JP2005202094A - Substrate of display apparatus, method for manufacturing thin film device, thin film device, liquid crystal display apparatus and electro-luminescence display apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve resistance to moisture and oxygen by mixing moisture absorbent and oxygen absorbent to an adhesive layer and an insulated layer used when forming a substrate of a display apparatus. <P>SOLUTION: In the substrate 10 of the display apparatus in which a support substrate 11 and a thin film layer 13 are bonded by the adhesive layer 12, the moisture absorbent 14 is contained in the adhesive layer 12 or the oxygen absorbent is contained in the adhesive layer or the moisture absorbent and the oxygen absorbent are contained in the adhesive layer, or in the substrate 20 of the display apparatus in which the support substrate 21 and an electrode layer 23 are formed via an insulated layer 22, the moisture absorbent is contained in the insulator 22 or the oxygen absorber is contained in the insulated layer or the moisture absorbent and the oxygen absorbent are contained in the insulated layer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention provides a substrate for a display device and a thin film device that can easily extend the life by suppressing the intrusion of moisture and oxygen into a liquid crystal material or an organic electroluminescence (hereinafter abbreviated as EL) element. The present invention relates to a method, a thin film device, a liquid crystal display device, and an electroluminescence display device.

  In recent years, thin film devices have been required to be thinner, lighter, and more robust due to the downsizing of equipment used. However, since a thin film device is manufactured in an environment of high temperature and vacuum, there are limitations on the substrate used for manufacturing. For example, in a liquid crystal display device using a thin film transistor, a quartz substrate that can withstand a temperature of 1000 ° C. and a glass substrate that can withstand a temperature of 500 ° C. are used. Although thinning of these substrates is also under consideration, as long as quartz substrates and glass substrates are used, the substrate size must be reduced in consideration of the decrease in substrate rigidity, thereby reducing productivity. . In addition, as the substrate becomes thinner, the robustness rapidly decreases, which is a practical problem. As described above, the performance required for the manufacturing substrate is different from the performance required for actual use. In addition, there is an attempt to manufacture a thin film transistor directly on a thin, lightweight, and robust plastic substrate, but the difficulty is high in terms of heat-resistant temperature.

  Therefore, a technique for transferring a thin film device formed on a production substrate having a high heat-resistant temperature to an actual use substrate has been studied. As a transfer method, a peeling layer is provided and a device is peeled off after the device is manufactured (for example, see Patent Document 1), or a glass substrate is removed by etching (for example, see Patent Document 2). Etc. are being considered. By using these methods, a thin film device can be formed on a plastic substrate.

JP-A-10-125930 Japanese Patent Laid-Open No. 2003-68995

The problem to be solved is that in a liquid crystal display device and an organic EL liquid crystal display device using a plastic substrate, since the plastic substrate allows water and oxygen to pass through, moisture and oxygen enter the liquid crystal material and the organic EL element. There is a problem that the organic EL element deteriorates. In order to solve this problem, there is a technique for preventing water and oxygen from entering by forming a water vapor barrier layer and an oxygen barrier layer on a plastic substrate. However, in this technique, since the barrier layer is generally a thin film, pinholes, cracks, and the like exist, and it is difficult to completely prevent moisture and oxygen from entering. For example, the current water vapor barrier layer is about 0.1 g / (m ² · day · atm) at 40 ° C. and 90% RH. The liquid crystal in the cell is about 3.5 × 10 ⁻⁴ g / cm ² when the gap thickness is 3.5 μm. Assuming that 10% moisture is contained in the liquid crystal as a defective state, assuming that the diffusion is sufficiently fast at 40 ° C. and 90% RH and the barrier performance is rate-limiting, 3.5 × 10 ⁻⁴ × 0.1. /(0.1×10 ⁻⁴ ) = 3.5 days (84 hours), which is insufficient for a liquid crystal display device.

  The display device substrate of the present invention is a display device substrate in which a support substrate and a thin film layer are bonded by an adhesive layer. The adhesive layer contains a hygroscopic agent, an oxygen absorbing agent, or a hygroscopic agent. And an oxygen absorber.

  The display device substrate of the present invention is a display device substrate in which a support substrate and an electrode layer are formed via an insulating layer, the insulating layer contains a hygroscopic agent, an oxygen absorbing agent, or The main feature is that it contains a hygroscopic agent and an oxygen absorbing agent.

In the method for manufacturing a thin film device of the present invention, after a thin film device layer is formed on a first substrate, the second substrate is attached to the thin film device layer via a first adhesive layer or a covering layer and a first adhesive layer. A step of bonding, a step of completely or partially separating or removing the first substrate by a step including at least one of chemical treatment, mechanical polishing treatment, and ultraviolet irradiation treatment, and the first substrate of the thin film device layer A thin film device comprising: a step of adhering a first substrate left on or partially left of the substrate to a third substrate through a second adhesive layer; and a step of separating or removing the second substrate. The main feature of the manufacturing method is that the second adhesive layer contains one or both of a moisture absorbent that absorbs moisture and an oxygen absorbent that absorbs oxygen.

  The thin film device of the present invention is a thin film device manufactured by the method of manufacturing a thin film device of the present invention, wherein the second adhesive layer has one or both of a moisture absorbent that absorbs moisture and an oxygen absorbent that absorbs oxygen. The main feature is that it is included.

  The liquid crystal display device of the present invention includes a first substrate attached to the first thin film layer with an adhesive layer, and a second substrate provided opposite to the first substrate, the second thin film layer being formed via an insulating layer. In the liquid crystal display device comprising: a substrate; and a liquid crystal layer sealed between the first substrate and the second substrate in which the first thin film layer side and the second thin film layer side are opposed to each other. Containing at least one of a hygroscopic agent and an oxygen absorbing agent in the layer, or containing at least one of a hygroscopic agent and an oxygen absorbing agent in the insulating layer, or of the hygroscopic agent and the oxygen absorbing agent in the adhesive layer. The main feature is that at least one of them is included, and at least one of a hygroscopic agent and an oxygen absorbing agent is included in the insulating layer.

  In the liquid crystal display device of the present invention, after forming a thin film device layer on the first substrate, the second substrate is bonded onto the thin film device layer via the first adhesive layer or the covering layer and the first adhesive layer. A step of completely or partially separating or removing the first substrate by a step including at least one of chemical treatment, mechanical polishing treatment, and ultraviolet irradiation treatment, and the first substrate of the thin film device layer comprises: A thin film device manufactured by the step of adhering the formed first or partially left first substrate to a third substrate via a second adhesive layer and the step of separating or removing the second substrate. In the liquid crystal display device used, the second adhesive layer mainly includes one or both of a moisture absorbent that absorbs moisture and an oxygen absorbent that absorbs oxygen.

  The electroluminescence display device of the present invention is an electroluminescence display device in which a thin film layer including a light emitting layer and a supporting substrate are attached by an adhesive layer, wherein the adhesive layer absorbs moisture and absorbs oxygen. The main feature is that one or both of the oxygen agents are included.

  In the electroluminescence display device of the present invention, after the thin film device layer is formed on the first substrate, the second substrate is formed on the thin film device layer via the first adhesive layer or the covering layer and the first adhesive layer. A step of bonding, a step of completely or partially separating or removing the first substrate by a step including at least one of chemical treatment, mechanical polishing treatment, and ultraviolet irradiation treatment, and the first substrate of the thin film device layer The thin film device manufactured by the step of bonding the first substrate left or partially left to the third substrate via the second adhesive layer and the step of separating or removing the second substrate In the electroluminescence display device using the present invention, the second adhesive layer contains one or both of a moisture absorbent that absorbs moisture and an oxygen absorbent that absorbs oxygen. The main feature.

  The substrate of the display device of the present invention contains a hygroscopic agent in the adhesive layer, or contains an oxygen absorbing agent, or contains a hygroscopic agent and an oxygen absorbing agent, so that it tends to enter the thin film layer direction from the support substrate side. The moisture to be absorbed can be absorbed by the hygroscopic agent, and oxygen that tends to enter the thin film layer direction from the support substrate side can be absorbed by the oxygen absorbing agent, so that the substrate of the display device of the present invention can be used as a liquid crystal display device or an electro When used in a luminescence display device, there is an advantage that the lifespan can be extended by suppressing the deterioration of the liquid crystal or the electroluminescence light emitting layer.

  The substrate of the display device of the present invention contains a hygroscopic agent in the insulating layer, or contains an oxygen absorbing agent, or contains a hygroscopic agent and an oxygen absorbing agent, so that it tends to enter the electrode layer direction from the support substrate side. The moisture to be absorbed can be absorbed by the hygroscopic agent, and the oxygen that tends to enter the electrode layer direction from the support substrate side can be absorbed by the oxygen absorbing agent, so that the substrate of the display device of the present invention can be used as a liquid crystal display device or an electro When used in a luminescence display device, there is an advantage that the lifespan can be extended by suppressing the deterioration of the liquid crystal or the electroluminescence light emitting layer.

  Since the thin film device manufacturing method of the present invention uses one or both of a hygroscopic agent that absorbs moisture and an oxygen absorbing agent that adsorbs oxygen in the second adhesive layer, the thin film device layer from the third substrate side is used. Moisture that penetrates in the direction can be absorbed by the hygroscopic agent, and oxygen that tries to penetrate in the direction of the thin film device layer from the third substrate side can be absorbed by the oxygen absorbing agent. In a liquid crystal display device or an electroluminescence display device manufactured by the manufacturing method, there is an advantage that deterioration of the liquid crystal or the electroluminescence light emitting layer can be suppressed and the life can be extended.

  In the thin film device of the present invention, since the second adhesive layer includes one or both of a moisture absorbent that absorbs moisture and an oxygen absorbent that absorbs oxygen, the second adhesive layer tends to enter the thin film device layer direction from the third substrate side. Moisture can be absorbed by the hygroscopic agent, and oxygen that tends to enter the thin film device layer direction from the third substrate side can be absorbed by the oxygen absorbing agent, so that the liquid crystal display device using the thin film device of the present invention In the electroluminescence display device, there is an advantage that the life can be extended by suppressing the deterioration of the liquid crystal and the electroluminescence light emitting layer.

  The liquid crystal display device of the present invention includes at least one of a hygroscopic agent and an oxygen absorbing agent in the adhesive layer, or includes at least one of the hygroscopic agent and the oxygen absorbing agent in the insulating layer, or the hygroscopic agent in the adhesive layer. And at least one of oxygen absorbers and the insulating layer includes at least one of moisture absorbers and oxygen absorbers, so that moisture that tends to enter the thin film layer from the substrate side can be absorbed by the moisture absorber. Further, oxygen that tends to enter the thin film layer direction from the substrate side can be absorbed by the oxygen absorbing agent, so that there is an advantage that deterioration of the liquid crystal can be suppressed and the life can be extended.

  When the liquid crystal display device of the present invention adheres to the third substrate via the second adhesive layer on the thin film device layer side, the second adhesive layer is a moisture absorbent that absorbs moisture and an oxygen absorbent that absorbs oxygen. One or both of them can be absorbed by the moisture absorbent to absorb moisture from the third substrate side in the direction of the thin film device layer and absorb oxygen from the third substrate side in the direction of the thin film device layer. Since it can be absorbed by the oxygen agent, there is an advantage in that the deterioration of the liquid crystal can be suppressed and the life can be extended.

  In the electroluminescence display device of the present invention, since the adhesive layer includes one or both of a moisture absorbing agent that absorbs moisture and an oxygen absorbing agent that absorbs oxygen, the adhesive layer will enter the thin film layer including the light emitting layer from the support substrate side. Moisture absorption can be absorbed by the hygroscopic agent, and oxygen that tries to penetrate from the support substrate side toward the thin film layer including the light emitting layer can be absorbed by the oxygen absorbing agent. There is an advantage that can be extended.

  When the electroluminescent display device of the present invention adheres to the third substrate via the second adhesive layer on the thin film device layer side, the second adhesive layer is a moisture absorbent that absorbs moisture and an oxygen absorbent that absorbs oxygen. Since one or both of them are included, moisture that tends to enter the thin film device layer direction from the third substrate side can be absorbed by the hygroscopic agent, and oxygen that attempts to enter the thin film device layer direction from the third substrate side can be absorbed. Since it can be absorbed by the oxygen absorbing agent, there is an advantage that the lifetime of the light emitting layer can be suppressed and the life can be extended.

  For the purpose of improving the resistance to water and oxygen of a substrate of a display device, a thin film device manufacturing method, a thin film device, a liquid crystal display device and an electroluminescent display device, a hygroscopic agent and an oxygen scavenger are mixed in an adhesive layer and an insulating layer. This was achieved without providing a special layer.

  That is, as shown in FIG. 1 (1), the substrate 10 of the first display device is a substrate in which a support substrate 11 and a thin film layer 13 are bonded by an adhesive layer 12, and a hygroscopic agent 14 is contained in the adhesive layer 12. Or an oxygen absorbing agent (not shown), or a hygroscopic agent and an oxygen absorbing agent (not shown). For the adhesive layer 12, for example, an ultraviolet curable adhesive is used.

  As shown in FIG. 1 (2), the substrate 20 of the second display device is a substrate in which a support substrate 21 and an electrode layer 23 are formed with an insulating layer 22 interposed therebetween. The agent 24 is included, or although not illustrated, an oxygen absorbing agent is included, or although not illustrated, a moisture absorbing agent and an oxygen absorbing agent are included. For example, a coating type insulating film is used for the insulating layer 22.

  The substrate 10 of the first display device can be used as an element substrate of a liquid crystal display device or an electroluminescence display device, and the substrate 20 of the second display device can be used as a counter substrate of the liquid crystal display device. . For example, the substrate 10 of the first display device and the substrate 20 of the second display device are used, and a space is provided so that the thin film layer side and the electrode layer side face each other. Secondly, a liquid crystal display device can be formed by bonding the substrate 20 of the display device and enclosing liquid crystal in the space. The substrate of the first display device can be used for an electroluminescence display device. Details thereof will be described later.

  A method of manufacturing a thin film device includes a step of forming a thin film device layer on a first substrate and then bonding the second substrate to the thin film device layer via the first adhesive layer or the covering layer and the first adhesive layer. And a step of completely or partially separating or removing the first substrate by a step including at least one of chemical treatment, mechanical polishing treatment and ultraviolet irradiation treatment, and forming the first substrate of the thin film device layer. A step of adhering the first substrate left or partially left to the third substrate via the second adhesive layer, and a step of separating or removing the second substrate; Is a manufacturing method in which one or both of a hygroscopic agent that absorbs oxygen and an oxygen absorbing agent that adsorbs oxygen are used. For example, an ultraviolet curable adhesive is used for the second adhesive layer.

  A thin film device is manufactured by the method for manufacturing a thin film device.

  The liquid crystal display device includes: a first substrate attached to the first thin film layer with an adhesive layer; a second substrate provided opposite to the first substrate and having a second thin film layer formed through an insulating layer; A liquid crystal layer sealed between the first substrate and the second substrate in which the first thin film layer side and the second thin film layer side are opposed to each other, and a hygroscopic agent in the adhesive layer And at least one of oxygen absorbers. For example, an ultraviolet curable adhesive is used for the adhesive layer, and for example, a coating type insulating film is used for the insulating layer.

  The liquid crystal display device uses a thin film device manufactured by the method for manufacturing a thin film device, and the second adhesive layer is one or both of a moisture absorbing agent that absorbs moisture and an oxygen absorbing agent that absorbs oxygen. Is included. For example, an ultraviolet curable adhesive is used for the second adhesive layer.

  In the electroluminescence display device, a thin film layer including a light emitting layer and a support substrate are attached by an adhesive layer, and the adhesive layer is one of a moisture absorbent that absorbs moisture and an oxygen absorbent that absorbs oxygen. Or both. For the adhesive layer, for example, an ultraviolet curable adhesive is used.

  The electroluminescence display device uses a thin film device manufactured by the method for manufacturing a thin film device, and the second adhesive layer is one of a hygroscopic agent that absorbs moisture and an oxygen absorbing agent that absorbs oxygen, or It includes both. For example, an ultraviolet curable adhesive is used for the second adhesive layer.

  Examples of the hygroscopic agent and the oxygen absorbing agent used in the substrate of the display device, the thin film device manufacturing method, the thin film device, the liquid crystal display device, and the electroluminescence display device are as follows. It is preferable to use calcium oxide, silica gel, calcium chloride, magnesium chloride or the like as the hygroscopic agent. In addition, the oxygen absorbing agent includes an oxygen absorbing agent mainly composed of iron and titanium oxide containing oxygen defects, an oxygen absorbing agent mainly composed of ascorbic acid, an oxygen absorbing agent mainly composed of glycerin, and 1,2-glycol. It is preferable to use an oxygen absorbing agent that is a main agent and an oxygen absorbing agent that is mainly a sugar alcohol. The hygroscopic agent and the oxygen absorbing agent have a particle size of 10 μm or less, for example, 1 μm to 10 μm. Accordingly, the thickness of the adhesive layer or the insulating layer is larger than the particle size of the hygroscopic agent and the oxygen absorbing agent. The thickness was 10 μm to 15 μm.

  A thin film device manufacturing method, a thin film device and a liquid crystal display device according to a first embodiment of the present invention will be described with reference to manufacturing process cross-sectional views of FIGS. In this example, an active substrate for transmissive liquid crystal was fabricated on a plastic substrate.

First, a method for forming a thin film device layer will be described with reference to FIG. As shown in FIG. 2, a protective layer 102 of the first substrate 101 is formed on the first substrate 101 at the time of subsequent etching with hydrofluoric acid. As the first substrate 101, a glass substrate having a thickness of about 0.4 mm to 1.1 mm, for example, 0.7 mm is used. A quartz substrate may be used instead of the glass substrate. The protective layer 102 is formed using a material that can withstand hydrofluoric acid. For example, a molybdenum (Mo) layer is used, and the protective layer 102 is formed to a thickness of, for example, 500 nm. Although the thickness of the molybdenum layer is 500 nm this time, there is no problem even if the thickness is appropriately changed as long as it can withstand hydrofluoric acid. The molybdenum protective layer 102 can be formed by sputtering, for example. Thereafter, the insulating layer 103 is formed. The insulating layer 103 is formed, for example, by forming a silicon oxide (SiO ₂ ) film to a thickness of 500 nm. The insulating layer 103 can be formed by, for example, a plasma CVD method.

  Next, general low-temperature polysilicon technology such as “2003 FPD Technology Encyclopedia” (published on March 25, 2003, p.166-183 and p.198-201), “'99 latest liquid crystal process technology” (Press Journal 1998, p. 53-59), “Flat Panel Display 1999” (Nikkei Business Publications, 1998, p. 132-139), etc. A thin film device layer including a TFT was formed by a thin film transistor (hereinafter referred to as TFT) process. An example of a method for forming the thin film device layer will be described below.

First, a conductive film for forming the gate electrode 104 was formed over the insulating layer 103 formed over the first substrate 101 with the protective layer 102 interposed therebetween. For example, a molybdenum (Mo) film having a thickness of 100 nm was used as the conductive film. As a method for forming the molybdenum film, for example, a sputtering method was used. Then, the conductive film was formed on the gate electrode 104. The gate electrode 104 was formed by patterning using a general photolithography technique and etching technique. Next, a gate insulating film 105 was formed so as to cover the gate electrode 104. The gate insulating film 105 is formed of, for example, a silicon oxide (SiO ₂ ) layer or a stacked body of a silicon oxide (SiO ₂ ) layer and a silicon nitride (SiN _x ) layer by a plasma CVD method. Further, an amorphous silicon layer (thickness 30 nm to 100 nm) was continuously formed.

This amorphous silicon layer was irradiated with a XeCl excimer laser pulse having a wavelength of 308 nm and melted and recrystallized to produce a crystalline silicon layer (polysilicon layer). Using this polysilicon layer, a polysilicon layer 106 serving as a channel formation region was formed, and a polysilicon layer 107 consisting of an n ⁻ type doped region and a polysilicon layer 108 consisting of an n ⁺ type doped region were formed on both sides thereof. . Thus, the active region has an LDD (Lightly Doped Drain) structure for achieving both a high on-current and a low off-current. A stopper layer 109 was formed on the polysilicon layer 106 to protect the channel when n ⁻ -type phosphorus ions were implanted. The stopper layer 109 is formed of, for example, a silicon oxide (SiO ₂ ) layer.

Further, a passivation film 110 made of a silicon oxide (SiO ₂ ) layer or a laminate of a silicon oxide (SiO ₂ ) layer and a silicon nitride (SiN _x ) layer was formed by plasma CVD. A source electrode 111 and a drain electrode 112 connected to each polysilicon layer 108 were formed on the passivation film 110. Each of the source electrode 111 and the drain electrode 112 is formed of a conductive material such as aluminum, an aluminum alloy, or a refractory metal.

  After forming each source electrode 111 and drain electrode 112, a color filter 113 was formed. The color filter 113 was formed by applying a color resist on the entire surface and then patterning with a lithography technique. A contact hole 113C is formed in the color filter 113 so that the source electrode 111 and a liquid crystal driving electrode to be formed later are connected. This color filter forming step was performed three times to form three colors of RGB (red, green, and blue). Next, a protective film 114 was formed for planarization. The protective film 114 is made of, for example, a polymethylmethacrylic acid resin. A contact hole 114C is formed in the protective film 114 so that the source electrode 111 and the liquid crystal driving electrode are connected. Thereafter, a pixel electrode 115 connected to the source electrode 111 was formed. The pixel electrode 115 is formed of a transparent electrode, for example. The transparent electrode is formed of indium tin oxide (ITO), for example, and a sputtering method is used as the formation method.

  Through the above steps, a transmissive active matrix substrate was fabricated on the first substrate 101. In addition, a bottom gate type polysilicon TFT is manufactured this time, but the same can be applied to a top gate type polysilicon TFT or an amorphous TFT.

  Next, a process of transferring the thin film device layer 121 on the first substrate 101 onto the plastic substrate will be described.

  As shown in FIG. 3 (1), the first bonding is performed while heating the protective layer 102, the insulating layer 103, and the thin film device layer 121 on the first substrate 101 to 80 ° C. to 140 ° C. with a hot plate 122. The agent 123 was applied to a thickness of about 1 mm, the second substrate 124 was placed on top, and cooled to room temperature while being pressurized. As the second substrate 124, for example, a molybdenum substrate having a thickness of 1 mm was used. Alternatively, a glass substrate may be used for the second substrate 124. Alternatively, the first adhesive 123 may be applied on the second substrate 124 and the thin film device layer 121 side of the first substrate 101 on which the thin film device layer 121 is formed from the protective layer 102 may be placed thereon. As the first adhesive 123, for example, a hot melt adhesive was used.

  Next, as shown in FIG. 3B, the first substrate 101 to which the second substrate 124 was attached was immersed in hydrofluoric acid (HF) 125, and the first substrate 101 was etched. This etching is automatically stopped at the protective layer 102 because the aluminum oxide layer which is the protective layer 102 is not etched by the hydrofluoric acid 125. As an example, the hydrofluoric acid 125 used here has a weight concentration of 50%, and this etching time was 3.5 hours. The concentration and etching time of the hydrofluoric acid 125 can be changed as long as the glass of the first substrate 101 can be completely etched.

  As a result of the etching with hydrofluoric acid 125, as shown in FIG. 4C, the first substrate 101 [see FIG. 3B] is completely etched, and the protective layer 102 is exposed.

Next, a mixed layer (for example, 72 wt% phosphoric acid (H ₃ PO ₄ ), ₃ wt% nitric acid (HNO ₃ ), and 10 wt% acetic acid (CH ₃ COOH)) is used to form the protective layer 102 (see FIG. 4 (3)). A molybdenum layer (thickness: 500 nm) was etched. This is because there is a problem if there is an opaque molybdenum layer in order to manufacture a transmissive liquid crystal panel. The time required to etch a 500 nm thick molybdenum layer with the mixed acid is about 1 minute. As a result of this etching, as shown in FIG. 4 (4), this mixed acid does not etch the silicon oxide that is the first insulating layer 103, so that the etching automatically stops at the first insulating layer 103.

Next, as shown in FIG. 4 (5), after the etching, a second adhesive layer 126 was formed on the back side of the thin film device layer 121, that is, on the surface of the insulating layer 103. For the second adhesive layer 126, for example, an ultraviolet curable adhesive mixed with a moisture absorbent 127 was used. As the moisture absorbent 127, calcium oxide (CaO) was used. About 30 wt% of calcium oxide particles having a particle size of about 1 to 10 μm were mixed with the adhesive. The thickness of the adhesive is 10-15 μm. Therefore, this time, the hygroscopic agent 127 was mixed at 15 × 10 ⁻⁴ × 0.3 = 4.5 × 10 ⁻⁴ g / cm ² . Calcium oxide can chemically adsorb water by a reaction of CaO + H ₂ O → Ca (OH) ₂ . Due to the presence of the moisture absorbent 127, moisture that has permeated through the plastic substrate can be adsorbed here, and water does not penetrate into the thin film device layer 121, so that the life of the liquid crystal display device can be extended. This time, calcium oxide is used as the moisture absorbent 127, but silica gel (SiO _x ), calcium chloride (CaCl ₂ ), magnesium chloride (MgCl ₂ ), or the like may be used. As the coating method, spray coating is used this time, but other methods such as dip coating and spin coating may be used. Alternatively, calcium oxide may be sprayed after first applying the ultraviolet curing adhesive.

Subsequently, as shown in FIG. 5 (6), a third substrate 128 was attached to the second adhesive layer 126. For example, a polycarbonate film having a thickness of 0.2 mm was used for the third substrate 128. A barrier layer having a water vapor transmission rate of 0.1 g / m ² · day · atm (at 40 ° C. and 90% RH) is formed on this polycarbonate film. Thereafter, the second adhesive layer 126 was cured by irradiating ultraviolet rays.

  Next, the substrate is dipped in alcohol (not shown), and the first adhesive layer 123 (see FIG. 3 (1)) made of a hot-melt adhesive is melted to form the second substrate 124 (see FIG. 3 (1)). ))] Was removed. Next, heat treatment was performed at 80 ° C. for 1 hour. By this heat treatment, the portion of the UV curable adhesive that was not cured due to the calcium oxide particles present in the second adhesive layer 126 was cured. As a result, as shown in FIG. 5 (7), a thin film device (active substrate) 100 in which the thin film device layer 121 was placed on the third substrate 128 via the second adhesive layer 126 and the insulating layer 103 was obtained.

  In the above description, the hygroscopic agent 127 is mixed in the second adhesive layer 126. However, for example, a second adhesive layer in which an oxygen absorbing agent is mixed may be used. More preferably, the second adhesive layer 126 is a mixture of a hygroscopic agent and an oxygen absorbing agent. The oxygen absorber includes an oxygen absorber based on iron, titanium oxide containing oxygen defects, an oxygen absorber based on ascorbic acid, an oxygen absorber based on glycerin, and 1,2-glycol as the main agent. It is preferable to use an oxygen absorbing agent that has a sugar alcohol as a main ingredient. The hygroscopic agent and the oxygen absorbing agent have a particle size of 10 μm or less, for example, 1 μm to 10 μm, and accordingly, the thickness of the second adhesive layer 126 is thicker than the particle size of the hygroscopic agent and the oxygen absorbing agent, It is preferable to set it as 10 micrometers-15 micrometers.

  Next, an example of manufacturing the counter substrate will be described with reference to a schematic cross-sectional view of FIG.

As shown in FIG. 6, an insulating layer (for example, a hard coat layer) 132 is formed as a counter substrate 130 on a support substrate 131 made of a polycarbonate film having a thickness of 0.2 mm. The insulating layer 132 is mixed with a hygroscopic agent 133. As the hygroscopic agent 133, calcium oxide (CaO) was used as in the active substrate. About 30 wt% of calcium oxide particles having a particle size of about 1 to 10 μm were mixed with the adhesive. The insulating layer 132 is thicker than the hygroscopic agent 133 and has a thickness of 10 to 15 μm. The insulating layer 132 was cured by both ultraviolet curing and heat curing. Further, a barrier layer (not shown) having a water vapor transmission rate of 0.1 g / m ² · day · atm (at 40 ° C., 90% RH) is formed on the polycarbonate film. Further, a transparent electrode 134 is formed on the entire surface on the insulating layer 132 side. For example, ITO (indium tin oxide) was used for the transparent electrode 134. This ITO film was formed by sputtering, for example.

  Next, although not shown, an alignment film (for example, a polyimide film) is applied to the counter substrate 130 and the active substrate 100, and an alignment process is performed to perform a rubbing process.

  Next, as shown in FIG. 7, a sealant (not shown) was applied to the active substrate 100, and a number of spacers 135 were dispersed on the counter substrate 130.

Then, after the active substrate 100 and the counter substrate 130 were bonded together, the sealing agent was cured by irradiating with ultraviolet rays while being pressurized at, for example, 1 kg / cm ² . Next, after cutting into the size of the panel by laser processing, liquid crystal was injected from the injection port, the injection port was covered with a mold resin, and the mold resin was cured to produce a liquid crystal display device.

  In the liquid crystal display device, the counter substrate 130 described with reference to FIG. 6 is used. However, as shown in FIG. 8, in the liquid crystal display device shown in FIG. 7, the insulating layer 132 of the counter substrate 130 contains a hygroscopic agent. It is also possible to use those that are not. Note that it is more preferable that the insulating layer 132 of the counter substrate 130 includes the moisture absorbent 133.

In the first embodiment, since the second adhesive layer 126 and the insulating layer 132 containing the hygroscopic agents 127 and 133 are located near the liquid crystal layer, the resistance to water is increased and the life of the liquid crystal display device is improved. In this example, a hygroscopic agent of about 4.5 × 10 ⁻⁴ g / cm ² was used as the hygroscopic agent, but the calcium oxide used this time can absorb about 30% of its own water. Therefore, water of about 4.5 × 10 ⁻⁴ × 0.3 = 1.4 × 10 ⁻⁴ g / cm ² can be absorbed. Assuming that the water vapor transmission rate of the plastic substrate is 0.1 g / m ² · day · atm, it is assumed that diffusion is sufficiently fast at 40 ° C. and 90% RH and that the barrier performance is rate-limiting. 1.4 × 10 ⁻⁴ /(0.1×10 ⁻⁴ ) = 14 days (336 hours), which is (336 + 84) / 84 = 5 times longer than 84 hours when nothing is done.

  A second embodiment of the thin film device manufacturing method and the thin film device and the liquid crystal display device of the present invention will be described with reference to the manufacturing process sectional views of FIGS. In the second example, an active substrate for reflective liquid crystal was produced on a plastic substrate.

  First, a method for forming a thin film device layer will be described with reference to FIG. As shown in FIG. 9, an amorphous silicon layer 202 is formed on the first substrate 201. As the first substrate 101, a glass substrate having a thickness of about 0.4 mm to 1.1 mm, for example, 0.7 mm is used. A quartz substrate may be used instead of the glass substrate. The film thickness of the amorphous silicon layer 202 is 50 nm, for example. If this film thickness is 10 nm to 1 μm, there is no problem. A plasma CVD method was used as a method for forming the amorphous silicon layer 202. In the plasma CVD method, a low temperature is desirable so that the amorphous silicon layer 202 contains a large amount of hydrogen and as long as the thin film device layer is not peeled off during manufacturing. This time, the film was formed at 150 ° C. There is no problem even if the amorphous silicon layer 202 is formed by low pressure CVD, atmospheric pressure plasma CVD, ECR, or sputtering.

  Next, a protective insulating layer 203 is formed over the amorphous silicon layer 202. The protective insulating layer 203 is formed with a thickness of 100 nm, for example. The protective insulating layer 203 can be formed by a plasma CVD method, for example.

  Thereafter, general low-temperature polysilicon technology such as “2003 FPD Technology Encyclopedia” (published on March 25, 2003, p.166-183 and p.198-201), “'99 latest liquid crystal process technology” ( Press Journal 1998, p. 53-59), “Flat Panel Display 1999” (Nikkei BP, 1998, p. 132-139), etc. A thin film device layer including a TFT was formed by a process (hereinafter referred to as TFT). An example of a method for forming the thin film device layer will be described below.

First, a conductive film for forming the gate electrode 204 was formed over the protective insulating layer 203 formed over the first substrate 201 with the amorphous silicon layer 202 interposed therebetween. For example, a molybdenum (Mo) film having a thickness of 100 nm was used as the conductive film. As a method for forming the molybdenum film, for example, a sputtering method was used. Then, the conductive film was formed on the gate electrode 204. The gate electrode 204 was formed by patterning using a general photolithography technique and etching technique. Next, a gate insulating film 205 was formed so as to cover the gate electrode 204. The gate insulating film 205 is formed of a silicon oxide (SiO ₂ ) layer or a stacked body of a silicon oxide (SiO ₂ ) layer and a silicon nitride (SiN _x ) layer, for example, by plasma CVD. Further, an amorphous silicon layer (thickness 30 nm to 100 nm) was continuously formed.

This amorphous silicon layer was irradiated with a XeCl excimer laser pulse having a wavelength of 308 nm and melted and recrystallized to produce a crystalline silicon layer (polysilicon layer). Using this polysilicon layer, a polysilicon layer 206 serving as a channel formation region was formed, and a polysilicon layer 207 composed of an n ⁻ type doped region and a polysilicon layer 208 composed of an n ⁺ type doped region were formed on both sides thereof. . Thus, the active region has an LDD (Lightly Doped Drain) structure for achieving both a high on-current and a low off-current. A stopper layer 209 is formed on the polysilicon layer 206 to protect the channel when n ⁻ type phosphorus ions are implanted. The stopper layer 209 is formed of a silicon oxide (SiO ₂ ) layer, for example.

Further, a passivation film 210 made of a silicon oxide (SiO ₂ ) layer or a laminate of a silicon oxide (SiO ₂ ) layer and a silicon nitride (SiN _x ) layer was formed by plasma CVD. A source electrode 211 and a drain electrode 212 connected to each polysilicon layer 208 were formed on the passivation film 210. Each of the source electrode 211 and the drain electrode 212 is formed of a conductive material such as aluminum, an aluminum alloy, or a refractory metal.

  After forming the source electrode 211 and the drain electrode 212, a protective layer 213 was formed to protect the element and to perform planarization. The protective layer 213 is formed of, for example, a polymethyl methacrylic resin material. The protective layer 213 is formed so that the surface of the protective layer 213 is uneven so that the surface of the reflective layer formed on the protective layer 213 is uneven in the next step. Next, a contact hole 213C was formed by a normal contact hole forming technique so that the source electrode 211 and a liquid crystal driving electrode formed later were connected to the protective film 213. Thereafter, a reflective layer 214 was formed on the surface of the protective layer 213 and the inner surface of the contact hole 213C. The reflective layer 214 was formed by depositing silver (Ag) by sputtering, for example.

  After forming the reflective layer 214, a color filter 215 was formed. This was formed by applying a color resist on the entire surface and then patterning with a lithography technique. Next, a contact hole 215 </ b> C was formed so that the source electrode 211 and a liquid crystal driving electrode to be formed later were connected to the color filter 215. This color filter forming step was performed three times to form three colors of RGB (red, green, and blue).

  Thereafter, pixel electrodes 216 were formed on the surface of the color filter 215 and the inner surface of the contact hole 215C. The pixel electrode 216 is formed by depositing, for example, indium tin oxide (ITO) by sputtering, for example. Accordingly, the pixel electrode 216 is formed to be connected to the source electrode 211.

  Through the above steps, an active matrix substrate was produced on the first substrate 201 made of a glass substrate. In addition, a bottom gate type polysilicon TFT is manufactured this time, but the same can be applied to a top gate type polysilicon TFT or an amorphous TFT.

  Next, a process of transferring the thin film device layer on the first substrate 201 onto the plastic substrate will be described.

  As shown in FIG. 10A, the second substrate 223 is formed on the thin film device layer 221 formed on the first substrate 201 via the amorphous silicon layer 202 and the protective insulating layer 203 via the first adhesive 222. Paste. As the second substrate 223, for example, a molybdenum substrate having a thickness of 1 mm was used. Alternatively, a glass substrate may be used for the second substrate 223. Alternatively, the first adhesive 222 may be formed on the second substrate 223, and the thin film device layer 221 side of the first substrate 201 on which the amorphous silicon layer 202 to the thin film device layer 221 are formed may be placed. . For the first adhesive 222, for example, a hot melt adhesive was used.

  Next, xenon chlorine (XeCl) excimer laser light was irradiated from the first substrate 201 side made of a glass substrate. Since glass transmits the excimer laser light, the laser light is absorbed by the amorphous silicon layer 202. When the amorphous silicon layer 202 absorbs ultraviolet rays, hydrogen is generated, and the thin film device layer 221 and the first substrate 201 are separated from each other with the amorphous silicon layer 202 as a boundary. Details of this technique are disclosed in Japanese Patent Laid-Open No. 10-125930. As a result, as shown in FIG. 10B, the protective insulating layer 203 was exposed.

Next, as illustrated in FIG. 10C, the second adhesive layer 224 was formed on the protective insulating layer 203. The second adhesive layer 224 is formed, for example, by applying an ultraviolet curable adhesive in which a hygroscopic agent 225 and an oxygen absorbing agent 226 are mixed. As a coating method, spray coating, dip coating or spin coating can be used. This time, calcium oxide (CaO) was used as the moisture absorbent 225, and iron (Fe) was used as the oxygen absorbent 226. In both cases, the particle size was about 1 μm to 10 μm, and the calcium oxide particles were mixed in the adhesive with about 30 wt%, and the iron particles were mixed in about 10 wt%. The presence of the hygroscopic agent 225 and the oxygen absorbing agent 226 can adsorb moisture and oxygen that have permeated through the plastic substrate here, and water does not permeate the thin film device layer 221, thereby extending the life of the liquid crystal. it can. Although calcium oxide is used as the moisture absorbent 225 this time, silica gel (SiO), calcium chloride (CaCl ₂ ), magnesium chloride (MgCl ₂ ), or the like is preferably used. Further, as the oxygen absorber 226, in addition to iron, an oxygen absorber mainly composed of titanium oxide containing oxygen defects, an oxygen absorber based on ascorbic acid, an oxygen absorber based on glycerin, 1, 2, -It is preferable to use an oxygen-absorbing agent mainly composed of glycol and an oxygen-absorbing agent mainly composed of sugar alcohol. In addition, spray coating is used as the coating method this time, but other methods such as dip coating and spin coating may be used. Further, after the second adhesive layer 224 is applied first, a hygroscopic agent and an oxygen absorbing agent may be sprayed. The hygroscopic agent 225 and the oxygen absorbing agent 226 have a particle size of 10 μm or less, for example, 1 μm to 10 μm. Accordingly, the thickness of the second adhesive layer 224 is the same as that of the hygroscopic agent and the oxygen absorbing agent. It is preferably 10 μm to 15 μm thicker than the diameter.

Subsequently, as shown in FIG. 11 (4), a third substrate 227 was attached to the second adhesive layer 224. The third substrate 227 is made of, for example, a polycarbonate film having a thickness of 0.2 mm. After the third substrate 227 was attached, the second adhesive layer 224 was cured by irradiating with ultraviolet rays. The polycarbonate film has a barrier layer (not shown) having a water vapor transmission rate of 0.1 g / m ² · day · atm (at 40 ° C., 90% RH) and an oxygen transmission rate of 0.1 cc / m ² · day · atm. Z).

Next, the substrate is dipped in alcohol (not shown), and the first adhesive layer 222 (see FIG. 10 (1)) made of hot melt adhesive is melted to form the second substrate 223 (see FIG. 10 (1)). ))] Was removed. Next, heat treatment was performed at 80 ° C. for 1 hour. By this heat treatment, the portion of the UV curable adhesive that was not cured due to the calcium oxide particles present in the second adhesive layer 224 was cured. As a result, as shown in FIG. 11 (5), the thin film device layer 221 is exposed, and the thin film device layer 221 is placed on the third substrate 227 via the second adhesive layer 224 and the protective insulating layer 203 ( Active substrate) 200 was obtained.
100 was obtained.

Next, a general assembly process for a liquid crystal display device may be performed. For example, as shown in FIG. 6, the counter substrate 130 is formed. Thereafter, although not shown, an alignment film (for example, a polyimide film) is applied to the counter substrate 130 and the active substrate 200, and an alignment process for performing a rubbing process is performed. Next, a sealant (not shown) was applied to the active substrate 200, and a number of spacers (not shown) were dispersed on the counter substrate 130. Then, after the active substrate 200 and the counter substrate 130 were bonded together, the sealing agent was cured by irradiating ultraviolet rays while applying pressure, for example, at 1 kg / cm ² . Next, after cutting into the size of the panel by laser processing, liquid crystal was injected from the injection port, the injection port was covered with a mold resin, and the mold resin was cured to produce a liquid crystal display panel.

  In the second embodiment, since the second adhesive layer 224 containing a hygroscopic agent is near the liquid crystal layer, the resistance to water is increased, and the life of the liquid crystal display device is improved. Further, in the second embodiment, since oxygen absorbing agent is mixed in addition to the hygroscopic agent, resistance to oxygen is improved as compared with the first embodiment.

  One embodiment of the method for manufacturing a thin film device, the thin film device and the electroluminescence display device of the present invention will be described with reference to the manufacturing process sectional views of FIGS. In this example, an active matrix substrate was produced on a plastic substrate by a transfer method to produce an active matrix organic electroluminescence (hereinafter abbreviated as EL) display.

First, a method for forming a thin film device layer will be described with reference to FIG. As shown in FIG. 12, a protective layer 102 of the first substrate 101 is formed on a first substrate 301 to be a manufacturing substrate at the time of etching using hydrofluoric acid to be performed later. As the first substrate 101, a glass substrate having a thickness of about 0.4 mm to 1.1 mm, for example, 0.7 mm is used. A quartz substrate may be used instead of the glass substrate. The protective layer 102 is formed using a material that can withstand hydrofluoric acid. For example, a molybdenum (Mo) layer is used, and the protective layer 102 is formed to a thickness of, for example, 500 nm. Although the thickness of the molybdenum layer is 500 nm this time, there is no problem even if the thickness is appropriately changed as long as it can withstand hydrofluoric acid. The protective layer 102 can be formed by sputtering, for example. Thereafter, the insulating layer 103 is formed. The insulating layer 103 is formed, for example, by forming a silicon oxide (SiO ₂ ) film to a thickness of 500 nm. The insulating layer 103 can be formed by, for example, a plasma CVD method.

  That is, general low-temperature polysilicon technology, for example, “2003 FPD Technology Encyclopedia” (published on March 25, 2003, p.166-183 and p.198-201), “'99 latest liquid crystal process technology” ( Press Journal 1998, p. 53-59), “Flat Panel Display 1999” (Nikkei BP, 1998, p. 132-139), etc. A thin film device layer including a TFT was formed by a process (hereinafter referred to as TFT). An example of a method for forming the thin film device layer will be described below.

First, a conductive film for forming the gate electrode 304 was formed over the first substrate 301. For example, a molybdenum (Mo) film having a thickness of 100 nm was used as the conductive film. As a method for forming the molybdenum film, for example, a sputtering method was used. Then, the conductive film was processed to form a gate electrode 304. The gate electrode 304 was formed by patterning using a general photolithography technique and etching technique. Next, a gate insulating film 305 was formed so as to cover the gate electrode 304. The gate insulating film 305 is formed of a silicon oxide (SiO ₂ ) layer or a stacked body of a silicon oxide (SiO ₂ ) layer and a silicon nitride (SiN _x ) layer, for example, by plasma CVD. Further, an amorphous silicon layer (thickness 30 nm to 100 nm) was continuously formed.

This amorphous silicon layer was irradiated with a XeCl excimer laser pulse having a wavelength of 308 nm, melted and recrystallized to produce a crystalline silicon layer. Using this polysilicon layer, a polysilicon layer 306 serving as a channel formation region was formed, and a polysilicon layer 307 composed of an n ⁻ type doped region and a polysilicon layer 308 composed of an n ⁺ type doped region were formed on both sides thereof. . Thus, the active region has an LDD (Lightly Doped Drain) structure for achieving both a high on-current and a low off-current. A stopper layer 309 is formed on the polysilicon layer 306 to protect the channel when n ⁻ type phosphorus ions are implanted. The stopper layer 309 is formed of, for example, a silicon oxide (SiO ₂ ) layer.

Further, a passivation film 310 made of a silicon oxide (SiO ₂ ) layer or a laminate of a silicon oxide (SiO ₂ ) layer and a silicon nitride (SiN _x ) layer was formed by plasma CVD. A source electrode 311 and a drain electrode 312 connected to each polysilicon layer 308 were formed on the passivation film 310. Each source electrode 311 and drain electrode 312 is made of, for example, aluminum.

  In this way, a thin film transistor (TFT) was formed by a low temperature polysilicon bottom gate type thin film transistor (TFT) process.

  Next, after forming a protective insulating layer 313 with, for example, a methyl methacrylate resin-based resin on the passivation film 310 so as to cover the source electrode 311, the drain electrode 312, and the like by, for example, spin coating, a general photolithography technique is used. Then, the protective insulating layer 313 was removed so that the source electrode 311 and the anode electrode of the organic EL element to be formed later could be connected by etching technique.

  Next, an organic EL element was formed over the protective insulating layer 313. The organic EL element includes an anode electrode 314, an organic layer, and a cathode electrode 317. The anode electrode 314 is formed, for example, by depositing chromium (Cr) by sputtering, and is connected to the source electrode 311 of each TFT so that an electric current can flow individually.

  The organic layer has a structure in which an organic hole transport layer 315 and an organic light emitting layer 316 are laminated. As the organic hole transport layer 315, for example, copper phthalocyanine was formed to a thickness of 30 nm by vapor deposition. The organic light emitting layer 316 is green, Alq3 [tris (8-quinolinolato) aluminum (III)] is 50 nm thick, and blue is bathocuproine (2,9-dimethyl-4,7-diphenyl-1, 10phenanthroline) to a thickness of 14 nm and red as BSB-BCN [2,5-bis {4- (N-methoxyphenyl-N-phenylamino) styryl} benzene-1,4-dicarbonitrile] to a thickness of 30 nm. did.

As the cathode electrode 317, indium tin oxide (In ₂ O ₃ + SnO ₂ : ITO) was used.

  This time, the above structure was used as an organic EL element, but an electrode was combined with an electron transport layer, a hole transport layer, an electron injection layer, a hole injection layer, an electron blocking layer, a hole blocking layer, and a light emitting layer. A known structure may be used.

Further, a passivation film 318 was formed so as to cover the cathode electrode 317. This time, as the passivation film 318, a silicon nitride (SiN _x ) film having a thickness of, for example, 200 nm is formed by sputtering. Alternatively, the passivation film 318 may be formed by a CVD method, a vapor deposition method, or the like.

  Hereinafter, the TFT layer to the organic EL layer are referred to as a thin film device layer. Next, a process of transferring the thin film device layer on the first substrate 301 onto the plastic substrate is shown.

  As shown in FIG. 13 (1), the first adhesive layer 323 is formed, for example, as a hot melt adhesive while heating a thin film device layer 321 formed on the first substrate 301 to 80 ° C. to 140 ° C. with a hot plate 322. For example, applied to a thickness of about 1 mm. Next, the second substrate 324 was placed on the first adhesive layer 323, and the second substrate 324 was cooled to room temperature while being pressed toward the first substrate 301. As the second substrate 324, for example, a molybdenum (Mo) substrate having a thickness of 1 mm was used. Alternatively, a hot melt adhesive may be applied on the second substrate 324, and the thin film device layer 321 side of the first substrate 301 on which the thin film device layer 321 is formed may be placed.

  Next, as shown in FIG. 13B, the first substrate 301 to which the second substrate 324 was attached was immersed in hydrofluoric acid 325, and the first substrate 301 was etched. This etching is automatically stopped at the protective layer 302 because the aluminum oxide layer which is the protective layer 302 is not etched by the hydrofluoric acid 325. As an example, the hydrofluoric acid 325 used here has a weight concentration of 50%, and this etching time was 3.5 hours. There is no problem even if the concentration of hydrofluoric acid 325 and the etching time are changed as long as the glass of the first substrate 301 can be completely etched.

  As a result of the etching with hydrofluoric acid 325, as shown in FIG. 14 (3), the first substrate 301 [see FIG. 13 (2)] is completely etched, and the protective layer 302 is exposed.

Next, with a mixed acid [for example, phosphoric acid (H ₃ PO ₄ ) 72 wt%, nitric acid (HNO ₃ ) 3 wt% and acetic acid (CH ₃ COOH) 10 wt%], the protective layer 302 [see FIG. A molybdenum layer (thickness: 500 nm) was etched. The time required to etch a 500 nm thick molybdenum layer with the mixed acid is about 1 minute. As a result of this etching, as shown in FIG. 14 (4), this mixed acid does not etch the silicon oxide that is the first insulating layer 303, so that the etching automatically stops at the first insulating layer 303.

Next, as shown in FIG. 14 (5), after the etching, a second adhesive layer 326 was formed on the back side of the thin film device layer 321, that is, on the surface of the insulating layer 303. For the second adhesive layer 326, for example, an ultraviolet curable adhesive mixed with a hygroscopic agent 327 was used. Silica gel (SiO _x ) was used as the moisture absorbent 327. About 30 wt% of silica gel particles having a particle size of about 1 to 10 μm were mixed with the adhesive. The thickness of the adhesive is 10-15 μm. By the presence of the moisture absorbent 327, moisture that has permeated through the plastic substrate can be adsorbed here, and water does not permeate the thin film device layer 321, so that the lifetime of the organic EL element can be extended. This time, silica gel (SiO _x ) was used as a moisture absorbent, but calcium oxide, calcium chloride (CaCl ₂ ), or the like may be used. As the coating method, spray coating is used this time, but other methods such as dip coating and spin coating may be used. Alternatively, calcium oxide may be sprayed after first applying the ultraviolet curing adhesive.

Subsequently, as shown in FIG. 15 (6), a third substrate 328 was attached to the second adhesive layer 326. For the third substrate 328, for example, a polycarbonate film having a thickness of 0.2 mm was used. On this polycarbonate film, a barrier layer (not shown) having a water vapor transmission rate of 0.1 g / m ² · day · atm (at 40 ° C., 90% RH) is formed. Thereafter, the second adhesive layer 326 was cured by irradiating with ultraviolet rays.

  Next, the substrate is dipped in alcohol (not shown), and the first adhesive layer 323 (see FIG. 13 (1)) made of a hot melt adhesive is melted to dissolve the second substrate 324 [see FIG. 13 (1). ))] Was removed. Next, heat treatment was performed at 80 ° C. for 1 hour. By this heat treatment, the portion of the UV curable adhesive that was not cured due to the calcium oxide particles present in the second adhesive layer 326 was cured. As a result, as shown in FIG. 15 (7), a thin film device (active substrate) 300 was obtained in which the thin film device layer 321 was placed on the third substrate 328 via the second adhesive layer 326 and the insulating layer 303.

  Thereafter, although not shown in the drawing, it may be carried out in a generally assembled process of an organic electroluminescence display device.

  In the above description, the hygroscopic agent 327 is mixed in the second adhesive layer 326. However, for example, a second adhesive layer in which an oxygen absorbing agent is mixed may be used. More preferably, the second adhesive layer 326 is a mixture of a hygroscopic agent and an oxygen absorbing agent. The oxygen absorber includes an oxygen absorber based on iron, titanium oxide containing oxygen defects, an oxygen absorber based on ascorbic acid, an oxygen absorber based on glycerin, and 1,2-glycol as the main agent. It is preferable to use an oxygen absorbing agent that has a sugar alcohol as a main ingredient. The hygroscopic agent and the oxygen absorbing agent have a particle size of 10 μm or less, for example, 1 μm to 10 μm, and accordingly the thickness of the second adhesive layer 326 is thicker than the particle size of the hygroscopic agent and the oxygen absorbing agent, It is preferable to set it as 10 micrometers-15 micrometers.

  In the third embodiment, since the second adhesive layer 326 including the hygroscopic agent 327 is near the organic EL layer, the resistance to water can be improved. Furthermore, oxygen resistance can also be improved by mixing an oxygen absorbing agent in the second adhesive layer 326. Therefore, the lifetime of the organic EL element can be extended.

  The display device substrate, thin film device manufacturing method, thin film device, liquid crystal display device, and electroluminescence display device of the present invention are applied to display devices such as liquid crystal display devices and organic electroluminescence display devices using plastic substrates. Is preferred.

It is a schematic structure sectional view explaining a substrate of a display device of the present invention. It is manufacturing process sectional drawing which shows 1st Example which concerns on the manufacturing method of a thin film device of this invention, a thin film device, and a liquid crystal display device. It is manufacturing process sectional drawing which shows 1st Example which concerns on the manufacturing method of a thin film device of this invention, a thin film device, and a liquid crystal display device. It is manufacturing process sectional drawing which shows 1st Example which concerns on the manufacturing method of a thin film device of this invention, a thin film device, and a liquid crystal display device. It is manufacturing process sectional drawing which shows 1st Example which concerns on the manufacturing method of a thin film device of this invention, a thin film device, and a liquid crystal display device. It is manufacturing process sectional drawing which shows 1st Example which concerns on the manufacturing method of a thin film device of this invention, a thin film device, and a liquid crystal display device. It is manufacturing process sectional drawing which shows 1st Example which concerns on the manufacturing method of a thin film device of this invention, a thin film device, and a liquid crystal display device. It is manufacturing process sectional drawing which shows 1st Example which concerns on the manufacturing method of a thin film device of this invention, a thin film device, and a liquid crystal display device. It is manufacturing process sectional drawing which shows 2nd Example which concerns on the manufacturing method of a thin film device of this invention, a thin film device, and a liquid crystal display device. It is manufacturing process sectional drawing which shows 2nd Example which concerns on the manufacturing method of a thin film device of this invention, a thin film device, and a liquid crystal display device. It is manufacturing process sectional drawing which shows 2nd Example which concerns on the manufacturing method of a thin film device of this invention, a thin film device, and a liquid crystal display device. It is manufacturing process sectional drawing which shows one Example which concerns on the manufacturing method of the thin film device of this invention, a thin film device, and an electroluminescent display apparatus. It is manufacturing process sectional drawing which shows one Example which concerns on the manufacturing method of the thin film device of this invention, a thin film device, and an electroluminescent display apparatus. It is manufacturing process sectional drawing which shows one Example which concerns on the manufacturing method of the thin film device of this invention, a thin film device, and an electroluminescent display apparatus. It is manufacturing process sectional drawing which shows one Example which concerns on the manufacturing method of the thin film device of this invention, a thin film device, and an electroluminescent display apparatus.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 11 ... Support substrate, 12 ... Adhesive layer, 13 ... Hygroscopic agent, 14 ... Thin film layer, 21 ... Support substrate, 22 ... Insulating layer, 23 ... Hygroscopic agent, 24 ... Electrode layer

Claims (14)

In the substrate of the display device in which the support substrate and the thin film layer are bonded by the adhesive layer,
A substrate for a display device, wherein the adhesive layer contains a hygroscopic agent. In the substrate of the display device in which the support substrate and the thin film layer are bonded by the adhesive layer,
An oxygen absorbing agent is included in the adhesive layer. A substrate of a display device. In the substrate of the display device in which the support substrate and the thin film layer are bonded by the adhesive layer,
A substrate of a display device, wherein the adhesive layer contains a hygroscopic agent and an oxygen absorbing agent. In the substrate of the display device in which the support substrate and the electrode layer are formed via the insulating layer,
A substrate of a display device, wherein the insulating layer contains a hygroscopic agent. In the substrate of the display device in which the support substrate and the electrode layer are formed via the insulating layer,
An oxygen absorbing agent is included in the insulating layer. A substrate of a display device. In the substrate of the display device in which the support substrate and the electrode layer are formed via the insulating layer,
A substrate of a display device, wherein the insulating layer includes a hygroscopic agent and an oxygen absorbing agent. Bonding a second substrate to the thin film device layer via the first adhesive layer or the coating layer and the first adhesive layer after forming the thin film device layer on the first substrate;
Separating or removing the first substrate completely or partially by a process including at least one of chemical treatment, mechanical polishing treatment, and ultraviolet irradiation treatment;
Bonding the first substrate left or partially left of the first substrate of the thin film device layer to a third substrate via a second adhesive layer;
A method of manufacturing a thin film device comprising: separating or removing the second substrate;
A method of manufacturing a thin film device, wherein the second adhesive layer includes one or both of a hygroscopic agent that absorbs moisture and an oxygen absorbing agent that adsorbs oxygen. Bonding a second substrate to the thin film device layer via the first adhesive layer or the coating layer and the first adhesive layer after forming the thin film device layer on the first substrate;
Separating or removing the first substrate completely or partially by a process including at least one of chemical treatment, mechanical polishing treatment, and ultraviolet irradiation treatment;
Bonding the first substrate left or partially left of the first substrate of the thin film device layer to a third substrate via a second adhesive layer;
In the thin film device manufactured by separating or removing the second substrate,
The thin film device, wherein the second adhesive layer contains one or both of a moisture absorbent that absorbs moisture and an oxygen absorbent that absorbs oxygen. A first substrate attached to the first thin film layer with an adhesive layer;
A second substrate provided opposite to the first substrate and having a second thin film layer formed through an insulating layer;
In a liquid crystal display device having a liquid crystal layer sealed between the first substrate and the second substrate in which the first thin film layer side and the second thin film layer side are opposed to each other,
The liquid crystal display device, wherein the adhesive layer includes at least one of a hygroscopic agent and an oxygen absorbing agent. A first substrate attached to the first thin film layer with an adhesive layer;
A second substrate provided opposite to the first substrate and having a second thin film layer formed through an insulating layer;
In a liquid crystal display device having a liquid crystal layer sealed between the first substrate and the second substrate in which the first thin film layer side and the second thin film layer side are opposed to each other,
The liquid crystal display device, wherein the insulating layer includes at least one of a hygroscopic agent and an oxygen absorbing agent. A first substrate attached to the first thin film layer with an adhesive layer;
A second substrate provided opposite to the first substrate and having a second thin film layer formed through an insulating layer;
In a liquid crystal display device having a liquid crystal layer sealed between the first substrate and the second substrate in which the first thin film layer side and the second thin film layer side are opposed to each other,
Including at least one of a hygroscopic agent and an oxygen absorbing agent in the adhesive layer,
The liquid crystal display device, wherein the insulating layer includes at least one of a hygroscopic agent and an oxygen absorbing agent. Forming a thin film device layer on the first substrate and then bonding the second substrate on the thin film device layer via the first adhesive layer or the coating layer and the first adhesive layer;
Separating or removing the first substrate completely or partially by a process including at least one of chemical treatment, mechanical polishing treatment, and ultraviolet irradiation treatment;
Bonding the first substrate left or partially left of the first substrate of the thin film device layer to a third substrate via a second adhesive layer;
In a liquid crystal display device using a thin film device manufactured by separating or removing the second substrate,
The liquid crystal display device, wherein the second adhesive layer includes one or both of a moisture absorbing agent that absorbs moisture and an oxygen absorbing agent that absorbs oxygen. In the electroluminescence display device in which the thin film layer including the light emitting layer and the support substrate are attached by the adhesive layer,
The electroluminescent display device, wherein the adhesive layer includes one or both of a moisture absorbing agent that absorbs moisture and an oxygen absorbing agent that absorbs oxygen. Forming a thin film device layer on the first substrate and then bonding the second substrate on the thin film device layer via the first adhesive layer or the coating layer and the first adhesive layer;
Separating or removing the first substrate completely or partially by a process including at least one of chemical treatment, mechanical polishing treatment, and ultraviolet irradiation treatment;
Bonding the first substrate left or partially left of the first substrate of the thin film device layer to a third substrate via a second adhesive layer;
In an electroluminescence display device using a thin film device manufactured by separating or removing the second substrate,
The electroluminescent display device, wherein the second adhesive layer includes one or both of a moisture absorbent that absorbs moisture and an oxygen absorbent that absorbs oxygen.

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