TW477992B - Niobium capacitor and process for producing same - Google Patents

Abstract

A capacitor comprising two electrodes, and a dielectric interposed between the two electrodes; said dielectric having a two-layer structure composed of a first layer predominantly comprised of niobium oxide Nbox (X=2.5) and a second layer predominantly comprised of a mixture of niobium oxide Nbox (X=2.5) and Nbox (X=2.0). Preferably, the amount of Nbox (X=2.5) in the first layer and the amount of the Nbox mixture in the second layer are at least 90 weight %; the ratio of Nbox (X=2.5) to Nbox (X=2.0) in the second layer is 1/4 to 4/1 by mol; and the amount of the first layer is 0.01 to 10 vol.% based on the sum of the two layers. One of the electrodes is preferably made of a partially nitrided niobium, especially a partially nitrided niobium prepared by nitriding a sintered niobium body.

Description

經濟扪智慧財產局員工消費合作社印製 477992 A7 _ B7 五、發明說明（1 ) 本發明係有關於一種每單位重量之容量大且漏電流（ 以下簡稱「LC」）特性良好之鈮電容器及其製造方法。 近年來，藉1C及印刷基板等之小型化、高積體化形成 之行動電話、筆記型個人電腦、電子記事本等之小型及輕 量之電子機器廣泛普及，用以於該等電子機器之電容器針 對小型且大容量之開發需求也隨之增強。 用以於以上領域之電容器中，钽電解電容器雖有點重 量’其容量也大，且性能良好，所以被廣泛使用。該鉅電 解電容器係使用氧化钽作為電介質。 進而’針對電容器容量的加大，也討論用以電容率比 氧化钽大之氧化鈮及氧化鈦作為電介質之鈮電容器及鈦電 容器之開發。但是，卻由於將氧化鈮及氧化鈦用以作為電 介質之電容器時，因其LC特性不夠充分，而缺乏實用性 ，所以需要改善。 本發明之目的在於提供一種鈮電容器，其係具有優異 之電介質特性之氧化鈮電介質者，該鈮電容器之每單位重 量之容量大，且LC特性良好者。 本發明之另一目的在於提供一種製造鈮電容器之方法 ，其係使該鈮電容器之每單位重量之容量大，且LC特性 良好，又LC值之不均勻度小者。 本發明人係經研究後得知：將氧化鈮作為電介質之鈮 電容器之LC特性不充分之原因之一係因氧對用以構成氧 化銳之說之結合量過剩或不足所致者；根據該知見，而終 究完成本發明。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 4 -----I.-----^----I I I I ^-------- (請先閱讀背面之注意事項再填寫本頁) 477992 ^:濟部智^-財產局員工消費合作社印製 A7 B7 五、發明說明（2) 根據本發明係提供一種鈮電容器，該電容器之特徵在 於該構成係由兩電極及夾設在該兩電極間之電介質所形成 者’而該電介質之構成係包含有二層構成，該二層構成係 :以氧化鈮NbOx(X=2.5)為主要組成之第1層；以友以氧化 鈮NbOx(X=2.5)與氧化鈮NbOx(X=2.0)為主要組成之第2層 者。 進而，根據本發明係提供一種製造鈮電容器之方法， 該方法之特徵在於··該電容器之構成包含有將鈮之一部分 氮化之燒結體為一方之電極、另一電極，及夾設在該兩電 極間之電介質者；而該方法係使前述燒結體氮化時，藉於 鈮粉成型體燒結後，將該燒結體置於氮氣環境中加以進行 用以實施本發明之最佳態樣 本發明之鈮電容器係用以一種夾設在兩電極間之電介 質，該電介質之構成係包含有2層構成，該2層構成係：以 氧化鈮NbOx(X=2.5)為主要組成之第1層；以及以氧化鈮 NbOx(X=2.5)及氧化鈮NbOx(X=2.0)之混合物為主要組成之 第2層者。 一般而言，將氧化鈮之構造以NbOx(X係指氧係與鈮 結合之莫耳比）表示時，指使氧係以X值0.9、1.0、1.1、2.0 及2.5之比例結合者。具以上結合值之氧化鈮係藉以X線光 電子分光法解析而可鑑定者。用以於本發明且Χ=2·5之氧 化鈮係可舉Nb205例者為佳。又，Χ=2·0之氧化鈮係可以 Nb02例者為佳。 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） I I I I-----I I I · ·1111111 ^« — — — — — 1 — (請先閱讀背面之注意事項再填寫本頁) 經;-&部智慧財產局員工消費合作社印製 477992 Α7 ____ _ Β7 五、發明說明（3 ) 在以上氧化鈮中，利用具以NbOx(X=2.5)為主要組成 之第1層以及以NbOx(X=2.5)及NbOx(X=2.0)之混合物為主 要組成之第2層之二層構造之氧化鈮作為電介質，以作成 電容器，可得到一 LC值極低之電容器❶雖然該原因尚未 完全解明，但可推測出：以不具前述特定的2層構造之氧 化銳為主要組成作成電介質時，由於電介質中之氧由電介 質側朝電極側，或附著在電極上之内含氧由電極側朝電介 質側移動，致使電介質本身之特性不安定，而導致LC值 增加者。而相對地，在使用前述特定2層構造之氧化鈮為 電介質之本發明之電容器係，即使產生前述氧之移動，但 這也局限於電介質内部，所以在表面上形成平衡狀態，致 使電介質本身之特性也趨於安定者。 用以於本發明之氧化捉電介質中，「作為主要組成」 意指NbOx(X=2.5)佔第1層之60重量％以上，又，NbOx (X= 2.5)及NbOx(X=2.0)之混合物佔第2層之60重量％以上者。 電容器之LC值係ΙμΑ以下者為佳，在作成如此電容器時， 使第1層之氧化鈮中之NbOx(X=2.5)含量以及NbOx(X=2.5) 及NbOx(X=2.〇)之混合物含量係各為9〇重量。/〇以上，特別 是95重量。/〇以上者為佳。 進而，用以作為具良好LC值之電容器時，使第2層中 之NbOx(X=2.5)及NbOx(X=2.0)之莫耳比係在於1 : 4〜4 ·· 1 範圍内者為佳’又在於1 : 3〜3: 1範圍内者更佳。第1層 係相對於電介質之第2層之比例係以〇·〇ι〜1〇含量〇/〇，尤 其是具0.04〜3容量％者為佳。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 6 -----------HI--— It---I----- (請先閱讀背面之注意事項再填寫本頁) /外2 A7 B7 經濟部智^^產局口肖工消費合作社印製 五、發明說明（4 ) 用以形成具有前述2層構造之氧化鈮電介質層之方法 係採用諸如：使含鈮之烷氧錯合物、乙醯乙酸錯合物等之 範錯合物附著在電極上，隨即加以熱分解及/或加水分解 之方法；或，諸如後述，用以形成由鈮或鈮之一郜分氮化 之氮化鈮形成之電極時，藉使該電極電解氧化，或諸如前 述’用以將銳錯合物附著在電極上後，在获電極上熱分解 及，/或加水分解等之方式，在電極上形成氧化鈮電介質層 之方法。依情況而定也可使用多種方法的組合。在將鈮電 極或將鈮之一部分氮化之鈮電極電解氧化而製作氧化鈮電 介質時’本發明之電容器構建成電極電容器，而鈮電極或 將銳之一部分氮化之鈮電極則成為陽極❶在鈮電極或在將 銳之一部分氮化之鈮電極上使鈮錯合物分解而製作氧化鈮 電介質時，該電極係理論上是沒有極性，可為陽極，也可 為陰極。 用以將銳電極或將銳一部分氣化之捉電極電解氧化時 ’通常是用質子酸水溶液，諸如0.1 〇/〇磷酸水溶液或硫酸 水溶液作為電解液。在將鈮錯合物熱分解及/或加水分解 製作時，根據鈮錯合物之種類、濃度、分解溫度、分解時 間、分解時之環境氣體之種類及其濃度，又在鈮電極或將 銳之一部分氮化之鈮電極電解氧化製作時，根據所使用之 電極之種類、形狀、電解液之種類、濃度、電解溫度、時 間等’使NbOx中之X值產生變化，所以需要先檢查由準備 實驗所製作之電介質之X線光電子分光法之圖中，決定好 條件。 本纸張尺度適用中國國家標準（CNS)A4規格（210x297公釐） — — — — — — — — — — — — — ·1111111 ^ ·1111111 ί請先閲讀背面之注意事項再填寫本頁) 477992 A7 ___ B7 五、發明說明（5 ) <請先閱讀背面之注意事項再填寫本頁) 一般，分解溫度高，分解時間愈長，分解環境氣體中 之氧氣濃度愈高，又電解液濃度愈高，電解溫度高且時間 愈長，所得到之氧化鈮NbOxiX值有愈大之傾向。 本發明之電介質層只要是設於兩電極間，即寸發揮其 作用效果，因此不需特別限定其形態，又不具一定厚度也 可。進而具有使電極組裝在電介質内之形狀部位也可。 在本發明之電容器中所使用之一方電極之材料係可以 紹、鈕、鈦、鈮、將鈮之一部份氮化之氮化鈮、及以上金 屬之合金等為例。 電極形狀有諸如板狀、箔狀、棒狀、燒結艘。電容器 之大小係參照所需要之電容器容量而決定。若呈板狀、箔 狀、棒狀時可用折彎、捲繞，以增加每單位體積之電極表 面積使用。作為燒結體電極使用時，可將前述金屬之微粉 末加壓成形後，藉於10G〜10·6Τ〇ΓΓ之減壓下，以500〜2000 C、數分鐘〜數小時燒成製作之。 經濟部智慧財產局員工消費合作社印制衣 在前述電極材料中，因為使用鈮或鈮之一部分氮化之 氮化鈮，可得到每單位重量之容量大之電容器，所以為佳 ’尤其是使用氮化鈮時可使LC特性變得更好，因此更佳 。即，使將鈮之一部分氮化之氮化鈮作為電極之鈮電容器 係宜作為供高容量且低LC之需求之電路用之電容器。 該氮化鈮係可藉將鈮之一部分氮化，諸如在氮氣環境 下氮化形成。在氮化鈮中之結合氮之含量係藉鈮金屬之形 狀而可改變，而粒徑在30微米程度以下之粉末係根據氮化 鈮之重量，通常在10〜200,000ppm範圍内，而在於10〜 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟郎智^^產局員工消費合作社印製 477992 A7 五、發明說明（6 ) 150,000Ppm範圍者為佳，又在於1〇〇〜1〇〇〇〇ppm範圍内 者更佳。 氮化反應溫度雖未特別限制，在工業上係採用室溫〜 2,000 C ’而以250〜2,000eC為佳，且反應時間係:ι〜50小 時左右，即可得到含有所需氮量之氮化鈮。一般而言可在 高溫且短時間内將表面氮化者。即使以室溫左右之低溫度 ，在氮氣環境下放置鈮金屬之微粉末數十小時以上時，也 可传到具有所需氮量數十ppm〜數百ppm之氣化媒。 作成由將銳之一部分氮化之燒結體構成之電極時，如 前述，用以將鈮粉或成型品氮化後隨即燒結之方法製作也 可，或，也可採用將鈮粉之成型品燒結後氮化之方法。根 據後者之燒結後氮化之方法，可得到LC值之不均勻度小 之電容器，因此為佳。即，依照前者方法將鈮粉氮化後再 將該成型品燒結時，因燒結時之加熱而有使燒結體之微細 構造形成不均之情況產生。相對地，將鈮粉之成型體燒結 後再氮化時，可得到具均勻微細構造之電極，且可使電容 器之LC值之不均勻度降低者。 未氮化之鈮燒結體係可用以諸如將鈮粉之成型體在真 空下且以高溫燒結製造之❶具體而言，藉將鈮加壓成型後 ，在10·丨〜l(T6Torr之減壓下且以1，〇〇〇〜2,000°c ,放置數 分鐘〜數小時，則可得到該燒結體〃一般而言，燒結溫度 係根據妮粉之粒徑而有變化，粒徑愈小，以低溫愈佳。 用以氮化燒結體之條件及氮化量係與將前述鈮粉氮化 時者相同。一般而言，在溫度2,000°C下放置數10小時， 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐〉 9 ------- I — — — — — — -^ί! (請先閱讀背面之注意事項再填寫本頁) 477992 A7Printed by the Economic and Intellectual Property Bureau's Consumer Cooperatives 477992 A7 _ B7 V. Description of the Invention (1) The present invention relates to a niobium capacitor with a large capacity per unit weight and good leakage current (hereinafter referred to as "LC") characteristics and its characteristics. Production method. In recent years, small and lightweight electronic devices such as mobile phones, notebook personal computers, and electronic notebooks formed by miniaturization and high integration of 1C and printed circuit boards have been widely used for these electronic devices. Capacitor development needs for small and large capacitors have also increased. Among the capacitors used in the above fields, tantalum electrolytic capacitors are widely used because of their large capacity and good performance. This giant electrolytic capacitor uses tantalum oxide as the dielectric. Furthermore, in view of the increase in capacitor capacity, the development of niobium capacitors and titanium capacitors using niobium oxide and titanium oxide having a permittivity larger than tantalum oxide as a dielectric is also discussed. However, when niobium oxide and titanium oxide are used as capacitors for dielectrics, their LC characteristics are not sufficient and their practicality is lacking, so they need to be improved. An object of the present invention is to provide a niobium capacitor, which is a niobium oxide dielectric having excellent dielectric characteristics, a niobium capacitor having a large capacity per unit weight and good LC characteristics. Another object of the present invention is to provide a method for manufacturing a niobium capacitor, which is one in which the capacity per unit weight of the niobium capacitor is large, the LC characteristics are good, and the unevenness of the LC value is small. The inventors have learned after research that one of the reasons for the insufficient LC characteristics of niobium capacitors using niobium oxide as a dielectric is due to an excess or deficiency of the amount of oxygen that is used to form the sharp oxide; according to the Knowing, and finally completing the present invention. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 4 ----- I .----- ^ ---- IIII ^ -------- (please first Read the notes on the back and fill in this page again) 477992 ^: Jibu Zhi ^-printed by the Consumer Bureau of the Property Bureau A7 B7 V. Description of the invention (2) According to the present invention, a niobium capacitor is provided. The capacitor is characterized by the composition It is formed by two electrodes and a dielectric sandwiched between the two electrodes, and the composition of the dielectric includes a two-layer structure. The two-layer structure is composed of niobium oxide NbOx (X = 2.5) as the main component. 1 layer; the second layer consisting mainly of niobium oxide NbOx (X = 2.5) and niobium oxide NbOx (X = 2.0). Furthermore, according to the present invention, there is provided a method for manufacturing a niobium capacitor, which is characterized in that the structure of the capacitor includes one electrode, the other electrode, and a sandwiched portion of a sintered body in which a portion of the niobium is nitrided. The dielectric between the two electrodes; and the method is to nitrate the aforementioned sintered body by sintering the niobium powder molded body, and then the sintered body is placed in a nitrogen environment to carry out the best state of the invention. The niobium capacitor is a dielectric sandwiched between two electrodes. The composition of the dielectric includes a two-layer structure. The two-layer structure is a first layer mainly composed of niobium oxide NbOx (X = 2.5); And the second layer whose main composition is a mixture of niobium oxide NbOx (X = 2.5) and niobium oxide NbOx (X = 2.0). Generally speaking, when the structure of niobium oxide is expressed as NbOx (X is the molar ratio of the oxygen system to niobium), it means that the oxygen system is combined with the X values of 0.9, 1.0, 1.1, 2.0, and 2.5. Niobium oxide with the above binding value can be identified by X-ray photoelectron spectroscopy analysis. The niobium oxide used in the present invention and X = 2.5 is preferably Nb205 cases. In addition, the niobium oxide system with X = 2 · 0 is preferably Nb02. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) III I ----- III · · 1111111 ^ «— — — — — 1 — (Please read the notes on the back before filling (This page) is printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Intellectual Property, 477992 Α7 ____ _B7 V. Description of the Invention (3) In the above niobium oxide, the first component with NbOx (X = 2.5) as the main component is used. Layer and a two-layer, two-layer structure of niobium oxide with a mixture of NbOx (X = 2.5) and NbOx (X = 2.0) as the main composition as a dielectric to make a capacitor, a capacitor with an extremely low LC value can be obtained. The reason has not been fully understood, but it can be inferred that when the dielectric is composed mainly of oxidized sharp material without the aforementioned specific two-layer structure, the oxygen in the dielectric moves from the dielectric side to the electrode side, or contains oxygen inside the electrode. Moving from the electrode side to the dielectric side causes the characteristics of the dielectric itself to be unstable, leading to an increase in the LC value. In contrast, in the capacitor system of the present invention using the specific two-layer structure of niobium oxide as the dielectric, even if the aforementioned movement of oxygen occurs, this is also limited to the inside of the dielectric, so a state of equilibrium is formed on the surface, causing the dielectric itself Traits also tend to stabilize. As used in the oxidative trapping dielectric of the present invention, "as a main component" means that NbOx (X = 2.5) accounts for more than 60% by weight of the first layer, and that NbOx (X = 2.5) and NbOx (X = 2.0) The mixture accounts for more than 60% by weight of the second layer. The LC value of the capacitor is preferably less than 1 μA. When making such a capacitor, the content of NbOx (X = 2.5) and NbOx (X = 2.5) and NbOx (X = 2.〇) in the first layer of niobium oxide are made. The mixture contents were each 90% by weight. / 〇 or more, especially 95 weight. / 〇 or more is preferred. Furthermore, when used as a capacitor with a good LC value, the molar ratio of NbOx (X = 2.5) and NbOx (X = 2.0) in the second layer is in the range of 1: 4 to 4 ·· 1 Jia 'is again in the range of 1: 3 ~ 3: 1. The ratio of the first layer to the second layer of the dielectric is 0.001 to 10, and the content is preferably 0.04 to 3% by volume. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 6 ----------- HI --- It --- I ----- (Please read the back first (Please note this page before filling out this page) / Outer 2 A7 B7 Printed by the Ministry of Economic Affairs ^^ Production Bureau Mouth Xiao Gong Consumer Cooperative Co., Ltd. V. Description of Invention (4) The method for forming a niobium oxide dielectric layer with the two-layer structure Adopting methods such as: attaching vanadium complexes containing niobium-containing alkoxy complexes, acetoacetic acid complexes, and the like, followed by thermal decomposition and / or hydrolytic decomposition; or, such as described later, to form When an electrode is formed of niobium or niobium nitride nitrided with niobium, one of niobium, the electrode is thermally decomposed on the electrode by electrolytic oxidation of the electrode, or after it is used to attach a sharp complex to the electrode as described above. A method of forming a niobium oxide dielectric layer on the electrode by means of water decomposition. Depending on the situation, a combination of methods can also be used. When a niobium electrode or a niobium electrode which is a part of niobium is electrolytically oxidized to produce a niobium oxide dielectric, the capacitor of the present invention is constructed as an electrode capacitor, and a niobium electrode or a niobium electrode which is a sharp part of the niobium is used as an anode. In the case of a niobium electrode or a niobium complex formed by decomposing a sharply nitrided niobium electrode to produce a niobium oxide dielectric, the electrode system is theoretically non-polar and may be an anode or a cathode. When electrolytically oxidizing a sharp electrode or a capture electrode that vaporizes a sharp portion, an aqueous protonic acid solution, such as a 0.1 / 0 phosphoric acid aqueous solution or a sulfuric acid aqueous solution, is usually used as the electrolyte. When the niobium complex is thermally decomposed and / or hydrolyzed, according to the type, concentration, decomposition temperature, decomposition time, and type and concentration of the ambient gas during the decomposition, the niobium electrode or Part of the nitrided niobium electrode is produced by electrolytic oxidation. The X value in NbOx will change according to the type and shape of the electrode used, the type, concentration, electrolytic temperature, and time of the electrolyte. The X-ray photoelectron spectroscopy of the dielectric produced in the experiment determines the conditions. This paper size applies to China National Standard (CNS) A4 specifications (210x297 mm) — — — — — — — — — — — — · 1111111 ^ · 1111111 (Please read the precautions on the back before filling out this page) 477992 A7 ___ B7 V. Description of the invention (5) < Please read the notes on the back before filling out this page) Generally, the higher the decomposition temperature, the longer the decomposition time, the higher the oxygen concentration in the decomposition ambient gas, and the more the electrolyte concentration The higher, the higher the electrolysis temperature and the longer the time, the higher the NbOxiX value of the obtained niobium oxide tends to be. As long as the dielectric layer of the present invention is provided between two electrodes, its effect can be exerted, so its shape is not particularly limited, and it does not need to have a certain thickness. Further, it may have a shape portion in which the electrode is incorporated in the dielectric. The material of one of the square electrodes used in the capacitor of the present invention can be exemplified by Ni, Ni, Nb, Niobium Nitride, which is a part of Niobium, and alloys of the above metals. Electrode shapes include plate, foil, rod, and sintered vessels. The size of the capacitor is determined by referring to the required capacitor capacity. If it is plate-shaped, foil-shaped or rod-shaped, it can be bent and rolled to increase the electrode surface area per unit volume. When used as a sintered body electrode, the fine powder of the aforementioned metal can be pressed and formed, and then fired at 500 to 2000 C for several minutes to several hours under a reduced pressure of 10G to 10.6T0ΓΓ. In the aforementioned electrode materials, it is better to use niobium or niobium nitride that is a part of niobium to obtain a capacitor with a large capacity per unit weight, so it is better to use it, especially nitrogen. When niobium is made, the LC characteristics become better and therefore better. That is, a niobium capacitor using niobium nitride, which is a part of niobium nitride, as an electrode is suitable as a capacitor for a circuit having a high capacity and a low LC requirement. The niobium nitride system can be formed by nitriding a part of niobium, such as nitriding under a nitrogen environment. The content of bound nitrogen in niobium nitride can be changed by the shape of the niobium metal, and powders with a particle size of less than 30 microns are usually in the range of 10 ~ 200,000 ppm based on the weight of niobium nitride, but it is 10 ~ This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Economic Lang Zhi ^ ^ Printed by the Production Bureau Employee Consumer Cooperative 477992 A7 V. Invention description (6) It is better to have a range of 150,000Ppm, but also Those in the range of 100 to 10,000 ppm are more preferable. Although the nitriding reaction temperature is not particularly limited, industrially, room temperature to 2,000 C 'is preferred, and 250 to 2,000 eC is preferred, and the reaction time is about 1 to 50 hours to obtain nitrogen containing the required amount of nitrogen. Of niobium. Generally, the surface can be nitrided at high temperature and in a short time. Even at a low temperature of about room temperature, when the fine powder of niobium metal is left in a nitrogen environment for more than tens of hours, it can be transmitted to a gasification medium having a required nitrogen amount of several tens ppm to several hundreds ppm. When forming an electrode composed of a sharply nitrided sintered body, as described above, it can be produced by nitriding a niobium powder or a molded product and then sintering it, or it can also be a sintering of a niobium powder molded product. After nitriding method. According to the latter method of nitriding after sintering, a capacitor with small nonuniformity in LC value can be obtained, so it is preferable. That is, when the niobium powder is nitrided in accordance with the former method and the molded product is sintered, the fine structure of the sintered body may be uneven due to heating during sintering. In contrast, when the formed body of the niobium powder is sintered and then nitrided, an electrode with a uniform and fine structure can be obtained, and the unevenness of the LC value of the capacitor can be reduced. The non-nitrided niobium sintering system can be used, for example, to make niobium powder compacts under vacuum and sinter at high temperature. Specifically, by pressing the niobium under pressure, the pressure is reduced to 10 · 丨 ~ l (T6Torr under reduced pressure). The sintered body can be obtained at a temperature of 1,000 to 2,000 ° C for several minutes to several hours. Generally speaking, the sintering temperature varies according to the particle size of Ni powder. The smaller the particle size, the lower the temperature. The conditions and amount of nitriding for nitriding the sintered body are the same as those for nitriding the niobium powder. Generally speaking, it is placed at a temperature of 2,000 ° C for several 10 hours. CNS) A4 specification (210 X 297 mm) 9 ------- I — — — — — —-^ ί! (Please read the notes on the back before filling this page) 477992 A7

烴杳部智慧財產局員工湞費合作社印製 五、發明說明（7 ) 則可得到目標氮量之鈮燒結體。在高溫下且短時間内氮化 ’又，即使是室溫也在氮氣環境中放置鈮燒結體數10小時 ’即可得到氮量數百重量ppm之鈮燒結體。又，藉將氮加 壓導入，可縮短氮化時間。反言之，將氮在減壓卞導入時 ，可使氮化時間遲緩。例如，即使在1/ΙΟΟΤογγ之極端減 壓下放置前述銳燒結體，在數十小時之範圍之時間内，也 幾乎不會發生氣化。 如前述，藉燒結後再氮化之方法作成之將鈮之一部分 氮化之鈮燒結體作為一方之電極，以構成電容器時，則可 得到LC值之不均勻度小之電容器，而抑制該lc值之不均 勻度之效果不只用以於使用氧化鈮作為電容器之電介質時 之狀態，還可用以於使用諸如後述之氧化钽、高分子物質 ’陶瓷化合物等之狀態。在用以氧化藏以外之電介質之具 體例係用以作為氧化钽電介質時，可以含钽錯合物為例， 諸如，將鈕之烷氧錯合物、乙醯乙酸錯合物等附著在電極 上後，再加水分解及/或熱分解製造者。以高分子物質而 言諸如有氟樹脂、醇酸樹脂、丙烯酸樹脂、聚乙稀對苯二 曱酸等聚酯樹脂、乙烯系樹脂、乙烯笨樹脂、笨酚樹脂等 ’以高分子物質電介質層而言，諸如日本公開公報特開平 7·63045號所揭示者，在具有細孔或空隙部之金属表面上 形成有BaTi03、SrTi03、BaSn03等之辦欽碟型化合物。 另外，本發明之電容器之另一方之電極係沒有特別限 制’可選自在鋁電解電容器業界中公知之電解液、由有機 半導體構成之導電性有機化合物、由無機半導艘構成之無 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ί I-----^ -------^--------- {請先閱讀背面之注意事項再填寫本頁) 10 477992 A7 ________ B7 經濟都智慧財產局員工消費合作社印製 五、發明說明（ 機導電性化合物中之至少一種，又最好使用由電導率10·2 Swm·1〜1 之有機半導體及無機半導體中之至少一 種者。使用電導率li^S.cm·1〜ΙΟ^ππΓ1範圍内之化合物 者，可使所作成之電容器之阻抗值更小，且使在高·頻之容 量更大。 有機半導體之具體例係諸如有：由苯並毗喀啉4量體 及氣醌形成之有機半導體、以四硫代四氩蔥為主要組成之 有機半導體、以四氰合醌二甲烷為主要組成之有機半導體 ’及以下列一般式（1)或（2)表示之高分子上將雜質導入所 形成之導電性高分子為主要組成之有機半導體。Printed by the staff of the Intellectual Property Bureau of the Ministry of Hydrocarbons at the expense of cooperatives V. Invention description (7) The niobium sintered body with the target nitrogen content can be obtained. Nitriding at a high temperature for a short period of time ', and leaving the niobium sintered body in a nitrogen atmosphere for 10 hours even at room temperature' can obtain a niobium sintered body having a nitrogen content of several hundred ppm by weight. In addition, nitrogen can be shortened by introducing nitrogen under pressure. Conversely, when nitrogen is introduced under reduced pressure, the nitriding time can be delayed. For example, even if the sharp sintered body is placed under an extremely reduced pressure of 1/100 Τογγ, gasification hardly occurs in a range of tens of hours. As mentioned above, a niobium sintered body made of a part of niobium, which is made by the method of sintering and then nitriding, is used as one electrode to form a capacitor, and a capacitor with small unevenness in LC value can be obtained, and the lc is suppressed. The effect of the value non-uniformity is not only applied to the state when niobium oxide is used as the dielectric of the capacitor, but also applied to states such as tantalum oxide, a polymer substance, and a ceramic compound described later. When a specific example of a dielectric other than oxidative storage is used as a tantalum oxide dielectric, a tantalum complex may be used as an example, such as attaching a button alkoxide complex, acetic acid acetate complex, etc. to an electrode After the application, the manufacturer can add water and / or thermal decomposition. In terms of high molecular substances, such as polyester resins such as fluororesin, alkyd resin, acrylic resin, polyethylene terephthalic acid, vinyl resins, ethylene stupid resins, stupid phenol resins, etc. For example, as disclosed in Japanese Laid-Open Patent Publication No. Hei 6.63045, Chitin-type compounds such as BaTi03, SrTi03, and BaSn03 are formed on a metal surface having pores or voids. In addition, the electrode system on the other side of the capacitor of the present invention is not particularly limited, and may be selected from electrolytic solutions known in the aluminum electrolytic capacitor industry, conductive organic compounds composed of organic semiconductors, and non-paper-size paper composed of inorganic semiconductors. Applicable to China National Standard (CNS) A4 (210 X 297 mm) ί I ----- ^ ------- ^ --------- {Please read the precautions on the back before (Fill in this page) 10 477992 A7 ________ B7 Printed by the Consumers ’Cooperative of the Economic and Intellectual Property Bureau V. Invention Description (At least one of the organic conductive compounds, and it is best to use an organic compound with a conductivity of 10 · 2 Swm · 1 ~ 1 At least one of a semiconductor and an inorganic semiconductor. Using a compound having an electrical conductivity in the range of li ^ S.cm · 1 ~ ΙΟ ^ ππΓ1 can reduce the resistance value of the capacitor to be made, and the capacitance at a high frequency Specific examples of organic semiconductors are: organic semiconductors formed from benzopicaline 4 and quinone, organic semiconductors mainly composed of tetrathiotetrazine, and tetracyanoquinodimethane. Organic semiconductors And an organic semiconductor mainly composed of a conductive polymer formed by introducing an impurity into a polymer represented by the following general formula (1) or (2).

X (1) (式中，R1〜R4係指氫、碳原子數1〜6之烷基或碳原 子數1〜6之烷氧基；X係指氧、硫或氮原子；R5係指只在 X為原子時存在，氩或破原子數1〜6之烧基；R1與R2， 及R3與R4係各自相互結合，也可使該等原子相結合之苯環 上之碳原子一起形成環。）X (1) (where R1 to R4 refer to hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; X means oxygen, sulfur or nitrogen atom; R5 means only When X is an atom, argon or a broken group having 1 to 6 atomic atoms; R1 and R2, and R3 and R4 are each bonded to each other, and the carbon atoms on the benzene ring where these atoms are combined can also form a ring together .)

(2) · —111— ^ i — — — — — — ^ilm —--線 {請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 11 477992 經;&部智慧时產局員工消費合作社印製 A7 ' L-------- 五、發明說明（9 ) 子數1〜6之烧氧基，X係指氧、硫或氣原子；r3係指只在 X為氮原子時存在，氫或碳原子數1〜6之烷基；Rl與R2係 相互結合，也可使該等原子相結合之苯環上之碳原子一起 形成環。.） 用以式（1)或式（2)表示之導電性高分子之具體例係諸 如有：聚笨胺、聚環氧對苯、聚苯硫化物、聚硫笨、聚呋 喃，及聚甲基”比喀等。又，無機半導體係可用以二氧化鉛 或一氧化猛為主要組成之無機半導艘、由四三氧化鐵形成 之無機半導體等為例。前述電極材料也可用以組合二種類 以上者。 進而，另一方之電極係固體時，可用以諸如在該電極 上依序將碳漿、銀漿積層，以諸如環氧樹脂材料封口，構 成電容器。又使該電容器具有用以與鈮燒結體一體燒結成 型’或在後期溶接之銳或组導線也可。又，另一方電極為 液體時’可將由前述電極與電介質構成之構造體，以諸如 收容在與另一方電極連接之罐子裏之方式，而形成電容器 。此時可設計成，在將鈮之一部分氮化之鈮燒結體之電極 側以前述鈮或鉅導線為中介朝外導出，同時藉絕緣性橡膠 等使罐子與另一方電極絕緣者《又，即使存在有電介質與 電極之連接不完全之部位，諸如一部分電介質與電極之接 觸有欠缺的部位時也無所謂。 以下，針對本發明，用實施例加以明確說明。 又，鈮粉、鈮燒結體及電容器之特性可藉下列方法測 量且加以檢討。 本紙張尺度適用中國國家標準（CNS)A4規格（210x297公爱） 12(2) · —111— ^ i — — — — — — ^ ilm —-- line {Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 (Mm) 11 477992 Printed A7 'L by the Consumer Cooperatives of the Ministry of Wisdom and Time Production Bureau; 5. Description of the Invention (9) Benzyloxy group with the number of 1 to 6, X refers to Oxygen, sulfur, or gas atom; r3 refers to an alkyl group with 1 to 6 hydrogen or carbon atoms only when X is a nitrogen atom; R1 and R2 are bonded to each other, and the benzene ring that can combine these atoms Carbon atoms together form a ring. .) Specific examples of the conductive polymer represented by formula (1) or formula (2) are, for example, polybenzylamine, polyepoxy p-benzene, polyphenylene sulfide, polythiobenzyl, polyfuran, and polymer. "Methyl" Bika and the like. In addition, the inorganic semiconductor system can be an inorganic semiconductor with lead dioxide or monoxide as the main composition, an inorganic semiconductor formed of iron tetraoxide and the like. The aforementioned electrode materials can also be used in combination. Two or more types. Furthermore, when the other electrode is a solid, a capacitor such as a carbon paste and a silver paste can be laminated on the electrode in sequence, and sealed with an epoxy resin material to form a capacitor. It is also possible to sinter integrally with the niobium sintered body or to sharpen or group wires that are later dissolved. When the other electrode is a liquid, a structure composed of the foregoing electrode and the dielectric may be used to house the electrode connected to the other electrode. Can be used to form a capacitor in a can. At this time, it can be designed to lead out of the niobium sintered body part of the niobium niobium sintered body through the aforementioned niobium or giant wire as an intermediary, and at the same time use insulating rubber It is not necessary to insulate the can from the other electrode, even if there is a part where the connection between the dielectric and the electrode is incomplete, such as a part where the contact between the dielectric and the electrode is inadequate. Hereinafter, the present invention will be clarified by examples. Note. The characteristics of niobium powder, niobium sintered body, and capacitors can be measured and reviewed by the following methods. This paper size applies the Chinese National Standard (CNS) A4 specification (210x297). 12

(請先Mit背面之注意事項再填寫本頁) ·裝--------訂--------- 477992 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（10) (1) 粉末之平均粒徑 將用以粒度分布測定器（商品名「microtrack」）所測 定之D5G值（累積重量為50%之粒徑值）作為鈮粉之平均粒徑 (單位·· μΐη)。 (2) 結合氮量 與鈮粉及其燒結體相結合之氮量係用以由熱傳導度以 求出氮量之LECO公司製之氮量測定器算出。 (3) 電容器之容量 電容器之容量（單位：pF)係用以將電容器之電極與 LCR測定器（HP公司製）之端子直接連接，以120Hz(諸如 1〜15)或100kHz(諸如16〜36)測定者。 (4) 電容器之漏電流（LC)值 電容器之漏電流（LC)值（μΑ)係用以將電容器之電極與 測定器之端子直接連接，再外加電壓4 V，經過1分鐘後測 定者。LC值係指電容器20個之平均值。 (5) 電容器之漏電流值之不均勻度（2 σ ) 與電容器20個之LC值之平均值同時求取標準偏差， 用以將標準偏差（σ)之2倍值（2σ)作為不均勻值。 實施例1 在寬度7mm、長度120mm、厚度100mm之组箔之中心 處，將粗0.3mm</>、長10mm之组線的一部分（2mm左右）溶 接後燒捲，再將钽導線接合，形成電極。 另一方面，在另外準備之五丙基鈮酸鹽（鈮錯合物）之 3%甲苯溶液中，將前述電極以由鈕導線之上方算起剩7mm 本紙張尺度適用中國國家標準（CNS)A4規格（210x 297公爱） 13 — — — — — — — — — — — — — I I I I I I I I ^* _1111111 ^^ (請先M讀背面之注意事項再填寫本頁) 477992 .¾¾部智慧时產局員工消費合作社印制衣 A7 B7 五、發明說明（11) 之狀態浸泡後再拿起，在空氣環境中以200t3小時，隨即 以85°C之水蒸氣中1小時，進而在氮氣環境中以50(TC1小 時之方式重覆進行處理，在電極上形成了氧化鈮之電介質 層。該氧化鈮係藉X線光電子分光分析，確認NbOx(X=2.5) 佔99重量％之第1層下有NbOx(X=2.5)及NbOx(X=2.0)之混 合物（莫耳比3 : 2)佔99重量％之第2層（第1層相對於第2層 之比例為0.4容量％)。 接著’依序將電極浸泡在”比喀溶液、過硫酸銨及甲苯 磺酸之混合水溶液中重覆施以處理，在電介質上形成聚咄 嗔層。進而’藉依序在碳漿、銀漿中浸泡、乾燥後使之積 層後，裝設陰極導線，以環氧樹脂封口，形成電容器，測 定其容量及LC值。將結果示於表3。 實施例2 將粒徑分布10〜30μπι、平均粒徑14μιη之鈮粉約O.lg 與徑〇.3mm0、長度15mm之钽導線一起成形，得到一大 小3mmx3mmx2mm之成形體（钽導線在成形體中埋入2mm ，而在外突出有12mm。）。其次，將該成形體在真空中以 1500 °C燒結，構成鈮燒結體。接著，在5%磷酸水溶液中 ’用以26V生成，在室溫中持續5小時後，在燒結體上形 成氧化鈮之電介質層。藉以分析，可確認該電介質層係由 示於表2之組成形成者。 進而，將該電極浸泡在硝酸錳水溶液中後，反覆以250 °C熱分解，在電介質層上形成氧化錳之無機半導體層。隨 即’用以與實施例1同樣方式，將碳漿、銀漿依序積層， 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） 14 ---------裝·丨_丨丨丨丨—訂--------- {請先閱讀背面之注意事項再填寫本頁) 477992 A7 B7 .經;5部智慧时產局8工消費合作社印製 五、發明說明（！2) 以環氧樹脂封口，得到電容器。將該電容器之特性示於表 3 ° 實施例3 將兴在實施例2中得到者相同之鈮燒結體置於氮氣環 境中，以常壓且在300eC下2小時，得到部分氮化之鈮燒結 體（結合氮量2000重量ppm)。將實施例2中之鈮燒結體以部 分氮化之鈮燒結體代替外，其餘以相同方式製作電容器， 測定其容量及LC值。並將結果示於表3。 實施例4 同樣使用在實施例2中所用之鈮粉，先在50(TC之氮氣 環境中施以氮化，形成結合氮量約3000重量ppm之氮化鈮 粉後，經用以與實施例2同樣之條件處理，得到電容器。 將該電容器之特性示於表3。 實施例5 使用平均粒徑3μιη者作為鈮粉，且，將氮化溫度改為 400°C外，其餘用以與實施例4同樣方式製作電容器。將電 介質之組成示於表2,並將該電容器之特性示於表3。 實施例6 在實施例2中，將燒結體之生成條件設定成0.5%醋酸 水溶液中26V ' 10小時外，其餘與實施例4同樣製作一電 容器。將所製作之電介質之組成示於表2,並將電容器之 特性示於表3。 實施例7〜11 生成條件用以表1所揭露之條件進行電介質形成處理 ---------------^--- ί請先閱讀背面之注意事項再填寫本頁) 訂： -•線- 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 15 477992 Α7 _____ Β7 五、發明說明（13) ，以代替在實施例1之空氣環境中以2 〇 〇 t 3小時，隨即以8 5 °(：水蒸氣中1小時進而在氮氣環境中500°c 1小時之電介質 之電介質形成處理。除此之外，用以實施例1同樣之方式 製作電谷器。將電介質之組成示於表2，並將電容器之特 性示於表3。 表1 ——1_iL 質居形 成倏株 空氣中200X： 10小時 實施例7 水蒸氣中85r 10小時 ----氣氣環壌中500°c 5+時 空氣中25(TC 10小時 實施例8 水蒸氣中85°C 1小時 ----- 氤氧環培中8〇0°C 2]、時 空氣中125t 3小時 實施例9 水蒸氣中85°C 1小時 --氮氣璟请中500°C 1小時 f施例10 氮氣璟琦中800°C 10分鎊 f施例11 空ϋ中80T：_50小時 實施例12 將實施例2中燒結體之生成條件改變成磷酸水溶液濃 度0.03%、26V、室溫30分鐘外，其餘與實施例2同樣之方 式製作電容器。將所製作之電介質之組成示於表2，並將 電容器之特性示於表3。 本紙張尺度適用中國國家標準（CNS)A4規格（210x 297公釐） 丨！！ ！·裝 (請先W讀背面之注意事項再填寫本頁) 經;§郭智慧財產局員工消費合作社印製(Please fill in the notes on the back of Mit before filling in this page) · Installation -------- Order --------- 477992 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (10) (1) Average particle size of powder The D5G value (particle size value of 50% cumulative weight) measured by a particle size distribution measuring device (brand name "microtrack") is used as the average particle size (unit of niobium powder) Μ μηη). (2) Combined nitrogen content The nitrogen content combined with the niobium powder and its sintered body is calculated from a nitrogen content measuring device manufactured by LECO Corporation based on the thermal conductivity to determine the nitrogen content. (3) Capacitor capacity Capacitor capacity (unit: pF) is used to directly connect the electrode of the capacitor to the terminal of the LCR tester (made by HP) at 120Hz (such as 1 ~ 15) or 100kHz (such as 16 ~ 36) ) Tester. (4) Capacitor leakage current (LC) value Capacitor leakage current (LC) value (μΑ) is used to directly connect the capacitor electrode to the terminal of the tester, and then apply a voltage of 4 V, and measure after 1 minute. The LC value refers to the average of 20 capacitors. (5) The non-uniformity of the leakage current value of the capacitor (2 σ) and the average value of the LC values of 20 capacitors are used to calculate the standard deviation at the same time, which is used as the non-uniformity of 2 times the standard deviation (σ). value. Example 1 At the center of a group of foils with a width of 7mm, a length of 120mm, and a thickness of 100mm, a part (about 2mm) of a group wire having a thickness of 0.3mm < / > and a length of 10mm was melted, and then the tantalum wire was bonded. Form an electrode. On the other hand, in a 3% toluene solution of pentapropyl niobate (niobium complex) prepared separately, the above electrodes are 7mm left from the top of the button wire. The paper size applies the Chinese National Standard (CNS) A4 specifications (210x 297 public love) 13 — — — — — — — — — — — — — — IIIIIIII ^ * _1111111 ^^ (Please read the notes on the back before filling this page) 477992. Printed clothes A7 B7 of the employee's consumer cooperative V. Description of invention (11) After soaking, pick it up, 200t for 3 hours in the air environment, then in water vapor at 85 ° C for 1 hour, and then in the nitrogen environment for 50 hours (TC was processed for 1 hour, and a dielectric layer of niobium oxide was formed on the electrode. This niobium oxide was confirmed by X-ray photoelectron spectroscopy to confirm that NbOx (X = 2.5) accounted for 99% by weight of NbOx under the first layer. (X = 2.5) and NbOx (X = 2.0) mixture (Molar ratio 3: 2) of 99% by weight of the second layer (the ratio of the first layer to the second layer is 0.4% by volume). Sequentially immerse the electrode in a mixed solution of Bika solution, ammonium persulfate and toluenesulfonic acid Repeatedly apply the treatment to form a polyfluorene layer on the dielectric. Then, by soaking and drying the carbon paste and silver paste in sequence, the cathode leads are installed, sealed with epoxy resin, and capacitors are formed. The capacity and LC value were measured. The results are shown in Table 3. Example 2 A niobium powder having a particle size distribution of 10 to 30 μm and an average particle size of about 14 μm was about 0.1 g and a tantalum wire having a diameter of 0.3 mm0 and a length of 15 mm. A molded body having a size of 3mmx3mmx2mm was obtained (the tantalum wire was embedded 2mm in the molded body and 12mm protruded outside.) Second, the molded body was sintered in a vacuum at 1500 ° C to form a niobium sintered body. A% phosphoric acid aqueous solution was generated at 26V, and a dielectric layer of niobium oxide was formed on the sintered body after 5 hours at room temperature. By analysis, it was confirmed that the dielectric layer was formed by the composition shown in Table 2. Further After immersing the electrode in an aqueous solution of manganese nitrate, it was thermally decomposed at 250 ° C to form an inorganic semiconductor layer of manganese oxide on the dielectric layer. Then, in the same manner as in Example 1, the carbon paste and silver paste were used. Ordinal product layer, This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 public love) 14 --------- Loading · 丨 _ 丨 丨 丨 丨 -Order --------- {Please (Please read the notes on the back before filling this page) 477992 A7 B7. Script; printed by 5 Wisdom Time Bureau 8 Industrial Consumer Cooperatives 5. Description of the invention (! 2) Sealed with epoxy resin to get the capacitor. The characteristics are shown in Table 3 ° Example 3 A niobium sintered body obtained in the same manner as in Example 2 was placed in a nitrogen environment at 300 eC under normal pressure for 2 hours to obtain a partially nitrided niobium sintered body (bound nitrogen Amount of 2000 ppm by weight). The niobium sintered body in Example 2 was replaced with a partially nitrided niobium sintered body, and the remaining capacitors were fabricated in the same manner, and their capacity and LC value were measured. The results are shown in Table 3. Example 4 The niobium powder used in Example 2 was also used. Nitriding was performed in a nitrogen atmosphere at 50 ° C. to form a niobium nitride powder with a combined nitrogen content of about 3000 ppm by weight. The capacitor was processed under the same conditions to obtain a capacitor. The characteristics of the capacitor are shown in Table 3. Example 5 An average particle size of 3 μm was used as the niobium powder, and the nitriding temperature was changed to 400 ° C, and the rest was used for implementation. Example 4 A capacitor was fabricated in the same manner. The composition of the dielectric is shown in Table 2, and the characteristics of the capacitor are shown in Table 3. Example 6 In Example 2, the production conditions of the sintered body were set to 26 V in a 0.5% acetic acid aqueous solution. 'After 10 hours, a capacitor was fabricated in the same manner as in Example 4. The composition of the produced dielectric is shown in Table 2 and the characteristics of the capacitor are shown in Table 3. Examples 7 to 11 The production conditions were disclosed in Table 1. Conditions for dielectric formation processing ^^ --- ί Please read the precautions on the back before filling this page) Order:-• Line-This paper size applies to China National Standard (CNS) A4 Specification (210 X 297 mm) 15 477992 Α7 _____ Β7 Five Description of the invention (13), instead of the dielectric dielectric of 2000t for 3 hours in the air environment of Example 1, followed by 8 5 ° (1 hour in water vapor and 500 ° c 1 hour in nitrogen environment) Forming process. In addition, an electric valley device was made in the same manner as in Example 1. The composition of the dielectric is shown in Table 2, and the characteristics of the capacitor are shown in Table 3. Table 1 ——1_iL 200X in the air: 10 hours Example 7 85r in water vapor 10 hours ---- 500 ° c in air-gas loop 5 + 5 in air (TC 10 hours Example 8 85 ° C in water vapor 1 hour --- -8000 ° C in oxygen cyclic culture 2), 125t in air for 3 hours Example 9: 85 ° C in water vapor for 1 hour-nitrogen 璟 500 ° C for 1 hour f Example 10 nitrogen Medium 800 ° C 10 cents pound f Example 11 80T in air: _50 hours Example 12 The production conditions of the sintered body in Example 2 were changed to a phosphoric acid aqueous solution concentration of 0.03%, 26V, and room temperature for 30 minutes. A capacitor was fabricated in the same manner as in Example 2. The composition of the produced dielectric is shown in Table 2, and the characteristics of the capacitor are shown in Table 3. ! Scale applicable Chinese National Standard (CNS) A4 size (210x 297 mm) Shu !!-loaded (W Please read the Notes on the back to fill out this page) by; § Guo Zhihui Property Office employees consumer cooperatives printed

16 477992 A716 477992 A7

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.經濟部智慧豺產局員工消費合作社印製 五、發明說明（i4) 表2 實施例 電介質層之組成 (NbOx) 第1層之 X·1 第1層在電介質中 所有之比例(容量％) 第2層之莫耳比_2 (X=2.5) ： (X=2.0) 2 2.5 0.8 1 0.8 3 2.5 0.8 1 0.8 4 2.5 0.8 1 0.8 5 2.5 0.8 1 0.8 6 2.5 1.7 1 1.25 7 2.5 0.9 1 0.33 8 2.5 8.7 1 0·25 9 2.5 0.02 1 4 10 2.5 12 1 1.02 11 2.5 0.008 1 6·3 12 2.5 1.2 1 5 *1在實施例1〜12之第1層中之NbOx(X=2.5)之比例全部為99% *2在實施例卜12之第2層中之NbOx(X=2.5)及NbOx (Χ=2·0)之混合 物之比例全部為99% *3所含有之NbOx(X=1.0)約75重量％ ----------I I I I ^ i — — — — — — — — — — — — — (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 17 477992 A7 _ _ B7 五、發明說明（15) 表3 實施例 容量（uF) LC(4V)fuA) 1 6 0.09 2 40 0.12 3 42 0.03·1 4 42 0·04·2 5 136 0.07 6 42 0.08 7 6 0.11 8 6 0.48 9 6 0.54 10 6 1.1 11 6 1.4 12 4ft -_2^5 *1LC值之不均勻度2σ=0·02 *2LC值之不均勻度2σ=0·14 ^ ------^--------^--------- <請先閱讀背面之注意事項再填寫本頁) 實施例13〜1 5 經濟邬智¾財產局員工消費合作社印製 用以將多個與實施例4同樣製作之業經生成之燒結艘（ 接$忍電介質與實施例2同樣之組成），進而在與實施例4同 樣之生成液中外加逆電壓，破壞電介質層。隨後，將該燒 結體藉以140°C且以表4中所示之時間放置，修復電介質層 〇 接著用以與實施例4同樣之方式製作電容器。將電介 質層之組成及電容器之性能示於表4。 18 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 477992 A7 B7 五、發明說明（l6) 表4 實施例 放置時間 (分鐘） 第1層中之 Χ=2·5 之 含量(％产 第2層中之 Χ=2·5 之 含量(％)*2 容量 LC (μΑ) 4 — 99 99 42 * 0.04 13 15 92 94 43 0.80 14 8 87 91 41 1.5 15 4 82 88 40 2.9 註：第1層及第2層都剩下NbOu。 經濟^¾5¾^產局員工消費合作社印製 實施例16〜20 將由平均粒徑3μπι之鈮粉構成之成型體（體積約 3x3.5xl.8mm)以1220。(：、1〇·6Τογγ燒結，製作多個燒結體 。將該燒結體在表5所揭示之條件下氮化，作成一部分氮 化之鈮燒結體。隨即，藉於磷酸水溶液中以20V生成時， 在燒結體上形成氧化鈮之電介質。進而，在電介質上，藉 以40°C接觸醋酸鉛30%水溶液與過硫酸銨30%水溶液之等 量混合液數次，作為另一方電極，形成二氧化鉛及硫酸鉛 之混合物（二氧化鉛97%)。接著，在另一方電極上依序浸 泡碳漿、銀漿，以環氧樹脂封口，製作電容器。將所製作 之電容器之容量、LC值及其不均勻度（2σ)示於表7。 --------------裝--------訂---------線 {請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 19 477992 A7 B7 五、發明說明（l7) 表5 實施例 氮 化條 件 11化 會 Ippm、 16 常溫 常壓 20小時放置 300 17 400°C 常壓 3小時放置 4,〇〇〇 18 600°C 常壓 4小時放置 19,000 19 1,000°C 常壓 5小時放置 103,000 20 300°C 常壓 20分鐘放置 3,800 實施例21〜26 將實施例17使用表6中所揭露之化合物作為另一方電 極，其餘用以與實施例17同樣做法製作電容器。將所製作 之電容器之性能示於表7。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 20 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 477992 A7 B7 五、發明說明（is) 實施例 21 22 23 24 25 26 表6 另一方電極及電導率(S · cnT1) 四硫代四氫蔥冬氯醗錯合物 2x10° 苯並吡喀林低聚物之氯酕錯 合物 5χ10ϋ 聚朝咄喀之甲苯磺酸混入 5x10】 朝聚笨胺之甲苯磺酸混入 3x10' 朝聚塞吩之曱苯磺酸混入 4χ10ι 二氧化錳及二氧化鉛 (二氧化鉛95重量％) 5Χ101 電極形成方法 朝左述化合物溶液 中浸泡乾燥之重復 朝左述化合物溶液 中浸泡乾燥之重復 在吡喀液中氧化 反應之重覆 在苯胺液中氧化 反應之重覆 在塞吩液中氧化 反應之重覆 硝酸錳之熱分解 (在250°C2次重復)後 ，在醋酸鉛溶液中 之氧化反應之重覆 (請先閱讀背面之注意事項再填寫本頁) 實施例27、28(比較例） 除了在實施例16及實施例21時沒有進行燒結體之氮處 理外，其餘以與實施例16及實施例21同樣做法製作電容器 。將製作之電容器之性能示於表7。 實施例29、30(比較例） 氮處理在實施例18及實施例20時是在製成燒結體後進 行，但在此是以在製作燒結體前之鈮粉狀態進行，其餘用 21 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） 經漘部智慧財產局員工消費合作社印製 477992 A7 B7 五、發明說明（19) 以與實施例18及實施例20同樣之做法製作電容器。將製作 之電容器之性能示於表7。 表7 實施例 容量(100kHz) LC 值(nAV 平均 不均勻度 16 140 1.0 0.1 17 129 0.7 0.1 18 134 1.0 0.1 19 118 1.3 0.2 20 137 0.8 0.1 21 108 1.4 0.2 22 106 1.5 0.2 23 130 0.8 0.1 24 120 0.9 0.1 25 119 0.8 0.1 26 131 0.7 0.1 27(比） 139 36 4.8 28(比） 109 44 8.2 29 (It) 130 2.6 1.0 30(比） --- 120 3.2 1.7 實施例3 1 在實施例18中是藉生成形成電介質，而例31是在五乙 基鈮酸鹽液中浸泡燒結體，拉上來後，再在85°C蒸氣中反 應，進而以35〇它乾燥，形成氧化鈮之電介質，其餘用以 -----Γ---^---^裝 i·!^----^訂 --------- (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumers' Cooperative of the Ministry of Economic Affairs and Intellectual Property Bureau. 5. Description of the invention (i4) Table 2. Composition of the dielectric layer in the embodiment (NbOx) The first layer of X · 1 The proportion of the first layer in the dielectric (capacity%) Morse ratio_2 of the second layer (X = 2.5): (X = 2.0) 2 2.5 0.8 1 0.8 3 2.5 0.8 1 0.8 4 2.5 0.8 1 0.8 5 2.5 0.8 1 0.8 6 2.5 1.7 1 1.25 7 2.5 0.9 1 0.33 8 2.5 8.7 1 0 · 25 9 2.5 0.02 1 4 10 2.5 12 1 1.02 11 2.5 0.008 1 6 · 3 12 2.5 1.2 1 5 * 1 NbOx (X = 2.5) in the first layer of Examples 1 to 12 All ratios are 99% * 2 The ratio of the mixture of NbOx (X = 2.5) and NbOx (X = 2 · 0) in the second layer of Example 12 is all 99% * 3 The NbOx (X = 1.0) Approximately 75% by weight ---------- IIII ^ i — — — — — — — — — — — — — (Please read the notes on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 Specification (210 X 297 mm) 17 477992 A7 _ _ B7 V. Description of Invention (15) Table 3 Example Capacity (uF) LC (4V) fuA) 1 6 0.09 2 40 0.12 3 42 0.03 1 4 42 0 04 2 5 136 0.07 6 42 0.08 7 6 0. 11 8 6 0.48 9 6 0.54 10 6 1.1 11 6 1.4 12 4ft -_2 ^ 5 * 1 unevenness of LC value 2σ = 0 · 02 * 2 unevenness of LC value 2σ = 0 · 14 ^ ------ ^ -------- ^ --------- < Please read the notes on the back before filling out this page) Example 13 ~ 1 5 Economy and Wisdom ¾ Printed by the Staff Consumer Cooperative of the Property Bureau It is used to combine a plurality of sintered vessels that have been produced in the same manner as in Example 4 (the dielectric composition is the same as that in Example 2), and then a reverse voltage is applied to the generated solution similar to that in Example 4 to destroy the dielectric layer. Subsequently, the sintered body was allowed to stand at 140 ° C for the time shown in Table 4 to repair the dielectric layer. Next, a capacitor was produced in the same manner as in Example 4. Table 4 shows the composition of the dielectric layer and the performance of the capacitor. 18 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 477992 A7 B7 V. Description of the invention (16) Table 4 Example placement time (minutes) X = 2 · 5 in the first layer Content (% in the second layer of X = 2 · 5 content (%) * 2 Capacity LC (μΑ) 4 — 99 99 42 * 0.04 13 15 92 94 43 0.80 14 8 87 91 41 1.5 15 4 82 88 40 2.9 Note: NbOu is left on both the first and second layers. Economy ^ ¾5¾ ^ Printed by the Bureau of Industry and Consumer Cooperatives Example 16 ~ 20 A molded body composed of niobium powder with an average particle size of 3μm (volume about 3x3.5xl. 8mm) was sintered at 1220. (:, 10.6Tγ) to produce a plurality of sintered bodies. The sintered bodies were nitrided under the conditions disclosed in Table 5 to form a portion of the nitrided niobium sintered bodies. When the medium is generated at 20V, a dielectric of niobium oxide is formed on the sintered body. Furthermore, on the dielectric, an equal amount of a mixed solution of a 30% aqueous solution of lead acetate and a 30% aqueous solution of ammonium persulfate is contacted at 40 ° C for several times as another electrode. To form a mixture of lead dioxide and lead sulfate (lead dioxide 97%). Then, in another Carbon electrodes and silver paste were soaked in order on the square electrodes, and sealed with epoxy resin to make capacitors. The capacitance, LC value, and non-uniformity (2σ) of the capacitors are shown in Table 7. ------ -------- Installation -------- Order --------- Line {Please read the precautions on the back before filling this page) This paper size applies to Chinese national standards (CNS ) A4 specification (210 X 297 mm) 19 477992 A7 B7 V. Description of the invention (l7) Table 5 Example Nitriding Conditions 11 ppm Ippm, 16 Normal temperature and normal pressure 20 hours, 300 17 400 ° C Normal pressure and 3 hours 4,00〇18 600 ° C 4 hours at atmospheric pressure 19,000 19 1,000 ° C 5 hours at atmospheric pressure 103,000 20 300 ° C 20 minutes at atmospheric pressure 3,800 Examples 21 to 26 Example 17 is disclosed using Table 6 The compound is used as the other electrode, and the rest is used to make a capacitor in the same manner as in Example 17. The performance of the capacitor is shown in Table 7. (Please read the precautions on the back before filling this page) Staff of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Consumer Cooperatives 20 This paper is sized for China National Standard (CNS) A4 (210 X 297 mm) 477992 A7 B7 V. Description of the invention (is) Example 21 22 23 24 25 26 Table 6 The other electrode and conductivity (S · cnT1) Tetrathiotetrahydroallium chloropyrene complex 2x10 ° Benzocarpine Oligomers of Chlorofluorene Complex 5 × 10ϋ Toluenesulfonic acid mixed with polychamozene 5 × 10] Toluenesulfonic acid mixed with polybenzylamine 3x10 ′ Toluenesulfonic acid mixed with polyphenylene 4 × 10ι Manganese dioxide and lead dioxide (Lead dioxide 95% by weight) 5 × 101 Electrode formation method Repeatedly immersed and dried in the compound solution shown on the left Repeatedly immersed and dried in the compound solution on the left repeated Repeating the oxidation reaction in the pika solution Repeating the oxidation reaction in the aniline solution Overlaid oxidation reaction in the stope solution After repeated thermal decomposition of manganese nitrate (repeated 2 times at 250 ° C), the repeated oxidation reaction in lead acetate solution (please read the precautions on the back before filling this page) Implementation Examples 27 and 28 (Comparative Examples) A capacitor was produced in the same manner as in Example 16 and Example 21 except that the nitrogen treatment of the sintered body was not performed in Examples 16 and 21. The performance of the fabricated capacitor is shown in Table 7. Examples 29 and 30 (comparative examples) Nitrogen treatment was performed after the sintered body was produced in Examples 18 and 20, but here, it was performed in the state of niobium powder before the sintered body was produced, and 21 papers were used for the rest. Standards apply to China National Standard (CNS) A4 specifications (210 X 297 public love). Printed by the Consumers ’Cooperative of the Ministry of Economic Affairs and Intellectual Property Bureau. 477992 A7 B7. 5. Description of the invention (19) In the same way as in Example 18 and Example 20. Make capacitors. The performance of the fabricated capacitor is shown in Table 7. Table 7 Example capacity (100kHz) LC value (nAV average unevenness 16 140 1.0 0.1 17 129 0.7 0.1 18 134 1.0 0.1 19 118 1.3 0.2 20 137 0.8 0.1 21 108 1.4 0.2 22 106 1.5 0.2 23 130 0.8 0.1 24 120 0.9 0.1 25 119 0.8 0.1 26 131 0.7 0.1 27 (ratio) 139 36 4.8 28 (ratio) 109 44 8.2 29 (It) 130 2.6 1.0 30 (ratio) --- 120 3.2 1.7 Example 3 1 In Example 18 The dielectric is formed by formation. In Example 31, the sintered body is soaked in a pentaethyl niobate solution. After being pulled up, it is reacted in steam at 85 ° C and dried at 35 ° C to form a dielectric of niobium oxide. Use ----- Γ --- ^ --- ^ install i ·! ^ ---- ^ Order --------- (Please read the precautions on the back before filling this page)

477992 A7 —__ B7 •經濟都智殳时產局8工消費合作社印製 五、發明說明（2〇) 與實施例18同樣之做法製作電容器，將所製造之電容器示 於表8。 實施例32 在實施例18中是藉生成形成電介質，而例32是在五乙 基组酸鹽液中浸泡，拉上來後，在85eC蒸氣中反應，進而 以450°C乾燥，在燒結體上形成氧化钽之電介質層。其次 將異丁基三丙基銨四氣硼酸鹽電解質5%溶解之二甲基甲 胺及乙二醇之混合液所構成之電解液附著在燒結體上， 放入罐頭加以封口，製作電容器。將所製造之電容器之性 能不於表8。 f施例33、34(比較例） 該例是在實施例27及28中沒有對燒結體進行氮處理外 ’其餘用以實施例27及28同樣之做法製作電容器。將所製 作之電容器之性能示於表8。 t施例35、36(比_你|) 實施例27及28是將氮處理在燒結體製作後進行，而例 35、36是用以製作燒結體前之鈮粉狀態進行，其餘係用以 與實施例27及28同樣之方法製作電容器。將所製作之電容 器之性能示於表8❶ ---------------裝--- (請先閱讀背面之注意事項再填寫本頁) 訂： ;線· 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 23 477992 Α7 Β7 五、發明說明（20 表8 實施例 _ LC值（uA)__ _ 平均 不均勻度（2σ ) 31 1.8 0.3 32 0.5 0.1 33(比） 53 9.6 34(比） 16 4.2 35(比） 4.0 1.7 36(比） 2.4 1.1 經濟部智慧討產局員工消費合作社印製 產業上之可利用性 本發明係用以將夾設在兩電極間之電介質以具特定組 成之氧化鈮之二層構造構成之電容器係，每單位重量之容 量大且LC特性良好，進而將電容器之一方電極用以鈮或 鈮之部分氮化之氮化鈮構成時，可使每單位重量之容量更 大。尤其電極係用以鈮之一部份氮化之氮化鈮構成時，可 進而改善LC特性等之性能。又，使電極藉以一部份氮化 之1化說構成時，藉在將鈮燒結後再氮化之方法製作電極 時，可得到LC值之不均勻度小之電容器。 是故，本發明之電容器係可供作為通用電子機器用之 小型且高容量之電容器之用。又，LC值之不均勻度小之 電容器係可用以於平滑電路。 本紙張尺度適用中國國家標準（CNS〉A4規格（21〇 x 八益 ----J1IL---•裝 i--丨.----^訂---------^9 (請先閱讀背面之注意事項再填寫本頁) 24477992 A7 —__ B7 • Printed by the Economic and Industrial Development Bureau, the Industrial and Commercial Bureau, and the 8th Industrial Cooperative Cooperative. 5. Description of the Invention (20) The capacitors were made in the same manner as in Example 18, and the capacitors are shown in Table 8. Example 32 In Example 18, a dielectric was formed by formation, and Example 32 was soaked in a pentaethyl group salt solution, pulled up, reacted in 85eC vapor, and then dried at 450 ° C on the sintered body. A dielectric layer of tantalum oxide is formed. Next, an electrolytic solution composed of a 5% dissolved solution of dimethylmethylamine and ethylene glycol in isobutyltripropylammonium tetraborate electrolyte was adhered to the sintered body, put in a can, and sealed to make a capacitor. The performance of the manufactured capacitor is different from Table 8. fExamples 33 and 34 (comparative examples) In this example, except that the sintered body was not subjected to nitrogen treatment in Examples 27 and 28, the capacitors were fabricated in the same manner as in Examples 27 and 28. The performance of the produced capacitor is shown in Table 8. tExamples 35 and 36 (比 _ 你 |) Examples 27 and 28 are performed after the nitrogen treatment is performed on the sintered body, while Examples 35 and 36 are performed on the state of the niobium powder before the sintered body is made, and the rest are used to A capacitor was produced in the same manner as in Examples 27 and 28. The performance of the produced capacitor is shown in Table 8 ❶ 装 --- (Please read the precautions on the back before filling this page) Order:; line · this paper The scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 23 477992 A7 B7 V. Description of the invention (20 Table 8 Example _ LC value (uA) __ _ average unevenness (2σ) 31 1.8 0.3 32 0.5 0.1 33 (ratio) 53 9.6 34 (ratio) 16 4.2 35 (ratio) 4.0 1.7 36 (ratio) 2.4 1.1 Utilization in the printing industry for employees' cooperatives in the Intellectual Property Bureau of the Ministry of Economic Affairs This invention is used to A capacitor system composed of a two-layer structure of a dielectric with a specific composition of niobium oxide having a specific composition has a large capacity per unit weight and good LC characteristics. One of the capacitor's electrodes is then used for the nitriding of niobium or niobium. When the niobium nitride is formed, the capacity per unit weight can be made larger. Especially when the electrode is composed of niobium nitride which is a part of the niobium, the performance of the LC characteristics can be further improved. Furthermore, the electrode can be used as a unit. In the case of partial nitridation, the electricity is produced by sintering niobium and then nitriding. At the extreme time, a capacitor with small unevenness in LC value can be obtained. Therefore, the capacitor of the present invention can be used as a small and high-capacity capacitor for general electronic equipment. In addition, the unevenness in LC value is small. Capacitors can be used for smoothing circuits. This paper size applies to Chinese national standards (CNS> A4 specifications (21〇x 八 益 ---- J1IL --- • 装 i-- 丨 .---- ^ Order --- ------ ^ 9 (Please read the notes on the back before filling this page) 24

Claims (1)

477992 A8 B8 C8 D8 华/ 修正/更正/補光 申請專利範圍 第88121903號專利申請案申請專利範圍修正本修正日期：90年12月 1. 一種鈮電容器，該電容器係由兩電極，及夾設在兩電極 間之電介質所構成，而該電介質之構成係包含有2層構 造： 第1層，其係以氧化鈮NbOx(X=2.5)為主要組成者； 及 第2層，其係以氧化鈮NbOx(X=2.5)與NbOx(X=2.0) 之混合物為主要組成者。 2. 如申請專利範圍第1項之鈮電容器，其係使前述電介質 之第1層中所含有之氧化鈮NbOx(X=2.5)之含量至少90 重量％者。 3. 如申請專利範圍第1項之鈮電容器，其係使前述電介質 之第2層中所含有之氧化鈮NbOx(X=2.5)及NbOx(X= 2.0) 之混合物之含量至少90重量％者。 4. 如申請專利範圍第2項之鈮電容器，其係使前述電介質 之第2層中所含有之氧化鈮NbOx(X=2.5)及NbOx(X= 2.0) 之混合物之含量至少90重量％者。 5. 如申請專利範圍第1項之鈮電容器，其係使前述電介質 之第2層中所含有之氧化鈮NbOx(X=2.5)與NbOx(X= 2.0) 之莫耳比為1 : 4〜4 : 1者。 6. 如申請專利範圍第2項之鈮電容器，其係使前述電介質 之第2層中所含有之氧化鈮NbOx(X=2.5)與NbOx(X= 2.0) 之莫耳比為1 : 4〜4 : 1者。 7. 如申請專利範圍第3項之鈮電容器，其係使前述電介質 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) ·、τ· 25 477992 A8 B8 C8 一 _ D8 六、申請專利範圍 之第2層中所含有之氧化鈮NbOx(X=2.5)與Nb〇x(x= 2 〇) 之莫耳比為1 : 4〜4 : 1者。 8·如申請專利範圍第4項之鈮電容器，其係使前述電介質 之第2層中所含有之氧化銳NbOx(X=2.5)與NbOx(X= 2 0) 之莫耳比為1 · 4 ^ 4 : 1者。 9.如申請專利範圍第1項之鈮電容器，其係使前述第丨層佔 第1層及第2層所構成之電介質層中之比率為〜 容量％者。 10·如申請專利範圍第2項之鈮電容器，其係使前述第1層佔 第1層及第2層所構成之電介質層中之比率為〇 〇1〜1〇 谷量％者。 11.如申請專利範圍第3項之鈮電容器，其係使前述第1層佔 第1層及第2層所構成之電介質層中之比率為〇〇1〜1〇 容量％者。 12·如申請專利範圍第4項之鈮電容器，其係使前述第1層佔 第1層及第2層所構成之電介質層中之比率為〇〇1〜1〇 容量％者。 13·如申請專利範圍第5項之鈮電容器，其係使前述第1層佔 第1層及第2層所構成之電介質層中之比率為〇〇1〜1〇 容量％者。 14·如申請專利範圍第6項之鈮電容器，其係使前述第1層及 第2層所構成之電介質層中之第1層的比率為〇〇ι〜1〇 容量％者。 15·如申請專利範圍第7項之鈮電容器，其係使前述第1層佔 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） ...................…；裝.......-.......-:訂----------------，：線： (請先閲讀背面之注意事項再填寫本頁) 26 - "f//992 A8 B8 C8 D8 、申請專利範'圍 第1層及第2層所構成之電介質層中之比率為〇〇1〜1〇 容量％者。 16·如申請專利範圍第8項之鈮電容器，其係使前述第1層及 第2層所構成之電介質層中之第1層的比率為〇〇1〜1〇 容量％者。 17·如申請專利範圍第1至16項中任一項之鈮電容器，其係. 使電極之一方用以鈮或鈮之一部分氮化之氮化鈮構成 者。 18·如申請專利範圍第17項之鈮電容器，其中前述氮化鈮中 所含有之結合氮之量係根據氮化銳之重量，為丨〇〜 200,〇〇〇 重量 ppm。 19 ·如申租專利範圍第18項之銳電容器，其係使另一電極用 以選自具電導率1 OdS.cnT1〜1 C^S.cnr1之有機半導體及 無機半導體中之至少一種化合物所構成者。 20·如申請專利範圍第18項之鈮電容器，其中氮化鈮係，藉 使鈮置於氮氣環境中以室溫〜2〇〇〇。(：處理1〜50小時， 使鈮之一部分氮化之方法製作者。 21.如申請專利範圍第18項之鈮電容器，其中前述由氮化鈮 構成之電極係用以將鈮燒結後而使鈮之一部分氮化之 方法製作者。 22·如申請專利範圍第2〇項之鈮電容器，其係使另一電極用 以選自具電導率lt^S.cnT1〜ΙΟ^ππΓ1之有機半導體及 無機半導體中之至少一種化合物所構成者。 23·如申請專利範圍第21項之鈮電容器，其係使另一電極用 本紙張尺度翻巾_家標準（⑽）A4規格（2歡公楚） 1Ί 1:[4! (請先閲讀背面之注意事項再填寫本頁) 訂丨 "+/ /y^2 A8 B8 C8 D8 、申請專利範圍 以選自具電導率1〇-23*(：111-1〜1033*(：111-1之有機半導體及 無機半導體中之至少一種化合物所構成者·。 24· —種製造鈮電容器之方法，該方法之特徵在於用以使一 部分氮化之鈮之燒結體作為一方之電極、另一方之電極 ，及夾設在兩電極間之電介質構成鈮電容器者； 該方法係藉於將鈮粉之成型體燒結後，將所得到之 燒結體置於氮氣環境中，製作前述氮化鈮燒結體者。 25·如申請專利範圍第24項之製造鈮電容器之方法，其係 使氮化鈮中所含有之結合氮之量根據氮化鈮之重量，為 10〜200,000 重量 ppm。 26·如申請專利範圍第24項之製造鈮電容器之方法，其係以 氧化鈮構成電介質者。 27.如申請專利範圍第25項之製造鈮電容器之方法，其係以 氧化銳構成電介質者。 28·如申請專利範圍第26項之製造銳電容器之方法，其係使 電介質由2層構造形成，即，該2層構造係指以氧化鈮 Nb〇x(X=2.5)為主要組成之第1層，以及以氧化鈮 Nb〇x(X =2.5)及氧化鈮NbOx(X=2.0)之混合物為主要組 成之第2層者。 組 ------------------裝—— (請先閲讀背面之注意事項再填寫本頁) •線τ 29·如申請專利範圍第27項之製造鈮電容器之方法，其係使 電介質由2層構造形成，即，該2層構造係指以氧化鈮 Nb〇x(X=2.5)為主要組成之第1層，以及以氧化鈮 Nb〇x(x :=2.5)及氧化鈮NbOx(X=2.0)之混合物為主要 成之第2層者。 本紙張尺度翻1中國國家鮮（CNS) A4規格（210X297公釐） 28 -- 六、申請專利範園 3 0 ·如申請專利範圍第2 6項之製造鈮電容器之方法，其係藉 .使鈮之一部份氮化之鈮電極在電解液中生成，或使於鈮 之一部份氮化之鈮電極上將含鈮錯合物施以加水分解 、熱分解，或加水分解及熱分解兩者，在該氮化銳電極 上形成由氧化銳構成之電介質者。 31·如申請專利範圍第27項之製造銳電容器之方法，其係藉 使鈮之一部份氮化之鈮電極在電解液中生成，或在鈮之 一部份氮化之鈮電極上將含鈮錯合物施以加水分解、熱 解或加水刀解及熱分解兩者，在該氮化銳電極上形 成由氧化鈮構成之電介質。 32·如申請專利範圍第28項之製造鈮電容器之方法，其係藉 使鈮之一部份氮化之鈮電極在電解液中生成，或在鈮之 一部份氮化之鈮電極上將含鈮錯合物施以加水分解、熱 刀解或加水分解及熱分解兩者，在該氮化鈮電極上形 成由氧化銳構成之電介質。 33·如申請專利範圍第29項之製造鈮電容器之方法，其係藉 使鈮之一部份氮化之鈮電極在電解液中生成，或在鈮之 一部份氮化之鈮電極上將含鈮錯合物施以加水分解、熱 分解，或加水分解及熱分解兩者，在該氮化鈮電極上形 成由乳化銳構成之電介質。 申明專利範圍第24至33項中任一項之製造銳電容器 之方法，其係使前述另一方之電極用以選自具電導率 之有機半導體及無機半導體中之 至少一種化合物所構成者。 本紙張尺度適用中國國家標準(cn^Tm規格(210Χ297公贊)477992 A8 B8 C8 D8 Hua / Amendment / Correction / Supplementary light Patent Application Range No. 88121903 Patent Application Application Patent Range Amendment Date: December 1990 1. A niobium capacitor, which consists of two electrodes and sandwiched between them The dielectric is composed of two electrodes, and the composition of the dielectric includes two layers: the first layer, which is mainly composed of niobium oxide NbOx (X = 2.5); and the second layer, which is composed of oxide The main composition is a mixture of niobium NbOx (X = 2.5) and NbOx (X = 2.0). 2. As for the niobium capacitor in the first scope of the patent application, the content of niobium oxide NbOx (X = 2.5) contained in the first layer of the aforementioned dielectric is at least 90% by weight. 3. As for the niobium capacitor in the first scope of the patent application, the content of the mixture of niobium oxide NbOx (X = 2.5) and NbOx (X = 2.0) contained in the second layer of the aforementioned dielectric is at least 90% by weight. . 4. As for the niobium capacitor in the second item of the patent application, the content of the mixture of niobium oxide NbOx (X = 2.5) and NbOx (X = 2.0) contained in the second layer of the aforementioned dielectric is at least 90% by weight. . 5. As for the niobium capacitor in the first item of the patent application scope, the molar ratio of the niobium oxide NbOx (X = 2.5) and NbOx (X = 2.0) contained in the second layer of the aforementioned dielectric is 1: 4 ~ 4: 1 person. 6. As for the niobium capacitor in the second scope of the patent application, the molar ratio of the niobium oxide NbOx (X = 2.5) and NbOx (X = 2.0) contained in the second layer of the aforementioned dielectric is 1: 4 ~ 4: 1 person. 7. For the niobium capacitors in the scope of patent application No. 3, the paper size of the aforementioned dielectric is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page). τ · 25 477992 A8 B8 C8 I_ D8 VI. The molar ratio of the niobium oxides NbOx (X = 2.5) and Nb〇x (x = 2 〇) contained in the second layer of the patent application range is 1: 4 ~ 4: 1 person. 8. The niobium capacitor according to item 4 of the scope of patent application, wherein the molar ratio of the oxidized sharp NbOx (X = 2.5) and NbOx (X = 2 0) contained in the second layer of the aforementioned dielectric is 1. 4 ^ 4: 1 person. 9. The niobium capacitor according to item 1 of the scope of the patent application, wherein the ratio of the aforementioned first layer to the dielectric layer composed of the first layer and the second layer is ~ capacity%. 10. As for the niobium capacitor in the second item of the patent application, the ratio of the first layer to the dielectric layer composed of the first layer and the second layer is 0.001% to 10% by volume. 11. For a niobium capacitor according to item 3 of the scope of patent application, the ratio of the first layer to the dielectric layer composed of the first layer and the second layer is 0.001% to 10% by capacity. 12. The niobium capacitor according to item 4 of the scope of patent application, wherein the ratio of the first layer to the dielectric layer composed of the first layer and the second layer is 0.001% to 10% by capacity. 13. The niobium capacitor according to item 5 of the scope of patent application, wherein the ratio of the first layer to the dielectric layer composed of the first layer and the second layer is 0.001% to 10% by capacity. 14. The niobium capacitor according to item 6 of the scope of patent application, wherein the ratio of the first layer among the dielectric layers composed of the first layer and the second layer described above is 100% to 10% by capacity. 15 · If the niobium capacitor in the scope of the patent application No. 7 is applied, the aforementioned first layer occupies this paper standard and applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ............ .............; installed .......-.......-: order ---------------- ,: line: (please (Read the precautions on the back before filling in this page) 26-" f // 992 A8 B8 C8 D8, the patent application scope 'the dielectric layer composed of the first layer and the second layer is 0.001 ~ 1 〇Capacity%. 16. For a niobium capacitor according to item 8 of the scope of patent application, the ratio of the first layer among the dielectric layers composed of the first layer and the second layer described above is 0.001% to 10% by capacity. 17. The niobium capacitor according to any one of claims 1 to 16 of the scope of application for patent, which is composed of niobium nitride in which one side of the electrode is niobium or a part of niobium nitride. 18. The niobium capacitor according to item 17 of the scope of the patent application, wherein the amount of the combined nitrogen contained in the aforementioned niobium nitride is based on the weight of the nitride, and is from 0 to 200,000 ppm by weight. 19 · If the sharp capacitor of item 18 of the patent application scope is leased, the other electrode is used for at least one compound selected from organic semiconductors and inorganic semiconductors having a conductivity of 1 OdS.cnT1 ~ 1 C ^ S.cnr1. Constructor. 20. The niobium capacitor according to item 18 of the scope of patent application, wherein the niobium nitride is based on niobium under a nitrogen atmosphere at room temperature to 20000. (: Producer of a method for nitriding a part of niobium for 1 to 50 hours. 21. For example, the niobium capacitor according to item 18 of the application, wherein the aforementioned electrode composed of niobium nitride is used for sintering niobium to make Producer of a method of partial nitriding of niobium. 22. For example, the niobium capacitor of the scope of application for patent No. 20, the other electrode is used to select an organic semiconductor with conductivity lt ^ S.cnT1 ~ IO ^ ππΓ1 and Made of at least one compound in an inorganic semiconductor. 23. For example, a niobium capacitor in the scope of patent application No. 21, which is to turn the other electrode with the paper size _ home standard (⑽) A4 size (2 Huangongchu) 1Ί 1: [4! (Please read the precautions on the back before filling this page) Order quot; + / / y ^ 2 A8 B8 C8 D8, apply for a patent range to select from the conductivity 1〇-23 * (: 111-1 ~ 1033 * (: At least one compound of organic semiconductor and inorganic semiconductor of 111-1. 24. —A method for manufacturing a niobium capacitor, the method is characterized in that a part of the niobium is nitrided Sintered body as one electrode and the other electrode And a method of forming a niobium capacitor with a dielectric sandwiched between the two electrodes; the method is to prepare the aforementioned niobium nitride sintered body by sintering the formed body of the niobium powder and placing the obtained sintered body in a nitrogen atmosphere. · The method for manufacturing a niobium capacitor according to item 24 of the patent application, wherein the amount of the combined nitrogen contained in the niobium nitride is 10 to 200,000 ppm by weight based on the weight of the niobium nitride. 26 · The method of manufacturing a niobium capacitor according to item 24 is a method in which a niobium oxide is used to form a dielectric. 27. The method of manufacturing a niobium capacitor in the scope of application for item 25 is a method of forming a dielectric with a sharp oxide. The method for manufacturing sharp capacitors according to item 26, wherein the dielectric is formed by a two-layer structure, that is, the two-layer structure refers to a first layer mainly composed of niobium oxide Nb0x (X = 2.5), and niobium oxide The mixture of Nb〇x (X = 2.5) and niobium oxide NbOx (X = 2.0) is the second layer of the main composition. Group --------------- (Please read the notes on the back before filling out this page) • Line τ 29 · If the scope of patent application The method for manufacturing a niobium capacitor according to item 27, wherein the dielectric is formed of a two-layer structure, that is, the two-layer structure refers to a first layer mainly composed of niobium oxide Nb0x (X = 2.5), and niobium oxide The mixture of Nb〇x (x: = 2.5) and niobium oxide NbOx (X = 2.0) is the second layer of the main component. The size of this paper is increased by 1. China National Fresh (CNS) A4 specification (210X297 mm) 28- 6. Applying for a patent Fan Yuan 30 · If the method of manufacturing a niobium capacitor according to item 26 of the patent application scope, it is to make a part of niobium nitrided niobium electrode in the electrolyte, or A part of the nitrided niobium electrode is subjected to hydrolytic decomposition, thermal decomposition, or both hydrolytic decomposition and thermal decomposition to form a dielectric composed of oxide sharp on the nitrided electrode. 31. If the method for manufacturing sharp capacitors according to item 27 of the patent application scope is to generate a niobium electrode partially niobium in an electrolytic solution, or to use a niobium electrode partially nitrided on the niobium electrode, The niobium-containing complex is subjected to hydrolysis, pyrolysis or hydroknife decomposition and thermal decomposition to form a dielectric composed of niobium oxide on the sharpened nitride electrode. 32. If the method for manufacturing a niobium capacitor according to item 28 of the scope of patent application is based on the formation of a niobium electrode in which a part of the niobium is nitrided in an electrolytic solution, or the The niobium-containing complex is subjected to hydrolytic decomposition, thermal knife decomposition, or hydrolytic decomposition and thermal decomposition to form a dielectric composed of oxide oxide on the niobium nitride electrode. 33. If the method for manufacturing a niobium capacitor according to item 29 of the patent application scope is to generate a niobium electrode in which a part of niobium is nitrided in an electrolytic solution, or The niobium-containing complex is hydrolyzed, thermally decomposed, or both hydrolyzed and thermally decomposed to form a dielectric composed of an emulsified sharp on the niobium nitride electrode. The method for manufacturing sharp capacitors according to any one of claims 24 to 33, which is a method in which the electrode of the other party is composed of at least one compound selected from the group consisting of organic semiconductors and inorganic semiconductors having conductivity. This paper size applies to Chinese national standards (cn ^ Tm specifications (210 × 297 praise)