. When the vapor sticks, the use of the substrate and the utilization rate must be considered. The rate of increase of the rate of increase of the rate of evaporation is due to the fact that the temperature of the substrate of the real material can be the source of evaporation. 5. Inventory (14) The process of the invention is better. First, the temperature of the substrate is first formed, and the time of the temperature is therefore per source and the substrate and, depending on each shape and the like, the degree can be reduced even when the distance is too large, not the base. At the same time, the distance of the substrate is reduced, and it is an example of the present invention. The distance of the film layer is large enough to observe that the substrate of the present invention is not warm. The evaporation source produces a plate. Focus. It is considered that when the vaporization is low, the efficiency of the evaporation source, the temperature of the substrate, and the empty reaction room between the substrate and the use of the efficiency controller, the distance between them may be feasible. This invention will be accompanied by τ, and the invention is not limited to this example for a clearer description. However, the scope belongs to the present invention. ~ 彳 lj 子, as long as it does not depart from the spirit of the present invention and [Example 1] Step (A) (Formation of the first electrode)

518908 V. Description of the invention (15) An indium tin oxide (ITO) layer is formed on a glass substrate having a thickness of 0.7 mm by sputtering, so that its sheet resistance becomes 15Ω / 0 ; And then remove unnecessary portions by etching (patterning) to obtain an IT0 anode (first electrode) (hereafter, = in this paragraph, the substrate with the first electrode is simply referred to as, substrate, ). This substrate was placed in a neutral cleaning solution for ultrasonic cleaning, then placed in isopropyl alC0h0l, and then fully dried, and then subjected to UV-ozone cleaning at 110 ° C for 5 minutes. Step (B) (formation of organic thin film), the -side of the substrate, the side other than the first electrode, is adhered and fixed to a heat release and absorption device having a substrate supporting device, and the substrate is fixed for two resistance heating Type vacuum deposition device and has substrate temperature control. . =. = In this example ', in order to increase the adhesion between the substrate and the substrate holder, it is pressed down with the indium sheet and interposed therebetween. The vacuum deposition device used in this example has 5 basic sources (= 〇⑴atl0n _rce). The distance from the evaporation source to the substrate is approximately ⑽ The heat release and absorption device is made of stainless steel. The connection of the inert liquid is as follows: 2: The surface of the release and absorption device is in contact with the substrate, and the basin and clothing are subjected to this high thermal height (Ry) = 800 nm or less. And (2) Take Next, all the raw material blankets that will form each layer are described below. Your other hair

Page 18 518908 V. Description of the invention (16) (1) 200 mg of substance for the hole transport layer (N, N'-diphenyl-N, N, -bis (1) -Nayl)-(1,1, -bisphenyl) -4, 4'-diamine (N, N'-diphenyl-N, N, -bis (α -naphthyl) -1,1'-biphenyl- 4,4'-diamine; referred to as α-NPD), placed on a molybdenum boat, and the molybdenum boat was set in an evaporation source. The structure of α-NPD is shown below.

(2) 200 mg of the substance used in the green iuminescent layer and also in the electron transport layer (iectron transport layer), namely di (8-Quillin) | Lu complex (tris ( 8-quinolinolato) aluminum complex; referred to as Alq3), placed in a molybdenum boat, and the molybdenum boat is set in an evaporation source. The structure of A 1 q 3 is shown below.

Page 19 518908 V. Description of the invention (17)

(3) Put 2 g of aluminum and 0.5 g of lithium as the cathode in a separate tungsten boat, and set this tungsten boat in the evaporation source. Lithium needs to be set up quickly to suppress oxidation on its surface, and immediately after it is set out, the vacuum reaction chamber is started.

Then, the number of steps of the degree of vacuum inside the vacuum reaction chamber will be reduced to -5 Pa (Pa ^, operating the substrate temperature control device (㈣ 心 ❺ cor ^ t ^ olleo, and start to control the substrate temperature. It will include "-NpD iiL Heating 'h When the deposition rate is stable at about ° "nm / sec, open the main square 彳 ττ > plate and form the formation of the transport layer of the turtle hole. In the phase gate method, the deposition rate is about 01 to A light emitting layer having a thickness of 7. is formed. (Organic layers can be formed using only a photomask, and the shape is two. &Amp; Step (C) (Formation of the second electrode). The pattern of the organic layer will be used in advance. The photomask used for forming the cathode and the 518908 V. Description of the invention (18) ------- The photomask for the organic compound thin layer is set in the vacuum reaction chamber, and each photomask can be made from a vacuum reaction chamber Choose the order of doing) After setting the photomask used to form the cathode, heat the lithium-containing tungsten boat and aluminum-containing tungsten f 'sub to control the deposition rate of lithium and aluminum, so that the lithium to aluminum ratio becomes about 0 ·· 1% and then 'open the main window. The formation rate of the cathode layer is 2 nm / sec. When the thickness of the electrode layer reaches 250 nm, the main window plate is closed and the heating of these two sources is stopped. In the present invention, steps (B) and (c) are processed by vapor deposition. Vacuum-deposited Technology is a method of heating an evaporation source under vacuum to generate vapor or cluster, and depositing vapor or molecular clumps on a substrate. For the above heating, electron beam heating (electron beam heat ing) can be used. ) 'It includes applying an electron beam to a substance to directly heat it' or using resistance heating, etc. In this example, a lithium / aluminum mixture is used as the cathode. Lithium is mixed into the inscription 'to obtain High electron injection efficiency, and the height of lithium can be as high as several tens from the interface between the organic layer and the cathode. When the thickness of the bell-containing aluminum layer reaches the above several tens of nm, the deposited deposition may stop, after that The cathode that continues to form may be only aluminum. After the formation of all layers is completed, the product is cooled to room temperature under the operation of the substrate temperature controller so that the temperature change rate of the substrate becomes 15 ° C or lower. After slowly dried nitrogen introduced into the vacuum chamber when the vacuum chamber becomes the atmospheric pressure, the product will be rapidly removed, and dried in the presence of nitrogen, and with a cap adhesive seal it.

518908

[Example 2]

Page 22 518908 V. Description of the invention (20) Step (A) (Formation of the first electrode) The method of forming an ITO anode layer on a substrate and cleaning it is the same as in Example 1 to complete step (A). Step (B) (Formation of Organic Thin Film) This step and the next step (C) use the same vacuum deposition apparatus, such as the vacuum deposition apparatus in Example 1. In the same manner as in Example 1, the substrate was fixed to a heat release and absorption device having a substrate supporting device, and the subsequent substances used to form each layer were separately placed on a boat and a corresponding evaporation source was set. It used the same boat as in Example 1, namely, a boat made of molybdenum for organic matter and a boat made of tungsten for cathode matter. (1) 20 mg of α-NPD is used as the material of the hole transport layer. (2) 200 mg of DPVBi (4, 4 '-bis (, 2' -diphenylvinyl) bi pheny 1) was used as the substance of the blue light-emitting layer. The structure of D P V B i is shown below.

Page 23 518908 V. Description of the invention (21) (3) 200g of Alq is used as the electron transport layer. (4) 2 g of A 1 is used as the material of the cathode. (5) 0 · 5 g of Li is used as the material of the cathode. The way to set L i is the same as in Example 1. The discharging method is the same as in Example 1. When the degree of vacuum reaches 10-5 Pa (p a), the substrate temperature is controlled by the substrate temperature control device. After that, the molybdenum boat containing a-NPD was slowly heated. When the deposition rate was stabilized at about 0.1 nm / sec, the main window plate was opened and a material layer started to form. When the thickness of this layer reaches 50 nm, the main window plate is closed, and the formation of the hole transport layer is completed. In the same manner, DPVBi was deposited at a deposition rate of about 0.1 nm / sec to form a light-emitting layer having a thickness of ㈣. In the same manner, Alq3 was deposited at a deposition rate of about 0.1 nm / sec. In order to form an electron transporting layer with a thickness of 40 nm, these organic layers are formed using only one photomask and a pattern of the organic layer is formed. Step (C) (Formation of the Second Electrode) 'The method of forming the cathode is the same as in Example 1. When the second, = two, f predetermined change rate, the temperature of the substrate is reduced to ^ ^ using the same sealing method as in Example 1 until the electro-excitation photon is used as the substrate Temperature Yue 丨 | After crying out, the temperature of the completed element is two to two, the vacuum reaction chamber is opened and the finished surface temperature is about 60 ° C, and 4 light-emitting areas are formed on Γ t, and each / σ C. Four 偾 | a are formed on a substrate plate, all of which are 2nm X 2nm, so that the four pixels have the same structure on the same substrate. 518908 V. Description of the invention (22) [Comparative Example 2] Take Example 2 Method to produce an organic electroluminescent device with the same structure as in Example 2, except The plate temperature controller did not operate during the material layer formation step (heating of the α-NPD evaporation source-formation of the NpD layer-completion plus =: stop operation-heating of the DPVBi evaporation source-shaped 'DpvJ layer-completion ~ heating-stop operation- Heating of Alq evaporation source—forming layer—complete heating—stop operation—heating of cathode material evaporation source—forming of cathode material layer—complete heating—stop operation—removal). After the substrate temperature controller is not operated, the substrate temperature will change from every A heating source ^ gradually increases at the beginning of heating, and increases rapidly with the opening of the main window, and continues to increase until the main window is closed. When the main window is closed and the heating of the source is stopped, the temperature of the substrate will increase. Simultaneous rapid decline .: Potential, especially when the cathode material is deposited. The maximum value of the substrate temperature increase rate during the formation of the cathode layer is 22t: / s; The maximum value is -181; = more than 70 ° C, about 80. (: about. The soil plate / dish degree in the formation of the organic layer, Alq (the most evaporation temperature among organic materials) layer During the formation, the substrate temperature was over 1.5X: / sec. The temperature was too high. [Example 3] Step (A) (Formation of the first electrode) An ITO anode layer was formed on the substrate and washed. 1 is the same to complete step (A). ', Method step (B) (formation of organic thin film)

518908

V. Description of the invention (23) In this step and the next step (c), the same vacuum deposition equipment is used, such as the vacuum deposition equipment in Example 1. In the same manner as in Example 1, the substrate was fixed to a heat release and absorption device having a substrate supporting device. Substances used to form each layer were placed on the boat and placed opposite each other: and the source was generated. The same boat as in Example 1 was used, that is, a boat made of molybdenum for organic materials and a boat made of tungsten for cathode materials. (1) 20 mg of α-NPD is used as the material of the hole transport layer. (2) 100 mg of DCM (4- (dicyanome thy lene) -2iethy 1-6- (p-dimethylaniinostytyl) -4H-pyran) as the red light-emitting layer

The structure of DCM is shown below.

(3) 200 mg of Alq (4) 2 g of A1 as the cathode material. (5) 0.5g of Li is used as the material of the cathode. The method of setting Li is the same as in Example 1.

Page 26 518908 V. After the description of the invention (24), the discharge method is the same as in Example 1. When the degree of vacuum reaches 10-5 Pa (Pa), the substrate temperature is controlled by the substrate temperature control device. After that, the boat containing a-NP is slowly heated, and when the deposition speed is shifted to about 0.1 nm / sec, the main window plate is opened and a material layer starts to form. When the thickness of this layer reaches 50 nm, the main window plate is closed and the formation of the hole-passing layer is completed. The molybdenum boat containing A1 q and the molybdenum boat containing dcm were successively heated; the deposition rate of Alq and DCM was controlled so that the weight ratio of DCM to Alq became 1%; and the main window was opened. When the thickness of the Alq-DCM mixed layer reaches 50 nm, only the main window plate of the evaporation source containing DCM is closed, and the heating is stopped. The Alq in the light-emitting layer has the function of a host material, so that X is doped with D C M (* light-emitting materials). After that, in order to form an electron transport layer, only 41 (1, I thickness is. Therefore, the organic layer is formed using a light-emitting layer (a1q / dcm mixed layer) and an electron transport layer ^ Alq). /, The same shape as in Example 1, and a pattern of an organic layer was formed. Step (C) (Formation of the second electrode) The method of forming the cathode in the same manner as in Example 1 is as follows. 1 = Reduces the temperature of the substrate at speed. The same sealing method as in Example 1 was used to control the temperature of the substrate to electrically excite the light source. After the components were taken out, the reaction chamber was opened and the surface was highest: During the operation of the temperature controller of the substrate, the base temperature is about 6 (rc, and does not exceed 7 (rc. 4 light-emitting areas are formed on a piece of base 518908 V. Invention Description (25)) and the mother is uniform. It is 2ππι X 2πιη, so that 4 pixels have the same structure on a certain board. [Comparative Example 3] Using the method in Example 3, an organic electroluminescent device having the same structure as in Example 3 was manufactured, except for the substrate temperature. The controller did not operate during the material layer formation step (heating of the α-NPD evaporation source-formation of the α -NPD layer-completion of heating-stopping operation-heating of Alq and DCM evaporation sources-formation of ^^ and DCMj-completion of DCM evaporation sources Heating-continue heating of Mq evaporation source ~ complete heating of A lq evaporation source-stop operation-heating of cathode material evaporation source ~ formation of cathode material layer-complete heating-stop operation-take out). After no operation from substrate temperature controller, The temperature of the substrate will gradually increase from the beginning of each heating source, and it will increase quickly as the main window panel is opened and continue to increase until the main window panel is closed. F The main window panel is closed ^ and the mother-evaporation source is heating stop Later, the temperature of the substrate will be rapidly reduced at the same time, especially when the cathode material is deposited. During the formation of the cathode, the maximum temperature increase rate of the substrate is 21 ': 3 Ϊ f layer After the formation, the maximum temperature decrease rate of the substrate is ―1.8, and the soil plate temperature exceeds 70 ° C, which is about 80 ° C. In the formation of the highest layer, Mq (Among organic substances, AU has over 1.5 = During the formation of the t layer, 'the substrate temperature changed at a faster rate [Example 4] The same material as that used in Example 1 was used to fabricate the organic electro-laser element, and the condition deposition device was used to manufacture 2 5 6 ( Number of anodes) χ

Page 28 518908 V. Description of the invention (26) 2 (number of cathodes) dot green organic electric laser panel, which has the same layer structure as that of Example 1. The shape (r〇w) direction of each pixel and the direction of each column (column) are 〇33 coffee height / 〇〇4_ Second, the system uses the same materials as in Example 1, thickness and example " head: seal: the The shape of the glass substrate, the anode, the organic layer mask, the cathode light sheet, and ΠΐΓν are different from those in Example 1. The formation of the film layer is based on the substrate temperature controller of the mesh, and the temperature change rate of the substrate: control: 75 ports Second or less than this absolute value. Even if the J-plate temperature controller is formed in the film layer, the temperature controller continues to operate—for a while, when the substrate temperature drops to a wide range, the dry nitrogen is slowly introduced into the vacuum reaction chamber when the pressure becomes atmospheric pressure. Quickly self-adhesive; followed by zinc i: sealed in the sleeve in the presence of dry nitrogen: and will be used as a substrate temperature controller until the vacuum reaction chamber is opened, and the top panel is removed. During the operation of the substrate temperature controller, the maximum temperature on the surface of the substrate was about 60 ° C, and did not exceed 70 t: [Comparative Example 4] Excited by :: 4 The method of manufacturing the same structure as in Example 4 Organic electricity period 3 m except substrate temperature control There is no step in the formation of the material layer. After the substrate temperature controller is not operated, the substrate temperature will gradually increase when the source is heated. With the opening of the main window, k B increases, and continues to increase until the main window is closed. So far, when the main window is closed: 2-after the heating of the evaporation source is stopped, the temperature of the substrate will decrease rapidly at the same time, especially when the cathode material is deposited. During the formation of the cathode layer, the maximum temperature of the substrate increases Value is 2 π /

Η

Page 29 518908 V. Description of the invention (27) seconds [After the formation of the cathode layer, the maximum substrate temperature reduction rate is 1 · a During the formation of the organic layer, the substrate temperature increases at a rate greater than 1. $ C / second It depends on the substance of the organic layer. During the formation of the cathode, the temperature exceeded 70 t. [Example 5] A blue organic electro-optical laser panel having the same film structure as that of Example 2 was fabricated. A glass substrate having an anode pattern, an organic layer mask, and a cathode light envelope was used as in Example 4. The formation of the film layer uses the same soil plate temperature controller as in Example 2, and the temperature change rate of the substrate is controlled at 0.75 t; this absolute I ° Even after the film layer is formed, the substrate temperature is controlled by nf operation—for a while When the temperature of the substrate is lowered to room temperature, slowly place the gray section ^. When the pressure inside the vacuum reaction chamber is ^, Qiao Rishou, will quickly generate the panel self-vacuum reaction = underneath, sealed in the sleeve and adhered. Continue to operate the imr until the vacuum reaction chamber is opened, and the completed panel temperature production is about 60%, which is used as the substrate temperature controller, and the maximum fox degree on the substrate surface is about von b (JC, and not more than 70. (3. 〔 Comparative Example 5] Excitation of the ΓΓ method: The organic electric phase with the same structure as in Example 5 was performed as W 二 The substrate temperature controller was not formed in the material layer. Step IV After the temperature controller was not operated, the substrate temperature It will gradually increase from the beginning of heating: as the main window opens and closes the door t τ ′ and continues to increase until the main window closes. When the main window is closed and the mother-evaporation source heating stops, the substrate The temperature will be at the same time: fast;

518908 V. Description of invention (28) Decline. Such a trend occurs especially when a cathode material is deposited. During the formation of the cathode layer, the maximum temperature increase rate of the substrate was 2 ° C / sec; after the formation of the cathode layer, the maximum temperature decrease rate of the substrate was 5 c. During the formation of the organic layer, the temperature of the substrate increases faster than u. 〇 / sec 'depends on the substance of the organic layer. During the formation of the cathode, the base temperature exceeded 70 ° C. [Example 6] A red organic electro-optical laser panel having the same film structure as that of Example 3 was manufactured. "Make a glass pot substrate with an anode pattern, an organic layer mask, and a cathode light mountain envelope, the same as in Example 4, and make a film layer." The system uses the same I-plate temperature controller as in Example 3, and the temperature of the substrate changes rapidly. When the substrate temperature drops to room temperature, slowly turn the bunny bug into the vacuum reaction chamber. When the inside of the vacuum reaction chamber The pressure ", when pressed, the generated panel is quickly self-vacuum reacted = in the presence of rat gas, sealed in the sleeve and adhered. Continue to operate the device until the vacuum reaction chamber is opened, and the temperature of the completed panel is about, and Do not exceed the heart. &Amp; The surface of the board was operated during the "face [Comparative Example 6]. From the second, the solitary quotation, the system did not prepare the material layer in the preparation step; after the soil plate temperature was controlled to no operation, the substrate, and the sound of the sound from the solid-heat heating source began to gradually increase, with The main window: Er Yue Ding Kai

IH1

Page 31 518908 V. Description of the invention (29) It increases rapidly and continues to increase until the main window panel is closed. When the main window is closed and the heating of each evaporation source is stopped, the temperature of the substrate will decrease rapidly at the same time. Such a trend occurs especially when a cathode material is deposited. During the formation of the cathode layer, the maximum value of the substrate temperature increasing rate was two. ○ / and, after the formation of the cathode layer, the maximum temperature decrease rate of the substrate was 1.5 t. During the formation of the organic layer, the temperature of the substrate increases at a rate greater than 15 t: / sec, which depends on the substance of the organic layer. During the formation of the cathode, the substrate temperature exceeded 70 ° C. [Comparison between Examples and Comparative Examples] The organic electric laser elements manufactured in Examples 1 to 3 and Comparative Examples 1 to 3 were measured for voltage-current characteristics between -15V and H5V. This measurement is performed in the following two directions: (1) the positive direction (n0rmal direction) where the applied voltage is increased from 0V to + 1 5V, and (2) the applied voltage is reduced from 0v to a direction of 15v). ^^^^ (reverse Each element was repeated three times. The measurement was performed from the skull Φ = Li Xun, to check the reproducibility of the voltage-current characteristics of the element. Figure 3 shows the measurement of the example i and the comparison teaching example} The horizontal axis represents the applied voltage, and the vertical axis represents the difference between the voltage and current characteristics. In example i and from Figure 3 it can be clearly seen that the logarithm of the heart i ;: yi pair value. + # ^ Compared with the positive direction of Comparative Example 1 between the car parent example 1, the current is about 10-30 at a voltage of 10 ¥. At the same time, the difference related to the leakage current in the reverse direction is large. In the example 518908 5. In the description of the invention (30), the current is almost fixed at 0-3A, even when the voltage is reduced. In contrast, in Comparative Example 1, when the absolute value of the voltage becomes larger, the leakage current increases. When comparing at 5 V, the leakage current ratio 1 of Comparative Example 1 is 2 to 4 larger. In Example 1, 'both positive and negative Good reproducible data can be obtained by applying both voltages. Conversely, in Comparative Example 1, under the application of voltages in the opposite direction, there is a deviation in the leakage current flow, even in the manufacture on a substrate This trend is also seen in Comparative Examples 2 and 3. In Examples 2 and 3, data with high reproducibility and small deviations as in Example 1 can be obtained. From these obtained data, the rectification ratio is Use the following formula to calculate. The results are shown in Table 1. Rectification ratio = I current when +1 5 V is applied 丨 / 丨 current when -1 5 V is applied 518908 V. Description of the invention (31) Table 1 Rectification ratio example 1 fishing 108 comparison example 1 104 to 106 example 2 fishing 108 comparison example 2 104 to 106 example 3 about 108 comparison example 3 104 to 10 δ ... ..... --------

As is clear from Table 1, in the present invention, the manufactured organic electro-optical laser element has a low leakage current in the reverse direction and has excellent results in rectification. Each of the 256 x 64-point organic electro-optical laser panels manufactured in Examples 4 to 6 and Comparative Examples 4 to 6 was connected to a driver circuit. In 丨 / 6 4 the power and solid; the current data h 5 Tigers sent by themselves (anode side), the column side (cathode side) consecutively ϋ ϋ to? Ground; 卩 This way it is acted to display letters, words, pictures; 4 temples, and the presence of interference can be observed on the exterior. The presence or absence of this interference is listed in Table 2. It can be clearly seen from Table 2 that η plate 1, ', and 8 have organic matrix lasers of simple matrix actuation type. 518908 V. Description of the invention (32) Table 2 Interference example 1 does not exist Comparative example 1 Existing example 2 Exists Example 2 Exist Example 3 Exist Comparative Example 3 Exist

HHi Page 35

Claims (1)

518908— fr year f month ιϋ J7l, Kebowei No. 89113202 1 · A method for manufacturing an organic electric laser device, at least comprising: (A) forming a first electrode on a substrate; (B) forming one or more organic layers on the first electrode A compound film, the (or) organic compound film including a light-emitting layer; and (C) forming a second electrode on the (or) organic compound film layer, wherein the temperature of the substrate is maintained at 70 ° C or lower, The rate of substrate temperature change is maintained at 1.5 ° c / sec or below this absolute value, between steps (B) and (C) 'between steps (B) and (C), and step (c) is completed At this time, the temperature of the substrate becomes room temperature. 2. The method for manufacturing an organic electro-optical laser device according to item 1 of the scope of the patent application, wherein steps (B) and (C) are performed by vacuum deposition. 3. The method for manufacturing an organic electric laser device according to item 2 of the scope of the patent application, wherein the vacuum deposition in steps (8) and ((:), the vacuum deposition device used has at least: I (1) has a smooth A substrate support on the surface for supporting a substrate; and (A soil plate temperature control device for controlling the temperature of the film-forming surface of the substrate, the substrate temperature control device is composed of at least ...) 2-1) —temperature sensor; (2-2) —computing device; (2-3) —heat release and absorption device. The characteristics of the layer are: "Please be formed by the manufacturing process of the organic electro-laser as described in item 1 of the patent scope. 5 · —Organic Thunder Laser u 518908 __ Case No. 89113202 6. Scope of Patent Application The plurality of organic electro-laser elements described in item 4 are arranged in a matrix manner. 6 · A vacuum deposition device having at least: (1) a substrate support having a smooth surface for supporting a substrate; and (2) — A substrate temperature control device for controlling the temperature substrate of the substrate on the lamination film forming surface, the substrate temperature control device is composed of at least: (2-1) a temperature sensor; (2-2) — a computing device; (2-3) —Heat release and absorption device; wherein the substrate support and the heat release and absorption device are integrated into a component. 7. A vacuum deposition device having at least: (1) a substrate support having a smooth surface to support a substrate; and (2)-a substrate temperature control device for controlling the The temperature of the substrate, the substrate temperature control device is composed of at least (2-1)-temperature sensor; (2-2)-computing device; (2-3)-heat release and absorption device; Tian Zhong The substrate temperature control device can maintain the pulse rate of the film-forming side surface of the substrate at 70 or lower, and the temperature production change rate of the film-forming side surface of the substrate can be maintained at 1.5 ° C / sec or lower. This absolute value is 8. A vacuum deposition device having at least: (1) a substrate support having a smooth surface for supporting a mounting plate; and protecting the substrate 2138-3320-pf2 Page 37 518908 _ Case No. 89113202 9 / year and month \ 〇f __ ^ _ VI. Patent Application Scope (2) — substrate temperature control device for controlling the substrate on the film forming surface > The JDL degree substrate includes at least: (2-1) a temperature sensor; (2-2) — a computing device; (2-3) — a heat release and absorption device; The surface roughness of the substrate support having a smooth surface measured by JIS B 0 6 0 1 1 994 is (1) the arithmetic average roughness (Ra) is 2000 nm or less' and (2) the maximum height (Ry ) Is 80 nm or less. 9. The vacuum deposition apparatus according to item 8 of the scope of the patent application, wherein a soft metal is filled between the substrate support having a smooth surface and the substrate without a gap therebetween. 10. The vacuum deposition device according to item 6, 7, or 8 of the scope of the patent application, wherein the vacuum reaction chamber has an evaporation source of the film-forming material 'and is provided with a substrate support opposite to the evaporation source. 1 1 · The vacuum deposition device described in item 10 of the scope of patent application, further comprising an electron beam heating device or a resistance heating device for heating the film forming material. 2 · The vacuum deposition device described in Item 67 or 8 of the declared patent scope has an electron beam heating device or resistance heating for heating the film forming material. 2138-3320-pf2.ptc Page 38