TWI647300B - 硏磨用組成物、硏磨方法以及基板的製造方法 - Google Patents
硏磨用組成物、硏磨方法以及基板的製造方法 Download PDFInfo
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- TWI647300B TWI647300B TW103132790A TW103132790A TWI647300B TW I647300 B TWI647300 B TW I647300B TW 103132790 A TW103132790 A TW 103132790A TW 103132790 A TW103132790 A TW 103132790A TW I647300 B TWI647300 B TW I647300B
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- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
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Classifications
-
- 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
- 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]
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
本發明之研磨用組成物係使用於將研磨對象物研磨之用途,該研磨對象物具有包含多晶矽之層,且研磨用組成物包含研磨粒以及氧化劑,pH值為6以上。作為前述研磨粒較佳為使用矽酸膠。且,本發明之研磨方法之特徵為使用前述研磨用組成物,來研磨研磨對象物,該研磨對象物具有包含多晶矽之層。且,本發明之基板的製造方法之特徵為包含藉由前述研磨方法來研磨基板之研磨步驟,該基板具有包含多晶矽之層。
Description
本發明為關於使用於將研磨對象物研磨之用途之研磨用組成物,該研磨對象物具有包含多晶矽之層、研磨方法以及基板的製造方法。
在近年微細化以及高密度化之半導體裝置的製造中,有使用非常微細的圖型形成技術。由於配線的多層化等要因,半導體裝置的表面構造變得更加複雜,表面膜的初期段差也變得更大。作為用來去除基板上所形成之特定膜的初期段差之廣域平坦化技術,有利用化學機械性研磨(Chemical mechanical polishing:CMP)步驟。具有多晶矽膜之研磨對象物的CMP中,有使用多晶矽用之研磨用組成物。
將具有X(Å)之初期段差的多晶矽膜以V(Å/分)之研磨速度來研磨時,若可選擇性地僅研磨段差區域的上側部分(凸部的上方)的話,則以X/V(分)的研磨時間即能夠去
除段差。然而,實際上,因CMP步驟中的化學性蝕刻、研磨墊片的彎曲等原因,段差區域的下側部分(凹部的底部),雖然速度比同區域的上側部分(凸部的上方)還低,但也是會被研磨。
對前述多晶矽用之研磨用組成物來說,要求使以下所定義之段差消除效率接近1,亦即,盡可能地能夠選擇性地來研磨段差部分的上側(凸部的上方)。段差消除效率為僅研磨特定厚度的研磨對象物之表面時,將研磨對象物表面上某處上的段差之研磨前與研磨後之間的差(Å)(亦即,研磨所造成的段差之消除量(Å)),除以前述特定之厚度(Å)所得之值。且,段差因相鄰接之凸部以及凹部而被形成時,也可以稱為是自凹部的最低部分至凸部的最高部分的距離。此時,前述特定之厚度等同於研磨前之凸部的最高部分之高度位置與研磨後之凸部的最高部分之高度位置之間的差。
專利文獻1中有揭示一種為了研磨多晶矽膜所使用之研磨用組成物。專利文獻1之研磨用組成物中含有作為研磨粒之矽酸膠、作為鹼之四甲基氫氧化銨(TMAH)、作為水溶性高分子之羥乙基纖維素、水等。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開2004-266155號公報
另外,專利文獻1之研磨用組成物有著尚未充分地滿足關於多晶矽之研磨特性,尤其是段差消除效率的要求性能之問題。
本發明之目的為提供一種使用在將具有包含多晶矽之層的研磨對象物研磨之用途中,更適合的研磨用組成物,且提供一種使用其研磨用組成物之研磨方法以及基板的製造方法。
為了達到上述之目的,在本發明之一型態中,提供一種研磨用組成物,其特徵為使用於將研磨對象物研磨之用途,該研磨對象物具有包含多晶矽之層,且該研磨用組成物包含研磨粒以及氧化劑,pH值為6以上。
前述研磨粒為矽酸膠較佳。前述研磨粒的平均一次粒徑為5nm~400nm較佳。前述氧化劑為過氧化物較佳。前述研磨用組成物進一步包含分子量在100以上,且選自糖類、水溶性高分子以及界面活性劑中之至少1種化合物較佳。前述研磨對象物亦可在表面上具有段差。且,前述研磨用組成物,於研磨壓力15.2kPa且定盤旋轉數93rpm之研磨條件下,來研磨前述具有段差之研磨對象物的表面時,此時的段差消除效率為0.4以上較佳。
且,本發明之另一型態中,提供一種研磨方法,其特
徵為使用前述研磨用組成物,來研磨研磨對象物,該研磨對象物具有包含多晶矽之層。且,本發明之再另一型態中,提供一種基板的製造方法,其包含藉由前述研磨方法,來研磨基板之研磨步驟,該基板具有包含多晶矽之層。
藉由本發明,能夠提供一種研磨用組成物,其能夠適用於將研磨對象物研磨之用途中,該研磨對象物具有包含多晶矽之層。
[實施發明之形態]
以下,說明本發明之一實施形態。
本實施形態之研磨用組成物是將研磨粒以及氧化劑,以此等之單獨或與其他成分組合後,混合於水中來製造。如此所得之研磨用組成物的pH值,因應必要,可使用pH調整劑,調整成6以上之所期望之值。前述其他成分較為分子量為100以上且選自糖類、水溶性高分子以及界面活性劑中之至少1種化合物較佳。此研磨用組成物係使用於將研磨對象物研磨之用途,該研磨對象物具有包含多晶矽之層。
作為研磨粒之具體例,有舉出氧化矽、氧化鋁、氧化鈰、氧化鋯、氧化鈦、氧化錳、碳化矽、氮化矽等。其中,較佳為氧化矽,更佳為矽酸膠或氣相二氧化矽。使用
此等之研磨粒時,能夠得到更平滑之研磨面。研磨粒亦可單獨使用一種,亦可組合二種以上來使用。
使用矽酸膠時,亦可為表面不經修飾的矽酸膠以及表面經修飾的矽酸膠中之任一者。作為表面修飾之矽酸膠,有舉例如在表面有固定磺酸或羧酸等有機酸之矽酸膠,或表面經氧化鋁等金屬氧化物取代的矽酸膠。對矽酸膠之有機酸的固定是藉由在矽酸膠的表面上使有機酸的官能基產生化學性鍵結來進行。對矽酸膠之磺酸的固定,能夠以例如“Sulfonic acid-functionalized silica through quantitative oxidation of thiol groups”,Chem.Commun.246-247(2003)中所記載之方法來進行。具體來說,使具有3-氫硫丙基三甲氧矽烷等氫硫基之矽烷偶合劑與矽酸膠偶合後,藉由以過氧化氫來氧化氫硫基,能夠得到在表面上固定有磺酸之矽酸膠。對矽酸膠之羧酸的固定能夠以例如“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)所記載之方法來進行。具體來說,使包含光反應性2-硝苄酯之矽烷偶合劑與矽酸膠偶合後,藉由光照射,能夠得到在表面上固定有羧酸之矽酸膠。且,氧化鋁之矽酸膠表面的取代,如例如日本特開平6-199515號公報之記載所述,藉由於矽酸膠中添加鋁化合物並使其反應來進行。具體的來說,藉由於矽酸膠中添加鋁酸鹼並加熱,能夠得到表面經氧化鋁取代之矽酸膠。
研磨用組成物中所包含之研磨粒的平均一次粒徑為5nm以上較佳,更佳為10nm以上。隨著研磨粒的平均一次粒徑變大,研磨用組成物所產生之研磨對象物的研磨速度也會跟著提升。且,研磨表面有段差之研磨對象物時,段差會更有效率地被消除。
研磨用組成物所包含之研磨粒的平均一次粒徑為400nm以下較佳,更佳為300nm以下,再更佳為200nm以下。隨著研磨粒的平均一次粒徑變小,容易得到缺陷低且粗度較小的研磨後表面。
且,研磨粒的平均一次粒徑能夠由以氮吸附法(BET法)所得之研磨粒的比表面積之測定值來算出。
研磨粒的平均二次粒徑為10nm以上較佳,為15nm以上更佳,為20nm以上再更佳。且,研磨粒的平均二次粒徑為450nm以下較佳,為350nm以下更佳,為220nm以下再更佳。研磨粒的平均二次粒徑之值只要在如此之範圍內,即能使研磨用組成物所產生之研磨對象物的研磨速度更加提升,並在使用研磨用組成物來研磨時,更能夠抑制此時研磨對象物表面上的表面缺陷之發生。另外,於此所謂的二次粒子意指,研磨粒在研磨用組成物中聚集所形成之粒子,研磨粒的平均二次粒徑能夠藉由例如動態光散射法來測定。
研磨用組成物中之研磨粒的含量為0.1質量%以上較佳,更佳為1質量%以上。隨著研磨粒的含量變多,研磨用組成物所產生之研磨對象物的研磨速度也跟著更加提
升。
研磨用組成物中之研磨粒的含量為50質量%以下較佳,更佳為40質量%以下。隨著研磨粒的含量變少,除了研磨用組成物之製造成本跟著降低之外,也容易得到使用研磨用組成物之研磨所得之缺陷較少之表面。且,隨著研磨粒的含量變少,研磨後殘留在表面上的研磨粒的量也跟著降低,其結果,會提升殘留研磨粒的洗淨去除性。且,研磨表面有段差之研磨對象物時,段差會更有效率地被消除。
研磨用組成物中所包含之氧化劑在6以上的pH值範圍中,會執行研磨對象物之多晶矽表面的化學性研磨。尤其是,並對研磨具有段差之研磨對象物時的段差之消除有貢獻。作為氧化劑的具體例,有舉出過氧化物、過碘酸、過碘酸鹽、過錳酸鹽、釩酸鹽、次氯酸鹽、氧化鐵、臭氧等。作為過氧化物的具體例,有舉出過氧化氫、過乙酸、過碳酸鹽、過氧化脲、過氯酸、過氯酸鹽以及過硫酸鈉、過硫酸鉀及過硫酸銨等過硫酸鹽等。其中,過硫酸鹽以及過氧化氫以研磨速度之觀點來看較佳,以在水溶液中的安定性以及環境負擔之觀點來看,過氧化氫特別佳。氧化劑為亦可單獨使用一種,亦可組合二種以上來使用。
研磨用組成物中之氧化劑的含量為0.01質量%以上較佳,更佳為0.03質量%以上。隨著氧化劑的含量變多,研磨用組成物所得之研磨後的表面之缺陷跟著受到抑制。且,研磨具有段差之研磨對象物時,段差會更有效率地被
消除。
研磨用組成物中之氧化劑的含量為15質量%以下較佳,更佳為10質量%以下。隨著氧化劑的含量變少,除了研磨用組成物的製造成本跟著降低之外,也能夠減輕使用完畢之研磨用組成物的處理,亦即廢液處理的負擔。且,研磨具有段差之研磨對象物時,段差會更有效率地被消除。
研磨用組成物具有6以上的pH值。研磨用組成物之pH值較佳為7以上,更佳為8以上。研磨用組成物之pH值的上限並無特別限定,但較佳為未滿12。藉由將研磨用組成物的pH值設在如此之弱酸性至鹼性之範圍間,能提升研磨用組成物所產生之多晶矽的研磨特性,具體來說是多晶矽的研磨速度。且,研磨具有段差之研磨對象物時,段差會更有效率地被消除。
研磨用組成物的pH值之調整所使用的pH調整劑能自習知的酸、鹼基或此等鹽中選出。
作為能夠作為pH調整劑使用之酸的具體例,有舉出鹽酸、硫酸、硝酸、氟酸、硼酸、碳酸、次亞磷酸、亞磷酸以及磷酸等無機酸、或甲酸、乙酸、丙酸、丁酸、戊酸、2-丁酸甲酯、n-己酸、3,3-二丁酸甲酯、2-丁酸乙酯、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、丁二酸、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、乳酸、二乙醇酸、2-呋喃
羧酸、2,5-呋喃二羧酸、3-呋喃羧酸、2-四氫呋喃羧酸、甲氧基乙酸、甲氧苯基乙酸、苯氧乙酸等有機酸。酸亦可單獨使用一種,亦可組合二種以上來使用。
作為能夠作為pH調整劑使用之鹼基的具體例,有舉出鹼金屬之氫氧化物或其鹽、鹼土類金屬之氫氧化物或其鹽、四級氫氧化銨或其鹽、氨、胺等。作為鹼金屬的具體例,有舉出鉀、鈉等。作為鹽的具體例,有舉出碳酸鹽、碳酸氫鹽、硫酸鹽、乙酸鹽等。作為四級氫氧化銨的具體例,有舉出四甲基氫氧化銨、四甲基氫氧化銨、氫氧化四乙銨等。作為胺的具體例,有舉出甲胺、二甲胺、三甲胺、乙胺、二乙胺、三乙胺、乙二胺、單乙醇胺、N-(β-胺乙基)乙醇胺、六亞甲二胺、二伸乙三胺、三伸乙四胺、無水哌嗪、哌嗪六水和物、1-(2-胺乙基)哌嗪、N-甲基哌嗪、胍等。鹼基亦可單獨使用一種,亦可組合二種以上來使用。
其中,氨、銨鹽、鹼金屬氫氧化物、鹼金屬鹽以及四級氫氧化銨化合物作為鹼基較佳。更佳為氨、鉀化合物、氫氧化鈉、四級氫氧化銨化合物、碳酸氫銨、碳酸銨、碳酸氫鈉以及碳酸鈉。再較佳為鉀化合物。作為鉀化合物的示例,有舉出鉀的氫氧化物或鹽,具體來說,有舉出氫氧化鉀、碳酸鉀、碳酸氫鉀、硫酸鉀、乙酸鉀、氯化鉀等。
亦可將上述酸之銨鹽或鹼金屬鹽等鹽來替代上述之酸,或與上述酸組合來使用。
如先前所述,研磨用組成物亦可含有分子量為100以
上且選自糖類、水溶性高分子以及界面活性劑中之至少1種化合物。藉由含有相關之化合物,能夠更加提升研磨用組成物所產生之段差消除效率。以下,在方便上,亦將此化合物稱作段差消除助劑。段差消除助劑藉由對研磨後之多晶矽表面賦予親水性,具有提升附著在研磨後表面之汙垢等異物的洗淨去除性之功能。
於此所謂之糖類意指後述之水溶性高分子以外的碳水化合物,具體來說意指單糖、二糖類、寡糖以及此等之衍生物。作為單糖的具體例,有舉出四碳糖等之丁糖類、核糖、木糖、***糖等之五碳糖類、葡萄糖、半乳糖、甘露糖、果糖等之己糖類、七碳醣等之庚糖類等。作為二糖類的具體例,有舉出海藻糖、麥芽乙糖(麥芽糖)、乳糖(Lactose)、轉化糖(蔗糖)、纖維雙糖、乳膠糖、異麥芽酮糖等。作為寡糖的具體例,有舉出棉子糖、龍膽三糖、蜜三糖、岩藻糖基乳糖、唾液酸乳(sialyllactose)、麥芽三糖、纖維三糖、葡萄糖基海藻糖等之三糖類以及水蘇糖、乳酸-N-四碳醣、及麥芽四碳醣等之四糖類等。主要能夠使用由醛素反應所得之寡糖,作為如此之寡糖的具體例,有舉出木寡糖、低聚果糖、乳酸寡糖、麥芽寡糖、異麥芽寡糖、菊粉低聚糖(inulo-oligosaccharide)、乳酸轉化糖、乳果寡糖、洋菜寡醣(agarooligosaccharide)等。作為糖類之衍生物的具體例,有舉出糖的還原體、糖的氧化體,例如陽離子化糖般地附加有官能基之糖、配糖體、糖與胺基酸等之複合物等。作為單糖之衍生物的具體例,有舉出於
葡萄糖上附加胺基之葡萄胺糖等。糖類亦可單獨使用一種,亦可組合二種以上來使用。
作為水溶性高分子的具體例,有舉出聚羧酸、聚羧酸醯胺、聚羧酸酯、聚膦酸、聚苯乙烯磺酸等之聚磺酸、多糖類、纖維素衍生物、氧化乙烯聚合物、乙烯系聚合物、陽離子性聚合物等之水溶性聚合物以及此等之共聚合物、其鹽、衍生物等。作為聚羧酸、聚羧酸醯胺、聚羧酸酯或聚羧酸鹽的具體例,有舉出聚天冬胺酸、聚麩胺酸、聚離胺酸、聚蘋果酸、聚甲基丙烯酸、聚甲基丙烯酸銨鹽、聚甲基丙烯酸鈉鹽、聚馬來酸、聚亞甲基丁二酸、聚丁烯酸、聚(p-苯乙烯羧酸)、聚丙烯酸、聚丙醯胺、胺基聚丙醯胺、聚丙烯酸甲酯、聚丙烯酸乙酯、聚丙烯酸銨鹽、聚丙烯酸鈉鹽、聚醯胺酸、聚醯胺酸銨鹽、聚醯胺酸鈉鹽、聚乙醛酸等。作為多糖類的具體例,有舉出肝糖、褐藻酸、果膠、果膠酸、澱粉、直鏈澱粉、支鏈澱粉、寒天、卡特蘭多醣、普魯南糖、古亞膠、蒟蒻聚甘露糖、卡拉膠、大瑪琳膠、三仙膠等。作為纖維素衍生物的具體例,有舉出羧甲基纖維素、羥乙基纖維素等。作為乙烯系聚合物的具體例,有舉出聚乙烯醇、聚乙烯吡啶、聚乙烯吡咯啶酮、聚丙烯醛等。作為陽離子性聚合物的具體例,有舉出陽離子化纖維素衍生物、陽離子性澱粉、陽離子化古亞膠衍生物、二烯丙基四級銨鹽/丙烯醯胺共聚合物、4級化聚乙烯吡咯啶酮衍生物、二氰二胺-二伸乙三胺縮合物。水溶性高分子亦可單獨使用一種,亦可組合二種以上來使
用。
作為界面活性劑的具體例,有舉出陰離子性界面活性劑、陽離子性界面活性劑、兩性界面活性劑以及非離子性界面活性劑。
陰離子性界面活性劑被分類成例如硫酸系界面活性劑、磺酸系界面活性劑、磷酸系界面活性劑、膦酸系界面活性劑以及羧酸系界面活性劑。作為陰離子性界面活性劑的具體例,有舉出烷基硫酸酯、聚氧乙烯烷基硫酸酯、聚氧乙烯烷基硫酸、烷基硫酸、烷基醚硫酸酯、高級醇硫酸酯、烷基磷酸酯、烷基苯磺酸鹽磺酸、α-烯烴磺酸、烷基磺酸、聚苯乙烯磺酸、烷基萘磺酸、烷基二苯醚二磺酸、聚氧乙烯烷基醚乙酸、聚氧乙烯烷基醚磷酸、聚氧乙烯烷基磷酸酯、聚氧化乙烯磺基琥珀酸、烷基磺基琥珀酸、或此等之鹽、牛磺酸系界面活性劑、肌胺酸系界面活性劑、羥乙磺酸系界面活性劑、N-醯基酸性胺基酸系界面活性劑、高級脂肪酸鹽、醯化多胜肽等。作為烷基磺酸或其鹽的具體例,有舉出十二烷基磺酸以及十二烷基磺酸鹽等。
陽離子性界面活性劑被分類成例如聚氧乙烯烷基胺型界面活性劑、烷基烷醇醯胺型界面活性劑、烷基胺鹽型界面活性劑、氧化胺型界面活性劑、第四級銨鹽型界面活性劑以及三級醯胺型界面活性劑。作為陽離子性界面活性劑的具體例,有舉出椰子胺乙酸酯,硬脂胺乙酸酯,月桂基二甲氧化胺,硬脂酸二甲基胺基丙基醯胺,烷基三甲基銨鹽,烷基二甲基銨鹽,烷基二甲基苯甲基銨鹽等。
在兩性界面活性劑中被分類成烷基苄鹼系界面活性劑、烷基氧化胺系界面活性劑等。作為兩性界面活性劑的具體例,有舉出可可苄鹼、月桂醯胺丙基苄鹼、椰子醯胺丙基苄鹼、月桂醯兩性基乙酸鈉、可可醯兩性基乙酸鈉、椰子油醯胺丙基苄鹼、月桂基苄鹼(月桂基二甲基胺乙酸苄鹼)等。
非離子性界面活性劑的具體例中有包含聚氧乙烯烷基醚、聚氧化烯基烷醚、蔗糖脂肪酸酯、去水山梨醇脂肪酸酯、甘油脂肪酸酯、聚氧化乙烯脂肪酸酯、聚氧乙烯烷基胺、烷基烷醇醯胺等。
界面活性劑亦可單獨使用一種,亦可組合二種以上來使用。
段差消除助劑的分子量較佳為100以上,更佳為200以上,再較佳為300以上。段差消除助劑的分子量為100以上時,研磨用組成物所產生的段差消除效率會提升。段差消除助劑的分子量上限雖無特別限定,但較佳為500,000以下,更佳為400,000以下,再較佳為300,000以下。段差消除助劑的分子量若在500,000以下,則段差消除助劑在水溶液中的分散性會提升。另外,於此所謂的分子量為當段差消除助劑為具有單量體之重複構造的聚合物時,其質量平均分子量。質量平均分子量的測定,能夠使用習知的方法,例如以GPC-MALS法來進行。分子量比較低的水溶性聚合物之質量平均分子量亦可藉由NMR法來測定。
研磨用組成物中,段差消除助劑的含量為0.0001質量%(1ppm)以上較佳,更佳為0.001質量%(10ppm)以上。隨著段差消除助劑的含量變多,研磨用組成物所產生的段差消除效率也跟著更加提升。
研磨用組成物中,段差消除助劑的含量為5質量%以下較佳,更佳為0.5質量%以下。隨著段差消除助劑的含量變少,研磨用組成物所產生的研磨速度也跟著更加提升。
本實施形態所使用之研磨用組成物在不損害本發明之效果的範圍內,亦可因應必要進一步含有其他添加劑。作為其他添加劑的示例,有舉出pH安定劑(緩衝劑)、分散媒或溶劑、防腐劑、防黴劑、防銹劑、螫合劑、提升研磨粒之分散性的分散劑、容易將研磨粒的凝集體再分散之分散助劑等。
pH安定劑有舉例如,弱酸與強鹼基之組合鹽,或弱酸與弱鹼基之組合鹽。作為pH安定劑的具體例,有舉出碳酸鉀等。
分散媒或溶劑是為了分散或溶解研磨用組成物中的各成分所使用。分散媒或溶劑為水較佳。在不損害其他成分之作用下,使用盡可能不含有雜質的水更佳。作為如此之水的具體例,有舉出使用離子交換樹脂將雜質離子去除後,通過濾網來將異物去除之純水、或超純水或蒸餾水。
作為防腐劑以及防黴劑的具體例,有舉出2-甲基-4-異噻唑啉-3-酮或5-氯-2-甲基-4-異噻唑啉-3-酮等之異噻唑
啉系防腐劑、對羥苯甲酸酯類、苯氧乙醇等。防腐劑以及防黴劑亦可單獨使用一種,亦可組合二種以上來使用。
接著,針對本實施形態的研磨方法以及基板的製造方法來說明。
在本實施形態的研磨方法以及基板的製造方法中,使用上述之研磨用組成物,來研磨具有包含多晶矽之層的基板表面。此時,能夠將多晶矽良好地研磨。尤其是,研磨在表面上具有起因於配線的多層化等所產生之段差的基板時,能夠有效率地消除段差。如先前所述,僅研磨特定厚度之研磨對象物的表面時,將研磨對象物表面上某處的段差之研磨前與研磨後之間的差(Å),除以前述特定厚度(Å)所得之值的段差消除效率,其越靠近1,表示段差之區域的上側部分(凸部的上方)能藉由選擇性研磨而越有效率地消除段差。段差消除效率在研磨壓力為15.2kPa,定盤旋轉數為93rpm的研磨條件之下,為0.4以上較佳,為0.5以上更佳。
藉由使用本實施形態之研磨用組成物,能有效率地消除多晶矽膜上之段差的理由尚不明朗,但推測如下。一般來說,在弱酸性至鹼性的pH範圍中,由於會發生多晶矽的溶解,故不僅是段差之區域的上側部分(凸部的上方),同區域的下側部分(凹部的底部)也會持續被去除,因此其結果為段差消除效率變低。然而,多晶矽膜是藉由研磨用組成物中的氧化劑而被氧化,因此,即使是在弱酸性至鹼性的pH範圍中,也難以受到溶解。並認為此點是藉由使
用本實施形態之研磨用組成物,能夠提高段差消除效率之理由。
另外,添加分子量為100以上,且選自糖類、水溶性高分子以及界面活性劑中之至少1種化合物的段差消除助劑時,段差消除助劑會以氫鍵或疏水性相互作用而吸附於多晶矽之氧化部分上,藉此形成保護膜。其結果,能夠更進一步防止段差之區域的下側部分(凹部的底部)受到溶解並被去除。因此,藉由使用段差消除助劑,來更加提升研磨用組成物所得之段差消除效率。
且,上述之段差消除的機制是推測所得,本發明並非限定於任何上述機制中。
由上述實施形態,能夠得到如以下之效果。
(1)藉由使用上述實施形態之研磨用組成物,能夠將多晶矽良好地研磨。具體來說,使用上述實施形態之研磨用組成物,來研磨包含多晶矽之層時,能夠得到較高的多晶矽去除速度,同時還能夠有效率地消除在包含多晶矽之層的表面上之段差。因此,上述實施形態之研磨用組成物能夠適合使用於研磨包含多晶矽之層之用途,尤其是,適合使用於研磨並去除包含其多晶矽之層的表面上之段差之用途。
(2)上述實施形態之研磨用組成物含有段差消除助劑時,能夠更加提升段差消除效率。
且,上述實施形態亦可進行如以下之變更。
.上述實施形態之研磨用組成物亦可藉由以水稀釋研
磨用組成物之原液來調製。
.使用上述實施形態之研磨用組成物而被研磨之研磨對象物,只要是具有包含多晶矽之層即可,亦可進一步具有多晶矽以外所成之層。
.上述實施形態之研磨用組成物亦可藉由:分別將氧化劑與其以外之研磨用組成物的成分供給至研磨裝置中,並在研磨裝置內使其混合來調製。氧化劑與其以外之研磨用組成物的成分亦可在研磨裝置所附屬的研磨用組成物供給槽內來混合。
.使用上述實施形態之研磨用組成物而被研磨之研磨對象物的表面亦可為平坦,亦可具有段差。段差的大小並無特別限定,只要是與以一般半導體裝置之圖型形成技術所生成者相同程度之大小的段差即可。研磨用組成物能夠使用於表面上具有例如100Å以上,進而為1000Å以上之段差的研磨對象物之研磨中。
[實施例]
接著,舉出實施例以及比較例,進一步具體說明本發明。
在實施例1~9中,於研磨粒中添加pH調整劑以及水後,再添加氧化劑來調製研磨用組成物。在實施例10~20中,於研磨粒中添加pH調整劑以及水後,再添加氧化劑以及段差消除助劑或其他添加劑來調製研磨用組成物。在
比較例1~5中,於研磨粒中添加pH調整劑以及水來調製研磨用組成物。將各示例的研磨用組成物中之詳細成分以及測定各示例的研磨用組成物之pH值的結果表示於表1。
表1中,A表示平均一次粒徑為30nm,且平均二次粒徑為62nm之矽酸膠,B表示平均一次粒徑為10nm,且平均二次粒徑為25nm之矽酸膠,C表示平均一次粒徑為90nm,且平均二次粒徑為180nm之矽酸膠。
表1中之分子量表示:段差消除助劑或其他添加劑為具有單體之重複構造的聚合物時,其質量平均分子量。
表1之“多晶矽膜的研磨速率”欄表示:使用各示例的研磨用組成物,以表2所示之條件,研磨直徑為200mm之多晶矽膜覆蓋晶片之表面時的多晶矽去除速度。多晶矽去除速度之值為:將使用大日本SCREEN製造有限公司之光干擾式膜厚測定裝置“LAMBDA ACE VM-2030”所測定之研磨前後之各基板的厚度差,除以研磨時間(60秒)所求出。
表1之“段差消除效率”欄表示:將直徑為200mm,且初期段差為2000Å之多晶矽膜圖型晶片的表面,使用各示例的研磨用組成物,並以表2所示之條件,僅研磨1000Å之厚度時的段差消除效率。段差消除效率之值為:將初期段差與研磨後所殘留的段差之間的差之段差消除量(Å),除以所研磨之厚度(Å)(於此為1000Å)所求出。另外,段差為使用原子力顯微鏡(AFM)來測定。
如表1所示,在實施例1~9中,能夠得到在實用上能夠滿足之程度的多晶矽的研磨速度。且,亦能得到較高的段差消除效率。使用含有段差消除助劑之研磨用組成物的實施例10~19中,有確認到能夠將段差消除效率更加提升。相對於此,使用pH值未滿6之研磨用組成物的比較例1、2中,無法得到在實用上能夠滿足之程度的多晶矽的研磨速度。且,使用不含有氧化劑之研磨用組成物的比較例3~5中,會有段差消除效率較差之結果。
Claims (9)
- 一種研磨用組成物,其特徵為使用於將研磨對象物研磨之用途,該研磨對象物具有包含多晶矽之層,該研磨用組成物包含研磨粒、氧化劑,以及選自糖類、水溶性高分子及陽離子性界面活性劑以外之界面活性劑中之至少1種化合物(但,聚丙烯酸除外),且pH值為8以上未滿12;前述化合物之分子量為100以上500,000以下,研磨用組成物中之前述研磨粒之含量為0.1質量%以上50質量%以下,研磨用組成物中之前述氧化劑之含量為0.01質量%以上15質量%以下,前述氧化劑為過氧化物、過碘酸、過碘酸鹽、過錳酸鹽、釩酸鹽、次氯酸鹽、氧化鐵或臭氧。
- 如請求項1之研磨用組成物,其中,前述研磨粒為矽酸膠。
- 如請求項1或請求項2之研磨用組成物,其中,前述研磨粒的平均一次粒徑為5nm~400nm。
- 如請求項1或請求項2之研磨用組成物,其中,前述氧化劑為由過氧化氫、過乙酸、過碳酸鹽、過氧化脲、過氯酸、過氯酸鹽及過硫酸鹽之中所選出之過氧化物。
- 如請求項1或請求項2之研磨用組成物,其係進一步含有作為pH調整劑之氫氧化鉀或氫氧化鈉。
- 如請求項1或請求項2之研磨用組成物,其中,前述研磨對象物在表面上具有段差。
- 如請求項6之研磨用組成物,其中,於研磨壓力為15.2kPa且定盤旋轉數為93rpm之研磨條件下,來研磨前述具有段差之研磨對象物的表面時,此時的段差消除效率為0.4以上1以下。
- 一種研磨方法,其特徵為使用如請求項1或請求項2之研磨用組成物來研磨研磨對象物,該研磨對象物具有包含多晶矽之層。
- 一種基板的製造方法,其特徵為包含藉由如請求項8之研磨方法,來研磨基板之研磨步驟,該基板具有包含多晶矽之層。
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JP2013074036A (ja) * | 2011-09-27 | 2013-04-22 | Toshiba Corp | Cmp用スラリーおよび半導体装置の製造方法 |
US9688884B2 (en) * | 2011-11-25 | 2017-06-27 | Fujimi Incorporated | Polishing composition |
JP2013138053A (ja) * | 2011-12-28 | 2013-07-11 | Fujimi Inc | 研磨用組成物 |
JP2014099581A (ja) * | 2012-04-27 | 2014-05-29 | Hitachi Chemical Co Ltd | スラリー、研磨液セット、研磨液、基体の研磨方法及び基体 |
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- 2014-03-14 JP JP2014052608A patent/JP2015086355A/ja active Pending
- 2014-09-18 WO PCT/JP2014/074705 patent/WO2015046015A1/ja active Application Filing
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TW201137065A (en) * | 2010-03-31 | 2011-11-01 | Fujifilm Corp | Polishing liquid and polishing method |
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