TWI431659B - Excimer lamp - Google Patents
Excimer lamp Download PDFInfo
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- TWI431659B TWI431659B TW098111695A TW98111695A TWI431659B TW I431659 B TWI431659 B TW I431659B TW 098111695 A TW098111695 A TW 098111695A TW 98111695 A TW98111695 A TW 98111695A TW I431659 B TWI431659 B TW I431659B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J65/00—Lamps without any electrode inside the vessel; Lamps with at least one main electrode outside the vessel
- H01J65/04—Lamps in which a gas filling is excited to luminesce by an external electromagnetic field or by external corpuscular radiation, e.g. for indicating plasma display panels
- H01J65/042—Lamps in which a gas filling is excited to luminesce by an external electromagnetic field or by external corpuscular radiation, e.g. for indicating plasma display panels by an external electromagnetic field
- H01J65/046—Lamps in which a gas filling is excited to luminesce by an external electromagnetic field or by external corpuscular radiation, e.g. for indicating plasma display panels by an external electromagnetic field the field being produced by using capacitive means around the vessel
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J5/00—Details relating to vessels or to leading-in conductors common to two or more basic types of discharge tubes or lamps
- H01J5/50—Means forming part of the tube or lamps for the purpose of providing electrical connection to it
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J61/00—Gas-discharge or vapour-discharge lamps
- H01J61/02—Details
- H01J61/30—Vessels; Containers
- H01J61/35—Vessels; Containers provided with coatings on the walls thereof; Selection of materials for the coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
- H01J9/24—Manufacture or joining of vessels, leading-in conductors or bases
- H01J9/245—Manufacture or joining of vessels, leading-in conductors or bases specially adapted for gas discharge tubes or lamps
- H01J9/247—Manufacture or joining of vessels, leading-in conductors or bases specially adapted for gas discharge tubes or lamps specially adapted for gas-discharge lamps
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B41/00—Circuit arrangements or apparatus for igniting or operating discharge lamps
- H05B41/14—Circuit arrangements
- H05B41/26—Circuit arrangements in which the lamp is fed by power derived from dc by means of a converter, e.g. by high-voltage dc
- H05B41/28—Circuit arrangements in which the lamp is fed by power derived from dc by means of a converter, e.g. by high-voltage dc using static converters
- H05B41/2806—Circuit arrangements in which the lamp is fed by power derived from dc by means of a converter, e.g. by high-voltage dc using static converters with semiconductor devices and specially adapted for lamps without electrodes in the vessel, e.g. surface discharge lamps, electrodeless discharge lamps
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Plasma & Fusion (AREA)
- Manufacturing & Machinery (AREA)
- Vessels And Coating Films For Discharge Lamps (AREA)
Description
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。The present invention relates to an excimer lamp used for treating a surface to be processed by a surface treatment such as a cleaning treatment, an ashing treatment, a film formation treatment, or the like by irradiation with ultraviolet rays.
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。In the glass substrate of the liquid crystal display device, the object to be processed such as a semiconductor wafer, vacuum ultraviolet light having an ultraviolet ray having a wavelength of 200 nm or less is developed, and the vacuum ultraviolet light and the ozone generated thereby are processed. In the technique of the treatment body, for example, a cleaning treatment technique for removing an organic contaminant adhering 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, has been developed and put into practical use.
作為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，為了有效率地放射更高強度的紫外線進行著很多的嘗試。As an apparatus for irradiating vacuum ultraviolet light, for example, excimer light which emits vacuum gas by applying a discharge gas in a discharge vessel formed by a medium, and applying an alternating high voltage via a discharge vessel to generate an excimer discharge is used. Excimer lamp. In such an excimer lamp, many attempts have been made to efficiently emit higher intensity ultraviolet rays.
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)。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).
在此種構成的準分子燈中，在放電容器內所發生的紫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。In the excimer lamp of such a configuration, ultraviolet rays that are not directly emitted toward the light emitting portion in the ultraviolet rays generated in the discharge vessel are incident on the ultraviolet reflecting layer, and are formed by the plurality of fine particles constituting the ultraviolet reflecting layer. The surface is repeatedly refracted and reflected, diffused and reflected, and emitted from the light emitting portion. Thereby, ultraviolet rays can be efficiently emitted.
在放射紫外線的燈中，作為構成放電容器的材料，例如廣泛地使用二氧化矽玻璃。因此，作為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脹係數之相差，或是作成極小而為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。Among the lamps that emit ultraviolet rays, as the 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 different 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. The bismuth oxide glass of the same material as the discharge vessel is preferred.
表面處理的被處理物，是多為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。作為此種形狀的放電容器所成的準分子燈，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。The surface-treated object is 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.
作為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是成為連結上壁板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。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 formed in the discharge spaces S which are disposed to face each other. The excimer light is emitted from the lower wall 22 having the light emitting portion to the outside.
專利文獻1：日本特開2007-335350號公報Patent Document 1: Japanese Laid-Open Patent Publication No. 2007-335350
專利文獻2：日本特開2004-113984號公報Patent Document 2: Japanese Laid-Open Patent Publication No. 2004-113984
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。However, in an excimer lamp including an ultraviolet reflecting layer formed of fine particles containing cerium oxide particles, if the lighting is performed for a long period of time, the illuminance maintenance rate gradually decreases 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 changes with the lighting time.
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。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.
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，其特徵為：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矽粒子中的OH基濃度是10wtppm以上，將上述堆積體A的設置面積作為a(cm2 )，將上述堆積體B的設置面積作為b(cm2 )，將堆積體B的比表面積作為c(cm2 /g)，將放電容器的內表面積作為d(cm2 )時，各個的關係為滿足b≧-5.0×10-7 ac+0.35a、且b>0.02d為其特徵者。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 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 The ceria is composed of fine particles having a high particle size, and the deposition body B is composed of fine particles containing cerium oxide particles containing an OH group, and the OH group concentration in the ceria particles constituting the ultraviolet ray reflection layer is 10 wtppm. above, the area of the stacked body a is provided as a (cm 2), provided the area of the stacked body B as b (cm 2), the specific surface area B of the stacked body as c (cm 2 / g) The internal surface area of the discharge vessel as d (cm 2), each satisfy a relationship b ≧ -5.0 × 10 -7 ac + 0.35a, and b> 0.02d by its characteristics.
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子，來抑制降低紫外線反射層的反射率。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 having a higher melting point than the cerium oxide to suppress the decrease in the reflectance of the ultraviolet reflecting layer.
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10wtppm以上，反射維持率及照度維持率都可維持高值，而有關於長時間點燈時的照度維持事先發揮優異的效果。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. The reflectance of the ultraviolet reflecting layer is maintained, the degree of illuminance reduction of the excimer lamp is suppressed, and the vacuum ultraviolet light is efficiently emitted. In particular, when the concentration of the OH group in the cerium oxide particles constituting the ultraviolet ray reflecting layer is 10 wtppm or more, the reflection maintaining ratio and the illuminance maintaining ratio can be maintained at a high value, and the illuminance at the time of long-time lighting is maintained in advance. Excellent results.
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為主成分的不純氣體。以水作為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。The ultraviolet reflecting layer formed on the inner surface of the discharge vessel corresponding to the position where the electrode is provided is an OH group, and is exposed to the discharge plasma to emit an impure gas containing 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.
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的設置面積作為b(cm2 )，將堆積體B的比表面積作為c(cm2 /g)，將放電容器的內表面積作為d(cm2 )時，各個的關係為藉由滿足Considering the specific surface area of the deposit B, the installation area a (cm 2 ) of the deposit A, the installation area of the deposit B is b (cm 2 ), and the specific surface area of the deposit B is c (cm 2 /g). When the internal surface area of the discharge vessel is taken as d (cm 2 ), the relationship is satisfied by
b≧-5.0×10-7 ac+0.35a、且b>0.02dB≧-5.0×10 -7 ac+0.35a, and 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。The amount of the impure gas discharged from the deposit A does not exceed the amount of the impure gas which the deposit B can adsorb, and the impure gas is not left in the discharge space. 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.
第1圖是表示本發明的準分子燈10的一例的構成概略的說明用斷面圖。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。1 is a cross-sectional view for explaining an outline of an example of an example of the excimer lamp 10 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).
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。The excimer lamp 10 is 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 21, and a pair of side wall plates 23 connected to the upper wall plate 21 and the lower wall plate 22, and the upper wall The 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.
在放電容器20的內部，以如10～80kPa的壓入封入有放電用氣體。作為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作為中心波長的準分子發光，而在封入有氬(Ar)與氯(Cl)的混合氣體的準分子燈，則產生以175nm作為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191nm作為中心波長的準分子發光，在封入有氬(Ar)與氟(F)的混合氣體的準分子燈，則產生以波長193nm作為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207nm作為中心波長的準分子發光，在封入有氪(Kr)與氯(Cl)的混合氣體的準分子燈，則產生以222nm作為中心波長的準分子發光，在封入有氙(Xe)與氯(Cl)的混合氣體的準分子燈，則產生以308nm作為中心波長的準分子發光。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 radiation intensity, but the center wavelength of the emitted excimer light emission is different by the 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 (Cl) is generated. Excimer light having a center wavelength of 175 nm, and an excimer lamp sealed with a mixed gas of krypton (Kr) and iodine (I), emits excimer light having a center wavelength of 191 nm, and argon (Ar) and fluorine are enclosed therein. The excimer lamp of the mixed gas of (F) generates an excimer wavelength having a wavelength of 193 nm as a center wavelength, and an excimer lamp in which a mixed gas of krypton (Kr) and bromine (Br) is enclosed, and 207 nm is generated as a center. Excimer light of a wavelength, excimer lamp sealed with a mixed gas of krypton (Kr) and chlorine (Cl), emits excimer light having a center wavelength of 222 nm, and contains xenon (Xe) and chlorine (Cl). The excimer lamp of the mixed gas produces excimer luminescence with a center wavelength of 308 nm.
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是成為網狀構造，而形成從網孔之間能透射光。作為材質，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)。The outer surface of the upper wall plate 21 of the discharge vessel 20 is provided with a high voltage supply electrode 11, and the outer surface of the lower wall plate 22 is provided with a ground electrode 12, and these electrodes 11, 12 are disposed to face each other. Such electrodes 11 and 12 have a mesh structure and are capable of transmitting light from between the meshes. As the material, for example, aluminum, nickel, gold, or the like is used, for example, 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).
在上述準分子燈10中，為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11的領域的一部分。又，堆積體B32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及下壁板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，將形成於對應在上壁板21的內表面的高電壓供應電極11的領域的紫外線反射層30稱為堆積體A31，而將形成於放電容器20的內表面的其他領域的紫外線反射層30稱為堆積體B32。In the excimer lamp 10, in order to efficiently utilize the vacuum ultraviolet light generated by the excimer discharge, the ultraviolet reflective layer 30 formed of fine particles is provided on the inner surface of the discharge space S with respect to the discharge vessel 20. The ultraviolet reflecting layer 30 is composed of a stacked body A31 and a stacked body B32. The stack A31 is a part of the inner surface of the discharge space S formed on the opposite side of the discharge vessel 20 provided with the high voltage supply electrode 11, that is, the high voltage supply electrode 11 formed on the inner surface corresponding to the upper wall 21 Part of the field. Further, the deposition body B32 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 from the corresponding electrodes 11 and 12. The field deviates from the inner surface of the upper wall panel 21 and the lower wall panel 22, and any one of the inner surfaces of the side wall panel 23 and the end wall panel 24. That is, the ultraviolet reflecting layer 30 formed in the field of the high voltage supply electrode 11 corresponding to the inner surface of the upper wall plate 21 is referred to as a stack A31, and ultraviolet rays reflected in other fields formed on the inner surface of the discharge vessel 20 are referred to. Layer 30 is referred to as stack B32.
一方面，在放電容器20的下壁板22對應於接地電極12的內表面藉由末形成有紫外線反射層30，構成光射出部。On the other hand, the lower wall plate 22 of the discharge vessel 20 is formed with the ultraviolet ray reflection layer 30 corresponding to the inner surface of the ground electrode 12 to constitute a light exit portion.
堆積體A31，是厚度為例如5～1000μm，由二氧化矽粒子，及融點比二氧化矽還要高且透射紫外線的微小粒子所構成。融點比二氧化矽還要高且透射紫外線的微小粒子是有例如氧化鋁、氟化鋰、氟化鎂、氟化鈣、氟化鋇等。The deposition body A31 is composed of fine particles having a thickness of, for example, 5 to 1000 μm, which is composed of cerium oxide particles and a melting point higher than that of cerium oxide and transmitting ultraviolet rays. The fine particles having a melting point higher than that of cerium oxide and transmitting ultraviolet rays are, for example, alumina, lithium fluoride, magnesium fluoride, calcium fluoride, barium fluoride or the like.
真空紫外光射入至此種堆積體A31，則一部分是在微小粒子的表面反射，又一部分是被折射而透射於粒子內部，而在其他表面再反射或折射，在複數微小粒子中，藉由重複此種反射、折射，真空紫外光是被擴散反射。When vacuum ultraviolet light is incident on the deposition body A31, part of it is reflected on the surface of the fine particles, and part is refracted and transmitted to the inside of the particle, and is re-reflected or refracted on the other surface, and is repeated in the plurality of fine particles. Such reflection, refraction, and vacuum ultraviolet light are diffusely reflected.
然而，二氧化矽粒子是藉由在準分子燈10所發生的電漿的熱被熔融，粒界被消失，無法擴散反射真空紫外光而有降低反射率的情形。尤其是，形成於對應在高電壓供應電極11的領域的堆積體A31是容易受到電漿的熱，而構成堆積體A31的二氧化矽粒子是容易被熔融。一方面，融點比二氧化矽還要高的微小粒子是即使暴露在依電漿的熱時也不會被熔融。因此，在堆積體A31藉由混入融點比二氧化矽還要高的微小粒子，以互相鄰接的微小粒子彼此間被結合而可防止粒界消失，而可抑制堆積體A31的反射率的降低。However, the cerium oxide particles are melted by the heat of the plasma generated in the excimer lamp 10, the grain boundaries are eliminated, and the vacuum ultraviolet light cannot be diffused and reflected, and the reflectance is lowered. In particular, the deposition body A31 formed in the field corresponding to the high voltage supply electrode 11 is susceptible to heat of the plasma, and the cerium oxide particles constituting the deposition body A31 are easily melted. On the one hand, the fine particles whose melting point is higher than that of cerium oxide are not melted even when exposed to heat depending on the plasma. Therefore, by depositing fine particles having a melting point higher than that of cerium oxide in the deposition body A31, the adjacent fine particles are bonded to each other, thereby preventing the grain boundary from disappearing, and suppressing the decrease in the reflectance of the stacked body A31. .
堆積體B32是厚度例如10～1000μm，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。The deposit B32 has a thickness of, for example, 10 to 1000 μm 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.
即使真空紫外光射入至堆積體B32，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。Even if vacuum ultraviolet light is incident on the deposition body B32, reflection and refraction are repeatedly generated in the plurality of fine particles, and the vacuum ultraviolet light is diffused and reflected. Further, the deposition body B32 is formed on the inner surface of the discharge vessel 20 other than the fields of the electrodes 11 and 12, and thus is not easily affected by heat due to plasma. Therefore, even if the deposited body B32 is not formed by only the cerium oxide particles, the grain boundary disappearing due to the bonding of the adjacent fine particles is unlikely to occur.
微小粒子是如以下地被定義的粒子徑，為在例如0.01～20μm範圍者，中心粒徑(個數基準的粒度分佈的最大值)，在堆積體A31中，例如以0.1～10μm者較佳，更佳為0.1～3μm，而在堆積體B2也相同，例如0.1～20μm者較佳。The fine particles are particle diameters as defined below, and are, for example, in the range of 0.01 to 20 μm, the center particle diameter (the maximum value of the particle size distribution based on the number), and in the deposit A31, for example, preferably 0.1 to 10 μm. More preferably, it is 0.1 to 3 μm, and the same is true for the deposition body B2, for example, 0.1 to 20 μm.
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為觀察範圍，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像的任意粒子時的該平行線的間隔的弗雷特(Feret)直徑。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). For example, the Freit diameter of the parallel line when the arbitrary particles of the projected image are enlarged by two parallel lines in a certain direction.
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值與最小值的粒子徑的範圍，例如以0.1μm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)成為最大的區分的中心值。In addition, the "central particle size" is a range of the particle diameters of the maximum and minimum particle diameters of the particle diameters obtained as described above, for example, in a range of 0.1 μm, and is divided into, for example, 15 It is distinguished that the number of particles (degrees) belonging to each division becomes the center value of the largest division.
在該準分子燈10中，點燈電力被供應於高電壓供應電極11，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。In the excimer lamp 10, when the lighting power is supplied to the high voltage supply electrode 11, excimer discharge occurs in the discharge space S between the electrodes 11 and 12 via the discharge vessel 20. 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 in the direction toward the upper wall plate 21, but the ultraviolet ray reflection layer 30 is diffused and emitted, and is emitted to the outside through the light emitting portion.
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。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.
然而，長時間點燈具備上述紫外線反射層30的準分子燈10，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為其主要原因之一的紫外線反射層30的反射率。However, when the excimer lamp 10 including the ultraviolet ray reflection layer 30 was turned on for a long period of 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 cause of the decrease in illuminance from all aspects, and have considered whether or not the reflectance of the ultraviolet ray reflection layer 30 which is one of the main causes is lowered.
在此，測定點燈初期的準分子燈10的紫外線反射層30的反射強度光譜，及長時間點燈後的準分子燈10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10的紫外線反射層30，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30而產生照度降低。Here, the reflection intensity spectrum of the ultraviolet-ray reflection layer 30 of the excimer lamp 10 at the initial stage of lighting and the reflection intensity spectrum of the ultraviolet-ray reflection layer 30 of the excimer lamp 10 after long-time lighting are measured, and both are comparatively analyzed. As a result, in the ultraviolet ray reflection layer 30 of the excimer lamp 10 after the long-time lighting, the absorption band generates an ultraviolet region, and it is understood that a part of the ultraviolet ray is absorbed in the ultraviolet ray reflection layer 30 to cause a decrease in illuminance.
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-O-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‧)。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 ultraviolet rays or plasma during discharge, and are subjected to radiation damage to generate wavelengths absorbing ultraviolet rays. The internal defects of light, while the ultraviolet rays are absorbed in internal defects, so that the diffuse reflection is suppressed. The internal defect refers to the Si-O-Si bond of the cerium oxide particles exposed to ultraviolet rays or plasma, the Si-Si defect having an absorption end near a wavelength of 163 nm, or the E'center having an absorption band at a wavelength of 215 nm (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為二氧化矽粒子，而成為照度降低的原因的紫外領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。For the reason described above, the internal defect that generates light that absorbs the wavelength in the ultraviolet region is cerium oxide particles, and the light absorption at the wavelength in the ultraviolet region, which causes illuminance reduction, may 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, by preventing internal defects from occurring in the cerium oxide particles constituting the ultraviolet ray reflection layer 30, it is possible to suppress a decrease in illuminance, and it is possible to maintain a high illuminance maintenance ratio even when lighting for a long period of time.
為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OH基就有效。藉由含有OH基，可抑制在含有於紫外線反射層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。In order to prevent internal defects in the cerium oxide particles, it is effective to contain OH groups in the cerium oxide particles. By containing an OH group, it is possible to suppress the occurrence of internal defects in the ceria particles contained in the ultraviolet ray reflection layer 30, and it is possible to prevent the reflectance of the ultraviolet ray reflection layer 30 from being lowered.
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是藉由例如稱為「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PEO樹脂(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，燒成溫度是例如作為500℃～1100℃。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 a "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 in which water and a PEO resin (polyethylen oxide) are combined, fine particles are mixed to adjust the dispersion, and the dispersion is introduced into the discharge vessel forming material. Further, after the dispersion liquid is adhered to a predetermined region of the inner surface of the discharge vessel forming material, the water and the PEO resin are evaporated and dried to form a particle deposition layer. Here, the baking temperature is, for example, 500 ° C to 1100 ° C.
作為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基的二氧化矽粒子，一面供應水蒸氣，一面進行電爐加熱(例如1000℃)，來製作含有多量OH基的二氧化矽粒子的情形。藉由使用經此種處理的二氧化矽粒子，可形成含有含著OH基的二氧化矽粒子的微小粒子所成的紫外線反射層30。As an example of a method in which the cerium oxide particles contain an OH group, the cerium oxide particles not containing an OH group are supplied with water vapor while being heated by an electric furnace (for example, 1000 ° C) to prepare a OH group containing a large amount of OH groups. The case of cerium oxide particles. By using the cerium oxide particles thus treated, the ultraviolet ray reflection layer 30 composed of fine particles containing OH group-containing cerium oxide particles can be formed.
又，作為其他方法，使用未含有OH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OH基。又，使用未含有OH基的二氧化矽粒子經燒成而形成紫外線反射層30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OH基。Further, as another method, after the cerium oxide particles not containing an 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 an OH group, the cerium oxide particles may be contained in the cerium oxide particles by heating the electric furnace while supplying water vapor.
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。Further, since the commercially available cerium oxide particles are obtained by the production method, and the OH group is also contained therein, it is preferable to have a high concentration of OH groups by the above method. .
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30的二氧化矽粒子的OH濃度可調整成任意數值。例如，即使保持溫度為一定，隨著延長保持時間，可除去更多的OH基。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OH基濃度的二氧化矽粒子的微小粒子所成的紫外線反射層30。The concentration of the OH group contained in the cerium oxide particles can be adjusted to an arbitrary value by adjusting the OH concentration of the cerium oxide particles constituting the ultraviolet ray reflecting layer 30 by selecting various temperature exhausting conditions. For example, even if the temperature is kept constant, more OH groups can be removed as the holding time is extended. Considering the amount of OH groups previously contained in the cerium oxide particles, by modulating the amount of OH groups removed by warm exhaust gas, ultraviolet reflections of fine particles containing cerium oxide particles having an arbitrary OH group concentration can be formed. Layer 30.
表示有關於準分子燈的第1實驗。Indicates the first experiment on excimer lamps.
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。An excimer lamp having an ultraviolet reflecting layer was produced in accordance with the configuration shown in the first (a) and (b) drawings.
放電容器是材質為二氧化矽玻璃，尺寸為15mm×43mm×350mm、厚度為2.5mm。The discharge vessel is made of cerium oxide glass and has a size of 15 mm × 43 mm × 350 mm and a thickness of 2.5 mm.
高電壓供應電極及接地電極的尺寸是30mm×300mm。The size of the high voltage supply electrode and the ground electrode is 30 mm x 300 mm.
紫外線反射層是由將中心粒徑1.5μm的二氧化矽粒子作成成分比90重量%，將中心粒徑1.5μm的氧化鋁粒子作成成分比10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℃。The ultraviolet ray reflection layer is composed of a cerium oxide particle having a center particle diameter of 1.5 μm as a component ratio of 90% by weight, and an alumina particle having a center particle diameter of 1.5 μm as a component ratio of 10% by weight. It was formed, and the firing temperature was 1000 °C.
作為放電用氣體，將氙以40kPa封入在放電容器內。As a discharge gas, helium was sealed in a discharge vessel at 40 kPa.
針對於具有上述構成的準分子燈，測定二氧化矽粒子中的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500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。With respect to the excimer lamp having the above configuration, the OH group concentration, the reflection retention ratio, and the illuminance maintenance ratio in the cerium oxide particles were measured. All of the ultraviolet reflecting layers were taken out from the discharge vessel and measured by a temperature rise-off gas analysis method. 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.
將燈1～5的測定結果表示於表1。The measurement results of the lamps 1 to 5 are shown in Table 1.
第2圖是針對於表示於表1的測定結果，在橫軸作為二氧化矽粒子中的OH基濃度(wtppm)，在縱軸作為反射維持率(%)，而標示燈1～5的數值的圖表。Fig. 2 is a graph showing the results of the measurement shown in Table 1, in which the horizontal axis is the OH group concentration (wtppm) in the cerium oxide particles, and the vertical axis is the reflection maintaining ratio (%), and the values of the lamps 1 to 5 are indicated. Chart.
又，第3圖是針對於表示於表1的測定結果，在橫軸作為二氧化矽粒子中OH基濃度(wtppm)，在縱軸作為照度維持率(%)，而標示燈1～5的數值的圖表。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. Numerical chart.
又，表示於第2圖及第3圖的圖表，橫軸是成為對數刻度的單對數圖表。Further, in the graphs shown in FIGS. 2 and 3, the horizontal axis is a single logarithmic graph which is a logarithmic scale.
由以上結果，可讀取到二氧化矽粒子中的OH基濃度不足10wtppm，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基濃度成為10wtppm以上，則反射維持率及照度維持率都成為90%以上，而長時間點燈準分子燈，也可維持處理能力的情形。如第2圖及第3圖所示地，可知OH基濃度由不足10wtppm成為10wtppm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10wtppm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。As a result of the above, when the concentration of the OH group in the cerium oxide particles is less than 10 wtppm, the reflection retention ratio and the illuminance maintenance ratio are both low, and the long-time lighting of the excimer lamp may reduce the processing ability. 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 processing ability can be maintained even when the excimer lamp is turned on for a long time. As shown in Fig. 2 and Fig. 3, when the OH group concentration is less than 10 wtppm and 10 wtppm or more, the reflection retention ratio and the illuminance maintenance ratio are rapidly increased, and it is considered that the OH group in the cerium oxide particles is determined. When the concentration is 10 wtppm or more, there is a significant difference, and there is an effect that the illuminance at the time of long-time lighting is maintained.
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10wtppm以上，也發生在準分子燈以172nm作為中心波長的準分子發光的照度較低的情形。又，在作為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的放電的顏色有成為綠色的情形，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550nm附近作為中心波長的綠色光。However, even when the concentration of the OH group in the cerium oxide particles constituting the ultraviolet ray reflection layer 30 is 10 wtppm or more, the illuminance of the excimer luminescence with the 172 nm as the center wavelength of the excimer lamp is low. In the lighting of the excimer lamp 10 in which the xenon lamp 10 is sealed 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 helium atom and an oxygen atom are bonded (XeO) is generated. On the other hand, green light having a central wavelength of around 550 nm is emitted by the molecule.
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(H2 O)作為主成分的不純氣體放出至放電空間S內者。以水作為主成分的不純氣體在電漿中被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。Further, the OH group contained in the cerium oxide particles constituting the ultraviolet ray reflection layer 30 is a discharge plasma generated by being exposed to the discharge space, and is heated to have water (H 2 O) as a main component. The impure gas is released into the discharge space S. The oxygen atoms generated by the decomposition of the impure gas containing water as a main component in the plasma are discharged from the OH group contained in the cerium oxide particles constituting the ultraviolet ray reflection layer 30 to the discharge space 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30時，則有微小粒子的凹凸之故，因而表面積變成比末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，也成為高溫而容易放出不純氣體。When the ultraviolet ray reflection layer 30 formed of the fine particles is formed on the inner surface of the discharge vessel 20, the unevenness of the fine particles is caused, so that the surface area becomes longer than the surface of the flat discharge vessel 20 in which the ultraviolet ray reflection layer 30 is formed. Big. 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 30 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 discharge an impurity gas.
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、12間所發生的放電電漿，所以利用被加熱將不純氣體放出至放電空間S內。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, 12, so that the impure gas is heated by being heated. Released into the discharge space S.
一方面，堆積體B32是形成於由高電壓供應電極11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11、12間所發生的放電電漿。所以，相信從堆積體B32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。On the one hand, the deposition body B32 is formed on the inner surface of the upper wall plate 21 which is deviated from the high voltage supply electrode 11 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 11 and 12. Therefore, it is believed that impure gas is hardly generated from the stacked body B32. Conversely, it is believed that the deposit B32 is a person that adsorbs impure gas, and this case can be confirmed by the following experiment.
作為第2實驗對象，製作在放電容器20的內表面，僅形成堆積體B，而未形成堆積體A的準分子燈。作為放電用氣體使用氙，而在封入放電用氣體之際也混入氧，將事先作為不純氣體封入有氧的準分子燈作為實驗對象。被封入於放電空間S的氧濃度是作為160wtppm，而放電用氣體的壓力是作為40kPa。作為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550nm的放電光，藉此，容易地可判別氧混入在放電空間S的情形。As a second experimental object, an excimer lamp in which only the deposit B was formed on the inner surface of the discharge vessel 20 and the deposit A was not formed was produced. As the discharge gas, ruthenium was used, and when the discharge gas was sealed, oxygen was also 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 oxygen, the reaction with the rare gas causes a large decrease in the contrast degree, and discharge light having a wavelength of 550 nm is generated, whereby the oxygen can be easily mixed into the discharge space S.
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，作為比較例準備末形成有堆積體B的燈4。針對於各個燈，測定一直到準分子放電成為穩定為止的連續點燈15分鐘後的550nm的發光強度，而將其作為「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550nm發光強度，將其作為「550nm發光強度點燈5小時後」。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. Moreover, as a comparative example, the lamp 4 in which the deposit B was formed was prepared. For each of the lamps, the luminescence intensity at 550 nm after 15 minutes from the continuous lighting until the excimer discharge was stabilized was measured, and this was taken as "the initial stage of the 550 nm emission intensity lighting". Thereafter, the excimer lamp was continuously lit, and the 550 nm emission intensity after continuous lighting for 5 hours was measured, and this was referred to as "550 nm luminous intensity for 5 hours".
將第2實驗結果表示於表2。「550nm發光強度點燈5小時後」的數值，是將「550nm發光強度點燈初期」的數值作為100時表示作為相對值。在具備堆積體B的燈1～燈3中，550nm發光強度點燈5小時後的數值減少成100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，在末形成有堆積體B的燈4中，550nm發光強度點燈5小時後的數值仍維持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550nm的光，可知氧被吸附在堆積體B。又，堆積體B是為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。The results of the second experiment are shown in Table 2. The value of "After 5 hours of 550 nm luminous intensity lighting" is a relative value when the value of "initial 550 nm luminous intensity lighting" is taken as 100. In the lamp 1 to the lamp 3 including the stack B, the value after 5 hours of 550 nm luminous intensity is reduced to 100 or less, and the molecule (XeO) in which a ruthenium atom and an oxygen atom are bonded is reduced as compared with the initial stage of lighting. Quantity. 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 formed, the value after 5 hours of 550 nm luminous intensity was maintained at 100, and it was found that the amount of oxygen mixed in the discharge space beforehand 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 excimer lamp to reduce the light of 550 nm, and it was found that oxygen was 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.
以下，在第2實驗被確認的氧被吸附在堆積體B的現象，是為了確認是否為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同樣的構成的燈5～7作為第3實驗。又，作為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550nm的發光強度，將其作為「550nm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550nm的發光強度，將其作為「550nm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550nm發光強度，將其作為「550nm發光強度48小時經過後的點燈5小時後」。Hereinafter, the phenomenon in which oxygen confirmed in the second experiment is adsorbed to the deposit B is to confirm whether or not the light is generated by the excimer lamp, and the third experiment is performed. The lamps 5 to 7 having the same configuration as the lamps 1 to 3 of the second experimental object were used as the third experiment. Moreover, as a comparative example, the lamp 8 in which the deposit B was not formed was prepared. For each of the lamps, the luminescence intensity at 550 nm after 15 minutes of continuous lighting was measured, and this was taken as "the initial stage of 550 nm luminous intensity lighting". Then, it was left still under the light for 48 hours, and after standing, it was turned on, and the luminous intensity of 550 nm which was continuously lit for 15 minutes was measured, and this was made into "after the 550 nm luminous intensity of 48 hours passed." Thereafter, the lighting of the excimer lamp was continued, and the 550 nm luminous intensity after continuous lighting for 5 hours was measured, and this was taken as "after 5 hours of lighting after 48 hours of 550 nm luminous intensity".
將第3實驗結果表示於表3。「550nm發光強度48小時經過後」及「550nm發光強度點燈48小時經過後的點燈5小時後」的數值，是將「550nm發光強度點燈初期」的數值作為100時表示作為相對值。在具備堆積體B的燈5～燈7中，對於550nm發光強度48小時經過後為數值為100，而550nm發光強度48小時經過後的點燈5小時後的數值減少至10～11，可知點燈準分子燈才會減少氧。作為氧被吸附於堆積體B的原理，為在堆積體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。The results of the third experiment are shown in Table 3. The value of "After 48 hours of 550 nm luminous intensity" and "5 hours after lighting of 550 nm luminous intensity lighting for 48 hours" is a relative value when the value of "initial 550 nm luminous intensity lighting" is taken as 100. In the lamp 5 to the lamp 7 having the deposition body B, the value of the 550 nm luminous intensity after 48 hours elapses is 100, and the value after 5 hours of lighting after the 550 nm luminous intensity is 48 hours is reduced to 10 to 11, which is known. The light excimer lamp will reduce 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.
一方面，在未形成有堆積體B的燈8中，550nm發光強度48小時經過，及550nm發光強度48小時經過後的點燈5小時後都仍維持數值為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。On the other hand, in the lamp 8 in which the deposit B was not formed, the luminescence intensity at 550 nm passed for 48 hours, and the luminescence intensity at 550 nm for 48 hours passed after 5 hours of lighting, and the value was maintained at 100, so that it was found that it was mixed in advance. The amount of oxygen in the discharge space did not change.
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)，使用由其量求出比表面積的被稱為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。The fine particles constituting the deposition body B are adsorbed to the impure gas by being exposed on the surface of the discharge space, 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 a BET method in which the specific surface area is determined from the amount. 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.
以下，表示為了確認本發明的效果所進行的第4實驗。Hereinafter, a fourth experiment performed to confirm the effects of the present invention is shown.
依照表示於第1(a)、(b)圖的構成，製作具備堆積體A及堆積體B的準分子燈。An excimer lamp including the stacked body A and the stacked body B was produced in accordance with the configuration shown in the first (a) and (b) drawings.
放電容器是材質為二氧化矽玻璃，尺寸為15mm×43mm×540mm，厚度為2.5mm。The discharge vessel is made of cerium oxide glass and has a size of 15 mm × 43 mm × 540 mm and a thickness of 2.5 mm.
高電壓供應電極及接地電極的尺寸是32mm×500mm。The size of the high voltage supply electrode and the ground electrode is 32 mm x 500 mm.
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，為36mm×504mm。The size of the light-emitting portion corresponding to the region in which the stacked body B is not formed in the lower wall plate is 2 mm larger than the ground electrode, and is 36 mm × 504 mm.
堆積體A與堆積體B是藉由流下法分別形成，燒成溫度是作為1000℃。The deposition body A and the deposition body B were separately formed by a downflow method, and the firing temperature was 1000 °C.
將溫排氣以800℃，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。The warm exhaust gas was subjected to a condition of 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.
所製作的燈的堆積體A的OH基含有量是500wtppm。The OH group content of the deposited body A of the produced lamp was 500 wtppm.
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、成分比為共通，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的設置面積變更為160cm2 、128cm2 、107cm2 、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(1-4)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A。As shown in Table 4, four types of the configuration (1-1), the configuration (1-2), the configuration (1-3), and the configuration (1-4) were prepared for the configuration of the deposition body A. In each of the four configurations, 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 , 128cm 2 , 107cm 2 , 40cm 2 . 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 deposit A in the configuration (1-4), the smaller the amount of impure gas. 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 to be smaller than 160 cm 2 of the area in which the high voltage supply electrode is formed. Therefore, it is not the entire area of the inner surface of the discharge vessel provided with the high voltage supply electrode, but the accumulation body A is formed in a part thereof.
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16×104 cm2 /g、4×104 cm2 /g、1×104 cm2 /g不相同者。又，構成(2-4)的比表面積是成為4×104 cm2 /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。In addition, as shown in Table 5, four types of the configuration (2-1), the configuration (2-2), the configuration (2-3), and the configuration (2-4) are prepared for the configuration of the deposition body B. The configuration (2-1), the configuration (2-2), and the configuration (2-3) are composed only of cerium oxide particles, and the configuration (2-4) is composed of cerium oxide particles and alumina 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 have a specific surface area of 16 × 10 4 cm 2 /g and 4 × 10 4 cm. 2 / g, 1 × 10 4 cm 2 / g are not the same. Further, the specific surface area of the constitution (2-4) is 4 × 10 4 cm 2 /g. The larger the specific surface area of the deposition body B, the more the impure gas is adsorbed. Therefore, the larger the specific surface area of the deposition body B constituting (2-1), the larger the surface area of the discharge space, and thus the mixing. The amount of impure gas in the discharge space is reduced as the lighting is performed, and as the specific surface area of the deposition body B constituting (2-3) is smaller, the amount of impure gas mixed into the discharge space becomes smaller as the lighting is performed.
對於將堆積體A作為構成(1-1)者，將堆積體B作為構成(2-1)～構成(2-4)者準備作為實驗對象。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作為構成(1-2)、構成(1-3)、構成(1-4)者，準備將堆積體B作為構成(2-1)～構成(2-3)者。In the case where the deposit A is used as the configuration (1-1), the deposit B is prepared as an object of the experiment (2-1) to (2-4). In addition, for each of the combinations, five types of the installation area of the deposit B are prepared. In the same manner, in the case where the deposit A is configured (1-2), (1-3), and (1-4), the deposit B is prepared as the configuration (2-1) to (2-3). By.
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為0.6W/cm2 的條件下進行點燈，測定連續點燈15分鐘後的波長150nm～200nm的波長領域的氙準分子光的照度，及在一定的管壁負荷下500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15分鐘後的照度作為初期照度，而將500小時連續點燈之後的照度與初期照度之相對值作為照度維持率，並將「500小時照度維持率」算出作為[(500小時點燈後的照度)/(剛點燈後的照度)](%)。作為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500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小時為止之期間被全部放出，而之後就不會放出。With respect to each of the excimer lamps thus constituted, the tube wall load of the discharge vessel was set to 0.6 W/cm 2 , and the wavelength range of 150 nm to 200 nm after continuous lighting for 15 minutes was measured. The illuminance of the excimer 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 constant wall load. The illuminance after 15 minutes of continuous lighting was used as the initial illuminance, and the relative value of the 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 hour point). Illumination after the lamp) / (illumination after the light is turned on)] (%). The reason for 500 hours is as follows. The illuminance reduction of the impure gas continues for 500 hours, but the subsequent illuminance does not decrease, so the impure gas contained in the ultraviolet ray reflection layer may be completely released during the period of 500 hours, and then will not be released.
作為產品的規格，被要求80%以上的照度維持之故，因而作為判定將500小時照度維持率成為80%時作為「○」，而500小時照度維持率成為80%以下時作為「×」。In the specification of the product, 80% or more of the illuminance is required to be maintained. Therefore, it is determined as "○" when the 500-hour illuminance maintenance rate is 80%, and "x" when the 500-hour illuminance maintenance rate is 80% or less.
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1mm的位置，固定紫外線照度測定器42成為相對向於準分子燈10，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5.0kV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12的網孔被放射的真空紫外光的照度。As shown in Fig. 4, the illuminance measurement is performed by attaching the excimer lamp 10 to the ceramic support table 41 disposed inside the aluminum container 40, and fixing the ultraviolet illuminance at a position 1 mm from the surface of the excimer lamp 10. The device 42 is opposed to the excimer lamp 10, and an alternating high voltage of 5.0 kV is applied between the electrodes 11 and 12 of the excimer lamp 10 in a state in which the internal atmosphere of the aluminum container 40 is replaced with nitrogen, whereby the discharge vessel is placed. A discharge occurs inside the 20, and the illuminance of the vacuum ultraviolet light emitted through the mesh of the ground electrode 12 is measured.
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500小時照度維持率成為80%以上的準分子燈中，堆積體B的設置面積成為最小的組合。例如，堆積體A的構成為「構成(1-1)」的組合，而堆積體B的構成為「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18等。The experimental results are shown in Figures 5 and 6. As a result, in each of the combinations of the configuration of the deposit A and the structure of the deposit B, in the excimer lamp in which the illuminance maintenance rate of 500 hours is 80% or more, the installation area of the deposit B is the smallest. For example, the configuration of the deposit body A is a combination of "constitution (1-1)", and the configuration of the deposit body B is "composition (2-1)", which is suitable for the lamp 3, and is similar to the lamp 8 , lamp 13, lamp 18, and the like.
針對於如此地被抽出的組合，將列述堆積體A的構成，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。With respect to the combination thus extracted, the configuration of the deposit A, the configuration of the deposit B, the specific surface area of the deposit B, and the installation area of the deposit B are shown in Table 6.
第7圖是表示表6的結果的圖表。將橫軸作為堆積體B的比表面積(×104 cm2 /g)，而將縱軸作為堆積體B的設置面積(cm2 )，每一堆積體A的構成地標示數值。Fig. 7 is a graph showing the results of Table 6. The horizontal axis is the specific surface area (×10 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 value of each deposition body A is indicated by a numerical value.
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)具備作為堆積體A的準分子燈，即使增加比表面積，設置面積是也不會成為比10cm2 還要低的數值。In Tables 6 and 7, the larger the specific surface area, the smaller the installation area necessary for suppressing the decrease in illuminance is. With respect to the respective configurations of the stacked body A, that is, the configuration (1-1), the configuration (1-2), and the configuration (1-3), the installation areas are each 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 value lower than 10 cm 2 .
在將構成(1-4)具備作為堆積體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，成為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為0.02倍。In the excimer lamp having the configuration (1-4) as the deposition body A, since the installation area of the deposition body B is too small for the internal volume of the discharge vessel, the impurity gas diffused into the discharge space reaches the deposition body B. The probability of getting low becomes impossible to show the adsorption effect. That is, the size of the discharge space can be said to have the minimum area of the deposition body B necessary. The size of the discharge space is expressed by the internal surface area of the discharge vessel. At this time, the internal 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 0.02 times the internal surface area of the discharge vessel.
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。Hereinafter, each configuration of the stacked body A of FIG. 7 is derived, that is, each of 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 by Table 7.
第8圖是針對於表7的結果，將橫軸作為堆積體A的設置面積(cm2 )，而將縱軸作為堆積體B的比表面積與設置面積之關係的傾斜(×10-4 g)，而標示數值者。Fig. 8 is a graph showing the results of Table 7, with the horizontal axis as the installation area (cm 2 ) of the deposition body A and the vertical axis as the inclination of the relationship between the specific surface area of the deposition body B and the installation area (×10 -4 g ), and the value is marked.
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的設置面積作為a(cm2 )時，堆積體B的比表面積與設置面積之關係的傾斜，是可表示作為-5.0×10-7 ×a。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 having a negative inclination with respect to the installation area (cm 2 ) of the deposit A. When the installation area of the deposit A is a (cm 2 ), the inclination of the relationship between the specific surface area of the deposit B and the installation area can be expressed as -5.0 × 10 -7 × a.
第9圖是針對於表7的結果，將橫軸作為堆積體A的設置面積(cm2 )，而將縱軸作為堆積體B的比表面積與設置面積之關係的切片(cm2 )，而標示數值者。9 is a result of Table 7, and the horizontal axis is the installation area (cm 2 ) of the deposition body A, and the vertical axis is the slice (cm 2 ) of the relationship between the specific surface area of the deposition body B and the installation area. Mark the value.
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的設置面積作為a(cm2 )時，堆積體B的比表面積與設置面積之關係的切片，是可表示作為0.35×a。As can be seen 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 (cm 2 ) of the deposit A. When the installation area of the deposit A is a (cm 2 ), the slice of the relationship between the specific surface area of the deposit B and the installation area can be expressed as 0.35 × a.
又，由第7圖堆積體B的設置面積是對於堆積體B的比表面積，以「堆積體B的比表面積與設置面積之關係的傾斜」，可說具有作為「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的設置面積作為b(cm2 )，而將堆積體B的比表面積作為c(cm2 /g)時，可表示為In addition, the installation area of the deposit B in Fig. 7 is the specific surface area of the deposit B, and the "inclination of the relationship between the specific surface area of the deposit B and the installation area", and it can be said that the specific surface area of the deposit B is Set the proportional relationship of the slice of the relationship of the areas. 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 (cm 2 ), and the specific surface area of the deposition body B is taken as c (cm). 2 / g), can be expressed as
b=(堆積體B的比表面積與設置面積之關係的傾斜)×c+(堆積體B的比表面積與設置面積之關係的切片)b = (inclination of the relationship between the specific surface area of the deposit B and the set area) × c + (slice of the relationship between the specific surface area of the deposit B and the set area)
又，由第8圖及第9圖的結果，將堆積體A的設置面積作為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為-5.0×10-7 ×a，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為0.35×a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。Moreover, when the installation area of the deposit A is a (cm 2 ) as a result of the eighth figure and the ninth figure, the inclination of the relationship between the specific surface area of the deposit B and the installation area can be expressed as -5.0×10. -7 × a, and the slice of the relationship between the specific surface area of the deposition body B and the installation area is 0.35 × a. Therefore, the relationship between the installation area of the deposition body B of Fig. 7 and the specific surface area of the deposition body B is It can be expressed as follows.
b=-5.0×10-7 ac+0.35ab=-5.0×10 -7 ac+0.35a
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500小時照度維持率成為80%以上，而被讀取判定成為○。Further, from the experimental results of Figs. 5 and 6, the installation area b of the deposition body B is larger than the relationship between the installation area of the deposition body B shown in Fig. 5 and the specific surface area of the deposition body B. When the value is large, the 500-hour illuminance maintenance rate is 80% or more, and the reading is judged to be ○.
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，為了抑制照度降低。堆積體B的設置面積滿足以下的關係就可以。From the above results, it was found that in the excimer lamp including the deposit A containing the OH group, the illuminance was suppressed from being lowered. The installation area of the deposit B can satisfy the following relationship.
將堆積體A的設置面積作為a(cm2 )，將堆積體B的設置面積作為b(cm2 )，將堆積體B的比表面積作為c(cm2 /g)時，為When the installation area of the deposit A is a (cm 2 ), the installation area of the deposit B is b (cm 2 ), and when the specific surface area of the deposit B is c (cm 2 /g),
b≧-5.0×10-7 ac+0.35aB≧-5.0×10 -7 ac+0.35a
又，針對於第7圖中，在將構成(1-4)具備作為堆積體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為比10cm2 還要低值，而堆積體B的比表面積與設面積之關係不會成為將構成(1-1)、構成(1-2)、構成(1-3)具備作為堆積體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)具備作為堆積體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)具備作為堆積體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)具備作為堆積體A的情形。In addition, in the excimer lamp including 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 10 cm 2 . In addition, the relationship between the specific surface area of the deposit B and the set area is not to be included as the deposit A in the configuration (1-1), the configuration (1-2), and the configuration (1-3). Therefore, in Table 7, FIG. 8, and FIG. 9, the case where the configuration (1-4) is provided as the deposit A is not considered. In other words, the condition that the installation area of the deposit B is satisfied is the case where the configuration (1-4) is provided as the deposit A. Therefore, in the case where the installation area is required to be satisfied, it is necessary to remove the configuration (1-4) as the deposit A.
將構成(1-4)具備作為堆積體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的設置面積是對於放電容器的內表面積成為0.02倍左右時。因此，為了抑制照度降低，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為d(cm2 )時，也必須滿足以下的條件。In the case where the configuration (1-4) is provided as the deposition body A, the installation area of the deposition body B is too small for the internal volume of the discharge vessel, and thus the effect of adsorption cannot be exhibited. That is, the installation area of the deposit B is about 0.02 times the inner surface area of the discharge vessel. Therefore, in order to suppress the decrease in illuminance, when the internal surface area of the discharge vessel is d (cm 2 ) in relation to the installation area b (cm 2 ) of the deposit B, the following conditions must be satisfied.
b>0.02db>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，為了抑制照度，堆積體B的構成必須滿足以下的關係。將堆積體A的設置面積作為a(cm2 )，將堆積體B的設置面積作為b(cm2 )，將堆積體B的比表面積作為c(cm2 /g)，將放電容器的內表面積作為d(cm2 )時，必須滿足如下。From the above results, it is understood that in the excimer lamp including the stacked body A containing the OH group, in order to suppress the illuminance, the structure of the deposited body B must satisfy the following relationship. The installation area of the deposit A is taken as a (cm 2 ), the installation area of the deposit B is b (cm 2 ), and the specific surface area of the deposit B is c (cm 2 /g), and the inner surface area of the discharge vessel is set. As d (cm 2 ), it must be satisfied as follows.
b≧-5.0×10-7 ac+0.35a，且b>0.2d。B≧-5.0×10 -7 ac+0.35a, and 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，而有效率地可射出真空紫外光。By satisfying the above relationship, the amount of the impure gas discharged from the deposit A does not exceed the amount of the impure gas which the deposit B can adsorb, and the impure gas does not remain in the discharge space. Therefore, it is possible to suppress the decrease in illuminance of excimer light emission caused by the combination of the oxygen atoms contained in the impure gas and the discharge gas, and to suppress the decrease in illuminance even when lighting for a long period of time, and to efficiently emit the vacuum ultraviolet light.
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，而為堆積體A或堆積體B的表面假設為平滑加以計測的數值。又，放電容器的內表面積d(cm2 )也假設其表面為平滑加以計測的數值。Further, the installation area setting area stacked body A a (cm 2) and a bulk body B b (cm 2), is not taken into account the uneven fine particles, and the surface is assumed stacked body A or stacked body B is a smooth be The measured value. Further, the internal surface area d (cm 2 ) of the discharge vessel is also assumed to be a value measured by smoothing the surface.
10．．．準分子燈10. . . Excimer lamp
11．．．高電壓供應電極11. . . High voltage supply electrode
12．．．接地電極12. . . Ground electrode
20．．．放電容器20. . . Discharge capacitor
21．．．上壁板twenty one. . . Upper wall
22．．．下壁板twenty two. . . Lower wall
23．．．側壁板twenty three. . . Side wall panel
24．．．端壁板twenty four. . . End wall
30．．．紫外線反射層30. . . Ultraviolet reflective layer
31．．．堆積體A31. . . Stack A
32．．．堆積體B32. . . Stack B
40．．．鋁製容器40. . . Aluminum container
41．．．支撐台41. . . Support table
42．．．紫外線照度測定器42. . . Ultraviolet illuminance tester
S．．．放電空間S. . . Discharge space
第1圖是表示本發明的準分子燈的一例子的構成的概略的說明用斷面圖，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。Fig. 1 is a cross-sectional view showing the outline of an example of an excimer lamp of the present invention, and Fig. 1(a) is a cross-sectional view showing a cross section along the longitudinal direction of the discharge vessel, first (b) The figure is a cross-sectional view taken along line AA.
第2圖是表示準分子燈的實驗結果。Figure 2 is an experimental result showing an excimer lamp.
第3圖是表示準分子燈的實驗結果。Figure 3 is a graph showing the experimental results of the excimer lamp.
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。Fig. 4 is a cross-sectional view showing a method of measuring the illuminance of the excimer lamp of the embodiment.
第5圖是表示準分子燈的實驗結果。Figure 5 is a graph showing the experimental results of the excimer lamp.
第6圖是表示準分子燈的實驗結果。Figure 6 is a graph showing the experimental results of the excimer lamp.
第7圖是表示準分子燈的實驗結果。Figure 7 is a graph showing the experimental results of the excimer lamp.
第8圖是表示準分子燈的實驗結果。Figure 8 is a graph showing the experimental results of the excimer lamp.
第9圖是表示準分子燈的實驗結果。Figure 9 is a graph showing the experimental results of the excimer lamp.
第10圖是表示習知的準分子燈的構成的概略的說明用立體圖。Fig. 10 is a perspective view showing the outline of a configuration of a conventional excimer lamp.
10．．．準分子燈10. . . Excimer lamp
11．．．高電壓供應電極11. . . High voltage supply electrode
12．．．接地電極12. . . Ground electrode
20．．．放電容器20. . . Discharge capacitor
21．．．上壁板twenty one. . . Upper wall
22．．．下壁板twenty two. . . Lower wall
23．．．側壁板twenty three. . . Side wall panel
24．．．端壁板twenty four. . . End wall
30．．．紫外線反射層30. . . Ultraviolet reflective layer
31．．．堆積體A31. . . Stack A
32．．．堆積體B32. . . Stack B
S．．．放電空間S. . . Discharge space
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