JP2003197612A - Method for manufacturing electronic element, method for manufacturing circuit board, method for manufacturing electronic device, electrooptic device and its manufacturing method, electronic apparatus and patterning apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel manufacturing method having high flexibility in selecting a material and to provide a patterning apparatus suitable for conducting the method. <P>SOLUTION: An electronic element having at least one material among a conductive material, a semiconductor material and an insulating material, a circuit board, an electronic device and an electrooptic device are manufactured by a patterning apparatus 1. A method for manufacturing the electronic element and so forth, comprises steps of disposing a base in a vacuum atmosphere substantially regulated to the vacuum, discharging at least one of the conductive material, the semiconductor material and the insulating material or at least one of a precursors of these materials from a nozzle 3 into the atmosphere, and disposing at least one material at a predetermined position on the base. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an electronic element such as a transistor, a method for manufacturing a circuit board having the same, a method for manufacturing an electronic device, an electro-optical device and a method for manufacturing the same, an electronic apparatus, and The present invention relates to a patterning device that is preferably used in these manufacturing methods.

[0002]

2. Description of the Related Art Conventionally, as a method of manufacturing a transistor, a vapor deposition method (Japanese Patent Laid-Open No. 8-228034, Japanese Patent Laid-Open No. 8-22) is used.
8035, Japanese Patent Laid-Open No. 2001-94107, etc., and an inkjet method (USP 6,087,196 etc.) and the like are known.

[0003]

By the way, in the manufacture of electronic elements such as transistors, a new patterning method with a high degree of freedom in material selection is provided by diversifying materials for various components. Is desired. Therefore, it is an object of the present invention to provide a new manufacturing method with a high degree of freedom in material selection and a patterning apparatus suitable for carrying out this method.

[0004]

To achieve the above object, a method of manufacturing an electronic device according to the present invention is a method of manufacturing an electronic device including at least one material selected from a conductive material, a semiconductor material and an insulating material. The substrate is placed in a vacuum atmosphere substantially adjusted to a vacuum, and at least one of the materials or at least one of the precursors of the materials is discharged from a nozzle into the vacuum atmosphere, The at least one material is arranged at a predetermined position on the base.

According to this method of manufacturing an electronic element, at least one of a conductive material, a semiconductor material, an insulating material or at least one of precursors of these materials is discharged from a nozzle into a vacuum atmosphere. The material or precursor can be discharged, for example, in a vaporized state and ideally in a molecular beam form. Therefore, the material can be arranged by freely selecting and using the material or the precursor without any particular limitation. Further, by arranging the material or precursor at a predetermined position on the substrate, patterning can be performed without the need for a mask.

In the above-mentioned method of manufacturing an electronic device, it is preferable that the electronic device is a diode. By doing so, the degree of freedom in selecting the material for forming the diode can be increased.

In the method of manufacturing an electronic device described above, the electronic device is preferably a transistor. In this way, the degree of freedom in selecting the material for forming the transistor can be increased.

In the method of manufacturing an electronic device described above, at least one of the materials or at least one of precursors of the material is a material for forming a gate electrode, and the material is provided at a predetermined position on the substrate. It is preferable to form the gate electrode by arranging By doing so, the degree of freedom in selecting the material for forming the gate electrode can be increased.

In the method of manufacturing an electronic device, at least one of the materials or at least one of the precursors of the material is a semiconductor material, and the material is arranged at a predetermined position on the substrate. The semiconductor layer is preferably formed by By doing so, the degree of freedom in selecting the material for forming the semiconductor layer can be increased.

In the method of manufacturing an electronic device described above, the semiconductor material is preferably an organic semiconductor material. By doing so, the degree of freedom in selecting the material for forming the semiconductor layer can be increased.

In the method of manufacturing an electronic device, at least one of the materials or at least one of the precursors of the material is an insulating material, and the material is arranged at a predetermined position on the substrate. It is preferable to form the gate insulating film. By doing so, the degree of freedom in selecting the material for forming the gate insulating film can be increased.

A method of manufacturing a circuit board according to the present invention is characterized in that a plurality of electronic elements are formed by the method of manufacturing an electronic element described above. According to this method of manufacturing a circuit board, the material or precursor thereof can be freely selected and used without particular limitation, and the material can be arranged. Further, by arranging the material or precursor at a predetermined position on the substrate, patterning can be performed without the need for a mask.

A method of manufacturing an electronic device of the present invention is characterized by using the above-described method of manufacturing an electronic element. According to the method for manufacturing the electronic device, the material or the precursor thereof can be freely selected and used without any limitation.
The material can be arranged. Further, by arranging the material or precursor at a predetermined position on the substrate, patterning can be performed without the need for a mask.

A method of manufacturing an electro-optical device according to the present invention is characterized by using the above-described method of manufacturing an electronic element. According to this method of manufacturing the electro-optical device, the material or the precursor thereof can be freely selected and used without being particularly limited, and the material can be arranged. Further, by arranging the material or precursor at a predetermined position on the substrate, patterning can be performed without the need for a mask.

In the method of manufacturing the electro-optical device, it is preferable that the electro-optical device includes a liquid crystal element. By doing so, the degree of freedom in selecting the material of the electro-optical device including the liquid crystal element can be increased.

In the method of manufacturing an electro-optical device, it is preferable that the electro-optical device includes an electrophoretic element. By doing so, the degree of freedom in selecting the material of the electro-optical device including the electrophoretic element can be increased.

In the above-described method of manufacturing the electro-optical device, it is preferable that the electro-optical device includes an organic EL element. By doing so, the degree of freedom in selecting the material of the electro-optical device including the organic EL element can be increased.

In the above-described method of manufacturing an electro-optical device including an organic EL element, at least one of the materials or at least one of the precursors of the material is a light emitting layer or a hole in the organic EL element. It is a material for forming at least one of an injection layer and a hole transport layer, and it is preferable to form the organic EL element by disposing the material at a predetermined position on the substrate. By doing so, the degree of freedom in selection can be increased for at least one forming material of the light emitting layer, the hole injecting layer, and the hole transporting layer.

The electro-optical device according to the present invention is characterized by being obtained by the above-mentioned method for manufacturing the electro-optical device. According to this electro-optical device, at least one of a conductive material, a semiconductor material, and an insulating material, or at least one of precursors of these materials is discharged from a nozzle into a vacuum atmosphere, whereby a conductive material, Since at least one material of the semiconductor material and the insulating material is arranged at a predetermined position on the substrate, the material or the precursor can be freely selected and used without any particular limitation. It has a high degree of freedom.

The electronic equipment of the present invention is characterized by including the electro-optical device as a display means.
According to this electronic device, the electro-optical device serving as the display unit has a high degree of freedom in selecting the material when manufacturing the electro-optical device.

In the patterning apparatus of the present invention, a vacuum chamber that is adjusted to a substantially vacuum, a nozzle that discharges at least one material of a conductive material, a semiconductor material, and an insulating material, and a substrate that is patterned are mounted. And a movable mechanism that relatively moves the positions of the nozzle and the substrate on the stage. According to this patterning device, by discharging the material into the vacuum chamber, the material can be easily and stably discharged. Therefore, by moving the relative position between the nozzle and the substrate by the movable mechanism and ejecting the material or its precursor onto the substrate, patterning can be performed without the need for a mask. The material or precursor can be freely selected and used without any particular limitation.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
FIG. 1 is a diagram showing a schematic configuration of a patterning device of the present invention, in which reference numeral 1 is a patterning device. The patterning device 1 is configured to include a vacuum chamber 2, a nozzle 3 attached to the vacuum chamber 2, and a stage 4 provided in the vacuum chamber 2.

The vacuum chamber 2 is connected to a vacuum device 6 via a pipe 5, and the stage 4 is placed in the internal space thereof.
And a door (not shown) for loading and unloading the substrate S to be patterned is hermetically attached. The end of the pipe 5 is opened in the vacuum chamber 2 so that the inside of the vacuum chamber 2 can be evacuated to a high vacuum atmosphere by the operation of a vacuum device described later.

The vacuum device 6 is constructed so that the inside of the chamber 2 can be adjusted to a high degree of vacuum by combining a molecular turbo pump, a rotary pump and the like. Here, the inside of the vacuum chamber 2 is preferably 10 ⁻³ torr (1.33322 × 1) by the vacuum device 6.
0 ^-1 Pa) or less, more preferably 10 ^-5 torr (1.
It is designed to be adjusted to a high vacuum atmosphere of 33322 × 10 ⁻³ Pa) or less. If the vacuum atmosphere is set to 10 ^-3 torr or less, for example, even a material that is difficult to be discharged can be easily discharged, and if it is set to 10 ^-5 torr or less, more kinds of materials can be discharged. The material to be ejected can be easily vaporized to form a molecular beam. As for the vacuum device 6, these pumps are sufficiently separated from the vacuum chamber 2 or a vibration isolation function is added to the pump or the like so that vibrations of the pumps constituting the device do not propagate into the vacuum chamber 2. It is preferable to leave it.

The nozzle 3 has a nozzle hole 3a formed at its front end side inside the vacuum chamber 2, and its rear end side outside the vacuum chamber 2 serving as a material supply chamber 7
Further, a carrier gas supply source 8 is connected to the material supply chamber 7. The material supply chamber 7 is
For storing and holding a patterning material, for example, a state in which a forming material such as a light emitting layer, an electron transporting layer and a hole transporting layer of an organic electroluminescence device is held in a holder (not shown) such as a cell or a crucible. This is to store this. The material supply chamber 7 is provided with heating means 9 for heating the forming material held in the holder to liquefy or vaporize it. As the heating means 9, a general electric heater, a laser such as a YAG laser, a high-frequency heating device, or the like can be adopted. It is appropriately selected according to the degree of ease of conversion.

The carrier gas supply source 8 is mainly helium,
An inert gas such as argon or nitrogen is pressure-fed to the material supply chamber 7 as a carrier gas. Depending on the material, a reactive gas that reacts with the material may be pressure-fed to the material supply chamber 7 as a carrier gas. The carrier gas that is pressure-fed to the material supply chamber 7 entrains the liquefied or vaporized material in the material supply source 7 on the side of the discharge mechanism described later. Here, the preparation of the material in the material supply chamber 7, that is, the preparation of the material in the liquid state or the gas state, is appropriately selected in relation to the ejection mechanism of the nozzle 3 described later, The degree of heating by the heating means 9 and the like are determined.
Depending on the discharge mechanism of the nozzle 3, the material may be discharged into the vacuum chamber 2 without using the carrier gas from the carrier gas supply source 8.

The nozzle 3 has a discharge mechanism 10 at the tip thereof.
Is provided. The discharge mechanism 10 is not particularly limited and various types can be used. For example, a mechanism with a general mechanical shutter, a mechanism with a continuous system such as a charge control type and a pressure vibration type, an electromechanical conversion type (so-called piezo type), an electrothermal conversion type, an electrostatic suction type on-demand type It is possible to use the mechanism by.

Here, the mechanical shutter mechanism means that a shutter (not shown) is provided in the nozzle hole 3a, and the shutter is mechanically opened / closed to intermittently disperse the material that has been carried under pressure by the carrier gas. The discharge is performed in a pulsed manner. Note that the material inside the nozzle 3 is spontaneously discharged from the nozzle hole 3a as the shutter is opened and closed due to the pressure difference between the inside of the vacuum chamber 2 outside the nozzle hole 3a and the inside of the nozzle 3 without using a carrier gas. It is also possible to adopt a configuration that allows it.

The charge control type is a type in which an electric charge is applied to the sent material by a charging electrode and the flight direction of the material is controlled by a deflection electrode so that the material is ejected from the nozzle hole 3a. The pressure-vibration type is a type in which an ultra-high pressure of about 30 kg / cm ² is applied to the material to eject the material toward the nozzle tip side. When the material is discharged and a control voltage is applied, electrostatic repulsion occurs between the materials, and the materials are scattered so that they do not pass through the nozzle holes 3a.

The electromechanical conversion system utilizes the property that the piezo element is deformed by receiving a pulsed electric signal. The piezo element is deformed so that a flexible substance is introduced into a space storing the material. A pressure is applied to the material so that the material is extruded from this space and discharged from the nozzle hole 3a. Here, for the space for storing the material, for example, a minute material storage space communicating with the internal space of the material supply chamber 7 may be formed.

In the electrothermal conversion system, generally, a heater provided in the space in which the material is stored rapidly vaporizes the material to generate bubbles, and the pressure of the bubble causes the material in the space to be removed. It is designed to be discharged.
In addition, in this invention, this can be used as a heating means. The electrostatic suction method is a method in which a minute pressure is applied to the space in which the material is stored to form a meniscus of the material in the nozzle, and electrostatic attraction is applied in this state before the material is pulled out. For each of these mechanisms such as charge control type, pressure vibration type, electromechanical conversion type, electrothermal conversion type, and electrostatic suction type, it is possible to control the discharge of material by using the mechanical shutter mechanism in combination. May be performed more reliably, or intermittent ejection may be performed reliably.

The stage 4 is arranged immediately below the nozzle hole 3a, and holds and fixes a substrate S for manufacturing an electro-optical device, such as an organic electroluminescence element, as will be described later. On the stage 4, the substrate S held and fixed is attached to the nozzle hole 3a in the X direction.
Mechanism 11 that enables movement in the Y, Y, and Z directions
Is provided. That is, the movable mechanism 11 includes a Z movable portion (not shown) for moving and positioning the substrate S in the vertical direction (Z direction) with respect to the nozzle hole 3a, and the stage 4 horizontally with respect to the nozzle hole 3a. Direction (X direction, Y
Direction) and an X movable part (not shown) and a Y movable part (not shown) for moving and positioning the movable parts respectively. The movement of these movable parts is controlled by a control part (not shown). It is configured so that it can be controlled as set. The X movable part, the Y movable part, and the Z movable part are configured by, for example, linear motors. Further, the stage 4 is provided with a water cooling type temperature adjusting means (not shown) on the mounting surface side thereof, whereby the substrate S on the stage 4 can be adjusted to a desired temperature. There is.

Next, an example in which patterning by the patterning device 1 having such a configuration is applied to the manufacture of electronic elements will be described. Note that the examples described here relate to a method of manufacturing a thin film transistor (TFT) or a capacitive element as an electronic element, and a method of manufacturing a circuit board (also an electronic device in the present invention) formed by forming a plurality of these electronic elements. As an example, specifically, a method for manufacturing an active matrix type circuit substrate for a liquid crystal device (electro-optical device) in which a driver circuit and a pixel portion are integrally formed on the same substrate as shown in FIG. Is. Here, in FIG. 2, a CM is used as a basic circuit forming a driver circuit.
An OS circuit is shown, and a TFT having a double gate structure is shown as a pixel thin film transistor (TFT).

First, a schematic structure of a circuit board (electronic device) obtained by this manufacturing method will be described with reference to FIG. In FIG. 2, reference numeral 101 is a substrate having heat resistance, and a quartz substrate, a silicon substrate, a ceramics substrate, a metal substrate (typically a stainless substrate) or the like is used as the substrate 101. However, whichever substrate is used, a base film (preferably an insulating film containing silicon as a main component) is provided as necessary. Code 10
Reference numeral 2 denotes a silicon oxide film provided as a base film, on which an active layer of a driver TFT, an active layer of a pixel TFT, and a semiconductor layer to be a lower electrode of a storage capacitor (capacitance element) are formed.

The active layer of the driver TFT is the source region 10 of an N-channel type TFT (hereinafter referred to as NTFT).
3, a drain region 104, an LDD (lightly doped drain) region 105 and a channel forming region 106, and a source region 107, a drain region 108 and a channel forming region 109 of a P-channel TFT (hereinafter referred to as PTFT). . The active layer of the pixel TFT (here, NTFT is used) is the source region 11
0, drain region 111, LDD regions 112a and 112
b and the channel forming regions 113a and 113b. Further, the semiconductor layer extended from the drain region 111 is used as the lower electrode 114 of the storage capacitor.

In FIG. 2, the lower electrode 114 is the pixel TF.
Although it is directly connected to the drain region 111 of T,
The lower electrode 114 and the drain region 11 are connected indirectly.
1 may be electrically connected to the structure. A known doping element for the semiconductor layer is added to the lower electrode 114. A gate insulating film is formed so as to cover the active layer and the lower electrode of the storage capacitor. In addition, in this example, the dielectric 118 of the storage capacitor is the pixel TFT.
Is formed thinner than the gate insulating film 117.

As described above, the lower electrode 114 of the storage capacitor is made to contain a doping element to lower the resistance of the lower electrode 114, and the dielectric of the storage capacitor is further thinned to increase the area for forming the capacitance. You can earn capacity without. Further, here, the gate insulating film 117 of the pixel TFT and the gate insulating film 115 of the driver TFT,
Although the same insulating film having the same film thickness is used for 116, for example, at least two or more types of TFTs having different gate insulating films may be provided on the same substrate depending on the circuit characteristics.

The gate wiring (gate electrode) 11 of the driver TFT is formed on the gate insulating films 115, 116 and 117.
9, 120 and gate wiring of the pixel TFT (gate electrode)
121 is formed. At the same time, the upper electrode 122 of the storage capacitor is formed on the dielectric 118 of the storage capacitor, whereby the lower electrode 114 and the dielectric 11 are formed.
8, the upper electrode 122 constitutes a holding electrode (capacitive element). The material for forming the gate wirings 119 to 121 and the upper electrode 122 of the storage capacitor is 800 to 11
A conductive film having heat resistance that can withstand a temperature of 50 ° C. (preferably 900 to 1100 ° C.) is used. Specifically, a conductive silicon film (for example, a phosphorus-doped silicon film, a boron-doped silicon film, or the like), a metal film (for example, a tungsten film, a tantalum film, a molybdenum film, a titanium film, or the like), and further, the metal film is silicided. A silicide film, a nitrided nitride film (a tantalum nitride film, a tungsten nitride film, a titanium nitride film, etc.) is used, which may have a single-layer structure or a laminated structure in which a plurality of types are combined. When the metal film is used, it is desirable to have a laminated structure with a silicon film in order to prevent oxidation of the metal film. Further, in terms of preventing oxidation, a structure in which a metal film is covered with a silicon nitride film is effective. In FIG. 2, a silicon nitride film 123 is provided to prevent the gate wirings 119 to 121 and the upper electrode 122 from being oxidized.

Reference numeral 124 is a first interlayer insulating film, which is formed of an insulating film containing silicon (single layer or laminated). As the insulating film containing silicon, a silicon oxide film, a silicon nitride film, a silicon oxynitride film (having a higher content of nitrogen than oxygen), a silicon nitride oxide film (having a higher content of oxygen than nitrogen) ) Is used. A contact hole is provided in the first interlayer insulating film 124, and the driver TFT
Source wirings (source electrodes) 125 and 126, drain wirings (drain electrodes) 127, source wirings (source electrodes) 128 and drain wirings (drain electrodes) 129 of the pixel TFTs are formed. A passivation film 130 and a second interlayer insulating film 131 are formed thereon, and a black mask (light shielding film) 132 is further formed thereon. In addition, a third mask is placed on the black mask 132.
After the interlayer insulating film 133 is formed and the contact hole is provided, the pixel electrode 134 is formed.

Although the black mask (light-shielding film) 132 is formed on the second interlayer insulating film 131 in FIG. 2, it is not particularly limited and may be formed if necessary. For example, a light shielding film may be provided on the counter substrate,
A structure in which a light-shielding film made of the same material as the gate wiring is provided under each TFT may be used. Second interlayer insulating film 13
A resin film having a small relative dielectric constant is preferably used as the first and third interlayer insulating films 133. Specifically, a polyimide film,
An acrylic film, a polyamide film, a BCB (benzocyclobutene) film or the like is used.

Further, as the pixel electrode 134, a transparent conductive film typified by an ITO film is used for manufacturing a transmissive liquid crystal device, and an aluminum film is typified for manufacturing a reflective liquid crystal device. A metal film having high reflectance is used. In FIG. 2, the pixel electrode 134 is the drain electrode 1
The pixel electrode 134 and the drain region 1 are electrically connected to the drain region 111 of the pixel TFT via 29.
The structure may be such that 11 and 11 are directly connected.

Next, a method of manufacturing the circuit board (electronic device) having such a configuration will be described. Although the circuit board shown in FIG. 2 is basically formed, the reference numerals of the respective constituent elements will be described by using the reference numerals different from those shown in FIG. 2 for convenience of explanation. First, as shown in FIG. 3A, a quartz substrate 201 is prepared as a substrate, and a 20 nm thick silicon oxide film (base film) 202 and an amorphous silicon film (not shown) are not exposed to the atmosphere. The film is continuously formed as it is. By doing so, it is possible to prevent impurities such as boron contained in the atmosphere from adsorbing to the lower surface of the amorphous silicon film. Although an amorphous silicon (amorphous silicon) film is used in this example, another semiconductor film may be used. It may be a microcrystalline silicon (microcrystal silicon) film or an amorphous silicon germanium film. Further, as a method for forming the base film and the semiconductor film, PCVD method, LPCV
Although the D method or the sputtering method can be used, FIG.
The film forming method using the patterning device 1 shown in can also be adopted.

Next, the amorphous silicon film is crystallized. In this example, the technique described in JP-A-9-313260 was used as the crystallization means. The technique described in the publication is nickel, cobalt, palladium, germanium, platinum, iron as a catalyst element for promoting crystallization of a silicon film,
It uses elements selected from copper. That is, nickel was selected as the catalyst element, a layer containing nickel was formed on the amorphous silicon film, and heat treatment was performed at 550 ° C. for 14 hours to crystallize. Then, the formed crystalline silicon (polysilicon) film was patterned to form the semiconductor layer 203 of the driver TFT and the semiconductor layer 204 of the pixel TFT. Note that an impurity element (phosphorus or boron) for controlling the threshold voltage of the TFT may be added to the crystalline silicon film before and after the semiconductor layers of the driver TFT and the pixel TFT are formed. This process is NTFT or P
It may be performed only for the TFT or both.

Next, as shown in FIG. 3B, resist masks 205a, 2a are formed on the active layers 203a, 204a.
05b is formed, and phosphorus is added as a doping element.
The concentration of phosphorus added is 5 × 10 ¹⁸ to 1 × 10 ²⁰ ato
It is preferably ms / cm ³ . In this way, regions 203b and 204b (hereinafter referred to as phosphorus-doped regions) to which phosphorus is added are formed. Regarding the resist mask 205a, a part (or the whole) of a region to be a source region or a drain region of the driver TFT later.
Are formed so as to be exposed. Similarly, the resist mask 205b is also formed and arranged so that part (or all) of the source region or the drain region of the pixel TFT is exposed later. At this time, since the resist mask is not arranged in the region serving as the lower electrode of the storage capacitor, phosphorus is entirely added, and the phosphorus-doped region 204
b. It is preferable to oxidize the surface of the active layer before forming the resist masks 205a and 205b. By providing the silicon oxide film, the adhesion between the active layer and the resist mask can be improved, and the active layer can be prevented from being contaminated with organic substances.

Next, as shown in FIG. 3C, the resist masks 205a and 205b are removed, and heat treatment at 500 to 650 ° C. is applied for 2 to 16 hours to getter the catalytic element used for crystallization of the silicon film. I do. A temperature of about ± 50 ° C. from the maximum temperature of the heat history is required to exert the gettering action, but the heat treatment for crystallization requires 550 to 600 ° C.
Since it is performed at a temperature of 500 ° C., the gettering action can be sufficiently achieved by the heat treatment at 500 to 650 ° C. In this example, 6
By applying a heat treatment at 00 ° C. for 8 hours, the catalytic element (nickel) is moved in the direction of the arrow, and the phosphorus-doped region 2
Capture was performed by gettering with phosphorus contained in 03b and 204b. In this way, gettering regions (regions corresponding to the phosphorus-doped regions 203b and 204b) are formed, and the concentration of nickel contained in the regions 203a and 204a is sufficiently reduced. The gettering region remains as the lower electrode of the storage capacitor and remains as a part or the whole of the source region or the drain region of the driver TFT and the pixel TFT.

Next, as shown in FIG. 3D, a gate insulating film 206 is formed. As a method for forming the gate insulating film 206, a method using the patterning device 1 shown in FIG. 1 is preferably adopted. That is, the substrate 201 is placed in the vacuum chamber 2 shown in FIG. The inside of the chamber 4 is kept in a vacuum atmosphere. Further, if necessary, a substrate 201 on the stage 4 may be adjusted by temperature adjusting means (not shown).
Is adjusted to a desired temperature (for example, the temperature at which the forming material injected from the nozzle holes 3a in a vaporized state is sufficiently cooled to be liquefied or solidified). In addition, the gate insulating film 206 previously held by the holder in the material supply chamber 7
The forming material is heated to a predetermined temperature by the heating means 9.

Although silicon oxide is preferably used as the material for forming the gate insulating film 206, silicon nitride may be used in addition to silicon oxide. In that case, a laminated structure in which a film made of silicon nitride is provided on a film made of silicon oxide, or a silicon oxynitride film in which nitrogen is added to silicon oxide may be used. When such a forming material is heated to a predetermined temperature by the heating means 9 as described above,
A carrier gas such as helium is introduced into the material supply chamber 7 from a carrier gas supply source 8, and the discharge mechanism 10 is operated to discharge the forming material into the vacuum chamber 2 through the nozzle holes 3a with the carrier gas entrained in the carrier gas. Let Then, the forming material is ejected in the vaporized state by ejecting the forming material into the vacuum chamber 2 which is a pressure atmosphere sufficiently lower than the inside of the nozzle 3 which is at almost normal pressure. In the ideal case where the vacuum chamber 2 has a particularly high degree of vacuum, the forming material may be ejected in a molecular beam shape.

Therefore, the movable mechanism 11 is controlled by the control unit.
Of the nozzle hole 3a and the substrate 201
It is possible to inject a desired amount of this forming material to a predetermined position on the substrate 201 by moving the relative positional relationship with and as set in advance. When the forming material is injected onto the substrate 201 in this manner, the forming material is applied to the substrate 2
By being cooled to the temperature of 01, it is solidified and fixed there. The gate insulating film 206 may be formed by a plasma CVD method or a sputtering method instead of the patterning apparatus 1. The gate insulating film 206 thus formed is used for the pixel TF.
It functions as a gate insulating film of T and is formed to have a film thickness of, for example, about 50 to 200 nm.

After the gate insulating film 206 is formed, it is taken out of the vacuum chamber 2 and a resist mask (not shown) is provided as shown in FIG. 3 (e) to selectively remove the gate insulating film. At this time, the gate insulating film 206 is left on the pixel TFT, and the driver TFT and the region to be the storage capacitor are removed. Then 800-1150 ° C
15 minutes to 8 at a temperature of (preferably 900 to 1100 ° C.)
The heat treatment process for a time (preferably 30 minutes to 2 hours) is performed in an oxidizing atmosphere (thermal oxidation process). In this heat treatment step, the effect of repairing defects and the like in the crystal grains of the active layer is obtained, so that a crystalline silicon film having extremely good crystallinity is formed. Note that the oxidizing atmosphere may be a dry oxygen atmosphere, a wet oxygen atmosphere, or an atmosphere containing a halogen element in the oxygen atmosphere. When the thermal oxidation process is performed in an atmosphere containing a halogen element, the effect of removing nickel can be expected, which is effective.

The surface of the semiconductor layer exposed in the region to be the storage capacitor by performing the thermal oxidation process in this way is
As shown in FIG. 4A, a silicon oxide film (thermal oxide film) 207 having a thickness of about 5 to 50 nm is formed. Finally, the silicon oxide film 207 functions as a storage capacitor dielectric, and the silicon oxide film 206 functions as a gate insulating film of the pixel TFT and the driver TFT. Although not shown for simplification, the oxidation reaction also progresses at the interface between the gate insulating film 206 made of the silicon oxide film remaining in the pixel TFT and the driver TFT and the semiconductor layers 203 and 204 thereunder. Therefore, the gate insulating film 20 of the pixel TFT is finally obtained.
The film thickness of 6 is about 50 to 200 nm.

After the thermal oxidation step is completed,
As shown in FIG. 4B, the gate wiring (gate electrode) 209 (NTFT side) of the driver TFT, 210 (PTF)
T side), gate wiring (gate electrode) 21 of the pixel TFT
First, the upper wiring (upper electrode) 212 of the storage capacitor is formed. The method using the patterning device 1 shown in FIG. 1 is also suitably adopted for forming each of these wirings (electrodes). That is, the substrate 20 on which the silicon oxide film 207 is formed
1 is placed in the vacuum chamber 2 shown in FIG. 1 and placed on the stage 4, and a wiring (electrode) material, that is, a conductive material is placed on the stage 4 in the same manner as in the case where the gate insulating film 206 is formed first. Each gate wiring 209 is discharged onto the substrate 201.
˜211 and the upper wiring 212 are formed. At this time, the operation of the movable mechanism 11 is controlled by the control unit, and the nozzle hole 3a
By moving the relative positional relationship between the substrate 201 and the substrate 201 as set in advance, it is possible to inject a desired amount of each wiring material at a predetermined position on the substrate 201, and thus a photolithography process or the like is required. Instead, each wiring is patterned to form gate wirings 209 to 211,
The upper wiring 212 can be formed respectively.

By forming the respective wirings in this manner, and particularly by forming the upper wiring 212, the upper wiring 2 is formed.
12, the phosphorus-doped region 204b, and the silicon oxide film 207 form a capacitive element which is an electronic element of the present invention. As a wiring (electrode) material, that is, a conductive material, conductive silicon (for example, phosphorus-doped silicon,
Boron-doped silicon, etc.), metal (eg, tungsten, tantalum, molybdenum, titanium, etc.), metal silicide obtained by siliciding the metal, nitrided metal nitride (tantalum nitride, tungsten nitride, titanium nitride, etc.)
Are used. Further, these materials can be formed into either a single layer structure made of a single material or a laminated structure made of a plurality of kinds of materials.

Incidentally, these gate wirings 209 to 211,
Also when forming the upper wiring 212, a low pressure thermal CVD method or the like can be adopted. In addition, since the pixel TFT has a double gate structure, the gate wiring 211 has two gate wirings.
Although described here, the wiring is actually the same. In addition, the gate wirings 209 to 211 and the storage capacitor upper wiring 21.
As 2, a laminated film of a silicon film / a tungsten nitride film / a tungsten film from the lower layer (or a silicon film / a tungsten silicide film from the lower layer) can be used, and a conductive film other than this can also be used.

Next, a silicon nitride film 213 having a thickness of about 25 nm is formed so as to cover the gate wirings 209 to 211 and the storage capacitor upper wiring 212. This silicon nitride film 213
As for the formation, the method using the patterning device 1 shown in FIG. 1 can be adopted, and the conventional method such as the CVD method can also be adopted. This silicon nitride film 2
The element 13 prevents the gate wirings 209 to 211 and the upper wiring 212 of the storage capacitor from being oxidized, and at the same time, functions as an etching stopper when the sidewall made of a silicon film is removed later. At this time, the silicon nitride film 213
It is effective to perform plasma treatment using a gas containing hydrogen (for example, ammonia gas) as a pretreatment for forming the. By this pretreatment, hydrogen activated (excited) by plasma is confined in the active layer (semiconductor layer), so that hydrogen termination is effectively performed. Furthermore, when nitrous oxide gas is added in addition to hydrogen-containing gas, the generated water cleans the surface of the object to be treated, and in particular, it is possible to effectively prevent contamination by boron or the like contained in the atmosphere.

Next, an amorphous silicon film (not shown) is formed.
Then, anisotropic etching with a chlorine-based gas was performed, and FIG.
Form sidewalls 214-218 as shown in (c).
To achieve. After forming the sidewalls 214 to 218,
For the semiconductor layers 203 and 204, phosphorus is used as a doping element.
Is added. At this time, the gate wirings 209 to 211 are protected.
Capacitive upper electrode 212 and side wall 214-
218 serves as a mask to self-align the impurity regions 219.
~ 223 are formed. Added to the impurity regions 219 to 223.
Regarding the concentration of phosphorus added, 5 × 10¹⁹~ 1 x 10^{twenty one}
atoms / cm ³ Adjust so that In addition, phosphorus
The ion addition process is based on the ion implantation
Plasma method without mass separation
A doping method may be used. Also, in this example,
Was used to add impurities, but it is not particularly limited.
Instead of the sidewall, a photomask is used.
A ghost mask may be used.

Next, as shown in FIG. 4D, the sidewalls 214 to 218 are removed, and the phosphorus adding step is performed again. In this step, the dose is lower than that in the phosphorus addition step. In this way, the side wall 214-
A low concentration impurity region is formed in a region where phosphorus is not added using 218 as a mask. The concentration of phosphorus added to the low concentration impurity region is 5 × 10 ^{17 to} 5 × 10 5.
Adjust so that it is ¹⁸ atoms / cm ³ . Further, similarly to the step shown in FIG. 4C, the phosphorus addition step may use an ion implantation method in which mass separation is performed or a plasma doping method in which mass separation is not performed.

N for forming a CMOS circuit by this process
A TFT source region 224, an LDD region 225, and a channel formation region 226 are formed. In addition, the source region 227, the drain region 228, the LDD region 22 of the pixel TFT.
9a, 229b, channel forming regions 230a, 230b
Is formed. Further, the lower electrode 231 of the storage capacitor is formed. Further, a low-concentration impurity region 232 is also formed in a region which becomes a PTFT of the CMOS circuit, similarly to the NTFT.

Next, as shown in FIG.
The resist mask 23 is provided except for the region which becomes the PTFT of the circuit.
3, 234, and boron is added as a doping element. In this step, it is added in a dose amount so as to form an impurity region having a higher concentration than the already added phosphorus. Specifically, 1 × 10 ^{20 to} 3 × 10 ²¹ atoms / cm ³
The concentration is adjusted so that boron is added. As a result, all the impurity regions having N-type conductivity formed in the regions to be PTFTs are inverted in conductivity type by boron, and become impurity regions having P-type conductivity. of course,
Also in the boron process, an ion implantation method that performs mass separation may be used, or a plasma doping method that does not perform mass separation may be used. Further, the practitioner may set optimum values for the conditions such as the acceleration voltage and the dose amount.

By this step, the source region 235, the drain region 236 and the channel forming region 237 of the PTFT forming the CMOS circuit are formed. Further, the drain region 238 of the NTFT of the CMOS circuit is formed. The doping order is not limited to this example. For example, after the step shown in FIG.
Prior to the formation step of 8, the step of forming low concentration impurity regions by adding phosphorus may be performed. In addition, this phosphorus addition step may be performed separately for the region to be the storage capacitor and the region to be the driver TFT and the pixel TFT having a thick gate insulating film.

After forming all the impurity regions in this way, the resist mask 23 is formed as shown in FIG.
Remove 3,234. Then, the added impurities are activated by laser light or heat treatment to form channel formation regions 239 to 241, source regions 243 to 245, and drain regions 246 to 248. If activation is only performed, a temperature range of 300 to 700 ° C. for about 2 hours is sufficient, but here, a heat treatment process is performed at a temperature range of 750 to 1150 ° C. for 20 minutes to 12 hours. This step activates phosphorus or boron added to each impurity region, and at the same time, nickel (catalyst element used at the time of crystallization) remaining in the channel formation region is removed by the gettering action of phosphorus to the source region and the drain region. It also serves as the step of gettering again.

Next, as shown in FIG. 5C, a first interlayer insulating film 249 made of a silicon oxide film is formed. This first
For the formation of the interlayer insulating film 249, the method using the patterning device 1 shown in FIG. 1 can be adopted.
Also, a conventional method such as a CVD method can be adopted.
Then, a contact hole is formed in the first interlayer insulating film 249, and thereafter, the source wirings 250 to 252 and the drain wiring 253 are buried in the contact hole.
254 are formed. These wirings are also shown in FIG.
The method using the patterning device 1 shown in FIG. 1 can be adopted, and by using this method, it is particularly easy to embed the wiring material in the contact hole. That is, the nozzle mechanism 3 a of the patterning device 1 is previously moved by the movable mechanism 11.
This is because by vaporizing the wiring material into the contact hole, the wiring material is discharged in this state while facing the contact hole. Note that the source wirings 250 to 252 and the drain wirings 253 and 254 thus formed are preferably formed of, for example, a stacked film in which a conductive film containing aluminum as its main component is sandwiched between titanium films. The material is changed according to the laminated structure, and the ejection from the nozzle 3 of the patterning device 1 is performed.

Here, the drain wiring 253 is CM
It is used as a wiring common to the NTFT and the PTFT forming the OS circuit. Further, as described above, since the source region and the drain region contain nickel at a high concentration, good ohmic contact with the source wiring and the drain wiring can be realized. In this way, each wiring 250-
By forming 252, 253, and 254, a driver TFT and a pixel TFT which are electronic elements of the present invention are formed. After that, a passivation film 255 is formed. As the passivation film 255, a silicon nitride film, a silicon oxynitride film, a silicon nitride oxide film, or a stacked film of these insulating films and a silicon oxide film can be used.
The method of using the patterning device 1 shown in FIG. 1 can also be adopted for forming such a passivation film 255.

As a pretreatment for forming the silicon nitride film, plasma treatment using ammonia gas may be performed, and then the passivation film 255 may be formed. When such pretreatment is performed, hydrogen activated (excited) by plasma is confined by the passivation film 255, so that hydrogen termination of the active layer (semiconductor layer) of the TFT is promoted. Furthermore, when nitrous oxide gas is added in addition to hydrogen-containing gas, the generated water cleans the surface of the object to be treated, and in particular, it is possible to effectively prevent contamination by boron or the like contained in the atmosphere.

Next, an acrylic film having a thickness of 1 μm, for example, is formed as the second interlayer insulating film 256. Then, a titanium film having a thickness of 200 nm is formed thereon and patterned to form a black mask 257. Here, also when the second interlayer insulating film 256 and the black mask 257 are formed, the patterning device 1 shown in FIG.
The method of using can be adopted. In that case, in particular, in forming the black mask 257, direct patterning can be performed without requiring a photolithography process or an etching process. After that, an acrylic film is formed again as the third interlayer insulating film 258 to form a contact hole, and a pixel electrode 259 made of an ITO film is formed to obtain a circuit board. In forming the pixel electrode 259, the method using the patterning device 1 shown in FIG. 1 can be adopted.

Further, by forming a liquid crystal element by providing a known liquid crystal cell on this circuit board, a liquid crystal device defined as an electro-optical device in the present invention is obtained. Figure 6
6A and 6B are views for explaining the structure of a liquid crystal cell for forming such a liquid crystal element, and reference numeral 260 in FIG. 6 denotes a counter substrate. The counter substrate 260 is arranged on the side opposite to the circuit substrate (not shown) and is made of a transparent substrate such as a glass substrate or a quartz substrate. On the inner surface side of the counter substrate 260, a large number of microlenses 261 for condensing light incident from the counter substrate 260 side to the circuit board (not shown) side are provided. Adhesive 262 on the formed side
The cover glass 263 is attached by.

Light shielding films 264 are formed on the inner surface of the cover glass 263 at positions corresponding to the boundaries between the microlenses 261, and the ITO film is formed on the entire surface of the cover glass 263 while covering the light shielding films 264. A counter electrode 265 made of a transparent conductive material such as is formed. Then, an alignment film 266 made of an organic thin film such as a polyimide thin film is formed on the inner surface side of the counter electrode 265,
Further, a liquid crystal device is formed by sealing the liquid crystal 267 between the counter substrate 260 thus formed and the circuit substrate. Also in the manufacture of the liquid crystal device having such a configuration, the patterning device 1 shown in FIG. 1 described above is used in the formation of the respective components in the liquid crystal cell, for example, the light shielding film 264, the counter electrode 265, the alignment film 266 and the like.
The method of using can be adopted.

The circuit board can be applied to an electro-optical device other than the liquid crystal device, such as an electrophoretic device. The electrophoretic device utilizes a phenomenon called electrophoretic phenomenon in which charged particles dispersed in a liquid migrate by application of an electric field. A cell is formed by sandwiching it between a pair of electrodes, and thereby an electrophoretic element is formed.

FIG. 7 is a diagram showing a sectional structure of a pixel portion in such an electrophoretic device. This electrophoretic device is basically on a circuit board 300 having the same configuration as the circuit board shown in FIG. The counter substrate 301 is attached to the above. The common electrode 30 is provided on the counter substrate 301.
2 are formed, and the common electrode 302 and the pixel electrode 3 are formed.
The electronic ink layer 304 is disposed between the first and the second electrodes 03.
A drain electrode (not shown) of a TFT (not shown) which is a switching element formed on the circuit board 300 is connected to the pixel electrode 303, and the applied voltage is controlled by the drain electrode (not shown). The electric field applied to the electronic ink layer in between can be controlled.
In this example, at least one of the common electrode 302 and the pixel electrode 303 is a transparent electrode, and the display surface of the electrophoretic device is on the transparent electrode side.

As shown in FIG. 8A, the electronic ink layer 304 includes a transparent binder 305 having a light transmitting property and a plurality of microcapsules 306 dispersed in the binder 305 in a uniform and fixed state. It is composed of The electronic ink layer 304 has a thickness of about 1.5 to 2 times the outer diameter (diameter) of the microcapsules 306, and the binder 305 is made of a silicone resin or the like. The microcapsule 306 is a hollow and spherical capsule body 307 having a light-transmitting property, a liquid (solvent) 308 filled therein, and the liquid 30.
8 and a plurality of charged particles 309 dispersed therein, and the liquid 308 and the charged particles 309 are formed to have substantially the same specific gravity. The charged particles 309 are negatively charged, and are formed of a nucleus 310 and a coating layer 311 that covers the nucleus 310. Such charged particles 30
9 and the liquid 308 are set so that their respective colors are different from each other. For example, the color of the charged particles 309 is white, and the color of the liquid 308 is blue, red, green, or black. It

In the electrophoretic device having such a structure, when an electric field is applied to the microcapsules 306 from the outside, the charged particles 309 move in the microcapsules 306 in the direction opposite to the direction of the electric field. To do. As a result, for example, in FIG. 6, the display surface is the upper side surface (the counter substrate 30).
1 surface), when the charged particles 309 move to the upper side in FIG. 7, the color of the liquid 308 (for example, blue,
Charged particles 309 that stand out against the background of red, green, or black)
The color (for example, white) is visible (see FIG. 8B). On the contrary, when the charged particles 309 move to the lower side (circuit board 300 side) in FIG.
Only 8 colors (eg blue, red, green, or black) will be visible (see FIG. 8 (c)). The charged particles 3 moved in a direction opposite to the direction of the electric field by applying the electric field.
Since the specific gravity of 09 is almost the same as that of the liquid 308,
Even after the electric field disappears, it tries to stay at that position for a long time. That is, the color of the charged particles 309 or the liquid 308 appearing on the display surface is held for a while (from several minutes to tens of minutes),
It has a memory property. Therefore, by controlling the application of the electric field for each pixel, information according to the application pattern is displayed, but the information is also retained for a relatively long time.

Also in such an electrophoretic device, the method of using the patterning device 1 of FIG. 1 can be adopted for the circuit board as described above, and also for the cell side forming the electrophoretic element, for example, A method using the patterning device 1 of FIG. 1 for forming a common electrode or the like can be adopted. Further, in an electronic device in which such an electrophoretic device is applied to a display unit and which is required to have flexibility such as electronic paper, at least a thin film transistor serving as the driving element is used as a circuit board for forming the driving element. It is preferable to use an organic semiconductor element having a channel portion formed of an organic film. Note that the electronic paper is configured by including a rewritable sheet 320 having a texture and flexibility similar to paper as shown in FIG. 9 and a display device 321 including the above-described electrophoretic device.

The above-mentioned organic semiconductor element has, for example, a structure as shown in FIG. In FIG. 10, reference numeral 350 is a substrate, and a gate electrode 351 is formed on the substrate 350. A gate insulating film 352 made of an insulator having a high dielectric constant is formed on the substrate 350 in a state of covering the gate electrode 351. The gate insulating film 3
An organic semiconductor layer 353 is formed on 52. Then, by forming the source electrode 354 and the drain electrode 355 on the organic semiconductor layer 353, an organic semiconductor element to be a thin film transistor is formed.

For the production of such an organic semiconductor element, the method using the patterning apparatus 1 shown in FIG. 1 is preferably adopted. That is, first, the gate electrode material is provided on the substrate 350 to form the gate electrode 351, and the patterning device 1 is also suitably used for this formation. To form the gate electrode 351 by the patterning device 1, first, the substrate 201 is evacuated to the vacuum chamber 2
It is placed inside and placed on the stage 4 with the upper surface side facing upward, and further held and fixed there. Further, if necessary, a substrate 201 on the stage 4 may be adjusted by temperature adjusting means (not shown).
Is adjusted to a desired temperature (for example, the temperature at which the forming material injected from the nozzle holes 3a in a vaporized state is sufficiently cooled to be liquefied or solidified). Further, the forming material of the gate electrode 351 held in advance by the holder in the material supply chamber 7 is heated to a predetermined temperature by the heating means 9.

Here, as the material for forming the gate electrode 351, for example, metals such as chromium, titanium, copper, aluminum, molybdenum, tungsten, nickel, gold, platinum, palladium and indium, and alloys using these metals,
Inorganic materials such as polysilicon, amorphous silicon, tin oxide, indium oxide, and indium tin oxide (ITO), and organic materials such as conductive polyaniline, conductive polypyrrole, and conductive polythiophene are used. One or a plurality of types are selected and used. When such a forming material is heated to a predetermined temperature by the heating means 9 as described above, that is, an appropriate temperature according to the material, a carrier gas such as helium is introduced from the carrier gas supply source 8 into the material supply chamber 7. The discharging mechanism 10 is operated to discharge the forming material into the vacuum chamber 2 through the nozzle holes 3a while entraining the forming gas in the carrier gas. Then, the forming material is ejected in the vaporized state by ejecting the forming material into the vacuum chamber 2 which is a pressure atmosphere sufficiently lower than the inside of the nozzle 3 which is at almost normal pressure. In the ideal case where the vacuum chamber 2 has a particularly high degree of vacuum, the forming material may be ejected in a molecular beam shape.

Therefore, the movable mechanism 11 is controlled by the control unit.
Of the nozzle hole 3a and the substrate 201
It is possible to inject a desired amount of this forming material to a predetermined position on the substrate 350 by moving the relative positional relationship with the predetermined position. When the forming material is injected onto the substrate 350 in this way, the forming material is injected onto the substrate 3
By being cooled to a temperature of 50, it is solidified and fixed there. When the gate electrode 351 is formed by the patterning apparatus 1 in this way, the gate electrode 351 can be formed in a desired pattern without using a mask and thus a photolithography process or the like.

Next, a gate insulating film 352 is formed in a state of covering the gate electrode 351, and the patterning device 1 shown in FIG. 1 is also suitably used for forming the gate insulating film 352. Although various materials can be used as the material for forming the gate insulating film 352 without limitation, a metal oxide thin film, preferably barium strontium titanate or titanic acid zirconate, is used as an insulator having a high dielectric constant. Barium, lead zirconate titanate, lead lanthanum titanate, strontium titanate, barium titanate, barium magnesium fluoride, bismuth titanate, strontium bismuth titanate, strontium bismuth tantalate, bismuth tantalate niobate, niobate tantalate. Inorganic materials such as strontium bismuth, tantalum pentoxide, titanium dioxide, yttrium trioxide, tantalum oxide, vanadium oxide, and titanium oxide are preferably used. In addition, polychloropyrene, polyethylene terephthalate,
Organic materials such as polyoxymethylene, polyvinyl chloride, polyvinylidene fluoride, cyanoethyl pullulan, polymethyl methacrylate, polysulfane, polycarbonate and polyimide can also be used. Note that particularly when the gate insulating film 352 is formed of the above-mentioned inorganic material, it is possible to improve the film quality by performing annealing treatment at an appropriate temperature in the range of 150 to 400 ° C. after the film is formed, This is preferable because the dielectric constant can be increased.

Next, an organic semiconductor layer 353 is formed on the gate insulating film 352, and the organic semiconductor layer 353 is formed.
The patterning device 1 shown in FIG. 1 is also preferably used for forming. As a material for forming the organic semiconductor layer 353, a polymer semiconductor or an oligomer semiconductor that exhibits an increase in field-effect mobility as the gate voltage increases is used. Specifically, naphthalene, anthracene, tetracene, pentacene, hexacene, and One or more of its derivatives and polyacetylene are used. In particular, when used for p-channel, the degree of oligopolymerization is 4 or more and 8 or more, which are bonded via 2 to 5 carbon atoms.
The following oligomers of thiophene; alternating co-oligomers of vinylene with 3 to 6 thiophene rings and thiophene as the end group, linked through 2 to 5 carbon atoms, and thienylene; benzo [1,2- b: 4,5 '] dithiophene linear dimers and trimers; said oligomer having a substituent (for example, an alkyl substituent having 1 to 20 carbon atoms) on 4 or 5 carbon atoms of the terminal thiophene. A p, p'-diaminobiphenyl complex in a polymer matrix can be used, and particularly α-
Hexathienylene (α-6T) is preferably used. In particular, when it is used for p-channel, 1, 4,
5,8-naphthalene tetracarboxylic dianhyde (NTCDA: naphthalene tetracarboxylic dianhy
dride), 1,4,5,8-naphthalene tetracarboxyl diimide (NTCDI: naphthalene tetracarboxyl)
lic diimide), 11,11,12,12-tetracyanonaphtho-2,6-quinodimethane (TCNNQD: tetr)
acyanonaphtho-2,6-quinodimethane) etc. can also be used. When such an organic semiconductor material is formed by the patterning device 1 described above, the organic semiconductor material can be formed directly on the gate insulating film 352 of the substrate 350 without requiring a solvent, which facilitates the processing. Also, the quality of the obtained film is good without deterioration due to the solvent.

Thereafter, the source electrode 354 and the drain electrode 355 are formed on the organic semiconductor layer 353.
The patterning device 1 shown in FIG. 1 is also preferably used for forming the source / drain electrodes 354 and 355. If the source / drain electrodes 354 and 355 are formed by the patterning device 1, these can be formed into a desired pattern without using a mask, as in the case of the gate electrode 351 described above. As the material for forming the source / drain electrodes 354 and 355, the same material as that used for the gate electrode 351 can be used.

The organic semiconductor device thus obtained,
That is, in the organic semiconductor element which is an electronic element in the present invention, since at least one of the constituent elements is formed by the patterning device 1, the degree of freedom in material selection is increased, and thus the element is configured in a better combination. be able to.

The electro-optical device of the present invention can be applied to a display device including an organic electroluminescence element (organic EL element) other than the liquid crystal device and the electrophoretic device described above. 11 and 12 show an example in which the electro-optical device of the invention is applied to an active matrix type display device using an organic EL element. In these figures, reference numeral 20 is a display device.

This display device 20 is a circuit diagram shown in FIG.
As shown in FIG. 3, a plurality of scanning lines 31, a plurality of signal lines 32 extending in a direction intersecting the scanning lines 31, and a plurality of common power supply lines 33 extending in parallel with the signal lines 32 are provided on a transparent substrate. And are wired respectively, and scanning line 3
1 for each intersection of 1 and the signal line 32
A is provided and configured. For the signal line 32, a data side drive circuit 21 including a shift register, a level shifter, a video line, and an analog switch is provided. On the other hand, for the scanning line 31, the scanning side drive circuit 22 including a shift register and a level shifter
Is provided. In addition, in each of the pixel regions 20A,
A first thin film transistor 42 to which a scanning signal is supplied to the gate electrode via the scanning line 31, a holding capacitor cap for holding an image signal supplied from the signal line 32 via the first thin film transistor 42, and a holding capacitor. The second thin film transistor 43 to which the image signal held by the cap is supplied to the gate electrode, and the second thin film transistor 4
A pixel electrode 41 into which a drive current flows from the common power supply line 33 when electrically connected to the common power supply line 33 via
The light emitting section 40 sandwiched between the pixel electrode 41 and the counter electrode 54 is provided.

Under such a structure, when the scanning line 31 is driven and the first thin film transistor 42 is turned on,
The potential of the signal line 32 at that time is held in the storage capacitor cap, and the conduction state of the second thin film transistor 43 is determined depending on the state of the storage capacitor cap. Then, a current flows from the common power supply line 33 to the pixel electrode 41 via the channel of the second thin film transistor 43, and further, a current flows to the counter electrode 54 via the light emitting unit 40, whereby the light emitting unit 40.
Emits light according to the amount of current flowing through it.
Here, the planar structure of each pixel 20A is, as shown in FIG. 12 which is an enlarged plan view in a state in which a counter electrode and an organic electroluminescence element are removed, four sides of a pixel electrode 41 having a rectangular planar shape, a signal line 32, common power supply line 33,
The arrangement is surrounded by the scanning lines 31 and other scanning lines for pixel electrodes (not shown).

Next, a method of manufacturing such a display device 20 will be described with reference to FIGS. 13 to 15, only a single pixel 20A is shown in order to simplify the description. First, a substrate is prepared.
Here, in the organic electroluminescence element, it is possible to take out the emitted light from the light emitting layer described later from the substrate side, or to take out from the side opposite to the substrate. When the emitted light is taken out from the substrate side, a transparent or translucent material such as glass, quartz, or resin is used as the substrate material, and particularly inexpensive soda glass is preferably used. When using soda glass,
It is preferable to apply a silica coat to this because it has the effect of protecting soda glass, which is weak against acid and alkali, and also has the effect of improving the flatness of the substrate. Further, a color filter film, a color conversion film containing a light emitting substance, or a dielectric reflection film may be arranged on the substrate to control the emission color. Further, in the case of the configuration in which the emitted light is extracted from the side opposite to the substrate, the substrate may be opaque. In that case, a ceramic sheet such as alumina, a metal sheet such as stainless steel that has been subjected to an insulation treatment such as surface oxidation, or a heat A curable resin, a thermoplastic resin or the like can be used.

In this example, a transparent substrate 23 made of soda glass or the like is prepared as the substrate as shown in FIG. 13 (a). On the other hand, if necessary, a base protective film (not shown) made of a silicon oxide film having a thickness of about 200 to 500 nm is formed by plasma CVD using TEOS (tetraethoxysilane) or oxygen gas as a raw material. . Next, the temperature of the transparent substrate 23 is set to about 350 ° C., and a thickness of about 30 to 7 is formed on the surface of the base protective film by the plasma CVD method.
Semiconductor film 24 made of 0 nm amorphous silicon film
To form.

Subsequently, the semiconductor film 24 is crystallized into a polysilicon film by performing a crystallization process such as laser annealing or solid phase growth method. In the laser annealing method, for example, an excimer laser with a beam length of 4
A line beam of 00 mm is used, and its output intensity is, for example, 200 mJ / cm ² . For line beams,
The line beam is scanned so that a portion corresponding to 90% of the peak value of the laser intensity in the short direction overlaps each area. Next, as shown in FIG. 13B, the semiconductor film (polysilicon film) 24 is patterned to form an island-shaped semiconductor film 25. Note that the method using the patterning device 1 shown in FIG. 1 described above can also be employed for forming the island-shaped semiconductor film 25. The process can be eliminated.

Then, a thickness of about 6 is formed on the surface by plasma CVD using TEOS or oxygen gas as a raw material.
A gate insulating film 26 made of a silicon oxide film or a nitride film having a thickness of 0 to 150 nm is formed. Note that the method using the patterning device 1 shown in FIG. 1 can also be adopted for the formation of the gate insulating film 26. Here, the semiconductor film 2
Reference numeral 5 is a channel region and a source / drain region of the second thin film transistor 43 shown in FIG. 11, but a semiconductor film to be a channel region and a source / drain region of the first thin film transistor 42 at different cross-sectional positions. Is also formed. That is, in the manufacturing process shown in FIGS. 13 to 15, two types of transistors 42 and 43 are manufactured at the same time, but since they are manufactured by the same procedure, in the following description, regarding the transistor, only the second thin film transistor 43 will be described. However, the description of the first thin film transistor 42 is omitted.

Next, as shown in FIG. 13C, a conductive film made of a metal such as aluminum, tantalum, molybdenum, titanium, or tungsten is formed by a sputtering method, and then this is patterned to form a gate electrode 43A.
To form. In addition, in forming the gate electrode 43A,
A method using the patterning device 1 shown in FIG. 1 can be adopted. If formed by this method, the gate electrode 4
Since 3A can be directly formed into a desired shape, a patterning process such as a lithography process and an etching process can be omitted. Next, with the gate electrode 43A formed, high-concentration phosphorus ions are implanted to form the source / drain regions 43a and 43b in the semiconductor film 25 in a self-aligned manner with respect to the gate electrode 43A. The portion into which the impurities are not introduced becomes the channel region 43c.

Next, as shown in FIG. 13D, after forming the interlayer insulating film 27, the contact holes 60 and 61 are formed.
And the relay electrodes 62 and 63 are embedded in these contact holes 60 and 61. Such a relay electrode 62,
A method using the patterning device 1 shown in FIG. 1 can also be adopted for filling 63, and using this method facilitates filling the electrode material with the electrode material as described above. That is, the movable mechanism 11 is previously
The nozzle hole 3a of the patterning device 1 is made to face the contact hole 60 (61) and the electrode material is discharged in this state, so that the vaporized electrode material can well enter the contact hole 60 (61). is there.

Then, as shown in FIG. 13E, the patterning device 1 shown in FIG. Or a film forming method such as a sputtering method and a patterning method such as photolithography and etching. At this time, the wirings of the signal line 32, the common power supply line 33, and the scanning line are formed to be thick enough to function as partition walls, as will be described later, without being caught by the thickness required for the wirings. Specifically, each wiring is formed to have a thickness of about 1 to 2 μm. Here, the respective wirings and the relay electrode 63 may be formed in the same step, and in that case,
A method using the patterning device 1 shown in FIG. 1 is preferably adopted. In that case, the relay electrode 62 is formed of a transparent electrode material described later.

Then, the interlayer insulating film 28 is formed so as to also cover the upper surface of each wiring, and a contact hole (not shown) is formed at a position corresponding to the relay electrode 62 so that the contact hole is also filled. A film made of SnO ₂ doped with ITO or fluorine, and a transparent electrode material such as ZnO or polyaniline is formed on the film, and the film is patterned to form a signal line 32, a common power supply line 33, and a scanning line (not shown). The pixel electrode 41 electrically connected to the source / drain region 43a is formed at a predetermined position surrounded by (). Note that the method using the patterning device 1 shown in FIG. 1 can also be adopted for the formation of the pixel electrode 41. If this method is used, as described above, the patterning process such as the lithography process and the etching process is performed. Can be eliminated.

Here, the signal line 32 and the common power supply line 33,
Further, the portion sandwiched by the scanning lines (not shown) is a place where the hole transport layer and the light emitting layer are formed, as described later.
That is, the partition 50 that separates the pixels 20A is formed from these wirings and the interlayer insulating film 28 that covers the wirings. Then, under such a structure, a sufficient height is provided between the formation location of the hole transport layer or the light emitting layer, that is, the coating (injection) position of these forming materials and the surrounding partition wall 50. The step 55 is formed. After the partition wall 50 including each wiring is formed in this manner, the hole transport layer is formed in the pixel 20A surrounded by the partition wall 50. A method using the patterning device 1 shown in FIG. 1 is preferably used for the hole transport layer and the light emitting layer described later. In order to form the hole transport layer by the patterning device 1, first, the substrate 23 is put in the vacuum chamber 2 and placed on the stage 4 with the upper surface side facing upward, and further held and fixed there. If necessary, the substrate 23 on the stage 4 is liquefied by a temperature adjusting means (not shown) to a desired temperature, that is, the forming material ejected in a vaporized state from the nozzle holes 3a is sufficiently cooled. Alternatively, the temperature is adjusted so that it can solidify. Further, the material for forming the hole transport layer, which has been held in advance by the holder in the material supply chamber 7, is heated to a predetermined temperature by the heating means 9.

Here, as the material for forming the hole transport layer,
Known materials can be used without particular limitation,
Examples thereof include a pyrazoline derivative, an arylamine derivative, a stilbene derivative, a triphenyldiamine derivative, polyethylenedioxythiophene, and a mixture of polyethylenedioxythiophene and polystyrenesulfonic acid. Specifically, JP-A-63-70257 and 63-
175860, JP-A-2-135359, 2
-135361, 2-209988, 3-37
Examples thereof include those described in JP-A No. 992 and JP-A No. 3-152184, but triphenyldiamine derivatives are preferable, and among them, 4,4′-bis (N (3-methylphenyl) -N-phenylamino). Biphenyl is preferred. Note that a hole injection layer may be formed instead of the hole transport layer, or both the hole injection layer and the hole transport layer may be formed. In this case, the material for forming the hole injection layer is, for example, copper phthalocyanine (CuPc).
Or polyphenylene vinylene, which is polytetrahydrothiophenylphenylene, 1,1-bis- (4-N, N-
Ditolylaminophenyl) cyclohexane, tris (8
-Hydroxyquinolinol) aluminum, etc., but copper phthalocyanine (CuPc) is particularly preferably used.

When such a forming material is heated to a predetermined temperature by the heating means 9 as described above, a carrier gas such as helium is introduced into the material supply chamber 7 from the carrier gas supply source 8 and the discharge mechanism 10 is operated. The material is discharged into the vacuum chamber 2 through the nozzle holes 3 a in a state where the material is entrained in the carrier gas. Then, the forming material is discharged into the vacuum chamber 2 which is a pressure atmosphere sufficiently lower than the inside of the nozzle 3 which is at about normal pressure, and
As shown in FIG. 4A, this forming material is ejected in a vaporized state. Therefore, by controlling the operation of the movable mechanism 11 by the control unit and thereby moving the relative positional relationship between the nozzle holes 3a and the substrate 23 as set in advance, the forming material 56 is moved to a predetermined position on the substrate 23. A desired amount can be emitted to a position, that is, an area of each pixel 20A surrounded by the partition wall 50. When the forming material is ejected onto the pixels 20A in this manner, the forming material is cooled to the temperature of the substrate 23 and is liquefied or solidified and fixed there. At this time, when the discharged forming material 56 becomes liquid on the substrate 23,
Although it tries to spread horizontally due to its liquidity,
Since the partition wall 50 is formed so as to surround the injection position, the forming material 56 is prevented from spreading over the partition wall 50 and outside thereof.

When the forming material 56 thus discharged is liquefied on the substrate 23, the substrate 23 is once taken out of the vacuum chamber 2 and is cooled or irradiated with light as necessary. As shown in FIG. 14B, a solid hole transport layer 40A can be formed on the pixel electrode 41. Here, when the discharged forming material 56 is solidified on the substrate 23, the light emitting layer is continuously formed without performing the above process. Instead of forming the hole transport layer 40A, the hole injection layer may be formed using copper phthalocyanine (CuPc) or the like as described above. Further, it is particularly preferable to form the hole injection layer on the pixel electrode 41 side prior to the formation of the hole transport layer 40A and further form the hole transport layer 40A. By thus forming the hole injecting layer together with the hole transporting layer 40A, it is possible to control the rise of the driving voltage and prolong the driving life (half-life).

Then, as in the case of the material for forming the hole transport layer (and / or the hole injection layer) described above, FIG.
As shown in FIG. 15, the patterning device 1 discharges (injects) the light emitting layer forming material 57 onto the substrate 23, thereby forming the light emitting layer 40B as shown in FIG. The material 57 for forming the light emitting layer is not particularly limited,
It is possible to use low-molecular organic luminescent dyes and polymer luminescent materials, that is, luminescent materials composed of various fluorescent materials and phosphorescent materials. Among the conjugated polymers as the light emitting substance, those containing an arylene vinylene structure are particularly preferable. Examples of the low molecular weight fluorescent substance include dyes such as naphthalene derivative, anthracene derivative, perylene derivative, polymethine type, xanthene type, coumarin type, cyanine type, metal complex of 8-hydroquinoline and its derivative, aromatic amine, tetraphenylcyclo Pentadiene derivatives, etc., or JP-A-57-5
Known materials described in, for example, 1781 and 59-194393 can be used.

When a polymeric fluorescent substance is used as a material for forming the light emitting layer, a polymer having a fluorescent group in its side chain can be used, but preferably, it contains a conjugated structure in its main chain, and particularly, Polythiophene, poly-p-phenylene, polyarylene vinylene, polyfluorene and its derivatives are preferred. Of these, polyarylene vinylene and its derivatives are preferable. The polyarylene vinylene and its derivatives are polymers containing a repeating unit represented by the following chemical formula (1) in an amount of 50 mol% or more of all repeating units. Although it depends on the structure of the repeating unit, it is more preferable that the repeating unit represented by the chemical formula (1) accounts for 70% or more of all repeating units. -Ar-CR = CR'- (1) [wherein Ar has 4 carbon atoms involved in a conjugated bond]
Or more and 20 or less arylene group or heterocyclic compound group, R and R'each independently represent hydrogen, carbon number 1 to 2
A group selected from the group consisting of an alkyl group having 0, an aryl group having 6 to 20 carbon atoms, a heterocyclic compound having 4 to 20 carbon atoms, and a cyano group is shown. ]

The polymeric fluorescent substance includes, as repeating units other than the repeating unit represented by the chemical formula (1), an aromatic compound group or a derivative thereof, a heterocyclic compound group or a derivative thereof, and a group obtained by combining them. May be included. Further, the repeating unit represented by the chemical formula (1) or another repeating unit is an ether group, an ester group,
They may be linked by a non-conjugated unit having an amide group, an imide group or the like, or the repeating unit may contain these non-conjugated portions. In the polymeric fluorescent substance, Ar in the chemical formula (1) is an arylene group or a heterocyclic compound group having 4 to 20 carbon atoms involved in a conjugated bond, which is represented by the following chemical formula (2). Examples thereof include an aromatic compound group or a derivative group thereof, a heterocyclic compound group or a derivative group thereof, and a group obtained by combining them.

[0098]

[Chemical 1] (R1 to R92 are each independently hydrogen and a carbon number of 1 to
A group selected from the group consisting of an alkyl group having 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. )

Among 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 preferred. More preferably, phenylene group, biphenylene group, naphthalenediyl group, pyridine-2,5
A diyl group and a thienylene group.

When R and R'in the chemical formula (1) are hydrogen or a substituent other than a cyano group, examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group,
Propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, lauryl group and the like, methyl group, ethyl group, pentyl group, hexyl group,
Heptyl group and octyl group are preferred. As the aryl group, a phenyl group and a 4-C1 to C12 alkoxyphenyl group (C1 to C12 have 1 to 12 carbon atoms are shown.
The same applies to the following. ), 4-C1 to C12 alkylphenyl groups, 1-naphthyl groups, 2-naphthyl groups and the like. From the viewpoint of solvent solubility, Ar of the chemical formula (1) is
Having one or more groups selected from an alkyl group having 4 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. Preferably.

Examples of these substituents are as follows. 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, a hexyl group, a heptyl group and an 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, lauryloxy group, pentyloxy group, hexyloxy group. , Heptyloxy group and octyloxy group are preferred. Examples of the alkylthio group having 4 to 20 carbon atoms include a butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, an octylthio group, a decyloxy group and a laurylthio group, and a pentylthio group, a hexylthio group, a heptylthio group and an octylthio group are preferable. Examples of the aryl group include a phenyl group, a 4-C1-C12 alkoxyphenyl group, a 4-C1-C12 alkylphenyl group, a 1-naphthyl group, a 2-naphthyl group and the like. A phenoxy group is illustrated as an aryloxy group. Examples of the heterocyclic compound group include 2-thienyl group, 2-pyrrolyl group, 2-furyl group, 2-, 3- or 4-pyridyl group. The number of these substituents varies depending on the molecular weight of the polymeric fluorescent substance and the constitution of the repeating unit, but from the viewpoint of obtaining a polymeric fluorescent substance having high solubility, the number of these substituents is 1 or more per 600 molecular weight. Is more preferable.

The polymeric fluorescent substance may be a random, block or graft copolymer, or a polymer having an intermediate structure between them, for example, a random copolymer having a block property. May be. From the viewpoint of obtaining a polymeric fluorescent substance having a high fluorescence quantum yield, a random copolymer having a block property or a block or graft copolymer is preferable to a completely random copolymer. Further, since the organic electroluminescence element formed here utilizes fluorescence from the thin film, the polymeric fluorescent substance having fluorescence in a solid state is used.

When a solvent is used for the polymeric fluorescent substance,
In this case, chloroform and methyl chloride are preferable.
Amine, dichloroethane, tetrahydrofuran, toluene,
Xylene etc. are illustrated. Structure and molecule of polymeric fluorescent substance
Depending on the amount, usually 0.1 wt% or more in these solvents
It can be dissolved. Further, as the polymeric fluorescent substance
The molecular weight is 10 in terms of polystyrene³ -10 ⁷ And
Preferably, the degree of polymerization of the
It also depends on the ratio of. Generally, from the viewpoint of film formability
The total number of the return structure is preferably 4 to 10,000, and further
Preferably 5 to 3000, particularly preferably 10 to 200
It is 0.

The method for synthesizing such a polymeric fluorescent substance is not particularly limited, but for example, a dialdehyde compound in which two aldehyde groups are bonded to an arylene group and a compound in which two halogenated methyl groups are bonded to an arylene group. An example is the Wittig reaction from a diphosphonium salt obtained from and triphenylphosphine. Further, as another synthesis method, a halogenated methyl group is added to the arylene group.
An example is a dehydrohalogenation method from a bonded compound. Furthermore, a sulfonium salt decomposition method for obtaining the polymeric fluorescent substance by heat treatment from an intermediate obtained by polymerizing a sulfonium salt of a compound in which two methyl halide groups are bonded to an arylene group with an alkali is exemplified. In any of the synthetic methods, a compound having a skeleton other than an arylene group is added as a monomer, and the structure of the repeating unit contained in the resulting polymeric fluorescent substance can be changed by changing the proportion thereof. You may add and adjust so that the repeating unit shown by (1) may be 50 mol% or more, and may copolymerize. Of these, Wittig
The method by reaction is preferable from the viewpoint of reaction control and yield.

More specifically, a method for synthesizing an arylene vinylene-based copolymer, which is one example of the polymeric fluorescent substance, will be described. For example, when a polymeric fluorescent substance is obtained by the Wittig reaction, for example, first, a bis (methyl halide) compound, more specifically, for example, 2,5-dioctyloxy-p-xylylene dibromide is added to N, N- A phosphonium salt is synthesized by reacting with triphenylphosphine in a dimethylformamide solvent, and this is condensed with a dialdehyde compound, more specifically, for example, terephthalaldehyde, using lithium ethoxide, for example, in ethyl alcohol. By the Wittig reaction, a 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 types of diphosphonium salts and / or two or more types of dialdehyde compounds may be reacted to obtain a copolymer. When these polymeric fluorescent substances are used as the material for forming the light emitting layer, the purity thereof affects the light emitting characteristics, and therefore it is desirable to carry out purification treatments such as reprecipitation purification and fractionation by chromatography after the synthesis.

Further, as a material for forming the light emitting layer made of the above polymeric fluorescent substance, red,
Light-emitting layer forming materials of three colors, green and blue, are used, and each is injected by the patterning device 1 to the pixel 20A at a preset position and patterned. Note that as the above-described light emitting substance, a substance in which a guest material is added to a host material can also be used.

As such a light emitting material, for example, a high molecular weight organic compound or a low molecular weight material is used as a host material, and a fluorescent dye or a phosphorescent substance for changing the light emitting characteristics of the light emitting layer obtained as a guest material is contained. The following are preferably used. As a high molecular weight organic compound, in the case of a material having low solubility, for example, a precursor is applied and then heat-cured as shown in the following chemical formula (3) to form a conjugated high molecular weight organic electroluminescent layer. Some are capable of producing a light emitting layer. For example, in the case of a sulfonium salt as a precursor, there is a sulfonium salt that is removed by heating to form a conjugated polymer organic compound. In addition, there are some materials having high solubility that can be applied to the material as it is and then the solvent can be removed to form the light emitting layer.

[0108]

[Chemical 2]

The above-mentioned high molecular weight organic compound is solid and has strong fluorescence, and can form a homogeneous solid ultrathin film. Moreover, it has a high forming ability and a high adhesiveness with the ITO electrode, and after solidification, forms a strong conjugated polymer film.

As such a high molecular weight organic compound, for example, polyarylene vinylene is preferable. Polyarylene vinylene is soluble in an aqueous solvent or an organic solvent and is easily prepared as a coating solution when applied to the second substrate 11,
Furthermore, because it can be polymerized under certain conditions,
Optically high quality thin film can be obtained. Examples of such polyarylene vinylene include PPV (poly (para-phenylene vinylene)), MO-PPV (poly (2,5-dimethoxy-1,4-phenylene vinylene)), and CN-PPV (poly (2,5). -Bishexyloxy-1,4-phenylene- (1-cyanovinylene))), MEH-PPV (poly [2-methoxy-5-
(2'-Ethylhexyloxy)]-para-phenylene vinylene), PPV derivative, PTV (poly (2,5
-Thienylenevinylene)), etc., PFV (poly (2,5-furylenevinylene)),
Examples thereof include poly (paraphenylene) and polyalkylfluorene. Among them, PP as shown in the chemical formula (4)
Those composed of precursors of V or PPV derivatives and polyalkylfluorenes represented by the chemical formula (5) (specifically, polyalkylfluorene-based copolymers represented by the chemical formula (6)) are particularly preferable. PPV or the like has strong fluorescence and is also a conductive polymer in which π electrons forming a double bond are non-localized on the polymer chain, so that a high-performance organic electroluminescence device can be obtained.

[0111]

[Chemical 3]

[0112]

[Chemical 4]

[0113]

[Chemical 5]

In addition to the PPV thin film, a high molecular weight organic compound or a low molecular weight material capable of forming a light emitting layer, that is, a material used as a host material in this example is, for example, aluminum quinolinol complex (Alq3) or distyryl biphenyl, Further, BeBq2 and Zn (OX shown in the chemical formula (7) are used.
Z) ₂ , and TPD, ALO, DPVBi and the like which have been conventionally used, in addition to pyrazoline dimer, quinolidine carboxylic acid, benzopyrylium perchlorate, benzopyranoquinolidine, rubrene, phenanthroline europium. Complexes and the like are mentioned, and these 1
It is possible to use a composition for an organic electroluminescence device containing one kind or two or more kinds.

[0115]

[Chemical 6]

On the other hand, examples of the guest material added to such a host material include fluorescent dyes and phosphorescent substances as described above. In particular, the fluorescent dye can change the light emission characteristics of the light emitting layer, and is effective as, for example, a means for improving the light emitting efficiency of the light emitting layer or changing the light absorption maximum wavelength (emission color). That is, the fluorescent dye can be used not only as a light emitting layer material but also as a dye material having a light emitting function itself. For example, the energy of excitons generated by carrier recombination on the conjugated polymer organic compound molecule can be transferred onto the fluorescent dye molecule.
In this case, since light emission occurs only from the fluorescent dye molecule 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 emission spectrum of the light emitting layer simultaneously becomes that of fluorescent molecules, which is also effective as a means for changing the emission color.

The current quantum efficiency referred to here is a scale for considering the light emission performance based on the light emission function, and is defined by the following formula. η E = Energy of emitted photon / input electric energy and conversion of light absorption maximum wavelength by doping with a fluorescent dye makes it possible to emit, for example, three primary colors of red, blue and green, resulting in a full color display. It becomes possible. Further, by doping with a fluorescent dye, the luminous efficiency of the electroluminescent element can be significantly improved.

As the fluorescent dye, DCM-1 of the laser dye,
Alternatively, it is preferable to use rhodamine, a rhodamine derivative, penylene or the like. A light emitting layer can be formed by doping a host material such as PPV with these fluorescent dyes. However, since many of these fluorescent dyes are water-soluble, a sulfonium salt which is a water-soluble PPV precursor is used. If doping is performed and then heat treatment is performed, a more uniform light emitting layer can be formed. Specific examples of such a fluorescent dye include Rhodamine B, Rhodamine B base, Rhodamine 6G, Rhodamine 101 perchlorate and the like, and a mixture of two or more thereof may be used.

When forming a light emitting layer which emits green light, it is preferable to use quinacridone, rubrene, DCJT and derivatives thereof. Similar to the above-mentioned fluorescent dyes, these fluorescent dyes can be formed into a light emitting layer by doping a host material such as PPV. However, since these fluorescent dyes are often water-soluble,
If a sulfonium salt that is a water-soluble PPV precursor is doped and then heat-treated, a more uniform light-emitting layer can be formed.

Further, in the case of forming a light emitting layer which emits blue colored light, distyrylbiphenyl and its derivative are preferably used. For these fluorescent dyes,
Similar to the above-mentioned fluorescent dyes, a light emitting layer can be formed by doping a host material such as PPV. However, since most of these fluorescent dyes are water-soluble, sulfonium which is a water-soluble PPV precursor. If a salt is doped and then heat-treated, a more uniform light emitting layer can be formed.

As another fluorescent dye which emits blue colored light, coumarin and its derivatives can be mentioned. These fluorescent dyes have good compatibility with PPV and can easily form a light emitting layer. Further, among these, particularly coumarin, which is insoluble in the solvent itself, may be soluble in the solvent by increasing the solubility by appropriately selecting the substituent. Specific examples of such a fluorescent dye 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. Is mentioned.

Further, as another fluorescent dye which emits blue colored light, tetraphenyl butadiene (TPB) or TPB derivative, DPVBi and the like can be mentioned.
These fluorescent dyes are soluble in an aqueous solution like the red fluorescent dye and the like, and have good compatibility with PPV so that the light emitting layer can be easily formed. With regard to the above fluorescent dyes, only one kind may be used for each color, or two or more kinds may be mixed and used. As such a fluorescent dye, those represented by the chemical formula (8), those represented by the chemical formula (9), and those represented by the chemical formula (10) are used.

[0123]

[Chemical 7]

[0124]

[Chemical 8]

[0125]

[Chemical 9]

These fluorescent dyes are preferably added in an amount of 0.5 to 10 wt%, and preferably 1.0 to 5.0 wt% to the host material composed of the conjugated high molecular weight organic compound by the method described later. More preferably.
If the amount of the fluorescent dye added is too large, it will be difficult to maintain the weather resistance and durability of the resulting light emitting layer, while if the amount added is too small, the effect of adding the fluorescent dye as described above will be sufficiently obtained. Because there is no.

Further, as a phosphorescent substance as a guest material added to the host material, Ir represented by the chemical formula (11) is used.
(Ppy) ₃ , Pt (thpy) ₂ , PtOEP and the like are preferably used.

[0128]

[Chemical 10]

When the phosphor material represented by the chemical formula (11) is used as the guest material, the host material is particularly CBP, DCTA, TCPB represented by the chemical formula (12).
Alternatively, DPVBi and Alq3 described above are preferably used. Further, the fluorescent dye and the phosphorescent substance may both be added to the host material as a guest material.

[0130]

[Chemical 11]

When the light emitting layer 40B is formed of such a host / guest light emitting material, for example, a plurality of material supply systems such as the nozzles 3 are formed in the patterning device 1 in advance, and the nozzles 3 form the host material. By simultaneously ejecting the guest material and the guest material at a preset amount ratio, it is possible to form the light emitting layer 40B made of a light emitting substance obtained by adding a desired amount of the guest material to the host material.

When the light emitting layer 40B is formed on the hole transporting layer 40A of each pixel 20A in this manner, the patterning device 1 is used to form the light emitting layer 40B in the same manner as the hole transporting layer 40A and the light emitting layer 40B. The forming material is discharged (injected) onto the substrate 23 to form the electron transport layer 40C as shown in FIG. The material for forming the electron transport layer is not particularly limited, and includes oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane. And derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, 8-hydroxyquinoline and metal complexes of derivatives thereof, and the like. Specifically, similar to the above material for forming the hole transport layer, JP-A-63-70257, JP-A-63-175860, and JP-A-2-135359.
No. 2-135361, No. 2-209988, No. 3-37992, No. 3-152184, etc. are illustrated, Especially 2- (4-biphenylyl) -5- (4 -T-butylphenyl) -1,3,4-
Oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum are preferred.

The material for forming the hole transporting layer 40A and the material for forming the electron transporting layer 40C may be mixed with the material for forming the light emitting layer 40B and used as the material for forming the light emitting layer.
In that case, although the amount of the hole transport layer forming material or the electron transport layer forming material used varies depending on the kind of the compound used, etc., consider them in an amount range that does not impair sufficient film formability and emission characteristics. And determined appropriately. Usually, it is 1 to 40% by weight, more preferably 2 to 30% by weight, based on the light emitting layer forming material.

Here, regarding the film thicknesses of the hole transport layer 40A, the light emitting layer 40B, and the electron transport layer 40C thus formed, the discharge amount from the nozzle hole 3a is set beforehand in advance. It is formed to have a preferable thickness (for example, 65 nm). For the adjustment of the discharge amount, the nozzle hole 3
This can be performed by setting the inner diameter of a and the flow rate of the carrier gas appropriately. After that, FIG.
As shown in (c), the counter electrode 54 is formed on the entire surface of the transparent substrate 23 or in a stripe shape to obtain an organic EL element. As a matter of course, the method using the patterning device 1 shown in FIG. 1 can be adopted for the formation of the counter electrode 54. In addition, this counter electrode 54
May be formed of a single layer made of a single material such as Al, Mg, Li, or Ca or an alloy material of Mg: Ag (10: 1 alloy), and may be formed of a metal (including an alloy) having two layers or three layers. ) May be formed as a layer. Specifically, Li ₂
A laminated structure of O (about 0.5 nm) / Al, LiF (about 0.5 nm) / Al, MgF ₂ / Al can also be used.

The display device thus obtained, that is, the display device which becomes the electro-optical device in the present invention, has at least one of its constituent elements formed by the patterning device 1, so that the degree of freedom in material selection is increased. Therefore, the device can be configured with a better combination. The hole injection layer (not shown), the hole transport layer 40A, the light emitting layer 40B, and the electron transport layer 4 described above.
In addition to 0C, a hole blocking layer, for example, a light emitting layer 4
0B may be formed on the side of the counter electrode 54 to extend the life of the light emitting layer 40B. As a material for forming such a hole blocking layer, for example, BC represented by the chemical formula (13) is used.
Although PAl and BAlq represented by the chemical formula (14) are used, BAlq is preferable from the viewpoint of extending the life.

[0136]

[Chemical 12]

[0137]

[Chemical 13]

Further, in the present example, each material is discharged into the vacuum chamber 2 in a vaporized state. However, by adjusting the degree of vacuum in the vacuum chamber 2 and the degree of heating by the heating means 9 May be ejected as a liquid such as mist or mist, or may be ejected in the form of fumes.

The electronic device of the present invention may be, for example, a FRAM (Ferroelect) in addition to the device including the semiconductor element, the liquid crystal element, the electrophoretic element, and the organic EL element.
The present invention is also applicable to various memory devices including a memory element (electronic element) such as ricRAM) and MRAM (Magnetic RAM), and an apparatus including an electronic element including a diode such as a light emitting diode. That is, FRAM and MRA
In a memory element such as M, for example, a method using the patterning device 1 for forming the ferroelectric film (insulating film) is preferably adopted, and in that case, the degree of freedom in selecting the ferroelectric material (insulating material) is high. It is possible to construct a better device because of the high value.

The present invention can be applied to an electronic device having a light emitting diode, for example, the device shown in FIG. The device 70 shown in FIG.
1 and the organic LED 72 are monolithically integrated on the same substrate 73. The organic TFT 71 includes a gate electrode 74 formed on a substrate 73, a dielectric layer 75 formed so as to cover the gate electrode 74, a source electrode 76 and a drain electrode 77 formed on the dielectric layer 75, and these electrodes. And an organic semiconductor layer 78 formed so as to cover the. Here, the organic TFT 71 basically has the same structure as the organic semiconductor element shown in FIG. 10, although the positions of the source / drain electrodes and the organic semiconductor layer are slightly different.

The organic LED 72 has an anode 79 formed on the substrate 73, a hole transport layer 80 formed so as to cover the anode 79, and an electron transport layer 81 formed on the hole transport layer 80. , A cathode 82 formed on the electron transport / emitter layer 81. The anode 79 is formed by directly extending the drain electrode 77 on the substrate 73, and the hole transport layer 80 is formed by extending the organic semiconductor layer 78 on the anode 79. is there.

Even in the case of such a device 70, the method using the patterning device 1 shown in FIG. For example, the gate electrode 7
4, the method using the patterning device 1 is preferably adopted not only for forming the organic semiconductor layer 78 (hole transport layer 80), the electron transport / emitter layer 81, and the cathode 82, but also for the four, the source electrode 76, the drain electrode 77 (anode 79). To be done. Here, as the material for forming the organic semiconductor layer 78, the same material as in the case of the organic semiconductor element shown in FIG. 10 can be used. Further, as a material for forming the electron transport / emitter layer 81, polyphenylene / vinylene and aluminum 8-hydroxyquinolinate (Alq.), 2- (4-biphenylyl) -5- (4-tert-butylphenyl)- 1, 3,
4-oxadiazole (PBD), 2-naphthyl-4,
5-bis (4-methoxyphenyl) -1,3-oxazole), bis- (8-hydroxyoxyquinaldine) aluminum phenoxide, bis (10-hydroxyoxybenzo-quinolinate (zinc) (ZnBq2) and the like are used. As the material for forming the cathode 82, a material that can efficiently inject electrons into the electron transport / emitter layer 81 is used, and specifically, aluminum or calcium is preferably used.

Even in such an electronic device, since at least one of the constituent elements is formed by the patterning device 1, the degree of freedom in selecting the material is increased, and therefore, the device is constructed in a better combination. be able to.

Next, specific examples of electronic equipment provided with the electro-optical device of the above example, that is, a liquid crystal device, an electrophoretic device, or a display device using an organic EL element will be described. FIG. 17A is a perspective view showing an example of a mobile phone. In FIG. 17A, reference numeral 500 denotes a mobile phone main body, and 501 denotes a display unit including the electro-optical device. FIG. 17B is a perspective view showing an example of a portable information processing device such as a word processor and a personal computer.
In FIG. 17B, 600 is an information processing device, 601.
Is an input unit such as a keyboard, 603 is an information processing main body, 6
Reference numeral 02 denotes a display unit including the electro-optical device. FIG. 17C is a perspective view showing an example of a wrist watch type electronic device. In FIG. 17 (c), 700 indicates a watch body, and 701 indicates a display means including the electro-optical device. Since the electronic device shown in FIGS. 17A to 17C is provided with the electro-optical device, the degree of freedom in selecting the components is increased,
The electronic device is provided with a display unit that can obtain excellent display quality.

[0145]

As described above, in the method of manufacturing an electronic device of the present invention, at least one of a conductive material, a semiconductor material, an insulating material or at least one of precursors of these materials is used. Since the material is ejected from the nozzle into a vacuum atmosphere, the material or precursor can be ejected, for example, in a vaporized state, and ideally in a molecular beam shape. Therefore, the material can be arranged by freely selecting and using the material or the precursor without any particular limitation. Further, by arranging the material or precursor at a predetermined position on the substrate, patterning can be performed without the need for a mask.

In the method for manufacturing a circuit board of the present invention,
Since a plurality of electronic elements are formed by the above-described method for manufacturing an electronic element, the material or precursor thereof can be freely selected and used without particular limitation, and the material can be arranged. Further, by arranging the material or precursor at a predetermined position on the substrate, patterning can be performed without the need for a mask.

In the method of manufacturing the electronic device of the present invention,
Since the above-described method for manufacturing an electronic device is used, the material or precursor thereof can be freely selected and used without particular limitation, and the material can be arranged. Further, by arranging the material or precursor at a predetermined position on the substrate, patterning can be performed without the need for a mask.

In the method of manufacturing the electro-optical device of the present invention, since the method of manufacturing the electronic element is used, the material or the precursor thereof can be freely selected and used without any particular limitation. Can be placed. Also,
By placing the material or precursor at a predetermined position on the substrate, patterning can be performed without the need for a mask. Further, in the electro-optical device of the present invention, since it is obtained by the method for manufacturing the electro-optical device described above, the material or the precursor can be freely selected and used without any particular limitation. The degree of freedom of selection is high.

In the electronic apparatus of the present invention, since the electro-optical device described above is provided as the display means, the electro-optical device serving as the display means has a high degree of freedom in selection of the material when manufacturing the electro-optical device. Will be things.

In the patterning device of the present invention, by discharging the material into the vacuum chamber, the material can be easily and stably discharged. Therefore, by moving the relative position between the nozzle and the substrate by the movable mechanism and ejecting the material or its precursor onto the substrate, patterning can be performed without the need for a mask. The material or precursor can be freely selected and used without any particular limitation.

[Brief description of drawings]

FIG. 1 is a side view showing a schematic configuration of an example of a patterning device of the present invention.

FIG. 2 is a side sectional view showing a schematic configuration of a circuit board (electronic device) according to the present invention.

3 (a) to 3 (e) are side cross-sectional views of relevant parts for explaining a method of manufacturing the circuit board (electronic device) shown in FIG. 2 in order of steps.

4A to 4D are side cross-sectional views of main parts for sequentially explaining the steps following FIG.

5A to 5C are side cross-sectional views of main parts for sequentially explaining the steps following FIG.

FIG. 6 is a side sectional view for explaining a schematic configuration of a liquid crystal cell.

FIG. 7 is a side cross-sectional view of a main portion showing a schematic configuration of a pixel portion in an electrophoretic device.

8A to 8C are diagrams for explaining a conceptual configuration of an electronic ink layer and an operation when a voltage is applied.

9 is a perspective view of electronic paper formed by the electrophoretic device shown in FIG. 7. FIG.

FIG. 10 is a side sectional view showing a schematic configuration of an example of an organic semiconductor element.

FIG. 11 is a circuit diagram of a display device using an organic EL element as an electro-optical device according to the invention.

12 is an enlarged plan view showing a planar structure of a pixel portion in the display device shown in FIG.

13A to 13E are side cross-sectional views of main parts for explaining the method of manufacturing the display device shown in FIGS. 11 and 12 in the order of steps.

14A to 14C are side sectional views of main parts for sequentially explaining the step following FIG.

15A to 15C are side sectional views of main parts for sequentially explaining the step following FIG.

FIG. 16 is a side sectional view of an essential part for explaining an example of an electronic device including a light emitting diode.

17A and 17B are diagrams showing a specific example of an electronic apparatus provided with the electro-optical device of the invention, FIG. 17A is a perspective view showing an example when applied to a mobile phone, and FIG. FIG. 10 is a perspective view showing an example of a case applied, and FIG. 7C is a perspective view showing an example applied to a wristwatch type electronic device.

[Explanation of symbols]

1 ... Patterning device, 2 ... Vacuum chamber, 3 ... Nozzle, 3a ... Nozzle hole, 4 ... Stage, 11 ... Movable mechanism

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01L 29/786 H01L 29/78 617J 51/00 618A 617V 618B 29/28 F term (reference) 2H092 GA59 JA25 JA29 JA42 JA44 JA46 JB13 JB32. DD18 DD31 DD37 DD43 DD44 DD51 DD63 DD91 EE03 EE06 EE12 EE14 EE16 EE17 EE18 FF13 FF14 FF18 FF22 GG08 GG09 GG10 HGH20 5F045 AA18 AB32 AB33 AB39 CC15 DP03 BB14 BB14 FF14 BB14DD01 FF14 BB02 FF14 BB02 FF02 FF02 5F103 A02 DD03 DD05 DD13 EE01 EE02 EE03 EE04 EE05 EE06 EE07 EE08 EE09 EE14 EE15 EE28 EE41 EE44 EE45 FF0 1 FF02 FF03 FF04 FF09 FF21 FF23 FF28 FF30 GG01 GG02 GG05 GG13 GG25 GG32 GG41 GG43 GG45 GG47 HJ01 HJ04 HJ13 HJ18 HJ23 HL03 HL04 HL12 HL21 HL23 HM15 NN03 NN04 NN22 NN23 NN24 NN27 NN32 NN35 NN73 NN78 PP01 PP03 PP06 PP10 PP34 QQ01 QQ09 QQ11 QQ25 QQ28

Claims (17)

[Claims] 1. A method of manufacturing an electronic device comprising at least one material selected from a conductive material, a semiconductor material and an insulating material, wherein a substrate is placed in a vacuum atmosphere adjusted to a substantially vacuum, and At least one of the materials or at least one of the precursors of the materials is discharged from the nozzle into the vacuum atmosphere, and the at least one material is arranged at a predetermined position on the substrate. Manufacturing method of electronic device. 2. The method for manufacturing an electronic device according to claim 1, wherein the electronic device is a diode. 3. The electronic device is a transistor.
A method for manufacturing the electronic device described. 4. At least one of the materials or at least one of precursors of the materials is a material for forming a gate electrode, and the gate electrode is formed by arranging the material at a predetermined position on a substrate. The method for manufacturing an electronic element according to claim 3, wherein the electronic element is formed. 5. A semiconductor layer is formed by arranging at least one of the materials or at least one of precursors of the material is a semiconductor material and disposing the material at a predetermined position on a substrate. 3. The method for manufacturing an electronic element according to 3. 6. The method of manufacturing an electronic device according to claim 5, wherein the semiconductor material is an organic semiconductor material. 7. A gate insulating film is formed by arranging at least one of the materials or at least one of precursors of the material is an insulating material, and disposing the material at a predetermined position on a substrate. Item 3. A method of manufacturing an electronic element according to Item 3. 8. A method for manufacturing a circuit board, wherein a plurality of electronic elements are formed by the manufacturing method according to claim 1. 9. A method of manufacturing an electronic device, which uses the manufacturing method according to claim 1. 10. A method of manufacturing an electro-optical device, characterized by using the manufacturing method according to claim 1. 11. The method of manufacturing an electro-optical device according to claim 10, wherein the electro-optical device includes a liquid crystal element. 12. The method of manufacturing an electro-optical device according to claim 10, wherein the electro-optical device includes an electrophoretic element. 13. The method of manufacturing an electro-optical device according to claim 10, wherein the electro-optical device includes an organic EL element. 14. At least one of said materials or at least one of said material precursors is organic E
14. The organic EL element according to claim 13, which is a material for forming at least one of a light emitting layer, a hole injection layer, and a hole transport layer in the L element, and the material is arranged at a predetermined position on the substrate. Manufacturing method of electro-optical device. 15. An electro-optical device obtained by the manufacturing method according to claim 10. 16. An electronic device comprising the electro-optical device according to claim 15 as display means. 17. A vacuum chamber that is adjusted to a substantially vacuum, a nozzle that discharges at least one material of a conductive material, a semiconductor material, and an insulating material, and a stage that mounts a substrate to be patterned. A patterning device comprising a movable mechanism that relatively moves the positions of the nozzle and the substrate on the stage.