200952032 六、發明說明： 【發明所屬之技術領域】 本發明是關於一種被使用於將依照射紫外線的洗淨處 理’灰化處理，成膜處理等的表面處理進行於被處理體所 用的準分子燈。 【先前技術】 @ 在液晶顯示裝置的玻璃基板，半導體晶圓等的被處理 體’被開發了利用照射波長200nm以下的紫外線的真空紫 外光，而藉由真空紫外光及由此所生成的臭氧的作用進行 處理被處理體的技術，開發了例如除去附著於被處理體的 表面的有機污染物質的洗淨處理技術，或是在被處理體的 表面形成氧化膜的氧化膜形成處理技術，而被實用化。 作爲照射真空紫外光的裝置，例如使用著具備在介質 所成的放電容器內封入放電用氣體，經由放電容器而藉由 φ 施加交流高電壓來發生準分子放電，而放射真空紫外光的 準分子發光的準分子燈者。在此種準分子燈中，爲了有效 率地放射更高強度的紫外線進行著很多的嘗試。 具體地來說明，揭示著在準分子燈的放電容器的內表 面進行著形成紫外線反射層的情形，紫外線反射層藉由積 層透射紫外線的微小粒子，例如僅二氧化矽，或是二氧化 矽與其他的微小粒子，例如氧化鋁、氟化鎂、氟化鈣、氟 化鋰、氧化鎂等所形成的技術（參照專利文獻1 )。 在此種構成的準分子燈中，在放電容器內所發生的紫 -5- 200952032 外線中朝光射出部未直接放射的紫外線，被射入至紫外線 反射層’而藉由在構成紫外線反射層的複數微小粒子的表 面重複進行折射、反射而被擴散反射，會從光射出部被放 射。藉此，有效率地可放射紫外線。 · 在放射紫外線的燈中，作爲構成放電容器的材料，例 如廣泛地使用二氧化矽玻璃。因此，作爲構成紫外線反射 層的微小粒子，避免與構成放電容器的二氧化矽玻璃的熱 0 脹係數之相差’或是作成極小而爲了提高紫外線反射層對 於二氧化矽玻璃的附著性，構成含有與放電容器相同材質 的二氧化矽玻璃較佳。 表面處理的被處理物，是多爲例如如液晶面板的玻璃 基板的平坦形狀者。所以，光射出部與被處理物相同的平 坦形狀的放電容器所成的準分子燈，是減少光射出部與被 處理物之間隙，就可抑制依氧氣的紫外線的吸收之故，因 而有效率地可進行表面處理。作爲此種形狀的放電容器所 φ 成的準分子燈，例如在專利文獻2，公開著方型形狀的放 電容器所成的準分子燈。 作爲光出射部平坦的放電容器所成的準分子燈，有如 第10圖所示的構造。準分子燈10是由二氧化矽玻璃所成 的扁平方型放電容器20所構成，該放電容器20是成爲連 結上壁板21、下壁板22、側壁板23及端壁板24的構造 ，而在內部封入有放電用氣體。又’在上壁板21的外表 面具備高電壓供應電極11，而在下壁板22的外表面具備 接地電極12，而此些電極11、12是在配置成互相地相對 -6- 200952032 的放電空間S所發生的準分子發光，是經兼具光射出部的 下壁板22被射出至外部。 專利文獻1 :日本特開2007-335350號公報 專利文獻2 :日本特開2004-1 13984號公報 【發明內容】 然而，在具備含有二氧化矽粒子的微小粒子所成的紫 外線反射層的準分子燈中，若長時間予以點燈，則照度維 持率會繼時性地慢慢地降低。所以，例如在進行洗淨處理 等的表面處理時，即使擬以一定照度加以處理，也會產生 準分子燈的處理能力隨著點燈時間有所變化的問題。 本發明是依據如以上的事項而發明者，其目的在於提 供一種具備有二氧化矽粒子的微小粒子所成的紫外線反射 層，即使長時間點燈時，也可抑制減小照度降低的程度， 有效率地可射出真空紫外光的準分子燈。 本發明第1項的發明的準分子燈，是具備具放電空間 的二氧化矽玻璃所構成的放電容器，在介裝有形成該放電 容器的二氧化矽玻璃的狀態下設有一對電極，而且在放電 空間內封入有放電用氣體所成，而在上述放電容器的內表 面的一部分形成有紫外線反射層的準分子燈，其特徵爲： 上述紫外線反射層是由：形成於對應在一方的電極的領域 的至少一部分的堆積體A，及形成於對應在電極的領域以 外的至少一部分的堆積體B所構成，上述堆積體A是由： 含著OH基的二氧化矽粒子，及融點比二氧化矽還要高的 200952032 微小粒子所構成’上述堆積體B是含有含著OH基的二氧 化矽粒子的微小粒子所構成，構成上述紫外線反射層的二 氧化政粒子中的OH基濃度是1 0wtPPm以上。 又，本發明第2項發明，是在本發明的第1項發明中 ，將上述堆積體A的設置面積作爲a( cm2)，將上述堆 ’積體B的設置面積作爲b( cm2)，將堆積體B的比表面 積作爲c ( cm2/ g)，將放電容器的內表面積作爲d( cm2 赢 )時，各個的關係爲滿足 ❹ -5.0x1 0'7ac + 0.35a ' 且 b > 0.02d 爲其特徵者。 藉由在紫外線反射層混入融點比二氧化矽還要高的微 小粒子，防止以互相鄰接的微小粒子彼此間被結合而消失 粒界的情形，而可抑制降低紫外線反射層的反射率，尤其 是，形成於對應在電極的領域的堆積體A是容易受到電漿 的熱之故，因而必須混入融點比二氧化矽還要高的微小粒 φ 子，來抑制降低紫外線反射層的反射率。 又，藉由在構成紫外線反射層的二氧化矽粒子含有 OH基，抑制內部缺陷生成於含有於紫外線反射層的二氧 化矽粒子，防止依紫外線反射層所致的紫外領域的波長的 光吸收而維持紫外線反射層的反射率，抑制減小準分子燈 的照度降‘低程度，而有效率地可射出真空紫外光。尤其是 ，藉由將構成紫外線反射層的二氧化矽粒子中的OH基濃 度作成lOwtppm以上，反射維持率及照度維持率都可維持 高値，而有關於長時間點燈時的照度維持事先發揮優異的 -8 - 200952032 效果。 形成於對應在設有電極的位置的放電容器的內表面的 紫外線反射層，是含有OH基，則暴露於放電電漿而放出 以水作爲主成分的不純氣體。以水作爲主成分的不純氣體 與放電用氣體結合，則電漿發光的照度會降低。然而，藉 由在對應於未設有電極的位置的放電容器的內表面的一部 分也形成紫外線反射層，吸附該紫外線反射層所放出的水 ，及同時地水在電漿中被分解所產生的氧氣，而可抑制準 分子發光的照度降低，因此，即使在長時間點亮準分子燈 時，也可抑制減小照度降低的程度，而有效率地可射出真 空紫外光。 考慮堆積體B的比表面積，將堆積體A的設置面積a (cm2)，將堆積體B的設置面積作爲b( cm2)，將堆積 體B的比表面積作爲c( cm2/ g)，將放電容器的內表面 積作爲d( cm2)時，各個的關係爲藉由滿足 bg-5.0xl0.7ac+〇.35a、且 b>0.02d 從堆積體A所放出的不純氣體的量，不會超過堆積體B可 吸附的不純氣體的量，而在放電空間作成不會殘留不純氣 體。因此，可抑制含有於不純氣體的氧氣原子與放電用氣 體結合所引起的準分子發光的照度降低，即使長時間點燈 準分子燈時，也可抑制照度降低，而有效率地可射出真空 紫外光。 【實施方式】 -9- 200952032 第1圖是表示本發明的準分子燈ίο的一例的構成槪 略的說明用斷面圖。第1(a)圖是表示沿著放電容器20 的長度方向斷面的斷面圖，第1(b)圖是表示第1(a) 圖的A-A線的斷面圖。 該準分子燈10，是具備兩端被氣密地密封而在內部形 成有放電空間S的斷面矩形狀的中空長度狀的放電容器20 。該放電容器20是由：上壁板21及相對向於上壁板21 g 的下壁板22，及連結於上壁板21與下壁板22的一對側壁 板23，及將此些上壁板21、下壁板22，及一對側壁板23 所成的四方筒狀體的兩端予以密封般地所設置的一對端壁 板24所構成。放電容器20是由良好地透射真空紫外光的 二氧化矽玻璃，例如合成石英玻璃所形成。 在放電容器20的內部，以如10〜80kPa的壓入封入 有放電用氣體。作爲放電用氣體即使選擇任何氣體，對放 射強度的繼時性變化也不會有影響，惟藉由放電用氣體的 Q 種類，所放射的準分子發光的中心波長是不相同。例如， 在封入有氙（Xe )的準分子燈，則產生以172nm作爲中 心波長的準分子發光，而在封入有氬（Ar)與氯（C1)的 混合氣體的準分子燈，則產生以175nm作爲中心波長的準 分子發光，在封入有氪（Kr)與碘（I)的混合氣體的準 分子燈，則產生以1 9 1 nm作爲中心波長的準分子發光，在 封入有氬（A〇與氟（F)的混合氣體的準分子燈，則產 生以波長193 nm作爲中心波長的準分子波長，在封入有氪 (Kr )與溴（Br )的混合氣體的準分子燈，則產生以 -10- 200952032 2 0 7nm作爲中心波長的準分子發光’在封入有氪（Kr)與 氯（C1 )的混合氣體的準分子燈’則產生以222nm作爲中 心波長的準分子發光，在封入有氙（Xe)與氯（C1)的混 合氣體的準分子燈，則產生以3 08nm作爲中心波長的準分 子發光。 在放電容器20的上壁板21的外表面具備高電壓供應 電極11，而在下壁板22的外表面具備接地電極12，而這 些電極11、12是配置成互相相對向。此種電極11、12是 成爲網狀構造，而形成從網孔之間能透射光。作爲材質， 例如使用鋁、鎳、金等，例如藉由網印，或真空蒸鍍的手 段所形成。又，各個電極11、12是被連接於適當的高頻 電源（未圖示）。 在上述準分子燈10中，爲了有效率地利用藉由準分 子放電所發生的真空紫外光，在相對於放電容器20的放 電空間S的內表面設有微小粒子所成的紫外線反射層30 。該紫外線反射層30是由堆積體A31及堆積體B32所構 成。堆積體A31是形成於相對面於設有高電壓供應電極 11的放電容器20的放電空間S的內表面的一部分，亦即 ，形成於對應在上壁板21的內表面的高電壓供應電極n 的領域的一部分。又，堆積體B23是形成於相對面於未設 有高電壓供應電極11或接地電極12的放電容器20的放 電空間S的內表面的一部分’亦即，形成於從對應於電極 11、12的領域偏離的上壁板21及;p壁板22的內表面，以 及側壁板23及端壁板24的內表面中的任一領域。亦即， -11 - 200952032 將形成於對應在上壁板21的內表面的高電壓供」 的領域的紫外線反射層30稱爲堆積體A31，而 放電容器20的內表面的其他領域的紫外線反射局 堆積體B32。 一方面，在放電容器20的下壁板22對應於 12的內表面藉由未形成有紫外線反射層30，構 部。 _ 堆積體 A31，是厚度爲例如5〜1 000 /zm， 矽粒子，及融點比二氧化矽還要高且透射紫外線 子所構成。融點比二氧化矽還要高且透射紫外線 子是有例如氧化鋁、氟化鋰、氟化鎂、氟化鈣、 〇 真空紫外光射入至此種堆積體A31，則一部 小粒子的表面反射，又一部分是被折射而透射於 ，而在其他表面再反射或折射，在複數微小粒子 φ 重複此種反射、折射，真空紫外光是被擴散反射 然而，二氧化矽粒子是藉由在準分子燈10 電漿的熱被熔融，粒界被消失’無法擴散反射真 而有降低反射率的情形。尤其是，形成於對應在 應電極11的領域的堆積體A3 1是容易受到電漿 構成堆積體A3 1的二氧化矽粒子是容易被熔融。 融點比二氧化矽還要高的微小粒子是即使暴露在 熱時也不會被熔融。因此，在堆積體A3 1藉由混 二氧化矽還要高的微小粒子’以互相鄰接的微小 塵電極11 將形成於 ί 30稱爲 接地電極 成光射出 由二氧化 的微小粒 的微小粒 氟化鋇等 分是在微 粒子內部 中，藉由 〇 所發生的 空紫外光 高電壓供 的熱，而 一方面， 依電漿的 入融點比 粒子彼此 -12- 200952032 間被結合而可防止粒界消失，而可抑制堆積體A3 1的反射 率的降低。 堆積體B32是厚度例如1〇〜i〇〇0;t/m，由含有二氧化 矽粒子的微小粒子所構成。構成堆積體B32的微小粒子是 僅由二氧化矽粒子所構成者，或是在其他含有與氧結合的 物質，且混存著透射紫外線的物質所成的絕緣性微小粒子 所構成者，例如氧化鋁、氟化鋰、氟化鎂、氟化鈣、氟化 鋇也可以。 即使真空紫外光射入至堆積體B3 2，在複數微小粒子 中也藉由重複產生反射、折射，真空紫外光是被擴散反射 。又，堆積體B32是形成於對應在電極11、12的領域以 外的放電容器20的內表面者之故，因而不容易受到電漿 所致的熱的影響。因此，即使藉由僅由二氧化矽粒子所成 者未構成堆積體B32，也不容易發生以鄰接的微小粒子彼 此間結合所引起的粒界消失。 微小粒子是如以下地被定義的粒子徑，爲在例如0.0 1 〜20"m範圍者，中心粒徑（個數基準的粒度分佈的最大 値），在堆積體A3 1中，例如以0.1〜1 〇 /z m者較佳，更 佳爲0.1〜3 " m，而在堆積體B2也相同，例如0.1〜20 y m 者較佳。 在此所謂「粒子徑」，是指將對於紫外線反射層30 的表面朝垂直方向切剖時的切剖面的厚度方向的大約中間 位置作爲觀察範圍，藉由掃描型電子顯微鏡（SEM )取得 擴大投影像，而以一定方向的兩條平行線隔著該擴大投影 -13- 200952032 像的任意粒子時的該平行線的間隔的弗雷特（Feret)直徑 〇 又，「中心粒徑」，是指將針對於如上述所得到的各 粒子的粒子徑的最大値與最小値的粒子徑的範圍，例如以 0.1//m的範圍分成複數區分，例如區分成的15區分，屬 於各個區分的粒子個數（度數）成爲最大的區分的中心値 〇 在該準分子燈10中，點燈電力被供應於高電壓供應 電極12，則經由放電容器20而在兩電極11、12間的放電 空間S會發生準分子放電。藉此，形成有準分子之同時， 從該準分子分子放射著真空紫外光。在放電空間S所發生 的真空紫外光的一部分，是直接經兼具光射出部的下壁板 22而被射出至外部。又，一部分的真空紫外光是朝上壁板 21的方向被放射，惟在紫外線反射層30被擴散放射，而 經光射出部朝外部被射出。 藉由構成紫外線反射層30的微小粒子具有與真空紫 外光的波長相同程度的粒子徑者，而有效率地可擴散反射 真空紫外光。 然而，長時間點燈具備上述紫外線反射層30的準分 子燈1 0，則無法維持初期照度，確認了隨著點燈時間徐徐 地降低照度。發明人等是由所有方面來檢討照度降低的原 因，考慮到是否會降低成爲其主要原因之一的紫外線反射 層3 0的反射率。 在此，測定點燈初期的準分子燈1 〇的紫外線反射層 -14- 200952032 3 0的反射強度光譜，及長時間點燈後的準分子燈1 〇的紫 外線反射層30的反射強度光譜，比較解析兩者。由該結 果，在長時間點燈後的準分子燈1 〇的紫外線反射層3 0， 吸收帶產生紫外領域，可知藉由紫外線的一部分被吸收於 紫外線反射層3 0而產生照度降低。 產生於紫外線反射層30的紫外領域的吸收帶，是構 成紫外線反射層30的二氧化矽粒子在放電中曝露在紫外 ρ 線或電漿，而受到放射損傷（radiation damage )，產生吸 收紫外領域的波長的光的內部缺陷，而紫外線被吸收在內 部缺陷，使得擴散反射被抑制。內部缺陷是指二氧化矽粒 子的 Si-0-Si結合曝露在紫外線或電漿所產生的波長 163nm附近具有吸收端的Si-Si缺陷，或在波長215nm附 近有吸收帶的E’center(Si·)。 由如上述的理由，產生吸收紫外領域的波長的光的內 部缺陷爲二氧化矽粒子，而成爲照度降低的原因的紫外領 φ 域的波長的光吸收是可能依存於二氧化矽粒子的內部缺陷 。又，在透射氧化鋁、氟化鋰、氟化鎂、氟化鈣、氟化鋇 等所成的二氧化矽粒子以外的紫外線的微小粒子’即使曝 露於紫外線或電漿也不會產生放射損傷。因此’藉由在構 成紫外線反射層30的二氧化矽粒子防止產生內部缺陷’ 可抑制照度降低，而即使長時間點燈也可保持高照度維持 率。 爲了防止在二氧化矽粒子產生內部缺陷，在二氧化矽 粒子含有基就有效。藉由含有OH基’可抑制在含有 -15- 200952032 於紫外線反射層30的二氧化矽粒子生成內部缺陷的情形 ，而可防止降低紫外線反射層30的反射率。 以下’針對於含有含著OH基的二氧化矽粒子的微小 粒子所成的紫外線反射層30的形成方法加以說明。紫外 線反射層30是藉由例如稱爲「流下法」的方法，在放電 容器形成材料的內表面的所定領域，形成有含有二氧化矽 粒子的粒子堆積層。例如’在具有組合水與PE〇樹脂（ p polyethylen oxide)的黏性的溶劑，混合微小粒子來調整 分散液，而將該分散液流進放電容器形成材料內。又，將 分散液附著於放電容器形成材料的內表面的所定領域之後 ’經乾燥、燒成進行蒸發水與PEO樹脂，藉此，可形成粒 子堆積層。在此，燒成溫度是例如作爲500°C〜1100°C。 作爲在二氧化矽粒子含有OH基的方法的一例子，藉由 將未含有OH基的二氧化砂粒子，一面供應水蒸氣，一面進 行電爐加熱（例如1 000 °C )，來製作含有多量OH基的二 φ 氧化矽粒子的情形。藉由使用經此種處理的二氧化矽粒子 ，可形成含有含著0H基的二氧化矽粒子的微小粒子所成 的紫外線反射層3 0。 又，作爲其他方法，使用未含有0H基的二氧化矽粒 子附著於放電容器形成材料的內表面的所定領域之後，藉 由一面供應水蒸氣一面進行燒成，也可在二氧化矽粒子含 有0H基。又，使用未含有0H基的二氧化矽粒子經燒成 而形成紫外線反射層3 0之後，藉由一面再供應水蒸氣一 面進行電爐加熱，也可在二氧化矽粒子含有〇H基。 -16- 200952032 又，藉由購入可得到的二氧化矽粒子，是利用其製法 也含有OH基的產品，惟在其中也有OH基濃度少的產品 之故，因而以上述方法一旦含有高濃度的OH基較佳。 含有於二氧化矽粒子的OH基的濃度，是藉由選擇各 種溫排氣條件，可將含有於構成紫外線反射層3 0的二氧 化矽粒子的〇 Η濃度可調整成任意數値。例如’即使保持 溫度爲一定，隨著延長保持時間’可除去更多的〇HS。 考慮事先含有於二氧化矽粒子的OH基的量’藉由調製利 用溫排氣來除去OH基的量，就可形成含有任意的 濃度的二氧化矽粒子的微小粒子所成的紫外線反射層30。 表示有關於準分子燈的第1實驗。 依照表示於第1(a) 、（b)圖的構成，來製作具備紫 外線反射層的準分子燈。 〔準分子燈的基本構成〕 放電容器是材質爲二氧化矽玻璃，尺寸爲15mmx43mm x350mm、厚度爲 2.5mm。 高電壓供應電極及接地電極的尺寸是30mmx3()()mm° 紫外線反射層是由將中心粒徑的二氧化砂粒 子作成成分比90重量％，將中心粒徑1 .5 V m的氧化銘粒 子作成成分比1 〇重量％經混合者所構成’藉由流下法分別 形成，而燒成溫度是作成1000°C。 作爲放電用氣體，將氙以4OkPa封入在放電容器內。 針對於具有上述構成的準分子燈’測定二氧化砍粒子 -17- 200952032 中的OH基濃度，反射維持率，及照度維持率。從放電容 器削取所有紫外線反射層，使用昇溫脫離氣體分析法進行 測定。藉此，算出含有於紫外線反射層的二氧化矽粒子中 的OH基濃度。又，求出含於被削取的紫外線反射層的二 氧化矽粒子的成分比，而由成分比算出對於僅二氧化矽粒 子的重量的OH基的重量進行計算。又，使用真空紫外光 分光裝置（VUV )或紫外線照度測定器，進行測定對於初 期狀態的5 00小時連續點燈後的紫外線反射層的反射維持 率，及照度維持率。 將燈1〜5的測定結果表示於表1。 [表1] 二氧化矽粒子中OH基濃度 (wtppm ) 反射維持率 (%) 照度維持率 (%) 燈1 5 78 72 燈2 7 82 79 燈3 10 98 96 燈4 42 96 92 燈5 132 96 94 第2圖是針對於表示於表1的測定結果，在橫軸作爲 二氧化矽粒子中的〇H基濃度（wtppm )，在縱軸作爲反射 維持率（％)，而標示燈1〜5的數値的圖表。 又，第3圖是針對於表示於表1的測定結果，在橫軸作 爲二氧化矽粒子中OH基濃度（wtppm)，在縱軸作爲照度 維持率（％)，而標示燈1〜5的數値的圖表。 "18- 200952032 又，表示於第2圖及第3圖的圖表，橫軸是成爲對數刻 度的單對數圖表》 由以上結果，可讀取到二氧化矽粒子中的〇H基濃度不 足lOwtppm，則反射維持率及照度維持率都低，而長時間 點燈準分子燈’則有降低處理能力的情形。一方面，讀取 到二氧化矽粒子中的OH基濃度成爲10wtppm以上，則反 射維持率及照度維持率都成爲9 0 %以上，而長時間點燈準 ϋ 分子燈，也可維持處理能力的情形。如第2圖及第3圖所 不地’可知ΟΗ基濃度由不足i〇wtppm成爲lOwtppm以上 時’反射維持率及照度維持率都會急劇地變高，由此被認 定將二氧化矽粒子中的OH基濃度作成l〇wtPPm以上會有 顯著差異，有關於長時間點燈時的照度維持上發揮優異的 效果。 然而，即使將構成紫外線反射層30的二氧化矽粒子 中的OH基濃度作成10 wtppm以上，也發生在準分子燈以 φ 172nm作爲中心波長的準分子發光的照度較低的情形。又 ，在作爲放電用氣體封入有氙的準分子燈10的點燈中， 發生在放電空間S的放電的顏色有成爲綠色的情形，被確 認了產生氙原子與氧原子所結合的分子（XeO )，而由該 分子放射著以5 50nm附近作爲中心波長的綠色光。 又，含有於構成紫外線反射層30的二氧化矽粒子的 OH基，是曝露在放電空間內所生成的放電電漿，則藉由 被加熱而會將以水（H20 )作爲主成分的不純氣體放出至 放電空間S內者。以水作爲主成分的不純氣體在電漿中被 -19- 200952032 分解所產生的氧原子，是從含有於構成紫外線反射層30 的二氧化矽粒子的OH基被放出至放電空間S。 在放電容器20的內表面形成有微小粒子所成的紫外 線反射層3 0時，則有微小粒子的凹凸之故’因而表面積 變成比未形成有紫外線反射層30的平坦的放電容器20的 表面還要大。不純氣體是由曝露在放電電漿的紫外線反射 層30被放出所產生之故，因而比形成有紫外線反射層30 p 的情形發生更多的不純氣體。又，構成紫外線反射層30 的微小粒子，是一個粒子的體積小之故，因而與放電容器 20相比較，熱容量較小。所以，即使在發生放電電漿的數 10ns左右的短時間內被加熱，也成爲高溫而容易放出不純 氣體。 堆積體A31是形成於對應在上壁板21的內表面的高 電壓供應電極11的領域之故，因而直接曝露於在電極11 、1 2間所發生的放電電漿，所以利用被加熱將不純氣體放 φ 出至放電空間S內。 一方面，堆積體B32是形成於由高電壓供應電極Π 偏離的上壁板21或是由接地電極12偏離的下壁板22的 內表面，或是形成於側壁板23或端壁板24的內表面的任 一領域之故，因而雖相對面於放電空間S，惟不會直接曝 露於在電極1 1、1 2間所發生的放電電漿。所以’相信谭 堆積體B3 2幾乎不會發生不純氣體。相反地，相信堆積體 B32是吸附不純氣體者，由以下實驗可實證這種情形。 作爲第2實驗對象，製作在放電容器20的內表面’ -20- 200952032 僅形成堆積體B，而未形成堆積體A的準分子燈。作爲放 電用氣體使用氙，而在封入放電用氣體之際也混入氧，將 事先作爲不純氣體封入有氧的準分子燈作爲實驗對象。被 封入於放電空間S的氧濃度是作爲160wtppm，而放電用 氣體的壓力是作爲40kPa。作爲不純氣體混入有氧時，則 與稀有氣體反應而對照度降低的影響很大，又，會產生波 長5 5 0nm的放電光，藉此，容易地可判別氧混入在放電空 D 間S的情形。 準備具備將微小粒子構成於放電容器的內表面的粒子 的成分比不相同的堆積體B的3種準分子燈。燈1是具備 僅二氧化矽粒子作成的堆積體B，燈2是具備二氧化矽粒 子與氧化鋁粒子所成的堆積體B，燈3是具備二氧化矽粒 子與氟化鈣粒子所成的堆積體B。又，作爲比較例準備未 形成有堆積體B的燈4。針對於各個燈，測定一直到準分 子放電成爲穩定爲止的連續點燈15分鐘後的550nm的發 Q 光強度，而將其作爲「550nm發光強度點燈初期」。之後 ，繼續點燈準分子燈，測定連續點燈5小時後的5 5 Onm發 光強度，將其作爲「550nm發光強度點燈5小時後」。 -21 - 200952032 [表2] 堆積 ί體Β的構成 550mn 發 光強度點 燈初期 550nm發光 強度點燈 5小時後 材料 粒子徑 (/zm) 中心粒徑 (/zm) 成分比 (wt%) 厚度 (urn) 燈1 二氧化砂 0.1 〜3·0 0.3 100 20 100 10 燈2 二氧化矽 0.1 〜3.0 0.3 70 20 100 10 氧化鋁 0.2 〜5.0 0.3 30 燈3 二氧化矽 0.1 〜3.0 0.3 70 20 100 12 氟化鈣 0.1 〜6.0 0.4 30 燈4 Μ — — — — 100 100 將第2實驗結果表示於表2。「5 5 0nm發光強度點燈 5小時後」的數値，是將「5 5 Onm發光強度點燈初期」的 數値作爲1〇〇時表示作爲相對値。在具備堆積體B的燈1 〜燈3中，5 5 0nm發光強度點燈5小時後的數値減少成 1 00以下，而減少與點燈初期相比較，氙原子與氧原子所 結合的分子（XeO )的數量。亦即，減少事先混入在放電 空間中的氧。一方面，在未形成有堆積體B的燈4中， ❹ 5 5 Onm發光強度點燈5小時後的數値仍維持100，而可知 事先混入在放電空間中的氧氣量並未變化。藉此，在準分 子燈的放電容器的內表面設置堆積體B就可確認減少 . 55 0nm的光’可知氧被吸附在堆積體B。又，堆積體B是 爲了未被曝露於放電電漿，所吸附的不純氣體可能未被放 出至放電空間。 以下’在第2實驗被確認的氧被吸附在堆積體B的現 象’是爲了確認是否爲藉由準分子燈的點燈所產生者，而 進行第3實驗。將具有與第2實驗對象的燈1〜3同樣的 -22- 200952032 構成的燈5〜7作爲第3實驗。又，作爲比較例準備未形 成有堆積體B的燈8。針對於各個燈，測定連續點燈15 分鐘後的5 5 0nm的發光強度，將其作爲「5 50nm發光強度 點燈初期」。然後，仍未點燈下放置48小時，放置後進 行點燈，測定連續點燈15分鐘的55 Onm的發光強度，將 其作爲「55 Onm發光強度48小時經過後」。之後，繼續 準分子燈的點燈，測定連續點燈5小時後的5 5 Onm發光強 度’將其作爲「5 5 Onm發光強度4 8小時經過後的點燈5 小時後」。 [表3] 堆積1 豊B的構成 550nm 發光強 度點燈 初期 550nm發光 強度48小 時經過後 550nm發光 強度48小時 經過後的點 燈5小時後 材料 粒子徑 (ym) 中心粒徑 〇m) 成分比 (wt%) 厚度 (/m) 燈5 二氧化矽 0.1 〜3.0 0.3 100 20 100 100 10 燈6 二氧化矽 0.1-3.0 0.3 70 20 100 100 10 氧化鋁 0_2 〜5_0 0.3 30 燈7 二氧化矽 0.1 〜3.0 0.3 70 20 100 100 11 mm 0.1 〜6.0 0.4 30 燈8 4πΤ. — — — 100 100 100 將第3實驗結果表示於表3。「550 nm發光強度48小 時經過後」及「5 5 Onm發光強度點燈4 8小時經過後的點 燈5小時後」的數値，是將「550ηιη發光強度點燈初期」 的數値作爲100時表示作爲相對値。在具備堆積體B的燈 5〜燈7中’對於55 Onm發光強度48小時經過後爲數値爲 -23- 200952032 1 00，而5 5 Onm發光強度4 8小時經過後的點燈5小時後的 數値減少至1 〇〜11，可知點燈準分子燈才會減少氧。作爲 氧被吸附於堆積體B的原理，爲在堆積體B的微小粒子表 面，利用點燈才發生的紫外線會使氧產生化學反應而會產 生被吸附的化學吸附。 一方面，在未形成有堆積體B的燈8中，55 Onm發光 強度48小時經過，及5 50nm發光強度48小時經過後的點 _ 燈5小時後都仍維持數値爲100之故，因而可知事先混入 在放電空間中的氧氣量並未變化。 構成堆積體B的微小粒子，是被曝露在放電空間的表 面會吸附不純氣體之故，因而面臨於放電空間的表面積愈 大愈可吸附更多的不純氣體。因此，「比表面積」，亦即 ，含有於單位重量的粉體中的全粒子的表面積總和愈大， 愈可吸附更多的不純氣體。比表面積是例如在微小粒子的 表面事先吸附佔有面積既知的分子氣體（例如氮），使用 φ 由其量求出比表面積的被稱爲BET法的測定方法進行測定 。測定構成堆積體B的微小粒子的比表面積時，則將曝露 於堆積體B的放電空間的表面曝露於分子氣體而被吸附， 由其量求出比表面積。 以下，表示爲了確認本發明的效果所進行的第4實驗 <實驗對象> 依照表示於第1(a) 、（b)圖的構成，製作具備堆積 -24- 200952032 體A及堆積體B的準分子燈。 〔準分子燈的基本構成〕 放電容器是材質爲二氧化砍玻璃，尺寸爲15mmx43mm X540mm > 厚度爲 2.5mm。 高電壓供應電極及接地電極的尺寸是32mmx500mm。 在下壁板中對應於未形成有堆積體B的領域的光射出 部的尺寸是比接地電極還要大2mm，爲36mmx504mm。 堆積體A與堆積體B是藉由流下法分別形成，燒成溫 度是作爲l〇〇〇°C。 將溫排氣以800 °C，1小時（昇溫後的時間）的條件 進行之後，在放電容器內封入氙。其封入量是40kPa。 所製作的燈的堆積體A的OH基含有量是500wtppm。 如表4所示地，針對於堆積體A的構成，準備了構成 (1-1)、構成（1-2)、構成（1-3)、構成（1-4)的4種 。4種各該構成是在材料、粒子徑、中心粒徑、成分比爲共 通，惟將形成於對應在上壁板的內表面的高電壓供應電極 的領域的堆積體 A的設置面積變更爲160cm2、128cm2、 10 7cm2、40cm2。被放出於放電空間內的不純氣體的量，是 依存於堆積體A的設置面積，因此，如構成（1-1)地堆積 體A的設置面積愈大，則不純氣體的量愈多，而如構成（ΙΑ ) 地堆 積體 A 的設 置面 積愈小 ，則不 純氣體 的量會 變少。 又，在構成（1-2)、構成（1-3)、構成（1-4)中，形成有 堆積體A的設置面積，比形成有高電壓供應電極的面積的 -25- 200952032。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 light. [Prior Art] @In the glass substrate of a liquid crystal display device, a processed object such as a semiconductor wafer, vacuum ultraviolet light having an ultraviolet ray having a wavelength of 200 nm or less is developed, and vacuum ultraviolet light and ozone generated thereby are developed. The technique of processing the object to be processed, for example, a cleaning treatment technique for removing an organic contaminant attached to the surface of the object to be processed, or an oxide film formation treatment technique for forming an oxide film on the surface of the object to be processed, and It has been put into practical use. As an apparatus for irradiating vacuum ultraviolet light, for example, an excimer that emits a discharge gas in a discharge vessel formed by a medium, and an excimer discharge is generated by applying a high-voltage alternating current to φ via a discharge vessel to emit a vacuum ultraviolet light is used. Luminous excimer lamp. In such an excimer lamp, many attempts have been made to efficiently emit higher intensity ultraviolet rays. Specifically, it is disclosed that the ultraviolet reflecting layer is formed on the inner surface of the discharge vessel of the excimer lamp, and the ultraviolet reflecting layer is formed by laminating fine particles that transmit ultraviolet rays, such as only cerium oxide or cerium oxide. Other fine particles such as alumina, magnesium fluoride, calcium fluoride, lithium fluoride, magnesium oxide, and the like (see Patent Document 1). In the excimer lamp of such a configuration, ultraviolet rays that are not directly emitted toward the light emitting portion in the purple line of the purple-5-200952032 generated in the discharge vessel are incident on the ultraviolet reflecting layer 'by forming the ultraviolet reflecting layer The surface of the plurality of fine particles is repeatedly refracted and reflected, diffused and reflected, and is emitted from the light emitting portion. Thereby, ultraviolet rays can be efficiently emitted. In a lamp that emits ultraviolet light, as a material constituting the discharge vessel, for example, ceria glass is widely used. Therefore, the fine particles constituting the ultraviolet ray reflection layer are prevented from being "differenced from the thermal expansion coefficient of the cerium oxide glass constituting the discharge vessel" or are formed to be extremely small, and the adhesion of the ultraviolet ray reflection layer to the cerium oxide glass is increased. Preferably, the cerium oxide glass of the same material as the discharge vessel is used. The surface-treated object to be processed is, for example, a flat shape of a glass substrate such as a liquid crystal panel. Therefore, the excimer lamp formed by the flat discharge vessel having the same light-emitting portion and the object to be processed reduces the gap between the light-emitting portion and the workpiece, thereby suppressing the absorption of ultraviolet rays by oxygen, and thus is efficient. The surface can be surface treated. As an excimer lamp formed by the discharge vessel of such a shape, for example, Patent Document 2 discloses an excimer lamp formed by a rectangular discharge vessel. The excimer lamp formed as a discharge vessel having a flat light-emitting portion has a structure as shown in Fig. 10. The excimer lamp 10 is composed of a flat rectangular discharge vessel 20 made of ceria glass, and the discharge vessel 20 has a structure in which the upper wall plate 21, the lower wall plate 22, the side wall plate 23, and the end wall plate 24 are joined. The discharge gas is sealed inside. Further, 'the upper surface of the upper wall plate 21 is provided with the high voltage supply electrode 11, and the outer surface of the lower wall plate 22 is provided with the ground electrode 12, and the electrodes 11, 12 are arranged to be mutually opposed to each other -6-200952032 The excimer light emission generated in the space S is emitted to the outside through the lower wall 22 having the light emitting portion. Patent Document 1: Japanese Laid-Open Patent Publication No. 2004-335350. SUMMARY OF THE INVENTION However, an excimer of an ultraviolet reflecting layer formed of fine particles containing cerium oxide particles is provided. In the lamp, if the light is turned on for a long time, the illuminance maintenance rate will gradually decrease gradually. Therefore, for example, when surface treatment such as a washing treatment is performed, even if it is intended to be treated with a certain illuminance, there is a problem that the processing ability of the excimer lamp varies with the lighting time. The present invention has been made in view of the above, and an object of the invention is to provide an ultraviolet-ray reflective layer comprising fine particles containing cerium oxide particles, which can reduce the degree of reduction in illuminance even when lighting for a long period of time. An excimer lamp that efficiently emits vacuum ultraviolet light. The excimer lamp according to the first aspect of the present invention is a discharge vessel including a cerium oxide glass having a discharge space, and a pair of electrodes are provided in a state in which the bismuth oxide glass forming the discharge vessel is interposed, and An excimer lamp in which a discharge gas is sealed in a discharge space and an ultraviolet reflection layer is formed on a part of an inner surface of the discharge vessel, wherein the ultraviolet reflection layer is formed by a corresponding electrode The deposit body A of at least a part of the field and the deposit B formed at least in part other than the field of the electrode, the stack A is composed of: cerium oxide particles containing an OH group, and a melting point ratio 200952032, which is composed of fine particles, is high in composition. The above-mentioned deposited body B is composed of fine particles containing cerium oxide particles containing an OH group, and the concentration of OH groups in the oxidized political particles constituting the ultraviolet reflecting layer is 1 0wtppm or more. According to a second aspect of the present invention, in the first aspect of the invention, the installation area of the stack A is a (cm2), and the installation area of the stack "B" is b (cm2). When the specific surface area of the deposit B is c (cm2/g) and the internal surface area of the discharge vessel is taken as d (cm2 win), the relationship is ❹ -5.0x1 0'7ac + 0.35a ' and b > 0.02 d is its characteristic. By mixing fine particles having a higher melting point than cerium oxide in the ultraviolet reflecting layer, it is possible to prevent the adjacent fine particles from being bonded to each other and disappearing the grain boundary, thereby suppressing the reduction of the reflectance of the ultraviolet reflecting layer, especially Therefore, the deposit A formed in the field corresponding to the electrode is susceptible to heat of the plasma, and therefore it is necessary to mix fine particles φ with a melting point higher than that of the cerium oxide to suppress the decrease of the reflectance of the ultraviolet reflecting layer. . In addition, the cerium oxide particles constituting the ultraviolet ray reflecting layer contain an OH group, thereby suppressing generation of internal defects in the cerium oxide particles contained in the ultraviolet ray reflecting layer, thereby preventing light absorption in the ultraviolet region due to the ultraviolet ray reflecting layer. Maintaining the reflectance of the ultraviolet reflecting layer, suppressing the decrease of the illuminance of the excimer lamp to a low degree, and efficiently emitting the vacuum ultraviolet light. In particular, when the concentration of the OH group in the cerium oxide particles constituting the ultraviolet ray-reflecting layer is 10% by weight or more, the reflection retention ratio and the illuminance maintenance ratio can be maintained high, and the illuminance maintenance at the time of long-time lighting is excellent in advance. -8 - 200952032 effect. The ultraviolet reflecting layer formed on the inner surface of the discharge vessel corresponding to the position where the electrode is provided is an impure gas containing OH groups and exposed to the discharge plasma to emit water as a main component. When the impure gas containing water as a main component is combined with the gas for discharge, the illuminance of the plasma luminescence is lowered. However, by forming an ultraviolet reflecting layer at a portion of the inner surface of the discharge vessel corresponding to the position where the electrode is not provided, the water discharged from the ultraviolet reflecting layer is adsorbed, and at the same time, water is decomposed in the plasma. Oxygen can suppress the decrease in illuminance of excimer light emission. Therefore, even when the excimer lamp is turned on for a long period of time, it is possible to suppress the degree of reduction in illuminance, and to efficiently emit vacuum ultraviolet light. Considering the specific surface area of the deposit B, the installation area a (cm2) of the deposit A, the installation area of the deposit B is b (cm2), and the specific surface area of the deposit B is c (cm2/g), and the discharge is performed. When the internal surface area of the container is d (cm2), the relationship is such that the amount of impure gas released from the deposit A by bg-5.0xl0.7ac+〇.35a and b>0.02d does not exceed the stack. B can adsorb the amount of impure gas, and in the discharge space, no impurity gas remains. Therefore, it is possible to suppress the decrease in illuminance of excimer light emission caused by the combination of the oxygen atom contained in the impure gas and the gas for discharge, and to suppress the decrease in illuminance even when the excimer lamp is turned on for a long time, and efficiently emit the vacuum ultraviolet ray. Light. [Embodiment] -9-200952032 Fig. 1 is a cross-sectional view showing a schematic configuration of an example of an excimer lamp ίο of the present invention. Fig. 1(a) is a cross-sectional view showing a cross section along the longitudinal direction of the discharge vessel 20, and Fig. 1(b) is a cross-sectional view taken along line A-A of Fig. 1(a). The excimer lamp 10 has a hollow length discharge vessel 20 having a rectangular cross section in which both ends are hermetically sealed and a discharge space S is formed inside. The discharge vessel 20 is composed of an upper wall plate 21 and a lower wall plate 22 opposite to the upper wall plate 21g, and a pair of side wall plates 23 connected to the upper wall plate 21 and the lower wall plate 22, and The wall plate 21, the lower wall plate 22, and the pair of side wall plates 23 are formed by sealing a pair of end wall plates 24 provided at both ends of the rectangular tubular body. The discharge vessel 20 is formed of cerium oxide glass, such as synthetic quartz glass, which transmits vacuum ultraviolet light well. Inside the discharge vessel 20, a discharge gas is sealed by press-fitting at, for example, 10 to 80 kPa. Even if any gas is selected as the discharge gas, there is no influence on the temporal change of the emission intensity. However, the center wavelength of the emitted excimer light is different by the Q type of the discharge gas. For example, in an excimer lamp sealed with xenon (Xe), excimer light emission with a center wavelength of 172 nm is generated, and an excimer lamp sealed with a mixed gas of argon (Ar) and chlorine (C1) is generated. Excimer light with a center wavelength of 175 nm as an excimer lamp enclosing a mixed gas of krypton (Kr) and iodine (I) produces excimer luminescence with a center wavelength of 191 nm, and argon is enclosed therein. An excimer lamp of a mixed gas of cerium and fluorine (F) generates an excimer wavelength having a wavelength of 193 nm as a center wavelength, and an excimer lamp sealed with a mixed gas of krypton (Kr) and bromine (Br) is produced. Excimer luminescence with a wavelength of -10 200952032 2 0 7 nm as the center wavelength 'excimer lamp enclosed with a mixed gas of krypton (Kr) and chlorine (C1 ) produces excimer luminescence with a center wavelength of 222 nm, and is enclosed An excimer lamp having a mixed gas of xenon (Xe) and chlorine (C1) generates excimer light emission having a center wavelength of 308 nm. The outer surface of the upper wall 21 of the discharge vessel 20 is provided with a high voltage supply electrode 11, And the ground is provided on the outer surface of the lower wall 22 The electrodes 12 and 12 are disposed to face each other. The electrodes 11 and 12 have a mesh structure and are capable of transmitting light from between the meshes. As a material, for example, aluminum, nickel, gold, or the like is used. For example, it is formed by screen printing or vacuum evaporation. Further, each of the electrodes 11 and 12 is connected to an appropriate high-frequency power source (not shown). In the above excimer lamp 10, in order to efficiently The ultraviolet ray reflection layer 30 formed of fine particles is provided on the inner surface of the discharge space S with respect to the discharge vessel 20 by vacuum ultraviolet light generated by excimer discharge. The ultraviolet ray reflection layer 30 is composed of a stack A31 and stacked. The body A32 is formed by a part of the inner surface of the discharge space S formed on the opposite surface of the discharge vessel 20 provided with the high voltage supply electrode 11, that is, formed on the inner surface corresponding to the upper wall plate 21. A part of the field of the high voltage supply electrode n. Further, the deposition body B23 is a part of the inner surface of the discharge space S formed on the opposite surface of the discharge vessel 20 where the high voltage supply electrode 11 or the ground electrode 12 is not provided, that is, Formed in any of the upper wall 21 and the inner surface of the p wall 22 deviated from the fields corresponding to the electrodes 11, 12, and the inner surfaces of the side wall plate 23 and the end wall plate 24. That is, - 11 - 200952032 The ultraviolet ray reflection layer 30 formed in the field corresponding to the high voltage supply on the inner surface of the upper wall plate 21 is referred to as a stack A31, and the ultraviolet ray reflection layer stack B32 of the other surface of the inner surface of the discharge vessel 20 On the one hand, the lower wall 22 of the discharge vessel 20 corresponds to the inner surface of the 12, and is not formed with the ultraviolet reflective layer 30. The accumulation body A31 is a thickness of, for example, 5 to 1 000 /zm, ruthenium particles. And the melting point is higher than that of cerium oxide and transmits ultraviolet rays. The melting point is higher than that of cerium oxide and the ultraviolet ray is such that aluminum oxide, lithium fluoride, magnesium fluoride, calcium fluoride, yttrium vacuum ultraviolet light is incident on the deposition body A31, and the surface of a small particle The reflection, in part, is refracted and transmitted, and is re-reflected or refracted on other surfaces. Repeating such reflection and refraction in the plurality of tiny particles φ, the vacuum ultraviolet light is diffused and reflected, however, the cerium oxide particles are Molecular lamp 10 The heat of the plasma is melted, and the grain boundary is disappeared. 'There is no possibility of diffusing the reflection and reducing the reflectance. In particular, the deposited body A3 1 formed in the field corresponding to the electrode 11 is a cerium oxide particle which is easily subjected to the plasma constituting the stacked body A3 1 and is easily melted. The fine particles with a higher melting point than cerium oxide are not melted even when exposed to heat. Therefore, in the deposit A31, the fine particles which are higher by the mixing of the cerium oxide' are formed by the micro-dust electrodes 11 adjacent to each other, and the micro-particles which are formed by the TiO 30 are called the ground electrode to emit light and the fine particles of the oxidized fine particles are emitted. The bismuth of bismuth is the heat supplied by the high voltage of the empty ultraviolet light generated in the interior of the microparticles. On the one hand, the infusion point of the plasma is combined with the particles -12-200952032 to prevent the granules. The boundary disappears, and the decrease in the reflectance of the deposit A3 1 can be suppressed. The deposit B32 has a thickness of, for example, 1 〇 to i 〇〇 0; t/m, and is composed of fine particles containing cerium oxide particles. The fine particles constituting the deposition body B32 are composed of only cerium oxide particles or other insulating fine particles containing a substance which is combined with oxygen and which is mixed with ultraviolet ray, for example, oxidized. Aluminum, lithium fluoride, magnesium fluoride, calcium fluoride, and cesium fluoride may also be used. Even if vacuum ultraviolet light is incident on the deposition body B3 2, reflection and refraction are repeatedly generated in the plurality of fine particles, and the vacuum ultraviolet light is diffused and reflected. Further, since the deposition body B32 is formed on the inner surface of the discharge vessel 20 in addition to the fields of the electrodes 11, 12, it is less likely to be affected by heat due to plasma. Therefore, even if the deposit B32 is not formed by the cerium oxide particles alone, the grain boundary disappearance due to the bonding of the adjacent fine particles to each other is less likely to occur. The fine particles are particle diameters as defined below, and are, for example, in the range of 0.01 to 20 " m, the center particle diameter (the maximum 粒度 of the particle size distribution based on the number), and in the stack A3 1 , for example, 0.1 to 0.1 1 〇 / zm is preferred, more preferably 0.1 to 3 " m, and the same is true for the deposition body B2, for example, 0.1 to 20 ym. Here, the "particle diameter" means that an approximately intermediate position in the thickness direction of the cross section when the surface of the ultraviolet ray reflection layer 30 is cut in the vertical direction is used as an observation range, and an enlarged projection is obtained by a scanning electron microscope (SEM). Like the two parallel lines in a certain direction, the Freit diameter of the interval of the parallel line when the arbitrary projection of the image of the projection -13-200952032 is enlarged is separated, and the "central particle diameter" means For the range of the maximum 値 and the minimum 値 particle diameter of the particle diameters of the respective particles obtained as described above, for example, the range of 0.1//m is divided into plural numbers, for example, 15 divisions are classified, and the particles belonging to each division are divided. The number (degree) becomes the center of the largest division. In the excimer lamp 10, the lighting power is supplied to the high voltage supply electrode 12, and the discharge space S between the electrodes 11 and 12 passes through the discharge capacitor 20. An excimer discharge occurred. Thereby, while the excimer is formed, vacuum ultraviolet light is emitted from the excimer molecule. A part of the vacuum ultraviolet light generated in the discharge space S is directly emitted to the outside through the lower wall 22 having the light emitting portion. Further, a part of the vacuum ultraviolet light is radiated toward the upper wall 21, but the ultraviolet ray reflection layer 30 is diffused and emitted, and is emitted to the outside through the light emitting portion. The fine particles constituting the ultraviolet ray reflection layer 30 have a particle diameter which is the same as the wavelength of the vacuum ultraviolet light, and can efficiently diffuse and reflect the vacuum ultraviolet light. However, when the quasi-molecular lamp 10 of the ultraviolet ray reflection layer 30 was turned on for a long time, the initial illuminance could not be maintained, and it was confirmed that the illuminance was gradually lowered with the lighting time. The inventors have reviewed the reason why the illuminance is lowered by all aspects, and it is considered whether or not the reflectance of the ultraviolet ray reflection layer 30 which is one of the main causes is lowered. Here, the reflection intensity spectrum of the ultraviolet ray reflection layer-14-200952032 30 of the excimer lamp 1 初期 at the initial stage of the lighting, and the reflection intensity spectrum of the ultraviolet ray reflection layer 30 of the excimer lamp 1 长时间 after the long-time lighting are measured, Compare and resolve both. As a result, in the ultraviolet ray reflecting layer 30 of the excimer lamp 1 after the long-time lighting, the absorption band generates the ultraviolet region, and it is understood that the illuminance is lowered by a part of the ultraviolet ray being absorbed by the ultraviolet ray reflection layer 30. The absorption band generated in the ultraviolet region of the ultraviolet ray reflection layer 30 is such that the cerium oxide particles constituting the ultraviolet ray reflection layer 30 are exposed to the ultraviolet ray line or the plasma during discharge, and are subjected to radiation damage to generate an ultraviolet absorbing field. The internal defects of the wavelength of light, while the ultraviolet rays are absorbed in the internal defects, so that the diffuse reflection is suppressed. The internal defect means that the Si-0-Si bond of the cerium oxide particles is exposed to a Si-Si defect having an absorption end at a wavelength of 163 nm generated by ultraviolet rays or plasma, or an E'center having an absorption band at a wavelength of 215 nm (Si· ). For the reason described above, the internal defect of the light that absorbs the wavelength in the ultraviolet region is cerium oxide particles, and the light absorption at the wavelength of the ultraviolet ray domain which is the cause of the decrease in illuminance is likely to depend on the internal defects of the cerium oxide particles. . In addition, fine particles of ultraviolet rays other than cerium oxide particles formed by transmitting alumina, lithium fluoride, magnesium fluoride, calcium fluoride, or cesium fluoride do not cause radiation damage even when exposed to ultraviolet rays or plasma. . Therefore, the illuminance reduction can be suppressed by preventing the occurrence of internal defects in the cerium oxide particles constituting the ultraviolet ray reflection layer 30, and the high illuminance maintenance ratio can be maintained even when lighting is performed for a long period of time. In order to prevent internal defects in the cerium oxide particles, it is effective in the cerium oxide particles. By containing the OH group', it is possible to suppress the formation of internal defects in the cerium oxide particles containing the -15-200952032 in the ultraviolet ray reflecting layer 30, and it is possible to prevent the reflectance of the ultraviolet ray reflecting layer 30 from being lowered. Hereinafter, a method of forming the ultraviolet ray reflection layer 30 formed of fine particles containing OH group-containing cerium oxide particles will be described. The ultraviolet ray reflection layer 30 is formed by a method called "flow down method" in which a particle deposition layer containing cerium oxide particles is formed in a predetermined region of the inner surface of the discharge vessel forming material. For example, in a solvent having a viscosity of a combination of water and p polyethylen oxide, fine particles are mixed to adjust the dispersion, and the dispersion is introduced into the discharge vessel forming material. Further, the dispersion liquid is adhered to a predetermined area on the inner surface of the discharge vessel forming material, and then dried and fired to evaporate water and PEO resin, whereby a particle deposition layer can be formed. Here, the baking temperature is, for example, 500 ° C to 1100 ° C. As an example of the method of containing an OH group in the cerium oxide particles, the oxidized sand particles not containing the OH group are supplied with water vapor while being heated by an electric furnace (for example, 1 000 ° C) to produce a large amount of OH. The case of a base of two φ cerium oxide particles. By using the cerium oxide particles thus treated, an ultraviolet ray reflecting layer 30 composed of fine particles containing cerium oxide particles containing OH groups can be formed. Further, as another method, after the cerium oxide particles not containing the OH group are attached to a predetermined region of the inner surface of the discharge vessel forming material, the cerium oxide particles may be contained in the cerium oxide particles by firing while supplying water vapor. base. Further, after the ultraviolet ray blocking layer 30 is formed by firing the cerium oxide particles not containing the OH group, the cerium oxide particles may be contained in the cerium oxide particles by heating the electric steam on one side. -16- 200952032 Further, by purchasing commercially available cerium oxide particles, products which also contain OH groups by the production method thereof, but also have a product having a small OH group concentration, and thus, when the above method contains a high concentration The OH group is preferred. The concentration of the OH group contained in the cerium oxide particles can be adjusted to an arbitrary number of enthalpy concentrations of the cerium oxide particles constituting the ultraviolet ray blocking layer 30 by selecting various temperature and exhaust conditions. For example, even if the temperature is kept constant, more 〇HS can be removed with an extended holding time. Considering the amount of the OH group previously contained in the cerium oxide particles, by modulating the amount of OH groups removed by warm exhaust gas, the ultraviolet ray reflecting layer 30 formed by the fine particles containing the cerium oxide particles of an arbitrary concentration can be formed. . Indicates the first experiment on excimer lamps. An excimer lamp having an ultraviolet reflection layer was produced in accordance with the configuration shown in Figs. 1(a) and (b). [Basic Structure of Excimer Lamp] The discharge vessel is made of cerium oxide glass and has a size of 15 mm x 43 mm x 350 mm and a thickness of 2.5 mm. The size of the high-voltage supply electrode and the grounding electrode is 30mm×3()()mm°. The ultraviolet-ray reflective layer is made of a oxidized sand particle having a center particle diameter of 90% by weight and a center particle diameter of 1.5 V. The composition of the particles was formed by mixing the mixture with a weight ratio of 1% by weight, and was formed by a downflow method, and the firing temperature was 1000 °C. As a discharge gas, helium was sealed in a discharge vessel at 40 kPa. The OH group concentration, the reflection retention ratio, and the illuminance maintenance ratio in the oxidized chopped particles -17 to 200952032 were measured for the excimer lamp having the above configuration. All of the UV-reflecting layers were removed from the discharge vessel and measured by temperature-off gas analysis. Thereby, the OH group concentration in the cerium oxide particles contained in the ultraviolet ray reflection layer was calculated. Further, the component ratio of the cerium oxide particles contained in the ultraviolet ray-reflecting layer to be removed was determined, and the weight of the OH group for the weight of only the cerium oxide particles was calculated from the component ratio. Further, the reflection maintaining ratio and the illuminance maintenance ratio of the ultraviolet ray reflection layer after continuous lighting for 500 hours in the initial state were measured using a vacuum ultraviolet spectrometer (VUV) or an ultraviolet illuminance measuring instrument. The measurement results of the lamps 1 to 5 are shown in Table 1. [Table 1] OH group concentration (wtppm) in cerium oxide particles Reflection retention rate (%) Illuminance maintenance rate (%) Lamp 1 5 78 72 Lamp 2 7 82 79 Lamp 3 10 98 96 Lamp 4 42 96 92 Lamp 5 132 96 94 Fig. 2 is a measurement result shown in Table 1, with the 〇H group concentration (wtppm) in the horizontal axis as the cerium oxide particle and the reflection maintaining ratio (%) in the vertical axis, and the indicator lamp 1~ 5 number of charts. Further, Fig. 3 is a measurement result shown in Table 1, and the OH group concentration (wtppm) in the horizontal axis is used as the cerium oxide particle, and the illuminance maintenance rate (%) is plotted on the vertical axis, and the lamps 1 to 5 are marked. A number of charts. "18- 200952032 Further, the graphs shown in Fig. 2 and Fig. 3, the horizontal axis is a logarithmic graph which becomes a logarithmic scale. From the above results, the 〇H group concentration in the cerium oxide particles can be read to be less than 10 wtppm. , the reflection maintenance rate and the illuminance maintenance rate are both low, and the long-time lighting of the excimer lamp' has a situation in which the processing capability is lowered. On the other hand, when the concentration of the OH group in the cerium oxide particles is 10 wtppm or more, the reflection retention ratio and the illuminance maintenance ratio are both 90% or more, and the long-term lighting of the molecular lamp can maintain the processing ability. situation. As shown in Fig. 2 and Fig. 3, the reflectance maintenance ratio and the illuminance maintenance rate are sharply increased when the concentration of the ruthenium base is less than 10% by weight of i〇wtppm, and it is considered that the cerium oxide particles are in the cerium oxide particle. The OH group concentration is significantly different from the above, and the illuminance at the time of long-time lighting is excellent. However, even when the concentration of the OH group in the cerium oxide particles constituting the ultraviolet ray reflecting layer 30 is 10 wtppm or more, the illuminance of the excimer light having the φ 172 nm as the center wavelength of the excimer lamp is low. Further, in the lighting of the excimer lamp 10 in which the enthalpy is enclosed as the discharge gas, the color of the discharge generated in the discharge space S is green, and it is confirmed that a molecule in which a ruthenium atom and an oxygen atom are bonded (XeO) is generated. And the green light having a central wavelength of around 50 50 nm is emitted by the molecule. Further, the OH group contained in the cerium oxide particles constituting the ultraviolet ray reflecting layer 30 is a discharge plasma generated by being exposed to the discharge space, and the impure gas containing water (H20) as a main component is heated by heating. Released to the discharge space S. The oxygen atoms generated by the decomposition of the impure gas containing water as a main component in the plasma by -19-200952032 are discharged from the OH group contained in the cerium oxide particles constituting the ultraviolet ray reflection layer 30 to the discharge space S. When the ultraviolet ray reflection layer 30 formed of the fine particles is formed on the inner surface of the discharge vessel 20, the irregularities of the fine particles are formed. Thus, the surface area becomes larger than the surface of the flat discharge vessel 20 in which the ultraviolet ray reflection layer 30 is not formed. Bigger. The impure gas is generated by the ultraviolet reflective layer 30 exposed to the discharge plasma, and thus more impurity gas is generated than in the case where the ultraviolet reflective layer 30p is formed. Further, since the fine particles constituting the ultraviolet ray reflection layer 30 have a small volume of one particle, the heat capacity is small as compared with the discharge vessel 20. Therefore, even if it is heated in a short time of about 10 ns of the discharge plasma, it becomes a high temperature and it is easy to emit an impurity gas. The deposition body A31 is formed in the field of the high voltage supply electrode 11 corresponding to the inner surface of the upper wall plate 21, and thus is directly exposed to the discharge plasma generated between the electrodes 11 and 12, so that the use of being heated will be impure. The gas is discharged into the discharge space S. On the one hand, the accumulation body B32 is formed on the inner surface of the upper wall plate 21 which is deviated from the high voltage supply electrode 或是 or the lower wall plate 22 which is deviated from the ground electrode 12, or is formed on the side wall plate 23 or the end wall plate 24. In any field of the inner surface, the surface is opposed to the discharge space S, but is not directly exposed to the discharge plasma generated between the electrodes 1 1 and 12. Therefore, it is believed that there is almost no impure gas in the Tan stack B3 2 . Conversely, it is believed that the accumulation body B32 is a person who adsorbs impure gas, and this case can be confirmed by the following experiment. As a second experimental object, an excimer lamp in which only the deposition body B was formed on the inner surface '-20-200952032 of the discharge vessel 20 and the deposition body A was not formed was produced. As the discharge gas, helium was used, and when the discharge gas was sealed, oxygen was mixed, and an excimer lamp in which oxygen was previously sealed as an impurity gas was used as an experimental object. The oxygen concentration enclosed in the discharge space S was 160 wtppm, and the pressure of the discharge gas was 40 kPa. When the impure gas is mixed with aerobic gas, the reaction with the rare gas causes a large decrease in the contrast degree, and a discharge light having a wavelength of 550 nm is generated, whereby the oxygen can be easily mixed between the discharge spaces D. situation. Three kinds of excimer lamps each having a deposition body B having a composition ratio of particles having fine particles formed on the inner surface of the discharge vessel are prepared. The lamp 1 is a deposit B made of only cerium oxide particles, the lamp 2 is a stack B composed of cerium oxide particles and alumina particles, and the lamp 3 is made of cerium oxide particles and calcium fluoride particles. Stack B. Further, as a comparative example, the lamp 4 in which the stacked body B was not formed was prepared. For each of the lamps, the Q-ray intensity at 550 nm after 15 minutes from the continuous lighting until the quasi-molecular discharge became stable was measured, and this was taken as "the initial stage of the 550 nm luminous intensity lighting". Thereafter, the spotlight lamp was continuously turned on, and the 5 5 Onm light intensity after 5 hours of continuous lighting was measured, and this was referred to as "550 hours of 550 nm luminous intensity after lighting". -21 - 200952032 [Table 2] 堆积 Β Β 550 550 550 550 550 550 550 550 550 550 550 550 550 550 550 550 550 550 550 550 550 550 550 550 550 550 550 550 550 550 550 550 550 550 550 550 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Urn) lamp 1 dioxide sand 0.1 to 3 · 0 0.3 100 20 100 10 lamp 2 cerium oxide 0.1 ~ 3.0 0.3 70 20 100 10 alumina 0.2 〜 5.0 0.3 30 lamp 3 cerium oxide 0.1 ~ 3.0 0.3 70 20 100 12 Calcium fluoride 0.1 to 6.0 0.4 30 lamp 4 Μ — — — — 100 100 The results of the second experiment are shown in Table 2. The number of "5 5 0 nm luminous intensity after 5 hours" is expressed as relative 将 when the number of "5 5 Onm luminous intensity lighting" is 1 〇〇. In the lamp 1 to the lamp 3 having the stack B, the number of 550 hours after the luminescence intensity of 550 nm is reduced to less than 100, and the molecule in which the cesium atom and the oxygen atom are combined is reduced as compared with the initial stage of the lighting. The number of (XeO). That is, the oxygen mixed in the discharge space in advance is reduced. On the other hand, in the lamp 4 in which the stacked body B was not formed, the number of ❹ 5 5 Onm luminous intensity after 5 hours of illumination was maintained at 100, and it was found that the amount of oxygen previously mixed in the discharge space did not change. As a result, it was confirmed that the deposition body B was provided on the inner surface of the discharge vessel of the quasi-molecular lamp. The light of 55 0 nm was observed to be adsorbed on the deposition body B. Further, the deposited body B is not exposed to the discharge plasma, and the adsorbed impure gas may not be discharged to the discharge space. In the following, the phenomenon in which the oxygen confirmed in the second experiment is adsorbed on the deposit B is to confirm whether or not the light is generated by the lighting of the excimer lamp, and the third experiment is performed. The lamps 5 to 7 having the same -22 to 200952032 as the lamps 1 to 3 of the second experimental object were used as the third experiment. Further, as a comparative example, a lamp 8 in which the stacked body B was not formed was prepared. For each of the lamps, the 650 nm light emission intensity after 15 minutes of continuous lighting was measured, and this was taken as "the initial stage of the 5 50 nm luminous intensity lighting". Then, it was left unlit for 48 hours, and after standing, it was lit, and the luminous intensity of 55 Onm which was continuously lit for 15 minutes was measured, and this was taken as "55 Onm luminous intensity after 48 hours passed". Thereafter, the lighting of the excimer lamp was continued, and the 5 5 Onm luminous intensity after 5 hours of continuous lighting was measured as "5 5 hours after the 5 5 Onm luminous intensity was elapsed for 4 hours." [Table 3] Stacking 1 豊B composition 550 nm Luminous intensity lighting initial 550 nm luminous intensity 48 hours after 550 nm luminous intensity 48 hours after lighting, material particle diameter (ym) center particle diameter 〇m) composition ratio (wt%) Thickness (/m) Lamp 5 Ceria 0.1 to 3.0 0.3 100 20 100 100 10 Lamp 6 Ceria 0.1-3.0 0.3 70 20 100 100 10 Alumina 0_2 ~ 5_0 0.3 30 Lamp 7 Ceria 0.1 ~3.0 0.3 70 20 100 100 11 mm 0.1 ～6.0 0.4 30 Lamp 8 4πΤ. — — — 100 100 100 The results of the third experiment are shown in Table 3. The number of "after 550 nm luminous intensity of 48 hours passed" and "5 5 Onm luminous intensity lighting after 4 hours of lighting" is the number of "550ηιη luminous intensity lighting early" as 100 Time is expressed as relative ambiguity. In the lamp 5 to the lamp 7 having the stack B, 'the number of illuminating intensity of 55 Onm is -23-200952032 1 00 after 48 hours elapsed, and 5 5 hours after 5 hours of illumination intensity is turned on for 5 hours. The number of lamps is reduced to 1 〇 to 11 and it is known that the lighting of the excimer lamp reduces oxygen. The principle that oxygen is adsorbed to the deposit B is that the ultraviolet rays generated by the lighting on the surface of the fine particles of the deposit B cause a chemical reaction of oxygen to cause adsorption of chemical adsorption. On the other hand, in the lamp 8 in which the stacked body B is not formed, the 55 Onm luminous intensity passes for 48 hours, and the point 50 after the elapse of 48 hours of the 50 50 nm luminous intensity maintains the number 値 of 100 after 5 hours. It can be seen that the amount of oxygen previously mixed in the discharge space does not change. The fine particles constituting the deposition body B are exposed to the surface of the discharge space to adsorb the impure gas, so that the larger the surface area of the discharge space, the more the impure gas can be adsorbed. Therefore, the "specific surface area", that is, the larger the total surface area of the total particles contained in the powder per unit weight, the more the impure gas can be adsorbed. The specific surface area is, for example, a molecular gas (for example, nitrogen) which is known to adsorb an occupied area in advance on the surface of fine particles, and is measured by a measurement method called BET method in which the specific surface area is determined from the amount of φ. When the specific surface area of the fine particles constituting the deposition body B is measured, the surface of the discharge space exposed to the deposition body B is exposed to a molecular gas and adsorbed, and the specific surface area is determined from the amount. In the following, the fourth experiment <experiment object> performed to confirm the effects of the present invention is shown. According to the configuration shown in Figs. 1(a) and (b), the body A and the deposit B having the stack -24 - 200952032 are produced. Excimer lamp. [Basic composition of excimer lamp] The discharge vessel is made of oxidized chopped glass with a size of 15mmx43mm X540mm > thickness of 2.5mm. The size of the high voltage supply electrode and the ground electrode is 32 mm x 500 mm. The size of the light exit portion in the lower wall corresponding to the region in which the deposit B was not formed was 2 mm larger than the ground electrode and was 36 mm x 504 mm. The deposit A and the deposit B are separately formed by a downflow method, and the firing temperature is taken as l〇〇〇°C. The temperature was exhausted at 800 ° C for 1 hour (time after the temperature rise), and then the crucible was sealed in the discharge vessel. Its enclosed amount is 40 kPa. The OH group content of the deposited body A of the produced lamp was 500 wtppm. As shown in Table 4, four types of components (1-1), (1-2), (1-3), and (1-4) were prepared for the structure of the deposit A. In the four materials, the material, the particle diameter, the center particle diameter, and the composition ratio are common, but the installation area of the deposit A formed in the field of the high voltage supply electrode corresponding to the inner surface of the upper wall is changed to 160 cm 2 . , 128cm2, 10 7cm2, 40cm2. The amount of the impure gas that is placed in the discharge space depends on the installation area of the deposit A. Therefore, the larger the installation area of the deposit A in the configuration (1-1), the larger the amount of impure gas. The smaller the installation area of the deposited body A is (少), the less the amount of impure gas will be. Further, in the configuration (1-2), the configuration (1-3), and the configuration (1-4), the installation area of the deposition body A is formed, which is -25-200952032 than the area in which the high voltage supply electrode is formed.
160cm2還要小之故，因而並不是設有高電壓供應電極的放 電容器的內表面的全領域，而是在其一部分形成有堆積體A160cm2 is still small, so it is not the entire area of the inner surface of the discharge vessel provided with the high voltage supply electrode, but a stack body A is formed in a part thereof.
[表4] 材料 粒子徑 (V m) 中心粒徑 (// m) 成分比 (wt%) 厚度 (/zm) 堆積體A的 設置面積 (cm2) 構成（1-1) 二氧化矽 0.1 〜3.0 0.8 90 50 160 氧化鋁 0·2 〜5.0 0.3 10 構成(1-2) 二氧化矽 0.1 〜3.0 0.8 90 50 128 氧化鋁 0.2 〜5.0 0.3 10 構成(1-3) 二氧化矽 0.1 〜3.0 0.8 90 50 107 氧化鋁 0.2 〜5.0 0.3 10 構成（1-4) 二氧化矽 0.1 〜3.0 0.8 90 50 40 氧化鋁 0.2 〜5.0 0.3 10 又，如表5所示地，針對於堆積體B的構成，準備了 構成（2-1)、構成（2-2)、構成（2-3)、構成（2-4)的 4種。構成（2-1)、構成（2-2)、構成（2-3)是僅由二 氧化矽粒子所構成，而構成（2-4 )是由二氧化矽粒子及氧 化鋁粒子所構成。構成（2-1)、構成（2-2)、構成（2-3 )是藉由變更二氧化矽粒子的粒子徑’將比表面積作成 104cm2/g、4xl04cm2 / g、lxl〇4cm2 / g 不相同者。又，構 成（2-4)的比表面積是成爲4xl04cm2/g。堆積體B的比 表面積愈大而吸附愈更多的不純氣體之故’因而如構成（2_ 1)地堆積體B的比表面積愈大而面臨於放電空間的表面積 較大之故，因而混進放電空間內的不純氣體的量隨著點燈會 -26- 200952032 減少，而如構成（2-3 )地堆積體B的比表面積愈小，混進 放電空間內的不純氣體的量隨著點燈會變少。 m 5] 材料 粒子徑 (Ai m) 中心粒徑 (V m) 成分比 (wt%) 厚度 m) 比表面積 (xl04cm2/g) 構成(2-1) 二氧化矽 0.1 〜0.6 0.3 100 20 16 構成(2-2) 二氧化矽 0.1 〜3.0 0.8 100 20 4 構成(2-3) 二氧化砂 0.2 〜6.0 1.2 100 20 1 構成(2-4) 二氧化矽 0.1 〜3.0 0.8 90 20 4 氧化鋁 0.2 〜0.5 0.3 10 對於將堆積體A作爲構成（1-1)者，將堆積體B作 爲構成（2-1)〜構成（2-4)者準備作爲實驗對象。又， 對於各該組合，準備變更堆積體B的設置面積者5種類。 同樣地，對於將堆積體A作爲構成（1-2 )、構成（1-3 ) 、構成（1-4)者，準備將堆積體B作爲構成（2-1)〜構 φ 成（2-3)者。 針對於如此地所構成的各該準分子燈，在放電容器的 管壁負荷成爲〇.6W/cm2的條件下進行點燈，測定連續點燈 15分鐘後的波長150nm〜2 00nrn的波長領域的氙準分子光的 照度，及在一定的管壁負荷下5 00小時連續點燈之後的波長 150nm〜200nm的波長域的氙準分子光的照度。將連續點燈 1 5分鐘後的照度作爲初期照度，而將500小時連續點燈之 後的照度與初期照度之相對値作爲照度維持率，並將「500 小時照度維持率」算出作爲〔（500小時點燈後的照度）/ -27- 200952032 (剛點燈後的照度）〕（％ )。作爲500小時的理由是如 下所述。依不純氣體的照度降低仍繼續至5 00小時，惟其 以後的照度是不會降低，因此含有於紫外線反射層的不純 氣體是可能在500小時爲止之期間被全部放出，而之後就 不會放出。 作爲產品的規格，被要求80%以上的照度維持之故， 因而作爲判定將500小時照度維持率成爲80%時作爲「〇 g 」，而500小時照度維持率成爲80%以下時作爲「X」。 如第4圖所示地，照度測定是在配置於鋁製容器40 的內部的陶瓷製支撐台41上固定準分子燈10，而且在距 準分子燈10的表面lmm的位置，固定紫外線照度測定器 42成爲相對向於準分子燈1〇,在以氮置換鋁製容器40的 內部氣氛的狀態下，在準分子燈10的電極11、12間施加 5. OkV的交流高電壓，藉此在放電容器20的內部發生放電 ，測定經由接地電極1 2的網孔被放射的真空紫外光的照 鲁 度。 將實驗結果表示於第5圖及第6圖。由該結果，在堆 積體A的構成與堆積體B的構成的各該組合中，抽出5 00 小時照度維持率成爲80%以上的準分子燈中，堆積體B的 設置面積成爲最小的組合。例如，堆積體A的構成爲「構 成（1-1)」的組合，而堆積體B的構成爲「構成（2-1) 」的組合中，適合於燈3，作成同樣，適合於燈8、燈13、 燈1 8等。 針對於如此地被抽出的組合，將列述堆積體A的構成 -28- 200952032 ，堆積體B的構成，堆積體B的比表面積，堆積體B的設 置面積者表示於表6。 [表6] 堆積體A 的構成 堆積體B 的構成 堆積體B的比表面積 (xl04cm2/g) 堆積體B的設置面積 (cm2) 構成（1-1) 構成(2-1) 16 43 構成(2-2) 4 53 構成(2-3) 1 55 構成(2-4) 4 53 構成（1-2) 構成(2-1) 16 35 構成(2-2) 4 43 構成(2-3) 1 45 構成（1-3) 構成(2-1) 16 29 構成(2-2) 4 35 構成(2-3) 1 37 構成(1-4) 構成(2-1) 16 10 構成(2-2) 4 10 構成(2-3) 1 14 第7圖是表示表6的結果的圖表。將橫軸作爲堆積體 B的比表面積（xl〇4cm2/g)，而將縱軸作爲堆積體B的 設置面積（cm2 )，每一堆積體a的構成地標示數値。 在表6及第7圖，表示比表面積愈大，抑制照度降低所 必需的設置面積變小的情形。針對於堆積體A的各構成’ 亦即針對於構成（1-1)、構成（1-2)、構成（1-3)，設置 面積是分別與比表面積成比例。但是，在將構成（1-4 )具 備作爲堆積體A的準分子燈，即使增加比表面積，設置面 積是也不會成爲比l〇cm2還要低的數値。 -29 - 200952032 在將構成（1-4)具備作爲堆積體A的準分子燈中’ 對於放電容器的內容積，堆積體B的設置面積過小之故’ 因而擴散至放電空間內的不純氣體到達至堆積體B的機率 變低，成爲無法表現出吸附效果。亦即，對於放電空間的 大小，可說具有最低限度所必需的堆積體B的面積。將放 電空間的大小以放電容器的內表面積表示，這時候，內表 面積是大約500cm2，對此，堆積體B的設置面積是10cm2 。因此，是低限所需的堆積體B的設置面積，是對於放電 容器的內表面積爲〇.〇2倍。 以下，導出第7圖的堆積體A的各構成，亦即構成（ 1-1)、構成（1-2)、構成（1-3)的近似直線的各該傾斜與 切片。將該結果，以列述堆積體A的構成，堆積體A的設 置面積，堆積體B的比表面積與設置面積之關係的傾斜， 堆積體B的比表面積與設置面積之關係的切片者表示於表7 ❹ [表7] 堆積體A 的構成 堆積體A的 設置面積 (cm2) 堆積體B的比表面積與 設置面積之關係的傾斜 (xi〇'4g) 堆積體B的比表面積與 設置面積之關係的切片 (cm2) 構成(1-1) 160 -0.81 56 構成(1-2) 128 -0.67 45 構成(1-3) 107 -0.52 37 第8圖是針對於表7的結果，將橫軸作爲堆積體a的 設置面積（cm2)，而將縱軸作爲堆積體B的比表面積與設 -30- 200952032 置面積之關係的傾斜（xi〇_4g)，而標示數値者。 由圖表可知’堆積體B的比表面積與設面積之關係的 傾斜，是對於堆積體A的設置面積（cm2 )具有負的傾斜的 比例關係。將堆積體A的設置面積作爲a ( cm2 )時，堆積 體B的比表面積與設置面積之關係的傾斜，是可表示作爲 -5 ·0χ 1 0-7xa 〇 第9圖是針對於表7的結果，將橫軸作爲堆積體a的 g 設置面積（cm2 )’而將縱軸作爲堆積體B的比表面積與設 置面積之關係的切片（cm2)，而標示數値者。 由圖表可知，堆積體B的比表面積與設面積之關係的 切片，是對於堆積體A的設置面積（cm2)具有正的傾斜的 比例關係。將堆積體A的設置面積作爲a ( cm2 )時，堆積 體B的比表面積與設置面積之關係的切片，是可表示作爲 0.3 5 xa ° 又，由第7圖堆積體B的設置面積是對於堆積體B的 φ 比表面積，以「堆積體B的比表面積與設置面積之關係的 傾斜」，可說具有作爲「堆積體B的比表面積與設置面積 之關係的切片」的比例關係。藉此，第5圖的堆積體B的 設置面積與堆積體B的比表面積之關係，是將堆積體B的 設置面積作爲b( cm2)，而將堆積體B的比表面積作爲c (cm2/g)時，可表示爲 b=(堆積體B的比表面積與設置面積之關係的傾斜 )xc+ (堆積體B的比表面積與設置面積之關係的切片） -31 - 200952032 又，由第8圖及第9圖的結果，將堆積體a的設置面 積作爲a( cm2)時，則堆積體b的比表面積與設置面積之 關係的傾斜是可表示作爲-5.0xl(r7xa，而堆積體B的比表 面積與設置面積之關係的切片是可表示作爲〇.35xa之故， 因而第7圖的堆積體B的設置面積與堆積體b的比表面積 之關係是如下地可表示。 b = -5.0xl0'7ac + 0.35a g 又，由第5圖及第6圖的實驗結果，堆積體b的設置 面積b’是若比表示於第5圖的堆積體B的設置面積與堆 積體B的比表面積之關係的量還要大，則5〇〇小時照度維 持率成爲80%以上，而被讀取判定成爲〇。 由以上結果’可知在具備含有OH基的堆積體A的準 分子燈中，爲了抑制照度降低。堆積體B的設置面積滿足 以下的關係就可以。 將堆積體A的設置面積作爲a( cm2)，將堆積體b φ 的設置面積作爲b( cm2)，將堆積體B的比表面積作爲c (cm2/ g )時，爲 -5.0xl0*7ac + 0.35a 夂，針對於第7圖中，在將構成（1-4)具備作爲堆積 體A的準分子燈中，即使增加堆積體B的比表面積，堆積 體B的設置面積是不會成爲比10cm2還要低値，而堆積體 B的比表面積與設面積之關係不會成爲將構成（1-1)、構 成（1 -2 )、構成（1 -3 )具備作爲堆積體A的情形。所以， 在表7及第8圖、第9圖中，不考慮將構成（1-4)具備作 -32- 200952032 爲堆積體A的情形。亦即，應滿足上述堆積體b的設置面 積的條件’是作成除掉將構成（1_4)具備作爲堆積體a的 情形者。因此，在須滿足設置面積的條件，必須除掉將構成 (1 -4 )具備作爲堆積體A的情形^ 將構成（1-4)具備作爲堆積體A的情形，對於放電容 器的內容積，堆積體B的設置面積過小之故，因而無法表 現出吸附的效果的情形。亦即，堆積體B的設置面積是對 0 於放電容器的內表面積成爲0.02倍左右時。因此，爲了抑 制照度降低，針對於堆積體B的設置面積b(cm2)的關係 ，將放電容器的內表面積作爲d(cm2)時，也必須滿足以 下的條件。 b> 0.02d 由以上結果，可知在具備含有OH基的堆積體a的準 分子燈中’爲了抑制照度’堆積體B的構成必須滿足以下 的關係。將堆積體A的設置面積作爲a( cin2)，將堆積體 φ B的設置面積作爲b( cm2 )，將堆積體B的比表面積作爲 c ( cm2/ g)，將放電容器的內表面積作爲d ( cm2 )時，必 須滿足如下。 bg-5.0xl(T7ac+0.35a，且 b>0.2d。 藉由滿足上述關係，從堆積體A所放出的不純氣體的 量，不會超過堆積體B可吸附的不純氣體的量，而在放電 空間不會殘留不純氣體。因此，可抑制含有於不純氣體的 氧原子與放電用氣體結合所致的準分子發光的照度降低， 即使長時間點燈時，也可抑制照度降低，而有效率地可射 -33- 200952032 出真空紫外光。 又，堆積體A的設置面積a(cm2)及堆積體B的設 置面積b ( cm2 )，是未考慮到微小粒子的凹凸，而爲堆積 體A或堆積體B的表面假設爲平滑加以計測的數値。又， 放電容器的內表面積d( cm2)也假設其表面爲平滑加以計 測的數値。 ©【圖式簡單說明】 第1圖是表示本發明的準分子燈的一例子的構成的槪 略的說明用斷面圖，第1 (a)圖是表示沿著放電容器的長 度方向的斷面的斷面圖，第1 ( b)圖是表示A-A線斷面 圖。 第2圖是表示準分子燈的實驗結果。 第3圖是表示準分子燈的實驗結果。 第4圖是表示用以說明實施例的準分子燈的照度的測 _ 定方法的斷面圖。 第5圖是表示準分子燈的實驗結果。 第6圖是表示準分子燈的實驗結果。 第7圖是表示準分子燈的實驗結果。 第8圖是表示準分子燈的實驗結果。 第9圖是表示準分子燈的實驗結果。 第10圖是表示習知的準分子燈的構成的槪略的說明 用立體圖。 -34- 200952032 【主要元件符號說明】 1 0 :準分子燈 η:高電壓供應電極 1 2 :接地電極 20 :放電容器 2 1 :上壁板 22 :下壁板 23 :側壁板 24 :端壁板[Table 4] Material particle diameter (V m) Center particle diameter (// m) Component ratio (wt%) Thickness (/zm) Setting area of deposit A (cm2) Composition (1-1) Cerium oxide 0.1 ~ 3.0 0.8 90 50 160 Alumina 0·2 ~ 5.0 0.3 10 Composition (1-2) Ceria 0.1 to 3.0 0.8 90 50 128 Alumina 0.2 to 5.0 0.3 10 Composition (1-3) Ceria 0.1 to 3.0 0.8 90 50 107 Alumina 0.2 to 5.0 0.3 10 Composition (1-4) Ceria 0.1 to 3.0 0.8 90 50 40 Alumina 0.2 to 5.0 0.3 10 Further, as shown in Table 5, for the constitution of the deposition body B, Four types of configuration (2-1), configuration (2-2), configuration (2-3), and configuration (2-4) were prepared. The configuration (2-1), the configuration (2-2), and the configuration (2-3) are composed only of the cerium oxide particles, and the configuration (2-4) is composed of the cerium oxide particles and the aluminum oxide particles. The configuration (2-1), the configuration (2-2), and the configuration (2-3) are performed by changing the particle diameter ' of the cerium oxide particles to 104 cm 2 /g, 4 x 10 4 cm 2 /g, and 1 x 10 4 cm 2 /g. The same. Further, the specific surface area of the composition (2-4) was 4 x 10 cm 2 /g. The larger the specific surface area of the deposit B, the more the impure gas is adsorbed. Therefore, the larger the specific surface area of the deposit B as in the formation (2_1), the larger the surface area of the discharge space, and thus the mixing The amount of impure gas in the discharge space decreases with the lighting meeting -26- 200952032, and the smaller the specific surface area of the stacked body B as constituted by (2-3), the amount of impure gas mixed into the discharge space will follow the lighting Fewer. m 5] Particle diameter (Ai m) Center particle diameter (V m) Component ratio (wt%) Thickness m) Specific surface area (xl04cm2/g) Composition (2-1) Cerium oxide 0.1 to 0.6 0.3 100 20 16 Composition (2-2) Ceria 0.1 to 3.0 0.8 100 20 4 Composition (2-3) Silica 0.2 to 6.0 1.2 100 20 1 Composition (2-4) Ceria 0.1 to 3.0 0.8 90 20 4 Alumina 0.2 ～0.5 0.3 10 For the case where the deposit A is used as the configuration (1-1), the deposit B is prepared as the object of the configuration (2-1) to the configuration (2-4). In addition, for each of the combinations, five types of the installation area of the deposit B are prepared. Similarly, in the case where the deposit A is used as the configuration (1-2), the configuration (1-3), and the configuration (1-4), the deposition body B is prepared as the configuration (2-1) to the configuration φ (2- 3). With respect to each of the excimer lamps thus configured, the tube wall load of the discharge vessel was set to 〇6 W/cm 2 , and the wavelength range of 150 nm to 00 nrn after continuous lighting for 15 minutes was measured. The illuminance of the quasi-molecular light, and the illuminance of the quasi-excimer light in the wavelength range of 150 nm to 200 nm after continuous lighting for 500 hours under a certain wall load. The illuminance after continuous lighting for 15 minutes was used as the initial illuminance, and the relative illuminance after the continuous lighting for 500 hours was used as the illuminance maintenance rate, and the "500-hour illuminance maintenance rate" was calculated as [(500 hours). Illumination after lighting) / -27- 200952032 (illuminance after lighting) (%). The reason for 500 hours is as follows. The illuminance reduction of the impure gas continues for up to 500 hours, but the subsequent illuminance does not decrease, so the impure gas contained in the ultraviolet reflecting layer may be completely released during the period of 500 hours, and then will not be released. As the specification of the product, 80% or more of the illuminance is required to be maintained. Therefore, it is determined as "〇g" when the 500-hour illuminance maintenance rate is 80%, and "X" when the 500-hour illuminance maintenance rate is 80% or less. . As shown in Fig. 4, the illuminance measurement is performed by fixing the excimer lamp 10 on the ceramic support table 41 disposed inside the aluminum container 40, and fixing the ultraviolet illuminance at a position of 1 mm from the surface of the excimer lamp 10. In the state in which the internal gas of the aluminum container 40 is replaced with nitrogen, the AC 42 is applied with an alternating high voltage of 5.0 volts between the electrodes 11 and 12 of the excimer lamp 10. A discharge occurs inside the discharge vessel 20, and the illuminance of the vacuum ultraviolet light emitted through the mesh of the ground electrode 12 is measured. The experimental results are shown in Figures 5 and 6. As a result, in each of the combinations of the configuration of the stacked body A and the configuration of the stacked body B, in the excimer lamp in which the illuminance maintenance ratio of the 500-hour hour is 80% or more, the installation area of the deposited body B is the smallest combination. For example, the configuration of the deposit body A is a combination of "form (1-1)", and the configuration of the deposit body B is "combination (2-1)", which is suitable for the lamp 3, and is similar to the lamp 8 , lamp 13, lamp 18 and so on. With respect to the combination thus extracted, the configuration of the stacked body A will be described -28-200952032, and the configuration of the stacked body B, the specific surface area of the deposited body B, and the installation area of the deposited body B are shown in Table 6. [Table 6] Composition of the deposited body A The specific surface area of the deposited body B (x10 cm 2 /g) The installed area of the deposited body B (cm 2 ) Composition (1-1) Composition (2-1) 16 43 Composition ( 2-2) 4 53 Structure (2-3) 1 55 Structure (2-4) 4 53 Structure (1-2) Structure (2-1) 16 35 Structure (2-2) 4 43 Structure (2-3) 1 45 Structure (1-3) Structure (2-1) 16 29 Structure (2-2) 4 35 Structure (2-3) 1 37 Structure (1-4) Structure (2-1) 16 10 Structure (2- 2) 4 10 Composition (2-3) 1 14 Figure 7 is a graph showing the results of Table 6. The horizontal axis is the specific surface area (xl 〇 4 cm 2 /g) of the deposition body B, and the vertical axis is the installation area (cm 2 ) of the deposition body B, and the number of structures of each deposition body a is indicated by 値. Tables 6 and 7 show the case where the larger the specific surface area, the smaller the installation area necessary for suppressing the decrease in illuminance. With respect to the respective configurations of the stacked body A, that is, for the configuration (1-1), the configuration (1-2), and the configuration (1-3), the installation areas are respectively proportional to the specific surface area. However, in the excimer lamp having the configuration (1-4) as the deposition body A, even if the specific surface area is increased, the installation area does not become a number lower than l〇cm2. -29 - 200952032 In the excimer lamp having the configuration (1-4) as the deposit A, 'the internal volume of the discharge vessel B is too small for the internal volume of the discharge vessel', so that the impure gas diffused into the discharge space reaches The probability of the deposit B is lowered, and the adsorption effect cannot be exhibited. That is, the size of the discharge space B can be said to have the minimum required area of the deposition body B. The size of the discharge space is expressed by the internal surface area of the discharge vessel. At this time, the inner surface area is about 500 cm 2 , and the arrangement area of the deposition body B is 10 cm 2 . Therefore, the installation area of the deposition body B required for the lower limit is 〇.〇2 times the internal surface area of the discharge container. Hereinafter, each configuration of the stacked body A of Fig. 7 is derived, that is, the inclination and the slice of the approximate straight line constituting (1-1), the configuration (1-2), and the configuration (1-3). This result shows the structure of the deposit A, the installation area of the deposit A, the inclination of the relationship between the specific surface area of the deposit B and the installation area, and the slicer of the relationship between the specific surface area of the deposit B and the installation area is shown in Table 7 ❹ [Table 7] Configuration area of the deposit A: The installation area (cm2) of the deposit A The inclination of the relationship between the specific surface area of the deposit B and the installation area (xi〇'4g) The specific surface area and the installation area of the deposit B Section of relationship (cm2) Composition (1-1) 160 -0.81 56 Composition (1-2) 128 -0.67 45 Composition (1-3) 107 -0.52 37 Figure 8 is for the result of Table 7, the horizontal axis As the installation area (cm2) of the deposition body a, the vertical axis is used as the inclination (xi〇_4g) of the relationship between the specific surface area of the deposition body B and the area of the -30-200952032, and the number is marked. As can be seen from the graph, the inclination of the relationship between the specific surface area of the deposit B and the set area is a proportional relationship with respect to the installation area (cm2) of the deposit A. When the installation area of the deposit A is a (cm2), the inclination of the relationship between the specific surface area of the deposit B and the installation area can be expressed as -5 · 0 χ 1 0 - 7xa 〇 Fig. 9 is for Table 7. As a result, the horizontal axis represents the area (cm2) of g of the deposit a, and the vertical axis represents the slice (cm2) of the relationship between the specific surface area of the deposit B and the installation area, and the number is marked. As is clear from the graph, the slice of the relationship between the specific surface area of the deposit B and the set area has a proportional relationship with respect to the installation area (cm2) of the deposit A. When the installation area of the deposit A is a (cm2), the slice of the relationship between the specific surface area of the deposit B and the installation area can be expressed as 0.3 5 xa °, and the installation area of the stack B by the seventh figure is The φ specific surface area of the deposit B is proportional to the relationship between the specific surface area of the deposit B and the installation area, and has a proportional relationship as a "slice of the relationship between the specific surface area of the deposit B and the installation area". Therefore, the relationship between the installation area of the deposition body B in FIG. 5 and the specific surface area of the deposition body B is such that the installation area of the deposition body B is b (cm2), and the specific surface area of the deposition body B is c (cm2/). g) can be expressed as b = (inclination of the relationship between the specific surface area of the deposit B and the set area) xc + (slice of the relationship between the specific surface area of the deposit B and the set area) -31 - 200952032 As a result of the ninth figure, when the installation area of the deposit a is a (cm2), the inclination of the relationship between the specific surface area of the deposit b and the installation area can be expressed as -5.0xl (r7xa, and the stack B) The slice of the relationship between the specific surface area and the installation area is 〇.35xa, and therefore the relationship between the installation area of the deposit B of Fig. 7 and the specific surface area of the deposit b can be expressed as follows: b = -5.0xl0 '7ac + 0.35ag Further, from the experimental results of Fig. 5 and Fig. 6, the installation area b' of the deposition body b is the ratio of the installation area of the deposition body B shown in Fig. 5 to the specific surface area of the deposition body B. The amount of relationship is even larger, and the illuminance maintenance rate of 5 〇〇 is 80% or more, and is read and judged. From the above results, it is understood that in the excimer lamp including the deposition body A containing an OH group, the illuminance is reduced. The installation area of the deposition body B satisfies the following relationship. The installation area of the deposition body A is taken as a ( cm2), the area where the deposition body b φ is set is b (cm2), and when the specific surface area of the deposition body B is c (cm2/g), it is -5.0xl0*7ac + 0.35a 夂, for the seventh In the excimer lamp having the configuration (1-4) as the deposition body A, even if the specific surface area of the deposition body B is increased, the installation area of the deposition body B does not become lower than 10 cm 2 and is deposited. The relationship between the specific surface area of the body B and the area is not such that the configuration (1-1), the configuration (1 -2), and the configuration (1 -3) are provided as the deposition body A. Therefore, in Tables 7 and 8 In the figure and the ninth figure, the case where the configuration (1-4) is provided as -32-200952032 as the deposit A is not considered. That is, the condition that the installation area of the above-mentioned stack b should be satisfied is formed by being removed. (1_4) has the situation as the deposit body a. Therefore, it must be removed in the condition that the set area must be satisfied. In the case where the configuration (1 - 4 ) is provided as the deposition body A, the configuration (1-4) is provided as the deposition body A. Since the internal volume of the discharge vessel is too small, the installation area of the deposition body B is too small, so that it cannot be expressed. In the case of the effect of the adsorption, that is, the installation area of the deposition body B is about 0.02 times the internal surface area of the discharge vessel. Therefore, in order to suppress the decrease in the illuminance, the installation area b (cm2) of the deposition body B is In the relationship, when the internal surface area of the discharge vessel is taken as d (cm2), the following conditions must also be satisfied. b> 0.02d From the above results, it is understood that the following relationship must be satisfied in order to suppress the illuminance of the deposit B in the quasi-molecular lamp including the OH group-containing deposit a. The area where the deposit A is set is a (cin2), the area where the deposit φ B is set is b (cm2), the specific surface area of the deposit B is c (cm2/g), and the inner surface area of the discharge vessel is taken as d (cm2) must be satisfied as follows. Bg-5.0xl (T7ac+0.35a, and b>0.2d. By satisfying the above relationship, the amount of impure gas released from the stack A does not exceed the amount of impure gas that the stack B can adsorb, but Since the impurity gas does not remain in the discharge space, the illuminance of the excimer light emission caused by the combination of the oxygen atom contained in the impurity gas and the discharge gas can be suppressed, and the illuminance can be suppressed and the efficiency can be suppressed even when the lamp is turned on for a long time. In addition, the installation area a (cm2) of the deposit A and the installation area b (cm2) of the deposit B are not considered to be irregularities of the fine particles, but are the stack A. Or the surface of the stack B is assumed to be a smooth measured number. In addition, the internal surface area d (cm2) of the discharge vessel is also assumed to be a smooth number measured on the surface. © [Simple diagram] Figure 1 is a representation BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1(a) is a cross-sectional view showing a cross section along the longitudinal direction of the discharge vessel, and FIG. 1(b) is a schematic cross-sectional view showing an example of the configuration of the excimer lamp of the present invention. Is a cross-sectional view of the AA line. Figure 2 shows the standard deviation. Fig. 3 is a cross-sectional view showing a method for measuring the illuminance of the excimer lamp of the embodiment. Fig. 5 is a cross-sectional view showing the method of measuring the illuminance of the excimer lamp of the embodiment. The experimental results of the lamp. Fig. 6 is an experimental result showing an excimer lamp. Fig. 7 is an experimental result showing an excimer lamp. Fig. 8 is an experimental result showing an excimer lamp. Fig. 9 is a view showing an experimental result of an excimer lamp. Fig. 10 is a perspective view showing a schematic configuration of a conventional excimer lamp. -34- 200952032 [Explanation of main component symbols] 1 0 : Excimer lamp η: high voltage supply electrode 1 2 : ground Electrode 20: discharge vessel 2 1 : upper wall plate 22 : lower wall plate 23 : side wall plate 24 : end wall plate
3 0 :紫外線反射層 3 1 :堆積體A3 0 : ultraviolet reflective layer 3 1 : stack A
32 :堆積體B 40 :鋁製容器 41 :支撐台 42 :紫外線照度測定器 S :放電空間 -3532 : Stacking body B 40 : Aluminum container 41 : Support table 42 : Ultraviolet illuminance measuring device S : Discharge space -35