TWI833002B - Morphology control in synthesis of metal nanostructures - Google Patents
Morphology control in synthesis of metal nanostructures Download PDFInfo
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- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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Abstract
Description
本發明係關於金屬奈米結構之合成以及由該金屬奈米結構所製備的透明導電。 The present invention relates to the synthesis of metal nanostructures and transparent conductors prepared from the metal nanostructures.
透明導電包含光學透明且導電的膜。目前銀奈米線(AgNW)的重要應用之一係用於形成電子裝置的透明導電(TC)層,電子裝置係例如觸控面板、光伏打電池、平面液晶顯示器(LCD)、有機發光二極體(OLED)等。各種技術已基於一或多個如導電奈米結構之導電媒介製備透明導電。一般而言,導電奈米結構形成具有長程互連性的滲透網絡(percolating network)。 Transparent conductive includes optically clear and electrically conductive films. One of the important applications of silver nanowires (AgNW) is currently used to form transparent conductive (TC) layers in electronic devices such as touch panels, photovoltaic cells, flat liquid crystal displays (LCDs), and organic light-emitting diodes. body (OLED), etc. Various techniques have been developed to produce transparent conductors based on one or more conductive media such as conductive nanostructures. Generally speaking, conductive nanostructures form percolating networks with long-range interconnectivity.
隨著使用透明導電的應用數目持續增加,需要改善的製備方法以滿足導電奈米結構的需求。TC層的電性質及光學性質強烈取決於形成滲透網絡的導電奈米線的實體尺寸。傳統製備方法對於導電奈米線的性質(例如長度、直徑、及長寬比(aspect ratio))並無法提供充足的控制。 As the number of applications using transparent conductivity continues to increase, improved preparation methods are needed to meet the demands of conductive nanostructures. The electrical and optical properties of the TC layer strongly depend on the physical size of the conductive nanowires forming the permeable network. Traditional fabrication methods do not provide sufficient control over the properties of conductive nanowires (such as length, diameter, and aspect ratio).
根據一方案,本發明提供一種金屬奈米結構之合成中的控制形態的方法。該方法包含提供第一階段反應混合物,其中該第一階段反應 混合物包含多元醇溶劑、包覆劑(capping agent)、及鹵鹽(halide salt)。該方法包含將該第一階段反應混合物加熱至反應溫度。該方法包含添加第二階段反應混合物至經加熱的該第一階段反應混合物以提供合併的混合物,其中該第二階段反應混合物包含溶解於多元醇溶劑中的金屬鹽。該方法包含使該合併的混合物中的反應進行一段總反應時間。該第二階段反應混合物係在小於該總反應時間之10%的時距內添加至該第一階段反應混合物。 According to one aspect, the present invention provides a method for controlling morphology in the synthesis of metal nanostructures. The method includes providing a first stage reaction mixture, wherein the first stage reaction The mixture includes a polyol solvent, a capping agent, and a halide salt. The method includes heating the first stage reaction mixture to reaction temperature. The method includes adding a second stage reaction mixture to the heated first stage reaction mixture to provide a combined mixture, wherein the second stage reaction mixture includes a metal salt dissolved in a polyol solvent. The method includes allowing the reaction in the combined mixture to proceed for a total reaction time. The second stage reaction mixture is added to the first stage reaction mixture in a time interval of less than 10% of the total reaction time.
以上概述呈現簡要摘述以提供對於本文所述之系統及/或方法之一些方案的基本理解。此概述並非本文所述之系統及/或方法的廣泛說明。其並非旨在指出關鍵/重要元件或勾劃此系統及/或方法的範圍。其唯一目的係在於以簡化形式呈現一些概念以作為下文呈現之更詳細說明的前言。 The above summary presents a brief summary to provide a basic understanding of some aspects of the systems and/or methods described herein. This summary is not an extensive description of the systems and/or methods described herein. It is not intended to identify key/critical elements or to delineate the scope of the system and/or method. Its sole purpose is to present some concepts in a simplified form as a prelude to the more detailed description that is presented below.
100:方法 100:Method
102、104、106、108:步驟 102, 104, 106, 108: Steps
儘管本文呈現的技術可以各種替代形式實施,圖式中描繪的特定實施態樣僅為補充本文所提供之說明的幾個實例。該等實施態樣不應被理解為限制性的,例如限制所附申請專利範圍。 Although the technology presented herein may be implemented in various alternative forms, the specific implementation aspects depicted in the drawings are but a few examples that supplement the description provided herein. These embodiments should not be construed as limiting, such as limiting the patent scope of the appended applications.
所揭露之標的可採取特定部件及部件之安排的實體形式,其實施態樣將詳細描述於本說明書以及描繪於構成說明書之一部分的所附圖式中,其中: The subject matter disclosed may take physical form in the form of specific components and arrangements of components, implementations of which are described in detail in this specification and illustrated in the accompanying drawings forming a part of this specification, in which:
第1圖呈現根據本發明之方法的一個實例。 Figure 1 presents an example of a method according to the invention.
第2A圖為根據實施例1中所概述之細節製備的先前技術的銀奈米線網絡,於60,000放大倍率下的SEM影像。 Figure 2A is an SEM image at 60,000 magnification of a prior art silver nanowire network prepared according to the details outlined in Example 1.
第2B圖為根據實施例2中所概述之細節製備的先前技術的銀奈米線網絡,於60,000放大倍率下的SEM影像。 Figure 2B is an SEM image at 60,000 magnification of a prior art silver nanowire network prepared according to the details outlined in Example 2.
第2C圖為根據本發明且於實施例3概述之所製備的銀奈米線網絡,於60,000放大倍率下的SEM影像。 Figure 2C is an SEM image at 60,000 magnification of the silver nanowire network prepared according to the present invention and summarized in Example 3.
第2D圖為根據本發明且於實施例4概述之所製備的銀奈米線網絡,於60,000放大倍率下的SEM影像。 Figure 2D is an SEM image at 60,000 magnification of the silver nanowire network prepared according to the present invention and summarized in Example 4.
第2E圖為根據本發明且於實施例5概述之所製備的銀奈米線網絡,於60,000放大倍率下的SEM影像。 Figure 2E is an SEM image at 60,000 magnification of the silver nanowire network prepared according to the present invention and summarized in Example 5.
第3圖為實施例1及2(先前技術)及本發明方法實施例3至5所各自形成的滲透奈米線網絡中,奈米線寬度/直徑之出現頻率的圖。 Figure 3 is a graph showing the occurrence frequency of nanowire width/diameter in the permeable nanowire network formed in Embodiments 1 and 2 (prior art) and Embodiments 3 to 5 of the method of the present invention.
第4圖為實施例1及2(先前技術)及本發明方法實施例3至5所形成的滲透奈米線網絡,其奈米線的長度分布圖。 Figure 4 shows the length distribution diagram of the nanowires in the permeable nanowire network formed in Embodiments 1 and 2 (prior art) and Embodiments 3 to 5 of the method of the present invention.
以下將參照所附圖式更完整地描述本發明標的,圖式構成說明書之一部分且說明性地顯示特定例示實施態樣。本說明書並不旨在作為已知概念之廣泛或詳細的探討。相關領域中具通常知識者普遍已知的細節可能被省略,或以摘述的方式來處理。 The subject matter of the present invention will be described more fully hereinafter with reference to the accompanying drawings, which constitute a part of this specification and which illustratively show certain exemplary embodiments. This description is not intended to be an extensive or detailed exploration of known concepts. Details generally known to those of ordinary skill in the relevant art may be omitted or treated in a summarized manner.
本文中的特定用語僅係基於方便而使用,且不應被視為所揭露之標的之限制。本文所用之相關文字最佳係參照圖式來理解,其中類似 之元件符號係用於指出類似或相似的項目。另外,在圖式中,特定特徵可能以稍微概略的形式示出。 The specific terms used herein are used for convenience only and should not be construed as limitations of the subject matter disclosed. The relevant text used in this article is best understood with reference to diagrams, which are similar to The component symbol is used to indicate similar or similar items. Additionally, in the drawings, certain features may be shown in somewhat schematic form.
以下標的可以各種不同形式實施,例如方法、裝置、元件、及/或系統。因此,此標的並不旨在建構為受限於本文所列作為實例的任何說明性實施態樣。而是,本文中提供實施態樣僅為說明性的。這些實施態樣可例如有硬體、軟體、韌體、或其任何組合之形式。 The following subject matter may be implemented in various forms, such as methods, apparatus, components, and/or systems. Accordingly, this subject matter is not intended to be construed as limited to any illustrative implementations set forth herein as examples. Rather, implementation aspects are provided herein for illustrative purposes only. These implementations may, for example, be in the form of hardware, software, firmware, or any combination thereof.
本文提供一種金屬奈米結構之合成中的控制形態的方法。該方法包含提供第一階段反應混合物,其中該第一階段反應混合物包含多元醇溶劑、包覆劑、及鹵鹽。該方法包含將該第一階段反應混合物加熱至反應溫度。該方法包含添加第二階段反應混合物至經加熱的該第一階段反應混合物以提供合併的混合物,其中該第二階段反應混合物包含溶解於多元醇溶劑中的金屬鹽。該方法包含使該合併的混合物中的反應進行一段總反應時間。該第二階段反應混合物係在小於該總反應時間之10%的時距內添加至該第一階段反應混合物。 This article provides a method for controlling morphology in the synthesis of metal nanostructures. The method includes providing a first-stage reaction mixture, wherein the first-stage reaction mixture includes a polyol solvent, a coating agent, and a halide salt. The method includes heating the first stage reaction mixture to reaction temperature. The method includes adding a second stage reaction mixture to the heated first stage reaction mixture to provide a combined mixture, wherein the second stage reaction mixture includes a metal salt dissolved in a polyol solvent. The method includes allowing the reaction in the combined mixture to proceed for a total reaction time. The second stage reaction mixture is added to the first stage reaction mixture in a time interval of less than 10% of the total reaction time.
此種奈米結構可為導電性且用於在裝置中形成奈米結構的滲透導電網絡。如本文所用,「導電奈米結構」或「奈米結構」一般係指導電性奈米尺寸結構,例如其至少一維度係小於500奈米、或小於250奈米、100奈米、50奈米、或25奈米。一般而言,奈米結構係由金屬材料製成,金屬材料係例如元素金屬(如過渡金屬)或金屬化合物(如金屬氧化物)。金屬材料亦可為雙金屬材料或金屬合金,其包含二或更多種類的金屬。合適的金屬包括但不限於銀、金、銅、鎳、鍍金的銀、鉑、及鈀。 Such nanostructures can be electrically conductive and used to form a permeable conductive network of nanostructures in a device. As used herein, "conductive nanostructure" or "nanostructure" generally refers to conductive nanometer-sized structures, such as at least one dimension smaller than 500 nanometers, or smaller than 250 nanometers, 100 nanometers, 50 nanometers , or 25nm. Generally speaking, nanostructures are made of metallic materials, such as elemental metals (such as transition metals) or metal compounds (such as metal oxides). The metallic material can also be a bimetallic material or a metal alloy, which contains two or more types of metals. Suitable metals include, but are not limited to, silver, gold, copper, nickel, gold plated silver, platinum, and palladium.
奈米結構可為任何形狀或幾何形式。給定之奈米結構的形態可以簡化的方式藉由其長寬比來界定,其中長寬比為奈米結構之長度相對於直徑的比。例如,某些奈米結構為等向性地成形(即,長寬比=1)。典型的等向性奈米結構包括奈米粒子。在較佳實施態樣中,奈米結構為異向性地成形(即,長寬比≠1)。異向性奈米結構通常沿其長度具有縱向軸。例示性異向性奈米結構包括奈米線、奈米棒(nanorod)、及奈米管,如本文所定義。 Nanostructures can be of any shape or geometry. The morphology of a given nanostructure can be defined in a simplified manner by its aspect ratio, which is the ratio of the nanostructure's length to its diameter. For example, some nanostructures are isotropically shaped (ie, aspect ratio = 1). Typical isotropic nanostructures include nanoparticles. In a preferred embodiment, the nanostructures are anisotropically shaped (ie, aspect ratio ≠ 1). Anisotropic nanostructures typically have a longitudinal axis along their length. Exemplary anisotropic nanostructures include nanowires, nanorods, and nanotubes, as defined herein.
奈米結構可為實心或中空。實心奈米結構包括例如奈米粒子、奈米棒、及奈米線(「NW」)。NW通常係指長且薄的奈米結構,其具有長寬比為大於10、較佳大於50、更佳大於100、且最佳大於200。一般而言,奈米線的長度係大於500奈米、大於1微米、大於5微米、或大於10微米。在一實例中,NW係介於5微米至10微米範圍內。「奈米棒」通常為短且寬的異向性奈米結構,其具有長寬比為不大於10、不大於50、不大於100,或不大於200。雖然本發明可應用於製備任何種類的奈米結構,但為了簡潔起見,將描述銀奈米線(「AgNW」或簡稱為「NW」)之合成以作為實例。然而,應理解本發明並不限於此,且本發明涵蓋各種奈米結構、金屬等。 Nanostructures can be solid or hollow. Solid nanostructures include, for example, nanoparticles, nanorods, and nanowires ("NWs"). NW generally refers to long and thin nanostructures with an aspect ratio greater than 10, preferably greater than 50, more preferably greater than 100, and most preferably greater than 200. Generally speaking, the length of the nanowire is greater than 500 nanometers, greater than 1 micrometer, greater than 5 micrometers, or greater than 10 micrometers. In one example, the NW is in the range of 5 microns to 10 microns. "Nanorods" are generally short and wide anisotropic nanostructures with an aspect ratio of no greater than 10, no greater than 50, no greater than 100, or no greater than 200. Although the present invention can be applied to prepare any kind of nanostructure, for the sake of simplicity, the synthesis of silver nanowires ("AgNW" or simply "NW") will be described as an example. However, it should be understood that the present invention is not limited thereto, and the present invention covers various nanostructures, metals, etc.
TC層的電性質及光學性質係強烈取決於NW的實體尺寸,即,其長度及直徑,且更概括而言,其長寬比。具有較大長寬比的NW形成更有效的導電網絡,其藉由允許較低的線密度來對於給定之膜電阻率達成較高的透明度。由於每個NW可被視為一導電,各自NW長度及直徑將會 影響整體NW網絡的導電性,且因此影響最終膜的導電性。例如,隨著奈米線變得更長,形成導電網絡所需的奈米線更少;且隨著NW變得更薄,NW的電阻率增加,此使得所形成的膜對於給定數目的NW而言更不導電。 The electrical and optical properties of the TC layer are strongly dependent on the physical dimensions of the NW, that is, its length and diameter, and more generally, its aspect ratio. NWs with larger aspect ratios form more efficient conductive networks, which achieve higher transparency for a given film resistivity by allowing lower line density. Since each NW can be considered as a conductor, the respective NW length and diameter will Affects the conductivity of the overall NW network, and therefore the conductivity of the final film. For example, as nanowires become longer, fewer nanowires are needed to form a conductive network; and as NWs become thinner, the resistivity of the NWs increases, which makes the resulting film resistant to a given number of NW is less conductive.
類似地,NW長度及直徑將會影響TC層的光學透明性及光散射(霧度)。由於奈米線僅佔膜非常少部分,NW網絡為光學透明的。然而,奈米線會吸收及散射光,因此NW長度及直徑將會很大部分地決定導電NW網絡的光學透明性及霧度。一般而言,較薄的NW能夠增加透射及降低TC層中的霧度,這些對於電子應用是理想的性質。 Similarly, NW length and diameter will affect the optical transparency and light scattering (haze) of the TC layer. Since the nanowires occupy only a very small portion of the film, the NW network is optically transparent. However, nanowires absorb and scatter light, so the NW length and diameter will largely determine the optical transparency and haze of the conductive NW network. In general, thinner NWs can increase transmission and reduce haze in the TC layer, which are desirable properties for electronic applications.
另外,TC層中的低長寬比的奈米結構(合成製程中的副產物)會造成增加的霧度,因為這些結構會散射光而對網絡的導電性無貢獻。由於製備金屬奈米結構的合成方法通常會製造出包含多種奈米結構形態(理想及不理想)的組合物,因此需要純化此種組合物以提升高長寬比奈米結構的保留。 In addition, low aspect ratio nanostructures in the TC layer (a by-product of the synthesis process) can cause increased haze because these structures scatter light without contributing to the conductivity of the network. Since synthetic methods for preparing metal nanostructures often produce compositions containing multiple nanostructure morphologies (ideal and non-ideal), such compositions need to be purified to enhance the retention of high aspect ratio nanostructures.
然而,NW可被以越來越小的直徑(例如數十奈米之範圍)合成,且這些較小直徑緊密地與不欲的副產物(如低長寬比奈米結構)之尺寸相符。由於NW與副產物之間之尺寸、組成、及結構的相似性,純化高長寬比NW以用於高品質TC膜是很困難的。合成具有均勻長度及寬度分布的NW有助於純化此種高長寬比奈米結構的能力,因為此種均勻的群體表現最相似,且能允許相較於低長寬比副產物地對高長寬比NW最具選擇性的純化條件。因此,理想的是發展製備具有均勻長度及寬度分布的高長 寬比NW的方法,及/或相較於其他低長寬比奈米結構有利於NW形成的方法。 However, NWs can be synthesized at increasingly smaller diameters (e.g., in the tens of nanometer range), and these smaller diameters closely match the size of undesirable byproducts (e.g., low aspect ratio nanostructures). Due to the similarity in size, composition, and structure between NWs and by-products, it is difficult to purify high aspect ratio NWs for use in high-quality TC membranes. Synthesizing NWs with uniform length and width distributions facilitates the ability to purify such high aspect ratio nanostructures, as such uniform populations behave most similarly and allow optimal processing of high aspect ratio NWs compared to low aspect ratio by-products. Selective purification conditions. Therefore, it would be ideal to develop high-length fabrics with uniform length and width distribution. The method of NW with aspect ratio, and/or the method that is more beneficial to the formation of NW compared with other low aspect ratio nanostructures.
一旦純化,所保留之高長寬比NW可用於形成具有所欲電性質及光學性質的TC。 Once purified, the retained high aspect ratio NWs can be used to form TCs with desired electrical and optical properties.
因此,有利的是發展製備相較於目前技術水準較佳之較薄或較長、或更佳之較薄且較長的NW之受控制的合成方法。還較佳的是,這些合成方法製備出具有均勻長度及寬度分布的NW。最終,較佳的是發展相較於其他低長寬比奈米結構更有利於製備NW的合成方法。 Therefore, it would be advantageous to develop controlled synthetic methods for producing NWs that are preferably thinner or longer, or better still, both thinner and longer than the current state of the art. It is also preferred that these synthesis methods produce NWs with uniform length and width distribution. Ultimately, it would be preferable to develop synthetic methods that are more conducive to the preparation of NWs than other low aspect ratio nanostructures.
本文描述控制NW之製備以符合所述標準的方法。 This article describes methods to control the preparation of NWs to comply with these standards.
根據一些實施態樣,導電NW可藉由改善TC膜之光學性質的合成方法製備。本合成方法藉由如下步驟控制NW的長度及寬度分布且同時獲得高產率的奈米線:使用多元醇線合成反應物組合物,引入各種不同的添加劑,以及使用多元醇線合成方法步驟及條件。 According to some embodiments, conductive NWs can be prepared by a synthesis method that improves the optical properties of the TC film. This synthesis method controls the length and width distribution of NWs and simultaneously obtains high-yield nanowires through the following steps: using polyol wires to synthesize reactant compositions, introducing various additives, and using polyol wire synthesis method steps and conditions .
所得的結果是一種獨特的NW長度及寬度分布,其在反應中以NW對低長寬比奈米結構之高比例混合。隨後用於進一步去除低長寬比奈米結構的純化(例如沉降過程方法)可維持這種獨特的NW長度及直徑分布以併入至最終TC材料中。 The result is a unique NW length and width distribution that is mixed in the reaction with a high ratio of NW to low aspect ratio nanostructures. Subsequent purification (eg, sedimentation process methods) used to further remove low aspect ratio nanostructures can maintain this unique NW length and diameter distribution for incorporation into the final TC material.
在一些測試樣品中,乙二醇(EG)、聚乙烯吡咯烷酮(PVP)、氯化鈉(NaCl)、溴化鈉(NaBr)、及硝酸銀(AgNO3)係在混合物中 混合,然後在氮氣覆層(nitrogen blanket)下加熱至生成銀奈米結構之混合物的反應溫度。一旦反應完成,則從加熱中移除,反應完成係定義為當多數(>90%)銀離子(Ag+)被還原成銀金屬(Ag0)時。銀離子濃度係藉由對反應期間取得之反應混合物的等分試樣進行電位滴定法來監測。粗混合物係藉由如下表徵:掃描式電子顯微鏡(SEM)以量測NW寬度,以及暗場(DF)顯微鏡搭配訂製之影像分析軟體以量測NW長度及低長寬比副產物對高長寬比NW的比例。該等測試樣品代表用於控制NW寬度及長度分布、及/或NW對副產物之比例的不同策略。每個測試樣品的平均NW寬度、長度、及低長寬比副產物(即,「退件品(Objects)」)對NW的比例係統整於表1。 In some test samples, ethylene glycol (EG), polyvinylpyrrolidone (PVP), sodium chloride (NaCl), sodium bromide (NaBr), and silver nitrate (AgNO 3 ) were mixed in the mixture and then covered with nitrogen. The mixture is heated under a nitrogen blanket to the reaction temperature of the mixture forming the silver nanostructure. Remove from heat once the reaction is complete, defined as when the majority (>90%) of the silver ions (Ag + ) have been reduced to silver metal (Ag 0 ). Silver ion concentration was monitored by potentiometric titration of aliquots of the reaction mixture taken during the reaction. The crude mixture was characterized by scanning electron microscopy (SEM) to measure NW width, and dark field (DF) microscopy with custom image analysis software to measure NW length and low aspect ratio by-products versus high aspect ratio The ratio of NW. The test samples represent different strategies for controlling NW width and length distribution, and/or NW to byproduct ratio. The average NW width, length, and low aspect ratio by-products (i.e., "objects") to NW ratios for each test sample are systematically summarized in Table 1.
在反應的內涵中,計時可以多種方式定義。在一實施態樣中,計時可指反應的總時間,因此以下稱為「總反應時間」。或者,計時可指發生於由反應起始及結束所界定之時間段之內的特定時間點。最後,計時可指一或多種反應劑加入反應器及/或反應混合物的「添加時間」。 Within the connotation of reaction, timing can be defined in many ways. In one implementation, the timing may refer to the total time of the reaction, hence it is referred to as the "total reaction time" below. Alternatively, timing may refer to a specific point in time occurring within a time period defined by the start and end of a reaction. Finally, timing can refer to the "addition time" for one or more reactants to be added to the reactor and/or reaction mixture.
在多元醇反應的許多先前技術實例中,銀鹽係於反應起始時、伴隨其他反應劑、在加熱混合物之前添加。一般而言,在這些實例中,銀鹽加入至反應混合物的添加時間係未定義的。 In many prior art examples of polyol reactions, the silver salt was added at the beginning of the reaction, along with the other reactants, before heating the mixture. In general, the time at which the silver salt is added to the reaction mixture is undefined in these examples.
或者,在其他先前技術實例中,銀鹽僅於反應混合物被加熱至反應溫度時添加。一般而言,在這些實例中,銀鹽加入至反應混合物的添加時間係相對長,即大於總反應時間之10%。 Alternatively, in other prior art examples, the silver salt is added only when the reaction mixture is heated to reaction temperature. Generally speaking, in these examples, the addition time of the silver salt to the reaction mixture is relatively long, that is, greater than 10% of the total reaction time.
本發明提供的是,藉由謹慎控制時間點及銀鹽的添加時間使得可達成精準控制NW寬度及長度分布。在一實例中,本發明呈現出,將銀鹽的添加時間限制至小於總反應時間之10%可使得反應中形成的NW之數目增加(相對於低長寬比副產物),以及所形成的NW之平均直徑降低。 What the present invention provides is that by carefully controlling the time point and the addition time of the silver salt, precise control of the NW width and length distribution can be achieved. In one example, the present invention demonstrates that limiting the addition time of the silver salt to less than 10% of the total reaction time can increase the number of NWs formed in the reaction (relative to low aspect ratio by-products), as well as the number of NWs formed in the reaction. The average diameter of NW decreases.
將添加時間限制至小於總反應時間之10%可被稱為「短」、「快」、或其他類似的表述方式。截然不同地,大於總反應時間之10%的添加時間可被稱為「慢」、「長」、或其他類似的表述方式。應理解,使添加時間小於10%係本發明之一方案。本發明之其他方案為:使添加時間小於總反應時間之5%、使添加時間小於總反應時間之2.5%、使添加時間小於總反應時間之1%、以及使添加時間小於總反應時間之0.5%。 Limiting the addition time to less than 10% of the total reaction time may be referred to as "short", "fast", or other similar expressions. In contrast, an addition time greater than 10% of the total reaction time may be referred to as "slow", "long", or other similar expressions. It should be understood that making the addition time less than 10% is an aspect of the present invention. Other solutions of the present invention are: making the addition time less than 5% of the total reaction time, making the addition time less than 2.5% of the total reaction time, making the addition time less than 1% of the total reaction time, and making the addition time less than 0.5 of the total reaction time. %.
第1圖呈現根據本發明方法之一實例。第1圖的例示方法100由步驟102開始,在步驟102中提供第一階段反應混合物。第一階段反應混合物可包含多元醇溶劑、包覆劑、及鹵鹽。在步驟104中,將第一階段反應混合物加熱至反應溫度。在步驟106中,將第二階段反應混合物添加至經加熱的第一階段反應混合物以提供合併的混合物。第二階段反應混合物可包含溶解於多元醇溶劑中的金屬鹽。在步驟108中,使該合併的混合物中的反應進行一段總反應時間。應理解,在步驟106中將第二階段反應混合物添加至第一階段反應混合物係在小於總反應時間之10%的時距內進行。 Figure 1 presents an example of a method according to the invention. The illustrative method 100 of Figure 1 begins with step 102 in which a first stage reaction mixture is provided. The first stage reaction mixture may include a polyol solvent, a capping agent, and a halide salt. In step 104, the first stage reaction mixture is heated to reaction temperature. In step 106, the second stage reaction mixture is added to the heated first stage reaction mixture to provide a combined mixture. The second stage reaction mixture may comprise a metal salt dissolved in a polyol solvent. In step 108, the reaction in the combined mixture is allowed to proceed for a total reaction time. It should be understood that the addition of the second stage reaction mixture to the first stage reaction mixture in step 106 occurs within a time interval of less than 10% of the total reaction time.
提供先前技術方法與根據本發明之方法的一些比較會是有用的。因此,以下簡短指出五個實施例。 It would be useful to provide some comparisons of prior art methods and the method according to the present invention. Therefore, five embodiments are briefly indicated below.
實施例1為先前技術方法,其在反應開始時、於加熱反應混合物之前引入銀鹽。實施例1方法的產物係示於第2A圖,其為先前技術網絡在60,000放大倍率下的SEM影像。 Example 1 is a prior art method in which the silver salt is introduced at the beginning of the reaction, before heating the reaction mixture. The product of the method of Example 1 is shown in Figure 2A, which is an SEM image of a prior art network at 60,000 magnification.
實施例2為先前技術方法,其在反應混合物被加熱至反應溫度時引入銀鹽,其中添加時間大於總反應時間之10%。實施例2方法的產物係示於第2B圖,其為先前技術網絡在60,000放大倍率下的SEM影像。 Example 2 is a prior art method in which the silver salt is introduced when the reaction mixture is heated to reaction temperature, where the addition time is greater than 10% of the total reaction time. The product of the method of Example 2 is shown in Figure 2B, which is an SEM image of a prior art network at 60,000 magnification.
實施例3為根據本發明之一方案的方法。實施例3的方法包含在反應混合物被加熱至反應溫度時引入銀鹽,其中添加時間小於總反應時間之10%。實施例3方法的產物係示於第2C圖,其為根據本發明之一方案的網絡在60,000放大倍率下的SEM影像。 Embodiment 3 is a method according to one aspect of the present invention. The method of Example 3 includes introducing the silver salt while the reaction mixture is heated to reaction temperature, wherein the addition time is less than 10% of the total reaction time. The product of the method of Example 3 is shown in Figure 2C, which is an SEM image at 60,000 magnification of a network according to one aspect of the present invention.
另外,作為實施例3之視需要的變化,對NW分布的控制可藉由調諧氯離子(Cl-)及溴離子(Br-)在反應混合物中的相對負載量來達成。鹵離子(例如Cl-及Br-)在反應的早期階段幫助NW形成核,且控制總鹵負載量(即,Cl-及Br-之總和)、或Br-對Cl-的比例、或二者,可影響NW長度及寬度分布以及所形成之低長寬比副產物及高長寬比NW的相對數目。此可被稱為鹵調諧(halide tuning)以進一步控制NW形態(及降低低長寬比副產物的形成)。 In addition, as an optional variation of Example 3, the control of the NW distribution can be achieved by tuning the relative loading amounts of chloride ions (Cl - ) and bromide ions (Br - ) in the reaction mixture. Halide ions (such as Cl - and Br - ) help NW nucleation in the early stages of the reaction and control the total halide loading (i.e., the sum of Cl - and Br - ), or the ratio of Br - to Cl - , or both , can affect the NW length and width distribution as well as the relative numbers of low aspect ratio by-products and high aspect ratio NWs formed. This can be called halide tuning to further control the NW morphology (and reduce the formation of low aspect ratio by-products).
實施例4為根據本發明之一方案的方法。具體而言,該實施例方法仍使用小於總反應時間之10%的添加時間且還包含以Br-鹽替代所有Cl-鹽,但保持相同的總鹵濃度。此替代可導至平均NW直徑的降低。實 施例4方法的產物係示於第2D圖,其為根據本發明之一方案的網絡在60,000放大倍率下的SEM影像。 Embodiment 4 is a method according to one aspect of the present invention. Specifically, this example method still uses an addition time of less than 10% of the total reaction time and also includes replacing all Cl - salts with Br - salts, but maintaining the same total halogen concentration. This substitution can result in a decrease in the average NW diameter. The product of the method of Example 4 is shown in Figure 2D, which is an SEM image at 60,000 magnification of a network according to one aspect of the present invention.
在實施例5中顯示,謹慎地調諧Br-及Cl-鹽的相對負載量可維持僅用Br-之實施例中所獲致之降低的NW直徑,同時增加高長寬比NW對低長寬比副產物的相對數目。實施例5方法的產物係示於第2E圖,其為根據本發明之一方案的網絡在60,000放大倍率下的SEM影像。 It is shown in Example 5 that careful tuning of the relative loadings of Br- and Cl- salts can maintain the reduced NW diameter obtained in the Br - only examples while increasing the contribution of high aspect ratio NWs to low aspect ratio byproducts relative number. The product of the method of Example 5 is shown in Figure 2E, which is an SEM image at 60,000 magnification of a network according to one aspect of the present invention.
以下針對該五個實施例提供更詳細的討論。 A more detailed discussion is provided below for these five embodiments.
在實施例1中,銀鹽係於反應開始時添加。實施例1方法包含以下步驟:在1公升反應容器中,將420公克乙二醇(EG)、56.2公克聚乙烯吡咯烷酮(PVP)(分子量:1,300,000)溶液(於EG中5%(重量/重量))、2.45公克NaCl溶液(於EG中5%(重量/重量))、2.26公克NaBr溶液(於EG中5%(重量/重量))、及16.21公克硝酸銀(AgNO3)溶液(於EG中14%(重量/重量))加熱至170℃並在氮氣(N2)覆層下攪拌60分鐘。將反應混合物自加熱中移出然後使其在氮氣覆層下冷卻至室溫並同時攪拌。奈米線的平均寬度及長度分別為21.6奈米及15.9微米。低長寬比退件品對NW的比例為7.03。 In Example 1, the silver salt was added at the beginning of the reaction. The method of Example 1 includes the following steps: In a 1-liter reaction vessel, 420 grams of ethylene glycol (EG) and 56.2 grams of polyvinylpyrrolidone (PVP) (molecular weight: 1,300,000) solution (5% (weight/weight) in EG ), 2.45 grams of NaCl solution (5% (w/w) in EG), 2.26 grams of NaBr solution (5% (w/w) in EG), and 16.21 grams of silver nitrate (AgNO 3 ) solution (14 in EG % (wt/wt)) heated to 170°C and stirred under nitrogen (N 2 ) blanket for 60 minutes. The reaction mixture was removed from the heat and allowed to cool to room temperature under a blanket of nitrogen while stirring. The average width and length of the nanowires are 21.6 nanometers and 15.9 micrometers respectively. The ratio of low aspect ratio returns to NW is 7.03.
在實施例2中,銀鹽係在反應溫度下以大於總反應時間之10%的添加時間添加。實施例2方法包含以下步驟:在1公升反應容器中,將476公克乙二醇(EG)、2.81公克聚乙烯吡咯烷酮(PVP)(分子量:1,300,000)、2.45公克NaCl溶液(於EG中5%(重量/重量))、及2.26公克NaBr溶液(於EG中5%(重量/重量))加熱至170℃並在氮氣(N2) 覆層下攪拌50分鐘。向攪拌混合物中,藉由注射泵以1.35毫升/分鐘之添加速率於10分鐘過程中添加13.50毫升硝酸銀(AgNO3)溶液(於EG中14%(重量/重量))。然後將上述反應混合物於170℃在氮氣覆層下攪拌1小時。將反應混合物自加熱中移出然後使其在氮氣覆層下冷卻至室溫並同時攪拌。在此實施例中,此添加時間(即,10分鐘)與1小時比較係相對慢或長。奈米線的平均寬度及長度分別為21.3奈米及15.2微米。低長寬比退件品對NW的比例為7.03。 In Example 2, the silver salt was added at the reaction temperature with an addition time greater than 10% of the total reaction time. The method of Example 2 includes the following steps: in a 1-liter reaction vessel, 476 grams of ethylene glycol (EG), 2.81 grams of polyvinylpyrrolidone (PVP) (molecular weight: 1,300,000), 2.45 grams of NaCl solution (5% in EG) w/w)), and 2.26 g of NaBr solution (5% (w/w) in EG) was heated to 170°C and stirred under nitrogen (N 2 ) blanket for 50 minutes. To the stirred mixture, 13.50 ml of silver nitrate (AgNO 3 ) solution (14% (w/w) in EG) was added via syringe pump at an addition rate of 1.35 ml/min over the course of 10 minutes. The reaction mixture was then stirred at 170°C for 1 hour under a blanket of nitrogen. The reaction mixture was removed from the heat and allowed to cool to room temperature under a blanket of nitrogen while stirring. In this example, this addition time (ie, 10 minutes) is relatively slow or long compared to 1 hour. The average width and length of the nanowires are 21.3 nanometers and 15.2 micrometers respectively. The ratio of low aspect ratio returns to NW is 7.03.
在實施例3中,銀鹽係在反應溫度下以小於總反應時間之10%的添加時間添加。實施例3方法包含以下步驟:在1公升反應容器中,將476公克乙二醇(EG)、2.81公克聚乙烯吡咯烷酮(PVP)(分子量:1,300,000)、2.45公克NaCl溶液(於EG中5%(重量/重量))、及2.26公克NaBr溶液(於EG中5%(重量/重量))加熱至170℃並在氮氣(N2)覆層下攪拌50分鐘。向攪拌混合物中,於3秒過程中添加16.21公克硝酸銀(AgNO3)溶液(於EG中14%(重量/重量))。然後將上述反應混合物於170℃在氮氣覆層下攪拌1小時。將反應混合物自加熱中移出然後使其在氮氣覆層下冷卻至室溫並同時攪拌。在此實施例中,此添加時間(即,3秒)與1小時比較係相對短或快。奈米線的平均寬度及長度分別為16.2奈米及6.2微米。低長寬比退件品對NW的比例為2.55。 In Example 3, the silver salt was added at the reaction temperature with an addition time less than 10% of the total reaction time. The method of Example 3 includes the following steps: in a 1-liter reaction vessel, 476 grams of ethylene glycol (EG), 2.81 grams of polyvinylpyrrolidone (PVP) (molecular weight: 1,300,000), 2.45 grams of NaCl solution (5% in EG) w/w)), and 2.26 g of a NaBr solution (5% (w/w) in EG) was heated to 170°C and stirred under a nitrogen ( N2 ) blanket for 50 minutes. To the stirred mixture, 16.21 grams of silver nitrate ( AgNO3 ) solution (14% (w/w) in EG) was added over the course of 3 seconds. The reaction mixture was then stirred at 170°C for 1 hour under a blanket of nitrogen. The reaction mixture was removed from the heat and allowed to cool to room temperature under a blanket of nitrogen while stirring. In this example, this addition time (ie, 3 seconds) is relatively short or fast compared to 1 hour. The average width and length of the nanowires are 16.2 nanometers and 6.2 micrometers respectively. The ratio of low aspect ratio returns to NW is 2.55.
在實施例4中,在反應溫度下以小於總反應時間之10%的添加時間使用僅用Br-之變數。實施例4方法包含以下步驟:在1公升反應容器中,將477公克乙二醇(EG)、2.81公克聚乙烯吡咯烷酮(PVP)(分子 量:1,300,000)、及6.78公克NaBr溶液(於EG中5%(重量/重量))加熱至170℃並在氮氣(N2)覆層下攪拌50分鐘。向攪拌混合物中,於3秒過程中添加16.21公克硝酸銀(AgNO3)溶液(於EG中14%(重量/重量))。然後將上述反應混合物於170℃在氮氣覆層下攪拌1小時。將反應混合物自加熱中移出然後使其在氮氣覆層下冷卻至室溫並同時攪拌。奈米線的平均寬度及長度分別為13.3奈米及5.4微米。低長寬比退件品對NW的比例為9.75。 In Example 4, a Br - only variant was used at reaction temperature with an addition time of less than 10% of the total reaction time. The method of Example 4 includes the following steps: In a 1-liter reaction vessel, 477 grams of ethylene glycol (EG), 2.81 grams of polyvinylpyrrolidone (PVP) (molecular weight: 1,300,000), and 6.78 grams of NaBr solution (5% in EG (wt/wt)) was heated to 170°C and stirred under nitrogen ( N2 ) blanket for 50 minutes. To the stirred mixture, 16.21 grams of silver nitrate ( AgNO3 ) solution (14% (w/w) in EG) was added over the course of 3 seconds. The reaction mixture was then stirred at 170°C for 1 hour under a blanket of nitrogen. The reaction mixture was removed from the heat and allowed to cool to room temperature under a blanket of nitrogen while stirring. The average width and length of the nanowires are 13.3 nanometers and 5.4 micrometers respectively. The ratio of low aspect ratio returns to NW is 9.75.
在實施例5中,在反應溫度下以小於總反應時間之10%的添加時間使用精細調諧的鹵濃度。實施例5方法包含以下步驟:在1公升反應容器中,將477公克乙二醇(EG)、2.81公克聚乙烯吡咯烷酮(PVP)(分子量:1,300,000)、2.10公克NaCl溶液(於EG中5%(重量/重量))、及3.70公克NaBr溶液(於EG中5%(重量/重量))加熱至170℃並在氮氣(N2)覆層下攪拌60分鐘。向攪拌混合物中,於3秒過程中添加16.8公克硝酸銀(AgNO3)溶液(於EG中14%(重量/重量))。然後將上述反應混合物於170℃在氮氣覆層下攪拌1小時。將反應混合物自加熱中移出然後使其在氮氣覆層下冷卻至室溫並同時攪拌。奈米線的平均寬度及長度分別為12.8奈米及5.7微米。低長寬比退件品對NW的比例為3.52。 In Example 5, a finely tuned halogen concentration was used at reaction temperature with an addition time of less than 10% of the total reaction time. The method of Example 5 includes the following steps: in a 1-liter reaction vessel, 477 grams of ethylene glycol (EG), 2.81 grams of polyvinylpyrrolidone (PVP) (molecular weight: 1,300,000), 2.10 grams of NaCl solution (5% in EG) w/w)), and 3.70 g of NaBr solution (5% (w/w) in EG) was heated to 170°C and stirred under nitrogen ( N2 ) blanket for 60 minutes. To the stirred mixture, 16.8 grams of silver nitrate ( AgNO3 ) solution (14% (w/w) in EG) was added over the course of 3 seconds. The reaction mixture was then stirred at 170°C for 1 hour under a blanket of nitrogen. The reaction mixture was removed from the heat and allowed to cool to room temperature under a blanket of nitrogen while stirring. The average width and length of the nanowires are 12.8 nanometers and 5.7 micrometers respectively. The ratio of low aspect ratio returns to NW is 3.52.
根據本發明所形成的銀奈米線的實體尺寸之實例係列於下表1中。 Examples of physical dimensions of silver nanowires formed in accordance with the present invention are listed in Table 1 below.
表1平均NW寬度、長度、及退件品/NW比例
實施例1至5的NW寬度及長度分布係分別示於第3圖及第4圖。注意在第4圖中,實施例1及2(即,先前技術)的長度分布曲線的峰值顯著低於實施例3至5(即,本發明)的長度分布曲線的峰值。還注意在第3圖中,實施例1及2(即,先前技術)的寬度(直徑)分布曲線的峰值相較於實施例3至5(即,本發明)的寬度分布曲線的峰值係顯著地更偏向右。 The NW width and length distributions of Examples 1 to 5 are shown in Figure 3 and Figure 4 respectively. Note that in Figure 4, the peak value of the length distribution curve of Examples 1 and 2 (ie, the prior art) is significantly lower than the peak value of the length distribution curve of Examples 3 to 5 (ie, the present invention). Also note that in Figure 3, the peak value of the width (diameter) distribution curve of Examples 1 and 2 (i.e., the prior art) is significant compared to the peak value of the width distribution curve of Examples 3 to 5 (i.e., the present invention). The ground is more to the right.
作為統整,本發明提供一種金屬奈米結構之合成中的控制形態的方法。該方法包含提供第一階段反應混合物,其中該第一階段反應混合物包含多元醇溶劑、包覆劑、及鹵鹽。該方法包含將該第一階段反應混合物加熱至反應溫度。該方法包含添加第二階段反應混合物至經加熱的該第一階段反應混合物以提供合併的混合物,其中該第二階段反應混合物包含溶解於多元醇溶劑中的金屬鹽。該方法包含使該合併的混合物中的反應進行一段總反應時間。該第二階段反應混合物係在小於該總反應時間之10%的時距內添加至該第一階段反應混合物。 As a whole, the present invention provides a method for controlling morphology in the synthesis of metal nanostructures. The method includes providing a first-stage reaction mixture, wherein the first-stage reaction mixture includes a polyol solvent, a coating agent, and a halide salt. The method includes heating the first stage reaction mixture to reaction temperature. The method includes adding a second stage reaction mixture to the heated first stage reaction mixture to provide a combined mixture, wherein the second stage reaction mixture includes a metal salt dissolved in a polyol solvent. The method includes allowing the reaction in the combined mixture to proceed for a total reaction time. The second stage reaction mixture is added to the first stage reaction mixture in a time interval of less than 10% of the total reaction time.
本發明提供對添加時間的變化。作為一些實例,添加時間係小於總反應時間之5%、添加時間係小於總反應時間之2.5%、添加時間係小於總反應時間之1%、以及添加時間係小於總反應時間之0.5%。 The present invention provides for variation in addition time. As some examples, the addition time is less than 5% of the total reaction time, the addition time is less than 2.5% of the total reaction time, the addition time is less than 1% of the total reaction time, and the addition time is less than 0.5% of the total reaction time.
本發明提供總反應時間可定義為開始添加第二階段反應混合物與停止加熱合併的反應物之間的持續時間。在一些實例中,總反應時間係小於360分鐘、總反應時間係小於240分鐘、總反應時間係小於120分鐘、以及總反應時間係小於60分鐘。 The present invention provides that the total reaction time can be defined as the duration between starting to add the second stage reaction mixture and stopping heating of the combined reactants. In some examples, the total reaction time is less than 360 minutes, the total reaction time is less than 240 minutes, the total reaction time is less than 120 minutes, and the total reaction time is less than 60 minutes.
本發明提供,當總反應時間係以特定持續時間呈現時,添加時間亦可界定為特定持續時間。作為一些實例,添加時間可為小於10分鐘、添加時間可為小於5分鐘、添加時間可為小於1分鐘、以及添加時間可為小於30秒。 The present invention provides that when the total reaction time is presented as a specific duration, the addition time can also be defined as a specific duration. As some examples, the addition time can be less than 10 minutes, the addition time can be less than 5 minutes, the addition time can be less than 1 minute, and the addition time can be less than 30 seconds.
本發明提供使用各種材料。作為實例,多元醇包含以下之至少一者:乙二醇、1,2-丙二醇、1,3-丙二醇、甘油、及1,2-丁二醇。作為實例,包覆劑包含聚乙烯吡咯烷酮。作為實例,鹵鹽包含以下之至少一者:溴鹽、氯鹽、或溴鹽及氯鹽二者。作為實例,金屬鹽包含以下之至少一者:銀鹽、銅鹽、及金鹽。作為實例,金屬鹽包含硝酸銀。 The present invention provides for the use of a variety of materials. As examples, the polyol includes at least one of: ethylene glycol, 1,2-propanediol, 1,3-propanediol, glycerin, and 1,2-butanediol. As an example, the coating agent includes polyvinylpyrrolidone. As examples, halide salts include at least one of: bromide salts, chloride salts, or both bromide salts and chloride salts. As examples, metal salts include at least one of the following: silver salts, copper salts, and gold salts. As an example, metal salts include silver nitrate.
本發明提供各種反應劑濃度。作為實例,銀鹽的濃度可為至少10mM,但小於120mM。作為實例,鹵鹽的總濃度可為至少2mM,但小於30mM。作為實例,溴鹽與氯鹽的莫耳比可為至少0.2,但小於5。 The present invention provides various reactant concentrations. As an example, the concentration of silver salt may be at least 10mM, but less than 120mM. As an example, the total concentration of halide salts may be at least 2mM, but less than 30mM. As an example, the molar ratio of bromide salt to chloride salt may be at least 0.2, but less than 5.
本發明提供各種結果。作為實例,所得之金屬奈米結構具有小於或等於20奈米的平均寬度及至少5微米的平均長度、或小於或等於15 奈米的平均寬度及至少5微米的平均長度。作為實例,所得之金屬奈米結構具有寬度的變異係數為小於30%。 The present invention provides various results. As an example, the resulting metal nanostructure has an average width of less than or equal to 20 nanometers and an average length of at least 5 microns, or less than or equal to 15 microns. An average width of nanometers and an average length of at least 5 microns. As an example, the resulting metal nanostructure has a coefficient of variation of width less than 30%.
本申請案主張於2019年4月3日提交之美國臨時申請案第62/828,644號、標題為「MORPHOLOGY CONTROL IN SYNTHESIS OF METAL NANOWIRES」的優先權,其併於此以供參考。 This application claims priority from U.S. Provisional Application No. 62/828,644, titled "MORPHOLOGY CONTROL IN SYNTHESIS OF METAL NANOWIRES", filed on April 3, 2019, which is hereby incorporated by reference.
除非另外指示,「第一」、「第二」、及/或類似用語並不旨在暗示時間方案、空間方案、序列等。反而,此類用語僅用於作為特徵、元素、物品等的指示、名稱等。例如,第一物體及第二物體一般而言係對應於物品A及物品B或二個不同或相同物品或同一物品。 Unless otherwise indicated, "first," "second," and/or similar terms are not intended to imply a temporal scheme, spatial scheme, sequence, or the like. Rather, such terms are used only as designators, names, etc. of features, elements, items, etc. For example, the first object and the second object generally correspond to item A and item B or two different or identical items or the same item.
另外,本文所用之「實例」係指用作為例示、說明等,且並非必須為有利的。如本文所用,「或」旨在為包含性的「或」而非排除性的「或」。另外本申請案所用的「一」通常被建構為指「一或多」,除非另外指明或在內文中導向為單數形式。又,A及B之至少一者及/或類似用語一般係指A或B或者A及B二者。另外,至於用於詳細說明及申請專利範圍的「包括」、「具有」、「帶有」、及/或其變化形式,此類用語係旨在類似於術語「包含」地為包含性的。 In addition, the "example" used in this article means that it is used as an illustration, explanation, etc., and does not necessarily have to be advantageous. As used herein, "or" is intended to be an inclusive "or" and not an exclusive "or." In addition, "a" as used in this application is generally constructed to mean "one or more" unless otherwise specified or directed to the singular form in the context. In addition, at least one of A and B and/or similar terms generally refer to A or B or both A and B. Additionally, with respect to the terms "includes," "has," "with," and/or variations thereof when used in detailed descriptions and claims, such terms are intended to be inclusive similar to the term "includes."
儘管發明標的已經由特定於結構特徵及/或方法學規則的文字描述,應理解在所附申請專利範圍中界定之標的並非必要限定於上述特定特徵或規則。而是,上述特定特徵或規則係揭露以作為實施至少部分請求項的例示形式。 Although inventive subject matter has been described in terms specific to structural features and/or methodological rules, it is to be understood that the subject matter defined in the appended claims is not necessarily limited to the specific features or rules described above. Rather, the specific features or rules described above are disclosed as exemplary forms of implementing at least some of the claimed claims.
本文提供實施態樣的各種操作。本文所描述之在一些操作或所有操作中的順序不應建構為隱含該等操作必須仰賴順序。本領域技術人士可察知具有本說明之優點的替代性次序。另外,將理解並非所有操作均必須存在於本文所提供之每個實施態樣中。 This article provides various operations for implementation. The order in some or all operations described herein should not be construed to imply that such operations must rely on the order. Those skilled in the art will recognize alternative sequences that have the advantages of this description. Additionally, it will be understood that not all operations necessarily exist in every implementation provided herein.
另外,儘管本發明係針對一或多個實施方式呈現及描述,本領域其他技術人士基於對本說明書及所附圖式的閱讀與理解可思及等效的替換及變化。本發明包含所有這種替換及變化,且僅限於以下申請專利範圍的範圍。特別而言,對於由上述元件(例如,元素、來源等)進行的各種功能,用於描述此種元件的用語係旨在對應於可進行所描述之元件之特定功能的任何元件(例如,功能上的等效物),儘管不是所揭露之結構的結構上的等效物,除非另外指示。另外,儘管本發明特定特徵可能僅由多個實施方式中的一個揭露,若對於任何給定或特定應用而言可為理想及有利的,則此種特徵可與一或多個其他實施方式的其他特徵結合。 In addition, although the present invention has been presented and described with respect to one or more embodiments, equivalent substitutions and changes may be contemplated by others skilled in the art based on a reading and understanding of this specification and the accompanying drawings. The present invention includes all such substitutions and changes and is limited to the scope of the following claims. In particular, for the various functions performed by the above-described elements (e.g., elements, sources, etc.), the terms used to describe such elements are intended to correspond to any element (e.g., function) that performs the specified function of the described element. equivalents), although not structural equivalents to the disclosed structures, unless otherwise indicated. Additionally, although specific features of the invention may be disclosed in only one of the various embodiments, such features may be combined with one or more other embodiments if such features are desirable and advantageous for any given or particular application. Combined with other features.
100:方法 100:Method
102、104、106、108:步驟 102, 104, 106, 108: Steps
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