1297720 A7 B7 五、發明説明（ 技術領域 本發明尤其揭示一種半導體製程中之化學機械撤光（簡稱 為"CMP")製程中所用之黏漿。本發明揭示一種用於加工 SiN或SiON膜（··氮化物膜”之簡寫），且對Si〇膜（”氧化物膜 "之簡寫）之CMP黏漿。 相關技藝之敘述 近年來，在半導體製程中形成細微圖案之方法受到相當 的矚目。因此，強烈的要求對在晶片及晶圓表面上硬化不 均勻之廣泛平整化技術。 CMP製程為半導體裝置製造中使用微影蝕刻法之平整化 技術。IBM在1980年代末期發展出藉由合併化學移除法及 機械拋光法之CMP製程。 由於最近半導體裝置之極小化，高密度及多層結構、因 此需調整現行CMP製程之晶圓抛光速度，且包含黏裝中之 化學添加劑，以達到區域平整化。 更詳細而言，可化學去除之物質係藉由使用具有高反應 性之化學物質去除，且晶圓表面係藉由同時使用係研磨料 機械加工。液相黏漿係注入晶圓表面與旋轉彈性墊之間。 CMP製程基本上係達到高密度及高積體度之超過64M之 記憶半導體與超過250 MHz之非記憶半導體。 一般使用之CMP黏漿為氧化物CMP黏漿。氧化物膜以該 黏漿至少如氮化物膜一般快的拋光二次。因此，使用氮化 物膜作為終止層，造成氧化物膜之拋光。氧化物CMP黏漿 之N/0(亦即氮化物對氧化物）選擇性低於〇 5。 - 4- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 1297720 A7 B7 五、發明説明（2 ) 然而，以波紋狀金屬柙製程，使用氧化物CMp黏漿撤 光氮化物膜時，氧化物膜之拋光逮率比氮化物膜快，且因 此發生氣化物膜之凹陷現象成為層間之介電層。其會破壞 後續之微影餘刻或餘刻製程，且使得依據CMP製程形成遮 蔽氮化物膜成為不可能。 因此，氧化物CMP黏漿無法用於抛光沉積在具有氧化 物膜之基材圖案上之氮化物膜。 發明概要 據此，本發明揭示具有N/0>1之氮化物對氧化物蝕刻選 擇性之CMP黏漿，且亦揭示以使用組合物之CMP法製造之 半導體裝置。 本發明揭示一種CMP黏衆組合物，其藉由以鱗酸改變黏 漿之pH使氮化物及氧化物膜之拋光速度產生差異造成對氮 化物膜之選擇性。 附圖簡要敘述 以下將配合下列附圖敘述揭示之CMP黏漿，其使用方法 及以其製備之半導體裝置，其中： 圖1說明H3P04之重量比對黏漿pH改變之圖；以及 圖2說明N/0選擇性對黏漿pH改變之圖。 較佳具艘例之詳細敘述 氮化物CMP黏漿藉由含研磨料及磷酸造成對氮化物之選 擇性。其中，黏漿之pH範圍在1至5間，較好為1至3， 且更好在1至2間。 CMP黏漿中包含之研磨料用量為黏漿之〇·ι至2〇wt%。 -5- 本紙張尺度適財H S家榡準(CNS) M規格(灿χ 297公寶） 1297720 A7 B7 五、發明説明（3 ) 磷酸之添加量為黏漿之0 01至20wt%，較好為0.2至 10wt% 0 當黏漿中研磨料之用量低於黏漿之0.1 wt〇/〇時，拋光速度 無法達到預定之水準。當研磨料之用量超過黏漿之20wt% 時，因為機械因素容易產生刮痕，且增加黏漿之初期成 本。 另外，磷酸拋光氮化物膜比氧化膜快。因此，藉由添加 磷酸可增加超過氧化物膜之對氮化物膜之選擇性。 當黏漿中添加磷酸時，pH維持在1至5間，較好1至 3，更好1至2。其中之pH可藉由使用含羥基（-oh)之緩衝 液調整。 當磷酸之用量低於黏漿之O.Olwt%時，因為未產生磷 酸，因此無法獲得期望之低pH及化學反應。當磷酸之用量 超過黏漿之20wt%時，會造成破壞平整化之負面蝕刻或其 他化學反應。 添加於黏漿中之研磨料為一般之研磨料。例如，使用含 Ce02、Mn02、Zr02、Al2〇3或Si02之研磨料。較好使用 含Ce02之研磨料。 其中，研磨料之顆粒粒徑違約100奈米至約500奈米。 較好，研磨料以膠體懸浮液留在黏漿中。 當研磨料之顆粒粒徑低於100奈米時，會降低拋光速度 使產率降低。當研磨料之平均顆粒粒徑超過5〇〇奈米時， 研磨料無法充分的分散，因此造成刮痕。 黏漿係藉由使用氧化物膜當作波紋狀金屬柙極製程中之 -6- 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐） 1297720 A7 B7 五、發明説明（4 ) 層内介電層之终止層或形呈電容器接觸之自動排列接觸(簡 寫為SAC )製程’用於CMP或形成圖案之製程。另外，當 依據化學蒸氣沉積（簡寫為"CVD”）沉積欲拋光之氮化物 膜’且藉由使用揭示之黏聚於其上進行CMP製程時，會降 低對氧化物膜之蝕刻選擇性〇 本發明另一目的係提供一種藉由使用揭示之黏漿，以 CMP製程使SiN或SiON膜形成圖案之方法，尤其是將揭示 之黏漿加於波紋狀金屬柙極製程中之方法及形成電容器之 SAC 法。 用作終止層之SiO膜係在SiN或SiON膜之下部形成。 以下將參考下列實力詳述揭示之氮化物CMP黏聚，但並 非限制用。 黏漿係藉由添加去離子水及磷酸於含Ce02研磨料之HS-8005-A9 (Hitachi Chemical)CMP黏漿中。 比較例1 藉由添加去離子水稀釋含5wt% Ce〇2研磨料之HS_ 8005-A9 CMP黏漿。製備含 lwt% Ce〇2 之 1〇 L CMP黏 漿。其中之pH為8.19(參考圖1)。 發明例1 將0.02wt%之填酸添加於比較例1中製備之黏漿中。其 中之pH為3·00(參考圖1)。 發明例2 將0.20wt%之雄酸添加於比較例1中數備之黏衆中。其 中之pH為1.97(參考圖1)。 -7 - 1297720 A7 B7 五、發明説明（5 ) 發明例3 將0.50wt%之磷酸添加於比較例1中製備之黏漿中。其 中之pH為1.86(參考圖1)。 發明例4 將l.OOwt%之磷酸添加於比較例1中製備之黏漿中。其 中之pH為1.67(參考圖1)。 發明例5 將5.00wt%之磷酸添加於比較例1中製備之黏漿中。其 中之pH為1.18(參考圖1)。 發明例6 比較例1及發明例1至5中製備之黏漿之N/O拋光選擇 性係依據CMP製程，使用氧化物膜如高密度電漿（HDP)氧 化物膜或未摻雜脂矽酸鹽玻璃（USG)氧化物膜，及氮化物 膜如電漿提昇之氮化物（PEN)膜，或低鴨蛋化物（LPN)膜製 得。其中之拋光條件為輸送壓力3 psi，且檯轉動為70 rpm 〇 結果，當磷酸之用量超過〇.50wt%時，亦即pH低於 1· 86時，N/0拋光選擇性超過1。另〆方面，當使用電漿 提昇之氮化物膜時，選擇性約為2。意指氮化物膜之拋光 比氧化物膜快（參考圖2)。 結果，當磷酸之用量超過〇.50wt%時，亦即pH低於 1.86時，N/0拋光選擇性超過1。亦即，當pH低於1.86 時，選擇性超過1。另一方面，當使用電漿提昇之氮化物 膜時，選擇性約為2。意指氮化物膜之拋光比氧化物膜快 (參考圈2) 〇 -8- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐）1297720 A7 B7 V. INSTRUCTION DESCRIPTION (Technical Field The present invention particularly discloses a slurry used in a chemical mechanical light removal (referred to as "CMP") process in a semiconductor process. The present invention discloses a process for processing SiN or SiON films ( · The abbreviation of the nitride film", and the CMP paste of the Si 〇 film ("oxide film"). Description of the Related Art In recent years, the method of forming a fine pattern in a semiconductor process has attracted considerable attention. Therefore, there is a strong demand for extensive planarization techniques for hardening unevenness on wafer and wafer surfaces. The CMP process is a planarization technique using lithography etching in the fabrication of semiconductor devices. IBM developed in the late 1980s by merging. Chemical removal and mechanical polishing CMP process. Due to the recent miniaturization of semiconductor devices, high density and multilayer structure, it is necessary to adjust the wafer polishing speed of the current CMP process, and include chemical additives in the adhesive to reach the region. In more detail, chemically removable substances are removed by using highly reactive chemicals and wafers The surface is machined by simultaneous use of abrasives. The liquid phase is injected between the surface of the wafer and the rotating elastic pad. The CMP process is basically a memory semiconductor with a high density and a high total of more than 64M and more than 250. Non-memory semiconductor of MHz. The CMP slurry generally used is an oxide CMP slurry. The oxide film is polished twice as fast as the nitride film. Therefore, the nitride film is used as a termination layer to cause oxidation. Polishing of the film. The N/0 (ie, nitride to oxide) selectivity of the oxide CMP slurry is lower than 〇5. - 4- This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 PCT) 1297720 A7 B7 V. INSTRUCTIONS (2) However, when the oxide CMp paste is used to remove the nitride film by the corrugated metal crucible process, the polishing rate of the oxide film is faster than that of the nitride film, and thus occurs. The depression phenomenon of the vapor film becomes a dielectric layer between the layers, which will destroy the subsequent lithography or residual process, and it becomes impossible to form a masking nitride film according to the CMP process. Therefore, the oxide CMP paste cannot be used. Toss A nitride film deposited on a substrate pattern having an oxide film. SUMMARY OF THE INVENTION Accordingly, the present invention discloses a CMP paste having a nitride-to-oxide etch selectivity of N/0>1, and also discloses a combination using A semiconductor device manufactured by the CMP method of the present invention. The present invention discloses a CMP adhesive composition which is selective for a nitride film by changing the pH of the slurry with scaly acid to cause a difference in the polishing rate of the nitride and the oxide film. BRIEF DESCRIPTION OF THE DRAWINGS The CMP slurry disclosed in the following figures will be described below, the method of use thereof and the semiconductor device prepared therewith, wherein: Figure 1 illustrates a graph of the weight ratio of H3P04 versus the pH of the slurry; and Figure 2 illustrates A plot of N/0 selectivity versus pH change in the slurry. DETAILED DESCRIPTION OF THE PREFERRED NUMERICAL EXAMPLES Nitride CMP pastes are selective for nitrides by the inclusion of abrasives and phosphoric acid. Among them, the pH of the slurry ranges from 1 to 5, preferably from 1 to 3, and more preferably from 1 to 2. The amount of the abrasive contained in the CMP slurry is 黏·2 to 2% by weight of the slurry. -5- This paper scale is suitable for HSS standard (CNS) M specification (Cancun 297 public treasure) 1297720 A7 B7 V. Invention description (3) Phosphoric acid addition is 0 01 to 20wt% of the pulp, preferably 0.2 to 10% by weight 0 When the amount of the abrasive in the slurry is less than 0.1 wt〇/〇 of the slurry, the polishing rate cannot reach the predetermined level. When the amount of the abrasive exceeds 20% by weight of the slurry, scratches are easily caused by mechanical factors, and the initial cost of the slurry is increased. In addition, the phosphoric acid polished nitride film is faster than the oxide film. Therefore, the selectivity to the nitride film over the oxide film can be increased by the addition of phosphoric acid. When phosphoric acid is added to the slurry, the pH is maintained between 1 and 5, preferably 1 to 3, more preferably 1 to 2. The pH can be adjusted by using a hydroxyl-containing (-oh) buffer. When the amount of phosphoric acid is less than 0.1% by weight of the slurry, since the phosphoric acid is not produced, the desired low pH and chemical reaction cannot be obtained. When the amount of phosphoric acid exceeds 20% by weight of the slurry, it may cause a negative etching or other chemical reaction that destroys the flattening. The abrasive added to the slurry is a general abrasive. For example, an abrasive containing Ce02, MnO 2, ZrO 2 , Al 2 〇 3 or SiO 2 is used. It is preferred to use an abrasive containing Ce02. Wherein, the particle size of the abrasive material is from about 100 nm to about 500 nm. Preferably, the abrasive is retained in the slurry as a colloidal suspension. When the particle size of the abrasive is less than 100 nm, the polishing rate is lowered to lower the yield. When the average particle diameter of the abrasive exceeds 5 Å, the abrasive is not sufficiently dispersed, thus causing scratches. The viscose is used in the corrugated metal bungee process by using an oxide film. -6- This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 1297720 A7 B7 V. Invention description (4) The termination layer of the dielectric layer in the layer or the automatic alignment contact (abbreviated as SAC) process in the form of a capacitor contact is used for the CMP or patterning process. In addition, when the nitride film to be polished is deposited according to chemical vapor deposition (abbreviated as "CVD") and the CMP process is performed by using the disclosed adhesion, the etching selectivity to the oxide film is lowered. Another object of the present invention is to provide a method for patterning a SiN or SiON film by a CMP process by using the disclosed paste, in particular, a method of applying the disclosed paste to a corrugated metal drain process and forming a capacitor The SAC method is used as the termination layer. The SiO film is formed under the SiN or SiON film. The following is a description of the nitride CMP cohesive disclosed in the following strengths, but it is not limited. The slurry is added by adding deionized water. And phosphoric acid in HS-8005-A9 (Hitachi Chemical) CMP slurry containing Ce02 abrasive. Comparative Example 1 HS_8005-A9 CMP slurry containing 5 wt% Ce〇2 millbase was diluted by adding deionized water. 1 〇L CMP slurry containing 1 wt% Ce〇2, wherein the pH was 8.19 (refer to Fig. 1). Inventive Example 1 0.02 wt% of acid was added to the viscous slurry prepared in Comparative Example 1, wherein pH was It is 3·00 (refer to Fig. 1). Inventive Example 2 0.20% by weight of maleic acid is added It was added to the viscosity of the sample prepared in Comparative Example 1. The pH was 1.97 (refer to Fig. 1). -7 - 1297720 A7 B7 5. Inventive Note (5) Inventive Example 3 0.50% by weight of phosphoric acid was added to the comparative example. In the viscous slurry prepared in 1. The pH was 1.86 (refer to Fig. 1). Inventive Example 4 1.0 wt% of phosphoric acid was added to the viscous slurry prepared in Comparative Example 1, wherein the pH was 1.67 (refer to Fig. 1) Inventive Example 5 5.00 wt% of phosphoric acid was added to the viscous slurry prepared in Comparative Example 1, wherein the pH was 1.18 (refer to Fig. 1). Inventive Example 6 The viscous prepared in Comparative Example 1 and Inventive Examples 1 to 5 The N/O polishing selectivity of the slurry is based on a CMP process using an oxide film such as a high density plasma (HDP) oxide film or an undoped bismuth silicate glass (USG) oxide film, and a nitride film such as electricity. Pulp-enhanced nitride (PEN) film, or low-boiled egg (LPN) film, which is polished at a pressure of 3 psi and a table rotation of 70 rpm. When the amount of phosphoric acid exceeds 〇.50wt% That is, when the pH is lower than 1.86, the N/0 polishing selectivity exceeds 1. On the other hand, when the plasma film is used to lift the nitride film, the selectivity is about 2. The nitride film is polished faster than the oxide film (refer to Fig. 2). As a result, when the amount of phosphoric acid exceeds 〇50% by weight, that is, when the pH is lower than 1.86, the N/0 polishing selectivity exceeds 1. That is, when When the pH is lower than 1.86, the selectivity exceeds 1. On the other hand, when a plasma-lifted nitride film is used, the selectivity is about 2. Means that the nitride film is polished faster than the oxide film (Reference Circle 2) 〇 -8- This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm)