TW578206B - Ion-beam deposition process for manufacturing binary photomask blanks - Google Patents

Abstract

An ion-beam film deposition process is described for fabricating binary photomask blanks for selected lithographic wavelengths < 400 nm, the said film essentially consisting of the MOxCyNz compound where M is selected from chromium, molybdenum, tungsten, or tantalum or combination thereof in a single layer or a multiple layer configuration.

Description

578206 578206 五 、發明説明（ 本發明係關於利用離^ 二元式光罩坯料。這此、，束沉積技術製造光微影蝕刻之 光。而且，本發明光罩可用於短波長（即&lt;4〇〇毫微米） 及/或其化合物或其組:有路、•、錄金屬 &lt;早或多層塗層的二元式光罩。 .技術 微影蝕刻是將顯微# 移至石夕晶圓上的方法或影像’通常透過一光罩轉 之積體電路時，電子兩造電腦微處理器及記憶體裝置用 光罩或模緣板投射 =像通吊係以一電磁波源透過 。通常，光罩是透明感光層或光阻上 案的“鉻，，。經常被㈣“Λ/ —層具有這些電路特徵圖 /為一兀式，，光罩之“鉻，，光罩使顯像輻 ，:…^鉻〈圖案。遮蔽‘‘路，，層存在區域的光。 =寸求知用於製造高密度積體電路之光學微影 '^ 土低万、100笔微米之臨界尺寸。但是，隨著特徵尺 寸的P低’以特疋波長的光使晶圓上最小特徵尺寸顯像之 解析度係受光的繞射所m在,丨.r _ 凡耵所限制。因此，需要較短波長的光， 即&lt;400毫微米的光以使較細特徵顯像。成功產生光學微影 蚀刻所用的目標波長包括248毫微米（Μ雷射波長）、193 宅微米（ArF雷射波長）及157毫微米（F2雷射波長）和更短。 對於光罩坯料的製造係偏好薄膜沉積物理方法。這些一 般在真2 1：中進行之方法包括輝光放電喷濺沉積、圓柱形 磁子噴濺、平面磁子噴賤及離子束沉積。各方法之細節描 述可在參考文獻.1 978年#丑約Academic出版社所出版 -4- 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 578206 A7 _ B7 五、發明説明（2 )578206 578206 V. Description of the invention (The present invention relates to the use of a detachable binary photomask blank. Here, the beam deposition technology is used to produce light lithographic etching light. Moreover, the photomask of the present invention can be used for short wavelengths (that is, < (400 nm) and / or its compound or group thereof: Binary mask with Lu, •, metal &lt; early or multi-layer coating ... Technical lithographic etching is to move the microscopy # to Shi Xi When the method or image on the wafer is usually passed through a photomask integrated circuit, the electronic microprocessor and the memory device are projected with a photomask or a mold edge plate. The image transmission system is transmitted by an electromagnetic wave source. Usually, the photomask is a "chrome" on the transparent photosensitive layer or photoresistor. Often, the "Λ /" layer has these circuit characteristics. It is a type of "chrome," and the photomask makes the display Image spoke:… ^ chrome <pattern. Shields the light in the area where the layer exists. = Inquire for the optical lithography used to make high-density integrated circuits. ^ The critical size of the soil is 100 million micrometers. However, as the feature size P is lower, light with a special wavelength makes the smallest feature size on the wafer The resolution of the image is limited by the diffraction of light m, 丨. R _ Fan 耵. Therefore, a shorter wavelength of light, that is, <400 nm light is required to make finer features visible. Optics are successfully produced The target wavelengths used for lithographic etching include 248 nm (M laser wavelength), 193 nm (ArF laser wavelength), and 157 nm (F2 laser wavelength) and shorter. For the manufacture of photomask blanks, thin films are preferred. Physical methods of deposition. These methods generally performed in true 2: 1 include glow discharge sputtering deposition, cylindrical magneton sputtering, planar magneton sputtering, and ion beam deposition. Details of each method can be found in reference.1 978 # Ugly about Academic Press -4- This paper size applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 578206 A7 _ B7 V. Description of the invention (2)

Vossen及Kern所著的“薄膜程序，，中找到。製造薄膜光罩之 方法最普遍的是平面磁子噴錢。 平面磁子噴濺構型物係由兩個平行板電極所組成的： 一個電極含有欲藉噴濺沉積之材料並稱為陰極；然而第二 個電極或陽極係放置欲被塗覆之基板。在負陰極與正陽極 之間一氣體（如ArO或氣體混合物（Ar + 〇2)的存在下施予一 %壓’ RF或DC會產生電漿放電（正離子氣體物種及負電荷電 子），從此離子移動並被加速至陰極，於該處他們噴濺或沉 積標的物材料於基板上。存在於陰極附近之磁場（磁子噴濺） 增強電漿密度並因此加速噴濺沉積速率。 若噴濺標的物是一種金屬如鉻（Cr)，以惰性氣體如紅噴 濺將於基板上產生Cr金屬膜。當放電包含反應性氣體如〇2 、I、C〇2或CH3 ’他們與標的物結合或在生長膜表面以於基 板上形成一氧化物、氮化物、碳化物或其組合物薄膜。通 常二元式光罩之化學組合物是複雜的，而且整個薄膜厚度 的化學經常是分段或分層變化的。“路，，二元式光罩通常包 含一種鉻氧-碳-氮化物（Cl*0xCyNz)組合物，其薄膜頂面富有 氧化物’而薄膜深處内含有較多氮化物。富有氧化物之頂 4表面賦予抗反射特徵，同時以化學方式將該膜分段提供 吸引人的各向異性溼蝕刻性質，同時富有氮化物的組合物 造成高吸光度。 在離子束沉積（IBD)中，電漿放電係被包含在一分離室 (離子“槍”或源）中，而且離子被施加在該槍“出口，，處一系 列栅極上 &lt; 電壓抽出及加速（也可能進行其他無柵極之離 -5- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公董) 表面-種較乾淨的好噴㈣比，IBD方法提供生長膜 荷電粒子至乂： ：#:序(杈少附加粒子）’因為捕捉及運送 造具有較少：二'聚不像噴賤時，不在生長膜附近。製 小至低於二 需求對下一代臨界電路特徵將縮 係操作在㈣ 微影蝕刻是極重要的。而且，1BD方法 (IBD用之血：統磁予噴激方法低至少十倍之總氣體壓力下 ”里昼力為〜1(Γ托）°此造成較低的化學污染量 氡化二利用此方法可沉積具有最少量或無氧化物含量之 氣髀離η ’ ibd方法具有獨立控制沉積通量及反應性 流)和能量的能力，其在平面磁子喷錢法中 或^子γ獨互技制的。各個離子檢以低能量，但高氧 :二:通！炮擊生長膜以產生氧化物或氮化物或其他化 二:ΠΓ力對™方法而言是獨特的，而且可在寬廣的 H k供薄膜化學及其他薄膜性質之精確控制。而 :在雙離子束沉積中，可調整標的物、基板與離子搶間 最佳化薄膜均勾度及膜應力，然而磁子喷濺之幾 可係限制在平行板電極系統。 當磁子噴濺係廣泛地用於電子工業以複製地沉積不同 種類之塗層時，噴料漿中的程序控制是不準確的，因為 揉法調整人射在生長膜上之離子的方向、能量及通量（參考 膜之材料科學，Mllton0hring，Academicd^M992 137頁）。在此所提作為一種製造具有簡單或複雜 '單層 或多層化學之新穎替換方法的雙離子束沉積法中，可獨: 控制這些沉積參數。 -6- 578206 A7 —~—---------B7 五、發明説明（4 ) 登Jg概述 、本發明係關於_種製備微影㈣波長小於侧毫微米用 式光罩链料的離子束沉積方法，該方法包括藉源自 p氣體之離子進行路、鈿、鎢絲“或其組合物之離子 束&gt;儿積’以沉積至少一層MOxCyNz化合物於一基板上，其中m 係選自由鉻、鉬、鎢或妲或其組合物所組成之群； 其中： x範圍係從約〇· 00至約3. 00 ; y範圍係從約〇· ο〇至約1. 〇〇 ; 及z範圍係從約〇· 〇〇至約2.⑼。 更特別地’本發明係關於一種製備微影蝕刻波長小於 400毫微米用之二元式光罩㈣的雙離子束沉積方法，該方 法包括沉積至少一層MOxCyNzt合物於—基板上，其中M係選 自銘'、细、鎢或或其組合， (a) 藉源自一群氣體之離子進行鉻、鉬、鎢或鈕及/或 其組合之離子束沉積，及 (b) 藉源自一群氣體之輔助源的第二離子束炮擊該基 板，其中孩層或這些層係藉源自輔助源氣體之炮擊氣體離 子與從該標的物或多個標的物所沉積在基板上之物質進行 化學結合所形成的； 其中： X範圍係從約0· 00至約3. 00 ; y範圍係從约〇· 〇〇至約1. 〇〇 ; 及Z範圍係從約〇· 〇〇至約2. 〇〇。 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公Vossen and Kern's "Thin Film Procedure," found in. The most common method for making thin film masks is planar magnetron spraying. The planar magneton sputtering structure is composed of two parallel plate electrodes: one The electrode contains the material to be deposited by sputtering and is called the cathode; however, the second electrode or anode places the substrate to be coated. A gas (such as ArO or a gas mixture (Ar + 〇) is placed between the negative cathode and the positive anode. 2) Applying a% pressure in the presence of RF or DC will generate a plasma discharge (positive ion gas species and negatively charged electrons), from which the ions move and are accelerated to the cathode, where they spray or deposit the target material On the substrate. The magnetic field (magnetron sputtering) existing near the cathode enhances the plasma density and therefore accelerates the sputtering deposition rate. If the sputtering target is a metal such as chromium (Cr), it will be sprayed with an inert gas such as red. Cr metal film is generated on the substrate. When the discharge contains a reactive gas such as 〇2, I, Co2 or CH3, they are combined with the target or grow on the film surface to form an oxide, nitride, carbide on the substrate. Or a combination thereof Thin film. The chemical composition of binary photomasks is usually complex, and the chemistry of the entire film thickness is often changed in stages or layers. "Look, binary photomasks usually contain a chromium-oxygen-carbon-nitrogen (Cl * 0xCyNz) composition, the top surface of the film is rich in oxides and the nitride is deeper in the film. The oxide-rich top 4 surface imparts anti-reflection characteristics, and chemically provides the film in sections Attractive anisotropic wet-etching properties, while a nitride-rich composition results in high absorbance. In ion beam deposition (IBD), the plasma discharge system is contained in a separation chamber (ion "gun" or source), And ions are applied to the gun's "exit," a series of grids &lt; voltage extraction and acceleration (other gridless ionization is also possible -5- this paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 Gong Dong) Surface-a kind of cleaner and better spraying ratio, IBD method provides growth film charged particles to 乂 :: #: order (less additional particles on the branch) 'because capture and transport have less: two' unlike When spraying, not growing Near the film. Making it smaller than two is necessary for the next generation of critical circuit characteristics. It is extremely important to operate the shrinkage system in lithographic etching. Moreover, the 1BD method (blood for IBD: the uniform magnetic pre-spray method is at least ten times lower Under the total gas pressure, the daytime force is ~ 1 (Γ Torr). This results in a lower amount of chemical pollution. Using this method, gas with minimal or no oxide content can be deposited. The ability to independently control the deposition flux and reactive flow) and energy, which is produced by the plane magnetron spray method or the γ-independent technique. Each ion is detected with low energy, but high oxygen: two: pass! Grow films to produce oxides or nitrides or other compounds: The ΠΓ force is unique to the ™ method and provides precise control of film chemistry and other film properties over a wide range of Hk. And: in dual ion beam deposition, the target, substrate and ion grabbing can be adjusted to optimize the film's uniformity and film stress. However, the number of magneton sputtering can be limited to the parallel plate electrode system. When the magnetron sputtering system is widely used in the electronics industry to deposit different types of coatings repeatedly, the program control in the spray slurry is inaccurate because the kneading method adjusts the direction of the ions on the growth film, Energy and Flux (Refer to Materials Science for Membrane, Mllton 0hring, Academicd ^ M992, p. 137). In the dual ion beam deposition method mentioned here as a novel alternative method for manufacturing simple or complex 'single-layer or multi-layer chemistry, these deposition parameters can be controlled independently: -6- 578206 A7 — ~ —--------- B7 V. Description of the invention (4) Overview of Deng Jg, the present invention is about _ a kind of photomask chain material for preparing lithography with a wavelength less than the side nanometer. Ion beam deposition method, which includes performing ion beams from a gas, plutonium, tungsten wire, or a combination thereof by using ions derived from p gas to deposit at least one layer of MOxCyNz compound on a substrate, where m is Selected from the group consisting of chromium, molybdenum, tungsten or rhenium or a combination thereof; wherein: the range of x is from about 0.00 to about 3. 00; the range of y is from about 0.00 to about 1.0; And z range is from about 0.00 to about 2.⑼. More particularly, the present invention relates to a dual ion beam deposition method for preparing a binary mask ㈣ for lithography etching with a wavelength less than 400 nm, which The method includes depositing at least one layer of a MOxCyNzt compound on a substrate, wherein M is selected from the group consisting of Mg, F, T, or a combination thereof, (a) chromium, molybdenum, tungsten, or buttons and / or The combined ion beam deposition, and (b) bombarding the substrate by a second ion beam derived from a secondary source of gas, wherein the child Or these layers are formed by chemically combining the shelled gas ions derived from the auxiliary source gas with the substance deposited on the substrate from the object or objects; where: X ranges from about 0.00 to about 3. 00; y range is from about 0.00 to about 1.0; and Z range is from about 0.00 to about 2.0. This paper size applies Chinese National Standard (CNS) A4 specifications ( 210 X 297 male

裝 訂Binding

578206 A7 _______B7 五、發明説明（5 ) 節描述 在此所用特定名詞係定義於下。 本發明中’以最廣定義來了解在此所用“光罩，，一詞或 ‘‘光罩坯料’’ 一詞係包括已圖案化或未_圖案化之光罩坯料 。所用“多層”一詞係相當於包含以兩層間具有清楚分界線 或兩區域間至少一種光學性質明顯改變所沉積之薄膜層的 光阻坯料。該層可為超薄（1-2單層）或遠較厚。疊層可控制 光罩远料之光學及蚀刻性質。 二元式坯料之光學密度係定義為入射光強度相對於穿 透光強度之比例以1 0為底的對數。 見離子東沉積方法 一種單離子束沉積方法之典型構型係表示於圖2中。據 了解此系統係在一經真空幫浦抽掉大氣中之氣體的槽室中 。在此單IBD方法中，將一具有能量之離子束（通常以電子 源中和之）從一沉積槍（1)導向標的物固定器（3)所支撐的 標的物材料（2)。當炮擊離子的能量高於該特定材料之噴濺 臨界能量，一般〜50 eV時，標的物材料（2)被噴濺出來。 源自沉積槍（1)之離子通常係選自惰性氣體源如He、Ne、奸 、Kr、Xe ’雖然也可使用反應性氣體如〇2、、c〇2、&amp;、 CH3或其組合。當這些離子係源自惰性氣體源時，標的物材 料被噴濺，然後如薄膜般沉積在基板（4) 其中 ⑷具有基板固定器⑸。當這些離子係源自反應 時，他們可與標的物材料（2)結合，而且此化學合併物之產 物係為被噴濺及如薄膜般沉積在基板上之物。 &amp;張尺度適财関家標準(CNf^規格(⑽χ 297公⑹--~-- 578206 A7 - —_B7 _ 五、發明説明（6 ) 通常，炮擊離子應具有數彳百eV的能量，以200 eV至1 〇 KeV 範圍為佳。離子通量或流應足夠高（&gt;1〇i3個離子/平方釐米 /秒）得以保持實際沉積速率（&gt;〇· 1毫微米/分鐘）。一般而言 ，程序壓力係約1〇_4托，較佳範圍為10-3—10-5托。標的物材 料可為元素，如Cr、Mo、Ta、W，或其可為多成分如M〇xCry ’或其可為一種化合物如CrN。此基板可放置在離標的物一 段距離方向處，即可最佳化薄膜性質如厚度、均句度、最 小應力等之處。 •為獲得一薄膜性質，例如光學穿透率，可利用雙離子束 ’儿積方法弄寬程序範圍或寬容度。而且，可利用雙離子束 方法獨立地改變一特定薄膜性質而不影響其他組性質。 雙離子克沉猜古法 在光罩製造中離子束方法包括一種具有較少附加（缺點） 粒子、較大薄膜密度與極佳不透明度即極佳平滑度與較低 光政射，對微影蝕刻波長&lt;4〇〇毫微米而言特別重要的方法 。雙離子槍構型係以流程圖方式表示於圖丨中。在此方法中 ，將一具有能量之離子束（通常以電子源中和之）從一沉積 槍⑴導向標的物材料⑵’當炮擊離子的能量高於嘴錢臨 界能量，一般〜50 eV時’標的物材料（2)被噴濺出來。源 自沉積槍之離子通常係選自惰性氣體源如以、Ne、Ar 士 、Xe，雖然也可使用反應性氣體如〇2、⑽、F2、cH3或 其組合。當這些離子係源自惰性氣體源時，他們喷賤標的 物材料⑵，如Cr材料’然後如薄膜般沉積在基板⑷上。 當這些氣體離子係源自反應性源，如氧時，他們可在標的 -9- 本纸張尺度適用中國國家標準(CNS) A4規格(2i〇x297公6 578206 A7578206 A7 _______B7 V. Description of the Invention (5) Description of specific terms used herein is defined below. The term "mask," or "mask blank," as used herein, is understood in its broadest definition to include a patterned or unpatterned mask blank. The term "multilayer" used The word system is equivalent to a photoresist blank containing a thin film layer deposited with a clear dividing line between two layers or at least one optical property between two regions. The layer can be ultra-thin (1-2 single layers) or much thicker. The lamination can control the optical and etching properties of the distant material of the mask. The optical density of the binary blank is defined as the logarithm of the ratio of the intensity of the incident light to the intensity of the transmitted light with a base of 10. See the method of ion deposition The typical configuration of the ion beam deposition method is shown in Figure 2. It is understood that this system is in a tank that vacuum pumps out gases in the atmosphere. In this single IBD method, an ion beam with energy is used. (Usually neutralized by an electron source) from a deposition gun (1) to the target material (2) supported by the target holder (3). When the energy of the shelled ions is higher than the critical energy of the spray of the specific material, Generally ~ 50 eV, the target material The material (2) is sprayed out. The ions originating from the deposition gun (1) are usually selected from inert gas sources such as He, Ne, Kr, Kr, Xe. Although reactive gases such as 02, c can also be used. 2. &amp;, CH3 or a combination thereof. When these ions are derived from an inert gas source, the target material is sprayed and then deposited as a thin film on the substrate (4) where ⑷ has a substrate holder ⑸. When these ions are From the reaction, they can be combined with the target material (2), and the product of this chemical combination is a substance that is sprayed and deposited on the substrate like a thin film. &Amp; ^ Specifications (⑽χ 297 公 ⑹-- ~-578206 A7-—_B7 _ V. Description of the invention (6) Generally, the shelled ions should have energy of several hundred eV, preferably in the range of 200 eV to 10 KeV. Ions The flux or flow should be high enough (> 10i3 ions / cm2 / s) to maintain the actual deposition rate (> 0.1nm / min). In general, the program pressure is about 10-4 Support, the preferred range is 10-3-10-5 Torr. The target material can be an element, such as Cr, Mo, Ta, W, or it can be Multi-components such as MoxCry 'or it can be a compound such as CrN. This substrate can be placed at a distance from the target to optimize film properties such as thickness, uniformity, minimum stress, etc. • In order to obtain a film property, such as optical transmittance, a dual ion beam method can be used to widen the program range or tolerance. Moreover, the dual ion beam method can be used to independently change a specific film property without affecting other groups of properties. . The ion beam method of dual ion countermeasures in the manufacture of photomasks includes a method with fewer additional (disadvantage) particles, larger film density, and excellent opacity, ie, excellent smoothness and low light emission. A method which is particularly important for the etching wavelength &lt; 400 nm. The dual ion gun configuration is shown in a flow chart in Figure 丨. In this method, an ion beam with energy (usually neutralized by an electron source) is directed from a deposition gun to the target material. 'When the energy of the bombarded ions is higher than the critical energy of the mouth, generally ~ 50 eV' The target material (2) was sprayed out. The ions originating from the deposition gun are usually selected from inert gas sources such as Is, Ne, Ar, and Xe, although reactive gases such as 02, Krypton, F2, cH3, or combinations thereof may also be used. When these ions originate from an inert gas source, they spray the target material ⑵, such as Cr material, and then deposit it on the substrate ⑷ as a thin film. When these gas ions are derived from a reactive source, such as oxygen, they can be used at the standard -9- this paper size applies the Chinese National Standard (CNS) A4 specification (2i〇297297 6 578206 A7

^表面以化學方式結合，然後此化學合併物 口貧濺及如薄騰护、主六並L、仏 你為被 、“ μ I“貝在基板上之物。在雙離子束沉積中， :、自弟二搶或輔助源之具有能量的離子炮擊基板 ， 源自輔助搶⑻之離子係選自由反應性氣體如，但不限於⑴ 、N” C〇” F” CH3或其組合組成之群，其在基板上盥自栌 :物⑵所嘴賤出之物質通量化學結合。因此，若源自沉： A r離子係用於噴濺c r標的物’同時源自輔助源之氧 離子炮擊生長膜’㈣量將在基板上與具有能量之氧離子 化學結合形成一氧化路膜。 通常，源自沉積源之炮擊離子應具有數佰”的能量，以 200 eV至10 KeV範圍為佳。離子通量或流應足夠高（〉ι〇π 個離子/平方釐米/秒）得以保持實際沉積速率（〉〇·〗毫微米 /分/童^。一般而言，程序壓力係約UT托，較佳範圍為 10 3-1(Γ5托。本發明之較佳標的物材料為元素Cr、m〇、界、 Ta或其化合物。此基板可放置在離標的物一段距離方向處 ，即可取佳化薄膜性質如厚度、均勻度、最小應力等之處 。源自輔助槍（6)之離子的能量通常係低於沉積槍（1)的。 該輔助槍提供一可調整之低能量離子通量，其中此低能量 離子係在生長膜表面與所濺射的原子反應·。對於，，輔助，，離 子，以一般&lt;500 eV之低能量離子為佳，否則該離子可能造 成不想要的触刻或薄膜移除。在移除速率太高的極端例子 中，薄膜生長是可忽略的，因為移除率超過累積或生長速 率。但是，在某些例子中，較高的輔助能量可賦予生長膜 有利的性質，如降低應力，但這些較具能量之離子的較佳 -10- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐)^ The surface is chemically bonded, and then the chemical combination is poorly splashed and thin, such as thin Tenghuo, the main six and L, and you are the quilt, "μ I" shell on the substrate. In the dual ion beam deposition, the ion bombarded substrate with energy from the second sibling or auxiliary source is selected from the group consisting of reactive gases such as, but not limited to, ⑴, N ”C〇” F The group consisting of CH3 or a combination thereof is chemically combined on the substrate with the flux of the material out of the mouth of the object. Therefore, if it is derived from Shen: A r ions are used to spray the cr target. The amount of oxygen ion bombarded growth film from the auxiliary source will chemically combine with the oxygen ion with energy on the substrate to form an oxide film. Generally, the bombarded ions from the deposition source should have several hundred "energy, with 200 The eV to 10 KeV range is preferred. The ion flux or flow should be high enough (> ιππ ions / cm2 / s) to maintain the actual deposition rate (> 0 ·〗 nanometers / minute / child ^. In general, the program pressure is about UT Torr, The preferred range is 10 3-1 (Γ5 Torr. The preferred target material of the present invention is the element Cr, m0, boundary, Ta, or a compound thereof. This substrate can be placed at a distance from the target, which is better. Properties of the thin film such as thickness, uniformity, minimum stress, etc. The energy of the ions originating from the auxiliary gun (6) is usually lower than that of the deposition gun (1). The auxiliary gun provides an adjustable low-energy ion flux Among them, this low-energy ion reacts with the sputtered atoms on the surface of the growth film. For, the auxiliary, and ions are generally low-energy ions <500 eV, otherwise the ions may cause unwanted contact Film or film removal. In extreme cases where the removal rate is too high, film growth is negligible because the removal rate exceeds the cumulative or growth rate. However, in some cases, higher auxiliary energy can give growth Advantageous properties of the membrane, such as reduced application , But the energy of ions the more preferred -10- applies the present paper China National Standard Scale (CNS) A4 size (210 X 297 mm)

裝 訂Binding

線 578206Line 578206

通ι通常必須小於沉積原子的通量。 在光罩坯料之雙離子束沉積中，沉積程序所用氣體離子 源最好係選自由惰性氣體，包括但不限於He、Ne、Ar、Kr ' Xe或其組合組成之群’然而用於協助炮擊之氣體離子源 最好係選自由反應性氣體包括’但不限於〇2、N2、CO” F2 、、CH3或其組合組成之群。但是，在特殊狀況中，沉積氣體 源也可包3 -部分反應性氣體’特別是當程序係適合在標 的物上形成化學化合物時。相反地，當輔助氣體源係包含 邵分惰性氣體可能是特殊狀況，特別是當有力炮擊生長膜 係有利於改良薄膜性質，如降低内膜應力。 各個辅助離子槍以低能量，但高氧或氮離子通量炮擊生 長膜以產生氧化物或氮化物或其他化學化合物的能力對 IBD方法而言是獨特的’而且可在寬廣的程序範圍中提供薄 膜化學及其他薄膜性質之精確控制。而且，在雙離子束冗 積中，可調整標的物、基板與離子槍間的角度以最佳化= 膜均勻度及膜應力，然而磁子噴賤之幾何係限制在平行板、 電極系繞。 利用雙IBD方法，任何這些沉積操作可合併以製造更複 雜的結構。例如當成功地由源自輔助槍之反應性氮離子先 炮擊該膜，接著以氧離子炮擊之，可從元素。標的物藉沉 積製得疊。如Cr()x/c：rNy中，當疊中之膜層 化物變換成氮化物時，以單標的物進行雙離子束沉積 提供明顯優料統磁子噴賤技術之優點。财沉積^原子 時’雙I耐的辅助源可迅速地在_N2間轉換，反應性The flux must generally be less than the flux of the deposited atoms. In the dual ion beam deposition of photomask blanks, the gas ion source used in the deposition process is preferably selected from the group consisting of inert gases, including but not limited to He, Ne, Ar, Kr 'Xe or a combination thereof', but is used to assist in shelling The gas ion source is preferably selected from the group consisting of reactive gases including, but not limited to, 02, N2, CO, F2, CH3, or a combination thereof. However, in special circumstances, the deposition gas source can also include 3- Partially reactive gases' especially when the program system is suitable for the formation of chemical compounds on the target. Conversely, when the auxiliary gas source system contains the inert gas, it may be a special situation, especially when a strong shelling of the growth film system is beneficial to the improvement of the film. Properties such as reducing internal membrane stress. The ability of each auxiliary ion gun to bombard the growing membrane with low energy but high oxygen or nitrogen ion flux to produce oxides or nitrides or other chemical compounds is unique to the IBD method 'and It can provide precise control of thin film chemistry and other thin film properties in a wide range of procedures. Moreover, in the dual ion beam redundancy, the target, substrate and ion can be adjusted. The angle between them is optimized = film uniformity and film stress. However, the geometry of the magnetron jet is limited to parallel plates and electrode windings. Using the dual IBD method, any of these deposition operations can be combined to make more complex structures. For example, when the membrane is successfully bombarded with reactive nitrogen ions from the auxiliary gun first, and then bombarded with oxygen ions, the element can be made from the target by deposition. For example, in Cr () x / c: rNy, when When the layered film in the stack is transformed into nitride, the dual ion beam deposition with a single target provides obvious advantages of the magnetron spraying technology. The secondary source of double I resistance can be quickly used in the deposition of atoms. _N2 conversion, reactive

襞 π襞 π

線 -11 -Line -11-

子赁濺會在標的物表面產生一氧化物層，該氧化物層必須 在形成一冨有氮化物表面以噴濺氮化物層之前移開。 利用單離子源以離子束沉積可製造具有複雜化學化合 物如S13化之薄膜時，此方法係比雙離子束沉積的限制更多 。例如’ Huang等人在“藉單離子束嘴濺沉積所沉積之氮化 矽薄膜的結構及組成研究，，，薄固態膜299 (1 997) 1 〇4_1〇9 况明，當離子束電壓係在約8〇〇伏特之窄範圍内時，只形成 具有SnN4性質的膜。在雙離子束噴濺時，在寬廣的程序條 件範圍内及實際沉積速率下，可獨立地調整源自輔助源之 氮原子通量以配合從沉積離子源所沉積的標的物原子通量。 本發明係關於用於沉積一單層或多層通式為Μ〇‘Νζ之鉻 、鉬、鎢或鈕化合物於石英或玻璃基材上以製造不透明光 罩坯料的雙離子束沉積方法，其中M為鉻、鉬、鎢或鈕。 本發明係提供一種用於入射波長小於4〇〇毫微米之光罩 坯料之新穎的單層或多層膜沉積技術。該基板可為任何機 械上安定的材料，其在所用入射光之波長下是透明的。關 於可取得性及成本，係以如石英、CaF2及煙燻矽石（玻璃）. 之基板為佳。. 本發明提供具有鬲光學密度之單層或化學沿薄膜厚度 方向分段變化之不透明材料的雙離子束沉積。 最好本發明包括單或多層MOxCyNzi雙離子束沉積，其中m 係選自鉻、鉬、鎢或鈕或其組合，其中χ範圍係從約〇·⑽ 至約3· 00，y範圍係從約〇· 〇〇至約丨·⑼，ζ範圍係從約〇· 〇〇 至約2. 〇〇。 -12- AT B7Sub-sputtering produces an oxide layer on the surface of the target, which must be removed before forming a nitrided surface to sputter the nitride layer. When a single ion source is used for ion beam deposition to produce thin films with complex chemical compounds such as S13, this method has more limitations than dual ion beam deposition. For example, 'Huang et al., "Study on the structure and composition of silicon nitride thin films deposited by single ion beam nozzle sputtering deposition, thin solid film 299 (1 997) 1 〇 04_1〇9 In a narrow range of about 800 volts, only a film with SnN4 properties is formed. During dual ion beam sputtering, the source from the auxiliary source can be independently adjusted over a wide range of process conditions and actual deposition rates The nitrogen atomic flux is to match the atomic flux of the target substance deposited from the deposition ion source. The present invention relates to the deposition of a single or multiple layers of chromium, molybdenum, tungsten or button compounds of general formula Mo'Nζ on quartz or A dual ion beam deposition method for manufacturing an opaque mask blank on a glass substrate, where M is chromium, molybdenum, tungsten, or a button. The present invention provides a novel mask blank for incident wavelengths less than 400 nm. Single-layer or multi-layer film deposition technology. The substrate can be any mechanically stable material that is transparent at the wavelength of the incident light used. For availability and cost, materials such as quartz, CaF2, and fumed silica ( Glass). Substrate Preferably, the present invention provides a single-layer or dual-ion beam deposition of opaque material with a 鬲 optical density or chemically varying in sections along the thickness of the film. Preferably, the present invention includes single or multi-layer MOxCyNzi dual-ion beam deposition, where m is selected From chromium, molybdenum, tungsten, or a button, or a combination thereof, where χ ranges from about 0.00⑽ to about 3,000, y ranges from about 0.00 to about 〇, and z ranges from about 〇. 〇 〇 to about 2. 〇〇. -12- AT B7

罩坯料，其光學密度係 578206 五、發明説明 較佳係本發明包括MOxCyN,型之光 超過約2個單位。 光學性質 光予性質(折射率“n”及消光係數“k”)係由可變角分光橢 回對％儀以三個入射角從186_8〇〇毫微米，對應於15_6.65 eV之能量範圍結合光學反射及穿透數據測得。由光學性質 之j譜從屬性的知識，可算得膜厚、光學穿料及反射率 般々見，〇. S. Heavens ,薄固態墨汁光學性質，5卜62 頁，Dover，Νγ，1991 ,其以應用方式併入本文中。 圖形簡述 圖1為雙離子束沉積方法之概要圖。 圖2為氮化矽之單離子束沉積方法的代表圖，其係利用 矽（Si)標的物並以源自單離子源或，，槍，，之氮及氬離子噴濺 之0 、 實例··不诱明“络，，采軍The cover material has an optical density of 578206. 5. Description of the invention It is preferred that the present invention includes MOxCyN, and the type of light exceeds about 2 units. Optical properties The optical properties (refractive index "n" and extinction coefficient "k") are determined by a variable angle spectroscopic elliptical return% meter at three incident angles from 186_800 nm, corresponding to an energy range of 15_6.65 eV Measured with optical reflection and transmission data. From the knowledge of the properties of the j-spectrum of optical properties, film thickness, optical penetration, and reflectivity can be calculated. See S. Heavens, Optical Properties of Thin Solid Ink, 5 pp. 62, Dover, Nγ, 1991. Application methods are incorporated herein. Brief Description of the Figures Figure 1 is a schematic diagram of a dual ion beam deposition method. Fig. 2 is a representative diagram of a single ion beam deposition method of silicon nitride, which uses a silicon (Si) target and is derived from a single ion source or, a gun, a nitrogen and argon ion sputter, and an example. · Don't seduce "college"

Ci:Cx〇yNz·，通常用於傳統光微影蝕刻中作為光罩，可在 一商用工具（Veeco IBD-21〇)中從Cr標的物利用雙離子束 沉積製得。從Cr標的物沉積期間，藉低能量離子炮擊之可 控制生長膜的化學，其中該低能量離子係衍生自c〇2與經紅 稀釋過之I的氣體混合物。沉積離子束源係利用4 ^㈣之 Xe操作在1 500伏特電壓及200毫安培離子束電流下。具有i8 seem N2、4 seem C〇2及2 seem Ar之輔助源係操作在1〇〇伏 特電壓及15 0毫安培電流下。基板為5英吋矩形石英板，〇. 〇 9 英吋厚。沉積係持續15分鐘並產生一約2 3 8毫微米厚之膜， -13- 本紙浪尺度適用中國國家樣準(CNS) A4規格(210 X 297公:¢)Ci: CxOyNz., Which is commonly used as a photomask in traditional photolithography etching, can be prepared from a Cr target using a dual ion beam deposition in a commercial tool (Veeco IBD-21〇). During the deposition of Cr target, the chemistry of the growth film can be controlled by bombardment with low energy ions, wherein the low energy ions are derived from a gas mixture of CO2 and red diluted I. The deposited ion beam source was operated at 4 ㈣ Xe at a voltage of 1,500 volts and an ion beam current of 200 milliamperes. The auxiliary source with i8 seem N2, 4 seem Co2 and 2 seem Ar is operated at a voltage of 100 volts and a current of 150 milliamps. The substrate is a 5 inch rectangular quartz plate, 0.09 inch thick. The deposition system lasted 15 minutes and produced a film with a thickness of about 2 3 8 nanometers. -13- The scale of this paper is suitable for China National Standard (CNS) A4 (210 X 297 male: ¢)

裝 訂Binding

578206 A7 B7 五、發明説明（11 ) 其在248毫微米下所測得之光學密度大於3，適合用於光微 影蝕刻中之二元式光罩應用。利用X-射線光電子光度計所 獲得該膜之化學組成物的深度輪廓揭露〇含量為約60%，氮 含量為約21%，氧含量為約19%，碳含量係低於1%。 -14- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐）578206 A7 B7 V. Description of the invention (11) The optical density measured at 248 nm is greater than 3, which is suitable for binary photomask applications in photolithographic etching. The depth profile of the chemical composition of the film obtained by using an X-ray photoelectron photometer revealed that the content was about 60%, the nitrogen content was about 21%, the oxygen content was about 19%, and the carbon content was less than 1%. -14- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

578206 第091108097號專利申請案 中文申請專利範圍替換本(92年7月）申請專利範圍578206 Patent Application No. 091108097 Chinese Patent Application Replacement (July 1992) Patent Application 1. :種雙離子束沉積方法，其可用於製備微 於彻毫微米之二元式光罩起料，該方法包 一層MOxCyNz化合物於一基板上，其中 :貝/ 、鎢或姮或其組合， 系選自鉻、鉬 U)藉源自一群氣體之離子進行鉻、鉬 或其化合物之離子束沉積，及 ⑻藉源自-群氣體之輔助源的第二離子束炮擊該基 ;，其中該層或這些層係藉源自輔助源氣體之跑 ^體離子與從該標的物或多個標的物所沉積在 基板上之物質進行化學結合所形成； 其中： 鴣或Is及/ X範圍係從〇·〇〇至3.00 ; y範圍係從〇·〇〇至1.00 ;及 Z範圍係從〇·〇〇至2.00。 2.如申請專利範圍第1之方法，其中該步驟⑷之氣體係 選自由 He、Ne、Ar、Kr、Xe、c〇2、n2、％、&amp;、cH3 n2o、H20、NH3、cf4、CH4、C2H2或其氣體組合所 組成之群。 3·如中請專利範圍第巧之方法，其中該步驟⑻之氣體係 選自由 He、Ne、Ar、Kr、Xe、C〇2、n2、〇2、F2 ' Ch3 、KO、Ηβ、NH3、CF4、CH4、C2H2或其氣體組合所 組成之群。 4·如申請專利範圍第丨項之方法，其中所選的微影蝕刻波 長係選自由157毫微米、193亳微米、24 8毫微米及365 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐)1 .: A dual ion beam deposition method that can be used to prepare binary photomasks smaller than nanometers in thickness. This method includes a layer of MOxCyNz compound on a substrate, in which: shellfish, tungsten, or thorium or a combination thereof Is selected from chromium, molybdenum U) ion beam deposition of chromium, molybdenum or its compounds by ions originating from a group of gases, and bombarding the base by a second ion beam originating from an auxiliary source of -group gas; The layer or layers are formed by chemically combining running ions originating from the auxiliary source gas with substances deposited on the substrate from the target or targets, where: 鸪 or Is and / X range are From 0.00 to 3.00; y ranges from 0.00 to 1.00; and Z ranges from 0.00 to 2.00. 2. The method as claimed in claim 1, wherein the gas system of step ⑷ is selected from He, Ne, Ar, Kr, Xe, c02, n2,%, &amp;, cH3 n2o, H20, NH3, cf4, A group consisting of CH4, C2H2 or its gas combination. 3. The method as claimed in the patent claims, wherein the gas system of step ⑻ is selected from He, Ne, Ar, Kr, Xe, Co2, n2, 02, F2 'Ch3, KO, Ηβ, NH3, A group consisting of CF4, CH4, C2H2, or a combination of gases. 4. The method according to item 丨 of the scope of patent application, wherein the selected lithography etching wavelength is selected from 157 nm, 193 亳 m, 24 8 nm and 365. This paper size is applicable to Chinese National Standard (CNS) A4 specifications ( 210X 297 mm) 裝 訂Binding 578206 8 8 8 8 A BCD 六、申請專利範圍 毫微米所組成之群。 5.如申請專利範圍第1項之方法，其中所沉積膜之不透明 度或光學密度係大於2單位。 -2- 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐）578206 8 8 8 8 A BCD VI. Application scope Patent group consisting of nanometers. 5. The method of claim 1 in the scope of patent application, wherein the opacity or optical density of the deposited film is greater than 2 units. -2- This paper size applies to China National Standard (CNS) A4 (210X297 mm)