200536930 九、發明說明： 【發明所屬之技術領域】 發明領域 本發明係關於用於拋光半導體薄層之二氧化鈽游激， 5其具有良好分散液安定性及絕佳拋光效能而不會產生刮 痕。 【先前技術】 發明背景 水性二氧化鈽（鈽氧化物）淤漿廣用於半導體薄層或絕 1〇緣溥層之化學機械拋光(CMP)，但習知二氧化鈽淤漿之缺點 為二氧化鈽粒子於長期儲存期間沉降，而當再度分散時附 ♦，因而產生大型粒子。如此曾經多方面嘗試借助於分散 劑及分散裝置來改良二氧化鈽淤漿之分散安定性。 晚近隨著形成於半導體層上之互連電路圖案的縮小， 15以及半導體晶片間之間隙的縮小，也需開發不會產生刮痕 之二氧化鈽淤漿。日本專利公開案第2003-171653號提示一 種二氧化鈽淤漿，包含粒子大小大於3微米之含量低於1〇/。 之二次二氧化鈽粒子，但此種淤漿仍然產生刮痕，不適合 用於拋光小於0.16微米之狹窄線寬之晶圓顯微圖案。 20 因此，需要由二氧化鈽拋光淤漿中完全去除造成產生 刮痕之磨姓性粒子，晚近顯示即使具有粒子大小大於7〇〇奈 米特別大於1微米之微量粒子，實際上仍然於晶圓表面產生 刮痕。 就此方面而言，曰本專利公開案第2003-188122號提示 200536930 一種二氧化鈽淤漿包含具有體積平均粒子大小為1至95奈 米之磨姓粒子，纟中大小大於0.56微米之粒子之存在濃: 低於100,000/1毫升。但此種〉於浆由於磨钱粒子過度微細而 有拋光速率低及平面化特性不良等問題。 5 【明内】 發明概要 如此，本發明之主要目的係提供一種二氧化飾游漿， 其包含顯著較低濃度之大型粒子，因而具有良好分散液安 定性，絕佳拋光效能特性，可有利地用於半導體元件及電 10 致發光元件之CMP(化學機械拋光）。 根據本發明之一方面，提供一種用於拋光一半導體薄 層之二氧化鈽水性淤漿，包含具有平均體積粒子大小由0.1 被米至0.2微米之範圍之二氧化飾粒子，及其係特徵在於當 於施加平均離心力（g)= 1，970 go經歷2分鐘時間離心(g0為重 15 力加速度）時，固型物含量減少20%重量比或以下。 I：實施方式3 較佳實施例之詳細說明 本發明拋光二氧化鈽淤漿之特徵在於當其置於施加平 均離心力（g)=l，970 g〇 (g〇=重力加速度；9.8米/秒平方）下離 20 心2分鐘時，固型物含量之減少量為20 wt°/〇或以下，如此實 質上不含具有平均粒子大小大於0.7微米之二氧化鈽粒 子，該等粒子於形成線寬小於0.16微米之顯微圖案之基材 上可產生刮痕。 根據本發明，二氧化鈽淤漿具有藉鐳射散射粒徑分布 200536930 分析器測得之平均__^心 D】00於0.5至0.7微米之範圍 “乾圍’以及 成賴諸之粒子大小（亦心°：^於粒徑分布累加值變 徑）。 、水中存在之最大粒子之粒 5 10 15 本發明之二氧化鈽水性 斤 ΚΙ於漿之製備方法，可經由將二 乳化鈽粉末分散於水，然後#心所 、 前文定義之㈣之固型物含旦 7 P W漿’至如 .μ "里減少改變至變成低於20 wt% 局止。 :二首先’二氧化鈽粉末根據任一種習知程序，例 水至約。一叫 末，或以習知程序製傷，及2^=粉末可為市售粉 燒碳酸飾、氫氧化鈽、硝酸鈽 =至900 c假 氣化辅，#s W 乳化飾或乙酸錦來獲得二 乳化飾，使用減錢絲粉化如此所狀 得具有平均粒子直徑為10 乳化鈽’獲 與研磨過程可以相反順序進行。”—减_末。炮燒 較佳使时散劑_二氧化m 鈽淤漿呈有pH 4至όΗ Q 、、°果所侍二氧化 水八有ΡΗ 4至ρΗ 9。分散劑可基於二氧化飾 面位能值選用，較佳係使用陰離子性化合物。分=之表 表例為聚(丙稀酸)、聚(乙稀基硫酸)、聚(甲基丙二:;之： 丙烯醯胺及聚芳基胺。分散劑之重量平均旦▲)、-ι，〇〇〇至寧0。若分子量係小於1G()()，貞 里較佳為 不穩定；而若分子量大於5_，則二氧 鈽游襞變 過高而無法獲得良好儲存安定性。基於使用之點度變 氧化鈽， 20 200536930 分散劑可為0.1至10 Wt%範圍之習知用量。當分散劑含量低 於0.1 wt%時，淤漿之安定性變差；而當分散劑含量高於10 wt%時，未黏著之分散劑留在淤漿而使淤漿之儲存安定性 變差。 5 根據本發明，隨後如此均句分散之二氧化鈽淤漿接受 離心程序。本發明中，二氧化鈽淤漿係於數千rpm較佳為 1，000至5,000 rpm，來強制去除具有粒徑大於700奈米之相 對大型粒子。離心可使用圓柱形離心機進行，游漿通過圓 • 柱形離心機之方式為淤漿被填裝於底部，然後由旋轉離心 10 機頂部通風，來強制淤漿内存在的相對大尺寸粒子沾黏於 離心機之内側壁上。 二氧化鈽淤漿離心至如前文說明，於規定之離心條件 下，具有固型物含量減少變化為20 wt%或以下，較佳10 wt% 或以下為止。本發明定義之固型物含量變化值，允許評比 15 存在於具有相同平均體積粒徑之該指定兩種淤漿之大型粒 子之相對含量。 • 如此離心之淤漿若有所需可進一步以習知方式使用過 渡器過濾、。 可滿足前述固型物含量變化要求之本發明淤漿，具有 20 絕佳長期儲存安定性，如此可防止粒子的附聚，且於拋光 過程減少產生之刮痕量達90%或以上；此外本發明淤漿具 有平均粒子大小足夠以良好拋光生產力拋光基材。因此， 本發明淤漿可有利地用於晶圓之CMP製程，用來形成具有 低於0.16微米之窄線寬之顯微圖案，以及用於中間層絕緣 200536930 膜或淺溝槽隔離(STI)之CMP。 本發明將於下列實施例進一步舉例說明，但該等實施 例絕非意圖囿限本發明之範圍。 製備例1 :二氧化鈽粉末之製備 5 氫氧化鈽於75〇°c氧化獲得二氧化鈽粉末，二氧化鈽粉 末使用球磨機研磨獲得使用XRD(X光繞射）分析器測量具 有平均粒子直徑約4〇奈米之二氧化鈽粉末。 製備例2 :抛光層之製備 二氧化矽層根據PE-TEOS(電漿加強式原矽酸四乙酯） 10方法形成於8忖石夕晶圓上之10，_埃厚度而獲得抛光層。 製備例3 :二氧化鈽淤漿之製備 8〇〇克製備例1所得之二氧化鈽粉末分散於9,26〇克去 離子水，使用槳葉授拌器㈣3〇分鐘，獲得二氧化飾水性 懸浮液。20克分散劑含有濃度40 wt%，重量平均分子量 15 3，_之聚（丙稀酸），以攪拌添加至如上所得二氧化飾懸浮 液。反應期間使用不含強驗離子之水性氨或水性瑣酸稀釋 而維持洛液之pH於4-8。所得溶液於2〇〇 Mpa壓力下，使用 问壓可濕潤分散裔製作為游襞而獲得8二氧化飾於裝。 盘漿之製備 20 實施例1 製備例3所得二氧化鈽淤漿經由圓柱形離心機，以 1，500 rpm速度旋轉離心，添加去離子水至其中而獲得5 根據本發明之二氧化鈽於漿。 實施例2 9 200536930 重複實施例1之程序，但轉速改變為2,000 rpm，獲得5 wt%二氧化鈽拋光淤漿。 實施例3 重複如上貫施例1之程序，但所得二氧化飾於浆於離心 5後進一步通過1微米過渡器過滤，獲得5 wt%二氧化飾拋光 淤漿。 比較例1 製備例3所得二氧化鈽於漿單純於去離子水稀釋，未經 離心’獲得5 wt%二氧化鈽拋光淤漿。 10 比較例2 製備例3所得二氧化鈽淤漿經3微米過濾器過濾，未經 邊“且以去離子水稀釋，獲得5 wt%二氧化飾拋光於毁。 比較例3 :二氧化鈽粉末之製備 氫氧化鈽於65(TC氧化獲得二氧化鈽粉末，二氧化鈽粉 15末使用球磨機研磨獲得使用X RD (X光繞射）分析器測量具 有平均粒子直徑約25奈米之二氧化鈽粉末。二氧化鈽粉末 如製備例3製作為游装，及離心與稀釋而獲得5 wt%二氧化 鈽拋光淤漿。 里型物含量之ϋ 20 貝施例1之二氧化鈽淤漿於各種條件下離心測試，來測 疋固型物含1^之變化（固型物含量降低程度，Wt%)，試驗結 果顯示於表1。 10 200536930 表1200536930 IX. Description of the invention: [Technical field to which the invention belongs] Field of the invention The present invention relates to osmium dioxide migration for polishing semiconductor thin layers. 5 It has good dispersion stability and excellent polishing performance without generating scratches. mark. [Prior Art] Background of the Invention Water-based hafnium dioxide (hafnium oxide) slurry is widely used in chemical mechanical polishing (CMP) of semiconductor thin layers or insulating edges. However, the disadvantages of conventional hafnium dioxide slurry are two. Hafnium oxide particles settle during long-term storage, and when re-dispersed, they form large particles. In this way, many attempts have been made to improve the dispersion stability of the rhenium dioxide slurry by means of a dispersant and a dispersing device. Recently, as the interconnection circuit patterns formed on the semiconductor layer have been reduced, and the gap between semiconductor wafers has been reduced, it is also necessary to develop a hafnium dioxide slurry that does not cause scratches. Japanese Patent Laid-Open No. 2003-171653 suggests a rhenium dioxide slurry containing a particle size greater than 3 microns and a content of less than 10 /. Secondary hafnium dioxide particles, but this slurry still produces scratches, and is not suitable for polishing wafer micropatterns with narrow line widths less than 0.16 microns. 20 Therefore, it is necessary to completely remove the abrasive particles that cause scratches from the polishing slurry of hafnium dioxide, and it has recently been shown that even with trace particles with a particle size greater than 700 nm and particularly greater than 1 micron, they are actually still on the wafer. Scratches on the surface. In this regard, Japanese Patent Publication No. 2003-188122 reminds 200536930 that a plutonium dioxide slurry contains particles having a volume average particle size of 1 to 95 nanometers, and the presence of particles larger than 0.56 microns in the puppet. Concentrate: less than 100,000 / 1 ml. However, this kind of slurry has problems such as a low polishing rate and poor planarization characteristics due to excessively fine particles of money. 5 [Mei Nai] Summary of the Invention In this way, the main purpose of the present invention is to provide a diluent decorative slurry, which contains large particles with a significantly lower concentration, so it has good dispersion stability, excellent polishing performance characteristics, and can be advantageously used. CMP (chemical mechanical polishing) for semiconductor devices and electroluminescent devices. According to one aspect of the present invention, there is provided an aqueous osmium dioxide slurry for polishing a semiconductor thin layer, which includes dioxide decorative particles having an average volume particle size ranging from 0.1 μm to 0.2 μm, and is characterized in that: When the average centrifugal force (g) = 1,970 go is applied for 2 minutes, centrifugation (g0 is a 15-force acceleration of weight), the solid content is reduced by 20% by weight or less. I: Detailed description of the preferred embodiment 3 The polishing osmium dioxide slurry of the present invention is characterized in that when it is placed under an average centrifugal force (g) = 1,970 g0 (g0 = acceleration of gravity; 9.8 m / s) (Square) When the core is removed from the center for 2 minutes, the reduction of solid content is 20 wt ° / 0 or less, so it does not substantially contain thorium dioxide particles with an average particle size greater than 0.7 microns. These particles form a line Scratches can occur on substrates with micropatterns less than 0.16 microns wide. According to the present invention, the thorium dioxide slurry has an average __ ^ heart D as measured by a laser scattering particle size distribution 200536930 analyzer. 00 is in the range of 0.5 to 0.7 micrometers, "dry circumference" and the size of the particles (also Heart °: ^ in the particle size distribution cumulative value reduction), the largest particles in water 5 10 15 The preparation method of the water-soluble osmium dioxide of the present invention in the pulp can be obtained by dispersing the di-emulsified hydration powder in water , And then # 心 所, the previously defined solid content containing 7 PW pulp 'to such as .μ " in the reduction and change to become less than 20 wt% limit.: Two first' Plutonium dioxide powder according to any Known procedures, examples of water to about. One is called the end, or wounds by conventional procedures, and 2 ^ = powder can be commercially available powder burning carbonic acid decoration, osmium hydroxide, osmium nitrate = to 900 c false gasification auxiliary, #s W Emulsified ornament or acetic acid bromide to obtain the second emulsified ornament, using minus silk to pulverize it so that it has an average particle diameter of 10. Emulsification can be performed in the reverse order of the grinding process. "— MIN_END. Burning is preferred to make the time-dispersing agent _ dioxide m 钸 slurry pH 4 to 至 Η Q, ° 所 侍 所 所 所 所 所 所 所 至 4 to ρ Η 9. The dispersant can be selected based on the surface energy value of the dioxide, and an anionic compound is preferably used. The table of points = Table examples are poly (acrylic acid), poly (ethylene sulphuric acid), poly (methyl propylene diamine :; of: acrylamide and polyarylamine. The average weight of the dispersant ▲), -ι, 〇〇〇 至 宁 0. If the molecular weight is less than 1G () (), it is preferably unstable; and if the molecular weight is more than 5_, the dioxin migration becomes too high to obtain good storage stability. Based on the degree of osmium oxide used, 20 200536930 dispersants can be used in conventional amounts ranging from 0.1 to 10 Wt%. When the content of the dispersant is less than 0.1 wt%, the stability of the slurry becomes poor; and when the content of the dispersant is more than 10 wt%, the non-adhesive dispersant remains in the slurry, which makes the storage stability of the slurry worse. . 5 According to the present invention, the homogeneous dispersed rhenium dioxide slurry is then subjected to a centrifugation procedure. In the present invention, the thorium dioxide slurry is at several thousands rpm, preferably 1,000 to 5,000 rpm, for forcibly removing relatively large particles having a particle size larger than 700 nm. Centrifugation can be performed using a cylindrical centrifuge. The slurry is filled in the bottom through a circular column centrifuge. The top of the centrifuge is then vented to force the relatively large particles in the slurry to contaminate. Stick to the inside wall of the centrifuge. Centrifuging the dysprosium dioxide slurry as described above, under the specified centrifugation conditions, the solid content content changes to 20 wt% or less, preferably 10 wt% or less. The change value of the solid content as defined in the present invention allows to evaluate the relative content of large particles existing in the specified two slurries having the same average volume particle size. • If necessary, the slurry thus centrifuged can be further filtered by conventional means, such as using a transit filter. The slurry of the present invention, which can meet the requirements for the change of the solid content, has an excellent long-term storage stability of 20, which can prevent agglomeration of particles and reduce the amount of scratches generated during the polishing process by 90% or more; The inventive slurry has an average particle size sufficient to polish a substrate with good polishing productivity. Therefore, the slurry of the present invention can be advantageously used in the CMP process of wafers, used to form micropatterns with narrow line widths below 0.16 microns, and used for interlayer insulation 200536930 film or shallow trench isolation (STI) CMP. The invention is further illustrated by the following examples, but these examples are by no means intended to limit the scope of the invention. Preparation Example 1: Preparation of Hafnium Dioxide Powder 5 Hafnium Hydroxide was oxidized at 75 ° C to obtain Hafnium Dioxide powder, and Hafnium Dioxide powder was ground using a ball mill to obtain an XRD (X-Ray Diffraction) Analyzer. 40nm osmium dioxide powder. Preparation Example 2: Preparation of a Polishing Layer A silicon dioxide layer was formed on a 10-angstrom-thickness wafer on an 8-stone wafer according to a PE-TEOS (plasma-reinforced tetraethyl orthosilicate) 10 method to obtain a polishing layer. Preparation Example 3: Preparation of 800 g of dysprosium dioxide slurry. The dysprosium dioxide powder obtained in Preparation Example 1 was dispersed in 9,260 g of deionized water. The paddle blender was used for 30 minutes to obtain a water-dioxide decorative finish. suspension. 20 g of the dispersant contained a poly (acrylic acid) having a concentration of 40 wt% and a weight average molecular weight of 15 3, and were added with stirring to the above-mentioned dioxide suspension. During the reaction, dilute with aqueous ammonia or aqueous acid without strong test ions to maintain the pH of the Luo solution at 4-8. The obtained solution was produced as a peregrine falcon using a pressure-wettable dispersant at a pressure of 200 Mpa to obtain 8 dioxide decoration. Preparation of Dish Pulp 20 Example 1 The osmium dioxide slurry obtained in Preparation Example 3 was centrifuged at 1,500 rpm through a cylindrical centrifuge, and deionized water was added to obtain 5 osmium dioxide in the slurry according to the present invention. . Example 2 9 200536930 The procedure of Example 1 was repeated, but the rotation speed was changed to 2,000 rpm to obtain a 5 wt% hafnium dioxide polishing slurry. Example 3 The procedure of Example 1 was repeated as above, but the obtained dioxide decoration was centrifuged at 5 and further filtered through a 1 micron transitioner to obtain a 5 wt% slurry for polishing the decoration. Comparative Example 1 The osmium dioxide slurry obtained in Preparation Example 3 was simply diluted with deionized water, and a 5 wt% osmium dioxide polishing slurry was obtained without centrifugation '. 10 Comparative Example 2 The ytterbium dioxide slurry obtained in Preparation Example 3 was filtered through a 3 micron filter, and the edge was diluted with deionized water to obtain 5 wt% of the titanium dioxide polishing and polishing. Comparative Example 3: ytterbium dioxide powder Preparation of thorium hydroxide at 65 (TC oxidation to obtain thorium dioxide powder, 15 thorium dioxide powder was ground using a ball mill to obtain thorium dioxide with an average particle diameter of about 25 nm measured using an X RD (X-ray diffraction) analyzer. Powder. The osmium dioxide powder is prepared as a package as in Preparation Example 3, and is centrifuged and diluted to obtain a 5 wt% osmium dioxide polishing slurry. The content of the content is 20%. The osmium dioxide slurry of Example 1 is used in various Centrifugal test under the conditions to measure the change in solid content of 1% (solid content reduction, Wt%), the test results are shown in Table 1. 10 200536930 Table 1
拋光淤號性質之評屮 實施例1至3及比較例1至3之淤漿使用粒徑分布分析器 5 LA910(日本堀場(Horiba))檢驗，結果顯示於表2。 此外，為了檢驗長期儲存期間可附聚之粒子含量，實 施例1至3及比較例1至3之拋光淤漿使用管狀離心機（漢尼 爾（Hanil)科學工業公司MP 80，韓國）接受離心測試，來去 除沉澱粒子，及測定固型物含量之變化。 10 特別，40毫升各5 wt%一氧化鈽游漿經稱重，填裝入高 11.5厘米體積50毫升之試驗管内，於4,000 rpm(離心機中2 至試驗管底部距離變成14厘米，離心機中軸之試驗管頂部 距離變成2.5厘米，如此施加於於漿之離心力變成i，97〇 g〇) 離心2分鐘，而獲得上清液，上清液經稱重測定於漿之固型 15物含量變化之重量百分比。結果顯示於表2。當存在於淤漿 之相對大型粒子數量增加時，固型物含量變化增加，亦即 藉離心去除之粒子數量以wt%表示為增加。 此外，使用實施例1至3及比較例1至3所得之個別二氧化 鈽淤漿，製備例2所得拋光層使用蜜拉（Mirra)設備（美國 2〇 AMAT公司品)拋光，蜜拉設備為8吋晶圓用CMP拋光機，具 有IC1000/suba IV堆疊襯墊(美國羅德(Rodel)公司產品)於3.5 11 200536930 psi壓力下進行拋光90秒。拋光淤漿係以150毫升/分鐘之速率 進給，上板離心速率為104 rpm，下板離心速率為110 rpm。 拋光後於層上生成尺寸大於0.16微米之刮痕數目使用 AIT-XP(美國KLA天工（Tenco)公司產品）測定，拋光量使用 5 熱波光學探針(Therma-wave Optiprobe) 300系歹》J(美國熱波 公司產品）測定。結果也列舉於表2。 表2 平均粒徑 (奈米） 固型物含量 降低wt% 刮痕數目 (數目/晶圓） 抛光量 (埃/分鐘） 實施例 1 163 8.2 30 4530 2 122 7.7 19 4270 3 158 6.2 7 4480 比較例 1 172 28.5 245 4660 2 165 21.2 186 4510 3 85 7.6 28 980 由表2可知根據本發明之二氧化鈽淤漿具有絕佳分散 液安定性，比較先前淤漿，於夠高曝光速率時，生成之刮 ® 10痕數目顯著減少。 雖然已經舉例說明本發明之若干較佳具體例，但可未 悖離如隨附之申請專利範圍界定之本發明之精髓於其中做 多種變化及修改。 【圖式簡單說明】 15 (無） 【主要元件符號說明】 (無） 12Evaluation of polishing slurry properties The slurries of Examples 1 to 3 and Comparative Examples 1 to 3 were tested using a particle size distribution analyzer 5 LA910 (Horiba, Japan). The results are shown in Table 2. In addition, in order to check the content of agglomerable particles during long-term storage, the polishing slurries of Examples 1 to 3 and Comparative Examples 1 to 3 were centrifuged using a tubular centrifuge (Hanil Scientific Industries MP 80, Korea). Testing to remove precipitated particles and determine changes in solids content. 10 In particular, 40 ml of each 5 wt% miconium oxide slurry was weighed and filled into a test tube with a volume of 11.5 cm and a volume of 50 ml. At 4,000 rpm (the distance from 2 in the centrifuge to the bottom of the test tube became 14 cm, the centrifuge The distance between the top of the test tube on the bottom axis becomes 2.5 cm, and the centrifugal force applied to the slurry becomes i, 970 g. 0) Centrifugation for 2 minutes to obtain the supernatant. The supernatant is weighed to determine the solid content of 15 substances in the slurry. Change in weight percent. The results are shown in Table 2. When the number of relatively large particles present in the slurry increases, the change in solid content increases, that is, the number of particles removed by centrifugation is expressed as an increase in wt%. In addition, the individual rhenium dioxide slurries obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were used, and the polishing layer obtained in Preparation Example 2 was polished using Mirra equipment (product of 20AMAT, USA). 8-inch wafer CMP polisher with IC1000 / suba IV stacked pad (Rodel, USA) was polished at 3.5 11 200536930 psi for 90 seconds. The polishing slurry was fed at a rate of 150 ml / min, with an upper plate centrifugation rate of 104 rpm and a lower plate centrifugation rate of 110 rpm. After polishing, the number of scratches with a size larger than 0.16 microns was measured using AIT-XP (product of KLA Tenco, USA). The polishing amount was measured using 5 Therma-wave Optiprobe 300 series. J (American heat wave company product) measurement. The results are also listed in Table 2. Table 2 Average particle size (nanometer) Solid content reduced by wt% Number of scratches (number / wafer) Polishing amount (angstroms / minute) Example 1 163 8.2 30 4530 2 122 7.7 19 4270 3 158 6.2 7 4480 Comparison Example 1 172 28.5 245 4660 2 165 21.2 186 4510 3 85 7.6 28 980 It can be seen from Table 2 that the hafnium dioxide slurry according to the present invention has excellent dispersion stability. Compared with the previous slurry, when the exposure rate is high enough, it produces The number of Scratch® 10 marks is significantly reduced. Although some preferred specific examples of the present invention have been illustrated, various changes and modifications can be made therein without departing from the essence of the present invention as defined by the scope of the attached patent application. [Schematic description] 15 (none) [Description of main component symbols] (none) 12