TW201440203A - Method for fabricating electronic device and laminate for fabricating method - Google Patents
Method for fabricating electronic device and laminate for fabricating method Download PDFInfo
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- TW201440203A TW201440203A TW102140398A TW102140398A TW201440203A TW 201440203 A TW201440203 A TW 201440203A TW 102140398 A TW102140398 A TW 102140398A TW 102140398 A TW102140398 A TW 102140398A TW 201440203 A TW201440203 A TW 201440203A
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- light
- flexible substrate
- adhesive
- transmitting support
- layer
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Classifications
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- H01L27/1218—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 with a particular composition or structure of the substrate
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Abstract
Description
本發明是有關於一種具備薄型電晶體(transistor)的液晶/有機電致發光(Electroluminescence，EL)顯示器、電子紙或X射線感測器等、太陽電池等電子元件、特別是具有可撓性的電子元件的製造方法及用於該製造方法的積層體。 The present invention relates to a liquid crystal/organic electroluminescence (EL) display having a thin transistor, an electronic paper or an X-ray sensor, and the like, and an electronic component such as a solar cell, particularly flexible. A method of manufacturing an electronic component and a laminate for use in the method of manufacturing.
於具備薄膜電晶體(Thin Film Transistor，TFT)的液晶顯示器、有機EL顯示器等電子元件中，通常使用玻璃基板作為形成TFT的基板，應對電子元件的可撓性(flexible)化、輕量化、薄型化的要求，正在推進該玻璃基板的厚度的薄型化。另外，另一方面為了實現進一步的可撓性化、輕量化、薄膜化，亦研究了使用塑膠基板等樹脂膜或薄型金屬基板來作為形成TFT的基板。 In an electronic component such as a liquid crystal display or an organic EL display including a thin film transistor (TFT), a glass substrate is generally used as a substrate for forming a TFT, and flexibility, weight reduction, and thinness of the electronic component are required. The demand for this is increasing the thickness of the glass substrate. On the other hand, in order to achieve further flexibility, weight reduction, and film formation, a resin film such as a plastic substrate or a thin metal substrate has been studied as a substrate for forming a TFT.
特別是金屬基板，由於與樹脂膜相比耐熱性更高，另外與薄型玻璃基板相比不脆(破裂)，故作為必需高溫製程的元件中可應用的可撓性基板而有用。 In particular, the metal substrate is more resistant to heat than the resin film, and is less brittle (breaking) than the thin glass substrate. Therefore, it is useful as a flexible substrate that can be applied to an element requiring high-temperature processing.
作為於可撓性基板上具備含有TFT等具有特定功能的元件的結構體(以下稱為功能元件結構體)的電子元件的製作方 法，有以下方法：於可撓性基板上直接形成功能元件結構體的方法(直接法)；及於如玻璃基板般的剛性(rigid)基板上形成功能元件結構體，將功能元件結構體自基板上剝離後轉印至可撓性基板上的方法(間接法或轉印法)。 As a manufacturer of an electronic component including a structure including an element having a specific function such as a TFT (hereinafter referred to as a functional element structure) on a flexible substrate The method includes a method of directly forming a functional element structure on a flexible substrate (direct method), and forming a functional element structure on a rigid substrate such as a glass substrate, and the functional element structure is self-contained A method of transferring onto a flexible substrate after peeling off the substrate (indirect method or transfer method).
間接法或轉印法需要將功能元件結構體自基板上剝離後轉印至可撓性基板上的追加步驟，由於該步驟的良率差，故不適於製造，就良率的觀點而言較佳為利用直接法進行製造。 The indirect method or the transfer method requires an additional step of transferring the functional device structure from the substrate and then transferring it onto the flexible substrate. Since the yield of the step is poor, it is not suitable for manufacturing, and from the viewpoint of yield. Jia is manufactured using the direct method.
於直接法中，可撓性基板可採用將已捲成卷狀的長條基板連續地捲出、並經由至少一個步驟後捲取的捲對捲(roll-to-roll)方式，亦適於大量生產。然而，該方式中製造設備新穎，視電子元件不同而需要各種捲對捲製造裝置。另一方面，於使用現有的玻璃或矽晶圓(silicon wafer)般的剛性基板時，已確立的批次(batch)式製造裝置已有市售，藉由挪用該製造裝置，能以低成本迅速地製造電子元件。 In the direct method, the flexible substrate may be a roll-to-roll method in which a long substrate that has been wound into a roll is continuously wound up and wound up through at least one step, and is also suitable for a roll-to-roll method. Mass production. However, the manufacturing equipment in this manner is novel, and various roll-to-roll manufacturing apparatuses are required depending on the electronic components. On the other hand, when a conventional rigid substrate such as a glass or a silicon wafer is used, an established batch type manufacturing apparatus is commercially available, and the manufacturing apparatus can be used at a low cost. Quickly manufacture electronic components.
於利用批次式製造裝置來使用可撓性基板時，有以下問題：由於其膜薄性或可撓性，故操作性差，於步驟中產生翹曲，或因於可撓性基板上製膜的材料的影響而產生變形。 When a flexible substrate is used in a batch type manufacturing apparatus, there is a problem in that the film is thin or flexible, so that workability is poor, warpage occurs in the step, or film formation on the flexible substrate is caused. Deformation caused by the influence of materials.
作為解決該問題的方法，已提出了以下方法：於批次式製造裝置中，以固定於矽或玻璃等具有剛性的支撐體(以下稱為支撐體)上的狀態來使用可撓性基板，通過步驟後自可撓性基板上剝離支撐體(專利文獻1等)。 As a method for solving this problem, a method has been proposed in which a flexible substrate is used in a state in which it is fixed to a rigid support (hereinafter referred to as a support) such as tantalum or glass in a batch type manufacturing apparatus. After the step, the support is peeled off from the flexible substrate (Patent Document 1 and the like).
於將可撓性基板固定於支撐體上而用於批次式的現有 的製造製程的情形時，於製造製程中，若於可撓性基板與支撐體之間亦稍許產生剝離部分，則可能於該部位產生變形或翹曲。因此，為了於製造製程中使可撓性基板不產生翹曲或變形，必須以於製程中途亦不產生局部的剝離的方式將可撓性基板牢固地固定於支撐體上。 For the existing batch type for fixing the flexible substrate to the support In the case of the manufacturing process, if a peeling portion is slightly generated between the flexible substrate and the support during the manufacturing process, deformation or warpage may occur at the portion. Therefore, in order to prevent warpage or deformation of the flexible substrate during the manufacturing process, it is necessary to firmly fix the flexible substrate to the support so as not to cause partial peeling during the manufacturing process.
另一方面，於製造功能元件後將支撐體自可撓性基板上剝離時，較佳為儘可能容易地剝離。 On the other hand, when the support body is peeled off from the flexible substrate after the functional element is manufactured, it is preferable to peel off as easily as possible.
即，可撓性基板與支撐體理想的是以於功能元件的製作製程中不剝離、但於製程結束後可容易地剝離的方式貼附。 In other words, the flexible substrate and the support are preferably attached so as not to be peeled off during the manufacturing process of the functional device, but can be easily peeled off after the completion of the process.
然而，以於功能元件的製作製程中不剝離、但於製程結束後可容易地剝離的方式將兩者黏接非常困難。若兩者的黏接力過弱，則於功能元件的製作製程中剝離，反之若過強，則難以剝離支撐體，若強行剝離則可能使所製作的功能元件或可撓性基板產生損傷。另外，亦想到了利用藉由加熱或紫外線(Ultraviolet，UV)照射而黏接強度降低的黏著劑使兩者黏接的方法，但現狀為該些方法中亦局部地產生氣泡，或因黏著劑的黏著強度並未完全消失而無法良好地自可撓性基板上剝離支撐體。另外，於功能元件的製作製程中，例如於藉由電漿化學氣相沈積(Chemical Vapor Deposition，CVD)將非晶矽(amorphous silicon)製膜的情形時，必須將基板溫度提高至350℃左右的高溫，此時有以下問題：黏接力降低而可撓性基板自支撐體上剝離，或於高溫下進行黏接劑的硬化，於步驟結束後無法自可撓性基板上剝離支撐體。 However, it is very difficult to bond the two in a manner that does not peel off during the manufacturing process of the functional element, but can be easily peeled off after the end of the process. If the adhesion between the two is too weak, it will be peeled off during the manufacturing process of the functional element. On the other hand, if it is too strong, it is difficult to peel off the support, and if it is forcibly peeled off, the produced functional element or the flexible substrate may be damaged. In addition, a method of bonding the two by using an adhesive which has a reduced adhesive strength by heating or ultraviolet (UV) irradiation is also conceivable, but the present state of the art also locally generates bubbles or adhesives. The adhesive strength did not completely disappear and the support could not be peeled off well from the flexible substrate. In addition, in the manufacturing process of the functional device, for example, when the amorphous silicon is formed by plasma chemical vapor deposition (CVD), the substrate temperature must be raised to about 350 ° C. At this time, there is a problem in that the adhesive force is lowered and the flexible substrate is peeled off from the support, or the adhesive is hardened at a high temperature, and the support cannot be peeled off from the flexible substrate after the step.
於專利文獻1中，揭示有一種半導體裝置的製作方法，該製作方法中，使用黏接層將樹脂膜基板或薄型金屬基板貼合於固定用支撐體上，於基板上形成發光元件，形成發光元件後自固定基板側照射雷射光，藉此使黏接層的一部分或全部氣化而將固定用支撐體分離。 Patent Document 1 discloses a method of fabricating a semiconductor device in which a resin film substrate or a thin metal substrate is bonded to a fixing support using an adhesive layer, and a light-emitting element is formed on the substrate to form a light-emitting device. After the element is irradiated with the laser light from the side of the fixed substrate, a part or all of the adhesive layer is vaporized to separate the fixing support.
於專利文獻1中，如段落[0018]中亦記載般，採用兼具以下物性的黏接層作為貼合於固定用支撐體上時所用的黏接層，即，在用於分離的雷射光下全部或一部分氣化，另外不因元件形性步驟中的加熱而氣化，藉此可使用基板的厚度為50μm~300μm的極薄基板藉由批次製程來製造可靠性高的發光裝置。 In Patent Document 1, as described in the paragraph [0018], an adhesive layer having the following physical properties is used as an adhesive layer used for bonding to a fixing support, that is, laser light for separation. All or a part of the gasification is vaporized, and the gas is not vaporized by the heating in the element shape step, whereby a highly reliable light-emitting device can be manufactured by a batch process using an extremely thin substrate having a substrate thickness of 50 μm to 300 μm.
[先前技術文獻] [Previous Technical Literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本專利4869471號公報 [Patent Document 1] Japanese Patent No. 4,486,471
然而，於藉由專利文獻1中記載的方法實際使用不鏽鋼基板來製作功能元件的情形時，利用雷射光自玻璃固定基板上剝離時，元件的一部分劣化，確認到元件的特性均勻性的劣化(參照後述比較例1)。 In the case where the functional element is actually produced by using the stainless steel substrate by the method described in Patent Document 1, when the laser light is peeled off from the glass fixed substrate, a part of the element is deteriorated, and deterioration of the characteristic uniformity of the element is confirmed ( Reference is made to Comparative Example 1) described later.
本發明是鑒於上述情況而成，其目的在於提供一種於可撓性金屬基板上以批次方式來製造高性能的可撓性電子元件的方法、及適於該方法的可撓性基板與支撐體的貼合積層體。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for manufacturing a high-performance flexible electronic component in a batch manner on a flexible metal substrate, and a flexible substrate and support suitable for the method. The body is laminated to the laminate.
本發明的電子元件的製造方法製造以下電子元件，上述 電子元件是於在鋁材上具備多孔質陽極氧化絕緣膜的可撓性基板的上述多孔質陽極氧化絕緣膜上，形成含有具有特定功能的元件的結構體而成，並且上述電子元件的製造方法的特徵在於：準備可撓性基板及光透射性支撐體；於光透射性支撐體的表面的貼附可撓性基板的貼附區域中，施用於含有具有特定功能的元件的結構體的形成步驟中具有耐熱性的黏接劑；於光透射性支撐體上經由黏接劑來貼附可撓性基板與形成結構體的面為相反側的面；於多孔質陽極氧化絕緣膜上形成含有具有特定功能的元件的結構體；自光透射性支撐體的背面側照射雷射光，藉此使黏接劑的黏接力降低而將光透射性支撐體自可撓性基板上剝離。 The method of manufacturing an electronic component of the present invention produces the following electronic component, The electronic component is a structure in which a device having a specific function is formed on the porous anodized insulating film having a flexible substrate having a porous anodized insulating film on an aluminum material, and the electronic component is manufactured. It is characterized in that a flexible substrate and a light-transmitting support are prepared, and a structure in which a component having a specific function is applied to a surface of the light-transmitting support attached to the flexible substrate is formed. a heat-resistant adhesive in the step; the surface of the flexible substrate and the surface on which the structure is formed is attached to the light-transmitting support via an adhesive; and the porous anodic oxide insulating film is formed. The structure of the element having a specific function; the laser light is irradiated from the back side of the light-transmitting support, whereby the adhesive force of the adhesive is lowered to peel the light-transmitting support from the flexible substrate.
於本發明的電子元件的製造方法中，光透射性支撐體的剝離較佳為自貼附區域的一端起朝向另一端一面二維掃描一面照射雷射光，藉此使黏接劑的黏接力降低，自開始照射的一端側起緩緩地實施。 In the method for producing an electronic component of the present invention, it is preferable that the peeling of the light-transmitting support is irradiated with laser light two-dimensionally from one end of the attaching region toward the other end, thereby lowering the adhesive force of the adhesive. It is gradually implemented from the one end side where the irradiation is started.
此處，視雷射光的光源的態樣不同，貼附區域的一端及另一端可為點(spot)狀亦可為線(line)狀。於所照射的雷射光為點狀的情形時，二維掃描是於主掃描方向與副掃描方向兩個方向上掃描來實施，於所照射的雷射光為線狀的情形時，二維掃描是於與線大致正交的方向上進行掃描來實施。 Here, depending on the aspect of the light source of the laser light, one end and the other end of the attachment region may be in the form of a spot or a line. When the irradiated laser light is in a dot shape, the two-dimensional scanning is performed by scanning in both the main scanning direction and the sub-scanning direction, and when the irradiated laser light is linear, the two-dimensional scanning is The scanning is performed in a direction substantially orthogonal to the line.
於本發明的電子元件的製造方法中，可撓性基板與光透射性支撐體較佳為線膨脹係數之差為4ppm/K以下。 In the method for producing an electronic component of the present invention, it is preferable that the difference between the linear expansion coefficient of the flexible substrate and the light-transmitting support is 4 ppm/K or less.
於本發明的電子元件的製造方法中，於可撓性基板包含鋁材與多孔質陽極氧化絕緣膜的情形時，較佳為光透射性支撐體的線膨脹係數為3ppm/K~9ppm/K，於可撓性基板是在鋁材的表面上具備多孔質陽極氧化絕緣膜、且在背面上具備碳鋼或鐵氧體(ferrite)系鋼材而成的情形時，較佳為光透射性支撐體的線膨脹係數為6ppm/K~13ppm/K。 In the method of manufacturing an electronic component of the present invention, when the flexible substrate comprises an aluminum material and a porous anodized insulating film, it is preferred that the light-transmitting support has a linear expansion coefficient of 3 ppm/K to 9 ppm/K. In the case where the flexible substrate is provided with a porous anodized insulating film on the surface of the aluminum material and carbon steel or ferrite-based steel material on the back surface, it is preferably a light-transmitting support. The linear expansion coefficient of the body is 6ppm/K~13ppm/K.
另外，本發明的第一積層體可較佳地用於上述本發明的電子元件的製造方法，且上述第一積層體是將線膨脹係數為3ppm/K~9ppm/K的光透射性支撐體、與於鋁材上具備多孔質陽極氧化絕緣膜的可撓性基板經由黏接劑積層而成的積層體，並且自該積層體的光透射性支撐體側照射雷射光，藉此黏接劑的黏接力降低而可將光透射性支撐體自可撓性基板上剝離。 Further, the first laminate of the present invention can be preferably used in the above-described method for producing an electronic component of the present invention, and the first laminate is a light-transmitting support having a linear expansion coefficient of 3 ppm/K to 9 ppm/K. And a laminate in which a flexible substrate having a porous anodized insulating film on an aluminum material is laminated via an adhesive, and laser light is irradiated from the side of the light-transmitting support of the laminate to thereby bond the adhesive The adhesive force is lowered to peel the light-transmitting support from the flexible substrate.
另外，本發明的第二積層體同樣可較佳地用於本發明的電子元件的製造方法中，且上述第二積層體是將線膨脹係數為6ppm/K~13ppm/K的光透射性支撐體、與於鋁材的表面上具備多孔質陽極氧化絕緣膜且於背面上具備碳鋼或鐵氧體系鋼材而成的可撓性基板經由黏接劑積層而成的積層體；並且自該積層體的光透射性支撐體側照射雷射光，藉此黏接劑的 黏接力降低而可將光透射性支撐體自可撓性基板上剝離。 Further, the second laminate of the present invention can be preferably used in the method of manufacturing an electronic component of the present invention, and the second laminate is a light-transmitting support having a linear expansion coefficient of 6 ppm/K to 13 ppm/K. a laminate having a porous anodized insulating film on the surface of the aluminum material and having a carbon steel or a ferrite-based steel material on the back surface, which is formed by laminating a flexible substrate; and from the laminate The light transmissive support side of the body illuminates the laser light, thereby the adhesive The light transmissive support can be peeled off from the flexible substrate by reducing the adhesive force.
線膨脹係數為3ppm/K~9ppm/K的光透射性支撐體較佳為無鹼玻璃或硼矽酸玻璃，上述線膨脹係數為6ppm/K~13ppm/K的光透射性支撐體較佳為鈉鈣玻璃(soda-lime glass)或白板鉀玻璃。 The light-transmitting support having a linear expansion coefficient of 3 ppm/K to 9 ppm/K is preferably an alkali-free glass or a borosilicate glass, and the light-transmitting support having a linear expansion coefficient of 6 ppm/K to 13 ppm/K is preferably Soda-lime glass or whiteboard potassium glass.
於本說明書中，所謂「可撓性基板」，是指即便於25℃的溫度條件下將該基板彎曲成曲率半徑R=100mm的圓弧狀亦不被破壞的基板。即便為相同材質，可撓性亦視厚度而不同，即便為相同材料，亦可能厚度薄的基板具有可撓性，但厚度厚的基板不具有可撓性。 In the present specification, the term "flexible substrate" means a substrate which is not damaged by bending the substrate into an arc shape having a curvature radius R of 100 mm even under a temperature condition of 25 ° C. Even if it is the same material, the flexibility differs depending on the thickness. Even if it is the same material, the substrate having a small thickness may have flexibility, but the substrate having a large thickness may not have flexibility.
於本說明書中，所謂「光透射性支撐體」，是指對自光透射性透明支撐體的背面側所照射的雷射光之透射率為10%以上的支撐體。 In the present specification, the term "light-transmitting support" means a support having a transmittance of laser light irradiated from the back side of the light-transmitting transparent support of 10% or more.
於本說明書中，所謂「具有耐熱性的黏接劑」，是指於該溫度下可維持使物體黏接的狀態的黏接劑，另外，所謂「使黏接劑的黏接力降低」，是指使黏接劑的黏接力降低至可將黏接劑所黏接的可撓性基板與光透射性支撐體的黏接接合解除的狀態的程度。 In the present specification, the term "adhesive having heat resistance" refers to an adhesive which maintains a state in which an object is adhered at this temperature, and "the adhesive force of the adhesive is lowered" is It means that the adhesive force of the adhesive is lowered to such an extent that the adhesive bonding of the flexible substrate to which the adhesive is adhered and the light-transmitting support are released.
所謂「鋁材」，是指以鋁作為主成分的金屬材料，可為純鋁、於純鋁中固溶有微量的不可避免的雜質者，或亦可為鋁與其他金屬元素的合金材料。具體是指鋁含量為90質量%以上的金屬材料。尤其較佳為雜質少、鋁含量為99質量%以上的金屬材料。 The term "aluminum material" refers to a metal material containing aluminum as a main component, and may be pure aluminum, a trace amount of unavoidable impurities dissolved in pure aluminum, or an alloy material of aluminum and other metal elements. Specifically, it means a metal material having an aluminum content of 90% by mass or more. In particular, a metal material having less impurities and an aluminum content of 99% by mass or more is preferable.
此處，可撓性基板及光透射性支撐體的線膨脹係數是設定為如以下般測定的值。將試樣放置於溫度可變的熱板上，在無負荷的狀態下測定各溫度下的試樣表面的測試點間距離，將自室溫起至500℃為止的測試點間距離變化率作為線膨脹係數(Coefficient of thermal expansion，CTE)。 Here, the linear expansion coefficient of the flexible substrate and the light-transmitting support is set to a value measured as follows. The sample is placed on a hot plate with variable temperature, and the distance between the test points on the surface of the sample at each temperature is measured under no load, and the rate of change between test points from room temperature to 500 ° C is taken as a line. Coefficient of thermal expansion (CTE).
本發明的電子元件的製造方法藉由以下方式製造電子元件(於在鋁材上具備多孔質陽極氧化絕緣膜的可撓性基板上形成具有特定功能的元件而成的電子元件)：經由在元件形成步驟中具有耐熱性的黏接劑將於鋁材上具備多孔質陽極氧化絕緣膜的可撓性基板與光透射性支撐體貼附而製成積層體後，於多孔質陽極氧化絕緣膜上形成元件，形成元件後，自光透射性支撐體的背面側照射雷射光，藉此使黏接劑的黏接力降低而將光透射性支撐體自可撓性基板上剝離。根據該製造方法及積層體，可於利用批次製程的元件形成時，維持良好的操作性，實施元件形性而不產生製程中的可撓性基板的翹曲、及由在可撓性基板上製膜的材料所引起的變形，且於形成元件後，實施光透射性支撐體的剝離而不產生元件的劣化、特性均勻性的劣化。因此，根據本發明，可於可撓性金屬基板上以批次方式來製造高性能的可撓性電子元件。 In the method for producing an electronic component of the present invention, an electronic component (an electronic component in which an element having a specific function is formed on a flexible substrate having a porous anodized insulating film on an aluminum material) is manufactured by: The adhesive having heat resistance in the forming step is formed by laminating a flexible substrate having a porous anodized insulating film on the aluminum material and a light-transmitting support to form a laminate, and then forming the porous anodized insulating film. After the element is formed, the laser light is irradiated from the back side of the light-transmitting support, whereby the adhesive force of the adhesive is lowered to peel the light-transmitting support from the flexible substrate. According to the manufacturing method and the laminated body, it is possible to maintain good workability when forming a component by a batch process, and to perform element shape without causing warpage of the flexible substrate in the process, and on the flexible substrate. The deformation caused by the material of the upper film is formed, and after the element is formed, the peeling of the light-transmitting support is performed without deterioration of the element and deterioration of the uniformity of the characteristics. Therefore, according to the present invention, a high-performance flexible electronic component can be manufactured in a batch manner on a flexible metal substrate.
1、1A、1B、1C‧‧‧積層體 1, 1A, 1B, 1C‧‧‧ laminated body
2‧‧‧結構體 2‧‧‧structure
3‧‧‧電子元件 3‧‧‧Electronic components
3A‧‧‧光電轉換元件 3A‧‧‧ photoelectric conversion components
3B‧‧‧有機EL顯示器 3B‧‧‧Organic EL display
3C‧‧‧FPD 3C‧‧‧FPD
3D‧‧‧有機薄膜太陽電池 3D‧‧‧Organic thin film solar cell
10、10A、10B、10C‧‧‧可撓性基板 10, 10A, 10B, 10C‧‧‧flexible substrate
11‧‧‧黏接劑 11‧‧‧Adhesive
12‧‧‧光透射性支撐體 12‧‧‧Light Transmissive Support
20‧‧‧下部電極(背面電極)/導電層 20‧‧‧lower electrode (back electrode) / conductive layer
30‧‧‧光電轉換半導體層/光電轉換層 30‧‧‧Photoelectric conversion semiconductor layer/photoelectric conversion layer
40‧‧‧緩衝層 40‧‧‧buffer layer
50、93、128‧‧‧上部電極 50, 93, 128‧‧‧ upper electrode
61‧‧‧第1開槽部/分離槽 61‧‧‧1st slotted/separated slot
62‧‧‧第2開槽部/分離槽 62‧‧‧2nd slotted/separated slot
63‧‧‧第3開槽部/分離槽 63‧‧‧3rd slotted/separation slot
71‧‧‧緩衝層(Si3N4) 71‧‧‧ Buffer layer (Si 3 N 4 )
72‧‧‧SiO2層(絕緣膜) 72‧‧‧SiO 2 layer (insulation film)
73‧‧‧SiN膜 73‧‧‧SiN film
80‧‧‧薄膜電晶體/TFT 80‧‧‧Thin Film Transistor/TFT
81‧‧‧閘極電極 81‧‧‧gate electrode
82‧‧‧絕緣層 82‧‧‧Insulation
83‧‧‧活性層(通道) 83‧‧‧Active layer (channel)
84、85‧‧‧源極/汲極電極 84, 85‧‧‧ source/drain electrodes
88‧‧‧層間絕緣平坦化層 88‧‧‧Interlayer insulation flattening layer
90‧‧‧電容器 90‧‧‧ capacitor
91、124‧‧‧下部電極 91, 124‧‧‧ lower electrode
94‧‧‧通孔 94‧‧‧through hole
95‧‧‧畫素電極 95‧‧‧ pixel electrodes
96‧‧‧有機EL層 96‧‧‧Organic EL layer
97‧‧‧透明電極 97‧‧‧Transparent electrode
98‧‧‧有機EL元件 98‧‧‧Organic EL components
99‧‧‧樹脂膜 99‧‧‧ resin film
100‧‧‧光檢測器 100‧‧‧Photodetector
101‧‧‧鋁材/被陽極氧化鋁材/被陽極氧化金屬體/光檢測器用下部電極 101‧‧‧Aluminum/Anodic Alumina/Anodic Oxide Metal/Photodetector Lower Electrode
101s‧‧‧表面 101s‧‧‧ surface
102‧‧‧多孔質陽極氧化絕緣膜/有機光電轉換部 102‧‧‧Porous anodized insulating film/organic photoelectric conversion unit
102a‧‧‧氧化鋁(Al2O3)層 102a‧‧‧Alumina (Al 2 O 3 ) layer
102b‧‧‧微細孔 102b‧‧‧micropores
103‧‧‧鋼材/光檢測器用上部電極 103‧‧‧ Upper electrode for steel/photodetector
105‧‧‧閃爍體 105‧‧‧Scintillator
108‧‧‧密封膜 108‧‧‧ sealing film
109‧‧‧保護膜 109‧‧‧Protective film
126‧‧‧有機光電轉換半導體層/光電轉換層 126‧‧‧Organic photoelectric conversion semiconductor layer/photoelectric conversion layer
132‧‧‧氣體阻障膜 132‧‧‧ gas barrier film
134‧‧‧匯流排電極 134‧‧‧ bus bar electrode
C‧‧‧單元 C‧‧‧ unit
L‧‧‧雷射光 L‧‧‧Laser light
x、y‧‧‧方向 x, y‧‧‧ direction
圖1為示意性地表示本發明的電子元件的製造方法的圖。 Fig. 1 is a view schematically showing a method of manufacturing an electronic component of the present invention.
圖2A為表示具備以下可撓性基板的態樣的積層體的構成的概略剖面圖，即，於鋁材的單面上具備多孔質陽極氧化絕緣膜的可撓性基板。 2A is a schematic cross-sectional view showing a configuration of a laminate including the following flexible substrate, that is, a flexible substrate including a porous anodized insulating film on one surface of an aluminum material.
圖2B為表示具備以下可撓性基板的態樣的積層體的構成的概略剖面圖，即，於鋁材的表面上具備多孔質陽極氧化絕緣膜、且於背面上具備碳鋼或鐵氧體系鋼材而成的可撓性基板。 2B is a schematic cross-sectional view showing a configuration of a laminate including the following flexible substrate, that is, a porous anodized insulating film is provided on the surface of the aluminum material, and a carbon steel or ferrite system is provided on the back surface. A flexible substrate made of steel.
圖2C為表示具備以下可撓性基板的態樣的積層體的構成的概略剖面圖，即，於鋁材的兩面上具備多孔質陽極氧化絕緣膜的可撓性基板。 2C is a schematic cross-sectional view showing a configuration of a laminate including the following flexible substrate, that is, a flexible substrate provided with a porous anodized insulating film on both surfaces of an aluminum material.
圖3為表示圖2A所示的態樣的可撓性基板的製造方法的概略剖面圖。 Fig. 3 is a schematic cross-sectional view showing a method of manufacturing the flexible substrate shown in Fig. 2A.
圖4為表示本發明的帶有絕緣層的可撓性金屬基板的熱膨脹特性的圖。 Fig. 4 is a view showing the thermal expansion characteristics of the flexible metal substrate with an insulating layer of the present invention.
圖5為表示藉由本發明的電子元件的製造方法所製造的薄膜化合物太陽電池的要部的剖面圖。 Fig. 5 is a cross-sectional view showing a main part of a thin film compound solar cell produced by the method for producing an electronic component of the present invention.
圖6為表示藉由本發明的電子元件的製造方法所製造的有機EL顯示器的要部的剖面圖。 Fig. 6 is a cross-sectional view showing a main part of an organic EL display manufactured by the method for producing an electronic component of the present invention.
圖7為表示藉由本發明的電子元件的製造方法所製造的X射線平板檢測器(Flat Panel Detector，FPD)的要部的剖面圖。 Fig. 7 is a cross-sectional view showing a main part of an X-ray flat panel detector (FPD) manufactured by the method for producing an electronic component of the present invention.
圖8為表示藉由本發明的電子元件的製造方法所製造的有機薄膜太陽電池的要部的剖面圖。 8 is a cross-sectional view showing a main part of an organic thin film solar cell manufactured by the method for producing an electronic component of the present invention.
參照圖式，對本發明的電子元件的製造方法及適於該製造方法的積層體加以說明。圖1為示意性地表示本發明的電子元件的製造方法的要部(剝離步驟)的態樣的圖。另外，圖2A~圖2C為分別表示適於本發明的電子元件的製造方法的積層體的實施形態1A、實施形態1B、實施形態1C的構成的概略剖面圖。為了容易看清，適當變更各部的比例尺來表示。 A method of manufacturing an electronic component of the present invention and a laminate suitable for the method of the present invention will be described with reference to the drawings. Fig. 1 is a view schematically showing an aspect of a main part (peeling step) of a method of manufacturing an electronic component of the present invention. 2A to 2C are schematic cross-sectional views showing the configuration of the first embodiment, the first embodiment, and the first embodiment of the laminated body of the electronic component manufacturing method of the present invention. In order to make it easy to see, the scale of each part is changed as appropriate.
如圖所示，本發明的電子元件的製造方法為製造電子元件3的方法，上述電子元件3是於在鋁材101上具備多孔質陽極氧化絕緣膜102的可撓性基板10的多孔質陽極氧化絕緣膜102上，形成含有具有特定功能的元件的結構體2而成，並且上述電子元件的製造方法的特徵在於：準備可撓性基板10及光透射性支撐體12，於光透射性支撐體12的表面的貼附可撓性基板10的貼附區域中，施用於含有具有特定功能的元件的結構體2的形成步驟中具有耐熱性的黏接劑11，於光透射性支撐體12上經由黏接劑11來貼附可撓性基板10與形成結構體2的面為相反側的面，於多孔質陽極氧化絕緣膜102上形成含有具有特定功能的元件的結構體2，自光透射性支撐體12的背面側照射雷射光L，藉此使黏接劑11的黏接力降低而將光透射性支撐體12自可撓性基板10上剝離。此處，如圖2A~圖2C所示，可撓性基板10於形成結構體2之側具備多孔質陽極氧化絕緣膜102。於圖1中，未示出可撓性基板10的構成。 As shown in the figure, the method of manufacturing an electronic component of the present invention is a method of manufacturing an electronic component 3 which is a porous anode of a flexible substrate 10 having a porous anodized insulating film 102 on an aluminum material 101. The structure 2 including a device having a specific function is formed on the oxide insulating film 102, and the method for manufacturing the electronic device is characterized in that the flexible substrate 10 and the light-transmitting support 12 are prepared for light-transmitting support. In the attachment region of the surface of the body 12 to which the flexible substrate 10 is attached, the adhesive 11 having heat resistance applied to the structure 2 including the element having a specific function is applied to the light-transmitting support 12 The surface of the flexible substrate 10 opposite to the surface on which the structural body 2 is formed is attached via the adhesive 11 to form a structure 2 including an element having a specific function on the porous anodic oxide insulating film 102. The back side of the transmissive support 12 is irradiated with the laser light L, whereby the adhesive force of the adhesive 11 is lowered to peel the light-transmitting support 12 from the flexible substrate 10. Here, as shown in FIG. 2A to FIG. 2C, the flexible substrate 10 is provided with a porous anodized insulating film 102 on the side where the structural body 2 is formed. In FIG. 1, the configuration of the flexible substrate 10 is not shown.
另外，圖1所示的剝離步驟中，示出以下態樣：於基板 面內方向(xy方向)上一面二維掃描一面照射來自雷射光源的雷射光L，藉此使黏接劑11的黏接力降低，自開始照射的一端側起緩緩實施剝離。 In addition, in the peeling step shown in FIG. 1, the following aspect is shown: on the substrate In the in-plane direction (xy direction), the laser beam L from the laser light source is irradiated while being scanned two-dimensionally, whereby the adhesive force of the adhesive 11 is lowered, and peeling is gradually performed from the one end side from which the irradiation is started.
雷射光L只要為可藉由照射於黏接劑11而在不對結構體2造成不良影響的情況下使黏接劑11的黏接力降低的光，則並無特別限制。如圖所示，雷射光L較佳為以於可撓性基板10的與光透射性支撐體12的黏接面上聚光的方式照射。圖1中，未示出雷射光L的聚光手段。 The laser light L is not particularly limited as long as it can illuminate the adhesive 11 and reduce the adhesion of the adhesive 11 without adversely affecting the structure 2 . As shown in the figure, the laser light L is preferably irradiated so as to condense on the adhesion surface of the flexible substrate 10 to the light-transmitting support 12. In Fig. 1, the light collecting means of the laser light L is not shown.
雷射光L較佳為黏接劑11的光吸收率高的光，能量密度是選擇使黏接劑的黏接力降低所必需的強度。於黏接劑11為後述實施例中使用的硬化矽酮樹脂的情形時，較佳為釔鋁石榴石(Yttrium-Aluminum Garnet，YAG)雷射光。 The laser light L is preferably light having a high light absorptivity of the adhesive 11, and the energy density is a strength required to reduce the adhesive force of the adhesive. In the case where the adhesive 11 is a hardened fluorenone resin used in the examples described later, Yttrium-Aluminum Garnet (YAG) laser light is preferable.
雷射光源可使用脈波振盪型或連續光的任一種，為了儘可能使熱難以傳至結構體2側，雷射光L較佳為脈波光。雷射光源可使用：準分子雷射(excimer laser)等氣體雷射或YAG、YVO4等固體雷射及其二次諧波、三次諧波驅動，半導體雷射或其光纖放大器(fiber amplifier)驅動等。 As the laser light source, any of pulse wave oscillation type or continuous light can be used, and in order to make heat difficult to pass to the side of the structure 2 as much as possible, the laser light L is preferably pulse wave light. Laser sources can be used: gas lasers such as excimer lasers or solid lasers such as YAG and YVO 4 , and their second and third harmonic drives, semiconductor lasers or their fiber amplifiers. Drive, etc.
另外，於黏接劑11藉由紫外光而發生光分解的情形時，雷射光L較佳為準分子雷射所代表的紫外線雷射。 Further, in the case where the adhesive 11 is photodecomposed by ultraviolet light, the laser light L is preferably an ultraviolet laser represented by an excimer laser.
圖1中，對雷射光L為點光的態樣進行了圖示，但雷射光L亦可設定為以下態樣：使用在圖1中的x方向或y方向上延伸的線光源，於與線光源正交的方向上掃描。 In Fig. 1, the aspect in which the laser light L is a spot light is illustrated, but the laser light L can also be set to the following aspect: using a line light source extending in the x direction or the y direction in Fig. 1, The line sources are scanned in a direction orthogonal to the line.
如「發明所欲解決的問題」的項中所記載般，本發明者確認到，於藉由專利文獻1中記載的方法使用(不鏽鋼基板)作為可撓性金屬基板來製作功能元件的情形時，於利用雷射光自玻璃固定基板上剝離時，元件的一部分劣化，元件的特性均勻性劣化。 As described in the section of the "Problem to be Solved by the Invention", the inventors of the present invention have found that when a functional element is produced using a (stainless steel substrate) as a flexible metal substrate by the method described in Patent Document 1, When the laser light is peeled off from the glass fixed substrate, a part of the element is deteriorated, and the characteristic uniformity of the element is deteriorated.
於專利文獻1的製造方法中，本發明者等人對元件劣化、均勻性的劣化的要因進行了研究，結果認為其原因在於，於使用不鏽鋼基板的情形時，用於剝離的雷射光雖然因不鏽鋼基板的遮光性而未到達上部功能層，但由於熱傳導而亦容易對上部功能層造成熱影響，因而對具有充分的遮光性、且可充分抑制向上部功能層的熱傳導的可撓性基板的構成進行了研究。 In the manufacturing method of the patent document 1, the inventors of the present invention have studied the cause of deterioration of the element and the deterioration of the uniformity, and as a result, it is considered that the reason for the use of the stainless steel substrate is that the laser light for peeling is used. Although the stainless steel substrate has a light-shielding property and does not reach the upper functional layer, it is also susceptible to thermal influence on the upper functional layer due to heat conduction. Therefore, the flexible substrate can have sufficient light-shielding properties and can sufficiently suppress heat conduction to the upper functional layer. The composition was studied.
結果發現，如圖2A~圖2C所示，將於鋁材101的表面上具備多孔質陽極氧化絕緣膜102的可撓性基板10A~可撓性基板10C作為基板，經由在上部功能層結構體2的形成步驟中具有耐熱性的黏接劑11，將可撓性基板10(10A、10B、10C)與形成結構體2的面為相反側的面與光透射性支撐體12貼附而形成積層體1A~積層體1C，使用該積層體1A~積層體1C，於多孔質陽極氧化絕緣膜102上形成上部功能層結構體2，其後自光透射性支撐體12的背面側照射雷射光L，藉此使黏接劑11的黏接力降低而將光透射性支撐體12自可撓性基板10上剝離，藉此可於剝離時不對上部功能層造成不良影響的情況下以批次方式來製造高性能的可撓性電子元件3。 As a result, as shown in FIG. 2A to FIG. 2C, the flexible substrate 10A to the flexible substrate 10C including the porous anodized insulating film 102 on the surface of the aluminum material 101 is used as a substrate, and the upper functional layer structure is passed through. The heat-resistant adhesive 11 in the forming step of 2 is formed by attaching the flexible substrate 10 (10A, 10B, 10C) to the surface opposite to the surface on which the structural body 2 is formed, and the light-transmitting support 12 The laminated body 1A to the laminated body 1C, the upper functional layer structure 2 is formed on the porous anodic oxide insulating film 102 by using the laminated body 1A to the laminated body 1C, and then the laser beam is irradiated from the back side of the light-transmitting support body 12 L, whereby the adhesive force of the adhesive 11 is lowered, and the light-transmitting support 12 is peeled off from the flexible substrate 10, whereby the batch can be removed without causing adverse effects on the upper functional layer during peeling. To manufacture high performance flexible electronic components 3.
可認為上述可撓性基板10A~可撓性基板10C由於存在熱傳導良好的鋁材101，故相較於熱到達多孔質陽極氧化絕緣膜102上而溫度上升的情況，熱於面內擴散而溫度不易上升。鋁的熱傳導率為237W/(m．K)，不鏽鋼(Stainless Steel，SUS)430為25W/(m．K)，另一方面，對多孔質陽極氧化膜另進行測定，結果為6W/(m．K)左右。因此，於具有鋁及多孔質陽極氧化膜的帶有絕緣層的金屬基板的情況下，可預防剝離時的元件的特性劣化，從而可提供具有均勻特性的高性能的可撓性電子元件。進而，該基板與簡單的金屬基板不同，因具有絕緣層，故可形成將多個電子元件積體而成的電子元件。 It is considered that the flexible substrate 10A to the flexible substrate 10C have an aluminum material 101 having good heat conduction, so that the temperature rises as compared with the case where heat reaches the porous anodic oxide insulating film 102, and the temperature is diffused in the surface and the temperature is increased. Not easy to rise. The thermal conductivity of aluminum is 237 W/(m.K), and the stainless steel (Stainless Steel, SUS) 430 is 25 W/(m.K). On the other hand, the porous anodized film is further measured, and the result is 6 W/(m). .K) around. Therefore, in the case of a metal substrate with an insulating layer having aluminum and a porous anodized film, deterioration of characteristics of the element at the time of peeling can be prevented, and a high-performance flexible electronic element having uniform characteristics can be provided. Further, unlike the simple metal substrate, the substrate has an insulating layer, so that an electronic component in which a plurality of electronic components are integrated can be formed.
若使用SUS430般的熱傳導率稍差的不鏽鋼基板，則難以充分緩和由雷射光所致的局部的溫度上升，於基板中局部地出現高溫部位，該熱導致元件劣化。 When a stainless steel substrate having a slightly lower thermal conductivity than SUS430 is used, it is difficult to sufficiently alleviate a local temperature rise due to laser light, and a high-temperature portion locally appears in the substrate, which causes deterioration of the element.
鋁材由於熱傳導良好，故由雷射光所致的局部的溫度上升亦立即於面內熱擴散，不會出現局部的高溫部位。進而，藉由具有熱傳導差的絕緣膜，可於幾乎不存在對元件的熱損傷的情況下剝離。 Since the aluminum material has good heat conduction, the local temperature rise caused by the laser light is also immediately diffused in the in-plane heat, and local high temperature portions do not occur. Further, by the insulating film having poor heat conduction, peeling can be performed with little thermal damage to the element.
尤其多孔質膜與整體(bulk)膜相比可使熱傳導更差，故就防止對元件的熱損傷而言為良好的結構。 In particular, the porous film can make heat conduction worse than that of a bulk film, so that it is a good structure for preventing thermal damage to the element.
為了將局部加熱的熱設定為基板面內方向的熱流、且抑制向具有元件層的基板表面的熱流，較佳為鋁材的厚度為2μm以上且多孔質陽極氧化膜的膜厚為2μm以上。若於不鏽鋼基板般的 可撓性基板上形成幾微米(μm)的絕緣膜，則由應力導致絕緣膜剝離或產生裂縫，但由陽極氧化所形成的多孔質絕緣膜可形成並無此種膜剝離或裂縫的幾微米的絕緣膜，另外亦有如上述般可減小熱傳導率的效果。 In order to set the heat of local heating to the heat flow in the in-plane direction of the substrate and to suppress the heat flow to the surface of the substrate having the element layer, the thickness of the aluminum material is preferably 2 μm or more and the thickness of the porous anodized film is 2 μm or more. If it is like a stainless steel substrate When an insulating film of several micrometers (μm) is formed on a flexible substrate, the insulating film is peeled off or cracked due to stress, but the porous insulating film formed by anodization can form a few micrometers without such film peeling or cracking. The insulating film also has the effect of reducing the thermal conductivity as described above.
可知如此般於鋁材上形成有多孔質陽極氧化絕緣膜的可撓性基板滿足上述條件，為於雷射剝離時對元件的損傷非常少的構成，表明可製成高性能的可撓性電子元件。 It is understood that the flexible substrate in which the porous anodized insulating film is formed on the aluminum material satisfies the above conditions, and is a structure in which damage to the element is extremely small at the time of laser peeling, indicating that high-performance flexible electrons can be produced. element.
圖2A所示的積層體1A是於在鋁材101上具備多孔質陽極氧化絕緣膜102的可撓性基板10A與形成結構體2的面為相反側的面上，經由黏接劑11積層光透射性支撐體12而成，藉由自該積層體的光透射性支撐體12側照射雷射光L，黏接劑11的黏接力降低而可將光透射性支撐體12自可撓性基板10A上剝離。 The laminated body 1A shown in FIG. 2A is a surface on the opposite side of the surface on which the flexible substrate 10A including the porous anodized insulating film 102 is provided on the aluminum material 101 and the surface on which the structural body 2 is formed, and the light is laminated via the adhesive 11 The transmissive support 12 is formed by irradiating the laser light L from the side of the light-transmitting support 12 of the laminate, and the adhesive force of the adhesive 11 is lowered to allow the light-transmitting support 12 to be self-flexible from the flexible substrate 10A. Stripped on.
迄今為止，本申請人已對在鋁材的表面上具備多孔質陽極氧化絕緣膜的可撓性基板(多孔質陽極氧化基板)提出了日本專利4700130號公報等的若干申請。於日本專利4700130號公報中，作為於經由太陽電池的製造步驟後亦具有良好的絕緣特性與機械強度及可撓性的太陽電池用的帶有絕緣層的金屬基板，揭示了以下構成：具有包含鋼、鐵基合金鋼及Ti的任一種的金屬基材，設置於該金屬基材的至少一個面上的鋁材以及將該鋁材的表面陽極氧化而成的絕緣層，並且於金屬基材與鋁材的界面上具備金屬基材的成分與鋁的合金層。 A number of applications such as Japanese Patent No. 4700130 have been proposed for a flexible substrate (porous anodized substrate) having a porous anodized insulating film on the surface of an aluminum material. Japanese Patent No. 4,700,130 discloses a metal substrate with an insulating layer for a solar cell which has good insulating properties, mechanical strength and flexibility after a manufacturing step of a solar cell, and has the following configuration: a metal substrate of any one of steel, iron-based alloy steel and Ti, an aluminum material provided on at least one surface of the metal substrate, and an insulating layer formed by anodizing the surface of the aluminum material, and on the metal substrate The interface with the aluminum material has an alloy layer of a component of a metal substrate and aluminum.
然而，本申請人等以多孔質陽極氧化基板於量產性高的 捲對捲製程中的使用作為對象反覆進行了研究，對於迄今為止提出申請的多孔質陽極氧化基板，並未進行關於批次製程中的使用的研究。 However, the applicant and the like have a porous anodized substrate for high mass productivity. The use in the roll-to-roll process has been studied as an object. For the porous anodized substrate which has been applied for so far, no research has been conducted on the use in the batch process.
如上所述，本發明者發現：多孔質陽極氧化基板具有補償塑膠膜基板(可撓性且具有低熱傳導性，但缺乏耐熱性)、與金屬基板(可撓性且耐熱性高，但熱傳導性高而可能對上部功能層造成熱損傷)兩者的缺點的特性，即，兼具作為熱傳導率高的金屬的鋁材的良好的面內方向熱擴散性、與作為多孔質氧化物層的陽極氧化皮膜的高絕緣性。 As described above, the present inventors have found that a porous anodized substrate has a compensating plastic film substrate (flexible and low in thermal conductivity but lacking heat resistance), and a metal substrate (flexible and heat resistant, but thermally conductive) a characteristic that is high in thermal damage to the upper functional layer), that is, a good in-plane thermal diffusivity of an aluminum material having a metal having a high thermal conductivity, and an anode as a porous oxide layer High insulation of the oxide film.
進而，本發明者對電子元件的功能元件形成後的雷射剝離步驟時的應力的影響、黏接材的特性進行了努力研究，終於確立了一種電子元件的製造方法，該電子元件的製造方法可預防剝離時的元件的特性劣化，從而可製造具有均勻特性的高性能的可撓性電子元件。 Further, the inventors of the present invention have made an effort to study the influence of the stress at the time of the laser peeling step after the formation of the functional element of the electronic component and the characteristics of the adhesive material, and finally established a method of manufacturing an electronic component, and a method of manufacturing the electronic component. The deterioration of the characteristics of the element at the time of peeling can be prevented, so that a high-performance flexible electronic component having uniform characteristics can be manufactured.
圖2B所示的積層體1B除了成為於鋁材101的未形成多孔質陽極氧化絕緣膜102之側的面上具備碳鋼或鐵氧體系鋼材103的披覆(clad)材以外，與積層體1A相同，圖2C所示的積層體1C除了於鋁材101的兩個面上具備多孔質陽極氧化絕緣膜102以外，與積層體1A相同。多孔質陽極氧化絕緣膜102可形成於鋁材101的單面上，亦可形成於兩面上，於欲抑制電子元件的使用時的捲曲(curl)的情形時，較佳為形成於兩面上。 The laminated body 1B shown in FIG. 2B is a clad material including a carbon steel or a ferrite-based steel material 103 on a surface of the aluminum material 101 on the side where the porous anodized insulating film 102 is not formed, and a laminated body. In the same manner as 1A, the laminated body 1C shown in FIG. 2C is the same as the laminated body 1A except that the porous anodized insulating film 102 is provided on both surfaces of the aluminum material 101. The porous anodized insulating film 102 may be formed on one surface of the aluminum material 101 or may be formed on both surfaces. When it is desired to suppress curl during use of the electronic component, it is preferably formed on both surfaces.
於圖2A~圖2C的態樣中，亦可於形成結構體2的多孔 質陽極氧化絕緣膜102的正上方設置保護層，只要不損及耐熱性及絕緣性即可。若列舉一例，則可列舉二氧化矽玻璃或SiN等。 In the aspect of FIG. 2A to FIG. 2C, the porous structure 12 can also be formed. A protective layer is provided directly above the anodic oxide insulating film 102 as long as it does not impair heat resistance and insulation properties. Examples of the examples include cerium oxide glass, SiN, and the like.
於可撓性基板10(10A、10B、10C)中，鋁材101的厚度並無特別限制，若過薄則妨礙上述基板面內的熱傳導。因此，鋁材101的厚度較佳為2μm以上。 In the flexible substrate 10 (10A, 10B, 10C), the thickness of the aluminum material 101 is not particularly limited, and if it is too thin, heat conduction in the surface of the substrate is hindered. Therefore, the thickness of the aluminum material 101 is preferably 2 μm or more.
進而，於10A及10C的構成中，考慮到兼具基板的自支撐性與可撓性，鋁材101的厚度更佳為5μm~200μm。 Further, in the configuration of 10A and 10C, the thickness of the aluminum material 101 is preferably 5 μm to 200 μm in consideration of both the self-supporting property and the flexibility of the substrate.
另外，多孔質陽極氧化絕緣膜102的厚度亦無特別限制，只要考慮電子元件所要求的絕緣性能及可撓性來設計即可。通常於0.5μm~50μm的範圍內選擇，為了抑制向上述基板表面的熱流，較佳為2μm以上。 Further, the thickness of the porous anodized insulating film 102 is not particularly limited, and may be designed in consideration of insulation properties and flexibility required for an electronic component. It is usually selected in the range of 0.5 μm to 50 μm, and is preferably 2 μm or more in order to suppress heat flow to the surface of the substrate.
如圖3所示，將被陽極氧化鋁材101自表面101s側起電解氧化至中途為止，藉此可形成於鋁材101上具備多孔質陽極氧化絕緣膜102的可撓性基板10A，上述多孔質陽極氧化絕緣膜102包含多個有底的微細孔102b及氧化鋁(alumina)(Al2O3)層102a。 As shown in FIG. 3, the anodized aluminum material 101 is electrolytically oxidized from the surface 101s side to the middle, whereby the flexible substrate 10A having the porous anodized insulating film 102 on the aluminum material 101 can be formed. The anodic oxide insulating film 102 includes a plurality of bottomed micropores 102b and an alumina (Al 2 O 3 ) layer 102a.
電解氧化可藉由以下方式實施：將被陽極氧化金屬體101作為陽極，將碳或鋁等作為陰極(對向電極)，使該些電極浸漬於陽極氧化用電解液中，於陽極與陰極之間施加電壓。電解液並無限制，可較佳地使用含有硫酸、磷酸、鉻酸、草酸、胺磺酸(sulfamic acid)、苯磺酸、醯胺磺酸等酸中的一種或兩種以上的酸性電解液。藉由陽極氧化所生成的陽極氧化皮膜的結構是記載 於益田秀樹的「利用陽極氧化法的中孔徑氧化鋁的製備與作為功能材料的應用」、「材料技術」(Vol.15、No.10、1997年、p.34)等中。 Electrolytic oxidation can be carried out by using an anodized metal body 101 as an anode, carbon or aluminum or the like as a cathode (counter electrode), and immersing the electrodes in an anodizing electrolytic solution at the anode and the cathode. Voltage is applied between them. The electrolytic solution is not limited, and an acidic electrolyte containing one or more of an acid such as sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid or guanaminesulfonic acid can be preferably used. . The structure of the anodized film formed by anodization is described Yu Yoshida's "Preparation of a medium-aperture alumina using anodization and its application as a functional material" and "Material Technology" (Vol. 15, No. 10, 1997, p. 34).
通常，彼此鄰接的微細孔102b彼此的間距可控制於10nm~500nm的範圍內，另外，微細孔的孔徑可控制於5nm~400nm的範圍內。於日本專利特開2001-9800號公報或日本專利特開2001-138300號公報中，揭示有將微細孔的形成位置或孔徑控制得更細小的方法。藉由使用該些方法，可大致規則地排列形成於上述範圍內具有任意的孔徑及深度的微細孔102b。 Generally, the pitch of the micropores 102b adjacent to each other can be controlled within a range of 10 nm to 500 nm, and the pore diameter of the micropores can be controlled within a range of 5 nm to 400 nm. A method of controlling the formation position or the pore diameter of the fine pores to be finer is disclosed in Japanese Laid-Open Patent Publication No. 2001-9800 or Japanese Patent Laid-Open No. 2001-138300. By using these methods, the fine pores 102b having an arbitrary pore diameter and depth formed in the above range can be arranged substantially regularly.
另外，圖2B所示的可撓性基板10B為於鋁材101的未形成多孔質陽極氧化絕緣膜102之側的面上具備碳鋼或鐵氧體系鋼材103的披覆材，該鋼材可列舉日本專利特開2009-132996等中記載的包含碳鋼、鐵氧體系不鏽鋼的鋼材。該構成的可撓性基板10B為可撓性且高強度的帶有絕緣層的金屬基板。 In addition, the flexible substrate 10B shown in FIG. 2B is a coated material having a carbon steel or a ferrite-based steel material 103 on a surface of the aluminum material 101 on the side where the porous anodized insulating film 102 is not formed. A steel material containing carbon steel or ferrite stainless steel described in Japanese Laid-Open Patent Publication No. 2009-132996. The flexible substrate 10B having such a configuration is a flexible and high-strength metal substrate with an insulating layer.
於可撓性基板10B中，鋼材103的厚度並無特別限制，若過厚則損及基板的可撓性，若過薄則損及基板的強度。較佳為5μm~200μm，更佳為20μm~100μm。於該構成中，於鋁材與鋼材的界面上不可避免地存在凹凸。為了防止由該凹凸導致多孔質陽極氧化絕緣膜102直接與鋼材103接觸、及確保上述基板面內的熱傳導，鋁材101的厚度較佳為2μm以上。此處，所謂厚度，是指結構剖面中界面凹凸的中心線的間隔。再者，於該構成中，亦可為如可撓性基板10C般於鋼材103的兩側上具備鋁材101及 形成於其表面上的多孔質陽極氧化絕緣膜102的對稱結構。 In the flexible substrate 10B, the thickness of the steel material 103 is not particularly limited, and if it is too thick, the flexibility of the substrate is impaired, and if it is too thin, the strength of the substrate is impaired. It is preferably 5 μm to 200 μm, more preferably 20 μm to 100 μm. In this configuration, irregularities are inevitably present at the interface between the aluminum material and the steel material. The thickness of the aluminum material 101 is preferably 2 μm or more in order to prevent the porous anodic oxide insulating film 102 from directly contacting the steel material 103 and ensuring heat conduction in the surface of the substrate. Here, the thickness refers to the interval of the center line of the interface unevenness in the structural cross section. Further, in this configuration, the aluminum material 101 may be provided on both sides of the steel material 103 as in the case of the flexible substrate 10C. A symmetric structure of the porous anodized insulating film 102 formed on the surface thereof.
積層體1A~積層體1C是用於含有具有特定功能的元件的結構體2的批次式的製造製程中，故必須於結構體2的製造製程中具有耐久性。 Since the laminated body 1A to the laminated body 1C is a batch type manufacturing process for the structural body 2 containing an element having a specific function, it is necessary to have durability in the manufacturing process of the structural body 2.
具有特定功能的元件並無特別限制，可列舉「先前技術」的項中亦列舉的具備薄膜電晶體(TFT)的元件，例如太陽電池、有機EL顯示器、X射線平板檢測器(Flat Panel Detector，FPD)等光電轉換元件等。 The element having a specific function is not particularly limited, and examples thereof include a thin film transistor (TFT) element also listed in the "Prior Art" item, such as a solar cell, an organic EL display, and an X-ray flat panel detector (Flat Panel Detector, FPD) and other photoelectric conversion elements.
於TFT的情況下，製造時所必需的基板等的耐熱性較佳為350℃以上，更佳為400℃以上，進而佳為450℃以上。 In the case of the TFT, the heat resistance of the substrate or the like necessary for the production is preferably 350 ° C or higher, more preferably 400 ° C or higher, and still more preferably 450 ° C or higher.
黏接劑11只要具有結構體2的製造步驟中所要求的耐熱性，且藉由雷射光L的照射而黏接力降低從而可將可撓性基板10與光透射性支撐體12剝離，則並無特別限制，較佳為藉由儘可能溫和的條件的雷射光L的照射而可容易地剝離。所謂具有製造步驟中所要求的耐熱性，是指於製造步驟時的最高製程溫度下可維持使物體黏接的狀態，不使黏接劑分解而不產生脫氣成分。 The adhesive 11 can have the heat resistance required in the manufacturing process of the structural body 2, and the adhesive force can be lowered by the irradiation of the laser light L, whereby the flexible substrate 10 and the light-transmitting support 12 can be peeled off. It is not particularly limited, and it is preferably easily peeled off by irradiation of the laser light L under the conditions as gentle as possible. The heat resistance required in the production step means that the object can be adhered to the state at the highest process temperature in the manufacturing step, and the binder is not decomposed without generating a degassing component.
較佳的黏接劑可列舉：環氧樹脂、丙烯酸系樹脂、聚烯烴樹脂、聚胺基甲酸酯樹脂或矽酮樹脂，就耐熱性的觀點而言，較佳為矽酮樹脂。矽酮樹脂中，根據硬化機制而分為縮合反應型矽酮、加成反應型矽酮、紫外線硬化型矽酮及電子束硬化型矽酮，均可使用。就硬化反應的容易性及耐熱性高的方面而言，該些矽酮樹脂中較佳為加成反應型矽酮。 Preferred examples of the binder include an epoxy resin, an acrylic resin, a polyolefin resin, a polyurethane resin, or an anthrone resin. From the viewpoint of heat resistance, an anthrone resin is preferable. The anthrone resin can be classified into a condensation reaction type anthrone, an addition reaction type anthrone, an ultraviolet curing type anthrone, and an electron beam curing type anthrone depending on the curing mechanism. The fluorenone resin is preferably an addition reaction type fluorenone in terms of easiness of the hardening reaction and high heat resistance.
矽酮樹脂於形態方面有溶劑型、乳液(emulsion)型及無溶劑型，可使用任一類型。該些形態中，較佳為無溶劑型。其原因在於生產性、安全性、環境特性的方面優異。另外其原因在於：由於不含於形成樹脂層時的硬化時、即加熱硬化、紫外線硬化或電子束硬化時產生發泡的溶劑，故不易於樹脂層中殘留氣泡。 The anthrone resin has a solvent type, an emulsion type, and a solventless type in terms of form, and any type can be used. Among these forms, a solventless type is preferred. The reason is excellent in terms of productivity, safety, and environmental characteristics. The reason for this is that since the solvent which is foamed at the time of curing at the time of forming the resin layer, that is, heat curing, ultraviolet curing, or electron beam curing, is not contained, bubbles are not easily left in the resin layer.
可用作黏接劑的矽酮樹脂具體而言，以市售的商品名或型號可列舉：KNS-320A、KS-847(均為信越矽酮公司製造)、TPR6700(GE東芝矽酮公司製造)、乙烯基矽酮「8500」(荒川化學工業股份有限公司製造)與甲基氫化聚矽氧烷「12031」(荒川化學工業股份有限公司製造)的組合、乙烯基矽酮「11364」(荒川化學工業股份有限公司製造)與甲基氫化聚矽氧烷「12031」(荒川化學工業股份有限公司製造)的組合、乙烯基矽酮「11365」(荒川化學工業股份有限公司製造)與甲基氫化聚矽氧烷「12031」(荒川化學工業股份有限公司製造)的組合等。再者，KNS-320A、KS-847及TPR6700為預先含有主劑及交聯劑的矽酮。 The fluorenone resin which can be used as an adhesive is specifically a commercially available product name or model: KNS-320A, KS-847 (all manufactured by Shin-Etsu Chemical Co., Ltd.), TPR6700 (made by GE Toshiba Ketone Co., Ltd.) ), a combination of vinyl ketone "8500" (manufactured by Arakawa Chemical Industries Co., Ltd.) and methyl hydrogenated polyoxane "12031" (manufactured by Arakawa Chemical Industries Co., Ltd.), and vinyl ketone "11364" (Arakawa) Chemical Industry Co., Ltd.), a combination of methyl hydrogenated polyoxane "12031" (manufactured by Arakawa Chemical Industries Co., Ltd.), vinyl fluorenone "11365" (manufactured by Arakawa Chemical Industries Co., Ltd.) and methyl hydrogenation A combination of polyoxane "12031" (manufactured by Arakawa Chemical Industries Co., Ltd.). Further, KNS-320A, KS-847, and TPR6700 are an anthrone including a main component and a crosslinking agent in advance.
尤佳可列舉：日本專利特開2012-86527等中記載的於超過450℃的製造製程中具有耐熱性、且可容易地於短時間內剝離的有機聚矽氧烷系黏接劑等。 In particular, an organic polyoxyalkylene-based adhesive which has heat resistance in a manufacturing process exceeding 450 ° C and which can be easily peeled off in a short time, as described in JP-A-2012-86527, etc., is mentioned.
黏接材11的施用方法並無特別限制，旋塗、棒塗等塗佈方法等簡易而較佳。黏接材11的塗佈量只要根據黏接材11的物性以剝離特性變良好的方式適當設計即可。 The method of applying the adhesive member 11 is not particularly limited, and a coating method such as spin coating or bar coating is simple and preferable. The coating amount of the adhesive material 11 may be appropriately designed so that the peeling property becomes good according to the physical properties of the adhesive material 11.
黏接材11只要施用至光透射性支撐體12的表面的貼附 可撓性基板10的貼附區域中即可，以將可撓性基板10於含有特定的功能性元件的結構體2的製造步驟中牢固地固定於光透射性支撐體12上的方式施用黏接材11。 The adhesive material 11 is attached to the surface of the light-transmitting support 12 as long as it is attached In the attachment region of the flexible substrate 10, the flexible substrate 10 may be firmly adhered to the light-transmitting support 12 in the manufacturing step of the structural body 2 including the specific functional element. Bonding material 11.
於本實施形態中，關於貼附區域並未圖示，以於光透射性支撐體12的整個表面上均一地施用黏接材11的態樣來表示，但只要於結構體2的製造步驟中牢固地固定，則貼附量區域與黏接材施用區域的大小亦可不同。 In the present embodiment, the attachment region is not shown, and is expressed by uniformly applying the adhesive member 11 over the entire surface of the light-transmitting support 12, but it is only required in the manufacturing step of the structural body 2. If it is firmly fixed, the size of the attachment area and the application area of the adhesive material may be different.
所謂光透射性支撐體，如上所述，表示對雷射光的透射率為10%以上的支撐體。較佳的透射率為60%以上，更佳為80%以上。 As described above, the light-transmitting support means a support having a transmittance of laser light of 10% or more. A preferred transmittance is 60% or more, and more preferably 80% or more.
光透射性支撐體12只要具有結構體2的製造步驟中的耐熱性，則並無特別限制，於結構體2的製造步驟及步驟後的雷射剝離時，若光透射性支撐體12與可撓性基板10的線膨脹係數差大，則基板有時整體產生皺褶，或多孔質陽極氧化絕緣膜102中產生裂縫。因此，可撓性基板10與光透射性支撐體12的線膨脹係數較佳為儘可能接近，該些的線膨脹係數(CTE：Coefficient of Temperature Expansion)之差較佳為4ppm/K以內，更佳為2ppm/K以內。 The light-transmitting support 12 is not particularly limited as long as it has heat resistance in the manufacturing process of the structure 2, and the light-transmitting support 12 and the light-transmissive support 12 can be used in the manufacturing process of the structure 2 and the laser peeling after the step. When the linear expansion coefficient difference of the flexible substrate 10 is large, wrinkles may occur in the entire substrate, or cracks may occur in the porous anodic oxide insulating film 102. Therefore, the linear expansion coefficient of the flexible substrate 10 and the light-transmitting support 12 is preferably as close as possible, and the difference in coefficient of temperature expansion (CTE) is preferably within 4 ppm/K. Good is less than 2ppm/K.
關於可撓性基板10的線膨脹係數，如上所述，將試樣(可撓性基板10)放置於溫度可變的熱板上，於無負荷的狀態下測定各溫度下的試樣表面的測試點間距離，將自室溫起至500℃為止的測試點間距離變化率作為線膨脹係數(CTE)。 Regarding the linear expansion coefficient of the flexible substrate 10, as described above, the sample (the flexible substrate 10) is placed on a hot plate having a variable temperature, and the surface of the sample at each temperature is measured under no load. The distance between test points is a linear expansion coefficient (CTE) as a rate of change between test points from room temperature to 500 °C.
圖4為表示利用上述方法對可撓性基板10C(圖中的類型A)及可撓性基板10B(圖中的類型B)測定的熱膨脹特性的圖，上述可撓性基板10C於鋁材101的兩面上具備陽極氧化絕緣膜102，上述可撓性基板10B於鐵氧體系不鏽鋼鋼材103與鋁材101的披覆材上具備陽極氧化絕緣膜102。圖4的圖表的傾斜率相當於線膨脹係數(CTE)。 4 is a view showing thermal expansion characteristics of the flexible substrate 10C (type A in the drawing) and the flexible substrate 10B (type B in the drawing) by the above method, and the flexible substrate 10C is in the aluminum material 101. An anodized insulating film 102 is provided on both surfaces, and the flexible substrate 10B is provided with an anodized insulating film 102 on a coating material of the ferrite-based stainless steel material 103 and the aluminum material 101. The slope rate of the graph of Fig. 4 corresponds to a coefficient of linear expansion (CTE).
用於測定的可撓性基板10C及可撓性基板10B的層構成分別為陽極氧化絕緣膜/Al/陽極氧化絕緣膜=10μm/20μm/10μm，鐵氧體系不鏽鋼SUS430(18%鉻(Cr)鋼)/Al/陽極氧化絕緣膜=50μm/20μm/10μm。 The layer configuration of the flexible substrate 10C and the flexible substrate 10B for measurement is an anodized insulating film/Al/anodized insulating film=10 μm/20 μm/10 μm, respectively, and a ferrite system stainless steel SUS430 (18% chromium (Cr)). Steel) / Al / anodized insulating film = 50 μm / 20 μm / 10 μm.
可撓性基板10C及可撓性基板10B的CTE分別為約5ppm/K及10ppm/K。再者，該數值為多孔質陽極氧化絕緣膜102與鋁材101、及多孔質陽極氧化絕緣膜102與鋁材101與鐵氧體系鋼材103的材料組合的結果，本發明者確認到，於上述較佳剖面構成(厚度等)的範圍內幾乎未變化。這是指確認到，亦於僅於單面上具備多孔質陽極氧化絕緣膜102的可撓性基板10A的態樣中，另外亦於可撓性基板10B中設定為對稱結構即多孔質陽極氧化絕緣膜102、鋁材101、鐵氧體系鋼材103、鋁材101及多孔質陽極氧化絕緣膜102的帶有絕緣層的金屬基板中，CTE分別為約5ppm/K及10ppm/K左右。 The CTE of the flexible substrate 10C and the flexible substrate 10B are about 5 ppm/K and 10 ppm/K, respectively. In addition, the numerical value is a combination of the porous anodized insulating film 102, the aluminum material 101, and the porous anodized insulating film 102 and the material of the aluminum material 101 and the ferrite system steel material 103, and the inventors confirmed that There is almost no change in the range of the preferred cross-sectional configuration (thickness, etc.). In this case, it is also confirmed that the flexible substrate 10A having the porous anodized insulating film 102 on one surface is also provided with a symmetric structure, that is, a porous anodization in the flexible substrate 10B. In the insulating substrate 102, the aluminum material 101, the ferrite system steel material 103, the aluminum material 101, and the porous anodized insulating film 102, the insulating substrate has a CTE of about 5 ppm/K and about 10 ppm/K, respectively.
因此，於可撓性基板10A及可撓性基板10C的構成、即於鋁材101的單面或兩面上具備多孔質陽極氧化絕緣膜102的可 撓性基板10的情況下，光透射性支撐體12較佳為CTE為3ppm/K~9ppm/K者，該支撐體中，透明性優異的基材可較佳地例示硼矽酸玻璃及無鹼玻璃。 Therefore, in the configuration of the flexible substrate 10A and the flexible substrate 10C, that is, the porous anodized insulating film 102 may be provided on one surface or both surfaces of the aluminum material 101. In the case of the flexible substrate 10, the light-transmitting support 12 preferably has a CTE of 3 ppm/K to 9 ppm/K. Among the supports, a substrate excellent in transparency can preferably be exemplified by borosilicate glass and Alkali glass.
另外，於可撓性基板10B的構成、即於鐵氧體系不鏽鋼鋼材103與鋁材101的披覆材上具備多孔質陽極氧化絕緣膜102的可撓性基板10、以及於可撓性基板10B中設定為對稱結構即多孔質陽極氧化絕緣膜102、鋁材101、鐵氧體系鋼材103、鋁101材及多孔質陽極氧化絕緣膜102的帶有絕緣層的金屬基板的情形時，光透射性支撐體12較佳為CTE為6ppm/K~13ppm/K者，該支撐體中，透明性優異的基材可較佳地例示白板鉀玻璃及鈉鈣玻璃。 In the flexible substrate 10B, the flexible substrate 10 including the porous anodized insulating film 102 on the ferrite-based stainless steel material 103 and the aluminum material 101, and the flexible substrate 10B. In the case of a metal substrate with an insulating layer which is a symmetrical structure, that is, a porous anodized insulating film 102, an aluminum material 101, a ferrite system steel material 103, an aluminum 101 material, and a porous anodized insulating film 102, light transmittance The support 12 preferably has a CTE of 6 ppm/K to 13 ppm/K. Among the supports, a substrate having excellent transparency can be preferably exemplified by white potassium glass and soda lime glass.
光透射性支撐體12的厚度可選擇可用於製造裝置的任意厚度，若過薄則操作變困難而不發揮支撐體的功能，另外可能元件形成後的結構體整體發生翹曲。通常的厚度為0.3mm~1.2mm。 The thickness of the light-transmitting support 12 can be selected to be any thickness that can be used to manufacture the device. If it is too thin, the operation becomes difficult without exerting the function of the support, and the entire structure after the element formation may be warped. The usual thickness is from 0.3 mm to 1.2 mm.
如以上所述，本發明的電子元件的製造方法中，藉由以下方式來製造電子元件3(於在鋁材101上具備多孔質陽極氧化絕緣膜102的可撓性基板10(10A、10B、10C)上形成具有特定功能的元件(結構體2)而成的電子元件3)：經由於元件形成步驟中具有耐熱性的黏接劑11將於鋁材101上具備多孔質陽極氧化絕緣膜102的可撓性基板10與光透射性支撐體12貼附而製成積層體1(1A、1B、1C)後，於多孔質陽極氧化絕緣膜102上形成元 件(結構體2)，形成元件後，自光透射性支撐體12的背面側照射光L，藉此使黏接劑11的黏接力降低而將光透射性支撐體12自可撓性基板10上剝離。根據該製造方法及積層體1，可於利用批次製程的元件形成時，維持良好的操作性，實施元件形性而不於製程中產生可撓性基板10的翹曲、及由在可撓性基板10上製膜的材料所引起的變形，且於形成元件後，實施非可撓性支撐體的剝離而不產生元件的劣化、特性均勻性的劣化。因此，根據本發明，可於可撓性金屬基板上以批次方式來製造高性能的可撓性電子元件。 As described above, in the method of manufacturing an electronic component of the present invention, the electronic component 3 (the flexible substrate 10 (10A, 10B, including the porous anodized insulating film 102) on the aluminum material 101 is manufactured by the following method. 10C) An electronic component 3) in which an element (structure 2) having a specific function is formed: The porous anodic oxide insulating film 102 is provided on the aluminum material 101 via the adhesive 11 having heat resistance in the element forming step. After the flexible substrate 10 and the light-transmitting support 12 are attached to each other to form the laminated body 1 (1A, 1B, 1C), the porous anodic oxide insulating film 102 is formed on the porous anodic oxide insulating film 102. After the component (structure 2) is formed, the light L is irradiated from the back side of the light-transmitting support 12, whereby the adhesive force of the adhesive 11 is lowered to bring the light-transmitting support 12 from the flexible substrate 10. Stripped on. According to the manufacturing method and the laminated body 1, it is possible to maintain good workability when forming a component by a batch process, and to perform element shape without causing warpage of the flexible substrate 10 during the process, and being flexible The deformation caused by the material formed on the substrate 10 and after the formation of the element, the peeling of the non-flexible support is performed without deterioration of the element and deterioration of the uniformity of the characteristics. Therefore, according to the present invention, a high-performance flexible electronic component can be manufactured in a batch manner on a flexible metal substrate.
上述本發明的電子元件的製造方法及積層體可較佳地用於以下所示的光電轉換元件(薄膜化合物系太陽電池)(電子元件3)或有機EL顯示器、X射線檢測器及有機薄膜太陽電池的製造等。 The method for producing an electronic component of the present invention and the laminate can be preferably used for a photoelectric conversion element (thin film compound solar cell) (electronic component 3) or an organic EL display, an X-ray detector, and an organic thin film solar cell shown below. Battery manufacturing, etc.
對於任一電子元件而言，首先準備經由黏接劑11將可撓性基板10與光透射性基材12貼合而成的積層體1，於積層體1的可撓性基板10上(多孔質陽極氧化絕緣膜102上)形成電子元件。 For any of the electronic components, first, a laminate 1 in which the flexible substrate 10 and the light-transmitting substrate 12 are bonded via the adhesive 11 is prepared on the flexible substrate 10 of the laminate 1 (porous The anodic oxide insulating film 102 is formed with an electronic component.
<光電轉換元件> <Photoelectric Conversion Element>
圖5為藉由上述本發明電子元件的製造方法及積層體所製造的薄膜化合物系光電轉換元件3A的示意剖面圖。光電轉換元件3A為將以下積層結構設定為基本構成的元件，即，於可撓性基板10上依序積層有下部電極(背面電極)20、光電轉換半導體層30、 緩衝層40及上部電極50的積層結構。 Fig. 5 is a schematic cross-sectional view showing a thin film compound-based photoelectric conversion element 3A produced by the method for producing an electronic component of the present invention and a laminate. The photoelectric conversion element 3A is an element having a basic laminated structure in which a lower electrode (back surface electrode) 20, a photoelectric conversion semiconductor layer 30, and a lower layer are sequentially laminated on the flexible substrate 10. The laminated structure of the buffer layer 40 and the upper electrode 50.
於光電轉換元件3A中，形成有僅貫穿下部電極20的第1開槽部61、貫穿光電轉換層30及緩衝層40的第2開槽部62、以及貫穿光電轉換層30及緩衝層40及上部電極50的第3開槽部63。於上述構成中，藉由第1開槽部~第3開槽部而獲得將元件分離成多個單元C的結構。另外，藉由在第2開槽部62內填充上部電極50，而獲得將某個單元C的上部電極50串列連接於鄰接的單元C的下部電極20的結構。 In the photoelectric conversion element 3A, the first groove portion 61 that penetrates only the lower electrode 20, the second groove portion 62 that penetrates the photoelectric conversion layer 30 and the buffer layer 40, and the through-the photoelectric conversion layer 30 and the buffer layer 40 are formed. The third groove portion 63 of the upper electrode 50. In the above configuration, the first grooved portion to the third grooved portion are configured to separate the element into a plurality of cells C. Further, by filling the upper electrode 50 in the second groove portion 62, a structure is obtained in which the upper electrode 50 of a certain cell C is connected in series to the lower electrode 20 of the adjacent cell C.
於光電轉換元件3A中，亦可於下部電極20的正下方(可撓性基板10與下部電極20之間)具備鹼(土)金屬供給層或防擴散層等，上述鹼(土)金屬供給層於光電轉換層的成膜時對該層供給鹼金屬及/或鹼土金屬，上述防擴散層抑制上述鹼金屬等自上述金屬供給層向可撓性基板10側的擴散。 In the photoelectric conversion element 3A, an alkali (earth) metal supply layer or a diffusion prevention layer or the like may be provided directly under the lower electrode 20 (between the flexible substrate 10 and the lower electrode 20), and the alkali (earth) metal supply may be provided. The layer is supplied with an alkali metal and/or an alkaline earth metal at the time of film formation of the photoelectric conversion layer, and the diffusion prevention layer suppresses diffusion of the alkali metal or the like from the metal supply layer toward the flexible substrate 10 side.
首先，準備經由黏接劑11將可撓性基板10與光透射性基材12貼合而成的積層體1，於積層體1的可撓性基板10上(多孔質陽極氧化絕緣膜102上)，藉由濺鍍法等來形成例如450nm厚的包含鉬(Mo)等過渡金屬的下部電極層20。 First, a laminate 1 in which the flexible substrate 10 and the light-transmitting substrate 12 are bonded via the adhesive 11 is prepared on the flexible substrate 10 of the laminate 1 (porous anodized insulating film 102). A lower electrode layer 20 containing a transition metal such as molybdenum (Mo), for example, 450 nm thick is formed by a sputtering method or the like.
繼而，藉由雷射切割(laser scribe)將導電層20的一部分去除而形成分離槽61，於其上藉由蒸鍍法等來形成化合物半導體系光電轉換層30。 Then, a part of the conductive layer 20 is removed by laser scribe to form the separation groove 61, and the compound semiconductor-based photoelectric conversion layer 30 is formed thereon by a vapor deposition method or the like.
光電轉換層30可較佳地使用藉由CdTe等II-VI族半導體、或CuInGaSe2所代表的I-III-VI族半導體所構成者。I-III-VI 族半導體可列舉：CuAlS2、CuGaS2、CuInS2、CuAlSe2、CuGaSe2、AgAlS2、AgGaS2、AgInS2、AgAlSe2、AgGaSe2、AgInSe2、AgAlTe2、AgGaTe2、AgInTe2、Cu(In,Al)Se2、Cu(In,Ga)(S,Se)2、Cu1-zIn1-xGaxSe2-ySy(式中，0≦x≦1、0≦y≦2、0≦z≦1)(CI(G)S)、Ag(In,Ga)Se2及Ag(In,Ga)(S,Se)2等。 The photoelectric conversion layer 30 can preferably be composed of a Group II-VI semiconductor such as CdTe or an I-III-VI semiconductor represented by CuInGaSe 2 . Examples of the I-III-VI group semiconductor include CuAlS 2 , CuGaS 2 , CuInS 2 , CuAlSe 2 , CuGaSe 2 , AgAlS 2 , AgGaS 2 , AgInS 2 , AgAlSe 2 , AgGaSe 2 , AgInSe 2 , AgAlTe 2 , AgGaTe 2 , AgInTe 2 , Cu(In,Al)Se 2 , Cu(In,Ga)(S,Se) 2 , Cu 1-z In 1-x Ga x Se 2-y S y (wherein, 0≦x≦1 0≦y≦2, 0≦z≦1) (CI(G)S), Ag(In,Ga)Se 2 and Ag(In,Ga)(S,Se) 2 and the like.
該化合物半導體系光電轉換層的形成時，尤佳為多源同時蒸鍍法。其代表性的方法可列舉三階段法(J.R.圖塔爾等人(J.R.Tuttle et.al)，「材料研究學會論文集(Mat.Res.Soc.Symp.Proc.)」，Vol.426(1996)p.143.等)，例如於CuInGaSe2的情況下，於高真空中最初於基板溫度400℃下同時蒸鍍In、Ga、Se，繼而升溫至500℃~560℃而同時蒸鍍Cu、Se後，進一步同時蒸鍍In、Ga、Se。例如，將三階段法中的第二階段、第三階段的基板溫度設定為550℃，使用努特生池(knudsen-Cell，K cell)作為蒸發源將Cu(In0.7Ga0.3)Se2成膜2μm。 In the formation of the compound semiconductor-based photoelectric conversion layer, a multi-source simultaneous vapor deposition method is particularly preferable. A representative method can be cited as a three-stage method (JR Tuttle et al., "Mat. Res. Soc. Symp. Proc.", Vol. 426 (1996). In the case of CuInGaSe 2 , for example, In, Ga, and Se are simultaneously vapor-deposited at a substrate temperature of 400° C. in a high vacuum, and then heated to 500° C. to 560° C. while vapor-depositing Cu and Se. Thereafter, In, Ga, and Se are further vapor-deposited at the same time. For example, the substrate temperature of the second stage and the third stage in the three-stage method is set to 550 ° C, and Cu(In 0.7 Ga 0.3 )Se 2 is formed using a knudsen-Cell (K cell) as an evaporation source. The membrane was 2 μm.
形成光電轉換層30後，於光電轉換層30上形成緩衝層40。例如藉由化學浴沈積(Chemical Bath Deposition，CBD)法等以例如50nm的厚度形成CdS作為緩衝層40，將自緩衝層40表面的既定位置起至光電轉換層30為止的層去除，藉由機械切割(Mechanical scribe)等來圖案化而形成分離槽62。 After the photoelectric conversion layer 30 is formed, the buffer layer 40 is formed on the photoelectric conversion layer 30. For example, CdS is formed as a buffer layer 40 by a chemical bath deposition (CBD) method or the like, for example, at a thickness of 50 nm, and a layer from a predetermined position on the surface of the buffer layer 40 to the photoelectric conversion layer 30 is removed by mechanical means. A separation groove 62 is formed by patterning by mechanical scribe or the like.
繼而，自分離槽62及緩衝層40的上表面，例如藉由濺鍍法以300nm的厚度形成Al-ZnO層作為透明電極50，進而，藉由機械切割等來圖案化而形成分割單元的分離槽63，獲得形成於 積層體1的可撓性基板10上的光電轉換元件結構體2。 Then, from the upper surface of the separation trench 62 and the buffer layer 40, an Al-ZnO layer is formed as a transparent electrode 50 by a sputtering method at a thickness of 300 nm, and further, separation of the division unit is performed by patterning by mechanical cutting or the like. Slot 63, obtained in formation The photoelectric conversion element structure 2 on the flexible substrate 10 of the laminated body 1.
最後，自積層體1的背面側照射雷射光L，使黏接材11的黏接力降低而將光透射性基材12自積層體1上剝離，獲得於可撓性基板10上形成光電轉換元件結構體2而成的光電轉換元件3A。 Finally, the laser beam L is irradiated from the back side of the laminated body 1 to reduce the adhesive force of the adhesive member 11, and the light-transmitting substrate 12 is peeled off from the laminated body 1 to form a photoelectric conversion element on the flexible substrate 10. The photoelectric conversion element 3A made of the structure 2.
<有機EL顯示器> <Organic EL display>
圖6為示意性地表示藉由上述本發明電子元件的製造方法及積層體所製造的有機EL顯示器3B的構成要部的剖面圖。 FIG. 6 is a cross-sectional view schematically showing a configuration of an organic EL display 3B manufactured by the method for producing an electronic component of the present invention and the laminated body.
如圖6所示，有機EL顯示器3B具有以下構成：於可撓性基板10上積層有TFT 80及位於TFT 80上的有機EL元件98作為含有具有特定功能的元件的結構體2的構成。 As shown in FIG. 6, the organic EL display 3B has a configuration in which a TFT 80 and an organic EL element 98 located on the TFT 80 are laminated on the flexible substrate 10 as a structure 2 including an element having a specific function.
於有機EL顯示器3B的製造中，亦首先準備經由黏接劑11將可撓性基板10與光透射性基材12貼合而成的積層體1，於積層體1上形成TFT 80，於TFT 80上形成有機EL元件98。 In the production of the organic EL display 3B, first, the laminate 1 in which the flexible substrate 10 and the light-transmitting substrate 12 are bonded via the adhesive 11 is prepared, and the TFT 80 is formed on the laminate 1 in the TFT. An organic EL element 98 is formed on 80.
於本實施形態中，於積層體1的多孔質陽極氧化絕緣膜102上藉由電漿CVD將緩衝層(Si3N4)71成膜，進而於緩衝層(Si3N4)71上以200nm的厚度於整個面上藉由電漿CVD來形成SiO2層(絕緣膜)72。關於成膜溫度，均於350℃下進行成膜。 In the present embodiment, the buffer layer (Si 3 N 4 ) 71 is formed on the porous anodized insulating film 102 of the laminated body 1 by plasma CVD, and further on the buffer layer (Si 3 N 4 ) 71. A thickness of 200 nm is formed on the entire surface by plasma CVD to form an SiO 2 layer (insulating film) 72. Film formation was carried out at 350 ° C for the film formation temperature.
形成SiO2層72後，對各畫素形成薄膜電晶體80(以下稱為TFT 80)。此處，同時形成電容器(capacitor)90。 After the SiO 2 layer 72 is formed, a thin film transistor 80 (hereinafter referred to as TFT 80) is formed for each pixel. Here, a capacitor 90 is simultaneously formed.
例如，藉由濺鍍法以50nm的厚度形成鉬(Mo)膜後，藉由光微影法及蝕刻法進行圖案化，藉此形成TFT 80的閘極電極 81及電容器90的下部電極91。 For example, a molybdenum (Mo) film is formed by a sputtering method at a thickness of 50 nm, and then patterned by photolithography and etching to form a gate electrode of the TFT 80. 81 and the lower electrode 91 of the capacitor 90.
再者，閘極電極81及下部電極91的材質不限定於Mo，可使用其他公知的導電性材料。例如可列舉：Al、Cr、Ta、Ti、Au、Ag等金屬，Al-Nd、APC等合金，氧化錫、氧化鋅、氧化銦、氧化銦錫(ITO)、氧化銦鋅(IZO)等金屬氧化物導電膜，聚苯胺、聚噻吩、聚吡咯等有機導電性化合物，或該些物質的混合物。 Further, the material of the gate electrode 81 and the lower electrode 91 is not limited to Mo, and other known conductive materials can be used. Examples thereof include metals such as Al, Cr, Ta, Ti, Au, and Ag, alloys such as Al-Nd and APC, and metals such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). An oxide conductive film, an organic conductive compound such as polyaniline, polythiophene, or polypyrrole, or a mixture of the same.
另外，成膜方法或圖案化方法亦只要根據所使用的材料等來適當選擇即可，成膜方法除了濺鍍法以外，例如可列舉：真空蒸鍍法、離子電鍍(ion plating)法等物理方式，CVD、電漿CVD法等化學方式，印刷方式、塗佈方式等濕式方式。 In addition, the film formation method or the patterning method may be appropriately selected depending on the material to be used and the like. The film formation method may be, for example, a vacuum deposition method or an ion plating method, in addition to the sputtering method. The method is a chemical method such as CVD or plasma CVD, or a wet method such as a printing method or a coating method.
另外，關於圖案化方法，可藉由剝離(lift-off)法來進行圖案化，亦可使用具有與欲形成的閘極電極的圖案相對應的開口部的金屬罩幕(蔽蔭罩幕(shadow mask))。 Further, regarding the patterning method, patterning may be performed by a lift-off method, or a metal mask (shading mask) having an opening corresponding to the pattern of the gate electrode to be formed may be used ( Shadow mask)).
形成閘極電極81及下部電極91後，形成SiO2層(厚度：200nm)作為絕緣層82。絕緣層82於TFT80中作為閘極絕緣層而發揮功能，於電容器90中作為填埋電極間的介電質而發揮功能。 After the gate electrode 81 and the lower electrode 91 are formed, an SiO 2 layer (thickness: 200 nm) is formed as the insulating layer 82. The insulating layer 82 functions as a gate insulating layer in the TFT 80, and functions as a dielectric between the buried electrodes in the capacitor 90.
關於SiO2的成膜，利用電漿CVD於成膜溫度350℃下進行成膜。 The film formation of SiO 2 was carried out by plasma CVD at a film formation temperature of 350 °C.
形成InGaZnO4層(厚度：50nm)作為活性層(通道)83。活性層亦是與閘極電極的形成同樣地分別藉由濺鍍法等來進行成膜，並根據形狀來進行圖案化。 An InGaZnO 4 layer (thickness: 50 nm) was formed as an active layer (channel) 83. Similarly to the formation of the gate electrode, the active layer is formed by sputtering or the like, and patterned according to the shape.
再者，各層的材料只要適當選擇即可。例如，閘極絕緣 層82可為包含SiNx、SiON、Al2O3、Y2O3、Ta2O5、HfO2等絕緣體的一層結構，或將該些絕緣體化合物的兩種以上積層而成的積層結構。另外，亦可使用聚醯亞胺般的高分子絕緣體。 Furthermore, the materials of the respective layers may be appropriately selected. For example, the gate insulating layer 82 may be a one-layer structure including an insulator such as SiN x , SiON, Al 2 O 3 , Y 2 O 3 , Ta 2 O 5 , HfO 2 , or two or more layers of the insulator compounds. a layered structure. Further, a polymer insulator such as polyimide may be used.
就遷移率及特性均勻性的觀點而言，活性層83較佳為非晶質氧化物半導體，具體可列舉：含有In、Ga及Zn的至少一種的氧化物，例如含In的氧化物、含有In及Zn的氧化物以及含有In、Ga及Zn的氧化物等，組成結構較佳為InGaO3(ZnO)m(m為小於6的自然數)。該些結構是載子為電子的n型半導體。再者，亦可將ZnO．Rh2O3、CuGaO2、SrCu2O2般的p型氧化物半導體用於活性層，亦可使用日本專利特開2006-165529號公報中揭示的氧化物半導體。 The active layer 83 is preferably an amorphous oxide semiconductor from the viewpoint of mobility and uniformity of properties, and specific examples thereof include an oxide containing at least one of In, Ga, and Zn, for example, an oxide containing In, and containing The oxide of In and Zn and the oxide containing In, Ga, and Zn are preferably InGaO 3 (ZnO) m (m is a natural number less than 6). These structures are n-type semiconductors whose carriers are electrons. Furthermore, ZnO can also be used. A p-type oxide semiconductor such as Rh 2 O 3 , CuGaO 2 or SrCu 2 O 2 is used for the active layer, and an oxide semiconductor disclosed in Japanese Laid-Open Patent Publication No. 2006-165529 can also be used.
其他活性層亦可使用液晶顯示器中用於TFT中的非晶矽、多晶矽。非晶矽是藉由電漿CVD於成膜溫度350℃下成膜。多晶矽可藉由使用準分子雷射對非晶矽進行雷射退火(laser anneal)而獲得。 Other active layers may also be used for amorphous germanium or polycrystalline germanium in TFTs in liquid crystal displays. Amorphous germanium is formed by plasma CVD at a film formation temperature of 350 °C. Polycrystalline germanium can be obtained by laser annealing an amorphous germanium using a pseudomolecular laser.
其後，例如藉由光微影法及蝕刻法等將活性層圖案化，藉由濺鍍法將成為源極/汲極電極84、源極/汲極電極85及電容器90的上部電極93的AlNd(厚度：100nm)成膜，形成源極/汲極電極84、源極/汲極電極85及上部電極93的圖案。再者，源極/汲極電極84、源極/汲極電極85及上部電極93的形成亦可適當採用閘極電極81的形成中例示的材料、成膜方法、圖案化方法等。 Thereafter, the active layer is patterned by, for example, photolithography and etching, and the source/drain electrode 84, the source/drain electrode 85, and the upper electrode 93 of the capacitor 90 are formed by sputtering. AlNd (thickness: 100 nm) was formed into a film, and a pattern of the source/drain electrode 84, the source/drain electrode 85, and the upper electrode 93 was formed. Further, the source/drain electrode 84, the source/drain electrode 85, and the upper electrode 93 may be formed by a material exemplified in the formation of the gate electrode 81, a film formation method, a patterning method, or the like.
藉由以上步驟，形成底部閘極型且相較於源極/汲極電極 84、源極/汲極電極85而先形成活性層83的頂部接觸型的TFT 80。再者，TFT 80的結構不限定於上述結構，只要適當選擇即可。例如，亦可為於源極/汲極電極之後形成活性層的底部接觸型的TFT，亦可為相較於閘極電極而先形成源極/汲極電極的頂部閘極型的TFT。 By the above steps, the bottom gate type is formed and compared to the source/drain electrodes 84. The source/drain electrode 85 forms the top contact type TFT 80 of the active layer 83 first. Further, the configuration of the TFT 80 is not limited to the above configuration, and may be appropriately selected. For example, it may be a bottom contact type TFT in which an active layer is formed after a source/drain electrode, or a top gate type TFT in which a source/drain electrode is formed in comparison with a gate electrode.
形成源極/汲極電極84、源極/汲極電極85後，於TFT 80、電容器90上形成層間絕緣平坦化層88而將積層面平坦化。例如，使用丙烯酸系樹脂藉由旋轉塗佈來形成樹脂層(厚度：1.5μm)。另外，作為層間絕緣平坦化層，亦可自可撓性基板側如無機絕緣層/平坦化樹脂層般設定為兩層構成。作為無機絕緣層可利用SiO2、Si3N4、SiON等無機絕緣膜，平坦化樹脂層中可利用上述丙烯酸系樹脂等。 After the source/drain electrodes 84 and the source/drain electrodes 85 are formed, an interlayer insulating planarization layer 88 is formed on the TFTs 80 and the capacitors 90 to planarize the layers. For example, a resin layer (thickness: 1.5 μm) is formed by spin coating using an acrylic resin. Further, the interlayer insulating planarization layer may be formed in a two-layer structure from the side of the flexible substrate such as the inorganic insulating layer/flattening resin layer. As the inorganic insulating layer, an inorganic insulating film such as SiO 2 , Si 3 N 4 or SiON can be used, and the above-mentioned acrylic resin or the like can be used for the planarizing resin layer.
繼而，於樹脂層88中形成使源極電極84的一部分露出的未圖示的通孔(through hole)、及使上部電極93的一部分露出的通孔94後，形成經由通孔94而與源極電極84的一部分連接、成為陽極或陰極的畫素電極95。 Then, a through hole (not shown) that exposes a part of the source electrode 84 and a through hole 94 that exposes a part of the upper electrode 93 are formed in the resin layer 88, and then formed through the through hole 94 and the source. A part of the electrode electrode 84 is connected to the pixel electrode 95 which becomes an anode or a cathode.
畫素電極95例如是藉由以下方式形成：藉由濺鍍法來形成Al、Mo、IZO、ITO等的導電膜後，藉由光微影法及蝕刻法來進行圖案化。另外，亦可使用與欲形成的畫素電極的圖案相對應的金屬罩幕來形成畫素電極。 The pixel electrode 95 is formed, for example, by forming a conductive film of Al, Mo, IZO, ITO or the like by a sputtering method, and then patterning by a photolithography method and an etching method. Alternatively, a metal mask may be formed using a metal mask corresponding to the pattern of the pixel electrode to be formed.
形成畫素電極95後，形成有機EL層96。有機EL層96是設定為至少含有發光層的層，視需要而形成電洞注入層、電 洞傳輸層、電子注入層、電子傳輸層、阻擋層等。含有陽極及陰極的有機EL元件98的構成例如可採用如下層構成，但不限定於該系層構成，只要根據目的等來適當決定即可。 After the pixel electrode 95 is formed, the organic EL layer 96 is formed. The organic EL layer 96 is a layer set to include at least a light-emitting layer, and a hole injection layer and electricity are formed as needed. Hole transport layer, electron injection layer, electron transport layer, barrier layer, and the like. The configuration of the organic EL element 98 including the anode and the cathode can be configured, for example, as follows. However, the configuration is not limited to the layer structure, and may be appropriately determined depending on the purpose and the like.
．陽極/發光層/陰極 . Anode / luminescent layer / cathode
．陽極/電洞傳輸層/發光層/電子傳輸層/陰極 . Anode/hole transport layer/light-emitting layer/electron transport layer/cathode
．陽極/電洞傳輸層/發光層/阻擋層/電子傳輸層/陰極 . Anode/hole transport layer/light-emitting layer/barrier layer/electron transport layer/cathode
．陽極/電洞傳輸層/發光層/阻擋層/電子傳輸層/電子注入層/陰極 . Anode/hole transport layer/light-emitting layer/barrier layer/electron transport layer/electron injection layer/cathode
．陽極/電洞注入層/電洞傳輸層/發光層/阻擋層/電子傳輸層/陰極 . Anode/hole injection layer/hole transport layer/light-emitting layer/barrier layer/electron transport layer/cathode
．陽極/電洞注入層/電洞傳輸層/發光層/阻擋層/電子傳輸層/電子注入層/陰極 . Anode/hole injection layer/hole transport layer/light-emitting layer/barrier layer/electron transport layer/electron injection layer/cathode
．陽極/電洞傳輸層/阻擋層/發光層/電子傳輸層/陰極 . Anode/hole transport layer/barrier layer/light-emitting layer/electron transport layer/cathode
．陽極/電洞傳輸層/阻擋層/發光層/電子傳輸層/電子注入層/陰極 . Anode/hole transport layer/barrier layer/light-emitting layer/electron transport layer/electron injection layer/cathode
．陽極/電洞注入層/電洞傳輸層/阻擋層/發光層/電子傳輸層/陰極 . Anode/hole injection layer/hole transport layer/barrier layer/light-emitting layer/electron transport layer/cathode
．陽極/電洞注入層/電洞傳輸層/阻擋層/發光層/電子傳輸層/電子注入層/陰極 . Anode/hole injection layer/hole transport layer/barrier layer/light-emitting layer/electron transport layer/electron injection layer/cathode
另外，例如於製造全彩(full color)顯示的有機EL顯示器的情形時，使用與紅色、藍色、綠色相對應的有機發光材料，以各色的畫素規則地排列的方式分別使用金屬罩幕藉由蒸鍍法來選擇 性地成膜，形成發光層。 Further, for example, in the case of manufacturing an organic EL display of a full color display, an organic light-emitting material corresponding to red, blue, and green is used, and metal masks are respectively used in a manner of regularly arranging pixels of respective colors. Choose by evaporation The film is formed into a film to form a light-emitting layer.
繼形成有機EL層96之後，於整個面上將ITO成膜，形成透明電極97作為取出光之側的電極。光取出側的電極97無需依畫素而分割，只要藉由濺鍍法於有機EL層96上的整個面上成膜而製成設定為共通電極即可。 After the formation of the organic EL layer 96, ITO is formed on the entire surface to form a transparent electrode 97 as an electrode on the side from which light is taken out. The electrode 97 on the light extraction side is not required to be divided by the pixel, and may be formed as a common electrode by sputtering on the entire surface of the organic EL layer 96.
形成共通電極97後，為了防止水分或氧對有機EL元件造成的劣化而形成阻斷水分或氧的阻障層，阻障層可列舉氮化矽、氧化矽、氮氧化矽、氧化鋁等無機物。 After the formation of the common electrode 97, a barrier layer for blocking moisture or oxygen is formed in order to prevent deterioration of the organic EL element by moisture or oxygen. Examples of the barrier layer include inorganic substances such as tantalum nitride, cerium oxide, cerium oxynitride, and aluminum oxide. .
其後，為了進行密封，經由黏接劑等來貼附具有阻障性的透明的樹脂膜99。構成樹脂膜99的樹脂材料可列舉：聚對苯二甲酸乙二酯、聚萘二甲酸丁二酯、聚萘二甲酸乙二酯等聚酯，聚苯乙烯、聚碳酸酯、聚醚碸、聚芳酯(polyarylate)、聚醯亞胺、聚環烯烴、降冰片烯樹脂、聚(氯三氟乙烯)等有機材料。 Thereafter, in order to perform sealing, a transparent resin film 99 having barrier properties is attached via an adhesive or the like. Examples of the resin material constituting the resin film 99 include polyesters such as polyethylene terephthalate, polybutylene naphthalate, and polyethylene naphthalate, polystyrene, polycarbonate, and polyether oxime. Organic materials such as polyarylate, polyimine, polycycloolefin, norbornene resin, poly(chlorotrifluoroethylene).
最後，可自積層體1的背面側照射雷射光L，使黏接材11的黏接力降低而將光透射性基材12自積層體1上剝離，製造於可撓性基板10上形成發光元件結構體2而成的有機EL顯示器3B。 Finally, the laser light L can be irradiated from the back side of the laminated body 1 to reduce the adhesive force of the adhesive material 11, and the light-transmitting substrate 12 can be peeled off from the laminated body 1 to be formed on the flexible substrate 10 to form a light-emitting element. The organic EL display 3B made of the structure 2.
<X射線平板檢測器> <X-ray flat panel detector>
圖7為示意性地表示藉由本實施形態的製造方法及積層體1所製造的FPD 3C的構成要部的剖面圖。 FIG. 7 is a cross-sectional view schematically showing a configuration of a part of the FPD 3C manufactured by the manufacturing method of the embodiment and the laminated body 1.
如圖7所示，FPD3C具有以下構成：於可撓性基板10上，積層有具有a-Si作為通道層的TFT 80、位於TFT 80上的有機系材料的光檢測器100及閃爍體(scintillator)105作為含有具 有特定功能的元件的結構體2的構成。於FPD 3C的製造中，亦首先準備經由黏接劑11將可撓性基板10與光透射性基材12貼合而成的積層體1，於積層體1上形成TFT 80，於TFT 80上形成光檢測器100及閃爍體105。 As shown in FIG. 7, the FPD 3C has a configuration in which a TFT 80 having a-Si as a channel layer, a photodetector 100 of an organic material on the TFT 80, and a scintillator are laminated on the flexible substrate 10. ) 105 as a containment The structure of the structure 2 of the element having a specific function. In the production of the FPD 3C, first, the laminate 1 in which the flexible substrate 10 and the light-transmitting substrate 12 are bonded via the adhesive 11 is prepared, and the TFT 80 is formed on the laminate 1 on the TFT 80. The photodetector 100 and the scintillator 105 are formed.
於積層體1的多孔質陽極氧化絕緣膜102上藉由電漿CVD來形成SiN膜73，繼而將Ti/Al/Ti成膜，經由通常的光微影步驟來形成閘極電極81及電容器90的下部電極91。 The SiN film 73 is formed on the porous anodic oxide insulating film 102 of the laminated body 1 by plasma CVD, and then Ti/Al/Ti is formed into a film, and the gate electrode 81 and the capacitor 90 are formed through a usual photolithography step. Lower electrode 91.
繼而，藉由電漿CVD來連續形成SiO2絕緣膜、非晶質Si層、SiN保護膜(未圖示)。成膜溫度為350℃。於通常的光微影步驟中將非晶質Si層及Si保護膜圖案化而形成非晶質Si活性層(通道)83。SiO2絕緣膜於TFT 80中作為閘極絕緣層82而發揮功能，於電容器90中作為填埋電極間的介電質而發揮功能。 Then, an SiO 2 insulating film, an amorphous Si layer, and a SiN protective film (not shown) are continuously formed by plasma CVD. The film formation temperature was 350 °C. The amorphous Si layer and the Si protective film are patterned in a normal photolithography step to form an amorphous Si active layer (channel) 83. The SiO 2 insulating film functions as the gate insulating layer 82 in the TFT 80, and functions as a dielectric between the buried electrodes in the capacitor 90.
繼而，將成為源極/汲極電極84、源極/汲極電極85及電容器90的上部電極93的Mo膜成膜，形成源極/汲極電極84、源極/汲極電極85及上部電極93的圖案。藉由以上步驟來形成TFT 80及電容器90。 Then, a Mo film which becomes the source/drain electrode 84, the source/drain electrode 85, and the upper electrode 93 of the capacitor 90 is formed, and the source/drain electrode 84, the source/drain electrode 85, and the upper portion are formed. The pattern of the electrode 93. The TFT 80 and the capacitor 90 are formed by the above steps.
繼而，於該TFT 80及電容器90上塗佈形成平坦化膜88，於平坦化膜88中形成用以與電容器90連接的貫通介層窗(via)後，形成光檢測器用下部電極101。於其上形成包含感光性有機材料的有機光電轉換部102及光檢測器用上部電極103，而形成光檢測器100。 Then, a planarizing film 88 is formed on the TFT 80 and the capacitor 90, and a via is connected to the capacitor 90 in the planarizing film 88 to form a photodetector lower electrode 101. The organic photoelectric conversion unit 102 including the photosensitive organic material and the upper electrode 103 for the photodetector are formed thereon to form the photodetector 100.
再者，此處示出了使用有機材料作為光檢測器100的光 電轉換部102的例子，亦可使用通常的Si。 Furthermore, light using an organic material as the photodetector 100 is shown here. As an example of the electric conversion unit 102, normal Si can also be used.
其後，將片狀閃爍體105貼附於光檢測器100上。閃爍體105的材料可適當應用CaWO4、Gd2O2S、CsI等。繼而，於閃爍體105上進一步貼附密封膜108。 Thereafter, the sheet-like scintillator 105 is attached to the photodetector 100. As the material of the scintillator 105, CaWO 4 , Gd 2 O 2 S, CsI or the like can be suitably used. Then, the sealing film 108 is further attached to the scintillator 105.
最後，可自積層體1的背面側照射雷射光L，使黏接材11的黏接力降低而將光透射性基材12自積層體1上剝離後，貼附防止可撓性基板10的破損的保護膜109(聚對苯二甲酸乙二酯(Polyethylene terephthalate，PET)膜)，製造於可撓性基板10上形成光電轉換元件結構體2而成的X射線FPD 3C。 Finally, the laser beam L can be irradiated from the back side of the laminated body 1 to reduce the adhesive force of the adhesive member 11, and the light-transmitting substrate 12 is peeled off from the laminated body 1 and then attached to prevent breakage of the flexible substrate 10. The protective film 109 (polyethylene terephthalate (PET) film) is produced by forming the photoelectric conversion element structure 2 on the flexible substrate 10 to form an X-ray FPD 3C.
<有機薄膜太陽電池> <Organic Thin Film Solar Cell>
圖8為示意性地表示藉由上述本發明電子元件的製造方法及積層體而製造的有機薄膜太陽電池3D的構成要部的剖面圖。 FIG. 8 is a cross-sectional view showing a main part of a configuration of an organic thin film solar cell 3D manufactured by the method for producing an electronic component of the present invention and the laminate.
如圖8所示，有機薄膜太陽電池3D為將以下積層結構設定為基本構成的元件，即，於可撓性基板10上依序積層有下部電極124、有機光電轉換半導體層126、緩衝層40及上部電極128的積層結構。 As shown in FIG. 8, the organic thin film solar cell 3D is an element having a basic laminated structure, that is, a lower electrode 124, an organic photoelectric conversion semiconductor layer 126, and a buffer layer 40 are sequentially laminated on the flexible substrate 10. And a laminated structure of the upper electrode 128.
於有機薄膜太陽電池3D的製造中，亦首先準備經由黏接劑11將可撓性基板10與光透射性基材12貼合而成的積層體1，繼而將以純水3.92質量份、35%鹽酸0.05質量份、乙醇12.53質量份及四乙氧基矽烷4.17質量份的比例混合的塗佈液塗佈於可撓性基板10的陽極氧化皮膜表面上，加以乾燥。塗佈是藉由浸漬塗佈(dip coat)來進行。其後，將塗佈有塗佈液的積層體1放入至300℃ 的恆溫槽中，進行10分鐘的熱處理，形成厚度為300nm的保護層。 In the production of the organic thin film solar cell 3D, first, the laminate 1 in which the flexible substrate 10 and the light-transmitting substrate 12 are bonded via the adhesive 11 is prepared, and then 3.92 parts by mass of pure water is used. A coating liquid in which 0.05 parts by mass of hydrochloric acid, 12.53 parts by mass of ethanol, and 4.17 parts by mass of tetraethoxy decane were mixed was applied onto the surface of the anodized film of the flexible substrate 10 and dried. Coating is carried out by dip coating. Thereafter, the layered body 1 coated with the coating liquid was placed at 300 ° C In the thermostatic bath, heat treatment was performed for 10 minutes to form a protective layer having a thickness of 300 nm.
於如此而製作的積層體1的保護層面上連續地真空蒸鍍鈦(膜厚5nm)與銀(膜厚為100nm)，形成下部電極124。此時，以元件面積成為16cm2的方式使用蔽蔭罩幕。 Titanium (film thickness: 5 nm) and silver (film thickness: 100 nm) were continuously vacuum-deposited on the protective layer of the laminated body 1 thus produced to form the lower electrode 124. At this time, a shadow mask was used so that the element area became 16 cm 2 .
關於下部電極124的其他材料，於作為負極而發揮功能的情形時，例如可較佳地使用鎂、鋁、鈣、鈦、鉻、錳、鐵、銅、鋅、鍶、銀、銦、錫、鋇、鉍等金屬或該些金屬的合金。 When other materials of the lower electrode 124 function as a negative electrode, for example, magnesium, aluminum, calcium, titanium, chromium, manganese, iron, copper, zinc, lanthanum, silver, indium, tin, or the like can be preferably used. Metals such as ruthenium, osmium or the like.
另一方面，於下部電極124作為正極而發揮功能的情形時，例如可較佳地使用鉻、鈷、鎳、銅、鉬、鈀、銀、鉭、鎢、鉑、金等金屬或該些金屬的合金，透明導電性氧化物(Transparent Conductive Oxide，TCO)，聚苯胺、聚噻吩、聚吡咯等導電性聚合物。進而，適於下部電極124的導電性聚合物層是詳細揭示於日本專利特開2012-43835號公報中，較佳為聚噻吩衍生物，更佳為聚伸乙二氧噻吩-聚苯乙烯磺酸(Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate)，PEDOT-PSS)。該些金屬、TCO、導電性聚合物可僅使用一種，亦可將兩種以上混合或積層。 On the other hand, when the lower electrode 124 functions as a positive electrode, for example, a metal such as chromium, cobalt, nickel, copper, molybdenum, palladium, silver, rhenium, tungsten, platinum, or gold or the like can be preferably used. Alloy, Transparent Conductive Oxide (TCO), conductive polymer such as polyaniline, polythiophene, polypyrrole. Further, the conductive polymer layer suitable for the lower electrode 124 is disclosed in detail in Japanese Laid-Open Patent Publication No. 2012-43835, preferably a polythiophene derivative, more preferably a polyethylene dioxythiophene-polystyrene sulfonate. Acid (Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate), PEDOT-PSS). These metals, TCOs, and conductive polymers may be used alone or in combination of two or more.
於下部電極124上旋轉塗佈PEDOT-PSS水溶液(賀利氏貴金屬(Heraeus Precious Metals)製造，克萊維奧斯(Clevios)P VP.AI 4083)，於140℃下加熱處理15分鐘。藉此形成電洞傳輸層(膜厚為0.04μm)。 A PEDOT-PSS aqueous solution (manufactured by Heraeus Precious Metals, Clevios P VP. AI 4083) was spin-coated on the lower electrode 124, and heat-treated at 140 ° C for 15 minutes. Thereby, a hole transport layer (film thickness of 0.04 μm) was formed.
於電洞傳輸層上，將以下組成物於乾燥氮氣環境下旋轉塗佈於電洞傳輸層上，於140℃下加熱處理15分鐘，上述組成物是使作為供電子材料的P3HT(默克(Merck)製造，lisicon SP001)與作為受電子材料的ICBA(西格瑪-奧德里奇(Sigma-Aldrich)製造)以重量比1：1溶解於二氯苯中而成。藉此，形成體異質(bulk hetero)接合型的光電轉換層126。光電轉換層126的膜厚為0.2μm。 On the hole transport layer, the following composition was spin-coated on a hole transport layer in a dry nitrogen atmosphere and heat-treated at 140 ° C for 15 minutes. The above composition was used as an electron donating material for P3HT (Merck ( Merck), lisicon SP001) and ICBA (manufactured by Sigma-Aldrich) as an electron-accepting material were dissolved in dichlorobenzene in a weight ratio of 1:1. Thereby, a bulk heterojunction type photoelectric conversion layer 126 is formed. The film thickness of the photoelectric conversion layer 126 was 0.2 μm.
光電轉換層126是自高效率地表現出光電轉換過程的材料中選擇而構成，上述光電轉換過程是受到太陽光等的可見光而生成激子(電子-電洞對)後，該激子解離成電子與電洞，將電子向負極側傳輸、將電洞向正極側傳輸的過程。於製成有機薄膜太陽電池的情形時，形成含有包含有機材料的供電子區域(施體)的光電轉換層，就轉換效率的觀點而言，可較佳地應用體異質接合型的光電轉換層126(以下亦稱為「體異質層」)。 The photoelectric conversion layer 126 is configured by selecting a material that efficiently exhibits a photoelectric conversion process. After the photoelectric conversion process generates excitons (electron-hole pairs) by visible light such as sunlight, the excitons are dissociated into Electrons and holes, the process of transmitting electrons to the negative side and transferring holes to the positive side. In the case of forming an organic thin film solar cell, a photoelectric conversion layer containing an electron donating region (donor) containing an organic material is formed, and from the viewpoint of conversion efficiency, a bulk heterojunction type photoelectric conversion layer can be preferably used. 126 (hereinafter also referred to as "body heterogeneous layer").
體異質層為將供電子材料(施體)與受電子材料(受體)混合而成的有機光電轉換層。供電子材料與受電子材料的混合比是以轉換效率達到最高的方式調整，通常自質量比為10：90~90：10的範圍內選擇。此種混合層的形成方法例如可使用共蒸鍍法。或者，亦可藉由對兩種有機材料使用共同的溶劑進行溶劑塗佈來製作此種混合層。 The bulk heterogeneous layer is an organic photoelectric conversion layer in which an electron donating material (donor) and an electron accepting material (acceptor) are mixed. The mixing ratio of the electron-donating material to the electron-accepting material is adjusted in such a manner that the conversion efficiency is the highest, and is usually selected from the range of the mass ratio of 10:90 to 90:10. A method of forming such a mixed layer can be, for example, a co-evaporation method. Alternatively, such a mixed layer can also be produced by solvent-coating two organic materials using a common solvent.
體異質層的膜厚較佳為10nm~500nm，尤佳為20nm~300nm。 The film thickness of the bulk heterolayer is preferably from 10 nm to 500 nm, and more preferably from 20 nm to 300 nm.
供電子材料(亦稱為施體或電洞傳輸材料)為其最高佔據分子軌道(Highest Occupied Molecular Orbital，HOMO)能階為4.5eV~6.0eV的π電子共軛系化合物。 The electron donating material (also known as the donor or hole transport material) is a π-electron conjugated compound having a Highest Occupied Molecular Orbital (HOMO) energy level of 4.5 eV to 6.0 eV.
具體可例示：使各種芳烴(例如噻吩、咔唑、茀、矽雜茀、噻吩並吡嗪(thienopyrazine)、噻吩並苯并噻吩、二噻吩並矽羅、喹噁啉、苯并噻二唑、噻吩並噻吩等)偶合而成的共軛系聚合物、苯乙炔系聚合物、卟啉類、酞菁類等。除此以外，亦可應用在「化學評論(Chemical Reviews)」(第107卷、953頁~1010頁(2007年))中作為電洞傳輸材料(Hole-Transporting Materials)而記載的化合物組群或「美國化學會志(Journal of the American Chemical Society)」(第131卷、16048頁(2009年))中記載的卟啉衍生物。 Specifically, it can be exemplified by various aromatic hydrocarbons (for example, thiophene, carbazole, anthracene, anthracene, thienopyrazine, thienobenzothiophene, dithienofluorene, quinoxaline, benzothiadiazole, A conjugated polymer obtained by coupling thienothiophene or the like, a phenylacetylene polymer, a porphyrin or a phthalocyanine. In addition, it can also be applied to a compound group described as "Hole-Transporting Materials" in "Chemical Reviews" (Vol. 107, pp. 953-1010 (2007)) or A porphyrin derivative described in "Journal of the American Chemical Society" (Vol. 131, p. 16548 (2009)).
該些化合物中，尤佳為使選自由噻吩、咔唑、茀、矽雜茀、噻吩並吡嗪、噻吩並苯并噻吩、二噻吩並矽羅、喹噁啉、苯并噻二唑、噻吩並噻吩所組成的組群中的結構單元偶合而成的共軛系聚合物。具體例可列舉：聚-3-己基噻吩(P3HT)、聚-3-辛基噻吩(P3OT)、「美國化學會志(Journal of the American Chemical Society)」(第130卷、3020頁(2008年))中記載的各種聚噻吩衍生物，「先進材料(Advanced Materials)」(第19卷、2295頁(2007年))中記載的PCTBT，「美國化學會志(Journal of the American Chemical Society)」(第130卷、732頁(2008年))中記載的PCDTQx、PCDTPP、PCDTPT、PCDTBX、PCDTPX，「自然光子 學(Nature Photonics)」(第3卷、649頁(2009年))中記載的PBDTTT-E、PBDTTT-C、PBDTTT-CF，「先進材料(Advanced Materials)」(第22卷，E135頁~E138頁(2010年))中記載的PTB7等。 Among these compounds, it is particularly preferred to be selected from the group consisting of thiophene, carbazole, anthracene, anthracene, thienopyrazine, thienobenzothiophene, dithienofluorene, quinoxaline, benzothiadiazole, thiophene. A conjugated polymer obtained by coupling structural units in a group consisting of thiophenes. Specific examples include poly-3-hexylthiophene (P3HT), poly-3-octylthiophene (P3OT), and Journal of the American Chemical Society (Vol. 130, 3020 (2008) Various polythiophene derivatives described in "), "Advanced Materials" (Vol. 19, page 2295 (2007)), PCTBT, "Journal of the American Chemical Society" PCDTQx, PCDTPP, PCDTPT, PCDTBX, PCDTPX, "Nature Photon", (Vol. 130, 732 (2008)) PBDTTT-E, PBDTTT-C, PBDTTT-CF, "Advanced Materials" (Vol. 22, E135-E138), as described in Nature Photonics (Vol. 3, p. 649 (2009)). PTB7 and the like described in page (2010).
受電子材料(亦稱為受體或電子傳輸材料)為其最低未佔分子軌道(Lowest Unoccupied Molecular Orbital，LUMO)能階為3.5eV~4.5eV的π電子共軛系化合物。 The electron-accepting material (also known as the acceptor or electron-transporting material) is a π-electron conjugated compound having a lowest Unoccupied Molecular Orbital (LUMO) energy level of 3.5 eV to 4.5 eV.
具體可列舉：富勒烯(fullerene)及其衍生物、苯乙炔系聚合物、萘四羧酸醯亞胺衍生物、苝四羧酸醯亞胺衍生物等。該些化合物中，較佳為富勒烯衍生物。富勒烯衍生物的具體例可列舉：C60、苯基-C61-丁酸甲酯(於文獻等中被稱為PCBM、[60]PCBM或PC61BM的富勒烯衍生物)、C70、苯基-C71-丁酸甲酯(於大量文獻等中被稱為PCBM、[70]PCBM或PC71BM的富勒烯衍生物)、及「先進功能材料(Advanced Functional Materials)」(第19卷、779頁~788頁(2009年))中記載的富勒烯衍生物、「美國化學會志(Journal of the American Chemical Society)」(第131卷、16048頁(2009年))中記載的富勒烯衍生物SIMEF、「美國化學會志(Journal of the American Chemical Society)」(第132卷、1377頁(2010年))中記載的富勒烯衍生物ICBA等。 Specific examples thereof include fullerene and its derivatives, phenylacetylene polymers, naphthalene tetracarboxylic acid quinone imine derivatives, and perylenetetracarboxylic acid quinone imine derivatives. Among these compounds, a fullerene derivative is preferred. Specific examples of the fullerene derivative include C 60 , phenyl-C 61 -butyric acid methyl ester (referred to as PCBM in the literature, etc., [60] fullerene derivative of PCBM or PC61BM), C 70 , phenyl-C 71 -butyric acid methyl ester (referred to as PCBM, [70] fullerene derivative of PCBM or PC71BM in a large number of literatures, etc.), and "Advanced Functional Materials" (19th Vol. 1, pp. 779-788 (2009), fullerene derivatives, "Journal of the American Chemical Society" (Vol. 131, p. 16048 (2009)) The fullerene derivative, SIMEF, and the fullerene derivative ICBA described in "Journal of the American Chemical Society" (Vol. 132, p. 1377 (2010)).
於光電轉換層126上連續地真空蒸鍍鋁(膜厚為2nm)與銀(膜厚為10nm)。此時，以元件面積成為16cm2的方式使用蔽蔭罩幕。繼而，於上部電極128上真空蒸鍍銀(膜厚為0.4μm) 作為匯流排(bus)電極134。此時，使用條紋圖案(stripe pattern)的蔽蔭罩幕，形成線寬為0.3mm且間距成為20mm的條紋狀匯流排電極134。進而，於導入有Ar氣體及O2氣體的真空度為1Pa的環境中，一面將基板加熱至160℃，一面藉由高頻磁控濺鍍介隔開口為16cm2的蔽蔭罩幕將ITO(膜厚為0.1μm)成膜，形成於鋁層與ITO層之間具有匯流排電極134的成為鋁/銀/ITO的三層積層結構的光透射性的上部電極128。 Aluminum (having a film thickness of 2 nm) and silver (having a film thickness of 10 nm) were continuously vacuum-deposited on the photoelectric conversion layer 126. At this time, a shadow mask was used so that the element area became 16 cm 2 . Then, silver (having a film thickness of 0.4 μm) was vacuum-deposited on the upper electrode 128 as a bus electrode 134. At this time, a stripe-shaped bus bar electrode 134 having a line width of 0.3 mm and a pitch of 20 mm was formed using a mask mask of a stripe pattern. Further, there is introduced in the Ar gas and O 2 gas degree of vacuum of the environment 1Pa, one surface of the substrate is heated to 160 ℃, side by high-frequency magnetron sputtering 16cm drain port is spaced apart from the dielectric mask the ITO curtain 2 (Film thickness: 0.1 μm) was formed into a film, and a light-transmitting upper electrode 128 having a three-layer laminated structure of aluminum/silver/ITO having a bus bar electrode 134 between the aluminum layer and the ITO layer was formed.
上部電極128因使光入射至光電轉換層中，故較佳為由透明導電膜所形成。透明導電膜例如可列舉：金屬、金屬氧化物、導電性聚合物、該些物質的混合物或積層結構等。具體例可列舉：氧化錫、氧化鋅、氧化銦、氧化銦錫(ITO)、氧化銦鋅(IZO)、氧化銦鎢(IWO)等TCO，作為上述下部電極124而列舉的金屬及金屬合金的超薄膜，聚苯胺、聚噻吩、聚吡咯等導電性聚合物等。作為TCO的材料，尤佳為ITO、IZO、氧化錫、摻銻氧化錫(ATO)、摻氟氧化錫(FTO)、氧化鋅、摻銻氧化鋅(AZO)、摻鎵氧化鋅(GZO)的任一種材料。 Since the upper electrode 128 is made to enter light into the photoelectric conversion layer, it is preferably formed of a transparent conductive film. Examples of the transparent conductive film include a metal, a metal oxide, a conductive polymer, a mixture of these materials, or a laminated structure. Specific examples thereof include TCO such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), and indium tungsten oxide (IWO), and metals and metal alloys exemplified as the lower electrode 124. Ultra-thin film, conductive polymer such as polyaniline, polythiophene, or polypyrrole. As a material of TCO, it is preferably ITO, IZO, tin oxide, antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), zinc oxide, antimony-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO). Any material.
上部電極128只要利用公知的方法來形成即可。例如只要利用以下方法來形成即可：考慮與上述構成材料的適性，自利用塗佈或印刷的濕式成膜法或者利用真空蒸鍍法、濺鍍法、離子電鍍法等PVD法或CVD法的乾式成膜法等中適當選擇的方法。 The upper electrode 128 may be formed by a known method. For example, it may be formed by the following method: from the wet film formation method by coating or printing, or the PVD method or the CVD method using a vacuum deposition method, a sputtering method, or an ion plating method, considering the suitability of the above-mentioned constituent materials. A method of appropriately selecting a dry film forming method or the like.
以上的步驟是使用有機EL元件製造裝置來進行，上述有機EL元件製造裝置是將形成鋁及銀的真空蒸鍍裝置與形成ITO 的濺鍍裝置分別直接連結於真空度為1×10-4Pa以下的簇(cluster)型真空搬送系統而成。 The above steps are carried out using an organic EL element manufacturing apparatus that directly connects a vacuum vapor deposition apparatus for forming aluminum and silver and a sputtering apparatus for forming ITO to a degree of vacuum of 1 × 10 -4 Pa. The following cluster-type vacuum transfer system is used.
進而，準備積層有氮化矽膜及丙烯酸酯聚合物的PEN膜作為氣體阻障膜132。將該氣體阻障膜132插入作為密封劑(sealant)的乙烯-乙酸乙烯酯共聚物(EVA)膜，於140℃下真空加熱積層，積層氣體阻障膜132。再者，氣體阻障膜132是以最表面的氮化矽膜與上部電極128相向的方式真空加熱積層。 Further, a PEN film in which a tantalum nitride film and an acrylate polymer are laminated is prepared as the gas barrier film 132. This gas barrier film 132 was inserted into an ethylene-vinyl acetate copolymer (EVA) film as a sealant, and the laminate was vacuum-heated at 140 ° C to laminate a gas barrier film 132. Further, the gas barrier film 132 is vacuum-heated so that the outermost tantalum nitride film faces the upper electrode 128.
最後，可自積層體1的背面側照射雷射光L，使黏接材11的黏接力降低而將光透射性基材12自積層體1上剝離，製造於可撓性基板10上形成光電轉換元件結構體2而成的有機薄膜太陽電池3D。 Finally, the laser light L can be irradiated from the back side of the laminated body 1 to reduce the adhesive force of the adhesive material 11, and the light-transmitting substrate 12 can be peeled off from the laminated body 1 to be fabricated on the flexible substrate 10 to form photoelectric conversion. Organic thin film solar cell 3D made of element structure 2.
以上，作為本發明的電子元件的製造方法的實施形態，對製造光電轉換元件、有機EL顯示器、X射線FPD及有機薄膜太陽電池的情形進行了說明，但本發明不限定於上述實施形態。所製造的電子元件只要根據目的來選擇即可，例如於電子紙或液晶顯示器的製造中亦可較佳地應用本發明。亦可如被動式矩陣(passive matrix)方式般，設定為將分別形成於兩面的樹脂膜上的電極(配線)以縱橫交叉的方式相向配置、且於該些電極間設置有機EL元件或電子紙中所用的顯色材料或顯示材料而成的電子元件，亦可為彩色濾光片(color filter)般的被動式元件。 In the embodiment of the method for producing an electronic component of the present invention, the case of manufacturing a photoelectric conversion element, an organic EL display, an X-ray FPD, and an organic thin film solar cell has been described. However, the present invention is not limited to the above embodiment. The electronic component to be manufactured may be selected according to the purpose, and the present invention can be preferably applied to, for example, the manufacture of an electronic paper or a liquid crystal display. In the passive matrix method, electrodes (wirings) respectively formed on the resin films on both surfaces are arranged to face each other in a crisscross manner, and an organic EL element or an electronic paper is disposed between the electrodes. The electronic component used for the color developing material or the display material may also be a passive element like a color filter.
[實施例i] [Example i]
(實施例1~實施例15，比較例1) (Example 1 to Example 15, Comparative Example 1)
使用表1所示的實施例1~實施例15及比較例1的積層體，對本發明的電子元件的製造方法及積層體進行評價。黏接材是使用藉由以下方法所製作的硬化矽酮樹脂層。 The method for producing an electronic component and the laminate of the present invention were evaluated using the laminates of Examples 1 to 15 and Comparative Example 1 shown in Table 1. The adhesive material was a hardened fluorenone resin layer produced by the following method.
將作為成分(A)的直鏈狀乙烯基甲基聚矽氧烷(「VDT-127」，25℃下的黏度為700cP~800cP(厘泊)；阿茲馬克思(AZmax)製造，有機聚矽氧烷1mol中的乙烯基的mol%：0.325)、與作為成分(B)的直鏈狀甲基氫化聚矽氧烷(「HMS-301」、25℃下的黏度為25cP~35cP(厘泊)；阿茲馬克思(AZmax)製造，一分子內的鍵結於矽原子上的氫原子的個數：8個)，以所有烯基與鍵結於所有矽原子的氫原子之莫耳比(氫原子/烯基)成為0.9的方式混合，相對於該矽氧烷混合物100重量份，添加作為成分(D)的1-乙炔基-1-環己醇0.3質量份。繼而，相對於成分(A)與成分(B)的合計量，以鉑換算計成為1500ppm的方式添加鉑系觸媒(信越矽酮股份有限公司製造，CAT-PL-56)，獲得有機聚矽氧烷組成物。 Linear vinyl methyl polyoxyalkylene as component (A) ("VDT-127", viscosity at 25 ° C from 700 cP to 800 cP (centipoise); manufactured by AZmax, organic polyfluorene Molar% of vinyl group in 1 mol of oxyalkylene: 0.325), and linear methyl hydrogenated polyoxyalkylene as component (B) ("HMS-301", viscosity at 25 ° C is 25 cP to 35 cP (centipoise) ); Azmax (AZmax), the number of hydrogen atoms bonded to a helium atom in one molecule: 8), the molar ratio of all alkenyl groups to the hydrogen atoms bonded to all helium atoms ( The hydrogen atom/alkenyl group was mixed at a ratio of 0.9, and 0.3 parts by mass of 1-ethynyl-1-cyclohexanol as the component (D) was added to 100 parts by weight of the mixture of the oxirane. Then, a platinum-based catalyst (CAT-PL-56, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the total amount of the component (A) and the component (B) in a ratio of 1,500 ppm in terms of platinum to obtain an organic polyfluorene. Oxysilane composition.
藉由旋塗機將所得的組成物塗佈於光透射性支撐體的表面上(2000rpm，20秒鐘，塗佈量為20g/m2)。其後，使塗佈於透射性支撐體上的混合物於大氣中於180℃下加熱硬化60分鐘，於光透射性支撐體上形成包含厚度為30μm的硬化矽酮樹脂層的黏接材。再者，硬化矽酮樹脂層的表面張力為20.2N/m。 The obtained composition was applied onto the surface of the light-transmitting support by a spin coater (2000 rpm, 20 seconds, and the coating amount was 20 g/m 2 ). Thereafter, the mixture applied to the transmissive support was heat-cured at 180 ° C for 60 minutes in the air to form an adhesive material comprising a hardened fluorenone resin layer having a thickness of 30 μm on the light-transmitting support. Further, the surface tension of the hardened fluorenone resin layer was 20.2 N/m.
於所得的積層體上，分別於陽極氧化絕緣膜的表面依序形成1000nm的SiO2膜/100nm的Mo膜/100nm的Sn膜，其後 自光透射性支撐體的背面側藉由二維掃描來照射YAG雷射，進行剝離。 On the obtained laminate, a 1000 nm SiO 2 film/100 nm Mo film/100 nm Sn film was sequentially formed on the surface of the anodized insulating film, respectively, and then a two-dimensional scan was performed from the back side of the light transmissive support. The YAG laser was irradiated and peeled off.
關於SiO2膜的成膜，藉由旋塗法(AZ Spinfi1600)進行成膜後，於400℃的爐內煅燒60分鐘。Mo膜及Sn膜是藉由室溫下的濺鍍成膜來成膜。 The film formation of the SiO 2 film was carried out by a spin coating method (AZ Spinfi 1600), and then fired in a furnace at 400 ° C for 60 minutes. The Mo film and the Sn film are formed by sputtering at room temperature to form a film.
另外，YAG雷射是於射束(beam)寬度為200μm×2.5μm、能量密度為100kW/cm2且掃描速度為200mm/s的條件下依次掃描照射。 Further, the YAG laser was sequentially scanned and irradiated under the conditions of a beam width of 200 μm × 2.5 μm, an energy density of 100 kW/cm 2 and a scanning speed of 200 mm/s.
此處，可撓性基板及光透射性支撐體的線膨脹係數是藉由上述方法而求出。 Here, the linear expansion coefficient of the flexible substrate and the light-transmitting support is obtained by the above method.
評價是根據剝離後的可撓性基板上的Sn膜的狀態來進行。將Sn膜並無熔解及裂縫或皺褶等的情況評價為良好，將Sn膜中稍許可見裂縫或皺褶但未見熔解而不成問題的情況評價為尚可，將Sn膜中可見熔解的情況評價為不可。Sn膜熔解的情況下，可認為膜表面的溫度上升至作為熔點的231.9℃以上。 The evaluation was performed based on the state of the Sn film on the flexible substrate after peeling. The case where the Sn film was not melted, cracked or wrinkled, and the like was evaluated as good, and the case where the crack or wrinkle was slightly permitted in the Sn film but no melting was observed was not considered as a problem, and the melted in the Sn film was observed. The situation is evaluated as not possible. When the Sn film is melted, it is considered that the temperature of the film surface rises to 231.9 ° C or higher which is a melting point.
如表1所示，對於使用本發明的積層體所製造的實施例1~實施例15，於Sn層中未見熱損傷，但於使用厚度相同的SUS430的比較例1中，可見Sn膜熔融的痕跡，可確認表面達到230℃以上。 As shown in Table 1, in Examples 1 to 15 produced by using the laminate of the present invention, no thermal damage was observed in the Sn layer, but in Comparative Example 1 using SUS430 having the same thickness, Sn film melting was observed. Traces of the surface can be confirmed to reach 230 ° C or more.
「實施例16」 "Example 16"
使用實施例3的積層體來製作上述實施形態的有機EL顯示器。關於雷射剝離步驟的條件，與實施例3同樣地進行雷射剝離， 於雷射剝離步驟的前後，有機EL元件的發光效率未見變化，另外層間絕緣平坦化層的丙烯酸系樹脂亦未見變色，可製作特性良好的可撓性有機EL顯示器。 The organic EL display of the above-described embodiment was produced using the laminate of Example 3. Regarding the conditions of the laser peeling step, laser peeling was performed in the same manner as in Example 3. Before and after the laser peeling step, the luminous efficiency of the organic EL element was not changed, and the acrylic resin of the interlayer insulating planarization layer was not discolored, and a flexible organic EL display having good characteristics could be produced.
1‧‧‧積層體 1‧‧ ‧ laminated body
2‧‧‧結構體 2‧‧‧structure
3‧‧‧電子元件 3‧‧‧Electronic components
10‧‧‧可撓性基板 10‧‧‧Flexible substrate
11‧‧‧黏接劑 11‧‧‧Adhesive
12‧‧‧光透射性支撐體 12‧‧‧Light Transmissive Support
L‧‧‧雷射光 L‧‧‧Laser light
x、y‧‧‧方向 x, y‧‧‧ direction
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| CN110506306A (en) * | 2017-03-31 | 2019-11-26 | 夏普株式会社 | Display device, the manufacturing method of display device, display device producing device |
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| JP2016038556A (en) * | 2014-08-11 | 2016-03-22 | 株式会社ジャパンディスプレイ | Manufacturing method of flexible display device |
| JP6555869B2 (en) * | 2014-10-17 | 2019-08-07 | キヤノン株式会社 | Capacitive transducer |
| US9850406B2 (en) * | 2014-11-07 | 2017-12-26 | International Business Machines Corporation | Adhesive resins for wafer bonding |
| US9786856B2 (en) * | 2015-08-20 | 2017-10-10 | Dpix, Llc | Method of manufacturing an image sensor device |
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| CN110506306A (en) * | 2017-03-31 | 2019-11-26 | 夏普株式会社 | Display device, the manufacturing method of display device, display device producing device |
| CN110506306B (en) * | 2017-03-31 | 2021-07-13 | 夏普株式会社 | Display device, method of manufacturing display device, and apparatus for manufacturing display device |
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