4026¾¾ b7_ 五、發明説明（1 ) 發明範疇 本發明係關於積體電路前、後段製程之領域，更特定言 之，本發明係關於晶圓經化學機械研磨（Chemical Mechanical Polishing，CMP)後或成.長閘極氧化層前、用以去除其表面殘 餘污染物之有效清潔溶液。 發明背景 在積體電路之後段製程--多重導體内連線（Multilevel Interconnects)之製造中，介電層沉積時往往隨著晶圓表面金 屬層之高低起伏而成形，此時產生之不平坦現象會導致晶 圓於後續微影製程中衍生聚焦景深（DOF)之問題，進而影響 微影影像傳遞之精確度與解析度。欲改善積體電路後段製 程中因介電層於晶圓表面不均勻沉積所造成之良率降低問 題，必須仰賴優良的平坦化製程（Planarization process)。 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 業界已知之平坦化技術，包含旋塗式玻璃製程（Spin on Glass , SOG )及化學機械研磨製程（Chemical Mechanical Polishing， CMP)。旋塗式玻璃製'程相當簡易，且對介電層高低起伏外 觀之填溝能力相當良好，然旋塗式玻璃製程僅能達成局部 平坦化，且易產生不欲之微粒、龜裂或剝離之現象。因 此，化學機械研磨成爲目前VLSI及ULSI製程中爲達成全面 平坦化之主流技術。 化學機械研磨之原·理在於將晶圓於適當化學助劑之存在 下進行機械式研磨。進行化學機械研磨之裝置通常包含一 研磨台及一握柄，該握柄係以固定晶片之背面，晶片之正 面則壓於铺有一層研磨墊之研磨台上，此時，輔助化學機 -4 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 402635 五、發明説明（2 研磨 < 化學試劑係沿 化學撫Mm. 圪g持績供應至研厝墊上，以利 化予機械研磨之進行。. 及日好、人 匕子碱劑產生之化學反應，以 及阳片於研磨台上所承受之 λ 械式研磨，便可將晶片表面 出心沈積層逐漸去除。 化學機械研磨中使用之化學試劑一般通稱 =，進行介電層的化學機械研磨使用之研磨泥聚通常 /矽土加上鹼性氫氧化鉀或氨水混合而成，進行鎢全 =學機械研磨使用之研磨泥㈣通常由分散狀銘土加 上稍故鐵混合而成。 然而，化學機械研磨是—项相當貌辩之製程，晶圓進行 ❹機械研磨之後’表面上往往殘留許多不易去除之微粒 π木物’此等微粒淳染物除來自於研磨泥浆外，亦來自該 ”工研磨θθ圓本身。此外，晶圓表面殘留之金屬冷染物亦爲 化學機械研磨之另—項缺點。 經濟部中央標準局員工消費合作社印製 爲去除化學機械研磨後產生之污染物，業界於化學機械 研磨後通常會進行-清洗步驟。傳統上係利用刷洗、噴洗 及超音波振盪等技術，並配合氨水溶液以達到清潔晶圓表 面殘餘π染物ι效果。然而，部份晶片（例如複晶矽或矽 表面）經傳統化學機械研磨後，其表面薄膜會由親水性轉 爲疏水性，此等表面薄膜性質之改變會導致氨水溶液之去 污能力降低，而造成製品良率之下降。 關於化學機械研磨後於晶圓表面所產生污染物之去除， 已見於許多先前技藝中。例如，Ν Miyashita等人於19%年在 CMP-MIC會譎中所發表之論文_「適用於溝道分離方法之新 一 5 — 本紙張尺度適用中國國冬標準（CNS ) A4規格（210 X 297公楚：） Α7 Β7 五、發明説明（3 ) 穎後-化學機械研磨清潔方法（A new post CMP cleaning method for trencli isolation process)」，此文獻中係利用界面活性劑進行化 學機械研磨，使得複晶矽薄膜表面於化學機械研磨後仍爲 親水性，並使廢料於研磨之同時排除，因此將化學機械研 磨製轾中產生之污染物儘量減至最低，而使化學機械研磨 後之清潔可有效進行。 N. Takenaka等人於 1995 年發表於]Material Research Society期刊 (Mat. Res. Soc. Symp. Proc. Vol 386)中之「使用冰洗猶器清洗之後 -化學機械研磨清潔方法（Post CMP cleaning using ice scrubber cleaning)」，此文獻中主要利用冰粒子以接近音速之高速衝 擊矽晶圓之表面，並利用去離子水消除殘留自研磨泥漿之 污染物。4026¾¾ b7_ V. Description of the invention (1) The scope of the invention The invention relates to the field of front-end and back-end processes of integrated circuits. More specifically, the present invention relates to the formation of wafers after chemical mechanical polishing (CMP). An effective cleaning solution to remove residual contaminants on the surface before long gate oxide layer. BACKGROUND OF THE INVENTION In the fabrication of multilevel interconnects in the back-end process of integrated circuits, the dielectric layer is often formed during the deposition of the metal layer on the surface of the wafer during the deposition process. It will cause the problem of DOF in the subsequent lithography process, which will affect the accuracy and resolution of the lithography image transmission. To improve the yield reduction caused by the uneven deposition of the dielectric layer on the wafer surface in the back-end process of the integrated circuit, an excellent planarization process must be relied on. Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Flattening technologies known in the industry, including spin on glass (SOG) and chemical mechanical polishing processes (Chemical Mechanical Polishing Process) Mechanical Polishing (CMP). The spin-on glass manufacturing process is very simple, and the trench filling ability of the undulating appearance of the dielectric layer is quite good. However, the spin-on glass manufacturing process can only achieve local flattening, and is prone to produce unwanted particles, cracks or peeling. Phenomenon. Therefore, chemical mechanical polishing has become the mainstream technology to achieve comprehensive flattening in the VLSI and ULSI processes. The principle of CMP is to mechanically polish wafers in the presence of appropriate chemical additives. The device for chemical mechanical polishing usually includes a polishing table and a handle. The handle is used to fix the back of the wafer, and the front of the wafer is pressed on the polishing table with a layer of polishing pad. At this time, the auxiliary chemical machine-4 -This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 X 297 mm) 402635 V. Description of invention (2 Grinding < Chemical reagents are supplied along with chemical Mm. 圪 g to the research pad to facilitate Chemical mechanical polishing is carried out .. As well as the chemical reaction of Nichio, human dagger alkaline agent, and lambda mechanical grinding that the positive film is subjected to on the polishing table, the core layer on the surface of the wafer can be gradually removed. The chemical reagents used in mechanical polishing are generally referred to as =, the grinding mud used for chemical mechanical polishing of the dielectric layer is usually mixed with silica plus alkaline potassium hydroxide or ammonia, and the whole tungsten is used for mechanical polishing Grinding mud is usually made by dispersing intaglio soil with a little iron. However, chemical mechanical polishing is a fairly obvious process. After wafers are subjected to mechanical polishing, a lot of residues are often left on the surface. Many difficult-to-remove particles π wood objects. In addition to grinding particles, these fine particles also come from the "grinding θθ circle itself. In addition, the metal cold-stained materials remaining on the wafer surface are also chemical mechanical polishing. Disadvantages. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs to remove pollutants generated after chemical mechanical grinding, the industry usually performs a cleaning step after chemical mechanical grinding. Traditionally, brushing, spray washing and ultrasonic vibration are used And combined with ammonia solution to achieve the effect of cleaning the residual π dye on the wafer surface. However, after some wafers (such as polycrystalline silicon or silicon surface) are polished by traditional chemical mechanical, the surface film will change from hydrophilic to hydrophobic, These changes in the properties of the surface film will reduce the decontamination ability of the ammonia solution and reduce the yield of the product. The removal of contaminants generated on the wafer surface after chemical mechanical polishing has been seen in many previous techniques. For example, A paper published by Ν Miyashita et al. In the CMP-MIC conference in 19% _ "A New 5 for Channel Separation Methods — This paper size applies the Chinese National Winter Standard (CNS) A4 specification (210 X 297 Gongchu :) Α7 Β7 V. Description of the invention (3) A new post CMP cleaning method for trencli isolation process "In this document, chemical mechanical polishing is performed using surfactants, so that the surface of the polycrystalline silicon film is still hydrophilic after chemical mechanical polishing, and the waste is eliminated at the same time as polishing. Therefore, Contaminants are minimized so that cleaning after CMP can be performed efficiently. Published by N. Takenaka et al. In 1995 in the Journal of Material Research Society (Mat. Res. Soc. Symp. Proc. Vol 386) "Post CMP cleaning using ice scrubber cleaning", in this document, ice particles are mainly used to impact the surface of a silicon wafer at a speed close to the speed of sound, and are removed by deionized water. Contaminants remaining from the grinding mud.
Allison Chang等人於1996年2月在CMP-MIC會議中發表「以 去離子水進行之後-化學機械研磨微粒之移除〇Post-CMP particle removal with .DI water)」一文，其中係利用去離子水將進. 行化學機械研磨後之晶圓表面予以清潔。 經濟部中央標準局員工消費合作社印製 (讀先聞讀背面之注意事項异填寫本頁) _ _*Allison Chang et al. Published the article "Post-CMP particle removal with .DI water) at the CMP-MIC conference in February 1996, in which deionization was used. Water will clean the wafer surface after chemical mechanical polishing. Printed by the Consumers' Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs
Sudipto R. Roy 等人於 1995年 1 月在 Electrochem. Soc.期刊第 142 本中發表「内層介電層之後-化學機械平面化清潔方法（Post chemical-mechanical planarization cleanup process for interlayer dielectric films)」一文，此文獻中敎示利用稀釋氣水及去離子水對150 mm之濕晶圓進行清潔。 T. L. Myers 等人於 1995年 10 月在 Solid State Technology 期刊中發 表「後-鎢化學機械硏磨清潔：主題及解決方案（Post-tungsten CMP cleaning: issues, and solution)」一文，此文獻中利用旋轉-洗 -6 - 本紙張尺度適用中國國家標準（CNS ) A4規格（2Π3Χ297公釐) 經 中 標 準 員 工 消 費 合 社 印 製 A7 B7 兩液體間或液體與固體間表面張力之化學成份，例士 402635 •~~~______ 五、發明説日月（4 滌乾燥法以進行鎢金屬之後_化學機械研磨清潔方法。 上述先illi技蟄均無法有效改良晶圓經化學機械研磨後之 表面性質以提供良好之清潔效果，因此，業界仍積極尋求 —種可有效清除晶圓表面經化學機械研磨後殘留之污染物 (例如微粒與金屬污染物等），卻毋需如傳統RCA步驟使用 如鹽酸及硫酸等強酸化學品，同時更具經濟效益之後-化 學機械研磨清潔溶液。 . 潜1明簡述 本發明係關於-種清除晶圓經化學機械硏磨後殘餘污染 物之+液，其包含氨水溶液及界面活性劑。本發明之溶液 其進一步包含一種螯合劑。 碧：明説明 、本發明提供一種用於化學機械研磨（CMP)後之新穎清潔溶 夜，該溶液係包含氨水溶液、界面活性劑及選擇性使用之 螯合劑，其可將晶圓經化學機械研磨後其表面薄膜之疏水 性轉變爲親水性，而有效去除晶圓之殘餘污染物。 本發明之技術改良係在傳統進行化學機械研磨使用之氨 水溶液中、添加界面活性劑及視情況選用螯合劑，不受限 =理淪，咸信界面活性劑之添加可使該經化學機械研磨之 晶圓表面薄膜之疏水性改變爲親水性，故使傳統氨水溶液 對微粒之去除力大爲提昇，螯合劑之使用則可減少晶 之金屬離子污染物。 ° 本發明中所稱之「界面活性劑」，係指業界已知 ft A·: .κ, _ ^ . 降低 —7 該 本纸張尺度適用規格（210x1^^· 一請先閲讀背面4¾意事項存填寫本Sudipto R. Roy et al. Published the article "Post chemical-mechanical planarization cleanup process for interlayer dielectric films" in the Electrochem. Soc. Journal 142 in January 1995 In this document, it is shown that a 150 mm wet wafer is cleaned with dilute water and deionized water. TL Myers et al. Published a post-tungsten CMP cleaning: issues, and solution in the Solid State Technology journal in October 1995. -洗 -6-This paper size is in accordance with Chinese National Standard (CNS) A4 (2Π3 × 297 mm). Printed by China Standards Consumer Co., Ltd. A7 B7. Chemical composition of surface tension between two liquids or between liquids and solids. Case 402635 • ~~~ ______ V. Inventing the Sun and Moon (4 Drying method to perform tungsten metal after _ chemical mechanical polishing cleaning method. The above-mentioned illi technology cannot effectively improve the surface properties of the wafer after chemical mechanical polishing to provide good Cleaning effect, therefore, the industry is still actively looking for a kind of pollutants (such as particulates and metal contaminants) that can effectively remove the chemical mechanical polishing of the wafer surface, but it is not necessary to use traditional RCA steps such as hydrochloric acid and sulfuric acid. After strong acid chemicals, and more economical at the same time-chemical-mechanical grinding cleaning solution. After the wafer is subjected to chemical mechanical honing, the + solution of residual pollutants includes an ammonia solution and a surfactant. The solution of the present invention further includes a chelating agent. Bi: It is stated that the present invention provides a chemical mechanical polishing ( The new clean solution after CMP), this solution contains ammonia solution, surfactant and selective chelating agent, which can change the hydrophobicity of the surface film of the wafer to hydrophilic after chemical mechanical polishing, and it is effective Removal of residual contaminants on the wafer. The technical improvement of the present invention is to add a surfactant and a chelating agent as appropriate in the ammonia aqueous solution traditionally used for chemical mechanical polishing. Addition can change the hydrophobicity of the wafer surface film after chemical mechanical polishing to hydrophilicity, so that the traditional ammonia solution can greatly improve the removal of particles, and the use of chelating agents can reduce the crystalline metal ion contamination. ° The term “surfactant” as used in the present invention refers to the ft A ·: .κ, _ ^. Known in the industry. Reduction—7 This paper is applicable to the standard (210x 1 ^^ · Please read the back of the first 4 ¾ Please fill in this matter
經濟部中央標準局員工消費合作社印製 獅635 A7 _______B7 五、發明説明（5 ) ' ' 界面/¾'性劑可爲四取代基氫氧化錄，其上之取代基較佳係 直鐘或具支鍵之CrC2。纟兕基。較佳地，該界面活性劑係選自 由氫氧化四甲基铵’氫氧化四乙基鼓，氫氧化四丙基録， 氫氧化四丁基铵’氫氧化四戊基餘，氫氧化四己基銨，氫 氧化四’庚基銨及氫氧化四辛基簽所組成之群。 氣水丨谷液與界面活性劑之用量比例係自1 : 1至5〇 〇〇〇 : 1，較佳係自5 : 1至10,000 : 1 ,更佳係自10 :丨至5,000 : J， 最佳係自10 : 1至1，〇〇〇 : 1。 當添加適量的、如上所述之四取代基氫氧化銨界面活性 劑至業界一般用以清洗經化學機械研磨之晶圓表面薄膜之 氨水溶液中時，由於此化合物具有含四個烷基之銨陽離子 以及每基離子’因此可改良晶圓表面薄膜之性質，使得氨 水溶液對薄膜之溼潤性變得較好，因此得到較佳之微粒清 潔效果。 本發明之「螯合劑」係已知由金屬離子與配位清基配位 鍵結而成之化合物，適用於本發明之螯合劑係例如：乙二 胺基四醋酸（EDTA)、三醋酸銨或乙二醇_二_(巨_胺基_乙美 醚）-N，N-四醋酸，較佳係乙二胺基四醋酸。螯合劑之用量 範圍係自1 PPm至10,000 ppm，較佳係自5 Ppm至5,〇〇〇 ppm，最 佳係自 10 ppm 至 1000 ppm。 不受限於理論’咸信螯合劑之使用可減少晶圓上諸如 鈣、鐵、銅、鋅及鉀等金屬離子污染物之含量，而提昇氛 水溶液之清潔效果。 本發明之優點在於，當清洗經化學機械研磨之晶圓表面 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閣讀背面之注意事項再填寫本頁) n I -11 nn —n·^— nn--5Jn^— < 經濟部中央標準局員工消費合作社印製 40SG85 ^ —----- 五、發明説明（6 ) ~~~~〜 淳膜時，毋需改變原先之清洗步驟，僅需在業界通常用以 清洗經化學機械研磨之晶圓表面薄膜的氨水溶液中添加界 面活性劑及選擇性使用螯合劑，即可改良晶片表面薄膜之 4水性，增進氨水溶液之清潔功效，而呈現較佳之微粒及 金屬離子去除效果。此外，本發明之清潔溶液不會使經化 學機械研磨之材料（例如二氧化矽或複晶矽）形成缺陷，因 此可提高產品之良率。 . 本發明t新穎清潔溶液可適用於晶圓後段製程中有關化 學機械研磨後殘餘污染物之去除，尤其係可應用於複晶矽 及二氧化矽薄膜經化學機械研磨後之清潔。在晶圓材料之 生產製％中，當成長一全之晶棒經由切割及研磨後，亦可 以本發明t新穎清潔溶液進行清潔，其效果遠比傳統清潔 /合液爲佳。本發明之新穎清潔溶液另可應用於半導體製程 中成長閘極氧化層前之清潔步驟，以及其它關於微粒、有 機物、金屬離子的去除應用中，清潔效果皆相當良好。 星式簡單説明 圖1係晶圓（例如複晶矽或矽薄膜）經化學機械研磨後之 表面薄膜性質。 々圖2係例示本發明之新穎清潔溶液對該經化學機械研磨 後晶圓表面薄膜性質之影響。 圖〇顯不以四種不同溶液清潔經化學機械研磨後晶圓表 面薄膜之殘留粒子數。 圖4顯示以五種不同清潔溶液清除經化學機械研磨後晶 圓衣·面薄膜不同金屬污染物之比較結果。 —9 - 本纸張尺^^财_家―（⑶&视格（2⑴χ 2^^ --;-- i.·-------Q衣！ Γ靖先聞讀背面之注t·事項#填寫本頁j -訂.Lion 635 A7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs _______ B7 V. Description of the invention (5) The 'Interface / ¾' sex agent can be a tetra-substituted hydroxide, and the substituents on it are preferably straight or Branched CrC2.纟 兕 基. Preferably, the surfactant is selected from the group consisting of tetramethylammonium hydroxide, tetraethyl hydroxide, tetrapropyl hydroxide, tetrabutylammonium hydroxide, tetrapentyl hydroxide, and tetrahexyl hydroxide. A group of ammonium, tetra'heptyl ammonium hydroxide and tetraoctyl hydroxide. The ratio of gas water and valley liquid to surfactant is from 1: 1 to 5000: 1, preferably from 5: 1 to 10,000: 1, more preferably from 10: 丨 to 5,000: J, The optimal range is from 10: 1 to 1,000: 1. When an appropriate amount of the tetra-substituted ammonium hydroxide surfactant as described above is added to the ammonia solution commonly used in the industry to clean chemically polished wafer surface films, the compound has ammonium containing four alkyl groups. The cations and ions per radical can therefore improve the properties of the film on the surface of the wafer, so that the wettability of the ammonia solution to the film becomes better, so that a better particle cleaning effect is obtained. The "chelating agent" of the present invention is a compound known to be formed by a metal ion and a coordination complex being bonded, and suitable chelating agents of the present invention are, for example, ethylenediaminetetraacetic acid (EDTA), ammonium triacetate Or ethylene glycol_di_ (macro_amino_ethylene glycol ether) -N, N-tetraacetic acid, preferably ethylenediamine tetraacetic acid. The amount of the chelating agent ranges from 1 PPm to 10,000 ppm, preferably from 5 Ppm to 5,000 ppm, and most preferably from 10 ppm to 1000 ppm. Without being limited to the theory, the use of salty chelating agents can reduce the content of metal ion contaminants such as calcium, iron, copper, zinc, and potassium on the wafer, and improve the cleaning effect of the aqueous atmosphere. The advantage of the present invention is that when cleaning the surface of the wafer after chemical mechanical polishing, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the precautions on the back before filling this page) n I- 11 nn —n · ^ — nn--5Jn ^ — < Printed by the Consumer Cooperatives of the Central Standards Bureau, Ministry of Economic Affairs, printed 40SG85 ^ ------- V. Description of the invention (6) ~~~~~ The original cleaning steps need to be changed. Only by adding surfactant and selective chelating agent to the ammonia solution commonly used in the industry to clean chemically polished wafer surface films, the water surface of the wafer surface films can be improved and improved. The cleaning effect of ammonia solution shows better removal effect of particles and metal ions. In addition, the cleaning solution of the present invention does not cause defects in chemically mechanically ground materials (such as silicon dioxide or polycrystalline silicon), thereby improving the yield of the product. The novel cleaning solution of the present invention can be applied to the removal of residual contaminants after chemical mechanical polishing in the back-end wafer process, and is particularly applicable to the cleaning of polycrystalline silicon and silicon dioxide films after chemical mechanical polishing. In the production system of wafer materials, after a full-grown crystal rod is cut and ground, it can also be cleaned with the novel cleaning solution of the present invention, and the effect is far better than the traditional cleaning / mixing solution. The novel cleaning solution of the present invention can also be applied to the cleaning step before the gate oxide layer is grown in the semiconductor process, and in other applications related to the removal of particles, organic objects, and metal ions, the cleaning effect is quite good. Star-shaped brief description Figure 1 Surface film properties of wafers (such as polycrystalline silicon or silicon thin film) after chemical mechanical polishing. Figure 2 illustrates the effect of the novel cleaning solution of the present invention on the properties of the film on the wafer surface after chemical mechanical polishing. Figure 0 shows the number of particles remaining on the wafer surface film after chemical mechanical polishing was not cleaned with four different solutions. Figure 4 shows the comparison results of five different cleaning solutions to remove different metal contaminants from the crystal round coat and facial film after chemical mechanical polishing. —9-This paper ruler ^^ 财 _ 家 ― （⑶ & Sight (2⑴χ 2 ^^-;-i. · ------- Q clothes! Γ Jingxian read the note on the back t Matters # Fill in this page.
I A7 B7 _263& --^___ 五、發明説明（ 圖1顯示晶圓（你丨4 麻& ( Η後0日硬或矽薄膜）經傳統化學機械研 倍後’其表面蓮腊^ &丄 專肤係由親水性轉變爲疏水性。 (請先閱讀背面之注f事項异填寫本頁) 圖2則顯示經佞用太议πη .. 用本發明 < 新穎清潔溶液對該經化學機 械研磨後晶圓進杆、、主、正1 # . , 仃β洗後，其疏水性表面已轉爲親水性 考〇 * 圖3係傳、’先4》谷液與根據本發明之不同清潔溶液對經 化學機械研磨後晶圓表面薄膜之殘留微粒之清潔效果比 車父。" +，’曲線係傳統上使用之氨水溶液，，，◊”曲線係根據 本發明=種清潔溶液，其中除傳統使用之氨水溶液外， 另添加了氫氧化四甲基録，”▲，，曲線係根據本發明之另一 種清潔落液’其係於傳统之氨水溶液中添加乙二胺基四醋 I， _曲，線係根據本發明之另—種清潔溶液，其係於傳 統之氨水溶液中添加氫氧化四甲基銨及乙：胺基四醋酸。 根據圖3 ’以傳統後_化學機械研磨清潔步驟中使用之氛水 岭液β洗心晶圓，其表面薄膜上殘留之微粒數目遠比以本 :明之新穎清潔溶液清洗者爲多。換言之，本發明之新穎 經濟部中央標準局員工消費合作社印製 凊潔溶液對晶圓表面薄膜殘留之微粒具有遠超過傳統氨水 溶液之清潔效果。 圖4係傳統清潔溶液與根據本發明之不同清潔溶液對經 化學機械研磨後晶圓表面薄膜之金屬污染物清潔效果之比 較。係傳統上於後-化學機械研磨清潔步驟中使用之第 一種清潔溶液，去離子水；圈係傳統上於後-化竽機械研 磨清潔步驟中使用之第二種清潔溶液，氨水溶液；圜係根 據本發明之一種清潔溶液，其係於傳統之氨水溶液中添加 一 1〇 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 402635 A7 B7 五、發明説明（8 ) 氫氧化四曱，基銨，□係根據本發明之另一種清潔溶液，其 係於傳統之氨水溶液中添加乙二胺基四醋酸，圓係根據本 發明之另一種清潔溶液，其係於傳統之氨水溶液中添加氳 氧化四曱基按及乙二胺基四醋酸。根據圖4，經傳統後-化 學機械研磨清潔步驟中使用之去離子水或氨水溶液清洗之 晶圓，其表面薄膜上殘留之金屬污染物遠比以本發明之新 穎清潔溶液清洗者爲多。亦即，本發明之新穎清潔溶液對 晶圓表面薄膜殘留之金屬污-染物具有遠超過傳統後-化學 機械研磨步驟使用之去離子水或氨水溶液之清潔效果。 以下實例係進一步説明本發明之可實施性。 實施例 樣本及溶液之製備 ⑴樣本 以業界習知方式製造厚度爲550 nm之氧化層樣本。 ⑵後-化學機械研磨清潔溶液之配製 以業界習知方式製備以下樣本： 溶液1):氨水溶液； 溶液2):氨與氫氧化四甲基銨之100比1水溶液； 溶液3):氨與乙二胺基四醋酸（EDTA)之水溶液（乙二胺基 四醋酸含量爲100 ppm); 溶液4):氨與氫氧化四曱基銨及乙二胺基四醋酸（EDTA) ... 之水溶液（比例範圍100:1:100 ppm)。 實驗步驟 (1)經化學機械研磨後晶圓表面薄膜之殘留微粒數目測試 -11 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） A7 B7 五、發明説明（9 ) 首先成長一經LPCVD攙雜之複矽晶薄膜至厚度3 00 nm於 一般技藝人士習知之6 17寸晶圓上’該6付晶圓係事先成長 550 nm之氧化層，接著以西方科技公司（Westech Co.)生產之 型號爲372m之研磨器及以客寶公司（Cabot Co.)生產之稀釋 Cabot SC-1研磨泥漿進行彼等複矽晶之化學機械研磨實驗。 經化學機械研磨後，分別將經稀釋之溶液1)至4)噴灑於4個 晶圓上，隨後以聚丙烯酸乙烯酯刷·子配合該清潔溶液及以 超音波震盪方式進行晶片之潔淨。 利用表面知目苗儀掃目苗各晶圓衣面薄膜1 ’所何之殘留微粒 數目如下： 使用溶液 晶圓表面薄膜殘留微粒數目（個） 溶液1) /氨水溶液 12 7 8 溶液2) /氨與氳氧化四曱 基銨之100比1水溶液 1 22 溶液3) /氨與乙二胺基四 醋酸之水溶液（乙二胺基 四醋酸：100 ppm) 2 17 溶液4) /氨與氫氧化四甲 基銨及乙二胺基四醋酸之 100:1:100 ppm 水溶液 7 4 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注t事項—填寫本頁) 經化學機械研磨後晶圓表面薄膜之殘留微粒數目與相關 之粒子大小分配亦可見於圖3中。其中，” + ”曲線代表溶 液1)，〃 ◊〃曲線代表溶液2)，” 曲線代表溶液3)，” ”曲 -12 - 本紙張尺度適用中國國家標準（CNS ) A4規格（2【0X297公釐) i i A7 402635 Β7 經濟部中央標準局員工消費合作社印製 五、發明説明（1Q) 線代表溶液4)。 由上述實驗結果可知，使用本發明之清潔溶液進行後-化 學機械研磨材料之清洗，可呈現較佳之微粒去除效果。 ⑵經化學機械研磨後晶圓表面金屬污染物之移除率測試 方法如上述（1)，然除了稀釋之溶液1)至4)以外，另增加一 去離子水清洗溶液對照組。以TXRF測定各晶圓表面金屬污 染物之移除率，所得數據如下： 清潔處理 金屬離子污染物（ppm) 使用溶液 鈣 鐵 銅 .鋅 去離子水 271.73 1886.43 2.88 20.59 161.98 溶液1) /氨水溶液 286.85 832.47 4.05 85.21 2.70 溶液2) /氨水與氫氧化四 曱基銨之100比1水溶液 140.17 364.45 0.27 76.02 <0.1 溶液3) /氨水與乙二胺基 四醋酸之水溶液（乙二胺 基四醋酸：100 ppm) 1.46 331.06 <0.1 0.36 <0.1 溶液4) /氨水與氫氧化四 曱基銨及乙二胺基四醋酸 之100:1:100 ppm水溶液 11.44 259.95 0.24 0.85 <0.1 此結果亦可見於圖4。 圖4中之柱狀圖代表以去離子水爲清潔溶液；翅柱狀 圖代表以溶液1)爲清潔落液画柱狀圖代表以溶液'2)爲清潔 溶液；□柱狀圖代表以容液3)爲清潔溶液；®柱狀圖代表 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） (請先閱讀背面之.注意事灰界填寫本頁) Η裝· 訂 經濟部中央標準局員工消費合作社印製 A7 B7I A7 B7 _263 &-^ ___ V. Description of the invention (Figure 1 shows the wafer (you 4 linen & (next day 0 hard or silicon thin film) after the traditional chemical mechanical polishing) its surface lotus wax ^ & The skin is changed from hydrophilic to hydrophobic. (Please read the note f on the back of the page to fill in this page) Figure 2 shows the use of warfare πη .. Using the present invention < novel cleaning solution for the warp After the chemical mechanical polishing, the wafer rods, main, and positive 1 #., 仃 β have been washed, and the hydrophobic surface has been converted to hydrophilicity. Fig. 3 Series, "First 4" Valley fluid and the solution according to the present invention The cleaning effect of different cleaning solutions on the residual particles on the wafer surface film after chemical mechanical polishing is better than that of the car parent. &Quot; +, 'The curve is the ammonia solution traditionally used, and the "" curve is according to the present invention = a cleaning solution In addition to the traditional ammonia solution, tetramethyl hydroxide is added, "▲", the curve is according to another clean liquid of the present invention, which is the addition of ethylenediamine tetraamine to the traditional ammonia solution. Vinegar I, Koji, thread is another cleaning solution according to the present invention, which is Tetramethylammonium hydroxide and ethyl: aminotetraacetic acid were added to the conventional ammonia aqueous solution. According to Fig. 3, the wafer was washed with the atmospheric hydroline fluid β used in the traditional post-chemical mechanical polishing cleaning step, and the surface film remained. The number of particles is far more than that of the clean cleaning solution. In other words, the cleaning solution printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs of the present invention has far more particles on the wafer surface film than the traditional ammonia solution. Fig. 4 is a comparison of the cleaning effect of the conventional cleaning solution and different cleaning solutions according to the present invention on the metal contaminants of the wafer surface film after chemical mechanical polishing. It is traditionally used in the post-chemical mechanical polishing cleaning step. The first cleaning solution, deionized water; the ring is the second cleaning solution traditionally used in the post-chemical cleaning mechanical grinding cleaning step, the ammonia solution; the cleaning solution according to the present invention, which is based on the traditional Add 10 to the ammonia solution. The paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 402635 A7 B7 V. Description of the invention (8) Tetraammonium hydroxide, ammonium hydroxide, □ is another cleaning solution according to the present invention, which is added with ethylenediaminetetraacetic acid in a traditional ammonia aqueous solution, and the circle is another one according to the present invention A cleaning solution, which is added with a conventional tetrahydroammonium oxide and ethylenediamine tetraacetic acid to a conventional ammonia aqueous solution. According to FIG. 4, the deionized water or the ammonia aqueous solution used in the traditional post-chemical mechanical grinding cleaning step is cleaned. There are far more metal contaminants on the surface film of the wafer than those cleaned by the novel cleaning solution of the present invention. That is, the novel cleaning solution of the present invention has far more traditional metal stains and stains on the surface film of the wafer than conventional ones. Cleaning effect of de-ionized water or ammonia solution used in the post-chemical mechanical grinding step. The following examples further illustrate the feasibility of the present invention. Examples Preparation of Samples and Solutions ⑴ Samples An oxide layer sample with a thickness of 550 nm was manufactured in a manner known in the industry. Hou-chemical mechanical polishing cleaning solution preparation The following samples are prepared in a manner known in the industry: Solution 1): Aqueous ammonia solution; Solution 2): 100: 1 aqueous solution of ammonia and tetramethylammonium hydroxide; Solution 3): Ammonia and Aqueous solution of ethylenediaminetetraacetic acid (EDTA) (ethylenediaminetetraacetic acid content is 100 ppm); Solution 4): ammonia and tetramethylammonium hydroxide and ethylenediaminetetraacetic acid (EDTA) ... of Aqueous solution (ratio of 100: 1: 100 ppm). Experimental steps (1) Test for the number of particles remaining on the wafer surface film after chemical mechanical polishing -11-This paper size is applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) A7 B7 V. Description of the invention (9) First, a LPCVD-doped compound silicon thin film was grown to a thickness of 3 00 nm on a 6 17-inch wafer known to ordinary artisans. The 6 wafers were grown with an oxide layer of 550 nm in advance, and then Westech Co. .) The grinder model 372m and the diluted Cabot SC-1 grinding slurry produced by Cabot Co. were used to perform chemical mechanical grinding experiments on their complex silicon crystals. After chemical mechanical polishing, the diluted solutions 1) to 4) were sprayed on 4 wafers respectively, and then the cleaning solution was cleaned by ultrasonic cleaning with a polyacrylic acid brush and a combination of the cleaning solution. The number of residual particles on each wafer-coating film 1 'of the seedlings of the eye-catching seedlings using a surface-seeing seedling meter is as follows: The number of residual particles on the wafer surface film using the solution (a) Solution 1) / Ammonia solution 12 7 8 Solution 2) / 100: 1 aqueous solution of ammonia and osmium tetramethylammonium oxide 1 22 solution 3) / aqueous solution of ammonia and ethylenediaminetetraacetic acid (ethylenediaminetetraacetic acid: 100 ppm) 2 17 solution 4) / ammonia and hydroxide 100: 1: 100 ppm aqueous solution of tetramethylammonium and ethylenediaminetetraacetic acid 7 4 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the note on the back-fill in this page) After chemical mechanical grinding The number of residual particles on the wafer surface film and the related particle size distribution can also be seen in Figure 3. Among them, "+" curve represents solution 1), 〃 ◊〃 curve represents solution 2), "curve represents solution 3)," "Qu-12-This paper size is applicable to China National Standard (CNS) A4 specification (2 [0X297 public Ii) ii A7 402635 Β7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. The invention description (1Q) line representative solution 4). From the above experimental results, it can be known that the cleaning solution of the present invention is used for post-chemical mechanical abrasive material cleaning It can show better particle removal effect. 测试 The test method for the removal rate of metal contaminants on the wafer surface after chemical mechanical polishing is as described in (1) above. In addition to the diluted solutions 1) to 4), another deionization is added. The control group of water cleaning solution. The removal rate of metal contaminants on the surface of each wafer was measured by TXRF. The data obtained are as follows: Clean treatment of metal ion contaminants (ppm) Use solution calcium iron copper. Zinc deionized water 271.73 1886.43 2.88 20.59 161.98 solution 1) / Ammonia solution 286.85 832.47 4.05 85.21 2.70 Solution 2) / Aqueous solution of ammonia and tetramethylammonium hydroxide in a ratio of 100 to 1 Aqueous solution 140.17 364.45 0.27 76.02 < 0.1 Solvent 3) / Aqueous solution of ammonia and ethylenediaminetetraacetic acid (ethylenediaminetetraacetic acid: 100 ppm) 1.46 331.06 < 0.1 0.36 < 0.1 Solution 4) / Ammonia and tetramethylammonium hydroxide and ethylenediamine 100: 1: 100 ppm aqueous solution of tetraacetic acid 11.44 259.95 0.24 0.85 < 0.1 This result can also be seen in Figure 4. The bar graph in Figure 4 represents deionized water as the cleaning solution; the fin bar graph represents solution 1) For the cleaning liquid, draw a histogram to represent the solution '2) as the cleaning solution; □ The histogram represents to contain the liquid 3) as the cleaning solution; ® The histogram represents the paper size applicable to the Chinese National Standard (CNS) Α4 specifications ( 210X 297 mm) (Please read the back first. Note the gray world to fill out this page) Outfitting and ordering Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7
^0^635 發明説明（11 以溶液4)爲清潔溶液。 根據上述教撼^ . · 11 、P ’使用本發明之清潔溶液進行後-化學 機械研磨材料泛、.主 ^洗’可王現較佳金屬離子去除效果，尤 以對銅離子之去除力最爲明顯。 π以：t5青專利範圍係以進—步界定本發明之合理保護範 是，技藝人士基於本發明之揭示所可達成 列。一、見（改艮，亦應歸屬本發明合理保護範圍之 14 一 本紙張尺度適用中國國家標準（CNS ) Α4規格（21〇X297公瘦）^ 0 ^ 635 Description of the invention (11: Solution 4) is a cleaning solution. According to the above teaching ^. · 11, P 'After using the cleaning solution of the present invention-chemical mechanical abrasive material pan, main washing' can be a better metal ion removal effect, especially the copper ion removal force is the most As obvious. π: The scope of the T5 patent is to further define the reasonable protection scope of the present invention, which is a list that can be achieved by the skilled person based on the disclosure of the present invention. I. (Revised, which should also belong to the reasonable protection scope of the present invention. 14) The paper size is applicable to China National Standard (CNS) A4 specifications (21 × 297 male thin)