Semiconductor device

Abstract

To provide an element which is made into a thin film and lightweight, a semiconductor device, a display device and a light-emitting apparatus, provide an element which is hard to be damaged, a semiconductor device, a display device and a light-emitting apparatus, and provide an element having flexibility, a semiconductor device, a display device and a light-emitting apparatus.SOLUTION: Provided are: an element having a substrate, a first resin layer which is formed in contact with the substrate, a second resin layer which is formed in contact with the first resin layer, and a first layer which is formed in contact with the second resin layer, wherein the second resin layer is configured by containing a polyimide resin as a main component, and on an interface between the first resin layer and the second resin layer, a substance is detected which ranges from 300 or more and 950 or less in a mass-to-charge ratio in LC / MS (liquid chromatography mass spectrometry) measurement; a semiconductor device using the element; a display device; and a light-emitting apparatus.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] One embodiment of the present invention is an element, a semiconductor device, a display device, a peeling method, and a manufacturing method of an element-display device. Regarding the law.

[0002] Note that one embodiment of the present invention is not limited to the above technical field. The technical field of one aspect relates to an article, a method, or a manufacturing method. One aspect of the present invention is a process, machine, manufacture, or composition. Therefore, the present invention more specifically disclosed herein The technical field of one embodiment of the present invention is a semiconductor device, a display device, a liquid crystal display device, a light-emitting device, a lighting device, etc. As examples of the present invention, the present invention relates to a device, a power storage device, a storage device, a driving method thereof, or a manufacturing method thereof. Some examples include: [Background technology]

[0003] By laminating and processing various thin films on a glass substrate, semiconductor elements and surface Glass is highly heat resistant and has high rigidity, making it suitable for a variety of applications. It is possible to fabricate elements on the substrate, and elements fabricated on a glass substrate are It is also widely used in displays.

[0004] On the other hand, a glass substrate with sufficient rigidity needs to be thick and large. The weight of the glass increases and it becomes difficult to handle. Glass is also fragile and vulnerable to impacts. Therefore, it is also prone to damage.

[0005] Therefore, semiconductor devices and display devices using resin substrates that are light and not easily damaged are attracting attention. be.

[0006] However, resins are generally sensitive to heat and cannot withstand the heat applied to fabricate high-performance elements. In addition, they are prone to bending, expansion, and contraction, making them difficult to machine with high precision. There is also the problem that it is difficult to do so.

[0007] By the way, in the semiconductor device and the display device using a resin substrate, the substrate has flexibility. By using materials such as these, it is possible to give the material a curved surface or change its shape. This is a feature that is difficult to achieve in devices that use hard and brittle glass substrates.

[0008] Such semiconductor devices and display devices are expected to be used in a variety of applications. Reference 1 describes a possible application of organic EL (Electroluminescence) elements. A flexible light emitting device is disclosed. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] JP 2014-197522 A Summary of the Invention [Problem to be solved by the invention]

[0010] One embodiment of the present invention is a thin and lightweight element, a semiconductor device, a display device, and a light-emitting device. Another object of the present invention is to provide an element, a semiconductor device, and a semiconductor device that are not easily damaged. It is an object of the present invention to provide a semiconductor device, a display device, and a light-emitting device. According to one embodiment of the present invention, there is provided a flexible element, a flexible semiconductor device, a flexible display device, and a flexible light-emitting device, The objective is to provide

[0011] One aspect of the present invention is to provide a thin, lightweight, and inexpensive element, semiconductor device, display device, and light-emitting device. Another object of the present invention is to provide an optical device that is less likely to be damaged. The present invention aims to provide an inexpensive element, a semiconductor device, a display device, and a light-emitting device. Another embodiment of the present invention is a flexible and inexpensive element, semiconductor device, display device, and It is an object of the present invention to provide a light emitting device.

[0012] One embodiment of the present invention is a thin and lightweight element, a semiconductor device, a display device, and a light-emitting device. Another object of the present invention is to provide a method for manufacturing the same. The present invention aims to provide a method for manufacturing a semiconductor device, a display device, and a light-emitting device. Another embodiment of the present invention is a flexible element, a flexible semiconductor device, a flexible display device, and It is an object of the present invention to provide a method for manufacturing a light emitting device.

[0013] One aspect of the present invention is to provide a thin, lightweight, and inexpensive element, semiconductor device, display device, and light-emitting device. Another object of the present invention is to provide a method for manufacturing an optical device. To provide a method for manufacturing a damage-resistant and inexpensive element, a semiconductor device, a display device, and a light-emitting device, respectively. Another object of the present invention is to provide a flexible and inexpensive element, It is an object of the present invention to provide methods for manufacturing a semiconductor device, a display device, and a light-emitting device.

[0014] Note that the description of these problems does not preclude the existence of other problems. However, it is not necessary to solve all of these problems. It is possible to extract other issues from the description in the section. [Means for solving the problem]

[0015] One aspect of the present invention is a substrate, a first resin layer formed in contact with the substrate, and a substrate for forming a first resin layer on the first resin layer. A second resin layer formed in contact with the oil layer, and a first layer formed in contact with the second resin layer. The second resin layer is mainly composed of a polyimide resin, and the first resin layer is At the interface between the resin layer and the second resin layer, LC / MS (liquid chromatography mass spectrometry) was performed. ) A device that detects substances with a mass-to-charge ratio of 300 or more and 950 or less in the measurement. do.

[0016] In addition, another aspect of the present invention is a method for detecting a mass-to-charge ratio in the LC-MS measurement. This is an element that detects substances with a ratio of 350 or more and 900 or less.

[0017] In addition, another aspect of the present invention is a method for detecting a mass-to-charge ratio in the LC-MS measurement. An element in which 5 or more, preferably 10 or more, substances having a ratio of 300 to 950 are detected It is.

[0018] In addition, another aspect of the present invention is an element having the above-mentioned structure, wherein the substrate has flexibility. do.

[0019] Another embodiment of the present invention is a semiconductor device having the above structure, in which a transistor is formed in the first layer. It is a semiconductor device that is

[0020] Another embodiment of the present invention is a semiconductor device having the above-described structure, wherein the transistor has a channel formation region. The semiconductor device is a transistor having a metal oxide therein.

[0021] In addition, another aspect of the present invention is a liquid crystal display device having the above-mentioned structure, wherein a display element is formed in the first layer. It is a display device.

[0022] In another aspect of the present invention, a first resin layer mainly composed of polyimide is formed on a substrate. forming a layer to be peeled off on the first resin layer; and irradiating the first resin layer with laser light. By this, in the mass-to-charge ratio in LC / MS measurement, A separation region containing a substance having a molecular weight of 300 or more and a molecular weight of 950 or less is formed, and the preparation substrate and the layer to be peeled are separated. This is a peeling method in which separation occurs in the separation region.

[0023] In another aspect of the present invention, a first resin layer mainly composed of polyimide is formed on a substrate. forming a peeled layer including a transistor on the first resin layer; By irradiating the first resin layer with a laser beam, a quality control agent for LC / MS measurement is formed inside the first resin layer. A separation region is formed containing a substance having a charge ratio of 300 or more and 950 or less, and the preparation group is This is a peeling method for separating the plate and the layer to be peeled at the separation region.

[0024] In addition, another aspect of the present invention is the above-mentioned configuration, A separation region containing 5 or more, preferably 10 or more, substances having a molecular weight of 300 to 950. The peeling method has the following features.

[0025] In another aspect of the present invention, in the above-mentioned configuration, an LC / MS measurement device is provided inside the first resin layer. At the mass-to-charge ratio at a given concentration, a separation region containing substances with mass ratios of 350 to 900 is formed. The peeling method is a method for separating the preparation substrate and the layer to be peeled at the separation region.

[0026] In addition, another aspect of the present invention is the above-mentioned configuration, A separation region containing 5 or more, preferably 10 or more, substances having a molecular weight of 350 to 900. The peeling method has the following features.

[0027] Another embodiment of the present invention is a semiconductor device having the above-described structure, wherein the transistor has a channel formation region. The present invention relates to a method for manufacturing a semiconductor device including a metal oxide.

[0028] Another aspect of the present invention is a display device having the above-described structure, in which the peeled layer includes a display element. This is a method for making the device.

[0029] Another aspect of the present invention is a light-emitting device having the above-described structure, wherein the peeled layer includes a light-emitting element. This is the method of production.

[0030] In this specification, the term "light-emitting device" includes an image display device using a light-emitting element. In addition, a connector, such as an anisotropic conductive film or TCP (Tape Carrier), is attached to the light emitting element. The module has a printed wiring board attached to the end of the TCP. The module or light emitting element is equipped with a COG (Chip On Glass) method. The module on which the IC (integrated circuit) is directly mounted may have a light emitting device. In addition, the lighting fixture may include a light-emitting device. Effect of the Invention

[0031] One embodiment of the present invention is a thin and lightweight element, a semiconductor device, a display device, and a light-emitting device. Alternatively, one embodiment of the present invention can provide an element, a semiconductor device, a display, or the like that is not easily damaged. Alternatively, one embodiment of the present invention can provide an integrated device and a light-emitting device. Another embodiment of the present invention is a flexible element, a semiconductor device, A device, a display device and a light emitting device can each be provided.

[0032] One aspect of the present invention is to provide a thin, lightweight, and inexpensive element, semiconductor device, display device, and light-emitting device. Alternatively, one aspect of the present invention is to provide an optical device using an element, a semiconductor device, and a light emitting device, which are less likely to be damaged and inexpensive. A semiconductor device, a display device, and a light-emitting device can be provided. Alternatively, one embodiment of the present invention can provide a flexible element or semiconductor device. It is possible to provide an element, a semiconductor device, a display device, and a light-emitting device which have excellent properties and are inexpensive.

[0033] One embodiment of the present invention is a thin and lightweight element, a semiconductor device, a display device, and a light-emitting device. Alternatively, one embodiment of the present invention provides a method for manufacturing an element or semiconductor that is not easily damaged. According to another aspect of the present invention, a method for manufacturing a light-emitting device, a display device, and a light-emitting device can be provided. In this manner, a method for manufacturing an integrated element or a semiconductor device can be provided. The present invention provides a method for manufacturing a flexible element, a semiconductor device, a display device, and a light-emitting device. Can be provided.

[0034] One aspect of the present invention is to provide a thin, lightweight, and inexpensive element, semiconductor device, display device, and light-emitting device. Alternatively, one embodiment of the present invention provides a method for manufacturing an optical device that is not easily damaged and is inexpensive. It is possible to provide a method for manufacturing a semiconductor device, a display device, and a light-emitting device. One embodiment of the present invention can provide a method for manufacturing an integrated and inexpensive element or semiconductor device. Another embodiment of the present invention is a flexible and inexpensive element, semiconductor device, display device, and and a method for manufacturing a light emitting device.

[0035] Another aspect of the present invention is a novel light-emitting element, a display module, a lighting module, The present invention can provide a module, a light-emitting device, a display device, an electronic device, and a lighting device. Alternatively, a light emitting element with high luminous efficiency can be provided. Spray module, lighting module, light emitting device, display device, electronic device, and lighting device Each can be provided.

[0036] It is sufficient for one embodiment of the present invention to exhibit any one of the above-described effects. [Brief description of the drawings]

[0037] [Figure 1] 4A to 4C are diagrams showing a peeling process. [Diagram 2] 4A to 4C are diagrams showing a peeling process. [Diagram 3] 4A to 4C are diagrams showing a peeling process. [Figure 4] 4A to 4C are diagrams showing a peeling process. [Diagram 5] 1A to 1C are diagrams showing a peeling process and an element. [Figure 6] 1A to 1C are diagrams illustrating a peeling process and a light-emitting device or a display device. [Figure 7] 4A to 4C are diagrams showing a peeling process. [Figure 8] 4A to 4C are diagrams showing a peeling process. [Figure 9] 4A to 4C are diagrams showing a peeling process. [Figure 10] 4A to 4C are diagrams showing a peeling process. [Figure 11] 4A to 4C are diagrams showing a peeling process. [Figure 12] 1A to 1C are diagrams showing a peeling process and an element. [Figure 13] 1A and 1B are diagrams showing an element and a light-emitting device or a display device. [Figure 14] 4A to 4C are diagrams showing a peeling process. [Figure 15] 1A and 1B are diagrams illustrating a light-emitting device or a display device. [Figure 16] A diagram showing an electronic device. [Figure 17] FIG. [Figure 18] FIG. [Figure 19] Chromatograph obtained by LC / MS analysis of the release layer surface using a PDA detector. [Figure 20] Absorption spectrum of polyimide film. [Figure 21] Chromatographs using a PDA detector obtained from LC / MS analysis of comparison samples 1 and 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0038] Hereinafter, the embodiment of the present invention will be described in detail with reference to the drawings. The present invention is not limited to the above description, and the form and details are not limited thereto without departing from the spirit and scope of the present invention. It will be readily understood by those skilled in the art that various modifications may be made. It should not be construed as being limited to the description of the embodiment modes.

[0039] The elements formed on the substrate, such as a glass substrate, are separated from the substrate and connected to a different substrate. There are various methods proposed for bonding. Generally, peeling using a resin layer or an inorganic layer is used. A separation layer is used to form weak adhesion at the interface or inside, and the The method of separating the elements from the substrate is adopted, but the substrate is not so thin that it can be easily separated. If the adhesion between the device and the substrate is weakened, the device may peel off during the formation process. On the other hand, if the adhesion is too strong, there is a high possibility of breakage due to the force applied when separating.

[0040] Therefore, in the present invention, the elements formed on the peeled layer are separated from the substrate with good yield. The present invention provides a peeling method that can separate elements with a high yield. It becomes possible to prevent cost increases due to product defects and provide products at low prices. become.

[0041] In one embodiment of the present invention, separation is performed using a release layer made of polyimide resin. Since resin is relatively heat resistant, the heating limit temperature for the elements formed in the upper layer is set high. Since sufficient heating is possible, the reliability of the elements can be improved. It is also possible to use elements that are manufactured at a higher temperature. Since it is possible to heat the device at temperatures up to 350°C, it is possible to manufacture semiconductor devices using metal oxides with excellent characteristics. It is also easier to form.

[0042] First, a release layer made of polyimide resin is formed on the substrate. The following can be used: A solution containing a polyimide precursor is applied to the substrate to convert it into imidization. The polyimide film formed by applying a polyimide with high usability is also available. It does not matter whether it is a polyimide film or a polyimide film formed by other methods. stomach.

[0043] Next, a layer to be peeled is formed on the peeling layer. The layer to be peeled may be a single layer or a layer consisting of multiple layers. However, devices that are to be separated from the substrate and transferred to another substrate or device for use For example, transistors, display elements, light-emitting elements, etc. are included in this category. It is also possible to form multiple types of elements on the same substrate. Any material can be used as the layer to be peeled off.

[0044] After forming the peelable layer, the layer opposite the glass substrate is sealed with a sealant or adhesive. The support substrate is attached. The support substrate may be used as it is without being separated, or may be attached to another substrate. A temporary substrate may be used on the assumption that a separation step will be performed.

[0045] After the support substrate is attached, the peeling layer is irradiated with laser light through the formation substrate. The layer to be peeled has a sufficient heat resistance, rigidity, and other properties to allow the formation of an element included in the layer to be peeled off. The material has a sufficiently small expansion coefficient, and specifically, a glass substrate is preferable.

[0046] By irradiating the laser light, the polyimide molecules inside the polyimide film, which is the layer to be peeled off, This causes the breakdown of the molecules contained in the membrane, including The strength of the layer to be peeled off is reduced, making it possible to separate the layer from the supporting substrate with a sufficiently small force.

[0047] At the interface where separation occurs, various molecules are present that are generated by the decomposition of the polyimide film. Prevent unintentional peeling and prevent damage to the layer to be peeled off, and Good peeling that allows the substrate to be separated from the layer to be peeled with appropriate trigger and force It has been found that when the material has a desired performance, decomposition products of a specific molecular weight exist at the interface. Ta.

[0048] As mentioned above, the interface that exhibited good peeling performance had one or more substances with molecular weights of 1000 or less. In addition, the substances present at the peeled interface are washed away with any organic solvent, and the obtained The washing solution was analyzed by LC / MS (liquid chromatography mass spectrometry) and found to have a mass-to-charge ratio of One ion with an m / z of 300 to 950, preferably 350 to 900; The better the peeling ability, the higher the mass-to-charge ratio (m / z) detected at the interface. 300 to 950 (preferably 350 to 900) The number of substances increases, so 5 or less is recommended. The above substances, more preferably 10 or more substances, even more preferably 20 or more substances, Preferably, 30 or more substances are detected. The number of substances to be detected is determined by the number of substances having the same mass-to-charge ratio or molecular weight. Even if the amount is small, the retention time is If the difference is different, it is a different substance. In the chromatograms obtained by the DA detector, the interface with better peelability exhibited a higher mass charge distribution. The amount of a substance with a charge ratio (m / z) of 300 to 950, preferably 350 to 900, In other words, the area intensity ratio becomes larger. The substances or ions detected from the peeled interface are all poly. This is a substance that is generated as a result of decomposition of the polyimide by laser irradiation. This does not include any substances or ions originating from the film that is being exposed.

[0049] Therefore, the laser beam is irradiated to generate such decomposition products, and the peeling is performed. This will allow products requiring high yields to be manufactured at low cost. This will enable us to provide

[0050] In the case of using a glass substrate and a polyimide film of about 1 μm thickness as a peeling layer, For example, A XeCl excimer laser with a wavelength of 308 nm is used as the laser oscillator for the laser light. The set energy of the device was 980 mJ, the repetition frequency was 60 Hz, and the scan speed was 11.7 mm / sec., and by adjusting the optical system, the cross section of the laser light is a 0.6 mm x 300 mm line. The attenuator is used in the optical system to reduce the irradiation energy. Of course, other lasers may be used.

[0051] It is preferable that a transistor is formed in the peeled layer. It is preferable that the transistor has a channel forming region having a metal oxide. It can function as a semiconductor.

[0052] The transistor channel formation region is made of low temperature polysilicon (LTPS). When using a layered polysilicon, the temperature is about 500 to 550°C. Since heat must be applied, the release layer must have high heat resistance.

[0053] However, transistors that use metal oxide in the channel formation region can be heated to temperatures below 350°C, The layer to be peeled off does not need to have high heat resistance. Therefore, the heat resistance temperature of the layer to be peeled off can be lowered, and the range of materials to be selected can be expanded. Moreover, compared with the case where LTPS is used, the process can be simplified, which is preferable.

[0054] In this embodiment, since the separation region is formed inside the separation layer, the thickness of the separation layer is 15n The thickness of the release layer is preferably 50 nm to 20 μm. By making the release layer as thin as possible within the above-mentioned film thickness range, It is possible to achieve lighter weight, thinner films, lower costs, and improved flexibility.

[0055] The following describes the elements, semiconductor devices, light-emitting devices, and display devices of this embodiment mode, as well as their manufacturing methods. The details will be explained together.

[0056] The thin films (insulating films, semiconductor films, conductive films, etc.) that make up these elements and devices are formed by sputtering. Chemical Vapor Deposition (CVD) ) method, vacuum evaporation method, pulsed laser deposition (PLD) method ition) method, Atomic Layer Deposition (ALD) method The CVD method can be a plasma chemical vapor deposition (PCVD) method. The deposition method may be a metal organic chemical vapor deposition (ECVD) method or a thermal CVD method. Metal Organic CVD (MOCVD) method may also be used.

[0057] Thin films (insulating films, semiconductor films, conductive films, etc.) that make up the display device are formed by spin coating, dipping, Spray application, inkjet, dispensing, screen printing, offset printing, document printing Shaped by tar knife, slit coat, roll coat, curtain coat, knife coat, etc. It can be achieved.

[0058] The thin film can be processed by lithography or the like. The island-shaped thin film may be formed by a film formation method using a mask. The thin film may be processed by a photolithography method, a sandblasting method, a lift-off method, or the like. In the lithography method, a resist mask is formed on the thin film to be processed, and then the thin film is etched. A method of processing the thin film and removing the resist mask, and a method of forming a photosensitive thin film and then and a method in which the thin film is processed into a desired shape by performing exposure and development.

[0059] When light is used in the lithography method, the light used for exposure is, for example, i-line (wavelength 365 nm). m), g-ray (wavelength 436 nm), h-ray (wavelength 405 nm), or a mixture of these In addition, ultraviolet light, KrF laser light, ArF laser light, etc. can be used. Also, exposure may be performed by immersion lithography. Examples of light that can be used include extreme ultraviolet (EUV) and X-rays. Alternatively, an electron beam may be used in place of the light used for exposure. Extremely fine processing is possible using ultraviolet light, X-rays, or electron beams, and is therefore preferred. When exposure is performed by scanning a beam such as an electron beam, a photomath No sc is required.

[0060] For etching thin films, there are dry etching, wet etching, and sandblasting methods. etc. can be used.

[0061] [Production method example 1] Hereinafter, a peeling method according to one embodiment of the present invention will be described using a display device as an example. A release layer 23 is formed on the substrate 4 (FIG. 1).

[0062] FIG. 1A shows an example in which a resin layer 24 is formed on the entire surface of a substrate 14 by a coating method. The method for forming the resin layer 24 is not limited to this, and a printing method or the like may also be used.

[0063] The resin layer 24 can be formed using various resin materials (including resin precursors). The layer 24 is preferably formed using a material having thermosetting properties. The resin layer 24 is formed using a material that does not have photosensitivity (also called a non-photosensitive material).

[0064] The resin layer 24 is formed using a material containing a polyimide resin or a polyimide resin precursor. The resin layer 24 is preferably made of, for example, a material containing a polyimide resin and a solvent, or It can be formed using a material containing a thiocyanic acid and a solvent.

[0065] The resin layer 24 is preferably formed by using a spin coater. This makes it possible to form a uniform thin film on a large substrate.

[0066] The release layer 23 has a viscosity of 5 cP or more and less than 500 cP, preferably 5 cP or more and less than 100 cP. More preferably, the thickness of the film is formed by using a solution having a viscosity of 10 cP or more and 50 cP or less. The lower the viscosity of the liquid, the easier it is to apply. Also, the lower the viscosity of the solution, the less air bubbles are likely to be trapped. This allows for control and the formation of high-quality films.

[0067] Other methods for forming the resin layer 24 include dipping, spray coating, inkjet, Dispense, screen printing, offset printing, doctor knife, slit coat, Examples of coating methods include roll coating, curtain coating, and knife coating.

[0068] The fabrication substrate 14 has a rigidity sufficient for easy transportation and a thickness sufficient for the fabrication process of the elements to be formed later. The material has a heat resistance sufficient to withstand the temperature, and is transparent to the laser light irradiated in the peeling process. Materials that can be used for the fabrication substrate 14 include, for example, Examples include glass, quartz, sapphire, and resin. Among these, glass is versatile and has a high price. It is also preferable from the viewpoint of cost and area. Examples of the glass include aluminoborosilicate glass and aluminoborosilicate glass.

[0069] Next, a first heat treatment is performed on the resin layer 24 to form a release layer 23 (FIG. 1( B).

[0070] The first heat treatment reduces degassed components (e.g., hydrogen, water, etc.) in the peeling layer 23. In particular, it is possible to heat the release layer 23 at a temperature equal to or higher than the manufacturing temperature of each layer to be formed on the release layer 23. This is preferable because it is possible to greatly reduce degassing from the peeling layer 23 during the manufacturing process of the transistor. The width can be restricted.

[0071] For example, when the manufacturing temperature of the transistor is up to 350° C., the film to be the peeling layer 23 is Heating is preferably performed at 0°C or higher and 450°C or lower, more preferably 400°C or lower, and more preferably 375°C or lower. It is more preferable to heat the transistor at a temperature of 0.1° C. or less. Therefore, outgassing from the release layer 23 can be significantly suppressed.

[0072] When the maximum temperature in the manufacture of the transistor is equal to the temperature of the first heat treatment, By carrying out the heat treatment, the maximum temperature in the manufacture of the display device can be prevented from becoming too high. ,preferable.

[0073] By increasing the treatment time, the heating temperature can be increased even if the heating temperature is relatively low. Therefore, it is possible to achieve peelability equivalent to that achieved under the above conditions by changing the configuration of the heating device. If the heat temperature cannot be increased, it is preferable to extend the treatment time.

[0074] The time for the first heat treatment is, for example, preferably 5 minutes to 24 hours, and more preferably 30 minutes to 12 hours. The first heat treatment is preferably performed for 1 hour or less, and more preferably for 1 hour or more and 6 hours or less. The time is not limited to this. For example, the first heat treatment may be performed by RTA (Rapid Thermal Annealing). In cases where the thermal annealing method is used, the time may be less than 5 minutes.

[0075] Heating devices include electric furnaces and resistance heating elements that use heat conduction or heat radiation. Various equipment can be used, such as equipment that heats the workpiece with a gas. For example, as Rapid Thermal Anneal) equipment, LRTA (Lamp Rap) An RTA device such as a LR id Thermal Anneal device can be used. TA equipment includes halogen lamps, metal halide lamps, xenon arc lamps, carbon Light emitted from lamps such as arc lamps, high-pressure sodium lamps, and high-pressure mercury lamps (electromagnetic The GRTA device uses high-temperature gas to heat the material being treated. By using an RTA device, the processing time can be shortened. This is preferable for mass production. In addition, the heat treatment is performed using an in-line heating device. It is acceptable to do so.

[0076] The thickness of the release layer 23 may vary from the thickness of the resin layer 24 due to the heat treatment. For example, the solvent contained in the resin layer 24 is removed, and the hardening proceeds, increasing the density. As a result, the volume of the peeling layer 23 may decrease, and the peeling layer 23 may become thinner than the resin layer 24. Alternatively, the volume of the resin layer 24 increases due to the inclusion of heating atmosphere components during the heat treatment. In some cases, the release layer 23 may become thicker than the above.

[0077] Before the first heat treatment, a heat treatment (prebaking) is performed to remove the solvent contained in the resin layer 24. The temperature of the pre-baking process is determined appropriately depending on the material used. For example, the temperature can be set to 50°C or higher and 180°C or lower, 80°C or higher and 150°C or lower, or The first heat treatment can be performed at a temperature of 90° C. or more and 120° C. or less. Alternatively, the first heat treatment can be a pre-bake treatment. The first heat treatment may also serve as the first heat treatment, and the solvent contained in the resin layer 24 may be removed by the first heat treatment. .

[0078] The release layer 23 has flexibility. The preparation substrate 14 has lower flexibility than the release layer 23.

[0079] The thermal expansion coefficient of the release layer 23 is preferably 0.1 ppm / ° C. or more and 50 ppm / ° C. or less. It is preferable that the temperature is 0.1 ppm / ℃ or more and 20 ppm / ℃ or less. It is more preferable that the thermal expansion coefficient of the peeling layer 23 is 10 ppm / ° C. or more and 20 ppm / ° C. or less. The lower the temperature, the greater the risk of damage to transistors and layers that compose transistors due to heat. It is possible to suppress the occurrence of cracks.

[0080] In addition, when the peeling layer 23 is ultimately located on the display surface side of the display device, Since the light from the peeling layer 23 is transmitted through the peeling layer 23 and observed, the peeling layer 23 is not sensitive to visible light. It is preferable that the light transmittance is high.

[0081] Next, the layer to be peeled 21 is formed on the peeling layer 23. In the above embodiment, an example of forming a transistor and a display element is described. However, the present invention is not limited to the above, and any desired element may be formed by separating it from the fabrication substrate 14 and using it.

[0082] First, as the layer to be peeled 21, an insulating layer 31 is formed on the peeling layer 23 (FIG. 1(C)).

[0083] The insulating layer 31 is formed at a temperature equal to or lower than the heat resistance temperature of the peeling layer 23. Formation at low temperatures is preferred.

[0084] The insulating layer 31 is formed so that impurities contained in the peeling layer 23 will not affect the transistors in the peeled layer to be formed later. For example, the insulating layer 3 can be used as a barrier layer to prevent the diffusion of the oxide into the display element. In the first embodiment, when the peeling layer 23 is heated, moisture contained in the peeling layer 23 is absorbed into the transistors and the display elements. It is preferable that the insulating layer 31 has a function of preventing diffusion of the metal to the silicon. It is preferable that the resistance is high.

[0085] The insulating layer 31 may be, for example, a silicon nitride film, a silicon oxynitride film, a silicon oxide film, Using inorganic insulating films such as silicon oxynitride film, aluminum oxide film, and aluminum nitride film In addition, a hafnium oxide film, a yttrium oxide film, a zirconium oxide film, Gallium oxide film, tantalum oxide film, magnesium oxide film, lanthanum oxide film, cerium oxide film A film, a neodymium oxide film, etc. may be used. In addition, two or more of the above-mentioned insulating films may be stacked. In particular, a silicon nitride film is formed on the peeling layer 23, and a silicon oxide film is formed on the silicon nitride film. It is preferable to form a silicon film.

[0086] In this specification and the like, silicon oxynitride refers to a material having a composition containing more oxygen than nitrogen. Silicon oxide nitride refers to a material that contains more nitrogen than oxygen. Refers to materials with high content.

[0087] The higher the deposition temperature, the denser and more effective the inorganic insulating film becomes, so it is formed at a high temperature. It is preferable.

[0088] The substrate temperature during the deposition of the insulating layer 31 is preferably from room temperature (25° C.) to 350° C. C. or more and 300.degree. C. or less is more preferable.

[0089] Next, a transistor 40 is formed on the insulating layer 31 (FIG. 1(C)).

[0090] The structure of the transistor in the display device is not particularly limited. For example, The transistor may be a staggered type transistor, or an inverse staggered type transistor. In addition, the transistor may be of either a top gate structure or a bottom gate structure. Alternatively, gate electrodes may be provided above and below the channel.

[0091] Here, the transistor 40 is a bottom-gate transistor having a metal oxide layer 44. The metal oxide layer 44 serves as a semiconductor layer of the transistor 40. The metal oxide can function as an oxide semiconductor.

[0092] In this embodiment, an oxide semiconductor is used as the semiconductor of the transistor. If a semiconductor material with a wider band gap and lower carrier density is used, This is preferable because it can reduce the current when the transistor is in the off state.

[0093] The transistor 40 is formed at a temperature equal to or lower than the heat-resistant temperature of the peeling layer 23. It is preferable that the second heat treatment be performed at a temperature lower than that of the first heat treatment.

[0094] Specifically, first, the conductive layer 41 is formed on the insulating layer 31. The conductive layer 41 is formed by depositing a conductive film. Then, a resist mask is formed, the conductive film is etched, and the resist mask is removed. It can be formed by removing

[0095] The substrate temperature during the deposition of the conductive film is preferably from room temperature to 350° C., and more preferably from room temperature to 300° C. is more preferred.

[0096] The conductive layers of the display device are made of aluminum, titanium, chromium, nickel, and copper. , yttrium, zirconium, molybdenum, silver, tantalum, or tungsten, etc. Metals or alloys mainly made of metals can be used as single-layer or multi-layer structures. Alternatively, indium oxide, indium tin oxide (ITO), or indium containing tungsten Indium Zinc Oxide with Tungsten, Indium Zinc Oxide with Titanium materials, titanium-containing ITO, indium zinc oxide, zinc oxide (ZnO), gallium-containing A conductive material having light-transmitting properties, such as ZnO or ITO containing silicon, may also be used. In addition, polycrystalline silicon or oxide semiconductors that have been made low-resistance by including impurity elements, etc. Alternatively, a semiconductor such as silicon or a silicide such as nickel silicide may be used. A film containing graphene may also be used. The film containing graphene may be, for example, an acid formed in a film shape. The film containing graphene oxide can be formed by reducing the impurity element. A semiconductor such as an oxide semiconductor may be used. Alternatively, a conductive material such as silver, carbon, or copper may be used. It may be formed using a conductive paste or a conductive polymer such as polythiophene. Foam is inexpensive and therefore preferred, and conductive polymers are easy to apply and therefore preferred.

[0097] Next, the insulating layer 32 is formed. The insulating layer 32 is made of an inorganic insulating material that can be used for the insulating layer 31. The velum can be used.

[0098] Next, the metal oxide layer 44 is formed. The metal oxide layer 44 is formed after the metal oxide film is formed. A resist mask is formed, the metal oxide film is etched, and then the resist mask is removed. It can be formed by removing

[0099] The substrate temperature during the deposition of the metal oxide film is preferably 350°C or less, and more preferably from room temperature to 200°C or less. The temperature is more preferably from room temperature to 130° C., and even more preferably from room temperature to 130° C.

[0100] The metal oxide film is formed using either or both of an inert gas and oxygen gas. In addition, there is no particular limitation on the flow rate ratio of oxygen (oxygen partial pressure) during the formation of the metal oxide film. However, in order to obtain a transistor with high field effect mobility, metal oxide The flow rate ratio of oxygen (oxygen partial pressure) during the deposition of the film is preferably 0% or more and 30% or less. % or more and 30% or less is more preferable, and 7% or more and 15% or less is even more preferable.

[0101] The metal oxide film preferably contains at least indium or zinc. It is preferred that the metal comprises zinc and zinc.

[0102] The metal oxide preferably has an energy gap of 2.0 eV or more, and more preferably 2.5 eV or more. More preferably, it is 3.0 eV or more. In addition, by using metal oxides with a wide energy gap, the off-state current of transistors can be reduced. It can be reduced.

[0103] The metal oxide film can be formed by a sputtering method. A PECVD method, a thermal CVD method, an ALD method, a vacuum deposition method, or the like may also be used.

[0104] Next, the conductive layer 43a and the conductive layer 43b are formed. The conductive layer 43a and the conductive layer 43b are After forming a conductive film, a resist mask is formed, the conductive film is etched, and then a resist is formed. The conductive layer 43a and the conductive layer 43b can be formed by removing the mask. , and is connected to the metal oxide layer 44 .

[0105] When the conductive layers 43a and 43b are processed, the metal that is not covered with the resist mask is A portion of the metal oxide layer 44 may be thinned by etching.

[0106] The substrate temperature during the deposition of the conductive film is preferably from room temperature to 350° C., and more preferably from room temperature to 300° C. is more preferred.

[0107] In this manner, the transistor 40 can be manufactured (FIG. 1C). In this case, a part of the conductive layer 41 functions as a gate, and a part of the insulating layer 32 functions as a gate insulating layer. The conductive layer 43a and the conductive layer 43b function as either a source or a drain. It functions as one side.

[0108] Next, an insulating layer 33 is formed to cover the transistor 40 (FIG. 1(D)). It can be formed in a similar manner to the edge layer 31.

[0109] The insulating layer 33 may be a silicon oxide film or a silicon oxynitride film formed in an atmosphere containing oxygen. It is preferable to use an oxide insulating film such as a silicon oxide film. This involves laminating an insulating film, such as a silicon nitride film, on a silicon oxide film, which is difficult for oxygen to diffuse or penetrate. It is preferable that the oxide insulating film formed in an atmosphere containing oxygen releases a large amount of oxygen when heated. Such an oxide insulating film that releases oxygen and an insulating film that absorbs oxygen can be used. By laminating an insulating film that is difficult to diffuse or penetrate, a metal oxide layer is formed by heat treatment. As a result, oxygen vacancies in the metal oxide layer 44 and the metal oxide layer 45 can be filled. This makes it possible to repair defects at the interface between the metal oxide layer 44 and the insulating layer 33 and reduce defect levels. This makes it possible to realize a highly reliable display device.

[0110] Through the above steps, the insulating layer 31, the transistor 40, and the insulating layer 33 are formed on the release layer 23. This can be achieved (Figure 1(D)).

[0111] When an organic insulating film is used for the insulating layer 34, the temperature applied to the peeling layer 23 during the formation of the insulating layer 34 is The temperature is preferably from room temperature to 350°C, and more preferably from room temperature to 300°C.

[0112] When an inorganic insulating film is used for the insulating layer 34, the substrate temperature during film formation is preferably from room temperature to 350° C. The heating temperature is preferably from 100°C to 300°C, and more preferably from 100°C to 300°C.

[0113] Next, an opening is formed in the insulating layer 34 and the insulating layer 33 down to the conductive layer 43b.

[0114] Then, a conductive layer 61 is formed (FIG. 1(E)). The conductive layer 61 functions as a pixel electrode. The conductive film is then etched, and the resist mask is then removed to form the insulating film.

[0115] The conductive layer 61 is formed at a temperature equal to or lower than the heat resistant temperature of the release layer 23. It is preferable to form the film at a temperature lower than the processing temperature.

[0116] The substrate temperature during the deposition of the conductive film is preferably from room temperature to 350° C., and more preferably from room temperature to 300° C. is more preferred.

[0117] Next, the insulating layer 35 is formed to cover the end of the conductive layer 61 (FIG. 1(E)). An organic insulating film or an inorganic insulating film that can be used for the edge layer 31 can be used.

[0118] The insulating layer 35 is formed at a temperature equal to or lower than the heat-resistant temperature of the release layer 23. It is preferable to form the film at a temperature lower than the processing temperature.

[0119] When an organic insulating film is used for the insulating layer 35, the temperature applied to the peeling layer during the formation of the insulating layer 35 is room temperature. The temperature is preferably from room temperature to 350°C, and more preferably from room temperature to 300°C.

[0120] When an inorganic insulating film is used for the insulating layer 35, the substrate temperature during film formation is preferably from room temperature to 350° C. The heating temperature is preferably from 100°C to 300°C, and more preferably from 100°C to 300°C.

[0121] Next, an EL layer 62 and a conductive layer 63 are formed (FIG. 2(A)). It functions as a common electrode for the light emitting element 60 .

[0122] The EL layer 62 can be formed by a method such as a vapor deposition method, a coating method, a printing method, or a discharging method. When the L layer 62 is made for each pixel, a deposition method using a shadow mask such as a metal mask is used. Alternatively, the conductive layer can be formed by an ink jet method or the like.

[0123] The EL layer 62 may be made of either a low molecular weight compound or a high molecular weight compound. The compound may be included.

[0124] The conductive layer 63 can be formed by vapor deposition, sputtering, or the like.

[0125] The conductive layer 63 is heated at a temperature equal to or lower than the heat resistance temperature of the release layer 23 and the heat resistance temperature of the EL layer 62. In addition, it is preferable to form the second heat treatment at a temperature lower than the temperature of the first heat treatment.

[0126] In this manner, the light emitting element 60 can be formed (FIG. 2(A)). The conductive layer 61, a part of which functions as a pixel electrode, the EL layer 62, and a part of which functions as a common electrode are provided. It has a structure in which functional conductive layers 63 are laminated.

[0127] The light-emitting elements are top emission type, bottom emission type, and dual emission type. For the electrode from which light is extracted, a conductive film that transmits visible light is used. In addition, it is preferable to use a conductive film that reflects visible light for the electrode on the side from which light is not extracted. Here, it is assumed that a top-emission type light-emitting element is to be fabricated.

[0128] Next, an insulating layer 74 is formed to cover the conductive layer 63 (FIG. 2(B)). The light emitting element 60 functions as a protective layer that prevents impurities such as water from diffusing into the light emitting element 60. The conductive layer 63 is sealed by the insulating layer 74. After the conductive layer 63 is formed, the insulating layer 74 is sealed by the insulating layer 74 without exposing it to the air. It is preferred to form a border layer 74 .

[0129] The insulating layer 74 is heat-resistant to a temperature that is equal to or lower than the heat-resistant temperature of the peeling layer 23 and the heat-resistant temperature of the light-emitting element 60. The insulating layer 74 is preferably formed at a temperature lower than the temperature of the first heat treatment. stomach.

[0130] The insulating layer 74 is, for example, an inorganic insulating material having a high barrier property that can be used for the insulating layer 31 described above. It is preferable that the insulating film is formed by laminating an inorganic insulating film and an organic insulating film. It's fine.

[0131] The insulating layer 74 can be formed by using an ALD method, a sputtering method, or the like. The ALD method is preferable because it allows low-temperature film formation. 74 has good coverage, which is preferable.

[0132] Next, a protective layer 75 is formed on the insulating layer 74 (FIG. 2(C)). The protective layer 75 can be used as the layer located on the outermost surface. High is preferable.

[0133] When the protective layer 75 is made of an organic insulating film that can be used for the insulating layer 31, the surface This is preferable because it can prevent the surface of the display device from being scratched or cracked. .

[0134] In FIG. 3A, instead of a protective layer 75, a substrate 75 is attached to an insulating layer 74 using an adhesive layer 75b. An example of pasting a is shown below.

[0135] The adhesive layer 75b may be a light-curing adhesive such as an ultraviolet-curing adhesive, a reaction-curing adhesive, or a heat-curing adhesive. Various resins of various curing adhesives such as adhesives, anaerobic adhesives, etc. can be used. A card or the like may also be used.

[0136] The substrate 75a is made of, for example, polyethylene terephthalate (PET), polyethylene naphtha Polyester resins such as polyacrylonitrile resins, acrylic resins, Polyimide resin, polymethyl methacrylate resin, polycarbonate (PC) resin, polyethylene Polyethersulfone (PES) resin, polyamide resin (nylon, aramid, etc.), polysiloxane San resin, cycloolefin resin, polystyrene resin, polyamide-imide resin, polyurethane Tan resin, polyvinyl chloride resin, polyvinylidene chloride resin, polypropylene resin, polytetrafluoroethylene Polytetrafluoroethylene (PTFE) resin, ABS resin, cellulose nanofiber, etc. The substrate 75a can be made of various materials such as glass, quartz, resin, metal, alloy, and semiconductor. If the film is to be peeled off again and attached to a different substrate, the substrate 7 may be used. Any substrate may be used for 5a. In order to provide flexibility, the substrate 75a Depending on the thickness and material of the substrate, it is sufficient to use a substrate with a material and shape that has the required degree of flexibility. stomach.

[0137] Next, the fabrication substrate 14 and the release layer 23 are separated. The separation layer 23 is irradiated with laser light through the fabricated substrate 14 to form a separation region 25 in the separation layer 23. The separation region 25 is formed by irradiating the peeling layer 2 with laser light (FIG. 3(B)). The molecules constituting the peeling layer 23 are decomposed and become brittle. 3, but may be formed at the interface between the release layer 23 and the substrate 14. When the release layer 23 is made of a polyimide resin, the separation region 25 is In MS measurement, the mass-to-charge ratio is 300 to 950, preferably 350 to 900. The polyimide includes at least one of the substances derived from the ions of the above. It is a product of decomposition due to laser irradiation, and can be easily prepared by applying moderate force. 4 can be separated from each other. In the final product, the molecules remain on the separated surface as the separation region 25. Since the ions are present, their presence can be confirmed by measurement.

[0138] The laser to be irradiated is, for example, A XeCl excimer laser with a wavelength of 308 nm is used as the laser oscillator for the laser light. The set energy of the device was 980 mJ, the repetition frequency was 60 Hz, and the scan speed was 11.7 mm / sec., and by adjusting the optical system, the cross section of the laser light is a 0.6 mm x 300 mm line. The attenuator is used in the optical system to reduce the irradiation energy. Of course, other lasers may be used.

[0139] Thereafter, for example, a pulling force is applied to the separation region 25 in the vertical direction to form the fabrication substrate 1 The layer to be peeled off can be peeled off from the upper surface of the substrate 75a (FIG. 3(C)). By adsorbing a part of the adhesive and pulling it upward, the layer to be peeled off can be easily peeled off from the substrate 14. It is possible.

[0140] Here, during peeling, a liquid containing water, such as water or an aqueous solution, is added to the peeling interface, and the liquid By performing peeling so that the adhesive penetrates the surface, peelability can be improved. Static electricity generated in semiconductor devices can adversely affect functional elements such as transistors (semiconductor devices are It can suppress damage caused by electricity.

[0141] Before the separation, a part of the release layer 23 is separated from the production substrate 14 to form a starting point for separation. For example, the separation may be performed by inserting a sharp tool such as a blade into the separation area 25. Alternatively, a cutting point may be formed in the peeling layer 23 from the substrate 75a side using a sharp tool. Alternatively, a laser such as a laser ablation method may be used. The starting point of separation may be formed by a method using the above.

[0142] The separation region 25 exposed by separating the substrate 14 and the substrate 29 are bonded to each other by the adhesive layer 28. The substrate 29 may function as a support substrate for the display device. It is possible.

[0143] The adhesive layer 28 may be made of any of the materials that can be used for the adhesive layer 75b. The material 29 can be any material that can be used for the substrate 75a.

[0144] Through the above steps, a metal oxide is applied to the channel formation region of a transistor, and an EL element is formed. It is possible to manufacture a display device to which the above is applied.

[0145] In the display device thus manufactured, the interface between the adhesive layer 28 and the peeling layer 23 was measured by LC / MS. In the present invention, the mass-to-charge ratio of the ions is 300 to 950, preferably 350 to 900. In LC / MS measurements, at least one of the substances derived from The substances derived from ions with charge ratios between 300 and 950 were generated by decomposition due to laser irradiation. However, the other portion, that is, the interface between the peeling layer 23 and the layer to be peeled (the interface between the insulating layer 31 and the peeling layer 23) is It is not detected at the interface.

[0146] [Production method example 2] In the following manufacturing method examples, the description of the same parts as in the previously described manufacturing method examples will be omitted. There are times when this happens.

[0147] First, in the same manner as in the manufacturing method example 1, the insulating layer 33 to the protective layer 75 are formed. Each component is formed at a temperature equal to or lower than the heat resistance temperature of the release layer 23. is formed at a temperature lower than both the temperature of the first heat treatment and the temperature of the second heat treatment. is preferred.

[0148] Then, a laser beam is irradiated to remove at least the element to be peeled off from the fabrication substrate 14. A separation region 25 is formed inside the peeling layer 23 at the portion where the separation region 25 is to be formed. (FIG. 4(A)) Type of laser, wavelength The output and the like are the same as those in the manufacturing method 1. At this time, the peeling layer 23 is not irradiated with the laser light. Since the separation region 25 is not formed in the portion not irradiated with the laser light, it is easy to carry and the like. This can further prevent accidental peeling.

[0149] Next, starting points for separation are formed in the release layer 23 (FIGS. 4(B1) and (B2)).

[0150] For example, a sharp object such as a blade may be inserted from the protective layer 75 side to the inside of the end of the separation region 25. Insert the tool 65 and make a frame-shaped cut 64. This cut 64 becomes the starting point for separation.

[0151] Alternatively, the inside of the separation region 25 in the peeling layer 23 is irradiated with laser light in a frame shape, This may be the starting point for separation.

[0152] In addition, when a plurality of display devices are formed from one manufacturing substrate (multiple display devices are manufactured), As shown in FIG. 1, it is preferable to arrange a plurality of display devices inside the gap 64 like the separation region 25. This makes it possible to peel off a plurality of display devices from the formation substrate at once.

[0153] Alternatively, a plurality of isolation regions 25 may be formed on one substrate, and the isolation regions 25 may be arranged for each display device. A display element or a semiconductor element may be separately formed at the position of 5. An example of forming four separation regions is shown above. Each of the four separation regions has a frame-shaped cut 6. By inserting 4, each display device can be peeled off at a different time.

[0154] In the second example of the manufacturing method, a portion on the manufacturing substrate 14 where the separation region 25 is to be formed and a portion on the manufacturing substrate 14 where the separation region 25 is to be formed are provided. In the portion where the separation region 25 is not formed, the peeling layer 23 is brittle. Since the layer 21 is not peeled off from the substrate 14, it is difficult to peel it off. Unintended peeling from the production substrate 14 can be suppressed. Then, by forming a separation starting point, the preparation substrate 14 and the layer to be peeled 2 can be separated at a desired timing. Therefore, the timing of peeling can be controlled and high peeling can be achieved. This improves the yield of the peeling process and the manufacturing process of the display device. It is possible.

[0155] Next, the manufacturing substrate 14 and the transistor 40 are separated (FIG. 5(A)).

[0156] In the second manufacturing method, the peeling layer 23 is irradiated with laser light to form a film containing the The resin molecules are decomposed to form a separation region 25 which is a fragile region. By separating the layer 21 from the substrate 14, the layer 21 can be peeled off.

[0157] Next, the separation region 25 in the release layer 23 exposed by being separated from the fabrication substrate 14 and the substrate The substrate 29 is attached to the display device using an adhesive layer 28 (FIG. 5(B)). It can function as a supporting substrate.

[0158] Through the above steps, a metal oxide is applied to the channel formation region of a transistor, and an EL element is formed. It is possible to manufacture a display device to which the above is applied.

[0159] [Display device configuration example 1] 6A is a top view of the display device 10A. 13 is a cross-sectional view of a display unit 381 of the device 10A and an example of a cross-sectional view of a connection portion with an FPC 372. FIG.

[0160] The display device 10A can be manufactured by the above-mentioned manufacturing method example 2. It is possible to hold the bent state and to be repeatedly bent.

[0161] The display device 10A has a protective layer 75 and a substrate 29. The protective layer 75 side is the display surface of the display device. The display device 10A includes a display unit 381 and a drive circuit unit 382. FPC372 is attached to 0A.

[0162] The conductive layer 43c and the FPC 372 are electrically connected via the connector 76 (FIG. 6( The conductive layer 43c is made of the same material as the source and drain of the transistor. They can be formed in the same process.

[0163] The connector 76 may be made of various anisotropic conductive films (ACFs). Conductive Film) and Anisotropic Conductive Paste (ACP) Conductive Paste) can be used.

[0164] The display device shown in FIG. 6C includes a transistor 49 instead of the transistor 40. 6(B) in that a colored layer 97 is provided on the insulating layer 33. When a Tom emission type light emitting element 60 is used, a colored layer is provided between the light emitting element 60 and the substrate 29. It may have a layer 97 .

[0165] A transistor 49 shown in FIG. 6C has the following configuration in addition to the configuration of the transistor 40 shown in FIG. The semiconductor device has a conductive layer 45 which functions as a gate electrode.

[0166] The transistor 49 has a structure in which a semiconductor layer in which a channel is formed is sandwiched between two gates. By adopting such a configuration, the threshold voltage of the transistor can be controlled. By connecting the two gates together and applying the same signal to them, Such transistors have field effect transistors compared to other transistors. This allows for increased mobility and increased on-current. Furthermore, the area occupied by the circuit portion can be reduced. By using transistors with a large on-state current, it is possible to enlarge the display device, Even if the number of wirings increases when the resolution is increased, the signal delay in each wiring can be reduced. This makes it possible to suppress display unevenness.

[0167] Alternatively, a potential for controlling the threshold voltage is applied to one of the two gates, and a drive potential is applied to the other. By applying a potential for the gate, the threshold voltage of the transistor can be controlled.

[0168] As described above, when these display devices are manufactured, the peeling layer 23 is irradiated with laser light. As a result, the molecules of the resin contained in the peeling layer 23 are decomposed, and the separation region 25, which is a brittle region, is formed. The layer to be peeled 21 is peeled off from the fabrication substrate 14 by forming a separation region. Therefore, a display device manufactured by applying the manufacturing method of the display device of this embodiment mode can be used. In the region between the adhesive layer 28 and the release layer 23 (the interface between the adhesive layer 28 and the release layer 23), In the LC / MS measurement, the peeling layer 23 is decomposed by the laser light irradiation, and the generated At least one substance derived from an ion having a mass-to-charge ratio of 300 or more and 950 or less In the release layer 23 in which molecules of these molecular weights exist, the molecules are appropriately decomposed. As a result, it is possible to suppress unintentional peeling of the peeled layer 21 while providing a good Because of the peeling property, display devices can be manufactured with a high yield.

[0169] Fourier Transform Infrared Spectroscopy pectroscopy, FTIR), nuclear magnetic resonance spectroscopy ( 1 H-NMR), gas chromatography GC / MS, liquid chromatography / mass spectrometry (LC / MS), Time-of-flight secondary ion mass spectrometry (TOF-SIMS) and matrix-assisted laser desorption Using one or more analytical techniques such as ionization time-of-flight mass spectrometry (MALDI-TOFMS), Then, the surface of the separated release layer 23 (separation region 25) or the surface of the adhesive layer 28 is analyzed. This makes it possible to identify molecules present at the interface between the release layer 23 and the adhesive layer 28.

[0170] To perform analysis by LC / MS, the surface of the peeled interface side of the glass substrate after peeling and the layer to be peeled are The surface of the peeled interface side of the cellulose acetate was then washed with any solvent (toluene, chloroform, 1,1,3,3-hexanediol, etc.). Wash with HFIP or other similar cleaning solution. Dilute with any solvent (preferably an organic solvent used in LC / MS measurement, such as acetonitrile) Then, a measurement sample is prepared.

[0171] When analyzing a display device, first, the separation interface in the transistor structure of the display device is measured. Identify the layers that are in contact with each other, for example, the layers where polyimide is in contact with an adhesive (such as epoxy resin). The analytical method used to identify the peeled interface was TEM-EDX (transmission electron microscope - energy dispersive X-ray diffraction). X-ray analysis, etc.) are used. The area around the specified interface is analyzed by TOF-SIMS (time-of-flight secondary ion mass spectrometry). Analysis using analytical techniques that can obtain information on molecular weight distribution in the depth direction, such as mass spectrometry, Lateral molecular weight analysis such as ALDI-MS (matrix-assisted laser desorption / ionization mass spectrometry) It can be analyzed using an analytical method that can obtain fabric information. After identifying the surface, the surface is peeled off at the peeling interface to expose the surface, and then the surfaces of both peeling interfaces are arbitrarily The resulting cleaning solution is then washed with any solvent (toluene, chloroform, HFIP, etc.). Dilute with a solvent (preferably an organic solvent used in LC / MS measurements, such as acetonitrile) and measure Samples can be prepared and subjected to LC / MS analysis.

[0172] [Production method example 3] First, in the same manner as in the second manufacturing method, the layers from the release layer 23 to the insulating layer 31 are formed on the substrate 14. (Figure 7(A)).

[0173] Next, a transistor 80 is formed on the insulating layer 31 (FIG. 7(B)).

[0174] Here, transistor 80 is a transistor having a metal oxide layer 83 and two gates. This shows the case where a printer is made.

[0175] The transistor 80 is formed at a temperature equal to or lower than the heat-resistant temperature of the peeling layer 23. It is preferable to form the first heat treatment at a temperature lower than both the temperature of the first heat treatment and the temperature of the second heat treatment.

[0176] Specifically, first, the conductive layer 81 is formed on the insulating layer 31. The conductive layer 81 is formed by depositing a conductive film. Then, a resist mask is formed, the conductive film is etched, and the resist mask is removed. It can be formed by removing

[0177] Next, the insulating layer 82 is formed. The insulating layer 82 is made of an inorganic insulating material that can be used for the insulating layer 31. The velum can be used.

[0178] Next, a metal oxide layer 83 is formed. The metal oxide layer 83 is formed after forming the metal oxide film. A resist mask is formed, the metal oxide film is etched, and then the resist mask is removed. The metal oxide layer 83 can be formed by removing the metal oxide that can be used for the metal oxide layer 44. Materials can be used.

[0179] Subsequently, an insulating layer 84 and a conductive layer 85 are formed. The insulating layer 84 is used for the insulating layer 31. The insulating layer 84 and the conductive layer 85 are made of an insulating material that is capable of forming the insulating layer 84. After forming a film and a conductive film that will become the conductive layer 85, a resist mask is formed, and the insulating film and The conductive film is then etched, and the resist mask is then removed.

[0180] Next, the insulating layer 33 is formed to cover the metal oxide layer 83, the insulating layer 84, and the conductive layer 85. The edge layer 33 can be formed in a similar manner to the insulating layer 31 .

[0181] The insulating layer 33 preferably contains hydrogen. The hydrogen contained in the insulating layer 33 The metal oxide layer 83 is diffused thereinto, and the resistance of the metal oxide layer 83 is reduced. The metal oxide layer 83 in contact with the transistor 80 functions as a low resistance region, so that the on-state voltage of the transistor 80 is Increased current and improved field effect mobility are possible.

[0182] Next, an opening is formed in the insulating layer 33 down to the metal oxide layer 83 .

[0183] Subsequently, the conductive layer 86a and the conductive layer 86b are formed. After forming a conductive film, a resist mask is formed, the conductive film is etched, and then a resist is formed. The conductive layer 86a and the conductive layer 86b can be formed by removing the mask. , and is electrically connected to the metal oxide layer 83 through the opening in the insulating layer 33 .

[0184] In the above manner, the transistor 80 can be manufactured (FIG. 7B). In this case, a part of the conductive layer 81 functions as a gate, and a part of the insulating layer 84 functions as a gate insulating layer. A part of the insulating layer 82 functions as a gate insulating layer, and a part of the conductive layer 85 functions as a gate. The metal oxide layer 83 has a channel region and a low resistance region. The low resistance region is a portion connected to the conductive layer 86a. and a portion connected to conductive layer 86b.

[0185] Next, the insulating layer 34 to the light emitting element 60 are formed on the insulating layer 33 (FIG. 7(C)). For these steps, see Preparation Method 1.

[0186] Moreover, the steps of FIGS. 8(A) and 8(B) are carried out independently of the steps of FIGS. 7(A) to 7(C). In the same manner as in the process of forming the release layer 23 on the preparation substrate 14, a release layer 93 is formed on the preparation substrate 91. Form.

[0187] Next, an insulating layer 95 is formed on the release layer 93. Next, a coloring layer 97 and a shielding layer 98 are formed on the insulating layer 95. An optical layer 98 is formed (FIG. 8(B)).

[0188] For the insulating layer 95, the description of the insulating layer 31 can be applied.

[0189] A color filter or the like can be used as the colored layer 97. The colored layer 97 is Place it so that it overlaps with the display area of ​​the

[0190] A black matrix or the like can be used as the light-shielding layer 98. The light-shielding layer 98 is an insulating layer. Place it so that it overlaps with 35.

[0191] Next, the surface of the fabrication substrate 14 on which the transistors 80 and the like are formed and the colored layer of the fabrication substrate 91 are The surface on which 97 etc. are formed is attached using an adhesive layer 99 (FIG. 8(C)).

[0192] Next, the separation layer 23 is irradiated with laser light to form a separation region 25 (FIG. 9(A)), and then This forms the starting point of separation (FIG. 9(B)). Which of the preparation substrate 14 and the preparation substrate 91 will be separated first? Here, an example will be shown in which the fabrication substrate 14 is separated before the fabrication substrate 91 is separated.

[0193] The laser irradiation conditions for forming the separation region 25 are the same as those described in Example 1 of the manufacturing method. The same can be done as above.

[0194] As a method for forming the starting point of separation, for example, a separation starting point in the peeling layer 23a is formed from the side of the fabrication substrate 14. There is a method of irradiating the inside of the separation region 25 in a frame shape with laser light 66 (see FIG. 9(C)). (See the laser beam irradiation position 67.) In this method, the substrate 14 and the substrate 91 are made of glass. This is suitable for use with any hard substrate.

[0195] There is no particular limitation on the laser used to form the starting point of separation. For example, a continuous wave laser Laser light irradiation conditions (frequency, power) can be adjusted. The thickness, distribution, energy density, beam profile, etc. of the substrate and the peeling layer 23 are determined by the thickness, distribution, The position, material, etc. of the separation region 25 are taken into consideration for appropriate control.

[0196] In the manufacturing method example 4, when the separation region 25 is formed by irradiating the peeling layer 23 with laser light, In order to form the separation region 25, a portion is irradiated with the laser light and a portion is not irradiated with the laser light. A separation region 25 is formed in the irradiated portion, and the peeling layer 23 is easily separated from the production substrate 14. On the other hand, in the portion where the separation region is not formed, the separation layer 23 is fragile. Since no part of the peeling layer 23 is present, the peeling layer 23 remains in a state where it is difficult to separate from the production substrate 14 . As a result, the layer to be peeled 21 may be peeled off from the production substrate 14 at an unintended timing. Similarly, in order to form the separation region 94 from the top of the production substrate 91, When irradiating the laser beam, a portion to be irradiated with the laser beam and a portion not to be irradiated with the laser beam are provided. This prevents the release layer 93 from being separated from the production substrate 91 at an unintended timing. It is possible.

[0197] Then, by forming a separation starting point only on one of the release layer 23 and the release layer 93, the fabrication substrate The plate 14 and the preparation substrate 91 can be peeled off in separate steps. Furthermore, the yield of the manufacturing process of the display device can be increased.

[0198] Next, a separation starting point is formed in the peeling layer 23 (separation region 25) from the side of the fabricated substrate 14. The substrate 14 and the transistor 80 are separated (FIG. 10(A)). In this step, a frame-shaped laser beam is The inner part irradiated with the laser beam 66 (also referred to as the inner part irradiated with the laser beam 67 shown in FIG. 9(B)) 10A shows an example in which the frame-shaped In the outer portion irradiated with the laser beam 66, separation occurs in the adhesive layer 99 (adhesive layer 99 This is an example of, but not limited to, cohesive failure. For example, outside the irradiated area 67 In this case, the adhesive layer 99 is separated from the insulating layer 95 or the insulating layer 35 (interface failure or adhesion failure). (also called destruction) may occur.

[0199] Next, the peeling layer 23 exposed by being separated from the prepared substrate 14 and the substrate 29 are bonded to the adhesive layer 2 8 is used to attach the display device (FIG. 10(B)). The substrate 29 functions as a support substrate for the display device. do.

[0200] Next, a starting point for separation is formed in the release layer 93 (separation region 94) (FIG. 11(A)).

[0201] In FIG. 11A, the inner side from the substrate 29 side to the end of the separation region 94 in the peeling layer 93 A sharp tool 65 such as a blade is inserted into the substrate 29 to make a frame-shaped cut. This is suitable when using

[0202] Alternatively, in the same manner as when the separation starting point is formed in the peeling layer 23, the peeling layer 9 3 may be irradiated with laser light in a frame shape.

[0203] By forming the starting point of separation, the production substrate 91 and the peeling layer 93 can be separated at a desired timing. Therefore, the timing of peeling can be controlled and high peelability can be achieved. This makes it possible to increase the yield of the peeling process and the manufacturing process of the display device. do.

[0204] Next, the manufacturing substrate 91 and the transistor 80 are separated (FIG. 11(B)). 9 shows an example in which the inner portion of the cut is peeled off from the fabrication substrate 91.

[0205] Next, the peeling layer 93 exposed by being separated from the fabricated substrate 91 and the substrate 22 are bonded to the adhesive layer 1. 3 is used to attach the display device (FIG. 12(A)). The substrate 22 functions as a support substrate for the display device. It is possible.

[0206] In FIG. 12A, the light emitted from the light emitting element 60 passes through the colored layer 97 and the peeling layer 93. Therefore, the visible light transmittance of the peeling layer 93 is high. is preferred.

[0207] The peeling layer 93 may be removed. This further increases the light extraction efficiency of the light emitting element 60. In FIG. 12B, the peeling layer 93 is removed, and the insulating layer 9 is bonded to the insulating layer 9 by using the adhesive layer 13. 5 shows an example in which a substrate 22 is bonded to the substrate 22.

[0208] For the adhesive layer 13, the materials that can be used for the adhesive layer 75b can be used.

[0209] The substrate 22 may be made of any of the materials that can be used for the substrate 75a.

[0210] In Manufacturing Method Example 4, a display device is manufactured by performing the peeling method of one embodiment of the present invention twice. In one embodiment of the present invention, all of the functional elements constituting the display device are formed on a substrate. Even in the case of manufacturing a high-definition display device, a flexible substrate is required to have a high position. No high alignment accuracy is required. Therefore, flexible substrates can be easily attached. do.

[0211] As described above, when these display devices are manufactured, the peeling layer 23 and the peeling layer 93 are irradiated with laser light. By irradiating the light, the molecules of the resin contained in the release layer 23 and the release layer 93 are decomposed, The separation regions 25 and 94 are formed as weakened regions, and the separation regions 25 and 94 are separated from each other. By this, the element formation region can be peeled off from the fabrication substrate 14 and the fabrication substrate 91. Therefore, the adhesiveness of the display device manufactured by applying the manufacturing method of the display device of this embodiment mode is The area between the adhesive layer 28 and the release layer 23 (the interface between the adhesive layer 28 and the release layer 23) and the adhesive layer 13 The region between the adhesive layer 13 and the peeling layer 93 (the interface between the adhesive layer 13 and the peeling layer 93) is irradiated with laser light. In the LC / MS measurement, the peeling layer 23 or the peeling layer 93 was decomposed. , there is one or more substances derived from ions with a mass-to-charge ratio of 300 or more and 950 or less. In the release layer 23 and the release layer 93 in which molecules having a molecular weight of This prevents unintended peeling while providing good peeling performance, making it easy to walk. A display device can be manufactured with good adhesion.

[0212] [Variations] In the fourth example of the manufacturing method (FIG. 18C), the adhesive layer 99 is formed on the separation region 25 and the separation region 94. The adhesion of the outside of the separation area is high, so separation is not possible. If such a process is performed, peeling failure may occur, resulting in a decrease in the peeling yield.

[0213] Therefore, as shown in FIGS. 13A and 13B, the adhesive layer 99 is formed on the outside and the inside of the separation region 25. By configuring the film not to overlap with the outside of the separation region 94, it is possible to reduce peeling failure. become.

[0214] For example, if an adhesive with low fluidity or an adhesive sheet is used for the adhesive layer 99, the adhesive layer 9 It is easy to form the insulating layer 9 in an island shape (FIG. 13(A)).

[0215] Alternatively, a frame-shaped partition 96 is formed, and an adhesive layer 99 is filled and hardened inside the partition 96. (FIG. 13(B)).

[0216] When the partition 96 is used as a component of a display device, the partition 96 is made of a hardened resin. In this case, the partition wall 96 is also preferably disposed on the outside of the separation region 25 and the outside of the separation region 94. It is preferable not to overlap with

[0217] When the partition 96 is not used as a component of a display device, the partition 96 may be provided with an uncured or semi-cured In this case, the partition 96 is formed on the outside of the separation region 25 and on the It may overlap one or both of the outer regions 94 .

[0218] In this embodiment, the partition 96 is made of uncured resin, and the partition 96 is disposed on the outside and the inside of the separation region 25. 13 shows an example in which the outer periphery of the separation region 94 does not overlap with the outer periphery of the separation region 94.

[0219] In a configuration in which the adhesive layer 99 does not overlap the outside of the isolation region 25 and the outside of the isolation region 94 A method for forming the starting point of separation will be described below. In the following, an example of peeling off the manufacturing substrate 91 will be shown. The preparation substrate 14 can also be peeled off in a similar manner.

[0220] 14(A) to (E), the laser beam 66 is used when separating the preparation substrate 91 from the peeling layer 93. The irradiation position will be described.

[0221] As shown in FIG. 14A, the separation region 94 of the peeling layer 93 and the adhesive layer 99 overlap each other. By irradiating at least one location in the region with laser light 66, a starting point for separation can be formed.

[0222] It is preferable that the force for separating the preparation substrate 91 and the peeling layer 93 is concentrated at the starting point of the separation. It is preferable to form the starting point of separation near the edge of the adhesive layer 99 rather than the center. Among the vicinity, it is preferable to form the separation starting point near the corner as compared to the vicinity of the side.

[0223] 14(B) to (E) show an example of a laser light irradiation area 67. In FIG.

[0224] FIG. 14B shows one corner portion of the adhesive layer 99, which is an irradiated area 67 of the laser light.

[0225] By irradiating the laser beam continuously or intermittently, the starting point of peeling in the form of solid or dashed lines can be In FIG. 14C, three corners of the adhesive layer 99 are irradiated with laser light. In FIG. 16D, the laser light irradiation area 67 is located on one side of the adhesive layer 99. 14(E) shows an example in which the adhesive layer 99 is in contact with the substrate 91 and extends along one side of the adhesive layer 99. The laser beam is irradiated not only in the area where the adhesive layer 99 and the separation area 94 overlap, but also in the area where the adhesive layer 99 and the separation area 94 overlap. The non-insulated partition 96 and the separation region 94 may be located in an overlapping area.

[0226] Thereafter, the fabrication substrate 91 and the release layer 93 can be separated. A part of the partition wall 96 may remain. The partition wall 96 may be removed or may not be removed and may be used for the next step. You may proceed to the process.

[0227] [Display device configuration example 2] FIG. 15(A) is a top view of the display device 10B. FIG. 15(B) is a front view of the display device 10B. 3 is a cross-sectional view of a display portion 381 and a cross-sectional view of a connection portion with an FPC 372.

[0228] The display device 10B can be manufactured using the above-mentioned Manufacturing Method Example 5. It is possible to hold the bent state and to be repeatedly bent.

[0229] The display device 10B has a substrate 22 and a substrate 29. The substrate 22 side is the display side of the display device 10B. The display device 10B includes a display unit 381 and a drive circuit unit 382. FPC372 is attached to 10B.

[0230] The conductive layer 86c and the FPC 372 are electrically connected via the connector 76 (FIG. 15 (B) The conductive layer 86c is made of the same material and has the same structure as the source and drain of the transistor. It can be formed in a process.

[0231] As described above, when these display devices are manufactured, the peeling layer 23 is irradiated with laser light. As a result, the molecules of the resin contained in the peeling layer 23 are decomposed, and the separation region 25, which is a brittle region, is formed. The separation layer 93 is separated from the separation region to form the element formation region from the fabrication substrate 14. Therefore, the manufacturing method of the display device of this embodiment mode is applied to the manufacturing method of the display device. The area between the adhesive layer 28 and the peeling layer 23 of the display device (the area between the adhesive layer 28 and the peeling layer 23) At the interface with the laser beam, the peeling layer 23 is decomposed and the LC generated is formed. In the MS measurement, the number of substances derived from ions with a mass-to-charge ratio of 300 to 950 was 1 or more. The release layer 23 in which molecules of these molecular weights exist is decomposed to an appropriate degree. This prevents unintended peeling and provides good peeling performance. The display device can be manufactured with a high yield.

[0232] This embodiment mode can be appropriately combined with other embodiment modes. In the case where a plurality of configuration examples are shown in one embodiment, the configuration examples may be appropriately combined. It is possible to do this.

[0233] (Embodiment 1) In this embodiment, a display device according to one embodiment of the present invention and a manufacturing method thereof will be described with reference to drawings. do.

[0234] The display device of this embodiment has a first display element that reflects visible light and a second display element that emits visible light. and a display element.

[0235] The display device of the present embodiment has a structure in which light reflected by a first display element and light emitted by a second display element are mixed. Either one or both of these functions are capable of displaying images.

[0236] The first display element can be an element that displays by reflecting external light. Since the display does not have a light source, it is possible to reduce power consumption during display to an extremely low level.

[0237] The first display element can typically be a reflective liquid crystal element. As a display element, a shutter-type MEMS (Micro Electro Mechanical Systems) anical System) elements, optical interference type MEMS elements, microcapsules method, electrophoresis method, electrowetting method, electronic liquid powder method, etc. Applied elements and the like can be used.

[0238] It is preferable to use a light-emitting element as the second display element. Light has high color reproducibility (wide color gamut) because its brightness and chromaticity are not affected by external light. ), providing high contrast and vivid display.

[0239] The second display element may be, for example, an OLED (Organic Light Emitting Diode), LED(Light Emitting Diode), QLED(Q Self-luminous such as uantum-dot Light Emitting Diode A light emitting element can be used.

[0240] The display device of the present embodiment has a first mode in which an image is displayed using only the first display element, A second mode in which only the second display element is used to display an image, and a second mode in which only the first display element and A third mode for displaying an image using a second display element, and these modes are automatically or can be manually switched on and used.

[0241] In the first mode, an image is displayed using the first display element and external light. This is an extremely low power consumption mode because no external light is required. When light is incident (such as in a bright environment), the first display element uses the reflected light to display an image. For example, if the external light is sufficiently strong and is white light or light close to white light, The first mode is suitable for displaying characters. The first mode uses reflected light from outside, providing a display that is gentle on the eyes. This has the effect of reducing eye fatigue.

[0242] In the second mode, an image is displayed by utilizing the light emitted by the second display element. Extremely vivid (high contrast and high color reproducibility) regardless of brightness or chromaticity of external light. For example, this is useful when the illuminance is extremely low, such as at night or in a dark room. Also, if the surroundings are dark, a bright display may be too bright for the user. To prevent this, it is preferable to display the image with reduced brightness in the second mode. This not only reduces glare, but also reduces power consumption. is a mode suitable for displaying vivid images (still images and moving images).

[0243] In the third mode, both the reflected light from the first display element and the emitted light from the second display element are used. The display is more vivid than the first mode, but less obscuring than the second mode. For example, under indoor lighting or in the morning or evening, when the illuminance is low, This is effective when the chromaticity of the external light is not white, and when the chromaticity of the reflected light and the emitted light are By using a mixture of light and light, the images are presented in a way that makes them feel as if they are paintings. It becomes possible to show

[0244] By adopting such a configuration, a highly visible and convenient display device can be obtained regardless of the surrounding brightness. It is possible to realize a display device that can be used anywhere or in all weather conditions.

[0245] The display device of this embodiment mode includes a first pixel having a first display element and a second pixel having a second display element. The first pixels and the second pixels each have a matrix. It is preferable that the electrodes are arranged in a box shape.

[0246] Each of the first pixel and the second pixel may include one or more sub-pixels. For example, a pixel can have one subpixel (e.g., white (W)), three subpixels (e.g., white (W)), or The configuration (three colors of red (R), green (G), and blue (B), or yellow (Y), shear (C), magenta (M), or a four-subpixel configuration (red ( Four colors: red (R), green (G), blue (B), and white (W), or red (R), green (G), For example, four colors (e.g., blue (B), yellow (Y) and red (C)) can be applied.

[0247] The display device of the present embodiment performs full color display using either the first pixel or the second pixel. Alternatively, the display device of this embodiment mode may have a black and white display in the first pixel. The first pixel displays a first color or a grayscale image, and the second pixel displays a full color image. The black and white or grayscale display using the first pixel can be used to It is suitable for displaying information that does not require color display, such as

[0248] (Embodiment 2) In this embodiment, a CA that can be used for a transistor disclosed in one embodiment of the present invention is described. Explain the composition of C(Cloud-Aligned Composite)-OS .

[0249] CAC-OS is, for example, a metal oxide made up of elements with a size of 0.5 nm to 10 nm. Preferably, the material is unevenly distributed in a size range of 1 nm to 2 nm or less, or in the vicinity thereof. In the following, in the case of metal oxides, one or more metal elements are unevenly distributed. The region having the metal element has a size of 0.5 nm to 10 nm, preferably 1 nm or more. The state where particles are mixed in a size of 2 nm or less or close to that size is also called a mosaic or patch state. say.

[0250] The metal oxide preferably contains at least indium. In addition to these, it is preferable that the element M (M is gallium, aluminum, nium, silicon, boron, yttrium, tin, copper, vanadium, beryllium, titanium , Iron, Nickel, Germanium, Zirconium, Molybdenum, Lanthanum, Cerium, Neo may contain zinc, hafnium, tantalum, tungsten, or magnesium stomach.

[0251] For example, the In-M-Zn oxide having the CAC-OS structure is an indium oxide (hereinafter Bottom, InO X1 (X1 is a real number greater than 0.) or indium zinc oxide (Hereinafter, In X2 Zinc Y2 O Z2 (X2, Y2, and Z2 are real numbers greater than 0.) ) and oxides of element M (hereafter, MOX3 (X3 is a real number greater than 0.) or zinc oxide of element M (hereinafter, M X4 Zinc Y4 O Z4 (X4, Y4, and Z4 are 0 The material is separated into a mosaic shape, and the mosaic is a real number larger than the pixel size. InO X1 , or In X2 Zinc Y2 O Z2 The structure in which the Also called loud.

[0252] In other words, the In-M-Zn oxide with the CAC-OS structure is X3 is the main component Area and In X2 Zinc Y2 O Z2 , or InO X1 The main component is a mixture of Therefore, metal oxides are sometimes referred to as composite metal oxides. In this specification, for example, the atomic ratio of In to the element M in the first region is The first region is defined as a second region having a larger atomic ratio of In to the element M in the first region than the atomic ratio of In in the second region. In comparison, the concentration of In is assumed to be high.

[0253] In addition, a metal oxide having a CAC-OS structure is a laminate of two or more films with different compositions. For example, a film mainly made of In and a film mainly made of Ga are not included. This does not include a two-layer structure.

[0254] Specifically, the CAC-OS of In-Ga-Zn oxide (In- The Ga-Zn oxide may be specifically referred to as CAC-IGZO. The CAC-OS in n-Ga-Zn oxide is InOX1 , or In X2 Zinc Y2 O Z2 and gallium oxide (GaO X5 (X5 is a real number greater than 0.) or gallium zinc oxide (Ga X6 Zinc Y6 O Z6 (X6, Y6, and Z6 are The material is separated into mosaics, and the mosaic is created. Zinc-like InO X1 , or In X2 Zinc Y2 O Z2 is a cloud-like metal oxide. be.

[0255] In other words, the CAC-OS in the In-Ga-Zn oxide is GaO X5 The area where is the main component Area and In X2 Zinc Y2 O Z2 , or InO X1 The area where the main component is mixed with It is a composite metal oxide having a structure of GaO X5 The region where In is the main component and X 2Zn Y2 O Z2 , or InO X1 The area where the main component is the area where no clear boundary can be observed. There are cases where this is the case.

[0256] IGZO is a common name and refers to a compound made of In, Ga, Zn, and O. A typical example is InGaO3(ZnO). m1 (m1 is a natural number), or In ( 1+x0) Ga (1-x0) O3(ZnO) m0 (-1≦x0≦1, m0 is an arbitrary number) Examples of the crystalline compounds include those which are

[0257] The crystalline compound has a single crystal structure, a polycrystalline structure, or a CAAC structure. The CAAC structure is a structure in which multiple IGZO nanocrystals have a c-axis orientation and are aligned in the ab plane. is a layered crystal structure that is not oriented and is connected.

[0258] In this specification, CAC-IGZO refers to a metal oxide containing In, Ga, Zn, and O. In the oxide, a plurality of regions mainly composed of Ga and a plurality of regions mainly composed of In are They can be defined as metal oxides that are randomly dispersed in a mosaic pattern. .

[0259] The crystallinity of the CAC-OS in In-Ga-Zn oxide is evaluated by electron diffraction. For example, a ring-shaped area of ​​high brightness can be observed in an electron diffraction pattern image. In addition, multiple spots may be observed in the ring-shaped region.

[0260] The CAC-OS of In-Ga-Zn oxide is an IGZO-like structure with uniform distribution of metal elements. It has a different structure from the IGZO compound and has different properties from the In-Ga CAC-OS in GaO X5 The main components are In X2 Zinc Y2 O Z2 , or InO X1 The regions are separated into two groups, one where each element is the main component and the other where each element is the main component. The component regions have a mosaic-like structure.

[0261] Instead of gallium, aluminum, silicon, boron, yttrium, tin, and copper can be used. , vanadium, beryllium, titanium, iron, nickel, germanium, zirconium, molybdenum butene, lanthanum, cerium, neodymium, hafnium, tantalum, tungsten, or When magnesium is contained, CAC-OS is a nano-structure consisting of the metal element as the main component. In some areas, the particles are observed to be in the form of nanoparticles, while in others, the particles are observed to be in the form of nanoparticles, mainly composed of In. These are randomly distributed in a mosaic pattern.

[0262] Here, In X2 Zinc Y2 O Z2 , or InO X1 The area where GaO is the main component X5 This region has a higher electrical conductivity than the region where In is the main component. X2 Zinc Y 2O Z2 , or InO X1 When carriers flow through the area where Therefore, In X2 Zinc Y2 O Z2 , or InO X1 The area where is the main component However, by distributing them in a cloud-like shape in the metal oxide, high field-effect mobility (μ) can be achieved. do.

[0263] On the other hand, GaO X5 The region where the main components are In X2 Zinc Y2 O Z2 , or InO X This region has higher insulating properties than the region where GaO X5 etc. The main component is distributed in the metal oxide, which suppresses leakage current and provides good switching performance. This allows for switching operations.

[0264] Therefore, when the CAC-OS of the In-Ga-Zn oxide is used in a semiconductor device, Ga O X5 Insulation caused by X2 Zinc Y2 O Z2 , or InO X1 Caused by The complementary action of the conductivity and the on-state current (I on ), high field effect mobility (μ) and low off-state current (I off ) can be realized.

[0265] Semiconductor devices using CAC-OS in In-Ga-Zn oxide have high reliability. Therefore, the CAC-OS of In-Ga-Zn oxide is expected to be used in displays and other applications. It is ideal for a variety of semiconductor devices.

[0266] This embodiment mode can be combined with other embodiment modes as appropriate.

[0267] (Embodiment 3) In this embodiment, a display module and an electronic device according to one embodiment of the present invention will be described.

[0268] The display module 8000 shown in FIG. 16 is made up of an upper cover 8001 and a lower cover 8002. In between, touch panel 8004 is connected to FPC8003, and touch panel 8005 is connected to FPC8005. A display panel 8006, a frame 8009, a printed circuit board 8010, and a battery 8011 has.

[0269] For example, a display device manufactured using the peeling method according to one embodiment of the present invention is used as the display panel 8006. This allows display modules to be manufactured with high yields. Cut.

[0270] The upper cover 8001 and the lower cover 8002 are connected to the touch panel 8004 and the display panel 8 The shape and dimensions can be changed appropriately to match the size of 006.

[0271] The touch panel 8004 is a resistive or capacitive touch panel. The touch panel 8004 is not provided, and the display panel 8006 is overlapped with the touch panel 8006. It is also possible to provide the display panel 8006 with a touch panel function.

[0272] The frame 8009 protects the display panel 8006 and also prevents the operation of the printed circuit board 8010. It also functions as an electromagnetic shield to block electromagnetic waves generated by the frame. The plate 8009 may function as a heat sink.

[0273] The printed circuit board 8010 includes a power supply circuit, a signal circuit for outputting a video signal, and a clock signal. The power supply circuit is supplied with power from an external commercial power source. Alternatively, the power source may be a battery 8011 provided separately. This can be omitted if a commercial power source is used.

[0274] In addition, the display module 8000 includes additional components such as a polarizing plate, a retardation plate, and a prism sheet. It may also be provided as such.

[0275] According to one embodiment of the present invention, an electronic device having a curved surface and high reliability can be manufactured. According to one embodiment, a flexible and highly reliable electronic device can be manufactured.

[0276] Examples of electronic devices include television sets, desktop or notebook PCs, etc. Computers, monitors for computers, digital cameras, digital video cameras Cameras, digital photo frames, mobile phones, portable game consoles, personal digital assistants, audio playback Examples of such devices include large gaming machines such as pachinko machines.

[0277] In addition, the display device of one embodiment of the present invention can achieve high visibility regardless of the intensity of external light. Therefore, portable electronic devices, wearable electronic devices, and It can be suitably used for child book terminals and the like.

[0278] The mobile information terminal 800 shown in FIGS. 17A and 17B includes a housing 801, a housing 802, a display unit 8 03, a display unit 804, and a hinge unit 805.

[0279] The housing 801 and the housing 802 are connected by a hinge portion 805. The mobile information terminal 800 includes: It can be unfolded from the folded state (Fig. 17(A)) to the state shown in Fig. 17(B). do.

[0280] The display device manufactured by the peeling method according to one embodiment of the present invention is a display portion 803 and a display portion 804. This allows the production of portable information terminals with a high yield. The end can be made.

[0281] The display unit 803 and the display unit 804 display document information, still images, moving images, etc. When the display unit is to display document information, the display unit is capable of displaying at least one of the following: The terminal 800 can be used as an electronic book terminal.

[0282] The portable information terminal 800 can be folded, making it highly portable and versatile.

[0283] The housing 801 and the housing 802 are provided with a power button, an operation button, an external connection port, a speaker, a microphone, and a It may have an inch or the like.

[0284] A portable information terminal 810 shown in FIG. 17C includes a housing 811, a display unit 812, and an operation button 81. 3, an external connection port 814, a speaker 815, a microphone 816, a camera 817, etc.

[0285] A display device manufactured using the peeling method of one embodiment of the present invention can be used for the display portion 812. This makes it possible to manufacture portable information terminals with a high yield.

[0286] The mobile information terminal 810 has a touch sensor on the display unit 812. All operations, such as inputting characters, can be performed by touching the display 812 with a finger or a stylus. It can be done.

[0287] In addition, the operation button 813 is operated to turn the power on and off, and to display information on the display unit 812. For example, you can change the type of image displayed on the main screen from the email composition screen. You can switch to the menu screen.

[0288] In addition, a detection device such as a gyro sensor or an acceleration sensor is installed inside the mobile information terminal 810. By providing the above, the orientation of the mobile information terminal 810 (vertical or horizontal) can be determined and the screen of the display unit 812 can be adjusted. The display orientation can be switched automatically. The screen orientation can also be switched by The input is made by touching the display unit 812, by operating the operation button 813, or by inputting voice using the microphone 816. It can also be performed by using force or the like.

[0289] The mobile information terminal 810 is, for example, one or more devices selected from a telephone, a notebook, an information viewing device, etc. Or it has multiple functions. Specifically, it can be used as a smartphone. The information terminal 810 is, for example, a mobile phone, an electronic mail, a text reading and writing, a music playback, a video It can run various applications such as playback, internet communication, and games. do.

[0290] The camera 820 shown in FIG. 17(D) includes a housing 821, a display unit 822, an operation button 823, and a shutter. The camera 820 also has a removable lens 826. It is attached.

[0291] A display device manufactured using the peeling method of one embodiment of the present invention can be used for the display portion 822. This allows the camera to be manufactured with a high yield.

[0292] Here, the camera 820 and the lens 826 can be removed from the housing 821 and replaced. However, the lens 826 and the housing 821 may be integrated together.

[0293] The camera 820 captures still or moving images by pressing the shutter button 824. In addition, the display unit 822 has a function as a touch panel. It is also possible to take a picture by touching 2.

[0294] The camera 820 can be equipped with a strobe device, viewfinder, etc. Alternatively, these may be incorporated into the housing 821.

[0295] 18A to 18E are diagrams showing electronic devices. , a display unit 9001, a speaker 9003, and operation keys 9005 (power switch or operation switch switch), connection terminal 9006, sensor 9007 (force, displacement, position, speed, acceleration, Angular velocity, rotation speed, distance, light, liquid, magnetism, temperature, chemicals, sound, time, hardness, electric field, current The ability to measure voltage, power, radiation, flow rate, humidity, gradient, vibration, odor or infrared The device has a microphone 9008 and the like.

[0296] A display device manufactured using the peeling method according to one embodiment of the present invention is preferably used for the display portion 9001. This allows electronic devices to be manufactured with a high yield.

[0297] The electronic devices shown in FIGS. 18(A) to 18(E) can have various functions. Functions for displaying various information (still images, videos, text images, etc.) on the display unit, touch panel function Functions such as displaying calendars, dates, or times, and various software (programs) ) to control processing, wireless communication function, and wireless communication function to connect various computers The function to connect to a data network, and the function to transmit or receive various data using wireless communication functions. The function to be performed, read out the program or data recorded on the recording medium and display it on the display unit The electronic device shown in Figs. 18(A) to 18(E) can have the following functions. The functions are not limited to these, and other functions may be included.

[0298] FIG. 18A shows a wristwatch-type portable information terminal 9200, and FIG. 18B shows a wristwatch-type portable information 92 is a perspective view showing a terminal 9201.

[0299] The portable information terminal 9200 shown in FIG. 18A is a terminal for mobile telephone, e-mail, and document viewing and creation. It supports a variety of applications such as music playback, Internet communication, and computer games. In addition, the display surface of the display unit 9001 is curved. The portable information terminal 9200 can display information on a display surface. For example, a wireless headset can be used By communicating with each other, you can talk hands-free. The 9200 has a connection terminal 9006 and can directly exchange data with other information terminals via a connector. Also, charging can be performed via the connection terminal 9006. The charging operation may be performed by wireless power supply without going through the connection terminal 9006.

[0300] The portable information terminal 9201 shown in FIG. 18B is different from the portable information terminal shown in FIG. The display surface of the display unit 9001 is not curved. The shape is non-rectangular (circular in FIG. 18(B)).

[0301] 18(C) to (E) are perspective views showing a foldable portable information terminal 9202. FIG. 18C is a perspective view of the portable information terminal 9202 in an unfolded state, and FIG. The mobile information terminal 9202 changes from one of the unfolded state and the folded state to the other. FIG. 18(E) is a perspective view of the portable information terminal 9202 in a folded state. FIG.

[0302] The portable information terminal 9202 is highly portable when folded, and has a seam when unfolded. The display area of ​​the portable information terminal 9202 is large and has excellent visibility. 9001 is supported by three housings 9000 connected by hinges 9055 . The two housings 9000 are bent via the hinge 9055, so that the portable information terminal 9 202 can be reversibly transformed from an unfolded state to a folded state. For example, The portable information terminal 9202 can be bent with a radius of curvature of 1 mm or more and 150 mm or less.

[0303] This embodiment mode can be combined with other embodiment modes as appropriate. EXAMPLES

[0304] In this embodiment, a polyimide thin film is formed on a glass substrate, and then a release film is attached to the polyimide. The method is to bond the glass substrate to the glass plate and then irradiate the glass plate with a laser to form a peelable layer. A solution of soluble polyimide (product number at Tochigi Plant: S A suitable amount of O0100001) was dropped onto the substrate and spin-coated to form a film. The film was baked at 35°C for 1 hour, and a peeling film was attached after baking. Adhesive (Nissin Resin, CEP05) was applied in a line shape to the A 125μm film (PANAC Corporation, CT100 / Lumirror 125UF83) was placed. Then, an excimer laser (wavelength 1000 nm) was applied from the glass substrate side. : 308 nm) with an energy density of 439 (mJ / cm 2 After irradiation, The release layer was separated from the glass substrate by making a notch in the release film.

[0305] Regarding the release film having the separated peelable layer and the glass substrate after peeling, The surface of the release layer on the release film side was analyzed by LC / MS. The release film having a release layer and the glass substrate after the layer to be peeled off are cut into any size. The surface of the glass substrate on which the layer to be peeled was formed and the release film having the layer to be peeled were then The delaminated surface was then soaked in 15 drops of a mixture of acetonitrile and chloroform (volume ratio: 7:3). The solvent used for washing was used three times, and the resulting washing solution was used as the measurement sample. Acetonitrile and 1,1,1,3,3,3-hexafluoro-2-propanol are (abbreviation: HFIP) in a volume ratio of 7:3 was also used. Similarly, the release film (PET\CEP05) and the glass substrate were mixed with the above two types. The surface was washed with the combined solvent to prepare a reference sample.

[0306] The two samples and two reference samples prepared in the above manner were subjected to LC LC / MS analysis was performed using LC (liquid chromatography) separation. MS analysis (mass spectrometry) was performed using a Waters Acquity UPLC. The LC separation was performed using a Xevo G2 Tof MS. The column used for LC separation was Acquity. UPLC BEH C8 (2.1×100mm 1.7μm), column temperature 40℃ The mobile phase A was acetonitrile, and the mobile phase B was 0.1% formic acid aqueous solution. The sample injection volume was 5.0 μL.

[0307] A gradient method was used for LC separation, which changes the composition of the mobile phase. Up to 9 minutes, the mobile phase A:mobile phase B = 30:70, then the composition was changed and the mobile phase A:mobile phase B = 30:70 A linear gradient was used so that the ratio of mobile phase A to mobile phase B was 95:5. The same ratio was then applied and maintained for 15 minutes.

[0308] In the MS analysis, electrospray ionization was used. The capillary voltage was 3.0107 The voltage was 5 kV, the sample cone voltage was 30 V, and detection was performed in positive and negative mode. The mass range for measurement was m / z = 100 to 1200. The chromatogram of the PDA (photodiode array) detector obtained by the LC / MS analysis was The area ratios of the peaks detected in Figure 19 are summarized in Table 1. , ions were not detected in positive mode, so they were detected in negative mode. Only mass-to-charge charges are shown.

[0309] [Table 1]

[0310] As can be seen from Table 1, the mass charge distribution was observed from the separation interface of the peeled layer in multiple LC / MS measurements. Many substances derived from ions with charge ratios of 300 to 950 (5 or more, preferably 10 or more) This substance was generated by decomposition of the polyimide in the release layer due to laser absorption. This is what was done.

[0311] In Fig. 20, a laser with a wavelength of about 308 nm was applied to a polyimide film formed in the same manner as in the above experiment. The polyimide film has the following absorption rate when irradiated with laser light: It shows an absorptivity of 94.3%, absorbing almost all of the irradiated laser light. That is, by absorbing the irradiated laser light, the polyimide film is decomposed, and the LC / M In S measurements, many substances derived from ions with mass-to-charge ratios between 300 and 950 were detected. It is believed that this is what has led to this.

[0312] The soluble polyimide solution used here (product number at Tochigi Plant: SO0100001 This article explains the LC / MS analysis of low molecular weight components contained in a soluble polyimide solution. When the mixture was mixed with chloroform in a volume ratio of 1:1, precipitation of polyimide was confirmed. The mixture was left for 1 hour until the polyimide precipitated, and the resulting supernatant was separated from the mixture in acetonitrile. The above was diluted to a volume ratio of 10:1 to prepare Comparative Sample 1.

[0313] Similarly, 1,1,1,3,3,3-hexafluoro-2-propanediol was used instead of chloroform. A sample prepared using HFIP was used as comparative sample 2.

[0314] The two comparative samples prepared in the above manner were subjected to LC / MS analysis. The equipment and analytical conditions used for the MS analysis were the same as those used for analyzing the release layer surface described above.

[0315] Chromatograph of a PDA (photodiode array) detector obtained by LC / MS analysis The results are shown in FIG. 21. Note that FIG. 21(A) shows the results for Comparative Sample 1, and (B) shows the results for Comparative Sample 2. As can be seen from Figure 21(A)(B), nothing was detected in the PDA chromatograph. However, some ions were detected by the MS detector. The ratios and retention times are summarized in Table 2. Table 2 also shows that no ions were detected in the positive mode. Therefore, only the mass-to-charge ratios detected in the negative mode are shown.

[0316] [Table 2]

[0317] As can be seen from Table 2, the soluble polyimide solution contains chloroform and HFIP-soluble polyimide. It was confirmed that the mixture contained several types of low molecular weight components that could be detected by MS.

[0318] When comparing this comparative sample with the peeled sample, The low molecular weight components with mass-to-charge ratios (m / z) of 300 to 950 are soluble polyimides. It was confirmed that this was not something that was in the solution, but was generated during the peeling process. The low molecular weight components that are generated are present at the peeled interface, and therefore the generation of the low molecular weight components is considered to be a trigger. It is believed that good peelability was obtained.

[0319] Therefore, the generation of these substances embrittles the affected area, causing the embrittled area to peel off. The method of the present invention for removing the brittle layer caused by the deterioration of polyimide occurs. This is an extremely useful peeling method in the substrate fabrication process, as it allows you to set the peeling point whenever necessary. In other words, in the process where peeling is not allowed, the layer to be peeled off should be held on the substrate. Therefore, the substrate produced by the peeling method of the present invention has a low cost. It is possible to obtain a highly reliable peeled layer with short tact time at low cost. [Explanation of symbols]

[0320] 10A display device 10B display device 13 Adhesive layer 14 Preparation of substrate 21 Layer to be peeled 22 Substrate 23 Peeling layer 24 Resin layer 25 Separation area 28 Adhesive layer 29 Substrate 31 Insulating layer 32 Insulating layer 33 Insulating layer 34 Insulating layer 35 Insulating layer 40 Transistor 41 Conductive layer 43a Conductive layer 43b Conductive layer 43c conductive layer 44 Metal Oxide Layer 45 Conductive Layer 49 Transistor 60 Light emitting element 61 Conductive layer 62 EL layer 63 Conductive Layer 64 Break 65 Equipment 66 Laser Light 67 Irradiation area 74 Insulating Layer 75 Protective layer 75a Board 75b Adhesive layer 76 Connectors 80 Transistor 81 Conductive Layer 82 Insulating layer 83 Metal Oxide Layer 84 Insulating Layer 85 Conductive Layer 86a Conductive layer 86b Conductive layer 86c Conductive layer 91 Preparation Board 93 Peeling layer 94 Separation area 95 Insulating Layer 96 Bulkhead 97 Colored layer 98 Light blocking layer 99 Adhesive layer 372 FPC 381 Display section 382 Drive circuit section 800 Mobile Information Terminals 801 Case 802 Case 803 Display section 804 Display section 805 Hinge part 810 Mobile Information Terminal 811 Case 812 Display section 813 Operation button 814 External connection port 815 Speaker 816 Mike 817 Camera 820 Camera 821 Case 822 Display section 823 Operation button 824 Shutter button 826 Lens 8000 Display Module 8001 Top cover 8002 Lower cover 8003 FPC 8004 Touch Panel 8005 FPC 8006 Display Panel 8009 Frame 8010 Printed Circuit Board 8011 Battery 9000 Chassis 9001 Display section 9003 Speaker 9005 Operation key 9006 Connection terminal 9007 Sensor 9008 Microphone 9055 Hinge 9200 Mobile Information Terminal 9201 Portable information terminals 9202 Mobile information terminals

Claims

1. A semiconductor device having a second resin layer on and in contact with a first resin layer, and a transistor on the second resin layer, A semiconductor device, wherein when a surface of the first resin layer that is not in contact with the second resin layer is washed with a liquid and the washing liquid is subjected to mass spectrometry, a substance having a mass-to-charge ratio (m / z) of 300 or more and 950 or less is detected.

2. In claim 1, The element detects 10 or more substances having a mass-to-charge ratio of 300 or more and 950 or less in the mass spectrometry.

3. In claim 1 or 2, The mass spectrometry is carried out using liquid chromatography mass spectrometry.

4. In any one of claims 1 to 3, The semiconductor device, wherein the first resin layer is a layer containing polyimide as a main component.

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