TWI463002B - Slurry composition - Google Patents
Slurry composition Download PDFInfo
- Publication number
- TWI463002B TWI463002B TW100144169A TW100144169A TWI463002B TW I463002 B TWI463002 B TW I463002B TW 100144169 A TW100144169 A TW 100144169A TW 100144169 A TW100144169 A TW 100144169A TW I463002 B TWI463002 B TW I463002B
- Authority
- TW
- Taiwan
- Prior art keywords
- slurry composition
- ammonium salt
- quaternary ammonium
- benzyl group
- salt containing
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims description 65
- 239000002002 slurry Substances 0.000 title claims description 43
- 238000005498 polishing Methods 0.000 claims description 44
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 39
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 34
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- 239000007800 oxidant agent Substances 0.000 claims description 21
- 229910021645 metal ion Inorganic materials 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052721 tungsten Inorganic materials 0.000 claims description 11
- 239000010937 tungsten Substances 0.000 claims description 11
- -1 ammonium halide salts Chemical class 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical class N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- DVARTQFDIMZBAA-UHFFFAOYSA-O ammonium nitrate Chemical class [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims 1
- 235000005985 organic acids Nutrition 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 229910000420 cerium oxide Inorganic materials 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 102100021503 ATP-binding cassette sub-family B member 6 Human genes 0.000 description 1
- CZNJCCVKDVCRKF-UHFFFAOYSA-N Benzyl sulfate Chemical compound OS(=O)(=O)OCC1=CC=CC=C1 CZNJCCVKDVCRKF-UHFFFAOYSA-N 0.000 description 1
- 101100000375 Homo sapiens ABCB6 gene Proteins 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 1
- FWYSSOIRLVHQNC-UHFFFAOYSA-M benzyl(trimethyl)azanium;acetate Chemical compound CC([O-])=O.C[N+](C)(C)CC1=CC=CC=C1 FWYSSOIRLVHQNC-UHFFFAOYSA-M 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- ZSAWQMSQHFHNIZ-UHFFFAOYSA-N benzyl(trimethyl)azanium;nitrate Chemical compound [O-][N+]([O-])=O.C[N+](C)(C)CC1=CC=CC=C1 ZSAWQMSQHFHNIZ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- KDSGPAZGWJOGTA-UHFFFAOYSA-M dibenzyl(dimethyl)azanium;hydroxide Chemical compound [OH-].C=1C=CC=CC=1C[N+](C)(C)CC1=CC=CC=C1 KDSGPAZGWJOGTA-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- ZEBSLBFIKJAJFE-UHFFFAOYSA-M tetrabenzylazanium;hydroxide Chemical compound [OH-].C=1C=CC=CC=1C[N+](CC=1C=CC=CC=1)(CC=1C=CC=CC=1)CC1=CC=CC=C1 ZEBSLBFIKJAJFE-UHFFFAOYSA-M 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Mechanical Treatment Of Semiconductor (AREA)
Description
本發明是有關於一種組成物，且特別是有關於一種研漿組成物。This invention relates to a composition, and more particularly to a slurry composition.
在超大型積體電路(VLSI)製程中，化學機械研磨製程(chemical mechanical polishing，CMP)可提供晶圓表面全面性之平坦化(global planarization)，尤其當半導體製程進入次微米(sub-micron)領域後，化學機械研磨法更是一項不可或缺的製程技術。In a very large integrated circuit (VLSI) process, chemical mechanical polishing (CMP) provides global planarization of the wafer surface, especially when the semiconductor process enters sub-micron. After the field, chemical mechanical grinding is an indispensable process technology.
現行鎢基板的化學機械研磨是以費頓反應(Fenton’s reaction)(即，Fe3+ 與H2 O2 的組合)為基礎來進行，然而以此方法進行化學機械研磨的缺點為容易有Fe3+ 殘留且過氧化氫的消耗速率極快。The chemical mechanical polishing of the current tungsten substrate is based on Fenton's reaction (ie, a combination of Fe 3+ and H 2 O 2 ). However, the disadvantage of chemical mechanical polishing in this way is that Fe 3 is easily formed. + Residual and hydrogen peroxide consumption rate is extremely fast.
本發明提供一種研漿組成物，其中含至少一芐基的四級銨鹽能有效地降低氧化劑的消耗速率。The present invention provides a slurry composition in which a quaternary ammonium salt containing at least one benzyl group is effective in reducing the rate of consumption of the oxidizing agent.
本發明提出一種研漿組成物，其包括吸附有金屬離子的研磨粒、氧化劑以及含至少一芐基的四級銨鹽。The present invention provides a slurry composition comprising abrasive particles having metal ions adsorbed thereon, an oxidizing agent, and a quaternary ammonium salt containing at least one benzyl group.
依照本發明的一實施例所述，在上述之研漿組成物中，含至少一芐基的四級銨鹽的含量為0.1ppm至10000ppm。According to an embodiment of the present invention, in the slurry composition, the content of the quaternary ammonium salt containing at least one benzyl group is from 0.1 ppm to 10,000 ppm.
依照本發明的一實施例所述，在上述之研漿組成物中，含至少一芐基的四級銨鹽的含量為10ppm至5000ppm。According to an embodiment of the present invention, in the slurry composition, the content of the quaternary ammonium salt containing at least one benzyl group is from 10 ppm to 5000 ppm.
依照本發明的一實施例所述，在上述之研漿組成物中，含至少一芐基的四級銨鹽的芐基數目為1個、2個、3個或4個。According to an embodiment of the present invention, in the slurry composition, the number of benzyl groups of the quaternary ammonium salt containing at least one benzyl group is 1, 2, 3 or 4.
依照本發明的一實施例所述，在上述之研漿組成物中，含至少一芐基的四級銨鹽為選自鹵化銨鹽、氫氧化銨鹽、硝酸銨鹽、硫酸銨鹽及有機酸銨鹽中的至少一者。According to an embodiment of the present invention, in the slurry composition, the quaternary ammonium salt containing at least one benzyl group is selected from the group consisting of ammonium halide salts, ammonium hydroxide salts, ammonium nitrate salts, ammonium sulfate salts, and organic salts. At least one of the acid ammonium salts.
依照本發明的一實施例所述，在上述之研漿組成物中，含至少一芐基的四級銨鹽包括芐基三甲基銨。According to an embodiment of the present invention, in the slurry composition, the quaternary ammonium salt containing at least one benzyl group includes benzyltrimethylammonium.
依照本發明的一實施例所述，在上述之研漿組成物中，氧化劑包括過氧化氫。According to an embodiment of the invention, in the slurry composition described above, the oxidizing agent comprises hydrogen peroxide.
依照本發明的一實施例所述，在上述之研漿組成物中，氧化劑的含量為0.01重量%至20重量%。According to an embodiment of the present invention, the oxidizing agent is contained in the slurry composition in an amount of from 0.01% by weight to 20% by weight.
依照本發明的一實施例所述，在上述之研漿組成物中，金屬離子包括Fe3+ 、Fe2+ 、Cu2+ 、Ag+ 或上述任兩者以上的組合。According to an embodiment of the present invention, in the slurry composition, the metal ions include Fe 3+ , Fe 2+ , Cu 2+ , Ag + or a combination of any two or more thereof.
依照本發明的一實施例所述，在上述之研漿組成物中，金屬離子的含量為0.01 ppm至1000 ppm。According to an embodiment of the present invention, the metal ion is contained in the slurry composition in an amount of from 0.01 ppm to 1000 ppm.
依照本發明的一實施例所述，上述之研漿組成物用於對鎢基板進行化學機械研磨。According to an embodiment of the invention, the slurry composition is used for chemical mechanical polishing of a tungsten substrate.
基於上述，藉由使研漿組成物包括含有芐基的四級銨鹽能有效地降低氧化劑的消耗速率，以延長研漿組成物的使用期限(pot life)。Based on the above, the pot life can be effectively reduced by making the slurry composition include a quaternary ammonium salt containing a benzyl group to extend the pot life of the slurry composition.
另外，在使用本發明所提出之研漿組成物對鎢基板進行化學機械研磨時，由於能有效地降低氧化劑的消耗速率，因此能避免研磨速率隨時間快速下降。Further, when the tungsten substrate is subjected to chemical mechanical polishing using the slurry composition proposed by the present invention, since the rate of consumption of the oxidizing agent can be effectively reduced, the polishing rate can be prevented from rapidly decreasing with time.
為讓本發明之上述特徵和優點能更明顯易懂，下文特舉實施例，並配合所附圖式作詳細說明如下。The above described features and advantages of the present invention will be more apparent from the following description.
首先，說明本發明之研漿組成物，其適用於化學機械研磨製程中。First, the slurry composition of the present invention will be described, which is suitable for use in a chemical mechanical polishing process.
本發明之研漿組成物包括吸附有金屬離子的研磨粒、氧化劑以及含至少一芐基的四級銨鹽。含至少一芐基的四級銨鹽的芐基數目可以是1個、2個、3個或4個。在一實施例中，含至少一芐基的四級銨鹽可以包括1個芐基，諸如氫氧化芐基三甲基銨。在另一實施例中，含至少一芐基的四級銨鹽可以包括2個芐基，諸如氫氧化二芐基二甲基銨。在又一實施例中，含至少一芐基的四級銨鹽可以包括3個芐基，諸如氫氧化三芐基甲基銨。在再一實施例中，含至少一芐基的四級銨鹽可以包括4個芐基，諸如氫氧化四芐基銨。在一實施例中，以研磨組成物的總量計，含至少一芐基的四級銨鹽的含量例如是0.1ppm至10000ppm。在另一實施例中，以研磨組成物的總量計，含至少一芐基的四級銨鹽的含量例如是10ppm至5000ppm。在上述的實施例中是以含至少一芐基的四級銨鹽為氫氧化銨鹽為例，但在其他實施例中，含至少一芐基的四級銨鹽可以是選自鹵化銨鹽(諸如氯化芐基三甲基銨)、氫氧化銨鹽(諸如氫氧化芐基三甲基銨)、硝酸銨鹽(諸如硝酸芐基三甲基銨)、硫酸銨鹽(諸如硫酸芐基三甲基銨)及有機酸銨鹽(諸如醋酸芐基三甲基銨)的至少一者。The slurry composition of the present invention comprises abrasive particles having metal ions adsorbed thereon, an oxidizing agent, and a quaternary ammonium salt containing at least one benzyl group. The number of benzyl groups containing at least one quaternary ammonium salt may be 1, 2, 3 or 4. In one embodiment, the quaternary ammonium salt containing at least one benzyl group can include one benzyl group, such as benzyltrimethylammonium hydroxide. In another embodiment, the quaternary ammonium salt containing at least one benzyl group can include 2 benzyl groups, such as dibenzyldimethylammonium hydroxide. In yet another embodiment, the quaternary ammonium salt containing at least one benzyl group can include 3 benzyl groups, such as tribenzylmethylammonium hydroxide. In still another embodiment, the quaternary ammonium salt containing at least one benzyl group can include 4 benzyl groups, such as tetrabenzylammonium hydroxide. In one embodiment, the content of the quaternary ammonium salt containing at least one benzyl group is, for example, 0.1 ppm to 10,000 ppm based on the total amount of the polishing composition. In another embodiment, the content of the quaternary ammonium salt containing at least one benzyl group is, for example, 10 ppm to 5000 ppm based on the total amount of the polishing composition. In the above examples, the quaternary ammonium salt containing at least one benzyl group is exemplified as the ammonium hydroxide salt, but in other embodiments, the quaternary ammonium salt containing at least one benzyl group may be selected from the group consisting of ammonium halide salts. (such as benzyltrimethylammonium chloride), ammonium hydroxide (such as benzyltrimethylammonium hydroxide), ammonium nitrate (such as benzyltrimethylammonium nitrate), ammonium sulfate (such as benzyl sulfate) At least one of trimethylammonium) and an organic acid ammonium salt such as benzyltrimethylammonium acetate.
研磨粒的含量例如是0.01重量%至40重量%。在另一實施例中，研磨粒的含量可為0.1重量%至35重量%。研磨粒的材料例如是二氧化矽、金屬氧化物、聚合材料或金屬氧化物與聚合材料的混成物。二氧化矽例如是氣相二氧化矽或二氧化矽溶膠。二氧化矽溶膠可從矽酸鈉(sodium silicate)或矽酸鉀(potassium silicate)水解而得，或是從矽烷(silanes)水解或濃縮而得。金屬氧化物例如是沈澱型氧化鋁(precipitated alumina)、鍛燒型氧化鋁(calcined alumina)、沈澱型氧化鈦(precipitated titania)或鍛燒型氧化鈦(calcined titania)。The content of the abrasive particles is, for example, 0.01% by weight to 40% by weight. In another embodiment, the abrasive particles may be included in an amount of from 0.1% by weight to 35% by weight. The material of the abrasive particles is, for example, cerium oxide, a metal oxide, a polymeric material or a mixture of a metal oxide and a polymeric material. The cerium oxide is, for example, a gas phase cerium oxide or a cerium oxide sol. The cerium oxide sol can be obtained by hydrolysis of sodium silicate or potassium silicate or by hydrolysis or concentration of silanes. The metal oxide is, for example, precipitated alumina, calcined alumina, precipitated titania or calcined titania.
研磨粒所吸附的金屬離子例如是Fe3+ 、Fe2+ 、Cu2+ 、Ag+ 或上述任兩者以上的組合。在一實施例中，以研磨組成物的總量計，金屬離子的含量為0.01ppm至1000ppm。The metal ions adsorbed by the abrasive grains are, for example, Fe 3+ , Fe 2+ , Cu 2+ , Ag + or a combination of any two or more thereof. In one embodiment, the metal ion is present in an amount of from 0.01 ppm to 1000 ppm based on the total of the polishing composition.
氧化劑例如是過氧化氫。氧化劑的含量例如是0.01重量%至20重量%。The oxidizing agent is, for example, hydrogen peroxide. The content of the oxidizing agent is, for example, 0.01% by weight to 20% by weight.
在一實施例中，研漿組成物可以更包括水。水例如是去離子水。另外，研漿組成物也可以包括酸鹼調整劑、錯合劑等其他添加劑。In an embodiment, the slurry composition may further comprise water. The water is, for example, deionized water. Further, the slurry composition may also include other additives such as an acid-base conditioner and a binder.
在使用本發明之研磨組成物的化學機械研磨製程中，是藉由氧化劑與研磨粒所吸附的金屬離子反應為基礎來進行，其中氧化劑容易因與金屬離子反應而迅速分解。含至少一芐基的四級銨鹽能有效地減緩氧化劑的分解效率，因而可延長研漿組成物的使用期限。再者，含至少一芐基的四級銨鹽能避免研磨速率因氧化劑的快速分解而隨時間迅速下降，且不會導致研磨速率的損失。詳言之，在習知的研漿組成物中，為了降低金屬離子的活性，會在研漿組成物中加入錯合劑來與金屬離子螯合，但此舉會降低研磨速率。習知方法是使用較高劑量的金屬離子來補償研磨速率的降低，但高劑量的金屬離子可能殘留於待研磨物表面而造成待研磨物表面缺陷。相反地，本發明之研磨組成物中的四級銨鹽能有效地減緩氧化劑的分解效率但不會導致研磨速率的損失，也不會有金屬離子殘留的問題發生。In the chemical mechanical polishing process using the polishing composition of the present invention, it is carried out by reacting an oxidizing agent with a metal ion adsorbed by the abrasive particles, wherein the oxidizing agent is easily decomposed by reaction with metal ions. The quaternary ammonium salt containing at least one benzyl group can effectively slow down the decomposition efficiency of the oxidizing agent, thereby prolonging the service life of the slurry composition. Further, the quaternary ammonium salt containing at least one benzyl group can prevent the polishing rate from rapidly decreasing with time due to rapid decomposition of the oxidizing agent, and does not cause loss of the polishing rate. In particular, in conventional slurry compositions, in order to reduce the activity of metal ions, a miscending agent is added to the slurry composition to chelate with metal ions, but this reduces the polishing rate. A conventional method is to use a higher dose of metal ions to compensate for the decrease in the polishing rate, but high doses of metal ions may remain on the surface of the object to be polished to cause surface defects of the object to be polished. On the contrary, the quaternary ammonium salt in the abrasive composition of the present invention can effectively alleviate the decomposition efficiency of the oxidant without causing loss of the polishing rate, and there is no problem of residual metal ions.
舉例來說，本發明之一實施例的研漿組成物適用於對鎢基板進行化學機械研磨。在此實施例中，研漿組成物例如是包括吸附有Fe3+ 的二氧化矽研磨粒、過氧化氫以及含至少一芐基的四級銨鹽。其中，藉由過氧化氫與Fe3+ 進行費頓反應以對鎢基板進行化學機械研磨，過氧化氫會因與Fe3+ 反應而迅速分解。此時，含至少一芐基的四級銨鹽能有效地減緩過氧化氫的分解效率，進而延長研漿組成物的使用期限，且能避免研磨速率因過氧化氫的快速分解而隨時間迅速下降。For example, the slurry composition of one embodiment of the present invention is suitable for chemical mechanical polishing of a tungsten substrate. In this embodiment, the slurry composition is, for example, a ceria abrasive particle having Fe 3+ adsorbed thereon, hydrogen peroxide, and a quaternary ammonium salt containing at least one benzyl group. Among them, the tungsten substrate is subjected to a chemical mechanical polishing by a Felton reaction of hydrogen peroxide with Fe 3+ , and the hydrogen peroxide is rapidly decomposed by the reaction with Fe 3+ . At this time, the quaternary ammonium salt containing at least one benzyl group can effectively slow down the decomposition efficiency of hydrogen peroxide, thereby prolonging the service life of the slurry composition, and avoiding the rapid rate of polishing due to the rapid decomposition of hydrogen peroxide. decline.
以下，進行實際的實驗測試。其中，下述實驗例及比較例1與2所使用的化學機械研磨機台及實驗設定如下。The actual experimental test is performed below. Among them, the chemical mechanical polishing machine used in the following experimental examples and Comparative Examples 1 and 2 and the experimental settings were as follows.
化學機械研磨機台型號：Minimet 1000(Buehler)Chemical mechanical grinding machine model: Minimet 1000 (Buehler)
待研磨基材：鎢基板(UMAT公司製)Substrate to be polished: Tungsten substrate (manufactured by UMAT Corporation)
研磨墊：Politex(產品名，Dow Chemical公司製))Polishing pad: Politex (product name, manufactured by Dow Chemical Co., Ltd.)
研磨頭下壓力(down force)：2.546 psiDown force: 2.546 psi
平台速度(platen speed)：0 rpmPlaten speed: 0 rpm
研磨頭速度(head speed)：50 rpmHead speed: 50 rpm
研磨時間：300秒Grinding time: 300 seconds
實驗例的研磨組成物配方包括500克的3%吸附有鐵離子的奈米矽溶膠研磨顆粒、300ppm的氫氧化芐基三甲基銨以及5%過氧化氫。比較例1的研磨組成物配方包括500克的3%吸附有鐵離子的奈米矽溶膠研磨顆粒與5%過氧化氫。比較例2的研磨組成物配方包括500克的3%吸附有鐵離子的奈米矽溶膠研磨顆粒、300ppm的氫氧化四甲基銨以及5%過氧化氫。The polishing composition formulation of the experimental example included 500 g of 3% nano-sized cerium sol-coated abrasive particles adsorbed with iron ions, 300 ppm of benzyltrimethylammonium hydroxide, and 5% hydrogen peroxide. The polishing composition formulation of Comparative Example 1 included 500 grams of 3% nano-sized cerium sol-adsorbed particles with iron ions and 5% hydrogen peroxide. The polishing composition formulation of Comparative Example 2 included 500 grams of 3% nano sized cerium sol-coated abrasive particles adsorbed with iron ions, 300 ppm of tetramethylammonium hydroxide, and 5% hydrogen peroxide.
研磨測試及結果Grinding test and results
圖1為使用實驗例及比較例1與2的研磨組成物對鎢基板進行化學機械研磨實驗的研磨速率與存放時間的關係圖，其中以初始研磨速率為100%來計算各時間的研磨速率。1 is a graph showing the relationship between the polishing rate and the storage time of a chemical mechanical polishing experiment on a tungsten substrate using the polishing compositions of Experimental Examples and Comparative Examples 1 and 2, in which the polishing rate at each time was calculated at an initial polishing rate of 100%.
請參照圖1，比較例1與2的研磨組成物在放置1天與3天後，研磨速率分別下降至約75%與50%，以及比較例1的研磨組成物在放置5天後，研磨速率下降至約25%。相反地，實驗例的研磨組成物在放置5天內皆能維持與初始研磨速率相近的研磨速率。由此可知，相較於不包括含芐基的四級銨鹽的研磨組成物(即比較例1)或包括不含芐基的四級銨鹽的研磨組成物(即比較例2)，含芐基的四級銨鹽的研磨組成物能避免鎢基板的研磨速率隨時間增加而大幅下降。Referring to FIG. 1, the polishing compositions of Comparative Examples 1 and 2 were dropped to about 75% and 50%, respectively, after being left for 1 day and 3 days, and the polishing composition of Comparative Example 1 was ground after 5 days of standing. The rate drops to about 25%. In contrast, the polishing composition of the experimental example maintained a polishing rate similar to the initial polishing rate for 5 days. From this, it is understood that the polishing composition (ie, Comparative Example 2) or the polishing composition including the quaternary ammonium salt containing no benzyl group (ie, Comparative Example 2) is included as compared with the polishing composition not including the quaternary ammonium salt containing a benzyl group (ie, Comparative Example 1). The polishing composition of the quaternary ammonium salt of benzyl can prevent the polishing rate of the tungsten substrate from drastically decreasing with time.
綜上所述，本發明之研漿組成物包括含有芐基的四級銨鹽，其能有效地降低氧化劑的消耗速率，以延長研漿組成物的使用期限。也就是說，當研漿組成物中的氧化劑與金屬離子反應時，氧化劑可能會迅速地消耗，而導致研磨速率隨時間下降。然而，在使用本發明所提出之研漿組成物對諸如鎢基板等基板進行化學機械研磨時，由於含有芐基的四級銨鹽能降低氧化劑的消耗速率，因而能避免研磨速率因氧化劑的迅速消耗而隨時間下降。因此，研漿組成物具有較佳的穩定性與較長的使用期限。In summary, the slurry composition of the present invention comprises a quaternary ammonium salt containing a benzyl group, which can effectively reduce the rate of consumption of the oxidizing agent to extend the life of the slurry composition. That is, when the oxidizing agent in the slurry composition reacts with the metal ions, the oxidizing agent may be quickly consumed, resulting in a decrease in the polishing rate with time. However, when chemically mechanically grinding a substrate such as a tungsten substrate using the slurry composition proposed by the present invention, since the quaternary ammonium salt containing a benzyl group can reduce the rate of consumption of the oxidizing agent, the polishing rate can be prevented from being rapidly caused by the oxidizing agent. Consumption and decline with time. Therefore, the slurry composition has better stability and a longer service life.
雖然本發明已以實施例揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明之精神和範圍內，當可作些許之更動與潤飾，故本發明之保護範圍當視後附之申請專利範圍所界定者為準。Although the present invention has been disclosed in the above embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art can make some modifications and refinements without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.
圖1為使用實驗例及比較例1與2的研磨組成物對鎢基板進行化學機械研磨實驗的研磨速率與存放時間的關係圖。Fig. 1 is a graph showing the relationship between the polishing rate and the storage time of a chemical mechanical polishing experiment on a tungsten substrate using the polishing compositions of the experimental examples and Comparative Examples 1 and 2.
Claims (11)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW100144169A TWI463002B (en) | 2011-12-01 | 2011-12-01 | Slurry composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW100144169A TWI463002B (en) | 2011-12-01 | 2011-12-01 | Slurry composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201323589A TW201323589A (en) | 2013-06-16 |
| TWI463002B true TWI463002B (en) | 2014-12-01 |
Family
ID=49032798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW100144169A TWI463002B (en) | 2011-12-01 | 2011-12-01 | Slurry composition |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI463002B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US12291655B2 (en) * | 2021-04-27 | 2025-05-06 | DuPont Electronic Materials Holding, Inc. | Polishing composition and method of polishing a substrate having enhanced defect reduction |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005064285A (en) * | 2003-08-14 | 2005-03-10 | Hitachi Chem Co Ltd | Polishing solution and polishing method for cmp |
| US20060157671A1 (en) * | 2004-11-26 | 2006-07-20 | Ace Hightech Co., Ltd. | Slurry for use in metal-chemical mechanical polishing and preparation method thereof |
| TW200731382A (en) * | 2005-04-28 | 2007-08-16 | Advanced Tech Materials | Method of passivating chemical mechanical polishing compositions for copper film planarization processes |
| EP2048208A2 (en) * | 2002-02-11 | 2009-04-15 | DuPont Air Products NanoMaterials L.L.C. | Free radical-forming activator attached to solid and used to enhanced CMP formulations |
| CN102093816A (en) * | 2009-12-11 | 2011-06-15 | 安集微电子（上海）有限公司 | Chemical mechanical polishing liquid |
-
2011
- 2011-12-01 TW TW100144169A patent/TWI463002B/en active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2048208A2 (en) * | 2002-02-11 | 2009-04-15 | DuPont Air Products NanoMaterials L.L.C. | Free radical-forming activator attached to solid and used to enhanced CMP formulations |
| JP2005064285A (en) * | 2003-08-14 | 2005-03-10 | Hitachi Chem Co Ltd | Polishing solution and polishing method for cmp |
| US20060157671A1 (en) * | 2004-11-26 | 2006-07-20 | Ace Hightech Co., Ltd. | Slurry for use in metal-chemical mechanical polishing and preparation method thereof |
| TW200731382A (en) * | 2005-04-28 | 2007-08-16 | Advanced Tech Materials | Method of passivating chemical mechanical polishing compositions for copper film planarization processes |
| CN102093816A (en) * | 2009-12-11 | 2011-06-15 | 安集微电子（上海）有限公司 | Chemical mechanical polishing liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201323589A (en) | 2013-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101512732B (en) | Silicon carbide polishing method utilizing water-soluble oxidizers | |
| JP6940557B2 (en) | Tungsten chemical mechanical polishing to reduce oxide erosion | |
| JP7032327B2 (en) | Slurry composition for chemical-mechanical polishing | |
| JP2015029083A (en) | Chemical mechanical polishing slurry composition and method for copper using it and through silicon via application | |
| JP2018016812A (en) | Chemical mechanical polishing slurry for reducing corrosion and method of use thereof | |
| TWI619805B (en) | Grinding composition for hard and brittle materials, polishing method for hard and brittle material substrate, and manufacturing method | |
| CN104465362A (en) | Silicon carbide polishing method utilizing water-soluble oxidizers | |
| KR20180061400A (en) | Tungsten-treated slurry containing cationic surfactant | |
| KR20160009644A (en) | Use of chemical-mechanical polishing (cmp) composition for polishing substance or layer containing at least one iii-v material | |
| CN1863883A (en) | Pastes and methods for chemical mechanical planarization of copper | |
| CN102399494B (en) | Chemical mechanical polishing solution | |
| CN106967385B (en) | Halous acid salt silicon carbide etch agent | |
| CN102159657B (en) | Chemical-mechanical polishing liquid | |
| TWI838447B (en) | Chemical-mechanical polishing slurry for polishing tungsten | |
| CN102816530B (en) | A kind of chemical mechanical polishing liquid | |
| JP4657408B2 (en) | Metal film abrasive | |
| TWI566884B (en) | Composition for honing and method for producing compound semiconductor substrate using the same | |
| CN102533121B (en) | A kind of chemical mechanical polishing liquid of polish tungsten | |
| TWI463002B (en) | Slurry composition | |
| CN102477258B (en) | Chemically mechanical polishing liquid | |
| US20060157671A1 (en) | Slurry for use in metal-chemical mechanical polishing and preparation method thereof | |
| CN104479559B (en) | A kind of compositions being applicable to Waffer edge polishing and preparation method thereof | |
| US20240101865A1 (en) | Tungsten cmp composition including a sulfur containing anionic surfactant | |
| JP6285775B2 (en) | Metal-supported metal oxide particles for polishing and abrasives | |
| JP7575878B2 (en) | Polishing composition, its manufacturing method, and polishing method |