201128294 if 六、發明說明： 【發明所屬之技術領域] 本揭露案是關於可在半導體微影（semiconductor201128294 if VI. Description of the invention: [Technical field to which the invention pertains] The present disclosure relates to semiconductor lithography (semiconductor)
Uth〇graphy )製程中實施高密度關鍵尺寸（critical dimension，CD)之半調相移空白遮罩（half t〇nephaseshift blankmaSk )及半調相移光罩（ha丨f-tone phase shift photomask)，以及其製造方法，且更特定而言，是關於可 應用於248 rnn KrF微影及193 nm ArF微影中之半調相移 空白遮罩、半調相移光罩以及其製造方法。 【先前技術】 ,歸因於半導體積體電路之高度整合，作為半導體製造 製程之核心技術之微影技術正變得愈加重要。在微影技術 中’曝光（exposure light)之波長按照436 nm G線 (G-lme)、365 nm i 線（i-iine)、248 nm KrF 及 193 nm ArF 之次序前進至較短波長，以便增加半導體電路圖案之解析 度。將較短波長用於曝光極大地有助於增加解析度，但其 亦對焦深（depth of focus，DoF)具有負面效應，且相應 地，其在設計包含透鏡之光學系統的過程中引起嚴重問題。 為了改良DoF並減小設計之負擔，已出現一種相移光 罩。藉由使用相移空白遮罩而製造相移光罩。當前，在相 移空白遮罩中，特定而言說，已廣泛使用半調相移空白遮 罩。 藉由在大體上具有152 mm尺寸之基於6025合成石英 坡璃之6025基板上形成同時且實質上包含鉬及矽之相移 4 201128294. L *i-〇pif 膜，而製造先前技術半調相移空白遮罩。此時，諸如組成 比率、密度及結晶狀態等相移膜之特性在其厚度方向上是 大體上均一的。然而’在其厚度方向上具有均一特性之此 類相移膜在空白遮罩製程、光罩製程及半導體製造製程中 導致各種問題。 首先，關於空白遮罩製程，相移膜位於基板與金屬膜 之間。此時，相移膜之黏合力相對於基板及金屬膜而言是 重要的。當形成相移遮罩及金屬膜圖案以製造光罩時，若 相移膜之黏合力較弱，則相移膜可自金屬膜圖案脫離，其 導致故障。而且，在製造光罩的過程中，使用超音波移除 粒子。因此，若相移膜之黏合力較弱，相移膜圖案可能脫 離之可能性增加，則有必要增加相移膜之黏合力。 而且，在製造光罩的過程中，使用諸如硫酸或氨水之 化學物來執行用於移除粒子之沖洗製程（抑啪叩 process)。此時，若相移膜具有較弱耐化學性（chemicai resistance)’則可能損壞相移膜，且因此，可能失去相移膜 之功庇•。因此，需要具有較高财化學性之相移膜，且具體 而言，在相移膜之表面處需要高耐化學性。而且，歸因於 在沖洗製程期間未完全移除之殘餘化學物的緣故，可能出 現混濁（haze)問題。因此，在其厚度方向上具有均一特 性之相移膜的情況下，可能容易產生混濁，其導致光罩之 使用壽命縮短。 而且’當在透明基板與相移膜之間產生應力時，其間 的黏合力在製造光罩時減小，或歸因於殘餘應力而產生圖 5 201128294、 »11 案扭曲從而使對準（registration)特性劣化。而且，當製 造半導體元件時，使用光罩來執行微影製程，且在微i製 程中’-般自基板朝向相移膜輻射曝光。此時，耐曝光特 性，亦即，相移膜對曝光之抵制是重要的。然而，在具有 厚度方向上是均一的單—膜之相移膜的情況下， 耐曝光特性不受控制，且因此較弱。 用雷吏用相移以遮罩形成光罩時，可能藉由使 膜電阻之電子充電現象是重要的。在 度方向上是均—的單—膜之相移膜的情況 性歸因於高薄臈電阻而較低，進而降 低關鍵尺寸（CD)特性。 【發明内容】 本揭露案提供-種半調相移空白遮罩 述半調相移空白遮罩的方法，其可用於248細 ΡΜ：微影且可增強諸如相移膜之黏合力、耐 =而1=、混耻、薄膜之結晶狀態、組成比率、 殘餘應力及薄膜電阻等特性。 立包性f施例’提供一種半調相移空白遮罩’ ”已3透月基板、相移膜、金屬膜及光阻膜，A中相移膜 包括可變組成區，JL中禮点所、十、㈣ 膜/、中相移膜 丨 構4膜之元素中之至少一種元 素的組成科在所述膜之深度方向上連續改變。 半調性實施例提供一種藉由圖案化並融刻 +調相移工白遮罩而形成之半調相移光罩，所述半調相移 201128294.Uth〇graphy) implements a high-density critical dimension (CD) half t〇nephase shift blankmaSk and a ha丨f-tone phase shift photomask. And a method of fabricating the same, and more particularly, a halftone phase shift blank mask, a half phase shift mask, and a method of fabricating the same applicable to 248 rnn KrF lithography and 193 nm ArF lithography. [Prior Art] Due to the high integration of semiconductor integrated circuits, lithography, which is the core technology of semiconductor manufacturing processes, is becoming more and more important. In lithography, the wavelength of the exposure light is advanced to shorter wavelengths in the order of 436 nm G-line (G-lme), 365 nm i-line (i-iine), 248 nm KrF, and 193 nm ArF. Increase the resolution of the semiconductor circuit pattern. The use of shorter wavelengths for exposure greatly contributes to increased resolution, but it also has a negative effect on depth of focus (DoF) and, accordingly, causes serious problems in the design of optical systems containing lenses. . In order to improve the DoF and reduce the burden on the design, a phase shift mask has emerged. A phase shift mask is fabricated by using a phase shift blank mask. Currently, in phase shift blank masks, in particular, halftone phase shift blank masks have been widely used. Manufacturing prior art semi-phaked phase by forming a phase shift 4 201128294. L *i-〇pif film on a 6025 substrate based on 6025 synthetic quartz glass having a size of 152 mm substantially Move the blank mask. At this time, the characteristics of the phase shift film such as composition ratio, density, and crystal state are substantially uniform in the thickness direction thereof. However, such phase shifting films having uniform characteristics in the thickness direction cause various problems in the blank mask process, the mask process, and the semiconductor manufacturing process. First, with regard to the blank mask process, the phase shift film is located between the substrate and the metal film. At this time, the adhesion of the phase shift film is important with respect to the substrate and the metal film. When the phase shift mask and the metal film pattern are formed to fabricate the photomask, if the adhesion of the phase shift film is weak, the phase shift film can be detached from the metal film pattern, which causes malfunction. Moreover, ultrasonic waves are used to remove particles during the manufacture of the reticle. Therefore, if the adhesion of the phase shift film is weak and the possibility of the phase shift film pattern may be removed, it is necessary to increase the adhesion of the phase shift film. Moreover, in the process of manufacturing the reticle, a chemical such as sulfuric acid or ammonia is used to perform a rinsing process for removing particles. At this time, if the phase shift film has a weak checiesi resistance, the phase shift film may be damaged, and therefore, the phase shift film may be lost. Therefore, a phase shift film having a high chemical property is required, and in particular, high chemical resistance is required at the surface of the phase shift film. Moreover, haze problems may occur due to residual chemicals that are not completely removed during the rinsing process. Therefore, in the case of a phase shift film having uniform characteristics in the thickness direction thereof, turbidity may easily occur, which results in a shortened life of the photomask. Moreover, 'when stress is generated between the transparent substrate and the phase shifting film, the adhesion between them is reduced when the reticle is manufactured, or due to the residual stress, the distortion occurs in Fig. 5 201128294, »11 The characteristic is degraded. Moreover, when manufacturing a semiconductor device, a photomask is used to perform the lithography process, and in the microi process, the radiation exposure is irradiated from the substrate toward the phase shift film. At this time, the exposure resistance characteristic, that is, the phase shift film is resistant to the exposure is important. However, in the case of a phase shift film having a uniform single-film in the thickness direction, the exposure resistance characteristics are not controlled, and thus are weak. When the reticle is formed by masking with a phase shift by a thunder, it is possible to make the phenomenon of electron charging by the film resistance important. The condition of the phase-shift film of the mono-film in the direction of the degree is lower due to the high thin tantalum resistance, thereby lowering the critical dimension (CD) characteristics. SUMMARY OF THE INVENTION The present disclosure provides a method for semi-tone phase shifting blank masking of a halftone phase shifting blank mask, which can be used for 248 fine ray: lithography and enhanced adhesion of phase shifting film, resistance = And 1 =, shame, crystal state of the film, composition ratio, residual stress and sheet resistance. The vertical package f example provides a half-shift phase shift mask ' ” has 3 moon-transparent substrate, phase shift film, metal film and photoresist film, A phase shift film includes variable composition area, JL point The composition of at least one of the elements of the film of the film, the medium phase shift film, and the film of the medium phase film is continuously changed in the depth direction of the film. The semi-modulating embodiment provides a patterning and melting The half-tone phase shifting mask formed by engraving + phase shifting white mask, the halftone phase shift 201128294.
Ji-ropif 冑自鮮包含依序堆疊之相賴、金屬膜及光阻膜，以及 透明基板，且所述相移膜包括可變組成區，其中構成所述 膜之元素中之至少一種元素的組成比率在所述膜之深度方 向上連續改變。 根據另一例示性實施例，提供一種藉由在透明基板上 依序形成相移膜、金屬膜及光阻膜而製造半調相移空白遮 罩的方法，其t藉由在接通電漿之狀態下逐步地或連續地 改變構成製程條件之多個條件中之至少一者而形成相移 膜，且所述相移膜包括可變組成區，其中構成所述膜之元 素中之至少一種元素的組成比率在所述膜之深度方向上連 續改變。 【實施方式】 下文中，將參考附圖詳細描述例示性實施例。 圖1是根據例示性實施例之用於硬遮罩之半調相移空 白遮罩100的剖面圖。 參看圖卜根據例示性實施例之半調相移空白遮罩100 包含透明基板110、相移膜120、金屬膜130及光阻膜14〇。 相移膜120、金屬膜130及光阻膜140依序形成於透明基 板110上。 土 精由相對於基板基材執行多個研磨（lapping)及拋光 (polishing)製私而形成透明基板11〇。可由合成石英、氣 化鈣CaFz及摻F石英中的一者形成透明基板11〇β透明基 板110可具有6025之尺寸且可在192 nm波長下具有2 nm/6.35 mm之雙折射（birefringence)。此時，基板基材為 201128294 Γιι 具有99.9999%純度的氧化矽（Si02)，其使用合成石英錠 經由切片（slicing)及邊緣礙磨（edgegrinding)而製造， 且具有152xl52±0.2 mm之尺寸及6.3 mm或更大的厚度。 藉由相對於基板基材執行多個研磨製程及多個拋光 製程而製造透明基板110。首先，相對於具有152xl52±0.2 mm之尺寸及6.3 mm或更大厚度之基板基材執行多個研磨 製程。在執行單一研磨製程的情況下，考慮到製程效率， 使用具有相對大的粒子尺寸之拋光粒子在高壓下執行研磨 製程。在此情況下，可容易達成目標厚度減小；然而，可 能產生損壞，其包含自基板基材之表面在厚度方向上產生 的裂縫。可在後續製程中發現作為缺陷的在基板基底材料 中產生之内部裂縫。而且，歸因於拋光粒子之粗糙粒子) 寸，不可正確地達成目標厚度減小之準確性。因此，可^ 由執行多個研磨製程來製造根據當前例示性實施例之透曰 110,以便減少缺陷並相對於基板基材達成準確的€ 標厚度減小。用於基板基材之研磨製射的拋光粒子可3 自由碳化石夕（Sic)、金剛石（c)、氧化錯（Zr〇2)及氧十 銘（A1203)組成之群組中的—種或—種以上，且施加至^ 個研磨製程。而且’用於研磨製財之拋光粒子可具等 4 20 μιη的尺寸。若拋光粒子之尺寸小於4从m，則可 票厚度減小；然而，可能延長處理時間，進而沒 =f率。而且’若抛紐子之尺寸纽心 易達成目標厚度減小，且會降低缺陷水平。 不4 接下來’相對於經受多個研磨餘之基板基材而執七Ji-ropif 胄 self-fresh comprises sequentially stacked, metal film and photoresist film, and a transparent substrate, and the phase shift film comprises a variable composition region in which at least one of the elements constituting the film is formed The composition ratio continuously changes in the depth direction of the film. According to another exemplary embodiment, there is provided a method of fabricating a half-shift phase shift blank by sequentially forming a phase shift film, a metal film, and a photoresist film on a transparent substrate, wherein t is turned on by plasma a phase shift film formed by gradually or continuously changing at least one of a plurality of conditions constituting the process conditions, and the phase shift film includes a variable composition region in which at least one of the elements constituting the film is formed The composition ratio of the elements continuously changes in the depth direction of the film. [Embodiment] Hereinafter, exemplary embodiments will be described in detail with reference to the accompanying drawings. 1 is a cross-sectional view of a halftone phase shifting blank mask 100 for a hard mask, in accordance with an illustrative embodiment. Referring to FIG. 2, the halftone phase shift blank mask 100 according to an exemplary embodiment includes a transparent substrate 110, a phase shift film 120, a metal film 130, and a photoresist film 14A. The phase shift film 120, the metal film 130, and the photoresist film 140 are sequentially formed on the transparent substrate 110. The soil is formed by performing a plurality of lapping and polishing to form a transparent substrate 11 with respect to the substrate. The transparent substrate 11 may be formed of one of synthetic quartz, vaporized calcium CaFz, and F-doped quartz. The 〇β transparent substrate 110 may have a size of 6025 and may have a birefringence of 2 nm / 6.35 mm at a wavelength of 192 nm. At this time, the substrate substrate was 201128294 Γιι yttria (SiO 2 ) having a purity of 99.9999%, which was manufactured by slicing and edgegrinding using a synthetic quartz ingot, and having a size of 152 x 52±0.2 mm and 6.3. Mm or greater thickness. The transparent substrate 110 is fabricated by performing a plurality of polishing processes and a plurality of polishing processes with respect to the substrate substrate. First, a plurality of polishing processes are performed with respect to a substrate substrate having a size of 152 x 52 ± 0.2 mm and a thickness of 6.3 mm or more. In the case where a single grinding process is performed, the polishing process is performed under high pressure using polishing particles having a relatively large particle size in consideration of process efficiency. In this case, the target thickness reduction can be easily achieved; however, damage may occur which includes cracks generated in the thickness direction from the surface of the substrate substrate. Internal cracks generated in the substrate base material as defects can be found in subsequent processes. Moreover, due to the coarse particles of the polished particles, the accuracy of the target thickness reduction cannot be correctly achieved. Therefore, the lens 110 according to the present exemplary embodiment can be manufactured by performing a plurality of polishing processes in order to reduce defects and achieve an accurate reduction in thickness with respect to the substrate substrate. The polishing particles used for the polishing of the substrate substrate can be selected from the group consisting of: Sic, Diamond (c), Oxidation (Zr〇2), and Oxygen (A1203). More than one type, and applied to ^ grinding process. Moreover, the polishing particles used for the grinding and manufacturing can have a size of 4 20 μm. If the size of the polishing particles is less than 4 from m, the thickness of the ticket can be reduced; however, the processing time may be prolonged, and thus there is no =f rate. Moreover, if the size of the button is easy to achieve the target thickness is reduced, and the defect level will be reduced. No 4 next 'relative to the substrate substrate subjected to multiple grinding residues
8 S 201128294.f 多個拋光製程。用於椒光之漿料（slurry)包含氧化飾 (Ce〇2)、膠態二氧化矽（Si〇2)拋光粒子，及過氧化氫 (ΗΛ)，且使用硝酸（HN〇3)或氫氧化鉀（KOH)來控 制漿料之pH。可在6至12之範圍中控制拋光製程中之拋 光漿料之總體pH。具體而言，諸如氫氧化鉀（K〇H)之 無機驗提供综效作用（Synergy effect)之優點，因為無機 鹼對基板基材具有蝕刻效應。同時，拋光粒子在拋光製程 中以物理方式移除基板基材。此時，若拋光粒子具有5 或更大的尺寸，則可容易達成目標厚度減小；然而，可能 難以確保良好的表面粗縫度。而且，若拋光粒子具有5卿 或更小的尺寸，則經受研磨製程之基板基材可具有小量的 厚度減小。因此，將花費較長的處理時間，進而減少處理 效率。因此’在搬光製程中，拋絲子㈤：可具有在〇5 μηι至5 μηι範圍中之粒子尺寸。而且，用於多個拋光製程 中=膠態二氧化雜子之粒子尺寸可在2〇卿至叫 之範圍中。若膠態二氧化石夕粒子具有20 μηι歧小的尺 寸，則降低拋光製程之拋光效率，且若膠態二氧化石夕粒子 2 200 μηι或更大的尺寸，則可能不滿足必須在抛光製 私中保證之表面粗糙度。 r的，光製程改良表面粗财。因此，在執行多個拋光製 而拋Γ子之尺寸隨著多個拋光製程 製程*_對_的表面狀態，所以必須 -第二拋光製程移除更大量的基板基材。因此，在8 S 201128294.f Multiple polishing processes. Slurry for pepper light contains oxidized (Ce〇2), colloidal cerium (Si〇2) polishing particles, and hydrogen peroxide (ΗΛ), and uses nitric acid (HN〇3) or hydrogen. Potassium oxide (KOH) is used to control the pH of the slurry. The overall pH of the polishing slurry in the polishing process can be controlled in the range of 6 to 12. Specifically, an inorganic test such as potassium hydroxide (K〇H) provides an advantage of the Synergy effect because the inorganic base has an etching effect on the substrate substrate. At the same time, the polishing particles physically remove the substrate substrate during the polishing process. At this time, if the polishing particles have a size of 5 or more, the target thickness reduction can be easily achieved; however, it may be difficult to ensure a good surface roughness. Moreover, if the polishing particles have a size of 5 Å or less, the substrate substrate subjected to the polishing process can have a small thickness reduction. Therefore, it takes a long processing time, which in turn reduces processing efficiency. Therefore, in the light-transfer process, the spine (five): may have a particle size in the range of μ5 μηι to 5 μηι. Moreover, the particle size of the colloidal dioxins used in a plurality of polishing processes can be in the range of 2 〇 至. If the colloidal silica dioxide particles have a size of 20 μηι, the polishing efficiency of the polishing process is lowered, and if the colloidal silica dioxide particles are 2 200 μm or larger, it may not be necessary to be polished. The surface roughness guaranteed in private. r, the light process improves the surface of the rich. Therefore, in the case where a plurality of polishing processes are performed and the size of the throwing tweezers is in accordance with the surface state of the plurality of polishing process processes*_, the second polishing process must remove a larger amount of the substrate substrate. Thus, in
S 9 201128294 第一拋光製程中，具有高硬度及低可壓縮性之多孔鈽墊 (porous cerium pad)可用作拋光墊，且在第二拋光製程中， 可使用諸如SUBA#400至SUBA#800之軟塾。可根據基板 基材之移除量及表面狀態來選擇拋光墊。若使用 SUBA#400或更小的拋光墊，則歸因於拋光墊之相對高的 可壓縮性及彈性恢復率（elastic rec〇veryrate)以及低硬度 特性而增加處理時間，進而降也拋光效率。若使用 SUBA#800或更大的拋光墊，則歸因於拋光墊之低可壓縮 性及彈性恢復率以及高硬度特性而可能不容易達成目標表 面粗链度。用於第二拋光製程中之軟墊可具有或更大 的可壓縮性及65%或更大的彈性恢復率。在具有3%或更 大可壓縮性之拋光墊中，當將拋光壓力施加至二氧化矽粒 子時，圍繞粒子之起毛層（nap layer)彈性變形以便分佈 並吸收拋光壓力，相應地，抑制可紐生於基板表面之 表面上的具有凹入形狀之缺陷的形成。在具有或更大 彈性恢復率之拋光墊η為起毛層可容易被壓縮及恢 復，起毛層不允許較大二氧化矽粒子保持於起毛層中且 因此’可抑制凹形缺陷之m第三拋光製程中，作為 超軟墊之麂皮墊（suede pad)用作拋光墊。由於在第三拋 光製程中，必須儘可能地改良表面粗糙度及粒子特性，所 乂使用具有低硬度以及相對大的彈性恢復率及可壓縮性之 超軟拋光墊。用於第三拋光製程中之超軟拋光塾可具有6% 或6%以上之可壓縮性及72%或72%以上之彈性恢復率。 由於必須在第二拋光製程巾進—步嚴格㈣缺陷，所以抛 201128294. L· -TUplf 光墊具有比第二拋光製程中所使用之拋光墊更大的可壓縮 性及彈性恢復率。 用於抛光製程中之抛光塾中所包含之溝槽（groove) 可具有各種形狀。舉例而言’可使用具有25 mm間距、4 mm 寬度及0.5 mm深度之溝槽之拋光墊。拋光墊之溝槽藉由 在拋光製程期間將充分量的漿料供應至透明基板110而增 加透明基板110之拋光效率。亦可使用不具有溝槽之拋光 塾。溝槽之尺寸可根據拋光製程而變化’而且，可根據拋 光製程而判定具有溝槽之抛光墊的使用。 此外’若用於抛光製程中之拋光墊具有兩層或兩層以上結 構，則自直接相對方向（3钍吩智?)對應於第二層之拋光 墊之起毛層可具有200 μιη至600 μιη之範圍中的厚度。若 起毛層具有200 μηι或更小的厚度，則會減小拋光墊之彈 性恢復率，且因此，難以確保良好表面粗糙度，且鑒於包 含粒子之缺陷，其將為負面效應。若起毛層具有600 μιη 或更大的厚度，則降低確保表面粗糙度之拋光效率。 相移臈120將曝光之相位移位180。。相移膜120實質 上包含錮及矽，且可另外包含選自由氮、碳、氧及氟化物 組成之群组的至少一種元素。 構成相移膜120之元素中之至少一者具有一區（下文 稱作可變組成區”），其中其含量差在相移膜120之厚度 =向上等於或大於3 at%。而且，在相移膜12〇中，元素 含量在其厚度方向上是不同的，且可選擇性地控制可變組 成區之厚度。具有含量差之元素可為鉬及矽，且鉬或矽之 201128294 含量在相移膜120之厚度方向上可具有3 at%或更大的 差。當翻與妙之間的含量差為至少3 at%之區與剩餘區形 成介面時，鉬與矽之間的含量差為至少3 at%之區之厚度 可等於或小於50 A。若鉬或矽之含量在相移膜12〇之厚度 方向上具有3 at%或更大的差的區之厚度等於或大於5〇 A ’則可為為翻或碎之含罝在相移膜12〇之厚度方向上且 有3 at%或更大的差的區不與剩餘區形成介面。 、 構成相移膜120之元素之含量在相移膜12〇之寬度方 向上可為均一的。此時，相移膜12〇之寬度方向上之組成 均一性可等於或小於10%。可使用以下等式計算組成均一 性’且量測位置可為相移膜120之寬度方向上的至少5點。 可使用AES方法、XPS方法及RBS方法分析薄膜之組成。 [等式1] 組成均一性-ί最大組成比率-最小組成比率) (最大組成比率+最小組成比率）χ 100 相移膜120可在其厚度方向上具有自〇 2 g/cm3至2 〇 g/cm3之範圍中的密度差。若相移膜12〇之厚度方向上之密 度差小於0.2 g/cm3 ’則相移膜12〇具有類似於密度不改變 之狀態的狀態’且若密度變化大於2 〇 g/cm3，則相移膜12〇 中之應力可極大地改變。而且，相移膜12〇可在厚度方向 上具有殘餘應力差，且具體而言，可包含在其厚度方向上 之殘餘應力差等於或大於1〇 MPa的區。 當使用濺鍍方法形成相移膜12〇時，在表i中概括製 12 201128294 程條件。 [表1]S 9 201128294 In the first polishing process, a porous cerium pad having high hardness and low compressibility can be used as a polishing pad, and in the second polishing process, for example, SUBA#400 to SUBA#800 can be used. Soft palate. The polishing pad can be selected according to the amount of substrate substrate removed and the surface state. If a SUBA #400 or smaller polishing pad is used, the processing time is increased due to the relatively high compressibility and elastic recovery rate of the polishing pad and the low hardness characteristic, which in turn reduces the polishing efficiency. If SUBA #800 or larger polishing pad is used, it may not be easy to achieve the target surface thick chain attribute due to the low compressibility and elastic recovery rate of the polishing pad and high hardness characteristics. The cushion used in the second polishing process may have a greater compressibility and an elastic recovery rate of 65% or more. In a polishing pad having a compressibility of 3% or more, when a polishing pressure is applied to the ceria particles, the nap layer around the particles is elastically deformed to distribute and absorb the polishing pressure, and accordingly, the suppression may be The formation of a defect having a concave shape on the surface of the substrate surface. The polishing pad η having a greater or greater elastic recovery rate can be easily compressed and recovered as a raised layer, and the raised layer does not allow the larger cerium oxide particles to remain in the raised layer and thus can be suppressed from the third polishing of the concave defect. In the process, a suede pad as a super soft pad is used as a polishing pad. Since the surface roughness and particle characteristics must be improved as much as possible in the third polishing process, an ultra-soft polishing pad having a low hardness and a relatively large elastic recovery rate and compressibility is used. The ultra-soft polishing enamel used in the third polishing process may have a compressibility of 6% or more and an elastic recovery rate of 72% or more. Since the second polishing process must be subjected to strict (four) defects, the 201128294 L.-TUplf optical pad has greater compressibility and elastic recovery than the polishing pad used in the second polishing process. Grooves included in the polishing crucible used in the polishing process can have various shapes. For example, a polishing pad having a groove of 25 mm pitch, a width of 4 mm, and a depth of 0.5 mm can be used. The groove of the polishing pad increases the polishing efficiency of the transparent substrate 110 by supplying a sufficient amount of the slurry to the transparent substrate 110 during the polishing process. A polishing 不 without grooves can also be used. The size of the groove can vary depending on the polishing process' and the use of a polishing pad having a groove can be determined based on the polishing process. In addition, if the polishing pad used in the polishing process has two or more layers, the raised layer corresponding to the polishing pad of the second layer may have a thickness of 200 μm to 600 μm from the direct opposite direction (3 钍 智?) The thickness in the range. If the batt layer has a thickness of 200 μm or less, the elastic recovery rate of the polishing pad is reduced, and therefore, it is difficult to ensure good surface roughness, and it will be a negative effect in view of defects containing particles. If the raised layer has a thickness of 600 μm or more, the polishing efficiency which ensures the surface roughness is lowered. Phase shift 臈 120 shifts the phase of the exposure by 180. . The phase shift film 120 substantially contains ruthenium and osmium, and may additionally contain at least one element selected from the group consisting of nitrogen, carbon, oxygen, and fluoride. At least one of the elements constituting the phase shift film 120 has a region (hereinafter referred to as a variable composition region) in which the difference in content is at the thickness of the phase shift film 120 = upward is equal to or greater than 3 at%. In the film 12〇, the element content is different in the thickness direction thereof, and the thickness of the variable composition region can be selectively controlled. The element having the difference in content can be molybdenum and niobium, and the content of molybdenum or niobium 201128294 is in the phase. The film transfer film 120 may have a difference of 3 at% or more in the thickness direction. When the difference between the turn and the difference is at least 3 at%, the content difference between the molybdenum and the niobium is The thickness of at least 3 at% of the region may be equal to or less than 50 A. If the content of molybdenum or niobium has a difference of 3 at% or more in the thickness direction of the phase shift film 12 等于, the thickness of the region is equal to or greater than 5 〇A. 'The area which is turned or broken in the thickness direction of the phase shift film 12 且 and has a difference of 3 at% or more does not form an interface with the remaining area. The content of the element constituting the phase shift film 120 It may be uniform in the width direction of the phase shift film 12A. At this time, the group of the phase shift film 12's width direction The uniformity may be equal to or less than 10%. The composition uniformity may be calculated using the following equation 'and the measurement position may be at least 5 points in the width direction of the phase shift film 120. The film may be analyzed using the AES method, the XPS method, and the RBS method. Composition [Equation 1] Composition uniformity - ί maximum composition ratio - minimum composition ratio) (maximum composition ratio + minimum composition ratio) χ 100 phase shift film 120 may have a self-〇 2 g/cm 3 in its thickness direction 2 density difference in the range of 〇g/cm3. If the density difference in the thickness direction of the phase shift film 12〇 is less than 0.2 g/cm3′, the phase shift film 12〇 has a state similar to the state in which the density does not change' and if When the density change is greater than 2 〇g/cm3, the stress in the phase shift film 12〇 can be greatly changed. Moreover, the phase shift film 12〇 can have a residual stress difference in the thickness direction, and specifically, can be included in the thickness thereof. The residual stress difference in the direction is equal to or greater than 1 MPa. When the phase shift film 12 is formed by sputtering, the condition of 12 201128294 is summarized in Table i. [Table 1]
藉由在表1中所概括之製程條件下濺鍍矽化鉬目標 (target)而形成相移膜〗2〇,在矽化鉬目標中鉬含量為5〜3〇 at/〇，且其餘物為矽.此時，濺鍍目標在厚度方向及寬度 方向上具有均一元素分佈，且具體而言，組成均一性可等 於或小於10%。此外，濺鍍目標經由熱壓（hotpress，HP) 方法或熱均麗（hot iso-static pressure，HIP )方法而製造， 且可具有30 μιη或更小的粒子直徑。而且，濺鍍目標可在 其厚度方向或寬度方向上具有均一粒子尺寸分佈，且可在 其厚度方向或寬度方向上具有等於或小於1〇%之粒子尺寸 分伟誤差。 金屬膜130為多層膜。當金屬膜130具有二層結構 時，靠近基板而定位的下層充當光屏蔽膜且具有選自由The phase shift film is formed by sputtering a target of molybdenum molybdenum under the process conditions summarized in Table 1. The molybdenum content in the target of molybdenum molybdenum is 5 to 3 〇 at / 〇, and the rest is 矽At this time, the sputtering target has a uniform element distribution in the thickness direction and the width direction, and specifically, the composition uniformity may be equal to or less than 10%. Further, the sputtering target is manufactured by a hot press (HP) method or a hot iso-static pressure (HIP) method, and may have a particle diameter of 30 μm or less. Further, the sputtering target may have a uniform particle size distribution in the thickness direction or the width direction thereof, and may have a particle size fractal error equal to or less than 1% in the thickness direction or the width direction thereof. The metal film 130 is a multilayer film. When the metal film 130 has a two-layer structure, the lower layer positioned close to the substrate functions as a light shielding film and has a selected from
Cr、CrN、CrCN、CrON、CrCON 及 CrO、CrCO 組成之 群組之一者的主要成分，或其混合物。遠離金屬膜而 定位的上層充當抗反射膜，且具有選自由Cr、CrN、OCN、 CrON、CrCON、CrO及CrCO組成之群組之一者的主要成 刀，或其混合物。此時，抗反射膜在曝光之波長下具有 201128294 10%〜25%之反射率及2.5或更大的光學密度。具體而言， 在光學密度的情況下’金屬膜130單獨便可達成等於或大 於2.5之光學密度，或金屬膜BO與相移膜12〇組合可達 成等於或大於2.5之光學密度。 而且，金屬膜130包含在其厚度方向上具有3站％或 更大組成差且具有50 Α或更小厚度的區，且組成差為3 at%或更大的區具有在金屬膜13〇之深度方向上連續改變 的組成。 此時，形成組成在金屬膜130之深度方向上連續改變 的區意謂在一狀態下執行金屬膜130之沈積，所述狀態包 含用以控制金屬膜130之特性之製程條件在未關掉電漿之 狀態下連續或逐步改變的至少一區。亦即，金屬膜13〇之 組成在金屬膜130之深度方向上連續改變意謂在用於形成 金屬膜之錢鑛期間’製程條件連續或逐步改變。 此外，金屬膜130可具有三層結構，所述三層結構具 有光屏蔽膜、抗反射膜及钱刻終止膜。在金屬膜13〇之三 層結構中，充當光屏敝膜及抗反射膜的層由作為主要成分 之MoSi形成’且包含選自由MoSi、MoSiO、MoSiN、 MoSiC、MoSiCN、MoSiCO 及 MoSiCON 組成之群組的一 者，或其混合物。充當蝕刻終止膜的層由作為主要成分之 Cr 形成’且包含選自由 Cr、CrN、CrCN、CrON"、、 CrO及CrCO組成之群組的一者，或其混合物。此外，在 具有三層結構之金屬層130中，構成金屬層13〇之元素之 組成差在其厚度方向上等於或大於3 at%的區具有5〇人或 201128294 2 ίί，且構成金屬層130之元素之组成差等於或大 的區（其不具有介面）由組成在金屬膜13〇之厚 續改變的區_。而且，金屬層⑽可具有在 二“:二面之多層結構，或可具有如在相移膜120中-般組成在其厚度方向上連續改變的區。 130=卜。’姓刻終止膜可另外包含於相移膜120與金屬膜 光阻膜14〇可由包含強酸之光輯料形成，且包含呈 ==光_ UG之濃度之強_有機_可形成於光阻 、 下方。可由顯影劑顯影定位於光阻膜14〇下方之有 機薄膜而不管曝光製程之應用如何。光阻膜140可且右 1争_人至4,5〇〇A之範圍中的厚度。而且，具有7〇〇人'或 簿膜ϋ包含具有高於光阻膜14G之濃度之強酸的有機 成於光阻膜14G下方。此時，可由顯影劑顯影定 ^於先賴14〇下方之有機薄膜’科管曝光製程之應用 、可°塗覆於金屬膜130之表面上的光阻材料為化學增幅 义光阻（chemically amplified resist)。 圖2是繪示根據例雜實施例之製造用財調相移遮 罩之空白遮罩之方法的流程圖。 參看圖2，使用藉由使用HP或HIP方法製造的雜 目\在具有6G25尺寸之透縣板⑽上形成相移膜 120’且在長穿透減鍍設備中相移膜120具有M〇:Si=2.8(亦 即，Mo..Si=20at%:80at°/〇)之組成比率，如圖3中所示7。、 表2中概括用於沈積相移膜120之製程條件。 不 15 201128294 [表2] 製程條件 ~~- 第一沈積製程 第二沈積製程 ~ 濺鍍功率 0.7 kW 1.5 kW ^ 非反應C體(Ar)之流量 3 seem 3 seem 反應乳體(N2)之流重 5 seem 17 seem 製程壓力 一' 0.05 Pa 300' 0.08 Pa -360#' ~~ 製程時間 — ^在表2中所描述之製程條件下相對於相移膜120執行 第-沈積製程持續3G秒（操作S2()())。此時，氣體流量不 限於3〜5 seem，但基於體積百分比（v〇1%)，Ar氣之流量 可在10%〜70%範圍中，纟&氣之流量可在2〇%〜85%範圍 中。壓力亦可在0.01〜〇.4pa範圍中，且濺鍍功率可在 〇=〜13W/mm範圍中。接下來，連續地執行第二沈積製程 (操作S210>而且，在此情況下，可改變製程條件以控制 相移膜120之特性。 經由上文所描述之製程，可形成在厚度方向上具有兩 種特性之單層相移膜120。此時，當沈積條件自相移膜12〇 之下層至上層而改變，以便在透明基板110上形成不具有 下層與上層之間的介面的相移膜120時’Ar氣之流量維持 於3 seem ’且N2氣之流量自5~>9今13今17 seem逐漸增 加。濺鍍功率亦自〇.7+l.〇+i.2+1.5kW逐漸增加。依據 奥格分析（Auger analysis)，相移膜120之下層包含15 at% Mo、40 at% Si 及 45 at% N ’ 且上層包含 11 at% Mo、35 at%The main component of one of the group consisting of Cr, CrN, CrCN, CrON, CrCON, and CrO, CrCO, or a mixture thereof. The upper layer positioned away from the metal film serves as an antireflection film and has a main forming blade selected from one of the group consisting of Cr, CrN, OCN, CrON, CrCON, CrO, and CrCO, or a mixture thereof. At this time, the antireflection film has a reflectance of 201128294 10% to 25% and an optical density of 2.5 or more at the wavelength of exposure. Specifically, in the case of optical density, the metal film 130 alone can achieve an optical density equal to or greater than 2.5, or the combination of the metal film BO and the phase shift film 12 can reach an optical density equal to or greater than 2.5. Moreover, the metal film 130 includes a region having a composition difference of 3 stations% or more in the thickness direction thereof and having a thickness of 50 Å or less, and a region having a composition difference of 3 at% or more has a film in the metal film 13 The composition that changes continuously in the depth direction. At this time, forming a region in which the composition continuously changes in the depth direction of the metal film 130 means performing deposition of the metal film 130 in a state including process conditions for controlling the characteristics of the metal film 130 without turning off the power. At least one zone that changes continuously or stepwise in the state of the slurry. That is, the continuous change of the composition of the metal film 13〇 in the depth direction of the metal film 130 means that the process conditions are continuously or stepwise changed during the use of the money ore for forming the metal film. Further, the metal film 130 may have a three-layer structure having a light shielding film, an antireflection film, and a money stopper film. In the three-layer structure of the metal film 13〇, a layer serving as a light-screen germanium film and an anti-reflection film is formed of MoSi as a main component and contains a group selected from the group consisting of MoSi, MoSiO, MoSiN, MoSiC, MoSiCN, MoSiCO, and MoSiCON. One of the groups, or a mixture thereof. The layer serving as the etching stopper film is formed of Cr as a main component and contains one selected from the group consisting of Cr, CrN, CrCN, CrON ", CrO, and CrCO, or a mixture thereof. Further, in the metal layer 130 having the three-layer structure, the difference in the composition of the elements constituting the metal layer 13〇 is equal to or greater than 3 at% in the thickness direction thereof, and the metal layer 130 is composed of 5 〇 or 201128294 2 ίί. A region in which the difference in composition of elements is equal to or larger (which does not have an interface) is composed of a region _ which is continuously changed in the thickness of the metal film 13 . Moreover, the metal layer (10) may have a multilayer structure of two ": two sides, or may have a region in which the composition continuously changes in the thickness direction as in the phase shift film 120. 130 = 卜. Further, the phase shift film 120 and the metal film photoresist film 14 may be formed of a light-containing material containing a strong acid, and include a strong concentration of == light_UG. The organic_ may be formed under the photoresist, and may be formed by a developer. The organic film positioned under the photoresist film 14 is developed regardless of the application process of the exposure process. The photoresist film 140 can compete with the thickness in the range of 4, 5 Å A. Moreover, it has 7 〇〇. The human or film film contains an organic compound having a strong acid higher than the concentration of the photoresist film 14G under the photoresist film 14G. At this time, it can be developed by the developer to be exposed to the organic film under the 14 〇 exposure. The application of the process, the photoresist material which can be applied to the surface of the metal film 130 is a chemically amplified resist. FIG. 2 is a diagram showing the manufacturing phase shift mask according to an exemplary embodiment. Flow chart of the method of blank mask. Referring to Figure 2, use by using The hybrid manufactured by the HP or HIP method forms a phase shift film 120' on a 6G25-sized permeable plate (10) and the phase shift film 120 has a M 〇: Si = 2.8 (i.e., Mo) in the long penetration plating apparatus. The composition ratio of .Si=20at%: 80at°/〇) is as shown in Fig. 3. The process conditions for depositing the phase shift film 120 are summarized in Table 2. No 15 201128294 [Table 2] Process conditions~ ~- The first deposition process second deposition process ~ sputtering power 0.7 kW 1.5 kW ^ non-reactive C body (Ar) flow 3 seem 3 seem reaction milk (N2) flow weight 5 seem 17 seem process pressure a ' 0.05 Pa 300' 0.08 Pa - 360 #' ~~ Process time - ^ Performing the first deposition process with respect to the phase shift film 120 for 3 G seconds under the process conditions described in Table 2 (operation S2()()). The gas flow rate is not limited to 3~5 seem, but based on the volume percentage (v〇1%), the flow rate of Ar gas can be in the range of 10% to 70%, and the flow rate of 纟 & gas can be in the range of 2% to 85%. The pressure may also be in the range of 0.01 to 4.4 Pa, and the sputtering power may be in the range of 〇=~13 W/mm. Next, the second deposition process is continuously performed (operation S210>; and, in this case Next, the process conditions can be changed to control the characteristics of the phase shift film 120. Through the process described above, a single-layer phase shift film 120 having two characteristics in the thickness direction can be formed. At this time, when the deposition conditions are self-phase shifting The film 12 is changed from the lower layer to the upper layer to form a phase shift film 120 having no interface between the lower layer and the upper layer on the transparent substrate 110. The flow rate of the Ar gas is maintained at 3 seem' and the flow rate of the N2 gas is from 5 to 5 >9 Today 13 and 17 seem gradually increased. The sputtering power is also increased from .7+l.〇+i.2+1.5kW. According to Auger analysis, the lower layer of phase shift film 120 contains 15 at% Mo, 40 at% Si and 45 at% N ′ and the upper layer contains 11 at% Mo, 35 at%
Si及54 at% N。如上文所描述，由於相移膜120之上層包 含相對大量的氮，所以相移膜120可在化學耐久性 201128294 (chemical durability)、混濁度、對金屬膜之黏合力、殘餘 應力及非晶狀態方面達成優良特性。同時，由於相移膜12〇 之下層包含相對小量的氮，所以下層在曝光耐久性、對基 板之黏合力及薄膜電阻方面為優良的，且具體而言，在針 孔（pin holes)及粒子方面為優良的。而且，藉由達成多 層連續膜而在相移膜120中不具有介面可增強與針孔及粒 子有關的特性。同時，亦可能藉由施加機械擋板 (mechanical shutter)而製造具有介面之相移膜12〇。 接下來，金屬膜130經由濺鍍製程形成於相移膜12〇 上（操作S220)。此時，金屬膜130可包含至少兩個薄膜。 接下來’藉由使職塗方法（spin⑺ating)將包含強酸且 具有100 A厚度之有機薄膜形成於金屬膜13〇上（操作 S230)。可經由控制軟烤條件在不需要曝光製程的情況下 使用顯影劑而顯影有機薄膜。而且，若經由控.烤條件 在曝光製程之後未經由顯影製程顯影有機薄膜，則可僅經 由乾式侧（dryetehing)製㈣移除有機薄膜。接下來， 藉由塗覆正型（positivetype)化學增幅型光阻材料而將最 終光阻膜形成於有機薄膜上（操作S240)。經由上文所描 述之過程，可製造具有連續多層結構之半調相移空白遮 罩。此後，可藉由圖案化並蝕刻半調相移空白遮罩而形成 半調相移光罩。 / 藉由根據本發明之半調相移空白遮罩、半調 2製造方法，由__在其厚度方向上具有不同组成 比率’所以可根據树财之位置達成各種舰。因此， 17 201128294 ---—— A. 有可能製造在相移膜之黏合力、粒子、化學耐久性、曝光 耐久性、殘餘應力及薄膜電阻特性方面是優良的半調相移 空白遮罩。因此，可製造高品質半調相移光罩，且最終， 其允許製造高品質半導體元件。 Μ 雖然已參考特定實施例描述半調相移空白遮罩、半調 相移光罩及其製造方法’但其不限於此。因此，熟習此項技 術者將容易理解，在不脫離由所附申請專利範圍界定之本發 明之精神及範疇的情況下，可對其作出各種修改及改變。 【圖式簡單說明】 自結合附圖所進行之以下描述中可更詳細地理解例 示性實施例，附圖中： 圖1是根據例示性實施例之用於硬遮罩之空白遮罩的 剖面圖。 圖2是繪示根據例示性實施例之製造用於硬遮罩之空 白遮罩之方法的流程圖。 圖3是根據例示性實施例之用於製造用於硬遮罩之空 白遮罩之長穿透減鑛（long through sputtering)設備的示 意圖。 【主要元件符號說明】 1〇〇 :半調相移空白遮罩 110:透明基板 120 :相移膜 :金屬膜 14〇··光阻膜 S200〜S240 :操作Si and 54 at% N. As described above, since the upper layer of the phase shift film 120 contains a relatively large amount of nitrogen, the phase shift film 120 can have chemical durability 201128294 (chemical durability), turbidity, adhesion to the metal film, residual stress, and amorphous state. The aspect achieves excellent characteristics. Meanwhile, since the lower layer of the phase shift film 12 has a relatively small amount of nitrogen, the lower layer is excellent in exposure durability, adhesion to the substrate, and sheet resistance, and specifically, in pin holes and The particles are excellent. Moreover, the absence of an interface in the phase shift film 120 by achieving a multi-layer continuous film enhances pinhole- and particle-related properties. At the same time, it is also possible to fabricate the phase shifting film 12 having an interface by applying a mechanical shutter. Next, the metal film 130 is formed on the phase shift film 12A via a sputtering process (operation S220). At this time, the metal film 130 may include at least two films. Next, an organic film containing a strong acid and having a thickness of 100 A is formed on the metal film 13 by a spin coating method (operation S230). The organic film can be developed by controlling the soft bake condition using a developer without requiring an exposure process. Further, if the organic film is not developed through the developing process after the exposure process by the controlled baking condition, the organic film can be removed only by the dry side (four). Next, a final photoresist film is formed on the organic film by coating a positive type chemically amplified photoresist material (operation S240). Through the process described above, a halftone phase shifting blank mask having a continuous multilayer structure can be fabricated. Thereafter, a half-phase shift mask can be formed by patterning and etching a halftone phase shifting blank mask. By using the halftone phase shift blank mask and the halftone 2 manufacturing method according to the present invention, the __ has a different composition ratio in the thickness direction thereof, so that various ships can be achieved according to the position of the tree. Therefore, 17 201128294 --- -- A. It is possible to manufacture a half-tone phase shift blank mask which is excellent in the adhesion of the phase shift film, particles, chemical durability, exposure durability, residual stress and film resistance characteristics. Therefore, a high-quality half-phase shift mask can be manufactured, and finally, it allows fabrication of high-quality semiconductor elements. Μ Although the halftone phase shift blank mask, the halftone phase shift mask, and the method of manufacturing the same have been described with reference to the specific embodiments, it is not limited thereto. It will be apparent to those skilled in the art that various modifications and changes can be made without departing from the spirit and scope of the invention as defined by the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS Exemplary embodiments can be understood in more detail in the following description in conjunction with the drawings in which: FIG. 1 is a section of a blank mask for a hard mask in accordance with an exemplary embodiment. Figure. 2 is a flow chart illustrating a method of fabricating a blank mask for a hard mask, in accordance with an illustrative embodiment. 3 is a schematic illustration of a long through sputtering apparatus for fabricating a blank mask for a hard mask, in accordance with an illustrative embodiment. [Main component symbol description] 1〇〇: Halftone phase shift blank mask 110: Transparent substrate 120: Phase shift film: Metal film 14〇··Photoresist film S200~S240: Operation