1296814 九、發明說明· 【發明所屬之技術領域】 本發明係有關於一種場發顯示器（Field Emission Display ; FED)陰極面板電子發射源層之製作技術，尤指 一種以碳奈米管為電子發射源層之圖騰化製作技術。 【先前技術】 由於石炭奈米管（Carbon nanotubes)自1991年被 Iijima提出後（Nature 354，56 (1991))具備極高的電子 特性’並且已被多種電子元件内所使用，而碳奈米管可以 有很高的長寬比（aspect ratio)大於500以上，和高的剛 性其揚氏係數多在lOOOGPn以上，而碳奈米管之尖端或缺 陷處均為原子級規模的露出，以上這些特性因此被認為一 種理想的場電子發射源（electron field emitter)材料， 例如一種場發射顯示器之陰極板上之電子發射源之利 用。由於奈米碳管具備以上所示之物理特性，因此也可被 設計為多種製程如，網印或薄膜製程等以圖騰化於電子元 件使用。 本發明所謂的場發顯示器是一種利用電場俾使陰極 電子發射源（Cathode electron emitter)產生電子，藉由 該電子激發陽極板之螢光粉體，俾使螢光粉體產生光子發 光’其特色是輕、薄、有效顯示區域尺寸之大小可依製裎 及產口口品求製作’此外也沒有如平面液晶顯不器之視角問 題0 1296814 一種簡易之習知場發射顯示器la其結構至少包含陽 極3a與陰極4a，單元結構5a有單元陽極51a及單元陰極 52a，其間設置有阻隔壁（Hb) 53a，提供為陽極與陰極間 真空區域之間隔，及作為陽極與陰極之間之支撐，表閱第 一圖所示，一陽極3a至少包含一陽極玻璃基板31a，一陽 極導電層32a，一螢光粉體塗層（phosphors layer)33a; 而一陰極4a至少包含一陰極玻璃基板41a，一陰極導電層 42a，一電子發射源層43a;其中陽極3a與陰極4a之間隔 係由阻隔壁53a配置，其功能為保持陰極板與陽極板之間 之真空區域之維繫，並It提供之一外加電場，俾使陰極板 上之電子發射源層產生電子並射向陽極板上之螢光粉體 激發而使螢光粉體發光。該二極結構之場發射顯示器，陰 極與陽極之間隙可介於50μπι至200μπι之間，所需要之驅 動電場強度多無須超過10 V/μιη，或驅動電壓（Turn on Voltage)大於150V以上，即可使陰極產生電子，至於螢 光粉之發光效率則依選用之該螢光粉材料特性而定。 至於目前對於碳奈米管有多種備製方法，其中至少有 弧光放電法（arc-discharge)，雷射溶脫法（laser ablation)，化學蒸鍵沉積法（chemical vapor deposition，CVD)(以上方法可參閱11：1]111&，如1：1^6，¥〇1· 354，ρ·56 (1991) ; Τ· W· Ebbesen and Ρ· Μ· Ajayan， Nature, Vol. .358， ρ· 220(1992) ; and Β· I· Yakobson and R. Ε· Smalley， American Scientist, Vol. 85， p. 324(1997))，這些方法中其中一種以CVD之方式係可以藉 1296814 由觸媒（Catalyst)蒸鍍沉積成長碳奈米管被圖騰化 (pattern)於石夕晶圓（silicon wafer)上（可參閱 Fan et al·，Science，V〇l· 283，ρ· 512(1999)，and Xu et al，BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a field emission display (FED) cathode panel electron emission source layer fabrication technique, and more particularly to a carbon nanotube tube for electron emission. The totemization production technology of the source layer. [Prior Art] Since Carbon nanotubes have been proposed by Iijima since 1991 (Nature 354, 56 (1991)) have extremely high electronic properties' and have been used in various electronic components, and carbon nanotubes. The tube may have a high aspect ratio of more than 500, and a high rigidity, the Young's modulus is more than 1000 GPn, and the tip or defect of the carbon nanotube is exposed on an atomic scale. The characteristics are therefore considered to be an ideal field electron emitter material, such as the use of an electron emission source on the cathode plate of a field emission display. Since the carbon nanotubes have the physical properties shown above, they can also be designed for a variety of processes such as screen printing or film processing to be used for electronic components. The so-called field emission display of the present invention uses an electric field to cause a cathode electron emitter to generate electrons, and the electrons excite the phosphor powder of the anode plate to cause the phosphor powder to generate photon light. It is light, thin, and the size of the effective display area can be made according to the production and production of mouth and mouth products. In addition, there is no problem of viewing angle as a flat liquid crystal display. 0 1296814 A simple conventional field emission display la has at least its structure The anode 3a and the cathode 4a, the unit structure 5a has a unit anode 51a and a unit cathode 52a, and a barrier wall (Hb) 53a is provided therebetween, which is provided as a gap between the anode and the cathode, and serves as a support between the anode and the cathode. As shown in the first figure, an anode 3a includes at least an anode glass substrate 31a, an anode conductive layer 32a, and a phosphor powder layer 33a. The cathode 4a includes at least one cathode glass substrate 41a. a cathode conductive layer 42a, an electron emission source layer 43a; wherein the interval between the anode 3a and the cathode 4a is arranged by the barrier wall 53a, and its function is to maintain the cathode plate and the anode plate Maintaining of the vacuum area, and It provides one of the applied electric field to enabling electrons on the cathode plate and the electron emission source toward the phosphor layer to produce the powder of the anode plate of the fluorescence excitation light emitting powder. The field emission display of the two-pole structure, the gap between the cathode and the anode can be between 50μπι and 200μπι, and the required driving electric field strength does not need to exceed 10 V/μιη, or the driving voltage (Turn on Voltage) is greater than 150V, that is, The cathode can generate electrons, and the luminous efficiency of the phosphor depends on the characteristics of the phosphor material selected. As for the current preparation methods for carbon nanotubes, at least arc-discharge, laser ablation, chemical vapor deposition (CVD) (the above method) See 11:1] 111 &, such as 1:1^6, ¥〇1· 354, ρ·56 (1991); Τ·W· Ebbesen and Ρ· Μ· Ajayan, Nature, Vol. .358, ρ· 220 (1992); and Β· I· Yakobson and R. Small· Smalley, American Scientist, Vol. 85, p. 324 (1997)), one of these methods can be borrowed from 1296814 by CVD. Catalyst) vapor deposition of a growing carbon nanotube is totemized on a silicon wafer (see Fan et al., Science, V〇l. 283, ρ· 512 (1999), and Xu et al,
Appl· Phys· Lett·，Vol 74，p· 2549(1999))，然依本方 式之製作仍有部分困難存在··一、係在大於至少70(rc以 上之蒸鍍製程環境製作，目前僅適用於矽晶圓材料，尚無 法實施於玻璃基板上；二、所成長之碳奈米管之一端尚有 觸媒材料存在，仍需經過改質或處理或清除，俾使；g炭奈米 管有最高的電流密度產生，方可成為場發射顯示器商品化 產品的利用，二、所成長之碳奈米管結構鬆散，對於石夕晶 圓之附著力也較差；四、該實施製程繁複且設備及材料成 本較高。而另一種製程方式係以量產收集碳奈米管後，再 調配為溶液或塗料後再圖騰化實施沉積於基板上，由於本 方法係以調製方式製作為漿料，本方法可有利於對於以破 璃材質為基板之實施，大大降低材料成本與製程條件限 制。 然，以碳奈米管製作為漿料之方式實施於場發射_八 态1a以製作為陰極之電子發射源層43a，也仍得考庹 ^有類似前述之化學蒸鍍直接圖騰化碳奈米管其碳 管之結構鬆散及附著力不足等缺憾，對此業界已提供二= f法予以改善，-種方式係可對漿料添加選用適用之固f 劑如玻璃粉等改善方法，可參考台灣發明專利案公告Ϊ 527624賴不，即是以―種網印技術將碳奈米管聚料= 化於陰極電極為電子發射源層，其巾對於鼓米管'，、、 1296814 以添加一種玻璃粉為固著劑以增加與陰極導電層之附 著，另外一種方法可參酌美國專利案公告第6277318號， 係利用真空燒結方式軟化陰極導電層42a，俾使沉積於陰 極導電層上之碳奈米管包容於導電層間而達到提昇固著 碳奈米管之效果，不過以上這些方式仍有缺憾存在仍待克 服，其中之一乃該等製程僅適用於低解析之圖騰製作，首 先以網印印製碳奈米管之方法，仍受限網印之網布上絲徑 及開口率限制，因此最小圖騰面積仍至少需要80μιη以上， 所以無法再提供更高解析圖騰之要求，此外對於以真空燒 結模式則仍受限於陰極導電層之四周仍有會有碳奈米管 之附著致使電子發射源塗層，無法準直，且這些非規則露 出之碳奈米管易造成相鄰之導電層電極導通，此問題仍待 克服。職是，發明人乃設計一種可曝光顯影製作之礙奈米 管塗料，藉由一網印製程將塗料塗覆於陰極玻璃基板上， 再藉由曝光顯影製程圖騰化所需要之陰極碳奈米管之電 子發射源層態樣，據此以本方法製作可提供以下之優點 一、塗料調製簡易；二、塗料配方可控制適用之製程需求； 三、製作準直性高且高解析之圖騰；四、大大降低製程設 備需求及材料成本。 【發明内容】 有鑑於以習知技藝製作之場發射顯示器之陰極電子 發射源層之製作，以化學蒸鍍碳奈米管之方法，碳奈米管 之於陰極導電層附著力不足，且仍無法製作於玻璃基板 1296814 上，另，一種以網印印製碳奈米管電子發射源層之製作， 印製圖騰仍無法製作高解析之面板，且以上之各該製作後 之電子發射源層表面能需藉表面處理，以提昇碳奈米管之 電子產生效率以提昇電子密度，職是，發明人乃設計一種 對於場發射顯示器之陰極電子發射源層提供一種網印塗 佈配合曝光顯影製程製作技術，據此··一、可提供一簡易 網印塗佈實施於陰極玻璃基板；二、配合陰極導電層材料 特性及製程特性，調製塗料，可增加碳奈米管與陰極導電 層之附著力；三、以曝光顯影製程可製作高解析精密圖 騰，並可增加碳奈米管之露出，可提高電子之產生效率； 四、以本製程方式製程簡化，塗料成本低，可適用於玻璃 基板之製作。 本發明之主要目的，係提供一種顯影型之碳奈米管塗 料，可用一種簡易之網印製作塗覆塗料，再配合曝光顯影 製程圖騰化所需之電子發射源層。 本發明又一目的，係提供用於網印之顯影型之碳奈米 管塗料，藉由製作之曝光顯影過程可以使奈米碳管露出之 機會提高，避免碳奈米管被包覆於塗層内，可增加電子之 釋出。 本發明另一目的，係提供用於網印之顯影型之碳奈米 管塗料，可配合陰極電極特性添加適用之固著劑，以增添 碳奈米管於電極上的附著力。 為達上述所謂之諸目的，本發明係提供一種可以印刷 塗覆之顯影型碳奈米管塗料，以印刷並搭配曝光顯影製程 1296814 製作電子發射源層；其顯影型碳奈米管塗料係以水溶性樹 脂添加光反應起始劑製作為負型光阻劑，再添加以碳奈米 管及導電粉體，和添加必要之分散劑使前述添加之粉體均 勻分散，另，依製作後之塗層燒結需求，可著以固著劑以 增加碳奈米管與陰極電極之附著力。以上之調製為一種可 以配合印刷製程之高黏度塗料，其實施方法，係以印刷方 式先將顯影型碳奈米管塗料以印刷方式印製塗覆於陰極 玻璃基板上，經過一低溫焙烤使塗覆層乾燥成膜，接著以 汞燈紫外光進行曝光，以使欲圖騰化區域進行光反應進行 化學鏈結，隨後進行顯影，藉顯影過程除了可使不欲圖騰 化之區域溶解剝離外，由於圖騰化之塗層表層於顯影過程 亦有小部分光阻劑被顯影劑溶除，此將有助於塗層内之碳 奈米管露出於塗層表面，顯像後之塗層可經過一乾燥程序 後進行高温燒結，以使碳奈米管固著於陰極玻璃基板之陰 極電極上。 本發明一種顯影型碳奈米管塗料組成包含：溶劑；且 水溶性樹脂溶於該溶劑中；又具有光反應起始劑具負型光 阻特性且溶於該溶劑中；且具有碳奈米管，懸浮於該溶劑 中；此外固著劑亦為必要，可助碳奈米管於固著程序後附 著於該陰極構造之上。 本發明方法一種製作陰極電子發射源塗層的方法，係 使用顯影型碳奈米管塗料，包含有下列步驟：（1)首先以 印刷方式先將顯影型碳奈米管塗料以印刷方式印製塗覆 於陰極基板上；（2)其次經過一低溫預烤使塗覆層固化成 10 1296814 膜；（3)接著以激發汞燈產生紫外光並合配合圖騰化所需 之光罩進行曝光，以使欲圖騰化區域進行光反應進行化學 鏈結；（4)隨後進行顯影，由於係選用水溶性樹脂，可以 利用水為顯影劑進行顯影；及（5)經過一乾燥程序。 為了使貴審查委員能更進一步瞭解本發明之特徵 及技術内容，請參閱以下有關本發明之詳細說明與附圖， 然而所附圖式僅提供參考與說明用，並非用來對本發明加 以限制者，另，其他目的與優點，對於熟諳此技藝者而言， 在參考附圖及後文發明詳述後，亦將變得明瞭。 【實施方式】 本發明係提供一種可以印刷塗覆之顯影型碳奈米管 塗料，以印刷並配合曝光顯影製程製作電子發射源層；其 顯影型碳奈米管塗料係以水溶性樹脂如聚乙稀醇之水溶 液，配合添加光反應起始劑如重鉻酸鹽類以製作為一種負 型光阻劑，接著添加以竣奈米管，一般而言，添加之碳奈 米管由於具有大的長寬比特徵，因此需對於碳奈米管之長 度加以限制，以避免編織效應產生阻塞網板之網布影響覆 墨下料，另，需添加導電粉體如銀粉，氧化銦錫（ITO)等 以輔助降低電子發射源層之導電阻抗，又，添加必要之分 散劑使溶液中前述之粉體均勻分散，此外可依製作後之塗 層燒結需求，可著以固著劑如玻璃粉等配合玻璃基板之應 用以增加碳奈米管與陰極導電層之附著力。以上之調製為 一種可以配合印刷製程之高黏度塗料黏度至少50000 cps 11 1296814 以上，以利於印刷實施，其實施方法，係以印刷方式先將 顯影型碳奈米管塗料以印刷方式印製塗覆於陰極玻璃基 板上，經過一低溫預烤使塗覆層固化成膜，接著以激發汞 燈產生紫外光並合配合圖騰化所需之光罩進行曝光，以使 欲圖騰化區域進行光反應進行化學鏈結，隨後進行顯影， 由於係選用水溶性樹脂，可以利用水為顯影劑進行顯影， 成本低且可降低環保限制要求之顧慮，此外，以顯影過程 除了可使不欲圖騰化之區域溶解剝離外，由於圖騰化之塗 層表層於顯影過程亦有小部分光阻劑被顯影劑溶除，此將 有助於塗層内之碳奈米管露出於塗層表面；顯像後之塗層 可經過一乾燥程序後進行高溫燒結，以使碳奈米管固著於 陰極玻璃基板之陰極電極上。 據此本發明係調製一種可印刷塗覆之顯影型碳奈米 管塗料，以印尉並配合曝光顯影製程製作電子發射源層； 所謂的顯影型碳奈米管塗料之調製係以12%至16%重量百 分比之聚乙稀醇為基礎溶劑，添加5%至8%重量百分比之 重鉻酸鹽為光反應起始劑製作為光阻劑；隨後添加選用之 碳奈米管，其奈米碳管之管長，或是平均粒徑係配合印刷 技術調製決定，碳奈米管之平均粒徑係選用約為1/10至 3/10之於印刷塗層之相對厚度適用之；另、為提昇電子發 射源層之導電性，需添加12%至20%重量百分比之銀粉、 氧化銦錫、銦鹽類等導電粉體，粉體平均粒徑選用1. 0至 0. Ιμπι者；此外可配合隨後之燒結製程於本塗料中添加必 要之玻璃粉以增加碳奈米管之附著力；又，為增加前述粉 12 1296814 體於塗料中之均勻分散，可添加必要之分散劑或介面活性 劑，調製後之顯影型塗料最後黏度控制在5萬至20萬cps 間即可適用於以印刷製程之塗覆。 依本發明所調製之顯影型碳奈米管塗料其實施方 式，係以印刷方式塗覆於陰極玻璃基板上，印刷之網板可 預設圖騰化一塗覆區域以有效利用塗料，藉此一印刷塗覆 過程可印製一均句平坦之塗層；印製後之塗層以簡單焙烤 使塗層成膜並維持一溫度予以配合曝光；曝光方式係選用 以水銀激發之紫外燈管，照度至少5000 lux以上，並設 計一陰刻光罩，俾使被曝光區域可以被顯影後保留，經過 一時間之曝光即進行顯影，顯影劑係使用具一定溫度之 水，施以一加壓壓力以喷塗方式顯影，顯影後保留下之電 子發射源塗層圖騰與光罩之設計圖騰誤差可控制在5 μιη 以下，另、藉顯影方式之進行亦可將塗層表層少部分被水 溶除，此效果有助於碳奈米管之露出提昇電流密度之產 生；顯影後陰極板可以簡單焙烤移除殘留於陰極玻璃基板 上之顯影劑；顯影後之陰極板可進行高溫燒結，俾使電子 發射源層固著於陰極電極上。 為闡述本發明之喷塗方式製作電子發射源層，本發明 以下之應用表述具體實施例； 製作本發明之顯影型碳奈米管塗料備製係以重量百 分比10%之聚乙烯醇為基礎塗料，添加重量百分比5%之重 鉻酸鈉，及平均粒徑Ιμπι之碳奈米管重量百分比5%，及粉 體粒徑0. 5μπι之銀粉佔重量百分比15%，再添加必要之分 13 1296814 散劑或介面活性劑以輔助前述之粉體粒子之分散，此外， 配合製程後之燒結製程本塗料可決定是否添加必要之固 著劑如玻璃粉，如果係以一種真空燒結，可藉由陰極上之 電極直接固著碳奈米管，則本發明之塗料則可不添加固著 劑，但若係依一般之高溫燒則添加粉體粒徑0· 5μπι之玻璃 粉以為固著劑固著碳奈米管於陰極電極。以本發明之塗 料，以印刷製程塗覆於陰極玻璃基上以形成平均厚度約10 μπι之塗層，並以60培烤約10分鐘後，即進行曝光，以 照度為5000 lux之紫外光曝光1分鐘後，進行顯影，顯 影方式係以45°C之水溫，lKg/cm2之水藶以去離子水進行 顯影，顯影後陰極面板上之電子發射源圖騰，解析可達 ΙΟμπι，間隙ΙΟμπι間無圖騰之區域可以有0· 1%以下之塗料 殘留，間隙50μπι間無圖騰之區域可以有0.001%以下之塗 料殘留，顯影之圖騰準直性誤差保持在2· Ομπι以下，已可 滿足商品應用之需求，此外顯影後之平均塗層厚度約已縮 減為7. 5μιη，顯示有部分塗層表層已被溶除，此有助於碳 奈米管之露出，接著，顯影後之陰極玻璃基板先以100°C 焙烤約10分鐘以去除殘餘之顯影劑，接著再進行高溫燒 結，本發明之顯影型塗料態樣係以添加有玻璃粉之顯影型 碳奈米管塗料以一般高溫燒結，不以真空燒結實施，於高 溫燒結後，本態樣實施後之陰極電子發射源樣品，未採表 面處理，則直接檢測其電子產生效率，起始電場可以小於 2. 〇ν/μπι(電流密度至少ΙΟμΑ/cm2)，當電場達2. 5 V/μιη， 其電流密度至少達至少10mA/cm2以上，此與習知之同材料 14 1296814 Γ而刷製程不以曝光顯影製程所印製之圖 :半而=製作之電子發射源層實施以表面處理咖 9奈未官之電子產生效率，該等通常為起始電場可以約 密度至少1M/CIfi2)，當電場達3.5V/网， ;=、㈣僅可達謝相較，本發明實施之於場 錢用之電子發射源層之態樣電器表現電流密 二本發明之以喷塗方式製作電子發射源層之 坪細作業揭露。 ㈣=須_本發明顯影型碳奈歸塗料物質組成，本 ㈣成包含··溶劑；且水溶性樹脂溶於該溶劑 I.’又具有光反應起始劑具負型光阻特性且溶於該溶劑 且/、有石厌奈米官’懸洋於該溶劑中；此外固著劑亦為 ’、要’可助石炭奈米管於固著程序後附著於該陰極構造之 上0 本蚤明之顯影型碳奈米管塗料尚且可進一步包 t部特性，·可進一步具有導電粉體具降低塗層表面層之 t阻抗特性’亦可進一步具有分散劑可分佈於該溶劑之 、，具有使粉體或微粒均勻分散於溶劑中之特性，其 =¾粉體可為銀粉、銦鹽類或氧化銦錫之粉體，又該固著 =為破，粉或石肖化棉，該溶劑為水，而該水溶性樹脂可為 二=烯醇，该光反應起始劑可為重鉻酸鹽類，所調製之該 頌〜型妷奈米管塗料黏度若控制在50000至80000 〇卯之 SI乂^當，對於其中該固著程序而言，其可為加熱燒結 以形成陰極電子發射源塗層。 15 1296814 本發明之製作陰極電子發射源塗層的方法，係使用顯 影型碳奈米管塗料，包含有下列步驟：（1)會先以印刷方 式先將顯影型碳奈米管塗料以印刷方式印製塗覆於陰極 基板上；（2)其次經過一低溫預烤使塗覆層固化成膜；（3) 接著以激發光燈產生紫外光並合配合圖騰化所需之光罩 進行曝光，以使欲圖騰化區域進行光反應進行化學鏈結； (4)隨後進行顯影，由於係選用水溶性樹脂，可以利用水 為顯影劑進行顯影；及（5)經過一乾燥程序。 本發明製作陰極電子發射源塗層的方法可具各種之 細部變化如下描述，本發明進一步可包含一步驟，使得步 驟（5)的塗覆膜進行一特定固著程序以形成陰極電子發射 源塗層，且其中該固著程序可為燒結，又其中該紫外光曝 光步驟係以照度可為4 0 0 0 _ 6 0 0 0 1 ux之紫外光曝光0 · 5 - 3 分鐘；又該低溫預烤塗覆層步驟係可以40-80°C焙烤約 5-20分鐘；且該顯影步驟係可以溫度30-60°C及水壓 0.5-3Kg/cm2之去離子水進行顯影，其中該乾燥程序係可 為以90-110°C焙烤約5-20分鐘。 藉以上之詳細揭示驗證，本發明之優點如下； 1. 依本發明製作之顯影型碳奈米管塗料可以印刷方 式實施製程簡易，且塗覆之塗層厚度均勻，並配合曝光顯 影之製程製作高解析之陰極電子發射源層。 2. 依本發明所製作之以曝光顯影方式製作之電子發 射源層，可使碳奈米管之露出增加，提昇陰極電子發射源 之電子發生效率。 16 1296814 卿明製作之電子發射源層，塗_製^， 、、〜支何谷易且又裱保，已可實施於商業應用。 综上所述，本發明確可達到預期之使用目_，並 ^性及進步性’完全符合發明專利申請要件，錢利法 ^出申敬請詳查並齡本料利，則雖創作者之權 内容所為之等效钍Μ樹π _—厂…^晉及圖式 手效、、、口構艾化’均同理皆包含於本發明之範圍 内，以保障發明者之權益，於此_。《月之祀圍 【圖式簡單說明】 弟—圖、場發射顯示元件結構示意圖。 【主要元件符號說明】 場發射顯示器 陽極玻璃基板 螢光粉體層 陰極破璃基板 電子發射源層 單元陽極 阻隔壁 la 陽極 31a 陽極導電層 33a 陰極 41a 陰極導電層 43a 單元結構 51a 單元陰極 53a 3a 32a 4a 42a 5a 52aAppl· Phys· Lett·, Vol 74, p· 2549 (1999)), however, there are still some difficulties in the production of this method. First, it is made in an evaporation process environment greater than at least 70 (rc or more, currently only Applicable to 矽 wafer material, can not be implemented on the glass substrate; Second, the growth of the carbon nanotubes at one end of the catalyst material still exists, still need to be modified or treated or removed, 俾 make; g carbon nano The tube has the highest current density generation, which can be used as a commercial product of the field emission display. Second, the carbon nanotube structure is loose, and the adhesion to the Shixi wafer is also poor. 4. The implementation process is complicated and the equipment And the material cost is higher. The other process is to collect the carbon nanotubes in mass production, and then add them to the solution or coating, and then deposit them on the substrate by totemization. Since the method is prepared into a slurry by modulation, The method can be beneficial to the implementation of the glass material as the substrate, and the material cost and the process condition limit are greatly reduced. However, the carbon nanotube control is used as the slurry to perform the field emission _ eight states 1a to make the cathode The electron emission source layer 43a still has to be tested, and the chemical vapor deposition direct totemization carbon nanotube tube has a loose structure and insufficient adhesion, and the industry has provided a second=f method to improve the defect. , - The method can be used to add the appropriate solid agent such as glass powder to the slurry. Refer to the Taiwan invention patent case announcement Ϊ 527624, that is, the carbon nanotube tube is aggregated by the kind of screen printing technology. = The cathode electrode is an electron emission source layer, and the towel is added to the drum tube ',, 1296814 to add a glass powder as a fixing agent to increase adhesion to the cathode conductive layer. Another method can be considered in the US Patent Publication No. No. 6277318, softening the cathode conductive layer 42a by vacuum sintering, so that the carbon nanotubes deposited on the cathode conductive layer are contained between the conductive layers to achieve the effect of improving the fixed carbon nanotubes, but these methods still have drawbacks. The existence still needs to be overcome, one of which is that these processes are only suitable for low-resolution totem production. Firstly, the method of printing carbon nanotubes by screen printing is still limited by the wire diameter and opening rate limit of the screen printing mesh. Therefore, the minimum totem area still needs at least 80μηη, so it is no longer possible to provide a higher resolution totem. In addition, in the vacuum sintering mode, there is still a carbon nanotube attached around the cathode conductive layer to cause electrons. The source coating is not collimated, and these irregularly exposed carbon nanotubes are likely to cause the electrodes of adjacent conductive layers to be turned on. This problem still needs to be overcome. The inventor designed a kind of exposure-developable The rice tube coating is coated on the cathode glass substrate by a screen printing process, and then the electron emission source layer of the cathode carbon nanotube tube required for the totemization process of the exposure and development process is prepared by the method. The following advantages can be provided: 1. The coating is easy to be modulated; 2. The coating formulation can control the applicable process requirements; 3. The totem with high collimation and high resolution is produced; 4. The process equipment demand and material cost are greatly reduced. SUMMARY OF THE INVENTION In view of the fabrication of a cathode electron emission source layer of a field emission display fabricated by the prior art, the method of chemical vapor deposition of a carbon nanotube has insufficient adhesion of the carbon nanotube to the cathode conductive layer. It can't be made on the glass substrate 1296814, and the other is to make the carbon nanotube tube electron emission source layer by screen printing. The printed totem still can't make the high-resolution panel, and the above-mentioned fabricated electron emission source layer. The surface energy needs to be surface treated to enhance the electron generation efficiency of the carbon nanotubes to increase the electron density. The inventor has designed a screen printing coating with exposure and development process for the cathode electron emission source layer of the field emission display. Production technology, according to this, one can provide a simple screen printing coating on the cathode glass substrate; Second, with the cathode conductive layer material characteristics and process characteristics, modulation coating, can increase the adhesion of carbon nanotubes and cathode conductive layer Force; Third, the high-resolution precision totem can be produced by the exposure and development process, and the exposure of the carbon nanotubes can be increased, thereby improving the efficiency of electron generation; To the process of the present embodiment to simplify the manufacturing process, low cost of paint, applied to the production of the glass substrate. SUMMARY OF THE INVENTION A primary object of the present invention is to provide a development type carbon nanotube coating which can be coated with a simple screen printing and which is combined with an electron-emitting source layer required for the development of the exposure developing process. Another object of the present invention is to provide a developing type carbon nanotube coating for screen printing, which can increase the chance of the carbon nanotubes being exposed by the exposure and development process, and avoid the carbon nanotubes being coated with the coating. Within the layer, the release of electrons can be increased. Another object of the present invention is to provide a developed carbon nanotube coating for screen printing which can be combined with a cathode electrode to add a suitable fixing agent to increase the adhesion of the carbon nanotube to the electrode. In order to achieve the above-mentioned objects, the present invention provides a printable coated carbon nanotube coating which is printed and matched with an exposure and development process 1296814 to form an electron emission source layer; the developed carbon nanotube coating is The water-soluble resin is added with a photoreaction initiator to prepare a negative photoresist, and a carbon nanotube and a conductive powder are added, and the necessary dispersant is added to uniformly disperse the powder added, and further, after the preparation For coating sintering requirements, a fixing agent can be used to increase the adhesion of the carbon nanotubes to the cathode electrodes. The above modulation is a high-viscosity coating which can be combined with a printing process, and the implementation method is that the developing carbon nanotube coating is printed and applied on the cathode glass substrate by printing, and is coated by a low temperature baking. The coating is dried to form a film, and then exposed to ultraviolet light of a mercury lamp, so that the totemized region is photoreacted for chemical chaining, and then developed, and the developing process can dissolve and peel off the region which is not intended to be tossed, due to The totemized coating surface layer also has a small portion of the photoresist removed by the developer during the development process, which will help the carbon nanotubes in the coating to be exposed on the surface of the coating, and the developed coating can pass through a coating. After the drying process, high temperature sintering is performed to fix the carbon nanotubes on the cathode electrode of the cathode glass substrate. The developing type carbon nanotube coating composition of the invention comprises: a solvent; and the water-soluble resin is dissolved in the solvent; and the photoreaction initiator has negative resistive properties and is dissolved in the solvent; and has carbon nano The tube is suspended in the solvent; in addition, a fixing agent is also necessary to assist the carbon nanotube to adhere to the cathode structure after the fixing process. The method of the invention is a method for preparing a coating of a cathode electron emission source, which is a developing type carbon nanotube coating, which comprises the following steps: (1) first printing a developing type carbon nanotube coating by printing Applying to the cathode substrate; (2) secondly, after a low temperature pre-baking, the coating layer is cured into a film of 10 1296814; (3) then exposing the photomask formed by exciting the mercury lamp to generate ultraviolet light and cooperating with totemization, The chemical reaction is carried out by photoreaction of the region to be totemized; (4) development is subsequently carried out, since water-soluble resin is used, development can be carried out using water as a developer; and (5) after a drying procedure. The detailed description of the present invention and the accompanying drawings are intended to provide a further understanding of the invention. In addition, other objects and advantages will become apparent to those skilled in the art from a <RTIgt; [Embodiment] The present invention provides a development-type carbon nanotube coating which can be printed and coated, and is used for printing and matching an exposure and development process to produce an electron emission source layer; the developed carbon nanotube coating is a water-soluble resin such as poly An aqueous solution of ethylene glycol is added with a photoreaction initiator such as dichromate to prepare a negative photoresist, followed by adding a nanotube tube. Generally, the carbon nanotube to be added has a large The aspect ratio characteristics, therefore, it is necessary to limit the length of the carbon nanotubes to avoid the effect of the weaving effect on the mesh of the stencil stencil, and to add the conductive powder such as silver powder, indium tin oxide (ITO). And so on to assist in reducing the conductive impedance of the electron-emitting source layer, and adding the necessary dispersing agent to uniformly disperse the aforementioned powder in the solution, and further, depending on the sintering requirements of the coated coating, a fixing agent such as glass frit may be used. The use of a glass substrate is added to increase the adhesion of the carbon nanotube to the cathode conductive layer. The above modulation is a high-viscosity coating with a printing process of at least 50,000 cps 11 1296814 or more for printing implementation, and the printing method is to print the developing carbon nanotube coating by printing. On the cathode glass substrate, the coating layer is solidified into a film by a low-temperature pre-baking, and then exposed to a photomask required for the totemization by an ultraviolet lamp to excite the mercury lamp to perform photoreaction in the totemized region. Chemical chaining, followed by development, because water-based resin is selected, water can be used as a developer for development, the cost is low and the environmental protection requirements can be lowered, and in addition, the development process can dissolve the area that is not intended to be tossed. In addition to the stripping, a small portion of the photoresist is dissolved by the developer during the development of the toned coating layer, which will help the carbon nanotubes in the coating to be exposed on the surface of the coating; The layer can be sintered at a high temperature after a drying process to fix the carbon nanotube on the cathode electrode of the cathode glass substrate. Accordingly, the present invention prepares a printable coated developed carbon nanotube coating, and prints an electron emission source layer by printing with an exposure and development process; the so-called development type carbon nanotube coating is prepared by 12% to 16% by weight of polyethylene glycol as a base solvent, adding 5% to 8% by weight of dichromate as a photoreaction initiator to prepare a photoresist; then adding a carbon nanotube selected, the nanometer The length of the carbon tube, or the average particle size is determined by the printing technology. The average particle size of the carbon nanotubes is about 1/10 to 3/10 of the relative thickness of the printed coating. 0至0. Ιμπι。 In addition, the conductivity of the electron-emitting layer is increased by 12% to 20% by weight of silver powder, indium tin oxide, indium salt and other conductive powder, the average particle size of the powder is selected from 1.0 to 0. Ιμπι; In combination with the subsequent sintering process, the necessary glass powder is added to the coating to increase the adhesion of the carbon nanotubes; and, in order to increase the uniform dispersion of the powder 12 1296814 in the coating, a necessary dispersing agent or surfactant may be added. , modulated development coating After controlling the viscosity between 50,000 to 200,000 cps so as to be applicable to the coating of the printing process. The embodiment of the developed carbon nanotube coating prepared according to the present invention is applied to the cathode glass substrate by printing, and the printed screen can preset a coating area to effectively utilize the coating, thereby The printing and coating process can print a uniform coating; the printed coating is formed by simple baking to form a film and maintain a temperature for exposure; the exposure method is selected by mercury-activated ultraviolet lamp, illuminance At least 5000 lux or more, and design an intaglio mask, so that the exposed area can be retained after development, and developed after a period of exposure, the developer uses a certain temperature of water, applying a pressure to spray The coating method is developed, and the totem error of the electron emission source coating totem and the mask after the development can be controlled to be less than 5 μηη, and the surface of the coating layer can be dissolved by water by the development method. Helping the exposure of the carbon nanotubes to increase the current density; after development, the cathode plate can be simply baked to remove the developer remaining on the cathode glass substrate; the cathode after development High temperature sintering can be performed to enabling an electron emission source on the cathode electrode layer is adhered to. In order to illustrate the spraying method of the present invention, an electron emission source layer is produced. The following application of the present invention expresses a specific embodiment; The preparation of the developing type carbon nanotube coating of the present invention is based on a polyvinyl alcohol based coating of 10% by weight. Adding 5% by weight of sodium chromate, and 5% by weight of carbon nanotubes with an average particle diameter of Ιμπι, and powder particle size of 0.5% by weight of silver powder accounted for 15% by weight, and then adding the necessary points 13 1296814 a powder or an interfacial agent to assist in the dispersion of the aforementioned powder particles, and further, in combination with the sintering process after the process, the coating may determine whether or not to add a necessary fixing agent such as glass frit, if it is sintered in a vacuum, by using a cathode When the electrode is directly fixed to the carbon nanotube, the coating of the present invention may not be added with a fixing agent, but if it is fired at a high temperature, a glass powder having a particle diameter of 0.5 μm is added to fix the carbon nanoparticle as a fixing agent. The rice tube is on the cathode electrode. The coating of the present invention is applied to the cathode glass substrate by a printing process to form a coating having an average thickness of about 10 μm, and after baking for about 10 minutes at 60 liters, exposure is performed, and ultraviolet light having an illuminance of 5000 lux is exposed. After 1 minute, development is carried out. The development method is developed with deionized water at a water temperature of 45 ° C, and a water enthalpy of 1 Kg/cm 2 . After development, the electron emission source totem on the cathode panel can be resolved up to ΙΟμπι, gap ΙΟμπι The area without totem can have 0.1% or less of paint residue, and the area with no totem between 50μπι can have 0.001% or less of paint residue, and the totem collimation error of development is kept below 2·Ομπι, which can satisfy commodity application. The requirement, in addition, the average coating thickness after development has been reduced to about 7.5 μm, indicating that a portion of the coated surface layer has been dissolved, which facilitates the exposure of the carbon nanotube tube, and then, the developed cathode glass substrate is first Baking at 100 ° C for about 10 minutes to remove residual developer, followed by high temperature sintering. The developed coating form of the present invention is a developed carbon nanotube coating with glass frit added. Generally, the high-temperature sintering is not carried out by vacuum sintering. After the high-temperature sintering, the cathode electron emission source sample after the implementation of the present state is directly detected, and the electron generation efficiency is directly detected, and the initial electric field can be less than 2. 〇ν/μπι (current density is at least ΙΟμΑ/cm2), when the electric field reaches 2.5 V / μιη, the current density is at least 10 mA / cm 2 or more, which is the same as the conventional material 14 1296814 Γ and the brush process is not printed by the exposure and development process Figure: Half-time = fabricated electron emission source layer is implemented to surface-treating the energy of the electrons, which are usually the starting electric field can be about density of at least 1M/CIfi2), when the electric field reaches 3.5V/net; =, (4) Only reach the comparison, the state of the electronic emission source layer used in the field of the present invention expresses the current tightness. The present invention discloses the embossing operation of the electron emission source layer by spraying. (4) = must be _ the development of the carbon-return coating material composition of the present invention, the (four) into the solvent; and the water-soluble resin dissolved in the solvent I. 'has a photoreaction initiator with a negative photoresist characteristic and soluble The solvent and/or the stone anaesthesia official's suspended in the solvent; in addition, the fixing agent is also ', 'can help the charcoal nanotubes adhere to the cathode structure after the fixing process. The developing type carbon nanotube coating can further further include the t-characteristics, and can further have a conductive powder with a lowering of the t-resistance characteristic of the surface layer of the coating, and can further have a dispersing agent which can be distributed in the solvent. The powder or the particles are uniformly dispersed in the solvent, and the powder can be silver powder, indium salt or indium tin oxide powder, and the fixing is broken, powder or stone, and the solvent is Water, and the water-soluble resin may be a di-enol, and the photoreaction initiator may be a dichromate, and the viscosity of the 颂-type 妷 nanotube coating prepared is controlled at an SI of 50,000 to 80,000 Å.乂^当, for the fixing procedure, it can be heated and sintered to form a yin Coating the electron emission source. 15 1296814 The method for fabricating a coating of a cathode electron emission source according to the present invention is a developing type carbon nanotube coating comprising the following steps: (1) printing a developing carbon nanotube coating first by printing Printing is applied to the cathode substrate; (2) secondly, after a low temperature pre-baking, the coating layer is cured to form a film; (3) then the ultraviolet light is generated by the excitation light lamp and combined with the photomask required for totemization for exposure. The chemical reaction is carried out by photoreaction of the region to be totemized; (4) development is subsequently carried out, since water-soluble resin is used, development can be carried out using water as a developer; and (5) after a drying procedure. The method for fabricating a coating of a cathode electron emission source of the present invention may have various details as described below. The present invention may further comprise a step of subjecting the coating film of the step (5) to a specific fixing procedure to form a cathode electron emission source coating. a layer, and wherein the fixing process can be sintering, and wherein the ultraviolet light exposure step is performed by ultraviolet light exposure of 0. 5 - 3 1 ux at an illumination of 0 · 5 - 3 minutes; The baking coating step may be baked at 40-80 ° C for about 5-20 minutes; and the developing step may be developed by deionized water at a temperature of 30-60 ° C and a water pressure of 0.5-3 Kg/cm 2 , wherein the drying procedure It can be baked at 90-110 ° C for about 5-20 minutes. The advantages of the present invention are as follows: 1. The developed carbon nanotube coating prepared according to the present invention can be easily printed by a printing method, and the coating thickness is uniform, and is prepared by a process of exposure and development. Highly resolved cathode electron emission source layer. 2. The electron-emitting source layer produced by the exposure and development method produced by the present invention can increase the exposure of the carbon nanotubes and improve the electron generation efficiency of the cathode electron-emitting source. 16 1296814 The electron emission source layer produced by Qingming, coated with _, ^, 、, 支, 谷 谷, and 裱 ,, can be implemented in commercial applications. In summary, the present invention can indeed achieve the intended use of the target _, and ^ and the progress 'full compliance with the requirements of the invention patent application, Qian Lifa ^ Shen Shen please check the age of the material, but the creator The equivalent of the content of the eucalyptus π _ - factory ... ^ Jin and the graphical effect, and the mouth of the Aihua 'all are included in the scope of the present invention to protect the rights and interests of the inventors, this_. "The moon's circumference" [Simple diagram description] Brother - map, field emission display component structure diagram. [Main component symbol description] Field emission display Anode glass substrate Fluorescent powder layer Cathode glass substrate Electron emission source layer unit Anode barrier wall la Anode 31a Anode conductive layer 33a Cathode 41a Cathodic conductive layer 43a Unit structure 51a Unit cathode 53a 3a 32a 4a 42a 5a 52a
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