TWI393770B - Chemical mechanical polishing slurry for polishing polysilicon - Google Patents

Chemical mechanical polishing slurry for polishing polysilicon Download PDF

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TWI393770B
TWI393770B TW96107778A TW96107778A TWI393770B TW I393770 B TWI393770 B TW I393770B TW 96107778 A TW96107778 A TW 96107778A TW 96107778 A TW96107778 A TW 96107778A TW I393770 B TWI393770 B TW I393770B
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polishing
polishing liquid
ammonium salt
quaternary ammonium
cationic surfactant
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TW96107778A
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TW200837179A (en
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Judy Jian-Fen Jing
Andy Chun-Xiao Yang
Frank Lin Wang
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Anji Microelectronics Co Ltd
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Description

用於拋光多晶矽的化學機械拋光液Chemical mechanical polishing liquid for polishing polycrystalline germanium

本發明涉及一種化學機械拋光液，尤其涉及一種用於拋光多晶矽的化學機械拋光液。The present invention relates to a chemical mechanical polishing liquid, and more particularly to a chemical mechanical polishing liquid for polishing polycrystalline germanium.

在積體電路製造中，互連技術的標準在提高，一層上面又沉積一層，使得在襯底表面形成了不規則的形貌。現有技術中使用的一種平坦化方法就是化學機械拋光(Chemical mechanical polishing,CMP)，CMP工藝就是使用一種含磨料的混合物和拋光墊去拋光一矽片表面。在典型的化學機械拋光方法中，將襯底直接與旋轉拋光墊接觸，用一載重物在襯底背面施加壓力。在拋光期間，墊片和操作臺旋轉，同時在襯底背面保持向下的力，將磨料和化學活性溶液(通常稱為拋光液或拋光漿料)塗於墊片上，該拋光液與正在拋光的薄膜發生化學反應開始進行拋光過程。In the fabrication of integrated circuits, the standard of interconnect technology is increasing, and a layer is deposited on top of one layer, resulting in an irregular topography on the surface of the substrate. One method of planarization used in the prior art is chemical mechanical polishing (CMP), which uses an abrasive-containing mixture and a polishing pad to polish a ruthenium surface. In a typical chemical mechanical polishing process, the substrate is placed in direct contact with a rotating polishing pad and a load is applied to the backside of the substrate with a load. During polishing, the gasket and the table rotate while maintaining a downward force on the back of the substrate, applying abrasive and chemically active solutions (often referred to as polishing fluids or polishing slurries) to the gasket. The polished film undergoes a chemical reaction to begin the polishing process.

對於多晶矽的拋光，目前主要應用於兩種晶片，一種是DRAM，一種是Flash RAM。後者應用中往往在對多晶矽的拋光中會涉及到對二氧化矽的拋光。For the polishing of polysilicon, it is mainly applied to two types of wafers, one is DRAM and the other is Flash RAM. In the latter application, polishing of cerium oxide is often involved in the polishing of polycrystalline germanium.

在以往的主要利用以二氧化矽為研磨顆粒的鹼性漿料來拋光多晶矽層和二氧化矽層的情況下，多晶矽的去除速率往往比二氧化矽的除去速率高得多，易導致多晶矽的過量去除而產生凹陷，影響隨後的工藝。In the past, in the case of polishing the polycrystalline germanium layer and the germanium dioxide layer mainly by using an alkaline slurry containing cerium oxide as the abrasive particles, the removal rate of the polycrystalline germanium is often much higher than the removal rate of the germanium dioxide, which is liable to cause polycrystalline germanium. Excessive removal creates a depression that affects the subsequent process.

因此，拋光工藝中因多晶矽去除速率過高而產生表面凹陷的問題亟待解決。專利文獻US2003/0153189A1公開了一種用於多晶矽拋光的化學機械拋光液及方法，該拋光液包括一種聚合物表面活性劑和一種選自氧化鋁和氧化鈰的研磨顆粒，該聚合物表面活性劑為聚羧酸酯表面活性劑，用該漿料可以使多晶矽表面大塊區域的拋光速率大大高於溝槽內的拋光速率，從而減少凹陷。專利文獻US2005/0130428A1和CN1637102A公開了一種用於多晶矽化學機械拋光的漿料，該漿料成分包括一種或多種在多晶矽層上形成鈍化層的非離子表面活性劑及一種能形成第二鈍化層來能減小氮化矽或氧化矽除去速率的第二表面活性劑。這種非離子表面活性劑至少包括一種選自環氧乙烷－環氧丙烷嵌段共聚物醇和環氧乙烷－環氧丙烷三嵌段聚合物組成的組中的化合物，該漿料可以將多晶矽除去速率與絕緣體除去速率之間的選擇比至少減小大約50%。Therefore, the problem of surface depression due to excessive removal rate of polysilicon in the polishing process needs to be solved. The patent document US 2003/0153189 A1 discloses a chemical mechanical polishing liquid and method for polycrystalline silicon polishing, the polishing liquid comprising a polymer surfactant and an abrasive particle selected from the group consisting of alumina and cerium oxide, the polymer surfactant being A polycarboxylate surfactant with which the polishing rate of a large area of the surface of the polycrystalline crucible can be made much higher than the polishing rate in the trench, thereby reducing dishing. The patent documents US 2005/0130428 A1 and CN 1637102 A disclose a slurry for polycrystalline germanium chemical mechanical polishing comprising one or more nonionic surfactants forming a passivation layer on a polycrystalline germanium layer and a second passivation layer capable of forming a second passivation layer. A second surfactant capable of reducing the rate of removal of tantalum nitride or yttria. The nonionic surfactant comprises at least one compound selected from the group consisting of ethylene oxide-propylene oxide block copolymer alcohol and ethylene oxide-propylene oxide triblock polymer, and the slurry can be The selectivity ratio between the polysilicon removal rate and the insulator removal rate is reduced by at least about 50%.

本發明的目的是為了在鹼性條件下較好地拋光多晶矽，降低多晶矽的拋光速率及多晶矽對二氧化矽的拋光速率比，顯著提高多晶矽的平坦化效率，從而提供一種用於拋光多晶矽的化學機械拋光液。The purpose of the invention is to better polish polycrystalline germanium under alkaline conditions, reduce the polishing rate of polycrystalline germanium and the polishing rate ratio of polycrystalline germanium to germanium dioxide, and significantly improve the planarization efficiency of polycrystalline germanium, thereby providing a chemical for polishing polycrystalline germanium. Mechanical polishing fluid.

本發明的拋光液包含研磨顆粒和水，其特徵在於還包含一種或多種季銨鹽型陽離子表面活性劑。該季銨鹽型陽離子表面活性劑為單季銨鹽型和/或雙子型(Gemini)季銨鹽陽離子表面活性劑。The polishing liquid of the present invention comprises abrasive particles and water, and is characterized by further comprising one or more quaternary ammonium salt type cationic surfactants. The quaternary ammonium salt type cationic surfactant is a single quaternary ammonium salt type and/or a Gemini quaternary ammonium salt cationic surfactant.

本發明中，該單季銨鹽型陽離子表面活性劑為R1 R2 N＋ R3 R4 X－ ，其中：R1 為－Cm H2 m ＋ 1 ，8≦m≦22；R2 和R3 相同並為－CH3 或－C2 H5 ；R4 與R1 相同或為－CH3 、－C2 H5 、－CH2 －C6 H5 或－CH2 CH2 OH；X－ 為Cl－ 、Br－ 、CH3 SO4 － 、NO3 － 或C6 H5 －SO4 － 。In the present invention, the monoquaternary ammonium salt type cationic surfactant is R 1 R 2 N + R 3 R 4 X - , wherein: R 1 is -C m H 2 m + 1 , 8≦m≦22; R 2 Same as R 3 and is -CH 3 or -C 2 H 5 ; R 4 is the same as R 1 or is -CH 3 , -C 2 H 5 , -CH 2 -C 6 H 5 or -CH 2 CH 2 OH; X - is Cl - , Br - , CH 3 SO 4 - , NO 3 - or C 6 H 5 -SO 4 - .

本發明中，該雙子型(Gemini)季銨鹽陽離子表面活性劑為(R1 R2 N＋ R3 X－ )2 R5 ，其中：R1 為－Cm H2 m ＋ 1 ，8≦m≦18；R2 和R3 相同並為－CH3 或－C2 H5 ；R5 為苯二亞甲基、聚亞甲基－(CH2 )n －或聚氧乙烯基－CH2 CH2 －(OCH2 CH2 )p －，2≦n≦30，1≦p≦30；X－ 為Cl－ 或Br－ 。In the present invention, the Gemini quaternary ammonium salt cationic surfactant is (R 1 R 2 N + R 3 X - ) 2 R 5 , wherein: R 1 is -C m H 2 m + 1 , 8 ≦m≦18; R 2 and R 3 are the same and are -CH 3 or -C 2 H 5 ; R 5 is benzene dimethylene, polymethylene-(CH 2 ) n - or polyoxyethylene-CH 2 CH 2 -(OCH 2 CH 2 ) p -,2≦n≦30,1≦p≦30; X - is Cl - or Br - .

本發明中，該季銨鹽型陽離子表面活性劑的重量百分比濃度較佳地為0.0001~5%，更佳地為0.001~1%。In the present invention, the concentration by weight of the quaternary ammonium salt type cationic surfactant is preferably from 0.0001 to 5%, more preferably from 0.001 to 1%.

本發明中，該拋光液的pH值較佳地為7~12。In the present invention, the pH of the polishing liquid is preferably from 7 to 12.

本發明中，該研磨顆粒可為二氧化矽、三氧化二鋁、摻雜鋁或覆蓋鋁的二氧化矽、二氧化鈰、二氧化鈦和/或高分子聚合物研磨顆粒。該研磨顆粒的重量百分比濃度較佳為0.5~30%，更佳地為2~30%。In the present invention, the abrasive particles may be cerium oxide, aluminum oxide, doped aluminum or aluminum-coated cerium oxide, cerium oxide, titanium dioxide, and/or high molecular polymer abrasive particles. The weight percentage of the abrasive particles is preferably from 0.5 to 30%, more preferably from 2 to 30%.

本發明的拋光液還可以包括pH調節劑，粘度調節劑和/或消泡劑來達到本發明的發明目的。The polishing liquid of the present invention may further include a pH adjusting agent, a viscosity adjusting agent and/or an antifoaming agent to attain the object of the present invention.

本發明的拋光液由上面所述組分簡單混合即可制得。The polishing liquid of the present invention can be obtained by simply mixing the components described above.

本發明的積極進步效果在於：本發明的拋光液可以在鹼性條件下較好地拋光多晶矽，並且還可以顯著降低多晶矽的去除速率及多晶矽與二氧化矽的選擇比，顯著提高多晶矽的平坦化效率。The positive progress of the present invention is that the polishing liquid of the present invention can better polish polycrystalline germanium under alkaline conditions, and can also significantly reduce the removal rate of polycrystalline germanium and the selectivity ratio of polycrystalline germanium to germanium dioxide, and significantly improve the planarization of polycrystalline germanium. effectiveness.

關於本發明之優點與精神可以藉由以下的發明詳述及所附圖式得到進一步的瞭解。The advantages and spirit of the present invention will be further understood from the following detailed description of the invention.

實施例1~6Examples 1 to 6

下列表一中給比了拋光多晶矽的化學機械拋光液的實施例1~6，下列拋光液按表一中所給組分簡單混合，用本領域習知的pH調節劑調節至所需pH值即可，水為餘量。In Examples 1 to 6 of the chemical mechanical polishing liquid for polishing polycrystalline silicon in the following Table 1, the following polishing liquids were simply mixed according to the components given in Table 1, and adjusted to the desired pH value by a pH adjusting agent known in the art. Yes, water is the balance.

效果實施例1Effect Example 1

由表二資料顯示，與未添加季銨鹽型陽離子表面活性劑的拋光液相比，拋光液1~20均不同程度的降低了多晶矽的去除速率及多晶矽對二氧化矽的選擇比。According to the data in Table 2, compared with the polishing liquid without the addition of quaternary ammonium salt type cationic surfactant, the polishing liquid 1~20 reduced the removal rate of polycrystalline germanium and the selectivity ratio of polycrystalline germanium to germanium dioxide to different degrees.

拋光時的工藝參數為：下壓力3 psi、拋光盤(直徑14英寸)的轉速70 rpm、拋光頭轉速80 rpm、拋光漿料流速200 ml/min、拋光墊為PPG fast pad CS7、拋光機為Logitech LP50。The process parameters for polishing are: 3 psi downforce, 70 rpm for polishing disc (14 inches in diameter), 80 rpm for polishing head, 200 ml/min for polishing slurry, PPG fast pad CS7 for polishing pad, and polishing machine for polishing machine Logitech LP50.

本發明所使用的原料和試劑均為市售產品。The raw materials and reagents used in the present invention are all commercially available products.

藉由以上較佳具體實施例之詳述，係希望能更加清楚描述本發明之特徵與精神，而並非以上述所揭露的較佳具體實施例來對本發明之範疇加以限制。相反地，其目的是希望能涵蓋各種改變及具相等性的安排於本發明所欲申請之專利範圍的範疇內。The features and spirit of the present invention will be more apparent from the detailed description of the preferred embodiments. On the contrary, the intention is to cover various modifications and equivalents within the scope of the invention as claimed.

Claims (6)

一種用於拋光多晶矽的化學機械拋光液，包含：一研磨顆粒；一水；以及至少一季銨鹽型陽離子表面活性劑其中該季銨鹽型陽離子表面活性劑為雙子型季銨鹽陽離子表面活性劑；其中該季銨鹽型陽離子表面活性劑的重量百分比濃度為0.0001~5%；其中該研磨顆粒的重量百分比為0.5~30%。 A chemical mechanical polishing liquid for polishing polycrystalline germanium, comprising: an abrasive particle; a water; and at least one quaternary ammonium salt type cationic surfactant, wherein the quaternary ammonium salt type cationic surfactant is a gemini quaternary ammonium salt cationic surface active agent The quaternary ammonium salt type cationic surfactant has a concentration by weight of 0.0001% to 5%; wherein the abrasive particles are 0.5% to 30% by weight. 如申請專利範圍第1項所述之拋光液，其中該雙子型季銨鹽陽離子表面活性劑為(R1 R2 N+ R3 X- )2 R5 ，R1 為-Cm H2m+1 ，8≦m≦18，R2 和R3 相同並為-CH3 或-C2 H5 ，R5 為苯二亞甲基、聚亞甲基-(CH2 )n -或聚氧乙烯基-CH2 CH2 -(OCH2 CH2 )p -，2≦n≦30，1≦p≦30，X- 為Cl- 或Br- 。The polishing liquid according to claim 1, wherein the gemini quaternary ammonium salt cationic surfactant is (R 1 R 2 N + R 3 X - ) 2 R 5 and R 1 is -C m H 2m +1 , 8≦m≦18, R 2 and R 3 are the same and are -CH 3 or -C 2 H 5 , and R 5 is benzenedimethylene, polymethylene-(CH 2 ) n - or polyoxygen Vinyl-CH 2 CH 2 -(OCH 2 CH 2 ) p -, 2≦n≦30, 1≦p≦30, X - is Cl - or Br - . 如申請專利範圍第1項所述之拋光液，其中該季銨鹽型陽離子表面活性劑的重量百分比濃度為0.001~1%。 The polishing liquid according to claim 1, wherein the quaternary ammonium salt type cationic surfactant has a concentration by weight of 0.001 to 1%. 如申請專利範圍第1項所述之拋光液，其中該拋光液的pH值為7~12。 The polishing liquid according to claim 1, wherein the polishing liquid has a pH of 7 to 12. 如申請專利範圍第1項所述之拋光液，其中該研磨顆粒為二氧化矽、三氧化二鋁、摻雜鋁或覆蓋鋁的二氧化矽、二氧化鈰、二氧化鈦及/或高分子聚合物研磨顆粒。 The polishing liquid according to claim 1, wherein the abrasive particles are cerium oxide, aluminum oxide, doped aluminum or aluminum-covered cerium oxide, cerium oxide, titanium dioxide and/or high molecular polymer. Grinding the particles. 如申請專利範圍第1項所述之拋光液，其中該研磨顆粒的重量百分比為2~30%。 The polishing liquid according to claim 1, wherein the abrasive particles have a weight percentage of 2 to 30%.
TW96107778A 2007-03-07 2007-03-07 Chemical mechanical polishing slurry for polishing polysilicon TWI393770B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW517301B (en) * 2000-12-20 2003-01-11 Bayer Ag Polishing slurry for the chemical-mechanical polishing of silica films
US20030194868A1 (en) * 2000-11-16 2003-10-16 Miller Anne E. Copper polish slurry for reduced interlayer dielectric erosion and method of using same
US20050023247A1 (en) * 1999-12-30 2005-02-03 Andreas Michael T. Chemical-mechanical polishing methods

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050023247A1 (en) * 1999-12-30 2005-02-03 Andreas Michael T. Chemical-mechanical polishing methods
US20030194868A1 (en) * 2000-11-16 2003-10-16 Miller Anne E. Copper polish slurry for reduced interlayer dielectric erosion and method of using same
TW517301B (en) * 2000-12-20 2003-01-11 Bayer Ag Polishing slurry for the chemical-mechanical polishing of silica films

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