TWI608089B - Grinding composition - Google Patents
Grinding composition Download PDFInfo
- Publication number
- TWI608089B TWI608089B TW102135326A TW102135326A TWI608089B TW I608089 B TWI608089 B TW I608089B TW 102135326 A TW102135326 A TW 102135326A TW 102135326 A TW102135326 A TW 102135326A TW I608089 B TWI608089 B TW I608089B
- Authority
- TW
- Taiwan
- Prior art keywords
- polishing
- acid
- polishing composition
- abrasive grains
- polished
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 105
- 238000000227 grinding Methods 0.000 title description 10
- 238000005498 polishing Methods 0.000 claims description 195
- 239000002245 particle Substances 0.000 claims description 73
- 229910052751 metal Inorganic materials 0.000 claims description 70
- 239000002184 metal Substances 0.000 claims description 70
- 239000006061 abrasive grain Substances 0.000 claims description 51
- 230000004888 barrier function Effects 0.000 claims description 51
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 23
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- 239000007800 oxidant agent Substances 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 10
- 239000003002 pH adjusting agent Substances 0.000 claims description 9
- 230000007797 corrosion Effects 0.000 claims description 7
- 238000005260 corrosion Methods 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
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- 230000001186 cumulative effect Effects 0.000 claims description 5
- 239000011164 primary particle Substances 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
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Classifications
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- 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
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- 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
- C09K3/1436—Composite particles, e.g. coated particles
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- 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]
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Engineering (AREA)
Description
本發明係關於研磨用組成物。
近年來,伴隨LSI之高集積化、高性能化已開發新的微細加工技術。化學機械研磨(以下亦單記為CMP)法亦為其中一種,是頻繁被利用在LSI製造步驟、尤其是多層配線形成步驟之層間絕緣膜的平坦化、金屬插頭形成、嵌入配線(金屬鑲嵌法配線)形成之技術。
CMP之一般方法,係貼附研磨墊於圓形之研磨定盤(平台)上,將研磨墊表面以研磨劑浸漬,壓附形成基板之金屬膜的面,以加入從其背面之特定壓力(以下亦單記為研磨壓力)之狀態旋轉研磨定盤,藉由研磨劑與金屬膜凸部之機械摩擦,來去除凸部之金屬膜者。
另一方面,於配線之銅或銅合金等下層,作為為了防止對層間絕緣膜中之銅擴散之阻隔層,形成鉭、鉭合金、或鉭化合物等。據此,於嵌入銅或銅合金之配線部分之外,有必要將露出之阻隔層由CMP去除。
為了形成各配線層,首先,以鍍敷法等將準
備好之多餘配線材去除之金屬膜之CMP(以下亦稱為「金屬膜CMP」)以超過一階段或多階段進行,其次一般係藉由此進行去除露出於表面之阻隔層CMP(以下亦稱為「阻隔層CMP」)。然而,藉由金屬膜CMP,造成配線部分過度研磨引起即所謂碟形凹陷或侵蝕及牙狀凹陷(fang)之表面缺陷的問題。
為了減輕碟形凹陷,尋求於金屬膜CMP接著進行阻隔層CMP,調整金屬配線部分之研磨速度與障礙金屬部分之研磨速度,最終形成碟形凹陷或侵蝕等段差少之配線層。亦即,於阻隔層CMP,比較金屬配線部分,阻隔層或層間絕緣膜之研磨速度相對小的情況時,因為導致產生配線部分被快速研磨之碟形凹陷、或作為其結果之侵蝕,故期望阻隔層或絕緣膜之研磨速度為適當之大小。此除了提高阻隔層CMP之產出量的優點外,因為實際上藉由金屬膜CMP產生碟形凹陷多,故從如上述之理由亦期望追求相對性提高阻隔層或絕緣膜之研磨速度這點。
又,作為表面缺陷有必要抑制牙狀凹陷。作為產生牙狀凹陷的一個原因,在配線層與阻隔層或與所謂層間絕緣膜之配線層以外區域的邊界面,研磨液所包含之成分局部呈現不均勻,被認為是邊界面附近被過度研磨所造成。例如,研磨液所包含之研磨粒成分以高濃度存在於前述邊界面附近時,在該邊界面之研磨速度局部性地增大,認為是被過度研磨。
如此等,一邊相對性地高度維持對於配線層
之阻隔層及對於層間絕緣膜之研磨速度,一邊減低所謂侵蝕或牙狀凹陷之表面缺陷之技術,例如於日本特開2010-041029號公報及日本特開2010-041027號公報,已揭示係用以研磨半導體積體電路之銅膜、障礙金屬膜及層間絕緣膜之研磨液,包含具有特定矽烷醇基密度之二氧化矽粒子與有機酸之研磨液。
然而,於上述日本特開2010-041029號公報及日本特開2010-041027號公報所記載之研磨液,對於阻隔層及絕緣膜層之高研磨速度的維持、以及所謂牙狀凹陷或侵蝕之表面缺陷的抑制尚不夠充分,故追求進一步的改良。又,在金屬配線層,對於直接維持高研磨速度使碟形凹陷等段差缺陷減低尚有改良的餘地。
因此本發明之一目的係提供一種研磨用組成物,對於阻隔層及絕緣膜可充分維持高研磨速度,且可抑制所謂牙狀凹陷或侵蝕之表面缺陷。又,本發明之其他目的,係提供對於金屬配線層直接維持高研磨速度即實現碟形凹陷等段差缺陷的減低之手段。
為了解決上述課題,本發明者們重複銳意研究銳意研究。其結果,發現藉由使用包含研磨粒、氧化
劑、金屬防腐蝕劑、pH調整劑、及水,該研磨粒之長寬比為1.22以下,且在藉由雷射繞射散射法所求得前述研磨粒之粒度分布中,從微粒子側之累計粒子重量達到全粒子重量之90%時之粒子之直徑D90與達到全粒子之全粒子重量10%時之粒子之直徑D10的比D90/D10為1.5以上之研磨用組成物,而解決上述課題。尤其是關於以往對研磨速度與表面缺陷之2個課題係有權衡關係之研磨粒的長寬比與粒度分布,基於藉由維持在一定的值可解決上述課題之嶄新卓見,終至完成本發明。
亦即,本發明係提供一種研磨用組成物,其係使用於將具有阻隔層、金屬配線層、及絕緣膜之研磨對象物研磨之用途之研磨用組成物,其特徵為包含研磨粒、氧化劑、金屬防腐蝕劑、pH調整劑、及水,前述研磨粒之長寬比為1.22以下,且在藉由雷射繞射散射法所求得前述研磨粒之粒度分布中,從微粒子側之累計粒子重量達到全粒子重量之90%時之粒子之直徑D90與達到全粒子之全粒子重量10%時之粒子之直徑D10的比D90/D10為1.5以上。
11‧‧‧凹槽
12‧‧‧絕緣膜
13‧‧‧阻隔層
14‧‧‧金屬配線層
[圖1]為表示關係本發明研磨對象物之一例的剖面概略圖。
本發明係一種研磨用組成物,其係使用於將具有阻隔層、金屬配線層、及絕緣膜之研磨對象物研磨之用途之研磨用組成物,其特徵為包含研磨粒、氧化劑、金屬防腐蝕劑、pH調整劑、及水,前述研磨粒之長寬比為1.22以下,且在藉由雷射繞射散射法所求得前述研磨粒之粒度分布中,從微粒子側之累計粒子重量達到全粒子重量之90%時之粒子之直徑D90與達到全粒子之全粒子重量10%時之粒子之直徑D10的比D90/D10為1.5以上。藉由成為如此之構成,對於阻隔層及絕緣膜可充分維持高研磨速度,且可抑制所謂牙狀凹陷或侵蝕之表面缺陷。又,藉由成為如此之構成,直接高度維持Cu速度,可抑制碟形凹陷。
藉由使用本發明之研磨用組成物而得到如上述之效果,詳細理由雖尚不清楚,但已知以往除了增大研磨粒之長寬比以提高相對於研磨對象物之研磨速度之外,表面缺陷惡化。又,認為藉由縮小研磨粒之粒度分布幅度可減低表面缺陷。對於這點,於本發明,認為將研磨粒之長寬比定於一定值以下,亦即藉由將研磨粒之形狀更近似真圓形,排除對研磨粒之形狀成為原因之表面缺陷的影響。另一方面,規定粒度分布之幅度之比D90/D10為一定值以上,亦即藉由使用研磨粒粒度分布之幅度更廣者,增加粒徑大之研磨粒比例,作為其結果,認為可一邊維持高研磨速度,一邊防止碟形凹陷、牙狀凹陷等之表面缺陷。
尚且,上述機制係藉由推測者,本發明並非為被限定於上述機制者。
據此,本發明之研磨用組成物作為金屬配線層用CMP漿料,可對金屬配線層之CMP使用,又,作為阻隔層及/或絕緣層用CMP漿料,亦可對阻隔層及/或絕緣層之CMP使用,在雙方之CMP,可一邊維持高研磨速度,一邊抑制表面缺陷。故本發明之合適研磨用組成物係金屬配線研磨用組成物,其他合適之一實施形態,為阻隔層及/或絕緣層研磨用組成物。
關於本發明之研磨對象物係具有阻隔層、金屬配線層、及絕緣膜。
首先,將關係本發明之研磨對象物及半導體配線製程之一例遵循圖1進行說明。半導體配線製程通常包含以下步驟。
如圖1(a)所示,於基板(未圖示)上所設置之具有凹槽11之絕緣體層12之上,依順序形成阻隔層13及金屬配線層14。阻隔層13係於金屬配線層14形成之前,以如覆蓋絕緣體層12之表面般之方式形成於絕緣體層12之上。阻隔層13的厚度小於凹槽11之深度及寬度。金屬配線層14係接續於阻隔層13之形成,以如至少埋藏凹槽11般之方式形成於阻隔層13之上。
藉由CMP,至少去除金屬配線層14之外側部分及阻
隔層13之外側部分時,首先,如圖1(b)所示,去除金屬配線層14外側部分之大半。其次,如圖1(c)所示,為了露出阻隔層13外側部分的上面,故去除金屬配線層14外側部分的殘部。
然後,藉由CMP,去除至少位於凹槽11之外的金屬配線層14部分(金屬配線層14之外側部分)及位於凹槽11之外的阻隔層13部分(阻隔層13之外側部分)。其結果如圖1(d)所示,位於凹槽11中之阻隔層13部分(阻隔層13之內側部分)中至少一部分及位於凹槽11中之金屬配線層14部分(金屬配線層14之內側部分)中至少一部分殘留於絕緣體層12之上。亦即,於凹槽11之內側殘留阻隔層13之一部分及金屬配線層14之一部分。從而,凹槽11之內側所殘留之金屬配線層14的部分,發揮作為配線之功能。
作為阻隔層所包含之材料,並未特別限制,例如可列舉鉭、鈦、鎢、鈷;金、銀、白金、鈀、銠、釕、銥、鋨等貴金屬等。此等金屬可用合金或金屬化合物之形態包含於阻隔層。較佳為鉭或貴金屬。此等金屬可單獨或組合2種以上使用。
又,金屬配線層所包含之金屬亦無特別限制,例如可列舉銅、鋁、鉿、鈷、鎳、鈦、鎢等。此等之金屬可用合金或金屬化合物之形態包含於金屬配線層。因為企圖導電性高、LSI之高速化,故金屬配線層較佳為包含銅、或銅合金。尤其是本發明之研磨用組成物,這些金
屬可單獨或組合2種以上使用。
作為絕緣膜所包含之材料可列舉TEOS(四乙氧矽烷)等。
其次,對於本發明之研磨用組成物之構成進行詳細說明。
研磨用組成物中所包含之研磨粒,係具有機械性研磨研磨對象物之作用,藉由研磨用組成物提高研磨對象物的研磨速度。
所使用之研磨粒可為無機粒子、有機粒子、及有機無機複合粒子之任一者。作為無機粒子之具體例,例如可列舉由二氧化矽、氧化鋁、氧化鈰、二氧化鈦等金屬氧化物所成之粒子、氮化矽粒子、碳化矽粒子、氮化硼粒子。作為有機粒子之具體例,例如可列舉聚甲基丙烯酸甲酯(PMMA)粒子。該研磨粒可單獨或混合2種以上使用。又,該研磨粒可使用市售品或使用合成品。
此等研磨粒當中,以二氧化矽為佳,較佳為膠態二氧化矽。
研磨粒可經表面修飾。一般之膠態二氧化矽,因為於酸性條件下動電位之值接近零,於酸性條件下二氧化矽粒子之間彼此不電氣性排斥故容易引起凝集。對於此,即使於酸性條件以動電位如具有比較大負之值般的方式經表面修飾之研磨粒,在酸性條件下彼此強烈排斥而
分散成良好之結果,而提高研磨用組成物之保存安定性。如此表面修飾研磨粒,例如可藉由將鋁、鈦或鋯等之金屬或是該等之氧化物與研磨粒混合使其摻雜於研磨粒的表面而得到。
其中,特別優選的是固定化有機酸之膠態二氧化矽。對研磨用組成物中所包含之膠態二氧化矽表面之有機酸的固定化,例如藉由化學性鍵結有機酸之官能基於膠態二氧化矽之表面來進行。單單使膠態二氧化矽與有機酸共存並無法發揮對膠態二氧化矽之有機酸的固定化。若將有機酸之一種之磺酸固定化於膠態二氧化矽,例如可以“Sulfonic acid-functionalized silica through quantitative oxidation of thiol groups”,Chem.Commun.246-247(2003)所記載之方法進行。具體而言,藉由將具有3-巰丙基三甲氧基矽烷等硫醇基之矽烷偶合劑偶合於膠態二氧化矽後以過氧化氫氧化硫醇基,可得到磺酸固定化於表面之膠態二氧化矽。或是若能將羧酸固定化於膠態二氧化矽,例如可以”Novel Silane Coupling Agents Containing a Photolabile 2-Nitrobenzyl Ester for Introduction of a Carboxy Group on the Surface of Silica Gel”,Chemistry Letters,3,228-229(2000)所記載之方法進行。具體而言,將包含光反應性2-硝基苄基酯之矽烷偶合劑偶合於膠態二氧化矽之後藉由進行光照射,可得到羧酸固定化於表面之膠態二氧化矽。
研磨粒之平均一次粒徑的下限較佳為20nm以上,以25nm以上更佳,以30nm以上又更佳,以50nm以
上特佳。又,研磨粒之平均一次粒徑的上限較佳為200nm以下,以150nm以下更佳,以100nm以下又更佳。若為於如此之範圍,藉由研磨用組成物提高研磨對象物之研磨速度,又,可更加抑制於使用研磨用組成物進行研磨後之研磨對象物的表面產生表面缺陷。尚且,研磨粒之平均一次粒徑,例如基於以BET法測定之研磨粒之比表面積算出。
於以下,於研磨粒為二氧化矽時,對於從粒子之比表面積算出平均粒徑之方法進行具體說明。二氧化矽粒子之形狀假定為真球狀,粒子之直徑定為d(nm)、比重定為ρ(g/cm3)時,粒子n個之表面積A成為A=nπd2。粒子n個之質量N成為N=ρnπd3/6。比表面積S係以粉體之每單位質量之全構成粒子的表面積表示。如此的話,粒子n個之比表面積S成為S=A/N=6/ρd。因為二氧化矽粒子之比重為ρ=2.2,故平均粒徑(nm)成為=2727/S(m2/g)。
研磨粒之平均二次粒徑的下限較佳為25nm以上,以30nm以上更佳,以35nm以上又更佳。又,研磨粒之平均二次粒徑的上限較佳為300nm以下,以260nm以下更佳,以220nm以下又更佳。若為於如此之範圍,藉由研磨用組成物提高研磨對象物之研磨速度,又,可更加抑制於使用研磨用組成物進行研磨後之研磨對象物的表面產生表面缺陷。尚且、於此所謂二次粒子,係指研磨粒於研磨用組成物中會合所形成之粒子,此二次粒子之平均二次粒徑,例如可藉由動態光散射法進行測定。
研磨粒之平均二次粒徑可藉由pH、電傳導性或過濾等之物理性處理來控制。
研磨用組成物中研磨粒之含量的下限較佳為0.005重量%以上,以0.5重量%以上更佳,以1重量%以上又更佳,以3重量%以上最佳。又,研磨用組成物中研磨粒之含量的上限較佳為50重量%以下,以30重量%以下更佳,以20重量%以下又更佳。若為於如此之範圍,提高研磨對象物之研磨速度,又,可抑制研磨用組成物之成本,可更加抑制於使用研磨用組成物進行研磨後之研磨對象物的表面產生表面缺陷。
研磨用組成物中研磨粒之長寬比的上限為1.22以下,以1.20以下較佳,以1.18以下更佳。又,研磨用組成物中研磨粒之平均一次粒徑的下限雖並未特別限制,但以20nm以上為佳。若為於如此之範圍,可排除研磨粒之形狀對原因之表面缺陷的影響,可更加抑制於使用研磨用組成物進行研磨後之研磨對象物的表面產生表面缺陷。尚且,長寬比係由掃描型電子顯微鏡,藉由將外接於將研磨粒粒子之畫像之最小長方形長邊的長度除以相同長方形短邊的長度所得到值為500個研磨粒粒子的平均,可使用一般之畫像解析軟體求得。據此,長寬比的下限為1。研磨用組成物中研磨粒之長寬比可以組成物中進行測定,亦可使用調製組成物前之研磨粒進行測定。
在研磨用組成物中之研磨粒,在藉由雷射繞射散射法所求得之粒度分布中,從微粒子側之累計粒子重
量達到全粒子重量之90%時之粒子之直徑D90與達到全粒子之全粒子重量10%時之粒子之直徑D10的比D90/D10的下限為1.5以上,以1.8以上較佳,以2.0以上更佳。又,在研磨用組成物中之研磨粒,在藉由雷射繞射散射法所求得之粒度分布中,從微粒子側之累計粒子重量達到全粒子重量之90%時之粒子之直徑D90與達到全粒子之全粒子重量10%時之粒子之直徑D10的比D90/D10的上限雖並未特別限制,但以5.0以下為佳,以3.0以下更佳。若為於如此之範圍,提高研磨對象物之研磨速度,又,可更加抑制於使用研磨用組成物進行研磨後之研磨對象物的表面產生表面缺陷。尚且,於研磨金屬配線層之際,從減低碟形凹陷之觀點來看,D90/D10以3.0以下為佳。
研磨用組成物中之研磨粒的D90/D10係藉由pH、電傳導性、過濾等之物理性處理來控制。
作為關係本發明之氧化劑的具體例,可列舉過氧化氫、過乙酸、過碳酸鹽、過氧化脲、過氯酸;過硫酸鈉、過硫酸鉀、過硫酸銨等之過硫酸鹽等。此等氧化劑可單獨或混合2種以上使用。
其中,較佳為過硫酸鹽及過氧化氫,特佳為過氧化氫。
研磨用組成物中之氧化劑含量(濃度)的下限較佳為0.01重量%以上,以0.05重量%以上更佳,以
0.1重量%以上又更佳。隨著氧化劑含量增多,有藉由研磨用組成物提高研磨速度的優點。
又,研磨用組成物中之氧化劑含量(濃度)的上限較佳為10重量%以下,以5重量%以下更佳,以3重量%以下又更佳。隨著氧化劑含量減少,除了可抑制研磨用組成物之材料成本之外,具有可減輕研磨使用後之研磨用組成物的處理、亦即廢液處理之負荷。又,亦具有藉由氧化劑成為難以引起研磨對象物表面之過剩氧化之優點。
本發明之研磨用組成物,係包含用以分散或溶解各成分之作為分散介質或溶劑之水。從抑制阻礙其他成分作用的觀點來看,較佳係盡可能不含有雜質之水,具體而言,較佳為在離子交換樹脂去除雜質離子之後,通過過濾器去除異物之純水或超純水、或蒸餾水。
藉由加入金屬防腐蝕劑於研磨用組成物中,可更加抑制以使用研磨用組成物之研磨於配線之側面產生凹陷。又,可更加抑制於使用研磨用組成物進行研磨後之研磨對象物的表面產生碟形凹陷等之表面缺陷。
可使用之金屬防腐蝕劑雖並未特別限制,但較佳為雜環式化合物或界面活性劑。雜環式化合物中雜環
之員數並未特別限制。又,雜環式化合物可為單環化合物,亦可為具有縮合環之多環化合物。該金屬防腐蝕劑可單獨或混合2種以上使用。又,該金屬防腐蝕劑可使用市售品或使用合成品。
作為可使用雜環化合物作為金屬防腐蝕劑的具體例,例如可列舉吡咯化合物、吡唑化合物、咪唑化合物、三唑化合物、四唑化合物、吡啶化合物、吡嗪化合物、噠嗪化合物、氮茚(Pyrindine)化合物、吲哚嗪(Indolizine)化合物、吲哚化合物、異吲哚化合物、吲唑化合物、嘌呤化合物、喹嗪(Quinolizine)化合物、喹啉化合物、異喹啉化合物、萘錠(Naphthyridine)化合物、呔化合物、喹喔啉化合物、喹唑啉化合物、噌啉(Cinnoline)化合物、喋啶(Pteridine)化合物、噻唑化合物、異噻唑化合物、噁唑化合物、異噁唑化合物、呋呫化合物等之含氮雜環化合物。
進一步列舉具體之例時,作為吡唑化合物之例,例如可列舉1H-吡唑、4-硝基-3-吡唑羧酸、3,5-吡唑羧酸、3-胺基-5-苯基吡唑、5-胺基-3-苯基吡唑、3,4,5-三溴吡唑、3-胺基吡唑、3,5-二甲基吡唑、3,5-二甲基-1-羥基甲基吡唑、3-甲基吡唑、1-甲基吡唑、3-胺基-5-甲基吡唑、4-胺基-吡唑基[3,4-d]嘧啶、異嘌呤醇、4-氯-1H-吡唑基[3,4-D]嘧啶、3,4-二羥基-6-甲基吡唑基(3,4-B)-吡啶、6-甲基-1H-吡唑基[3,4-b]吡啶-3-胺等。
作為咪唑化合物之例,例如可列舉咪唑、1-
甲基咪唑、2-甲基咪唑、4-甲基咪唑、1,2-二甲基吡唑、2-乙基-4-甲基咪唑、2-異丙基咪唑、苯并咪唑、5,6-二甲基苯并咪唑、2-胺基苯并咪唑、2-氯苯并咪唑、2-甲基苯并咪唑、2-(1-羥基乙基)苯并(Benz)咪唑、2-羥基苯并(Benz)咪唑、2-苯基苯并(Benz)咪唑、2,5-二甲基苯并(Benz)咪唑、5-甲基苯并咪唑、5-硝基苯并(Benz)咪唑、1H-嘌呤等。
作為三唑化合物之例,例如可列舉1,2,3-三唑(1H-BTA)、1,2,4-三唑、1-甲基-1,2,4-三唑、甲基-1H-1,2,4-三唑-3-羧酸酯、1,2,4-三唑-3-羧酸、1,2,4-三唑-3-羧酸甲酯、1H-1,2,4-三唑-3-硫醇、3,5-二胺基-1H-1,2,4-三唑、3-胺基-1,2,4-三唑-5-硫醇、3-胺基-1H-1,2,4-三唑、3-胺基-5-苄基-4H-1,2,4-三唑、3-胺基-5-甲基-4H-1,2,4-三唑、3-硝基-1,2,4-三唑、3-溴-5-硝基-1,2,4-三唑、4-(1,2,4-三唑-1-基)酚、4-胺基-1,2,4-三唑、4-胺基-3,5-二丙基-4H-1,2,4-三唑、4-胺基-3,5-二甲基-4H-1,2,4-三唑、4-胺基-3,5-二庚基-4H-1,2,4-三唑、5-甲基-1,2,4-三唑-3,4-二胺、1H-苯并三唑、1-羥基苯并三唑、1-胺基苯并三唑、1-羧基苯并三唑、5-氯-1H-苯并三唑、5-硝基-1H-苯并三唑、5-羧基-1H-苯并三唑、5-甲基-1H-苯并三唑、5,6-二甲基-1H-苯并三唑、1-(1’,2’-二羧基乙基)苯并三唑、1-[N,N-雙(羥基乙基)胺基甲基]苯并三唑、1-[N,N-雙(羥基乙基)胺基甲基]-5-甲基苯并三唑、1-[N,N-雙(羥基乙基)胺基甲基]-4-甲基苯并三唑、2-
2’[(甲基-1H苯并三唑-1-基)甲基]亞胺基雙乙醇等。
作為四唑化合物之例,例如可列舉1H-四唑、5-甲基四唑、5-胺基四唑、及5-苯基四唑等。
作為吲唑化合物之例,例如可列舉1H-吲唑、5-胺基-1H-吲唑、5-硝基-1H-吲唑、5-羥基-1H-吲唑、6-胺基-1H-吲唑、6-硝基-1H-吲唑、6-羥基-1H-吲唑、3-羧基-5-甲基-1H-吲唑等。
作為吲哚化合物之例,例如可列舉1H-吲哚、1-甲基-1H-吲哚、2-甲基-1H-吲哚、3-甲基-1H-吲哚、4-甲基-1H-吲哚、5-甲基-1H-吲哚、6-甲基-1H-吲哚、7-甲基-1H-吲哚、4-胺基-1H-吲哚、5-胺基-1H-吲哚、6-胺基-1H-吲哚、7-胺基-1H-吲哚、4-羥基-1H-吲哚、5-羥基-1H-吲哚、6-羥基-1H-吲哚、7-羥基-1H-吲哚、4-甲氧基-1H-吲哚、5-甲氧基-1H-吲哚、6-甲氧基-1H-吲哚、7-甲氧基-1H-吲哚、4-氯-1H-吲哚、5-氯-1H-吲哚、6-氯-1H-吲哚、7-氯-1H-吲哚、4-羧基-1H-吲哚、5-羧基-1H-吲哚、6-羧基-1H-吲哚、7-羧基-1H-吲哚、4-硝基-1H-吲哚、5-硝基-1H-吲哚、6-硝基-1H-吲哚、7-硝基-1H-吲哚、4-腈-1H-吲哚、5-腈-1H-吲哚、6-腈-1H-吲哚、7-腈-1H-吲哚、2,5-二甲基-1H-吲哚、1,2-二甲基-1H-吲哚、1,3-二甲基-1H-吲哚、2,3-二甲基-1H-吲哚、5-胺基-2,3-二甲基-1H-吲哚、7-乙基-1H-吲哚、5-(胺基甲基)吲哚、2-甲基-5-胺基-1H-吲哚、3-羥基甲基-1H-吲哚、6-異丙基-1H-吲哚、5-氯-2-甲基-1H-吲哚等。
此等之中較佳之雜環化合物為三唑化合物,尤其是以1H-苯并三唑、5-甲基-1H-苯并三唑、5,6-二甲基-1H-苯并三唑、1-[N,N-雙(羥基乙基)胺基甲基]-5-甲基苯并三唑、1-[N,N-雙(羥基乙基)胺基甲基]-4-甲基苯并三唑、1,2,3-三唑、2-2’[(甲基-1H苯并三唑-1-基)甲基]亞胺基雙乙醇及1,2,4-三唑為佳。此等之雜環化合物為了提高對研磨對象物表面之化學性或物理性吸著力,於研磨對象物表面可形成更強固之保護膜。因此,使用本發明之研磨用組成物進行研磨之後,是有利於提高研磨對象物表面的平坦度。
又,作為金屬防腐蝕劑所使用之界面活性劑,可列舉陰離子性界面活性劑、陽離子性界面活性劑、兩性界面活性劑。
作為陰離子性界面活性劑之例,例如可列舉聚氧乙烯烷基醚乙酸、聚氧乙烯烷基硫酸酯、月桂基硫酸酯等之烷基硫酸酯、聚氧乙烯烷基醚硫酸、烷基醚硫酸、烷基苯磺酸、烷基磷酸酯、聚氧乙烯烷基磷酸酯、聚氧乙烯磺基琥珀酸、烷基磺基琥珀酸、烷基萘磺酸、烷基二苯基醚二磺酸、及此等之鹽(鈉鹽、銨鹽等)等。
作為陽離子性界面活性劑之例,例如可列舉烷基三甲基銨鹽、烷基二甲基銨鹽、烷基苄基二甲基銨鹽、烷基胺鹽等。
作為兩性界面活性劑之例,例如可列舉烷基甜菜鹼、烷基胺氧化物等。
作為非離子性界面活性劑之具體例,例如可列舉聚氧乙烯烷基醚等之聚氧亞烷基烷基醚、山梨糖醇脂肪酸酯、甘油脂肪酸酯、聚氧乙烯脂肪酸酯、聚氧乙烯烷基胺、及烷基烷醇醯胺。其中以聚氧亞烷基烷基醚為佳。
此等之中較佳之界面活性劑為聚氧乙烯烷基醚乙酸、聚氧乙烯烷基醚硫酸鹽、烷基醚硫酸鹽、及烷基苯磺酸鹽。此等之界面活性劑,為了提高對研磨對象物表面之化學性或物理性吸著力,於研磨對象物表面可形成更強固之保護膜。因此,使用本發明之研磨用組成物進行研磨之後,是有利於提高研磨對象物表面的平坦度。
研磨用組成物中金屬防腐蝕劑之含量的下限,較佳為0.001g/L以上,以0.005g/L以上更佳,以0.01g/L以上又更佳。又,研磨用組成物中金屬防腐蝕劑之含量的上限,較佳為10g/L以下,以5g/L以下更佳,以2g/L以下又更佳。若為於如此之範圍,提高使用研磨用組成物進行研磨後之研磨對象物表面的平坦度,又,藉由研磨用組成物提高研磨對象物之研磨速度。
本發明之研磨用組成物之pH的下限,較佳為2以上。隨著研磨用組成物pH之增大,可減少藉由研磨用組成物引起研磨對象物表面之過剩蝕刻之虞。
又,研磨用組成物之pH的上限,較佳為10以下。隨著研磨用組成物pH之變小,可更加抑制於藉由
使用研磨用組成物之研磨所形成之配線的側面產生凹陷。
尚且,研磨用組成物之pH於包含阻隔層進行研磨時,考慮研磨粒與被研磨膜之靜電性排斥作用,以pH為10以下為佳。又,將金屬配線層之研磨作為目的時,從銅層與阻隔層之研磨速度選擇比這點來看,研磨用組成物之pH以4~8為佳。
前述pH可藉由適量添加pH調節劑調整。為了將研磨用組成物之pH調整為所期望的值,所使用之pH調整劑可為酸及鹼之任一種,又,可為無機化合物及有機化合物之任一種。作為酸之具體例,例如可列舉硫酸、硝酸、硼酸、碳酸、次磷酸、亞磷酸及磷酸等之無機酸;甲酸、乙酸、丙酸、酪酸、吉草酸、2-甲基酪酸、n-己酸、3,3-二甲基酪酸、2-乙基酪酸、4-甲基戊酸、n-庚酸、2-甲基己酸、n-辛酸、2-乙基己酸、安息香酸、乙醇酸、水楊酸、甘油酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、馬來酸、苯二甲酸、蘋果酸、酒石酸、檸檬酸及乳酸等之羧酸、以及甲烷磺酸、乙烷磺酸及羥乙磺酸(Isethionic acid)等之有機硫酸等之有機酸等。作為鹼之具體例,可列舉硫氨、乙二胺及哌嗪等之胺、氫氧化鉀、氫氧化鈉、以及四甲基銨及四乙基銨等之第4級銨鹽。此等pH調節劑可單獨或混合2種以上使用。
本發明之研磨用組成物如有必要可進一步包含錯合
劑、防腐劑、防黴劑、還原劑、水溶性高分子、用以溶解難溶性有機物之有機溶劑等之其他成分。以下對於係較佳之其他成分之錯合劑進行說明。
研磨用組成物所包含之錯合劑係具有化學性蝕刻研磨對象物表面之作用,藉由研磨用組成物提高研磨對象物之研磨速度。
作為可使用之錯合劑之例,例如可列舉無機酸或其鹽、有機酸或其鹽、腈化合物、胺基酸、及螯合劑等。此等錯合劑可單獨或混合2種以上使用。又,該錯合劑可使用市售品或使用合成品。
作為無機酸之具體例,例如可列舉鹽酸、硫酸、硝酸、碳酸、硼酸、四氟硼酸、次磷酸、亞磷酸、磷酸、焦磷酸等。
作為有機酸之具體例,例如可列舉甲酸、乙酸、丙酸、酪酸、吉草酸、2-甲基酪酸、n-己酸、3,3-二甲基酪酸、2-乙基酪酸、4-甲基戊酸、n-庚酸、2-甲基己酸、n-辛酸、2-乙基己酸、乳酸、乙醇酸、甘油酸、安息香酸、水楊酸等之一價羧酸;草酸、丙二酸、琥珀酸、戊二酸、葡糖酸、己二酸、庚二酸、馬來酸、苯二甲酸、丁烯酸、蘋果酸、酒石酸、檸檬酸等之多元羧酸:等之羧酸。又,亦可使用甲烷磺酸、乙烷磺酸及羥乙磺酸(Isethionic acid)等之磺酸。
作為錯合劑可使用前述無機酸或前述有機酸之鹽。尤其是於使用弱酸與強鹽基之鹽、強酸與弱鹽基之鹽、或弱酸與弱鹽基之鹽時,可期待pH之緩衝作用。作為如此之鹽之例,例如可列舉氯化鉀、硫酸鈉、硝酸鉀、碳酸鉀、四氟硼酸鉀、焦磷酸鉀、草酸鉀、檸檬酸三鈉、(+)-酒石酸鉀、六氟磷酸鉀等。
作為腈化合物之具體例,例如可列舉乙睛、胺基乙睛、丙睛、丁睛、異丁睛、苯并腈、戊二腈、甲氧基乙睛等。
作為胺基酸之具體例,可列舉甘胺酸、α-丙胺酸、β-丙胺酸、N-甲基甘胺酸、N,N-二甲基甘胺酸、2-胺基酪酸、正纈胺酸、纈氨酸、白胺酸、正白胺酸、異白胺酸、苯基丙胺酸、脯胺酸、肌胺酸、鳥胺酸、蓖麻毒素、牛磺酸、絲胺酸、息寧胺酸、類絲胺酸、酪胺酸、二羥乙甘胺酸(Bicine)、三(羥甲基)甲基甘胺酸(Tricine)、3,5-二碘-酪胺酸、β-(3,4-二羥基苯基)-丙胺酸、甲狀腺素、4-羥基-脯胺酸、半胱胺酸、甲硫胺酸、乙硫胺酸、羊毛硫胺酸、胱硫醚(Cystathionine)、胱胺酸、氧化半胱胺酸、天冬胺酸、麩胺酸、S-(羧基甲基)-半胱胺酸、4-胺基酪酸、天冬醯胺酸、麩胺醯胺酸、氮絲胺酸、L-精胺酸、刀豆胺酸(Canavanine)、瓜胺酸、δ-羥基-蓖麻毒素、肌酸、組胺酸、1-甲基-組胺酸、3-甲基-組胺酸及色胺酸。
作為螯合劑之具體例,可列舉氮基三乙酸、
二乙烯三胺五乙酸、乙二胺四乙酸、N,N,N-三亞甲基膦酸、乙二胺-N,N,N’,N’-四亞甲基磺酸、反式環己烷二胺四乙酸、1,2-二胺基丙烷四乙酸、甘醇醚二胺四乙酸、乙二胺鄰羥基苯基乙酸、乙二胺二琥珀酸(SS體)、N-(2-羧酸乙酯)-L-天冬胺酸、β-丙胺酸二乙酸、2-膦醯基丁烷-1,2,4-三羧酸、1-羥基亞乙基-1,1-二膦酸、N,N’-雙(2-羥基苄基)乙二胺-N,N’-二乙酸、1,2-二羥基苯-4,6-二磺酸等。
此等之中,較佳為選擇自由無機酸或其鹽、羧酸或其鹽、及腈化合物所成之群中至少1種,從與研磨對象物所包含之金屬化合物之複合體構造的安定性觀點來看,以無機酸或其鹽更佳。又,作為上述之各種錯合劑,於使用具有pH調整功能者(例如各種酸等)時,可利用該錯合劑作為pH調整劑之至少一部分。
研磨用組成物中錯合劑之含量(濃度)的下限,雖因為即使少量亦發揮效果故並未特別限定,但以0.001g/L以上為佳,以0.01g/L以上較佳,以1g/L以上更佳。又,本發明之研磨用組成物中錯合劑之含量(濃度)的上限,以20g/L以下為佳,以15g/L以下較佳,以10g/L以下更佳。若為於如此之範圍,提高研磨對象物之研磨速度,又,使用研磨用組成物進行研磨之後,是有利於提高研磨對象物表面的平坦度。
本發明之研磨用組成物之製造方法並未特別限制,例如可藉由將研磨粒、氧化劑、金屬防腐蝕劑、及如有必要之其他成分於水中進行攪拌混合而得到。
混合各成分時之溫度雖並未特別限制,但以10~40℃為佳,為了提高溶解速度亦可加熱。又,混合時間亦並未特別限制。
如上述,本發明之研磨用組成物適合於使用具有阻隔層、金屬配線層、及絕緣膜之研磨對象物之研磨。據此,本發明係提供一種將具有阻隔層、金屬配線層、及絕緣膜之研磨對象物以本發明之研磨用組成物進行研磨之研磨方法。又,本發明係提供一種包含將具有阻隔層、金屬配線層、及絕緣膜之研磨對象物以前述研磨方法進行研磨之步驟之基板之製造方法。
作為研磨裝置,可使用有安裝保持具有研磨對象物之基板等之支持器與可變動旋轉數之馬達等、具有可安裝研磨墊(研磨布)之研磨定盤之一般的研磨裝置。
作為前述研磨墊,不特別限制可使用一般之不織布、聚胺基甲酸乙酯、及多孔質氟樹脂等。於研磨墊較佳為以滯留研磨液之方式實施溝加工。
研磨條件亦並未特別限制,例如,研磨定盤之旋轉速度較佳為10~500rpm,施加在具有研磨對象物基板之壓力(研磨壓力)較佳為0.5~10psi。供給研磨用
組成物於研磨墊之方法亦並未特別限制,例如,採用以泵等連續性供給之方法。此供給量雖並未特別限制,但以研磨墊表面經常覆蓋本發明之研磨用組成物為佳。
研磨終了後,將基板於流水中洗淨,由旋轉乾燥器等藉由將附著於基板上之水滴甩落使其乾燥,而得到具有阻隔層、金屬配線層、及絕緣膜之基板。
本發明之研磨用組成物可為一液型,可為一開始為二液型之多液型。又,本發明之研磨用組成物係將研磨用組成物之原液使用水等之稀釋液,例如可藉由稀釋為10倍以上來調製。
使用以下之實施例及比較例進一步詳細說明本發明。惟,本發明之技術的範圍並非只被限制於以下之實施例。
將下述表2所示條件之膠態二氧化矽作為研磨粒,過氧化氫作為氧化劑,且相對於組成物為0.6重量%、1H-BTA 1.2g/L(組成物)作為金屬防腐蝕劑,分別成為如前述濃度之方式於水中進行攪拌混合(混合溫度:約25℃、混合時間:約10分鐘),調製研磨用組成物。組成物之pH,作為pH調整劑一邊加硝酸一邊由pH計確認,調整為pH2.10。
膠態二氧化矽之比表面積的測定,使用Micromeritics Tex公司製之“Flow SorbII 2300”由BET法進行。又,膠態二氧化矽粒子之平均二次粒徑,以將動態光散射法作為原理之粒度測定裝置測定而求得。
作為使用於研磨用組成物之調整之研磨粒之膠態二氧化矽的長寬比,係由掃描型電子顯微鏡,測定藉由將外接於將膠態二氧化矽粒子之畫像之最小長方形長邊的長度除以相同長方形短邊的長度所得到值,算出500個膠態二氧化矽粒子之平均。尚且,測定係對於以掃描型電子顯微鏡所取得之畫像使用畫像解析軟體求得。
研磨對象物係於矽基板上,使用成膜Cu膜、Ta膜、及TEOS膜之12吋晶圓。使用所得到之研磨用組成物,將研磨對象物之表面以下述表1所示之第1研磨條件測定研磨60秒之際的研磨速度。研磨速度係使用將直流4探針法作為原理之片電阻測量儀,藉由將測定之研磨前後各自的膜厚度之差,除以研磨時間而求得。對於所測定之研磨速度,Cu膜之值若有200A/min以上且1000A/min以下、Ta膜之值若為200A/min以上、TEOS膜之值若為500A/min以上、及TEOS膜牙狀凹陷量之值若為50A以下則具有實用性水準。
使用所得到之研磨用組成物,將Cu/TEOS圖型晶圓(研磨前之Cu膜厚700nm、凹槽深度300nm)之表面,以上述表1所記載之第1研磨條件研磨至銅膜厚250nm為止。然後,將研磨後之銅圖型晶圓表面使用相同研磨用組成物,以上述表1所記載之第2研磨條件研磨至阻隔層
(材料:Ta)露出為止。以如此方式進行,在進行2段階之研磨後之Cu/TEOS圖型晶圓之0.25μm寬度之金屬嵌入配線部分與絕緣膜部分所交互形成之圖型部分與周邊之絕緣膜部分的邊界區域,進行牙狀凹陷之測定。尚且,牙狀凹陷之測定係使用觸針式之段差測定裝置。評估結果表示於下述表2。所測定之牙狀凹陷量的值若為50A以下則為實用之水準。
又,在進行上述2段階之研磨後之Cu/TEOS圖型晶圓之0.25μm寬度之金屬嵌入配線部分與絕緣膜部分所交互形成之圖型部分之區域進行侵蝕之測定。尚且,侵蝕之測定係使用觸針式之段差測定裝置。評估結果表示於下述表2。所測定之侵蝕量值若為50以下則為實用之水準。
如上述表2所示,認為使用實施例1~2之研磨用組成物時,與未滿足本發明之條件之比較例1~6之研磨用組成物相比,在相對於阻隔層及層間絕緣膜為高之研磨速度的維持以及侵蝕或牙狀凹陷等之表面缺陷之抑
制,發揮顯著優異之效果。
將下述表5所示條件之膠態二氧化矽作為研磨粒、過氧化氫作為氧化劑,且相對於組成物為1.2重量%、2-2’[(甲基-1H苯并三唑-1-基)甲基]亞胺基雙乙醇0.29g/L(組成物)、月桂基硫酸銨0.22g/L(組成物)、聚氧亞烷基烷基醚0.63g/L(組成物)作為金屬防腐蝕劑、甘胺酸10g/L(組成物)作為錯合劑,各自成為如前述濃度之方式於水中進行攪拌混合(混合溫度:約25℃、混合時間:約20分鐘),調製研磨用組成物。組成物之pH,作為pH調整劑一邊加氫氧化鉀一邊由pH計確認,調整為pH7.2。
研磨對象物係使用將膜厚1.5μm之金屬層(銅膜)形成於表面之矽基板(BTW)。將研磨對象物之表面以如下述表3所示之第1研磨條件,測定研磨60秒之際的研磨速度。研磨速度係使用將直流4探針法作為原理之片電阻測量儀,藉由將測定之研磨前後各自的膜厚度之差,除以研磨時間而求得。對於所測定之研磨速度,Cu膜之值若有5000A/min以上則具有實用性水準。
使用所得到之研磨用組成物,將銅圖型晶圓(Cu/TEOS圖型晶圓、研磨前之銅膜厚700nm、凹槽深度300nm)之表面,以上述表3所記載之第1研磨條件研磨至銅膜厚200nm為止。然後,將研磨後之銅圖型晶圓表面使用相同之研磨用組成物,以上述表4所記載之第2研磨條件研磨至阻隔層(材料:鉭)露出為止。以如此方式進行,在進行2段階之研磨後之銅圖型晶圓之100μm寬度之配線與100μm寬度之絕緣膜(材料:鉭)所交互並排之區域,使用原子間力顯微鏡測定碟形凹陷量(碟形凹陷深度)。評估結果表示於下述表5。尚且,所測定之碟形凹陷量的值若為400Å以下則為實用之水準,為“not clear”係表示未進行以第2研磨條件研磨至露出阻隔層之狀態。
如上述表5所示,於使用實施例3~5之研磨用組成物時,與未滿足本發明之條件之比較例6~9之研磨用組成物相比,在相對於金屬配線層為高之研磨速度的維持以及碟形凹陷等之表面缺陷之抑制,發揮顯著優異之效果。
本申請係基於2012年11月2日所申請之日本專利申請案號2012-243073號,參照其開示內容,被作為整體納入。
Claims (7)
- 一種研磨用組成物,其係使用於將具有阻隔層、金屬配線層、及絕緣膜之研磨對象物研磨之用途之研磨用組成物,其特徵為包含研磨粒(惟氧化鋁除外)、氧化劑、金屬防腐蝕劑、pH調整劑、及水之研磨用組成物,前述研磨粒之長寬比為1.22以下,且在藉由雷射繞射散射法所求得前述研磨粒之粒度分布中,從微粒子側之累計粒子重量達到全粒子重量之90%時之粒子之直徑D90與達到全粒子之全粒子重量10%時之粒子之直徑D10的比D90/D10為1.5以上。
- 如請求項1之研磨用組成物,其中,前述研磨粒為膠態二氧化矽。
- 如請求項1或2之研磨用組成物,其中,前述研磨粒之平均一次粒徑為20nm~200nm。
- 如請求項1或2之研磨用組成物,其中,前述阻隔層係包含鉭或貴金屬。
- 如請求項1或2之研磨用組成物,其中,前述D90/D10為3.0以下。
- 一種研磨方法,其係使用如請求項1~5中任一項記載之研磨用組成物研磨具有阻隔層、金屬配線層、及絕緣膜之研磨對象物。
- 一種基板之製造方法,其係包含以請求項6記載之研磨方法研磨具有阻隔層、金屬配線層、及絕緣膜之研磨對象物之步驟。
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JP6604061B2 (ja) * | 2015-07-10 | 2019-11-13 | 日立化成株式会社 | Cmp用研磨液及び研磨方法 |
JP6900366B2 (ja) * | 2015-08-12 | 2021-07-07 | ビーエイエスエフ・ソシエタス・エウロパエアBasf Se | コバルトを含む基板の研磨のための化学機械研磨(cmp)組成物の使用方法 |
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