WO1999044242A1 - Method of detaching thin-film device, method of transferring thin-film device, thin-film device, active matrix substrate, and liquid crystal display - Google Patents
Method of detaching thin-film device, method of transferring thin-film device, thin-film device, active matrix substrate, and liquid crystal display Download PDFInfo
- Publication number
- WO1999044242A1 WO1999044242A1 PCT/JP1999/000818 JP9900818W WO9944242A1 WO 1999044242 A1 WO1999044242 A1 WO 1999044242A1 JP 9900818 W JP9900818 W JP 9900818W WO 9944242 A1 WO9944242 A1 WO 9944242A1
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- Prior art keywords
- layer
- thin film
- separation layer
- substrate
- film device
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/1259—Multistep manufacturing methods
- H01L27/1262—Multistep manufacturing methods with a particular formation, treatment or coating of the substrate
- H01L27/1266—Multistep manufacturing methods with a particular formation, treatment or coating of the substrate the substrate on which the devices are formed not being the final device substrate, e.g. using a temporary substrate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/76—Making of isolation regions between components
- H01L21/762—Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers
- H01L21/7624—Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers using semiconductor on insulator [SOI] technology
- H01L21/76251—Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers using semiconductor on insulator [SOI] technology using bonding techniques
- H01L21/76254—Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers using semiconductor on insulator [SOI] technology using bonding techniques with separation/delamination along an ion implanted layer, e.g. Smart-cut, Unibond
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- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
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- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
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- H01L29/66742—Thin film unipolar transistors
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/13613—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit the semiconductor element being formed on a first substrate and thereafter transferred to the final cell substrate
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Definitions
- the present invention relates to a method for separating a thin film device, a method for transferring a thin film device, a thin film device, an active matrix substrate, and a liquid crystal display device.
- a process of forming a thin film transistor on a substrate by CVD or the like is performed. Since the process of forming a thin film transistor on a substrate involves high-temperature treatment, the substrate must be made of a material having excellent heat resistance, that is, a material having a high softening point and high melting point. Therefore, at present, quartz glass is used as a substrate that can withstand a temperature of about 100 ° C., and heat-resistant glass is used as a substrate that can withstand a temperature of about 500 ° C.
- the substrate on which the thin film devices are mounted must satisfy the conditions for manufacturing the thin film devices.
- the board to be used is determined so as to satisfy the manufacturing conditions of the device to be mounted.
- the above-mentioned “substrate” may not always be preferable.
- a quartz substrate, a heat-resistant glass substrate, or the like is used.
- these are very expensive, and therefore increase the product price.
- Liquid crystal displays used in portable electronic devices such as palmtops and portable telephones should be as inexpensive as possible, light, resistant to some deformation, and hard to break when dropped. Desirable, but in reality, glass substrates are heavy, vulnerable to deformation, and Usually there is fear.
- the present applicant has proposed a technique for forming a thin film device on a first substrate by a conventional process, and then peeling the thin film device from the first substrate and transferring the thin film device to a second substrate.
- a separation layer is formed between the first substrate and the thin film device that is the layer to be transferred.
- the thin film device which is the layer to be transferred is separated from the first substrate, and the layer to be transferred is transferred to the second substrate side.
- the stacking relationship of the transferred layer to the first substrate used when manufacturing the transferred layer and the stacking relationship of the transferred layer to the second substrate to which the transferred layer is transferred are different from each other. There was a problem that would.
- the present invention provides a method for peeling a thin film device from a substrate so as to easily peel the thin film device from a substrate before the step of causing a peeling phenomenon in the separation layer. It is an object of the present invention to provide a method, a thin film device manufactured using the same, an active matrix substrate, and a liquid crystal display device.
- Another object of the present invention is to make the stacking relationship of the transfer receiving layer with respect to the substrate used in the manufacture of the transfer receiving layer coincide with the stacking relationship of the transfer receiving layer with respect to the transfer body to which the transfer destination layer is transferred. And a method of transferring a thin film device. Disclosure of the invention
- the present invention provides a first step of forming a separation layer on a substrate
- a third step of peeling the board from the separation layer By causing a peeling phenomenon in the layer of the separation layer and / or at the interface, A third step of peeling the board from the separation layer;
- An ion implantation step of implanting ions into the separation layer is provided before the third step.
- a separation layer having the property of absorbing light is provided on a substrate such as a quartz substrate, which is highly reliable in device manufacturing, and a thin film device such as TFT is formed on the substrate.
- the thin film device is then bonded to a desired transfer body, for example, via an adhesive layer.
- the separation layer is irradiated with light, for example, to cause a separation phenomenon in the separation layer. This allows the thin film device to be peeled from the substrate, for example, by applying a force to the substrate.
- the third step includes a step of gasifying the ions implanted into the separation layer.
- a step of gasifying the ions implanted into the separation layer When the ions in the separation layer are gasified, an internal pressure is generated in the separation layer, and the separation phenomenon is promoted.
- the third step of (2) includes a step of irradiating the separation layer with light.
- the separation ions can be gasified by the light.
- the amount of light incident on the thin film device layer can be reduced, and deterioration of the characteristics can be prevented.
- the bonds of atoms or molecules forming the separation layer are cut by the ions to damage the separation layer in advance. This promotes the separation phenomenon in the separation layer that occurs in the subsequent separation step.
- the second step includes a thin film transistor forming step for forming a thin film transistor, the thin film transistor forming step includes a channel layer forming step, and the ion implantation step is performed after the channel layer forming step Is preferred.
- the channel forming step is a high-temperature processing step as compared with other steps. Therefore, if ions for promoting the separation phenomenon are implanted into the separation layer before that, ions may be released from the separation layer during the subsequent high-temperature treatment.
- the thin film transistor forming step includes a channel pattern forming step after the channel layer forming step, and the ion implantation step is performed after the channel pattern forming step.
- the area of the channel pattern itself which may be an obstacle to the implantation, even if ions for promoting the separation phenomenon are implanted from the channel pad side is reduced. Therefore, the ions can easily reach the separation layer.
- the ion implantation step is preferably performed by forming a mask on a region of the channel layer that will be a channel region.
- the step of masking the channel region and implanting ions may be performed before or after forming the channel pattern.
- the thin film transistor forming step includes: after the channel pattern forming step, a step of forming a gate insulating film on the channel pattern; and a step of forming a gate electrode on the gate insulating film. It is preferable to perform the ion implantation step using the gate electrode as a mask.
- the gate electrode Since the gate electrode is formed at a position facing the channel, the gate electrode can also be used as a mask for preventing ions from being implanted into the channel region. Note that a mask may be further formed on the gate electrode according to the ion acceleration voltage.
- the impurity ions implanted into at least one of the source region and the drain region in the channel pattern and the ions implanted into the separation layer with a lighter mass than the impurity ions are simultaneously implanted.
- the step of implanting ions into the separation layer and the step of implanting impurity ions into the source and / or drain regions can be used. Since ions are lighter in mass than impurity ions, they can reach the separation layer located deeper than the source and drain regions.
- the thin film transistor forming step includes a step of forming an amorphous silicon layer as the channel layer, and a crystallization step of laser annealing and crystallizing the amorphous silicon layer thereafter. It is preferably performed before the crystallization step.
- the crystallinity can be improved by the subsequent laser annealing process.
- the ions are hydrogen ions.
- hydrogen ions When the hydrogen ions are implanted into the separation layer, they can contribute to the actions described in claims 2 to 4.
- hydrogen ions are suitable for implementing the invention of claim 9 because they have a smaller mass than impurity ions (boron, phosphorus, etc.) implanted into the source and drain.
- impurity ions boron, phosphorus, etc.
- mainly ions that cause gasification according to claim 2 include nitrogen ions in addition to hydrogen ions.
- examples of the ions that mainly cause damage or decrease in adhesion according to claims 3 and 4 include Si ions in addition to hydrogen ions.
- the process temperature of the step performed after the ion implantation step is preferably less than 350 ° C.
- steps requiring a process temperature of 350 ° C or higher can be performed before the ion implantation step into the separation layer. preferable.
- the thin film device of the present invention is peeled off from the substrate by using the peeling method according to any one of (1) to (13). Since the thin film device can be easily peeled from the separation layer, a small mechanical pressure is required during the peeling, and defects depending on the magnitude of the load can be reduced.
- the active matrix substrate of the present invention is a thin substrate arranged in a matrix.
- This active matrix substrate can also reduce defects similarly to the invention of (13).
- a liquid crystal display device of the present invention is manufactured using the active matrix substrate described in (15).
- liquid crystal display device uses the active matrix substrate of (15), defects in the liquid crystal display device as a whole are reduced.
- the method for transferring a thin film device includes: a first step of forming a first separation layer on a substrate; and a second step of forming a transfer target layer including the thin film device on the first separation layer.
- the first separation layer is removed from the lower surface of the transferred layer, and the secondary transfer member is joined to the lower surface, and then the primary transfer member is separated from the transferred layer with the second separation layer as a boundary.
- the secondary transfer member exists at the position where the original substrate was located with respect to the transfer target layer, and the stacking relationship of the transfer target layer with respect to the original substrate and the secondary transfer member The stacking relation of the transfer receiving layer matches.
- a water-soluble adhesive or an organic solvent-soluble adhesive is used as the second separation layer, it is only necessary to contact the second separation layer with water or an organic solvent in order to release the primary transfer member.
- a first step of forming a first separation layer on a substrate, and forming a transferred layer including the thin film device on the first separation layer A second step, having a peeling action by heating or ultraviolet irradiation on the transfer-receiving layer;
- a fifth step of further removing the substrate a sixth step of bonding a secondary transfer member to the lower surface of the transfer-receiving layer, and heating or irradiating the second separation layer with ultraviolet light to form the second separation layer.
- an adhesive that can be peeled off by heat or ultraviolet light is used instead of the adhesive described in (17).
- FIG. 1 is a cross-sectional view showing a first step in the first embodiment of the method for transferring a thin film device of the present invention.
- FIG. 2 is a cross-sectional view showing a second step in the first embodiment of the method for transferring a thin film device of the present invention.
- FIG. 3 is a cross-sectional view showing a third step in the first embodiment of the method for transferring a thin film device of the present invention.
- FIG. 4 is a sectional view showing a fourth step in the first embodiment of the method for transferring a thin film device of the present invention.
- FIG. 5 is a sectional view showing a fifth step in the first embodiment of the method for transferring a thin film device of the present invention.
- FIG. 6 is a sectional view showing a sixth step in the first embodiment of the method for transferring a thin film device of the present invention.
- FIG. 7 is a diagram showing a change in transmittance of the first substrate (the substrate 100 in FIG. 1) with respect to the wavelength of the laser beam.
- FIG. 8 is a cross-sectional view showing a first step for forming the thin-film device of FIG.
- FIG. 9 is a sectional view showing a second step for forming the thin film device of FIG.
- FIG. 10 is a cross-sectional view showing a third step for forming the thin-film device of FIG.
- FIG. 11 is a cross-sectional view showing a fourth step for forming the thin-film device of FIG.
- FIG. 12 is a cross-sectional view showing a fifth step for forming the thin-film device of FIG.
- FIG. 13 is a sectional view showing a sixth step for forming the thin-film device of FIG.
- FIG. 14 is a cross-sectional view showing a seventh step for forming the thin-film device of FIG.
- FIG. 15 is a cross-sectional view for showing in detail the step shown in FIG.
- FIG. 16 is a cross-sectional view showing the details of the step shown in FIG.
- FIG. 17 is a cross-sectional view showing the details of the step shown in FIG.
- FIG. 18 is a cross-sectional view showing the details of the step shown in FIG.
- FIG. 19 is a perspective view of a microcomputer manufactured using the present invention in both (a) and (b).
- FIG. 20 is a diagram for explaining the configuration of the liquid crystal display device.
- FIG. 21 is a diagram showing a cross-sectional structure of a main part of the liquid crystal display device.
- FIG. 22 is a diagram for explaining a configuration of a main part of the liquid crystal display device.
- FIG. 23 is a cross-sectional view of a device showing a first step in a method for manufacturing an active matrix substrate using the present invention.
- FIG. 24 is a cross-sectional view of a device showing a second step in the method of manufacturing an active matrix substrate using the present invention.
- FIG. 25 is a cross-sectional view of a device showing a third step in the method of manufacturing an active matrix substrate using the present invention.
- FIG. 26 is a cross-sectional view of a device showing a fourth step of the method for manufacturing an active matrix substrate using the present invention.
- FIG. 27 shows the fifth step of the method of manufacturing an active matrix substrate using the present invention.
- FIG. 3 is a cross-sectional view of the device showing the above.
- FIG. 28 is a diagram for explaining another example of the method for transferring a thin film device of the present invention.
- FIG. 29 is a view for explaining still another example of the method for transferring a thin film device according to the present invention.
- FIG. 30 is a view for explaining a modification of the method for transferring a thin film device of the present invention.
- FIG. 31 is a cross-sectional view showing a step of implanting separation-promoting ions performed after the step of FIG.
- FIG. 32 is a cross-sectional view showing a step of implanting separation promoting ions performed after the step of FIG.
- FIG. 33 is a schematic cross-sectional view showing an additional step 1 in the second transfer performed after the step of FIG.
- FIG. 34 is a schematic cross-sectional view showing an additional step 2 at the time of double transfer performed after the step of FIG. 33.
- FIG. 35 is a schematic cross-sectional view showing an additional step 3 in the double transfer performed after the step of FIG. Explanation of reference numerals
- FIG. 1 to 6 are views for explaining a method of transferring a thin film device, which is a premise of the present invention.
- Step 1 As shown in FIG. 1, a separation layer (light absorbing layer) 120 is formed on a substrate 100.
- a separation layer (light absorbing layer) 120 is formed on a substrate 100.
- the substrate 100 and the separation layer 120 will be described.
- the substrate 100 As the substrate 100, a substrate having a light-transmitting property through which light can be transmitted is used.
- the light transmittance is preferably 10% or more, and more preferably 50% or more. If this transmittance is too low, the attenuation (loss) of light increases, and a larger amount of light is required to separate the separation layer 120.
- the substrate 100 is preferably made of a highly reliable material, and particularly preferably made of a material having excellent heat resistance.
- the process temperature increases depending on the type and forming method (for example, 350 ° C. to 100 ° C.).
- the substrate 100 is excellent in heat resistance, when forming the layer to be transferred 140 on the substrate 100, the film formation under the temperature condition or the like may be performed. This is because the range of setting the conditions is expanded. Therefore, the substrate 100 is preferably formed of a material having a strain point equal to or higher than Tmax, where Tmax is the maximum temperature at the time of forming the transfer layer 140.
- the constituent material of the substrate 100 preferably has a strain point of 350 ° C or more, more preferably 500 ° C or more. Examples of such a material include heat-resistant glass such as quartz glass, Coating 759 and NEC Glass O A-2.
- the thickness of the substrate 100 is not particularly limited, it is usually preferably about 0.1 to 5.0 mm, more preferably about 0.5 to 1.5 mm. If the thickness of the substrate 100 is too small, the strength is reduced. If the thickness is too large, light is easily attenuated when the transmittance of the substrate 100 is low. When the light transmittance of the substrate 100 is high, the thickness may exceed the upper limit. Note that the thickness of the substrate 100 is preferably uniform so that light can be uniformly emitted.
- the separation layer 120 may be one or more of a physical action (light, heat, etc.), a chemical action (chemical reaction with a chemical solution, etc.) or a mechanical action (tensile force, vibration, etc.). As a result, the bonding force is reduced or extinguished, thereby promoting the separation of the substrate 100 through the separation layer 120.
- the separation layer 120 has a property of absorbing irradiated light and causing separation in the layer and / or at the interface (hereinafter referred to as “intralayer separation” and “interfacial separation”). Can be mentioned.
- the irradiation of light loses or reduces the bonding force between atoms or molecules of the substance constituting the separation layer 120, that is, an abrasion occurs to cause delamination and / or interfacial delamination.
- an abrasion occurs to cause delamination and / or interfacial delamination.
- the gas may be released from the separation layer 120 by light irradiation, and the separation effect may be exhibited.
- the component contained in the separation layer 120 is released as a gas, and when the separation layer 120 absorbs light and instantaneously turns into a gas, the vapor is released and contributes to separation. There are cases.
- the present invention is characterized in that after forming the separation layer 120 having such characteristics, ions for promoting separation are implanted into the separation layer 120, whereby the separation layer 120 in a subsequent step is formed. It promotes the separation phenomenon at 0. Therefore, the type of the peeling promoting ion is not limited as long as it promotes the peeling phenomenon by the above-mentioned physical action, chemical action or mechanical action.
- examples of the composition of such a separation layer 120 include those described in the following A to E.
- This amorphous silicon may contain hydrogen (H).
- the H content is preferably about 2 at% or more, more preferably about 2 to 20 at%.
- H hydrogen
- the content of hydrogen (H) in amorphous silicon is adjusted by appropriately setting the conditions for film formation, such as the gas composition, gas pressure, gas atmosphere, gas flow rate, temperature, substrate temperature, and input power in CVD. be able to.
- hydrogen ions are used as separation-promoting ions at any time after the formation of the amorphous silicon layer, as described later. Ions can be implanted. This allows A certain amount or more of hydrogen can be contained in the amorphous silicon layer regardless of the processing conditions of the amorphous silicon.
- oxidizing Kei-containing, S i O, S i 0 2, S i 3 0 2 and the like, is a Kei acid compound, for example, K 2 S i 0 3, L i 2 S i 0 3, C a S i 0 3 ⁇ Z r S i 0 4 and Na 2 S i 0 3 .
- Titanium oxide T i O, T i 2 0 3, T i 0 2 .
- titanate compounds for example, B aT i 0 4, BaT I_ ⁇ 3, B a 2 T i 9 O 20 , B a T i 5 O u , CaT i 0 3, S r T i 0 3 ⁇ Pb T i 0 3 ⁇ MgT i 0 3, Z r T I_ ⁇ 2 ⁇ S n T i 0 4, Al 2 T i 0 5 and FeTi 3 .
- zirconate compounds such as B aZ r0 3, Z r S i 0 4, PbZ r0 3, MgZ r0 3, K 2 Z r0 3 and the like.
- Ceramics such as PZT, PLZT, PLLZT, PBZT or dielectrics (ferroelectrics)
- Nitride ceramics such as silicon nitride, aluminum nitride, and titanium nitride
- the organic polymer material may have an aromatic hydrocarbon (one or more benzene rings or a condensed ring thereof) in the structural formula.
- organic polymer materials include polyolefins such as polyethylene and polypropylene, polyimides, polyamides, polyesters, polymethyl methacrylate (PMMA), polyphenylene sulfide (PPS), and polyether sulfone (PE). S), epoxy resin and the like.
- Examples of the metal include Al, Li, Ti, Mn, In, Sn, Y, La, Ce, Nd, Pr, Gd, and Sm, or an alloy containing at least one of these. No.
- the thickness of the separation layer 120 varies depending on the purpose of peeling, the composition of the separation layer 120, the layer structure, the forming method, and other conditions, but is usually preferably about 1 nm to 20 ⁇ m. ⁇ ! The thickness is more preferably about 2 m, and further preferably about 5 nm to l ⁇ m. If the thickness of the separation layer 120 is too small, the uniformity of the film formation may be impaired and the separation may be uneven, and if the thickness is too large, good separation properties of the separation layer 120 are ensured. Therefore, it is necessary to increase the power (light amount) of light, and it takes time to remove the separation layer 120 later. Note that the thickness of the separation layer 120 is preferably as uniform as possible.
- the method for forming the separation layer 120 is not particularly limited, and is appropriately selected according to various conditions such as a film composition and a film thickness.
- various vapor deposition methods such as CVD (including MOCVD, low pressure CVD, ECR—CV D), evaporation, molecular beam evaporation (MB), sputtering, ion brazing, PVD, electric plating, immersion plating (
- Various coating methods such as electroless plating, Langmuir-Bleed Jet (LB) method, spin coating, spray coating, roll coating, etc., various printing methods, transfer methods, ink jet methods, etc.
- LB Langmuir-Bleed Jet
- a powder jetting method and the like can be mentioned, and it can also be formed by combining two or more of these.
- composition of the separation layer 120 is amorphous silicon (a-Si)
- a-Si amorphous silicon
- the separation layer 120 is made of a ceramic by a sol-gel method or when it is made of an organic polymer material, it is preferable to form the film by a coating method, particularly, spin coating.
- a transfer target layer (thin film device layer) 140 is formed on the separation layer 120.
- the details of the step 2 and subsequent steps will be described later with reference to FIGS. 8 to 18.
- the separation to the separation layer 120 is performed during the steps of FIGS. 8 to 13.
- a facilitating ion implantation step is performed.
- the thin film device layer 1 4 0 is, for example, is configured to include a S I_ ⁇ 2 film (intermediate layer) 1 4 2 TFT formed on (thin preparative Rungis evening), the TFT is Source and drain layers 144, channel layer 144, gate insulating film 144, gate electrode 150, and interlayer insulating film 15 formed by introducing an n-type impurity into the polysilicon layer. 4 and an electrode 152 made of, for example, aluminum.
- the SiO 2 film is used as the intermediate layer provided in contact with the separation layer 120, but another insulating film such as Si 3 N 4 may be used.
- the thickness of the SiO 2 film (intermediate layer) is determined as appropriate according to the purpose of its formation and the degree of the function that can be exhibited. ⁇ 5 ⁇ m, preferably 40 nn! More preferably, it is about
- the intermediate layer is formed for various purposes, for example, a protective layer for physically or chemically protecting the transferred layer 140, an insulating layer, a conductive layer, a laser light shielding layer, a barrier layer for preventing migration, One that exhibits at least one of the functions as a reflective layer is mentioned.
- the transfer layer (thin film device layer) 140 may be formed directly on the separation layer 120 without forming the intermediate layer such as the SiO 2 film.
- the layer to be transferred 140 is a layer including a thin film device such as TFT as shown on the right side of FIG.
- thin film devices include, in addition to TFTs, for example, thin film diodes, photoelectric conversion elements (optical sensors, solar cells) consisting of silicon PIN junctions, silicon resistance elements, other thin film semiconductor devices, and electrodes (eg, ITO, mesa). Transparent electrodes such as films), switching elements, memories, actuators such as piezoelectric elements, micro mirrors (piezo thin film ceramics), magnetic recording thin film heads, coils, inductors, thin film high magnetic permeability There are materials and micro magnetic devices, filters, reflective films, dichroic mirrors, etc. that combine them.
- Such thin film devices are usually formed through relatively high process temperatures, depending on the method of formation. Therefore, in this case, as described above, the substrate 10 As 0, a highly reliable one that can withstand the process temperature is required.
- the thin film device layer 140 is bonded (adhered) to the transfer body 180 via the adhesive layer 160.
- the adhesive constituting the adhesive layer 160 include a light-curable adhesive such as a reaction-curable adhesive, a thermosetting adhesive, and an ultraviolet-curable adhesive, and an anaerobic-curable adhesive.
- a light-curable adhesive such as a reaction-curable adhesive, a thermosetting adhesive, and an ultraviolet-curable adhesive
- an anaerobic-curable adhesive Various types of curable adhesives can be used.
- the composition of the adhesive may be, for example, any of an epoxy type, an acrylate type, and a silicone type.
- the formation of 0 is performed by, for example, a coating method.
- a curable adhesive is applied on the layer to be transferred (thin film device layer) 140, and a transfer member 180 is bonded thereon, and then the characteristics of the curable adhesive are used.
- the curable adhesive is cured by a curing method according to the above, and the layer to be transferred (thin film device layer) 140 and the transfer body 180 are adhered and fixed.
- the adhesive When the adhesive is of a light-curing type, light is irradiated from one side of the light-transmitting substrate 100 or the light-transmitting transfer body 180 (or from both outsides of the light-transmitting substrate and the transfer body). Shoot.
- a photocurable adhesive such as an ultraviolet curable adhesive, which hardly affects the thin film device layer is preferable.
- a water-soluble adhesive can be used as the adhesive layer 160 .
- this kind of water-soluble adhesive include Chemiseal U-451D (trade name) manufactured by Chemitek Co., Ltd. and Three Bond 304 (trade name) manufactured by Three Bond Co., Ltd. .
- an adhesive which is soluble in various organic solvents can be used.
- an adhesive exhibiting a peeling action by heating can also be used.
- this kind of adhesive for example, Riva Alpha (trade name) manufactured by Dong-Denko Corporation can be used.
- an adhesive exhibiting a peeling action by ultraviolet irradiation can also be used.
- this kind of adhesive for example, dicing tapes D-210 and D-636 for glass and ceramic manufactured by Lintec Corporation can be used.
- an adhesive layer 160 may be formed on the transfer body 180 side, and the transfer layer (thin film device layer) 140 may be bonded thereon.
- the transfer body 180 itself has an adhesive function, the formation of the adhesive layer 160 may be omitted.
- the transfer body 180 is not particularly limited, but includes a substrate (plate material), particularly a transparent substrate. Note that such a substrate may be a flat plate or a curved plate.
- the transfer body 180 may be inferior to the substrate 100 in properties such as heat resistance and corrosion resistance.
- the transfer layer (thin film device layer) 140 is formed on the substrate 100 side, and then the transfer layer (thin film device layer) 140 is transferred to the transfer body 180. This is because the characteristics required for 180, especially the heat resistance, do not depend on the temperature conditions and the like when forming the transfer target layer (thin film device layer) 140.
- the transfer body 180 can be made of a material having a glass transition point (T g) or softening point of preferably 800 ° C or lower, more preferably 500 ° C or lower, and further preferably 320 ° C or lower. .
- the mechanical properties of the transfer body 180 are preferably those having a certain degree of rigidity (strength), but may be those having flexibility and elasticity.
- Examples of the material for the transfer member 180 include various synthetic resins and various glass materials. In particular, various synthetic resins and ordinary (low melting point) inexpensive glass materials are preferable.
- the synthetic resin may be either a thermoplastic resin or a thermosetting resin.
- examples thereof include polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), and cyclic polyolefins.
- the glass material examples include silicate glass (quartz glass), alkali glass silicate, soda lime glass, potassium lime glass, lead (alkali) glass, barium glass, and borosilicate glass.
- silicate glass quartz glass
- alkali glass silicate soda lime glass
- potassium lime glass potassium lime glass
- lead (alkali) glass barium glass
- borosilicate glass examples include silicate glass (quartz glass), alkali glass silicate, soda lime glass, potassium lime glass, lead (alkali) glass, barium glass, and borosilicate glass.
- silicate glass soda lime glass
- potassium lime glass soda lime glass
- lead (alkali) glass soda lime glass
- barium glass barium glass
- borosilicate glass borosilicate glass.
- those other than silicate glass are preferable because they have a lower melting point than silicate glass, are relatively easy to mold and process, and are inexpensive.
- a large-size transfer body 180 can be integrally formed, and can be formed into a complex shape such as a shape having a curved surface or unevenness. Even if it is possible, it can be easily manufactured, and various advantages such as low material cost and low manufacturing cost can be enjoyed. Therefore, the use of synthetic resin is advantageous for manufacturing large and inexpensive devices (eg, liquid crystal displays).
- the transfer member 180 is, for example, one that constitutes an independent device like a liquid crystal cell, or one such as a color filter, an electrode layer, a dielectric layer, an insulating layer, or a semiconductor element. It may be a part of a device.
- the transfer body 180 may be a material such as metal, ceramics, stone, wood paper, or the like, or on any surface that constitutes an article (on a clock, on an air conditioner, on a printed circuit board). On the surface of structures such as walls, columns, ceilings, windowpanes, etc. There may be.
- This light is applied to the separation layer 120 after passing through the substrate 100.
- intra-layer peeling and / or interfacial peeling occurs in the separation layer 120, and the bonding force is reduced or eliminated.
- separation within the separation layer 120 and / or interfacial separation occurs is that abrasion occurs in the constituent material of the separation layer 120 and that the gas contained in the separation layer 120 is released. It is presumed that this is due to a phase change such as melting and transpiration occurring immediately after irradiation.
- the abrasion means that the fixed material (the constituent material of the separation layer 120) that has absorbed the irradiation light is excited photochemically or thermally, and the bonds of atoms or molecules on its surface or inside are cut off. It mainly appears as a phenomenon in which all or a part of the constituent material of the separation layer 120 undergoes a phase change such as melting and evaporation (vaporization). In addition, the phase change described above may result in a small firing state, and the bonding strength may be reduced.
- the separation layer 120 causes delamination, interfacial delamination, or both, depends on the composition of the separation layer 120 and various other factors, and one of the factors is as follows. And conditions such as the type of light to be irradiated, wavelength, intensity, and depth of arrival.
- separation-promoting ions are injected. ing.
- the separation promoting ions at least act as one of the following three or a combination of two or more of them, and promote the separation phenomenon of the separation layer 120 in the fourth step.
- the separation-promoting ions for example, hydrogen (H) or nitrogen (N) injected into the separation layer 120 are gasified by the fourth step, and thereby the separation layer 120 is separated. Is promoted.
- the other is the bonding of atoms or molecules constituting the separation layer 120 with the separation promoting ions, for example, hydrogen (H), nitrogen (N) or silicon (Si) in the separation promoting ion implantation step. Is cut and the separation layer 120 is damaged in advance. You. Therefore, in the separation layer 120 that has been damaged in advance, peeling occurs relatively easily by performing the fourth step.
- the separation promoting ions for example, hydrogen (H), nitrogen (N) or silicon (Si)
- the other one is to change the characteristics of the separation layer 120 by a separation promoting ion such as hydrogen (H), nitrogen (N) or silicon (Si) in a separation promoting ion implantation step.
- a separation promoting ion such as hydrogen (H), nitrogen (N) or silicon (Si) in a separation promoting ion implantation step.
- the adhesion between the separation layer 120 and the substrate 100 has been weakened in advance. Also in this case, in the separation layer 120 having weakened adhesion to the substrate, the separation is relatively easily caused by performing the fourth step.
- the light irradiated in the fourth step may be any light as long as it causes separation within the separation layer 120 and / or interfacial separation.
- X-rays ultraviolet rays, visible light, infrared rays ( Heat rays), laser light, millimeter waves, microwaves, electron beams, radiations (cored lines,? -Lines, and a-lines).
- a laser beam is preferable because the separation layer 120 is easily peeled off (ablation).
- This as a laser device for generating laser light various gas lasers, solid-state laser is (semiconductor laser) and the like, excimer one The, inter-Nd YAG les one The, A r, single THE, 00 2, single THE, A CO laser, a He—Ne laser, or the like is preferably used, and among them, an excimer laser is particularly preferable.
- the wavelength of the laser light to be irradiated is preferably about 100 nm to 350 nm.
- FIG. 7 shows an example of the transmittance of the substrate 100 with respect to the wavelength of light. As shown in the figure, it has a characteristic that the transmittance sharply increases for a wavelength of 200 nm. In such a case, light with a wavelength of 210 nm or more, such as Xe—C1 excimer laser light (wavelength 308 nm), KrF laser light (wavelength 248 nm), etc., is irradiated. I do.
- the separation layer 120 is given separation characteristics by causing a phase change such as outgassing, vaporization, and sublimation, the wavelength of the laser light to be applied is from 350 to 1200 nm. It is preferred to be on the order of magnitude.
- the energy density of the laser beam irradiated is preferably set to 1 0 ⁇ 5 0 0 0 m J / cm 2 approximately, 1 0 0 ⁇ 5 0 O m J / cm 2 is more preferable.
- the irradiation time is preferably about 1 to 100 nsec, and more preferably about 100 to 100 nsec. If the energy density is low or the irradiation time is short, sufficient abrasion or the like will not occur, and if the energy density is high or the irradiation time is long, transfer is performed by the irradiation light transmitted through the separation layer 120. Layer 140 may be adversely affected.
- the separation layer (laser absorption layer) may be used.
- a metal film 124 such as tantalum (T a) on 120.
- a force is applied to the substrate 100 to separate the substrate 100 from the separation layer 120.
- a separation layer may adhere to the substrate 100 after the separation.
- the remaining separation layer 120 is removed by, for example, a method such as cleaning, etching, asshing, polishing, or a combination thereof.
- the transfer target layer (thin film device layer) 140 is transferred to the transfer body 180.
- the separation layer is also attached to the separated substrate 100, it is similarly removed.
- the substrate 100 is made of an expensive or rare material such as quartz glass, the substrate 100 is preferably provided for reuse. That is, the present invention can be applied to a substrate 100 to be reused, and is highly useful.
- the transfer of the layer to be transferred (thin film device layer) 140 to the transfer body 180 is completed. Thereafter, the SiO 2 film adjacent to the transferred layer (thin film device layer) 140 is removed, and a conductive layer such as wiring and a desired protective film are formed on the transferred layer 140. Etc. can also be performed.
- the transferred layer (thin film device layer) 140 which is the object to be peeled, is not directly peeled off, but rather in the separation layer bonded to the transferred layer (thin film device layer) 140. Because of the peeling, the peeling (transfer) can be performed easily and surely and uniformly regardless of the characteristics, conditions, etc. of the material to be peeled (transferred layer 140). There is no damage to the transfer layer 140), and the high reliability of the transfer layer 140 can be maintained.
- a TFT having a CMOS structure is formed as the thin film device layer 140 on the substrate 100 and the separation layer 120, and an example of a specific manufacturing process for transferring the TFT to a transfer body. This will be described with reference to FIGS. It should be noted that a description will also be given of an ion implantation step for peeling promotion performed during this process.
- a separation layer for example, an amorphous silicon layer formed by LPCVD
- an intermediate layer for example, Si
- a light-transmitting substrate for example, a quartz substrate
- 0 2 film 1 4 2
- an amorphous silicon layer 1 4 3 formed by LPCVD, for example
- laser light is applied from above to the entire surface of the amorphous silicon layer 1 4 3. Irradiate and anneal.
- the amorphous silicon layer 144 is recrystallized into a polysilicon layer.
- the beam centers of the respective beams overlap each other (in the case of a Gaussian beam).
- the same location is irradiated with light twice or more. In this case, there is no adverse effect such as light leakage, and the amorphous silicon layer 144 can be sufficiently recrystallized by multiple irradiation.
- the timing of performing the ion implantation step for peeling promotion is that ion implantation can be performed without a mask after the formation of the separation layer 120 and before the laser annealing step for crystallization. Is preferred.
- (C) is most preferred.
- the process temperature for forming the amorphous silicon layer 143 that is, the process for forming the channel layer, currently requires a process temperature of about 425 ° C.
- the step of implanting the ion for promoting separation be performed at the implementation time (C) after the formation of the channel layer.
- this ion implantation step for promoting separation can be performed using a known ion implantation apparatus. That is, when hydrogen ions are implanted, for example, a gas containing hydrogen can be converted into plasma, and the hydrogen ions generated thereby can be accelerated by an electric field to be implanted into the separation layer 120.
- the ion implantation step may be performed (D) after laser annealing. In this case, by implanting ions while masking a portion to be a channel region, the transistor characteristics do not deteriorate. Note that the mask is removed after the ion implantation step.
- the polysilicon layer obtained by laser annealing is patterned to form islands 144a and 144b as channel patterns.
- the ion implantation step for promoting the separation is performed at the time (E) described above.
- a mask pad 201 is formed on the islands 144a and 144b at a portion facing the channel region in the islands 144a and 144b. Keep it. Then, in this state, ions for promoting separation, for example, hydrogen ions, are implanted toward the separation layer 120. Thus, no hydrogen is contained in the channel region, and the transistor characteristics do not deteriorate. Note that, when the ion implantation step for peeling promotion is completed, the mask pattern 201 is removed.
- 148a and 148b are formed by, for example, a CVD method.
- the delamination promoting ion implantation process is performed at the above-described (A) to (F).
- a mask pattern 202 is formed on the gate insulating films 148a and 148b in a portion facing the channel regions in the lands 144a and 144b. It is preferable to keep it.
- a mask layer 170 made of polyimide or the like is formed, and ion implantation of, for example, boron (B) is performed using a gate electrode 150b and the mask layer 170 as a mask by self-alignment.
- p + layers 172a and 172b are formed.
- the delamination promoting ion implantation process is performed at the above-described (A)
- the gate electrode 150b functions in the same manner as the mask pattern 201 in FIG. 31 or the mask pattern 202 in FIG. 32, but further includes a mask layer on the gate electrode 150b according to the acceleration voltage. Can be provided.
- a mask layer 174 made of polyimide or the like is formed, and the gate electrode 150a and the mask layer 174 are used as a mask, and ion implantation of, for example, phosphorus (P) is performed using self-alignment. I do.
- n + layers 146a and 146b are formed.
- the exfoliation promoting ion implantation step can be performed simultaneously with the phosphorus ion implantation step, in addition to the above-described (A) to (G) as the execution time (H). Also in this case, for example, a gas mixture of PH 3 (5%) + H 2 (95%) is turned into plasma, and the generated phosphorus ions and hydrogen ions are accelerated and guided to the substrate without passing through a mass spectrometer. . Then, even with the same accelerating voltage, heavy phosphorus ions stay in the upper polycrystalline silicon layer, while light hydrogen ions are implanted deeper and reach the separation layer 120.
- the gate electrode 150a functions in the same manner as the mask pattern 201 in FIG. 31 or the mask pattern 202 in FIG. 32, but is further provided on the gate electrode 150a according to the acceleration voltage.
- a mask layer can be provided.
- timings (G) and (H) of the above-described separation promotion ion implantation step were the same as the steps of implanting impurity ions into the source and drain regions in Steps 5 and 6, but were separated before and after. May be performed.
- electrodes 152a to 152d are formed.
- the TFT of the CMOS structure thus formed corresponds to the transfer layer (thin film device layer) 140 in FIGS. Note that a protective film may be formed over the interlayer insulating film 154.
- an epoxy resin is used as an adhesive layer on the TFT of the CMOS configuration.
- the layer 160 is formed, and then the TFT is attached to the transfer body (for example, a soda glass substrate) 180 via the epoxy resin layer 160. Subsequently, heat is applied to cure the epoxy resin, and the transfer body 180 and the TFT are bonded (joined).
- the adhesive layer 160 may be a photopolymer resin that is an ultraviolet curable adhesive.
- the polymer is cured by irradiating ultraviolet rays not from heat but from the transfer body 180 side.
- Xe—C 1 excimer laser light is irradiated from the back surface of the translucent substrate 100. This causes peeling in the layer of the separation layer 120 and / or in the interface.
- the substrate 100 is peeled off.
- the separation layer 120 is removed by etching. As a result, as shown in FIG. 18, the TFT of the CMOS configuration was transferred to the transcript 180.
- a transferred layer 140 composed of a thin film device layer is transferred twice, and in addition to the steps of FIGS. 1 to 6 of the first embodiment. The steps shown in FIGS. 33 to 35 are added.
- the separation layer 120 shown in FIGS. 2 to 5 is referred to as a first separation layer.
- the adhesive layer 160 in FIGS. 3 to 6 is referred to as a second separation layer.
- the transfer body 180 in FIGS. 3 to 6 is referred to as a primary transfer body. Therefore, according to the second embodiment, at the stage where the process of FIG. 6 is completed, the transfer target layer 140 is transferred to the primary transfer member 180 via the second separation layer 160. It will be.
- the material of the second separation layer 160 is not only a hot-melt adhesive and a water-soluble adhesive, but also the same material as the first separation layer 120 is used. I can do it.
- the ion implantation described in the first embodiment can be performed.
- the secondary transfer layer 200 is bonded to the lower surface (exposed surface) of the thin film device layer 140 via the bonding layer 190.
- the adhesive constituting the adhesive layer 190 include a light-curable adhesive such as a reaction-curable adhesive, a thermosetting adhesive, and an ultraviolet-curable adhesive, and an anaerobic-curable adhesive.
- a light-curable adhesive such as a reaction-curable adhesive, a thermosetting adhesive, and an ultraviolet-curable adhesive
- an anaerobic-curable adhesive Various types of curable adhesives can be used.
- the composition of the adhesive may be, for example, any of an epoxy type, an acrylate type, and a silicone type.
- Such an adhesive layer 190 is formed, for example, by a coating method.
- a curable adhesive is applied to the lower surface of the layer to be transferred (thin film device layer) 140, and the secondary transfer body 200 is further joined.
- the curable adhesive is cured by a curing method according to the characteristics described above, and the transfer receiving layer (thin film device layer) 140 and the secondary transfer body 200 are bonded and fixed.
- the adhesive is a photo-curing type
- light is preferably irradiated from the outside of the light-transmissible secondary transfer member 200.
- the adhesive if a light-curing adhesive such as an ultraviolet-curing type which does not easily affect the thin film device layer is used, the light-transmissive primary transfer member 180 side or the light-transmissive primary and Light irradiation may be performed from both sides of the next transfer member 180, 200.
- an adhesive layer 190 may be formed on the side of the secondary transfer member 200, and a layer to be transferred (thin film device layer) 140 may be bonded thereon.
- the formation of the adhesive layer 190 may be omitted.
- the secondary transfer body 200 is not particularly limited, but includes a substrate (plate material), particularly a transparent substrate.
- a substrate may be a flat plate or a curved plate.
- the secondary transfer member 200 may have inferior properties such as heat resistance and corrosion resistance as compared with the substrate 100.
- a transferred layer (thin film device layer) 140 is formed on the substrate 100 side, and then the transferred layer (thin film device layer) 14 is formed. Since 0 is transferred to the secondary transfer member 200, the characteristics required for the secondary transfer member 200, especially the heat resistance, do not depend on the temperature conditions and the like when the transfer target layer (thin film device layer) 140 is formed. It is. This is the same for the primary transfer member 180.
- the primary and secondary transfer members 180 and 200 should have a glass transition point (Tg) or softening point of Tmax or less.
- Tg glass transition point
- the primary and secondary transfer members 180 and 200 may be made of a material having a glass transition point (T g) or softening point of preferably 800 ° C or less, more preferably 500 ° C or less, and still more preferably 320 ° C or less. Can be configured.
- the mechanical properties of the primary and secondary transfer members 180 and 200 those having a certain degree of rigidity (strength) are preferable, but those having flexibility and elasticity may be used.
- the constituent materials of the primary and secondary transfer members 180 and 200 include various synthetic resins and various glass materials. In particular, various synthetic resins and ordinary (low melting point) inexpensive glass materials are used. preferable.
- the synthetic resin may be any of a thermoplastic resin and a thermosetting resin.
- examples of the synthetic resin include polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), and cyclic polyolefins.
- Modified polyolefin polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, polyimide, polyamide, polycarbonate, poly (4-methylbenzene-1), ionomer, acrylic resin, polymethyl methacrylate, ⁇ -methyl Krill-styrene copolymer (AS resin), butadiene-styrene copolymer, polycopolymer (EVOH), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), precyclohexane terephthalate Polyester, such as rate (PCT) Polyether, polyetherketone (PEK), polyetheretherketone (PEEK), polyetherimide, polyacetal (POM), polyphenylene oxide, modified polyphenylene oxide, polyarylate, aromatic polyester (liquid crystal polymer), polytetraflu Polyethylene, polyvinylidene fluoride, other fluoroplastics, styrene, polyolefin,
- Elastomers epoxy resins, phenolic resins, urea resins, melamine resins, unsaturated polyesters, silicone resins, polyurethanes, etc., or copolymers, blends, polymer alloys, etc. based on these materials. They can be used alone or in combination of two or more (for example, as a laminate of two or more layers).
- the glass material examples include silicate glass (quartz glass), alkali glass silicate, soda lime glass, potassium lime glass, lead (alkali) glass, barium glass, and borosilicate glass.
- silicate glass quartz glass
- alkali glass silicate soda lime glass
- potassium lime glass potassium lime glass
- lead (alkali) glass barium glass
- borosilicate glass examples include silicate glass (quartz glass), alkali glass silicate, soda lime glass, potassium lime glass, lead (alkali) glass, barium glass, and borosilicate glass.
- silicate glass soda lime glass
- potassium lime glass soda lime glass
- lead (alkali) glass soda lime glass
- barium glass barium glass
- borosilicate glass borosilicate glass.
- those other than silicate glass are preferable because they have a lower melting point than silicate glass, are relatively easy to mold and process, and are inexpensive.
- a secondary transfer member 200 made of a synthetic resin When a secondary transfer member 200 made of a synthetic resin is used, a large-sized secondary transfer member 200 can be integrally formed, and a member having a curved surface or unevenness can be used. Even if it is a complicated shape, it can be easily manufactured, and various advantages such as low material cost and low manufacturing cost can be enjoyed. Therefore, the use of a synthetic resin is advantageous in manufacturing a large and inexpensive device (for example, a liquid crystal display).
- the secondary transfer body 200 is, for example, a device that constitutes an independent device, such as a liquid crystal cell, or a device such as a color filter, an electrode layer, a dielectric layer, an insulating layer, or a semiconductor element. Alternatively, it may constitute a part of the device.
- the primary and secondary transfer members 180, 200 may be a material such as metal, ceramics, stone, wood, paper, or the like, or on any surface that constitutes an article (on the surface of a watch). , On the surface of an air conditioner, on a printed circuit board, etc.), or on the surface of a structure such as a wall, a pillar, a ceiling, or a window glass.
- the heat-meltable adhesive layer 160 as the second separation layer is heated and melted.
- the adhesive force of the heat-meltable adhesive layer 160 is weakened, so that the primary transfer member 180 can be detached by the thin-film device layer 140.
- the primary transfer member 180 can be reused repeatedly.
- the above-mentioned water-soluble adhesive is used as the second separation layer 160
- at least a region including the second separation layer 160 may be brought into contact with water, and preferably may be immersed in pure water.
- the above-mentioned organic solvent-meltable adhesive is used as the second separation layer 160, at least a region including the second separation layer 160 may be brought into contact with the organic solvent.
- the second separation layer 160 When the above-described adhesive exhibiting a peeling action by heating or ultraviolet irradiation is used as the second separation layer 160, at least the region including the second separation layer 160 is heated via another layer. Alternatively, ultraviolet irradiation may be performed. Further, when an ablation layer is used as the second separation layer in the same manner as the first separation layer 120, the second separation layer 160 is peeled off by light irradiation. At this time, the separation is promoted by the effect of the implanted ions.
- the thin film device layer 1 transferred to the secondary transfer body 200 is removed. 40 can be obtained.
- the lamination relationship of the thin film device layer 140 to the secondary transfer body 200 is the same as the lamination relationship of the thin film device layer 140 to the initial substrate 100 as shown in FIG. .
- the transfer of the layer to be transferred (thin film device layer) 140 to the secondary transfer member 200 is completed. Thereafter, the transferred layer (thin film device layer) 1 4 0 removal or S i 0 2 film adjacent, to perform the formation such conductive layers and a desired protective film such as wiring to the transfer layer 1 4 0 above Can also.
- the first separation layer 120 and the second separation layer 160 are not directly separated.
- the secondary transfer member 200 so that the transfer can be performed easily, reliably, and uniformly regardless of the characteristics, conditions, etc. of the material to be separated (transferred layer 140).
- the object to be separated (the layer to be transferred 140) is not damaged by the separation operation, and the high reliability of the layer to be transferred 140 can be maintained.
- a microcomputer constituted by using a thin film device as shown in FIG. It can be formed on a substrate.
- a CPU 300, a RAM 320, an input / output circuit 360, and a power supply voltage for these circuits are provided on a flexible board 182 made of plastic or the like, using thin film devices.
- a solar cell 340 having an amorphous silicon PIN junction is mounted.
- the microcomputer shown in Fig. 19 (a) is formed on a flexible substrate, so it is resistant to bending, as shown in Fig. 19 (b). is there.
- the active matrix type liquid crystal display device includes an illumination light source 400 such as a backlight, a polarizing plate 420, an active matrix substrate 440, a liquid crystal 460, a counter substrate 480, and a polarizing plate 500.
- an illumination light source 400 such as a backlight
- a polarizing plate 420 an active matrix substrate 440
- a liquid crystal 460 a liquid crystal 460
- a counter substrate 480 a polarizing plate 500.
- the illumination light source 400 is replaced by a reflection type liquid crystal panel employing a reflection plate, flexibility is improved. Therefore, it is possible to realize an active matrix type liquid crystal panel that is strong against impact and lightweight.
- the pixel electrode is formed of metal, the reflector and the polarizer 420 are not required.
- the active matrix substrate 440 used in the present embodiment has a TFT disposed in the pixel portion 442, and further includes a driver circuit (a driver built-in active matrix substrate equipped with a scanning line driver and a data line driver 444). It is.
- FIG. 21 is a cross-sectional view of a main part of the active matrix type liquid crystal display device
- FIG. 22 shows a circuit configuration of a main part of the liquid crystal display device.
- the gate is connected to the gate line G1
- one of the source and the drain is connected to the data line D1
- the other of the source and the drain is connected to the liquid crystal 460.
- TFT (M l) and liquid crystal 460 Including TFT (M l) and liquid crystal 460.
- the driver part 444 includes a TFT (M2) formed by the same process as the TFT (Ml) of the pixel portion.
- the TFT (Ml) in the pixel section 442 is a source / drain layer 1 100 a, 1 100 b, a channel 1 100 e, a gate insulating film 1200 a, and a gate. It includes an electrode 1300a, an insulating film 1500, and source / drain electrodes 1400a and 1400b.
- Reference numeral 1700 denotes a pixel electrode
- reference numeral 1702 denotes a region where the pixel electrode 1700 applies a voltage to the liquid crystal 460 (a voltage application region to the liquid crystal).
- the alignment film is omitted.
- the pixel electrode 1700 is made of I T0 (in the case of a light transmissive liquid crystal panel) or a metal such as aluminum (in the case of a reflective liquid crystal panel).
- the underlying insulating film (intermediate layer) 1000 under the pixel electrode 1700 is completely removed in the voltage application region 1702 to the liquid crystal, but the invention is not necessarily limited to this. However, if the base insulating film (intermediate layer) 1000 is thin and does not hinder voltage application to the liquid crystal, it may be left.
- the TFT (M2) constituting the driver part 444 includes the source / drain layers 1100c, llOOd, the channel 1100f, and the gate insulation. It comprises a film 1200b, a gate electrode 1300b, an insulating film 1500, and source and drain electrodes 1400c and 1400d.
- reference numeral 480 is, for example, a counter substrate (for example, a soda glass substrate), and reference numeral 482 is a common electrode.
- Reference numeral 1000 is an SiO 2 film
- reference numeral 1600 is an interlayer insulating film (for example, an SiO 2 film)
- reference numeral 1800 is an adhesive layer.
- Reference numeral 1900 is a substrate (transfer member) made of, for example, a soda glass substrate.
- a TFT (M1, M2) as shown in Fig. 23 is formed on a highly reliable and laser-transmissive substrate (eg, quartz substrate) 3000 through the same manufacturing process as in Figs. Then, a protective film 1600 is formed.
- Reference numeral 3100 denotes a separation layer (laser-absorbing layer) into which the ions for promoting separation are implanted.
- both TFTs (Ml, M2) are n-type M0 SFETs.
- the present invention is not limited to this, and may be a p-type MOSFET or a CMOS structure.
- the protective film 160 and the base insulating film 100 are selectively etched to selectively form openings 400 and 420. These two openings are formed simultaneously using a common etching process.
- the base insulating film (intermediate layer) 100 is completely removed at the opening 4200, but the present invention is not limited to this. If 100.sup.0 is thin and does not hinder voltage application to the liquid crystal, it may be left.
- a pixel electrode 170 made of a metal such as an ITO film or aluminum is formed. When an ITO film is used, a transmissive liquid crystal panel is used. When a metal such as aluminum is used, a reflective liquid crystal panel is used.
- the substrate 190 is bonded (bonded) via the adhesive layer 180.
- a single excimer laser beam is irradiated from the back surface of the substrate 300 to cause a separation phenomenon in the separation layer 120 by utilizing the action of the separation promoting ions. . Thereafter, the substrate 300 is peeled off. At this time, since no significant force is required for peeling, no mechanical damage occurs to TFT or the like.
- the separation layer (laser absorption layer) 310 is removed.
- an active matrix substrate 440 as shown in FIG. 27 is completed.
- the bottom surface of the pixel electrode 170 (the area denoted by reference numeral 1702) is exposed, and can be electrically connected to the liquid crystal.
- the orientation processing is performed to form an alignment layer on the active matrix substrate 4 4 0 insulation film (intermediate layer such as S i 0 2) 1 0 0 0 surface and the pixel electrode 1 7 0 2 surface .
- the alignment film is omitted.
- a common electrode facing the pixel electrode 179 is formed on the surface thereof, and the opposing substrate 480 whose surface is oriented and the active matrix substrate 440 of FIG.
- a liquid crystal display device as shown in Fig. 21 is completed.
- FIG. 28 shows a fifth embodiment of the present invention.
- the above-described thin film device transfer method is executed a plurality of times, and a plurality of patterns including the thin film device are transferred onto a substrate (transfer body) larger than the transfer source substrate. Forming an active matrix substrate.
- the transfer is performed a plurality of times on the large substrate 7000 to form the pixel portions 7100a to 7100OP.
- TFTs and wiring are formed in the pixel portion.
- reference numeral 72 10 is a scanning line
- reference numeral 7200 is a signal line
- reference numeral 7220 is a gate electrode
- reference numeral 7230 is a pixel electrode.
- a large-scale active matrix substrate equipped with a reliable thin-film device by repeatedly using a reliable substrate or performing multiple thin-film pattern transfers using multiple first substrates Can be created.
- FIG. 29 shows a sixth embodiment of the present invention.
- the feature of this embodiment is that the above-described method of transferring a thin film device is executed a plurality of times, and the design rules (that is, the design rules for pattern design) are different on a substrate larger than the transfer source substrate.
- the transfer of multiple patterns including thin film devices (ie, thin film devices with different minimum line widths).
- a driver circuit (8000 to 8032) created by a finer manufacturing process than the pixel part (7100a to 7100p) is transferred multiple times on the active matrix substrate with a driver. It is created around the substrate 6000.
- the shift register which constitutes the driver circuit, operates at a logic level under low voltage, so the breakdown voltage may be lower than that of the pixel TFT.Thus, the TFT is finer than the pixel TFT, and high integration is attempted. be able to.
- a plurality of circuits having different design rule levels can be realized on one substrate.
- Sampling means for sampling the data signal under the control of the shift register (the thin film transistor shown in Fig. 22) Since the pixel M2) requires a high breakdown voltage like the pixel TFT, it may be formed by the same process / design rule as the pixel TFT.
- an E CR- CVD method as an intermediate layer (S i H 4 + 0 2 gas, 1 00 ° C) was formed by.
- the thickness of the intermediate layer was 200 nm.
- an amorphous silicon film having a thickness of 5 Onm is formed on the intermediate layer by a low-pressure CVD method (Si 2 H 6 gas, 425 ° C.) as a transferred layer.
- the substrate was irradiated with laser light (wavelength 308 ⁇ ) to be crystallized to form a polysilicon film. Thereafter, predetermined patterning was performed on the polysilicon film to form a region serving as a source / drain channel of the thin film transistor.
- TE OS- CVD method after forming a gate insulating film S i 0 2 of 1 200 nm by (S i H 4 +0 2 gas), Mo or the like gate one gate electrode (polysilicon on the gate insulating film Then, ion implantation was performed using the gate electrode as a mask to form a self-aligned (self-aligned) source / drain region, forming a thin-film transistor. At this time, hydrogen ions were simultaneously injected into the separation layer. Thereafter, if necessary, an electrode and a wiring connected to the source and drain regions, and a wiring connected to the gate electrode are formed. A1 is used for these electrodes and wires, but is not limited thereto. If there is a concern that A1 may be melted by the subsequent laser irradiation, a metal having a higher melting point than A1 (a metal that does not melt by the subsequent laser irradiation) may be used.
- an ultraviolet-curing adhesive was applied on the thin film transistor (film thickness: 100 m), and the coating film was further transferred as a transfer body to a thickness of 20 Omm x 30 Omm x 1. After bonding a lmm large transparent glass substrate (soda glass, softening point: 740 ° C, strain point: 511 ° C), the glass substrate side is irradiated with ultraviolet light to cure the adhesive, These were adhered and fixed.
- Xe—C1 excimer laser (wavelength: 308 nm) is irradiated from the quartz substrate side, and the beam scan shown in Fig. 31 and subsequent figures is performed to peel off the separation layer (intra-layer peeling and (Interfacial peeling).
- the energy density of the irradiated Xe—C 1 excimer laser was 250 mJ / cm 2 , and the irradiation time was 20 nsec.
- Excimer laser irradiation includes spot beam irradiation and line beam irradiation.
- spot irradiation is performed on a predetermined unit area (for example, 8 nimx 8 mm), and this spot irradiation is performed. Irradiation was performed while beam scanning so that the irradiation areas of each time did not overlap (do not overlap in front, back, left and right). Also, in the case of line beam irradiation, the same unit area (for example, 378 mm x 0.1 band and 378 mm x 0.3 mm (these are areas where 90% or more of energy is obtained)) is also used. Irradiation was performed while beam scanning so that the irradiation areas of each time did not overlap.
- a predetermined unit area for example, 8 nimx 8 mm
- the quartz substrate and the glass substrate (transfer body) were peeled off at the separation layer, and the thin film transistor and the intermediate layer formed on the quartz substrate were transferred to the glass substrate side.
- the separation layer adhered to the surface of the intermediate layer on the glass substrate side was removed by etching, washing, or a combination thereof.
- the same treatment was applied to the quartz substrate, which was reused.
- the transfer from the quartz substrate to the glass substrate as in this embodiment is repeatedly performed on different areas in a plane, and the transfer is performed on the glass substrate. More thin film transistors than the number of thin film transistors that can be formed over the quartz substrate can be formed. Further, by repeatedly stacking the thin film transistors on a glass substrate, more thin film transistors can be similarly formed.
- the transfer of the thin film transistor was performed in the same manner as in Example 1 except that the separation layer was an amorphous silicon film containing 2 Oat% of H (hydrogen) in the separation layer formation process. Adjustment of the amount of H in the amorphous silicon film depends on the conditions during film formation by low-pressure CVD. Was appropriately set.
- the separation layer spin-coating the sol-gel process ceramic thin film formed by (pairs formed: P b T i 0 3, thickness: 2 0 Onm) and to other in the same manner as in Example 1, subjected to transfer of the thin film transistor was.
- the separation layer a ceramic thin film formed by laser ablation over Chillon (composition: P b (Z r, T i) ⁇ 3 (PZT), thickness: 5 onm) and to other than the can in the same manner as in Example 1
- the transfer of the thin film transistor was performed.
- the transfer of the thin film transistor was performed in the same manner as in Example 1 except that the separation layer was a polyimide film (thickness: 20 Onm) formed by spin coating.
- the thin film transistor was transferred in the same manner as in Example 1 except that the separation layer was a polyethylene sulfide film (thickness: 20 Onm) formed by spin coating.
- a thin film transistor was transferred in the same manner as in Example 1 except that the separation layer was an A1 layer (thickness: 30 Onm) formed by sputtering.
- the transfer of the thin film transistor was performed in the same manner as in Example 2 except that Kr-F excimer laser (wavelength: 248 nm) was used as the irradiation light.
- the energy density of the irradiated laser was 25 OmJ / cm 2 , and the irradiation time was 20 nsec.
- the transfer of the thin film transistor was performed in the same manner as in Example 2.
- the energy density of the irradiated laser was 40 OmJ / cm 2 , and the irradiation time was 20 nsec.
- the thin film transistor was transferred in the same manner as in Example 1 except that the thin film transistor was a polysilicon film (thickness: 8 Onm) formed by a high-temperature process at 1000 ° C. as the transfer target layer.
- a thin-film transistor was transferred in the same manner as in Example 1 except that a transparent substrate made of polycarbonate (glass transition point: 130 ° C) was used as the transfer body.
- a thin film transistor was transferred in the same manner as in Example 2 except that a transparent substrate made of an AS resin (glass transition point: 70 to 90 ° C.) was used as a transfer body.
- the thin film transistor was transferred in the same manner as in Example 3 except that a transparent substrate made of polymethylmethacrylate (glass transition point: 70 to 90 ° C) was used as the transfer body.
- a thin film transistor was transferred in the same manner as in Example 5, except that a transparent substrate made of polyethylene terephthalate (glass transition point: 67 ° C) was used as the transfer body.
- a thin-film transistor was transferred in the same manner as in Example 6 except that a transparent substrate made of high-density polyethylene (glass transition point: 77 to 90 ° C) was used as the transfer body. (Example 17)
- a thin film transistor was transferred in the same manner as in Example 9 except that a transparent substrate made of polyamide (glass transition point: 145 ° C) was used as the transfer body.
- a thin-film transistor was transferred in the same manner as in Example 10 except that a transparent substrate made of an epoxy resin (glass transition point: 120 ° C.) was used as a transfer body. (Example 19)
- the thin film transistor was transferred in the same manner as in Example 11 except that a transparent substrate made of polymethyl methacrylate (glass transition point: 70 to 90 ° C.) was used as the transfer body.
- the use of the transfer technique of the present invention makes it possible to transfer a thin-film device (transferred layer) to various types of transfer bodies, and in particular, applies excessive force to the separation of the substrate required for transfer.
- This makes it possible, for example, for materials that cannot be directly formed or are not suitable for forming thin films, materials that are easy to mold, materials that are inexpensive, and large objects that are difficult to move. It can be formed by transfer.
- the transfer body materials having inferior properties such as heat resistance and corrosion resistance as compared to the substrate material, such as various synthetic resins and glass materials having a low melting point, can be used. Therefore, for example, when manufacturing a liquid crystal display in which thin film transistors (especially polysilicon TFTs) are formed on a transparent substrate, a quartz glass substrate with excellent heat resistance is used as the substrate, and various synthetic resins and melting points are used as the transfer body. By using a transparent substrate made of an inexpensive and easily added material such as a low glass material, a large and inexpensive liquid crystal display can be easily manufactured. These advantages are not limited to liquid crystal displays, but apply to the manufacture of other devices.
- a transfer layer such as a functional thin film is formed on a highly reliable substrate, particularly a substrate having high heat resistance such as a quartz glass substrate. Since the patterning can be performed, a highly reliable functional thin film can be formed on the transfer member regardless of the material characteristics of the transfer member.
- the method for peeling a thin film device and the method for transferring a thin film device according to the present invention can be applied to a thin film device, an active matrix substrate, a liquid crystal display device, and the like.
- thin film devices include, besides TFTs, thin film diodes, photoelectric conversion elements (photo sensors, solar cells) consisting of silicon PIN junctions, silicon resistance elements, other thin film semiconductor devices, and electrodes (eg, ITO, mesa).
- Transparent electrodes such as membranes), switching elements, memories, piezoelectric elements, etc., microphones, piezo films (piezo thin film ceramics), magnetic recording thin film heads, coils, inductors, thin film heights Examples include magnetically permeable materials and micro magnetic devices combining them, filters, reflective films, dichroic mirrors, and the like.
- the present invention can be applied to a liquid crystal display device regardless of a reflection type, a transmission type, or a display mode.
- the present invention can be applied not only to a liquid crystal display device that displays characters and images, but also to a liquid crystal device in which a liquid crystal panel has a function as a light valve.
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
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- Recrystallisation Techniques (AREA)
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/403,319 US6700631B1 (en) | 1998-02-25 | 1999-02-23 | Method of separating thin-film device, method of transferring thin-film device, thin-film device, active matrix substrate, and liquid crystal display device |
KR10-1999-7009538A KR100499998B1 (ko) | 1998-02-25 | 1999-02-23 | 박막 디바이스의 박리방법, 박막 디바이스의 전사방법, 박막 디바이스, 액티브 매트릭스 기판 및 액정 표시장치 |
EP99903936A EP1014452B1 (en) | 1998-02-25 | 1999-02-23 | Method of detaching thin-film device |
DE69931130T DE69931130T2 (de) | 1998-02-25 | 1999-02-23 | Verfahren um ein dünnschicht-bauelement zu trennen |
US10/235,935 US6885389B2 (en) | 1998-02-25 | 2002-09-06 | Method of separating thin film device, method of transferring thin film device, thin film device, active matrix substrate and liquid crystal display device |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6059498 | 1998-02-25 | ||
JP10/60594 | 1998-02-25 | ||
JP29621698A JP3809733B2 (ja) | 1998-02-25 | 1998-10-02 | 薄膜トランジスタの剥離方法 |
JP10/296216 | 1998-10-02 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
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US09/403,319 A-371-Of-International US6700631B1 (en) | 1998-02-25 | 1999-02-23 | Method of separating thin-film device, method of transferring thin-film device, thin-film device, active matrix substrate, and liquid crystal display device |
US10/235,935 Division US6885389B2 (en) | 1998-02-25 | 2002-09-06 | Method of separating thin film device, method of transferring thin film device, thin film device, active matrix substrate and liquid crystal display device |
Publications (1)
Publication Number | Publication Date |
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WO1999044242A1 true WO1999044242A1 (en) | 1999-09-02 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP1999/000818 WO1999044242A1 (en) | 1998-02-25 | 1999-02-23 | Method of detaching thin-film device, method of transferring thin-film device, thin-film device, active matrix substrate, and liquid crystal display |
Country Status (8)
Country | Link |
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US (2) | US6700631B1 (ja) |
EP (2) | EP1014452B1 (ja) |
JP (1) | JP3809733B2 (ja) |
KR (1) | KR100499998B1 (ja) |
CN (1) | CN1160800C (ja) |
DE (1) | DE69931130T2 (ja) |
TW (1) | TW412774B (ja) |
WO (1) | WO1999044242A1 (ja) |
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- 1999-02-23 EP EP99903936A patent/EP1014452B1/en not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
---|---|
EP1686626A3 (en) | 2008-06-04 |
DE69931130D1 (de) | 2006-06-08 |
JPH11312811A (ja) | 1999-11-09 |
US6885389B2 (en) | 2005-04-26 |
US6700631B1 (en) | 2004-03-02 |
EP1014452A4 (en) | 2001-11-14 |
JP3809733B2 (ja) | 2006-08-16 |
KR20010006448A (ko) | 2001-01-26 |
CN1256794A (zh) | 2000-06-14 |
EP1014452A1 (en) | 2000-06-28 |
EP1686626A2 (en) | 2006-08-02 |
DE69931130T2 (de) | 2006-11-30 |
CN1160800C (zh) | 2004-08-04 |
KR100499998B1 (ko) | 2005-07-07 |
TW412774B (en) | 2000-11-21 |
EP1014452B1 (en) | 2006-05-03 |
US20030008437A1 (en) | 2003-01-09 |
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