經濟部智慧財產局員工消費合作社印製 I ^ 460855 A7 B7 五、發明說明（1 ) (技術領域）/ f 本發明有關於顯示裝置，特別是有關於使用Μ I Μ ( Metal-Insulator-Metal )型隧道二極體構造之電子線源之顯 示裝置。 (背景.技術） 使用Μ I Μ型隧道二極體構造之電子線源之顯示裝置 乃，例如記述於下述文獻（i )。 (i ) M. Suzuki and T. Kusunoki;、、Emission and Beam-Divergence Properties of an MIM-Cathode Array for Display Applications'，SID’97 DIGEST( 1 977)p.1 23- 1 26。 揭示於上述文獻（i )之Μ I M型二極體構造之微小 電子線源乃以，高效率、高定向性爲其特徵。隧道絕緣層 之厚度爲5.5nm。做爲電子放出部之上部電極係爲了 避免熱電子之散亂而定爲6 nm之薄而已。 記載於上述文獻（i)之MI Μ型二極體構造之電子 線源元件乃，在其構成上，在動作中有約1 OMV/cm 之高電場作用於隧道絕緣層，而約有0.4mA/cm2之 電流之流過。 在這種苛酷之條件下，構成隧道絕緣層之絕緣膜之歷 時的劣化係無法避免者。 觀測隧道二極體之歷時之變化而可知二極體電流會隨 著時間而減少，最後將會成爲被破壞。 此現象乃由於，在構成隧道絕緣層之絕緣膜中，被注 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -------------------訂--------- (請先閱讀背面之注咅？事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 A60855 A7 ____B7___*_ 五、發明說明（2 ) 入之熱電子之一部份之由存在於絕緣膜中之電子陷阱所捕 獲而成爲負之固定負載，而減弱了陰極側之結果，致使抑 制了電子注入爲其原因者。 再者，該劣化之不會歷時的劣化係表示，由高電場中 之熱電子而發生新.的電子陷阱之事實。 此現象乃構成限制Μ I Μ型二極體構造之電子線源元 件之動作壽命之最大的原因之一。 再者，以往構成隧道絕緣層之絕緣膜係，使用以氨水 來中和1〜3重量％之酒石酸水溶液，而以乙二醇來稀釋 者。而將化成電流密度限制於1 0 0 # A / c m 2以下，而 以陽極氧化來形成者。 此方法時雖然可以達成良好之初期特性，惟爲了長期 的維持特性就有問題。 (發明之揭示） 本發明係爲了解決上述先前技術之問題所創作，本發 明之目的乃提供一種使用了可以改善，Μ I Μ型二極體構 造之電子線源之隧道絕緣層之絕緣膜之膜質，以資提高動 作壽命之技術之顯示裝置者。 本發明乃主要係，具有：在表面形成螢光體層之第2 基板，及互相地面向於上述第2基板，而形成電子線源之 第1基板。 上述電子線源係具有疊層於第1基板上之第1導電膜 (下部電極）-絕緣膜-第2導電膜（上部電極）構造之 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐；) n n n ·ϋ n I t · n n n .^1 n n·-1、_ d n n n n n n I Λ . i aa^ t fv' (請先閱讀背面之注意事項再填寫本頁) ¢10855 A7 __B7__' 五、發明說明（3 ) 顯示裝置..中。. (請先閱讀背面之注意事項再填寫本頁) 上述絕緣膜乃使用下述之非水系化成液（a )〜（c )其中之一種而將上述第1導電膜予以陽極氧化形成之顯 示電極者。 (a )由含有：具有醇性羥基之有機溶媒，及無機羰 酸之鹽及有機羧酸之鹽（但限定於芳族羧酸鹽，或不含二 個以上之醇性羥基之脂肪族多價羧酸之鹽）中所選用之至 少一種溶質之非水系化成液。 (b )含有：非質子性有機溶媒，及由無機羰酸鹽及 有機羧酸鹽中所選用之至少一種之溶質之非水系化成液。 (c )含有，具有醇性羥基之有機溶媒，及非質子性 有機溶媒所成之混合溶媒，無機羰酸鹽及有機羧酸鹽所選 出之至少一種溶液之非水系化成液者。 (實施發明之最佳形態） 經濟部智慧財產局員工消費合作社印製 本案中所揭示之發明中代表性者之槪要說明於下。 本發明顯示裝置乃主要係，具有，在表面形成螢光 體層之第2基板（上基板），及互相地面向於上述第2基 板，而形成電子線源之第1基板（下基板）之顯示裝置， 上述電子線源係具有疊層於第1基板上之第1導電膜 -絕緣膜-第2導電膜構造之顯示裝置中，其特徵爲： 上述絕緣膜乃使用含有具有醇性羥基之有機溶媒，及 無機羰酸鹽及有機羧酸鹽（但限定於芳族羧酸鹽或不含有 二個以上之醇性羥基之脂肪族多價羧酸鹽）中所選用之一 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 460855 A7 _ __B7_' 五、發明說明（4 ) 種溶質之_非水系.化成液，而將上述第1導電膜予以陽極氧 化所成之絕緣膜者。 (請先閱讀背面之注意事項再填寫本頁) 又本發明之顯示裝置乃主要係，具有：在表面形成螢 光體層之第2基板（上基板），及互相地面向於上述第2 基板，而形成電子線源之第1基板（下基板）， 上述電子線源係具有疊層於第1基板之第1導電膜-絕緣膜-第2導電膜構造之顯示裝置中， 上述絕緣膜乃使用含有由非質子性有機溶媒，及無機 羰酸鹽及有機羧酸鹽所選用之一種溶質之非水系化成液而 將上述第1導電膜予以陽極氧化所形成之絕緣膜者。 又本發明之顯示裝置乃主要係，具有： 在表面形成螢光體層之第2基板（上基板），及 互相地面向於上述第2基板，而形成電子線源之第1 基板（下基板）， 上述電子線源係具有疊層於第1基板上之第1導電膜 -絕緣膜-第2導電膜構造之顯示裝置中，其特徵爲： 經濟部智慧財產局員工消費合作社印製 上述絕緣膜乃使用含有，具有醇性羥基之有機溶媒及 非質子性有機溶媒所成之混合溶媒，及由無機羰酸鹽及有 機羧酸鹽中所選出之至少一種溶質之非水系化成液，而將 上述第1導電膜予以陽極氧化所形成之絕緣膜者。 下面參照附圖詳細的說明本發明之實施形態。 又在說明實施形態之 圖中，具有同一機能者係標上 相同之標號省略其重複之說明。 第1圖表示本發明之實施形態之顯示裝置之槪略構成 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） A7 460Bbo __________B7___ 五、發明說明（5 ) (請先閱讀背面之注意事項再填寫本頁) 之展開斜.視圚。.本實施形態之顯示裝置係平面型之顯示裝 置，由表面形成有，金屬—絕緣膜—金屬構造（Μ I Μ構 造之微小電子線源陣列之下基板（第1基板）3，及形成 有條狀之螢光體層之上基板（第2基板）5，係由框玻璃 4而成互相面向地被構成。又第1圖中標號6係排氣管。 第2圖表示第1圖所示之下基板3(第1基板）之一 例之槪略構成圖。 同圖所示之下基板3乃由：形成於蘇打玻璃等之玻璃 基板1 1上之延伸於X方向之條狀之下部電極1 2，及形 成於下部電極1 2上之電場緩和層（或層間絕緣膜）1 3 ，及隧道絕緣層1 4，及形成於電場緩和層1 3及隧道絕 緣層1 4上之延伸於Υ方向之條狀之總線電極1 5，及形 成於總線電極1 5上之上部電極1 6所構成。 本例中下部電極1 2與總線電極1 5係互相略直交狀 地被形成，在於下部電極1 2與總線電極1 5之疊合之領 域內之一部份形成電子放出部1 7。 該電子放出部1 7乃去除了總線電極1 5，而上部電 極1 6係介著隧道絕緣層1 4而面向於下部電極1 2。 經濟部智慧財產局員工消費合作社印製 第3圖表示第1圖所示之上基板5 (第2基板）之一 例之槪略構成圖。 同圖所示之上基板5係由在蘇打玻璃等之玻璃基板 2 1上延伸於Υ方向之條狀之紅、綠、藍之螢光體層所成 之螢光體條1 8，乃形成於該螢光體條1 8上之金屬敷層 (A 1膜）膜1 9所構成。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐j 460855 A7 B7 五、發明說明（6 ) 本發-明之顯不裝置乃’弟2.圖所不之陵道絕緣層1 4 •係：使用含有具有醇性羥基之有機溶媒，及無機羰酸鹽及 有機羧酸鹽（但限定於芳族羧酸鹽或不含有二個以上之醇 性羥基之脂肪族多價羧酸鹽）中所選用之一種溶質之非水 系化成液（a )而將下部電極1 2予以陽極氧化所成之絕 緣膜爲其特徵。 又本發明之顯示裝置乃第2圖所示之隧道絕緣層14 係：使用含有由非質子性有機溶媒，及無機羰酸鹽及有機 羧酸鹽所選用之一種溶質之非水系化成液（b )而將上述 下部電極1 2予以陽極氧化所形成之絕緣膜爲其特徵。 或本發明之顯示裝置乃第2圖所示之隧道絕緣層1 4 係：使用含有，具有醇性羥基之有機溶媒及非質子性有機 溶媒所成之混合溶媒，及由無機羰酸鹽及有機羧酸鹽中所 選出之至少一種溶質之非水系化成液（c)，而將上述第 1導電膜予以陽極氧化所形成之絕緣膜爲其特徵。 本發明中，用爲陽極氧化用化成液之溶質之無機酸乃 以無機羰酸爲宜。 按無機羰酸係做爲質子的可解離之氫之結合於氧原子 之無機酸，該中心原子係非金屬或金屬均無妨。 具體的說由：硼酸、磷酸、硫酸、鎢酸、鉬酸、鉻酸 及釩酸以及過鍊酸所成之群所選擇之一以上之化合物爲宜 〇 本發明中，用爲陽極氧化用化成液之溶質之有機羧酸 乃得由，具有羧基之廣汎之有機化合物中可以選擇。羧基 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) --------訂--I------^-1 經濟部智慧財產局員工消費合作社印製 460855 A7 五、發明說明（7 之數目以_及結合. 合宜者乃， 芳（香）族 苯系芳環、複素 例如不含異 甲酸、.苯甲酸、 苯甲酸、茴香醇 基酸、龍膽酸、 又異芳族羧 甲酰酸以及肼基 又只要不會 官能基之芳族羧 例如硝基苯 (二）甲基胺苯 以使用。 脂肪族多價 位置並不 芳（香） 羧酸乃可 芳環及具 原子之芳 r -二羥 酸、2， 沒食子酸 酸即可例 苯甲酸等 損及本發 酸已可以 甲酸，氣 甲酸等之 特別的 族羧鹽 以使用 有羧基 族羧酸 基苯甲 4甲酚 、及P 示，煙 等。 明所期 使用。 茴內酐 具有硝 限定。 _ _ 及脂肪族多價羧酸鹽。 具有苯環、縮合苯環、非 之化合物。 ，可以例示水楊酸、苯二 酸、甲苯酰酸、t一丙基 酸、桂皮酸、N —甲基蒽 一羥基苯甲酸等。 酸，2 —糠酸，2 —噻吩 之效果，具有羧基以外之 ，（一）甲基胺苯甲酸、 基或氨基之芳族羧酸也可 經濟部智慧財產局員工消費合作社印製 羧酸乃可例示，酒石酸，枸櫞酸，羥基丙 二酸’蘋果酸，草酸，丙二酸，丁二酸，戊二，己二酸， 庚二酸’辛二酸，壬二酸，癸二酸，二甲基丙二酸，二乙 基丙二酸，二丙基丙二酸，二甲基戊二酸，3，3二甲基 戊二酸，3 —甲基己二酸，馬來酸，富馬酸，衣康酸，順 式甲基丁烯二酸，2 _甲基 酸等等。 又使用具有 有機羧酸鹽乃由 酸，2 —甲基一 2戊基 醇性羥基之溶媒做爲化成液時，該溶質之 芳族羧酸鹽及不含有二個以上之醇性羥基 /、裝------—訂---------r (請先閱讀背面之注意事項再填寫本頁) 4 6 0 8 5 5 a? B7 五、發明說明（8 ) 之脂肪族多谭竣酸鹽之群中來選用爲宜。 此時之芳族羧酸鹽可舉出上述之例示化合物。 又，脂肪族多價羧酸鹽乃，只要是不含二個以上之醇 性羥基，且具有二個以上之羧基之脂肪族化合物就不會特 別的限定其構造者。 使用脂肪族多價羧酸時，以碳數3〜9之脂肪族二羧 酸乃很合宜，所以分子中具有不飽和結合者或沒有不飽和 結合均可以。 會只要不損及本發明所期之效果，亦可使用羧基以外 之官能基之脂肪族多價羧酸也。 本發明可使用之脂肪族多價羧酸，乃例如枸櫞酸，羥 基丙二酸，蘋果酸，草酸，丙二酸，丁二酸，戊二酸，己 二酸，庚二酸，辛二酸，壬二酸，癸二酸，二甲基丙二酸 • . ，二乙基丙二酸，二丙基丙二酸，二甲基戊二酸，3，3 二甲基戊二酸，三甲基己二酸，馬來酸，富馬酸，衣康酸 ，丙二酸，枸櫞酸，戊二酸，二甲基丙二酸，順式甲基丁 烯二酸。 上述無機羰酸中，以硼酸、磷酸、硫酸、鎢酸、鉬酸 、鉻酸及釩酸爲宜，特別是鎢酸最合宜。 上述有機羧酸鹽中，以使用水楊酸、己二酸、壬二酸 、苯二甲酸、苯甲酸、r 一二羥基苯甲酸、馬來酸、富馬 酸、衣康酸、丙二酸、丁二酸、戊二酸、二甲基丙二酸、 及順式甲基丁烯二酸爲宜，其中特別是使用水楊酸、己二 酸、馬來酸、壬二酸及苯二甲酸爲最合宜。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注咅？事項再填寫本頁) 裝--------訂---------^νϊ 經濟部智慧財產局員工消費合作社印製 -ΊΊ - A7 在 60 855 ______B7__ 五、發明說明（9 ) 形成這些無機酸之鹽或有機羧酸之鹽之陽離子即不做 特別之限制。 (請先閱讀背面之注意事項再填寫本頁) 例如胺離子，鹼性金屬離子，1，2 , 3，或4級院 基胺離子、磷離子、離子等都可使用，其中以胺離子， 或1，2，3或4級烷基離子最合宜。 使用烷基胺離子之烷基之大小係可以考量溶媒之溶解 性而可選擇。 通常選擇碳數1〜4之烷基也。 這些溶質乃，可以單獨使用一種，或使用二種以上之 組合。 或組合無機酸或有機羧酸之鹽以外之溶質而使用亦可 以。 使用於本發明之化成液之溶質濃度係通常設定於 0 . 0 1〜3 0重量％之範圍。設定於0 . 1〜15重量 %之範圍內爲合宜。 本發明所使用之化成液乃，使用具有醇性羥基之溶媒 ，或非質子性有機溶媒做爲溶媒。 經濟部智慧財產局員工消費合作社印製 使用爲溶媒之具有醇性羥基之化合物之種類係不做特 別之限定。 合宜之溶媒乃，具有醇性羥基之脂肪族醇。例如可以 使用甲醇，乙醇，丙醇，異丙醇等之一價醇，或乙二醇’ 丙二醇等之二價醇，以及三價以上之多價醇均可使用。 例如甲基溶纖劑，或溶纖劑等，與醇性羥基而同時具 有烷氧基之溶媒亦可使用。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐): _ 1 ^ ' A7 d 60 855 B7___ 五、發明說明（10 ) 這些j溶媒係單獨地使用一種，或組合；!種以上而使用 均可以。 本發明中所使用之具有醇性羥基之溶媒以碳數1〜8 之溶媒爲宜，特別合宜之溶媒爲乙二醇、丙二醇之單獨或 混合溶媒。 本發明所使用之非質子性有機溶媒乃，極性溶媒，或 非極性溶媒均可使用。 極性溶媒乃可以例示，r — 丁內酯，τ—戊內酯，占 -戊內酯’等之內酯系溶媒，碳酸乙烯酯，碳酸丙烯酯， 碳酸丁烯酯等之碳酸酯系溶媒，N -甲基甲酰胺，N —乙 基甲醜胺，N，N，（二）甲基甲酰胺，N，N，（二） 乙基甲酰胺，N —甲基乙酰胺，N，N (二）甲基乙酰胺 ’ N，甲基吼11定並等之胺系溶媒，3 -甲氧基丙腈，戊二 腈等之腈系溶媒，三甲基磷酸酯，三乙基磷酸酯等之磷酸 酯系溶媒。 這些溶媒係可以單獨地使用一種，或二種以上之組合 來使用。 本發明所使用之溶媒以特別是碳酸丙烯酯，及T -丁 內酯之單獨或混合溶媒爲合宜。 本發明所使用之化成液乃以含有水0·1〜50重量 %爲宜水之含有量係0.1〜30重量％之範圍爲宜，而 0 . 1〜2 0重量％更合宜，1〜15重量％再更爲合宜 。3〜15重量％特別合宜。 調製本發明中所使用之化成液時，添加水之方法並不 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------' 裝--------訂 - -------r' (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制农 -1 460855 明說明（11 ) 特別限定。... _ 例如，在含有水之上述溶媒中溶解上述溶質以資調製 本發明所使用之化成液亦可，或在上述溶媒中溶解上述溶 質或添加了水以資調製本發明中所使用之化成液亦可以。 或利用使酸與鹼反應而生成上述溶質時所副生之水來 調製亦可以。 或組合上述之各方法亦可以。 使用本發明中所使用之化成液，而將第1導電膜（下 部電極）予以陽極氧化而形成絕緣膜（隧道絕緣層）之條 件係並不做特別之限定。 陽極氧化之溫度係，限定於化成液之安定的以液體地 存在之溫度範圍，通常以—20 °C〜1 50 °C之範圍，最 合宜係1 0〜1 0 0°C之範圍。 陽極氧化時之電流及電壓之控制方法乃不特別限定， 可以適當的組合在金屬表面形成氧化皮膜之條件。 通常係以預先規定之化成電壓（V f )爲止以一定電 流實施化成，達到了化成電壓後，即以一定時間以規定電 壓來實施陽極氧化也。 經濟部智慧財產局員工消費合作社印製 A7 B7 --- 五、發 (請先閱讀背面之注意事項再填寫本頁) 此時電流密度即以1 μ〜1 0 OmA/cm2之範圍內 ，最好以1 #〜ImA/cm2之範圍爲宜。 又，V f係通常設定於1〜5 Ο V之範圍，最好設定 於◦. 1〜2 Ο V之範圍內。 使用第1導電膜（下部電極）之金屬乃以由陽極氧化 而會形成阻擋皮膜之所謂「外殼金屬」爲對象，例如以鋁 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） A7 4.00855 _________B7 1 _ 五、發明說明（12 ) (A 1 或鋁合金爲宜。 純粹銘係在熱處理而容易發生缺陷，因此以微量地含 有錯以外之兀素之合金爲配線材料較合宜。 添加之元素乃可例示，銃（Sc)、釔（γ) 鋼（ L a )、镨（P r )、銳（N d )、釓（G d )、欽（ Ho)、餌（E r )、等之稀土類元素或，鈦（τ 土） 鉅（Ta)、銷（Zr)、給（Hf)、銳（Nb)鎢 (W)、鉬（Mo)等之「外殼金屬」元素也。 又，矽（S i)、銅（Cu)也可以。 本發明中’第1導電膜係以含有鈸（N d )之銘合金 爲宜。 第2導電膜（上部電極）乃得以遮蔽蒸著來形成敍（ I r) '白金（Pt)、金（Pu)膜來使用。 下面以實施例說明本發明之顯示裝置。 實施例1〜8，比較例1 本實施例係首先以下述之方法製作電子源元件。 (1 )以濺射法而在玻璃基板1 1推疊3 0 0 n m厚 之A 1 - N d ( 2原子％)之合金，而以光鈾法技術形成 了下部電極（第1導電膜）12。 (2 )接著，以抗蝕刻遮罩以後將成爲隧道絕緣層 1 4之部份，而以酒石酸胺水溶液及乙二醇之混合液（比 較例1 )做爲化成液而使用，藉由陽極氧化而下部電極 1 2之表面形成氧化銘，形成厚的電場緩和層1 3。 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐5 -----------iiv 裝--- (請先閱讀背面之注音？事項再填寫本頁)Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs I 460 855 A7 B7 V. Description of the Invention (1) (Technical Field) / f This invention relates to display devices, and in particular to the use of Μ I Μ (Metal-Insulator-Metal) Display device of electron source of tunnel-type diode structure. (Background.Technology) A display device using an electron beam source of the M I M type tunnel diode structure is described in, for example, the following document (i). (i) M. Suzuki and T. Kusunoki ;, Emission and Beam-Divergence Properties of an MIM-Cathode Array for Display Applications', SID’97 DIGEST (1 977) p.1 23-126. The tiny electron beam source of the M I M type diode structure disclosed in the aforementioned document (i) is characterized by high efficiency and high directivity. The thickness of the tunnel insulation layer is 5.5 nm. As the upper electrode of the electron emission portion, the thickness is only 6 nm in order to avoid the scattering of the hot electrons. The electron source device of the MI MF diode structure described in the above document (i) has a structure in which a high electric field of about 1 OMV / cm acts on the tunnel insulation layer, and about 0.4 mA / cm2 of current flow. Under such harsh conditions, the deterioration of the insulating film constituting the tunnel insulating layer over time cannot be avoided. Observing the diachronic changes of the tunnel diodes, it can be seen that the diode current will decrease with time and will eventually be destroyed. This phenomenon is due to the fact that in the insulating film constituting the tunnel insulation layer, the paper size applied to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -------------- ----- Order --------- (Please read the note on the back? Matters before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A60855 A7 ____ B7 ___ * _ V. Description of the invention ( 2) A part of the incoming hot electrons is captured by the electron traps existing in the insulating film and becomes a negative fixed load, which weakens the result on the cathode side, which suppresses electron injection as its cause. In addition, the deterioration that does not last for a while is a fact that a new electron trap is generated by a hot electron in a high electric field. This phenomenon constitutes one of the biggest reasons that limit the operating life of the electron source device of the MEMS diode structure. In addition, in the conventional insulating film system constituting the tunnel insulating layer, a 1 to 3% by weight aqueous solution of tartaric acid was neutralized with ammonia water, and diluted with ethylene glycol. The formation current density is limited to 100 0 A / cm2 or less, and is formed by anodization. Although this method can achieve good initial characteristics, it is problematic for long-term maintenance. (Disclosure of the Invention) The present invention was created to solve the above-mentioned problems of the prior art, and the object of the present invention is to provide an insulating film using a tunnel insulation layer of an electron wire source that can improve the M I M type diode structure. Film quality, a display device with technology to increase the operating life. The present invention mainly includes a second substrate on which a phosphor layer is formed on the surface, and a first substrate facing each other to form the electron beam source. The above-mentioned electron beam source has a first conductive film (lower electrode) -insulating film-second conductive film (upper electrode) structure laminated on the first substrate. The paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 mm;) nnn · ϋ n I t · nnn. ^ 1 nn · -1, _ dnnnnnn I Λ. I aa ^ t fv '(Please read the notes on the back before filling this page) ¢ 10855 A7 __B7__ 'V. Description of the invention (3) Display device ... (Please read the precautions on the back before filling this page) The above-mentioned insulating film is a display electrode formed by anodizing the above-mentioned first conductive film using one of the following non-aqueous chemical forming fluids (a) to (c) By. (a) It is composed of organic solvent with alcoholic hydroxyl groups, salts of inorganic carbonyl acids and salts of organic carboxylic acids (but limited to aromatic carboxylic acid salts, or aliphatics containing no more than two alcoholic hydroxyl groups. Non-aqueous chemical conversion solution of at least one solute selected from salts of valent carboxylic acids). (b) A non-aqueous organic solvent containing an aprotic organic solvent and at least one of the solutes selected from the group consisting of inorganic carbonyl salts and organic carboxylates. (c) A non-aqueous chemical conversion solution containing at least one solution selected from an organic solvent having an alcoholic hydroxyl group, a mixed solvent composed of an aprotic organic solvent, and an inorganic carbonyl acid salt and an organic carboxylic acid salt. (The best form of implementing the invention) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the representative of the inventions disclosed in this case is explained below. The display device of the present invention is mainly a display having a second substrate (upper substrate) on which a phosphor layer is formed on the surface, and a first substrate (lower substrate) facing the second substrate to form an electron beam source. In the device, the above-mentioned electron beam source is a display device having a first conductive film-insulating film-second conductive film structure laminated on a first substrate, wherein the above-mentioned insulating film is an organic film containing an alcoholic hydroxyl group. Solvent, and one of inorganic carbonyl acid salt and organic carboxylic acid salt (but limited to aromatic carboxylic acid salt or aliphatic polyvalent carboxylic acid salt which does not contain two or more alcoholic hydroxyl groups) This paper is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 460855 A7 _ __B7_ 'V. Description of the invention (4) _ non-aqueous. Chemical solution of solutes, and the insulation formed by anodizing the first conductive film above Film person. (Please read the precautions on the back before filling this page.) The display device of the present invention is mainly composed of a second substrate (upper substrate) on which a phosphor layer is formed on the surface, and the second substrate facing each other. The first substrate (lower substrate) forming the electron beam source is a display device having a first conductive film-insulating film-second conductive film structure laminated on the first substrate. The insulating film is used. An insulating film formed by anodizing the above-mentioned first conductive film containing a non-aqueous chemical conversion solution selected from an aprotic organic solvent and an inorganic carbonyl acid salt and an organic carboxylic acid salt. The display device of the present invention mainly includes a second substrate (upper substrate) on which a phosphor layer is formed on the surface, and a first substrate (lower substrate) facing the second substrate to form an electron beam source. The above-mentioned electronic wire source is a display device having a first conductive film-insulating film-second conductive film structure laminated on a first substrate, and is characterized in that the above-mentioned insulating film is printed by an employee consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. A non-aqueous chemical conversion solution containing at least one of the solutes selected from inorganic carbonyl salts and organic carboxylates is used as a mixed solvent formed by an organic solvent having an alcoholic hydroxyl group and an aprotic organic solvent. The first conductive film is an insulating film formed by anodization. Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In the drawings describing the embodiment, those having the same function are marked with the same reference numerals, and redundant descriptions are omitted. Figure 1 shows the outline of the display device according to the embodiment of the present invention. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) A7 460Bbo __________B7___ 5. Description of the invention (5) (Please read the back first Please fill in this page before opening). The display device of this embodiment is a flat-type display device, which is formed on the surface, with a metal-insulating film-metal structure (the substrate under the micro electron source array (the first substrate) 3 of the MEMS structure) 3, and The strip-shaped phosphor layer upper substrate (second substrate) 5 is formed by frame glass 4 facing each other. The first reference numeral 6 in the first figure is an exhaust pipe. The second figure shows the first figure A schematic diagram of an example of the lower substrate 3 (the first substrate). The lower substrate 3 shown in the same figure is formed by a strip-shaped lower electrode formed on a glass substrate 11 such as soda glass and extending in the X direction. 12 and the electric field relaxation layer (or interlayer insulation film) 1 3 formed on the lower electrode 12 and the tunnel insulation layer 14 and the extensions formed on the electric field relaxation layer 13 and the tunnel insulation layer 14 The strip-shaped bus electrode 15 and the upper electrode 16 formed on the bus electrode 15 are formed in this example. In this example, the lower electrode 12 and the bus electrode 15 are formed slightly orthogonal to each other, and the lower electrode is Electron emission is formed in a part of the overlapped area of 1 2 and bus electrode 15 1 7. The electron emission unit 17 is removed from the bus electrode 15 and the upper electrode 16 is facing the lower electrode 12 through the tunnel insulation layer 14 and printed by the consumer property cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The figure shows a schematic configuration diagram of an example of the upper substrate 5 (second substrate) shown in Fig. 1. The upper substrate 5 shown in the same figure is a strip extending in the direction of the Υ on a glass substrate 21 such as soda glass. The phosphor strip 18 formed by the red, green, and blue phosphor layers is composed of a metal cladding (A 1 film) film 19 formed on the phosphor strip 18. The paper dimensions Applicable to China National Standard (CNS) A4 specification (210 X 297 mm j 460855 A7 B7 V. Description of the invention (6) The present invention-Mingzhi display device is' brother 2. Lingdao road insulation layer shown in Figure 1 4 • Department : Use of organic solvents containing alcoholic hydroxyl groups, and inorganic carboxylic acid salts and organic carboxylic acid salts (but limited to aromatic carboxylic acid salts or aliphatic polyvalent carboxylic acid salts that do not contain two or more alcoholic hydroxyl groups) A non-aqueous chemical conversion solution (a) of a solute is used, and the insulating film formed by anodizing the lower electrode 12 is: The display device of the present invention is a tunnel insulation layer 14 shown in Fig. 2: a non-aqueous chemical composition containing a solute selected from an aprotic organic solvent, and an inorganic carbonyl salt and an organic carboxylate. The liquid (b) is characterized by an insulating film formed by anodizing the lower electrode 12 described above. Or the display device of the present invention is a tunnel insulating layer 1 4 shown in Fig. 2: It contains an alcoholic hydroxyl group. Organic solvent and aprotic organic solvent, a mixed solvent, and a non-aqueous chemical conversion solution (c) of at least one selected from inorganic carbonyl acid salt and organic carboxylic acid salt, and the first conductive film is applied. An insulating film formed by anodization is characteristic. In the present invention, the inorganic acid used as the solute of the anodizing chemical is preferably an inorganic carbonyl acid. In the case of an inorganic acid having an inorganic carbonyl acid as a proton, a dissociable hydrogen combined with an oxygen atom, the central atom may be a non-metal or a metal. Specifically, one or more compounds selected from the group consisting of boric acid, phosphoric acid, sulfuric acid, tungstic acid, molybdic acid, chromic acid and vanadic acid, and per-chain acid are suitable. In the present invention, it is used for anodizing Liquid solutes are derived from organic carboxylic acids and can be selected from a wide range of organic compounds with carboxyl groups. The size of carboxyl paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -------- Order--I ----- -^-1 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 460855 A7 V. Description of the invention (the number of 7 and its combination. It is suitable if the aromatic (fragrant) benzene aromatic ring, compound is free of isoformic acid, . Benzoic acid, benzoic acid, anisolic acid, gentisic acid, isoaromatic carboxylic acid and hydrazine, as long as it does not have aromatic carboxylic groups such as nitrobenzene (dimethyl) methylamine benzene The aliphatic polyvalent position is not aromatic (fragrant). The carboxylic acid is an aromatic ring and an atomic aromatic r-dihydroxy acid, 2, gallic acid can be exemplified by benzoic acid, etc., and the present acid can be formic acid. The special family carboxylates such as gas formic acid are used with carboxyl carboxylic benzoyl cresol, and P, smoke, etc. It is expected to be used. Anisic anhydride has nitrate limitation. _ And aliphatic polyvalent carboxylic acid Acid salt. Compounds having a benzene ring, a condensed benzene ring, and other compounds. Examples include salicylic acid, phthalic acid, and toluyl. , T-propyl acid, cinnamic acid, N-methylanthracene-hydroxybenzoic acid, etc. The effect of acid, 2-furanic acid, 2-thiophene, has other than carboxyl group, (a) methylamine benzoic acid, group or Aromatic carboxylic acids of amino groups can also be printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Examples of carboxylic acids are tartaric acid, citric acid, hydroxymalonic acid 'malic acid, oxalic acid, malonic acid, succinic acid, glutaric acid. , Adipic acid, pimelic acid 'suberic acid, azelaic acid, sebacic acid, dimethylmalonic acid, diethylmalonic acid, dipropylmalonic acid, dimethylglutaric acid, 3 , 3 dimethyl glutaric acid, 3-methyl adipic acid, maleic acid, fumaric acid, itaconic acid, cis methylbutenedioic acid, 2-methyl acid, etc. Also used organic The carboxylate is formed from a solvent of an acid and a 2-methyl-2pentyl alcoholic hydroxyl group as a chemical conversion solution. The aromatic carboxylate of the solute and the alcoholic hydroxyl group do not contain two or more alcoholic hydroxyl groups .-- ---— Order --------- r (Please read the notes on the back before filling out this page) 4 6 0 8 5 5 a? B7 V. Description of Invention (8) Fatty Tan Salt group It is preferable to select it. The aromatic carboxylate at this time may include the above-exemplified compounds. In addition, the aliphatic polyvalent carboxylate is not required as long as it does not contain two or more alcoholic hydroxyl groups and has two or more carboxyl groups. The structure of the aliphatic compound is not particularly limited. When using an aliphatic polyvalent carboxylic acid, an aliphatic dicarboxylic acid having 3 to 9 carbon atoms is very suitable, so there is no unsaturated bond in the molecule or no Saturated bonding is all right. As long as the desired effect of the present invention is not impaired, an aliphatic polyvalent carboxylic acid having a functional group other than a carboxyl group can also be used. The aliphatic polyvalent carboxylic acid that can be used in the present invention is, for example, citron Acid, hydroxymalonic acid, malic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dimethylmalonic acid •., Diethylmalonic acid, dipropylmalonic acid, dimethylglutaric acid, 3,3 dimethylglutaric acid, trimethyladipate, maleic acid, fumaric acid, clothing Conic acid, malonic acid, citric acid, glutaric acid, dimethylmalonic acid, cismethylbutenedioic acid. Among the above-mentioned inorganic carbonyl acids, boric acid, phosphoric acid, sulfuric acid, tungstic acid, molybdic acid, chromic acid, and vanadic acid are preferable, and tungstic acid is most suitable. Among the organic carboxylates, salicylic acid, adipic acid, azelaic acid, phthalic acid, benzoic acid, r-dihydroxybenzoic acid, maleic acid, fumaric acid, itaconic acid, and malonic acid are used. , Succinic acid, glutaric acid, dimethylmalonic acid, and cis methylbutenedioic acid are suitable, among which salicylic acid, adipic acid, maleic acid, azelaic acid, and benzene dicarboxylic acid are particularly suitable. Formic acid is most suitable. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back? Matters before filling out this page) Loading -------- Order ------ --- ^ νϊ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -ΊΊ-A7 at 60 855 ______B7__ V. Description of the invention (9) The cations that form these inorganic acid salts or organic carboxylic acid salts are not subject to special restrictions. . (Please read the precautions on the back before filling out this page) For example, amine ions, basic metal ions, 1, 2, 3, or 4 grade amine ions, phosphorus ions, ions, etc. can be used, among which amine ions, Or 1, 2, 3 or 4 alkyl ions are most suitable. The size of the alkyl group using the alkylamine ion can be selected in consideration of the solubility of the solvent. Usually, the alkyl group having 1 to 4 carbon atoms is also selected. These solutes can be used singly or in combination of two or more kinds. It may be used in combination with a solute other than a salt of an inorganic acid or an organic carboxylic acid. The solute concentration of the chemical conversion solution used in the present invention is usually set in the range of 0.01 to 30% by weight. It is desirable to set it within the range of 0.1 to 15% by weight. The chemical conversion solution used in the present invention uses a solvent having an alcoholic hydroxyl group or an aprotic organic solvent as a solvent. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The types of compounds with alcoholic hydroxyl groups used as solvents are not specifically limited. A suitable solvent is an aliphatic alcohol having an alcoholic hydroxyl group. For example, monovalent alcohols such as methanol, ethanol, propanol, isopropanol, or divalent alcohols such as ethylene glycol 'propylene glycol, and polyvalent alcohols of trivalent or higher can be used. For example, a methyl cellosolve, or a cellosolve, a solvent having an alcoholic hydroxyl group and an alkoxy group can also be used. This paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm): _ 1 ^ 'A7 d 60 855 B7___ V. Description of the invention (10) These j solvents are used alone or in combination; Any of the above can be used. The solvent having an alcoholic hydroxyl group used in the present invention is preferably a solvent having a carbon number of 1 to 8, and a particularly suitable solvent is a single or mixed solvent of ethylene glycol and propylene glycol. The aprotic organic solvent used in the present invention may be a polar solvent or a non-polar solvent. Polar solvents are exemplified by lactone-based solvents such as r-butyrolactone, τ-valerolactone, and di-valerolactone, carbonate solvents such as ethylene carbonate, propylene carbonate, and butene carbonate, N-methylformamide, N-ethylformamide, N, N, (di) methylformamide, N, N, (di) ethylformamide, N-methylacetamide, N, N ( 2) Methylacetamide 'N, methylamine and other amine-based solvents, 3-methoxypropionitrile, glutaronitrile and other nitrile solvents, trimethyl phosphate, triethyl phosphate, etc. Phosphate ester solvent. These solvents can be used singly or in combination of two or more kinds. The solvent used in the present invention is preferably a single or mixed solvent of propylene carbonate and T-butyrolactone in particular. The chemical conversion solution used in the present invention is preferably water containing 0.1 to 50% by weight, preferably 0.1 to 30% by weight of water, and 0.1 to 20% by weight, more suitably 1 to 15%. % By weight is even more expedient. 3 to 15% by weight is particularly suitable. When preparing the chemical conversion solution used in the present invention, the method of adding water is not applicable to the Chinese standard (CNS) A4 specification (210 X 297 mm) for this paper. ----------- ' ------- Order- ------- r '(Please read the precautions on the back before filling out this page) Printed by Agricultural Consumers Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-1 460855 Instructions (11) Specially limited. ..._ For example, it is also possible to dissolve the solute in the above-mentioned solvent containing water to prepare the chemical conversion solution used in the present invention, or to dissolve the solute in the above-mentioned solvent or add water to prepare the used in the present invention. Chemical fluids are also acceptable. Alternatively, it may be prepared by using water by-produced when an acid and a base are reacted to generate the solute. Alternatively, the above methods may be combined. The conditions under which the first conductive film (lower electrode) is anodized using the chemical conversion solution used in the present invention to form an insulating film (tunnel insulating layer) are not particularly limited. The temperature of anodic oxidation is limited to the stable temperature range of the liquid in the form of liquid, usually in the range of -20 ° C to 150 ° C, and most preferably in the range of 10 to 100 ° C. The method for controlling the current and voltage during anodization is not particularly limited, and the conditions for forming an oxide film on the metal surface can be appropriately combined. Generally, the formation is performed at a predetermined current until a predetermined formation voltage (V f) is reached. After the formation voltage is reached, the anodic oxidation is performed at a predetermined voltage for a certain period of time. Printed by A7 B7 of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs --- V. (Please read the precautions on the back before filling out this page) At this time, the current density is within the range of 1 μ ~ 1 0 OmA / cm2. It is better to range from 1 # to ImA / cm2. In addition, V f is usually set in a range of 1 to 5 Ο V, and preferably set in a range of 1 to 2 Ο V. The metal using the first conductive film (lower electrode) is targeted at the so-called "shell metal" that will form a barrier film by anodization. For example, the aluminum paper size applies the Chinese National Standard (CNS) A4 (210 X 297) (%) A7 4.00855 _________B7 1 _ V. Description of the invention (12) (A 1 or aluminum alloy is preferred. Pure inscriptions are prone to defects due to heat treatment. Therefore, it is more appropriate to use alloys containing trace amounts of elements other than the wrong one as wiring materials. The added elements can be exemplified, thorium (Sc), yttrium (γ) steel (L a), thorium (P r), sharp (N d), thorium (G d), chin (Ho), bait (E r ), Or other rare earth elements, or "shell metal" elements such as titanium (τ soil) giant (Ta), pin (Zr), donor (Hf), sharp (Nb) tungsten (W), molybdenum (Mo), etc. It is also possible to use silicon (Si) and copper (Cu). In the present invention, the first conductive film is preferably an alloy containing rhenium (N d). The second conductive film (upper electrode) is shielded from vaporization. In order to form a (Ir) 'platinum (Pt) and gold (Pu) film for use. The display device of the present invention will be described below by way of an example. Example 1 8. Comparative Example 1 In this example, an electron source device was first manufactured by the following method. (1) A 1-N d (2 atomic%) with a thickness of 300 nm was pushed on a glass substrate 11 by sputtering. Alloy, and the lower electrode (the first conductive film) 12 was formed by the photo-uranium method. (2) Next, it will become a part of the tunnel insulation layer 14 with an anti-etching mask, and an aqueous solution of tartrate and B The mixed solution of diol (Comparative Example 1) was used as a chemical conversion solution, and the surface of the lower electrode 12 was oxidized by anodization to form a thick electric field relaxation layer 13. The paper dimensions are applicable to Chinese national standards (CNS ) A4 size (210 x 297 mm 5 ----------- iiv pack --- (Please read the note on the back? Matters before filling out this page)
V 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 d 60B55 五、發明說明（13 ) 陽極氧化條件乃，在於定電流（電流密度3 0 // A / c m 2 )狀態而昇至電壓8 Ο V爲止’其後即以定電 壓狀態實施陽極氧化。 (3 )接著以比較例1以外，而使用下述表1所示之 本發明之非水系化成液，而在下部電極1 2之表面之電子 放出部1 7之領域形成氧化鋁而形成薄的隧道絕緣層1 4 〇 陽極氧化條件即以定電流（電流密度1 Ο V A / c m 2 )狀態而昇至電壓4 V爲止，而後即以定電壓狀態實施2 小時。 (4 )最後形成總線電極1 5及上部電極1 6。 本例中，總線電極1 5乃以鋁及鉬之多層膜所構成， 又上部電極1 6係以測射而維持真空狀態之下，依序以遮 罩蒸著來依序形成銦（I r ; 1mm)、白金（Pt ; 2 m m )、金（A u ; 3 m m )而製作。 將以上述（1 )〜（4 )之程序所製作之Μ Γ M型二 極體構造之微小電子線源元件，在於真空容器內處以壓力 1X10_4Pa之下。而將下部電極12予以接地’對於 上部電極1 6賦加7 . 5 V之電壓而確認來自上部電極 1 6之電子放出。 接著，以二極體之電流密度能成爲0.4mA/cm2 地設定了初期電壓’維持該狀態的實施1小時之驅動’記 錄了其間之二極體電流之變動。 該結果與習用規格之「酒石酸與乙二醇」混合液（比 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公髮）_ -------------------訂---------r' (請先閱讀背面之注音？事項再填寫本頁) d6〇855 A7 B7 五、發明說明（14 ) 較例1 相比較時，具有使用本發明之化成.液而將下部電 極1 2予以陽極氧化所成之隧道絕緣層1 4之Μ I Μ型二 極體構造之微小電子線源元件時，即如下述表1所示確認 了電流之減少較少之事實。 如上所述，本實施例1〜8之Μ I Μ型二極體構造之 微小電子源元件中之隧道絕緣層1 4乃，電子陷阱密度少 ，在高電場且大動作電流條件下之電子陷阱之產生少，医| 此具有優異之壽命特性也。 -----------(1 --------訂---------#J; (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 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）' /i 6 Ο 8 5 5 A7 B7 五、發明說明（15 經濟部智慧財產局員工消費合作社印製 _ 据 〇 〇\ LO 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 卜 〇〇 o ON uSii· ππιη 盤 1 4 觀 Ornll Ρ 氍 氍 氍 鮏 鮏 黢 am fen 氍 鹱 11 11 11 11 11 1 1 1丨 r 磐 锲 Ν3 Κ] K] K1 Η 裝 _ ·!—> •4—> 4—» i—t +-> -1 1 Ό ν〇 +-» c〇 1 wt % 1 wt % 1 wt% 1 wt% 1 wt% 1 wt% 1 wt% 1 wt% 铤 〇 溶質種 狴 埕 二甲酸胺 鎢酸胺 越 氍 氍 氍 ! i 氍 氍 I 1 m 國 旧 喊 1 ! 擀 〇 1 1 r-Η C0 CO 寸 wo vo 〇〇 匡 翠 m 孽 m u 握 闺 辑 辑 辑 ㈣ m 辑 SJ 1¾ IK 1¾ 卹 IK IK 魏 -------------- I --------訂--------- (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） -Ιο- 4· 6 0 8 5 5 a? B7 五、發明說明（16 ) 實施例1 . (請先閱讀背面之注意事項再填寫本頁) 接著如第4圖所示，依上述程序，製作了將Μ I Μ型 二極體構造之微小電子線源元件排列成陣列（矩陣）狀之 下基板3。 接著使用玻璃來隔著下基板3，及形成條狀之螢光體 層之上基板5，以及框玻璃5，同時隔排氣管6做成真空 容器。 此時之玻璃糊之燒結條件係，於大氣中4 0 0 °C， 1 0分鐘接著以油擴散泵來抽真空容器之真空，以3 0 0 °C開始燒，而真空度到達於7 X 1 0— 5P a之時點封閉排 管完成了顯示裝置。 本實施例之顯示裝置之顯示實驗乃以漸進（ progressive )驅動方式爲之。 在此漸進之驅動方式中分別對於所選擇之畫素之下部 電極1 2有-3 . 0 V之掃瞄電壓脈衝之賦加，對於上部 電極1 6 (介著總線電極1 5 )有4 . 5 V之資料電壓脈 衝之賦加，所以從電子放出部1 7將放出電子。 經濟部智慧財產局員工消費合作社印製 該被放出之電子乃，由賦加於上基板5之間（間隙-=2mm)之3 KV之加速電壓所加速，到達於螢光體層 條1 8而引起發光，相對的在非選擇畫素即只對於下部電 極1 2，或上部電極1 6 (或總線電極1 5 )之其中之— ，賦加一3.0V之掃瞄電壓脈衝或4.5V之資料電壓 脈衝，所以對於電子放出部1 7並不放出電子也。 由此顯示實驗，本實施例之顯示裝置乃顯示了良好之 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） v -460855 a? _B7_ - 五、發明說明（17 ) 顯示特性也。. .. (請先閱讀背面之注意事項再填寫本頁) 上面乃依上述實施形態而具體的說明了本發明所開發 之發明，惟本發明並不限定於上述實施形態，在不逸脫本 發明之精神之範圍內當然仍可以做種種之變更也。 (產業上之利用可能性） 依本案所揭示之發明中之代表性者所可以獲得之效果 簡單的說明於下。 依本發明時，可以提高使用Μ I Μ型二極體構造之電 子線源元件之顯示裝置之動作壽命，其產業上之利用可能 性很大者。 圖式之簡單說明 第1圖表示本發明之實施形態之顯示裝置之槪略構成 .之展開斜視圖。 第2圖表示第1圖所示之下基板（第1基板）之一例 之槪略構成圖。 經濟部智慧財產局員工消費合作社印製 第3圖表示第1圖所示之上基板（第2基板）之一例 之槪略構成圖。 第4圖表示將第2圖所示之Μ I Μ型二極體構造之電 子線源元件之陣列狀配置狀態之模式圖。 主要元件對照 3 下基板 -ZLT- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）— Γ',^4 60 855 α7 經濟部智慧財產局員工消費合作社印製 .、發明說明（ 18 ) 4 . 框玻璃 5 上基板 6 排氣管 11 玻璃基板 12 下部電極 13 電場緩和層 14 隧道絕緣層 15 母線電極 16 上部電極 17 電子放出部 18 螢光體條 19 金屬敷層膜 21 玻璃基板 (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）V Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by d 60B55. V. Description of the invention (13) Anodizing conditions are based on constant current (current density 3 0 // A / cm 2) State until the voltage rises to 8 0 V ', and then anodizing is performed in a constant voltage state. (3) Next, in addition to Comparative Example 1, using the non-aqueous chemical conversion solution of the present invention shown in Table 1 below, alumina is formed in the area of the electron emission portion 17 on the surface of the lower electrode 12 to form a thin layer. The tunnel insulation layer 1 40 anodic oxidation conditions were raised to a voltage of 4 V at a constant current (current density 10 VA / cm 2), and then implemented at a constant voltage for 2 hours. (4) Finally, bus electrodes 15 and upper electrodes 16 are formed. In this example, the bus electrode 15 is composed of a multilayer film of aluminum and molybdenum, and the upper electrode 16 is sequentially formed with indium (I r 1mm), platinum (Pt; 2 mm), gold (Au; 3 mm). The micro electron source device of the M Γ M type diode structure manufactured by the procedures of (1) to (4) above is placed under the pressure of 1X10_4Pa in the vacuum container. The lower electrode 12 is grounded ', and a voltage of 7.5 V is applied to the upper electrode 16 to confirm that electrons from the upper electrode 16 are emitted. Next, an initial voltage was set at a current density of the diode of 0.4 mA / cm2, and the driving was performed for one hour while maintaining this state. The change in the diode current was recorded. The result is a mixture of "tartaric acid and ethylene glycol" with conventional specifications (the Chinese national standard (CNS) A4 specification (210 X 297) is applicable than this paper size) _ ------------- ------ Order --------- r '(Please read the note on the back? Matters before filling out this page) d6〇855 A7 B7 V. Description of the invention (14) When comparing with Example 1 When using a microelectronic wire source element with a MIMO diode structure of a tunnel insulation layer 14 formed by anodizing the lower electrode 12 with the chemical solution of the present invention, as shown in Table 1 below The fact that the reduction of the current is small was confirmed. As described above, the tunnel insulating layer 14 in the micro electron source element of the MEMS diode structure of the embodiments 1 to 8 has a low electron trap density and a high electron trap density. The generation of electron traps under the conditions of an electric field and a large operating current is small, and the medicine has excellent life characteristics. ----------- (1 -------- Order ---- ----- # J; (Please read the notes on the back before filling out this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is printed in accordance with China National Standard (CNS) A4 (210 X 297 mm) '/ i 6 Ο 8 5 5 A7 B7 V. Description of the invention (15 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs _ According to 〇〇 \ LO 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇o uSii · ππιη disk 1 4 View Ornll Ρ 氍 氍 氍 鮏 鮏 黢 am fen 氍 鹱 11 11 11 11 11 1 1 1r r 锲 33 Κ] K] K1 ___! — ≫ • 4— > 4— »i --T +-> -1 1 Ό ν〇 +-»c〇1 wt% 1 wt% 1 wt% 1 wt% 1 wt% 1 wt% 1 wt% 1 wt% Ammonium tungstate! I 氍 氍 I 1 m Country old shout 1! Roll out 〇1 1 r-Η C0 CO inch wo vo 〇〇 Kuang Cui m mumu Hold the boudoir series ㈣ m series SJ 1¾ IK 1¾ Shirt IK IK Wei -------------- I -------- Order --------- (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)-Ιο- 4 · 6 0 8 5 5 a? B7 V. Description of the invention (16) Example 1. (Please read the precautions on the back before filling out this page.) Then, as shown in Figure 4, according to the above procedure, a M I M type diode was produced. The structured micro electron source elements are arranged in an array (matrix) -like lower substrate 3. Next, glass is used to sandwich the lower substrate 3, the upper substrate 5 forming the strip-shaped phosphor layer, and the frame glass 5, and the exhaust pipe 6 is used to form a vacuum container. The sintering conditions of the glass paste at this time are at 400 ° C in the atmosphere for 10 minutes, and then the vacuum of the vacuum container is evacuated by an oil diffusion pump, and the firing is started at 300 ° C, and the degree of vacuum reaches 7 X The display device was completed by closing the pipe at the point of 10-5P a. The display experiment of the display device of this embodiment is performed in a progressive driving manner. In this progressive driving method, scanning voltage pulses of -3.0 V are added to the lower electrode 12 of the selected pixel, and 4 to the upper electrode 16 (via the bus electrode 15). The data voltage pulse of 5 V is added, so electrons will be emitted from the electron emission section 17. The released cooperative electron printed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs was accelerated by an acceleration voltage of 3 KV applied between the upper substrate 5 (gap-= 2mm) and reached the phosphor layer 18 Causes light emission, the relative non-selected pixels are only for one of the lower electrode 12 or the upper electrode 16 (or the bus electrode 15), and a 3.0V scanning voltage pulse or 4.5V data is added. The voltage pulses do not emit electrons to the electron emission portion 17 either. From this display experiment, the display device of this embodiment shows that the paper size is good. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) v -460855 a? _B7_-V. Description of the invention (17) Display Features too. ... (Please read the notes on the back before filling in this page) The above has specifically described the invention developed by the present invention in accordance with the above-mentioned embodiments, but the invention is not limited to the above-mentioned embodiments, without departing from the invention Of course, various changes can still be made within the scope of the spirit. (Industrial Applicability) The effects obtained by the representative of the inventions disclosed in this case are briefly explained below. According to the present invention, it is possible to increase the operating life of a display device using an electron source device of the M I and M type diode structure, and it is highly industrially applicable. Brief Description of the Drawings Fig. 1 is a developed perspective view showing a schematic configuration of a display device according to an embodiment of the present invention. Fig. 2 is a schematic configuration diagram showing an example of the lower substrate (first substrate) shown in Fig. 1. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Figure 3 shows a schematic diagram of an example of the upper substrate (second substrate) shown in Figure 1. Fig. 4 is a schematic view showing an array-like arrangement state of the electron source components of the MIMO diode structure shown in Fig. 2; Comparison of main components 3 Lower substrate-ZLT- This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 X 297 mm) — Γ ', ^ 4 60 855 α7 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs. Explanation (18) 4. Frame glass 5 Upper substrate 6 Exhaust pipe 11 Glass substrate 12 Lower electrode 13 Electric field relaxation layer 14 Tunnel insulation layer 15 Bus bar electrode 16 Upper electrode 17 Electron emitting part 18 Phosphor strip 19 Metal coating film 21 Glass substrate (Please read the precautions on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)