TW201544613A - Silver alloy target, method for making the same, and application thereof - Google Patents
Silver alloy target, method for making the same, and application thereof Download PDFInfo
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本發明係關於一種銀合金靶材及其製法與應用，特別是關於一種用於製作有機發光二極體(Organic Light Emitting diode，OLED)電極的銀合金靶材及其製法與該有機發光二極體電極。 The invention relates to a silver alloy target and a preparation method and application thereof, in particular to a silver alloy target for manufacturing an organic light emitting diode (OLED) electrode, a preparation method thereof and the organic light emitting diode Body electrode.
有機發光二極體為一種自發光元件。不同於需要背光源的液晶顯示器(liquid crystal display，LCD)，有機發光二極體本身即具有高對比的顯示特性，係可做為顯示器(display)的顯示像素，也可製作成為照明(lighting)的產品。 The organic light emitting diode is a self-luminous element. Unlike a liquid crystal display (LCD) that requires a backlight, the organic light-emitting diode itself has a high contrast display characteristic, and can be used as a display pixel of a display or as a lighting. The product.
現有技術提供一種主動式有機發光二極體(active matrix organic light emitting diode，AMOLED)，係將有機發光二極體製作於薄膜電晶體(thin film transistor，TFT)基板上而製成，其運作時係以薄膜電晶體驅動有機發光二極體發光。將主動式有機發光二極體應用於顯示器領域，所能達到的優勢包含：(1)薄、輕量化；(2)自發光性：主動式有機發光二極體具較高解析度、尖銳對比與較大發光範圍，不須如液晶顯示器之背光源；(3)高解析度[畫素尺寸小於5微米(μm)]及快速啟動[反應時間介於1至10微秒(μs)]；(4)寬廣視角：主動式有機發光二極體製 的顯示器視角可達180°；(5)全方位色彩；(6)低能源消耗：有機發光二極體以低電壓操作，可利用電池驅動，所需電壓約1至20伏特(volts)；(7)可撓性：主動式有機發光二極體製的顯示器可使用塑膠基板，開啟可撓式顯示器之可能。 The prior art provides an active organic light emitting diode (AMOLED), which is formed by fabricating an organic light emitting diode on a thin film transistor (TFT) substrate. The organic light emitting diode is driven by a thin film transistor. The advantages of using active organic light-emitting diodes in the display field include: (1) thinness and light weight; (2) self-luminance: active organic light-emitting diodes with higher resolution and sharp contrast With a large illumination range, it does not need a backlight such as a liquid crystal display; (3) high resolution [pixel size less than 5 micrometers (μm)] and fast start [reaction time between 1 and 10 microseconds (μs)]; (4) Wide viewing angle: active organic light emitting diode system Display viewing angle up to 180 °; (5) all-round color; (6) low energy consumption: organic light-emitting diodes operate at low voltage, can be driven by batteries, the required voltage is about 1 to 20 volts (volts); 7) Flexibility: The active organic light-emitting diode display can use a plastic substrate to open the flexible display.
依照發光結構，主動式有機發光二極體可分為下發光(bottom emission)型主動式有機發光二極體與上發光(top emission)型主動式有機發光二極體。 According to the light emitting structure, the active organic light emitting diode can be classified into a bottom emission type active organic light emitting diode and a top emission type active organic light emitting diode.
如圖4A所示，下發光型主動式有機發光二極體包含有一金屬製的陰極10、一發光層20、一透光材料製的陽極30及一玻璃基板40，該金屬製的陰極10、該發光層20、該透光材料製的陽極30及該玻璃基板40由上而下依序貼靠重疊。當該發光層20發光時，其光是朝向四面八方，但是往上的光被該金屬製的陰極10反射，使得所有的光均朝下穿透該透光材料製的陽極30及玻璃基板40，最後光從下面發射出去，如圖4A之箭頭所示，故稱為下發光型。 As shown in FIG. 4A, the lower light-emitting active organic light-emitting diode comprises a metal cathode 10, a light-emitting layer 20, an anode 30 made of a light-transmitting material, and a glass substrate 40. The metal cathode 10, The light-emitting layer 20, the anode 30 made of the light-transmitting material, and the glass substrate 40 are stacked in this order from top to bottom. When the light-emitting layer 20 emits light, the light is directed in all directions, but the upward light is reflected by the metal cathode 10, so that all the light penetrates the anode 30 and the glass substrate 40 made of the light-transmitting material downward. Finally, the light is emitted from below, as shown by the arrow in Fig. 4A, so it is called the lower illumination type.
反之，如圖4B所示，上發光型主動式有機發光二極體與下發光型主動式有機發光二極體不同之處在於：其陰極10A為透光材料所製，其陽極30A為高反射率材料所製。則當發光層發光時其往下方向的光會被此陽極30A反射，使得所有的光均朝上穿透透光材料製的陰極10A，最後光從上面發射出去，如圖4B之箭頭所示，故稱為上發光型。 On the contrary, as shown in FIG. 4B, the upper light-emitting active organic light-emitting diode is different from the lower light-emitting active organic light-emitting diode in that the cathode 10A is made of a light-transmitting material, and the anode 30A is highly reflective. Made of materials. Then, when the light-emitting layer emits light, the light in the downward direction is reflected by the anode 30A, so that all the light penetrates the cathode 10A made of the light-transmitting material upward, and finally the light is emitted from above, as shown by the arrow in FIG. 4B. Therefore, it is called the upper illuminating type.
由於上發光型主動式有機發光二極體的光線不用穿過薄膜電晶體基板，故上發光型主動式有機發光二 極體具有較大的開口率(aperture ratio)；為了能進一步提升上發光型主動式有機發光二極體的效率，其所需的陽極材料除了要具備高功函數(work function)外，尚需具備高反射率。一般反射率最高的金屬元素為銀，但銀(Ag)的功函數只有約4.2至4.7電子伏特(eV)，比起常用於製作陽極電極的銦錫氧化物(indium tin oxide，ITO)低了約0.6eV。故此，現有技術提供一種由一銦錫氧化物薄膜、一純銀薄膜及一銦錫氧化物薄膜依序重疊所構成的三層結構陽極(以下簡稱ITO/Ag/ITO陽極)，以達到同時具備高功函數及高反射率的特性之陽極的需求。 Since the light of the upper light-emitting active organic light-emitting diode does not need to pass through the thin film transistor substrate, the upper light-emitting active organic light-emitting diode The polar body has a large aperture ratio; in order to further improve the efficiency of the upper-emitting active organic light-emitting diode, the anode material required is required to have a high work function. High reflectivity. The metal element with the highest reflectivity is silver, but the work function of silver (Ag) is only about 4.2 to 4.7 electron volts (eV), which is lower than the indium tin oxide (ITO) commonly used to make anode electrodes. About 0.6eV. Therefore, the prior art provides a three-layer structure anode (hereinafter referred to as ITO/Ag/ITO anode) which is formed by sequentially overlapping an indium tin oxide film, a pure silver film and an indium tin oxide film, so as to achieve high at the same time. The need for an anode of work function and high reflectivity characteristics.
雖然ITO/Ag/ITO陽極可兼具有高反射率及高功函數之特性，但純銀薄膜在經過約150℃的加熱製程後會發生凝聚(agglomeration)而形成島狀的結構，反而造成反射率的下降；且純銀薄膜另具有容易被硫或硫化物侵蝕及難以附著於一般氧化物(例如：ITO)上之缺點。 Although the ITO/Ag/ITO anode can have both high reflectivity and high work function, the pure silver film undergoes agglomeration after a heating process of about 150 ° C to form an island-like structure, which in turn causes reflectance. And the pure silver film has the disadvantage of being easily attacked by sulfur or sulfide and difficult to adhere to a general oxide such as ITO.
縱然，K.Sugawara等人[Vacuum,83(2009),page 610-613]提出添加金、銅或鋁於純銀中以改善純銀薄膜凝聚的缺失；T.Suzukia等人[Vacuum,66(2002),page 501-504]則於純銀中同時添加鈀(Pd)及銅以同時改善純銀薄膜凝聚及受硫侵蝕的缺失。然而，無論是將金、銅或鋁添加於純銀中所製成的銀薄膜，或是同時添加鈀及銅於純銀中所製成的銀薄膜，該等銀薄膜與ITO薄膜之間皆無法獲得足夠的附著性，且該等銀薄膜之反射率皆顯著低於純銀薄膜。 Even though K. Sugawara et al. [Vacuum, 83 (2009), page 610-613] proposed the addition of gold, copper or aluminum in pure silver to improve the lack of solid silver film agglomeration; T. Suzukia et al [Vacuum, 66 (2002) , page 501-504] simultaneously added palladium (Pd) and copper in pure silver to simultaneously improve the agglomeration of pure silver film and the lack of sulfur attack. However, whether it is a silver film prepared by adding gold, copper or aluminum to pure silver, or a silver film prepared by simultaneously adding palladium and copper in pure silver, neither the silver film nor the ITO film can be obtained. Adequate adhesion, and the reflectivity of these silver films is significantly lower than that of pure silver film.
此外，台灣專利公告第I319976號案提供一種以銀為主要成分，並至少包含錫、鋅、鉛、鉍、銦、鎵， 及前述其中之一組合的元素所構成的銀合金材料，係可承受300℃的高溫。但該案僅教示該等銀合金材料適用於閘極及閘極佈線，並未對適合濺鍍之銀合金靶材(尤其是銀-銦合金靶材)的特性進行探討。 In addition, Taiwan Patent Publication No. I319976 provides a main component of silver and contains at least tin, zinc, lead, antimony, indium and gallium. The silver alloy material composed of the elements combined with one of the foregoing can withstand a high temperature of 300 °C. However, the case only teaches that these silver alloy materials are suitable for gate and gate wiring, and the characteristics of silver alloy targets (especially silver-indium alloy targets) suitable for sputtering are not discussed.
另外，為使有機發光二極體顯示器之解析度能更為提升，有機發光二極體電極之銀合金薄膜的精細度需更為提高。台灣專利公告第I385263號案提供一種有機發光二極體元件之反射電極膜形成用銀銦合金靶材，該銀銦合金靶材之銦的含量為0.1至1.5質量百分比，且該銀銦合金靶材之晶粒平均粒徑為150微米(μm)至400微米。該銀銦合金靶材雖可用於製作OLED之電極，但其於濺鍍製程中容易發生電弧異常放電及噴濺之問題，致使所製得銀銦合金薄膜的精細度不足，難以具體改善OLED顯示器之解析度。 In addition, in order to improve the resolution of the organic light-emitting diode display, the fineness of the silver alloy film of the organic light-emitting diode electrode needs to be further improved. Taiwan Patent Publication No. I385263 provides a silver-indium alloy target for forming a reflective electrode film of an organic light-emitting diode element, the indium content of the silver-indium alloy target being 0.1 to 1.5% by mass, and the silver-indium alloy target The average grain size of the material is from 150 micrometers (μm) to 400 micrometers. Although the silver indium alloy target can be used for the electrode of the OLED, it is prone to arc abnormal discharge and splashing during the sputtering process, resulting in insufficient fineness of the obtained silver indium alloy film, and it is difficult to specifically improve the OLED display. Resolution.
因此，現有技術仍未見有一種適用於濺鍍製程的銀合金靶材，亦未見有一種銀合金靶材可經由濺鍍製程製得一同時具有良好耐熱性、良好抗硫化性、對氧化物之高附著性、高反射率及高精細度等符合高解析度有機發光二極體顯示器需求的銀合金薄膜。 Therefore, there is no silver alloy target suitable for the sputtering process in the prior art, and no silver alloy target can be obtained through a sputtering process while having good heat resistance, good sulfur resistance, and oxidation. A silver alloy film that meets the requirements of high-resolution organic light-emitting diode displays, such as high adhesion, high reflectivity, and high definition.
有鑒於上述現有技術之缺點，本發明之主要目的在於提供一種銀合金靶材，該銀合金靶材係適用於濺鍍製程，且可經由濺鍍製程製得能應用於高解析度有機發光二極體顯示器的有機發光二極體之電極的銀合金薄膜。 In view of the above disadvantages of the prior art, the main object of the present invention is to provide a silver alloy target which is suitable for a sputtering process and can be applied to a high-resolution organic light-emitting device through a sputtering process. A silver alloy film of an electrode of an organic light emitting diode of a polar body display.
為了可達到前述之發明目的，本發明所採取之 一技術手段係提供一種實質上由銀及銦所構成的銀合金靶材，以該銀合金靶材之總重量為基準，銦的含量為大於0.25重量百分比(wt%)且不大於5wt%，且該銀合金靶材的平均晶粒尺寸界於33μm至126μm之間。 In order to achieve the aforementioned object of the invention, the present invention A technical means is to provide a silver alloy target substantially composed of silver and indium, and the content of indium is more than 0.25 weight percent (wt%) and not more than 5 wt% based on the total weight of the silver alloy target. And the average grain size of the silver alloy target is between 33 μm and 126 μm.
本發明另提供一種製造前述之實質上由銀及銦所構成的銀合金靶之方法，其步驟包含：提供一實質上由銀及銦所構成的銀合金鑄錠；以2.5至3的鍛造比熱鍛造該銀合金鑄錠以製得一鍛造後的胚料；多道次冷軋延該鍛造後的胚料以製得一初胚，其中，多道次冷軋延之各道次冷軋延之軋延比介於15%至30%之間，且該鍛造後的胚料於相鄰兩道次冷軋延之軋延方向相差45°至90°；以及，再結晶處理該初胚，得到該實質上由銀及銦所構成的銀合金靶材。 The present invention further provides a method of fabricating the above-described silver alloy target consisting essentially of silver and indium, the steps comprising: providing a silver alloy ingot substantially composed of silver and indium; and a forging specific heat of 2.5 to 3 Forging the silver alloy ingot to obtain a forged billet; and multi-pass cold rolling the forged billet to prepare an initial embryo, wherein the multi-pass cold rolling is performed in each pass cold rolling The rolling ratio is between 15% and 30%, and the forged blank is in a rolling direction of 45° to 90° in the rolling direction of the adjacent two passes; and the initial embryo is recrystallized. A silver alloy target consisting essentially of silver and indium is obtained.
本發明更提供一種有機發光二極體，係包含有由前述之實質上由銀及銦所構成的銀合金靶經濺鍍形成的銀合金薄膜，且該銀合金薄膜係為陽極。 The present invention further provides an organic light-emitting diode comprising a silver alloy thin film formed by sputtering of a silver alloy target substantially composed of silver and indium, and the silver alloy thin film is an anode.
藉由令該實質上由銀及銦所構成的銀合金靶材之銦的含量為大於0.25重量百分比(wt%)且不大於5wt%，且其平均晶粒尺寸界於33μm至126μm之間，該實質上由銀及銦所構成的銀合金靶材係具有適用於濺鍍製程，且可經由濺鍍製程製得兼具有良好耐熱性、良好抗硫化性、對氧化物之高附著性、高反射率及高精細度之特性的銀合金薄膜之優點，且包含以該銀合金薄膜作為陽極的 有機發光二極體，係能符合高解析度有機發光二極體顯示器之需求，則能應用於高解析度有機發光二極體顯示器。 By making the content of indium of the silver alloy target substantially composed of silver and indium greater than 0.25 weight percent (wt%) and not more than 5 wt%, and the average grain size thereof is between 33 μm and 126 μm, The silver alloy target consisting essentially of silver and indium is suitable for a sputtering process, and can be obtained by a sputtering process and has good heat resistance, good sulfur resistance, high adhesion to oxides, The advantages of a silver alloy film having high reflectance and high definition characteristics, and including the silver alloy film as an anode The organic light-emitting diode can be applied to a high-resolution organic light-emitting diode display in accordance with the requirements of a high-resolution organic light-emitting diode display.
較佳的，該實質上由銀及銦所構成的銀合金靶材之濺鍍面的X光繞射圖譜具有下列之特性：(111)繞射峰的強度大於(100)繞射峰與(110)繞射峰之強度相加之總和。據此，大幅度提高該實質上由銀及銦所構成的銀合金靶材於濺鍍時之濺鍍速率。 Preferably, the X-ray diffraction pattern of the sputtered surface of the silver alloy target consisting essentially of silver and indium has the following characteristics: (111) the intensity of the diffraction peak is greater than (100) the diffraction peak and 110) The sum of the intensities of the diffracted peaks. As a result, the sputtering rate of the silver alloy target substantially composed of silver and indium at the time of sputtering is greatly improved.
所述「實質上由銀及銦所構成的銀合金靶材」係指該銀合金靶材係接近完全由銀及銦所構成。如同本案所述技術領域具有通常知識者可理解及接受的，該由銀及銦所構成的銀合金靶材於運送或製造過程中無可避免的接觸而含有難以或無法與銀或銦分離的微量成份，舉例來說，構成該實質上由銀及銦所構成的銀合金靶材之原料，無法避免的會含有難以或無法與銀或銦分離的微量成份，例如：氮、氧、碳或硫，如此使得該由銀及銦所構成的銀合金靶材係並非完全但接近完全為由銀及銦所構成的。 The "silver alloy target consisting essentially of silver and indium" means that the silver alloy target is nearly completely composed of silver and indium. As can be understood and accepted by those of ordinary skill in the art, the silver alloy target composed of silver and indium contains inevitable contact during transport or manufacturing and contains difficult or inseparable separation from silver or indium. A trace component, for example, a material constituting the silver alloy target substantially composed of silver and indium, inevitably contains a trace component which is difficult or impossible to separate from silver or indium, such as nitrogen, oxygen, carbon or Sulfur, such that the silver alloy target composed of silver and indium is not completely but nearly completely composed of silver and indium.
較佳的，以該實質上由銀及銦所構成的銀合金靶材之總量為基準，該實質上由銀及銦所構成的銀合金靶材含有不大於100ppm的氮、氧、碳或硫。更具體而言，前述實質上由銀及銦所構成的銀合金靶材係由銀、銦及微量成份所組成，該微量成份可為氮、氧、碳、硫及其組合，以該實質上由銀及銦所構成的銀合金靶材之總量為基準，該微量成份之含量不大於100ppm。 Preferably, the silver alloy target substantially composed of silver and indium contains not more than 100 ppm of nitrogen, oxygen, carbon or the like based on the total amount of the silver alloy target substantially composed of silver and indium. sulfur. More specifically, the silver alloy target substantially composed of silver and indium is composed of silver, indium and a trace component, and the trace component may be nitrogen, oxygen, carbon, sulfur and combinations thereof. The total amount of the silver alloy target composed of silver and indium is based on the total amount of the trace component of not more than 100 ppm.
為了可達到前述之發明目的，本發明所採取之另一技術手段係提供一種實質上由銀、銦、鈀及銅所構成 的銀合金靶材，以該實質上由銀、銦、鈀及銅所構成銀合金靶材之總重量為基準，銦的含量大於等於0.25wt%且小於等於5wt%、鈀的含量大於等於0.25wt%且小於等於3.5wt%、銅的含量大於等於0.25wt%且小於等於3.0wt%，且其平均晶粒尺寸界於33μm至126μm之間。 In order to achieve the aforementioned object of the invention, another technical means adopted by the present invention provides a substantially composed of silver, indium, palladium and copper. The silver alloy target is based on the total weight of the silver alloy target composed of silver, indium, palladium and copper, and the content of indium is 0.25 wt% or more and 5 wt% or less, and the palladium content is 0.25 or more. The wt% is 3.5 wt% or less, the content of copper is 0.25 wt% or more and 3.0 wt% or less, and the average grain size thereof is between 33 μm and 126 μm.
本發明另提供一種製造前述之實質上由銀、銦、鈀及銅所構成的銀合金靶之方法，其步驟包含：提供一實質上由銀、銦、鈀及銅所構成的銀合金鑄錠；以2.5至3的鍛造比熱鍛造該銀合金鑄錠以製得一鍛造後的胚料；多道次冷軋延該鍛造後的胚料以製得一初胚，其中，多道次冷軋延之各道次冷軋延之軋延比介於15%至30%之間，且該鍛造後的胚料於相鄰兩道次冷軋延之軋延方向相差45°至90°；以及，再結晶處理該初胚，得到該實質上由銀、銦、鈀及銅所構成的銀合金靶材。 The present invention further provides a method of fabricating the above-described silver alloy target consisting essentially of silver, indium, palladium, and copper, the method comprising: providing a silver alloy ingot substantially composed of silver, indium, palladium, and copper The forging preform is prepared by hot forging the silver alloy ingot with a forging ratio of 2.5 to 3; the forged blank is obtained by multi-pass cold rolling to obtain an initial embryo, wherein the multi-pass cold rolling is performed. The rolling ratio of the cold rolling of each pass is between 15% and 30%, and the forging blank has a difference of 45° to 90° in the rolling direction of the adjacent two passes; The primary embryo is recrystallized to obtain a silver alloy target substantially composed of silver, indium, palladium, and copper.
本發明更提供一種有機發光二極體，係包含有由前述之實質上由銀、銦、鈀及銅所構成的銀合金靶經濺鍍形成的銀合金薄膜，且該銀合金薄膜係為陽極。 The present invention further provides an organic light emitting diode comprising a silver alloy thin film formed by sputtering of a silver alloy target substantially composed of silver, indium, palladium and copper, and the silver alloy thin film is an anode .
藉由令該實質上由銀、銦、鈀及銅所構成的銀合金靶材之銦的含量大於等於0.25wt%並小於等於5wt%、鈀的含量大於等於0.25wt%且小於等於3.5wt%、銅的含量大於等於0.25wt%且小於等於3.0wt%；以及，平均晶粒尺寸為33μm至126μm；該由銀、銦、鈀及銅所構成的銀合金靶材係具有適用於濺鍍製程，且可經由濺鍍製 程製得兼具有良好耐熱性、優良的抗硫化性、對氧化物之高附著性、高反射率及高精細度之特性的銀合金薄膜之優點，且該銀合金薄膜係可作為有機發光二極體顯示器之有機發光二極體的陽極，使得有機發光二極體顯示器具有高解析度之特點。 The content of indium in the silver alloy target consisting essentially of silver, indium, palladium, and copper is 0.25 wt% or more and 5 wt% or less, and the content of palladium is 0.25 wt% or more and 3.5 wt% or less. The content of copper is 0.25 wt% or more and 3.0 wt% or less; and the average grain size is 33 μm to 126 μm; the silver alloy target composed of silver, indium, palladium and copper has a suitable sputtering process. And can be sputtered The advantages of a silver alloy film having good heat resistance, excellent sulfur resistance, high adhesion to oxides, high reflectivity and high definition are obtained, and the silver alloy film can be used as organic light. The anode of the organic light-emitting diode of the diode display makes the organic light-emitting diode display have high resolution characteristics.
較佳的，該實質上由銀、銦、鈀及銅所構成的銀合金靶材之濺鍍面的X光繞射圖譜具有下列之特性：(111)繞射峰的強度大於(100)繞射峰與(110)繞射峰之強度相加之總和。據此，大幅度提高該實質上由銀、銦、鈀及銅所構成的銀合金靶材於濺鍍時之濺鍍速率。 Preferably, the X-ray diffraction pattern of the sputtered surface of the silver alloy target consisting essentially of silver, indium, palladium and copper has the following characteristics: (111) the intensity of the diffraction peak is greater than (100) winding The sum of the peaks and the intensity of the (110) diffraction peaks. As a result, the sputtering rate of the silver alloy target substantially composed of silver, indium, palladium, and copper at the time of sputtering is greatly improved.
所述「實質上由銀、銦、鈀及銅所構成的銀合金靶材」係指該銀合金靶材接近完全由銀、銦、鈀及銅所構成。如同本案所述技術領域具有通常知識者可理解及接受的，該由銀、銦、鈀及銅所構成的銀合金靶材於運送或製造過程中無可避免的接觸而含有難以或無法與銀、銦、鈀或銅分離的微量成份，舉例來說，構成該實質上由銀、銦、鈀及銅所構成的銀合金靶材之原料，無法避免的會含有難以或無法與銀、銦、鈀或銅分離的微量成份，例如：氮、氧、碳或硫，如此使得該由銀、銦、鈀及銅所構成的銀合金靶材並非完全但接近完全只由銀、銦、鈀及銅所構成。較佳的，以該實質上由銀、銦、鈀及銅所構成的銀合金靶材之總量為基準，該實質上由銀、銦、鈀及銅所構成的銀合金靶材含有不大於100ppm的氮、氧、碳或硫。更具體而言，前述實質上由銀、銦、鈀及銅所構成的銀合金靶材係由銀、銦、鈀、銅及微量成份所組成，該微量成份 可為氮、氧、碳、硫及其組合，以該實質上由銀、銦、鈀及銅所構成的銀合金靶材之總量為基準，該微量成份之含量不大於100ppm。 The "silver alloy target consisting essentially of silver, indium, palladium, and copper" means that the silver alloy target is nearly completely composed of silver, indium, palladium, and copper. As can be understood and accepted by those of ordinary skill in the art, the silver alloy target consisting of silver, indium, palladium, and copper contains inevitable contact during shipping or manufacturing and is difficult or impossible to with silver. A trace component separated from indium, palladium or copper, for example, a raw material constituting the silver alloy target substantially composed of silver, indium, palladium and copper, which cannot be avoided or is incapable of being compatible with silver or indium. a trace component separated by palladium or copper, such as nitrogen, oxygen, carbon or sulfur, such that the silver alloy target composed of silver, indium, palladium and copper is not completely but nearly entirely composed of silver, indium, palladium and copper. Composition. Preferably, the silver alloy target substantially composed of silver, indium, palladium and copper is not more than the total amount of the silver alloy target substantially composed of silver, indium, palladium and copper. 100 ppm of nitrogen, oxygen, carbon or sulfur. More specifically, the silver alloy target substantially composed of silver, indium, palladium, and copper is composed of silver, indium, palladium, copper, and a trace component. Nitrogen, oxygen, carbon, sulfur, and combinations thereof may be based on the total amount of the silver alloy target consisting essentially of silver, indium, palladium, and copper, and the content of the minor component is not more than 100 ppm.
綜上所述，藉由控制銀合金靶材之組成，該銀合金靶材可經由濺鍍製得兼具有良好耐熱性、抗硫化性、附著力及高反射率等特性的銀合金薄膜；另，藉由控制銀合金靶材的平均晶粒尺寸界於33μm與126μm之間，濺鍍時靶材的異常放電次數顯著地被抑制，達到減少薄膜缺陷的目的，不僅符合實用性，亦能廣泛的應用於有機發光二極體的產業與領域，相當具有發展潛力。 In summary, by controlling the composition of the silver alloy target, the silver alloy target can be obtained by sputtering to obtain a silver alloy film having good heat resistance, sulfur resistance, adhesion and high reflectivity; In addition, by controlling the average grain size of the silver alloy target to be between 33 μm and 126 μm, the abnormal discharge frequency of the target during sputtering is remarkably suppressed, thereby achieving the purpose of reducing film defects, which is not only practical but also Widely used in the industry and field of organic light-emitting diodes, it has considerable development potential.
10、10A‧‧‧陰極 10, 10A‧‧‧ cathode
20‧‧‧發光層 20‧‧‧Lighting layer
30、30A‧‧‧陽極 30, 30A‧‧‧ anode
40‧‧‧玻璃基板 40‧‧‧ glass substrate
圖1為實施例3之銀合金靶材以光學顯微鏡放大150倍之金相圖。 1 is a metallographic diagram of a silver alloy target of Example 3 magnified 150 times by an optical microscope.
圖2為實施例3之銀合金靶材經濺鍍所製成的薄膜經耐熱性測試後之表面的掃描式電子顯微鏡影像圖。 2 is a scanning electron microscope image of the surface of the silver alloy target of Example 3 after the heat resistance test.
圖3為對照例1之銀合金靶材經濺鍍所製成的薄膜經耐熱性測試後之表面的掃描式電子顯微鏡影像圖。 Fig. 3 is a scanning electron microscope image showing the surface of the silver alloy target of Comparative Example 1 after the heat resistance test.
圖4A為現有技術之下發光型主動式有機發光二極體之結構示意圖。 4A is a schematic structural view of a light-emitting active organic light-emitting diode according to the prior art.
圖4B為現有技術之上發光型主動式有機發光二極體之結構示意圖。 4B is a schematic structural view of a prior art light-emitting active organic light-emitting diode.
以下，將藉由具體實施例說明本發明之實施方式，熟習此技藝者可經由本說明書之內容輕易地了解本發 明所能達成之優點與功效，並且於不悖離本發明之精神下進行各種修飾與變更，以施行或應用本發明之內容。 Hereinafter, the embodiments of the present invention will be described by way of specific embodiments, and those skilled in the art can easily understand the present disclosure through the contents of the present specification. The present invention can be implemented or applied without departing from the spirit and scope of the invention.
為驗證本發明之銀合金靶材之組成對於其經由濺鍍製程所製得的銀合金薄膜之耐熱性、抗硫化性、對氧化物之附著性及反射率影響，下列所列舉之實施例1至10及對照例1至5之銀合金靶材及其所製得的銀合金薄膜係大致上經由如相同之製程步驟所製得，其不同之處在於，前述實施例及對照例的銀合金靶材中各成分之種類及其含量以及金屬鍍層之成分及厚度，各實施例及對照例之具體製備方法如下所述。 In order to verify the influence of the composition of the silver alloy target of the present invention on the heat resistance, the sulphide resistance, the adhesion to oxides, and the reflectance of the silver alloy film obtained by the sputtering process, the following exemplified Example 1 The silver alloy target of 10 to Comparative Examples 1 to 5 and the silver alloy thin film obtained therefrom were obtained substantially by the same process steps as the silver alloy of the foregoing examples and comparative examples. The specific preparation method of each component and the content and the composition and thickness of the metal plating layer in the target are as follows.
<銀合金靶材之製備方法> <Preparation method of silver alloy target>
依據表1所示之比例，混合銀(Ag)、銦(In)、鈀(Pd)及銅(Cu)等原料得到一混合金屬料，將該混合金屬料置於真空感應熔煉爐中於1×10-2至1×10-4托(torr)之真空度下加熱至1100至1300℃，於持溫約半小時後進行熔煉，待該混合金屬料完全熔化為一金屬熔湯後，將該金屬熔湯倒入一模具中。待該金屬熔湯冷卻固化為一銀合金鑄錠後，自模具中取出該銀合金鑄錠。 According to the ratio shown in Table 1, a mixed metal material is obtained by mixing materials such as silver (Ag), indium (In), palladium (Pd) and copper (Cu), and the mixed metal material is placed in a vacuum induction melting furnace at 1 Heating to a temperature of 1100 to 1300 ° C under a vacuum of ×10 -2 to 1 × 10 -4 torr, and smelting after holding the temperature for about half an hour, after the mixed metal material is completely melted into a molten metal, The molten metal is poured into a mold. After the molten metal is cooled and solidified into a silver alloy ingot, the silver alloy ingot is taken out from the mold.
接著，令該銀合金鑄錠經溫度為650℃至900℃且時間為1小時至2小時之熱處理溫度以得到一胚料，再將該胚料進行熱鍛造(forging)製程，為使該胚料積累一定的塑性變形能量，該熱鍛造製程之鍛造比(鍛造前胚 料之高度/鍛造後胚料之高度)係控制介於2.5至3之間。 Next, the silver alloy ingot is subjected to a heat treatment temperature of 650 ° C to 900 ° C for a period of 1 hour to 2 hours to obtain a billet, and the billet is subjected to a hot forging process for making the embryo The material accumulates a certain amount of plastic deformation energy, the forging ratio of the hot forging process (forging pre-embryo The height of the material / the height of the blank after forging is controlled between 2.5 and 3.
之後，令鍛造後之胚料隨即進行多道次的冷軋延(cold rolling)以製得一初胚，各道次冷軋延的軋延比(各道次冷軋延軋延前後初胚之厚度差/各道次冷軋延軋延前初胚之厚度)控制介於15%至30%，且該鍛造後的胚料於相鄰兩道次冷軋延之軋延方向相差45°至90°。 After that, the forged billet is then subjected to multiple passes of cold rolling to obtain an initial embryo, and the rolling ratio of each pass cold rolling is determined (the initial embryo before and after each pass cold rolling) The thickness difference / the thickness of the pre-emission of the cold rolling and rolling mills in each pass is controlled to be between 15% and 30%, and the forged billet is 45° in the rolling direction of the adjacent two passes. To 90°.
最後，將該初胚送進熱處理爐，藉由溫度為500℃至600℃且時間為1小時之再結晶處理製得實施例1至8及對照例1至6之銀合金靶材，且各銀合金靶材之微觀組織之平均晶粒尺寸為33μm至126μm。其中，實施例3之銀合金靶材以光學顯微鏡放大150倍之金相圖示於圖1中。 Finally, the priming is sent to a heat treatment furnace, and the silver alloy targets of Examples 1 to 8 and Comparative Examples 1 to 6 are obtained by recrystallization treatment at a temperature of 500 ° C to 600 ° C for 1 hour, and each The microstructure of the silver alloy target has an average grain size of from 33 μm to 126 μm. Among them, the silver alloy target of Example 3 is magnified 150 times by an optical microscope.
<銀合金薄膜之製備方法> <Preparation method of silver alloy film>
將實施例1至10及對照例1至5之銀合金靶材置入一濺鍍腔體，該濺鍍腔體包含一直流電源供應器、一接地遮蔽物、一氣體入口、一真空泵以及一用於置放基板(substrate)之基座。進行濺鍍時，將靶材與該直流電源供應器之陰極電連接，並置入一基板於該基座上。之後，透過該氣體入口通入流量為標準條件下每分鐘20立方公分(即，20 standard cubic centimeter per minute，20sccm)之氬氣於該濺鍍腔體中，令該直流電源供應器供應200瓦特(Watt)之直流電功率並令該真空泵維持該濺鍍腔體內之真空度5毫托(mtorr)，以進行濺鍍並製得所需厚度的銀合金薄膜厚度。 The silver alloy targets of Examples 1 to 10 and Comparative Examples 1 to 5 were placed in a sputtering chamber, which includes a DC power supply, a grounding shield, a gas inlet, a vacuum pump, and a A pedestal for placing a substrate. When sputtering is performed, the target is electrically connected to the cathode of the DC power supply, and a substrate is placed on the base. Thereafter, an argon gas having a flow rate of 20 cubic centimeters per minute (20 sccm) per minute under standard conditions is introduced into the sputtering chamber through the gas inlet, so that the DC power supply is supplied with 200 watts. The direct current power of (Watt) is such that the vacuum pump maintains a vacuum of 5 mTorr in the sputtering chamber to perform sputtering and to obtain a thickness of the silver alloy film of a desired thickness.
表1實驗例1至10及對照例1至5之銀合金
將實施例1至10與對照例1至5之銀合金靶材經由前述之銀合金薄膜之製備方法分別製成厚度為240奈米(nm)之銀合金薄膜，再將各銀合金薄膜以150℃、250℃、350℃及450℃四種退火溫度進行退火處理10分鐘，最後以掃描式電子顯微鏡(Scanning Electron Microscope，SEM)觀察各銀合金薄膜經退火處理後之表面形態。 The silver alloy targets of Examples 1 to 10 and Comparative Examples 1 to 5 were each formed into a silver alloy film having a thickness of 240 nm by the preparation method of the above silver alloy film, and then each silver alloy film was 150. Annealing treatment was carried out for 10 minutes at four annealing temperatures of °C, 250°C, 350°C and 450°C. Finally, the surface morphology of each silver alloy film after annealing was observed by Scanning Electron Microscope (SEM).
其中，各銀合金薄膜經150℃、250℃及350℃ 之退火溫度的退火處理後，各銀合金薄膜之表面仍維持平整。而各銀合金薄膜經450℃之退火溫度的退火處理後，如表1及圖2所示，實施例3之銀合金靶材所製得的銀合金薄膜之表面係維持平整，實施例1、2及4至10及對照例2至5所製得的銀合金薄膜之表面亦維持平整，類似於圖2。而如表1及圖3所示，對照例1之銀合金靶材所製得的銀合金薄膜之表面出現島狀結構。顯示對照例1之銀合金靶材所製得的銀合金薄膜之耐熱性較其他實施例及對照例所製得的銀合金薄膜為差。 Among them, each silver alloy film is passed through 150 ° C, 250 ° C and 350 ° C After annealing at the annealing temperature, the surface of each silver alloy film remained flat. After annealing each of the silver alloy films at an annealing temperature of 450 ° C, as shown in Table 1 and FIG. 2, the surface of the silver alloy film prepared in the silver alloy target of Example 3 was maintained flat, Example 1. The surfaces of the silver alloy films prepared in 2 and 4 to 10 and Comparative Examples 2 to 5 were also kept flat, similar to Fig. 2. As shown in Table 1 and FIG. 3, the surface of the silver alloy film obtained by the silver alloy target of Comparative Example 1 had an island structure. The heat resistance of the silver alloy film obtained by showing the silver alloy target of Comparative Example 1 was inferior to that of the silver alloy films obtained in the other Examples and Comparative Examples.
具體而言，由實施例1至5及對照例1至3之銀合金靶材所製得的銀合金薄膜之耐熱性測試結果得知，當一由銀及銦所構成的銀合金靶材之銦的含量大於等於0.25wt%時，該由銀及銦所構成的銀合金靶材所製得的銀合金薄膜之表面可維持平整，具有良好的耐熱性。 Specifically, the heat resistance test results of the silver alloy thin films obtained from the silver alloy targets of Examples 1 to 5 and Comparative Examples 1 to 3 were found to be a silver alloy target composed of silver and indium. When the content of indium is 0.25 wt% or more, the surface of the silver alloy film obtained from the silver alloy target composed of silver and indium can be kept flat and has good heat resistance.
將實施例1至10與對照例1至5之銀合金靶材經由前述之銀合金薄膜之製備方法分別製成厚度為80nm之銀合金薄膜。接著，令一紫外光-可見光光譜儀(UV-Vis Spectrophotometer，係PerkinElmer公司所製，型號：Lambda 35)對各銀合金薄膜進行反射率的量測，設定該紫外光/可見光光譜儀之波長範圍為430nm至470nm。 The silver alloy targets of Examples 1 to 10 and Comparative Examples 1 to 5 were each formed into a silver alloy film having a thickness of 80 nm by the above-described method for preparing a silver alloy film. Next, a UV-Vis Spectrophotometer (manufactured by PerkinElmer, Model: Lambda 35) was used to measure the reflectance of each silver alloy film, and the wavelength range of the ultraviolet/visible spectrometer was set to 430 nm. To 470nm.
如表1所示，相較於其他銀合金薄膜之反射率均大於86%，由對照例2至4之銀合金靶材所製得的銀合金薄膜之反射率皆低於86%，顯示利用銦的含量超過5wt%之銀合金靶材所製得的銀合金薄膜無法獲得所需之反射 率，不適用有機發光二極體顯示器。。 As shown in Table 1, the reflectances of the silver alloy films prepared by the silver alloy targets of Comparative Examples 2 to 4 were all less than 86%, and the reflectances of the silver alloy films of Comparative Examples 2 to 4 were all less than 86%. A silver alloy film made of a silver alloy target having an indium content of more than 5% by weight cannot obtain a desired reflection Rate, not suitable for organic light-emitting diode displays. .
具體而言，由實施例1至5及對照例1至3之銀合金靶材所製得的銀合金薄膜之反射率得知，當一由銀及銦所構成的銀合金靶材之銦的含量小於等於5wt%時，該由銀及銦所構成的銀合金靶材所製得的銀合金薄膜之反射率可達係86%以上。而由實施例6至10及對照例4與5之銀合金靶材所製得的銀合金薄膜之反射率可得知，當一由銀、銦、鈀及銅所構成的銀合金靶材之銦的含量小於等於5wt%、鈀的含量小於等於3.5wt%、銅的含量小於等於3.5wt%時，該由銀、銦、鈀及銅所構成的銀合金靶材所製得的銀合金薄膜之反射率可達86%以上。 Specifically, the reflectance of the silver alloy thin film obtained from the silver alloy targets of Examples 1 to 5 and Comparative Examples 1 to 3 was found to be indium of a silver alloy target composed of silver and indium. When the content is 5% by weight or less, the silver alloy film obtained from the silver alloy target composed of silver and indium has a reflectance of 86% or more. The reflectance of the silver alloy thin film obtained from the silver alloy targets of Examples 6 to 10 and Comparative Examples 4 and 5 can be known as a silver alloy target composed of silver, indium, palladium and copper. a silver alloy film prepared from a silver alloy target composed of silver, indium, palladium and copper when the content of indium is 5% by weight or less, the content of palladium is 3.5% by weight or less, and the content of copper is 3.5% by weight or less. The reflectivity can reach more than 86%.
將實施例1至10與對照例1至5之銀合金靶材經由前述之銀合金薄膜之製備方法分別製成厚度為150nm之銀合金薄膜。接著，將各銀合金薄膜置於通有硫蒸氣的密閉腔體中，觀察各銀合金薄膜之表面與硫蒸氣反應而變黑的情形，並紀錄各銀合金薄膜之表面變黑所需的時間，結果示於表1中。 The silver alloy targets of Examples 1 to 10 and Comparative Examples 1 to 5 were each formed into a silver alloy film having a thickness of 150 nm by the above-described method for preparing a silver alloy film. Next, each silver alloy film is placed in a closed cavity through which sulfur vapor is passed, and the surface of each silver alloy film is observed to react with sulfur vapor to turn black, and the time required for the surface of each silver alloy film to blacken is recorded. The results are shown in Table 1.
由各銀合金薄膜之表面變黑所需的時間可知其抗硫化的程度，該時間越長表示抗硫化的能力越高。由表1的結果可知，相較於其他銀合金薄膜之表面變黑所需的時間均可達100秒以上，對照例1之銀合金靶材所製得的銀合金薄膜之表面變黑的時間係低於80秒，顯示其抗硫化的能力最差。 The degree of resistance to vulcanization is known from the time required for the surface of each silver alloy film to blacken, and the longer the time, the higher the ability to resist vulcanization. From the results of Table 1, it can be seen that the time required for the surface of the other silver alloy film to darken can be more than 100 seconds, and the surface of the silver alloy film obtained by the silver alloy target of Comparative Example 1 is blackened. It is less than 80 seconds and shows its ability to resist vulcanization is the worst.
具體而言，由實施例1至5及對照例1至3之 銀合金靶材所製得的銀合金薄膜之抗硫化性測試結果得知，當一由銀及銦所構成的銀合金靶材之銦的含量大於等於0.25wt%時，該由銀及銦所構成的銀合金靶材所製得的銀合金薄膜之表面變黑所需的時間可達100秒以上，則具有良好的抗硫化性質。而由實施例6至10及對照例4與5之銀合金靶材所製得的銀合金薄膜之耐熱性測試結果可知，當一由銀、銦、鈀及銅所構成的銀合金靶材之銦的含量大於等於2.5wt%且小於等於5wt%，鈀的含量大於等於0.25wt%且小於等於3.5wt%、銅的含量大於等於0.25wt%且小於等於3.5wt%時，該由銀、銦、鈀及銅所構成的銀合金靶材所製得的銀合金薄膜之表面變黑所需的時間可達100秒以上，係具有良好的抗硫化性質。 Specifically, from Examples 1 to 5 and Comparative Examples 1 to 3 The sulfur resistance test results of the silver alloy film prepared by the silver alloy target show that when the content of indium of a silver alloy target composed of silver and indium is 0.25 wt% or more, the silver and indium are used. The time required for the black alloy film obtained by the silver alloy target to be blackened to be black for more than 100 seconds has good resistance to vulcanization. The results of the heat resistance test of the silver alloy thin films prepared from the silver alloy targets of Examples 6 to 10 and Comparative Examples 4 and 5 show that when a silver alloy target composed of silver, indium, palladium and copper is used, When the content of indium is 2.5 wt% or more and 5 wt% or less, the content of palladium is 0.25 wt% or more and 3.5 wt% or less, and the content of copper is 0.25 wt% or more and 3.5 wt% or less, the silver and indium are used. The surface of the silver alloy film obtained by using the silver alloy target composed of palladium and copper requires blackening time of more than 100 seconds, and has good sulfur resistance.
為了評估附著性，係使用一鍍有150nm的氧化銦錫(ITO)層的玻璃板作為前述之銀合金薄膜之製備方法之基板，再將實施例1至10與對照例1至5之銀合金靶材經由前述之銀合金薄膜之製備方法分別濺鍍形成厚度為150nm之銀合金薄膜於該氧化銦錫層上製得一待測樣品。接著，將該待測樣品放置於濕度為85%且溫度為85℃之高溫高濕環境下96小時後，以膠帶進行剝離試驗(peeling test)。該剝離試驗係將膠帶貼附於各銀合金薄膜之表面上後再撕除該膠帶，並檢視各銀合金薄膜與該氧化銦錫層之間是否相分離，即發生剝離現象。若一待測樣品未發生剝離現象，則該待測樣品之銀合金薄膜與氧化銦錫層之間具有良好的附著力。結果示於表1中。其中，所使用的膠帶 係為3M公司販售之Scotch Transparent Film Tape 60。 In order to evaluate the adhesion, a glass plate plated with a 150 nm indium tin oxide (ITO) layer was used as a substrate for the preparation method of the aforementioned silver alloy film, and silver alloys of Examples 1 to 10 and Comparative Examples 1 to 5 were further used. The target material is respectively sputter-plated to form a silver alloy film having a thickness of 150 nm on the indium tin oxide layer by the preparation method of the silver alloy film described above to prepare a sample to be tested. Next, the sample to be tested was placed in a high-temperature and high-humidity environment having a humidity of 85% and a temperature of 85 ° C for 96 hours, and then subjected to a peeling test with a tape. In the peeling test, the tape was attached to the surface of each silver alloy film, and then the tape was peeled off, and the phase separation between the respective silver alloy films and the indium tin oxide layer was examined, that is, peeling occurred. If the sample to be tested does not peel off, the silver alloy film of the sample to be tested has good adhesion with the indium tin oxide layer. The results are shown in Table 1. Among them, the tape used It is a Scotch Transparent Film Tape 60 sold by 3M Company.
由表1的結果可知，除對照例1及5之銀合金靶材所製得的銀合金薄膜與氧化銦錫之間出現剝落現象外，其餘的銀合金薄膜與氧化銦錫層之間未發生剝離現象，顯示其餘的銀合金薄膜與氧化銦錫層之間具有良好的附著力。 It can be seen from the results of Table 1 that the silver alloy film prepared by the silver alloy target of Comparative Examples 1 and 5 has a peeling phenomenon between the silver alloy film and the indium tin oxide, and the remaining silver alloy film and the indium tin oxide layer do not occur. The peeling phenomenon shows good adhesion between the remaining silver alloy film and the indium tin oxide layer.
具體而言，由實施例1至5及對照例1至3之銀合金靶材所製得的銀合金薄膜之附著力測試結果得知，當一由銀及銦所構成的銀合金靶材之銦的含量大於等於0.25wt%時，該由銀及銦所構成的銀合金靶材所製得的銀合金薄膜與氧化銦錫層之間係能具有良好的附著力。而由實施例6至10及對照例4與5之銀合金靶材所製得的銀合金薄膜之附著力測試結果可知，當一由銀、銦、鈀及銅所構成的銀合金靶材之銦的含量大於等於2.5wt%且小於等於5wt%，鈀的含量大於等於0.25wt%且小於等於3.5wt%、銅的含量大於等於0.25wt%且小於等於3.5wt%時，該由銀、銦、鈀及銅所構成的銀合金靶材所製得的銀合金薄膜與氧化銦錫層之間係能具有良好的附著力。 Specifically, the adhesion test results of the silver alloy films prepared from the silver alloy targets of Examples 1 to 5 and Comparative Examples 1 to 3 were found to be a silver alloy target composed of silver and indium. When the content of indium is 0.25 wt% or more, the silver alloy film obtained from the silver alloy target composed of silver and indium can have good adhesion to the indium tin oxide layer. The adhesion test results of the silver alloy films prepared from the silver alloy targets of Examples 6 to 10 and Comparative Examples 4 and 5 show that when a silver alloy target composed of silver, indium, palladium and copper is used, When the content of indium is 2.5 wt% or more and 5 wt% or less, the content of palladium is 0.25 wt% or more and 3.5 wt% or less, and the content of copper is 0.25 wt% or more and 3.5 wt% or less, the silver and indium are used. The silver alloy film made of the silver alloy target composed of palladium and copper has good adhesion to the indium tin oxide layer.
由試驗例1至4可知，藉由令一由銀及銦所構成的銀合金靶材之銦的含量大於等於0.25wt%且小於等於5wt%，該由銀及銦所構成的銀合金靶材所製得之銀合金薄膜係可兼具有良好耐熱性、高反射率、良好抗硫化性及對氧化銦錫之高附著性等特性。同時，藉由令一由銀、銦、鈀及銅所構成的銀合金靶材之銦的含量大於等於0.25wt% 且小於等於5wt%，鈀的含量大於等於0.25wt%且小於等於3.5wt%，銅的含量大於等於0.25wt%且小於等於3.5wt%，該由銀、銦、鈀及銅所構成的銀合金靶材所製得的銀合金薄膜係可兼具有良好耐熱性、高反射率、良好抗硫化性及對氧化銦錫之高附著性等特性。 According to Test Examples 1 to 4, the silver alloy target composed of silver and indium is obtained by making the content of indium of a silver alloy target composed of silver and indium equal to or more than 0.25 wt% and less than or equal to 5 wt%. The obtained silver alloy thin film has characteristics such as good heat resistance, high reflectance, good sulfur resistance, and high adhesion to indium tin oxide. At the same time, the content of indium in a silver alloy target composed of silver, indium, palladium and copper is 0.25 wt% or more. And the content of palladium is 0.25 wt% or more and 3.5 wt% or less, the content of copper is 0.25 wt% or more and 3.5 wt% or less, and the silver alloy is composed of silver, indium, palladium and copper. The silver alloy thin film obtained by the target can have characteristics such as good heat resistance, high reflectance, good sulfur resistance, and high adhesion to indium tin oxide.
為進一步探究本發明之銀合金靶材之組成、平均晶粒、結晶方向及其於濺鍍時之電弧數之關係，並推及於上述實施例1至10及對照例1至5之銀合金靶材所製得銀合金薄膜之特性，下列所列舉之實施例11至20及對照例6至19之銀合金靶材係大致上經由如上述實施例1至10及對照例1至5之銀合金靶材相同之製程步驟所製得。 In order to further investigate the composition, average crystal grain, crystal orientation and the number of arcs at the time of sputtering of the silver alloy target of the present invention, the silver alloys of the above Examples 1 to 10 and Comparative Examples 1 to 5 were derived. The properties of the silver alloy film produced by the target, the silver alloy targets of Examples 11 to 20 and Comparative Examples 6 to 19 listed below were substantially via silver as in Examples 1 to 10 and Comparative Examples 1 to 5 described above. The alloy target is prepared by the same process steps.
實施例11至20及對照例6至19之銀合金靶材係令銀、銦、鈀及銅等原料依據表2所示之組成比例，大致上經由如上述實施例1至10及對照例1至5之銀合金靶材相同之製程步驟所製得，惟，實施例11至20及對照例6至19之銀合金靶材之微觀組織之平均晶粒尺寸為33μm至189μm。其中，實施例11至20及對照例6至19之銀合金靶材之微觀組織之平均晶粒尺寸之量測請參閱試驗例5。 The silver alloy targets of Examples 11 to 20 and Comparative Examples 6 to 19 were such that the raw materials of silver, indium, palladium, and copper were substantially in accordance with the composition ratios shown in Table 2, as in Examples 1 to 10 and Comparative Example 1 described above. The procedure for the same procedure as the silver alloy target of 5 was obtained, except that the microstructures of the silver alloy targets of Examples 11 to 20 and Comparative Examples 6 to 19 had an average grain size of 33 μm to 189 μm. The measurement of the average grain size of the microstructures of the silver alloy targets of Examples 11 to 20 and Comparative Examples 6 to 19 is shown in Test Example 5.
取實施例11至20與對照例6至19之銀合金靶材，均等地將各銀合金靶材之濺鍍面區分成縱3×橫3之9個部位，從各部位之中央部位進行採樣，以取得大小為 10mm×10mm的試片。試片經研磨及拋光後，以光學顯微鏡進行150倍率之金相觀察並取得金相圖。於金相圖中，以20mm間隔交叉狀畫出縱橫合計4條之60mm線段，計算各直線所切斷之晶粒數。線段端之晶粒以0.5個來計數。以L=60000/(M．N)之公式來求取平均切片長度L(單位為μm)。由求取之平均切片長度L，其中，M為實倍率，N為切斷晶粒數之平均值，以d=(3/2)．L來計算試片之顯微組織之平均粒徑d(μm)；計算所得結果示於表2中。 Taking the silver alloy targets of Examples 11 to 20 and Comparative Examples 6 to 19, the sputtered surfaces of the respective silver alloy targets were equally divided into 9 portions of 3 × 3 and 3, and samples were taken from the central portion of each portion. To get the size 10 mm × 10 mm test piece. After the test piece was ground and polished, the metallographic observation was performed at 150 times with an optical microscope and a metallographic diagram was obtained. In the metallographic diagram, four 60 mm line segments of a total of four vertical and horizontal lines are drawn at intervals of 20 mm, and the number of crystal grains cut by each straight line is calculated. The crystal grains at the end of the line segment are counted in 0.5. The average slice length L (in μm) was obtained by the formula of L=60000/(M.N). From the average slice length L obtained, where M is the real magnification and N is the average of the number of cut grains, with d = (3/2). L was used to calculate the average particle diameter d (μm) of the microstructure of the test piece; the calculated results are shown in Table 2.
將量測完晶粒尺寸的試片以X光繞射儀(X-Ray Diffraction，XRD)進行量測分析。X光繞射圖譜中，各結晶面所對應的繞射峰之強度會與試片表面晶粒的結晶方向有正相關，是以，若某個結晶面對應的繞射峰強度愈高，對立方晶結構(Cubic)的材料而言，表示有更多晶粒的此個結晶方向垂直於量測面。在本發明中，則就(111)繞射峰的強度與(100)及(110)兩個繞射峰的強度之加總進行比較；所得結果如表2所示。其中，(111)繞射峰的強度、(100)繞射峰的強度及(110)繞射峰的強度分別以I(111)、I(100)及I(110)表示。 The test piece in which the grain size was measured was measured by X-Ray Diffraction (XRD). In the X-ray diffraction spectrum, the intensity of the diffraction peak corresponding to each crystal plane is positively correlated with the crystal orientation of the crystal grains on the surface of the test piece, so that if the diffraction peak corresponding to a crystal surface is higher, the cube is In the case of a Cubic material, this crystal direction indicating that there are more crystal grains is perpendicular to the measurement surface. In the present invention, the intensity of the (111) diffraction peak is compared with the sum of the intensities of the two diffraction peaks (100) and (110); the results are shown in Table 2. Among them, the intensity of the (111) diffraction peak, the intensity of the (100) diffraction peak, and the intensity of the (110) diffraction peak are represented by I (111) , I (100), and I (110) , respectively.
取實施例11至20與對照例6至19之銀合金靶材分別裝設於磁控濺鍍機中進行濺鍍，並以美國萬機儀器公司(MKS instruments Inc.)所產製的DC電源(型號：RPDG-50)之電弧計數功能，從放電開始計測45分鐘之異常放電次數，即電弧數。結果如表2所示。其中，當一銀 合金靶材之異常放電次數越少，表示該銀合金靶材於濺鍍時越不易產生電弧異常放電及噴濺之問題，則該銀合金靶材係能經由濺鍍製得高精細度的銀合金薄膜。 The silver alloy targets of Examples 11 to 20 and Comparative Examples 6 to 19 were respectively mounted in a magnetron sputtering machine for sputtering, and were used as a DC power source manufactured by MKS Instruments Inc. (Model: RPDG-50) The arc counting function measures the number of abnormal discharges, that is, the number of arcs, for 45 minutes from the start of discharge. The results are shown in Table 2. Among them, when a silver The less the abnormal discharge frequency of the alloy target, the more difficult the arc alloy target is to cause arc abnormal discharge and splashing during sputtering, the silver alloy target can be made into high-definition silver by sputtering. Alloy film.
如表2所示，由實施例11至14及對照例6至 10之銀合金靶材之組成、平均晶粒尺寸及電弧數可知，藉由令一由銀及銦所構成的銀合金靶材，其銦的含量大於等於0.25wt%且小於等於5wt%；以及其平均晶粒尺寸為34μm至125μm，該由銀及銦所構成的銀合金靶材係可具有低於6的電弧數，則該由銀及銦所構成的銀合金靶材於濺鍍時不易產生電弧異常放電及噴濺之問題，故能經由濺鍍製得高精細度的銀合金薄膜。 As shown in Table 2, from Examples 11 to 14 and Comparative Example 6 The composition, the average grain size, and the number of arcs of the silver alloy target of 10, the silver alloy target composed of silver and indium has a content of indium of 0.25 wt% or more and 5 wt% or less; The average grain size is 34 μm to 125 μm, and the silver alloy target composed of silver and indium may have an arc number lower than 6, so that the silver alloy target composed of silver and indium is not easily sputtered. The problem of abnormal arc discharge and splashing occurs, so that a high-definition silver alloy film can be obtained by sputtering.
如表2所示，由實施例15至20及對照例11至19之銀合金靶材之組成、平均晶粒尺寸及電弧數可知，藉由令一由銀、銦、鈀及銅所構成的銀合金靶材，其銦的含量大於等於0.25wt%且小於等於5wt%，其鈀的含量大於等於0.25wt%小於等於3.5wt%，其銅的含量大於等於0.25wt%且小於等於3.0wt%；以及其平均晶粒尺寸為33μm至126μm，該由銀、銦、鈀及銅所構成的銀合金靶材係可具有低於6的電弧數，則該由銀、銦、鈀及銅所構成的銀合金靶材於濺鍍時不易產生電弧異常放電及噴濺之問題，故能經由濺鍍製得高精細度的銀合金薄膜。 As shown in Table 2, the composition, average grain size, and number of arcs of the silver alloy targets of Examples 15 to 20 and Comparative Examples 11 to 19 are known to be composed of silver, indium, palladium, and copper. a silver alloy target having a content of indium of 0.25 wt% or more and 5 wt% or less, a palladium content of 0.25 wt% or more and 3.5 wt% or less, and a copper content of 0.25 wt% or more and 3.0 wt% or less. And an average grain size of 33 μm to 126 μm, the silver alloy target composed of silver, indium, palladium and copper may have an arc number lower than 6, and the silver alloy consists of silver, indium, palladium and copper. The silver alloy target is less prone to arc abnormal discharge and splashing during sputtering, so that a high-definition silver alloy film can be obtained by sputtering.
其中，如表1及表2所示，實施例9之銀合金靶材之組成與對照例12及13相同，且如前所述，實施例9之銀合金靶材之平均晶粒尺寸係介於33μm至126μm之間，係與對照例12及13相當，則實施例9之銀合金靶材與對照例12及13之銀合金鈀材係屬等效之範例，由實施例9之銀合金靶材於試驗例1至4之測試結果及對照例12與13於試驗例7之測試結果可推知，縱然實施例9及對照例12與13之銀合金靶材可經由濺鍍製程製得兼具有良好 耐熱性、優良的抗硫化性、對氧化物之高附著性及高反射率的銀合金薄膜，但於濺鍍時電弧數係超過6，則於濺鍍時易產生電弧異常放電及噴濺之問題，導致實施例9及對照例12與13之銀合金靶材製得的銀合金薄膜之精細度不足。 As shown in Tables 1 and 2, the composition of the silver alloy target of Example 9 was the same as that of Comparative Examples 12 and 13, and as described above, the average grain size of the silver alloy target of Example 9 was introduced. Between 33 μm and 126 μm, which is equivalent to Comparative Examples 12 and 13, the silver alloy target of Example 9 and the silver alloy palladium of Comparative Examples 12 and 13 are equivalent, and the silver alloy of Example 9 is used. The results of the test results of Test Examples 1 to 4 and the test results of Comparative Examples 12 and 13 in Test Example 7 can be inferred, even though the silver alloy targets of Example 9 and Comparative Examples 12 and 13 can be produced by a sputtering process. Good A silver alloy film with excellent heat resistance, excellent sulfur resistance, high adhesion to oxides, and high reflectance. However, when the number of arcs exceeds 6 during sputtering, abnormal arc discharge and splashing are likely to occur during sputtering. The problem was that the fineness of the silver alloy film produced in the silver alloy target of Example 9 and Comparative Examples 12 and 13 was insufficient.
此外，請參閱表2所示，相較於對照例6而言，實施例11、12之銀合金靶材係具有較小的平均晶粒尺寸，因此，相較於對照例6之銀合金靶材經濺鍍製得的銀合金薄膜而言，實施例11、12之銀合金靶材經濺鍍製得的銀合金薄膜係具有較佳的厚度及成份均勻性。同理，經比較實施例13、14與對照例7、實施例15、16與對照例11、實施例17、18與對照例18及實施例19、20與對照例19後可得知，實施例11至20銀合金靶材係能經濺鍍製得具有良好的厚度及成份均勻性的銀合金薄膜。 Further, referring to Table 2, the silver alloy targets of Examples 11 and 12 have a smaller average grain size than Comparative Example 6, and therefore, compared with the silver alloy target of Comparative Example 6 For the silver alloy thin film obtained by sputtering, the silver alloy thin film obtained by sputtering of the silver alloy target of Examples 11 and 12 has a preferable thickness and composition uniformity. Similarly, after comparing Examples 13 and 14 with Comparative Example 7, Examples 15, 16 and Comparative Example 11, Examples 17, 18 and Comparative Example 18, and Examples 19 and 20 and Comparative Example 19, it was confirmed that the implementation was carried out. The silver alloy targets of Examples 11 to 20 can be sputtered to obtain a silver alloy film having good thickness and composition uniformity.
另外，請參閱表2所示，經晶粒結晶方向量測後得知，實施例11至20之銀合金靶材的I(111)/[I(100)+I(110)]之值均大於1；即，(111)繞射峰的強度大於(100)繞射峰與(110)繞射峰之強度相加之總和；顯示實施例10至17之銀合金靶材之優選結晶方向為<111>。由於純銀之最密堆積方向為<111>，使得實施例11至20之銀合金靶材於濺鍍時，其構成原子會有更多機會被氣體離子撞擊，故實施例11至20之銀合金靶材係具有高濺鍍速率之優點。 In addition, as shown in Table 2, it was found from the grain crystal orientation that the values of I (111) / [I (100) + I (110) ] of the silver alloy targets of Examples 11 to 20 were More than 1; that is, the intensity of the (111) diffraction peak is greater than the sum of the (100) diffraction peak and the (110) diffraction peak; the preferred crystal orientation of the silver alloy target of Examples 10 to 17 is <111>. Since the closest packing direction of pure silver is <111>, the silver alloy targets of Examples 11 to 20 have more chances of being impinged by gas ions when they are sputtered, so the silver alloys of Examples 11 to 20 The target has the advantage of a high sputtering rate.
由第一部份之小結及第二部份之小結可知，本發明藉由令一由銀及銦所構成的銀合金靶材之銦的含量大 於等於0.25wt%並小於等於5wt%，且其平均晶粒尺寸為34μm至125μm；以及，令一由銀、銦、鈀及銅所構成的銀合金靶材之銦的含量大於等於0.25wt%且小於等於5wt%、鈀的含量大於等於0.25wt%且小於等於3.5wt%、銅的含量大於等於0.25wt%且小於等於3.0wt%，且其平均晶粒尺寸為33μm至126μm。該由銀及銦所構成的銀合金靶材及該銀、銦、鈀及銅所構成的銀合金靶材，兩者皆適用於濺鍍製程，且可經由濺鍍製程製得兼具有良好耐熱性、良好抗硫化性、對氧化物之高附著性、高反射率及高精細度之特性而能應用於符合高解析度有機發光二極體顯示器需求的有機發光二極體之電極的銀合金薄膜。 It can be seen from the summary of the first part and the summary of the second part that the present invention has a large content of indium by a silver alloy target composed of silver and indium. And equal to 0.25 wt% and less than or equal to 5 wt%, and an average crystal grain size of 34 μm to 125 μm; and, a silver alloy target composed of silver, indium, palladium, and copper has an indium content of 0.25 wt% or more And less than or equal to 5 wt%, palladium content of 0.25 wt% or more and 3.5 wt% or less, copper content of 0.25 wt% or more and 3.0 wt% or less, and an average crystal grain size of 33 μm to 126 μm. The silver alloy target composed of silver and indium and the silver alloy target composed of silver, indium, palladium and copper are both suitable for the sputtering process and can be prepared by the sputtering process. Silver, which is suitable for high-resolution organic light-emitting diode displays, can be applied to the electrodes of organic light-emitting diodes that meet the requirements of high-resolution organic light-emitting diode displays due to their high heat resistance, good resistance to vulcanization, high adhesion to oxides, high reflectivity and high definition. Alloy film.
簡言之，本發明藉由將預定比例之銦、或者銦、鈀與銅添加於銀中所製得的銀合金靶材，其不僅可製得具有良好耐熱性、抗硫化性、附著力等特性的銀合金薄膜，並可令該銀合金薄膜仍具有高反射率；另，藉由控制濺鍍靶材的平均晶粒尺寸介於33μm與126μm之間，如此可抑制濺鍍時靶材的異常放電次數，達到減少薄膜缺陷的目的，不僅符合實用性，亦能廣泛的應用於有機發光二極體的產業與領域，相當具有發展潛力，則確實能達成本發明之目的。 In short, the present invention can obtain not only good heat resistance, sulfur resistance, adhesion, etc., but also a silver alloy target obtained by adding a predetermined ratio of indium, or indium, palladium, and copper to silver. The characteristic silver alloy film can make the silver alloy film still have high reflectivity; and by controlling the average grain size of the sputtering target between 33 μm and 126 μm, the target of the target during sputtering can be suppressed The number of abnormal discharges can achieve the purpose of reducing film defects, which not only conforms to practicality, but also can be widely applied to the industry and field of organic light-emitting diodes, and has considerable development potential, and can indeed achieve the object of the present invention.
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| CN106560458A (en) * | 2016-10-24 | 2017-04-12 | 浙江大明玻璃有限公司 | Production process for thinned touch screen glass |
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| CN106560458A (en) * | 2016-10-24 | 2017-04-12 | 浙江大明玻璃有限公司 | Production process for thinned touch screen glass |
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