TW200405447A - Post-CMP cleaning of semiconductor wafer surfaces using a combination of aqueous and CO2 based cryogenic cleaning techniques - Google Patents

Post-CMP cleaning of semiconductor wafer surfaces using a combination of aqueous and CO2 based cryogenic cleaning techniques Download PDF

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TW200405447A
TW200405447A TW092113357A TW92113357A TW200405447A TW 200405447 A TW200405447 A TW 200405447A TW 092113357 A TW092113357 A TW 092113357A TW 92113357 A TW92113357 A TW 92113357A TW 200405447 A TW200405447 A TW 200405447A
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cleaning
scope
item
patent application
liquid
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TW092113357A
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TWI249783B (en
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Souvik Banerjee
Harlan Forrest Chung
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Eco Snow Systems Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
    • H01L21/02052—Wet cleaning only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
    • B08B7/0064—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by temperature changes
    • B08B7/0092—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by temperature changes by cooling
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
    • H01L21/02065—Cleaning during device manufacture during, before or after processing of insulating layers the processing being a planarization of insulating layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
    • H01L21/02074—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a planarization of conductive layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Cleaning Or Drying Semiconductors (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Cleaning In General (AREA)
  • Cleaning By Liquid Or Steam (AREA)

Abstract

The present invention provides for a new and improved method of aqueous and cryogenic enhanced (ACE) cleaning for semiconductor surfaces as well as the surfaces of metals, dielectric films particularly hydrophobic low k dielectric films, and CMP etch stop films to remove post-CMP contaminants. It is particularly useful for removing contaminants which are 0.3 μ m in size or smaller. The ACE cleaning process is applied to a surface which has undergone chemical-mechanical polishing (CMP). It includes the steps of cleaning the surface with an aqueous-based cleaning process, at least partially drying the surface, and, shortly thereafter, cleaning the surface with a CO2 cryogenic cleaning process. This process removes such contaminants from surfaces which are hydrophobic and hence difficult to clean with aqueous-based cleaning techniques alone.

Description

200405447 玖、發明說明： 【發明所屬之技術領域】 本發明係關於清潔半導體材料經化學機械研磨處理後之污染 物領域，尤其是關於使用結合水溶液及C02為主之低溫強化（ACE) 清潔技術以移除金屬及介電膜經化學機械研磨處理後的污染物。 【先前技術】 化學機械研磨（Chemical mechanical polishing ; CMP)係用於石夕 基材之裝置、光學元件及複合半導體為主之裝置製造過程中的金 屬及介電膜的整體平坦化。該CMP方法係在控制的壓力及溫度 下，及被稱為研磨漿（slurry)的化學物質存在時，在一濕研磨塾上 固定並轉動一半導體材料薄平基板；該研磨漿包括各種微粒，如 Cerria、氧化紹或矽膠，以及表面活性劑、飯刻劑及適於CMP方 法的其他添加劑。在CMP方法後，由研磨聚及其化學添加物和 反應副產物的微粒組成的污染物均留在晶圓表面，在進行1C製 造過程的任何其他步驟前，此類污染物必須移除，以避免降低裝 置的可靠性及使裝置產生缺陷；這些污染物的許多微粒均小於 0·3μιη 〇 用於移除後CMP污染物的傳統清潔技術，如結合超音波 (megasonics)及刷洗的水溶液化學清潔方法，不足以移除小尺寸的 污染物。傳統濕式技術使用液體流過晶圓表面來移除污染物，因 此，其效率受液流形成之邊界層的厚度限制；小於該邊界層的微 粒就被遮蔽不受該液流之物理拉力，因而仍留在晶圓表面；〇 ·3 μπι 以下研磨漿微粒上的凡得瓦（Van der Waals)力係離子雙層排斥 力，由濕式清潔技術中微粒與表面的zeta電位相似性產生，但不 足以充分地清潔晶圓表面。因此，使用該液流不能移除較小尺寸 的污染物。由於化學物質與氫鍵和額外產生的附著力，也使濕式 200405447 清潔技術之清潔能力進一步複雜化，並且大幅地降低了移除較小 尺寸污染物方法的效率。 超音波可與傳統濕式技術結合使用，以大幅降低邊界層的厚 度。在1MHz，邊界層的厚度可減至0.5μπι，但是，其仍不足以 有效移除由後CMP研磨漿組成的0.3μηι以下尺寸的小微粒，因 此，污染物仍留在晶圓表面。 使用低k介電膜，如雙鑲嵌積體化中的含碳之氧化物 (carbon-doped oxides)或有機膜，進一步增加了僅使用水溶液為主 化學物質的後CMP清潔的難度。這些膜層以及CMP停止層，如 碳化矽、氮化石夕及氧氮化矽疏水性很強，因此不能用水為主濕式 清潔方法清潔。 因此，需要發明一種清潔技術，其能夠從半導體晶圓或其他金 屬或介電膜表面移除0.3μιη以下微粒的後CMP污染物，特別是 當要移除微粒的表面為疏水性時。 【發明内容】 本發明提供一種新型並改良之清潔方法，其係可清潔半導體表 面及金屬、介電膜（特別是低k疏水介電膜）以及CMP蝕刻停止膜 表面，以移除後化學機械拋光（post-CMP)污染物。 本發明並提供一種方法，係用於從半導體、金屬、介電膜尤其 是低k疏水介電膜及CMP蝕刻停止膜表面以移除0.3μιη大小或 更小的後化學機械研磨（CMP)污染物。 本發明之ACE清潔方法包含一獨特之結合水與低溫清潔技 術，係從半導體、金屬或膜表面移除小污染物微粒。廣義而言， 本發明包含一清潔該表面以移除污染物微粒之方法，其步驟包 含：提供一經過化學機械研磨（CMP)的表面，使用一水溶液為主 清潔之方法清潔該表面，至少部分烘乾該表面，之後，使用C〇2 200405447 低溫清潔方法清潔該表面。使用此—方法可移除表面包括〇 3 以下小微粒及G.l_以下微粒的污染物微粒，還可移除難^1 水/合液為主清潔技術清潔的疏水性表面污染物。 ^ 【實施方式】 广一圖係顯示ACE清潔方法之一般步驟流程产咖 方法係包含下列步驟：用―水溶液m潔液清潔存有^ 巧染物的表面’視需要可使用超音波與/或洗刷，移除表面的大部 刀K再(：02低溫清潔方法S潔該表面。該水 好在低溫清潔步驟之前進行，以獲得最佳效果。 ο〜取 也可使用在業界廣為人知的標準濕式（水料）清潔方法。胸 年7月13曰核准的美國專利第5,922，136號揭露了該種方法的範 例。如-般範例，該濕式清潔方法之步驟主要包括用去離子水 洗半導體晶圓表面，使用_或多種水溶液為主，或以溶劑為主清 ，劑來清潔’之後再用去離子水清洗表面。若使用了_種以上水 溶液或溶劑為主之清潔劑’可重複該等步驟，在每次使用清潔劑 之間也可進仃清洗。該濕式（wet based)清潔方法包含使用可能含 有清潔劑的去料水(DI)。而且，濕式清潔方法可結合超音波及/ 或刷洗，以進一步移除污染物微粒。 在濕式清潔後’從晶圓表面移除大部分水，然後進行低溫清 潔⑽清潔最好緊接在濕式清潔之後，以減少微粒黏接的可能 性。該ACE清潔方法中並可併人業界廣為人知的標準低温清潔方 法1998年12 3 29日授予伊果思諾系統公司（Ec〇 Sn〇wSyst刪200405447 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to the field of cleaning pollutants after chemical mechanical polishing of semiconductor materials, and in particular, to the use of low temperature enhanced (ACE) cleaning technology based on a combination of aqueous solution and C02. Removes contaminants from metals and dielectric films after chemical mechanical polishing. [Previous technology] Chemical mechanical polishing (CMP) is used to flatten the metal and dielectric films in the manufacturing process of devices based on Shi Xi substrates, optical elements and composite semiconductors. The CMP method is to fix and rotate a thin flat substrate of a semiconductor material on a wet grinding pad under the control of pressure and temperature and the presence of a chemical substance called a slurry; the polishing slurry includes various particles, Such as Cerria, oxide or silicone, as well as surfactants, meal engraves and other additives suitable for CMP methods. After the CMP process, contaminants consisting of abrasive particles and their chemical additives and particles of reaction byproducts are left on the wafer surface. Such contaminants must be removed before any other steps in the 1C manufacturing process. Avoid reducing the reliability of the device and causing defects; many particles of these pollutants are less than 0.3 μm 〇 Traditional cleaning techniques for CMP pollutants after removal, such as chemical cleaning in combination with megasonics and scrubbing aqueous solutions Method is not sufficient to remove small size contaminants. Traditional wet technology uses liquid to flow through the wafer surface to remove contaminants. Therefore, its efficiency is limited by the thickness of the boundary layer formed by the liquid flow; particles smaller than the boundary layer are shielded from the physical force of the liquid flow. Therefore, it remains on the surface of the wafer; Van der Waals force on abrasive particles below 0.3 μm is an ion double-layer repulsion force, which is generated by the similarity of zeta potential between particles and the surface in wet cleaning technology. But it is not enough to clean the wafer surface sufficiently. Therefore, smaller sizes of contaminants cannot be removed using this stream. Due to the chemical bonding with hydrogen bonds and additional adhesion, the cleaning capability of wet 200405447 cleaning technology is further complicated, and the efficiency of the method of removing smaller-sized contaminants is greatly reduced. Ultrasound can be used in combination with traditional wet technologies to significantly reduce the thickness of the boundary layer. At 1 MHz, the thickness of the boundary layer can be reduced to 0.5 μm. However, it is still not enough to effectively remove small particles below 0.3 μm in size composed of the post-CMP slurry. Therefore, the contaminants remain on the wafer surface. The use of low-k dielectric films, such as carbon-doped oxides or organic films in dual damascene integration, further increases the difficulty of post-CMP cleaning using only aqueous solutions as the main chemical. These films and CMP stop layers, such as SiC, Nitride, and Silicon Oxide Nitride, are highly hydrophobic and cannot be cleaned with water-based wet cleaning methods. Therefore, there is a need to invent a cleaning technology that can remove post-CMP contamination of particles below 0.3 μm from the surface of semiconductor wafers or other metal or dielectric films, especially when the surface to be removed is hydrophobic. [Summary of the Invention] The present invention provides a new and improved cleaning method, which can clean the surface of semiconductors and metals, dielectric films (especially low-k hydrophobic dielectric films), and CMP etch stop film surfaces to remove chemical machinery after removal. Polishing (post-CMP) contaminants. The present invention also provides a method for removing post-chemical mechanical polishing (CMP) contamination from the surface of a semiconductor, a metal, a dielectric film, especially a low-k hydrophobic dielectric film, and a CMP etch stop film. Thing. The ACE cleaning method of the present invention includes a unique combination of water and low temperature cleaning technology to remove small pollutant particles from the surface of semiconductors, metals or membranes. Broadly speaking, the present invention includes a method of cleaning the surface to remove contaminant particles, the steps comprising: providing a chemical mechanical polishing (CMP) surface, using an aqueous solution as the main cleaning method to clean the surface, at least in part After drying the surface, the surface was cleaned using a CO 2 200405447 low temperature cleaning method. This method can be used to remove pollutant particles whose surfaces include small particles below 0.3 and particles below G.l_. It can also remove hydrophobic surface pollutants that are difficult to clean with water / hydrate-based cleaning techniques. ^ [Embodiment] The Guangyi diagram shows the general steps of the ACE cleaning method. The method of producing coffee includes the following steps: Use "aqueous solution m cleaning solution to clean the surface where ^ smart dyes are stored." Ultrasound and / or scrubbing can be used if necessary Remove most of the surface of the surface and clean the surface with (: 02 low-temperature cleaning method S. The water should be carried out before the low-temperature cleaning step to obtain the best results. Ο ~ can also be used in the industry standard wet type (Water material) cleaning method. An example of this method is disclosed in US Patent No. 5,922,136, which was approved on July 13, 2013. As an example, the steps of the wet cleaning method mainly include washing semiconductor crystals with deionized water. For round surfaces, use _ or a variety of aqueous solutions or solvents as the main cleaning agent to clean the surface, and then clean the surface with deionized water. If you use more than _ aqueous solutions or solvent-based cleaning agents, you can repeat these Steps can also be performed between each use of the cleaning agent. The wet based cleaning method includes the use of de-water (DI) which may contain a cleaning agent. Moreover, the wet cleaning method can be combined Sonic and / or scrubbing to further remove contaminant particles. After wet cleaning, 'remove most of the water from the wafer surface and then perform low temperature cleaning. Cleaning is best done immediately after wet cleaning to reduce particle stickiness. The ACE cleaning method can be combined with the standard low-temperature cleaning method widely known in the industry. It was awarded to EgoSnow Systems Co., Ltd. (Dec. 29, 1998).

Inc)的美目專利第5,853,962號即說明了該等技術的—範例。併入 ACE 、方法的錢溫清潔方法還可包含利用液體及/或蒸汽輔 助的新型低溫清潔技術。 C〇2低溫清潔技術之一範例為將於特定壓力（例如25γ時 850㈣之液態C〇2從—特別設計之噴嘴擴張，液體的快速擴張使 200405447 壓力及溫度降低，因而在C〇2氣體流内形成固態c〇2雪狀微粒； 該固態及氣態C〇2流係直接噴射到晶圓表面，移除污染物。微粒 污染物的移除，係藉由低溫微粒的動量轉換克服晶圓表面污染物 微粒的附著力而移除。因微粒上的壓力造成低溫微粒與晶圓表面 之介面上形成一液態C〇2薄層’有機污染物薄膜可溶解於此一液 態co2薄層而被移除。 ACE清潔方法可應用於半導體晶圓及晶圓表面，但是並不僅 限於矽為主材料。CMP不僅用於矽基材為主的裝置的製造，也用 於光學元件製造及複合半導體為主的裝置的製造，而此ACE清潔 方法也可應用於從經過CMP處理的金屬表面及介電膜移除污； 物。本文使用術言吾「晶圓」3戈「晶圓表面」時表示也可使用其他 材料，本發明之方法可以類似方式應用於其他材料。 ACE清潔方法併入了半導體行業已知的清潔技術。濕式或 水洛液清㈣清潔半導體晶圓表面之熟知方法，使用該方法係為 ^標準方法；但是，迄今為止，使用⑶2低溫清潔技術來清潔 一導體晶圓，從晶圓表面移除後CMp污染物，特別是移除〇 一 以下或甚至0.lum以下的污染物微粒尚不為人知；使用結合水溶 ，為主清潔方法’繼之以CQ2低溫清潔方法從晶圓表面移除後 CMP污染物微粒也還不為人知。結合水溶液為主清潔方法盘⑺ 低溫清潔方法可移除所有後⑽污染物，包括較小尺寸的微·2 濕核水溶液為㈣清潔不足以移除所有污染物，特別是較小尺 粒’也不足以移除疏水表面的污染物微粒；低溫清潔方法 =自身也不能移除所有CMP污染物。CMp中使用的添加劑包 清=的表面：性劑及舰抑制劑，這些添加劑無法使用低溫 二邮以$且右其殘留在晶圓表面’還會阻礙低溫清潔移除微 移除濕式清潔結合’是適合用於半導體行業從 私除Β曰0表面伋CMP污染物之理想清潔方法，此—發現讓人驚 200405447 喜；若與濕式清潔結合使用，低溫清潔即較單獨使用濕式清潔具 有更強移除晶圓表面上〇·3μπι以下小污染物微粒的能力，特別是 對難以清潔的疏水表面。 濕式清潔及低溫清潔方法均可分別併入各自技術熟知的步驟。在 此之前’其尚未結合用於移除晶圓表面污染物，低溫清潔尚未用 於半導體行業移除後CMP污染物。C〇2低溫清潔不依靠晶圓表面 的潤濕性，相反地，是依靠動量轉換，其甚至能移除低k疏水介 電膜上的CMP污染物，因此，此一清潔能力使低k銅整合方案 (copper-low众integrating scheme )能夠從傳統使用的技術節點擴 展至其他技術節點。 ” ACE清潔方法併入水溶液為主與低溫清潔技術，可克服單獨 使用水溶液為主清潔技術面臨的主要問題：邊界層對有效移除晶 圓表面之0·3μιτι以下甚至〇·1μΓη以下微粒的限制，及清潔疏水表 面的問題。純溫清潔方法係依靠動量轉換起侧，其巾以高速 到U圓表面的低溫微粒，藉由其衝擊力能夠克服污染物微粒的 附者力，-旦低溫微粒克服污染物微粒的附著力，^氣體流的 拉力即可完全移除表面的污染物微粒。此—清潔方法不依靠潤濕 表面□而不又表面或沈積於其上的薄膜之疏水/親水特性的限 ^彳、過私中，流經晶圓表面的[ο〗氣體也形成一邊界 :微粒層與水溶液邊界層影響不同，因為低溫清潔 :二：機制係動量轉換，而濕式清潔的係水力拉力。 co2低 >置被粒必須穿趟兮、真 時，由於作用盆上的拉^乂“以達到晶圓表®，在通過該層 度以鬆弛時間量測。鬆他時;^溫微粒的速度下降’其下降速 36。/。的時間，表亍 減度下降至其初速度的 τ=(2 P Pp Cc)/9n ιο 200405447 其中，r為低溫微粒的半徑，pp為低溫微粒的密度，Cc為 Cunningham 滑移校正因子（c_ingham _ c〇rrecU〇n ⑹⑽），η 為介質黏度。上式表示，若介質黏度高，則鬆弛時間常數低，表 示該低溫微粒在經過該邊界層時受了較大拉力，使其到達晶圓表 面時的速度及動量下降較快；上式亦表明，較大的微粒可以較高 的速度及動i到達aa圓表面，以克服晶圓表面上污染物微粒的附 著力。一計算範例顯*，要移除由凡得瓦附著於於晶圓表面的 Ο.ΙμΓΠ污染物微粒，直徑大於丨七咖的低溫微粒必須以大於ΐ4‘δ 的速度到達晶圓表面，一般的攻擊型喷嘴如Ec〇Sn〇wTM清潔工具 可，到該速度，能夠以至少14m/s的速度通過—鄭㈤厚邊界層 的最小低溫微粒為〇.2_。前述範例顯示，邊界層不是移除小尺 寸U粒的限制因素，因為移除小污染物微粒所需的低溫微粒的整 體尺寸分佈均可通過該C〇2氣體流經該晶圓表面時形成的該邊界 層0 實施例 濕式清潔方法 為在傳統濕式清潔方法中移除半導體晶圓的後CMp污染物， 先將该晶圓置於-流動水槽中用去離子水清洗—分鐘，接著向曰 圓喷麗水料為主的清_約兩分鐘，然後清潔晶圓。在前= 驟後，於流動水槽中再次用去離子水清洗該晶圓約-分鐘，然i ^晶圓旋乾機（spin dnse dryer)以約15〇()rpm的轉速乾燥約三分 此外’使用水溶液或溶劑為主的清潔劑清潔的步驟 個步射，並在各㈣之_㈣子水清洗。溶财為:業中1 遍用於清潔晶圓表面污染物的任何溶劑，包含但不限於s c n 係結合氫氧化銨、過氣化氫及水的混合物，混合比率的範圍一身 200405447 為 〇·2:1:5 至]·】ς 去離 ，，體積比為〇·5%到2%的氫氧化銨水溶液；以 稀釋的氫氟酸濃度為0.2至1.0% ;適於後CMP清潔的 藝八南f · 气彳 山 * μ | (女過氧化歲>)以及減少表面張力的表面活性劑。 湖=據待移除的污染物選擇。 乂 中’通常使用超音波及/或P VA刷子刷洗，該技術 ^ :所热知，且業界所熟知的任何方法皆可以使用。以下是清 你步驟的心說明，#作可时法之㈣，姉何已知或標準技 術也都可使用。 超音波及刷洗技術 *對於超g波清潔，可使用批次清潔（bMch deaning)或單晶圓清 /’·η方法在超音波清潔槽内使用批次清潔方法，晶圓係垂直放置 ^亥心内’超音波轉換器位於槽底；在單晶圓清潔系統中，晶圓 係j平放置，一超音波棒（wand)掃過晶圓表面。超音波轉換器或 超曰波棒的工作頻率約為8〇〇kHz到13MHz，超音波轉換器或超 音波=的振動導致黏性介質中之波衰減形成聲波，該聲波^流 動波流及形成小氣穴泡沐，三者均有較移除日日日圓表面的微粒。 刷洗使用PVA刷，這類刷子由海绵狀軟材料製成，可壓性高。 刷子^ a曰圓表面轉動，同時透過其核心導入清潔液體；刷子並不 接觸晶圓表面，而是水平懸置於晶圓表面上方，在刷子壓、推清 潔液體時透過水力拉力移動污染物微粒；因此，晶圓表面應是親 水f生的，使刷子犯％置於晶圓表面之上而又不接觸它。污染物微 粒一但被移動後仍停留懸浮在液體中，直到藉由液流移除晶圓表 面。 烘乾表面 在濕式清潔後’從晶圓表面移除大部分水，然後進行低溫清 潔。可將晶圓浸入酒精中移除大部分水，或用酒精喷灑晶圓同時 旋轉晶圓；若有需要時，可完全烘乾晶圓表面。 12 200405447 低溫清潔方法 低溫清潔最好緊接在濕式清潔之後的24小時内或更短時間内 進行’以減少微粒附著的可能性。標準低溫清潔方法在業界中廣 為人知，並可併入ACE清潔方法中。1998年12月29日授予伊 果思諾糸統公司（Eco-Snow Systems Inc)的美國專利第5,853,962 號說明了該技術的一範例。 第一圖係顯示典型清潔系統之一範例。該清潔容器12提供一 超潔淨、封閉或密封清潔區；在該清潔區内，晶圓丨係由真空固 定於一台板2。台板2與晶圓1保持於最高丨00〇C的控制溫度下； 在室溫及850psi壓力下，一氣缸内的液態c〇2首先通過一燒結同 軸過濾器4從液態氣流中過濾出非常小的微粒，使二氧化碳盡可 能純，減少氣流中的污染物；然後使該液態c〇2透過一小孔噴嘴 擴張，喷嘴直徑最好為〇 〇5,，至〇15” ；液體的快速擴張使溫度下 降，從而在以每分鐘約丨到3立方英尺的速度流動之氣態^流 中形成固態c〇2雪狀微粒；該固態及氣態c〇2流係以約3〇到2 度的角度（最好為約45度）流向晶圓表面；前述之噴嘴最 ％ 嘴嘴至晶圓視線纟…75"至G.5”的位置。在清絲程中，台= 在軌迢9上沿y軸方向前後移動，同時該清潔喷嘴的臂在執道⑺ 上沿X轴方向線性移動，這導致晶圓表面上產生_栅格形清潔圖 案，其步進大小及掃描速度均可按需要預先設定。並且清潔^的 ，度最好保持盡可能低，例如<_歡露點。低濕度可防止; 空氣在晶圓表面凝結及結冰，其可能因在污染物微粒與：圓 表面之間形成結晶橋（Crystalline bridges)而增加二者之間 力，並可藉由使贱或乾淨乾空氣流㈣低濕度。清潔 的低濕度加強了因⑵2流經財嘴及該⑽表面之摩捧生兩逢: 的靜電電荷，因此，在整個清潔過程中，清潔室内的靜^ 持令和《要，何由雙極電暈離子棒5執行。此线還呈有: 200405447 針σΑ嚅直接安裝於該c〇2喷嘴後， 的晶圓的電荷中和作用。 以增強安裝於一電接地台板上 對於微粒污染物’該移除機制主钱⑺2低溫微粒的動量轉 5服晶圓表面污染物微粒的附著力，—旦該等微粒「鬆弛」， 的拉力就可將其從晶圓表面移除。有機膜污染物的清潔 ’ 1 ’丁、精由低溫（：02對晶圓表面的衝擊壓力在有機污染物與晶圓 =面=的介面上形成—層薄co2液體，之後，該C02液體可溶 角午省有機污染物，並將之帶離晶圓表面。Inc.'s US Patent No. 5,853,962 illustrates an example of such technologies. The money-temperature cleaning method incorporated into the ACE method can also include new low-temperature cleaning techniques assisted by liquid and / or steam. One example of C02 cryogenic cleaning technology is to expand liquid C02 from a specially designed nozzle at a certain pressure (for example, 850㈣ at 25γ). The rapid expansion of the liquid reduces the pressure and temperature of 200405447. Solid solid C02 snow-like particles are formed inside; the solid and gaseous C02 flow is sprayed directly onto the wafer surface to remove pollutants. The removal of particulate pollutants is overcome by the momentum conversion of low-temperature particles Contaminant particles are removed by adhesion. The pressure on the particles causes a liquid C02 thin layer to form on the interface between the low-temperature particles and the wafer surface. The organic pollutant film can be dissolved in this liquid CO2 thin layer and removed. Except. ACE cleaning method can be applied to semiconductor wafers and wafer surfaces, but it is not limited to silicon-based materials. CMP is not only used to manufacture silicon-based devices, but also used to manufacture optical components and compound semiconductors. The ACE cleaning method can also be used to remove dirt from CMP-treated metal surfaces and dielectric films. This article uses a 3D "wafer surface" time table Other materials can also be used, and the method of the present invention can be applied to other materials in a similar manner. The ACE cleaning method incorporates cleaning techniques known in the semiconductor industry. Wet or hygroscopic cleaning methods are well known for cleaning the surface of semiconductor wafers. This method is a standard method; however, until now, a conductor wafer was cleaned using ⑶2 low-temperature cleaning technology, and the CMP contamination was removed from the wafer surface, especially the removal of less than 0.1 or even less than 0.1 lum. Contaminant particles are not well known; CMP contamination particles are not known after the removal of the surface of the wafer by the CQ2 low temperature cleaning method using a water soluble primary cleaning method. The low temperature cleaning method combined with an aqueous solution is also used. The cleaning method can remove all contaminated pollutants, including the smaller size of the micro · 2 wet nuclear aqueous solution. Plutonium cleaning is not enough to remove all pollutants, especially the smaller size is not enough to remove pollutants on hydrophobic surfaces. Particulates; low-temperature cleaning method = itself can not remove all CMP contaminants. Additives used in CMP package = surface: sex agents and ship inhibitors, these additives The agent cannot be used at low temperature, and its residue on the wafer surface 'will also prevent low-temperature cleaning, remove micro-removal, wet cleaning and bonding', which is suitable for the semiconductor industry to remove CMP contaminants from the surface Ideal cleaning method, this—it is surprising to find 200405447; if used in combination with wet cleaning, low-temperature cleaning has a stronger ability to remove small pollutant particles below 0.3 μm on the wafer surface than wet cleaning alone, Especially for difficult-to-clean hydrophobic surfaces. Wet cleaning and low-temperature cleaning methods can be incorporated into the respective well-known steps. Prior to this, it has not been combined to remove wafer surface contaminants, and low-temperature cleaning has not been used for semiconductors. After the industry removes CMP contaminants, CO2 low-temperature cleaning does not rely on the wettability of the wafer surface. Instead, it relies on momentum conversion, which can even remove CMP contaminants on low-k hydrophobic dielectric films. Therefore, This cleaning capability enables the low-k copper integration scheme to be extended from traditionally used technology nodes to other technology nodes. ”The ACE cleaning method incorporates water-based cleaning and low-temperature cleaning technology, which can overcome the main problem of using water-based cleaning technology alone: the boundary layer limits the effective removal of particles below 0 · 3μιτι and even 0 · 1μΓη particles on the wafer surface. , And the problem of cleaning hydrophobic surfaces. The pure temperature cleaning method relies on momentum to change the starting side, and its towels reach the U-shaped low-temperature particles at high speed. The impact force can overcome the attachment force of pollutant particles. Overcoming the adhesion of pollutant particles, the pulling force of the gas stream can completely remove the pollutant particles on the surface. This-cleaning method does not rely on wetting the surface, and the hydrophobic / hydrophilic properties of the surface or the film deposited on it In the limit of 彳 过 and over-private, the [ο〗 gas flowing through the wafer surface also forms a boundary: the particle layer and the aqueous solution boundary layer have different effects because of low temperature cleaning: two: the mechanism is the momentum conversion, and the wet cleaning system Hydraulic pulling force. Co2 low > The blanket must pass through. When it is true, due to the pull on the basin ^ 乂 "to reach the wafer table ®, the relaxation time is passed through the layer. Measurement. When loosening it; ^ the speed of the warm particles decreases' and its falling speed 36. /. Τ = (2 P Pp Cc) / 9n 2004 200447 where r is the radius of the low-temperature particles, pp is the density of the low-temperature particles, and Cc is the Cunningham slip correction factor (c_ingham _ c〇rrecU〇n ⑹⑽), η is the viscosity of the medium. The above formula indicates that if the viscosity of the medium is high, the relaxation time constant is low, indicating that the low-temperature particles are subjected to a large tensile force when passing through the boundary layer, causing the speed and momentum of the particles to decrease rapidly when they reach the surface of the wafer; the above formula also indicates that The larger particles can reach the aa round surface at a higher speed and speed to overcome the adhesion of pollutant particles on the wafer surface. A calculation example shows that, to remove the 0.1 μΓΠ pollutant particles attached to the wafer surface by van der Waals, low-temperature particles with a diameter greater than 丨 7 must reach the wafer surface at a speed greater than ΐ4'δ. Generally, Aggressive nozzles such as the EcoSnow ™ cleaning tool are available. At this speed, they can pass at a speed of at least 14m / s-the minimum low-temperature particles in the thick boundary layer of Zheng Cheng are 0.2_. The previous examples show that the boundary layer is not a limiting factor for removing small U particles, because the overall size distribution of the low temperature particles required to remove small pollutant particles can be formed when the CO2 gas flows across the wafer surface The boundary layer 0 embodiment of the wet cleaning method is to remove the CMP contamination of a semiconductor wafer in a conventional wet cleaning method. The wafer is first placed in a flowing water tank and washed with deionized water for one minute, and then It is about two minutes to clean the wafer, and then clean the wafer. Before = after, rinse the wafer again with deionized water in a flowing water tank for about -minutes, and then spin the dnse dryer at about 150 () rpm for about three minutes 'Use an aqueous solution or solvent-based cleaner to clean it step by step, and wash it in water. Dissolving property: Any solvent used in the industry to clean the surface of the wafer, including, but not limited to, a mixture of scn system combined with ammonium hydroxide, hydrogenated gas, and water. The mixing ratio ranges from 200405447 to 0.2. : 1: 5 to] ·] ς, with a volume ratio of 0.5% to 2% ammonium hydroxide aqueous solution; a diluted hydrofluoric acid concentration of 0.2 to 1.0%; suitable for post-CMP cleaning South f · Qiqi Mountain * μ | (Female Peroxide) & Surfactant to reduce surface tension. Lake = selected according to the pollutants to be removed.乂 Zhong ’is usually scrubbed with ultrasonic and / or P VA brushes. This technique is well known and any method well known in the industry can be used. The following is a clear explanation of your steps. # 作 可 时 法 ㈣, any known or standard technology can be used. Ultrasonic and brushing technology * For ultra-g wave cleaning, batch cleaning (bMch deaning) or single wafer cleaning / '· η method can be used in the ultrasonic cleaning tank. Batch cleaning method is used, and the wafers are placed vertically. The 'intra-cardiac' ultrasound converter is located at the bottom of the groove; in a single wafer cleaning system, the wafer system j is placed flat, and a wand is swept across the wafer surface. The operating frequency of the ultrasonic converter or ultrasonic rod is about 800kHz to 13MHz. The vibration of the ultrasonic converter or ultrasonic = causes the waves in the viscous medium to decay to form a sound wave. The sound wave flows and forms The small cavities are soaked, all of them have particles removed from the surface of the Japanese yen. For brushing, use PVA brushes. These brushes are made of soft sponge-like material and have high compressibility. The brush ^ a means that the circular surface rotates and the cleaning liquid is introduced through its core; the brush does not contact the wafer surface, but is suspended horizontally above the wafer surface. When the brush presses and pushes the cleaning liquid, pollutant particles are moved by hydraulic pull ; Therefore, the wafer surface should be hydrophilic, so that the brush% is placed on the wafer surface without touching it. Contaminant particles remain suspended in the liquid once they are moved, until the surface of the wafer is removed by the flow. Bake Surface After wet cleaning ’, most of the water is removed from the wafer surface and then cryogenically cleaned. You can immerse the wafer in alcohol to remove most of the water, or spray the wafer with alcohol while rotating the wafer; if necessary, you can completely dry the wafer surface. 12 200405447 Low-temperature cleaning method Low-temperature cleaning is best performed within 24 hours or less immediately after wet cleaning to reduce the possibility of particle attachment. Standard cryogenic cleaning methods are well known in the industry and can be incorporated into ACE cleaning methods. US Patent No. 5,853,962, issued to Eco-Snow Systems Inc on December 29, 1998, illustrates an example of this technology. The first figure shows an example of a typical cleaning system. The cleaning container 12 provides an ultra-clean, closed or sealed cleaning area; in the cleaning area, the wafer is fixed on a platen 2 by vacuum. The platen 2 and the wafer 1 are maintained at a controlled temperature of a maximum of 00 ° C. At room temperature and a pressure of 850 psi, the liquid co 2 in a cylinder is first filtered out of the liquid gas stream through a sintered coaxial filter 4 Small particles make carbon dioxide as pure as possible to reduce the pollutants in the air stream; then the liquid CO2 is expanded through a small hole nozzle, the diameter of the nozzle is preferably 0.05, to 0.15 "; the rapid expansion of the liquid The temperature is decreased to form solid snow particles in the gaseous stream flowing at a speed of about 3 to 3 cubic feet per minute; the solid and gaseous CO2 flow is at an angle of about 30 to 2 degrees (Preferably about 45 degrees) to the surface of the wafer; the aforementioned nozzles are most% of the nozzles to the position of the wafer sight 75 ... 75 " to G.5 ". During the cleaning process, the stage = moves forward and backward along the y-axis direction on the rail 迢 9, and at the same time, the arm of the cleaning nozzle moves linearly along the X-axis direction on the guide ⑺, which results in a grid-shaped cleaning on the wafer surface. The pattern, its step size and scanning speed can be preset as required. And clean the degree of ^, it is best to keep as low as possible, such as < _ Huanlu point. Low humidity can prevent; air condenses and freezes on the surface of the wafer, which may increase the force between the pollutant particles and the round surface by forming crystalline bridges, and can make the Clean and dry air with low humidity. The clean low humidity strengthens the electrostatic charge caused by ⑵2 flowing through the mouth and the surface of the ⑽⑽. Therefore, during the entire cleaning process, the static order in the clean room and the "how, why bipolar" Corona Ion Bar 5 performs. This line also shows: 200405447 The charge neutralization of the wafer after the pin σΑ 嚅 is directly mounted on the CO2 nozzle. In order to enhance the adhesion of particulate pollutants installed on an electrical ground plate, the main mechanism of the removal mechanism, the momentum of low-temperature particulates, and the adhesion of contaminant particles on the wafer surface, once the particles are "relaxed," the pulling force It can be removed from the wafer surface. Organic film contaminants are cleaned by low temperature (: 02 impact pressure on wafer surface is formed on the interface between organic pollutants and wafer = surface =-a thin layer of co2 liquid, after which the C02 liquid can be Dissolve the organic pollutants and remove them from the wafer surface.

在液體輔助低溫方法中，係使用具有高蒸汽壓力的一液體在低 溫清潔中或此步驟之前噴灑於晶圓表面，前述之液體包含異丙 醉、乙醇'丙酮、體積比為50%的乙醇_丙酮混合液、甲醇、子酸 甲酯、碘甲烷及漠乙烧，2002彳4月5曰提出的美國專利第 60/36^，85〕<中sf案更詳細地說明了該種方法，並經引用併入本 文。前述液體可於晶圓表面魏成—薄層，用於移除微粒，或於 晶圓表面錢成較厚_，在被低溫魏減時產生額外的拉力 移除該等微粒。前歧體可❹任何鮮裝置賴，㈣ 臺上用於向晶圓表面喷灑去離子水的聚四氟乙㈣TeflQn)喷霧嘴 觜此外，如2002年4月5日申請的美國專利第6〇/369,852號 :請案（經引用併入本文）說明的蒸汽輔助低溫清潔一樣，液體的 蒸汽可能凝結於晶®表面’最好賴液體覆蓋該晶圓十分鐘，·可 喷灑一層液體覆蓋或可反覆喷灑多層液體覆蓋晶圓以確保晶圓 保持濕潤；在前述覆蓋時間後’即㈣叫低溫噴灑（使用前述標 準技術）。藉由減少介入媒介組成的Hammaker常數，該液體減少 了晶圓表面微粒污染物的附著力，因此，c〇2低溫微粒可較容易 地移動晶圓表面的污染物。 14 200405447 【圖式簡單說明】 第一圖係顯示先前技術及本發明ACE技術之一般方法的流程 圖。 第二圖係顯示在co2低溫清潔方法中使用的一般裝置流程圖。 【主要元件符號對照說明】 1 晶圓 2 -- 台板 3— 喷嘴 4 -- 燒結同軸過濾器 5 - 雙極電暈離子棒 6 -- 超高效率渡網（Ulpa filter) 9 - 軌道 10 — 執道 12 -- 清洗容為In the liquid-assisted low-temperature method, a liquid with high vapor pressure is sprayed on the wafer surface during low-temperature cleaning or before this step. The aforementioned liquid contains isopropyl alcohol, ethanol 'acetone, and 50% ethanol by volume. Acetone mixture, methanol, methyl iodate, methyl iodide, and molybdenum, U.S. Patent No. 60/36 ^ 85, filed on April 5, 2002, sf case in more detail, And incorporated herein by reference. The aforementioned liquid can be formed into a thin layer on the surface of the wafer to remove particles, or a thick layer can be formed on the surface of the wafer. When the temperature is reduced by low temperature, an additional tensile force is generated to remove the particles. The front manifold can be used with any fresh device, such as polytetrafluoroethylene (TeflQn) spray nozzles for spraying deionized water on the wafer surface. In addition, such as US Patent No. 6 applied on April 5, 2002 〇 / 369,852: Like the steam-assisted cryogenic cleaning described in the application (incorporated by reference), the liquid vapor may condense on the surface of the crystal. 'It is best to cover the wafer for ten minutes with a liquid. Or multiple layers of liquid can be sprayed to cover the wafer repeatedly to ensure that the wafer remains moist; after the aforementioned coverage time, 'low temperature spraying' is used (using the aforementioned standard technology). By reducing the Hammaker constant of the intervening medium, the liquid reduces the adhesion of particulate contaminants on the wafer surface. Therefore, the CO2 low temperature particulates can more easily move the contaminants on the wafer surface. 14 200405447 [Brief description of the drawings] The first diagram is a flowchart showing a general method of the prior art and the ACE technology of the present invention. The second diagram is a flow chart of a general device used in a co2 low temperature cleaning method. [Comparison of main component symbols] 1 Wafer 2-Platen 3-Nozzle 4-Sintered coaxial filter 5-Bipolar corona ion rod 6-Ultra-high efficiency crossing grid (Ulpa filter) 9-Orbit 10- Docket 12-Washing Capacity

Claims (1)

200405447 拾、申請專利範圍： 種用於k半導體晶圓、金屬或薄膜表面移除化學機械研磨(CMp)污染 物的方法，係包含下列步驟： a) 用去離子水及/或一水溶液或溶劑為主清潔劑濕式清潔該表面； b) 至少部分烘乾該表面；及 c) 用C02低溫清潔該表面。 •如申請專利範圍第1項所述之方法，其中前述表面係藉由移除大部分水 而部分烘乾。 3 如申凊專利範圍第1項所述之方法，其中前述表面實質上是乾的。 4·如申請專利範圍第1項所述之方法，其中前述步驟(a)係包含下列步驟： 用去離子水清洗該表面，用一水溶液或溶劑為主的清潔劑清潔該表面， 及再用去離子水清洗該表面。 5·如申請專利範圍第4項所述之方法，其中前述步驟(a)進一步包含重複下 列步驟：用一或多種水溶液或溶劑為主清的潔劑清潔該表面，及用去離 子水清洗該表面。 6·如申凊專利範圍第1項所述之方法，其中前述步驟(a)包含用去離子水及 /或一水溶液或溶劑為主的清潔劑研磨該表面。 •如申請專利範圍第1項所述之方法，其中前述步驟(C)包含下列步驟：透 過一噴嘴用壓力擴張co2液體使其在一 co2氣體流中形成固態co2， 並將該C〇2氣體流導向該表面以移除污染物。 7 200405447 8·如申凊專利範圍第2項所述之方法，其中前述部分烘乾該表面係藉由將 该表面浸入一酒精並將該表面緩慢移出該酒精而移除大部分的水，或藉 由向該表面噴灑酒精時旋轉該表面而移除大部分的水。 9·如申請專利範圍第7項所述之方法，其中前述步驟(c)係在使用一具有高 条Α壓力的液體喷灑該表面的步驟之前，並在一段所需時間内讓該液體 留在該表面上。 1〇·如申凊專利範圍第7項所述之方法，其中前述步驟(c)係在使用-液體蒸 汽覆蓋該表面以減少該微粒表面附著力的步驟之前，並在一段所需時間 φ 内讓該蒸汽留在該表面。 種用於從半^r體晶圓、金屬或薄膜表面移除由後化學機械研磨處理所 產生的尺寸為0·3_或更小之污染物的方法，包含下列步驟： a) 濕式清潔該表面，係包含用去離子水清潔該表面，在去離子水 中用水/合液為主的清潔劑清潔該表面，或用去離子水及/或水溶液 清潔劑研磨該表面； b) 稭由移除大部分水至少部分烘乾該表面；及 # c) 用C〇2低溫清潔該表面，係包含下列步驟：透過一喷嘴用壓力 擴張C〇2液體以在一氣態⑺2流中形成固態OV並將該c〇2流導 向該表面以移除污染物。 12·如申請專利範圍第11項所述之方法，其中前述表面全部是乾的。 · 17 200405447 13. 如申請專利範圍第11項所述之方法，其中前述步驟(a)係包含下列步 驟：用去離子水清洗該表面，用一水溶液為主的清潔劑清潔該表面，及 再用去離子水清洗該表面。 14. 如申請專利範圍第11項所述之方法，其中前述步驟(c)係在使用一具有 高蒸汽壓力的液體喷灑該表面的步驟之前，並在一段所需時間内讓該液 體留在該表面。 15. 如申請專利範圍第11項所述之方法，其中前述步驟(c)係在使用一具有 高蒸汽壓力之液體蒸汽覆蓋該表面以減少該微粒表面附著力的步驟之 前，並在一段所需時間内讓該蒸汽留在該表面。200405447 Scope of patent application: A method for removing chemical mechanical polishing (CMp) contaminants on the surface of a semiconductor wafer, metal or film, including the following steps: a) using deionized water and / or an aqueous solution or solvent Wet clean the surface as a primary cleaner; b) dry the surface at least partially; and c) clean the surface with CO2 at low temperature. • The method as described in item 1 of the scope of patent application, wherein the aforementioned surface is partially dried by removing most of the water. 3 The method as described in claim 1 of the patent scope, wherein the aforementioned surface is substantially dry. 4. The method according to item 1 of the scope of patent application, wherein the aforementioned step (a) comprises the following steps: washing the surface with deionized water, cleaning the surface with an aqueous solution or solvent-based cleaner, and reusing The surface was washed with deionized water. 5. The method according to item 4 of the scope of patent application, wherein the foregoing step (a) further comprises repeating the following steps: cleaning the surface with one or more aqueous solution or solvent as the main cleaning agent, and cleaning the surface with deionized water surface. 6. The method according to item 1 of the scope of the patent application, wherein the aforementioned step (a) comprises grinding the surface with deionized water and / or an aqueous solution or solvent-based cleaner. The method according to item 1 of the scope of patent application, wherein the aforementioned step (C) comprises the following steps: expanding the co2 liquid through a nozzle with pressure to form a solid co2 in a co2 gas stream, and forming the CO2 gas Flow is directed to the surface to remove contaminants. 7 200405447 8. The method as described in item 2 of the scope of patent application, wherein the aforementioned partial drying of the surface is to remove most of the water by immersing the surface in an alcohol and slowly removing the surface from the alcohol, or Most of the water is removed by rotating the surface while spraying alcohol on the surface. 9. The method according to item 7 of the scope of patent application, wherein the aforementioned step (c) is before the step of spraying the surface with a liquid having a high A pressure, and the liquid is allowed to remain for a required period of time. On that surface. 10. The method as described in item 7 of the patent scope of claim 1, wherein the aforementioned step (c) is before the step of covering the surface with -liquid vapor to reduce the surface adhesion of the particles, and within a required time φ Let the steam stay on the surface. A method for removing contaminants with a size of 0.3 or less produced by a post-chemical mechanical polishing process from a semi-r wafer, metal or thin film surface, including the following steps: a) wet cleaning The surface includes cleaning the surface with deionized water, cleaning the surface with a detergent based on water / aqueous solution in deionized water, or grinding the surface with deionized water and / or an aqueous detergent; b) removing the straw Dry the surface at least partly with the exception of most water; and # c) clean the surface with CO 2 at low temperature, comprising the steps of expanding the CO 2 liquid with a pressure through a nozzle to form a solid OV in a gaseous stream, and The co2 stream was directed to the surface to remove contaminants. 12. The method according to item 11 of the scope of patent application, wherein the aforementioned surfaces are all dry. · 17 200405447 13. The method according to item 11 of the scope of patent application, wherein the aforementioned step (a) comprises the steps of: washing the surface with deionized water, cleaning the surface with an aqueous solution-based cleaner, and then The surface was washed with deionized water. 14. The method according to item 11 of the scope of the patent application, wherein the foregoing step (c) is preceded by a step of spraying the surface with a liquid having a high vapor pressure, and the liquid is left in the liquid for a required period of time. The surface. 15. The method according to item 11 of the scope of patent application, wherein the aforementioned step (c) is preceded by a step of covering the surface with a liquid vapor having a high vapor pressure to reduce the surface adhesion of the particles, and a period of time required. The steam is left on the surface for a time. 1818
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