494020 A7 B7 6663twf.doc/006 五、發明說明（(） 本發明是關於積體電路製程中的平坦化製程，且特別 是關於一種用來淸潔經化學機械硏磨（Chemical Mechanism Polishing，CMP)後之複晶砂薄膜表面的淸洗溶液。 對 EPROM (Erasable Programmable ROM)，EEPROM (Electrical Erasable Programmable ROM)或快聞性記憶體 (flash memory)之類的非揮發性記憶體而言，其浮置閘極 (Floating Gate)與控制閘極(Control Gate)之間的氧化砂薄膜 需要有低漏電流與高崩潰電場，以保存記憶胞中的資料。 由於厚度不均勻之複晶氧化矽薄膜和粗糙的複晶矽/複晶氧 化矽薄膜界面會造成高漏電流與低崩潰電場，故製程上需 仰賴優良之複晶砂薄膜平坦化製程(Planarization process)來 改善此問題。 目前廣爲業界使用之平坦化技術包含旋塗式玻璃法， (Spin-〇n Glass，SOG)以及化學機械硏磨法（Chemical Mechanism Polishing，CMP)。其中，化學機械硏磨法是現 在唯一能提供 VLSI (Very Large Scale Integration)甚至 ULSI (Ultra-Large Scale Integration)製程中全面性平坦化的技術。 其原理是利用機械式硏磨的作用，並配合適當的化學助劑 以將晶圓表面高低起伏的輪廓加以磨平的技術。進行化學 機械硏磨之裝置通常包含一用來進行晶圓硏磨之硏磨台以 及用來抓住被硏磨晶圓之握柄。在進行化學機械硏磨時’ 係以握柄抓住晶圓之背面，然後把晶圓之正面壓在鋪有一 層硏磨墊的硏磨台上，此時輔助化學機械硏磨之化學助劑 延輸送管持續供應在硏磨墊上。利用化學助劑所提供之化 3 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ----------------l· I--訂---i I I I I 1 ^ (請先閱讀背面之注咅？事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 494020 A7 B7 6663twf.doc/006 五、發明說明（之） 學反應及晶圓在硏磨台上所承受之機械硏磨，把晶圓上凹 凸不平之沈積層逐漸平坦化。 (請先閱讀背面之注意事項再填寫本頁) 在化學機械硏磨製程中所使用之化學助劑一般通稱爲 硏漿（Sluiry)，其中用來硏磨介電層的硏漿通常由膠狀矽土 加上鹼性氫氧化鉀或氨水混和而成，而用來硏磨鎢金屬硏 漿通常.由分散性鋁土加上硝酸鐵混合而成。 然而，化學機械硏磨爲一項非常容易造成污染的製 程，這是因爲經化學機械硏磨後之晶圓表面上往往會殘留 許多不易移除之微粒致污物，此等微粒物質除來自硏槳 外，亦來自被硏磨之晶圓本身。此外，晶圓表面殘留之金 屬離子污染物亦爲化學機械硏磨之另一缺點。部分晶圓(例 如複晶砂或政表面）經傳統化學機械硏磨後’硏磨微粒子 以及金屬離子污染即會殘留在矽晶片表面，其中硏磨微粒 子會在超大型積體電路中形成缺陷，而快速擴散之金屬離 子在高溫處理中只要一點濃度就可以在矽晶片中產生許多 晶相缺陷。 經濟部智慧財產局員工消費合作社印製 爲除去化學機械硏磨後產生之污染物，於化學機械硏 磨後必須加入一淸洗步驟。到目前爲止，積體電路製造工 廠中皆使用稀釋氨水來去除微粒子，其係利用刷洗、噴洗 及超音波淸洗等方式，並配合氨水溶液之化學作用以達到 淸潔晶圓表面致污物之效果。氨水除去微粒之原理是將矽 晶片表面腐蝕，並使微粒與矽晶片表面帶相同電荷，而彼 此互相排斥。然而，由於硏磨微粒子及金屬離子會殘留在 複晶矽之疏水性表面，而不易被氨水溶液去除，故會導致 4 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 494020 A7 B7 6663twf.doc/006 五、發明說明（>) 製品良率之降低。 關於化學機械硏磨後於晶圓表面所產生污染物之去除 方法，已見於許多文獻中。例如，N.Miyashita等人於1996 年在CMP-MIC會議中所發表之論文-「適用於溝渠隔離製 程之新穎的化學機械硏磨後淸潔方法（A new post CMP cleaning method for trench isolation process)」，此方法係利 用界面活性劑進行化學機械硏磨，使得複晶矽薄膜表面於 化學機械硏磨後仍爲親水性，並使廢料於硏磨之同時排 除。 然而，上述習知技藝之清洗溶液並無法有效地移除金 屬污染物，而不能有效地改良經化學機械硏磨後之晶圓表 面的性質。因此，業界仍積極尋求一種可有效淸除晶圓表 面經化學機械硏磨後殘留之污染物（例如微粒與金屬污染 物等），卻毋須要如傳統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化學機械硏磨後的淸潔溶 液。 本發明提供一種用來淸潔經化學機械硏磨後之複晶矽 薄膜表面的淸洗溶液，其係在氨水溶液中加入界面活性劑 與螯合劑，藉以降低晶圓上殘餘之微粒與金屬離子的污 染。本發明之技術改良係在傳統進行化學機械硏磨使用之 氨水溶液中，添加界面活性劑，並選用不同螯合劑。螯合 劑之使用可減少晶圓上諸如鈣、鐵、鉻、銅、鋅及鉀等金 屬離子污染物之含量，進而提升氨水溶液之淸潔效果。 適用於本發明之螯合劑係爲含有羧基（-CO〇l·!)的螯合 5 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） " -----------------r---訂-----------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 494020 A7 B7 6663twf.doc/006 五、發明說明（Zf ) 劑，例如是乙二氨基四醋酸(EDTA)、檸檬酸(citric acid)、 草酸（oxalic acid)、三醋酸銨，或乙二醇_二_(/5_胺基_乙 基醚）-N，N-四醋酸等等。螯合劑之用量範圍自ippm至 lOOOOppm，較佳係自5ppm至5000ppm，更佳係自l〇ppm 至 lOOOppm。 在化學機械硏磨後的淸潔過程中，當適量添加上述含 有竣基（-COOH)之蜜合劑至氨水溶液中時，由於此螯合劑 具有之竣基可和金屬離子反應形成穩定的金屬螯合物 (Metal-chelate)，故可有效地移除造成污染之金屬離子。 另外’添加在鹼性氨水溶液中的界面活性劑可使經化 學機械硏磨之薄膜表面由疏水性改爲親水性，故使氨水溶 液對微粒之去除力大爲提昇。本發明中所稱之「界面活性 劑」’係指業界已知可降低兩液體間或液體與固體間表面 張力之化學成份，例如，此界面活性劑可爲四取代基氫氧 化銨’其上之取代基較佳爲直鏈或具支鏈之CrC2Q烷基， 其中尤佳者爲氫氧化四甲基銨、氫氧化四乙基銨、氫氧化 四丙基銨、氫氧化四丁基銨、氫氧化四戊基銨、氫氧化四 己基銨、氫氧化四庚基銨，或是氫氧化四辛基銨。氨水溶 液中之氫氧化銨與界面活性劑之用量比係自1:1至50000 : 1，較佳係自5 : 1至10000 : 1，更佳係自10 : 1至5000 : 1，再佳係自10 : 1至1000 : 1。494020 A7 B7 6663twf.doc / 006 V. Description of the invention (() The present invention relates to the planarization process in the integrated circuit manufacturing process, and in particular to a chemical mechanism polishing (CMP) process for cleaning Rinse solution on the surface of the subsequent polycrystalline sand film. For non-volatile memory such as EPROM (Erasable Programmable ROM), EEPROM (Electrical Erasable Programmable ROM) or flash memory, its floating The oxide sand film between the Floating Gate and the Control Gate needs a low leakage current and a high breakdown electric field to preserve the data in the memory cell. Due to the uneven thickness of the polycrystalline silicon oxide film and The rough polycrystalline silicon / polycrystalline silicon oxide film interface will cause high leakage current and low breakdown electric field, so the process needs to rely on a good polycrystalline sand film planarization process (Planarization process) to improve this problem. Currently widely used in the industry The planarization technology includes a spin-on glass method (Spin-On Glass, SOG) and a chemical mechanical polishing method (Chemical Mechanism Polishing, CMP). Among them, chemical Mechanical honing is the only technology that can provide comprehensive flattening in VLSI (Very Large Scale Integration) and even ULSI (Ultra-Large Scale Integration) processes. Its principle is to use the role of mechanical honing and cooperate with appropriate chemistry Auxiliary technology is used to smooth the contour of the wafer surface. The equipment for chemical mechanical honing usually includes a honing table for wafer honing and a grip for holding the honed wafer. When performing chemical mechanical honing, 'hold the back of the wafer with a handle, and then press the front side of the wafer on a honing table with a layer of honing pad. At this time, the chemical The auxiliary extension pipe is continuously supplied on the honing pad. The chemical paper provided by the chemical auxiliary is used. 3 The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ---------- ------ l · I--Order --- i IIII 1 ^ (Please read the note on the back? Matters before filling out this page) Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs 494020 A7 B7 6663twf.doc / 006 V. Description of the invention (the) Chemical reaction and wafer honing The mechanical honing on the table gradually flattens the uneven deposits on the wafer. (Please read the precautions on the back before filling this page.) The chemical additives used in the chemical mechanical honing process are generally referred to as Sluiry (Sluiry), in which honing the dielectric layer of honing slurry is usually made of colloidal silica plus alkaline potassium hydroxide or ammonia water mixed, and honing tungsten metal honing slurry is usually made by dispersion Blended with alumina and ferric nitrate. However, chemical mechanical honing is a process that is very prone to contamination. This is because there are often many particulate contaminants that are not easily removed on the wafer surface after chemical mechanical honing. Outside of the paddle, it also comes from the honing wafer itself. In addition, metal ion contamination remaining on the wafer surface is another disadvantage of chemical mechanical honing. Some wafers (such as polycrystalline sand or political surfaces) will be left on the surface of the silicon wafer after 'honed particles and metal ion contamination after traditional chemical mechanical honing. Among them, the honed particles will form defects in the ultra-large integrated circuit. The fast-diffusing metal ions can generate many crystal phase defects in silicon wafers with only a little concentration during high temperature processing. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. To remove pollutants generated by chemical mechanical honing, a cleaning step must be added after chemical mechanical honing. So far, the integrated circuit manufacturing plants have used diluted ammonia to remove particles. It uses brushing, spray cleaning and ultrasonic cleaning, and cooperates with the chemical action of ammonia solution to achieve cleanliness on the wafer surface. The effect. The principle of ammonia particle removal is to corrode the surface of the silicon wafer and make the particles have the same charge as the surface of the silicon wafer, and they repel each other. However, since the honing particles and metal ions will remain on the hydrophobic surface of the polycrystalline silicon, it will not be easily removed by the ammonia solution. Therefore, the 4 paper sizes will be applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 494020 A7 B7 6663twf.doc / 006 V. Description of the invention (>) Product yield reduction. Methods for removing contaminants generated on the wafer surface after chemical mechanical honing have been found in many literatures. For example, a paper published by N. Miyashita et al. At the CMP-MIC conference in 1996-"A new post CMP cleaning method for trench isolation process" "This method uses chemical mechanical honing with a surfactant to keep the surface of the polycrystalline silicon film hydrophilic after chemical mechanical honing, and eliminates the waste while honing. However, the cleaning solutions of the above-mentioned conventional techniques cannot effectively remove metal contaminants, and cannot effectively improve the properties of the wafer surface after chemical mechanical honing. Therefore, the industry is still actively seeking a kind of pollutants (such as particulates and metal contaminants) that can effectively remove the chemical mechanical honing of the wafer surface, but it is not necessary to use strong acid chemicals such as hydrochloric acid and sulfuric acid as in the traditional RCA procedure. At the same time, it is a more economical chemical cleaning solution after honing. The present invention provides a cleaning solution for cleaning the surface of a polycrystalline silicon film after chemical mechanical honing. It is added with an surfactant and a chelating agent in an ammonia solution to reduce the residual particles and metal ions on the wafer. Pollution. The technical improvement of the present invention is to add a surfactant to the ammonia solution traditionally used for chemical mechanical honing, and select different chelating agents. The use of a chelating agent can reduce the content of metal ionic contaminants such as calcium, iron, chromium, copper, zinc, and potassium on the wafer, thereby improving the cleaning effect of the ammonia solution. The chelating agent suitable for the present invention is a chelating agent containing a carboxyl group (-CO〇l ·!) 5 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) " ------ ----------- r --- Order ----------- line (please read the precautions on the back before filling this page) Preparation 494020 A7 B7 6663twf.doc / 006 V. Description of the invention (Zf) agent, such as ethylenediaminotetraacetic acid (EDTA), citric acid, oxalic acid, ammonium triacetate, or ethylene glycol _Di _ (/ 5_amino_ethyl ether) -N, N-tetraacetic acid and so on. The amount of the chelating agent ranges from ippm to 1000 ppm, preferably from 5 ppm to 5000 ppm, and more preferably from 10 ppm to 1000 ppm. In the cleaning process after chemical mechanical honing, when an appropriate amount of the above-mentioned honey-containing compound (-COOH) is added to the ammonia solution, the stable group of the chelating agent can react with metal ions to form a stable metal chelate. Compound (Metal-chelate), so it can effectively remove the metal ions that cause pollution. In addition, the surfactant added in the alkaline ammonia solution can change the surface of the film subjected to chemical mechanical honing from hydrophobic to hydrophilic, so that the removal ability of the ammonia solution to the particles is greatly improved. The “surfactant” as used in the present invention refers to a chemical component known in the industry to reduce the surface tension between two liquids or between a liquid and a solid. For example, the surfactant may be a tetra-substituted ammonium hydroxide. The substituent is preferably a linear or branched CrC2Q alkyl group, among which tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, Tetrapentyl ammonium hydroxide, tetrahexyl ammonium hydroxide, tetraheptyl ammonium hydroxide, or tetraoctyl ammonium hydroxide. The ratio of the ammonium hydroxide to the surfactant in the ammonia solution is from 1: 1 to 50000: 1, preferably from 5: 1 to 10000: 1, more preferably from 10: 1 to 5000: 1, and even better From 10: 1 to 1000: 1.
在化學機械硏磨後的淸潔過程中，當適量添加上述四 取代基氫氧化銨界面活性劑至氨水溶液中時，此界面活性 劑中的四烷基銨陽離子會藉凡得瓦力附著在疏水性之Si-H 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ----------------l·——訂-------線·. (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 494020 A7 B7 6663twf.doc/006 五、發明說明（p) 表面，而令其成爲親水性。因此，氨水溶液對薄膜表面之 濕潤性會變的較好，而可得到較佳之微粒淸潔效果。 (請先閱讀背面之注意事項再填寫本頁) 本發明之優點在於當淸洗經化學機械硏磨之晶圓表面 薄膜時，無須改變原先之淸洗步驟，僅需在氨水溶液中添 加界面活性劑及螯合劑，添加界面活性劑即可改良晶片表 面薄膜之疏水性，添加螯合劑可有效地移除金屬離子，進 而增加氨水溶液之淸潔功效，而呈現較佳之微粒及金屬離 子去除效果。因此，本發明之淸潔溶液不會使經化學機械 硏磨之材料（例如二氧化矽或複晶矽）形成缺陷，而可提高 產品之良率。 經濟部智慧財產局員工消費合作社印製 另外，本發明所提出之淸潔溶液不僅可應用於複晶矽 及二氧化矽薄膜經化學機械硏磨後之淸潔過程中，亦可應 用前段製程之化學機械硏磨後的矽材表面淸潔過程中。例 如，在晶圓之生產製程中，當晶圓由成長完全之晶棒切割 下來並硏磨後，亦可以本發明之淸潔溶液進行淸潔，效果 遠比傳統淸潔溶液爲佳。此外，本發明之淸潔溶液另可應 用在半導體製程中成長閘極氧化層前之淸潔步驟，以及其 他關於微粒、有機物、金屬離子的去除應用中，淸潔效果 皆相當良好。 讓本發明之上述和其他目的、特徵、和優點能更明顯 易懂’下文特舉一較佳實施例，並配合所附圖式，作詳細 說明如下： 圖式之簡單說明 第1圖顯示利用化學機械硏磨方法之複晶矽電容器結 7 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 494020 6663twf.doc/006 _____B7_____ 五、發明說明（t ) 構。 第2圖顯示使用不同淸洗溶液淸潔後之複晶矽表面的 粗糙度。 第3圖顯示經化學機械硏磨及以不同溶液淸洗複晶矽 薄膜表面後，殘留在複晶矽表面之微粒的數目。 第4圖顯示經化學機械硏磨及以不同溶液淸洗複晶矽 薄膜表面後，殘留在複晶矽表面之金屬離子的濃度。 第5圖顯示經化學機械硏磨及以不同溶液淸洗複晶矽 薄膜表面後，電容之正崩潰電場的Weibull分佈比較。 第6圖係經化學機械硏磨後以不同溶液淸洗’電容 之崩潰電荷之Weibull分佈比較。 _忒之標號說明 100 :基底 110 :二氧化矽層 120 :第一複晶矽層 130 : TEOS氧化砂層 140 :第二複晶矽層 150 :二氧化矽層 160 :金屬洞 170 :金屬層 實施盤 首先要說明的是本實施例中樣本及淸潔溶液之製備過 程，然後再說明其測試步驟。 (1) ·樣本之製備過程 8 丨本紙張尺度準（CNS)A4規格（21〇x 297公^ -----------------*I—^—1—I—^ (請先閱讀背面之注意事項再填寫本頁) 494020 A7 B7 五 經濟部智慧財產局員工消費合作社印製 6663twf.doc/006 發明說明（Λ| ) 以業界習知方式製備電容，請參照第1圖，首先在 P-type基底100上以溼式氧化法成長厚度5000埃二氧化砂 層110，再以低壓化學沈積（LPCVD)沈積厚度3000埃之第 一複晶砂層120，然後以P0C13於此第一複晶砂層12〇中 摻雜磷元素，以使第一複晶矽層120阻値爲40至80歐姆/ 單位面積。接著以稀釋CABOT SC-1作爲硏漿，利用化學 機械硏磨法(CMP)磨平第一複晶矽層120，再以本發明所提 出之淸洗溶液進行一淸洗步驟。然後於第一複晶砂層120 上沈積 TE〇S (Tetra Ethyl Ortho Silicate)氧化砂層 130。接 著以快速加熱退火處理（Rapid Thermal Annealing，RTA)， 再馬上以低壓化學沈積法沈積厚度3000埃之第二複晶矽 層140,且以P0C13進行摻雜以使第二複晶矽層140阻値 爲40至80歐姆/單位面積。接著在黃光室開第一道光罩以 定義第二複晶砂層140，然後以溼式氧化法長出厚度1〇〇〇 埃之二氧化矽層150，再開第二道光罩做金屬洞（contact hole)160至第一複晶矽層上120。最後於基底100上蒸鍍厚 度5000埃之鋁金屬170,再開第三道光罩定義鋁金屬170 ’ 即完成可用來測試的電容。 (2)·化學機械硏磨後之淸潔溶液之配製 以業界習知方式製備以下樣本如表格一： 溶液0 :氨水溶液（NH40H，3%) 溶液A :氨水溶液（NH40H，2%) 溶液B!:氨水溶液（NH40H，2%)與氫氧化四甲基胺 (TMAH)(NH4〇H : TMAH=100 ")及乙二胺 9 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----r---^----------- (請先閱讀背面之注意事項再填寫本頁) 494020 A7 R7 6663twf.doc/006 五、發明說明（》） 基四醋酸（EDTA)(100ppm)之水溶液 溶液B2 :氨水溶液（NH4OH，2%)與氫氧化四甲基胺 (TMAH)(NH4〇H : TMAH=100 : 1)及乙二胺 基四醋酸（EDTA)之水溶液（200ppm) 溶液:氨水溶液（NH4〇H，2%)與氫氧化四甲基胺 (TMAH)(NH4〇H : TMAH=100 : 1)及檸檬酸 (Citric acid)(100ppm)之水溶液 溶液C2 :氨水溶液(NH4OH，2%)與氫氧化四甲基胺 (TMAH)(NH4〇H : TMAH=100 : 1)及檸檬酸 (Citric acid)(200ppm)之水溶液 溶液Di ••氨水溶液（NH4〇H，2%)與氫氧化四甲基胺 (TMAH)(NH4〇H ·· TMAH=100 : 1)及草酸 (Oxalic acid)(100ppm)之水溶液 溶液D2 :氨水溶液（NH40H，2%)與氫氧化四甲基胺 (TMAH)(NH4〇H : TMAH=100 : 1)及草酸 (Oxalic acid)(200ppm)之水溶液 另外，上述各淸潔溶液之成分列表如下： (請先閱讀背面之注咅？事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 表格一 Solution nh4〇h NH4〇H : TMAH Chelating agent PH 〇 3% 0 0 12.58 A 2% 0 0 12.58 B! 2% 100 1 EDTA lOOppm 12.75 b2 2% 100 1 EDTA 200ppm 12.70 C! 2% 100 1 Citric acid lOOppm 12.75 c2 2% 100 1 Citric acid 200ppm 12.75 〇! 2% 100 1 Oxalic acid lOOppm 12.70 d2 2% 100 1 Oxalic acid 200ppm 12.75 10 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 494020 A7 B7 6663twf.doc/006 五、發明說明（7) 測試結果 在第一複晶矽層120淸洗之後，使用Tencoi*-4500系 統偵測微粒子之數目，並由原子力顯微鏡（AFM)決定矽晶 片表面的粗糙度，且在電容製作完成後使用HP4145半導 體參數分析儀量測TEOS氧化矽層之品質。 各項量測之結果請參照第2-6圖。首先，使用不同淸 潔溶液之後，複晶矽薄膜的表面粗糙度請見第2圖，其顯 示只有使用較高濃度氨水(NH4〇H，3%)溶液，即〇溶液淸 洗，會得到較粗糙的複晶矽表面，其餘淸潔溶液淸洗複晶 矽表面，得到的粗糙度幾乎一樣，這表示複晶矽表面的粗 糙度只和氨水濃度有關。經化學機械硏磨後以不同溶液淸 潔微粒子留在複晶矽表面數目請見第3圖，其顯示C2溶 液及D2溶液去除微粒子之能力較好。經化學機械硏磨後 以不同溶液淸潔金屬離子留在複晶矽表面濃度請見第4 圖，其顯示C2溶液可以完全去除複晶矽表面上之金屬離 子。 第 5 圖顯示正崩潰電場（electric breakdown field，Ebd) 之Wdbull分佈，且第6圖顯示將電流強度爲20mA/cm2時， 正崩潰電荷（charge to Breakdown，Qbd)之 Weibull 分佈，其 中（---）符號表示以溶液◦爲淸潔溶液，（一 一）符號表示以溶液A爲淸潔溶液，（一參一）符號 表示以溶液匕爲淸潔溶液，（▽)符號表示以溶液匕爲 淸潔溶液，（一一）符號表示以溶液Cl爲淸潔溶液， (一◊)符號表示以溶液C2爲淸潔溶液，（一▲一）符 11 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------------r---訂----------線 (請先閱讀背面之注咅？事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 494020 A7 B7 6663twf.doc/006 五、發明說明（/ 〇) 號表示以溶液Di爲淸潔溶液，（一〇）符號表示以 溶液D2爲淸潔溶液。由如第5-6圖所示，使用〇溶液淸 潔後所形成之氧化矽薄膜有最低之Ebd及崩潰電荷（Qbd) ’ 而使用〇2溶液淸潔後所形成之氧化矽薄膜則有最高之Ebd 及崩潰電荷（Qbd)。這表示與其他淸潔溶液相較之下。本 發明較佳實施例之C2溶液可更有效地移除微粒或金屬離 子污染物。 雖然本發明已以一較佳實施例揭露如上，然其並非用 以限定本發明，任何熟習此技藝者，在不脫離本發明之精 神和範圍內，當可作各種之更動與潤飾，因此本發明之保 護範圍當視後附之申請專利範圍所界定者爲準。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 12 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）In the cleaning process after chemical mechanical honing, when an appropriate amount of the above-mentioned tetra-substituted ammonium hydroxide surfactant is added to an aqueous ammonia solution, the tetraalkylammonium cations in this surfactant will adhere to Van der Waals by Hydrophobic Si-H This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ---------------- l · ——Order ---- --- Line ·. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 494020 A7 B7 6663twf.doc / 006 V. Description of the invention (p) The surface is made into Hydrophilic. Therefore, the wettability of the ammonia solution on the surface of the film becomes better, and a better particle cleaning effect can be obtained. (Please read the precautions on the back before filling out this page) The advantage of the present invention is that when cleaning the surface film of a chemical mechanical honing wafer, there is no need to change the original cleaning step, just add interfacial activity to the ammonia solution Adding surfactants can improve the hydrophobicity of the film on the surface of the wafer. Adding chelating agents can effectively remove metal ions, which can increase the cleaning effect of ammonia solution, and present better removal effect of particles and metal ions. Therefore, the cleaning solution of the present invention does not cause defects in materials subjected to chemical mechanical honing (such as silicon dioxide or polycrystalline silicon), and can improve the yield of the product. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In addition, the cleaning solution proposed by the present invention can be used not only in the cleaning process of polycrystalline silicon and silicon dioxide films after chemical mechanical honing, but also in the previous process. The surface of the silicon material after chemical mechanical honing is being cleaned. For example, in the wafer manufacturing process, after the wafer is cut from a fully grown ingot and honed, the cleaning solution of the present invention can also be used for cleaning, the effect is far better than the traditional cleaning solution. In addition, the 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 matter, and metal ions, the cleaning effect is quite good. To make the above and other objects, features, and advantages of the present invention more comprehensible, a preferred embodiment is described below in conjunction with the accompanying drawings and described in detail as follows: Brief description of the drawings FIG. 1 shows the use of Chemical-mechanical honing method of polycrystalline silicon capacitor junction 7 This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 494020 6663twf.doc / 006 _____B7_____ V. Invention Description (t) Structure. Figure 2 shows the roughness of the polycrystalline silicon surface after cleaning with different cleaning solutions. Figure 3 shows the number of particles remaining on the surface of the polycrystalline silicon film after chemical mechanical honing and washing the surface of the polycrystalline silicon film with different solutions. Figure 4 shows the concentration of metal ions remaining on the surface of the polycrystalline silicon film after chemical mechanical honing and washing the surface of the polycrystalline silicon film with different solutions. Figure 5 shows the comparison of Weibull distributions of the positive collapse electric field of the capacitor after chemical mechanical honing and washing the surface of the polycrystalline silicon film with different solutions. Fig. 6 is a comparison of Weibull distribution of the collapsed charge of the capacitor's washed with different solutions after chemical mechanical honing. _ 忒 The description of the label 100: the substrate 110: the silicon dioxide layer 120: the first polycrystalline silicon layer 130: the TEOS sand layer 140: the second polycrystalline silicon layer 150: the silicon dioxide layer 160: the metal hole 170: the metal layer implementation The plate first needs to explain the preparation process of the sample and the cleaning solution in this embodiment, and then explains the test steps. (1) · Samples preparation process 8 丨 This paper size standard (CNS) A4 specification (21〇x 297 public ^ ----------------- * I — ^ — 1— I— ^ (Please read the notes on the back before filling this page) 494020 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 6663twf.doc / 006 Description of the Invention (Λ |) The capacitors are prepared in a manner known in the industry, please Referring to FIG. 1, firstly, a 5000 angstrom dioxide dioxide layer 110 is grown on a P-type substrate 100 by a wet oxidation method, and then a first polycrystalline sand layer 120 with a thickness of 3000 angstroms is deposited by low pressure chemical deposition (LPCVD). Phosphorus is doped in the first polycrystalline sand layer 120 so that the first polycrystalline silicon layer 120 is blocked to 40 to 80 ohms per unit area. Then, diluted CABOT SC-1 is used as a slurry, and chemical mechanical is used. The first polycrystalline silicon layer 120 is polished by a grinding method (CMP), and then a rinsing step is performed using the cleaning solution proposed in the present invention. Then TEOS (Tetra Ethyl Ortho Silicate) is deposited on the first polycrystalline sand layer 120. Oxidized sand layer 130. Next, by rapid thermal annealing (RTA), and then immediately deposited by a low pressure chemical deposition method. A second polycrystalline silicon layer 140 having a thickness of 3000 angstroms and doped with POC13 so that the second polycrystalline silicon layer 140 is blocked to 40 to 80 ohms / unit area. Then, a first photomask is opened in the yellow light chamber to Define the second polycrystalline sand layer 140, then grow a silicon dioxide layer 150 with a thickness of 1000 angstroms by a wet oxidation method, and then open a second photomask to make a contact hole 160 onto the first polycrystalline silicon layer. 120. Finally, the aluminum metal 170 with a thickness of 5000 angstroms is vapor-deposited on the substrate 100, and then a third photomask is defined to define the aluminum metal 170 'to complete the capacitor that can be used for testing. Prepare the following samples in a manner known in the industry, as shown in Table 1: Solution 0: Aqueous ammonia solution (NH40H, 3%) Solution A: Aqueous ammonia solution (NH40H, 2%) Solution B !: Aqueous ammonia solution (NH40H, 2%) and tetrahydroxide Methylamine (TMAH) (NH4〇H: TMAH = 100 ") and ethylenediamine 9 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ----- r --- ^ ----------- (Please read the notes on the back before filling this page) 494020 A7 R7 6663twf.doc / 006 V. Description of the invention (") Tetraacetic acid EDTA) (100ppm) aqueous solution B2: ammonia aqueous solution (NH4OH, 2%) and tetramethylamine hydroxide (TMAH) (NH4〇H: TMAH = 100: 1) and ethylenediamine tetraacetic acid (EDTA) Aqueous solution (200ppm) Solution: Aqueous solution of ammonia solution (NH4〇H, 2%), tetramethylamine hydroxide (TMAH) (NH4〇H: TMAH = 100: 1) and citric acid (100ppm) C2: Aqueous solution of ammonia solution (NH4OH, 2%) and tetramethylamine hydroxide (TMAH) (NH4〇H: TMAH = 100: 1) and Citric acid (200ppm). NH4〇H, 2%) and tetramethylamine hydroxide (TMAH) (NH4〇H · TMAH = 100: 1) and oxalic acid (100ppm) in aqueous solution D2: ammonia solution (NH40H, 2% ) And tetramethylamine hydroxide (TMAH) (NH4〇H: TMAH = 100: 1) and Oxalic acid (200ppm) in water. In addition, the ingredients of the above cleaning solutions are as follows: (Please read the back first The note? Please fill in this page for further information.) Printed Form 1 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Solution nh4〇h NH4〇H: TMAH Chelating agent PH 〇3% 0 0 12.58 A 2% 0 0 12.58 B! 2% 100 1 EDTA 100 ppm 12.75 b2 2% 100 1 EDTA 200ppm 12.70 C! 2% 100 1 Citric acid lOOppm 12.75 c2 2% 100 1 Citric acid 200ppm 12.75 〇! 2% 100 1 Oxalic acid lOOppm 12.70 d2 2% 100 1 Oxalic acid 200ppm 12.75 10 paper The dimensions are in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 494020 A7 B7 6663twf.doc / 006 V. Description of the invention (7) Test results After the first polycrystalline silicon layer was cleaned by 120, use Tencoi *- The 4500 system detects the number of particles, and the atomic force microscope (AFM) determines the surface roughness of the silicon wafer. After the capacitor is fabricated, the quality of the TEOS silicon oxide layer is measured using the HP4145 semiconductor parameter analyzer. Please refer to Figure 2-6 for the results of each measurement. First, after using different cleaning solutions, the surface roughness of the polycrystalline silicon thin film is shown in Figure 2. It shows that only using a higher concentration of ammonia (NH4OH, 3%) solution, that is, washing with 〇 solution, will get better The surface of the rough polycrystalline silicon was washed with the rest of the cleaning solution, and the roughness was almost the same. This means that the roughness of the polycrystalline silicon surface is only related to the ammonia concentration. After chemical mechanical honing, the number of clean particles remaining on the surface of the polycrystalline silicon with different solutions is shown in Figure 3, which shows that the C2 solution and D2 solution have better ability to remove particles. After chemical mechanical honing, the concentration of the metal ions remaining on the surface of the polycrystalline silicon in different solutions is shown in Figure 4, which shows that the C2 solution can completely remove metal ions on the surface of the polycrystalline silicon. Figure 5 shows the Wdbull distribution of the electric breakdown field (Ebd), and Figure 6 shows the Weibull distribution of the charge to Breakdown (Qbd) when the current intensity is 20 mA / cm2, where (- -) The symbol indicates that the solution is a cleaning solution, the (1-1) symbol indicates that the solution A is a cleaning solution, the (one parameter) symbol indicates that the solution is a cleaning solution, and the (▽) symbol indicates that the solution is a cleaning solution. For cleaning solution, (一一) symbol means solution Cl is used as cleaning solution, (一 淸) symbol means solution C2 is used for cleaning solution, (一 ▲ 一) symbol 11 This paper size applies Chinese National Standard (CNS) A4 Specifications (210 X 297 mm) ----------------- r --- order ---------- line (please read the note on the back first? Please fill out this page again) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 494020 A7 B7 6663twf.doc / 006 V. The invention description (/ 〇) means solution Di as the cleaning solution, (10) symbol means the solution D2 is the cleaning solution. As shown in Figures 5-6, the silicon oxide film formed after cleaning with 0 solution has the lowest Ebd and collapse charge (Qbd) ', and the silicon oxide film formed after cleaning with 0 solution has the highest Ebd and Qbd. This represents a comparison with other cleaning solutions. The C2 solution of the preferred embodiment of the present invention can more effectively remove particulate or metal ion contamination. Although the present invention has been disclosed as above with a preferred embodiment, it is not intended to limit the present invention. Any person skilled in the art can make various modifications and decorations without departing from the spirit and scope of the present invention. The scope of protection of the invention shall be determined by the scope of the attached patent application. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 12 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)