TWI505534B - Charge storage device, method of making same, method of making an electrically conductive structure for same, mobile electronic device using same, and microelectronic device containing same - Google Patents
Charge storage device, method of making same, method of making an electrically conductive structure for same, mobile electronic device using same, and microelectronic device containing same Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description
所揭示之本發明之實施例概略地係有關於蓄電裝置，及更明確言之，係有關於電容器，包括電氣雙層電容器。The disclosed embodiments of the present invention are generally directed to power storage devices and, more particularly, to capacitors, including electrical double layer capacitors.
蓄電裝置包括電池及電容器係全面性地用在電子裝置。更明確言之，電容器係廣用在自電氣環路及電力配送至電壓調節及電池替代之用途。隨著電容器技術之持續發展，已經萌生數型技術。舉例言之，電氣雙層電容器(EDLC)也稱作為超電容器(等其它名稱)係以高能儲存及電力密度、尺寸大、及重量輕為其特徵，如此變成用在若干應用方面有展望的候選者。Power storage devices, including batteries and capacitors, are used comprehensively in electronic devices. More specifically, capacitors are widely used in electrical loops and power distribution to voltage regulation and battery replacement. With the continuous development of capacitor technology, digital technology has emerged. For example, electric double layer capacitors (EDLC), also known as ultracapacitors (and other names), are characterized by high energy storage and power density, large size, and light weight, thus becoming candidates for prospects in several applications. By.
依據本發明之一實施例，係特地提出一種蓄電裝置包含彼此藉一電氣絕緣體隔開之一第一導電結構及一第二導電結構，其中該第一導電結構及第二導電結構中之至少一者包含含有多個通道之一多孔結構；及該等通道各自具有開放至該多孔結構表面之一開口。According to an embodiment of the present invention, a power storage device includes a first conductive structure and a second conductive structure separated by an electrical insulator, wherein at least one of the first conductive structure and the second conductive structure A porous structure comprising one of a plurality of channels; and each of the channels has an opening open to one of the surfaces of the porous structure.
所揭示之實施例從研讀後文詳細說明部分結合圖式中之附圖將更為明瞭，附圖中：第1及2圖為依據本發明之一實施例蓄電裝置之剖面圖；第3圖為依據本發明之一實施例一塊多孔矽之掃描電子顯微剖面影像；第4圖為依據本發明之一實施例在一蓄電裝置之一通道內部的電氣雙層之剖面代表圖；第5圖為依據本發明之實施例在一蓄電裝置之一通道之剖面圖，顯示各層及各種結構；第6圖為依據本發明之另一實施例一蓄電裝置之剖面圖；第7圖為流程圖顯示依據本發明之一實施例，一種針對蓄電裝置製造導電結構之方法；第8圖為依據本發明之一實施例，相對厚的導電結構之透視圖；第9圖為流程圖顯示依據本發明之一實施例一種製造蓄電裝置之方法；第10圖為方塊圖表示依據本發明之一實施例之行動電子裝置；及第11圖為方塊圖表示依據本發明之一實施例之微電子裝置。The embodiments of the present invention will be more apparent from the following detailed description, taken in conjunction with the accompanying drawings in which: FIGS. 1 and 2 are a cross-sectional view of a power storage device according to an embodiment of the present invention; A scanning electron microscopic cross-sectional image of a porous crucible according to an embodiment of the present invention; and FIG. 4 is a cross-sectional representation of an electric double layer inside a passage of a power storage device according to an embodiment of the present invention; FIG. 6 is a cross-sectional view showing a power storage device according to another embodiment of the present invention; FIG. 7 is a flow chart showing a cross-sectional view of a power storage device according to an embodiment of the present invention; In accordance with an embodiment of the present invention, a method of fabricating a conductive structure for a power storage device; FIG. 8 is a perspective view of a relatively thick conductive structure in accordance with an embodiment of the present invention; and FIG. 9 is a flow chart showing the present invention in accordance with the present invention. An embodiment of a method of manufacturing a power storage device; FIG. 10 is a block diagram showing a mobile electronic device according to an embodiment of the present invention; and FIG. 11 is a block diagram showing a micro power according to an embodiment of the present invention; Sub-device.
為求例示說明之簡單與清晰，圖式附圖例示說明一般組成方式，及可刪除眾所周知之特徵結構及技術之描述及細節，以免不必要地模糊了所描述的本發明實施例之討論。此外，所繪圖式中之元件並非必要照比例繪製。舉例言之，圖式中若干元件之尺寸可相對於其它元件誇大來協助改善對本發明之瞭解。不同圖式間之相同元件符號表示相同元件，而相似的元件符號可以但非必要表示相似的元件。The simplifications of the present invention are to be considered as illustrative and not restrictive. In addition, elements in the drawings are not necessarily drawn to scale. For example, the dimensions of several elements in the figures may be exaggerated relative to other elements to help improve the understanding of the invention. The same element symbols in the different figures represent the same elements, and similar element symbols may, but need not, represent similar elements.
詳細說明部分及申請專利範圍中，「第一」、「第二」、「第三」、「第四」等術語係用來區別相似的元件，但非必要描述特定排序或時間順序。須瞭解如此使用之各術語在適當情況下可互換，使得如此處所述本發明之實施例例如可以此處例示說明之順序以外之或其它順序操作。同理，若此處所述包法包含一串列步驟，則如此處呈現之此等步驟順序並非必要為可執行此等步驟之唯一順序，若干所陳述步驟可能可刪除，及/或此處未描述之某些其它步驟可能可添加至該方法。此外，「包含」、「包括」、「具有」及其任何變化詞意圖涵蓋非互斥之含括，使得包含一元件表單之處理程序、方法、物件或裝置並非必要限於此等元件，反而可含括此等處理程序、方法、物件或裝置所未明確列舉的或特有的其它元件。In the detailed description and the scope of the patent application, the terms "first", "second", "third", "fourth" are used to distinguish similar elements, but it is not necessary to describe a particular order or chronological order. It is to be understood that the terms so used are interchangeable, as appropriate, such that the embodiments of the invention, as described herein, may be, Similarly, if the package described herein includes a series of steps, the order of the steps as presented herein is not necessarily the only order in which the steps can be performed, and several stated steps may be deleted and/or Some other steps not described may be added to the method. In addition, "including", "including", "having" and any variations thereof are intended to encompass non-mutual exclusions, such that a process, method, article or device comprising a component form is not necessarily limited to such elements, but instead Other elements not specifically recited or specific to such processing procedures, methods, articles or devices are included.
詳細說明部分及申請專利範圍中，「左」、「右」、「前」、「後」、「頂」、「底」、「上」、「下」等術語(若有)係用於描述目的，而非必要用於描述永久性相對位置。須瞭解如此使用之各術語在適當情況下可互換，使得如此處所述本發明之實施例例如可以此處例示說明之方向性或其它方向性操作。如此處使用之「耦接」一詞係定義為以電氣或非電氣方式直接或間接連結。此處描述為彼此「相鄰」之物件可彼此實體接觸、彼此緊密鄰近，或彼此位在相同一般區域或地區，取決於何者適合該名詞所使用的上下文。此處出現「於一個實施例中」一語並非必要全部皆指同一個實施例。In the detailed description and the scope of the patent application, terms such as "left", "right", "before", "after", "top", "bottom", "upper" and "lower" (if any) are used to describe Purpose, not necessarily for describing permanent relative positions. It is to be understood that the terms so used are interchangeable as appropriate, such that the embodiments of the invention, as described herein, may be exemplified by the directional or other directional operations illustrated herein. The term "coupled" as used herein is defined to mean either directly or indirectly, electrically or non-electrically. Objects described herein as "adjacent" to each other may be in physical contact with each other, in close proximity to each other, or in the same general region or region, depending on which context is appropriate for the noun. The phrase "in one embodiment" is not necessarily all referring to the same embodiment.
於本發明之一個實施例中，一種蓄電裝置係包含彼此藉一電氣絕緣體隔開之一第一導電結構及一第二導電結構，其中該第一導電結構及第二導電結構中之至少一者包含含有多個通道之一多孔結構，及其中該等通道各自具有開放至該多孔結構表面之一開口。In one embodiment of the present invention, a power storage device includes a first conductive structure and a second conductive structure separated from each other by an electrical insulator, wherein at least one of the first conductive structure and the second conductive structure A porous structure comprising one of a plurality of channels, and wherein each of the channels has an opening open to one of the surfaces of the porous structure.
超電容器及類似的高表面積蓄電裝置可用在微電子裝置來儲存能量，用在電路中之電分路，用作為電力輸送之電路，用作為記憶體儲存元件，及用作為其它功能的主機。超電容器優於電池之優點為超電容器可快速充放電，原因在於超電容器並不仰賴化學反應來蓄電，及不會隨著使用壽命而顯著降級，即使快速充放電亦復如此。超電容器也比電池對溫度更不敏感。Ultracapacitors and similar high surface area power storage devices can be used in microelectronic devices to store energy, used in electrical shunts in circuits, as circuits for power delivery, as memory storage components, and as a host for other functions. The advantage of ultracapacitor over the battery is that the ultracapacitor can be quickly charged and discharged because the ultracapacitor does not rely on chemical reactions to store electricity, and does not significantly degrade with the service life, even in the case of rapid charge and discharge. Ultracapacitors are also less sensitive to temperature than batteries.
超電容器之發展路徑為其比較電池顯然最終可能達成更高的能量密度(就每千克(kg)能量及每升能量為單位)。如此超電容器結合電池使用來保護電池避免高電力叢發(因而延長電池壽命)。此外，若超電容器可提供高電力需求，則電池中之電極可製造成更薄。另外，超電容器可用作為電池替代。本發明之實施例可提高超電容器之能量密度達數個次冪幅度，例如藉由使用高k介電材料被覆之奈米材料來增加電極表面積，容後詳述。The development path of ultracapacitors is that it is clear that a battery may eventually achieve a higher energy density (in terms of energy per kilogram (kg) and energy per liter). Such ultracapacitors are used in conjunction with batteries to protect the battery from high power bursts (and thus extend battery life). In addition, if the ultracapacitor can provide high power requirements, the electrodes in the battery can be made thinner. In addition, ultracapacitors can be used as a battery replacement. Embodiments of the present invention can increase the energy density of an ultracapacitor by a few power amplitudes, such as by using a nanomaterial coated with a high-k dielectric material to increase the surface area of the electrode, as described in more detail below.
現在參考附圖，第1及2圖為依據本發明之實施例一種蓄電裝置100之剖面圖。如第1及2圖所示，蓄電裝置100包含一導電結構110及導電結構120彼此藉電絕緣體而彼此分開。此種電絕緣體可呈各種形式，容後詳述。電絕緣體110及120中之至少一者包含含多個通道之多孔結構，其各自具有開口至多孔結構表面。於該具體實施例中，導電結構110及導電結構120皆包含此種多孔結構。如此，導電結構110包含通道111，其具有開口112至相對應多孔結構表面115；及導電結構120包含通道121，其具有開口122至相對應多孔結構表面125。一個實施例中，此處導電結構110及120中只有一者包含有多個通道之多孔結構，另一個導電結構例如可為金屬電極或多晶矽結構。Referring now to the drawings, Figures 1 and 2 are cross-sectional views of a power storage device 100 in accordance with an embodiment of the present invention. As shown in FIGS. 1 and 2, the power storage device 100 includes a conductive structure 110 and a conductive structure 120 separated from each other by an electrical insulator. Such electrical insulators can take a variety of forms and will be described in detail later. At least one of the electrical insulators 110 and 120 comprises a porous structure comprising a plurality of channels each having an opening to the surface of the porous structure. In this embodiment, both the conductive structure 110 and the conductive structure 120 comprise such a porous structure. As such, the electrically conductive structure 110 includes a channel 111 having an opening 112 to a corresponding porous structure surface 115; and the electrically conductive structure 120 includes a channel 121 having an opening 122 to a corresponding porous structure surface 125. In one embodiment, only one of the conductive structures 110 and 120 herein comprises a porous structure having a plurality of channels, and the other conductive structure may be, for example, a metal electrode or a polysilicon structure.
蓄電裝置100之各種組態皆屬可能。於第1圖之實施例中，例如蓄電裝置100包含兩個分開多孔結構(導電結構110及導電結構120)其已經利用中介分隔件130而面對面連結。至於另一個實例，於第2圖之實施例中，蓄電裝置100包含一單一平面多孔結構，其中第一區段(導電結構110)係藉含有分隔件130之溝渠231而與第二區段(導電結構120)分開。導電結構中之一者為正端，及另一導電結構為負端。分隔件130允許離子移轉，但不容許流體移轉，諸如於電解液中所見。Various configurations of the power storage device 100 are possible. In the embodiment of FIG. 1, for example, power storage device 100 includes two separate porous structures (conductive structure 110 and conductive structure 120) that have been face-to-face joined by interposer 130. As another example, in the embodiment of FIG. 2, the power storage device 100 includes a single planar porous structure, wherein the first segment (the conductive structure 110) is separated from the second segment by the trench 231 containing the spacer 130 ( The conductive structures 120) are separated. One of the conductive structures is a positive end and the other conductive structure is a negative end. The separator 130 allows ion transfer but does not allow fluid to be transferred, such as seen in an electrolyte.
第2圖顯示連結導電結構110及導電結構120之材料小橋。若保留其未定址，則此橋可用作為二導電結構間之電短路。但有數種可能的解決之道。舉例言之，橋可使用拋光操作而被去除。另外導電結構可在晶圓之重度摻雜頂層或區形成，而溝渠向下延伸入下方輕度摻雜基體，該基體並非極佳導體。或者可使用絕緣體上矽結構。FIG. 2 shows a material bridge connecting the conductive structure 110 and the conductive structure 120. If it is left unaddressed, the bridge can be used as an electrical short between the two conductive structures. But there are several possible solutions. For example, the bridge can be removed using a polishing operation. In addition, the conductive structure can be formed on the heavily doped top or region of the wafer, while the trench extends down into the underlying lightly doped substrate, which is not an excellent conductor. Alternatively, an insulator upper structure can be used.
舉個實例，導電結構110及120之多孔結構可藉濕蝕刻法形成，其中施用至導電結構表面之液體蝕刻劑蝕刻去除部分導電結構，使得其至少以略為類似水在石頭上雕刻出渠道之方式進行。此乃為何各通道具有開口至導電結構表面之緣故；濕蝕刻法無法在多孔結構內部形成全然封閉的空腔，亦即不具有開口至表面的空腔，類似被捕捉在岩石內部的氣泡。無庸殆言，此等開口不會以其它材料覆蓋或以其它方式封閉，原因在於存在有或添加其它材料，實際上可能發生在若干實施例，但無論是否覆蓋所述開口之表面為依據本發明之至少一個實施例呈各多孔結構的通道特徵。(一個實施例，其中開口可被覆蓋係為其中磊晶矽層係作為電路或其它導線在通道頂部生長的位置)。依據本發明之實施例之多孔結構可以極為精確且一致的多孔結構製造(而與具有活性的碳相反)。如此允許快速充電(孔隙大小可最佳化來與離子大小可相容)，也改良電容(不含異常功能區)。但也允許電壓起伏波動之分佈狹窄。For example, the porous structures of the electrically conductive structures 110 and 120 can be formed by a wet etch process in which a liquid etchant applied to the surface of the electrically conductive structure etches away portions of the electrically conductive structure such that it at least engraves the channels on the stone with a slight water-like pattern. get on. This is why each channel has an opening to the surface of the conductive structure; the wet etching method cannot form a completely closed cavity inside the porous structure, that is, a cavity having no opening to the surface, similar to bubbles trapped inside the rock. Needless to say, such openings are not covered or otherwise enclosed by other materials, as other materials are present or added, which may actually occur in several embodiments, but whether or not the surface of the opening is covered is in accordance with the present invention. At least one embodiment is a channel feature of each porous structure. (An embodiment wherein the opening can be covered by where the epitaxial layer is grown as a circuit or other wire at the top of the channel). The porous structure according to an embodiment of the present invention can be fabricated with an extremely precise and uniform porous structure (as opposed to having active carbon). This allows for fast charging (pore size optimized to be compatible with ion size) and improved capacitance (without anomalous functional areas). But it also allows the distribution of voltage fluctuations to be narrow.
須注意關聯此處討論，以與前述不同方式所形成之多孔碳具有不同結構，藉由不含表面開口之完全封閉空腔為其特徵。結果，多孔碳並不適合或至少並不如所期望地用在至少本發明之若干實施例(但於此處值得一提者為某些其它結構(諸如下述厚導電結構)可含有全然封閉的空腔)。也須注意第1圖及第2圖描述多孔結構可高度理想地用在全部通道111及121只顯示為垂直延伸的實例。實際上，通道將於多個方向分支來形成纏結的失序圖案，該圖案可能略為類似第3圖所示多孔結構。It should be noted that as discussed herein, the porous carbon formed in a different manner from the foregoing has a different structure, characterized by a completely closed cavity free of surface openings. As a result, porous carbon is not suitable or at least not used as desired in at least some embodiments of the invention (but it is worth mentioning here that certain other structures (such as the thick conductive structures described below) may contain completely enclosed voids. Cavity). It should also be noted that Figures 1 and 2 depict an example in which the porous structure can be highly ideally used in all of the channels 111 and 121 to show only vertical extension. In fact, the channels will branch in multiple directions to form an entangled out-of-order pattern, which may be slightly similar to the porous structure shown in Figure 3.
第3圖為掃描電子顯微鏡(SEM)剖面影像顯示依據本發明之實施例之一塊多孔矽300。如圖所示，多孔矽300含有多個通道311，若干通道顯示為垂直伸長，而部分通道顯示為粗略圓孔。後述組群表示可見部分係水平取向之通道。須了解通道311可能沿其長度方向扭曲及旋轉，因此單一通道具有垂直部分及水平部分，以及既非完全垂直也非完全水平反而係落在中間的部分。Figure 3 is a scanning electron microscope (SEM) cross-sectional image showing a bulk porous crucible 300 in accordance with an embodiment of the present invention. As shown, the porous crucible 300 contains a plurality of channels 311, with a plurality of channels shown as being vertically elongated and a portion of the channels being shown as rough circular holes. The group described later indicates that the visible portion is a horizontally oriented channel. It will be appreciated that the passage 311 may be twisted and rotated along its length, such that the single passage has a vertical portion and a horizontal portion, and a portion that is neither completely vertical nor completely horizontal but instead is centered.
利用正確的蝕刻劑，可從幾乎任一種導電材料製造具有所述特性之多孔結構。舉個實例，藉由使用氫氟酸與乙醇之混合物蝕刻矽基體可形成多孔矽結構。概略言之，多孔矽及其它多孔結構可藉諸如陽極化及染料蝕刻等方法製造。With the correct etchant, a porous structure having the above characteristics can be fabricated from almost any conductive material. As an example, a porous tantalum structure can be formed by etching a tantalum matrix using a mixture of hydrofluoric acid and ethanol. In summary, porous tantalum and other porous structures can be fabricated by methods such as anodization and dye etching.
除了前述多孔矽之外，依據本發明之實施例特別適合用於蓄電裝置之若干其它材料為多孔鍺及多孔錫。使用多孔矽之可能優點包括其與既有之矽技術可相容。由於對該材料之既有技術結果，多孔鍺具有類似優點，比較矽，多孔鍺具有進一步可能的優點，其天然氧化物(氧化鍺)為水溶性因此容易去除。(形成在矽表面上的天然氧化物可能捕捉電荷，此乃非期望的結果，特別當矽的孔隙度係大於約20%時尤為如此)。多孔鍺也與矽技術具有高度可相容性。使用多孔錫之零帶隙材料之可能優點包括其導電性相對於若干其它導電性材料及半導性材料之導電性提高。其它材料也可用於多孔結構，包括矽碳化物；合金包括矽與鍺之合金；及金屬諸如銅、鋁、鎳、鈣、鎢、鉬及錳。矽-鍺合金優異地具有比純鍺結構遠更小的體積差。In addition to the foregoing porous tantalum, several other materials which are particularly suitable for use in power storage devices in accordance with embodiments of the present invention are porous tantalum and porous tin. Possible advantages of using porous tantalum include that it is compatible with existing tantalum techniques. Due to the prior art results of this material, porous tantalum has similar advantages. Comparatively, porous tantalum has further possible advantages, and its natural oxide (ruthenium oxide) is water soluble and thus easily removed. (The natural oxide formed on the surface of the crucible may capture charge, which is an undesirable result, especially when the porosity of the crucible is greater than about 20%). Porous tantalum is also highly compatible with niobium technology. Possible advantages of using a zero bandgap material of porous tin include an increase in conductivity of the electrical conductivity relative to several other electrically conductive materials and semiconducting materials. Other materials may also be used in the porous structure, including tantalum carbides; alloys including alloys of tantalum and niobium; and metals such as copper, aluminum, nickel, calcium, tungsten, molybdenum, and manganese. The ruthenium-iridium alloy excels in much smaller volume difference than the pure ruthenium structure.
本發明之實施例可使用極為狹窄之通道。於若干實施例中(容後詳述)，電解液被導入通道內部。電解液內之分子約為2奈米(nm)。因此於至少一個實施例中，各通道之最小尺寸係不小於2奈米，因而允許電解液沿通道之全長自由流動。Embodiments of the invention may use extremely narrow passages. In several embodiments (described in detail later), the electrolyte is introduced into the interior of the channel. The molecule in the electrolyte is approximately 2 nanometers (nm). Thus in at least one embodiment, the minimum dimension of each channel is no less than 2 nanometers, thereby allowing the electrolyte to flow freely along the entire length of the channel.
於相同或其它實施例中，各通道之最小尺寸係不大於1微米(μm)。通道之最小尺寸的上限可對特定實施例做選擇來最大化該等實施例之多孔結構表面積。較小的(例如較窄的)通道結果導致各導電結構之總表面積增加，原因在於較大數目之此等狹窄通道可嵌合入具有給定大小之導電結構內部。由於電容係與表面積成正比，以所述方式受大小約束之通道可能地且優異地導致具有電容增加之電容器。(通道之其它尺寸，例如其長度也經操控來增加表面積(或達成若干其它結果)，亦即較長的通道優於較短的通道，但其它方面比較前文討論之最小尺寸更不具關鍵重要性)。於其它實施例中，通道之最小尺寸可大於1微米，或許達10微米或以上。雖然其將減小表面積，但若有所需，此種大型通道可提供較為內部空間，其中將生長或以其它方式形成額外的結構。至少一個此種實施例討論如下。In the same or other embodiments, the minimum dimension of each channel is no more than 1 micrometer (μm). The upper limit of the minimum size of the channels can be selected for a particular embodiment to maximize the surface area of the porous structures of the embodiments. The smaller (e.g., narrower) channel results in an increase in the total surface area of each conductive structure because a larger number of such narrow channels can be fitted into the interior of a conductive structure of a given size. Since the capacitance is proportional to the surface area, the size-constrained channel in the manner described can potentially and excellently result in a capacitor with increased capacitance. (Other dimensions of the channel, such as its length, are also manipulated to increase surface area (or achieve some other result), ie longer channels are preferred over shorter channels, but other aspects are less critical than the minimum dimensions discussed above. ). In other embodiments, the smallest dimension of the channel can be greater than 1 micron, perhaps up to 10 microns or more. While it will reduce the surface area, such large channels may provide a relatively internal space where needed, where additional structures will be grown or otherwise formed. At least one such embodiment is discussed below.
蓄電裝置100進一步包含在多孔結構之至少一部分上及在通道111及/或通道121之至少若干內部之導電被覆物140。可能需要此種導電被覆物來維持或提升多孔結構之導電性，特別於多孔結構之孔隙度超過約20%時尤為如此。舉個實例，導電被覆物140可為矽化物。舉另一個實例，導電被覆物140可為金屬例如鋁、銅、及鎢，或其它電導體諸如氮化鎢、氮化鈦、及氮化鉭之被覆物。所列舉之各材料具有用在既有CMOS技術之優點。其它金屬諸如鎳及鈣也可用作為導電被覆物140。此等材料可使用諸如電鍍、化學氣相沉積(CVD)、及/或原子層沉積(ALD)之方法施用。此處須注意鎢之CVD方法為自限性，表示鎢將形成多個單層然後停止生長。所得導電被覆物薄層恰為蓄電裝置100之實施例所需，原因在於其不會變太厚因而封閉通道，且可防止CVD氣體滲透深入通道。若有所需，多孔結構也可以設計來增加結構之導電性的摻雜劑(例如硼、砷或磷用於多孔矽；例如砷或鎵用於多孔鍺)摻雜。Power storage device 100 further includes a conductive coating 140 on at least a portion of the porous structure and at least within a plurality of channels 111 and/or channels 121. Such conductive coatings may be required to maintain or enhance the electrical conductivity of the porous structure, particularly when the porosity of the porous structure exceeds about 20%. As an example, the electrically conductive coating 140 can be a telluride. As another example, the conductive coating 140 can be a metal such as aluminum, copper, and tungsten, or other electrical conductors such as tungsten nitride, titanium nitride, and tantalum nitride. Each of the listed materials has the advantage of being used in existing CMOS technology. Other metals such as nickel and calcium may also be used as the conductive coating 140. Such materials can be applied using methods such as electroplating, chemical vapor deposition (CVD), and/or atomic layer deposition (ALD). It should be noted here that the tungsten CVD method is self-limiting, indicating that tungsten will form multiple monolayers and then stop growing. The resulting thin layer of conductive coating is just as required for the embodiment of power storage device 100 because it does not become too thick and thus closes the channel and prevents CVD gas from penetrating deep into the channel. If desired, the porous structure can also be designed to increase the conductivity of the structure of dopants (e.g., boron, arsenic or phosphorus for porous germanium; for example, arsenic or gallium for porous germanium) doping.
於一個實施例中，分開導電結構110與導電結構120之電絕緣體包含介電材料。舉例言之，可使用以二氧化矽(SiO2 )氧化之多孔矽電極連同金屬或多晶矽材結構為另一個電極來製造極高電容之電容器。多孔矽之極高表面積可為此種電容器所能達成之高電容的主要貢獻因子。In one embodiment, the electrical insulator separating the electrically conductive structure 110 from the electrically conductive structure 120 comprises a dielectric material. For example, a very high capacitance capacitor can be fabricated using a porous tantalum electrode oxidized with cerium oxide (SiO 2 ) along with a metal or polycrystalline tantalum structure for the other electrode. The extremely high surface area of porous tantalum can be a major contributor to the high capacitance that such capacitors can achieve.
藉由將電解液150放置於多孔結構實體接觸，可更進一步增加，或甚至顯著增高電容。電解液150(以及其它此處所述之電解液)於圖形中係使用隨機排列之圓形表示。此種表示方式意圖傳遞一種構想，電解液為含有自由態離子之物質(液體或固體)。選用圓圈係為方便而絕非意圖暗示電解液成分或品質，包括絕非就離子大小、形狀、或數目做任何限制。依據本發明可使用典型的但非唯一類型電解液為離子性溶液。By placing the electrolyte 150 in contact with the porous structural entity, the capacitance can be further increased, or even significantly increased. Electrolyte 150 (and other electrolytes described herein) are represented in the figures using a randomly arranged circular representation. This representation is intended to convey the idea that the electrolyte is a substance (liquid or solid) containing free ions. The use of circles is convenient and is not intended to imply electrolyte composition or quality, including by no means limiting the size, shape, or number of ions. A typical but non-unique type of electrolyte can be used as an ionic solution in accordance with the present invention.
於一實施例中，此處使用電解液150，將導電結構110與導電結構120分開之電絕緣體可為經由電解質存在所形成的電氣雙層。此種電氣雙層示意顯示於第4圖可完成或替代前文描述之介電材料。如第4圖所示，電氣雙層(EDL)330已經形成在通道111中之一者內部。電氣雙層330為由兩層離子組成，其中一層為通道111側壁之電荷(第4圖中顯示為正，但也可為負)，而其中另一層係由電解液中之自由態離子形成。電氣雙層330電絕緣表面，如此提供電容器發揮功能所需之電荷分離。電解液超電容器之大型電容及因而具有大型蓄電潛力係來自於電解液離子與電極間之分隔距離小(約為1奈米)。In one embodiment, the electrolyte 150 is used herein, and the electrical insulator separating the conductive structure 110 from the conductive structure 120 can be an electrical double layer formed via the presence of an electrolyte. Such an electrical double layer diagram is shown in Figure 4 to complete or replace the dielectric material previously described. As shown in FIG. 4, an electrical double layer (EDL) 330 has been formed inside one of the channels 111. The electrical double layer 330 is composed of two layers of ions, one of which is the charge of the sidewall of the channel 111 (shown positive in Figure 4, but can also be negative), and the other layer is formed by free ions in the electrolyte. The electrical double layer 330 electrically insulates the surface, thus providing the charge separation required for the capacitor to function. The large capacitance of the electrolyte supercapacitor and thus the large storage potential are derived from the small separation distance between the electrolyte ions and the electrodes (about 1 nm).
須注意當蓄電裝置100放電時，電氣雙層耗散。如此表示於某些情況下，此處電氣雙層置換介電層，例如導電結構110及120可能有一段時間並未彼此藉電絕緣體分開，至少並非於電氣雙層中之具體實施例。此處述及「第一導電結構及第二導電結構彼此藉電絕緣體分開」特別包括當蓄電裝置充電時只存在有電絕緣體的情況。It should be noted that when the power storage device 100 is discharged, the electrical double layer is dissipated. This means that in some cases, the electrical double-layer dielectric layer, such as the conductive structures 110 and 120, may not be separated from each other by electrical insulators for a period of time, at least not in the specific embodiment of the electrical double layer. The term "the first conductive structure and the second conductive structure are separated from each other by the electrical insulator" as used herein specifically includes the case where only the electrical insulator is present when the power storage device is charged.
於若干實施例中，電解液150為有機電解液。舉個實例，電解液為有機材料諸如四氟硼酸四乙基銨於乙腈之液體或固體溶液。其它實例包括基於硼酸、硼酸鈉或弱有機酸溶液。另外，(非有機)水可用作為電解液，但可能造成安全性風險，若電容器超過某個溫度時，水可能沸騰而形成氣體，可能造成電容器***。In several embodiments, the electrolyte 150 is an organic electrolyte. As an example, the electrolyte is a liquid or solid solution of an organic material such as tetraethylammonium tetrafluoroborate in acetonitrile. Other examples include solutions based on boric acid, sodium borate or weak organic acids. In addition, (non-organic) water can be used as an electrolyte, but it may pose a safety risk. If the capacitor exceeds a certain temperature, the water may boil and form a gas, which may cause the capacitor to explode.
如前述，高能密度為電容器之期望特性。但典型電氣雙層只能忍受相對低電壓，或許2伏特或3伏特，如此限制實際上可達成的能量密度。為了增加可達成之能量密度，本發明實施例結合具有相對較高崩潰電壓之材料，如此提高電容器之總崩潰電壓。舉個實例，增加崩潰電壓之材料可為良好電絕緣體，或可為極其電化學惰性(例如汞)。若此等材料也具有高介電常數(該種情況下，於此處稱作為「高k材料」)，則該等材料具有電容增高及洩漏電流減低之額外效果。另外，分開層或材料也可用於此等目的，亦即一種材料連同分開高k材料而增高崩潰電壓。使用高崩潰電壓材料結合多孔結構及有機電解液之蓄電裝置具有比較不含此等組件之蓄電裝置遠更高的能量密度。As mentioned above, the high energy density is the desired characteristic of the capacitor. However, a typical electrical double layer can only withstand relatively low voltages, perhaps 2 volts or 3 volts, thus limiting the energy density that can actually be achieved. In order to increase the achievable energy density, embodiments of the present invention incorporate materials having relatively high breakdown voltages, thus increasing the total breakdown voltage of the capacitor. As an example, the material that increases the breakdown voltage can be a good electrical insulator, or can be extremely electrochemically inert (such as mercury). If such materials also have a high dielectric constant (in this case, referred to herein as "high-k material"), these materials have the added benefit of increased capacitance and reduced leakage current. In addition, separate layers or materials may also be used for such purposes, that is, a material that increases the breakdown voltage along with the separation of the high-k material. A power storage device that uses a high breakdown voltage material in combination with a porous structure and an organic electrolyte has a much higher energy density than a power storage device that does not include such components.
一種材料若其介電常數係大於SiO2 之介電常數亦即大於3.9，則典型地被視為高k材料。由於若干本發明實施例可使用SiO2 作為介電被覆物，SiO2 (以及任何其它具有3.9之介電常數之材料)明確地含括於如此處定義之「高k材料」之範圍。同時，須注意於其它實施例中，也可使用具有顯著較高介電常數之材料。舉若干實例，高k材料可為使用ALD、CVD、熱生長或濕化學所形成之氮化矽(SiN)、氧氮化矽(SiOx Ny )、氧化鉿(HfOx )、氧化鋯(ZrOx )、氧化鉭(TaOx )、氧化鈦(TiOx )或BaSrTiO3 ，全部皆具有約為20至50之介電常數。也可使用更加奇特的材料，但仍然具有較高介電常數(其數值以括弧指示於如下各材料旁)。此等材料例如包括(LaSr)2 NiO4 [105 ]、CaTiO3 [10,286]，及相關材料諸如CaCu3 Ti4 O12 [10,286]及Bi3 Cu3 Ti4 O12 [1,871]。於若干實施例中，可能期望選擇具有比電解液之介電常數(經常約為20附近)更高介電常數之高k材料。A material is typically considered a high-k material if its dielectric constant is greater than the dielectric constant of SiO 2 , i.e., greater than 3.9. Since several embodiments of the invention may use SiO 2 as the dielectric coating, SiO 2 (and any other material having a dielectric constant of 3.9) is expressly included within the scope of the "high-k material" as defined herein. At the same time, it should be noted that in other embodiments, materials having significantly higher dielectric constants can also be used. As a few examples, high-k materials can be tantalum nitride (SiN), yttrium oxynitride (SiO x N y ), hafnium oxide (HfO x ), zirconia formed using ALD, CVD, thermal growth or wet chemistry ( ZrO x ), yttrium oxide (TaO x ), titanium oxide (TiO x ) or BaSrTiO 3 all have a dielectric constant of about 20 to 50. More exotic materials can also be used, but still have a higher dielectric constant (the values are indicated by brackets next to each of the following materials). Such materials include, for example, (LaSr) 2 NiO 4 [10 5 ], CaTiO 3 [10, 286], and related materials such as CaCu 3 Ti 4 O 12 [10,286] and Bi 3 Cu 3 Ti 4 O 12 [1,871]. In several embodiments, it may be desirable to select a high k material having a higher dielectric constant than the dielectric constant of the electrolyte (often near about 20).
如前文高k材料之討論所提示，於本發明之若干實施例中，蓄電裝置100進一步包含具有至少3.9之介電常數之材料。如第5圖所示，其為依據本發明之實施例蓄電裝置100之通道111中之一者的剖面圖，蓄電裝置100包含介於電解液150與多孔結構110間之高k材料515。(第5圖中未顯示電氣雙層來避免不必要的複雜化圖式。)As suggested by the discussion of the foregoing high-k materials, in some embodiments of the invention, power storage device 100 further comprises a material having a dielectric constant of at least 3.9. As shown in FIG. 5, which is a cross-sectional view of one of the channels 111 of the electrical storage device 100 according to an embodiment of the present invention, the electrical storage device 100 includes a high-k material 515 interposed between the electrolyte 150 and the porous structure 110. (The electrical double layer is not shown in Figure 5 to avoid unnecessary complications.)
如前述，本發明之實施例藉由增加其表面積及/或藉由縮短分開導電結構間之距離來增加蓄電裝置之電容，先前各段揭示依據本發明之實施例達成此等結果之各項技術。依據額外實施例，電容器之表面積又可藉奈米結構存在於蓄電裝置之至少若干通道內部而增加。(如此處使用，「奈米結構」一詞表示具有至少一個尺寸約為奈米至數十奈米之結構。此種奈米結構可具有規則形狀或不規則形狀。「奈米粒子」粗略為球形奈米結構。「奈米線」為實心粗略圓柱形奈米結構。「奈米管」也意圖為粗略圓柱形之奈米結構，但與奈米線之差異在於其形成中空管。碳形成奈米管之能力顯然為獨特；由其它材料製造之奈米結構形成奈米線。)As described above, embodiments of the present invention increase the capacitance of the electrical storage device by increasing its surface area and/or by shortening the distance between the separate electrically conductive structures, and the prior paragraphs disclose various techniques for achieving such results in accordance with embodiments of the present invention. . According to additional embodiments, the surface area of the capacitor may in turn be increased by the presence of a nanostructure within at least some of the channels of the electrical storage device. (As used herein, the term "nanostructure" means having at least one structure having a size of from about nanometers to tens of nanometers. Such a nanostructure may have a regular shape or an irregular shape. "Nano particles" are roughly The spherical nanostructure. The "nano wire" is a solid roughly cylindrical nanostructure. The "nanotube" is also intended to be a roughly cylindrical nanostructure, but the difference from the nanowire is that it forms a hollow tube. The ability to form nanotubes is clearly unique; nanostructures made from other materials form nanowires.)
依據前文討論，及如第5圖所示，通道111含有奈米結構535。舉個實例，可有任一種適當材料(例如矽)或材料的組合(例如矽鍺，帶有矽芯或鍺芯)所製成之奈米粒子(或許於異丙醇溶液)或奈米線、碳奈米管、經矽被覆之碳奈米管等。類似通道111及121，以及多孔結構之其它部分，部分(或全部)奈米結構535於至少一個實施例可使用導電被覆物540被覆或部分被覆。如前述，此被覆物可為良好電導體(例如適當金屬、矽化物等)。至少部分奈米結構可含有摻雜劑來進一步增加其導電性。此外，於若干實施例中，至少部分奈米結構535係以防止奈米結構535與電解液150間之電化學反應之材料545被覆。材料545增加蓄電裝置之崩潰電壓。舉個實施，材料545可呈單層形式或其它液體金屬例如鍺或鍺-銦-錫合金於奈米結構535表面上之單層形式(或當存在有導電被覆物時，或許係在導電被覆物540上方)。According to the foregoing discussion, and as shown in FIG. 5, the channel 111 contains a nanostructure 535. As an example, there may be any suitable material (such as ruthenium) or a combination of materials (such as ruthenium, with a core or core) of nanoparticles (perhaps in isopropanol solution) or nanowires. , carbon nanotubes, carbon nanotubes coated with enamel. Similar to channels 111 and 121, as well as other portions of the porous structure, a portion (or all) of nanostructures 535 may be coated or partially coated with conductive coating 540 in at least one embodiment. As mentioned above, the covering can be a good electrical conductor (e.g., a suitable metal, telluride, etc.). At least a portion of the nanostructures may contain dopants to further increase their conductivity. Moreover, in some embodiments, at least a portion of the nanostructures 535 are coated with a material 545 that prevents electrochemical reaction between the nanostructures 535 and the electrolyte 150. Material 545 increases the breakdown voltage of the electrical storage device. Alternatively, material 545 may be in the form of a single layer or a single layer of other liquid metal such as tantalum or niobium-indium-tin alloy on the surface of nanostructure 535 (or in the presence of a conductive coating, perhaps in a conductive coating) Above the object 540).
其次轉向第6圖，將討論依據本發明之另一實施例之蓄電裝置600。如第6圖所示，蓄電裝置600包含於基體605上之多個奈米結構610，及進一步包含與至少若干奈米結構610做實體接觸之電解液650。(於該具體實施例中，奈米結構610為分開的奈米結構，亦即不似多孔結構之通道，例如為未包含在另一個結構內部之孤立結構。)舉個實例，電解液650可類似首先於第1圖所示之電解液150。電解液650的存在形成電氣雙層，亦即蓄電裝置600為EDLC。舉個實例，多個奈米結構610之第一子集形成蓄電裝置600之第一電極，及多個奈米結構610之第二子集形成蓄電裝置600之第二電極。Turning next to Fig. 6, a power storage device 600 in accordance with another embodiment of the present invention will be discussed. As shown in FIG. 6, power storage device 600 includes a plurality of nanostructures 610 on substrate 605, and further includes an electrolyte 650 in physical contact with at least a plurality of nanostructures 610. (In this particular embodiment, the nanostructures 610 are separate nanostructures, that is, channels that are not like porous structures, such as isolated structures that are not contained within another structure.) For example, the electrolyte 650 can Similar to the electrolyte 150 shown in Fig. 1 first. The presence of the electrolyte 650 forms an electrical double layer, that is, the electrical storage device 600 is an EDLC. As an example, a first subset of the plurality of nanostructures 610 form a first electrode of the electrical storage device 600, and a second subset of the plurality of nanostructures 610 form a second electrode of the electrical storage device 600.
單純係由奈米結構及電解液所組成的蓄電裝置可表示依據本發明之實施例一種有價值且高電容之超電容器。但如前文討論，經常期望增高崩潰電壓及/或增加電容及減少蓄電裝置之漏電流，如此於若干實施例中，高k材料615(回想前文，於此處定義為具有至少3.9之介電常數之材料)可放置在電解液650與奈米結構610間。於該具體實施例中，高k材料615可呈至少部分覆蓋奈米結構之被覆物形式。於若干實施例中，至少若干奈米結構610可額外以可防止奈米結構610與電解液650間之電化學反應的材料645被覆。舉個實例，材料645可類似第5圖所示材料545，因此於一個實施例中，可呈於奈米結構表面上之汞(或所述其它物質中之一者)單層。A power storage device consisting solely of a nanostructure and an electrolyte can represent a valuable and high capacitance ultracapacitor in accordance with an embodiment of the present invention. However, as discussed above, it is often desirable to increase the breakdown voltage and/or increase the capacitance and reduce the leakage current of the electrical storage device, such that in several embodiments, the high-k material 615 (recall, previously defined herein as having a dielectric constant of at least 3.9) The material can be placed between the electrolyte 650 and the nanostructure 610. In this particular embodiment, the high k material 615 can be in the form of a coating that at least partially covers the nanostructure. In some embodiments, at least a few nanostructures 610 can additionally be coated with a material 645 that prevents electrochemical reaction between the nanostructures 610 and the electrolyte 650. By way of example, material 645 can be similar to material 545 shown in Figure 5, so in one embodiment, a single layer of mercury (or one of the other materials) can be present on the surface of the nanostructure.
於若干實施例中，奈米結構610為從適當材料(例如矽、矽鍺(SiGe)、III-V化合物(諸如砷化鎵(GaAs)等)及其它)所製成的奈米線。於其它實施例中，奈米結構610包含碳奈米管。In several embodiments, nanostructure 610 is a nanowire made from a suitable material, such as germanium, germanium (SiGe), III-V compounds (such as gallium arsenide (GaAs), etc., and others). In other embodiments, the nanostructure 610 comprises a carbon nanotube.
第7圖為流程圖顯示依據本發明之實施例製造蓄電裝置之導電結構之方法700。Figure 7 is a flow chart showing a method 700 of fabricating a conductive structure for a power storage device in accordance with an embodiment of the present invention.
方法700之步驟710係提供包含多種奈米結構於溶劑之溶液。一個實施例中，溶劑為光阻材料，特別為厚光阻材料(厚度約為500微米)。於實施例中，溶液可包含光阻以外之溶劑。於特定實施例中，溶液包含導電性奈米粒子於異丙醇。使用光阻作為溶劑可為優異，原因在於其相當常用於微電子技術。若導電結構期望圖案化，則使用光阻也可簡化依據方法700之導電結構的圖案化。使用光阻作為溶劑之另一項可能優點係來自於溶劑中之奈米結構為碳奈米管。該種情況下，(以碳為主的)光阻之有機性質結果導致與有機奈米管具有高度可相容性。此種溶液內之碳-碳接觸獲得高導電性。Step 710 of method 700 provides a solution comprising a plurality of nanostructures in a solvent. In one embodiment, the solvent is a photoresist material, particularly a thick photoresist material (having a thickness of about 500 microns). In embodiments, the solution may comprise a solvent other than the photoresist. In a particular embodiment, the solution comprises conductive nanoparticles in isopropanol. The use of photoresist as a solvent can be excellent because it is quite commonly used in microelectronics. The use of photoresist also simplifies the patterning of the conductive structures in accordance with method 700 if the conductive structures are desired to be patterned. Another possible advantage of using photoresist as a solvent is that the nanostructure derived from the solvent is a carbon nanotube. In this case, the organic nature of the (carbon-based) photoresist results in a high compatibility with the organic nanotubes. The carbon-carbon contact in such a solution gives high conductivity.
方法700之步驟720係將溶液施用至基體上。舉個實例，基體可由矽(或許重度摻雜矽)、矽或其它具有導電薄膜(例如鋁)沉積於其上之材料、具有金屬薄膜被覆之玻璃板或更常見任一種具有足夠硬度可作為撐體之適當導電材料所製成。一個實施例中，步驟720包含將光阻材料電噴紡於基體上。電子噴紡涉及施加電荷使得纖維或其它奈米結構可在期望的配置方向取向。於一個實施例中，電子噴紡光阻材料形成多根纖維，其中至少部分具有至少500微米之長度。正規噴紡(不含電荷)乃電子噴紡之替代之道。任一種旋轉程序涉及良好均勻地將溶液施用至基體上。另外，溶液可單純傾倒在基體上而未旋轉，但使用此項技術厚度可能較難控制，溶液之需要量必須極為小心地測量及考慮來確保溶液不會濺出晶圓或基體的邊緣之外。Step 720 of method 700 applies the solution to the substrate. For example, the substrate may be made of tantalum (perhaps heavily doped with tantalum), tantalum or other material having a conductive film (such as aluminum) deposited thereon, a glass sheet coated with a metal film, or more generally having sufficient hardness to serve as a support. Made of a suitable conductive material. In one embodiment, step 720 includes electrospraying the photoresist material onto the substrate. Electrospinning involves the application of a charge such that the fibers or other nanostructures can be oriented in the desired configuration direction. In one embodiment, the electrospun photoresist material forms a plurality of fibers, at least a portion of which has a length of at least 500 microns. Regular spray spinning (without charge) is an alternative to electronic jet spinning. Any of the rotation procedures involves applying the solution to the substrate well and evenly. In addition, the solution can be simply poured onto the substrate without rotation, but thickness can be difficult to control using this technique. The amount of solution required must be measured and considered with extreme care to ensure that the solution does not spill out of the edge of the wafer or substrate. .
方法700之步驟730係將溶液及基體退火來形成導電結構。退火逐出溶劑而留下相當厚的結構。一個實施例中，退火可包含熱解反應。若有所需，部分溶劑可於初步(較低溫事件)或許藉由在烤爐內烤乾基體而逐出，至少部分造成溶液的硬化。Step 730 of method 700 is to anneal the solution and substrate to form a conductive structure. Annealing ejects the solvent leaving a relatively thick structure. In one embodiment, the annealing can comprise a pyrolysis reaction. If desired, some of the solvent may be ejected at a preliminary (lower temperature event) or by baking the substrate in an oven, at least in part causing hardening of the solution.
方法700之步驟740為在至少若干奈米結構上形成介電材料來改良崩潰電壓。如此例如可藉在奈米結構上沉積鋁或其它適當材料及然後氧化鋁或其它材料達成。A step 740 of method 700 is to modify the breakdown voltage by forming a dielectric material over at least a plurality of nanostructures. This can be achieved, for example, by depositing aluminum or other suitable material on the nanostructure and then alumina or other materials.
方法700之效能結果導致導電結構可能具有相當厚度。為了達成穩健電容，電容結構可具有一般厚度，基於奈米結構之既有電容結構容易忽略此一事實。於至少若干實施例中，方法700使用厚的有機光阻(例如SR8)，其可以500微米或以上之厚度噴紡在基體上。於熱解而逐出溶劑後，留下奈米結構形成在高表面積結構上，具有約略等於光阻原先厚度之厚度。所示該類型之結構範例係顯示於第8圖，此處於基體810上之奈米結構820為目測可見。就此方面而言，須注意第8圖類似先前之若干圖式，為結構之理想化代表，該等結構實際上遠較少排序，且遠較為類似不整齊的乾草堆或蜂窩等。The performance results of method 700 result in a conductive structure that may have a substantial thickness. In order to achieve a robust capacitance, the capacitor structure can have a general thickness, which is easily overlooked by the existing capacitor structure of the nanostructure. In at least some embodiments, method 700 uses a thick organic photoresist (e.g., SR8) that can be spun onto a substrate at a thickness of 500 microns or greater. After the solvent is removed by pyrolysis, the nanostructure is formed on the high surface area structure with a thickness approximately equal to the original thickness of the photoresist. An example of the structure of this type shown is shown in Figure 8, where the nanostructure 820 on the substrate 810 is visually visible. In this respect, it should be noted that Figure 8 is similar to the previous ones and is an idealized representation of the structure, which is actually much less ordered and far resembles an irregular haystack or honeycomb.
厚型導電結構之另一種製法係使用奈米壓印光刻術。此種方法涉及形成一光筆，然後朝光阻等向下實體加壓，而將光阻材料成形為谷及高原。此種方法無法如同方法700所達成者一般厚之導電結構厚度，但雖言如此，可能導致或許約50微米至100微米之相當穩健的厚度。Another method of making thick conductive structures uses nanoimprint lithography. This method involves forming a stylus and then pressing the photoresist down into a solid body to form a valley and a plateau. This approach does not have the same thick conductive structure thickness as the method 700 achieves, but, to this extent, may result in a rather robust thickness of perhaps between about 50 microns and 100 microns.
第9圖為流程圖顯示依據本發明之實施例一種製造蓄電裝置之方法900。Figure 9 is a flow chart showing a method 900 of fabricating a power storage device in accordance with an embodiment of the present invention.
方法900之步驟910係提供具有第一區段及第二區段之導電結構。一個實施例中，步驟910包含提供包含多個奈米結構於溶劑之溶液，將該溶液施用至基體，及退火該溶液及基體來形成導電結構。A step 910 of method 900 provides a conductive structure having a first segment and a second segment. In one embodiment, step 910 includes providing a solution comprising a plurality of nanostructures in a solvent, applying the solution to a substrate, and annealing the solution and the substrate to form a conductive structure.
於方法900之步驟920係將膜或其它分隔件放置於第一區段及第二區段間，其中該分隔件允許離子電荷的移轉。於一個實施例中，步驟920或另一步驟進一步包含第一區段與第二區段間蝕刻一溝渠，及將分隔件放置於溝渠內。In step 920 of method 900, a film or other separator is placed between the first section and the second section, wherein the spacer allows for the transfer of ionic charge. In one embodiment, step 920 or another step further includes etching a trench between the first segment and the second segment, and placing the spacer in the trench.
方法900之步驟930係將電解液放置成與導電結構實體接觸。Step 930 of method 900 places the electrolyte in contact with the electrically conductive structural entity.
第10圖為方塊圖表示依據本發明之一實施例之行動電子裝置1000。如第10圖所示，行動電子裝置1000包含一基體1010，於其上配置微處理器1020及與微處理器1020相關聯之蓄電裝置1030。蓄電裝置1030可位在遠離微處理器1020之基體1010上，以實線標示，或可位在微處理器1020本身上，如虛線標示。一個實施例中，蓄電裝置1030包含藉電絕緣體而彼此分開之第一及第二導電結構，此處第一及第二導電結構中之至少一者包含含有多個通道之多孔結構。舉個實例，此種實施例係類似第1圖至第5圖所示實施例中之一者或多者，且描述於附屬上下文。於另一實施例中，蓄電裝置1030包含多個奈米結構(例如分開的奈米結構)及與奈米結構中之至少部分實體接觸之電解液。舉個實例，此一實施例係類似第6圖所示實施例中之一者或多者且描述於隨附之上下文。Figure 10 is a block diagram showing a mobile electronic device 1000 in accordance with an embodiment of the present invention. As shown in FIG. 10, the mobile electronic device 1000 includes a base 1010 on which a microprocessor 1020 and a power storage device 1030 associated with the microprocessor 1020 are disposed. The power storage device 1030 can be located on the base 1010 remote from the microprocessor 1020, indicated by a solid line, or can be located on the microprocessor 1020 itself, as indicated by a dashed line. In one embodiment, power storage device 1030 includes first and second electrically conductive structures separated from each other by an electrical insulator, wherein at least one of the first and second electrically conductive structures comprises a porous structure comprising a plurality of channels. By way of example, such an embodiment is similar to one or more of the embodiments shown in Figures 1 through 5 and is described in the accompanying context. In another embodiment, power storage device 1030 includes a plurality of nanostructures (eg, separate nanostructures) and an electrolyte in contact with at least a portion of the entities in the nanostructure. By way of example, this embodiment is similar to one or more of the embodiments shown in Figure 6 and is described in the accompanying context.
於至少若干實施例中，蓄電裝置1030為含在行動電子裝置1000內部之多個蓄電裝置中之一者(全部於第10圖以方塊1030表示)。該等實施例之一或多者中，行動電子裝置1000進一步包含與蓄電裝置相關聯之切換網絡1040。當電容器放電時，電容器並未維持恆定電壓，反而係以指數方式衰減(不似電池，電池於放電期間電壓維持相對恆定)。切換網絡1040包含電路或若干其它機制，該等電路或機制切入及切出各個電容器，因而維持相對恆定電壓。舉例言之，蓄電裝置初步可彼此並聯，然後於某個電壓量衰減之後，蓄電裝置之一子集可藉切換網絡充電因而串聯使得其個別電壓貢獻可增強下降中的總電壓。一個實施例中，切換網絡1040可使用如技藝界使用之既有矽裝置技術實現(電晶體、矽受控整流器(SCR)等)，而於其它實施例中，可使用微機電系統(MEMS)繼電器或開關實現(須注意傾向於具有極低電阻)。In at least some embodiments, power storage device 1030 is one of a plurality of power storage devices contained within mobile electronic device 1000 (all represented by block 1030 in FIG. 10). In one or more of these embodiments, the mobile electronic device 1000 further includes a switching network 1040 associated with the power storage device. When the capacitor is discharged, the capacitor does not maintain a constant voltage, but instead decays exponentially (not like a battery, the battery maintains a relatively constant voltage during discharge). Switching network 1040 includes circuitry or a number of other mechanisms that cut and cut individual capacitors, thereby maintaining a relatively constant voltage. For example, the power storage devices may initially be connected in parallel with each other, and then after a certain amount of voltage is attenuated, a subset of the power storage devices may be charged by switching the network and thus connected in series such that their individual voltage contributions may enhance the total voltage in the drop. In one embodiment, the switching network 1040 can be implemented using both germanium device technology (transistor, germanium controlled rectifier (SCR), etc.) as used in the art, while in other embodiments, microelectromechanical systems (MEMS) can be used. Relay or switch implementation (note that there is a tendency to have very low resistance).
於若干實施例中，行動電子裝置1000進一步包含與蓄電裝置1030相關聯之感測器網絡1050。於至少若干實施例中，多個蓄電裝置各自有其本身之感測器，指示蓄電裝置之某些表現參數。舉例言之，感測器可指示既有電壓位準以及正在進行中之放電反應，二者為可由切換網絡所使用之參數，特別於所使用之介電材料(或其它電絕緣體)並非線性，反而具有隨著電壓而改變之介電常數之情況下尤為如此。該等情況下，較佳係連同感測器網絡包括有限狀態機，諸如知曉介電質的表現及據此而產生回應之電壓控制單元1060。知曉介電質如何表現之電壓控制單元可補償任何非線性。與蓄電裝置1030相關聯之溫度感測器1070也可含括來感測溫度(或其它安全性相關參數)。於本發明之某些實施例中，行動電子裝置1000進一步包含下列中之一者或多者：顯示裝置1081、天線/RF元件1082、網路介面1083、資料載入裝置1084(例如鍵盤或觸控螢幕)、麥克風1085、攝影機1086、視訊投影器1087、全球定位系統(GPS)接收器1088等。In some embodiments, mobile electronic device 1000 further includes a sensor network 1050 associated with power storage device 1030. In at least some embodiments, each of the plurality of power storage devices has its own sensor that indicates certain performance parameters of the power storage device. For example, the sensor can indicate both the voltage level and the ongoing discharge reaction, which are parameters that can be used by the switching network, particularly the dielectric material (or other electrical insulator) used, and are non-linear. This is especially true in the case of a dielectric constant that changes with voltage. In such cases, it is preferred to include a finite state machine along with the sensor network, such as a voltage control unit 1060 that knows the performance of the dielectric and responds accordingly. A voltage control unit that knows how the dielectric behaves can compensate for any non-linearities. Temperature sensor 1070 associated with power storage device 1030 can also be included to sense temperature (or other safety related parameters). In some embodiments of the present invention, the mobile electronic device 1000 further includes one or more of the following: a display device 1081, an antenna/RF component 1082, a network interface 1083, and a data loading device 1084 (eg, a keyboard or a touch Control screen), microphone 1085, camera 1086, video projector 1087, global positioning system (GPS) receiver 1088, and the like.
第11圖為方塊圖表示依據本發明之一實施例之微電子裝置1100。如第11圖所示，微電子裝置1100包含基體1110、基體1110上方之微處理器1120、及與微處理器1120相關聯之蓄電裝置1130。蓄電裝置1130可位在基體1110上而遠離微處理器1120(例如晶粒端電容器)，以實線表示；或可位在微處理器1120本身上(例如於微處理器上方的堆積層)，如以虛線表示。一個實施例中，蓄電裝置1130包含藉電絕緣體而彼此分開之第一及第二導電結構，此處第一及第二導電結構中之至少一者包含含多個通道之多孔結構。舉個實例，本實施例可類似第1圖至第5圖所示且於隨附之上下文中描述的實施例中之一者或多者。於另一個實施例中，蓄電裝置1130包含多個奈米結構(例如分散性奈米結構)及與至少部分奈米結構做實體接觸之電解液。舉個實例，本實施例可類似第6圖所示，且於隨附之上下文描述之實施例中之一者或多者。Figure 11 is a block diagram showing a microelectronic device 1100 in accordance with an embodiment of the present invention. As shown in FIG. 11, the microelectronic device 1100 includes a substrate 1110, a microprocessor 1120 above the substrate 1110, and a power storage device 1130 associated with the microprocessor 1120. The power storage device 1130 can be located on the substrate 1110 away from the microprocessor 1120 (eg, a die-end capacitor), indicated by a solid line; or can be located on the microprocessor 1120 itself (eg, a buildup layer above the microprocessor), As indicated by the dotted line. In one embodiment, power storage device 1130 includes first and second electrically conductive structures separated from each other by an electrical insulator, wherein at least one of the first and second electrically conductive structures comprises a porous structure comprising a plurality of channels. By way of example, the present embodiment may be similar to one or more of the embodiments illustrated in Figures 1 through 5 and described in the accompanying context. In another embodiment, power storage device 1130 includes a plurality of nanostructures (eg, a dispersed nanostructure) and an electrolyte that is in physical contact with at least a portion of the nanostructures. By way of example, the present embodiment may be similar to one or more of the embodiments described in FIG. 6 and described in the accompanying context.
此處揭示之蓄電裝置於若干實施例中可用作為微電子裝置1100內部之解耦合電容器，該微電子裝置為較小，如本文它處描述之理由，提供比較既有解耦合電容器遠更高的電容及遠更低的阻抗。如前文已述，蓄電裝置1130可為支援基體電路(IC)或晶片之一部分，或可位在微處理器晶粒本身上。舉例言之，依據本發明之實施例，可形成微處理器晶粒上之多孔矽(或其類，如前文描述)區域，然後在微處理器晶粒之基體上形成高表面積嵌入式解耦合電容器。由於矽的孔隙度，嵌入式電容器將具有極高表面積。所揭示之蓄電裝置之其它可能用途包括用作為記憶體儲存元件(此處嵌入式DRAM辦法之z方向尺寸問題可藉由大為增高每單位面積的法拉(farad)加以解決)，或作為升壓電路之電壓轉換器的組件，或許連同電路區塊、個別微處理器核心等使用。The power storage device disclosed herein can be used as decoupling capacitors within the microelectronic device 1100 in several embodiments, the microelectronic device being smaller, as described herein, providing a much higher ratio of existing decoupling capacitors. Capacitance and far lower impedance. As previously described, power storage device 1130 can be part of a support base circuit (IC) or wafer, or can be located on the microprocessor die itself. For example, in accordance with an embodiment of the present invention, a region of a porous germanium (or a class thereof as described above) on a microprocessor die can be formed and then a high surface area embedded decoupling is formed on the substrate of the microprocessor die. Capacitor. Due to the porosity of the crucible, the embedded capacitor will have an extremely high surface area. Other possible uses of the disclosed power storage device include use as a memory storage element (where the z-direction size problem of the embedded DRAM approach can be solved by greatly increasing the farad per unit area), or as a boost The components of the voltage converter of the circuit may be used in conjunction with circuit blocks, individual microprocessor cores, and the like.
舉個實例，較高電容值於本文中為較佳，原因在於電路部分名目上係在某個(相對低的)電壓跑，但取而代之，需要較高電壓來提高電壓可被升壓至較高值的速度(例如快取記憶體、輸入/輸出(I/O)應用程式)。此種操作方案可能優於較高電壓用在每一處之辦法；換言之，於只有小量電路需要較高電壓之情況下，可能較佳對該小部分電路從較低基準線電壓升高電壓，而非對大部分電路從較高基準線電路降低電壓。未來世代的微處理器也可利用此處所述該型電壓轉換器。有更多電容可資利用來環繞封裝體或微處理器晶粒部署，可協助解決環繞電路傳輸電壓之電晶體間具有無法忍受之高電感的既有問題。For example, a higher capacitance value is preferred in this paper because the circuit portion is in a (relatively low) voltage run, but instead a higher voltage is required to increase the voltage to be boosted to a higher voltage. The speed of the value (such as cache memory, input / output (I / O) application). Such an operation scheme may be superior to the method of using a higher voltage at each location; in other words, in the case where only a small amount of circuit requires a higher voltage, it may be preferable to raise the voltage from the lower reference line voltage for the small portion of the circuit. Instead of reducing the voltage from the higher baseline circuitry for most circuits. Future generation microprocessors can also utilize the voltage converters described herein. More capacitors can be utilized to surround the package or microprocessor die layout, helping to solve the problem of unacceptably high inductance between transistors that transmit voltage around the circuit.
雖然已經參考特定實施例描述本發明，但熟諳技藝人士將了解可未悖離本發明之精髓及範圍做出多項變化。據此，本發明實施例之揭示意圖舉例說明本發明之範圍，而非意圖為限制性。本發明之範圍僅受隨附之申請專利範圍要求之程度所限。舉例言之，熟諳技藝人士顯然易知此處討論之蓄電裝置及相關結構之方法可於多個實施例實現，前文有關若干此等實施例之討論並未必然表示全部可能實施例的完整描述。While the invention has been described with respect to the specific embodiments thereof, it will be understood Accordingly, the invention is not intended to be limited by the scope of the invention. The scope of the invention is limited only by the scope of the appended claims. For example, it is apparent to those skilled in the art that the methods of the present invention and the related structures can be implemented in various embodiments, and the foregoing discussion of a number of such embodiments does not necessarily represent a complete description of all possible embodiments.
此外，已經就特定實施例描述效果、其它優點及對問題的解決之道。但該等效果、優點、問題的解決之道及可能使得任何效果、優點或解決之道發生或變成更顯著之任何元件不應解譯為申請專利範圍之任一項或全部各項之關鍵性、必要的或主要的特徵或元素。Moreover, effects, other advantages, and solutions to problems have been described in terms of specific embodiments. However, such effects, advantages, solutions to problems, and any components that may cause any effect, advantage, or solution to occur or become more significant should not be interpreted as critical to any or all of the scope of the patent application. , necessary or major features or elements.
此外，若實施例及/或限制符合如下規定，則遵照專屬原則，此處揭示之實施例及限制不應公開給大眾：(1)於申請專利範圍中並未明確地申請專利；及(2)遵照相當物原則為或可能為申請專利範圍中明示元素及/或限制之相當物。In addition, if the embodiments and/or limitations are in accordance with the following principles, the embodiments and limitations disclosed herein are not disclosed to the public: (1) the patent is not explicitly applied in the scope of the patent application; and (2) The photographic principles are or may be equivalent to the express elements and/or limitations in the scope of the patent application.
100、600、1030、1130．．．蓄電裝置100, 600, 1030, 1130. . . Power storage device
110、120．．．導電結構110, 120. . . Conductive structure
111、121、311．．．通道111, 121, 311. . . aisle
112、122．．．開口112, 122. . . Opening
115、125．．．表面115, 125. . . surface
130．．．分隔件130. . . Separator
140、540．．．導電性被覆物140, 540. . . Conductive coating
150、650．．．電解液150, 650. . . Electrolyte
231．．．溝渠231. . . ditch
300．．．多孔矽300. . . Porous 矽
330．．．電氣雙層(EDL)330. . . Electrical double layer (EDL)
515、615．．．高k材料515, 615. . . High k material
535、610、820．．．奈米結構535, 610, 820. . . Nanostructure
545、645．．．材料545, 645. . . material
605、810、1010、1110．．．基體605, 810, 1010, 1110. . . Matrix
700、900．．．方法700, 900. . . method
710、720、730、740、910、920、930．．．方法步驟710, 720, 730, 740, 910, 920, 930. . . Method step
1000、1100．．．行動電子裝置1000, 1100. . . Mobile electronic device
1020、1120．．．微處理器1020, 1120. . . microprocessor
1040．．．切換網絡1040. . . Switch network
1050．．．感測器網絡1050. . . Sensor network
1060．．．電壓控制單元1060. . . Voltage control unit
1070．．．溫度感測器1070. . . Temperature sensor
1081．．．顯示裝置1081. . . Display device
1082．．．天線/RF元件1082. . . Antenna / RF component
1083．．．網路介面1083. . . Network interface
1084．．．資料載入裝置1084. . . Data loading device
1085．．．麥克風1085. . . microphone
1086．．．攝影機1086. . . camera
1087．．．視訊投影器1087. . . Video projector
1088．．．全球定位系統(GPS)接收器1088. . . Global Positioning System (GPS) Receiver
第1及2圖為依據本發明之一實施例蓄電裝置之剖面圖；1 and 2 are cross-sectional views showing a power storage device according to an embodiment of the present invention;
第3圖為依據本發明之一實施例一塊多孔矽之掃描電子顯微剖面影像；Figure 3 is a scanning electron micrograph image of a porous crucible according to an embodiment of the present invention;
第4圖為依據本發明之一實施例在一蓄電裝置之一通道內部的電氣雙層之剖面代表圖；Figure 4 is a cross-sectional view showing an electrical double layer inside a passage of a power storage device according to an embodiment of the present invention;
第5圖為依據本發明之實施例在一蓄電裝置之一通道之剖面圖，顯示各層及各種結構；Figure 5 is a cross-sectional view of a channel of a power storage device according to an embodiment of the present invention, showing layers and various structures;
第6圖為依據本發明之另一實施例一蓄電裝置之剖面圖；Figure 6 is a cross-sectional view showing a power storage device according to another embodiment of the present invention;
第7圖為流程圖顯示依據本發明之一實施例，一種針對蓄電裝置製造導電結構之方法；Figure 7 is a flow chart showing a method of fabricating a conductive structure for a power storage device in accordance with an embodiment of the present invention;
第8圖為依據本發明之一實施例，相對厚的導電結構之透視圖；Figure 8 is a perspective view of a relatively thick conductive structure in accordance with an embodiment of the present invention;
第9圖為流程圖顯示依據本發明之一實施例一種製造蓄電裝置之方法；Figure 9 is a flow chart showing a method of manufacturing a power storage device according to an embodiment of the present invention;
第10圖為方塊圖表示依據本發明之一實施例之行動電子裝置；及Figure 10 is a block diagram showing a mobile electronic device in accordance with an embodiment of the present invention; and
第11圖為方塊圖表示依據本發明之一實施例之微電子裝置。Figure 11 is a block diagram showing a microelectronic device in accordance with an embodiment of the present invention.
100‧‧‧蓄電裝置100‧‧‧Power storage device
110、120‧‧‧導電結構110, 120‧‧‧ conductive structure
111、121‧‧‧通道111, 121‧‧‧ channels
112、122‧‧‧開口112, 122‧‧‧ openings
115、125‧‧‧表面115, 125‧‧‧ surface
130‧‧‧分隔件130‧‧‧Parts
140‧‧‧導電性被覆物140‧‧‧Electrical coatings
150‧‧‧電解液150‧‧‧ electrolyte
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| US7486497B2 (en) * | 2003-10-10 | 2009-02-03 | Japan Gore-Tex, Inc. | Electrode for electric double layer capacitor, method for manufacturing same, electric double layer capacitor, and conductive adhesive |
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| US7486497B2 (en) * | 2003-10-10 | 2009-02-03 | Japan Gore-Tex, Inc. | Electrode for electric double layer capacitor, method for manufacturing same, electric double layer capacitor, and conductive adhesive |
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