Electro-optical device and method of manufacturing the same, circuit board and method of manufacturi

专利摘要:
The present invention provides an electro-optical device in which the external extraction efficiency of light can be improved and high visibility is realized. The organic EL display device has a plurality of material layers including the light emitting element 3, and the substrate 2 positioned at the outermost surface of the plurality of material layers positioned in the direction in which light from the light emitting element 3 is extracted. ) And the light emitting element 3, the first and second interlayer insulating layers 283 and 284 having a refractive index lower than that of the substrate 2 are disposed.
公开号:KR20030057371A
申请号:KR1020020083914
申请日:2002-12-26
公开日:2003-07-04
发明作者:미야자와다카시
申请人:세이코 엡슨 가부시키가이샤；
IPC主号:

专利说明:

ELECTRO-OPTICAL DEVICE AND METHOD OF MANUFACTURING THE SAME, CIRCUIT BOARD AND METHOD OF MANUFACTURING THE SAME, AND ELECTRONIC EQUIPMENT}
[17] The present invention provides an electro-optical device and a method of manufacturing the electro-optical device, in which the light emitted by the electro-optical device and the light modulated by the electro-optical device are efficiently taken out, an electronic device provided with the electro-optical device, a circuit board and a circuit board. It relates to a method for producing.
[18] Background Art Conventionally, in an electro-optical device such as a liquid crystal device and an organic EL (electroluminescence) device, there is a structure in which a plurality of circuit elements, electrodes, liquid crystals or EL elements are stacked on a substrate. For example, in an organic EL device, it has a light emitting element of the structure which pinched the light emitting layer containing a luminescent material in the electrode layer of an anode and a cathode, and has the light emission capability of the hole injected from the anode side, and the electron injected from the cathode side. The phenomenon of emitting light when recombining in the light emitting layer and deactivating from the excited state is used.
[19] In general, since the electro-optical device is composed of a plurality of material layers including an electro-optical element layer, when the electro-optical element layer extracts light emitted or modulated light to the outside, it is attenuated by the material layer through which light passes. In this case, sufficient light extraction efficiency may not be obtained.
[20] The present invention has been made in view of the above circumstances, and an object thereof is to provide an electro-optical device, a method for manufacturing the same, a circuit board, a method for manufacturing the same, and an electronic device that can improve the external extraction efficiency of light and realize high visibility. do.
[1] BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows one Embodiment of the electro-optical device of this invention, and is a schematic block diagram which shows the example applied to the electroluminescent display.
[2] FIG. 2 is an enlarged view illustrating a planar structure of a pixel unit in the display device of FIG. 1. FIG.
[3] 3 is a cross-sectional view taken along the line A-A of FIG. 2, showing an embodiment of the electro-optical device of the present invention.
[4] 4 shows an example of an electronic apparatus provided with the electro-optical device of the present invention.
[5] 5 shows an example of an electronic apparatus provided with the electro-optical device of the present invention.
[6] 6 shows an example of an electronic apparatus provided with the electro-optical device of the present invention.
[7] Explanation of the sign
[8] 2 boards
[9] 3 light emitting elements (electro-optical elements)
[10] 23 pixel electrode (electrode)
[11] 60 light emitting layer (electro-optic element layer)
[12] S1 organic EL display device (electro-optical device, circuit board)
[13] 222 Cathode (electrode)
[14] 282 gate insulation layer
[15] 283 First interlayer insulation layer (low refractive index layer)
[16] 284 Second interlayer insulating layer (low refractive index layer)
[21] MEANS TO SOLVE THE PROBLEM In order to solve the said subject, the electro-optical device of this invention is an electro-optical device in which the several material layer containing the electro-optical element layer which has an electro-optical element is laminated | stacked, and the light from the said electro-optical element is taken out. A plurality of material layers positioned in the direction are disposed, and a low refractive index layer having a refractive index lower than the refractive index of the surface material layer is disposed between the surface material layer located at the outermost surface of the plurality of material layers and the electro-optical element layer. It is characterized by being arranged.
[22] Here, the "light from the electro-optical element" does not refer only to the light emitted by the electro-optical element, but also includes light in which transmitted light and reflected light are modulated by the electro-optical element. By "surface material layer located at the outermost surface" is meant a material layer in contact with the outer world.
[23] According to the present invention, since light from the electro-optical element passes through the low refractive index layer that is lower than the surface material layer and then enters the surface material layer, the light incident on the low refractive index layer at an angle greater than or equal to the critical angle is different from that of the surface material layer. It is refracted in the direction of becoming below the critical angle at the interface, and is taken out of the total reflection condition in the surface material layer and taken out to the outside. Thereby, the light extraction efficiency improves and high visibility can be obtained. Further, the refractive index and the dielectric constant have a strong positive correlation, and the low dielectric constant layer can be formed by using the predetermined material layer as the low refractive index layer.
[24] As an example of the electro-optical element, a liquid crystal element, an electrophoretic element, an electron emitting element, or the like can be employed, but the configuration of the electro-optical device is particularly suitable when the electro-optical element is a light emitting element. Examples of light emitting devices include LED (light emitting diode) devices, LD (laser diode) devices, EL (electroluminescent) devices, light emitting devices using electron emitting devices, and the like.
[25] In the above-mentioned electro-optical device, by making the low refractive index layer an interlayer insulating layer, the extraction efficiency of light passing through the interlayer insulating layer can be improved.
[26] In addition, since the refractive index and the dielectric constant have a positive strong correlation, the interlayer insulating layer also has the advantage of reducing the capacitance generated between the wirings when the conductive member such as the wiring or the electrode is insulated. . Therefore, it becomes an electro-optical device which combines high light extraction efficiency and high speed operation.
[27] In this case, the refractive index of the low refractive index layer is set to 1.5 or less, preferably 1.2 or less.
[28] The low refractive index material may be a porous material capable of transmitting light, an airgel, porous silica, a material containing magnesium fluoride or the like, a gel in which fine particles of magnesium fluoride are dispersed, a fluorine-based polymer or a material containing the same, a porous polymer having a branched structure, and a predetermined structure. And a material in which at least one of inorganic fine particles and organic fine particles is contained in the material.
[29] As an example of the electro-optical device, an organic electroluminescent device may be used. An organic electroluminescent element has various advantages, for example, can be driven at low voltage, and has less viewing angle dependence than the liquid crystal element.
[30] In the above electro-optical device, an active element may be further provided. This enables active driving. Examples of the active element include a transistor including a thin film transistor, a thin film diode, and the like.
[31] The manufacturing method of the electro-optical device of the present invention includes the steps of disposing a thin film transistor on a first substrate, and forming a low refractive index layer on a second substrate including the thin film transistor and the first substrate. It features.
[32] The circuit board of the present invention is a circuit board in which a plurality of material layers are laminated on a substrate, wherein at least one low refractive index layer made of a low refractive index material having a lower refractive index than the substrate is arranged.
[33] In the circuit board, at least one of the plurality of material layers is an interlayer insulating layer, and the interlayer insulating layer is made of the low refractive index material.
[34] The refractive index of the low refractive index layer is 1.5 or less, preferably 1.2 or less.
[35] The low refractive index material may include a porous material that can transmit light, an airgel, porous silica, magnesium fluoride, a fluorine-based polymer, a porous polymer, or a material containing at least one of inorganic fine particles and organic fine particles, or magnesium fluoride. And gels in which fine particles are dispersed.
[36] In this case, the circuit board includes an active element, and examples of the active element include a transistor and the like.
[37] A method for manufacturing a circuit board of the present invention includes the steps of disposing a transistor on a first substrate, and forming a low refractive index layer on a second substrate including the transistor and the first substrate. .
[38] The electronic device of the present invention includes the electro-optical device or the circuit board of the present invention. According to the present invention, an electronic device having excellent display quality and having a bright screen display can be realized.
[39] Embodiment of embodiment
[40] EMBODIMENT OF THE INVENTION Hereinafter, the electro-optical device of this invention is demonstrated, referring FIG. 1, FIG. 2, FIG. 1 and 2 show an example in which the electro-optical device according to the present invention is applied to an active matrix display device using an organic electroluminescent element, in which FIG. 1 is an overall circuit diagram and FIG. 2 is an opposite electrode in FIG. And an enlarged plan view of each pixel in a state where the organic electroluminescent element which is a light emitting element is removed.
[41] In addition, in this embodiment, although the display apparatus using organic electroluminescent element (henceforth "EL element") is demonstrated as an example, the display apparatus using a liquid crystal element, an electrophoretic element, an electron emission element, etc., or LED (light emission) It is also applicable to display devices using light emitting elements such as diodes) and LD (laser diode) elements.
[42] As shown in FIG. 1, an organic electroluminescent display (hereinafter referred to as an "organic EL display device") S1 includes a substrate, a plurality of scan lines 131 wired on the substrate, and these scan lines 131. A plurality of data lines 132 wired to extend in a direction crossing each other, and a plurality of common feed lines 133 wired so as to extend in parallel to these data lines 132, and a scan line 131 and a data line ( Corresponding to each intersection of 132, the pixel (pixel area element) AR is provided and comprised.
[43] The data line 132 is electrically connected to the data line 132 having at least one of a shift register, a level shifter, a video line, a D / A converter, a decoder, a latch circuit, and an analog switch.
[44] On the other hand, a scan line driver circuit 80 having at least one of a shift register, a level shifter and a decoder is electrically connected to the scan line 131.
[45] In the present embodiment, the data line driver circuit 90 and the scan line driver circuit 80 are arranged together on the substrate, but each of the data line driver circuit 90 and the scan line driver circuit 80 is placed on the substrate. It can select suitably about whether to arrange | position or to arrange | position outside a board | substrate.
[46] As shown in FIG. 1, each of the pixel regions AR includes a first thin film transistor 22 and a first thin film transistor 22 to which a scan signal is supplied to a gate electrode through a scan line 131. A holding capacitor cap for holding an image signal supplied from the data line 132 through the second line, a second thin film transistor 24 for supplying the image signal held by the holding capacitor cap to the gate electrode, and the second thin film transistor 24; The pixel electrode 23 through which the driving current flows from the common feed line 133 when electrically connected to the common feed line 133 through the thin film transistor 24, and the pixel electrode (anode) 23 and the opposite electrode (cathode) The light emitting element 3 sandwiched between the 222 is provided. The light emitting element 3 may include light emitting elements such as LED (light emitting diode) elements and LD (laser diode) elements in addition to EL (electroluminescent) elements.
[47] When the first thin film transistor 22 is turned on by the scan signal supplied through the scan line 131, the charge corresponding to the data signal supplied through the data line 132 at that time is maintained at the holding capacitor cap. The conduction state of the second thin film transistor 24 is determined according to the state of the holding capacitor cap. In addition, a current flows from the common feed line 133 to the pixel electrode 23 through the channel of the second thin film transistor 24, and a current flows from the common layer 133 to the counter electrode 222 through the light emitting layer 60. ) Emits light in accordance with the amount of current flowing therethrough.
[48] Next, the planar structure of each pixel AR will be described with reference to FIG. 2. FIG. 2 is an enlarged plan view of FIG. 1 with a counter electrode or an organic electroluminescent element removed. As shown in FIG. 2, the pixel electrode 23 having a planar view having a rectangular shape has four sides: a data line 132, a common feed line 133, a scan line 131, and a scan line for another pixel electrode (not shown). Surrounded by The shape of the pixel electrode is not limited to the rectangular shape, but may be a circular or elliptical shape. When forming a material layer constituting an EL element such as a light emitting layer by using a liquid material as in the inkjet method described later, a uniform material layer is obtained by making the pixel electrode into a shape such as a circle or an ellipse without an angle in particular.
[49] Next, the cross-sectional structure of the organic EL display device will be described with reference to FIG. 3. 3 is a cross-sectional view of the arrow A-A of FIG.
[50] Here, the organic EL display device shown in Fig. 3 is a form of taking out light from the side of the substrate 2 on which a thin film transistor (TFT) is disposed, a so-called back emission type. Therefore, in this embodiment, the board | substrate 2 is a surface material layer located in the outermost surface from which the light from the light emitting element 3 is taken out. In addition, when another material layer is laminated on the surface of the board | substrate 2, this other material layer becomes a surface material layer.
[51] As shown in FIG. 3, the back emission type organic EL display device S1 includes a substrate 2 and an anode (pixel electrode) 23 made of a transparent electrode material such as indium tin oxide (IT0: Indium Tin 0xide). And a light emitting element 3 disposed on the anode 23, a cathode (counter electrode) 222 arranged to sandwich the light emitting element 3 between the anode 23, and the substrate 2. And a thin film transistor (hereinafter referred to as " TFT ") 24 as an energization control section for controlling the energization of the pixel electrode 23. FIG. In addition, a sealing layer 20 is provided on the upper layer of the cathode 222. The cathode 222 is made of at least one metal selected from aluminum (Al), magnesium (Mg), gold (Au), silver (Ag), and calcium (Ca). The cathode 222 includes an alloy of each of the above materials or a laminate. The TFT 24 operates in accordance with operation command signals from the scan line driver circuit 80 and the data line driver circuit 90 to perform energization control to the pixel electrode 23.
[52] The light emitting element 3 includes a hole transport layer 70 capable of transporting holes from the anode 23, a light emitting layer 60 containing an organic EL material which is one of electro-optic materials, and an upper surface of the light emitting layer 60. It consists of the electron carrying layer 50 schematically. In addition, a cathode (counter electrode) 222 is disposed on the upper surface of the electron transport layer 50.
[53] The TFT 24 is provided on the surface of the substrate 2 via a base protective layer 281 mainly composed of SiO ₂ . The TFT 24 includes a silicon layer 241 formed on an upper layer of the underlying protective layer 281, a gate insulating layer 282 provided on the upper layer of the underlying protective layer 281 so as to cover the silicon layer 241, and a gate. A gate electrode 242 provided at a portion of the upper surface of the insulating layer 282 facing the silicon layer 241, and a first interlayer insulating layer provided at an upper layer of the gate insulating layer 282 so as to cover the gate electrode 242 ( 283, a source electrode 243 connected to the silicon layer 241 through a contact hole opening through the gate insulating layer 282 and the first interlayer insulating layer 283, and the gate electrode 242. And a drain electrode disposed at a position opposite to the source electrode 243 and connected to the silicon layer 241 through a contact hole opening through the gate insulating layer 282 and the first interlayer insulating layer 283 ( 244 and a second interlayer insulating layer 284 provided on the first interlayer insulating layer 283 to cover the source electrode 243 and the drain electrode 244. Doing.
[54] In addition, the pixel electrode 23 is disposed on the upper surface of the second interlayer insulating layer 284, and the pixel electrode 23 and the drain electrode 244 are provided in the contact hole 23a provided in the second interlayer insulating layer 284. Connected via Further, a third insulating layer (bank layer) made of synthetic resin or the like between the cathode 222 and a portion other than the light emitting element (EL element) 3 on the surface of the second interlayer insulating layer 284 ( 221 is provided.
[55] In addition, a protective layer of a TFT may be provided on the upper layer of the drain electrode 244. As a formation material of this protective layer, the insulating layer containing silicon (a silicon nitride oxide layer or a silicon nitride layer is especially preferable) can be used. This protective layer serves to protect the formed TFT 24 from metal ions and moisture. In other words, the protective layer also serves as a protective layer that does not induce movable ions such as metal ions to the TFT 24 side.
[56] In addition, thermal deterioration of the light emitting device can be prevented by giving a heat radiation effect to the protective layer. However, when using an organic material as a light emitting element, since it deteriorates by bonding with oxygen, it is preferable not to use the insulating layer which is easy to release oxygen.
[57] As a translucent material which prevents permeation of movable ions and has a heat dissipation effect, at least one element selected from B (boron), C (carbon), and N (nitrogen), Al (aluminum), Si (silicon), P And an insulating layer containing at least one element selected from (phosphorus). For example, nitride of aluminum represented by aluminum nitride (AlxNy), carbide of silicon represented by silicon carbide (SixCy), nitride of silicon represented by silicon nitride (SixNy), nitride of boron represented by boron nitride (BxNy) And a phosphide of boron represented by boron phosphide (BxPy) can be used. In addition, the oxide of aluminum represented by aluminum oxide (Alx0y) is excellent in light transmittance and heat conductivity of 20 Wm <^-1> K <^-1> , and it can be said that it is one of the preferable materials. These materials have not only the above effects but also effects of preventing the ingress of moisture.
[58] You may combine another element with the said compound. For example, aluminum nitride oxide represented by AlNx0y may be used by adding nitrogen to aluminum oxide. This material has not only a heat dissipation effect but also an effect of preventing intrusion of moisture, movable ions and the like.
[59] In addition, an insulating film containing Si, Al, N, 0, M, provided that M is at least one of rare earth elements, preferably Ce (cerium), Yb (yterbium), Sm (samarium), and Er (elbium) And at least one element selected from Y (yttrium), La (lanthanum), Gd (gardium), Dy (dysprosium), and Nd (neodymium)). These materials have not only a heat dissipation effect but also an effect of preventing the ingress of moisture or movable ions.
[60] In addition, a carbon film containing at least a diamond thin film or amorphous carbon film (particularly close to diamond and its properties, such as diamond-like carbon) may be used. These have very high thermal conductivity and are very effective as a heat dissipation layer. However, when the film thickness becomes thick, the color becomes brown and the transmittance decreases. Therefore, it is preferable to use the film thickness as thin as possible (preferably 5 to 100 nm).
[61] In addition, since the purpose of the protective layer is to protect the TFT from movable ions and moisture to the last, it is preferable not to impair the effect. Therefore, although a thin film made of a material having the above heat dissipation effect can be used alone, these thin films and an insulating film (typically a silicon nitride film (SixNy) or a silicon nitride oxide film (SiOxNy) which can prevent the transmission of movable ions and moisture can be used. Laminating)) is effective.
[62] The region overlapping with the gate electrode 242 by sandwiching the gate insulating layer 282 in the silicon layer 241 is a channel region. In addition, a source region is provided on the source side of the channel region in the silicon layer 241. On the other hand, a drain region is provided on the drain side of the channel region. Among these, the source region is connected to the source electrode 243 through a contact hole that opens through the gate insulating layer 282 and the first interlayer insulating layer 283. On the other hand, the drain region is connected to the drain electrode 244 which becomes the same layer as the source electrode 243 through a contact hole that opens through the gate insulating layer 282 and the first interlayer insulating layer 283. The pixel electrode 23 is connected to the drain region of the silicon layer 241 through the drain electrode 244.
[63] In this example, since it is a structure (back emission type) which takes out the light emission from the light emitting layer 60 from the board | substrate 2 side in which the TFT 24 is provided, it is a material which forms the board | substrate 2, and permeate | transmits light. Possible transparent or translucent materials are used, for example transparent glass, quartz, sapphire or transparent synthetic resins such as polyester, polyacrylate, polycarbonate, polyetherketone and the like. In particular, inexpensive soda glass is used suitably as a formation material of a board | substrate. When soda glass is used, it is preferable to apply silica coating to the soda glass because it has the effect of protecting soda glass which is weak against acid alkali and also has the effect of improving the flatness of the substrate.
[64] In addition, the light emission color may be controlled by disposing a color filter film, a color conversion film containing a luminescent material, or a dielectric reflective film on the substrate.
[65] On the other hand, in the case of the structure (top emission type) which takes out emitted light from the opposite side to the board | substrate 2 with which the TFT 24 is provided, the board | substrate 2 may be opaque, and in that case, ceramics, such as alumina, An insulating treatment such as surface oxidation, a thermosetting resin, a thermoplastic resin, or the like can be used for metal sheets such as stainless steel.
[66] When the base protective layer 281 is formed, the substrate 2 is formed into a film by plasma CVD using TE0S (tetraethoxysilane), oxygen gas, or the like as a raw material, thereby reducing the thickness as the base protective layer 281. A silicon oxide film of 200 to 500 nm is formed.
[67] When forming the silicon layer 241, first, the temperature of the substrate 2 is set to about 350 ° C, and amorphous silicon having a thickness of about 30 to 70 nm on the surface of the underlying protective film 281 by plasma CVD or ICVD. Form a layer. Then, the amorphous silicon layer is crystallized by a laser annealing method, rapid heating method, solid state growth method, or the like to crystallize the amorphous silicon layer into a polysilicon layer. In the laser annealing method, for example, an excimer laser uses a line beam having a long dimension of 400 mm, and its output intensity is, for example, 200 mJ / cm ² . About the line beam, the line beam is scanned so that a portion corresponding to 90% of the peak value of the laser intensity in the short dimension direction overlaps with each area. Next, the polysilicon layer is patterned by the photolithography method to form an island-like silicon layer 241.
[68] The silicon layer 241 is a channel region and a source / drain region of the second thin film transistor 24 shown in FIG. 1, but the channel region and the source / drain region of the first thin film transistor 22 are different at different cross-sectional positions. A semiconductor film is also formed. That is, two kinds of transistors 22 and 24 are formed at the same time, but are made by the same procedure. In the following description, only the second thin film transistor 24 is described with respect to the transistor. The description will be omitted for the first thin film transistor 22.
[69] When the gate insulating layer 282 is formed, the surface of the silicon layer 241 is formed using a plasma CVD method as a raw material using TE0S, oxygen gas, or the like to form a silicon oxide film or nitride film having a thickness of about 60 to 150 nm. The gate insulating layer 282 is formed.
[70] The gate electrode 242 is formed on the gate insulating layer 282 by forming a conductive film containing a metal such as aluminum, tantalum, molybdenum, titanium, tungsten or the like by a sputtering method and then patterning the conductive film.
[71] In order to form the source region and the drain region in the silicon layer 241, after forming the gate electrode 242, the gate electrode 242 is used as a patterning mask, and phosphorus ions are implanted in this state. As a result, high concentration impurities are introduced into the gate electrode 242 in a self-aligned manner to form a source region and a drain region in the silicon layer 241. In addition, a portion where impurities are not introduced becomes a channel region.
[72] The first interlayer insulating layer 283 is made of a low refractive index material having a lower refractive index than that of the substrate 2, and is formed over the gate insulating layer 282.
[73] Examples of the material for forming the first interlayer insulating layer 283 include a silicon oxide film, a nitride film, a porous silicon oxide film (SiO ₂ film), and the like. The gate insulating layer 282, which is a porous SiO ₂ film, is formed by CVD (chemical vapor deposition) using Si ₂ H ₆ and O ₃ as reaction gases. When these reaction gases are used, large particles of SiO ₂ are formed in the gas phase and are deposited on the gate insulating layer 282. Therefore, the 1st interlayer insulation layer 283 has many voids in a layer, and becomes a porous body. In addition, the first interlayer insulating layer 283 becomes a low refractive index material by being a porous body, and light extraction efficiency can be improved.
[74] It is preferable that the low refractive index layer which becomes a porous body has a density of 0.4 g / cm <^3> or less.
[75] The refractive index of the first interlayer insulating layer 283 as the low refractive index layer is set to 1.5 or less, preferably 1.2 or less.
[76] In addition, an H (hydrogen) plasma treatment may be applied to the surface of the first interlayer insulating layer 283. Thereby, the dangling bond in the Si-0 bond of the surface of a space | gap is substituted by Si-H bond, and the moisture absorption resistance of a film | membrane becomes favorable. In addition, another SiO ₂ layer may be provided on the surface of the plasma-treated first insulating layer 283.
[77] In addition, the first interlayer insulating the reaction gas for forming the layer 283 by the CVD method in addition to _{Si 2 H 6 +0 3, Si} 2 H 6 +0 2, Si 3 H 8 +0 3, Si 3 H 8 It may be set to +0 ₂ . In addition to the above reaction gas, a reaction gas containing B (boron) and a reaction gas containing F (fluorine) may be used.
[78] A first insulating interlayer as in forming the interlayer insulating layer 283 as a porous material, SiO ₂ film having a porosity and, by stacking SiO ₂ films formed by the conventional reduced pressure chemical vapor deposition method, the porous body film quality is stable Layer 283 may be formed. In order to laminate these films, from SiH ₄ and 0 ₂ in the atmosphere under a reduced pressure, it is possible by generating the plasma intermittently, or periodically. Specifically, the first interlayer insulating layer 283 accommodates the substrate 2 in a predetermined chamber and, for example, maintains the substrate 2 at 400 ° C, using SiH ₄ and 0 ₂ as the reaction gas, thereby providing an RF voltage (high frequency). Voltage) is applied to the chamber. During film formation, while the SiH ₄ flow rate and the 0 ₂ flow rate are constant, the RF voltage is applied to the chamber at a period of 10 seconds. As a result, plasma is generated and extinguished at a cycle of 10 seconds. Thus, by using time-varying plasma, the process using reduced pressure CVD and the process using plasma CVD under reduced pressure can be repeatedly performed in one chamber. Further, by repeating the reduced pressure CVD and the plasma CVD under reduced pressure, an SiO ₂ film having a large number of voids is formed in the film. That is, the first interlayer insulating layer 283 has a porosity.
[79] The first interlayer insulating layer 283 may be formed of an airgel. An airgel is a light-transmitting porous body having a uniform ultrafine structure obtained by supercritical drying a wet gel formed by a sol-gel reaction of a metal alkoxide. There are aerogels based on silica airgel or alumina. Among these, the silica airgel is a material composed of tens of nm fine SiO ₂ particles in which voids occupy 90% or more of the volume and the remainder are aggregated in a resin phase, and the particle diameter is smaller than the wavelength of light, and thus has light transmittance. The refractive index is 1.2 or less. In addition, the refractive index can be adjusted by changing the porosity. Here, the refractive index of glass which is the material of the board | substrate 2 is 1.54, and the refractive index of quartz is 1.45.
[80] Silica airgel is produced through a process of producing a wet gel by the sol-gel method, a process of ripening the wet gel, and a supercritical drying process of drying the wet gel by the supercritical drying method to obtain an aerogel. The supercritical drying method is a method suitable for drying the gel material without shrinking the gel by substituting and removing a liquid in the gel material of the solid and liquid jelly in the gel phase, thereby obtaining an airgel having a high porosity.
[81] For example, when the first interlayer insulating layer 283 is formed by silica airgel, the wet gel, which is a raw material of the airgel, is coated on the gate insulating layer 282 by using a spin coating method or the like, and is formed by supercritical drying. . By the supercritical drying method using a supercritical fluid, the solvent in the wet gel is removed by replacing the solvent in the wet gel with the supercritical fluid. Supercritical fluids also include carbon dioxide (CO ₂ ), or alcohols such as methanol or ethanol, NH ₃ , H ₂ O, N ₂ O, methane, ethane, ethylene, propane, pentane, isopropanol, isobutanol, and cyclotri Fluoromethane, mono fluoromethane, cyclohexanol and the like can be used.
[82] When the low refractive index layer (each insulating layer) is formed by silica airgel, the wet gel is applied onto the substrate by spin coating or the like, and then supercritical drying may be performed, but the synthetic resin (organic substance) may be mixed with the wet gel. The synthetic resin in this case is a synthetic resin whose heat denaturation temperature is higher than the critical temperature of the supercritical fluid and which can transmit light. When alcohol is used as the supercritical fluid, for example, as the synthetic resin whose heat denaturation temperature is higher than the critical temperature of the alcohol and capable of transmitting light, hydroxylpropyl cellulose (HPC), polyvinyl butyral (PVB), and ethyl cellulose (EC) etc. (In addition, PVB and EC are soluble in alcohol and insoluble in water). When using an ether as a solvent, in the case of selecting a resin such as chlorinated polyethylene, and further use of CO ₂ as a solvent, it is preferred to select such as HPC.
[83] The low refractive index layer may be an airgel based on alumina in addition to the silica airgel, or may be a porous body capable of transmitting light at a low refractive index than the substrate 2. In addition, the porous body (aerogel) preferably has a density of 0.4 g / cm ³ or less.
[84] The low refractive index layer may not be a porous body, and may be an adhesive such as an epoxy adhesive (refractive index: 1.42) or an acrylic adhesive (refractive index: 1.43), which is made of a polymer material having a light refractive index lower than that of the substrate 2. Even when these adhesives are used alone, since the refractive index is lower than that of the glass and the quartz constituting the substrate 2, the light extraction efficiency can be improved.
[85] The low refractive index layer may be porous silica, or may be magnesium fluoride (refractive index: 1.38) or a material containing the same. The low refractive index layer by magnesium fluoride can be formed by sputtering. Or the gel which disperse | distributed the fine particle of magnesium fluoride may be sufficient. Or a fluoropolymer or a material containing the same, for example, a perfluoroalkyl-polyether, perfluoroalkylamine, or a perfluoroalkyl-polyether-perfluoroalkylamine mixed film.
[86] In addition, the low refractive index layer may be a mixture of a low refractive index fluorocarbon compound that is soluble or dispersible in a predetermined polymer binder.
[87] Polymeric binders include polyvinyl alcohol, polyacrylic acid, polyvinylpyrrolidone, polyvinylsulfonic acid sodium salt, polyvinylmethyl ether, polyethylene glycol, polyα-trifluoromethylacrylic acid, polyvinylmethyl ether-co-maleic anhydride And polyethylene glycol co-propylene glycol, polymethacrylic acid, and the like.
[88] Examples of the fluorocarbon compounds include perfluorooctanoic acid-ammonium salts, perfluorooctanoic acid-tetramethylammonium salts, perfluoroalkyl ammonium salts of C-7 and C-10, and purple of C-7 and C-10. Fluoroalkylsulfonic acid tetramethylammonium salt, alkyl quaternary ammonium fluoride, perfluoroadipic acid, and quaternary ammonium salts of perfluoroadipic acid, and the like.
[89] In addition, since the method of introducing voids as the low refractive index layer is effective, the voids may be formed between microparticles or as microvoids in the microparticles in addition to the airgel. As the fine particles, inorganic fine particles or organic fine particles can be used for the low refractive index layer.
[90] The inorganic fine particles are preferably amorphous. The inorganic fine particles are preferably oxides, nitrides, sulfides or halides of metals, more preferably metal oxides or metal halides, and most preferably metal oxides or metal fluorides. Metal atoms include Na, K, Mg, Ca, Ba, Al, Zn, Fe, Cu, Ti, Sn, In, W, Y, Sb, Mn, Ga, V, Nb, Ta, Ag, Si, B, Bi , Mo, Ce, Cd, Be, Pb and Ni are preferred, and Mg, Ca, B and Si are more preferred. You may use the inorganic compound containing two types of metal. Particularly preferred inorganic compounds are silicon dioxide, ie silica.
[91] Microvoids in the inorganic fine particles can be formed, for example, by crosslinking molecules of silica forming particles. Crosslinking the molecules of silica reduces the volume, and the particles become porous. The microporous (porous) inorganic fine particles can be prepared by the sol-gel method (described in Japanese Patent Application Laid-Open Nos. 53-112732 and 57-9051) or as a precipitation method (described in APPLIED 0PTICS, 27, pages 3356 (1988)). It can be synthesized directly as a dispersion. In addition, the powder obtained by the drying and precipitation method can be mechanically pulverized to obtain a dispersion. Commercially available porous inorganic fine particles (for example, silicon dioxide sol) may be used. Inorganic fine particles having microvoids are preferably used in a state of being dispersed in a suitable medium in order to form a low refractive index layer. As the dispersion medium, water, alcohols (eg, methanol, ethanol, isopropyl alcohol) and ketones (eg, methyl ethyl ketone, methyl isobutyl ketone) are preferable.
[92] It is preferable that organic microparticles | fine-particles are also amorphous. It is preferable that organic microparticles | fine-particles are polymer microparticles synthesize | combined by the polymerization reaction (for example, emulsion polymerization method) of a monomer. It is preferable that the polymer of organic fine particles contains a fluorine atom. Examples of monomers containing fluorine atoms used to synthesize fluorine-containing polymers include fluoro olefins (e.g., fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2, 2-dimethyl-1,3-dioxol), fluorinated alkyl esters of acrylic acid or methacrylic acid and fluorinated vinyl ethers. Copolymers of monomers containing fluorine atoms and monomers containing no fluorine atoms may be used. Examples of monomers containing no fluorine atom include olefins (e.g. ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride), acrylate esters (e.g. methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate), meta Methacrylates (e.g. methyl methacrylate, ethyl methacrylate, butyl methacrylate), styrenes (e.g. styrene, vinyltoluene, α-methylstyrene), vinyl ethers (e.g. methyl vinyl ether), Vinyl esters (eg, vinyl acetate, vinyl propionate), acrylamides (eg, N-tert-butylacrylamide, N-cyclohexylacrylamide), methacrylamides, and acrylonitrile.
[93] Microvoids in the organic fine particles can be formed, for example, by crosslinking a polymer forming the particles. Crosslinking the polymer reduces the volume and makes the particles porous. In order to bridge | crosslink the polymer which forms particle | grains, it is preferable to make 20 mol% or more of the monomer for synthesize | combining a polymer as a polyfunctional monomer. It is more preferable that it is 30-80 mol%, and, as for the ratio of a polyfunctional monomer, it is most preferable that it is 35-50 mol%. Examples of polyfunctional monomers include dienes (e.g. butadiene, pentadiene), esters of polyhydric alcohols and acrylic acid (e.g. ethylene glycol diacrylate, 1,4-cyclohexanediacrylate, dipentaerythritol hexaacrylate) , Esters of polyhydric alcohols and methacrylic acid (e.g. ethylene glycol dimethacrylate, 1,2,4-cyclohexane tetramethacrylate, pentaerythritol tetramethacrylate), divinyl compounds (e.g. divinylcyclo Hexane, 1,4-divinylbenzene), divinylsulfone, bis acrylamides (e.g. methylenebis acrylamide) and bis methacryl amides. The microvoids between the particles may be formed by stacking at least two fine particles.
[94] The low refractive index layer may be made of a material having fine pores and a particulate inorganic material. In this case, the low refractive index layer is formed by coating, and the fine pores are formed by activating gas treatment after application of the layer so that the gas leaves the layer. Alternatively, a low refractive index layer may be formed by mixing two or more kinds of ultra fine particles (for example, MgF ₂ and SiO ₂ ) and changing the mixing ratio in the film thickness direction. The refractive index changes by changing the mixing ratio. Ultrafine particles are bonded by SiO ₂ generated by thermal decomposition of ethyl silicate. In pyrolysis of ethyl silicate, carbon dioxide and water vapor are generated by combustion of the ethyl moiety. As carbon dioxide and water vapor leave the layer, a gap is formed between the ultrafine particles. Alternatively, a low refractive index layer may be formed by containing an inorganic fine powder made of porous silica and a binder, or two or more fine particles made of a fluorine-containing polymer may be stacked to form a low refractive index layer having voids formed between the fine particles.
[95] The porosity can be improved at the branch structure level. For example, a low refractive index can be obtained even by using a polymer having a branched structure such as a dendrimer.
[96] In addition, using the above materials, the low refractive index layer is preferably set to a refractive index of 1.5 or less, preferably 1.2 or less. When the quartz having a refractive index of 1.45, glass having a refractive index of about 1.54, or the like is used as the substrate 2, the refractive index becomes lower than that of the substrate 2.
[97] In order to form the source electrode 243 and the drain electrode 244, first, a contact hole corresponding to the source electrode and the drain electrode is formed by patterning the first interlayer insulating layer 283 using a photolithography method. Next, a conductive layer made of a metal such as aluminum, chromium, or tantalum is formed to cover the first interlayer insulating layer 283, and then patterned to cover a region where the source electrode and the drain electrode are formed in the conductive layer. The source electrode 243 and the drain electrode 244 are formed by patterning a conductive layer while providing a mask for a use.
[98] Similar to the first interlayer insulating layer 283, the second interlayer insulating layer 284 is made of a low refractive index material, and the first interlayer insulating layer 283 is formed in the same procedure as the method for forming the first interlayer insulating layer 283. 283). Here, after the second interlayer insulating layer 284 is formed, a contact hole 23a is formed in a portion corresponding to the drain electrode 244 in the second interlayer insulating layer 284.
[99] The anode 23 connected to the light emitting element 3 is made of transparent electrode material such as " SnO ₂ doped with ITO or fluorine, ZnO or polyamine, and the drain electrode of the TFT 24 through the contact hole 23a. It is connected to 244. In order to form the anode 23, a film made of the transparent electrode material is formed on the upper surface of the second interlayer insulating layer 284, and is formed by patterning the film.
[100] The third insulating layer (bank layer) 221 is made of synthetic resin such as acrylic resin and polyimide resin. The third insulating layer 221 is formed after the anode 23 is formed. In the specific method for forming the third insulating layer 221, for example, a resist obtained by dissolving a resist such as an acrylic resin or a polyimide resin in a solvent is applied by spin coating or dip coating to form an insulating layer. In addition, the constituent material of the insulating layer may be any one so long as it is not dissolved in a solvent of ink described later and is easily patterned by etching or the like. Further, the insulating layer is etched at the same time by photolithography or the like to form the opening 221a, whereby the third insulating layer 221 having the opening 221a is formed.
[101] Here, a region showing lyophilic (lipin ink) and a region showing liquid repellency (ink repellency) are formed on the surface of the third insulating layer 221. In this embodiment, each area | region is formed by a plasma processing process. Specifically, the plasma treatment step includes a preliminary heating step, a lip ink process for making the wall surface of the opening portion 221a and the electrode surface of the pixel electrode 23 kinetic ink, and ink repelling the upper surface of the third insulating layer 221. It has a ink repellent process and a cooling process made into a castle.
[102] That is, the substrate (the substrate 2 including the third insulating layer or the like) is heated to a predetermined temperature (for example, about 70 to 80 ° C.), and then oxygen is reacted as a reaction gas in an atmospheric atmosphere as a pro-inking step. Plasma processing (0 ₂ plasma processing) is performed. Subsequently, as an ink repelling process, plasma treatment (CF ₄ plasma treatment) using tetrafluoromethane as a reaction gas in an atmospheric atmosphere is carried out, and the heated substrate is cooled to room temperature for plasma treatment, and ink and ink repellency are performed. This is given to the predetermined location. In addition, the electrode surface of the pixel electrode 23 is slightly affected by the CF ₄ plasma treatment. However, IT0, which is a material of the pixel electrode 23, lacks affinity for fluorine. The hydroxyl group imparted is not substituted with a fluorine group, so that the ink-friendly property is maintained.
[103] In addition, although each of the 1st interlayer insulation layer 283 and the 2nd interlayer insulation layer 284 is made into the low refractive index layer, it is not necessary to make these two layers into a low refractive index layer, and only at least one layer has a low refractive index. It may be a layer.
[104] In addition to the first interlayer insulating layer 283 and the second interlayer insulating layer 284, the gate insulating layer 282 may also be formed of a low refractive index material. Although the extraction efficiency of light improves by doing in this way, in order to improve the performance of transistors, such as TFT, it may be desirable to form a gate insulating layer by a high dielectric constant material.
[105] In addition, since the layer made of the low refractive index material may be provided at a portion where light from the light emitting layer 60 passes, other layers than the insulating layer may be used as the low refractive index layer. The organic bank layer 221 may be a low refractive index layer.
[106] The hole transport layer 70 is formed on the upper surface of the anode 23. Here, the material for forming the hole transport layer 70 is not particularly limited, and a known one can be used, and examples thereof include pyrazoline derivatives, arylamine derivatives, stilbene derivatives, and triphenyldiamine derivatives. Specifically, it describes in Unexamined-Japanese-Patent No.63-70257, 63-175860, 2-135359, 2-135361, 2-209988, 3-37992, and 3-152184. Although triphenyl diamine derivative is preferable, 4,4'-bis (N (3-methylphenyl) -N-phenylamino) biphenyl is suitable among them.
[107] In addition, a hole injection layer may be formed instead of a hole transport layer, and both a hole injection layer and a hole transport layer may be formed. In that case, as a material for forming the hole injection layer, for example, polyphthalenevinylene, 1,1-bis- (4-N, N-di, which is copper phthalocyanine (CuPc) or polytetrahydrothiophenylphenylene Tolylaminophenyl) cyclohexane, tris (8-hydroxyquinolinol) aluminum, etc. are mentioned, It is especially preferable to use copper phthalocyanine (CuPc).
[108] The inkjet method is used when forming the hole injection / transport layer 70. That is, after discharging the composition ink containing the above-described hole injection / transport layer material on the electrode surface of the anode 23, the hole injection / transport layer 70 is formed on the electrode 23 by performing drying treatment and heat treatment. do. In addition, after this hole injection / transport layer formation process, in order to prevent oxidation of the hole injection / transport layer 70 and the light emitting layer (organic EL layer) 60, it is preferable to perform in inert gas atmosphere, such as nitrogen atmosphere and argon atmosphere. . For example, an inkjet head (not shown) is filled with composition ink containing a hole injection / transport layer material, the discharge nozzle of the inkjet head is opposed to the electrode surface of the anode 23, and the inkjet head and the substrate (substrate ( While relatively moving 2)), ink droplets whose liquid amount per drop is controlled are ejected from the ejection nozzle onto the electrode surface. Next, the hole injection / transport layer 70 is formed by drying the discharged ink droplets to evaporate the polar solvent contained in the composition ink.
[109] Moreover, as an example of composition ink, what melt | dissolved the mixture of polythiophene derivatives, such as polyethylene dioxythiophene, polystyrene sulfonic acid, etc. in polar solvents, such as isopropyl alcohol, can be used. Here, the discharged ink droplets spread on the electrode surface of the anode-inked anode 23 and are filled in the vicinity of the bottom of the opening portion 221a. On the other hand, ink droplets do not splash on the upper surface of the ink repellent third insulating layer 221. Therefore, even if the ink droplet is discharged from the predetermined discharge position on the upper surface of the third insulating layer 221, the upper surface does not get wet with the ink droplets, and the splattered ink droplets are introduced into the openings 221a of the third insulating layer 221. It is supposed to roll in.
[110] The light emitting layer 60 is formed on the upper surface of the hole injection / transport layer 70. The material for forming the light emitting layer 60 is not particularly limited, and a low molecular organic light emitting dye or a high molecular light emitting material, that is, a light emitting material made of various fluorescent materials or phosphorescent materials can be used. It is especially preferable that the conjugated polymer used as a luminescent material contains an arylene vinylene structure. In the low-molecular phosphor, for example, naphthalene derivatives, anthracene derivatives, perylene derivatives, polymethine-based, xanthene-based, coumarin-based and cyanine-based pigments, 8-hydroquinoline and metal complexes of derivatives thereof, aromatic amines and tetraphenylcyclo Pentadiene derivatives and the like, or known ones described in Japanese Patent Application Laid-Open No. 57--51781, 59-194393, and the like can be used.
[111] In the case of using a polymeric fluorescent substance as the material for forming the light emitting layer 60, a polymer having a fluorescent group in the side chain can be used. Preferably, the conjugated structure is included in the main chain, and in particular, polythiophene and polyp-phenyl Phenylene, polyarylenevinylene, polyfluorene and derivatives thereof are preferred. Among them, polyarylene vinylene and derivatives thereof are preferable. This polyarylene vinylene and its derivatives are polymers containing 50 mol% or more of all the repeating units with the repeating unit represented by following General formula (1). Although it depends on the structure of a repeating unit, it is more preferable that the repeating unit represented by General formula (1) is 70% or more of all the repeating units.
[112] -Ar-CR = CR'- (1)
[113] [Wherein Ar is an arylene group or a heterocyclic compound group having 4 to 20 carbon atoms involved in the conjugated bond, R and R 'are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, A group selected from the group consisting of an aryl group, a C4-20 heterocyclic compound, and a cyano group.]
[114] The polymeric fluorescent substance may contain an aromatic compound group or its derivative (s), a heterocyclic compound group or its derivative (s), a group obtained by combining them, etc. as repeating units other than the repeating unit represented by General formula (1). In addition, the repeating unit and other repeating unit represented by General formula (1) may be connected by the nonconjugated unit which has an ether group, an ester group, an amide group, an imide group, etc., and those nonconjugated parts may be contained in a repeating unit. .
[115] Ar of Formula (1) in the polymeric fluorescent substance is an arylene group or heterocyclic compound group having 4 to 20 carbon atoms involved in the conjugated bond, and an aromatic compound group represented by the following Formula (2), or the Derivative groups, heterocyclic compound groups or derivative groups thereof, and groups obtained by combining them are exemplified.
[116]
[117] (R ₁ to R ₉₂ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group and an alkylthio group; an aryl group having 6 to 18 carbon atoms and an aryloxy group; and a heterocyclic compound group having 4 to 14 carbon atoms). It is a flag chosen from the group which becomes.)
[118] Of these, phenylene group, substituted phenylene group, biphenylene group, substituted biphenylene group, naphthalenediyl group, substituted naphthalenediyl group, anthracene-9,10-diyl group, substituted anthracene-9,10-diyl group, pyridine-2, 5-diyl group, substituted pyridine-2,5-diyl group, thienylene group, and substituted thienylene group are preferable. More preferably, they are a phenylene group, a biphenylene group, a naphthalenediyl group, a pyridine-2, 5- diyl group, and a thienylene group.
[119] In the case where R and R 'in the general formula (1) are substituents other than hydrogen or cyano group, examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, An octyl group, a decyl group, a lauryl group, etc. are mentioned, A methyl group, an ethyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group are preferable. As an aryl group, a phenyl group, 4-Cl-Cl2 alkoxy phenyl group (Cl-Cl2 shows C1-C12. Is the same below.), 4-Cl-Cl2 alkyl phenyl group, 1-naphthyl group, 2-naphthyl group, etc. It can be illustrated.
[120] In view of solvent solubility, Ar in formula (1) is one or more alkyl group having 4 to 20 carbon atoms, alkoxy group and alkylthio group, aryl group having 6 to 18 carbon atoms and aryl oxy group and heterocyclic compound having 4 to 14 carbon atoms. It is preferred to have a group selected from the group.
[121] The following are illustrated as these substituents. Examples of the alkyl group having 4 to 20 carbon atoms include a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, and a lauryl group, and a pentyl group, hexyl group, heptyl group, and octyl group are preferable. Examples of the alkoxy group having 4 to 20 carbon atoms include butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and lauryloxy group, and the like. , Heptyloxy group and octyloxy group are preferable. Examples of the alkylthio group having 4 to 20 carbon atoms include butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, decyloxy group and laurylthio group, and the like. , Heptylthio group and octylthio group are preferable. As an aryl group, a phenyl group, 4-Cl-Cl2 alkoxyphenyl group, 4-Cl-Cl2 alkylphenyl group, 1-naphthyl group, 2-naphthyl group, etc. are illustrated. Phenoxy group is illustrated as an aryloxy group. As a heterocyclic compound group, 2-thienyl group, 2-pyrrolyl group, 2-pril group, 2-, 3-, or 4-pyridyl group, etc. are illustrated. Although the number of these substituents also changes with the molecular weight of the polymeric fluorescent substance and the structure of a repeating unit, it is more preferable that these substituents are 1 or more per 600 molecular weight from a viewpoint of obtaining high solubility polymeric fluorescent substance.
[122] The polymeric fluorescent substance may be a random, block or graft copolymer, or may be a polymer having an intermediate structure thereof, for example, a random copolymer having block properties. From the viewpoint of obtaining a polymeric fluorescent substance having a high quantum yield of fluorescence, a random copolymer having a block property or a block or graft copolymer is preferable to a completely random copolymer. In addition, since the organic electroluminescent element formed here uses the fluorescence from a thin film, the polymer fluorescent substance which uses the fluorescence in a solid state is used.
[123] When a solvent is used for the polymeric fluorescent substance, suitable examples include chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene and the like. Although it depends on the structure and molecular weight of a polymeric fluorescent substance, it can usually melt | dissolve in these solvent 0.1weight% or more.
[124] Moreover, as said polymeric fluorescent substance, it is preferable that molecular weight is 10 <^3> -10 <^7> in polystyrene conversion, and these degree of polymerization changes also with a repeating structure and its ratio. In view of the film formability, generally, the total number of the repeating structures is preferably 4 to 10,000, more preferably 5 to 3000, and particularly preferably 10 to 2000.
[125] Although it does not specifically limit as a synthesis method of such a polymeric fluorescent substance, For example, the diphosphonium salt obtained from the dialdehyde compound which two aldehyde groups couple | bonded with the arylene group, the compound which two methyl group halides were bonded with the arylene group, and triphenyl phosphine Wittig reaction from is illustrated. As another synthesis method, a dehalogenated hydrogen method from a compound in which two halogenated methyl groups are bonded to an arylene group is exemplified. Moreover, the sulfonium salt decomposition method which obtains the said polymeric fluorescent substance by heat processing from the intermediate obtained by superposing | polymerizing in sulfonium salt of the compound which two halogenated methyl groups couple | bonded with the arylene group by alkali is illustrated. In any synthesis method, the structure of the repeating unit contained in the resulting polymeric fluorescent substance can be changed by adding a compound having a skeleton other than an arylene group as a monomer and changing its abundance, so that the repeat represented by the formula (1) You may add and copolymerize so that a unit may be 50 mol% or more, and you may copolymerize. Among these, the method by the Wittig reaction is preferable from a viewpoint of reaction control or a yield.
[126] More specifically, a method of synthesizing an arylene vinylene copolymer which is one example of the polymer phosphor will be described. For example, when obtaining a polymeric fluorescent substance by a Wittig reaction, first, for example, a bis (methyl halide) compound, more specifically, for example, 2,5-dioctyloxy-p-xylene Dibromide is reacted with triphenylphosphine in an N, N-dimethylformamide solvent to synthesize a phosphonium salt, and this and a dialdehyde compound, more specifically, terephthalaldehyde, for example, ethyl alcohol By the Wittig reaction condensed using lithium ethoxide, the polymeric fluorescent substance containing a phenylene vinylene group and a 2, 5- dioctyloxy- p-phenylene vinylene group is obtained. At this time, two or more diphosphonium salts and / or two or more dialdehyde compounds may be reacted to obtain a copolymer.
[127] In the case where these polymeric fluorescent materials are used as the material for forming the light emitting layer, since the purity affects the luminescence properties, it is preferable to carry out purification treatment such as reprecipitation purification and fractionation by chromatograph after synthesis.
[128] As the material for forming the light emitting layer of the above-mentioned polymeric fluorescent substance, in order to display full color, three colors of red, green, and blue light emitting layer forming materials are used, each of which is previously determined by a predetermined patterning device (inkjet device). It is ejected to the pixel AR at the set position and patterned.
[129] In addition, the light emitting material may be a form in which a guest material is added to the host material.
[130] As such a luminescent material, a high molecular organic compound or a low molecular material, for example, is preferably used as a host material, including a fluorescent dye or phosphorescent material for changing the luminescence properties of the light emitting layer obtained as a guest material.
[131] In the case of a material having a low solubility, for example, a high molecular solubility compound may be produced by applying a precursor and then heat curing to form a light emitting layer of a conjugated polymer organic electroluminescent layer, as shown by the following general formula (3). . For example, when a precursor is a sulfonium salt, a sulfonium group leaves | separates by heat-processing, and becomes a conjugated high molecular organic compound.
[132] Moreover, in the material with high solubility, after apply | coating a material as it is, the solvent may be removed and it may be set as a light emitting layer.
[133]
[134] The polymer organic compound has a strong fluorescence as a solid, it can form a homogeneous solid ultra-thin film. In addition, it has abundant formation ability, high adhesion to the IT0 electrode, and forms a solid conjugated polymer film after solidification.
[135] As such a high molecular organic compound, polyarylene vinylene is preferable, for example. Since polyarylene vinylene can be easily prepared into a coating liquid when applied to the second base 11 in an aqueous solvent or an organic solvent, it can be polymerized under certain conditions. A high quality thin film can be obtained.
[136] Such polyarylene vinylenes include PPV (poly (para-phenylenevinylene)), M0-PPV (poly (2,5-dimethoxy-1,4-phenylenevinylene)), CN-PPV (poly (2,5-bis hexyloxy-1,4-phenylene- (1-cyanovinylene))), MEH-PPV (poly [2-methoxy-5- (2'-ethylhexyloxy) PPV derivatives such as] -para-phenylenevinylene), poly (alkylthiophenes) such as PTV (poly (2,5-thienylenevinylene)), and PFV (poly (2,5-prienevinylene) ), Poly (paraphenylene), polyalkyl fluorene, and the like, but among these, polyalkyl influenza such as those represented by formula (4) or precursors of PPV or PPV derivatives, or represented by formula (5) Orene (polyalkyl fluorene-based copolymer specifically as represented by General formula (6)) is especially preferable.
[137] PPV and the like have strong fluorescence and are also conductive polymers in which Electrons forming a double bond are delocalized in a polymer chain, and thus a high-performance organic electroluminescent device can be obtained.
[138]
[139]
[140]
[141] In addition, a high molecular organic compound or a low molecular material capable of forming a light emitting layer in addition to the above PPV thin film, that is, used as a host material in this example is, for example, an aluminum quinolinol complex (Alq ₃ ), distyryl biphenyl, or a chemical formula (7 BeBq ₂ , Zn (0XZ) ₂ , and in addition to those commonly used in the art such as TPD, AL0, and DPVBi, pyrazoline dimers, quinolidinecarboxylic acids, benzopyrilium perchlorates, benzopyranoquinolidines, Leurene, phenanthroline europium complex, etc. are mentioned, The composition for organic electroluminescent elements containing these 1 type, or 2 or more types can be used.
[142]
[143] On the other hand, as a guest material added to such a host material, fluorescent dye and phosphorescent substance are mentioned as mentioned above. In particular, the fluorescent dye can change the light emission characteristics of the light emitting layer, and is effective as a means for improving the light emission efficiency of the light emitting layer or for changing the light absorption maximum wavelength (light emission color), for example. That is, the fluorescent dye can be used not only as a light emitting layer material but as a dye material in charge of the light emitting function itself. For example, the energy of excitons generated by carrier recombination on conjugated polymeric organic compound molecules can be transferred onto fluorescent dye molecules. In this case, since light emission only occurs from fluorescent dye molecules having high fluorescence quantum efficiency, the current quantum efficiency of the light emitting layer also increases. Therefore, by adding a fluorescent dye to the material for forming the light emitting layer, the light emission spectrum of the light emitting layer also becomes a fluorescent molecule, and therefore, it is effective as a means for changing the light emission color.
[144] In addition, the current quantum efficiency here is a measure for considering light emission performance by light emission function, and is defined by the following formula.
[145] ηE = energy of input photons / input electrical energy
[146] By converting the light absorption maximum wavelength by the dope of the fluorescent dye, for example, three primary colors of red, blue, and green can be emitted, and as a result, a full color display body can be obtained.
[147] Further, by doping the fluorescent dye, the luminous efficiency of the electroluminescent element can be greatly improved.
[148] As a fluorescent dye, when forming the light emitting layer which emits red luminescence light, it is preferable to use DCM-1, a rhodamine or a rhodamine derivative, phenylene, etc. of a laser dye. The light emitting layer can be formed by doping these fluorescent dyes to a host material such as PPV, but since these fluorescent dyes are water soluble in many, they are more uniform when doped into a sulfonium salt which is a water-soluble PPV precursor and then subjected to heat treatment. It is possible to form one light emitting layer. Specific examples of such fluorescent dyes include rhodamine B, rhodamine B base, rhodamine 6G, and rhodamine 101 perchlorate, and mixtures of two or more thereof may be used.
[149] In addition, when forming the light emitting layer which emits green luminescence light, it is preferable to use quinacridone, a luene, DCJT, and its derivative (s). . Similarly to the above-mentioned fluorescent dyes, these fluorescent dyes can be formed by doping with a host material such as PPV. However, since these fluorescent dyes are often water-soluble, they are doped with sulfonium salts which are water-soluble PPV precursors. Subsequently, heat treatment makes it possible to form a more uniform light emitting layer.
[150] Moreover, when forming the light emitting layer which emits blue luminescence light, it is preferable to use distyryl biphenyl and its derivative (s). Similarly to the above-mentioned fluorescent dyes, these fluorescent dyes can be formed by doping with a host material such as PPV. However, since these fluorescent dyes are often water-soluble, they are doped with sulfonium salts which are water-soluble PPV precursors. Subsequently, heat treatment makes it possible to form a more uniform light emitting layer.
[151] Moreover, coumarin and its derivative (s) are mentioned as another fluorescent dye which has blue color light. These fluorescent dyes have good compatibility with PPV and easily form a light emitting layer. Moreover, although coumarin is especially insoluble in a solvent among these, the solubility is increased by selecting a substituent suitably, and some may be soluble in a solvent. Specific examples of such fluorescent dyes include coumarin-1, coumarin-6, coumarin-7, coumarin 120, coumarin 138, coumarin 152, coumarin 153, coumarin 311, coumarin 314, coumarin 334, coumarin 337, coumarin 343, and the like. .
[152] Moreover, as a fluorescent dye which has another blue luminescent light, tetraphenyl butadiene (TPB), a TPB derivative, DPVBi, etc. are mentioned. These fluorescent dyes are soluble in aqueous solution similarly to the above-mentioned red fluorescent dyes, and have good compatibility with PPV, making it easy to form the light emitting layer.
[153] As for the above-mentioned fluorescent dyes, only one type may be used for all the colorants, and two or more types may be mixed and used.
[154] As such fluorescent dyes, those represented by the formula (8), those represented by the formula (9), and those represented by the formula (10) are used.
[155]
[156]
[157]
[158] About these fluorescent dyes, it is preferable to add 0.5-10 wt% with respect to the host material which becomes the said conjugated type polymeric organic compound etc. by the method mentioned later, and it is more preferable to add 1.0-5.0 wt%. If the amount of the fluorescent dye added is too large, it is difficult to maintain the weather resistance and durability of the light emitting layer obtained. On the other hand, if the amount of the added dye is too small, the effect of adding the fluorescent dye as described above is not sufficiently obtained.
[159] In addition, as a phosphor substance as a guest material added to a host material, Ir (ppy) ₃ , Pt (thpy) ₂ , PtOEP, etc. which are represented by General formula (11) are used suitably.
[160]
[161] In the case where the phosphorescent material represented by the above formula (11) is used as a guest material, particularly as the host material, CBP, DCTA, TCPB represented by the formula (12), or the aforementioned DPVBi and Alq ₃ are suitably used.
[162] Moreover, about the said fluorescent dye and phosphorescent substance, these may all be added to a host material as a guest material.
[163]
[164] When the light emitting layer 60 is formed of such a host / guest light emitting material, for example, a plurality of material supply systems such as nozzles are formed in advance in a patterning device (inkjet device), and the host material and By simultaneously discharging the guest material in a predetermined ratio, the light emitting layer 60 can be formed of a light emitting material to which a desired amount of guest material is added to the host material.
[165] The light emitting layer 60 is formed by the same procedure as the method of forming the hole injection / transport layer 70. That is, after the composition ink containing the light emitting layer material is discharged to the upper surface of the hole injection / transport layer 70 by the inkjet method, the drying treatment and heat treatment are performed to thereby form the inside of the opening 221a formed in the third insulating layer 221. The light emitting layer 60 is formed on the hole injection / transport layer 70. This light emitting layer formation process is also performed in inert gas atmosphere as mentioned above. Since the ejected composition ink splashes in the ink repellent region, even if the ink droplet is out of the predetermined ejection position, the splatter ink droplet rolls into the opening 221a of the third insulating layer 221.
[166] The electron transport layer 50 is formed on the upper surface of the light emitting layer 60. The electron transporting layer 50 is also formed by the inkjet method similarly to the method of forming the light emitting layer 60. The material for forming the electron transport layer 50 is not particularly limited, and may include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, and tetracyanoan Traquinodimethane and its derivatives, fluorenone derivatives, diphenyl dicyanoethylene and its derivatives, diphenoquinone derivatives, 8-hydroxyquinoline and metal complexes thereof and the like are exemplified. Specifically, in the same manner as the material for forming the hole transporting layer, Japanese Patent Laid-Open Nos. 63-70257, 63-175860, 2-135359, 2-135361, 2-209988, and 3- 37992, the same as described in the 3-152184, etc. are illustrated, and especially 2- (4-biphenyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole , Benzoquinone, anthraquinone and tris (8-quinolinol) aluminum are suitable.
[167] In addition, the above-mentioned material for forming the hole injection / transport layer 70 and the material for forming the electron transporting layer 50 may be mixed with the material for forming the light emitting layer 60 and used as the light emitting layer forming material. The amount of the transport layer-forming material and the electron-transport layer-forming material used varies depending on the kind of the compound to be used, but is appropriately determined in consideration of them in both ranges that do not impair sufficient film forming properties and luminescent properties. Usually, it is 1-40 weight% with respect to a light emitting layer formation material, More preferably, it is 2-30 weight%.
[168] In addition, the hole injection / transport layer 70, the electron transport layer 50, etc. are not limited to the inkjet method, but can also be formed using the mask deposition method.
[169] The cathode 222 is formed on the entire surface of the electron transport layer 50 and the third insulating layer 221 or in a stripe shape. The cathode 222 may, of course, be formed of one layer made of a single material such as Al, Mg, Li, Ca, or an alloy material of Mg: Ag (10: 1 alloy), but may be formed of two or three layers of metal ( It may be formed as a layer). Specifically, a laminate structure of Li ₂ O (about 0.5 nm) / Al, LiF (about 0.5 nm) / Al, MgF ₂ / Al can also be used. The cathode 222 is a thin film made of the above-described metal and may transmit light.
[170] The sealing layer 20 blocks air from entering the organic EL element from the outside, and the film thickness and the material are appropriately selected. As a material which comprises the sealing layer 20, ceramic, silicon nitride, silicon oxynitride, silicon oxide, etc. are used, for example, silicon oxynitride is preferable from a viewpoint of transparency and gas barrier property. The sealing layer 20 may be formed on the cathode 222 by plasma CVD.
[171] As described above, since each of the insulating layers 283 and 284 made of a low refractive index material having a lower refractive index than that of the substrate 2 from the light emitting layer 60 is incident on the substrate 2, the respective insulating layers are at an angle greater than or equal to the critical angle. The light incident on (283, 284) is refracted in the direction of becoming less than or equal to the critical angle at the interface with the substrate 2, and is taken out of the total reflection condition in the substrate 2 to the outside. Thereby, the light extraction efficiency improves and high visibility can be obtained. In addition, there is a strong correlation between the refractive index and the dielectric constant. By making the insulating layers 283 and 284 into the low refractive index layers, the low dielectric constant layer can be obtained, and the inter-wire capacitance can be reduced. It is possible to improve operation performance such as speeding up.
[172] In addition to the hole injection / transport layer 70, the light emitting layer 60, and the electron transport layer 50 described above, a hole blocking layer is formed, for example, on the opposite electrode 222 side of the light emitting layer 60 to form the light emitting layer 60. May be used for a longer life. As the material for forming the hole blocking layer, for example, BCP represented by the formula (13) or BAlq represented by the formula (14) is used. However, BAlq is preferred from the viewpoint of prolongation of life.
[173]
[174]
[175] [Electronics]
[176] An example of the electronic apparatus provided with the organic electroluminescence display of the said embodiment is demonstrated.
[177] 4 is a perspective view showing an example of a mobile telephone. In Fig. 4, reference numeral 1000 denotes a mobile telephone body, and reference numeral 1001 denotes a display unit using the above organic EL display device.
[178] 5 is a perspective view showing an example of a wristwatch-type electronic device. In Fig. 5, reference numeral 1100 denotes a clock main body, and reference numeral 1101 denotes a display unit using the organic EL display device.
[179] 6 is a perspective view showing an example of a portable information processing apparatus such as a word processor and a personal computer. In Fig. 6, reference numeral 1200 denotes an information processing apparatus, reference numeral 1202 denotes an input unit such as a keyboard, reference numeral 1204 denotes a main body of the information processing apparatus, and reference numeral 1206 denotes a display unit using the organic EL display device.
[180] Since the electronic device shown in FIGS. 4-6 is equipped with the organic electroluminescence display of the said embodiment, it is excellent in display quality, and the electronic device provided with the organic electroluminescence display of a bright screen is realizable.
[181] In addition, the technical scope of this invention is not limited to the said embodiment, A various change can be added in the range which does not deviate from the meaning of this invention.
[182] For example, in the above embodiment, an example in which the light emitting layer and the hole transporting layer are sandwiched with a pair of electrodes as the configuration of the organic EL device is mentioned. In addition to the light emitting layer and the hole transporting layer, an electron transporting layer, a hole injection layer, and an electron injection layer You may insert the organic layer which has various functions, such as these. In addition, the specific material etc. which were provided in embodiment are only an example, and can be changed suitably.
[183] In addition, in the display apparatus S1 of the structure of this embodiment, the light emitting layer 60 which is an electro-optical element can be substituted by other optical display materials, such as a liquid crystal layer.
[184] In addition, in the said embodiment, what was called the back emission type which takes out light from the board | substrate 2 side in which TFT24 was arrange | positioned was demonstrated, but it is called the top emission type which takes out light from the opposite side to the board | substrate in which TFT was arrange | positioned. Also, the low refractive index layer of the present invention can be applied.
[185] According to the present invention, since light from the electro-optical element passes through a material layer made of a low refractive index material having a lower refractive index than that of the substrate, the light is incident on the low refractive index layer at an angle greater than or equal to a critical angle. It is refracted in the direction of becoming below a critical angle, and it is taken out from the total reflection condition in a board | substrate. Thereby, the light extraction efficiency improves and high visibility can be obtained. In addition, since the refractive index and the dielectric constant have a strong correlation, the low dielectric constant layer can be formed by using a predetermined material layer as the low refractive index layer, and the inter-wire capacitance can be reduced, thereby increasing the operating speed of the electro-optical device, etc. It can improve operation performance.

权利要求:
Claims (27)
[1" claim-type="Currently amended] An electro-optical device in which a plurality of material layers including an electro-optical element layer having an electro-optical element are stacked.
A plurality of material layers located in the direction from which light from the electro-optical element is taken out are arranged,
The low refractive index layer which has a refractive index lower than the refractive index of the said surface material layer is arrange | positioned between the surface material layer located in the outermost surface among the said several material layers, and the said electro-optic element layer.
[2" claim-type="Currently amended] The method of claim 1,
The electro-optical device is an electro-optical device, characterized in that the light emitting device.
[3" claim-type="Currently amended] The method according to claim 1 or 2,
The low refractive index layer is formed as an interlayer insulating layer.
[4" claim-type="Currently amended] The method according to claim 1 or 2,
And the refractive index of the low refractive index layer is 1.5 or less.
[5" claim-type="Currently amended] The method according to claim 1 or 2,
The refractive index of the low refractive index layer is an electro-optical device, characterized in that 1.2 or less.
[6" claim-type="Currently amended] The method according to claim 1 or 2,
The low refractive index material is an electro-optical device, characterized in that the porous material capable of transmitting light.
[7" claim-type="Currently amended] The method according to claim 1 or 2,
And the low refractive index material is at least one of aerogel, porous silica, magnesium fluoride, fluorine-based polymer and porous polymer.
[8" claim-type="Currently amended] The method according to claim 1 or 2,
The low refractive index material is an electro-optical device comprising at least one of inorganic fine particles and organic fine particles in a predetermined material.
[9" claim-type="Currently amended] The method of claim 8,
And the low refractive index material comprises a gel in which fine particles of magnesium fluoride are dispersed.
[10" claim-type="Currently amended] The method according to claim 1 or 2,
The electro-optical device is an organic electroluminescent device.
[11" claim-type="Currently amended] The method according to claim 1 or 2,
An electro-optical device, further comprising an active element.
[12" claim-type="Currently amended] The method of claim 11,
And said active element is a transistor.
[13" claim-type="Currently amended] The method of claim 12,
And said transistor is a thin film transistor.
[14" claim-type="Currently amended] Disposing a thin film transistor on a first substrate, and forming a low refractive index layer on a second substrate including the thin film transistor and the first substrate.
[15" claim-type="Currently amended] A circuit board in which a plurality of material layers are laminated on a substrate,
A circuit board comprising at least one low refractive index layer made of a low refractive index material having a lower refractive index than the substrate.
[16" claim-type="Currently amended] The method of claim 15,
At least one of the plurality of material layers is an interlayer insulating layer, and the interlayer insulating layer is made of the low refractive index material.
[17" claim-type="Currently amended] The method according to claim 15 or 16,
The refractive index of the low refractive index layer is a circuit board, characterized in that less than 1.5.
[18" claim-type="Currently amended] The method according to claim 15 or 16,
And the refractive index of the low refractive index layer is 1.2 or less.
[19" claim-type="Currently amended] The method according to claim 15 or 16,
The low refractive index material is a circuit board, characterized in that the porous material capable of transmitting light.
[20" claim-type="Currently amended] The method according to claim 15 or 16,
The low refractive index material is a circuit board, characterized in that at least one of aerogel, porous silica, magnesium fluoride, fluorine-based polymer, porous polymer.
[21" claim-type="Currently amended] The method according to claim 15 or 16,
The low refractive index material is a circuit board comprising at least one of inorganic fine particles and organic fine particles in a predetermined material.
[22" claim-type="Currently amended] The method of claim 21,
And the low refractive index material comprises a gel in which fine particles of magnesium fluoride are dispersed.
[23" claim-type="Currently amended] The method according to claim 15 or 16,
A circuit board further comprising an active element.
[24" claim-type="Currently amended] The method of claim 23, wherein
And the active element is a transistor.
[25" claim-type="Currently amended] Arranging a transistor on a first substrate; and forming a low refractive index layer on a second substrate including the transistor and the first substrate.
[26" claim-type="Currently amended] An electronic apparatus comprising the electro-optical device according to claim 1.
[27" claim-type="Currently amended] An electronic device provided with the circuit board of Claim 15 or 16.

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同族专利:

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公开号 | 公开日

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JP2003195775A|2003-07-09|

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KR100512047B1|2005-08-31|

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EP1976340A2|2008-10-01|

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CN1251556C|2006-04-12|

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CN1429054A|2003-07-09|

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EP1976340A3|2009-01-14|

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JP4182467B2|2008-11-19|

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CN1633224B|2010-08-11|

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CN1901244A|2007-01-24|

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TWI301605B|2008-10-01|

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EP1324642A3|2004-06-16|

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US20070170429A1|2007-07-26|

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US7211838B2|2007-05-01|

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CN1633224A|2005-06-29|

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EP1324642A2|2003-07-02|

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TW200301456A|2003-07-01|

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US7714328B2|2010-05-11|

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US20030160247A1|2003-08-28|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2001-12-27|Priority to JPJP-P-2001-00398522

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2001-12-27|Priority to JP2001398522A

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2002-12-26|Application filed by 세이코 엡슨 가부시키가이샤

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2003-07-04|Publication of KR20030057371A

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2005-08-31|Application granted

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2005-08-31|Publication of KR100512047B1

优先权:

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申请号 | 申请日 | 专利标题

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JPJP-P-2001-00398522|2001-12-27|

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JP2001398522A|JP4182467B2|2001-12-27|2001-12-27|Circuit board, electro-optical device and electronic apparatus|