TW526385B

TW526385B - Fluoride lens crystal for optical microlithography systems

Info

Publication number: TW526385B
Application number: TW89111007A
Authority: TW
Inventors: Robert W Sparrow
Original assignee: Corning Inc
Priority date: 1999-06-04
Filing date: 2000-06-03
Publication date: 2003-04-01

Abstract

The present invention provides fluoride lens crystals for VUV optical lithography systems and processes. The invention provides a barium fluoride optical lithography crystal for utilization in 157 nm optical microlithography elements which manipulate below 193 nm optical lithography photons. The invention includes a barium fluoride crystalline material for use in dispersion management of below 160 nm optical lithography processes.

Description

經濟部中央標準局灵工消费合作社印製 526385 五、發明説明發明領域：本發明係關於光學石版印刷，以及特別地關於光學微石版印刷晶體以使用於光學石版印刷系統中，該系統使用波長低於193nm之真空紫外線(Vuv)，優先地低於175咖，更優先地低於164nm，例如使用波長低於i57nm之VUV投射石版印刷折射系統。發明背景：半導體晶片例如為微處理器以及DRAM係使用所謂，，光學石版印刷"製造出。絲石版印刷器具包含照明透鏡系統作為照明圖案遮罩，光源以及投射透鏡系統以產生遮罩圖案影像於矽基質上。半V體性能已藉由減小外形尺寸而加以改善。因而需要對光學石版印刷器具之解析度加以改善。通常，轉移圖案之解析度直接地與透鏡系統之數值孔徑成正比以及與照 =光線之波長成反比。在198〇年代早期所使用光線波長為水燈泡g線條之436nm。而後波長減小至365ηπι(汞燈泡I線條）以及目前製造過程所使用波長為248nm，其由KrF雷射發，出。下-代石版印刷器具將改變光源為發射出193·光、、泉之ArF雷射。光學石版印刷自然地利用改良發射出π?· 氟化物雷射之光源。對於每一波長，製造透鏡需要不同的材料/在248nm波長下光學材料為熔融矽石。對於193〇111系，，需要共同使用熔融矽石以及氟化鈣之透鏡。在157麗下石夕石並不透射雷射光線。目前關使射H57nm波長下材料/、有氟化鈣。參閱丨996年7月日申請之8巧3%9號 (請先閲讀背面之注意事項再填寫本頁)Printed by Lingong Consumer Cooperative, Central Standards Bureau, Ministry of Economic Affairs 526385 V. Description of the Invention Field of the Invention: The present invention relates to optical lithographic printing, and in particular, to optical microlithographic printing of crystals for use in optical lithographic printing systems. The vacuum ultraviolet (Vuv) at 193nm is preferentially lower than 175, more preferably lower than 164nm, for example, a VUV projection lithography refractive system using a wavelength lower than i57nm. BACKGROUND OF THE INVENTION Semiconductor wafers, such as microprocessors and DRAMs, are manufactured using optical lithography ". The lithographic printing apparatus includes an illumination lens system as a lighting pattern mask, a light source, and a projection lens system to generate a mask pattern image on a silicon substrate. Half-V performance has been improved by reducing the size of the body. Therefore, the resolution of the optical lithographic printing apparatus needs to be improved. In general, the resolution of the transfer pattern is directly proportional to the numerical aperture of the lens system and inversely proportional to the wavelength of the illumination light. The wavelength of light used in the early 1980s was 436 nm of the g-line of the water bulb. Then the wavelength was reduced to 365ηπι (mercury bulb I line) and the current manufacturing process used a wavelength of 248nm, which was emitted by a KrF laser. The next-generation lithographic printing appliance will change the light source to emit 193 · light, ArF laser. Optical lithography naturally uses a modified light source that emits π? · Fluoride lasers. For each wavelength, different materials are required to make the lens / optical material is fused silica at a wavelength of 248nm. For the 193011 series, it is necessary to use a lens of fused silica and calcium fluoride together. At 157, Shi Xishi does not transmit laser light. At present, the material used at the wavelength of H57nm is calcium fluoride. Please refer to No. 8% 9% of the application dated July 996 (Please read the precautions on the back before filling this page)

4 經濟部中央標準局見工消費合作社印製 526385 • * A7 ~ ---——~-___ 五、發明説明（> ) 專利即日本1998年1月6日公告之10-13號專利，應年8月 2〇日申請以及1998年3月3日公告之日本第1(r9799號專利，兩個專利申請人均為Nikon Corporation。 . 投射光學石版印刷系統使用低於193nm波長之真空紫外線，其能夠達到較小外形尺寸之優點。該系統使用157㈣波長範圍之真空紫外線波長，其能夠改善較小外形尺寸之 =體線路。时在半導體卫業界製造集體線路巾所使用光學石版印⑽:_向使職短波長之光、_如為·面以及193mn波長，但是市場上所使用為波長低於1Q3nm真空紫 =線，例如157簡已受到所通過光學材料157·範圍之真空紫外線波長透難性所阻礙。為了有益於製造集體電路所使用157nm範圍例如為F2準分子雷射發射νϋν頻窗之紫外線光石版印刷，低於164nm以及在157nm之有益的光學特性光學石版印刷為需要的。本發明克服先前技術之問題以及提供氟化物光學石版印刷晶體，其能夠利用真空紫外線波長改善集體線路之掣造。. 、發明大要：本發明一項為低於光學石版印刷氟化鋇之晶體。氟化鎖晶體在157nm下折射性波長色散dn/d;l < -〇〇〇3。本發明另外一項包含色散控制晶體為等方性氟化鋇晶月立。優先地，氟化鋇在157· 6299nm折射性波長色散dn/d；^ 小於-0· 003以及157. 6299nm之折射率η>1. 56。本發明另外一項為包含低於160nm光學石版印刷方法，4 The Central Bureau of Standards of the Ministry of Economic Affairs has printed 526385 • * A7 ~ ------- ~ -___ V. Description of Invention (>) The patent is the Japanese Patent No. 10-13 published on January 6, 1998. The Japanese Patent No. 1 (r9799), which was filed on August 20, and published on March 3, 1998, both patent applicants are Nikon Corporation.. Projection optical lithography system uses vacuum ultraviolet light with a wavelength lower than 193nm. Can achieve the advantages of smaller size. The system uses vacuum ultraviolet wavelengths in the 157㈣ wavelength range, which can improve the smaller size of the body line. When used in the semiconductor health industry to manufacture collective line towels, optical lithographs: _ 向Use of short-wavelength light, such as · plane and 193mn wavelength, but the vacuum violet = line with a wavelength below 1Q3nm is used in the market, for example, 157 Jan has been subjected to the vacuum ultraviolet wavelength transmission of the 157 · range of optical materials. Obstructed. For the benefit of manufacturing collective circuits, UV light lithography in the 157nm range, such as F2 excimer laser emission νϋν frequency window, is useful below 164nm and beneficial light at 157nm. Characteristic optical lithography is needed. The present invention overcomes the problems of the prior art and provides fluoride optical lithographic printing crystals, which can use vacuum ultraviolet wavelengths to improve the control of collective lines.. The invention is: Optical lithography of crystals of barium fluoride. Fluorine-locked crystals have a refractive wavelength dispersion at 157 nm dn / d; l--0000. Another aspect of the present invention includes dispersion-controlling crystals that are isotropic barium fluoride crystals. Yue Li. Preferentially, barium fluoride has a refractive wavelength dispersion dn / d at 157.629 nm; ^ is less than -0.33 and a refractive index η > 1.56 of 157.629 nm. Another aspect of the present invention is to include less than 160 nm Optical lithography method,

(請先閱讀背面之注意事項再填寫本頁)(Please read the notes on the back before filling this page)

526385526385

經濟部中央標準局見工消费合作社印製 f包含提供低於16〇nm光學石版印刷照明雷射，提供氟化舞晶體光學元件，其提供氟化鋇晶體光學元件，其低於16〇nm 折射性波長色散如/(1又<-〇· 003,以及透射低於160nm光學石版印刷光線通過氟化鈣光學元件以及氟化鋇光學元件以形成光學石版印刷圖案。風本發明另外一項中，本發明包含一種製造色散控制光學石版印刷元件之方法。該方法包含提供氟化鋇來源材料二將氟化鋇來源材料熔融以形成預先結晶氟化鋇熔融物，將氟化鋇熔融物固化為氟化鋇晶體以及將氟化鋇晶體退火以產生等方性氟化鋇晶體，其l57nm折射性波長色散如八^入〈 -0· 003。本杳明其他特性及優點揭示於下列詳細說明，其部份可立即地由熟知此技術者了解或實施下列本發明詳細說明以及申請專利範圍而明瞭。· 人們了解先前一般說明以及下列詳細說明為本發明範例性以及在於提供一個架構以了解本發明原理及特性。為了減小石版印刷處理過程照明光線之波長以得到更高解析度為必需的，照明光線雷射照射具有有限頻寬。為了得到在⑽·節闕需要之騎度，使⑽有光學設計光學石版印刷益具製造商能夠使用高度線性狹窄雷射（小於2 ppm)或能夠使用兩種光學材料，其色散特性能夠補償雷射頻寬。本發明優先貫施例提供等方性光學石版印刷結晶材料作為νυν石版印刷色彩改正，特別是丨57_範圍以促使製造 (請先閱.讀背面之注意事項再填巧木頁〕 -JMm:The Central Bureau of Standards of the Ministry of Economic Affairs sees the printing of industrial and consumer cooperatives including the provision of optical lithographic printing lasers below 160nm, the provision of fluorinated dance crystal optics, which provides barium fluoride crystal optics, which has a refractive index below 160nm The characteristic wavelength dispersion is such as / (1 and <-0.003, and the transmission of optical lithographic printing light below 160 nm passes through the calcium fluoride optical element and the barium fluoride optical element to form an optical lithographic printing pattern. Wind In another aspect of the present invention The present invention includes a method for manufacturing a dispersion-controlled optical lithographic printing element. The method includes providing a barium fluoride source material and melting the barium fluoride source material to form a pre-crystallized barium fluoride melt, and solidifying the barium fluoride melt into Barium fluoride crystals and annealed barium fluoride crystals to produce isotropic barium fluoride crystals with a refraction wavelength dispersion of 1557 nm, such as ^ 〈<-0. 003. Other characteristics and advantages of the present invention are disclosed in the following detailed description, Part of it can be immediately understood by those skilled in the art to understand or implement the following detailed description of the present invention and the scope of patent application. People understand the previous general description to The following detailed description is exemplary of the present invention and it is to provide a framework to understand the principles and characteristics of the present invention. In order to reduce the wavelength of the illuminating light during the lithographic printing process to obtain higher resolution, it is necessary that the laser light irradiation of the illuminating light has a limited frequency. Wide. In order to obtain the required riding degree at the festival, manufacturers of optical lithography printing equipment with optical design can use highly linear narrow lasers (less than 2 ppm) or can use two optical materials whose dispersion characteristics can Compensation of radio frequency bandwidth. The present invention preferentially provides isotropic optical lithographic crystalline materials as νυν lithographic printing color correction, especially the 57_ range to promote manufacturing (please read first. Read the precautions on the back and fill in the wood Page] -JMm:

526385 A7 B7 五、發明説明（手）折射性透鏡能夠使用氟化物準分子雷射所發出光線，該雷射線條狹窄至低於2ppm。本發明範圍包含氟化物結晶材料，其能夠提供157匪光學石版印刷之優點。在優先實施例中使用色散控制光學石版印刷晶體以及頻寬不小於〇· 2ps (Picosecond)之157nm光學石版印刷照明雷射。詳細說明：材料折射性隨著通過能量之波長而變化以及稱為材料之色散。因此假如通過一種光學材料所製造出透鏡系統之光線為一個範圍之波長，其每一波長將具有不同的焦距因而減小解析度。該效應能夠藉由使用具有不同色散特性之第二種光學材料加以克服。該技術已知為色彩改正。為了使用作為色彩改正材料，必需符合之特定規格，即材料必需在操作波長下能夠透射，其必需為等方性以及必需具有最佳色散特性。在157nm下，具有量測至所需要程度精確度色政特性之材料只有氟化弼。採用157nm透射性以及為等方性之標準，能夠使用下列材料作為色彩改正之材料。 I·主要為驗金屬敗化物之材料經濟部中央標準局凡工消費合作社印製氟•化鐘，氟化納，氟化鉀，以及下列分子式材料:紐&其中 Μ為Li，Na，或K以及R為Ca，Sr，Ba或Mg。該材料可為腹迚3， KSrFa, KBaFs, KCaFs, LiMgFa, LiSrFa, LiBaFa, LiCaFs ， NaMgF3, NaSrF3, NaBaFs，以及NaCaF3。 II. I·主要為驗土金屬氟化物之材料 =匕齊，氟化編及a倾，每-材料能夠與其他材料丑同形成为子式為齡⑹…之混合晶體，其中_Ba，c/、 526385 A7 B7 五、發明説明（{) 或Sr以及Μ2為Ba’Ca或Sr以及X為界於0與1之間數值。非限制範例為Bao.sSr。·^ 其中χ=〇. 5以及Bao.25Sro.75F2，其中χ-0· 75。當χ=〇,材料為caF2, BaF2, SrF2。 III.主要為分子式沁4芯+1混合晶體材料，其中仏為以，此，或Sr以及R為鑭。在這些材料中晶體結構為等方性，义值最高為〇. 3。該为子式非限制性範例包含CaQ 72La() 28f2· 28,其中χ二〇. 28，或“&°.261?2.26,其中㈣· 26,或Sr〇.79La〇.21F2.21，其中x=0. 21。 ’ 經濟部中央標準局旯工消费合作社印製 1上述每一種材料I，η，及ΙΠ能夠使用已知,，St〇ckbarger 或Bridgman"晶體成長技術。該處理過程包含裝載將成長之材料粉末進人職容制。高純度石墨製造出職放置 T熱H内可義支撐結構體上，加熱器具有充份功率以提高溫度高於成長㈣之職。在組裝加熱器系統於綱週圍後，系統利用鐘形瓶加以閉合以及使用組合真空栗施以真=抽除。在達·-5托真空度，施加功率於加熱器以及，績性地提高持續到達到預先設定之數值。該預先設定值藉由：!:谷融知作界定出。在熔融功率下歷時數小時後，促使可移動支撐結構以及掛禍緩慢地在高溫爐中下降。當掛堝丁^下降時，其開始冷卻以及熔融材料開始冷凝。藉由連項性地降低，將持續性固化直舰融物冷卻時。在該溫度下，供應至尚溫爐功率減小低於熔融功率，坩堝提高回到加熱器，口在數小時期間内_熱平衡以及再藉由緩慢地減小加熱③辨以冷卻至室溫。_旦在室溫下，釋除真空，移本紙張尺度 ® ®^#^TcNS ) AAm^ (ΤΓ^Γ297^^ 526385 Α7 Β7 五、發明説明（6 ) 除鐘形瓶，而後加熱器以及晶體能夠由坩禍移除。、雖然Bridgman或Stockbarger晶體成長為I般氟化物為主材料晶體成長之方法，然而並非只可利用該方法。由這些材料產生碟狀大小及形狀為可加以變化，例如透鏡·直徑為118 250mm厚度為30-5〇_。碟狀物以傳統方式加以研磨為相同尺寸之透鏡以及具有所需要之曲率。透鏡具有一般性應用，例如所需要之色彩改正。透鏡能夠廣泛地加入光學糸統中，例如包含非限制性之醒雷射之系統，頻譜儀系統，顯微鏡以及望遠鏡。先前製造出之特定實施例為列舉性以及並非在於限制本發明。所有先前以及下列所引述專利以及文獻在此加入作為參考之用。熟知此技術者能夠由先前一般說明能夠很容易確定本發明貫質特性，以及能夠由本發明作出許多變化及改良於不同之應用以及情況，但是其並不會脫離本發明之精神與範圍/ ^ 經濟部中央標準局見工消費合作社印製本發明包含低於160nm光學晶體透射以使用於至少為〇· 2pm頻寬而低於160nm之石版印刷雷射。光學石版印刷晶體由專方性氟化鋇晶體所構成，其157nm透射性大於85%以及在157nm下折射性波長色散dn/dxeo oos。優先地氟化鋇晶體在157nm下折射性波長色散如/d Α<-〇· 004,以及優先地<-0. 0043。優先地氟化鋇晶體在157麗下折射率η> 1· 56。更優先地η^1· 6,以及更優先地η^1· 64。優先地，本纸張尺度適用中國國家標準（CNS ) Λ4規格（2ΐ〇χ 297公旋） 525m A7 B7 五、發明説明（y ) 經濟部中央標準局1工消費合作社印製氟化鋇晶體在157nm下折射性溫度常數dn/dt>8xl (TV°C，以及更優先地dn/dt-8· 5义10_6/。(：。在優先實施例中，光學石版印刷氟化鋇晶體具有較大尺寸之直徑>1〇〇_以及厚度>30mm，優先地直徑在118至250nm範圍内以及厚度在30至 50nm範圍内。當使用寬廣頻寬時，照明光源例如為F2準分子雷射頻寬至少為0· 5pm，氟化鋇晶體包含控制頻寬色散之光學元件。優先地氟化鋇光學石版印刷具有鈉污染含量〈 lOppm重量比，優先地<5ppm重量比，以及最優先地<ιρριη。優先地，氟化鋇光學石版印刷晶體具有稀土族元素總含量小於lppm重量比。優先地，氟化鋇光學石版印刷晶體氧污染總量小於50ppm重量比，以及優先地小於2〇ppm。該低污染量產生有益的光學特性，以及優先地晶體在157nm透射 -86%，以及更優先地-88%。本發明另外一項包含低於16〇nm控制色散之光學石版印刷晶體。控制色散光學石版印刷晶體包含等方性氟化鋇，其在157· 6299nm下折射性波長色散dn/d;l<—〇· 〇〇3以及在 157. 6299nm下折射率η>1. 56。優先地控制色散晶體如〈-0. 004,以及更優先地dn/dA<-〇· 0043。優先地，晶體折射率η>1. 6。本發明另外一項包含低於160nm光學石版印刷方法，其包含提供低於160nm光學石版印刷照明雷射，提供氟化鈣光學元件，以及板供氟化鋇晶體光學元件，其低於16〇nra折射性波長色散dn/dA<-〇. 〇〇3。本發明方法包含透射低於 nm光學石版印刷光線通過氟化鈣光學元件以及氟化鋇光學本紙張尺度適用中國國家標準（CNS ) Λ4規格（2i〇、x 297公旋） (請先閲讀背面之注意事項再填寫木頁) 、-口 526385 A7526385 A7 B7 V. Description of the invention (hand) The refractive lens can use the light emitted by the fluoride excimer laser, which is narrower than 2ppm. The scope of the present invention includes fluoride crystalline materials, which can provide the advantages of 157 optical lithography. In the preferred embodiment, a dispersion-controlled optical lithographic crystal and a 157 nm optical lithographic illumination laser with a bandwidth of not less than 0.2 ps (Picosecond) are used. Detailed description: Material refraction varies with the wavelength of passing energy and is called the material's dispersion. Therefore, if the light of a lens system manufactured by an optical material is a range of wavelengths, each wavelength will have a different focal length, thereby reducing the resolution. This effect can be overcome by using a second optical material with different dispersion characteristics. This technique is known as color correction. In order to be used as a color correction material, certain specifications must be met, that is, the material must be transmissive at the operating wavelength, it must be isotropic, and it must have the best dispersion characteristics. At 157nm, the only material that has the color accuracy to measure to the required degree of accuracy is thorium fluoride. Using 157nm transmission and isotropic standards, the following materials can be used as color correction materials. I · Materials for testing metal failures. Printed fluorine-chemical bells, sodium fluoride, potassium fluoride, and the following molecular formula materials printed by the Fangong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs: where M is Li, Na, or K and R are Ca, Sr, Ba or Mg. The material can be belches 3, KSrFa, KBaFs, KCaFs, LiMgFa, LiSrFa, LiBaFa, LiCaFs, NaMgF3, NaSrF3, NaBaFs, and NaCaF3. II. I · Materials for detecting metal fluorides in soil = darts, fluorinated braids, and a tilts. Each-material can be mixed with other materials to form a mixed crystal of the age formula ... / 、 526385 A7 B7 5. Description of the invention ({) or Sr and M2 are Ba'Ca or Sr and X is a value between 0 and 1. An unrestricted example is Bao.sSr. · ^ Where χ = 0.5 and Bao.25Sro.75F2, where χ-0.75. When χ = 〇, the materials are caF2, BaF2, SrF2. III. It is mainly a composite crystal material of Qin 4 cores + 1, in which ytterbium is based on this, or Sr and R are lanthanum. In these materials, the crystal structure is isotropic, with the highest meaning being 0.3. The non-limiting examples of this formula include CaQ 72La () 28f2 · 28, where χ / 2.28, or "& ° .261? 2.26, where ㈣ · 26, or Sr.79La〇.21F2.21, Where x = 0. 21. 'Printed by the Central Standards Bureau, Ministry of Economic Affairs, Machining and Consumer Cooperatives. Each of the above materials I, η, and ΙΠ can use known, Stochbarger or Bridgman " crystal growth techniques. This process includes Loading the growing material powder into the capacity system. Made of high-purity graphite and placed on the T-H internal support structure. The heater has sufficient power to raise the temperature higher than the growth temperature. In the assembly heater After the system is around the Gang, the system is closed with a bell jar and applied with a vacuum pump to give true = extraction. At a vacuum of -5 Torr, power is applied to the heater and the performance improvement continues until it reaches a preset The preset value is defined by:!: Gu Rongzhi. After several hours at the melting power, the movable support structure and the accident are slowly lowered in the high-temperature furnace. When the hanging pot is lowered As it begins to cool and melt the material Start to condense. By continuously reducing the temperature of the continuously solidified straight ship melt, at this temperature, the power supplied to the temperature-reducing furnace is lower than the melting power, and the crucible is raised back to the heater. During the hour _ thermal equilibrium and cooling to room temperature by slowly reducing the heating ③. Once the vacuum is released at room temperature, move the paper size ® ® ^ # ^ TcNS) AAm ^ (ΤΓ ^ Γ297 ^^ 526385 Α7 Β7 V. Description of the invention (6) The bell jar is removed, and then the heater and crystal can be removed by crucible. Although the Bridgman or Stockbarger crystal grows into a type I fluoride-based crystal growth method, however, This method is not the only one. The size and shape of the dish produced by these materials can be changed, such as a lens · 118 · 250mm in thickness · 30 ~ 50 °. The dish is conventionally ground into a lens of the same size and The lens has the required curvature. The lens has general applications, such as the required color correction. The lens can be widely used in optical systems, such as systems including non-limiting wake lasers, spectrum analyzer systems, Micromirrors and telescopes. The specific embodiments previously produced are illustrative and are not intended to limit the invention. All previously and following cited patents and documents are incorporated herein by reference. Those skilled in the art will be able to refer to the previous general description. It is easy to determine the consistency characteristics of the present invention, and many changes and improvements can be made by the present invention to different applications and situations, but it will not depart from the spirit and scope of the present invention. The invention includes transmission of optical crystals below 160 nm for use in lithographic lasers with a bandwidth of at least 0.2 pm and below 160 nm. Optical lithographic crystals are composed of specialized barium fluoride crystals, which have a transmission at 157nm of greater than 85% and a refractive wavelength dispersion dn / dxeo oos at 157nm. The barium fluoride crystal preferably has a refractive wavelength dispersion at 157 nm such as / d Α <-0.004, and preferentially < -0. 0043. The refractive index η of the barium fluoride crystal at 157 nm is preferentially 1.56. Η ^ 1 · 6 is more preferred, and η ^ 1 · 64 is more preferred. Preferentially, this paper size applies the Chinese National Standard (CNS) Λ4 specification (2ΐ〇χ 297 revolutions) 525m A7 B7 V. Description of the invention (y) Barium fluoride crystals printed by the Central Standards Bureau of the Ministry of Economic Affairs 1 Industrial Cooperative Cooperative Refractive temperature constant at 157nm dn / dt > 8xl (TV ° C, and more preferably dn / dt-8 · 5 meaning 10_6 /. (. In the preferred embodiment, optical lithographic printing of barium fluoride crystals has a larger The diameter of the dimension > 100_ and the thickness > 30mm, preferably the diameter is in the range of 118 to 250nm and the thickness is in the range of 30 to 50nm. When a wide bandwidth is used, the illumination light source is, for example, F2 excimer thunder band At least 0.5 pm, the barium fluoride crystal contains optical elements that control bandwidth dispersion. Preference is given to barium fluoride optical lithography having a sodium contamination content <10 ppm by weight, preferentially < 5 ppm by weight, and most preferentially < ιρριη. Preferentially, the barium fluoride optical lithographic crystal has a total rare earth element content of less than 1 ppm by weight. Preferentially, the total amount of oxygen pollution of the barium fluoride optical lithographic crystal is less than 50 ppm by weight, and preferably less than 20 ppm. Low contamination yields beneficial optical characteristics, and preferentially crystal transmission at 157nm-86%, and more preferentially -88%. Another aspect of the invention includes optical lithographic crystals with controlled dispersion below 160nm. Dispersion Control Optics The lithographic printing crystal contains isotropic barium fluoride, which has a refractive wavelength dispersion dn / d; l < -〇 · 〇〇3 at 157.6299 nm and a refractive index η > 1.56 at 157.629 nm. Controlled preferentially Dispersive crystals such as <-0. 004, and more preferably dn / dA <-0. 0043. Preferentially, the refractive index of the crystal η > 1.6. Another aspect of the present invention includes an optical lithographic printing method below 160 nm, which comprises Provide optical lithographic printing lasers below 160nm, provide calcium fluoride optical elements, and plate for barium fluoride crystal optical elements, which have a refractive index dispersion dn / dA <-〇.〇〇03. The invention method includes transmitting the optical lithographic printing light below nm through calcium fluoride optical elements and barium fluoride optics. The paper size applies the Chinese National Standard (CNS) Λ4 specification (2i〇, x 297 revolutions) (Please read the note on the back first) Fill in the items again Page), - oral 526385 A7

B7 發明説明經濟部中央標準局炅工消費合作社印製石版印刷圖案，優先地外形尺寸湖nm。 5光學元件優先地包含裝載氟化鋇晶體原料乂 w料炫融形成預先結晶a化鋇溶融物，以及持 tti卻氟化轉融物成城化鋇晶體。方法更進-步Ξ 氣化鋇晶體加熱^及緩慢地熱平衡地冷卻晶體以及將齓貝晶體形成為光學元件。優先地照明雷射頻寬20 5 卜;^^造控制色牛之方法。该方法包含提供氟化鋇原料 ft將統鋇來源材料舰以職預先結㈣化舰融 =將祕贿融_化純化鋇晶體，以及將氟化鎖晶體 ,&、处理以產生等方性氣化鋇晶體，在157nm下折射性波長色散dn/cU<-0.003。該方法優先地包含提供去除污染‘ 既化物清除劑以及將清除継統鋇來源材概融以去除 >可染物。優先地清除劑為氟化鉛。範例：、—製造出氟化鋇光學石版印刷晶體試樣。對製造出晶體進行157咖範圍折射率量測。對製造出晶體作157 2 透射照射。. 晶體在高純度石墨_容器中成長。高純度默化鋇粉禾衣置於_中。健綱再放置於在晶體成長加熱器裝置内可移動支撐、结構上，其利用充份功率以提高溫度高於 128〇它。氟化鋇粉末熔融高於128(rc成為預先結晶之氟化 =熔融物，而後坩堝降低經由含有128(rc熱梯度持續性地冷卻將熔融物固化為晶體形式。所形成氟化鋇晶體試樣再本紙張尺度適用中國國家標準（CNS) 規格⑺0x297公釐） //B7 Description of the invention The lithographic printing pattern is printed by the Masonry Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, and the outer dimension is preferentially lake nm. 5 The optical element preferentially contains a barium fluoride crystal raw material, which is melted to form a pre-crystallized barium alumina melt, and a tti-fluorinated transmelt to form a barium crystal. The method goes one step further-heating the barium vaporized crystal, slowly cooling the crystal in thermal equilibrium, and forming the cymbal crystal as an optical element. Prioritize lighting with a radio frequency bandwidth of 20 5 bu; ^^ method of controlling color cattle. The method includes providing a barium fluoride raw material ft and preliminarily melting the barium source material to melt the molten iron = melting and purifying the barium crystal, and locking the fluorinated crystal to & Barium vaporized crystal, refracting wavelength dispersion dn / cU < -0.003 at 157 nm. This method preferentially includes providing a decontamination ‘existing chemical scavenger, and general cleaning of barium source materials to remove > stains. The scavenger is preferably lead fluoride. Examples:,-Manufacture a crystal sample of barium fluoride optical lithography. A refractive index measurement in the range of 157 cm was performed on the manufactured crystal. The produced crystal was subjected to 157 2 transmission irradiation. The crystal grows in a high-purity graphite container. High purity hydrated barium powder. Jian Gang is then placed on a movable support and structure in the crystal growth heater device, which uses sufficient power to raise the temperature above 128 °. The barium fluoride powder melts higher than 128 (rc becomes the pre-crystallized fluorinated = melt, and then the crucible is lowered to solidify the melt into a crystalline form by continuously cooling with a thermal gradient containing 128 (rc). The formed barium fluoride crystal sample The size of this paper applies the Chinese National Standard (CNS) specification (0x297 mm) //

526385 Α7 Β7 五、發明説明進行分析。157nm透射雷射耐久性試樣顯示出外部透射度為86%。157皿絕對值折射率試樣顯示在2(rCT157nm之dn/ d λ (157. 6299)=-0. 〇〇4376± 0. 000004nm~l, ^157. 6299-^ 157nm波長下絕對折射率η( λ=157· 6299χ· 65669〇± 〇，⑻0006,以及20°C折射率溫度係數如/町（約為2(rc,丨大氣壓N2)二 10· 6(± 〇· 5)xl〇Vc以及dn/dT(約為20°C，真空）二 8.6(± 0.5)xl(TVt：。 ’…热知此祕者能夠由本發明作&多觀化及改變，但疋亚不:脫離本發明精神與範圍。這些變化及改變均含蓋於下列申請專利範圍内。經濟部中央標準局見工消费合作社印裂用適度尺浪 1紙本準標家526385 Α7 Β7 V. Description of the invention Analyze. The 157 nm transmission laser durability sample showed an external transmittance of 86%. The 157-plate absolute refractive index sample shows an absolute refractive index η at a wavelength of 2 (rCT157nm dn / d λ (157. 6299) =-0. 〇〇4376 ± 0. 000004nm ~ l, ^ 157. 6299- ^ 157nm (λ = 157 · 6299χ · 65669〇 ± 〇, ⑻0006, and 20 ° C refractive index temperature coefficient such as / （(about 2 (rc, 丨 atmospheric pressure N2) two 10.6 (± 〇 · 5) xl0Vc and dn / dT (approximately 20 ° C, vacuum) 2 8.6 (± 0.5) xl (TVt:... knows that this mysterious person can make & multi-view and change by the present invention, but Xi Ya does not: leave the present invention Spirit and scope. These changes and modifications are covered by the following patent application scope.

Μ 公 7 (請先閲讀背面之注意事項再填艿本頁)Ｍ公 7 (Please read the notes on the back before filling out this page)

Claims

526385公^ Jr /卜 A8 B8 C8 D8 々、申請專利範圍經濟部中央標準局員工消費合作社印製 1. 一種低於160舰光學石版印刷晶體，該光學石版印刷晶體由氟化鋇晶體所構成，該敗化鋇晶體在157nm透射度>85%，該晶體在157nm下折射率之波長色散dn/d；l < —〇〇〇3。 2·依據申請專利範圍第丨項之光學石版印刷晶體，其中色散 dn/d λ〈 -〇·〇〇4 〇 3 ·依據申請專利範圍第丨項之光學石版印刷晶體，其中色散 dn/dA < -〇· 〇〇3 〇 4. 依據申請專利範圍第丨項之光學石版印刷晶體，其中氟化鋇晶體在157nm下折射率η>ι. 56。 5. 依據申請專利範圍第丨項之光學石版印刷晶體，其中氟化鋇晶體在157nm下折射率心丨.6。 6. 依據申請專利範圍第丨項之光學石版印刷晶體，其中氟化鋇晶體在157nm下折射率心丨.β4。 7·依據申請專利範圍第丨項之光學石版印刷晶體，其中氟化鋇晶體在157nm下折射性溫度係數dn/d λ >8χ1 〇-6/^。 8·依據申請專利範圍第1項之光學石版印刷晶體，其中該晶體較大尺寸直徑>1〇〇_以及厚度>30nm。 9·依據申請專利範圍第丨項之光學石版印刷晶體，其中直徑在118至250nm範圍内以及厚度在3〇至5〇_範圍内。 10·依據申請專利範圍第丨項之光學石版印刷晶體，其中該晶體由控制頻寬色散之光學元件所構成。 U·依據申請專利範圍第1項之光學石版印刷晶體，其中氟化鋇日日體鈉含量量比。 12·依據申請專利範圍第丨項之光學石版印刷晶體，其中氟表紙㈤適用 f (請先閱讀背面之注意事項本育) -裝- 、1T 線- 526385 A8 B8 C8 D8 六·、申請專利範圍提供低於160mi光學石版印刷照明雷射提供氟化鋇晶體之光學元件田，端航學元件，-鋇晶體元件在腕m下折射陘波長色散^n/d λ < ~〇.〇〇3 ^低於·讀學石版印刷之光線通過_ 元 =及統鋇光學元件以產生光學石版印刷圖案。繼咖奴桃其娜_晶體裝載氟化鋇原料於容器内， H匕鋇晶體原料炫融以形成預先結晶之氟化鋇炼融物，持:買性凝結該IU匕鋇炫_成為氟化鎖晶體，對氟化鋇晶體加熱以及熱平衡地冷卻該晶體將氟化鋇晶體形成為光學元件。， 25.種控制色散光學石版印刷元件之方法，其包含· 提供氟化鋇來源之原料，一 · 將威鋇來源材料炼融以形成預先結晶氣化鎖炫融物；將氟化鋇溶融物固化為氟化鋇晶體；，將氟化鋇晶體退火以產生等方性I匕鋇晶體，其在⑸咖下折射性波長色散dnAiA< -0.003。經濟部中央標準局員工消费合作社印製 26·依〃據申請專利範圍第25項之方法，其包含提供去除污染物之氟化物清除劑以及將清除劑與氟化鋇來源材料熔去除污染物。柯 27· —種製造控制色散光學石版印刷晶體之方法，該晶體作為在157nm下改正氟化鈣色彩，該方法包含：，" 申請專利範園 A8 B8 C8 D8 4 提供I化物色概正材料. 改=^=蝴_職麻·物色彩將I化物色彩改正材料絲物固化為色彩改正材料物晶體·，將色彩改正材料氟化物晶體退火以產生等方性色彩改正材料氟化物晶體，其在157nm下折射性波長色散dn/d λ < -0· 003以及在157nnTF透射度>80%。 (請先閲讀背面之注意事項#填巧本頁) 訂丨，526385 ^ Jr / Bu A8 B8 C8 D8 々, applied for patent scope Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 1. An optical lithographic crystal below 160 ships, the optical lithographic crystal is composed of barium fluoride crystal, The degraded barium crystal has a transmittance of 157 nm > 85%, and a wavelength dispersion of the refractive index of the crystal at 157 nm, dn / d; l <-0.003. 2. Optical lithographic printing crystal according to item 丨 of the patent application, where the dispersion is dn / d λ <-〇〇〇〇 04 〇3. Optical lithographic printing crystal according to item 丨 of the patent application, where the dispersion is dn / dA & lt -〇 · 〇〇3 〇4. According to the patent application scope of the optical lithographic printing crystal, wherein the barium fluoride crystal at 157nm refractive index η> 56. 5. The optical lithographic printing crystal according to item 丨 of the patent application scope, wherein the barium fluoride crystal has a refractive index center at 157 nm. 6. 6. The optical lithographic crystal according to item 丨 of the patent application scope, in which the barium fluoride crystal has a refractive index center at β157 at 157 nm. 7. The optical lithographic crystal according to item 丨 of the patent application scope, wherein the barium fluoride crystal has a refractive temperature coefficient dn / d λ > 8 × 1 0-6 / ^ at 157 nm. 8. An optical lithographic crystal according to item 1 of the scope of patent application, wherein the crystal has a larger size diameter > 100 mm and a thickness > 30 nm. 9. An optical lithographic crystal according to item 丨 of the patent application scope, wherein the diameter is in the range of 118 to 250 nm and the thickness is in the range of 30 to 50 mm. 10. An optical lithographic crystal according to item 丨 of the patent application scope, wherein the crystal is composed of an optical element that controls the bandwidth dispersion. U. The optical lithographic printing crystal according to item 1 of the scope of the patent application, in which the ratio of the daily content of barium fluoride to the daily sodium content. 12 · According to the optical lithographic printing crystal of item 丨 of the patent application scope, in which the fluorine surface paper is suitable for f (please read the precautions on the back first)-equipment-、 1T line-526385 A8 B8 C8 D8 VI. Patent application scope Provides optical lithographic printing lasers below 160mi. Optical elements that provide barium fluoride crystals, end aeronautical elements, -barium crystal elements refract under the wrist m wavelength dispersion ^ n / d λ < ~ 〇.〇〇3 ^ The light below the reading lithography passes through the yuan element and the barium optical element to produce an optical lithography pattern. Following Canu Tao Qi Na_ crystals are loaded with barium fluoride raw materials in the container, H d barium crystal raw materials are fused to form a pre-crystallized barium fluoride smelt. The crystal is locked, and the barium fluoride crystal is heated and cooled in a thermal equilibrium to form the barium fluoride crystal as an optical element. 25. A method for controlling a dispersion optical lithographic printing element, comprising: providing a raw material of barium fluoride source, and smelting a barium fluoride source material to form a pre-crystallized vaporized lock melt; dissolving barium fluoride Solidified into barium fluoride crystals; annealing the barium fluoride crystals to produce isotropic barium I crystals, which have a refractive wavelength dispersion dnAiA < -0.003 under caffeine. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 26. The method according to item 25 of the patent application, which includes providing a fluoride scavenger to remove pollutants and melting the scavenger with barium fluoride source materials to remove pollutants. Ke 27 · —A method for manufacturing a dispersion-controlled optical lithographic printing crystal, which is used to correct the color of calcium fluoride at 157nm. The method includes: " Application for a patent Fanyuan A8 B8 C8 D8 4 Provide I-color material Modification = ^ = Butterfly_Material Color Material solidifies the silk material of the color correction material into color correction material crystals, and anneals the color correction material fluoride crystals to produce isotropic color correction material fluoride crystals, which Refractive wavelength dispersion dn / d λ < -0.03 at 157 nm and transmittance > 80% at 157 nnTF. (Please read the note on the back #Fill this page first) Order 丨,

經濟部中央標準局員工消費合作社印製 .I I I- I ----_ 衣纸張尺度適用中國國家襟準（CNS )八4减（210><297公1) 91. 8, 2 8 526385 mum\ 本案已向國（地區）申請專利申請曰期案號主張優先權美國US 1999/06/04 60/137,486 有有關微生物已寄存於寄存曰期寄存號碼第3頁 C:\Program Files\patl\p477. ptd 12 12 526385 蛵濟部中夬樣隼局員工消費合作、社印f A8 B8 C8 D8 六、申請專利範圍化鋇晶體稀土族元素.污染總含量小於lppm重量比。 13·依據申請專利範圍第1項之光學石版印刷晶體，其中氟化鋇晶體氣污染物含量小於50ppm重量比。 14·依據申請專利範圍第1項之光學石版印刷晶體，弟申氟化鋇晶體氧污染物含量小於2〇ppm，量比。 15·依據申請專利範圍第1項之光學石版印刷晶體，其中氟化鋇晶體在157nm透射度-86%。 16-依據申請專利範圍第1項之光學石版印刷晶體，其中氟化鋇晶體氧污染物含量小於2〇ppm重量比，在15 7nm透射度 -86% 〇 17· —種控制色散光學石版印刷晶體，其由等方性氣化鋇晶體所構成，該氟化鋇晶體在157. 6299nm下折射性波長色散dn/d λ < -0· 003以及 157. 6299nm折射率η>1. 56。 18·依據申請專利範圍第π項之控制色散光學石版印刷晶體，其中dn/d 久〈-0. 〇〇4。 19·依據申請專利範圍第17項之控制色散光學石版印刷晶體，其中dn/d λ < -0. 0043。 20.依據申請專利範圍第17項之控制色散光學石版印刷晶體，其中折射率η>1.6。 21·依據申請專利範圍第17項之控制色散光學石派印刷晶體，其中晶體在157nm外部量測之透射度>83%。 22·依據申請專利範圍第17項之控制色散光學石版印刷晶體，其中晶體在157nm外部量測之透射度>85%。 23. —種低於160nm光學石版印刷方法，其包含：象紙張尺度逋用中國國家榡準（CNS ) A4規格（210X29?公釐） (請先閲讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. II I- I ----_ Applicable to China National Standards (CNS) 8 and 4 minus (210 > &297; 1) 91. 8, 2 8 526385 mum \ This case has been filed with a country (region) for a patent application. The date of the application claims priority. US 1999/06/04 60 / 137,486 Some related microorganisms have been deposited in the deposit date. Page 3 C: \ Program Files \ patl \ p477. ptd 12 12 526385 Employees of the Ministry of Economic Affairs of the People's Republic of China Consumer Co-operation, Social Printing f A8 B8 C8 D8 Sixth, the scope of patent application for barium crystal rare earth elements. The total pollution content is less than 1ppm by weight. 13. The optical lithographic printing crystal according to item 1 of the scope of patent application, wherein the content of barium fluoride crystal gas pollutants is less than 50 ppm by weight. 14. According to the optical lithographic printing crystal of item 1 of the scope of patent application, the content of oxygen contamination of the barium fluoride crystal is less than 20 ppm, and the quantity ratio. 15. The optical lithographic crystal according to item 1 of the scope of patent application, wherein the transmission of barium fluoride crystals is -86% at 157 nm. 16- An optical lithographic crystal according to item 1 of the scope of patent application, wherein the content of oxygen pollutants in the barium fluoride crystal is less than 20 ppm by weight, and the transmittance is -86% at 157 nm. , Which is composed of an isotropic barium vaporized crystal, the barium fluoride crystal has a refractive wavelength dispersion dn / d λ < -0.03 and a refractive index η > 1. 56 at 157.629 nm. 18. The dispersion-controlling optical lithographic printing crystal according to item π of the scope of patent application, in which dn / d is <-0. 〇〇4. 19. The dispersion-controlling optical lithographic printing crystal according to item 17 of the scope of the patent application, in which dn / d λ < -0.004. 20. The dispersion-controlled optical lithographic printing crystal according to item 17 of the scope of patent application, wherein the refractive index η > 1.6. 21. The dispersion-controlling optical stone-based printed crystal according to item 17 of the scope of patent application, wherein the transmittance of the crystal measured outside of 157 nm > 83%. 22. The dispersion-controlling optical lithographic printing crystal according to item 17 of the scope of the patent application, in which the transmission of the crystal measured at an outside of 157 nm > 85%. 23. —A kind of optical lithographic printing method below 160nm, which includes: Paper size using China National Standard (CNS) A4 specification (210X29? Mm) (Please read the precautions on the back before filling this page)