200415220 玫、發明說明： 【I明所屬之技術領域】 本發明係有關於鎢之化學機械性拋光法（CMP)，特別係關 於具有可控制之靜態蝕刻速率之鎢Cmp溶液。鎢CMP研磨漿 係藉由鎢之蝕刻及機械性研磨兩項作用使鎢表面平整化。 在鎢之CMP程序中會有競爭性化學反應發生，其中首要之 化本反應係氧化反應。在氧化過程中，氧化劑係在基材之 表面形成氧化鎢。次要反應係複合反應，在該反應中，複 合劑係將氧化過程中於基材表面所形成之氧化薄膜溶解。 【先前技術】 "由於鎢具有高度之穩定性’故鶴研磨漿必需憑藉強力之 氧化劑。基於此，強氧化劑如卣氧化物，曾被使用及發表 當作鎢研磨漿之氧化劑。舉例而言，strein_人於美國專利 編號5,993,686案内揭示了氧化金屬鹽、氧化金屬複合物、 =金屬氧化酸（如··過乙酸及過琪酸）、鐵鹽（如：靖酸鹽）碗 酉久鹽、乙二胺四乙酸、擰檬酸 ^ 豕以盟鐵Λ化鉀、過氧化氫、 重絡酸4甲、破酸_、溴酸J — ^ f 二虱化二釩及其他相似化合 物、鋁鹽、鈉鹽、钾鹽、銨鹽、 W、、及叙鹽、鱗鹽及並仑本 陽離子鹽類之過氧化物、氯酸鹽、 二 口 ^ 匕鼠紅鹽、稍酸鹽、過 錳鉍鹽、過硫酸鹽及其混合物。200415220 Description of invention: [Technical field to which Iming belongs] The present invention relates to the chemical mechanical polishing method (CMP) of tungsten, and particularly relates to a tungsten Cmp solution having a controllable static etching rate. Tungsten CMP polishing slurry smoothes the surface of tungsten by the two effects of tungsten etching and mechanical polishing. In the CMP process of tungsten, a competitive chemical reaction will occur. The primary chemical reaction is an oxidation reaction. During the oxidation process, the oxidant forms tungsten oxide on the surface of the substrate. The secondary reaction is a composite reaction in which the compound dissolves the oxide film formed on the surface of the substrate during the oxidation process. [Prior art] " Because tungsten has a high degree of stability " crane grinding slurry must rely on a strong oxidant. Based on this, strong oxidants such as thorium oxide have been used and published as oxidants for tungsten slurry. For example, strein_ in US Patent No. 5,993,686 discloses metal oxide salts, metal oxide complexes, metal oxides (such as peracetic acid and perkidic acid), iron salts (such as: phosphonate) bowls Long salt, ethylenediaminetetraacetic acid, citric acid ^ 豕 Iron potassium lanthanide, hydrogen peroxide, complex acid 4A, acid breaking _, bromate J — ^ f divanadium divanate and other similar Compounds, aluminum salts, sodium salts, potassium salts, ammonium salts, W, and Syria salts, scaly salts, and chlorinated cation salts of peroxides, chlorates, two-mouthed ^ dagger rat red salts, slightly acid salts , Permanganese bismuth salt, persulfate and mixtures thereof.
00/cA . ] & 地 ’ Mravic等人於 WO 056號案中揭示其使用之過氧 、乳化虱、鐵氰化鉀、會 鉀、碘酸鉀、溴酸鉀、三氧化- 重、各酉义 .,A 釩、次氯酸、次氯酸鈉、 人鼠S艾鉀、；入鼠鉍鈣、次氯酸鎂、 、 ir λγ ^,ί l r1! §r /u 次鐵及其混合物。此 九、军L化剑如齒乳化物，可與美 、 、土 面進行化學反應而形成 831 83530 200415220 金屬氧化屬。之後’於CMP製程中之研磨漿可去除基 朴制之氧化鎢。以此方式，CMp法即可去除基材 的物質而使基材表面平整化。 力1鎢CMP程序中所使用之含碘酸鹽研磨漿可抑制靜態蝕 J ^序。雖然以碘酸鹽為基礎之研磨漿可成功地抑制靜能 钱刻’但仍有以下不期望之性質：⑴需磨擦力較大之銘顆 粒以去除氧化鎢，但會造成基材表面刮傷；（2)需要用以去 ^典〈週當設備，使之符合已建立之環境法規。⑺研磨裝 與抱光設備接觸會造成設備轉成不期望之黃褐色。 & 乂於美國專利編號5,958,288案中，Muellei^人提及如硝酸 鐵之3鐵氧化劑，可在鐵含量低於3〇⑽時，作為促進 去除鎢之催化劑。這些研磨漿之問題在於鎢之靜態蝕刻乃 為—種常見之副作用。在經CMP程序之後，殘留於基材表 面上 < 金屬研磨漿仍會持續蝕刻基材表面。有時，靜態蚀 刻對於某些半導體整合方案具有利之結果。但於大部分案 例中’減少靜態蝕刻可增進半導體之效能。此外，靜態飿 旬會造成如點蝕及鑰匙孔之類的表面缺陷。這些表面缺陷 會顯著地影響半導體元件之最後性質，並且限制其用途。00 / cA.] &Amp; Di 'Mravic et al. Disclosed in WO 056 the peroxidation, emulsified lice, potassium ferricyanide, potassium, potassium iodate, potassium bromate, trioxide-heavy, various meanings. ., A vanadium, hypochlorous acid, sodium hypochlorite, potassium sulphuric acid in humans and rats; bismuth calcium, magnesium hypochlorite, ir λγ ^, ί l r1! §R / u hypoferrous iron and mixtures thereof. The Nine Army's chemical swords, such as tooth emulsions, can chemically react with the United States, China, and the soil to form 831 83530 200415220 metal oxides. Afterwards, the basic tungsten oxide can be removed by the polishing slurry in the CMP process. In this way, the CMP method can remove the substance of the substrate and flatten the surface of the substrate. The iodate-containing abrasive slurry used in the Li 1 tungsten CMP process can suppress static corrosion. Although the iodate-based abrasive slurry can successfully suppress the static energy, it still has the following undesired properties: ⑴ The particles with larger friction are required to remove tungsten oxide, but it will cause scratches on the surface of the substrate (2) It is necessary to decompose the code of Zhoudang to meet the established environmental regulations. ⑺ Grinding equipment Contact with light-holding equipment can cause the equipment to turn into an undesired tan. & In U.S. Patent No. 5,958,288, Muellei mentioned that a 3 iron oxidant such as iron nitrate can be used as a catalyst to promote the removal of tungsten when the iron content is less than 30 ⑽. The problem with these slurries is that static etching of tungsten is a common side effect. After the CMP process, the residue on the surface of the substrate < metal polishing slurry will continue to etch the surface of the substrate. Sometimes, static etching has a beneficial effect on some semiconductor integration schemes. However, in most cases, 'reducing static etching can improve semiconductor performance. In addition, static weather can cause surface defects such as pitting and keyholes. These surface defects can significantly affect the final properties of semiconductor components and limit their use.
Grumbine等人於美國專利編號6,083,419案中揭示其使用 含氮之氧化劑以控制靜態蝕刻。但就目前所知，這些化合 物對於控制靜態蝕刻之效果有限。就目前之鎢拋光研磨漿 而。’持、纟胃性之需求為快速之鶴去除速率及有限之靜態餘 刻。此外，亦需要一拋光研磨漿，其可之減少因使用含碘 .鹽研磨漿所造成之刮傷、環境污染及外觀問題。 83530 415220 【發明内容】 本發明提供一種使半導體晶圓表面平整化之鎢CMp溶液 "包括一王要氧化劑，其係具有足夠之氧化力以使鎢金屬 乳化成氧化鶴，且該鶴CMP溶液尚具有—靜態#刻速率以 去除鎢金屬；一次要氧化劑，其可降低鎢CMp溶液之靜態 銀刻速率。該次要氧化劑乃選自由溴酸鹽及氯酸鹽組成; 群、、且中，GS5G重量百分比之研磨顆粒；以及剩餘部份之水 及非主要之雜質。 另一万面，本發明提供一種用於使半導體晶圓表面平整 化< 鎢CMP溶液，包括一含鐵之主要氧化劑，其係具有足 夠〈氧化力以使鶴金屬氧化成氧化鸫，且該鎢CMp溶液尚 具有一靜悲蝕刻速率以去除鎢金屬；一用於拋光方法之次 要氧化劑，其可降低紅MP溶液之靜祕刻速率，該次要 氧化剑乃4自由溴酸鹽、氣酸鹽及碘酸鹽組成之群組中；〇 ^重里百刀比之研磨顆粒；以及剩餘部份之水及非主要 之雜質。 【實施方式】 目則所知，次要氧化劑如溴酸鹽、氯酸鹽及碘酸鹽等會 反應形成覆蓋於鎢表面之薄膜，且對鎢拋光溶液及研磨漿 而f亦會形成一有效之抑制物。就本說明書而纟，拋光溶 液乃指水性拋光溶液，纟可包含及不包含研磨料。若拋光 溶液包含研磨料，則該拋光溶液亦為一拋光研磨漿。 泫It光办液藉由一具充分氧化能力之強氧化劑使鎢金屬 氧化成氧化鎢。最佳之情況為，該主要氧化劑乃選自由過 83530 200415220 氧化氫、鐵氰化物、重鉻酸鹽、三氧化二釩、次氣酸、次 氯酸鹽、硝酸鹽、過硫酸鹽、過錳酸鹽、氫氧化物及其組 合物組成之群組中。其它特定之實例包括鐵氰化鮮、鐵氯 化鋼、重鉻酸卸、重絡酸鋼、次氯酸#5、次氯酸抑、次氯 酸鈉、硝酸鉀、硝酸鈉、過錳酸鉀、過錳酸鈉及其組合物 。通常這些主要氧化劑之混合物可更為增加去除速率。該 抛光溶液典型含有總量〇.丨至12重量百分比之主要氧化劑 (就本說明書而言，所有濃度以重量百分比表示，除非有另 外提及）。當添加此類不穩定之主要氧化劑（如過氧化氫）於 拋光溶液時，通常需要於使用時或使用前加入。較佳之情 況為，該拋光溶液典型含有總量〇5至1〇重量百分比之主要 氧化Μ。取佳之情況為，該拋光溶液典型含有總量1至7.5 重量百分比之主要氧化劑。 況4 ’該主要氧化劑含有過氧化氫或-含鐵之 氧化2*取佳 < 情況為，該主要氧化劑為一含鐵氧化劑。 载氧化』即使於低濃度之情況下，仍可提供快速之鶴去 除速率。較佳$丨主 、 @/1^為，添加0.0005至1〇重量百分比之硝酸 鐵’可增加鎢去除诰 曰 佘、年，取佳之情況為，該研磨漿中含有 0.001至8重層""5Γ八^ 刀比之硝酸鐵。此外，拋光溶液中含有2至 •、重气百分广之硝酸鐵，對於形成抑制層更有效。 ^4a舁鎢鍵結形成靜態蝕刻抑制層。該抑制化 合物g在基材表面形 a p 、 成把防止金屬氧化物溶解之表面薄膜 。此屏障可有效地對 斤p ^ ^對於大邵分使鎢表面平整化所需之 知效虱化劑。除 '、y并障薄膜之外，次要氧化劑亦具有充 83530 200415220 分之氧化力以氧化鎢。然而，該次要氧化劑對於總共之鎢 氧化反應貢獻不大。但就含高量硝酸鐵成分之實例而言， 較高濃度之次要氧化劑對於鎢之氧化反應具顯著之貢獻。 對於大部分之主要氧化劑而言，次要氧化劑為溴酸鹽 (Br〇3 )、氯故鹽（CIO3 )或其混合物。但就含鐵主要氧化劑 <落液而言，該次要氧化劑可為溴酸鹽、氯酸鹽、碘酸鹽 或其混合物。但不幸的是，含蛾酸鹽之研磨漿通常有昂貴 之環境處置費用及外觀上變色之缺點。然而，就由硝酸鐵 落液所誘發之高量暗紅褐色而言，此問題較不嚴重。較佳 之h /兄為，固怨粉末狀化合物，可使添加溴酸鹽、氯酸鹽 及破I鹽至搬光溶液及研磨漿更有效率。此類化合物之特 定實例包括鹼金屬，如銨、鉀、鈉等；鹼土性金屬，如鎂 或其它鹽類。鹼性卣化合物較易購得或合成。較佳知情況 為，該固態粉末狀化合物係溴酸鉀（KBr〇3)、氯酸鉀（KC1…) 、碘酸鉀（KI〇3)或其混合物。基於環境之考量，此類鉀化合 物車乂鋼或其匕驗土金屬為佳。此外，亦可在拋光溶液中加 入氯、溴或碘作為基本成分或其他化合物。該主要氧化劑 即會以快速之動力學反應，分別將這些次要氧化劑氧化i 溴酸鹽、氯酸鹽或破酸鹽；由於此類主要氧化劑缺乏將氣 氧化 < 氧化能力，故此動力學並不適用於氟。同樣地，於 鎢氧化之過.中，過氯故鹽、過溴酸鹽及過硤酸鹽會分別 形成氯酸鹽、溴酸鹽及碘酸鹽。 較佳4情況為，該拋光溶液具有低於400埃/分鐘之靜能蝕 刻速率及至少3000埃/分鐘之去除速率。最佳之情況為了該 83530 -10- 200415220 拋光;谷液具有低於2 0 0埃/分鐘的靜態姓别速率及至少4 〇 〇 〇 埃/分鐘的去除速率。控制穩定性所需之次要氧化劑之用量 乃取決於拋光溶液之形式及特定之次要氧化劑。大抵而言 ，金屬撤光溶液中，次要氧化劑之濃度不超過其最大溶解 度。於部分實例中，超過此一濃度將會有固體狀未溶解之 /人要氧化劑顆粒殘留於拋光溶液中。未溶解之次要氧化劑 顆粒可能會干擾拋光溶液之拋光及蝕刻能力。 /人要氧化劑之濃度範圍可為一較小但有效之濃度至其於 特定拋光溶液中之溶解度極限。此次要氧化劑之溶解度極 「 限乃取決於拋光溶液之化學性質。在拋光溶液中，該溶解 度桎限範圍可自1 ·8 wt%至22 wt%。較佳之情況為，該次要 氧化劑濃度範圍自0.0001 ^%至7·5 wt% ;最佳之情況為， 及/入要氧化劑濃度範圍自0.001 Wt%至5 wt%。當拋光溶液中 ^有相對多量之硝酸鐵（2至7·5 wt%)時，該拋光溶液較佳之 情況為含有〇· 1至5 wt%之次要氧化劑。 Ο 視=況而定，該拋光溶液含有0至50 Wt%之研磨顆粒；較 {之h /兄為，戒拋光溶液含有0至30 wt%之研磨顆粒；最佳 2情況為，該拋光溶液含有〇至25^%之研磨顆粒。當該研 磨顆粒存在時，氧化鎢層即被機械式去除。可被接受之 磨顆粒實例包括下述：氧化銘、三氧化二錦、鑽石、氧化 H ^氧切、碳切、四氮化三碎、二氧化鈥或其組合 :較佳之情況為，該研磨顆粒為氧化鋁或二氧化矽；最 佳之情況為，該研磨顆粒為二氧切。此外，該研磨顆： 〈平均顆粒大小較佳之情況為低於250 nm;最佳之情沉為 83530 -11 - 200415220 ，該平均顆粒大小為低於1 5 0 nm ° 若拋光溶液中不含研磨顆粒，則較佳之情況為使用一固 定式之研磨墊。最佳之情況為，不含研磨顆粒之溶液僅使 用一聚合物墊，合併使用更為強效之主要氧化劑。 此外’该抛光落液視情況而定含有一複合劑以寶助鷂之 去除。當存在時，典型之複合劑為一羧酸，其可將氧化鶴 自基質上除去。舉例而言，可被接受之複合劑包括下述： 丙二酸、乳酸、磺基水楊酸（SSA)、甲酸、乙酸、丙酸、丁 酸、戊酸、己酸、庚酸、辛酸、壬酸及其混合物。典型之 拋光溶液可含有0至15 wt%之複合劑。最佳之情況為，該拋 光落液可含有0.5至5 wt°/〇之複合劑。某種狀況下，例如拋光 溶液中不含過氧化氫時，複合劑則不可或缺。 水溶液狀之拋光溶液含有剩餘之水及非必要之雜質。最 佳< h况為，琢水為去離子水。其次，該水溶液狀拋光溶 液可於酸性或鹼性pH值下操作。較佳之情況為，該拋光溶 液於酸性PH值下操作。最佳之情況為，該拋光溶液於？11值Grumbine et al., U.S. Patent No. 6,083,419, disclose the use of nitrogen-containing oxidants to control static etching. However, to date, these compounds have limited effectiveness in controlling static etching. For the current tungsten polishing slurry. The requirements for sustained and stomach-sucking properties are fast crane removal rate and limited static margin. In addition, a polishing slurry is also needed, which can reduce the scratches, environmental pollution and appearance problems caused by the use of iodine.salt-containing polishing slurry. 83530 415220 [Summary of the invention] The present invention provides a tungsten CMP solution for flattening the surface of a semiconductor wafer. The solution includes a primary oxidant, which has sufficient oxidizing power to emulsify tungsten metal into an oxide crane, and the crane CMP solution. It still has a -static # engraving rate to remove tungsten metal; a secondary oxidant, which can reduce the static silver engraving rate of tungsten CMP solution. The secondary oxidant is selected from the group consisting of bromate and chlorate; abrasive particles of GS5G by weight; and the remaining part of water and non-major impurities. On the other hand, the present invention provides a tungsten wafer CMP solution for flattening the surface of a semiconductor wafer. The tungsten CMP solution includes a main oxidizing agent containing iron, which has sufficient oxidizing power to oxidize crane metal to thorium oxide, and the Tungsten CMP solution still has a quiet etching rate to remove tungsten metal; a secondary oxidant used in the polishing method, which can reduce the quiet engraving rate of the red MP solution, the secondary oxidation sword is 4 free bromate, gas In the group consisting of acid salts and iodates; grinding particles with a weight ratio of 100 to 100 knives; and the remainder of water and non-major impurities. [Embodiment] At present, it is known that secondary oxidants such as bromate, chlorate and iodate will react to form a thin film covering the surface of tungsten, and will also form an effective solution for tungsten polishing solutions and grinding slurry. Its inhibitor. For the purposes of this specification, polishing solutions refer to aqueous polishing solutions, which may and may not include abrasives. If the polishing solution contains abrasives, the polishing solution is also a polishing slurry.泫 It light solution oxidizes tungsten metal to tungsten oxide by a strong oxidant with sufficient oxidation ability. In the best case, the main oxidant is selected from the group consisting of hydrogen oxide, ferricyanide, dichromate, vanadium trioxide, hypochlorous acid, hypochlorite, nitrate, persulfate, and permanganese. Acid, hydroxide, and combinations thereof. Other specific examples include ferricyanide, ferric chloride steel, dichromic acid unloading, heavy acid steel, hypochlorous acid # 5, hypochlorous acid, sodium hypochlorite, potassium nitrate, sodium nitrate, potassium permanganate, Sodium manganese and its composition. Mixtures of these primary oxidants usually increase the removal rate even more. The polishing solution typically contains a total of 0.1 to 12 weight percent of the primary oxidant (for the purposes of this specification, all concentrations are expressed in weight percent unless otherwise mentioned). When adding such unstable primary oxidants (such as hydrogen peroxide) to the polishing solution, it is usually necessary to add it during or before use. Preferably, the polishing solution typically contains the main oxide M in a total amount of 05 to 10% by weight. Preferably, the polishing solution typically contains a total of 1 to 7.5 weight percent of the main oxidant. Case 4 'The main oxidant contains hydrogen peroxide or -iron-containing oxidation 2 * is preferred < The case is that the main oxidant is an iron-containing oxidant. Carrier Oxidation can provide fast crane removal rate even at low concentrations. The best $ 丨 main, @ / 1 ^ is that adding 0.0005 to 10 weight percent of ferric nitrate can increase the removal of tungsten. The best case is that the slurry contains 0.001 to 8 heavy layers. &Quot; & quot 5Γ eight ^ knife ratio of iron nitrate. In addition, the polishing solution contains 2 to • ferrous nitrate with a wide range of heavy gas, which is more effective for forming the suppression layer. ^ 4a rhenium tungsten bond forms a static etch suppression layer. The inhibitory compound g forms a p on the surface of the substrate to form a surface film that prevents the metal oxide from dissolving. This barrier can effectively prevent the ps ^ ^ ^ ^ ^ ^ ^ ^ ^ required to level the surface of the tungsten phlegmatizing agent. In addition to the ', y, and barrier films, the secondary oxidant also has an oxidizing power of 83530 200415220 to oxidize tungsten. However, this secondary oxidant did not contribute much to the total tungsten oxidation reaction. However, in the case of high iron nitrate content, higher concentrations of secondary oxidants have a significant contribution to the oxidation reaction of tungsten. For most primary oxidants, the secondary oxidant is bromate (BrO3), chlorate (CIO3), or a mixture thereof. However, in the case of the iron-containing primary oxidant < drip liquid, the secondary oxidant may be bromate, chlorate, iodate, or a mixture thereof. Unfortunately, mothate-containing abrasives often have the disadvantages of expensive environmental disposal costs and discoloration in appearance. However, this problem is less severe in terms of the high amount of dark reddish brown that is induced by the fall of ferric nitrate. The better h / brother is that the solid compound can make the addition of bromate, chlorate, and broken salt to the polishing solution and grinding slurry more efficient. Specific examples of such compounds include alkali metals such as ammonium, potassium, sodium and the like; alkaline earth metals such as magnesium or other salts. Basic amidine compounds are more readily available or synthetic. Preferably, the solid powdery compound is potassium bromate (KBr03), potassium chlorate (KC1 ...), potassium iodate (KI03), or a mixture thereof. Based on environmental considerations, this type of potassium compound Che steel or earth metal is preferred. In addition, chlorine, bromine or iodine may be added to the polishing solution as a basic ingredient or other compound. The primary oxidant will react with rapid kinetics, respectively, to oxidize these secondary oxidants, i.e. bromate, chlorate, or broken salt; because such primary oxidants lack the ability to oxidize gas < Not suitable for fluorine. Similarly, during the oxidation of tungsten, perchlorate, perbromide and perrhenate will form chlorate, bromate and iodate, respectively. Preferably, the polishing solution has a static energy etching rate of less than 400 angstroms / minute and a removal rate of at least 3000 angstroms / minute. The best case is for this 83530-10-200415220 polishing; the valley fluid has a static surname rate below 200 Angstroms / minute and a removal rate of at least 4,000 Angstroms / minute. The amount of secondary oxidant required to control stability depends on the form of the polishing solution and the specific secondary oxidant. In general, the concentration of the secondary oxidant in the metal stripping solution does not exceed its maximum solubility. In some cases, above this concentration, solid undissolved / required oxidant particles will remain in the polishing solution. Undissolved secondary oxidant particles can interfere with the polishing and etching capabilities of the polishing solution. The concentration of the desired oxidant may range from a small but effective concentration to its solubility limit in a particular polishing solution. This time, the solubility of the primary oxidant is limited by the chemical properties of the polishing solution. In the polishing solution, the solubility limit can range from 1 · 8 wt% to 22 wt%. Preferably, the concentration of the secondary oxidant The range is from 0.0001 ^% to 7.5 wt%; the best case is that the concentration of the oxidant is from 0.001 Wt% to 5 wt%. When the polishing solution contains a relatively large amount of iron nitrate (2 to 7 · 5 wt%), the polishing solution preferably contains a secondary oxidant in the range of 0.1 to 5 wt%. 〇 As the case may be, the polishing solution contains 0 to 50 Wt% of abrasive particles; / Brother, the polishing solution contains 0 to 30 wt% of abrasive particles; best case 2 is that the polishing solution contains 0 to 25 ^% of abrasive particles. When the abrasive particles are present, the tungsten oxide layer is mechanically Examples of acceptable abrasive particles include the following: oxidized oxide, trioxide, diamond, oxidized H ^ oxygen cut, carbon cut, tetranitride, trioxide, or a combination thereof: preferably, The abrasive particles are alumina or silicon dioxide; optimally, the abrasive particles are In addition, the abrasive particles are: <The average particle size is preferably less than 250 nm; the best case is 83530 -11-200415220, and the average particle size is less than 150 nm. If the polishing solution does not contain For abrasive particles, it is better to use a fixed abrasive pad. The best case is to use only a polymer pad for the solution without abrasive particles, and use a more powerful primary oxidant in combination. The liquid, as the case may be, contains a complexing agent to remove it. The typical complexing agent, when present, is a carboxylic acid, which can remove the oxidized crane from the substrate. For example, acceptable complexing agents include The following: malonic acid, lactic acid, sulfosalicylic acid (SSA), formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, caprylic acid, nonanoic acid, and mixtures thereof. Typical polishing solutions are Contains 0 to 15 wt% of the complexing agent. The best case is that the polishing liquid may contain 0.5 to 5 wt ° / o of the complexing agent. Under certain conditions, such as when the polishing solution does not contain hydrogen peroxide, the compounding agent is compounded. An agent is indispensable. Contains residual water and non-essential impurities. The best condition is that the water is deionized water. Secondly, the aqueous polishing solution can be operated at acidic or alkaline pH. Preferably, the polishing The solution is operated at an acidic pH. In the best case, the polishing solution is at a value of? 11.
低万、6下“作。將次要氧化物混合於拋光溶液後，溶液之pH 值係以傳統之方法測量；調整時，可添加鹼，域氧化銨 •’或無機酸，如硝酸。硝酸與硝酸鐵合併使用日寺，可進一 步促進去除速率。 實例 设氯酸"甲係以不同重量百分比添加至鎢抛光研磨漿中。表I 提供鎢拋光研磨漿之組成。 83530 415220 硝酸鐵 丙二酸 乳酸 〃嗔基水楊_ 所得研磨漿之pH值以 表I ^1_磨漿於水 過氧化氫 4 Wt 〇/〇Low ten thousand, 6 times "operation. After mixing the secondary oxides in the polishing solution, the pH value of the solution is measured by traditional methods; when adjusting, alkali, ammonium oxide • or inorganic acids such as nitric acid can be added. Combined with ferric nitrate, the use of Risi can further promote the removal rate. For example, chloric acid is added to the tungsten polishing slurry in different weight percentages. Table I provides the composition of the tungsten polishing slurry. 83530 415220 Iron nitrate propylene diamine The pH value of the obtained grinding slurry is shown in Table I. ^ 1_Refining slurry in water hydrogen peroxide 4 Wt 〇 / 〇
〇·〇 1 wt % 0.07 wt % 1.5 wt % 0.01 wt 碉整至約3。之後 所得之 隨時間 1一严4足主约3 〇 研磨聚乃藉由CMP進行標準鎢基質之測量美W戶厣、7厂、 ^及抛先。丨思時間a子又。厚度改變量對蝕刻時間作圖，並量叫並 斜率以決定_速率。靜態㈣速率之數據如表η所示4 —^~ 鹤金屬拖光研磨漿 在pH值為3且含氯酸卸飯刻 r _聲態蝕刻速率（埃/分鐘） 0 ----- 340 0.01 200 0.1 126 —l—--- 70 /… /。鼠毆鉀研磨漿溶液$顯著減少鵠〇 · 〇 1 wt% 0.07 wt% 1.5 wt% 0.01 wt Rounded to about 3. After that, the obtained grinding time is about 30%. The grinding poly is measured by CMP with a standard tungsten matrix. U.S.A., No.7, No.7, and No.1.丨 Think time a child again. The amount of thickness change is plotted against the etch time and the amount is called the slope to determine the rate. The static radon rate data are shown in Table η. 4 — ^ ~ Crane metal topping polishing slurry at pH 3 and chloric acid-containing rice etcher _ Acoustic etching rate (Angstroms / minute) 0 ----- 340 0.01 200 0.1 126 —l —--- 70 /… /. Significant reduction in rodent potassium slurry solution
C 之靜態蝕刻麥略# r ^ 除速率。此外，增加氯酸鉀吁進一步提高溶 液:淨二蝕刻抑制能力（欲達到200埃/分鐘之靜態蝕刻速率 而氯i鉀精確量係取決於特定之研磨漿）。舉例而言， 83530 ' 13 - 200415220 相較於較為驗性之研磨漿溶液，一種使用氯 & a 性研磨漿溶液需要不同濃度之次要抑制劑以降低靜態姓刻 速率至200埃/分鐘以下。 Χ 添加一種選自由溴酸鹽、氯 之次要氧化劑可提供一同時具 I虫刻之鎢拋光溶液。此外，該 碘酸鹽研磨漿相關之表面刮傷 鹽或其混合物之拋光溶液可消 觀問題。 ❹組成之群組中 有快速鎢去除率及有限靜態 抛光溶液可排除與傳統式含 。最後’含有溴酸鹽、氯酸 除與碘酸鹽相關之環境及外 83530 14-C's static etching rate is slightly higher. In addition, the addition of potassium chlorate calls for a further increase in the solution: net second etch suppression capability (to achieve a static etch rate of 200 Angstroms / minute, and the exact amount of potassium iodide depends on the specific polishing slurry). For example, 83530 '13-200415220 Compared with the more experimental slurry solution, a chlorine & a slurry slurry solution requires different concentrations of secondary inhibitors to reduce the static engraving rate below 200 Angstroms / minute. . Χ Adding a secondary oxidant selected from bromate and chlorine can provide a tungsten polishing solution with simultaneous I engraving. In addition, the surface scratches associated with the iodate abrasive slurry or a polishing solution of a mixture thereof can obviate the problem. The group consisting of thorium has fast tungsten removal rate and limited static polishing solution, which can be excluded from the traditional type. Finally, it contains bromate and chloric acid. In addition to the environment related to iodate, 83530 14-