TWI385243B - 供相變材料之化學-機械研磨用之組合物及方法 - Google Patents
供相變材料之化學-機械研磨用之組合物及方法 Download PDFInfo
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- TWI385243B TWI385243B TW097128419A TW97128419A TWI385243B TW I385243 B TWI385243 B TW I385243B TW 097128419 A TW097128419 A TW 097128419A TW 97128419 A TW97128419 A TW 97128419A TW I385243 B TWI385243 B TW I385243B
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- Prior art keywords
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- composition
- cmp
- oxidizing agent
- weight
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- 238000000227 grinding Methods 0.000 claims description 13
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 11
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- 229910000420 cerium oxide Inorganic materials 0.000 claims description 8
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- 239000007864 aqueous solution Substances 0.000 claims description 6
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 claims description 6
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- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052787 antimony Inorganic materials 0.000 description 2
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- WFYASTPQDOUBSW-UHFFFAOYSA-N 1h-1,2,4-triazole Chemical compound C=1N=CNN=1.C1=NN=CN1 WFYASTPQDOUBSW-UHFFFAOYSA-N 0.000 description 1
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
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- RSRJCYZEMGBMDE-UHFFFAOYSA-J [K+].[K+].[K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O.[O-]S(=O)(=O)OOS([O-])(=O)=O Chemical compound [K+].[K+].[K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O.[O-]S(=O)(=O)OOS([O-])(=O)=O RSRJCYZEMGBMDE-UHFFFAOYSA-J 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 150000001413 amino acids Chemical class 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 150000001576 beta-amino acids Chemical class 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
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- 235000019262 disodium citrate Nutrition 0.000 description 1
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- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 description 1
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- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
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- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
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- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
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- 230000000737 periodic effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000008298 phosphoramidates Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000004838 photoelectron emission spectroscopy Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
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- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OUXVDHDFKSWBOW-UHFFFAOYSA-N tetraazanium sulfonatooxy sulfate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O.[O-]S(=O)(=O)OOS([O-])(=O)=O OUXVDHDFKSWBOW-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
-
- 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
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11C—STATIC STORES
- G11C13/00—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00
- G11C13/0002—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00 using resistive RAM [RRAM] elements
- G11C13/0004—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00 using resistive RAM [RRAM] elements comprising amorphous/crystalline phase transition cells
-
- 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
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mechanical Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Description
本發明係關於研磨組合物及使用該組合物以研磨基材之方法。尤其,本發明係關於適合供研磨含有相變材料(如鍺銻碲合金)之基材的化學-機械研磨組合物。
在電子記憶體應用上,相變隨機存取記憶體(Phase Change Random Access Memory,PRAM)裝置(亦稱作雙向(Ovonic)記憶裝置或PCRAM裝置)係使用一種可以在絕緣性非晶相及導電性晶相之間電性切換的相變材料(phase change material,PCM)。適用於該些應用的典型相變材料係使用週期表之各種VIB族(硫族化物(chalcogenide),如碲或釙)及VB族(如銻)元素並搭配一或多種金屬元素,如銦、鍺、鎵、錫或銀。特別有用的相變材料為鍺(Ge)銻(Sb)碲(Te)(germanium-antimony-tellurium,GST)合金,如一具有化學式Ge2
Sb2
Te5
(GST225)的合金。該些材料可視加熱/冷卻速率、溫度、及時間而可逆地改變物理狀態。其他可用的合金包括銻化銦(InSb)。PRAM裝置中的記憶資料係藉由不同物理相或狀態之導電性質而在最少損失的情況下得到保存。
供化學-機械研磨(CMP)基材表面用之組合物及方法係本領域所熟知者。供研磨半導體基材(如積體電路)之含金屬表面的研磨組合物(亦稱作研磨漿料、CMP漿料及CMP組合物)一般包含磨料、各種添加劑化合物等等,且經常搭配氧化劑使用。
在傳統的CMP技術中,係於CMP裝置中將一基材載具(研磨頭)安裝於一載具組件上,且放置於與一研磨墊接觸的位置。該載具組件提供一可控制的壓力(「向下作用力」或「向下壓力」)以推動該基材而使其壓在該研磨墊上。該墊及載具(與其上所附的基材)係彼此相對移動。該墊及基材之相對移動係用以摩擦該基材表面以自該基材表面去除一部分的材料,從而研磨該基材。一般而言,該基材表面之研磨可藉由研磨組合物的化學活性(如由於CMP組合物中的氧化劑、鉗合劑、腐蝕抑制劑、酸等等)及/或研磨組合物中所懸浮之磨料的機械活性而進一步輔助及控制。一般磨料包括例如二氧化矽(silica)、氧化鈰(ceria)、氧化鋁(alumina)、氧化鋯(zirconia)、二氧化鈦(titania)及氧化錫。
舉例言之,美國專利第5,527,423號(Neville等人)描述一種藉由使一金屬層之表面與一研磨漿料接觸而化學-機械研磨該金屬層的方法,該研磨漿料包含懸浮於一水性介質中之高純度細金屬氧化物顆粒。或者,該磨料可混入研磨墊中。美國專利第5,489,233號(Cook等人)揭示一種具有一表面紋理或圖案之研磨墊的使用,且美國專利第5,958,794號(Bruxvoort等人)揭示一種固定磨料式研磨墊(fixed abrasive polishing pad)。
CMP技術可用來製造採用相變材料的記憶裝置,然而,當用於研磨含有相對軟的相變材料如GST或InSb之基材時,現有的CMP組合物時常無法提供足夠的平坦性。尤其,許多相變材料(如GST或InSb)之物理性質,使其相對於PCM晶片中所使用的其他材料係「柔軟的」。舉例言之,一般含有相對高固體物濃度(如>3%)
之CMP研磨漿料係藉由磨料顆粒之機械性作用以去除相變材料(如GST合金),造成相變材料表面上的大量刮痕(scratching)。當使用這樣的高固體CMP組合物時,由於該CMP研漿無法去除所有的相變材料,因此於研磨之後,相變材料殘留物時常會留在下方的介電薄膜上。該相變材料殘留物在後續的裝置製造步驟中將引起其他整合問題。
共同擁有及審核中之美國專利第11/699,129號申請案係描述利用一微粒磨料搭配至少一鉗合劑、一視需要之氧化劑、及一水性載體,以研磨一相變材料之CMP組合物及方法。該磨料在該組合物中之濃度不超過3重量%。該鉗合劑包含一化合物或化合物之組合,該化合物及該化合物之組合可鉗合欲研磨基材中之PCM或其成分(如鍺、銦、銻及/或碲物種),或鉗合一於該CMP組合物研磨該基材期間,自PCM所形成之物質(如氧化產物)。
使用氧化劑之供研磨相變材料(如GST)之CMP組合物之一缺點為,在PCM之表面上會增長一氧化物塗覆層,降低PCM裝置之電效能。發展能減少基材表面上PCM氧化物之增長程度且相較於傳統的CMP組合物仍令人滿意地迅速去除相變材料的新CMP組合物,仍存在持續的需求。本發明便提供此等改良的CMP組合物。本發明之該些及其他優點,及其他的發明特徵,將可由此處所提供之發明描述而清楚知悉。
本發明提供一適於研磨一含有相變材料之基材的化學-機械研磨組合物。該CMP組合物包含一搭配離胺酸之微粒磨料、一視需
要之氧化劑、及一用於此之水性載體。該磨料之濃度較佳不超過6重量%。咸信離胺酸係用作一PCM氧化抑制劑,減少PCM表面上所不欲之氧化層的增長。
本發明亦提供一種以本發明CMP組合物研磨PCM基材表面的方法。一較佳的方法包含以下步驟:使一含PCM基材之一表面與一研磨墊及本發明之水性CMP組合物接觸;以及使研磨墊與基材之間產生相對運動,同時維持CMP組合物之一部分與該墊及基材間的表面接觸。上述相對運動係維持一段足以自基材磨掉至少一部分PCM的時間。
本發明提供一種在氧化劑存在下,可用於研磨含有相變材料之基材的CMP組合物。本發明CMP組合物係可提供PCM之平均去除,同時相對於傳統CMP組合物而言,減少基材表面上PCM氧化物的增長程度。本發明CMP組合物包含一於水性載體中的微粒磨料及離胺酸,所述水性載體例如為水(如去離子水)。在某些實施態樣中,組合物包含一鉗合劑,鉗合劑可鉗合被研磨基材中之PCM或其所含成分(如鍺、銦、銻及/或碲物種),或可鉗合於研磨過程中自PCM所形成之物質(如自PCM所形成之氧化產物)。在其他實施態樣中,組合物亦包含一氧化劑。
可用於本發明CMP組合物的微粒磨料包括任何適用於半導體材料之CMP的磨料。適合磨料的非限制性實施例包括二氧化矽(如發煙二氧化矽(fumed silica)及/或膠體狀二氧化矽)、氧化鋁、二氧化鈦、氧化鈰、氧化鋯、或前述二或多種磨料之組合,此為
CMP領域中所熟知。較佳的金屬氧化物磨料包括膠體狀二氧化矽、發煙二氧化矽及α-氧化鋁。磨料在組合物中的濃度較佳係不超過6重量%。磨料在CMP組合物中的濃度較佳係0.001至6重量%,更佳係0.01至5重量%,最佳係0.1至1重量%。當以本領域所熟知之雷射光散射技術測定時,磨料的平均粒徑較佳係5奈米至250奈米,更佳係50奈米至150奈米。
期望地,磨料係懸浮於CMP組合物中,更具體而言,係懸浮於CMP組合物之水性成分中。當磨料懸浮於CMP組合物中時,磨料較佳具膠狀穩定性。術語「膠體」意指磨料顆粒於液態載體中的懸浮。「膠狀穩定性」意指在最少沉降的情況下,於一段選定時間內保持懸浮狀態的維持性。於本發明之內文中,當懸浮物放置於一100毫升量筒中並於未攪拌下靜置2小時的時間,若懸浮於量筒之底部50毫升的顆粒濃度([B]以克/毫升計)及懸浮於量筒之頂部50毫升的顆粒濃度([T]以克/毫升計)間的濃度差,除以磨料組合物中的初始顆粒濃度([C]以克/毫升計)係小於或等於0.5(即([B]-[T])/[C]≦0.5),則認定磨料具膠狀穩定性。([B]-[T])/[C]之期望值係小於或等於0.3,且較佳係小於或等於0.1。
適用於本發明CMP組合物及方法的氧化劑包括但不限於過氧化氫、過硫酸鹽(如過硫酸銨、二過硫酸銨(ammonium dipersulfate)、過硫酸鉀、及二過硫酸鉀(potassium dipersulfate))、過碘酸鹽(如過碘酸鉀)、及前述二或多者之組合。過氧化氫尤其為較佳者。較佳地,氧化劑係存在組合物中,或以0.01至6重量%的濃度(以組合物與過氧化氫的總重量計),較佳以0.1至4重量%的濃度,
與CMP組合物搭配使用。
本發明組合物包含離胺酸,以組合物總重量計,其濃度較佳係0.01至5重量%,更佳係0.05至2重量%。咸信離胺酸能抑制PCM的氧化,尤其是GST氧化,且能在氧化劑(如過氧化氫)存在下之CMP期間,減少於PCM基材表面上產生的氧化產物含量。
本發明CMP組合物的pH值較佳係2至11,更佳係2至5,尤佳係2至4。CMP組合物可視需要包含一或多種pH緩衝材料,例如醋酸銨、檸檬酸二鈉等等。本領域已熟知許多此種pH緩衝材料。
本發明CMP組合物可視需要包含一或多種鉗合劑,鉗合劑可鉗合存在於被研磨基材中的PCM或其成分(如鍺、銦、銻及/或碲物種),或可鉗合於CMP過程中自其所形成的物質。合適之鉗合劑的非限制性實施例包含二羧酸(如草酸、丙二酸、琉珀酸、馬來酸、鄰苯二甲酸、酒石酸、天門冬氨酸(aspartic acid)、麩胺酸等等)、聚羧酸(如檸檬酸、1,2,3,4-丁烷四羧酸、聚丙烯酸、聚馬來酸等等)、氨基羧酸(如α-氨基酸、β-氨基酸、Ω-氨基酸等等)、磷酸鹽、聚磷酸鹽、氨基磷酸酯、磷羧酸、聚合鉗合劑、其鹽類、前述二或多者之組合等。較佳之鉗合劑包括草酸、丙二酸、琥珀酸、檸檬酸、其鹽類、及前述二或多者之組合。當使用時,鉗合劑在組合物中之濃度較佳係0.1至3重量%。
此外,本發明CMP組合物可包含其他視需要組分,如除生物劑、分散劑、黏度調節劑、緩衝劑、pH調節劑、金屬腐蝕抑制劑(如苯并三唑(benzotriazole)或1,2,4三唑(1,2,4-triazole))等等。
可藉由任何合適技術以製造本發明CMP組合物,許多技術係本
領域習知技術者所熟知者。可以批次或連續製程製造CMP組合物。一般來說,可以任意順序混合其成分而製造CMP組合物。此處所使用的術語「成分」包含個別的組分(如磨料、離胺酸、鉗合劑、酸、鹼、氧化劑等等)和組分之任意組合。例如,可將磨料分散於水中,加入離胺酸並藉由任何可將該些成分併入至CMP組合物中之方法混合。當存在氧化劑時,可在任何適合的時間添加至組合物中。在某些實施態樣中,直到當組合物已準備於CMP製程中使用時,才將氧化劑添加至CMP組合物中,例如,恰於開始研磨之前添加氧化劑。可在任何適合的時間調整pH值。
本發明CMP組合物亦可為一濃縮物形式,在使用之前再以適當量之水性載體稀釋之。於此一實施態樣中,CMP組合物濃縮物可包含以一含量分散或溶解於一水性載體中的各種成分,從而當以適當量之水性載體(如水)稀釋該濃縮物時,研磨組合物的各個成分在CMP組合物中的含量係於適用範圍內。
本發明亦提供一種化學-機械研磨含有PCM之基材的方法。一較佳的方法包含以下步驟:(i)使一基材之一表面與一研磨墊及一此處所描述之本發明CMP組合物接觸;以及(ii)在中間具研磨組合物的情況下相對於基材表面移動研磨墊,進而自基材磨掉至少一部分的PCM以研磨其表面。
本發明之CMP方法可用以研磨任何合適的基材,且尤其適用於研磨含GST合金、InSb等等的基材。較佳地,PCM為一GST合金(如Ge2
Sb2
Te5
)或InSb。基材較佳係亦包含一襯料(liner material)如Ti或TiN,及位於其下方的一層二氧化矽。在較佳方
法中,摩擦一PCM或一襯料層且於二氧化矽層終止。
本發明CMP方法尤其適合搭配一化學-機械研磨裝置使用。一般來說,CMP裝置包含:一研磨平台,使用時其係以一起因於軌道、線性或圓周運動的速度運轉;一研磨墊安裝在研磨平台上,且隨研磨平台移動;一載具組件,其托住一欲研磨之基材使其與該墊接觸且相對於研磨墊之表面移動,同時以一選定的壓力(向下作用力)推動基材,使其壓在該墊上以幫助基材表面之研磨。一般而言,係將一CMP組合物以泵送至研磨墊以幫助研磨製程。藉由移動的研磨墊及本發明CMP組合物在研磨墊上的混合研磨作用,而完成基材之研磨,該作用係磨掉至少部分基材表面,進而研磨該表面。
可使用任何適合的研磨墊(如研磨表面),以本發明CMP組合物將一基材平坦化或研磨。適合的研磨墊之非限制性實施例包括織造及非織造研磨墊,若需要,其可包含固定式磨料。此外,適合的研磨墊可包含任何具有適合的密度、硬度、厚度、壓縮性、壓縮時的回彈能力、壓縮模數、化學穩定性、及/或化學抗性的聚合物,如CMP領域中所熟知者。適合的聚合物,例如包括聚氯乙烯、聚氟乙烯、尼龍、氟碳化物、聚碳酸酯、聚酯、聚丙烯酸酯、聚醚、聚乙烯、聚醯胺、聚氨酯、聚苯乙烯、聚丙烯、其共形成的產物及其混合物。
期望地,CMP裝置更包含一原位研磨終點檢測系統,許多該類系統係為本領域所熟知者。本領域已熟知藉由分析自物件表面所反射的光線或其他射線來檢視及監測研磨製程的技術。例如,此
類方法係描述於美國專利第5,196,353號(Sandhu等人)、第5,433,651號(Lustig等人)、第5,949,927號(Tang)、第5,964,643號(Birang等人)。期望的是能針對被研磨的物件檢視或監測其研磨製程之進行而決定研磨終點,即決定何時對一特定物件終止研磨製程。
以下實施例係用以進一步說明本發明,但當然不應以任何方式解釋成以限制本發明範圍。
本實施例說明於過氧化氫存在下離胺酸之GST氧化抑制活性。
將個別的GST晶圓(1公分乘1公分,Ge2
Sb2
Te5
;GST225)浸到室溫下的各種測試水溶液中歷時100秒。一對照溶液之pH值為3,且含有1重量%之溶於水中的過氧化氫。其他測試溶液含有與苯并三唑(BTA;0.1重量%)、離胺酸(1重量%)、或丙二酸(3重量%)混合的過氧化氫(1重量%)。晶圓在被浸入測試溶液前具有一光亮的金屬外觀。浸泡後晶圓表面上的褐色表示一GST氧化層形成於表面上。評估之結果及測試溶液之組成係如表1所示。如表1中的資料所顯示,離胺酸有效地且實質上抑制GST氧化物塗覆層形成於晶圓表面上。BTA具有輕微的抑制效果,而單獨使用過氧化氫及使用與丙二酸混合之過氧化氫者則各自有一顯著的氧化層形成。
表1
本實施例說明於過氧化氫存在下利用電化學測量法測量離胺酸之GST氧化抑制活性。
將一GST225 (Ge2
Sb2
Te5
)旋轉盤電極(直徑1公分)浸入一含有1重量%之離胺酸及1重量%之過氧化氫的水溶液(pH值為3)中。實施線性掃描伏安法(linear sweep voltametry),且將相對於標準氫電極(standard hydrogen electrode,SHE)的電壓對腐蝕電流之對數(log[I])繪圖而獲得一塔弗曲線圖(Tafel plot)(第1圖)。以相同程序,使用一實質相似、浸在一pH值為3且含有3重量%之丙二酸及1重量%之過氧化氫水性溶液中的GST電極,獲得一供比較用的塔弗曲線圖(第1圖)。第1圖之塔弗曲線顯示離胺酸/過氧化氫溶液之腐蝕電流為0.22毫安培,同時丙二酸/過氧化氫溶液(不含離胺酸)之腐蝕電流為4.5毫安培。為供比較用,獲得對pH值2.9、1重量%之過氧化氫水溶液及pH值為2.9之水
的塔弗曲線圖(見第2圖)。在此實驗中1重量%之過氧化氫溶液之腐蝕電流為0.2毫安培,且水之腐蝕電流為0.17毫安培。此些結果顯示,相較於以一丙二酸及過氧化氫之水溶液所獲得的腐蝕電流,離胺酸顯著降低在酸性pH值下、於水性過氧化氫中的GST腐蝕電流。
本實施例說明利用X射線光射光譜法(x-ray photoemission spectroscopy,XPS)測量離胺酸之GST氧化抑制活性。
實施用氬濺射之利用成份縱深分佈(depth profiling)之XPS實驗以測定氧化層厚度,該氧化層厚度藉由在0.5重量%之離胺酸或3重量%之丙二酸存在下,以1重量%之過氧化氫(pH值為3)氧化GST225所獲得。藉由濺射一厚度已知的SiO2
樣本校正厚度測量。去除4奈米之表面薄膜之後,當氧化峰值消失時即獲得氧化厚度。觀測到的氧化厚度係顯示於表2(以SiO2
等效厚度計,單位為埃)。如表2中的數據所示,離胺酸減少鍺及銻之氧化層厚度達50%,對碲達66%。
本實施例說明本發明CMP組合物於CMP製程中有效去除GST薄膜的能力。
在1重量%之過氧化氫(以該研磨組合物及過氧化氫之混合重量計)存在下,於一使用IC1010型研磨墊的200毫米Mirra研磨機上,以研磨平台速率每分鐘93 rpm、載具速率87 rpm、向下壓力4磅-每平方英吋(psi)及漿料流率每分鐘200毫升(毫升/分鐘)的條件,研磨晶圓表面具有5000埃之Ge2
Sb2
Te5
薄膜的矽晶圓。經評估之CMP組合物各自含有1重量%之過氧化氫且pH值為3。比較組合物4A含有1重量%之膠體狀二氧化矽(平均粒徑為130奈米)及3重量%之丙二酸。(本發明之)組合物4B含有3.5重量%之膠體狀二氧化矽(平均粒徑為130奈米)及0.5重量%之離胺酸。GST去除速率(removal rate,RR)係顯示於表3。
比較組合物4A表示一種如共有且共同申請中之美國專利第11/699,129號(Dysard等人)申請案所教示的組合物,其教示使用不超過3重量%之磨料搭配丙二酸及相似材料。表3所示之組合物4B的去除速率顯示,即使在未存在丙二酸的情況下,本發明之組合物仍可達到極佳的GST去除速率。
第1圖顯示與含有1重量%之離胺酸及1重量%之過氧化氫的水溶液(pH值為3)接觸之GST電極,及與含有3重量%之丙二酸及1重量%之過氧化氫的水溶液(pH值為3)接觸之GST電極之
電化學腐蝕的塔弗曲線(電壓對log電流)的比較;第2圖顯示於1重量%之水性過氧化氫(pH值為2.9)中及於水(pH值為2.9)中所獲得之電化學GST腐蝕之塔弗曲線的比較。
Claims (16)
- 一種供研磨一含有相變材料之基材用之化學-機械研磨(CMP)組合物,該組合物包含:(a)一微粒磨料,其中該微粒磨料之濃度係0.001至6重量%且係選自以下群組:膠體狀二氧化矽、發煙二氧化矽(fumed silica)、及α-氧化鋁;(b)離胺酸,其中該離胺酸之濃度係0.01至5重量%;以及(c)一用於此之水性載體。
- 如請求項1所述之CMP組合物,更包含一氧化劑。
- 如請求項2所述之CMP組合物,其中該氧化劑之濃度係0.01至6重量%。
- 如請求項2所述之CMP組合物,其中該氧化劑包含至少一選自以下群組之氧化劑:過氧化氫、過硫酸鹽、過碘酸鹽及其鹽類。
- 如請求項2所述之CMP組合物,其中該氧化劑包含過氧化氫。
- 一種供研磨一含有相變材料之基材用之化學-機械研磨(CMP)方法,該方法包含在一氧化劑存在下以請求項1所述之CMP組合物研磨該基材之表面。
- 一種供研磨一含有相變材料之基材用之化學-機械研磨(CMP)方法,該方法包含以下步驟:(a)在一氧化劑存在下使該基材之一表面與一研磨墊及一水性CMP組合物接觸,該CMP組合物包含一水性載體、一 微粒磨料及離胺酸,其中該微粒磨料在該組合物中之濃度係0.001至6重量%且係選自以下群組:膠體狀二氧化矽、發煙二氧化矽(fumed silica)、及α-氧化鋁,且該離胺酸在該組合物中之濃度係0.01至0.5重量%;以及(b)使該研磨墊及該基材之間產生相對運動,同時維持該CMP組合物之一部分與該墊及該基材間的表面接觸,該接觸係經歷一段足以自該基材磨掉至少一部分該相變材料的時間。
- 如請求項7所述之方法,其中該氧化劑包含至少一選自以下群組之材料:過氧化氫、過硫酸鹽、過碘酸鹽及其鹽類。
- 如請求項7所述之方法,其中該氧化劑包含過氧化氫。
- 如請求項7所述之方法,其中該氧化劑之濃度係0.01至6重量%。
- 如請求項7所述之方法,其中該基材包含一鍺銻碲(germanium-antimony-tellurium,GST)合金之表層。
- 如請求項11所述之方法,其中該基材更包含一襯料(liner material)位於該表層之下。
- 如請求項12所述之方法,其中該襯料係選自以下群組:鈦、氮化鈦、及其混合物。
- 如請求項12所述之方法,其中該基材更包含一二氧化矽層位於該襯料之下。
- 如請求項14所述之方法,其中係各自研磨該GST合金及該襯料,且該研磨係止於該二氧化矽層。
- 如請求項7所述之方法,其中該基材包含銻化銦(indium antimonide,InSb)。
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