TWI534221B - TSV barrier layer polishing solution - Google Patents
TSV barrier layer polishing solution Download PDFInfo
- Publication number
- TWI534221B TWI534221B TW101127889A TW101127889A TWI534221B TW I534221 B TWI534221 B TW I534221B TW 101127889 A TW101127889 A TW 101127889A TW 101127889 A TW101127889 A TW 101127889A TW I534221 B TWI534221 B TW I534221B
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- TW
- Taiwan
- Prior art keywords
- barrier layer
- tantalum nitride
- tsv barrier
- polishing
- polishing rate
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims description 70
- 230000004888 barrier function Effects 0.000 title claims description 31
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000003112 inhibitor Substances 0.000 claims description 11
- 239000008139 complexing agent Substances 0.000 claims description 9
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- -1 azole compound Chemical class 0.000 claims description 8
- 229920003169 water-soluble polymer Polymers 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000003223 protective agent Substances 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 230000000844 anti-bacterial effect Effects 0.000 claims description 4
- BCZWPKDRLPGFFZ-UHFFFAOYSA-N azanylidynecerium Chemical compound [Ce]#N BCZWPKDRLPGFFZ-UHFFFAOYSA-N 0.000 claims description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003002 pH adjusting agent Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 claims description 4
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- DWHOIYXAMUMQTI-UHFFFAOYSA-L disodium;2-[(1-sulfonatonaphthalen-2-yl)methyl]naphthalene-1-sulfonate Chemical group [Na+].[Na+].C1=CC2=CC=CC=C2C(S(=O)(=O)[O-])=C1CC1=CC=C(C=CC=C2)C2=C1S([O-])(=O)=O DWHOIYXAMUMQTI-UHFFFAOYSA-L 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- NMDKWAQVRNUKQH-UHFFFAOYSA-N 2-benzylnaphthalene-1-sulfonic acid formaldehyde Chemical compound C=O.C(C1=CC=CC=C1)C1=C(C2=CC=CC=C2C=C1)S(=O)(=O)O NMDKWAQVRNUKQH-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 229940120146 EDTMP Drugs 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 2
- WQHQCQSAAOGHQP-UHFFFAOYSA-N formaldehyde;2-methylnaphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=CC2=C(S(O)(=O)=O)C(C)=CC=C21 WQHQCQSAAOGHQP-UHFFFAOYSA-N 0.000 claims description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 2
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 230000002401 inhibitory effect Effects 0.000 claims 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 235000012431 wafers Nutrition 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 230000007547 defect Effects 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- 239000002846 particulate organic matter Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- SRDOTWUOTQTGAK-UHFFFAOYSA-N C=O.C1(=CC=CC2=CC=CC=C12)S(=O)(=O)OCC1=CC=CC=C1 Chemical compound C=O.C1(=CC=CC2=CC=CC=C12)S(=O)(=O)OCC1=CC=CC=C1 SRDOTWUOTQTGAK-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- DDAQLPYLBPPPRV-UHFFFAOYSA-N [4-(hydroxymethyl)-2-oxo-1,3,2lambda5-dioxaphosphetan-2-yl] dihydrogen phosphate Chemical compound OCC1OP(=O)(OP(O)(O)=O)O1 DDAQLPYLBPPPRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001273 butane 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
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- XUZHLZDRCCUWEV-UHFFFAOYSA-N formaldehyde;methyl naphthalene-1-sulfonate Chemical compound O=C.C1=CC=C2C(S(=O)(=O)OC)=CC=CC2=C1 XUZHLZDRCCUWEV-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76898—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics formed through a semiconductor substrate
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Description
本發明涉及一種拋光液，尤其涉及一種用於拋光TSV阻擋層的化學機械拋光液。 The present invention relates to a polishing liquid, and more particularly to a chemical mechanical polishing liquid for polishing a TSV barrier layer.
參見圖5-7，為了提高積體電路(IC)的性能、進一步縮小尺寸、降低功耗和成本，小尺寸3D TSV(Through-Silicon-Via，矽通孔)封裝技術也由此應運而生。3D TSV是通過在晶片和晶片之間、晶圓和晶圓之間製作垂直導通，實現晶片之間互連的最新技術。與以往IC封裝鍵合和使用凸點的疊加技術不同，TSV能夠使晶片在三維方向堆疊的密度最大，外形尺寸最小，大大改善晶片速度和低功耗的性能。其主要優勢表現為：具有最小的尺寸和重量，將不同種類的技術集成到單個封裝中，用短的垂直互連代替長的2D互連，降低寄生效應和功耗等。 Referring to Figure 5-7, in order to improve the performance of integrated circuits (IC), further downsizing, power consumption and cost, small-size 3D TSV (Through-Silicon-Via) packaging technology has emerged. . 3D TSV is the latest technology for interconnecting between wafers by making vertical conduction between the wafer and the wafer, between the wafer and the wafer. Unlike previous IC package bonding and bump overlay technology, TSV enables wafers to be stacked in the three-dimensional direction with the highest density and smallest form factor, greatly improving wafer speed and low power consumption. Its main advantages are: the smallest size and weight, the integration of different kinds of technologies into a single package, the replacement of long 2D interconnects with short vertical interconnects, reducing parasitics and power consumption.
TSV製程的集成方式非常多，但都面臨一個共同的難題，即TSV製作都需要打通不同材料層，包括矽材料、IC中各種絕緣或導電的薄膜層。例如金屬銅，阻擋層金屬鉭，二氧化矽絕緣層以及氮化矽停止層等，各種膜層的厚度也比較高，這就需要在CMP過程中具有較高的去除速率和合適的拋光選擇比，才能實現對前程缺陷的最大矯正，並停止在氮化矽層，同時不能產生金屬的腐蝕和缺陷，表面顆粒物須控制在工藝要求的範圍。這對矽通孔阻擋層的CMP提出了更高的要求。目前還沒有商業化的TSV阻擋層拋光液的報導。 There are many ways to integrate TSV processes, but they all face a common problem, that is, TSV production needs to open different layers of materials, including germanium materials, various insulating or conductive thin film layers in ICs. For example, metallic copper, barrier metal ruthenium, ruthenium dioxide insulating layer, and tantalum nitride stop layer, etc., the thickness of various film layers is also relatively high, which requires a high removal rate and a suitable polishing selection ratio in the CMP process. In order to achieve the maximum correction of the defects in the future, and stop in the tantalum nitride layer, and can not produce metal corrosion and defects, the surface particles must be controlled within the scope of the process requirements. This puts higher demands on the CMP of the through-hole barrier layer. There are currently no reports of commercial TSV barrier polishing fluids.
本發明的目的是解決上述現有技術中存在的問題，提供一種具有較高的二氧化矽介質材料去除速率和較高的對氮化矽的拋光選擇比，對前程的缺陷具有較高的校正能力，不產生金屬腐蝕和缺陷，穩定性較好的化學機械拋光液。 The object of the present invention is to solve the above problems in the prior art, and to provide a higher removal rate of the ceria dielectric material and a higher polishing selection ratio for tantalum nitride, and a higher correction capability for the defects of the precursor. A chemical mechanical polishing fluid that does not produce metal corrosion and defects and has good stability.
本發明的技術方案如下：一種TSV阻擋層拋光液，其特徵在於，包含以下組分：磨料、組合金屬保護劑、絡合劑、氧化劑、氮化矽抑制劑和pH調節劑。 The technical solution of the present invention is as follows: A TSV barrier layer polishing liquid characterized by comprising the following components: an abrasive, a combined metal protective agent, a complexing agent, an oxidizing agent, a cerium nitride inhibitor, and a pH adjusting agent.
其中，所述磨料是二氧化矽溶膠或氣相法二氧化矽。所述磨料的粒徑為20-200nm，較佳的為40-120nm。所述磨料含量為10-50%，較佳的為20-30%。 Wherein the abrasive is a cerium oxide sol or a gas phase cerium oxide. The abrasive has a particle size of from 20 to 200 nm, preferably from 40 to 120 nm. The abrasive content is from 10 to 50%, preferably from 20 to 30%.
其中，組合金屬保護劑包括一種唑類化合物和一種水溶性聚合物。 Wherein, the combined metal protecting agent comprises an azole compound and a water soluble polymer.
其中，所述的唑類化合物為苯並三氮唑及其衍生物；所述水溶性聚合物為聚丙烯酸及其共聚物。 Wherein the azole compound is benzotriazole and a derivative thereof; and the water-soluble polymer is polyacrylic acid and a copolymer thereof.
其中，所述唑類化合物的濃度為0.01-0.5%；所述水溶性聚合物的濃度為0.005-0.1%。優選的，所述唑類化合物的濃度為0.05-0.2%；所述水溶性聚合物的濃度為0.01-0.05%。 Wherein the concentration of the azole compound is 0.01-0.5%; and the concentration of the water-soluble polymer is 0.005-0.1%. Preferably, the concentration of the azole compound is 0.05-0.2%; and the concentration of the water-soluble polymer is 0.01-0.05%.
其中，所述的絡合劑選自有機磷酸，PBTCA，HPAA，HEDP，EDTMP和ATMP中的一種或多種。所述絡合劑的濃度為0.05%-1%，優選0.1-0.5%。 Wherein the complexing agent is selected from one or more of the group consisting of organic phosphoric acid, PBTCA, HPAA, HEDP, EDTMP and ATMP. The concentration of the complexing agent is from 0.05% to 1%, preferably from 0.1% to 0.5%.
其中，所述氮化矽抑制劑為一種萘磺酸鹽的甲醛縮聚物，具有以下通式：
其中：，所述氮化矽抑制劑的濃度從50ppm到0.1%。 among them: The concentration of the tantalum nitride inhibitor ranges from 50 ppm to 0.1%.
其中，所述氮化矽抑制劑為亞甲基雙萘磺酸二鈉鹽，甲基萘磺酸甲醛縮聚物和/或苄基萘磺酸甲醛縮聚物。 Wherein, the cerium nitride inhibitor is methylene bis naphthalene sulfonic acid disodium salt, methyl naphthalene sulfonic acid formaldehyde polycondensate and/or benzyl naphthalene sulfonic acid formaldehyde polycondensate.
其中，所述pH調節劑為一種有機羧酸。 Wherein the pH adjusting agent is an organic carboxylic acid.
其中，所述有機羧酸選自草酸，丙二酸，丁二酸，檸檬酸和酒石酸中的一種或多種。 Wherein the organic carboxylic acid is selected from one or more of oxalic acid, malonic acid, succinic acid, citric acid and tartaric acid.
其中，所述氧化劑為過氧化物或過硫化物。所述氧化劑選自過氧化氫，過氧化鈉，過氧化鉀，過氧化苯甲醯，過硫酸鈉，過硫酸鉀和過硫酸銨中的一種或多種。 Wherein the oxidizing agent is a peroxide or a persulfide. The oxidizing agent is selected from one or more of hydrogen peroxide, sodium peroxide, potassium peroxide, benzammonium peroxide, sodium persulfate, potassium persulfate and ammonium persulfate.
其中，拋光液還包括：殺菌防黴變劑。所述殺菌防黴變劑為季銨鹽活性劑。 The polishing liquid further includes: a bactericidal anti-fungal agent. The bactericidal mold inhibitor is a quaternary ammonium salt active agent.
其中，所述拋光液的pH值為2-5，優選3-4。 Wherein, the polishing liquid has a pH of 2-5, preferably 3-4.
本發明具備的有益效果是：具有更高的Ta和SiO2的去除速率，氮化矽的去除速率小於100A/min，選擇比達到15-20。能夠較好地停止在氮化矽層，絡合劑以及組合金屬保護劑的共同作用下，很好的保護金屬銅，未發現金屬腐蝕，且金屬的去除速率碎雙氧水呈溫和的線性變化。拋光後表面的細線區域清晰銳利，無顆粒物和有機物質殘留等污染物。此外，對前程同拋光後的缺陷具有較大幅度的校正，具有較好的平坦化效率。浸泡後，具有較好的抗腐蝕性能。 The invention has the beneficial effects that the removal rate of Ta and SiO2 is higher, the removal rate of tantalum nitride is less than 100 A/min, and the selection ratio is 15-20. It can better stop the combination of the tantalum nitride layer, the complexing agent and the combined metal protective agent, and the metal copper is well protected. No metal corrosion is found, and the metal removal rate of the hydrogen peroxide is mild and linear. The fine line area of the polished surface is clear and sharp, and there are no pollutants such as particulate matter and organic matter residue. In addition, the front-end and the polished defects have a large correction, and have better planarization efficiency. After soaking, it has good corrosion resistance.
下面通過具體實施方式來進一步闡述本發明的優勢。 Advantages of the present invention are further illustrated by the following detailed description.
拋光條件： 拋光墊：IC pad Polishing conditions: Polishing pad: IC pad
拋光條件：70/90 rpm Polishing conditions: 70/90 rpm
拋光液流量：100ml/min Polishing fluid flow rate: 100ml/min
靜態腐蝕速率：將新鮮拋光的銅片放入漿液中浸漬15min，測量前後的膜層厚度。 Static Corrosion Rate: Freshly polished copper sheets were immersed in a slurry for 15 min, and the film thickness before and after measurement was measured.
蝶形凹陷：採用Semitech 854圖形晶圓測量80um金屬塊的蝶形凹陷。 Butterfly-shaped depression: The butterfly depression of the 80um metal block was measured using a Semitech 854 graphic wafer.
切片內的拋光均一性：為一個管芯(晶粒)內不同線寬的蝶形凹陷。 Polishing uniformity within the slice: a butterfly-shaped depression of different line widths within one die (grain).
空白晶片：PETEOS，Ta，Cu，Si3N4 Blank wafer: PETEOS, Ta, Cu, Si3N4
BTA：苯並三氮唑，PAA：聚丙烯酸，PBTCA：2-膦酸-1,2,4-三羧酸丁烷。DISN1，亞甲基雙萘磺酸二鈉鹽，DISN2：甲基萘磺酸鹽甲醛縮合物，DISN3：苄基萘磺酸鹽甲醛縮合物。HPAA：2-羥基膦醯基乙酸，HEDP：羥基乙叉二磷酸。參比(比較)拋光液為市售的阻擋層拋光液。 BTA: benzotriazole, PAA: polyacrylic acid, PBTCA: 2-phosphonic acid-1,2,4-tricarboxylic acid butane. DISN1, methylenebisnaphthalenesulfonic acid disodium salt, DISN2: methylnaphthalenesulfonate formaldehyde condensate, DISN3: benzylnaphthalenesulfonate formaldehyde condensate. HPAA: 2-hydroxyphosphinic acid acetic acid, HEDP: Hydroxyethylidene diphosphate. The reference (comparative) polishing fluid is a commercially available barrier polishing fluid.
從圖1-4中可以看出，本拋光液和對比拋光液相比，具有更高的Ta和SiO2的去除速率，添加氮化矽抑制劑後，使得氮化矽的去除速率小於100A/min，選擇比達到15-20。能夠較好地停止在氮化矽層，絡合劑以及組合金屬保護劑的共同作用下，很好的保護金屬銅，未發現金屬腐蝕，且金屬的去除速率碎雙氧水呈溫和的線性變化。拋光後表面的細線區域清晰銳利，無顆粒物和有機物質殘留等污染物。此外，對前程同拋光後的缺陷具有較大幅度的校正，具有較好的平坦化效率。浸泡後，圖形片表面無明顯變化，顯示了較好的抗腐蝕性能。 As can be seen from Figures 1-4, the polishing solution has a higher removal rate of Ta and SiO 2 than the comparative polishing solution, and the removal rate of tantalum nitride is less than 100 A after the addition of the tantalum nitride inhibitor. Min, the selection ratio reaches 15-20. It can better stop the combination of the tantalum nitride layer, the complexing agent and the combined metal protective agent, and the metal copper is well protected. No metal corrosion is found, and the metal removal rate of the hydrogen peroxide is mild and linear. The fine line area of the polished surface is clear and sharp, and there are no pollutants such as particulate matter and organic matter residue. In addition, the front-end and the polished defects have a large correction, and have better planarization efficiency. After immersion, there was no significant change in the surface of the graphic sheet, indicating good corrosion resistance.
圖1、2為拋光後圖形片的表面形貌；圖3、4為在拋光液中浸泡過的表面圖片；圖5-7為TSV矽通孔阻擋層拋光前後的拋面示意圖，其中：圖5為矽通孔(TSV)拋光前拋面示意圖 Figure 1 and Figure 2 show the surface topography of the polished pattern; Figures 3 and 4 show the surface images soaked in the polishing solution; Figure 5-7 shows the polished surface of the TSV through-hole barrier layer before and after polishing. 5 is a schematic diagram of the polished surface of the through hole (TSV) before polishing.
圖6為矽通孔(TSV)銅拋光後拋面示意圖 Figure 6 is a schematic view of a polished surface of a through-hole (TSV) copper after polishing
圖7為矽通孔(TSV)阻擋層拋光後拋面示意圖 Figure 7 is a schematic view of the polished surface of the through hole (TSV) barrier layer after polishing
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| JP6767442B2 (en) * | 2018-08-24 | 2020-10-14 | 株式会社東芝 | Measuring instrument, etching system, silicon concentration measurement method, and silicon concentration measurement program |
| CN111378375B (en) * | 2018-12-28 | 2022-05-13 | 安集微电子科技（上海）股份有限公司 | Chemical mechanical polishing solution |
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| US6083840A (en) * | 1998-11-25 | 2000-07-04 | Arch Specialty Chemicals, Inc. | Slurry compositions and method for the chemical-mechanical polishing of copper and copper alloys |
| US6964600B2 (en) * | 2003-11-21 | 2005-11-15 | Praxair Technology, Inc. | High selectivity colloidal silica slurry |
| DE602006002900D1 (en) * | 2005-03-09 | 2008-11-13 | Jsr Corp | Aqueous dispersion for chemical mechanical polishing, kit for their preparation and chemical-mechanical polishing process |
| CN100595892C (en) * | 2005-04-14 | 2010-03-24 | 昭和电工株式会社 | Polishing composition |
| JPWO2007029465A1 (en) * | 2005-09-09 | 2009-03-19 | 旭硝子株式会社 | Abrasive, method for polishing surface to be polished, and method for manufacturing semiconductor integrated circuit device |
| JPWO2008013226A1 (en) * | 2006-07-28 | 2009-12-17 | 昭和電工株式会社 | Polishing composition |
| CN101130665A (en) * | 2006-08-25 | 2008-02-27 | 安集微电子（上海）有限公司 | Polishing solution used for polishing low-dielectric materials |
| CN101168847A (en) * | 2006-09-04 | 2008-04-30 | 株式会社荏原制作所 | Electrolytic liquid for electrolytic polishing and electrolytic polishing method |
| US20080149884A1 (en) * | 2006-12-21 | 2008-06-26 | Junaid Ahmed Siddiqui | Method and slurry for tuning low-k versus copper removal rates during chemical mechanical polishing |
| WO2008157293A1 (en) * | 2007-06-15 | 2008-12-24 | Basf Se | Controlling passivating film properties using colloidal particles polyelectrolytes, and ionic additives for copper chemical mechanical planarization |
| JP5317436B2 (en) * | 2007-06-26 | 2013-10-16 | 富士フイルム株式会社 | Polishing liquid for metal and polishing method using the same |
| TW200923055A (en) * | 2007-11-20 | 2009-06-01 | Anji Microelectronics Co Ltd | Chemical mechanical polishing slurry for low-k material |
| CN101463225A (en) * | 2007-12-21 | 2009-06-24 | 安集微电子（上海）有限公司 | Chemico-mechanical polishing solution for barrier layer |
| CN101463227B (en) * | 2007-12-21 | 2013-06-12 | 安集微电子（上海）有限公司 | Chemico-mechanical polishing solution for barrier layer |
| JP5441345B2 (en) * | 2008-03-27 | 2014-03-12 | 富士フイルム株式会社 | Polishing liquid and polishing method |
| JP5314329B2 (en) * | 2008-06-12 | 2013-10-16 | 富士フイルム株式会社 | Polishing liquid |
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| TW201323547A (en) | 2013-06-16 |
| CN103146306B (en) | 2016-12-28 |
| CN103146306A (en) | 2013-06-12 |
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