200941540 九、發明說明 【發明所屬之技術領域】 本發明是關於具備石英玻璃所成的放電容器’在介設 有形該放電容器的石英玻璃的狀態下設有一對電極所成’ - 而在上述放電容器的內部發生準分子放電的準分子燈。 【先前技術】 0 近年來，開發了藉由將波長200nm以下的真空紫外 光照射在金屬、玻璃及其他材料所成的被處理體，而藉由 該真空紫外光及由此所生成的臭氧的作用來處理被處理體 的技術，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，使用例如藉由準分子放 電形成準分子分子，而將利用從該準分子分子所放射的光 〇 例如波長1 7〇nm附近的準分子燈具備作爲光源者。在此 種準分子燈中，爲了更有效率地放射更高強度的紫外線， 實施很多嘗試。 第1圖是表示準分子燈的構成的說明用斷面圖，（a) 是表示沿著放電容器2的長度方向的斷面的橫斷面圖，（b) 是表示（a)的A-A線斷面圖。 依據記載於日本特開2007-335350公報，準分子燈 1 ’是具備透射紫外線的合成石英玻璃所成的放電容器 2 ’而在該放電容器2的內側與外側分別設有電極5、6， -5- 200941540 在曝露於放電容器2的放電空間S的表面的一部分，形成 紫外線反射膜8。作爲紫外線反射膜8,僅由二氧化矽粒 子所成者，及僅由含有三氧化矽粒子的紫外線散射粒子所 成者被例示。 • 在該準分子燈1中，在放電容器2，形成有藉由未形 . 成有紫外線反射膜8進行出射在放電空間S內所發生的紫 外線的光出射部7。 © 依照此種構成的準分子燈1，在被曝露於放電容器2 的放電空間S的表面，藉由設有紫外線反射膜8，在設有 紫外線反射膜8的領域中，發生在放電空間S內的紫外線 藉由紫外線反射膜8被反射之故，因而會減小依透射於合 成石英玻璃所致的衰減。又，藉由紫外線反射膜8被反 射，而僅在構成光出射部7的領域，紫外線透射石英玻璃 被放射至外部之故，因而有效率地可照射在放電空間S內 所發生的紫外線。而且，紫外線反射膜8藉由以二氧化矽 〇 粒子作爲主體所構成，而對於合成石英玻璃所成的放電容 器2可得到高親和性。 專利文獻1 :日本特開2007-335350公報 【發明內容】 可是，近年來照射對象的液晶面板顯示元件的基板隨 著大面積化，準分子燈1也成爲長度化，例如被要求全長 度超過800nm的準分子燈1。然而，在此種長度化的準分 子燈1中，會在點燈中發生放電容器2破碎的不方便。 -6- 200941540 本發明是爲了解決上述問題而創作者，其目的是在於 提供在放電空間內發生準分子放電而放射真空紫外光的準 分子燈，可解決點燈中放電容器破碎的不方便的準分子 燈。 • 本案發明的第1項發明，是屬於內側管與外側管朝同 . 軸方向所配置的雙重管構造的石英玻璃所成的放電容器， 及介於形成該放電容器的石英玻璃的狀態設有一對電極所 〇 成’在放電空間內封入有氙氣體所成，在上述放電容器的 放電空間內發生準分子放電的準分子燈，其特徵爲： 上述內側管是藉由熔融石英玻璃所形成，上述外側管 是藉由合成石英玻璃所形成。 又，本案發明的第2項發明，是在本案發明的第1項 發明中，上述放電容器是在至少被曝露於內側管的外周面 的放電空間的表面全領域全面，形成有藉由包含二氧化矽 粒子的紫外線散射粒子所構成的紫外線反射膜，爲其特徵 ❿ 者。 又，本案發明的第3項發明，是在本案發明的第2項 發明中，上述內側管是藉由電性熔融石英玻璃所形成，上 述二氧化矽粒子是藉由合成石英玻璃所形成，爲其特徵 者。 又，本案發明的第4項發明，是在本案發明的第2項 發明或第3項發明中，形成於上述內側管的外周面的紫外 線反射膜的膜厚，是1〇μπι以上，爲其特徵者。 又，本案發明的第5項發明，是在本案發明的第2項 200941540 發明至第4項發明中任一項發明中，在上述紫外線散射粒 子，包含氧化鋁粒子，爲其特徵者。 依照本案發明第1項的準分子燈，將容易成爲高溫的 內側管藉由熔融石英玻璃所構成，而將溫度比內側管維持 還要低的外側管藉由合成石英玻璃所構成，藉此，依外側 . 管與內側管之間的熱脹所致的收縮差會變小，而可解決在 準分子燈的點燈中，使得放電容器破碎的不方便。 Q 又，依照本案發明的第2項發明的準分子燈，即使以 熔融石英玻璃來構成內側管，也藉由將紫外線反射膜形成 在被曝露於內側管外周面的放電空間的表面全領域全面， 就可防止真空紫外光被照射在內側管，而可抑制放電容器 的劣化。因此，即使在放電空間內發生準分子放電而放射 真空紫外光的準分子燈，也可將構成放電容器的內側管藉 由熔融石英玻璃所構成。 又，依照本案發明的第3項發明的準分子燈，在藉由 〇 電性熔融石英玻璃所形成的內側管外周面，形成包含合成 石英玻璃所成的二氧化矽粒子的紫外線散射粒子所成的紫 外線反射膜，藉此，包含缺氧型缺陷（Si-Si)的內側管與包 ' 含OH基的紫外線反射膜進行反應，以Si-H形態化學性 地耦合之故，因而提高內側管與紫外線反射膜之附著界面 的密接性，而有效果地可防止紫外線反射膜被剝落的情 形。 又，依照本案發明的準分子燈，藉由在內側管外周 面’形成紫外線反射膜成爲膜厚1 0 μ m以上，在紫外線反 -8- 200941540 射膜幾乎完全地遮斷真空紫外光，而可作爲真空紫外光不 會照射到內側管。因此，可防止紫外線的能量被蓄積在內 側管，而可抑制以紫外線所致的失真作爲原因的劣化。 又，依照本案發明的第5項發明的準分子燈，藉由在 - 紫外線反射膜包含氧化鋁粒子，而可防止以粒子彼此間被 . 耦合互相地鄰接的二氧化矽粒子與氧化鋁粒子而被維持著 粒界，就可抑制降低紫外線反射膜的反射率。 〇 【實施方式】 第1圖是表示準分子燈1的構成的說明用斷面圖，第 1U)圖是表示沿著放電容器2的長度方向的斷面的橫斷面 圖，第1(b)圖是表示第1(a)圖的A-A線斷面圖。 準分子燈1是具有圓筒狀外側管3與圓筒狀內側管4 所成的放電容器2。放電容器2是例如管軸方向的長度爲 800〜1600nm，外側管3的直徑爲25〜40 mm，而內側管4 G 的直徑成爲15〜30mm。 內側管4的直徑是構成比外側管3的直徑還要小，而 在外側管3的內部配置內側管4。沿著外側管3的管軸配 置有內側管4之故，因而放電容器2是成爲外側管3與內 側管4朝同軸方向所配置的雙重管構造。藉由焊著外側管 2與內側管4的端部形成有側端部9 ’而外側管3的內周 面3a與內側管4的外周面4b之間成爲氣密空間，使得氣 密地被密閉的環狀放電空間S形成於放電容器2的內部。 放電容器2是藉由良好地透射真空紫外光的石英玻璃 -9- 200941540 所構成，惟外側管3及側壁部9是由金屬不純物的濃度低 的合成石英玻璃所構成，而內側管4是由金屬不純物的濃 度比合成石英玻璃還要高的熔融石英玻璃所構成。 在外側管3，密接於外周面3b，設有如金屬網等的導 - 電性材料所成的網狀外側電極5。外側電極5是無縫地編 . 織金屬線成圓筒狀者之中插入放電容器2者，呈網狀形 狀，而從網目之間可放射出光。 Q 在內側管4，密接於內周面4a，設有如鋁所成的管狀 的內側電極6。內側電極6是沿著內側管4的管軸方向所 形成，惟在距管軸方向兩端約20mm的範圍形成有未設置 內側電極6的空隙。又，內側電極6是在斷面具有局部切 除的大約C形狀（槽狀）也可以。 外側電極5與內側電極6，是隔著構成放電容器2的 石英玻璃，配置成互相地相對的狀態。藉由如此地構成， 構成放電容器2的石英玻璃也可發揮作爲介質的功能。 〇 又，在放電容器2的放電空間S，作爲放電用氣體， 封入有氙氣體。在此，氙氣體是作成在常溫下壓力成爲如 10〜60kPa(100〜600mbar)的範圍內的封入量。 當高頻電壓供應於外側電極5與內側電極6之間，介 設功能作爲介質的石英玻璃的放電容器2而在兩電極間生 成著放電。爲了防止對周圍構件的漏電，將露出於準分子 燈1的外部所配置的外側電極5作爲接地電極，並將配置 於準分子燈1的內部的內側電極6作爲供應電極較佳。 在放電空間S封入有放電用氣體之故，因而藉由外側 -10- 200941540 電極5與內側電極6之間的放電形成準分子分子，而且發 生真空紫外光從該準分子分子所放射的準分子放電。作爲 放電用氣體使用氙氣體時，在波長具有峰値的真 空紫外線被放出。 • 當點亮準分子燈1，電力供應被形成於放電容器2的 . 表面外側電極5與內側電極6之故，因而也會傳熱到放電 容器2而被加溫。被曝露在放電空間S的內側管4的外周 0 面4b的面積，是比外側管3的內周面3a的面積還要小。 在外側電極5與內側電極6，接通有大約相同程度的電力 量之故，因而面積小的內側管4的外周面4b的每一單位 面積的接通電力，是成爲比外側管3的內周面3a的每一 單位面積的接通電力還要大。 又，外側管3的外周面3b是被曝露在外氣而容易被 散熱，惟內側管4是被圍繞在放電空間S之故’因而只要 未積極地冷卻內側管4的內周面4a’會容易蓄熱。雙重 φ 構造的放電容器2是藉由構造性特徵，在準分子燈1的點 燈中，內側管4會比外側管3成還要高溫。 不限於石英玻璃，物質是溫度變愈高’則具有愈膨脹 的性質。雙重管構造的放電容器2是在點燈時內側管4會 比外側管3成爲還高溫，而更大地膨脹之故，因而會發生 放電容器2破碎的不方便者。如此，發現了須將外側管3 藉由熱脹大的構件所構成’並須將內側管4藉由熱脹小的 構件所構成。 依據玻璃工學手冊（日本朝會書店）第48 8頁的記載’ -11 - 200941540 在合成石英玻璃中，150 °C的膨脹係數爲〇.54xl〇·6· Κ·1， 而在310°C的膨脹係數爲〇·59χ1(Γ6 · Κ—1。一方面，在熔 融石英玻璃，310°C的膨脹係數爲〇.55xl(T6 . Κ·1。由此些 數値，可知在石英玻璃中，熔融石英玻璃是熱脹比石英玻 - 璃還要小。 - 將容易成爲高溫的內側管4藉由熔融石英玻璃所構 成，並將溫度比內側管4維持在低的外側管3藉由合成石 〇 英玻璃所構成，藉此依外側管3與內側管4之間的熱脹所 致的收縮差變小，就可解決在準分子燈1的點燈中使得放 電容器2破碎的不方便。 又，合成石英玻璃，熔融石英玻璃，都是以二氧化矽 (Si〇2)作爲主成分的石英玻璃的一種之故，因而即使外側 管3與內側管4作成膨脹率不相同的構件，也容易進行加 工。 準分子燈1是爲了有效率地利用藉由準分子放電所發 Ο 生的真空紫外光，在被曝露於放電容器2的放電空間S的 表面’也可設置紫外線散射粒子所成的紫外線反射膜8, 尤其是在內側管4的外周面4b，被曝露在放電空間S的 表面全領域全面形成有紫外線反射膜8。一方面，外側管 3是藉由未形成有紫外線反射膜8，構成有用以將在放電 空間S所發生的真空紫外線照射有放電容器2的外部的光 出射部7。又，在外側管3的內周面3a或外周面3b的一 部分形成紫外線反射膜8，也可提高真空紫外光的利用效 率。 -12- 200941540 構成內側管4的熔融石英玻璃，是比合成石英玻璃， 容易吸收光的波長爲150nm〜3 80nm範圍的真空紫外光。 被吸收的紫外線的能量積有在放電容器2，而產生失真且 容易劣化。但是，藉由被曝露在內側管4的外周面4b的 - 放電空間S的表面全領域全面形成紫外線反射膜8，可防 . 止真空紫外光被照射在內側管4，而可抑制放電容器2的 劣化。 © 紫外線反射膜8是藉由其本體是高折射率的具真空紫 外光透射性的陶瓷所成的微小粒子所構成，具體上，藉由 包含二氧化矽粒子的紫外線散射粒子所構成。將紫外線散 射粒子藉由陶瓷所構成，藉此減低從紫外線反射膜8所發 生不純氣體的量，又，具有射於放電的特性。到達至該紫 外線散射粒子的真空紫外光的一部分在粒子表面被反射， 而且其他一部分折射而被入射至粒子內部，又，被入射於 粒子內部的很多光被透射（一部分被吸收），而在再出射時 〇 被折射。具有重複進行此種反射，折射的「擴散反射（散 射反射）」的功能。 作爲構成紫外線反射膜8的紫外線散射粒子，例如使 用著將合成石英玻璃粉末狀地作成細小粒子的二氧化矽粒 子。若二氧化矽粒子是由合成石英玻璃所構成，粒子徑爲 例如在〇.〇1〜20μιη的範圍內者，中心粒徑（數平均粒徑的 峰値）爲例如〇·1〜ΙΟμχη者較佳，更佳爲〇.3〜3.0μιη者。 又，被包含於紫外線反射膜8的二氧化矽粒徑的分布是不 會擴散劑到廣範圍者較佳，使用粒徑成爲中心粒徑的數値 -13- 200941540 的二氧化矽粒子成爲一半以上的方式被選別的二氧化矽粒 子較佳。 一般，光是碰到粒徑較大的粒子會反射，惟粒徑變 小，則光碰到粒子也不會反射，而會產生散射。光的散射 • 是依粒子的大小被分類成三種，粒子徑比波長還要小時’ . 則產生瑞利（R a y 1 e i g h)散射，而粒子徑與波長相同程度 時，則產生米民（Me i)散射，粒子徑比波長還要大時’則 〇 產生非選擇性散射。 尤其是，瑞利散射是被散射的光強度具依存於光的波 長的特徵。具體而言，若入射光的波長短，則散射光的強 度變小，而若入射光的波長長，則散射光的強度變小。若 在紫外線反射膜8發生該瑞利散射，則可將所謂紫外線或 真空紫外線的短波長的光，作成光強度大的散射光。 發生在準分子燈1的放電容器2內部的光波長是在 150nm〜380nm的範圍之故，因而藉由將二氧化矽粒子及 〇 氧化鋁粒子的粒子徑作成Ο.ΟΙμπι〜20μιη的範圍內，並藉 由將中心粒徑作成0.3 μιη〜3.0 μιη，就可作成在紫外線反 射膜8發生瑞利散射的情形。又，即使將二氧化矽粒子作 成比上述範圍還要更小而構成容易發生瑞利散射，則二氧 化矽粒子的燒結也進行而會消滅粒界，反而會失去光的散 射性能。 構成紫外線反射膜8的「粒子徑」，是指將紫外線反 射膜8對於其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 -14- 200941540 (SEM)取得擴大投影像，而以一定方向的兩條平行線隔著 該擴大投影像的任意粒子時的該平行線的間隔的弗雷特 (Feret’s)直徑。 又’構成紫外線反射膜8的「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Ο.ίμιη的範圍分成複數區分，例如 區分成約15區分，屬於各個區分的粒子個數（度數）成爲 Q 最大的區分的中心値。 構成紫外線散射粒子的二氧化矽粒子藉由局部熔融 等，而將紫外線反射膜8附著於放電容器2。一般，線膨 脹係數値相等或是近似者，具有容易接著的性質。二氧化 矽粒子是與石英玻璃所成的放電容器2，線膨脹係數値大 約相等之故，因而具有提高與放電容器2的接著力的功 ft ° 內側管4是在熔融石英玻璃中，尤其是由電性熔融石 〇 英玻璃（型式1)所構成者較佳。電性熔融石英玻璃（型式1) 是包含於材料中的OH濃度爲極低至lOppm以下，具有缺 氧型缺陷（Si-Si)的特徵。電性熔融石英玻璃（型式1)是幾 乎由二氧化矽與氧氣耦合（Si-O)所構成’惟在一部分具有 缺氧型缺陷（Si-Si)。 一方面，由合成石英玻璃所構成的二氧化矽粒子’是 幾乎藉由耦合二氧化矽與氧氣（Si-O)所構成’惟OH基存 在於一部分，缺氧型缺陷（Si-Si)是幾乎不存在。〇H基是 具有容易斷開原子間的化學耦合，而把氫氣（H)容易成爲 -15- 200941540 單獨的特徵。由合成石英玻璃所構成的二氧化矽粒子，是 包含於材料中的OH的濃度爲大約3 0 0ppm，而會斷開原 子間的化學耦合，容易發生成爲單獨的氫氣（H)。 構成紫外線反射膜8的合成石英玻璃的二氧化矽粒 子，是當成爲600°C以上的高溫，則發生斷開OH基原子 . 間的化學耦合而成爲單獨的氫氣（H)，使得氫氣（H)會擴 散。若將紫外線反射膜8附著於由熔融石英玻璃所構成的 〇 內側管4的外周面4b而以600 °c以上的高溫進行燒成， 則發生如下所示的化學式的反應。 [化1]200941540 IX. The present invention relates to a discharge vessel having quartz glass formed by providing a pair of electrodes in a state in which quartz glass having the discharge vessel is placed. An excimer lamp in which an excimer discharge occurs inside the container. [Prior Art] 0 In recent years, a vacuum-ultraviolet light having a wavelength of 200 nm or less is irradiated onto a metal, glass, and other materials, and the vacuum ultraviolet light and ozone generated thereby are developed. A technique for processing a target object, for example, a cleaning treatment technique for removing an organic contaminant attached to a surface of a target object or an oxide film formation treatment technique for forming an oxide film on the surface of the object to be processed, is put to practical use. As the means for irradiating the vacuum ultraviolet light, for example, excimer molecules are formed by excimer discharge, and an excimer lamp having a wavelength of about 1 〇 nm, which is emitted from the excimer molecule, is used as a light source. In such an excimer lamp, many attempts have been made to emit higher intensity ultraviolet rays more efficiently. Fig. 1 is a cross-sectional view for explaining the configuration of an excimer lamp, wherein (a) is a cross-sectional view showing a cross section along the longitudinal direction of the discharge vessel 2, and (b) is a line AA showing (a). Sectional view. According to JP-A-2007-335350, the excimer lamp 1' is a discharge vessel 2' made of synthetic quartz glass that transmits ultraviolet rays, and electrodes 5 and 6 are provided inside and outside the discharge vessel 2, respectively. 5-200941540 The ultraviolet reflecting film 8 is formed on a part of the surface of the discharge space S exposed to the discharge vessel 2. The ultraviolet reflecting film 8 is exemplified by only the cerium oxide particles and only the ultraviolet ray scattering particles containing the cerium oxide particles. In the excimer lamp 1, the discharge vessel 2 is formed with a light emitting portion 7 which is emitted from the ultraviolet ray reflecting film 8 and which is emitted into the ultraviolet ray in the discharge space S. © The excimer lamp 1 having such a configuration, on the surface of the discharge space S exposed to the discharge vessel 2, by providing the ultraviolet ray reflection film 8, in the field in which the ultraviolet ray reflection film 8 is provided, occurs in the discharge space S The ultraviolet rays inside are reflected by the ultraviolet reflecting film 8, and thus the attenuation by the transmission of the synthetic quartz glass is reduced. Further, since the ultraviolet ray reflecting film 8 is reflected, the ultraviolet ray transmitting quartz glass is radiated to the outside only in the field constituting the light emitting portion 7, so that the ultraviolet ray generated in the discharge space S can be efficiently irradiated. Further, the ultraviolet ray reflection film 8 is composed mainly of cerium oxide cerium particles, and high affinity is obtained for the discharge capacitor 2 formed of synthetic quartz glass. In the recent years, the substrate of the liquid crystal panel display element to be irradiated has a large area, and the excimer lamp 1 has also been lengthened. For example, it is required that the total length exceeds 800 nm. Excimer lamp 1. However, in such a lengthened quasi-molecular lamp 1, the inconvenience of the discharge of the discharge vessel 2 occurs in the lighting. -6- 200941540 The present invention has been made in order to solve the above problems, and an object thereof is to provide an excimer lamp which emits a vacuum ultraviolet light by generating an excimer discharge in a discharge space, and can solve the inconvenience of the discharge of the discharge capacitor in the lighting. Excimer lamp. The first invention of the present invention is a discharge vessel formed of quartz glass having a double tube structure in which an inner tube and an outer tube are oriented in the axial direction, and a state in which quartz glass is formed in a state in which the discharge vessel is formed. An excimer lamp in which an electrode is formed by enclosing a helium gas in a discharge space and an excimer discharge occurs in a discharge space of the discharge vessel, wherein the inner tube is formed of fused silica glass. The outer tube is formed by synthetic quartz glass. According to a second aspect of the present invention, in the first aspect of the invention, the discharge vessel is formed on the surface of the discharge space exposed to at least the outer peripheral surface of the inner tube, and is formed by the entire surface. The ultraviolet ray reflection film composed of the ultraviolet ray scattering particles of the cerium oxide particles is characterized by the ultraviolet ray. According to a third aspect of the present invention, in the second aspect of the invention, the inner tube is formed of electrically fused silica glass, and the ceria particle is formed by synthetic quartz glass. Its characteristics. According to a fourth aspect of the present invention, in the second aspect of the invention, the thickness of the ultraviolet ray reflection film formed on the outer circumferential surface of the inner tube is 1 〇μπι or more. Feature. According to a fifth aspect of the invention, in the invention of the invention of the invention of the invention of the invention of the invention of According to the excimer lamp of the first aspect of the present invention, the inner tube which is likely to be a high temperature is formed of fused silica glass, and the outer tube having a lower temperature than the inner tube is formed of synthetic quartz glass. According to the outer side, the difference in shrinkage caused by thermal expansion between the tube and the inner tube becomes small, and the inconvenience of breaking the discharge vessel in the lighting of the excimer lamp can be solved. Further, according to the excimer lamp of the second aspect of the invention, the inner tube is formed of fused silica glass, and the ultraviolet ray reflection film is formed on the surface of the discharge space exposed to the outer peripheral surface of the inner tube. In this way, vacuum ultraviolet light is prevented from being irradiated on the inner tube, and deterioration of the discharge vessel can be suppressed. Therefore, the inner tube constituting the discharge vessel can be constituted by fused silica glass even if the excimer lamp which emits the vacuum ultraviolet light in the discharge space generates excimer discharge. Further, in the excimer lamp according to the third aspect of the present invention, the outer peripheral surface of the inner tube formed of the fused silica glass forms ultraviolet ray scattering particles containing cerium oxide particles formed of synthetic quartz glass. The ultraviolet reflecting film, whereby the inner tube containing the oxygen-deficient type defect (Si-Si) reacts with the ultraviolet-reflecting film containing the OH group, and is chemically coupled in the Si-H form, thereby improving the inner tube The adhesion to the interface of the ultraviolet ray reflection film is effective to prevent the ultraviolet ray reflection film from being peeled off. Further, according to the excimer lamp of the present invention, by forming the ultraviolet ray reflection film on the outer peripheral surface of the inner tube to have a film thickness of 10 μm or more, the ultraviolet ray -8-200941540 film almost completely blocks the vacuum ultraviolet light. It can be used as vacuum ultraviolet light without illuminating the inner tube. Therefore, it is possible to prevent the energy of the ultraviolet rays from being accumulated in the inner side tube, and it is possible to suppress deterioration due to distortion due to ultraviolet rays. Further, according to the excimer lamp of the fifth aspect of the invention, the ultraviolet ray-reflecting film contains the alumina particles, thereby preventing the cerium oxide particles and the alumina particles which are adjacent to each other by the coupling of the particles. By maintaining the grain boundary, it is possible to suppress the decrease in the reflectance of the ultraviolet ray reflection film. [Embodiment] FIG. 1 is a cross-sectional view for explaining the configuration of the excimer lamp 1, and FIG. 1U is a cross-sectional view showing a cross section along the longitudinal direction of the discharge vessel 2, and the first (b) Fig. 1 is a cross-sectional view taken along line AA of Fig. 1(a). The excimer lamp 1 is a discharge vessel 2 having a cylindrical outer tube 3 and a cylindrical inner tube 4. The discharge vessel 2 has a length of, for example, 800 to 1600 nm in the tube axis direction, a diameter of 25 to 40 mm in the outer tube 3, and a diameter of 15 to 30 mm in the inner tube 4 G. The diameter of the inner tube 4 is smaller than the diameter of the outer tube 3, and the inner tube 4 is disposed inside the outer tube 3. Since the inner tube 4 is disposed along the tube axis of the outer tube 3, the discharge tube 2 has a double tube structure in which the outer tube 3 and the inner tube 4 are disposed in the coaxial direction. The end portion 9' is formed by welding the end portions of the outer tube 2 and the inner tube 4, and the inner peripheral surface 3a of the outer tube 3 and the outer peripheral surface 4b of the inner tube 4 become an airtight space, so that it is hermetically sealed. The hermetic annular discharge space S is formed inside the discharge vessel 2. The discharge vessel 2 is composed of quartz glass-9-200941540 which transmits vacuum ultraviolet light well, except that the outer tube 3 and the side wall portion 9 are composed of synthetic quartz glass having a low concentration of metal impurities, and the inner tube 4 is composed of A fused silica glass having a higher concentration of metal impurities than synthetic quartz glass. The outer tube 3 is in close contact with the outer peripheral surface 3b, and is provided with a mesh outer electrode 5 made of a conductive material such as a metal mesh. The outer electrode 5 is seamlessly knitted. When the metal wire is formed into a cylindrical shape, the discharge vessel 2 is inserted into a cylindrical shape, and light is emitted from the mesh. Q The inner tube 4 is in close contact with the inner peripheral surface 4a, and is provided with a tubular inner electrode 6 made of aluminum. The inner electrode 6 is formed along the tube axis direction of the inner tube 4, but a gap in which the inner electrode 6 is not provided is formed in a range of about 20 mm from both ends in the tube axis direction. Further, the inner electrode 6 may have a C shape (groove shape) having a partial cut in a cross section. The outer electrode 5 and the inner electrode 6 are placed in a state of being opposed to each other via the quartz glass constituting the discharge vessel 2. With such a configuration, the quartz glass constituting the discharge vessel 2 can also function as a medium. Further, in the discharge space S of the discharge vessel 2, helium gas is sealed as a discharge gas. Here, the helium gas is formed to have a pressure in a range of, for example, 10 to 60 kPa (100 to 600 mbar) at a normal temperature. When a high-frequency voltage is supplied between the outer electrode 5 and the inner electrode 6, a discharge vessel 2 of quartz glass functioning as a medium is interposed to generate a discharge between the electrodes. In order to prevent leakage of the surrounding member, the outer electrode 5 disposed outside the excimer lamp 1 is used as the ground electrode, and the inner electrode 6 disposed inside the excimer lamp 1 is preferably used as the supply electrode. Since the discharge gas is sealed in the discharge space S, the excimer molecules are formed by the discharge between the outer side-10-200941540 electrode 5 and the inner electrode 6, and the excimer from which the vacuum ultraviolet light is emitted from the excimer molecule occurs. Discharge. When helium gas is used as the discharge gas, the ultraviolet ray having a peak 波长 at the wavelength is released. • When the excimer lamp 1 is turned on, the power supply is formed in the surface outer electrode 5 and the inner electrode 6 of the discharge vessel 2, and thus heat is also transferred to the discharge container 2 to be warmed. The area of the outer peripheral surface 0b of the inner tube 4 exposed to the discharge space S is smaller than the area of the inner peripheral surface 3a of the outer tube 3. Since the outer electrode 5 and the inner electrode 6 are connected to the same amount of electric power, the electric power per unit area of the outer peripheral surface 4b of the inner tube 4 having a small area is larger than that of the outer tube 3. The power per unit area of the circumferential surface 3a is also large. Further, the outer peripheral surface 3b of the outer tube 3 is exposed to the outside air and is easily dissipated, but the inner tube 4 is surrounded by the discharge space S. Therefore, it is easy to cool the inner peripheral surface 4a' of the inner tube 4 without actively cooling it. Heat storage. The discharge vessel 2 of the double φ configuration is constructed by the fact that in the lighting of the excimer lamp 1, the inner tube 4 is at a higher temperature than the outer tube 3. Not limited to quartz glass, the substance is more turbulent when the temperature becomes higher. In the discharge tube 2 of the double pipe structure, the inner tube 4 is heated to a higher temperature than the outer tube 3 at the time of lighting, and the expansion of the discharge vessel 2 is inconvenient. Thus, it has been found that the outer tube 3 must be constructed by a member which is thermally expanded, and the inner tube 4 must be constituted by a member having a small thermal expansion. According to the glass engineering manual (Japan Chaohui Bookstore), page 48 8 ' -11 - 200941540 In synthetic quartz glass, the expansion coefficient at 150 °C is 54.54xl〇·6· Κ·1, and at 310° The coefficient of expansion of C is 〇·59χ1 (Γ6 · Κ-1. On the one hand, in fused silica glass, the expansion coefficient at 310 ° C is 〇.55xl (T6. Κ·1. From this number, it can be seen that in quartz glass In the fused silica glass, the thermal expansion is smaller than that of the quartz glass. - The inner tube 4 which is easy to be a high temperature is composed of fused silica glass, and the temperature is lower than the inner tube 4 at the outer tube 3 by the inner tube 4. Synthetic sapphire glass is formed, whereby the difference in shrinkage due to thermal expansion between the outer tube 3 and the inner tube 4 is reduced, so that the discharge of the discharge vessel 2 in the lighting of the excimer lamp 1 can be solved. Further, synthetic quartz glass and fused silica glass are one type of quartz glass containing ceria (Si〇2) as a main component, so that even the outer tube 3 and the inner tube 4 are formed as members having different expansion ratios. It is also easy to process. The excimer lamp 1 is used for efficient use. The vacuum ultraviolet light generated by the excimer discharge may be provided with ultraviolet ray scattering particles 8 formed by ultraviolet ray scattering particles on the surface of the discharge space S exposed to the discharge vessel 2, particularly on the outer peripheral surface 4b of the inner tube 4. The ultraviolet reflecting film 8 is integrally formed on the surface exposed to the discharge space S. On the one hand, the outer tube 3 is formed by the vacuum ultraviolet ray irradiated in the discharge space S by not forming the ultraviolet reflecting film 8 The light-emitting portion 7 is provided outside the discharge vessel 2. Further, the ultraviolet-ray reflection film 8 is formed on a part of the inner circumferential surface 3a or the outer circumferential surface 3b of the outer tube 3, and the utilization efficiency of the vacuum ultraviolet light can be improved. -12- 200941540 The fused silica glass of the inner tube 4 is vacuum ultraviolet light having a wavelength of 150 nm to 380 nm which is easy to absorb light than synthetic quartz glass. The energy of the absorbed ultraviolet light is accumulated in the discharge vessel 2, causing distortion and being easily deteriorated. However, by forming the ultraviolet ray reflection film 8 in the entire surface of the surface of the discharge space S exposed to the outer peripheral surface 4b of the inner tube 4, it is possible to prevent the vacuum ultraviolet light from being illuminated. In the inner tube 4, deterioration of the discharge vessel 2 can be suppressed. © The ultraviolet ray reflection film 8 is composed of fine particles formed by a vacuum ultraviolet light transmissive ceramic whose body is a high refractive index, specifically, by The ultraviolet ray scattering particles are composed of cerium oxide particles, and the ultraviolet ray scattering particles are made of ceramics, thereby reducing the amount of impure gas generated from the ultraviolet ray reflection film 8 and having characteristics of incident discharge. A part of the vacuum ultraviolet light of the scattering particles is reflected on the surface of the particle, and other portions are refracted and incident on the inside of the particle, and a large amount of light incident on the inside of the particle is transmitted (a part is absorbed), and when re-ejected refraction. It has the function of "diffusion reflection (scattering reflection)" which repeats such reflection and refraction. As the ultraviolet ray scattering particles constituting the ultraviolet ray reflection film 8, for example, cerium oxide particles in which fine particles of fine quartz particles are formed in a powder form are used. When the cerium oxide particles are composed of synthetic quartz glass, and the particle diameter is, for example, in the range of 〇.〇1 to 20 μm, the central particle diameter (peak of the number average particle diameter) is, for example, 〇·1 to ΙΟμχη. Good, better for 〇.3~3.0μιη. Further, the distribution of the particle diameter of the cerium oxide contained in the ultraviolet ray reflection film 8 is preferably such that the diffusion agent is not widely distributed, and the cerium oxide particles having the particle diameter of the center particle diameter of 値-13 to 200941540 are half. The above method is preferably selected from the cerium oxide particles. Generally, light hits a particle with a larger particle size, but if the particle size becomes smaller, the light will not reflect when it hits the particle, and scattering will occur. The scattering of light is classified into three types according to the size of the particles, and the particle diameter is smaller than the wavelength'. Then, Rayleigh (R ay 1 eigh) scattering is generated, and when the particle diameter is the same as the wavelength, the rice is produced. i) Scattering, where the particle diameter is larger than the wavelength, then 〇 produces non-selective scattering. In particular, Rayleigh scattering is characterized by the intensity of the scattered light depending on the wavelength of the light. Specifically, if the wavelength of the incident light is short, the intensity of the scattered light becomes small, and if the wavelength of the incident light is long, the intensity of the scattered light becomes small. When the Rayleigh scattering occurs in the ultraviolet ray reflection film 8, short-wavelength light of a so-called ultraviolet ray or vacuum ultraviolet ray can be made into scattered light having a large light intensity. Since the wavelength of light generated inside the discharge vessel 2 of the excimer lamp 1 is in the range of 150 nm to 380 nm, the particle diameter of the cerium oxide particles and the cerium oxide particles is made to be in the range of Ο.μπι to 20 μm. Further, by setting the center particle diameter to 0.3 μm to 3.0 μm, Rayleigh scattering can be caused in the ultraviolet ray reflection film 8. Further, even if the cerium oxide particles are made smaller than the above range and the Rayleigh scattering is likely to occur, the sintering of the cerium oxide particles proceeds, and the grain boundary is eliminated, and the scattering property of the light is lost. The "particle diameter" constituting the ultraviolet-ray reflective film 8 is an approximate intermediate position in the thickness direction of the cross-section when the ultraviolet-ray reflective film 8 is cut in the vertical direction, and is used as an observation range by a scanning electron microscope-14- 200941540 (SEM) Obtained a projected image, and the Freit's diameter of the parallel line when the arbitrary particles of the projected image are enlarged by two parallel lines in a certain direction. Further, the "central particle diameter" constituting the ultraviolet ray reflection film 8 is a range of the particle diameter of the maximum 値 and the minimum 粒子 of the particle diameter of each particle obtained as described above, for example, in the range of Ο.ίμιη. It is divided into plural numbers, for example, divided into about 15 divisions, and the number of particles (degrees) belonging to each division becomes the center of the division of Q maximum. The cerium oxide particles constituting the ultraviolet ray scattering particles are attached to the discharge vessel 2 by local melting or the like. Generally, the coefficient of linear expansion is equal or similar, and has a property of being easy to follow. The cerium oxide particles are a discharge vessel 2 made of quartz glass, and the coefficient of linear expansion 値 is approximately equal, thereby having a function of increasing the adhesion force to the discharge vessel 2. The inner tube 4 is in fused silica glass, especially It is preferably composed of an electrically fused stone enamel glass (type 1). The electrically fused silica glass (type 1) is characterized in that the OH concentration contained in the material is extremely low to 10 ppm or less and has an anoxic type defect (Si-Si). The electrically fused silica glass (type 1) is composed of almost cerium oxide coupled with oxygen (Si-O), but only partially has an anoxic type defect (Si-Si). On the one hand, the cerium oxide particles composed of synthetic quartz glass are formed almost by the coupling of cerium oxide and oxygen (Si-O), and the OH group is present in part, and the anaerobic defect (Si-Si) is Almost no. The 〇H group is characterized by easy chemical coupling between atoms, and hydrogen (H) is easily -15-200941540 alone. The cerium oxide particles composed of synthetic quartz glass have a concentration of OH contained in the material of about 300 ppm, which breaks the chemical coupling between the atoms and easily becomes a single hydrogen gas (H). When the cerium oxide particles of the synthetic quartz glass constituting the ultraviolet ray reflection film 8 are at a high temperature of 600 ° C or higher, chemical coupling between the OH group atoms is interrupted to become a single hydrogen gas (H), so that hydrogen gas (H) ) will spread. When the ultraviolet ray reflection film 8 is adhered to the outer peripheral surface 4b of the 内侧 inner tube 4 made of fused silica glass and fired at a high temperature of 600 ° C or higher, the chemical reaction of the following formula occurs. [Chemical 1]
SiOH + Si-Si — Si-O-Si + SiH 由紫外線反射膜8所發生的氫氣（Η)會擴散，與包含 於內側管4的缺氧型缺陷（Si-Si)的一邊的Si進行反應， 〇 如此地，分裂Si-Si耦合，而以Si-H的形式化學性地耦 合。 包含於電性熔融石英玻璃的缺氧型缺陷（Si-Si)，是與 二氧化矽與氧氣的耦合（Si-O)相比較，欠缺穩定性。在 此，包含於紫外線反射膜8的0H基斷開原子間的化學結 合而成爲單體，使得該氫氣（H)對缺氧型缺陷（Si-Si)伸出 援手而分裂Si-Si耦合，以Si-H的形式進行化學性耦合， 作成比缺氧型缺陷（Si-Si)還要穩定者。 如內側管4的外周面4b地，若將包含合成石英玻璃 -16 - 200941540 所成的二氧化矽粒子的紫外線散射粒子所成的紫外線反射 膜8形成在電性熔融石英玻璃所成的表面，則在內側管4 與紫外線反射膜8的附著界面，包含缺氧型缺陷（Si-Si)的 內側管4與包含OH基的紫外線反射膜8發生上述反應， ' 而以Si-H的形式進行化學性地耦合。藉此，在內側管4 - 與紫外線反射膜8之附著界面中，不但進行熔融構成紫外 線反射膜8的二氧化矽粒子，還與構成內側管4的熔融石 〇 英玻璃以Si-H的形式進行化學性地耦合之故，因而可提 高內側管4與紫外線反射膜8的密接性，且有效果地可預 防紫外線反射膜8被剝落的情形。 一方面，二氧化矽粒子是藉由在準分子燈1的放電空 間S所發生的電漿熱被熔融，而粒界被消失，成爲無法擴 散反射真空紫外光而有降低反射率的情形。作爲紫外線散 射粒子，不僅包含二氧化矽粒子還包含氧化鋁粒子藉此， 即使曝露在依電漿的熱時，也不會熔融比二氧化矽粒子具 Φ 有高融點的氧化鋁粒子之故，因而可防止以粒子彼此間耦 _ 合著互相鄰接的二氧化矽粒子與氧化鋁粒子的情形，而可 抑制降低紫外線反射膜8的反射率。 氧化鋁粒子是粒子徑爲例如在0.1〜ΙΟμιη的範圍內 者’而中心粒徑（數平均粒子徑的峰値），例如0.1〜3.0μηι 者較佳’更佳爲0.3〜Ι.Ομχη者。又，包含於紫外線反射 膜8的氧化鋁粒子的粒徑分布是不會擴展到廣範圍者較 佳，而使用粒徑成爲中心粒徑的數値的氧化鋁粒子選別成 爲半數以上的氧化鋁粒子較佳。 -17- 200941540 含有於紫外線反射膜8的氧化鋁粒子的比率，是二氧 化矽粒子與氧化鋁粒子的合計的例如lwt%以上較佳，更 佳爲5wt%以上，而最佳爲1 〇wt%。又，含有於紫外線反 射膜8的氧化鋁粒子的比率是二氧化矽粒子與氧化鋁粒子 • 的合計的7〇wt%以下較佳，更佳爲40wt%以下。 . 藉由紫外線反射膜8以上述混合比來構成著二氧化矽 粒子與氧化鋁粒子，即使長時間被點燈時，也確實地可抑 0 制二氧化矽粒子被熔融而把紫外線反射膜8的反射率會大 幅度地降低的情形，而且不會大幅度地降低氧化鋁粒子混 入所致的紫外線反射膜8對於放電容器2的黏合性（接著 性）之故，因而確實地可止紫外線反射膜8被剝落的情 形。 又，作爲紫外線散射粒子不僅包含二氧化矽粒子還包 含氧化銘粒子時，則「粒子徑」及「中心粒徑」，是不區 別爲二氧化矽粒子與氧化鋁粒子，將全部測定作爲紫外線 ❿ 散射粒子。 被使用作爲紫外線散射粒子的二氧化矽粒子及氧化鋁 粒子的製造，是都可利用固相法、液相法、氣相法的任何 方法，惟在此些中，由確實地可得到亞微細粒’微米尺寸 的粒子，以氣相法，尤其是化學蒸鑛法（CVD)較佳。 具體上，例如二氧化矽粒子是藉由將氯化矽與氧在 900〜1〇〇〇 °C予以反應，而氧化鋁粒子是藉由將原料的氯 化鋁與氧在1〇〇〇〜1200 °C予以加熱反應，就可加以合 成，而粒子徑是藉由控制原料濃度，反應場的壓力’反應 -18- 200941540 溫度就可調整。 紫外線反射膜8是例如稱爲「流下法」的方法，就可 形成。首先’調合流進放電容器形成材料內的被覆液。被 覆液是由紫外線散射粒子，黏合劑、分散劑，及溶劑所構 • 成。紫外線散射粒子是例如紫外線散射粒子與二氧化砂粒 - 子’黏合材是包含原矽酸四乙基，分散劑的矽烷親合劑， 溶劑是乙醇。 〇 藉由在被覆液含有分散劑，俾將被覆液作成凝膠化而 作成容易附著於放電容器形成材料，而且可將在被覆液中 均等地分散的紫外線散射粒子予以定影。 藉由在被覆液含有溶劑’可將被覆液的紫外線散射粒 子的含有濃度予以調整。 將被覆液流進放電容器形成材料的內部，而附著於所 定領域。 之後，將附著有被覆液的放電容器形成材料在氧氣氣 〇 氛中加熱成11 〇〇°c燒成1小時，則分散劑會加熱消失， 僅留下紫外線散射粒子與黏合劑。熔融石英玻璃是與合成 石英玻璃相比較純度未能達到該純度之故，因而融點比合 成石英玻璃還上昇，一直加熱到1100°c可進行燒成。 又’在以上，針對於具有兩端被密封而形成有環狀側 壁部9的雙重管構造的放電容器2的準分子燈1加以說 明，惟如第2圖所示地’針對於具有僅一方的端部被密封 而形成環狀側壁部9’另一方的端部是成爲形成有關閉外 側管3的圓盤狀外壁部1 〇與關閉內側管4的圓盤狀內壁 -19- 200941540 部1的3形狀的雙重管構造的放電容器2的準分子燈1’ 也可適用。 放電容器2是在一方的端部中，藉由側壁部9接合著 外側管3與內側管4，惟在另一方的端部中’外側管3被 - 外壁部1 0關閉，而內側管4被內壁部1 1被關閉’外側管 . 3與內側管4未被連接。因此，在點亮準分子燈時’即使 藉由石英玻璃的熱脹所伸展的長度爲在外側管3與內側管 0 4有所不同，而在另一方的端部藉由伸縮也可吸收伸展 量，而應力也不會集中在外側管3與內側管4被接合的側 壁部9。 又，將容易成爲高溫的內側管4由熔融石英玻璃所構 成，而將溫度比內側管4維持在較低的外側管3由合成石 英所構成，藉此，依外側管3與內側管4之間的熱脹所致 的收縮差變小，可解決在點燈準分子燈1中有放電容器2 破碎的不方便。 G 具有成爲表示於第2圖的3形狀的雙重管構造的放電 • 容器2的準分子燈1，特別適用在放電容器2朝軸方向長 的長度狀準分子燈1。 第3圖是表示紫外線反射膜8的膜厚與該光的透射率 的關係的圖表。 將縱軸作爲透射率（％)，並將橫軸作爲紫外線反射膜 的膜厚（μιη)’表示其關係。在熔融石英玻璃所成的試驗片 表面形成紫外線反射膜’而在形成有該紫外線反射膜的表 面照射真空紫外光。在此，針對於波長1 72nm的真空紫 -20- 200941540 外％ ’將對於照射於形成有紫外線反射膜的表面的照射強 度的透射紫外線反射膜及試驗片的光的放射強度的比率， 表示作爲透射率。又，在波長 WOnm〜波長200nm的範 圍的真空紫外線領域中，透射率是眾知表示大約同樣的趨 勢。 <紫外線反射膜的規格> 〇 二氧化矽粒子：合成石英玻璃製，粒子徑Ο.ίμιη〜 1 ·0μιη，中心粒徑 〇.3 μιη 氧化鋁粒子：高純度α氧化鋁製，粒子徑0.1 μ m〜 1 .Ομιη，中心粒徑 0.3 μιη 混合比：二氧化砂粒子：氧化銘粒子=90wt% : 1 Owt% 由圖表，可知可將紫外線反射膜的膜厚，可降低真空 紫外光的透射率。紫外線反射膜的膜厚爲1〇μηι以上的範圍 中，眾知不會透射真空紫外光。 © 在內側管4的外周面4b，膜厚成爲ΙΟμηι以上的方式 . 形成紫外線反射膜8，藉此，在紫外線反射膜8中幾乎完全 地遮斷真空紫外光’可作成真空紫外光未被照射至內側管 4。因此’防止I外線的能量被蓄積於內側管4，而可抑制 以紫外線所致的失真作爲原因的劣化。 之後’說明區別合成石英玻璃與溶融石英玻璃的檢證 方法。 在石英玻璃’ SB(A1)、硼（Β)、金（Au)、鐵（Fe)、紳 (K)、鈣（Ca)、銅（Cu)、鋰（Li)、鈉（Na)、磷（P)、鈦（Ti)等包 200941540 含作爲金屬不純物。包含於合成石英玻璃的金屬不純物’雖 僅包含接近於分析界限的程度（PPb水準），惟在熔融石英玻 璃，未包含著1〜20ppm左右的金屬不純物。因上，調查包 含於石英玻璃的金屬不純物的濃度，就可區別合成石英玻璃 ' 與熔融石英玻璃。 . 將放電容器2切出作爲分析用樣品的大小作爲試驗 片。以乙醇，純水之順序來洗淨試驗片，再以氟酸來蝕刻表 〇 面。以純水洗淨經蝕刻的試驗片，經充分地施以乾燥之後， 加以秤量。之後，將試驗片浸在氟酸使之溶解。溶解到無法 確認試驗片的形狀爲止。藉由加熱石英玻璃（Si〇2)與金屬不 純物被溶解的氟酸液，將二氧化矽成分與氟化氫酸蒸發作爲 氟化矽（SiF4)，則金屬不純物成分成爲殘渣，在殘渣放進硝 酸及硫酸，來溶解金屬不純物成分。以純水稀釋溶解液，作 爲樣品溶液。使用ICP發光分光分析裝置，定量樣品溶液 中不純物元素的濃度，進行換算質量。從金屬不純物的質量 G 對於試驗片的質量，可算出金屬不純物的濃度。 ^ 以下，將區別電性熔融石英玻璃（型式1)與氫氧熔融石 英玻璃（型式2)的驗證方法加以說明。 在熔融石英玻璃，有電性熔融石英玻璃（型式1)與氫 氧熔融石英玻璃（型式2)。電性熔融石英玻璃（型式1)，是 包含於材料中的OH的濃度極低爲l〇PPm以下，而具有缺 氧型缺陷（Si-Si)的特徵。一方面，氫氧熔融石英玻璃（型 式2)，是自含於材料中的〇H濃度爲大約300ppm，而幾 乎不存在缺氧型缺陷（Si-Si)。因此，調查包含於熔融石英 -22- 200941540 玻璃的OH的濃度，就可區別電性熔融石英玻璃（型式1) 與氫氧熔融石英玻璃（型式2)。 包含於石英玻璃的材料中的OH的濃度，是使用FT-IR(傅立葉變換紅外分光光度計）就可測定。作爲測定器， * 例如可使用巴利安製FTS-40。在FT-IR(傅立葉變換分光 - 光度計），當將紅外線照射在物質，利用某一波長的光受 到選擇性地吸收的特性，可求出OH的濃度。紅外吸收光 Q 譜是物質固有者之故，因而確認OH的吸收光譜，藉此， 由將紅外線照射在石英玻璃時的特定波長的光的吸收量， 就可測定OH的濃度。 【圖式簡單說明】 第1(a)圖及第1(b)圖是表示準分子燈的構成的說明用 斷面圖。 第2圖是表示準分子燈的構成的說明用斷面圖。 ❹ 第3圖是表示紫外線反射膜的膜厚’及其光的透射率 的關係的圖表。 【主要元件符號說明】 1 :準分子燈 2 :放電容器 3 :外側管 4 :內側管 5 :外側電極 -23- 200941540 6 :內側電極 7 :光出射部 8 :紫外線反射膜SiOH + Si-Si — Si—O—Si + SiH is diffused by hydrogen gas generated by the ultraviolet ray reflection film 8 and reacts with Si of one side of the oxygen deficiency type defect (Si—Si) contained in the inner tube 4 . Thus, the Si-Si coupling is split and chemically coupled in the form of Si-H. The oxygen-deficient defect (Si-Si) contained in the electrically fused silica glass is less stable than the coupling of cerium oxide and oxygen (Si-O). Here, the 0H group included in the ultraviolet ray reflection film 8 is chemically bonded between the atoms to become a monomer, so that the hydrogen gas (H) is extended to the oxygen deficiency type defect (Si-Si) and the Si-Si coupling is split. Chemically coupled in the form of Si-H, which is more stable than the oxygen-deficient defect (Si-Si). When the outer peripheral surface 4b of the inner tube 4 is formed, an ultraviolet ray reflection film 8 made of ultraviolet ray scattering particles containing cerium oxide particles formed of synthetic quartz glass-16 - 200941540 is formed on the surface of the electrically fused silica glass. Then, at the interface between the inner tube 4 and the ultraviolet ray reflection film 8, the inner tube 4 containing the oxygen-deficient type defect (Si-Si) and the ultraviolet ray reflection film 8 containing the OH group undergo the above reaction, and the Si-H is used. Chemically coupled. Thereby, in the interface between the inner tube 4 - and the ultraviolet ray reflection film 8, not only the cerium oxide particles constituting the ultraviolet ray reflection film 8 but also the fused silica glass constituting the inner tube 4 are in the form of Si-H. Since it is chemically coupled, the adhesion between the inner tube 4 and the ultraviolet ray reflection film 8 can be improved, and the ultraviolet ray reflection film 8 can be prevented from being peeled off. On the other hand, the cerium oxide particles are melted by the plasma heat generated in the discharge space S of the excimer lamp 1, and the grain boundary is eliminated, so that the reflection of the vacuum ultraviolet light cannot be diffused and the reflectance is lowered. The ultraviolet ray scattering particles include not only the cerium oxide particles but also the alumina particles, so that even when exposed to the heat of the plasma, the alumina particles having a higher melting point than the cerium oxide particles are not melted. Therefore, it is possible to prevent the reflectance of the ultraviolet ray reflection film 8 from being lowered by the case where the particles are coupled to each other and the cerium oxide particles and the alumina particles adjacent to each other are combined. The alumina particles are those in which the particle diameter is, for example, in the range of 0.1 to ΙΟμη, and the central particle diameter (peak of the number average particle diameter), for example, 0.1 to 3.0 μm is preferably 'more preferably 0.3 to Ι.Ομχη. Further, the particle size distribution of the alumina particles contained in the ultraviolet ray reflection film 8 is preferably not extended to a wide range, and the alumina particles having a number of ruthenium having a particle diameter of the center particle diameter are selected to be at least half of the alumina particles. Preferably. -17- 200941540 The ratio of the alumina particles contained in the ultraviolet ray reflection film 8 is preferably, for example, 1 wt% or more, more preferably 5% by weight or more, and most preferably 1 〇wt, of the total of the cerium oxide particles and the alumina particles. %. Further, the ratio of the alumina particles contained in the ultraviolet ray reflection film 8 is preferably 7 〇 wt% or less, more preferably 40 wt% or less, based on the total of the cerium oxide particles and the alumina particles. The cerium oxide particles and the alumina particles are formed by the ultraviolet ray reflection film 8 at the above-described mixing ratio, and even when the lamp is turned on for a long time, the cerium oxide particles are surely melted and the ultraviolet ray absorbing film 8 is fused. The reflectance is greatly lowered, and the adhesion (adhesion) of the ultraviolet ray reflection film 8 to the discharge vessel 2 due to the incorporation of alumina particles is not drastically reduced, so that the ultraviolet ray reflection can be surely prevented. The case where the film 8 is peeled off. In addition, when the ultraviolet ray scattering particles contain not only cerium oxide particles but also oxidized particles, the "particle diameter" and the "center particle diameter" are not distinguished from cerium oxide particles and alumina particles, and all of them are measured as ultraviolet ray. Scattering particles. The production of the cerium oxide particles and the alumina particles used as the ultraviolet ray scattering particles can be any method using a solid phase method, a liquid phase method, or a gas phase method, but in these cases, submicron is surely obtained. Particles of 'micron size are preferred by gas phase processes, especially chemical vapor deposition (CVD). Specifically, for example, the cerium oxide particles are reacted by reacting cerium chloride with oxygen at 900 to 1 ° C, and the alumina particles are obtained by using aluminum chloride and oxygen in the raw material. The reaction can be carried out by heating at 1200 °C, and the particle diameter can be adjusted by controlling the concentration of the raw material and the pressure of the reaction field as the reaction -18-200941540. The ultraviolet ray reflection film 8 can be formed, for example, by a method called "flow down method". First, the coating liquid flowing into the discharge vessel forming material is blended. The coating liquid is composed of ultraviolet scattering particles, a binder, a dispersing agent, and a solvent. The ultraviolet ray scattering particles are, for example, ultraviolet ray scattering particles and silica sand particles - the sub-adhesive material is a decane affinity agent containing tetraethyl orthosilicate, a dispersing agent, and the solvent is ethanol.藉 By dispersing the coating liquid in the coating liquid, the coating liquid is gelled to easily adhere to the discharge vessel forming material, and the ultraviolet scattering particles uniformly dispersed in the coating liquid can be fixed. The concentration of the ultraviolet ray scattering particles of the coating liquid can be adjusted by including the solvent in the coating liquid. The coating liquid flows into the inside of the discharge vessel forming material and adheres to a predetermined area. Thereafter, the discharge vessel forming material to which the coating liquid was attached was heated to 11 ° C for 1 hour in an oxygen atmosphere, and the dispersant was heated and disappeared, leaving only the ultraviolet scattering particles and the binder. Since the purity of the fused silica glass is not as high as that of the synthetic quartz glass, the melting point is higher than that of the synthetic quartz glass, and heating can be performed until it is heated to 1,100 °C. In the above, the excimer lamp 1 having the discharge tube 2 having the double tube structure in which the annular side wall portions 9 are sealed at both ends will be described. However, as shown in Fig. 2, there is only one side. The other end portion of the annular side wall portion 9' is sealed to form a disc-shaped outer wall portion 1 that closes the outer tube 3 and a disc-shaped inner wall that closes the inner tube 4 - 200941540 The excimer lamp 1' of the discharge vessel 2 of the 3-shaped double tube structure of 1 is also applicable. The discharge vessel 2 is in one end portion, and the outer tube 3 and the inner tube 4 are joined by the side wall portion 9, but in the other end portion, the outer tube 3 is closed by the outer wall portion 10, and the inner tube 4 is closed. It is closed by the inner wall portion 1 1 'the outer tube 3. The inner tube 4 is not connected. Therefore, when the excimer lamp is turned on, 'the length extended by the thermal expansion of the quartz glass is different between the outer tube 3 and the inner tube 0 4 , and the other end portion can be absorbed and stretched by the expansion and contraction. The amount is not concentrated on the side wall portion 9 where the outer tube 3 and the inner tube 4 are joined. Further, the inner tube 4 which is likely to be high in temperature is composed of fused silica glass, and the outer tube 3 having a lower temperature than the inner tube 4 is made of synthetic quartz, whereby the outer tube 3 and the inner tube 4 are formed. The difference in shrinkage caused by the thermal expansion between the two becomes small, and the inconvenience that the discharge vessel 2 is broken in the lighting excimer lamp 1 can be solved. G The excimer lamp 1 having the discharge/container 2 of the double-tube structure shown in Fig. 2 is particularly suitable for the long excimer lamp 1 in which the discharge vessel 2 is long in the axial direction. Fig. 3 is a graph showing the relationship between the film thickness of the ultraviolet ray reflection film 8 and the transmittance of the light. The vertical axis represents the transmittance (%), and the horizontal axis represents the relationship between the film thickness (μιη) of the ultraviolet ray reflection film. An ultraviolet reflecting film ' is formed on the surface of the test piece formed of fused silica glass, and vacuum ultraviolet light is irradiated on the surface on which the ultraviolet reflecting film is formed. Here, the ratio of the radiation intensity of the transmitted ultraviolet ray reflection film irradiated to the surface on which the ultraviolet ray reflection film is formed and the light of the test piece to the vacuum violet -20-200941540 outside the wavelength of 1 72 nm is expressed as Transmittance. Further, in the field of vacuum ultraviolet rays having a wavelength of WO nm to a wavelength of 200 nm, the transmittance is known to indicate about the same tendency. <Specification of Ultraviolet Reflective Film> Antimony cerium oxide particles: Synthetic quartz glass, particle diameter ί. ίμιη~ 1 ·0μιη, center particle size 〇.3 μιη Alumina particles: high purity α alumina, particle diameter 0.1 μ m~1 .Ομιη, center particle size 0.3 μιη Mixing ratio: silica sand particles: oxidized crystal particles = 90 wt%: 1 Owt% From the graph, it can be seen that the film thickness of the ultraviolet reflecting film can reduce the vacuum ultraviolet light. Transmittance. In the range where the film thickness of the ultraviolet ray reflection film is 1 〇 μηι or more, it is known that the vacuum ultraviolet light is not transmitted. © In the outer peripheral surface 4b of the inner tube 4, the film thickness is ΙΟμηι or more. The ultraviolet reflecting film 8 is formed, whereby the vacuum ultraviolet light is almost completely blocked in the ultraviolet reflecting film 8 'can be made into vacuum ultraviolet light without being irradiated To the inner tube 4. Therefore, the energy of the outer line of I is prevented from being accumulated in the inner tube 4, and deterioration due to ultraviolet rays can be suppressed as a cause. After that, a verification method for distinguishing synthetic quartz glass from molten quartz glass will be described. In quartz glass 'SB (A1), boron (Β), gold (Au), iron (Fe), strontium (K), calcium (Ca), copper (Cu), lithium (Li), sodium (Na), phosphorus (P), Titanium (Ti), etc. 200941540 is contained as a metal impurity. The metal impurity contained in the synthetic quartz glass contains only a degree close to the analysis limit (PPb level), but the fused silica glass does not contain a metal impurity of about 1 to 20 ppm. Therefore, by investigating the concentration of metal impurities contained in quartz glass, it is possible to distinguish between synthetic quartz glass and fused silica glass. The size of the discharge vessel 2 as a sample for analysis was cut out as a test piece. The test piece was washed in the order of ethanol and pure water, and the surface was etched with hydrofluoric acid. The etched test piece was washed with pure water, and after being sufficiently dried, it was weighed. Thereafter, the test piece was immersed in hydrofluoric acid to dissolve it. Soluble until the shape of the test piece cannot be confirmed. By heating the quartz glass (Si〇2) and the fluorine acid solution in which the metal impurities are dissolved, the cerium oxide component and the hydrogen fluoride acid are evaporated as cesium fluoride (SiF4), and the metal impurity component becomes a residue, and the residue is put into the nitric acid and Sulfuric acid to dissolve metal impurities. The solution was diluted with pure water as a sample solution. The concentration of the impurity element in the sample solution was quantified using an ICP emission spectroscopic analyzer to calculate the converted mass. From the mass of the metal impurity G For the mass of the test piece, the concentration of the metal impurity can be calculated. ^ Hereinafter, a verification method for distinguishing between electric fused silica glass (type 1) and hydrogen-oxygen molten quartz glass (type 2) will be described. In fused silica glass, there are electrically fused silica glass (type 1) and hydrogen oxysilicate glass (type 2). The electrically fused silica glass (type 1) is characterized in that the concentration of OH contained in the material is extremely low below 1 〇 PPm and has an anoxic type defect (Si-Si). On the one hand, the oxyhydroxide fused silica glass (Form 2) is a cerium H concentration contained in the material of about 300 ppm, and there is almost no oxygen deficiency type defect (Si-Si). Therefore, by investigating the concentration of OH contained in fused silica-22-200941540 glass, it is possible to distinguish between electrically fused silica glass (type 1) and oxyhydrogenated fused silica glass (type 2). The concentration of OH contained in the material of the quartz glass can be measured using an FT-IR (Fourier Transform Infrared Spectrophotometer). As the measuring device, * For example, FTA-40 manufactured by Balian can be used. In the FT-IR (Fourier Transform Spectrophotometer), the concentration of OH can be determined by irradiating infrared rays to a substance and utilizing a characteristic that light of a certain wavelength is selectively absorbed. Since the infrared absorption Q spectrum is inherent to the substance, the absorption spectrum of OH is confirmed, whereby the concentration of OH can be measured by the absorption amount of light of a specific wavelength when infrared rays are irradiated on the quartz glass. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1(a) and Fig. 1(b) are cross-sectional views for explaining the configuration of an excimer lamp. Fig. 2 is a cross-sectional view for explaining the structure of the excimer lamp. ❹ Fig. 3 is a graph showing the relationship between the film thickness of the ultraviolet ray reflection film and the transmittance of light. [Main component symbol description] 1 : Excimer lamp 2 : Discharge capacitor 3 : Outer tube 4 : Inner tube 5 : Outer electrode -23- 200941540 6 : Inside electrode 7 : Light exit portion 8 : Ultraviolet reflection film
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