TWI441844B - Polishing pad and manufacturing method thereof (1) - Google Patents
Polishing pad and manufacturing method thereof (1) Download PDFInfo
- Publication number
- TWI441844B TWI441844B TW99136728A TW99136728A TWI441844B TW I441844 B TWI441844 B TW I441844B TW 99136728 A TW99136728 A TW 99136728A TW 99136728 A TW99136728 A TW 99136728A TW I441844 B TWI441844 B TW I441844B
- Authority
- TW
- Taiwan
- Prior art keywords
- polishing
- polishing pad
- isocyanate
- diisocyanate
- molecular weight
- Prior art date
Links
Landscapes
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Description
本發明係關於研磨墊者，該研磨墊能夠安定而且以高研磨效率進行透鏡、反射鏡等的光學材料或矽晶圓、硬盤用之玻璃基板、鋁基板、以及一般的金屬研磨加工等要求高度表面平坦性之材料的平坦化加工。本發明之研磨墊可以合適地應用在特別是將矽晶圓還有在其上形成有氧化物層、金屬層等之元件於進一步積層‧形成該等之氧化物層或金屬層之前進行平坦化之步驟。The present invention relates to a polishing pad which is capable of stabilizing and high-polishing efficiency of optical materials such as lenses and mirrors, glass substrates for hard disks, glass substrates for hard disks, aluminum substrates, and general metal polishing processes. Flattening of materials with surface flatness. The polishing pad of the present invention can be suitably applied to planarization of, in particular, a germanium wafer and an element having an oxide layer, a metal layer or the like formed thereon before further layering or formation of the oxide layer or metal layer. The steps.
作為要求高度之表面平坦性的材料之代表可舉製造半導體積體電路(IC、LSI)之被稱為矽晶圓的單晶矽圓盤。矽晶圓在IC、LSI等的製造步驟中，為形成用於電路形成的各種薄膜之可信賴半導體接合，在積層‧形成氧化物層或金屬層之各步驟中，要求對表面進行高精度且平坦地精加工。在這種研磨精加工步驟中，一般來說研磨墊是固定在被稱為平台之可旋轉的支撐圓盤上，半導體晶圓等的加工物是固定在研磨頭上。然後利用雙方之運動，在平台與研磨頭之間產生相對速度，且在研磨墊上連續提供含有研磨粒之研磨漿料，藉以實行研磨操作。A representative of a material requiring a high degree of surface flatness is a single crystal germanium disk called a germanium wafer for manufacturing a semiconductor integrated circuit (IC, LSI). In the manufacturing process of IC, LSI, etc., in order to form a reliable semiconductor junction for forming various thin films for circuit formation, it is required to perform high precision on the surface in each step of forming an oxide layer or a metal layer. Flat finishing. In this polishing finishing step, generally, the polishing pad is fixed on a rotatable supporting disk called a platform, and a workpiece such as a semiconductor wafer is fixed to the polishing head. Then, using the motion of both sides, a relative speed is generated between the platform and the polishing head, and the abrasive slurry containing the abrasive grains is continuously supplied on the polishing pad to perform the grinding operation.
作為研磨墊之研磨特性係要求研磨對象之平坦性(planarity)以及面內均勻性優異，且研磨速度大。關於研磨對象之平坦性、面內均勻性係透過令研磨層高彈性率化在一定程度可以改善。另外，關於研磨速度係可以形成含有氣泡之發泡體從而增多漿料之保持量藉以提高。The polishing property of the polishing pad is required to be excellent in planarity and in-plane uniformity of the polishing target, and the polishing rate is large. The flatness and in-plane uniformity of the object to be polished can be improved to a certain extent by allowing the polishing layer to have a high modulus of elasticity. Further, regarding the polishing rate, it is possible to form a foam containing bubbles to increase the amount of the slurry to be supported.
作為滿足上述特性之研磨墊提出了包含合成樹脂之無發泡體的研磨墊、或者包含聚胺甲酸酯發泡體的研磨墊(專利文獻1、2)。As a polishing pad satisfying the above characteristics, a polishing pad containing a synthetic resin-free foam or a polishing pad containing a polyurethane foam has been proposed (Patent Documents 1 and 2).
但是，若利用包含發泡體之研磨墊，研磨對象與研磨墊之接觸面積就會減少，局部面壓會升高，因而會有在研磨對象之被研磨面容易產生刮痕(傷痕)之問題。However, when the polishing pad including the foam is used, the contact area between the polishing target and the polishing pad is reduced, and the partial surface pressure is increased, so that scratches (scars) are likely to occur on the surface to be polished of the object to be polished. .
另一方面，若利用研磨墊進行大量半導體晶圓之平坦化處理，研磨墊表面之微細凹凸部就會磨損，將漿料供給到半導體晶圓之加工面的性能就會下降，或者研磨速度會降低，平坦化特性會惡化。因此，在進行了指定片數之半導體晶圓的平坦化處理後，必須用修整器將研磨墊表面進行更新‧表面粗糙化(修整)。若進行指定時間之修整，就可以在研磨墊表面形成無數的微細凹凸部，墊表面成為起毛狀態。On the other hand, if a large number of semiconductor wafers are planarized by a polishing pad, the fine uneven portions on the surface of the polishing pad are abraded, and the performance of supplying the slurry to the processed surface of the semiconductor wafer is lowered, or the polishing speed is lowered. When lowered, the flattening characteristics deteriorate. Therefore, after the predetermined number of semiconductor wafers are planarized, it is necessary to update the surface of the polishing pad with a dresser and to roughen the surface (trimming). When the trimming is performed for a predetermined period of time, numerous fine uneven portions can be formed on the surface of the polishing pad, and the surface of the mat becomes a raised state.
包含習知的無發泡體之研磨墊有修整時的切速低，修整所花時間過多之問題。A polishing pad comprising a conventional non-foaming body has a problem that the cutting speed at the time of dressing is low and the time spent on dressing is excessive.
專利文獻1：特開2006-110665號公報Patent Document 1: JP-A-2006-110665
專利文獻2：專利第4128607號說明書Patent Document 2: Patent No. 4128607
本發明之目的在於提供研磨墊及其製造方法，該研磨墊難以在研磨對象之表面產生刮痕，而且會令修整性提高。An object of the present invention is to provide a polishing pad which is difficult to produce scratches on the surface of an object to be polished, and a method for producing the same, which improves the trimming property.
本發明人等為解決前述課題反復悉心研究之結果，發現利用以下所示之研磨墊可以達成上述目的，終而完成本發明。The inventors of the present invention have found that the above object can be attained by the following polishing mats in order to solve the above problems, and the present invention has been completed.
亦即，本發明係關於一種研磨墊，其特徵在於：於具有由無發泡聚胺甲酸酯所構成之研磨層的研磨墊中，前述無發泡聚胺甲酸酯為聚胺甲酸酯原料組成物之反應硬化物，該聚胺甲酸酯原料組成物含有：異氰酸酯末端預聚物，係令含有二異氰酸酯、高分子量多元醇以及低分子量多元醇之預聚物原料組成物發生反應而製得者；異氰酸酯改質體，係藉由加成3個以上之二異氰酸酯而業經多聚化者；以及，增鏈劑；且，前述異氰酸酯改質體之添加量相對於100重量份異氰酸酯末端預聚物為5～30重量份。That is, the present invention relates to a polishing pad characterized in that in the polishing pad having an abrasive layer composed of a non-foamed polyurethane, the aforementioned non-foamed polyurethane is a polyamic acid. a reaction hardened material of an ester raw material composition containing: an isocyanate terminal prepolymer which reacts a prepolymer raw material composition containing a diisocyanate, a high molecular weight polyol, and a low molecular weight polyol And an isocyanate modified body which is polymerized by addition of three or more diisocyanates; and a chain extender; and the above isocyanate modified body is added in an amount relative to 100 parts by weight of the isocyanate The terminal prepolymer is 5 to 30 parts by weight.
本發明在以無發泡聚胺甲酸酯形成研磨層此點上具有特徵。藉此，研磨對象與研磨層之接觸面積就會增大，施加在研磨對象上的面壓力較低且均勻，因而可以有效抑制被研磨面之刮痕的產生。The present invention is characterized in that the abrasive layer is formed of a non-foamed polyurethane. Thereby, the contact area between the object to be polished and the polishing layer is increased, and the surface pressure applied to the object to be polished is low and uniform, so that the occurrence of scratches on the surface to be polished can be effectively suppressed.
另外，本發明人等發現，併用前述異氰酸酯末端預聚物與異氰酸酯改質體(加成3個以上之二異氰酸酯而業經多聚化者)作為無發泡聚胺甲酸酯的原料，並利用該等與增鏈劑之反應，使化學交聯部份性地導入聚合物中(部分性地形成三次元交聯結構)，藉此可使無發泡聚胺甲酸酯變得硬且脆，修整時的切速變大，墊表面就會因此而容易更新。另外，不將異氰酸酯改質體導入異氰酸酯末端預聚物中而是使其與增鏈劑直接反應，藉此可在聚合物中導入規則的化學交聯。藉此，研磨層全體之脆性可以均勻化，而可抑制磨耗之偏差。In addition, the present inventors have found that the isocyanate terminal prepolymer and the isocyanate modified product (addition of three or more diisocyanates to be polymerized) are used as a raw material of the non-foamed polyurethane and used. The reaction with the chain extender causes the chemical cross-linking to be partially introduced into the polymer (partially forming a three-dimensional crosslinked structure), whereby the non-foamed polyurethane can be made hard and brittle. When the cutting speed is increased during dressing, the surface of the pad is easily renewed. Further, the isocyanate modified body is not introduced into the isocyanate terminal prepolymer but directly reacted with the chain extender, whereby regular chemical crosslinking can be introduced into the polymer. Thereby, the brittleness of the entire polishing layer can be made uniform, and the variation in abrasion can be suppressed.
前述高分子量多元醇以數量平均分子量500～5000的聚醚多元醇為佳，前述二異氰酸酯以甲苯二異氰酸酯以及二環己基甲烷二異氰酸酯為佳。另外，前述異氰酸酯改質體以三聚異氰酸酯型及/或縮二脲型之六亞甲基二異氰酸酯改質體為佳。透過利用該等物質就會抑制吸水時無發泡聚胺甲酸酯之膨脹，而且修整時的墊表面之更新性會提高。The high molecular weight polyol is preferably a polyether polyol having a number average molecular weight of 500 to 5,000, and the diisocyanate is preferably toluene diisocyanate or dicyclohexylmethane diisocyanate. Further, the isocyanate modified body is preferably a trimerized isocyanate type and/or a biuret type hexamethylene diisocyanate modified body. By using these substances, the expansion of the non-foamed polyurethane at the time of water absorption is suppressed, and the renewability of the pad surface at the time of dressing is improved.
異氰酸酯改質體相對於100重量份異氰酸酯末端預聚物必須添加5～30重量份。當異氰酸酯改質體之添加量低於5重量份時，因聚合物中之化學交聯的比例不充分，修整時的墊表面之更新性就會降低，同時吸水時無發泡聚胺甲酸酯還容易膨脹。另一方面，當超過30重量份時，聚合物中化學交聯之比例就會過剩，無發泡聚胺甲酸酯之硬度會過高，因而研磨對象之表面會容易產生刮痕。The isocyanate modified body must be added in an amount of 5 to 30 parts by weight based on 100 parts by weight of the isocyanate terminal prepolymer. When the amount of the isocyanate modified body added is less than 5 parts by weight, since the ratio of chemical crosslinking in the polymer is insufficient, the renewability of the surface of the mat during dressing is lowered, and at the same time, no foaming urethane is used when water is absorbed. The ester is also easy to swell. On the other hand, when it exceeds 30 parts by weight, the ratio of chemical crosslinking in the polymer is excessive, and the hardness of the non-foamed polyurethane is too high, so that the surface of the object to be polished is likely to be scratched.
另外，無發泡聚胺甲酸酯之ASKER D硬度以65～80度為佳。當ASKER D硬度低於65度時，研磨對象之平坦性就傾向於降低。另一方面，當大於80度時，平坦性良好，不過研磨對象之面內均勻性卻傾向於降低。另外，研磨對象之表面容易產生刮痕。Further, the ASKER D hardness of the non-foamed polyurethane is preferably 65 to 80 degrees. When the Asker D hardness is less than 65 degrees, the flatness of the object to be polished tends to decrease. On the other hand, when it is more than 80 degrees, the flatness is good, but the in-plane uniformity of the object to be polished tends to decrease. In addition, scratches are likely to occur on the surface of the object to be polished.
另外，從墊表面之更新性的觀點來看，本發明之研磨墊之切速以2μm/min以上為佳。Further, from the viewpoint of the renewability of the surface of the mat, the cutting speed of the polishing pad of the present invention is preferably 2 μm/min or more.
此外，本發明關於一種研磨墊之製造方法，其包含：將相對於100重量份異氰酸酯末端預聚物含有5~30重量份異氰酸酯改質體之第1成分與含有增鏈劑之第2成分予以混合後使其硬化，以製作無發泡聚胺甲酸酯的步驟；其中，該異氰酸酯改質體係藉由加成3個以上之二異氰酸酯而多聚化者，且該異氰酸酯末端預聚物係令含有二異氰酸酯、高分子量多元醇以及低分子量多元醇之預聚物原料組成物發生反應而製得者Further, the present invention relates to a method for producing a polishing pad comprising: subjecting a first component containing 5 to 30 parts by weight of an isocyanate modified body to 100 parts by weight of an isocyanate terminal prepolymer, and a second component containing a chain extender a step of hardening after mixing to prepare a non-foamed polyurethane; wherein the isocyanate upgrading system is polymerized by addition of three or more diisocyanates, and the isocyanate terminal prepolymer is Produced by reacting a prepolymer raw material composition containing a diisocyanate, a high molecular weight polyol, and a low molecular weight polyol
此外，本發明更關於一種半導體元件的製造方法，其包含利用前述研磨墊研磨半導體晶圓表面的步驟。Furthermore, the present invention is directed to a method of fabricating a semiconductor device comprising the step of polishing a surface of a semiconductor wafer using the polishing pad.
第1圖係表示CMP研磨中使用之研磨裝置的一例之概略結構圖。Fig. 1 is a schematic block diagram showing an example of a polishing apparatus used for CMP polishing.
第2圖係表示晶圓上之膜厚測定位置73點的概略圖。Fig. 2 is a schematic view showing a film thickness measurement position on the wafer at 73 o'clock.
本發明之研磨墊具有包含無發泡聚胺甲酸酯的研磨層。本發明之研磨墊可僅為前述研磨層，亦可為研磨層與其他層(例如緩衝層等)之積層體。The polishing pad of the present invention has an abrasive layer comprising a non-foamed polyurethane. The polishing pad of the present invention may be only the polishing layer described above, or may be a laminate of the polishing layer and other layers (for example, a buffer layer or the like).
聚胺甲酸酯樹脂之耐磨耗性優異，透過將原料組成進行各種改變可以容易地獲得具有所需之物性的聚合物，因 而作為研磨層之形成材料是特別合適之材料。The polyurethane resin is excellent in abrasion resistance, and a polymer having a desired physical property can be easily obtained by variously changing the composition of the raw material. The material for forming the polishing layer is a particularly suitable material.
前述無發泡聚胺甲酸酯係包含異氰酸酯末端預聚物、異氰酸酯改質體以及增鏈劑之聚胺甲酸酯原料組成物之反應硬化物，其中異氰酸酯末端預聚物係令預聚物原料組成物發生反應以製得，預聚物原料組成物包含二異氰酸酯、高分子量多元醇以及低分子量多元醇，異氰酸酯改質體係3個以上之二異氰酸酯透過加成多聚化而成。The above non-foamed polyurethane is a reaction hardened product comprising a polyisocyanate raw material composition of an isocyanate terminal prepolymer, an isocyanate modified body and a chain extender, wherein the isocyanate terminal prepolymer is a prepolymer The raw material composition is reacted to obtain a prepolymer raw material composition comprising a diisocyanate, a high molecular weight polyol, and a low molecular weight polyol, and an isocyanate reforming system in which three or more diisocyanates are subjected to addition polymerization.
二異氰酸酯可以不作特殊限定地使用聚胺甲酸酯領域中公知的化合物。可舉例如，2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、2,2’-二苯基甲烷二異氰酸酯、2,4’-二苯基甲烷二異氰酸酯、4,4’-二苯基甲烷二異氰酸酯、1,5-萘二異氰酸酯、對苯基二異氰酸酯、間苯基二異氰酸酯、對苯二亞甲基二異氰酸酯、間苯二亞甲基二異氰酸酯等的芳香族二異氰酸酯、亞乙基二異氰酸酯、2,2,4-三甲基六亞甲基二異氰酸酯、1,6-六亞甲基二異氰酸酯等的脂肪族二異氰酸酯、1,4-環己烷二異氰酸酯、4,4’-二環己基甲烷二異氰酸酯、異氟爾酮二異氰酸酯、降冰片烷二異氰酸酯等的脂環式二異氰酸酯等。該等係使用1種，混合使用2種以上均無妨。該等之中，以併用甲苯二異氰酸酯與二環己基甲烷二異氰酸酯為佳。As the diisocyanate, a compound known in the field of polyurethane can be used without particular limitation. For example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-di An aromatic diisocyanate such as phenylmethane diisocyanate, 1,5-naphthalene diisocyanate, p-phenyl diisocyanate, m-phenyl diisocyanate, p-xylylene diisocyanate or m-xylylene diisocyanate, Aliphatic diisocyanate such as ethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate or 1,6-hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 4 An alicyclic diisocyanate such as 4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate or norbornane diisocyanate. One type of these types may be used, and two or more types may be used in combination. Among these, it is preferred to use toluene diisocyanate and dicyclohexylmethane diisocyanate in combination.
另一方面，本發明中之異氰酸酯改質體係指，3個以上之二異氰酸酯透過加成多聚化而成之化合物或該等之混合物。前述異氰酸酯改質體可舉例如1)三羥甲基丙烷加成物型、2)縮二脲型、3)三聚異氰酸酯型等，特別以三聚異氰酸酯型和縮二脲型為佳。On the other hand, the isocyanate upgrading system in the present invention means a compound obtained by multimerization of three or more diisocyanates by addition polymerization or a mixture thereof. The isocyanate modified product may, for example, be 1) a trimethylolpropane addition type, 2) a biuret type, 3) a trimeric isocyanate type or the like, and particularly preferably a trimeric isocyanate type or a biuret type.
本發明中，形成異氰酸酯改質體之二異氰酸酯以使用脂肪族二異氰酸酯為佳，特別以使用1,6-六亞甲基二異氰酸酯為佳。另外，異氰酸酯改質體亦可為胺甲酸酯改質、脲甲酸酯改質以及縮二脲改質等的改質產物。In the present invention, it is preferred to use an isocyanate modified diisocyanate to use an aliphatic diisocyanate, and particularly preferably 1,6-hexamethylene diisocyanate. Further, the isocyanate modified body may be a modified product such as a urethane reforming, a ureaform modification, or a biuret reforming.
作為高分子量多元醇可舉聚四亞甲基醚二醇所代表之聚醚多元醇、聚己二酸丁二醇酯所代表之聚酯多元醇、聚己內酯多元醇、聚己內酯之類的聚酯二醇與碳酸亞烷基酯的反應物等所例示之聚酯聚碳酸酯多元醇、令碳酸亞乙酯與多元醇反應，接著令製得之反應混合物與有機二羧酸反應製得之聚酯聚碳酸酯多元醇、以及多羥基化合物與碳酸芳基酯利用酯交換反應製得之聚碳酸酯多元醇等。該等可以單獨使用，亦可併用2種以上。The high molecular weight polyol may be a polyether polyol represented by polytetramethylene ether glycol, a polyester polyol represented by polybutylene adipate, a polycaprolactone polyol, or a polycaprolactone. a polyester polycarbonate polyol exemplified by a reaction product of a polyester diol and an alkylene carbonate, etc., reacting ethylene carbonate with a polyol, and then preparing the reaction mixture with an organic dicarboxylic acid A polyester polycarbonate polyol obtained by the reaction, and a polycarbonate polyol obtained by transesterification of a polyhydroxy compound and an aryl carbonate. These may be used alone or in combination of two or more.
高分子量多元醇之數量平均分子量不作特殊限定，從製得之聚胺甲酸酯的彈性特性等的觀點來看以500～5000為佳，較佳的是1000～2000。數量平均分子量若低於500，硬鏈段就會增多，成為韌性低的聚胺甲酸酯。另一方面，數量平均分子量若超過5000，因聚胺甲酸酯會過軟而使由該聚胺甲酸酯製造之研磨墊傾向於平坦化特性差。The number average molecular weight of the high molecular weight polyol is not particularly limited, and is preferably from 500 to 5,000, more preferably from 1,000 to 2,000, from the viewpoint of the elastic properties of the obtained polyurethane. When the number average molecular weight is less than 500, the hard segment is increased to become a polyurethane having low toughness. On the other hand, if the number average molecular weight exceeds 5,000, the polishing pad made of the polyurethane tends to have poor flattening characteristics because the polyurethane is too soft.
低分子量多元醇可舉例如乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,6-己二醇、新戊二醇、1,4-環己烷二甲醇、3-甲基-1,5-戊二醇、二乙二醇、三乙二醇、1,4-雙(2-羥基乙氧基)苯、三羥甲基丙烷、甘油、1,2,6-己三醇、新戊四醇、四羥甲基環己烷、甲基葡萄糖苷、山梨醇、甘露醇、衛矛醇(dulcitol)、蔗糖、2,2,6,6-四(羥甲基)環己醇、二乙醇胺、N-甲基二乙醇胺以及三乙醇胺等。該等可以單獨使用，亦可併用2種以上。The low molecular weight polyol may, for example, be ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3 -butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, diethylene glycol, triethylene glycol , 1,4-bis(2-hydroxyethoxy)benzene, trimethylolpropane, glycerin, 1,2,6-hexanetriol, pentaerythritol, tetramethylolcyclohexane, methyl glucose Glycosides, sorbitol, mannitol, dulcitol, sucrose, 2,2,6,6-tetrakis (hydroxymethyl)cyclohexanol, diethanolamine, N-methyldiethanolamine, and triethanolamine. These may be used alone or in combination of two or more.
另外，作為異氰酸酯末端預聚物之原料成分，亦可併用乙二胺、甲苯二胺、二苯基甲烷二胺以及二亞乙三胺等的低分子量多元胺。另外，亦可併用單乙醇胺、2-(2-胺基乙基胺基)乙醇以及單丙醇胺等的醇胺。該等可以單獨使用，亦可併用2種以上。Further, as the raw material component of the isocyanate terminal prepolymer, a low molecular weight polyamine such as ethylenediamine, toluenediamine, diphenylmethanediamine or diethylenetriamine may be used in combination. Further, an alcoholamine such as monoethanolamine, 2-(2-aminoethylamino)ethanol or monopropanolamine may be used in combination. These may be used alone or in combination of two or more.
低分子量多元醇和低分子量多元胺等的混合量不作特殊限定，係依據製造之研磨墊(研磨層)所要求之特性適當確定，惟以異氰酸酯末端預聚物之原料成分之全體含活性氫基化合物之20～70%為佳。The mixing amount of the low molecular weight polyol and the low molecular weight polyamine or the like is not particularly limited and is appropriately determined depending on the characteristics required for the polishing pad (abrasive layer) to be produced, but the active hydrogen group-containing compound of the entire raw material component of the isocyanate terminal prepolymer is contained. 20 to 70% is preferred.
增鏈劑為具有至少2個以上之活性氫基之有機化合物，活性氫基可以例示羥基、伯胺基或仲胺基、硫醇基(SH)等。具體來說，可舉4,4’-亞甲基雙(鄰氯苯胺)(MOCA)、2,6-二氯-對苯二胺、4,4’-亞甲基雙(2,3-二氯苯胺)、3,5-雙(甲硫基)-2,4-甲苯二胺、3,5-雙(甲硫基)-2,6-甲苯二胺、3,5-二乙基甲苯-2,4-二胺、3,5-二乙基甲苯-2,6-二胺、1,3-丙二醇雙(4-胺基苯甲酸)酯、聚-1,4-丁二醇雙(4-胺基苯甲酸酯)、4,4’-二胺基-3,3’,5,5’-四乙基二苯基甲烷、4,4’-二胺基-3,3’-二異丙基-5,5’-二甲基二苯基甲烷、4,4’-二胺基-3,3’,5,5’-四異丙基二苯基甲烷、1,2-雙(2-胺基苯基硫)乙烷、4,4’-二胺基-3,3’-二乙基-5,5’-二甲基二苯基甲烷、N,N’-二仲丁基-4,4’-二胺基二苯基甲烷、3,3’-二乙基-4,4’-二胺基二苯基甲烷、間苯二甲胺、N,N’-二仲丁基-對苯二胺、間苯二胺以及對苯二甲胺等所例示之多元胺類，或者上述低分子量多元醇和低分子量多元胺。該等係使用1種，混合使用2種以上均無妨。The chain extender is an organic compound having at least two active hydrogen groups, and the active hydrogen group may, for example, be a hydroxyl group, a primary or secondary amino group, a thiol group (SH) or the like. Specifically, 4,4'-methylenebis(o-chloroaniline) (MOCA), 2,6-dichloro-p-phenylenediamine, 4,4'-methylene double (2,3- Dichloroaniline), 3,5-bis(methylthio)-2,4-toluenediamine, 3,5-bis(methylthio)-2,6-toluenediamine, 3,5-diethyl Toluene-2,4-diamine, 3,5-diethyltoluene-2,6-diamine, 1,3-propanediol bis(4-aminobenzoic acid) ester, poly-1,4-butanediol Bis(4-aminobenzoate), 4,4'-diamino-3,3',5,5'-tetraethyldiphenylmethane, 4,4'-diamino-3, 3'-diisopropyl-5,5'-dimethyldiphenylmethane, 4,4'-diamino-3,3',5,5'-tetraisopropyldiphenylmethane, 1 ,2-bis(2-aminophenylsulfanyl)ethane, 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, N, N '-Di-sec-butyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, m-xylylenediamine, N, Polyamines exemplified as N'-di-sec-butyl-p-phenylenediamine, m-phenylenediamine, and p-xylylenediamine, or the above-mentioned low molecular weight polyols and low molecular weight polyamines. One type of these types may be used, and two or more types may be used in combination.
異氰酸酯改質體相對於100重量份異氰酸酯末端預聚物必須添加5～30重量份，合適的是5～20重量份。另外，為獲得具有所需之研磨特性的研磨墊，對於增鏈劑之活性氫基(羥基、胺基)數之異氰酸酯成分的異氰酸酯基團數以0.80～1.20為佳，進一步以0.99～1.15為佳。當異氰酸酯基團數在前述範圍外時，就會發生硬化不良，不會獲得所要求之比重以及硬度，研磨特性傾向於降低。The isocyanate modified body must be added in an amount of 5 to 30 parts by weight, preferably 5 to 20 parts by weight, per 100 parts by weight of the isocyanate terminal prepolymer. Further, in order to obtain a polishing pad having desired polishing characteristics, the number of isocyanate groups of the isocyanate component of the active hydrogen group (hydroxyl group, amine group) of the chain extender is preferably 0.80 to 1.20, and further preferably 0.99 to 1.15. good. When the number of isocyanate groups is out of the above range, hardening failure occurs, the desired specific gravity and hardness are not obtained, and the polishing characteristics tend to be lowered.
無發泡聚胺甲酸酯可以應用熔融法、溶液法等公知的胺甲酸酯化技術製造，當考慮到成本、操作環境等之情形，以利用熔融法製造為佳。再者，依需要亦可加入抗氧化劑等的安定劑、潤滑劑、顏料、填充劑、抗靜電劑、其他添加劑。The non-foamed polyurethane can be produced by a known urethanation technique such as a melt method or a solution method, and it is preferably produced by a melt method in consideration of cost, operating environment, and the like. Further, a stabilizer such as an antioxidant, a lubricant, a pigment, a filler, an antistatic agent, and other additives may be added as needed.
另外，使用叔胺系等之公知的促進聚胺甲酸酯反應之觸媒亦無妨。觸媒之種類、添加量係混合步驟後考慮倒入指定形狀之模具的流動時間進行選擇。Further, it is also possible to use a known catalyst for promoting a polyurethane reaction such as a tertiary amine system. The type and amount of the catalyst are selected after the mixing step, and the flow time of the mold of the specified shape is considered.
無發泡聚胺甲酸酯之製造可為將各成分計量投入容器，且進行攪拌之分批方式，亦可為連續地將各成分供給到攪拌裝置並攪拌，且送出聚胺甲酸酯原料組成物以製造成形品之連續生產方式。The production of the non-foamed polyurethane may be a batch method in which each component is metered into a container and stirred, or the components may be continuously supplied to a stirring device and stirred, and the polyurethane raw material may be sent out. The composition is a continuous production method for producing a molded article.
另外，將異氰酸酯末端預聚物以及異氰酸酯改質體加入反應容器，之後投入增鏈劑，攪拌後倒入指定之大小的鑄模中以製作塊狀物，利用鉋狀或手鋸狀之切片機將該塊狀物切片之方法，或者在前述鑄模之階段形成薄片狀亦可。另外，亦可從T模頭擠出成形以直接製得片狀之無發泡聚胺甲酸酯。In addition, the isocyanate terminal prepolymer and the isocyanate modified body are added to the reaction vessel, and then the chain extender is added, stirred, and poured into a mold of a specified size to prepare a cake, which is formed by a planer or a hand saw-like slicer. The method of slicing the block may be formed into a sheet shape at the stage of the mold. Alternatively, it may be extruded from a T die to directly produce a sheet-like non-foamed polyurethane.
無發泡聚胺甲酸酯的ASKER D硬度以65～80度為佳，較佳的是70～75度。The ASKER D hardness of the non-foamed polyurethane is preferably from 65 to 80 degrees, more preferably from 70 to 75 degrees.
本發明之研磨墊(研磨層)與研磨對象接觸的研磨表面宜具有用以保持‧更新漿料之凹凸結構。包含無發泡體之研磨層缺乏保持‧更新漿料之作用，不過透過在研磨表面形成凹凸結構之作法，就可以效率良好地進行漿料之保持與更新，還可以防止因與研磨對象的吸附造成之研磨對象的破壞。只要凹凸結構是保持‧更新漿料之形狀就不作特殊限定，可舉例如XY格狀槽、同心圓狀槽、貫通孔、未貫通之孔、多棱柱、圓柱、螺旋狀槽、偏心圓狀槽、放射狀槽以及組合該等之槽而成者。另外，該等之凹凸結構一般具有規則性，不過為獲得理想的漿料之保持‧更新性，亦可每隔一定範圍就改變槽間距、槽寬、槽深度等。The polishing surface of the polishing pad (abrasive layer) of the present invention which is in contact with the object to be polished preferably has a concavo-convex structure for holding the ‧ renewed slurry. The polishing layer containing the non-foaming body lacks the effect of maintaining the slurry, but by forming the uneven structure on the polishing surface, the slurry can be efficiently maintained and renewed, and the adsorption to the object to be polished can be prevented. The damage caused by the grinding object. The uneven structure is not particularly limited as long as it retains the shape of the slurry, and examples thereof include an XY lattice groove, a concentric circular groove, a through hole, a non-through hole, a polygonal prism, a cylinder, a spiral groove, and an eccentric circular groove. Radial grooves and combinations of such grooves. Further, the uneven structure is generally regular, but the groove pitch, the groove width, the groove depth, and the like may be changed every certain range in order to obtain a desired slurry retention and renewal property.
前述凹凸結構之製作方法不作特殊限定，可舉例如，利用指定尺寸之車刀之類的夾具進行機械切削的方法、將樹脂倒入具有指定之表面形狀的模具使其硬化藉以製作之方法、用具有指定之表面形狀之壓板按壓樹脂以製作之方法、利用光刻法進行製作之方法、利用印刷技術進行製作之方法、採用二氧化碳雷射等的雷射光之製作方法等。The method for producing the uneven structure is not particularly limited, and examples thereof include a method of mechanically cutting using a jig such as a turning tool of a predetermined size, a method of pouring a resin into a mold having a predetermined surface shape, and hardening it. A method of producing a press-plate resin having a predetermined surface shape, a method of producing by a photolithography method, a method of producing by a printing technique, a method of producing laser light by using a carbon dioxide laser, or the like.
研磨層之厚度不作特殊限定，通常為0.8～4mm左右，以1.5～2.5mm為佳。製作前述厚度之研磨層之方法可舉利用手鋸方式或鉋子方式之切片機令前述無發泡聚胺甲酸酯之塊狀物達到指定厚度之方法、將樹脂倒入具有指定厚度之模槽的模具中使其硬化之方法、以及利用塗佈技術或片材成形技術之方法等。The thickness of the polishing layer is not particularly limited, and is usually about 0.8 to 4 mm, preferably 1.5 to 2.5 mm. The method for producing the polishing layer of the foregoing thickness may be a method of using a hand saw or a planer to make the block of the non-foamed polyurethane to a specified thickness, and pouring the resin into a mold having a specified thickness. A method of hardening the mold in the tank, a method using a coating technique or a sheet forming technique, and the like.
另外，研磨層之厚度偏差宜為100μm以下。厚度偏差超過100μm者在研磨層會有大的表面皺紋，形成對於研磨對象之接觸狀態不同之部分，對研磨特性給予惡劣影響。另外，為消除研磨層之厚度偏差，一般來說係在研磨初期利用令金剛石磨粒電沉積、熔合的修整器來對研磨層表面進行修整，而若超過上述範圍，修整時間就會延長，令生產效率降低。Further, the thickness deviation of the polishing layer is preferably 100 μm or less. When the thickness deviation exceeds 100 μm, there is a large surface wrinkle in the polishing layer, and a portion having a different contact state with respect to the polishing target is formed, which adversely affects the polishing property. In addition, in order to eliminate the thickness deviation of the polishing layer, the surface of the polishing layer is generally trimmed by a dresser for electrodepositing and fusing diamond abrasive grains at the initial stage of polishing, and if the above range is exceeded, the dressing time is prolonged. Production efficiency is reduced.
作為抑制研磨層之厚度偏差之方法，可舉將切為指定厚度之研磨片表面進行拋光的方法。另外，在進行拋光之際宜採用粒度等不同之研磨材料分階段地進行。As a method of suppressing variations in the thickness of the polishing layer, a method of polishing the surface of the polishing sheet cut to a predetermined thickness can be mentioned. Further, in the case of polishing, it is preferred to carry out the stepwise step using abrasive materials having different particle sizes or the like.
本發明之研磨墊亦可為前述研磨層與緩衝層貼合而成者。The polishing pad of the present invention may be formed by laminating the polishing layer and the buffer layer.
緩衝層係彌補研磨層之特性者。在CMP中，為兼具存在折衷關係之平面性與均勻性之兩者就必須緩衝層。平面性係指對具有圖案形成時產生之微小凹凸的研磨對象進行研磨時的圖案部之平坦性，均勻性係指研磨對象整體之均勻性。利用研磨層之特性來改善平面性，利用緩衝層之特性來改善均勻性。在本發明之研磨墊中，緩衝層宜使用比研磨層柔軟者。The buffer layer compensates for the characteristics of the abrasive layer. In CMP, a buffer layer is necessary for both planarity and uniformity in which there is a trade-off relationship. The planarity refers to the flatness of the pattern portion when polishing an object to be polished having minute irregularities generated during pattern formation, and the uniformity refers to the uniformity of the entire object to be polished. The properties of the abrasive layer are used to improve planarity, and the characteristics of the buffer layer are utilized to improve uniformity. In the polishing pad of the present invention, the buffer layer is preferably used to be softer than the abrasive layer.
緩衝層可舉例如聚酯不織布、尼龍不織布、丙烯酸不織布等的纖維不織布、或者浸漬有聚胺甲酸酯的聚酯不織布之類的樹脂浸漬不織布、聚胺甲酸酯泡沫、聚乙烯泡沫等的高分子樹脂發泡體、丁二烯橡膠、異戊二烯橡膠等的橡膠性樹脂、光敏性樹脂等。The buffer layer may, for example, be a fiber nonwoven fabric such as a polyester nonwoven fabric, a nylon nonwoven fabric or an acrylic nonwoven fabric, or a resin impregnated nonwoven fabric such as a polyurethane nonwoven fabric impregnated with polyurethane, a polyurethane foam, or a polyethylene foam. A rubber resin such as a polymer resin foam, a butadiene rubber or an isoprene rubber, or a photosensitive resin.
令研磨層與緩衝層貼合之手段可舉例如用兩面膠帶將研磨層與緩衝層夾持壓制之方法。The means for bonding the polishing layer to the buffer layer may be, for example, a method in which the polishing layer and the buffer layer are sandwiched and pressed by a double-sided tape.
兩面膠帶具有在不織布或薄膜等的基材之兩面設有黏結層的一般結構。若考慮到防止漿料向緩衝層之滲透等，就以基材使用薄膜為佳。另外，黏結層之組成可舉例如橡膠系黏結劑或丙烯酸系黏結劑等。若考慮金屬離子之含量，丙烯酸系黏結劑會因金屬離子含量少而合適。另外，因有時研磨層與緩衝層之組成不同，所以亦可令兩面膠帶之各黏結層之組成不同，以使各層之黏結力適當。The double-faced tape has a general structure in which a bonding layer is provided on both sides of a substrate such as a nonwoven fabric or a film. When it is considered to prevent penetration of the slurry into the buffer layer, it is preferred to use a film as the substrate. Further, the composition of the adhesive layer may, for example, be a rubber-based adhesive or an acrylic adhesive. When the content of the metal ion is considered, the acrylic binder is suitable because the metal ion content is small. Further, since the composition of the polishing layer and the buffer layer may be different, the composition of each of the bonding layers of the double-sided tape may be made different so that the bonding strength of each layer is appropriate.
本發明之研磨墊亦可在與平台黏結的面設有兩面膠帶。該兩面膠帶可以與上述同樣地使用具有在基材之兩面設有黏結層之一般結構的兩面膠帶。基材可舉例如不織布或薄膜等。若考慮到研磨墊在使用後從平台之剝離，就以使用薄膜作為基材為佳。另外，黏結層之組成可舉例如橡膠系黏結劑或丙烯酸系黏結劑等。若考慮金屬離子之含量，丙烯酸系黏結劑會因金屬離子含量少而合適。The polishing pad of the present invention may also be provided with a double-sided tape on the surface to which the platform is bonded. As the double-sided tape, a double-sided tape having a general structure in which a bonding layer is provided on both sides of the substrate can be used in the same manner as described above. The substrate may, for example, be a nonwoven fabric or a film. In view of the peeling of the polishing pad from the platform after use, it is preferred to use a film as the substrate. Further, the composition of the adhesive layer may, for example, be a rubber-based adhesive or an acrylic adhesive. When the content of the metal ion is considered, the acrylic binder is suitable because the metal ion content is small.
半導體元件係經歷利用前述研磨墊研磨半導體晶圓之步驟加以製造。半導體晶圓一般係指在矽晶圓上積層有配線金屬以及氧化膜者。半導體晶圓之研磨方法、研磨裝置不作特殊限制，例如，可以如第1圖所示地使用具備支撐研磨墊(研磨層)1的研磨定盤2、支撐半導體晶圓4的支撐台(研磨頭)5與用以向晶圓進行均勻加壓之支撐材料、研磨劑3之供給機構的研磨裝置等。研磨墊1係透過例如用兩面膠帶貼附來安裝在研磨定盤2上。研磨定盤2與支撐台5係配置使分別被其支撐的研磨墊1與半導體晶圓4呈相對狀態，各自具備旋轉軸6、7。另外，在支撐台5側設有用以將半導體晶圓4壓到研磨墊1的加壓機構。研磨之際，係邊令研磨定盤2與支撐台5旋轉邊將半導體晶圓4壓到研磨墊1上，邊供給漿料邊進行研磨。漿料之流量、研磨荷重、研磨定盤旋轉數以及晶圓旋轉數不作特殊限制，可適當調整來進行。The semiconductor component is manufactured by the step of polishing the semiconductor wafer using the aforementioned polishing pad. A semiconductor wafer generally refers to a layer of wiring metal and an oxide film laminated on a germanium wafer. The polishing method and the polishing apparatus for the semiconductor wafer are not particularly limited. For example, as shown in Fig. 1, a polishing plate 2 having a polishing pad (polishing layer) 1 and a support table for supporting the semiconductor wafer 4 (polishing head) can be used. 5) a polishing device for supplying a support material for uniformly pressurizing the wafer, a supply mechanism for the abrasive 3, and the like. The polishing pad 1 is attached to the polishing platen 2 by, for example, being attached with a double-sided tape. The polishing platen 2 and the support table 5 are disposed such that the polishing pad 1 supported by the polishing pad 2 and the semiconductor wafer 4 are opposed to each other, and each of the rotating shafts 6 and 7 is provided. Further, a pressurizing mechanism for pressing the semiconductor wafer 4 to the polishing pad 1 is provided on the support table 5 side. At the time of polishing, the semiconductor wafer 4 is pressed onto the polishing pad 1 while the polishing platen 2 and the support table 5 are rotated, and the slurry is supplied while being polished. The flow rate of the slurry, the polishing load, the number of rotations of the polishing plate, and the number of rotations of the wafer are not particularly limited and can be appropriately adjusted.
藉此將半導體晶圓4之表面突出的部分除去，將其研磨成平坦狀。之後，透過切割、接合、封裝等來製造半導體元件。半導體元件係用於演算處理裝置或存貯器等。Thereby, the portion where the surface of the semiconductor wafer 4 protrudes is removed, and is polished into a flat shape. Thereafter, the semiconductor element is fabricated by cutting, bonding, packaging, or the like. The semiconductor element is used for a calculation processing device or a memory or the like.
以下，將舉實施例說明本發明，惟本發明並不限定於該等實施例。Hereinafter, the present invention will be described by way of examples, but the invention is not limited to the examples.
數量平均分子量係利用GPC(凝膠滲透層析儀)進行測定，利用標準聚苯乙烯換算而成。The number average molecular weight is measured by GPC (gel permeation chromatography) and converted into standard polystyrene.
GPC裝置：島津製作所製、LC-10AGPC device: manufactured by Shimadzu Corporation, LC-10A
管柱：將Polymer Laboratories公司製、(PLgel，5μm，500)、(PLgel，5μm，100)、以及(PLgel，5μm，50)的3個管柱連接使用Column: Made by Polymer Laboratories, (PLgel, 5μm, 500 ), (PLgel, 5μm, 100 ), and (PLgel, 5μm, 50 ) 3 column connections used
流量：1.0ml/min濃度：1.0g/lFlow rate: 1.0ml/min concentration: 1.0g/l
注入量：40μlInjection volume: 40μl
管柱溫度：40℃Column temperature: 40 ° C
溶離液：四氫呋喃Dissolution: tetrahydrofuran
遵循JIS Z8807-1976進行。將製成之無發泡聚胺甲酸酯以及聚胺甲酸酯發泡體切割為4cm×8.5cm之條狀(厚度：任意)，以其作為比重測定用試料，在溫度23℃±2℃、濕度50%±5%之環境下靜置16小時。測定中係利用比重計(SARTORIUS公司製)測定比重。Follow JIS Z8807-1976. The prepared non-foamed polyurethane and polyurethane foam were cut into strips of 4 cm × 8.5 cm (thickness: arbitrary), and used as a sample for specific gravity measurement at a temperature of 23 ° C ± 2 Allow to stand for 16 hours in an environment of °C and humidity of 50% ± 5%. In the measurement, the specific gravity was measured using a hydrometer (manufactured by SARTORIUS).
遵循JIS K6253-1997進行。將製成之無發泡聚胺甲酸酯以及聚胺甲酸酯發泡體切割為2cm×2cm(厚度：任意)之大小，以其作為硬度測定用試料，在溫度23℃±2℃、濕度50%±5%之環境下靜置16小時。測定時係將試料重疊形成厚度6mm以上。利用硬度計(高分子計器公司製，ASKER D型硬度計)測定1分鐘後之硬度。Follow JIS K6253-1997. The prepared non-foamed polyurethane and the polyurethane foam were cut into a size of 2 cm × 2 cm (thickness: arbitrary), and used as a sample for hardness measurement at a temperature of 23 ° C ± 2 ° C, Allow to stand for 16 hours in an environment with a humidity of 50% ± 5%. In the measurement, the samples were stacked to have a thickness of 6 mm or more. The hardness after 1 minute was measured by a durometer (manufactured by Kobunshi Co., Ltd., ASKER D type hardness meter).
將製作成之研磨墊貼合在研磨裝置(岡本工作機械公司製，SPP600S)之平台上。利用修整器(Asahi Diamond公司製，M型)，在修整壓力50g/cm2 、平台旋轉數35rpm、流水量200ml/min以及修整時間30分鐘之條件下修整研磨層之表面。修整結束後，在研磨墊之半徑方向的中心位置以120°間隔切出3個樣品(20mm×20mm)。利用觸針式表面段差測定裝置(KLA-Tencor公司製，P-15)分別測定1次3個樣品之表面粗糙度，且分別算出三次平方根粗糙度Sq(μm)。然後，算出3個樣品之Sq值的平均值(平均Sq值)。平均Sq值以6～9μm為佳。再者，三次平方根粗糙度Sq係以平均面為XY面，縱方向為Z軸，測定之表面形狀曲線為z=f(x，y)時，以下述式求取。The polishing pad thus produced was attached to a platform of a polishing apparatus (SPP600S, manufactured by Okamoto Machine Co., Ltd.). The surface of the polishing layer was trimmed under the conditions of a dressing pressure of 50 g/cm 2 , a platform rotation number of 35 rpm, a flow rate of 200 ml/min, and a dressing time of 30 minutes using a dresser (manufactured by Asahi Diamond Co., Ltd.). After the trimming was completed, three samples (20 mm × 20 mm) were cut at intervals of 120° in the center position in the radial direction of the polishing pad. The surface roughness of each of the three samples was measured by a stylus type surface step difference measuring device (P-15 manufactured by KLA-Tencor Co., Ltd.), and the cubic root roughness Sq (μm) was calculated. Then, the average value (average Sq value) of the Sq values of the three samples was calculated. The average Sq value is preferably 6 to 9 μm. Further, the cubic root roughness Sq is obtained by the following equation when the average surface is the XY plane and the longitudinal direction is the Z axis, and the measured surface shape curve is z=f(x, y).
(式中，Lx是x方向之測定長度，Ly是y方向之測定長度。)(wherein Lx is the measured length in the x direction, and Ly is the measured length in the y direction.)
測定條件Measuring condition
測定面積：500μm×500μm(測定長度500μm)Measurement area: 500 μm × 500 μm (measurement length 500 μm)
掃描速度：掃描間距20μm/sScanning speed: scanning pitch 20μm/s
掃摹：51(10μm間距)Broom: 51 (10 μm pitch)
測定荷重：2mgMeasuring load: 2mg
將製作成之研磨墊貼合在研磨裝置(岡本工作機械公司製，SPP600S)之平台上。利用修整器(Asahi Diamond公司製，M型)，在修整荷重9.71bf、修整壓力50g/cm2 、平台旋轉數35rpm、流水量200ml/min以及修整時間30分鐘之條件下修整研磨層之表面。修整結束後，切出寬度20mm×長度610mm之條狀樣品。從該樣品之中心部每隔20mm測定厚度(單側15點、總計30點)。然後，在各測定位置算出與未經修整之中心部的厚度之差(磨耗量)，以算出該平均值。切速係利用下述式算出。在本發明中，切速以2μm/min以上為佳，較佳的是2～3μm/min。The polishing pad thus produced was attached to a platform of a polishing apparatus (SPP600S, manufactured by Okamoto Machine Co., Ltd.). The surface of the polishing layer was trimmed under the conditions of trimming load of 9.71 bf, dressing pressure of 50 g/cm 2 , platform rotation number of 35 rpm, flow rate of 200 ml/min, and dressing time of 30 minutes using a dresser (manufactured by Asahi Diamond Co., Ltd.). After the trimming was completed, a strip sample having a width of 20 mm and a length of 610 mm was cut out. The thickness was measured every 20 mm from the center of the sample (15 points on one side, 30 points in total). Then, the difference (abrasion amount) between the thicknesses of the unfinished center portions was calculated at each measurement position to calculate the average value. The cutting speed was calculated by the following formula. In the present invention, the cutting speed is preferably 2 μm/min or more, and more preferably 2 to 3 μm/min.
切速(μm/min)=磨耗量之平均值/(0.5×60)Cutting speed (μm/min) = average value of wear / (0.5 × 60)
採用SPP600S(岡本工作機械公司製)作為研磨裝置，利用製作成之研磨墊進行刮痕之評估。對8吋的矽晶圓製膜成1μm熱氧化膜，以下述條件將其研磨後，利用KLA-Tencor公司製的表面缺陷檢測裝置(Surfscan SP1 TBI)，以邊緣排除量(Edge Exclusion)5mm測定晶圓上0.19～2μm之缺陷的數目。研磨條件係在研磨中以流量150ml/min添加矽漿料(SS12 Cabot公司製)，研磨荷重係350g/cm2 、研磨定盤旋轉數係35rpm、晶圓旋轉數係30rpm。SPP600S (manufactured by Okamoto Machine Co., Ltd.) was used as a polishing device, and scratches were evaluated using the prepared polishing pad. A 8 μm ruthenium wafer was formed into a 1 μm thermal oxide film, and was polished under the following conditions, and then subjected to a surface defect detection device (Surfscan SP1 TBI) manufactured by KLA-Tencor Co., Ltd., and an edge exclusion amount (Edge Exclusion) of 5 mm was measured. The number of defects on the wafer from 0.19 to 2 μm. In the polishing conditions, a mash slurry (manufactured by SS12 Cabot Co., Ltd.) was added at a flow rate of 150 ml/min during polishing, and the polishing load was 350 g/cm 2 , the number of polishing disk rotations was 35 rpm, and the number of wafer rotations was 30 rpm.
採用SPP600S(岡本工作機械公司製)作為研磨裝置，利用製作成之研磨墊進行平均研磨速度之評估。對8吋的矽晶圓製膜成1μm熱氧化膜，以下述條件將其研磨1分鐘後，如第2圖所示地由晶圓上之指定位置73點的研磨後之膜壓測定值算出平均研磨速度。氧化膜之膜厚測定中係使用干涉式膜厚測定裝置(大塚電子公司製)。研磨條件係在研磨中以流量150ml/min添加矽漿料(SS12 Cabot公司製)，研磨荷重係350g/cm2 、研磨定盤旋轉數係35rpm、晶圓旋轉數係30rpm。SPP600S (manufactured by Okamoto Machine Co., Ltd.) was used as a polishing apparatus, and the average polishing rate was evaluated using the polishing pad produced. A 8 μm ruthenium wafer was formed into a 1 μm thermal oxide film, and after polishing for 1 minute under the following conditions, the measured value of the film pressure after polishing at a predetermined position on the wafer at 73 points was calculated as shown in FIG. 2 . Average grinding speed. In the measurement of the film thickness of the oxide film, an interference type film thickness measuring device (manufactured by Otsuka Electronics Co., Ltd.) was used. In the polishing conditions, a mash slurry (manufactured by SS12 Cabot Co., Ltd.) was added at a flow rate of 150 ml/min during polishing, and the polishing load was 350 g/cm 2 , the number of polishing disk rotations was 35 rpm, and the number of wafer rotations was 30 rpm.
在容器中加入1229重量份的甲苯二異氰酸酯(2,4-甲苯二異氰酸酯/2,6-甲苯二異氰酸酯=80/20之混合物)、272重量份的4,4’-二環己基甲烷二異氰酸酯、1901重量份的數量平均分子量1018之聚四甲醚二醇、198重量份的二乙二醇，在70℃使其反應4小時以製得異氰酸酯末端預聚物。以行星式攪拌脫泡裝置混合100重量份該預聚物、10重量份作為異氰酸酯改質體之多聚化1,6-六亞甲基二異氰酸酯(住化拜耳胺甲酸酯公司製、Sumidur N-3300、三聚異氰酸酯型)且使其脫泡。之後，將32.9重量的120℃熔融之4,4’-亞甲基雙(鄰氯苯胺)加入混合液，用行星式攪拌脫泡裝置混合且使其脫泡，以製備成聚胺甲酸酯原料組成物。將該組成物倒入長寬800mm、深度2.5mm之開放式模具(鑄模容器)中，在100℃進行16小時之後固化，以製得無發泡聚胺甲酸酯片材。接著，使用拋光機(AMITEC公司製)對該片材進行表面拋光處理以使厚度達到1.27mm為止，形成厚度精度齊整之片材。以直徑61cm之大小衝壓該經過拋光處理之片材，利用槽加工機((TECHNO)公司製)，在表面進行槽寬0.25mm、槽間距1.50mm、槽深0.40mm的同心圓狀之槽加工以製得研磨層。使用積層機在該研磨層之與槽加工面相反側之面上貼合兩面膠帶(積水化學工業公司製、雙面貼合帶)。此外，對經過電暈處理之緩衝層(東麗公司製，聚乙烯泡沫，TORAY PEF，厚度0.8mm)之表面進行拋光處理，使用積層機將其貼合到前述兩面膠帶上。此外，使用積層機在緩衝層之另一面貼合兩面膠帶以製作成研磨墊。1229 parts by weight of toluene diisocyanate (2,4-toluene diisocyanate/2,6-toluene diisocyanate=80/20 mixture) and 272 parts by weight of 4,4'-dicyclohexylmethane diisocyanate were added to the vessel. 1901 parts by weight of polytetramethylene glycol diol having a number average molecular weight of 1018 and 198 parts by weight of diethylene glycol were reacted at 70 ° C for 4 hours to obtain an isocyanate terminal prepolymer. 100 parts by weight of the prepolymer and 10 parts by weight of polyisomerized 1,6-hexamethylene diisocyanate as an isocyanate modified product in a planetary stirring and defoaming device (manufactured by Bayer Ammonium Co., Ltd., Sumidur) N-3300, trimeric isocyanate type) and defoamed. Thereafter, 32.9 weight of molten 4,4'-methylenebis(o-chloroaniline) at 120 ° C was added to the mixed solution, mixed with a planetary stirring defoaming device and defoamed to prepare a polyurethane. Raw material composition. The composition was poured into an open mold (molded container) having a length of 800 mm and a depth of 2.5 mm, and cured at 100 ° C for 16 hours to obtain a non-foamed polyurethane sheet. Next, the sheet was subjected to surface polishing treatment using a polishing machine (manufactured by AMITEC Co., Ltd.) to a thickness of 1.27 mm to form a sheet having a uniform thickness. The polished sheet is punched at a diameter of 61 cm, using a groove processing machine ( (Technical Co., Ltd.), a groove having a groove width of 0.25 mm, a groove pitch of 1.50 mm, and a groove depth of 0.40 mm was processed on the surface to obtain a polishing layer. A double-faced tape (manufactured by Sekisui Chemical Co., Ltd., double-sided bonding tape) was bonded to the surface of the polishing layer opposite to the groove processing surface by a laminator. Further, the surface of the corona-treated buffer layer (manufactured by Toray Industries, polyethylene foam, TORAY PEF, thickness: 0.8 mm) was subjected to a buffing treatment, and was bonded to the above-mentioned double-faced tape using a laminator. Further, a double-sided tape was attached to the other side of the buffer layer using a laminator to form a polishing pad.
除了在實施例1中，將Sumidur N-3300之添加量從10重量份變為5重量份，且將4,4’-亞甲基雙(鄰氯苯胺)之添加量從32.9重量變為29.7重量份以外，利用與實施例1同樣之方法製作成研磨墊。Except in Example 1, the addition amount of Sumidur N-3300 was changed from 10 parts by weight to 5 parts by weight, and the addition amount of 4,4'-methylene bis(o-chloroaniline) was changed from 32.9 weight to 29.7. A polishing pad was produced in the same manner as in Example 1 except for the parts by weight.
除了在實施例1中，使用10重量份作為異氰酸酯改質體之多聚化1,6-六亞甲基二異氰酸酯(住化拜耳胺甲酸酯公司製、Sumidur N-3200、雙縮脲型)替代Sumidur N-3300，且將4,4’-亞甲基雙(鄰氯苯胺)之添加量從32.9重量變為33.2重量份以外，利用與實施例1同樣之方法製作成研磨墊。In the same manner as in Example 1, 10 parts by weight of polyisomerized 1,6-hexamethylene diisocyanate (manufactured by Bayer Ammonium Co., Ltd., Sumidur N-3200, biuret type) was used as an isocyanate modified body. A polishing pad was produced in the same manner as in Example 1 except that Sumidur N-3300 was used, and the amount of 4,4'-methylenebis(o-chloroaniline) was changed from 32.9 to 33.2 parts by weight.
除了在實施例1中，不添加Sumidur N-3300，且將4,4’-亞甲基雙(鄰氯苯胺)之添加量從32.9重量變為26.6重量份以外，利用與實施例1同樣之方法製作成研磨墊。In the same manner as in Example 1, except that Sumidur N-3300 was not added and the amount of 4,4'-methylenebis(o-chloroaniline) was changed from 32.9 to 26.6 parts by weight. The method is made into a polishing pad.
除了在實施例1中，將Sumidur N-3300之添加量從10重量份變為35重量份，且將4,4’-亞甲基雙(鄰氯苯胺)之添加量從32.9重量變為48.8重量份以外，利用與實施例1同樣之方法製作成研磨墊。Except in Example 1, the addition amount of Sumidur N-3300 was changed from 10 parts by weight to 35 parts by weight, and the addition amount of 4,4'-methylene bis(o-chloroaniline) was changed from 32.9 weight to 48.8. A polishing pad was produced in the same manner as in Example 1 except for the parts by weight.
在容器中加入1229重量份的甲苯二異氰酸酯(2,4-甲苯二異氰酸酯/2,6-甲苯二異氰酸酯=80/20之混合物)、272重量份的4,4’-二環己基甲烷二異氰酸酯、1901重量份的數量平均分子量1018之聚四甲醚二醇、198重量份的二乙二醇，在70℃使其反應4小時以製得異氰酸酯末端預聚物。將100重量份該預聚物、20重量份作為異氰酸酯改質體之多聚化1,6-六亞甲基二異氰酸酯(住化拜耳胺甲酸酯公司製、Sumidur N-3300、三聚異氰酸酯型)以及3.6重量份的矽系界面活性劑(東麗道康寧矽酮製，SH-192)加入聚合容器內且使其混合，調整到80℃並減壓脫泡。之後，利用攪拌翼，在旋轉數900rpm下進行激烈攪拌約4分鐘以使氣泡進入反應體系內。向其中添加39.3重量份的預先在120℃熔融之4,4’-亞甲基雙(鄰氯苯胺)。將該混合液攪拌約70秒鐘後，倒向平底鍋型開放式模具(鑄模容器)中。在該混合液沒有流動性的時刻放入烘箱內，在100℃進行16小時後固化，以製得聚胺甲酸酯發泡體塊狀物。使用切片機(AMITEC公司製，VGW-125)對加熱到約80℃之前述聚胺甲酸酯發泡體塊狀物進行切片，以製得聚胺甲酸酯片材。接著，使用拋光機(AMITEC公司製)對該片材進行表面拋光處理以使厚度達到1.27mm為止，形成厚度精度齊整之片材。以直徑61cm之大小衝壓該經過拋光處理之片材，利用槽加工機((TECHNO)公司製)在表面進行槽寬0.25mm、槽間距1.50mm、槽深0.40mm的同心圓狀之槽加工以製得研磨層。之後，利用與實施例1同樣之方法製作成研磨墊。1229 parts by weight of toluene diisocyanate (2,4-toluene diisocyanate/2,6-toluene diisocyanate=80/20 mixture) and 272 parts by weight of 4,4'-dicyclohexylmethane diisocyanate were added to the vessel. 1901 parts by weight of polytetramethylene glycol diol having a number average molecular weight of 1018 and 198 parts by weight of diethylene glycol were reacted at 70 ° C for 4 hours to obtain an isocyanate terminal prepolymer. 100 parts by weight of the prepolymer, 20 parts by weight of polyisomerized 1,6-hexamethylene diisocyanate as an isocyanate modified product (manufactured by Bayer Ammonium Formate Co., Ltd., Sumidur N-3300, trimeric isocyanate) 3.6 parts by weight of a lanthanide surfactant (manufactured by Toray Dow Corningone, SH-192) was placed in a polymerization vessel and mixed, adjusted to 80 ° C, and defoamed under reduced pressure. Thereafter, vigorous stirring was carried out for about 4 minutes at a rotation number of 900 rpm using a stirring blade to allow bubbles to enter the reaction system. To this was added 39.3 parts by weight of 4,4'-methylenebis(o-chloroaniline) which was previously melted at 120 °C. The mixture was stirred for about 70 seconds and then poured into a pan-type open mold (molding container). The mixture was placed in an oven at the time when the mixture had no fluidity, and post-cured at 100 ° C for 16 hours to obtain a polyurethane foam cake. The aforementioned polyurethane foam block heated to about 80 ° C was sliced using a microtome (manufactured by AMITEC Co., Ltd., VGW-125) to obtain a polyurethane sheet. Next, the sheet was subjected to surface polishing treatment using a polishing machine (manufactured by AMITEC Co., Ltd.) to a thickness of 1.27 mm to form a sheet having a uniform thickness. The polished sheet is punched at a diameter of 61 cm, using a groove processing machine ( (Technical Co., Ltd.) processed a concentric groove having a groove width of 0.25 mm, a groove pitch of 1.50 mm, and a groove depth of 0.40 mm to obtain a polishing layer. Thereafter, a polishing pad was produced in the same manner as in Example 1.
1．．．研磨墊(研磨層)1. . . Abrasive pad (abrasive layer)
2．．．研磨定盤2. . . Grinding plate
3．．．研磨劑(漿料)3. . . Abrasive (slurry)
4．．．研磨對象(半導體晶圓)4. . . Grinding object (semiconductor wafer)
5．．．支撐台(研磨頭)5. . . Support table (grinding head)
6、7．．．旋轉軸6, 7. . . Rotary axis
第1圖係表示CMP研磨中使用之研磨裝置的一例之概略結構圖。Fig. 1 is a schematic block diagram showing an example of a polishing apparatus used for CMP polishing.
第2圖係表示晶圓上之膜厚測定位置73點的概略圖。Fig. 2 is a schematic view showing a film thickness measurement position on the wafer at 73 o'clock.
1．．．研磨墊(研磨層)1. . . Abrasive pad (abrasive layer)
2．．．研磨定盤2. . . Grinding plate
3．．．研磨劑(漿料)3. . . Abrasive (slurry)
4．．．研磨對象(半導體晶圓)4. . . Grinding object (semiconductor wafer)
5．．．支撐台(研磨頭)5. . . Support table (grinding head)
6、7．．．旋轉軸6, 7. . . Rotary axis
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW99136728A TWI441844B (en) | 2010-10-27 | 2010-10-27 | Polishing pad and manufacturing method thereof (1) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW99136728A TWI441844B (en) | 2010-10-27 | 2010-10-27 | Polishing pad and manufacturing method thereof (1) |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201217416A TW201217416A (en) | 2012-05-01 |
| TWI441844B true TWI441844B (en) | 2014-06-21 |
Family
ID=46552181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW99136728A TWI441844B (en) | 2010-10-27 | 2010-10-27 | Polishing pad and manufacturing method thereof (1) |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI441844B (en) |
-
2010
- 2010-10-27 TW TW99136728A patent/TWI441844B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| TW201217416A (en) | 2012-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5078000B2 (en) | Polishing pad | |
| US9126303B2 (en) | Method for production of a laminate polishing pad | |
| TWI363064B (en) | ||
| JP5088865B2 (en) | Polishing pad | |
| TWI450794B (en) | Polishing pad | |
| WO2014119367A1 (en) | Polishing pad | |
| JP5276502B2 (en) | Polishing pad and manufacturing method thereof | |
| JP4128606B2 (en) | Polishing pad | |
| JP5356098B2 (en) | Polishing pad and manufacturing method thereof | |
| JP6155018B2 (en) | Polishing pad | |
| KR101489720B1 (en) | Polishing pad and method for producing same | |
| TWI428362B (en) | Polishing pad and its manufacturing method (2) | |
| JP5453507B1 (en) | Polishing pad and manufacturing method thereof | |
| JP5465578B2 (en) | Polishing pad, method for manufacturing the same, and method for manufacturing a semiconductor device | |
| JP4128607B2 (en) | Polishing pad | |
| TWI441844B (en) | Polishing pad and manufacturing method thereof (1) | |
| JP5009020B2 (en) | Polishing pad | |
| JP2017113856A (en) | Polishing pad and method for producing the same | |
| JP5087440B2 (en) | Polishing pad, polishing pad manufacturing method, and semiconductor device manufacturing method | |
| KR101491530B1 (en) | Polishing pad and method for producing same | |
| JP5087439B2 (en) | Polishing pad, polishing pad manufacturing method, and semiconductor device manufacturing method | |
| JP6155019B2 (en) | Polishing pad |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |