JPWO2015174064A1 - Polyimide film manufacturing method, electronic device manufacturing method, and coating film peeling method - Google Patents

Abstract

Provided is a method for manufacturing an electronic device or the like in which a support and a base film are favorably bonded before the peeling treatment, and the support and the base film can be easily peeled after the peeling treatment. The method for manufacturing an electronic device according to the present invention is a method for manufacturing an electronic device in which a device (83) is formed on a base film, having at least a polyimide film as a base film, a soluble polyimide resin, a thermosetting crosslink A step (a) of coating a polyimide varnish containing a material and a solvent on a support (81), forming a coating film by drying at a temperature exceeding the glass transition point of the polyimide resin and less than the crosslinking start temperature of the crosslinking material; The step (c) of forming the device (83) on the polyimide film (82) obtained by a) and the polyimide film (82) obtained through the step (c) promote the crosslinking reaction of the crosslinking material. And a step (b) of peeling from the support (81).

Description

  The present invention relates to a method for producing a polyimide film and a method for peeling a coating film. Moreover, it is related with the manufacturing method of the said polyimide film, and the manufacturing method of the electronic device formed using the peeling method of a coating film.

  In recent years, flat panel displays such as liquid crystal displays and organic EL displays have been made thinner, and flexible displays such as flexible flat panel displays that can be bent freely have been developed. In the current mainstream flat panel display, glass is used as a substrate and it is heavy and easily damaged. However, since a base film is used, a flexible display has an advantage that it is very thin and light and is not easily damaged. Moreover, since flexibility can be provided, display on a curved surface is also possible. The development of electronic paper as a flexible display is also being promoted.

  In a flexible display, a resin film serving as a base film is generally formed on a glass substrate that is a support, and a device is mounted (formed) on the base film. And finally, it manufactures through the process of peeling a base film from a glass substrate. In Patent Document 1, a laminate in which a first material layer, a second material layer, and a layer to be peeled are stacked in this order on a substrate is formed, and the first material layer, the second material layer, and the like are separated before peeling. Proposes a method of separating at the interface or the interface of the second material layer by performing a treatment (laser light, pressurization, etc.) to partially reduce the adhesion of the second material layer and then peeling it off by physical means. .

JP 2003-163338 A

  The method of mounting a device on a base film is excellent in that an electronic device such as a flexible display can be easily manufactured. However, adhesiveness is provided between the glass substrate and the base film resin so that the glass substrate and the base film resin are not peeled when the device is mounted. For this reason, a technical device is required to peel the base film from the glass substrate after mounting. There are two methods of peeling: the method of burning the surface of the base film with laser light and the method of peeling with a strong force. However, the energy of the laser light may damage the device or damage the base film, resulting in product yield. There was a problem.

  In the manufacture of electronic devices such as flexible displays, the glass substrate and the base film are strongly bonded until the device is formed, and there is a strong demand in the market for a technology that can easily peel the base film from the glass substrate after the device is formed. It has been. In addition, although the subject in a flexible display was described, the same subject exists also in the various electronic devices which want to form a device on a base film.

  The present invention has been made in view of such a background. Before the release treatment, the support and the base film adhere well, and after the release treatment, the support and the base film can be easily peeled off, and the yield is high. It aims at providing the manufacturing method of an apparatus, the peeling method of a coating film, and the manufacturing method of the polyimide film used for at least one layer of the said base film.

As a result of extensive studies by the present inventors, it has been found that the problems of the present invention can be solved in the following modes, and the present invention has been completed.
[1] A polyimide varnish containing a soluble polyimide resin, a thermosetting cross-linking material and a solvent is coated on a support, and exceeds the glass transition point of the soluble polyimide resin and below the cross-linking start temperature of the thermosetting cross-linking material. A step (a) of forming a coating film by drying at a step, and a step (b) of peeling off the polyimide film obtained through the step (a) from the support after the crosslinking reaction of the crosslinking material is promoted. The manufacturing method of the polyimide film containing this.
[2] The method for producing a polyimide film according to [1], wherein in the step (b), the polyimide film is irradiated with flash light from the support side.
[3] A method of manufacturing an electronic device for forming a device on a base film, wherein the base film includes at least a polyimide film, and a polyimide varnish containing a soluble polyimide resin, a thermosetting crosslinking material, and a solvent. Obtained by steps (a) and (a) of coating on a support, forming a coating film by drying at a temperature lower than the glass transition point of the soluble polyimide resin and less than the crosslinking start temperature of the thermosetting crosslinking material. A step (c) of forming the device on the obtained polyimide film, and a step of peeling the polyimide film obtained through the step (c) from the support after promoting the crosslinking reaction of the crosslinking material ( and b) an electronic device manufacturing method.
[4] The method for manufacturing an electronic device according to [3], wherein the step (c) includes a thin film formation process by a vapor deposition method.
[5] The method for manufacturing an electronic device according to [3] or [4], wherein the step (b) irradiates the polyimide film with flash light from the support side.
[6] The method for manufacturing an electronic device according to [5], wherein the flash light is intensively applied to an edge portion of the polyimide film formed on the support.
[7] The electron according to [5] or [6], wherein a light absorption layer that absorbs the flash light is provided on the support that faces the edge of the polyimide film in plan view. Device manufacturing method.
[8] The electronic device manufacturing according to any one of [5] to [7], wherein, in the emitted light of the flash light, a band having a high light absorption rate of the polyimide film is selectively irradiated. Method.
[9] The method for manufacturing an electronic device according to [8], wherein the emission light of the flash light is cut by a filter in a band where the light absorption rate of the polyimide film is low.
[10] The method for manufacturing an electronic device according to [8] or [9], wherein the band having a high light absorption rate of the polyimide film is an ultraviolet region.
[11] The method for manufacturing an electronic device according to [9], wherein the filter cuts a wavelength of 400 nm or more.
[12] Before the step (c), the method further includes a step (d) of depressurizing an atmosphere around the support on which the polyimide film is formed,
The method for manufacturing an electronic device according to any one of [5] to [11], wherein when the flash light is irradiated, bubbles existing at an interface between the polyimide film and the support are expanded.
[13] The electronic device according to any one of [3] to [12], wherein the device is any one selected from the group consisting of a flexible display, a flexible device, a semiconductor device, a solar cell, and a fuel cell. Production method.
[14] A polyimide varnish containing a soluble polyimide resin, a thermosetting cross-linking material and a solvent is coated on a support, and exceeds the glass transition point of the soluble polyimide resin, and is less than the crosslinking start temperature of the thermosetting cross-linking material. (A) forming a polyimide film by drying, and (b) peeling the polyimide film obtained through the step (a) from the support after promoting the crosslinking reaction of the crosslinking material. The peeling method of the coating film containing these.
[15] The coating film peeling method according to [14], wherein in the step (b), the polyimide film is irradiated with flash light from the support side.

  According to the present invention, there are provided a method for manufacturing an electronic device and a method for peeling a coating film, which are well bonded to a support before the peeling treatment, can be easily peeled off after the peeling treatment, and have a high yield. In addition, there is an excellent effect that a method for producing a polyimide film used for at least one layer of the base film can be provided.

It is a figure which shows the principal part structure of the flash lamp annealing apparatus which concerns on 1st Embodiment. It is a flowchart which shows the process sequence in a flash lamp annealing apparatus. It is sectional drawing which shows the structure of a to-be-processed object. It is a figure which shows the state by which flash light was irradiated to the to-be-processed object. It is a figure which shows an example of a mode that the polyimide film which is a layer to be peeled is peeled from a glass substrate. It is a figure which shows the principal part structure of the flash lamp annealing apparatus of 2nd Embodiment. It is the top view which looked at the light-shielding plate from upper direction. It is a top view of the to-be-processed object in which the light absorption layer was formed. It is a figure which shows the state by which flash light was irradiated to the to-be-processed object in 3rd Embodiment. It is a figure which shows the principal part structure of the flash lamp annealing apparatus of 4th Embodiment. It is a figure which shows the radiation spectral distribution of a xenon flash lamp.

[Production method of polyimide film]
The method for producing a polyimide film according to the present invention includes at least the following steps (a) to (b).
In the step (a), a polyimide varnish containing a soluble polyimide resin, a thermosetting cross-linking material and a solvent is applied onto a support, the glass transition point of the soluble polyimide resin is exceeded, and the crosslinking start temperature of the thermosetting cross-linking material. It is the process of drying at less than and forming a coating film. Step (b) is a step of peeling the polyimide film obtained through step (a) from the support after promoting the crosslinking reaction of the crosslinking material.

  The polyimide varnish used in the step (a) includes at least a soluble polyimide resin, a thermosetting crosslinking material, and a solvent.

  The soluble polyimide resin is usually obtained by polycondensation and imidization of a tetracarboxylic dianhydride and a diamine monomer. If it has solvent solubility, the kind of polyimide resin will not be specifically limited, However, From a viewpoint of making the joining property to a support favorable, a thermoplastic polyimide resin is preferable.

  The tetracarboxylic dianhydride and diamine to be used preferably have an aromatic group in view of mechanical properties after film formation. Examples of aromatic tetracarboxylic dianhydrides include pyromellitic anhydride (1,2,4,5-benzenetetracarboxylic dianhydride), 3,3 ′, 4,4′-benzophenone tetracarboxylic acid Anhydrides, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride and the like can be mentioned. Examples of aromatic diamines include 4,4′-oxydiaminobenzene (4,4′-diaminodiphenyl ether), 1,3-bis- (3-aminophenoxy) benzene, 4,4′-bis- ( 3-aminophenoxy) biphenyl, 1,4-diaminobenzene, 1,3-diaminobenzene and the like.

  By using a soluble polyimide resin, a heating step for imidization is unnecessary. That is, a polyimide varnish containing a polyimide soluble in a solvent can be applied on a support and then dried to form a polyimide film. Therefore, the step of imidizing the coating film at a high temperature is not necessary, and it is easy to process and can be applied to a temperature lower than the crosslinking start temperature of the crosslinking material before the peeling treatment in the step (b) described later. The choice of a cross-linking material can be increased. In the method for producing a polyimide film of the present invention, it is possible to use a polyamic acid varnish, which is a polyimide precursor, instead of a polyimide varnish, or to blend a polyamic acid with a polyimide varnish. In general, since heating at 300 to 350 ° C. is necessary, the temperature is often higher than the crosslinking start temperature of a general crosslinking material. Moreover, although it is also possible to add a catalyst for the purpose of implementing imidization at low temperature, there exists a possibility that the hardening of a crosslinking material may be accelerated | stimulated or the physical property as a polyimide film may deteriorate. For this reason, it is desirable to use the polyimide varnish melt | dissolved in the solvent for the manufacturing method of this invention.

  As the cross-linking material, a thermosetting cross-linking material that starts a cross-linking reaction at a predetermined temperature is used. The crosslinking material has a crosslinking initiation temperature that is higher than the glass transition point of the polyimide resin used and lower than the heat resistance temperature of the support used.

  The cross-linking material is not particularly limited as long as it can promote the peeling between the support and the polyimide film by a cross-linking reaction. The addition amount of a crosslinking agent is 5-25 mass%, for example, and the preferable crosslinking start temperature of a crosslinking material is 150-400 degreeC, More preferably, it is 200 degreeC or more and 350 degrees C or less. By setting the temperature to 200 ° C. or higher, process stability can be improved and manufacturing yield can be increased. Moreover, deterioration by the heating of a polyimide film or the other member formed on a polyimide film can be prevented by setting it as 350 degrees C or less.

  The type of the cross-linking material is not limited as long as it matches the gist of the present invention, and examples thereof include a bismaleimide compound, a bisnadiimide compound, and a terminal bisacetylene compound.

  The solvent is not particularly limited as long as it can dissolve the soluble polyimide resin when it is made into a varnish. For example, even a solvent that does not dissolve a polyimide resin alone can be used as long as the polyimide resin can be dissolved when used in combination with another solvent. Solvents can be used alone or in combination.

  Although a support body is not limited unless it deviates from the meaning of this invention, a glass substrate (quartz substrate etc.), a sapphire substrate, a silicon substrate, a silicon carbide substrate etc. can be illustrated as a suitable example. A polyimide film is formed directly on the support.

  Examples of the step of applying the polyimide varnish include solution film forming methods such as spray coating, brush coating, dip coating, die coating, curtain coating, flow coating, spin coating, and screen printing. After application, the polyimide film is obtained by drying. Although a film thickness can be designed suitably according to a use, it is about 5-100 micrometers, for example. The drying temperature after coating must exceed the glass transition point of the soluble polyimide resin and be lower than the crosslinking start temperature of the cross-linking material. The drying temperature after coating is preferably 20 ° C. or lower than the crosslinking initiation temperature from the viewpoint of process stability.

  The polyimide film may be a single layer or may be formed from a plurality of layers. Moreover, the laminated body which laminated | stacked the layer which consists of another resin, the metal layer, the metal oxide layer, etc. on the upper layer of the polyimide film layer may be sufficient.

  The step (b) weakens the adhesive force between the support and the polyimide film by promoting the crosslinking reaction of the crosslinking material. The cross-linking reaction of the cross-linking material can be realized by setting the cross-linking material to a cross-linking start temperature or higher. The polyimide film and the support having a weak adhesive force can be easily separated by a known method. The means of step (b) is not limited as long as it does not depart from the gist of the present invention, but as a method for promoting the crosslinking reaction of the crosslinking agent, a method of irradiating the polyimide film with flash light from the support side is suitable. The flash light irradiation method is not particularly limited, and for example, it can be formed using a flash lamp. Furthermore, it is also effective to heat when irradiating flash light. A detailed process of the step (b) will be described later.

[Manufacturing method of electronic equipment]
Next, an example of an embodiment of an electronic device manufacturing method using the polyimide film manufacturing method of the present invention will be described.
The method for manufacturing an electronic device according to the present invention includes a step of forming a device on a polyimide film as a base film, and includes at least a step (c) in addition to the above-described steps (a) and (b). Is. Step (c) is performed before step (b) and is a step of forming a device on the polyimide film. Although the kind of device is not specifically limited, A flexible display, a flexible device, a semiconductor device, a solar cell, a fuel cell, etc. can be illustrated.

  The polyimide film functions as a base film for device formation. As the polyimide film, a layer composed only of the polyimide film formed by the step (a) or a layer composed of a laminated film obtained by laminating another layer on the polyimide film formed by the step (a) can be used. The polyimide film needs to have heat resistance capable of withstanding the process temperature when forming a device. Usually, when a device is mounted on a base film, the process temperature is often 300 ° C. or higher. Therefore, the polyimide resin used is preferably excellent in heat resistance. From this viewpoint, it is preferable to use a polyimide resin derived from an aromatic diamine and an aromatic tetracarboxylic dianhydride.

  Step (c) is a step of mounting a device on a polyimide film formed on a support by a known method. For example, it may include a thin film formation process in which a semiconductor layer, a metal layer, an insulating layer, and the like are stacked on a base film in a desired order using a vapor deposition method, a solution coating method, or the like. In addition, a manufactured device may be directly mounted.

  Various methods can be used for the step (b) as described above. Here, a method performed by irradiating the polyimide film with flash light from the glass substrate side will be described (irradiation step). When flash light is irradiated, due to the difference in light absorption rate and linear expansion coefficient between the glass substrate and the polyimide film, a difference occurs in the degree of temperature rise and the elongation rate due to heating, at the interface between the glass substrate and the polyimide film, A shear stress is generated in a direction parallel to the interface. In addition, the polyimide film contains an unreacted cross-linking material, and by irradiating flash light, these cross-linking materials are rapidly heated to a temperature exceeding the cross-linking start temperature, and the cross-linking reaction proceeds rapidly. . Due to these shear stresses, the adhesive force (bonding force) at the interface decreases. As a result, after irradiation with flash light, the polyimide film can be easily peeled from the glass substrate.

  After the irradiation step, the polyimide film having a reduced adhesive force with the glass substrate is peeled from the glass substrate (peeling step). Various known techniques can be employed as a method for peeling the polyimide film from the glass substrate. Hereinafter, an example of a more specific embodiment of the step (b) will be described.

[First Embodiment]
(Configuration of flash lamp annealing equipment)
FIG. 1 shows a schematic configuration diagram of a flash lamp annealing apparatus used in the first embodiment. The flash lamp annealing apparatus 1 is an apparatus that assists the peeling of the polyimide film by irradiating flash light onto the object 8 having a polyimide film formed on the glass substrate. The flash lamp annealing apparatus 1 includes, as main elements, a chamber 10 that houses the object 8 to be processed, a holding plate 20 that holds the object 8 to be processed, and a flash light source 70 that irradiates the object 8 with flash light. . Further, the flash lamp annealing apparatus 1 includes a control unit 3 that controls various operation mechanisms provided in the apparatus to advance the processing. In FIG. 1 and the subsequent drawings, the size and number of each part are exaggerated or simplified as necessary for easy understanding.

  The chamber 10 is provided below the flash light source 70, and includes a chamber side wall 11 and a chamber bottom 12. The chamber bottom 12 covers the lower part of the chamber side wall 11. A space surrounded by the chamber side wall 11 and the chamber bottom 12 is defined as the processing space 15. A chamber window 18 is attached to the upper opening of the chamber 10 to close it.

  The chamber window 18 constituting the ceiling portion of the chamber 10 is a plate-like member formed of quartz, and functions as a quartz window that transmits the light emitted from the flash light source 70 to the processing space 15. The chamber side wall 11 and the chamber bottom 12 constituting the main body of the chamber 10 are formed of a metal material having excellent strength and heat resistance such as stainless steel, for example.

  In order to maintain the airtightness of the processing space 15, the chamber window 18 and the chamber side wall 11 are sealed by an O-ring (not shown). That is, an O-ring is sandwiched between the peripheral edge of the lower surface of the chamber window 18 and the chamber side wall 11 to prevent gas from flowing in and out from these gaps.

  A holding plate 20 is provided inside the chamber 10. The holding plate 20 is a flat plate member made of metal (for example, aluminum). A plurality of support pins 22 are provided on the upper surface of the holding plate 20. The holding plate 20 supports the object 8 to be processed by the plurality of support pins 22 in the chamber 10 and holds the object 8 in a substantially horizontal posture. The support pin 22 may be movable up and down by a lift drive mechanism (not shown) (for example, an air cylinder).

  In addition, the holding plate 20 includes a heater 21. The heater 21 is configured by a resistance heating wire such as a nichrome wire, and generates heat when receiving power supply from a power supply source (not shown) to heat the holding plate 20. The holding plate 20 may be provided with a cooling mechanism such as a water cooling tube in addition to the heater 21.

  The holding plate 20 is provided with a temperature sensor (not shown) configured using a thermocouple. The temperature sensor measures the temperature near the upper surface of the holding plate 20, and the measurement result is transmitted to the control unit 3. The control unit 3 controls the output of the heater 21 based on the measurement result by the temperature sensor, and sets the holding plate 20 to a predetermined temperature. The object to be processed 8 held on the holding plate 20 is heated to a predetermined temperature by the heater 21 of the holding plate 20.

The flash lamp annealing apparatus 1 also includes a gas supply mechanism 40 that supplies a processing gas to the processing space 15 in the chamber 10 and an exhaust mechanism 50 that exhausts the atmospheric gas from the processing space 15. The gas supply mechanism 40 includes a processing gas supply source 41, a supply pipe 42 and a supply valve 43. The distal end side of the supply pipe 42 is connected to the processing space 15 in the chamber 10, and the proximal end side is connected to the processing gas supply source 41. A supply valve 43 is provided in the course of the supply pipe 42. By opening the supply valve 43, the processing gas is supplied from the processing gas supply source 41 to the processing space 15. The processing gas supply source 41 can supply an appropriate processing gas according to the type of the object to be processed 8 and the processing purpose, but supplies nitrogen gas (N ₂ ) in the first embodiment.

  The exhaust mechanism 50 includes an exhaust device 51, an exhaust pipe 52, and an exhaust valve 53. The distal end side of the exhaust pipe 52 is connected to the processing space 15 in the chamber 10, and the proximal end side is connected to the exhaust device 51. An exhaust valve 53 is provided in the course of the exhaust pipe 52. The exhaust device 51 includes, for example, a dry pump and a throttle valve. By opening the exhaust valve 53 while operating the exhaust device 51, the atmosphere of the processing space 15 can be exhausted outside the device. The atmosphere of the processing space 15 can be adjusted by the gas supply mechanism 40 and the exhaust mechanism 50. In addition, since the processing space 15 is a sealed space, if the atmosphere is exhausted by the exhaust mechanism 50 without supplying the processing gas from the gas supply mechanism 40, the atmosphere in the processing space 15 is reduced to below atmospheric pressure. Can do.

  The flash light source 70 is provided above the chamber 10. The flash light source 70 includes a plurality of flash lamps FL (11 for convenience of illustration in FIG. 1, but is not limited thereto), a reflector 72 provided so as to cover the entire upper part, It is configured with. The flash light source 70 irradiates the workpiece 8 held by the holding plate 20 in the chamber 10 with flash light from the flash lamp FL through the quartz chamber window 18.

  The plurality of flash lamps FL are rod-shaped lamps each having a long cylindrical shape, and are arranged in a plane so that their longitudinal directions are parallel to each other along the horizontal direction. In the first embodiment, a xenon flash lamp is used as the flash lamp FL. The xenon flash lamp FL has a rod-shaped glass tube (discharge tube) in which xenon gas is sealed inside, an anode and a cathode connected to a capacitor at both ends, and an outer peripheral surface of the glass tube. And an attached trigger electrode. Since xenon gas is an electrical insulator, electricity does not flow into the glass tube under normal conditions even if electric charges are accumulated in the capacitor. However, when the insulation is broken by applying a high voltage to the trigger electrode, the electricity stored in the capacitor instantaneously flows into the glass tube due to the discharge between the electrodes at both ends, and the excitation of the xenon atoms or molecules at that time Light is emitted. In such a xenon flash lamp FL, the electrostatic energy stored in the capacitor in advance is converted into an extremely short light pulse of, for example, 0.05 milliseconds to 100 milliseconds. Compared with this, it has the feature that it can irradiate extremely strong light.

  Further, the reflector 72 is provided above the plurality of flash lamps FL so as to cover all of them. The basic function of the reflector 72 is to reflect flash light emitted from a plurality of flash lamps FL toward the processing space 15.

  The controller 3 controls the various operation mechanisms provided in the flash lamp annealing apparatus 1. The configuration of the control unit 3 as hardware is the same as that of a general computer. That is, the control unit 3 stores a CPU that performs various arithmetic processes, a ROM that is a read-only memory that stores basic programs, a RAM that is a readable and writable memory that stores various information, control software, data, and the like. It is configured with a magnetic disk. The processing in the flash lamp annealing apparatus 1 proceeds as the CPU of the control unit 3 executes a predetermined processing program.

  In addition to the above configuration, the flash lamp annealing apparatus 1 is appropriately provided with various components. For example, the chamber side wall 11 is formed with a transfer opening for loading and unloading the workpiece 8. Further, in order to prevent an excessive temperature rise due to light irradiation from the flash lamp FL, a water cooling tube may be provided on the chamber side wall 11. Further, the flash lamp annealing apparatus 1 is provided with a pressure gauge for measuring the atmospheric pressure in the chamber 10.

(Polyimide film processing method using flash lamp annealing equipment)
Next, a processing procedure in the flash lamp annealing apparatus 1 having the above configuration will be described. FIG. 2 is a flowchart showing a processing procedure in the flash lamp annealing apparatus 1. Each processing step of the flash lamp annealing apparatus 1 described below proceeds by the control unit 3 controlling each operation mechanism of the flash lamp annealing apparatus 1.

  First, a carry-in process for carrying the object 8 into the chamber 10 is performed (step S1). The workpiece 8 may be carried in by a transfer robot outside the flash lamp annealing apparatus 1 or manually. FIG. 3 is a cross-sectional view showing the structure of the workpiece 8. The object to be processed 8 according to the first embodiment is configured by bonding a polyimide film 82 to the upper surface of a glass substrate 81. For example, quartz glass is used as the material of the glass substrate 81. The quartz glass substrate 81 transmits the flash light emitted from the flash lamp FL over almost the entire wavelength range. An appropriate support can be selected for the object to be processed 8 according to the wavelength band to be irradiated. The polyimide film 82 is formed into a coating film by the above-described method for forming a polyimide film that functions as a base resin film. A device 83 is mounted on the upper surface of the polyimide film 82 by a known method.

  The coating formation of the polyimide film 82 and the mounting of the device 83 are performed in a facility different from the flash lamp annealing apparatus 1. Since a polyimide film 82 is pasted on a glass substrate 81, which is a rigid substrate (also called a carrier substrate or a dummy substrate), and a device 83 is mounted thereon, a lot of existing equipment is diverted. Can be implemented. Then, after the device 83 is mounted, the object 8 as shown in FIG. 3 is carried into the chamber 10.

  Next, a holding process is performed in which the workpiece 8 carried into the chamber 10 is placed and held on the holding plate 20 via the support pins 22 (step S2). Here, the workpiece 8 is held by the holding plate 20 with the surface on which the device 83 is formed facing downward, that is, with the glass substrate 81 facing upward. Further, the workpiece 8 is supported by point contact by the plurality of support pins 22 and is held by the holding plate 20. The plurality of support pins 22 preferably support the edge portion of the glass substrate 81 on which the device 83 is not mounted.

  The holding plate 20 is preheated to a predetermined temperature by a built-in heater 21. The temperature of the holding plate 20 is controlled by the control unit 3. When the object to be processed 8 is supported in proximity to the holding plate 20 by the plurality of support pins 22, the entire object to be processed 8 including the polyimide film 82 on which the device 83 is mounted is heated. The temperature at which the workpiece 8 is heated is within a range that does not cause thermal damage to the device 83, and is set appropriately within a range that exceeds the glass transition point of the soluble polyimide resin and that is less than the crosslinking temperature of the crosslinking material. The In order to increase the heating efficiency at this time, the height position of the workpiece 8 supported by the plurality of support pins 22 is preferably closer to the upper surface of the holding plate 20.

  In addition, after the workpiece 8 is carried into the chamber 10 and the processing space 15 is closed, a decompression process is performed to decompress the interior of the chamber 10 (step S3). That is, by exhausting by the exhaust mechanism 50 without supplying gas from the gas supply mechanism 40, the atmosphere of the processing space 15 in the chamber 10 is reduced to less than atmospheric pressure. At this time, if it is necessary to further reduce the oxygen partial pressure in the chamber 10, the inside of the chamber 10 is decompressed after supplying the nitrogen gas from the gas supply mechanism 40 to replace the processing space 15 with a nitrogen atmosphere. May be.

After the workpiece 8 held on the holding plate 20 is heated to reach a predetermined temperature and the inside of the chamber 10 is reduced to below atmospheric pressure, a plurality of flashes of the flash light source 70 are controlled by the control unit 3. An irradiation process is performed to turn on the lamps FL at the same time (step S4). Flash light (including flash light reflected by the reflector 72) emitted from the flash lamp FL passes through the chamber window 18 and travels toward the object 8 to be processed held by the holding plate 20 in the processing space 15. The flash light emitted from the flash lamp FL is converted into a light pulse having a very short electrostatic energy stored in advance, and the irradiation time (pulse width) is extremely high in the range of 0.05 milliseconds to 100 milliseconds. It is preferably a short and strong flash (irradiation energy is about 10 J / cm ² or more and 20 J / cm ² or less). However, the implementation of the present invention is not limited to this, and is not limited to the above range as long as the adhesive force at the interface is sufficiently reduced at the interface between the glass substrate and the polyimide film. Further, the number of times of flash light irradiation may be only once or may be irradiated a plurality of times.

The reason why there is a lower limit to the suitable irradiation light energy is that the temperature of the interface between the polyimide film and the glass substrate cannot be sufficiently increased. Therefore, irradiation conditions with irradiation light energy lower than 10 J / cm ² may be adopted as long as the adhesive force at the interface is sufficiently lowered at the interface between the glass substrate and the polyimide film.

The reason why there is an upper limit to the suitable irradiation light energy is that if the energy is about the upper limit, the adhesive force at the interface is sufficiently lowered at the interface between the glass substrate and the polyimide film, and the energy exceeding the upper limit is given. There is no need for it, and the increase of the power consumption of the flash lamp is suppressed by not giving extra energy, and the damage to the device mounted on the polyimide film is suppressed by not giving extra energy. A point etc. are mentioned. Therefore, when the irradiation light energy satisfying the above points is higher than 20 J / cm ² due to various conditions such as the film thickness and composition of the polyimide film and the characteristics of the glass substrate as the substrate, it is 20 J / cm ² or more. Irradiation light energy is also adopted as a suitable condition.

  Advantages of multiple irradiation include prevention of damage due to overheating in the device mounted on the polyimide film and the polyimide film itself. When flash light is irradiated for a long time, the heat or the inside of the film may be overheated due to the heat reaching the deep part. In the present invention, since it is sufficient that the energy of flash light reaches even the interface between the polyimide film and the glass substrate, it is preferable to shorten the pulse width. However, if the pulse width is shortened while the energy is constant, the applied energy is reduced, and there is a possibility that the adhesive force at the interface cannot be sufficiently reduced. For this reason, by shortening the pulse width and irradiating the flash light multiple times, the applied energy is sufficiently maintained, the adhesive force at the interface is sufficiently reduced, and heat is prevented from reaching the device or the like. , Damage to the device can be prevented.

  FIG. 4 is a view showing a state in which flash light is irradiated on the object 8 to be processed. In the chamber 10, the workpiece 8 is held on the holding plate 20 with the glass substrate 81 facing upward. Flash light emitted from a flash lamp FL provided above the chamber 10 is irradiated from above the object 8 to be processed, that is, from the glass substrate 81 side. The glass substrate 81 transmits the flash light emitted from the flash lamp FL. As a result, the flash light passes through the upper glass substrate 81 and is irradiated onto the interface between the glass substrate 81 and the polyimide film 82. In the first embodiment, the flash light is irradiated to the entire surface of the object 8 to be processed.

  The interface between the glass substrate 81 and the polyimide film 82 absorbs flash light, rapidly increases in temperature, and then rapidly decreases in temperature. At this time, the temperature in the vicinity of the interface between both the glass substrate 81 and the polyimide film 82 rises. If the irradiation time is very short such that the irradiation time is about 0.05 milliseconds or more and 100 milliseconds or less, only the vicinity of the interface between the glass substrate 81 and the polyimide film 82 can be selectively heated. For this reason, it is prevented that the device 83 formed on the polyimide film 82 by flash light irradiation is heated more than necessary to cause thermal damage.

  When the vicinity of the interface between the glass substrate 81 and the polyimide film 82 is rapidly heated by flash light irradiation, the vicinity of the interface between the glass substrate 81 and the polyimide film 82 is heated and thermally expanded. At this time, since the linear expansion coefficient is different between the glass substrate 81 and the polyimide film 82, the degree of expansion is different even if the temperature is increased to the same temperature. Although depending on the types of the glass substrate 81 and the polyimide film 82, generally, the linear expansion coefficient of the polyimide film 82 is significantly larger than that of the glass substrate 81 (about several times or more).

  In addition, the polyimide film 82 in the vicinity of the interface is directly heated by the flash light irradiation (the glass substrate 81 transmits the flash light), and the glass substrate 81 is heated by the heat conduction from the polyimide film 82 that has been heated. Heated. Therefore, the ultimate temperature itself at the time of flash light irradiation is usually higher in the polyimide film 82 than in the glass substrate 81. For this reason, when the temperature in the vicinity of each interface between the glass substrate 81 and the polyimide film 82 is increased by the flash light irradiation, the polyimide film 82 is more thermally expanded than the glass substrate 81. As a result, as indicated by an arrow AR4 in FIG. 4, the polyimide film 82 tends to extend larger than the glass substrate 81 along the direction parallel to the interface at the interface between the glass substrate 81 and the polyimide film 82. Shear stress acts. When such a shear stress along the interface between the glass substrate 81 and the polyimide film 82 acts, the adhesive force between the glass substrate 81 and the polyimide film 82 at the interface decreases.

  Furthermore, in the present invention, a crosslinking material is added to the polyimide film 82. Most of the cross-linking materials contained in the polyimide film 82 are in an unreacted state until just before the flash light is irradiated in the irradiation step (step S4).

  In the irradiation step (step S4), the polyimide film 82 containing the unreacted cross-linking material is irradiated with flash light, so that the temperature rapidly rises to a temperature exceeding the cross-linking start temperature of the cross-linking material and is contained in the polyimide film 82. The cross-linking material rapidly undergoes a cross-linking reaction. Thereby, in addition to the thermal expansion of the polyimide film 82 itself as described above, the rapid cross-linking reaction of the cross-linking material contained in the polyimide film 82 tends to extend in a direction parallel to the interface direction of the polyimide film 82. Shear stress acts. Therefore, the shear stress along the interface between the glass substrate 81 and the polyimide film 82 acts more strongly, and the adhesive force between the glass substrate 81 and the polyimide film 82 is reliably reduced.

  Due to the decrease in the adhesive force due to the irradiation of flash light as described above, the polyimide film 82 can be peeled off very easily in the peeling step of Step S7 described later. That is, the process in the flash lamp annealing apparatus 1 according to the present invention assists the peeling of the polyimide film 82 formed on the glass substrate 81.

  After completion of the flash light irradiation on the object 8 to be processed, the decompression process of stopping exhausting by the exhaust mechanism 50 and supplying nitrogen gas from the gas supply mechanism 40 to the processing space 15 to restore the pressure inside the chamber 10 to atmospheric pressure. (Step S5). Then, the unloading process which unloads the to-be-processed body 8 from the chamber 10 is performed (step S6). Thereby, a series of peeling auxiliary processes in the flash lamp annealing apparatus 1 is completed.

  Next, the peeling process which peels the glass substrate 81 and the polyimide film 82 in the to-be-processed object 8 carried out from the chamber 10 is performed (step S7). FIG. 5 is a diagram illustrating an example of a state in which the polyimide film 82 that is the layer to be peeled is peeled from the glass substrate 81. The polyimide film 82 is peeled from the glass substrate 81 by peeling off the end of the polyimide film 82 and mechanically holding it by a holding member (not shown), and moving the holding member as indicated by the arrow in FIG. The

  Since the shearing stress acts on the interface between the glass substrate 81 and the polyimide film 82 due to the flash light irradiation in the irradiation process (step S4), the adhesive force at these interfaces is reduced, and the glass substrate 81 and the polyimide film 82 are not bonded. Adhesion is fragile. For this reason, when the polyimide film 82 is peeled from the glass substrate 81 in the peeling step (step S7), the polyimide film 82 can be easily peeled from the glass substrate 81 with a small stress.

  Instead of the gripping member, the polyimide film 82 may be peeled off from the glass substrate 81 by winding the end of the polyimide film 82 around a drum and rotating the drum. Alternatively, the polyimide film 82 may be peeled off from the glass substrate 81 by a known suction member such as a Bernoulli chuck.

  In the first embodiment, the interface between the glass substrate 81 and the polyimide film 82 having different linear expansion coefficients is heated by irradiating flash light, and the degree of their thermal expansion is different, so that the interface is parallel to the interface. A shear stress is generated along the line. Moreover, by making the polyimide film 82 contain a cross-linking material and causing a rapid cross-linking reaction of the cross-linking material by irradiation with flash light, the shear stress along the direction parallel to the interface in the polyimide film 82 is further enhanced. Yes.

  Due to the action of the shear stress, the adhesive force at the interface between the glass substrate 81 and the polyimide film 82 is reduced, and the adhesion thereof is weakened. For this reason, in a peeling process (step S7), the polyimide film 82 which is a layer to be peeled can be easily peeled from the glass substrate 81 with a small stress. Therefore, the polyimide film 82 can be peeled while minimizing physical damage to the polyimide film 82 and the device 83 mounted thereon.

  In the first embodiment, since flash light is collectively irradiated to the entire surface of the interface between the glass substrate 81 and the polyimide film 82, the adhesive force of the entire interface is lowered uniformly to weaken the adhesion. be able to. If the flash light having an irradiation time of 0.05 milliseconds to 100 milliseconds is collectively irradiated, the processing time can be remarkably shortened as compared with the conventional case where the laser light is scanned.

  In the first embodiment, the thermal expansion difference between the glass substrate 81 and the polyimide film 82 due to flash light irradiation, and the expansion / contraction (elasticity) of the polyimide film 82 due to the crosslinking reaction of the crosslinking material contained in the polyimide film 82. The change in the adhesive force is used to reduce the adhesive force at the interface, so that generation of dust can be suppressed as compared with conventional ablation by laser light irradiation. That is, by irradiating flash light to the interface between the glass substrate 81 and the polyimide film 82 to which a cross-linking material is added, the damage to the polyimide film 82 as the layer to be peeled is suppressed and the layer to be peeled is uniformly and cleanly. Peeling can be assisted. Furthermore, since the shearing stress generated at the interface between the glass substrate 81 and the polyimide film 82 becomes stronger by the addition of the crosslinking material than when the crosslinking material is not added, the adhesive force at the interface can be more reliably reduced.

  Moreover, in 1st Embodiment, the peeling assistance by flash light irradiation is performed in the atmosphere below atmospheric pressure. When the interface between the glass substrate 81 and the polyimide film 82 is irradiated with flash light and heated, a trace amount of gas is generated from the interface. When a slight amount of gas is generated by irradiating the interface with flash light in a state where the atmosphere around the glass substrate 81 to which the polyimide film 82 as a layer to be peeled is attached is reduced in pressure, the surroundings are in a reduced pressure state. Gas bubbles will expand. As a result, the adhesion between the glass substrate 81 and the polyimide film 82 is further weakened, and the polyimide film 82 that is the layer to be peeled can be peeled off from the glass substrate 81 more easily.

  Furthermore, in the first embodiment, before the flash light irradiation, the heater 21 built in the holding plate 20 does not cause thermal damage to the device 83 and the crosslinking material contained in the polyimide film 82 causes a crosslinking reaction. The to-be-processed object 8 is heated to the temperature which is not. Thereby, the interface between the glass substrate 81 and the polyimide film 82 is assisted by thermal energy at the time of flash light irradiation, and the polyimide film resulting from the difference in thermal expansion of the interface before and after the flash light irradiation and the crosslinking reaction by flash light irradiation. By making the change in expansion and contraction of 82 more steep and generating a greater shear stress, the adhesive force at the interface is further reduced, and the adhesion between the glass substrate 81 and the polyimide film 82 can be further weakened. it can.

  According to the manufacturing method of the electronic device according to the first embodiment, the device is less likely to be destroyed than the conventional manufacturing method in which the film surface is burned off with a laser beam or peeled off with a strong force. The device with the base film can be easily peeled without damaging the film. Therefore, the manufacturing method of the electronic device according to the first embodiment can be produced with a higher yield.

[Second Embodiment]
Next, an example of an electronic device manufacturing method different from the first embodiment will be described. The electronic device manufacturing method according to the second embodiment has the same basic configuration as that of the first embodiment except for the following points. That is, the electronic device manufacturing method according to the second embodiment is different from the first embodiment in the configuration of the flash lamp annealing apparatus and the irradiation method.

  As irradiation to a part of the region, for example, a method of irradiating the edge portion of the interface between the glass substrate and the polyimide film can be exemplified. The adhesive force between the glass substrate and the polyimide film tends to increase at the edge. If the edge cannot be easily peeled off without flash light irradiation, and other areas that are not edge light can be peeled off by a mechanical peeling method without flash light irradiation, A method of intensively irradiating the edge is effective. By this method, the polyimide film can be easily peeled from the glass substrate by reducing the adhesive strength of the edge and making the edge easily peelable. As described above, by adopting a configuration in which flash light is intensively applied to a part of a region such as a region where the adhesive strength is locally high, damage to the device due to flash light irradiation can be suppressed. In addition, since the irradiation area of the flash light is narrower than when the entire area is irradiated, there is an effect that the power consumption of the flash lamp can be reduced.

  FIG. 6 is a diagram showing a main configuration of the flash lamp annealing apparatus 1a according to the second embodiment. In the subsequent drawings, the same elements as those in the first embodiment are denoted by the same reference numerals.

  The flash lamp annealing apparatus 1 a of the second embodiment includes a light shielding plate 60 in the chamber 10. FIG. 7 is a plan view of the light shielding plate 60 as viewed from above. The light shielding plate 60 is a plate member having a rectangular shape in plan view, and is fixedly installed in the chamber 10 by a support member (not shown). The light shielding plate 60 is formed of a material that does not transmit the flash light of the flash lamp FL (for example, a metal material such as aluminum having excellent resistance to the flash light). The light shielding plate 60 is installed above the holding plate 20 in the chamber 10 and is provided so as to cover most of the object 8 to be processed held by the holding plate 20.

  In the second embodiment, as shown in FIG. 7, a light shielding plate 60 is provided so that only one side of the edge of the rectangular object 8 held by the holding plate 20 is exposed to the upper flash light source 70. It has been. Here, the edge part of the to-be-processed object 8 is an area | region outside the area | region in which the device 83 is formed. That is, the device 83 is not mounted over the entire surface of the polyimide film 82 formed on the glass substrate 81, and is not mounted in a region having a predetermined width from the end of the polyimide film 82 toward the inside. Thus, the device 83 is not mounted on the edge of the polyimide film 82, and a relatively unnecessary area is “the edge of the polyimide film 82”. In the second embodiment, the width is, for example, 5 mm to The range is 10 mm. In addition, the area | region of the glass substrate 81 corresponding to the edge part of the polyimide film 82 in which the device 83 is not mounted is called "the edge part of the glass substrate 81", and to-be-processed object including the polyimide film 82 and the glass substrate 81 The region 8 is referred to as “an edge portion of the workpiece 8”.

  In the second embodiment, as shown in FIG. 6, the flash light source 70 includes one flash lamp FL. A reflector 72 is provided above the flash lamp FL. The flash lamp FL of the second embodiment is installed immediately above the edge of the workpiece 8 that is not covered by the light shielding plate 60. That is, the flash lamp FL is disposed only at a position facing the end edge of the object 8 exposed from the light shielding plate 60. For this reason, the flash light emitted from the flash lamp FL is intensively applied to the edge portion of the workpiece 8 that is not covered by the light shielding plate 60.

  The remaining configuration of the flash lamp annealing apparatus 1a excluding the light shielding plate 60 and the flash light source 70 is the same as that of the flash lamp annealing apparatus 1 of the first embodiment. Further, the processing procedure in the flash lamp annealing apparatus 1a of the second embodiment is substantially the same as that of the first embodiment (see FIG. 2).

  In the second embodiment, a part of the flash light emitted from the flash lamp FL is shielded by the light shielding plate 60 and is held by the holding plate 20 during the irradiation of the flash light in the irradiation step (step S4). Among them, the flash light is selectively irradiated to the edge portion that is not covered by the light shielding plate 60. Therefore, the flash light is selectively applied to the edge portion of the interface between the glass substrate 81 and the polyimide film 82, and the edge portion is intensively heated. Since the device 83 is not mounted on the end edge, in the second embodiment, the flash is strong enough to heat the end surface of the polyimide film 82 to a considerably high temperature (for example, higher than the first embodiment). You may make it irradiate light.

  Since the linear expansion coefficient is different between the glass substrate 81 and the polyimide film 82, when the edge of the interface between the glass substrate 81 and the polyimide film 82 is irradiated with flash light and heated, it is caused by the difference in thermal expansion between them. The shear stress applied acts on the interface.

  Furthermore, in the present invention, a crosslinking material is added to the polyimide film 82. Here, since the process before irradiating the flash light is the same process as the first embodiment, the process is consistently performed at a temperature lower than the crosslinking start temperature of the crosslinking material, and the irradiation process (step The crosslinking material contained in the polyimide film 82 is in an unreacted state until immediately before the flash light is irradiated in S4).

  In the irradiation step (step S4), the crosslinking material contained in the edge of the polyimide film 82 is irradiated with flash light to the edge of the polyimide film 82 containing the unreacted crosslinking material. The temperature rapidly rises to a temperature above the crosslinking initiation temperature, and a crosslinking reaction occurs rapidly. Thereby, in addition to the thermal expansion of the polyimide film 82 itself as described above, the rapid cross-linking reaction of the cross-linking material contained in the polyimide film 82 tends to extend in a direction parallel to the interface direction of the polyimide film 82. Shear stress acts. Therefore, the shear stress along the interface between the glass substrate 81 and the polyimide film 82 acts more strongly at the edge of the workpiece 8, and the adhesive force between the glass substrate 81 and the polyimide film 82 is reliably reduced. Therefore, the edge portion of the polyimide film 82 is easily peeled off from the glass substrate 81.

  Also in the second embodiment, since flash light irradiation is performed in a reduced-pressure atmosphere less than atmospheric pressure, a minute amount is present at the interface between the glass substrate 81 and the polyimide film 82 in the edge portion of the workpiece 8. When the gas bubbles expand by heating, the adhesion between the glass substrate 81 and the polyimide film 82 is further weakened, and the edge of the polyimide film 82 is more easily peeled off.

  Here, when more intense flash light is applied, the polyimide film 82 can be more reliably peeled off, and the subsequent peeling step (step S7) can be facilitated. When stronger flash light is irradiated, a strong shearing stress acts on the interface with the glass substrate 81 at the edge of the polyimide film 82. Thereby, after flash light irradiation, a part of edge part of the polyimide film 82 peels so that it may turn up, and the mechanical holding | grip of the polyimide film 82 becomes easy in a subsequent peeling process (step S7). In the second embodiment, the following description will be made on the assumption that the edge portion of the polyimide film 82 is peeled off by irradiation with stronger flash light.

  Thereafter, in the peeling step (step S7), the edge portion of the polyimide film 82 peeled off by the flash light irradiation in the irradiation step (step S4) is mechanically held by the holding member, and the polyimide is formed in the same manner as in the first embodiment. The entire film 82 is peeled from the glass substrate 81.

  In the second embodiment, a part of the flash light is shielded by the light shielding plate 60, so that the flash light is irradiated only to the edge portion of the object 8 to be processed, and the edge of the interface between the glass substrate 81 and the polyimide film 82 is irradiated. Only the edge is heated. In general, the adhesion between the polyimide film 82 formed by the coating method and the glass substrate 81 tends to be stronger at the edge than in the vicinity of the center. Accordingly, as in the second embodiment, only the edge portion of the interface between the glass substrate 81 and the polyimide film 82 is heated by flash light irradiation to reduce the bonding force, and the edge portion of the polyimide film 82 is lowered to the glass substrate 81. If it is made to peel from, the polyimide film 82 which is a layer to be peeled can be easily peeled from the glass substrate 81 in the peeling step of the peeling step (step S7).

  Further, as in the first embodiment, since the bonding force at the interface is reduced by utilizing the difference in thermal expansion between the glass substrate 81 and the polyimide film 82 caused by flash light irradiation, conventional ablation by laser light irradiation, etc. The generation of dust can be reduced compared to the above. Therefore, even if it is like 2nd Embodiment, peeling of a to-be-separated layer can be assisted cleanly, suppressing the damage given to the polyimide film 82 which is to-be-separated layer.

  In particular, in the second embodiment, only the edge portion of the object 8 to be processed, which is an unnecessary region where the device 83 is not mounted, is heated by irradiating flash light, and thus the device 83 is thermally damaged. This can be surely prevented. Further, since it is not necessary to consider the thermal damage given to the device 83, the light emission intensity of the flash lamp FL can be considerably increased, and the edge portion of the polyimide film 82 is surely removed from the glass substrate 81 by the flash light irradiation. Can be peeled off.

[Third Embodiment]
The electronic device manufacturing method according to the third embodiment has the same basic configuration and manufacturing method as the electronic device manufacturing method according to the first embodiment except for the following points. That is, the third embodiment is different from the first embodiment in which the light absorption layer is not used in that the light absorption layer is formed on the glass substrate.

  The configuration of the flash lamp annealing apparatus is exactly the same as the flash lamp annealing apparatus 1 of the first embodiment. The processing procedure in the third embodiment is also substantially the same as that in the first embodiment (see FIG. 2). Therefore, the description of the same processing procedure as that in the first embodiment is omitted.

  In the third embodiment, the black light absorption layer 85 is formed on the edge of the glass substrate 81 before the object 8 is carried into the chamber 10. FIG. 8 is a plan view of the object 8 on which the light absorption layer 85 is formed as viewed from the glass substrate 81 side. A black light absorption layer 85 is formed on the surface of the glass substrate 81 at the edge of the rectangular object 8. Specifically, for example, the light absorption layer 85 may be formed by applying a black paint to the surface edge of the glass substrate 81. In addition, the edge part of the to-be-processed object 8 is an area | region outside the area | region where the device 83 is mounted similarly to 2nd Embodiment. In the third embodiment, the light absorption layer 85 is formed on the end edges of all four sides of the rectangular object 8.

  The target object 8 having the light absorption layer 85 formed on the end edge is carried into the chamber 10 (step S1) and held by the holding plate 20 (step S2). The workpiece 8 is held by the holding plate 20 with the glass substrate 81 facing upward. Therefore, the light absorption layer 85 formed on the edge of the object 8 also faces upward.

  In the third embodiment, the flash light is irradiated to the entire surface of the workpiece 8 during the irradiation of the flash light in the irradiation step (step S4), as in the first embodiment. FIG. 9 is a diagram illustrating a state in which flash light is irradiated on the object 8 to be processed according to the third embodiment. Flash light emitted from a flash lamp FL provided above the chamber 10 is irradiated from above the object 8 to be processed, that is, from the glass substrate 81 side. Since the light absorption layer 85 is black, the received flash light is absorbed over the entire wavelength range. For this reason, at the edge portion of the object 8 to be processed, the light absorption layer 85 is remarkably heated by flash light irradiation, and the edge of the interface between the glass substrate 81 and the polyimide film 82 by heat conduction from the light absorption layer 85. The edges are heated intensively. In the region inside the edge of the object 8 to be processed, the interface between the glass substrate 81 and the polyimide film 82 is heated by the flash light transmitted through the glass substrate 81 as in the first embodiment. The interface edge portion provided with the black light absorption layer 85 is heated more strongly than the inner region.

  Since the linear expansion coefficient is different between the glass substrate 81 and the polyimide film 82, when the flash light is irradiated to the interface between the glass substrate 81 and the polyimide film 82 and heated, the shear stress due to the difference between the thermal expansions is caused. Acts on the interface. In the third embodiment, in particular, since the edge portion of the interface between the glass substrate 81 and the polyimide film 82 is intensively heated, a strong shear stress acts on the edge portion of the interface. When this strong shear stress acts, the bonding force at the interface edge between the glass substrate 81 and the polyimide film 82 decreases, and the edge of the polyimide film 82 is peeled off from the glass substrate 81.

  Furthermore, in the present invention, a crosslinking material is added to the polyimide film 82. Here, in the process before irradiating the flash light, the treatment is consistently performed at a temperature lower than the crosslinking start temperature of the cross-linking material, and the polyimide is used until immediately before the flash light is irradiated in the irradiation process (step S4). The crosslinking material contained in the film 82 is in an unreacted state.

  In the irradiation step (step S4), the polyimide film 82 containing the unreacted cross-linking material is irradiated with flash light, so that the cross-linking material contained in the polyimide film 82 is rapidly increased to a temperature exceeding the cross-linking start temperature of the cross-linking material. The temperature rapidly rises to a cross-linking reaction. Thereby, in addition to the thermal expansion of the polyimide film 82 itself as described above, the rapid cross-linking reaction of the cross-linking material contained in the polyimide film 82 tends to extend in a direction parallel to the interface direction of the polyimide film 82. Shear stress acts. Therefore, the shear stress along the interface between the glass substrate 81 and the polyimide film 82 acts more strongly, and the adhesive force between the glass substrate 81 and the polyimide film 82 is reliably reduced.

  Also in the third embodiment, the inside of the chamber 10 is depressurized by the depressurization step (step S3), and the irradiation with flash light is performed in a depressurized atmosphere below atmospheric pressure in the irradiation step (step S4). As a result, a small amount of gas bubbles generated at the interface edge expands, and the adhesion between the glass substrate 81 and the polyimide film 82 further weakens, and the edge of the polyimide film 82 is reliably peeled off.

  Thereafter, in the peeling step (step S7), the edge portion of the polyimide film 82 peeled off by flash light irradiation is mechanically held by a holding member, and the entire polyimide film 82 is glass substrate 81 in the same manner as in the first embodiment. Peel from.

  In the third embodiment, a black light absorption layer 85 is formed on the edge of the glass substrate 81 of the object 8 to be processed, and the flash light is irradiated from the flash lamp FL to the object 8 to be processed. The black light absorption layer 85 having a high light absorption rate is remarkably heated by flash light irradiation, and the edge of the interface between the glass substrate 81 and the polyimide film 82 is intensively heated by heat conduction from the light absorption layer 85. Is done. As described above, the adhesion between the polyimide film 82 formed by the coating method and the glass substrate 81 tends to be stronger at the edge than in the vicinity of the center. Therefore, as in the third embodiment, the edge of the interface between the glass substrate 81 and the polyimide film 82 is intensively heated by flash light irradiation to reduce the bonding force, and the edge of the polyimide film 82 is made of glass. If peeled off from the substrate 81, the polyimide film 82 which is the layer to be peeled can be easily peeled off from the glass substrate 81 in the peeling step of step S7.

  Further, as in the first embodiment, since the bonding force at the interface is reduced by utilizing the difference in thermal expansion between the glass substrate 81 and the polyimide film 82 caused by flash light irradiation, conventional ablation by laser light irradiation, etc. The generation of dust can be reduced compared to the above. Therefore, even if it is like 3rd Embodiment, peeling of a to-be-separated layer can be assisted cleanly, suppressing the damage given to the polyimide film 82 which is to-be-separated layer.

[Fourth Embodiment]
Next, a fourth embodiment of the present invention will be described. The electronic device manufacturing method according to the fourth embodiment is the same in basic configuration and manufacturing method as the electronic device manufacturing method according to the first embodiment except for the following points. That is, the fourth embodiment is different from the first embodiment in which no optical filter is used in that an optical filter is used.

  In general, a polyimide film has an optical characteristic that easily absorbs light having a short wavelength (400 to 500 nm or less) and easily transmits light having a long wavelength (400 to 500 nm or more). Therefore, when the flash light from the flash lamp includes light in a long wavelength region, the flash light may pass through the polyimide film and the device may be overheated. In order to use light in the wavelength band that efficiently raises the temperature of the polyimide film, an optical filter that cuts light in the long wavelength range is used. Thereby, there is an effect that damage to a device or the like can be suppressed by adding a simple configuration of providing an optical filter. Depending on the light absorption spectrum of the polyimide film, an optical filter for cutting a specific wavelength band may be provided between the glass substrate and the flash lamp, or the glass substrate itself may be configured as the optical filter. FIG. 10 is a diagram showing a main configuration of the flash lamp annealing apparatus 1b according to the fourth embodiment. In FIG. 10, the same elements as those of the first embodiment are denoted by the same reference numerals.

  In the flash lamp annealing apparatus 1 b of FIG. 10, an optical filter 74 is disposed between the chamber window 18 of the chamber 10 and the flash light source 70. The optical filter 74 of the fourth embodiment is a plate-like optical member formed by dissolving a metal such as barium (Ba), arsenic (As), antimony (Sb), and cadmium (Cd) in quartz glass. More specifically, at least one metal selected from the group consisting of barium, arsenic, antimony and cadmium is dissolved and contained in quartz glass. By including a metal component in quartz glass, light in a predetermined wavelength region is reflected or absorbed from the light transmitted through the optical filter 74 and cut (shielded). The wavelength range to be cut depends on the type of metal dissolved in the quartz glass. The optical filter 74 of the present embodiment cuts a component on the long wavelength side having a wavelength of 400 nm or longer and transmits ultraviolet light having a wavelength shorter than 400 nm.

  Further, in order to prevent heating of the optical filter 74 due to absorption of flash light, a known spraying mechanism for blowing cooling air to the optical filter 74 may be provided.

  By providing the optical filter 74 between the chamber 10 and the flash light source 70, when the flash light emitted from the flash lamp FL passes through the optical filter 74, a component having a wavelength of 400 nm or more is cut. Then, the remaining flash light having a component in the ultraviolet region with a wavelength of less than 400 nm passes through the optical filter 74 and is irradiated onto the object 8 to be processed held on the holding plate 20.

  FIG. 11 is a diagram showing a radiation spectral distribution of a xenon flash lamp FL. As shown in the figure, the radiation spectral distribution of the xenon flash lamp FL ranges from the ultraviolet region to the near infrared region, and ultraviolet light having a wavelength shorter than 400 nm, visible light and infrared light having a longer wavelength are included. In the present embodiment, the component 8 having a wavelength of 400 nm or more is cut by the optical filter 74, whereby the flash light in the ultraviolet region shorter than the wavelength 400nm is irradiated to the object 8 to be processed.

  In the fourth embodiment, the glass substrate 81 is made of quartz glass, and transmits flash light in the ultraviolet region having a wavelength shorter than 400 nm. As a result, the ultraviolet flash light is irradiated through the glass substrate 81 through the interface between the glass substrate 81 and the polyimide film 82. In the fourth embodiment, the flash light in the ultraviolet region is irradiated to the entire surface of the object 8 to be processed.

  A general polyimide film has a high light absorptance with respect to light in the ultraviolet region, and a low light absorptance with respect to visible light and infrared light on the longer wavelength side than the ultraviolet region. For this reason, when flash light having a wavelength as shown in FIG. 11 is irradiated onto the object 8 as it is from the glass substrate 81 side, the flash light in the ultraviolet region is absorbed by the polyimide film 82, but on the longer wavelength side than the ultraviolet region. A part of the flash light in the visible light region and the infrared region is transmitted without being completely absorbed by the polyimide film 82 and reaches the device 83 mounted on the polyimide film 82. Thereby, when the device 83 is overheated, the device 83 may be damaged.

  Therefore, in the fourth embodiment, by further providing an optical filter 74, flash light in a wavelength region having a low light absorption rate in the polyimide film 82 is cut by the optical filter 74, and the polyimide film 82 is absorbed by the workpiece 8. Selectively irradiates flash light in an easy wavelength range. The ultraviolet flash light applied to the polyimide film 82 is efficiently absorbed by the polyimide film 82 and hardly irradiated to the device 83 mounted on the polyimide film 82. Therefore, it is possible to prevent the device 83 from being overheated by the flash light and causing damage to the device 83.

<Modification>
While the embodiments of the present invention have been described above, the present invention can be modified in various ways other than those described above without departing from the spirit of the present invention. For example, in each of the above embodiments, the object 8 is the polyimide film 82 attached on the glass substrate 81 with the device 83 mounted thereon. However, the object 8 is not limited to this. Various variations are possible.

  In the first embodiment, quartz glass is used as the material of the glass substrate 81. However, the present invention is not limited to this, and the glass substrate 81 may be configured using other known glass materials. Further, a glass obtained by adding various known additives to quartz glass may be used.

  In the first embodiment, the flash lamp annealing apparatus 1 holds the glass substrate 81 upward in the object 8 to be processed. However, the present invention is not limited to this, and the glass substrate in the object 8 to be processed is not limited thereto. 81 may be held downward. In this case, the flash light source 70 is also provided below the object 8 to be processed, and the flash light is irradiated from the glass substrate 81 side as in the first embodiment.

  In the second embodiment, only one side of the edge of the rectangular object 8 is exposed to the flash light source 70 above, but two or more sides of the edge are exposed to the flash light source 70. As described above, the light shielding plate 60 may be provided. Even in this case, only the edge part of the interface between the glass substrate 81 and the polyimide film 82 is heated by flash light irradiation to reduce the bonding force, and the polyimide film 82 as the peeled layer can be easily peeled off from the glass substrate 81. can do.

  Further, instead of the light shielding plate 60 used in the second embodiment, a filter (such as an ND filter) that does not completely shield the flash light but reduces the amount of the flash light may be used. By using the light shielding plate 60 as an ND filter, the edge portion of the workpiece 8 is heated intensively, and regions other than the edge portion can be heated by flash light, which is easier in the peeling step (step S7). Peeling is possible.

  In the case where the light shielding plate 60 is provided so that two or more sides of the edge of the workpiece 8 are exposed, the flash lamp FL may be arranged according to the shape of the exposed edge. For example, when the light shielding plate 60 is provided so that the end edges of all four sides of the rectangular object 8 are exposed, four flash lamps FL are arranged in a square shape in the flash light source 70. That is, the flash lamp FL is disposed at a position facing the edge of the workpiece 8 exposed from the light shielding plate 60.

  In the second embodiment, a light shielding plate 60 is provided so that the edge of the object 8 is exposed, and a flash light source 70 in which a plurality of flash lamps FL similar to those in the first embodiment are arranged in parallel is provided. You may make it provide. Alternatively, the flash lamp FL may be arranged only at a position facing the edge of the object 8 without providing the light shielding plate 60.

  In 3rd Embodiment, although the light absorption layer 85 was formed in the edge part of all four sides of the to-be-processed object 8 of a rectangle, it is not restricted to this about implementation of this invention, and it is more than one side of an edge part. The light absorption layer 85 may be formed. Even in this case, the temperature of the light absorption layer 85 is remarkably increased by the flash light irradiation, and the edge of the interface between the glass substrate 81 and the polyimide film 82 is intensively heated by the heat conduction from the light absorption layer 85. Thus, the bonding force is reduced, and the polyimide film 82 as the layer to be peeled can be easily peeled from the glass substrate 81.

  In the third embodiment, the light absorption layer 85 is formed on the edge of the glass substrate 81. Instead, the black light absorption layer 85 is formed on the edge of the polyimide film 82. You may make it form. Or you may make it form the black light absorption layer 85 in the edge part of both the glass substrate 81 and the polyimide film 82. FIG.

  Further, in the third embodiment, the light absorption layer 85 is not limited to black, and it is sufficient that the light absorption layer 85 is colored in a color in which the absorptance of flash light is a predetermined value or more.

  Further, by making the arrangement area of the plurality of flash lamps FL provided in the flash light source 70 sufficiently larger than that of the object to be processed 8, the illuminance of the flash light at the edge of the object to be processed 8 can be set to be other than the edge. It may be made larger than the region (region inside the edge). That is, if the arrangement area of the plurality of flash lamps FL is sufficiently larger than the object 8 to be processed, the number of flash lamps FL that affects the edge of the object 8 to be processed increases, and the flash light at the edge is increased. Illuminance will increase relatively. In this way, as in the third embodiment, the edge portion of the interface between the glass substrate 81 and the polyimide film 82 is intensively heated by the flash light irradiation, thereby reducing the bonding force at the interface. Thus, the polyimide film 82 as the layer to be peeled can be easily peeled from the glass substrate 81. In order to obtain such an illuminance increasing effect at the edge of the object 8 to be processed, it is necessary that the arrangement area of the plurality of flash lamps FL be 1.2 times or more the area of the object 8 to be processed.

  Further, the second embodiment and the third embodiment may be combined. That is, you may make it form the black light absorption layer 85 of 3rd Embodiment in the edge part of the to-be-processed object 8 exposed from the light-shielding plate 60 of 2nd Embodiment.

  In the above embodiment, the object to be processed 8 is heated by the heater 21 built in the holding plate 20 before the flash light irradiation, but the object to be processed 8 is heated by a halogen lamp instead of the heater 21. In addition to the heater 21, a heating mechanism using a halogen lamp may be installed. Heating with a halogen lamp is preferable when the distance between the workpiece 8 supported by the plurality of support pins 22 and the upper surface of the holding plate 20 is large, and heating with the heater 21 when the resin layer is transparent. preferable. Further, when the bonding force at the interface can be sufficiently reduced only by flash light irradiation, heating by the heater 21 or the halogen lamp before flash light irradiation is not essential.

  In the above embodiment, the flash light source 70 is provided with the xenon flash lamp FL, but various light sources using known techniques such as other rare gas flash lamps such as krypton may be used instead. it can.

<< Example >>
EXAMPLES Hereinafter, although this invention is demonstrated in detail with reference to an Example, this invention is not limited by these Examples.

(First embodiment)
[Formation of polyimide film]
Polyimide varnishes A and B shown in Table 1 below were prepared.

ポリイミドワニスＢは以下に述べる方法で調製した。すなわち、３００ｍＬのセパラブルフラスコにポリイミドワニスＭＰ２０Ａ（三井化学株式会社製）１５０．０ｇを入れ、この中に室温下で架橋開始温度が２００℃の架橋材１１．８ｇを添加し、加熱・冷却せずスリーワンモーターに接続した攪拌羽根を１８０ｒｐｍで回転させて１２時間攪拌させ、架橋材を溶解させることでワニスＢを得た。なお、Ｔｇは、塗膜から得られたポリイミドフィルムにおいて動的粘弾性測定装置を用いて測定した値である。

Polyimide varnish B was prepared by the method described below. That is, 150.0 g of polyimide varnish MP20A (Mitsui Chemicals Co., Ltd.) is placed in a 300 mL separable flask, and 11.8 g of a crosslinking material having a crosslinking initiation temperature of 200 ° C. is added thereto at room temperature, followed by heating and cooling. First, varnish B was obtained by rotating the stirring blade connected to the three-one motor at 180 rpm and stirring for 12 hours to dissolve the cross-linking material. In addition, Tg is the value measured using the dynamic viscoelasticity measuring apparatus in the polyimide film obtained from the coating film.

[Evaluation of adhesion between glass substrate and polyimide film]
Each polyimide varnish was applied to a 12.5 mm square glass substrate with an applicator with a width of 11.0 mm so that the thickness after drying was 20 μm, and the glass transition point of the polyimide resin was exceeded using an oven, and the thermosetting property The test piece was obtained by heating and drying at a temperature lower than the crosslinking start temperature of the cross-linking material for a predetermined time. A part of the test piece was irradiated with flash light by a flash lamp annealing (FLA) apparatus. The peel strength of each of the irradiated and non-irradiated test pieces was measured and evaluated. The irradiation energy was 5-15 J / cm ² . The results are shown in Table 2 below.

  Examples 1 and 2 and Comparative Example 1 are examples in which a crosslinking material is added. By adding a cross-linking material to varnish A, as shown in Table 1, Tg decreases from 200 ° C. to 156 ° C. due to the plastic effect. In Example 1 and Example 2 which are dried at a temperature exceeding the glass transition temperature and below the crosslinking start temperature of the crosslinking agent, the peel strength before irradiation with flash light is 0.7 kN / m, 0.6 kN. / M, and sufficient adhesive strength was obtained. Furthermore, the adhesive strength could be sufficiently reduced by flash light irradiation, and the polyimide film could be satisfactorily peeled from the glass substrate. On the other hand, in Comparative Example 1 where the glass transition temperature is exceeded and drying is performed at a temperature equal to or higher than the crosslinking start temperature of the crosslinking agent, the peel strength before irradiation with flash light is 0.3 kN / m. The strength was less than half that of Example 2. By performing flash light irradiation on this sample, the adhesive force was reduced by 1/3, but it was smaller than that of Examples 1 and 2 and the effect of reducing the adhesive force was low.

  Comparative Examples 2 to 4 are examples in which no crosslinking material is added. Since Comparative Examples 2 and 3 were dried below the glass transition point, the peel strength was not obtained at the stage before irradiation with flash light, and adhesion was not achieved. On the other hand, in Comparative Example 4 which was dried at a temperature exceeding the glass transition point, the peel strength was 0.9 kN / m before irradiation with flash light, and sufficient adhesive strength was obtained. However, the adhesive strength did not change before and after the flash light irradiation, and the polyimide film could not be peeled from the support.

  The method for manufacturing a polyimide film and the method for manufacturing an electronic device according to the present invention can be applied to various objects to be processed having a layer to be peeled attached on a substrate. In particular, since a device can be mounted on a base film and flexibility can be easily provided, a flexible display, a flexible device, an electronic device, a solar cell, a fuel cell, and a flat panel display (FPD), electronic paper, etc. It can utilize suitably for electronic devices, such as a semiconductor device.

  This application claims the priority on the basis of Japanese application Japanese Patent Application No. 2014-98642 for which it applied on May 12, 2014, and takes in those the indications of all here.

DESCRIPTION OF SYMBOLS 1 Flash lamp annealing apparatus 3 Control part 8 To-be-processed object 10 Chamber 11 Chamber side wall 12 Chamber bottom 15 Process space 18 Chamber window 20 Holding plate 21 Heater 22 Support pin 40 Gas supply mechanism 41 Process gas supply source 42 Supply pipe 43 Supply valve 50 Exhaust mechanism 51 Exhaust device 52 Exhaust piping 53 Exhaust valve 60 Light shielding plate 70 Flash light source 72 Reflector 74 Optical filter 81 Glass substrate 82 Polyimide film 83 Device 85 Light absorption layer

Claims (15)

A polyimide varnish containing a soluble polyimide resin, a thermosetting cross-linking material and a solvent is coated on a support and dried at a temperature exceeding the glass transition point of the soluble polyimide resin and less than the crosslinking start temperature of the thermosetting cross-linking material. Forming a coating film (a),
A method for producing a polyimide film comprising: (b) peeling the polyimide film obtained through the step (a) from the support after promoting the crosslinking reaction of the crosslinking material.   The manufacturing method of the polyimide film of Claim 1 which irradiates flash light to the said polyimide film from the said support body side in a process (b). A method of manufacturing an electronic device for forming a device on a base film,
As the base film, at least a polyimide film,
A polyimide varnish containing a soluble polyimide resin, a thermosetting cross-linking material and a solvent is coated on a support and dried at a temperature exceeding the glass transition point of the soluble polyimide resin and less than the crosslinking start temperature of the thermosetting cross-linking material. Forming a coating film (a),
Forming the device on the polyimide film obtained by the step (a) (c);
The manufacturing method of an electronic device including the process (b) which peels the said polyimide film obtained through the process (c) from the said support body after accelerating the crosslinking reaction of the said crosslinking material.   The method of manufacturing an electronic device according to claim 3, wherein the step (c) includes a thin film formation process by a vapor deposition method.   5. The method of manufacturing an electronic device according to claim 3, wherein in the step (b), the polyimide film is irradiated with flash light from the support side.   6. The method of manufacturing an electronic device according to claim 5, wherein the flash light is intensively applied to an edge portion of the polyimide film formed on the support.   The method for manufacturing an electronic device according to claim 5, wherein a light absorption layer that absorbs the flash light is provided on the support that faces the edge of the polyimide film in plan view.   8. The method of manufacturing an electronic device according to claim 5, wherein, in the emitted light of the flash light, a band having a high light absorption rate of the polyimide film is selectively irradiated.   9. The method of manufacturing an electronic device according to claim 8, wherein the emitted light of the flash light is cut by a filter in a band where the light absorption rate of the polyimide film is low.   The method for manufacturing an electronic device according to claim 8 or 9, wherein the band having a high light absorption rate of the polyimide film is an ultraviolet region.   The method for manufacturing an electronic device according to claim 9, wherein the filter cuts a wavelength of 400 nm or more. Before the step (c), the method further comprises a step (d) of depressurizing the atmosphere around the support on which the polyimide film is formed,
The method for manufacturing an electronic device according to any one of claims 5 to 11, wherein when the flash light is irradiated, bubbles present at an interface between the polyimide film and the support are expanded.   The method for manufacturing an electronic device according to any one of claims 3 to 12, wherein the device is any one selected from the group consisting of a flexible display, a flexible device, a semiconductor device, a solar cell, and a fuel cell. A polyimide varnish containing a soluble polyimide resin, a thermosetting cross-linking material and a solvent is coated on a support and dried at a temperature exceeding the glass transition point of the soluble polyimide resin and less than the crosslinking start temperature of the thermosetting cross-linking material. Forming a coating film (a),
A method of peeling a coating film comprising the step (b) of peeling the polyimide film obtained through the step (a) from the support after promoting the crosslinking reaction of the crosslinking material.   The coating film peeling method according to claim 14, wherein in the step (b), the polyimide film is irradiated with flash light from the support side.

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