JP2001047355A - Polymeride composition for polishing pad, and polishing pad using it - Google Patents
Polymeride composition for polishing pad, and polishing pad using itInfo
- Publication number
- JP2001047355A JP2001047355A JP22388199A JP22388199A JP2001047355A JP 2001047355 A JP2001047355 A JP 2001047355A JP 22388199 A JP22388199 A JP 22388199A JP 22388199 A JP22388199 A JP 22388199A JP 2001047355 A JP2001047355 A JP 2001047355A
- Authority
- JP
- Japan
- Prior art keywords
- polishing pad
- water
- polishing
- hardness
- soluble substance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、研磨パッド用重合
体組成物及びそれを用いた研磨パッドに関し、半導体ウ
エハ等の表面の研磨に用いる研磨パッドに好適に利用で
きる。The present invention relates to a polymer composition for a polishing pad and a polishing pad using the same, and can be suitably used as a polishing pad for polishing a surface of a semiconductor wafer or the like.
【０００２】[0002]
【従来の技術】半導体ウエハの表面は高い平坦性及び鏡
面性を有することが要求される。半導体ウエハだけでな
く、このような表面を形成することができる研磨方法と
してＣＭＰ（Ｃｈｅｍｉｃａｌ Ｍｅｃｈａｎｉｃａｌ
Ｐｏｌｉｓｈｉｎｇ）が近年注目されている。このＣ
ＭＰでは砥粒が分散されたアルカリ性水溶液等からなる
スラリー（水分散体）を用いる。このスラリーは研磨パ
ッドにより保持され、この研磨パッドと被研磨面とを摺
動することにより研磨を行うことができる。2. Description of the Related Art The surface of a semiconductor wafer is required to have high flatness and mirror finish. As a polishing method capable of forming such a surface as well as a semiconductor wafer, CMP (Chemical Mechanical) is used.
(Polishing) has attracted attention in recent years. This C
In the MP, a slurry (aqueous dispersion) composed of an alkaline aqueous solution in which abrasive grains are dispersed is used. The slurry is held by the polishing pad, and the polishing can be performed by sliding the polishing pad and the surface to be polished.
【０００３】これまで、研磨パッドの表面に保持するこ
とのできるスラリーの量等は、研磨時のスラリーの供給
量、研磨速度等に大きく影響することが知られている。
このため、微細な気泡を含有させることのできるウレタ
ン系樹脂を使用し、発泡させたこの樹脂の表面に現れる
穴（以下、「ポア」という。）にスラリーを保持させる
研磨パッドが多く使用されている。しかし、このポアの
大きさ及び数を正確に制御できるだけの十分な技術は確
立されていない。また、発泡させたウレタン系樹脂から
成る研磨パッドでは、内部に気泡を多く有するために押
し込み硬さの大きな研磨パッドを得ることは困難であ
る。しかし、この押し込み硬さは被研磨面に負荷される
圧力に影響し、研磨性能を大きく左右する因子である。
特表平８−５００６２２号公報においては、研磨パッド
に使用し得る高分子基材に高分子微少エレメントを含む
ものが開示されている。しかし、押し込み硬さ等には触
れられていない。Heretofore, it has been known that the amount of slurry that can be held on the surface of the polishing pad greatly affects the amount of slurry supplied during polishing, the polishing rate, and the like.
For this reason, a polishing pad that uses a urethane-based resin capable of containing fine bubbles and holds a slurry in a hole (hereinafter, referred to as “pore”) that appears on the surface of the foamed resin is often used. I have. However, sufficient technology has not been established to accurately control the size and number of the pores. Further, in the case of a polishing pad made of a foamed urethane resin, it is difficult to obtain a polishing pad having a large indentation hardness due to the presence of many bubbles inside. However, the indentation hardness affects the pressure applied to the surface to be polished, and is a factor largely affecting polishing performance.
Japanese Patent Publication No. Hei 8-500622 discloses a polymer base material which can be used for a polishing pad and contains a polymer microelement. However, the indentation hardness and the like are not mentioned.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、上記問題を
解決するものであり、スラリーの保持性を向上させ、押
し込み硬さを大きくすることにより研磨時に被研磨面に
負荷される圧力を最適化することができる研磨パッド用
重合体組成物及びこれを用いた研磨パッドを提供するこ
とを目的とする。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems and improves the retention of slurry and increases the indentation hardness to optimize the pressure applied to the surface to be polished during polishing. It is an object of the present invention to provide a polishing pad polymer composition that can be converted into a polishing pad and a polishing pad using the same.
【０００５】[0005]
【課題を解決するための手段】第１発明の研磨パッド用
重合体組成物は、非水溶性の熱可塑性重合体と、該熱可
塑性重合体中に分散された水溶性物質とを含み、温度２
３℃の水に７２時間浸漬した場合の体積膨潤率が２０％
以下であることを特徴とする。また、第２発明の研磨パ
ッド用重合体組成物は、非水溶性の熱可塑性重合体と、
該熱可塑性重合体中に分散された水溶性物質とを含み、
温度２３℃の水に７２時間浸漬した場合のショアーＤ硬
度の低下が１０以下であることを特徴とする。The polymer composition for a polishing pad of the first invention comprises a water-insoluble thermoplastic polymer and a water-soluble substance dispersed in the thermoplastic polymer. 2
20% volume swelling when immersed in 3 ° C water for 72 hours
It is characterized by the following. Further, the polymer composition for a polishing pad of the second invention, a water-insoluble thermoplastic polymer,
A water-soluble substance dispersed in the thermoplastic polymer,
The reduction in Shore D hardness when immersed in water at a temperature of 23 ° C. for 72 hours is 10 or less.
【０００６】上記「体積膨潤率」は２０％以下（より好
ましくは１０％以下、更に好ましくは３％以下）であ
る。この体積膨潤率が２０％を越える場合は強度及び押
し込み硬さが低下し、十分な研磨速度を得る研磨パッド
が得られ難くなる。尚、この体積膨潤率は測定対象は異
なるがＪＩＳ Ｋ ６２５８の全面浸せき試験に準ず
る。本発明では試験用液体は蒸留水であり、浸漬温度は
２３℃（２３±２℃）であり、浸漬時間７２時間（７０
〜７２時間）である。The "volume swelling ratio" is at most 20% (more preferably at most 10%, further preferably at most 3%). When the volume swelling ratio exceeds 20%, the strength and the indentation hardness decrease, and it becomes difficult to obtain a polishing pad having a sufficient polishing rate. The volume swelling ratio is in accordance with JIS K 6258 immersion test, although the measurement object is different. In the present invention, the test liquid is distilled water, the immersion temperature is 23 ° C. (23 ± 2 ° C.), and the immersion time is 72 hours (70 ° C.).
~ 72 hours).
【０００７】上記「ショアーＤ硬度の低下」は１０以下
（より好ましくは５以下）である。このショアーＤ硬度
の低下が１０を越える場合は強度及び研磨速度が十分な
研磨パッドが得られ難くなる。尚、本発明における浸漬
は第１発明におけると同様である。また、ショアーＤ硬
度は押し込み硬さを評価する硬度の１種であり、本発明
においては具体的な数値はＡＳＴＭ Ｄ２２４０に従う
ショアーＤ硬度により示す。The above-mentioned "reduction of Shore D hardness" is 10 or less (more preferably 5 or less). If the decrease in Shore D hardness exceeds 10, it becomes difficult to obtain a polishing pad with sufficient strength and polishing rate. The immersion in the present invention is the same as in the first invention. Shore D hardness is one type of hardness for evaluating indentation hardness, and specific numerical values in the present invention are indicated by Shore D hardness according to ASTM D2240.
【０００８】また、本発明の研磨パッド用重合体組成物
のショアーＤ硬度は３５〜９５（より好ましくは５０〜
９０、更には６０〜８５）であることが好ましい。この
範囲のショアーＤ硬度であると、特に、半導体ウエハの
研磨において被研磨面に負荷される圧力が好ましいもの
となり、研磨速度に優れた研磨パッドを得ることができ
る。The Shore D hardness of the polymer composition for a polishing pad of the present invention is 35 to 95 (more preferably 50 to 95).
90, more preferably 60 to 85). When the Shore D hardness is in this range, the pressure applied to the surface to be polished in polishing a semiconductor wafer is particularly preferable, and a polishing pad having an excellent polishing rate can be obtained.
【０００９】上記「熱可塑性重合体」としては、非水溶
性であれば限定されない。特にショアーＤ硬度が３５以
上（より好ましくは４０以上、更には５０以上）の重合
体を用いることが好ましい。ショアーＤ硬度が３５未満
である熱可塑性重合体から押し込み硬さの大きな研磨パ
ッドを得ることは困難となる。The "thermoplastic polymer" is not limited as long as it is water-insoluble. In particular, it is preferable to use a polymer having a Shore D hardness of 35 or more (more preferably 40 or more, and more preferably 50 or more). It becomes difficult to obtain a polishing pad having a large indentation hardness from a thermoplastic polymer having a Shore D hardness of less than 35.
【００１０】この熱可塑性重合体としては、ポリプロピ
レン、ポリエチレン、ポリブテン−１、ポリメチルペン
テン、エチレン−ビニルアルコール系共重合体、エチレ
ン−アクリル酸共重合体等のオレフィン系樹脂、ポリス
チレン、アクリロニトリル−スチレン共重合体、アクリ
ロニトリル-α−メチルスチレン共重合体、ＡＢＳ樹脂
等のスチレン系樹脂、ＳＢＳブロックコポリマー、ＳＥ
ＢＳブロックコポリマー等のスチレン系熱可塑性エラス
トマー、ポリメタクリル酸メチル、ポリアクリル酸エス
テル等の（メタ）アクリレート系樹脂、ナイロン６、ナ
イロン６，６、ナイロン１１、ナイロン１２、熱可塑性
ポリアミドエラストマー等のポリアミド系重合体等を挙
げることができる。Examples of the thermoplastic polymer include olefin resins such as polypropylene, polyethylene, polybutene-1, polymethylpentene, ethylene-vinyl alcohol copolymer, ethylene-acrylic acid copolymer, polystyrene, acrylonitrile-styrene. Copolymer, acrylonitrile-α-methylstyrene copolymer, styrene resin such as ABS resin, SBS block copolymer, SE
Styrene-based thermoplastic elastomers such as BS block copolymers, (meth) acrylate resins such as polymethyl methacrylate and polyacrylate, polyamides such as nylon 6, nylon 6,6, nylon 11, nylon 12, and thermoplastic polyamide elastomers And the like.
【００１１】更に、ポリカーボネート、ポリアクリロニ
トリル、ポリアセタ−ル、熱可塑性ポリオレフィンエラ
ストマー、熱可塑性ポリウレタンエラストマー、１，２
ポリブタジエン、熱可塑性ポリエステルエラストマー、
ポリブチレンテレフタレート等のポリエステル系重合体
等を挙げることができる。これら熱可塑性重合体のなか
でも、特に、オレフィン系重合体、熱可塑性ポリウレタ
ンエラストマー、熱可塑性ポリエステルエラストマー及
び熱可塑性ポリアミドエラストマーを使用することが好
ましい。尚、熱可塑性重合体は、酸無水物基、カルボキ
シル基、ヒドロキシル基、エポキシ基、アミノ基等によ
り変性されたものであってもよい。この変性により後述
する水溶性物質及び研磨に使用するスラリー等との親和
性等を調節することができる。また、熱可塑性重合体は
２種以上を組み合わせて用いることができる。Further, polycarbonate, polyacrylonitrile, polyacetal, thermoplastic polyolefin elastomer, thermoplastic polyurethane elastomer, 1,2
Polybutadiene, thermoplastic polyester elastomer,
Examples thereof include polyester polymers such as polybutylene terephthalate. Among these thermoplastic polymers, it is particularly preferable to use olefin polymers, thermoplastic polyurethane elastomers, thermoplastic polyester elastomers, and thermoplastic polyamide elastomers. Incidentally, the thermoplastic polymer may be modified with an acid anhydride group, a carboxyl group, a hydroxyl group, an epoxy group, an amino group, or the like. By this modification, it is possible to adjust the affinity with a water-soluble substance described later and a slurry used for polishing or the like. Further, two or more kinds of thermoplastic polymers can be used in combination.
【００１２】上記「水溶性物質」における「水溶性」と
は、水と接触することにより、熱可塑性重合体内から遊
離することができる性質をいう。従って、水溶性物質に
は、例えば、水溶性高分子等の水に溶解する物質の他、
吸水性樹脂等の水との接触により膨潤（ゲル化）し、こ
れにより遊離することのできる物質を含むものとする。
尚、この水溶性物質は後述のように、通常、種々の形状
を呈する分散体として熱可塑性重合体中に分散されてい
る。The term "water-soluble" in the above "water-soluble substance" means a property capable of being released from a thermoplastic polymer upon contact with water. Therefore, water-soluble substances include, for example, water-soluble substances such as water-soluble polymers,
It contains a substance that swells (gels) by contact with water, such as a water-absorbent resin, and can be released by this.
The water-soluble substance is usually dispersed in the thermoplastic polymer as a dispersion having various shapes, as described later.
【００１３】このような水溶性物質のうち有機系水溶性
物質としては、デキストリン、シクロデキストリン、マ
ンニット、糖類（乳糖等）、セルロース類（ヒドロキシ
プロピルセルロース、メチルセルロース等）、でんぷ
ん、蛋白質、ポリビニルアルコール、ポリビニルピロリ
ドン、ポリビニルスルホン酸、ポリアクリル酸、ポリエ
チレンオキサイド、水溶性の感光性樹脂、スルフォン化
ポリイソプレン等を挙げることができる。更に、水溶性
物質のうち無機系水溶性物質としては、酢酸カリウム、
硝酸カリウム、炭酸カリウム、炭酸水素カリウム、臭化
カリウム、リン酸カリウム、硫酸カリウム等を挙げるこ
とができる。尚、水溶性物質の溶出を抑制する必要のあ
るときは、水溶性物質にカップリング処理及び／又はコ
ーティング処理等行うことができる。また、これらの水
溶性物質は２種以上を組み合わせて用いることができ
る。Among such water-soluble substances, organic water-soluble substances include dextrin, cyclodextrin, mannitol, sugars (lactose, etc.), celluloses (hydroxypropylcellulose, methylcellulose, etc.), starch, protein, polyvinyl alcohol. , Polyvinyl pyrrolidone, polyvinyl sulfonic acid, polyacrylic acid, polyethylene oxide, water-soluble photosensitive resin, sulfonated polyisoprene, and the like. Further, among the water-soluble substances, as inorganic water-soluble substances, potassium acetate,
Examples thereof include potassium nitrate, potassium carbonate, potassium bicarbonate, potassium bromide, potassium phosphate, potassium sulfate and the like. When it is necessary to suppress the elution of the water-soluble substance, the water-soluble substance can be subjected to a coupling treatment and / or a coating treatment. These water-soluble substances can be used in combination of two or more kinds.
【００１４】この水溶性物質は第３発明のように、熱可
塑性重合体と水溶性物質との合計量の１０重量％以上
（通常９５重量％以下、より好ましくは２０〜９０重量
％、更には４０〜８０重量％）であることが好ましい。
この割合が１０重量％以下であると水溶性物質を含有す
る効果が十分に発揮されず、十分な量のポアを有する研
磨パッドを得難くなる。This water-soluble substance is, as in the third invention, 10% by weight or more (usually 95% by weight or less, more preferably 20 to 90% by weight, more preferably (40 to 80% by weight).
If this proportion is 10% by weight or less, the effect of containing the water-soluble substance is not sufficiently exhibited, and it becomes difficult to obtain a polishing pad having a sufficient amount of pores.
【００１５】これらの水溶性物質は重合体組成物中に分
散体として分散され、分散体の比重は０．６以上（より
好ましくは０．８〜３）であることが好ましい。この分
散体は、熱可塑性重合体中における水溶性物質の呈する
形状を一般的に表すものであり、塊状及び凝集体等全て
の形状を含むものとする。この分散体の比重が０．６以
下である場合は、分散体の内部に必要以上に多くの空間
があり、研磨パッド用重合体組成物の押し込み硬さが減
少し易く、十分な研磨速度を得ることのできる研磨パッ
ドが得られ難くなる。These water-soluble substances are dispersed in the polymer composition as a dispersion, and the specific gravity of the dispersion is preferably 0.6 or more (more preferably 0.8 to 3). This dispersion generally represents the shape of the water-soluble substance in the thermoplastic polymer, and includes all shapes such as lumps and aggregates. When the specific gravity of this dispersion is 0.6 or less, there is more space than necessary inside the dispersion, the indentation hardness of the polishing pad polymer composition tends to decrease, and a sufficient polishing rate is required. It becomes difficult to obtain a polishing pad that can be obtained.
【００１６】即ち、分散体は、第４発明のように、特
に、中空でないことが好ましい。中空でない形状として
は、例えば、内部が充填されている中実、内部に微細な
空隙を多く有する多孔質及び凝集等を挙げることができ
る。分散体が中空であると、研磨パッド用重合体組成物
のショアーＤ硬度等に代表される押し込み硬さが減少
し、十分な研磨速度を得ることのできる研磨パッドは得
られ難くなる。尚、この中空とは、外殻のみにより形成
されている形状をいう。但し、外殻が厚く、分散体中の
一箇所に微細な空隙を有し、比重が０．６以上の形状は
中空には含まれない。That is, the dispersion is preferably not hollow, as in the fourth invention. Examples of the non-hollow shape include a solid filled inside, porosity having many fine voids inside, and agglomeration. When the dispersion is hollow, the indentation hardness represented by the Shore D hardness of the polymer composition for a polishing pad is reduced, and it is difficult to obtain a polishing pad capable of obtaining a sufficient polishing rate. In addition, this hollow refers to a shape formed only by the outer shell. However, a shape having a thick outer shell, a fine void at one place in the dispersion, and a specific gravity of 0.6 or more is not included in the hollow.
【００１７】また、本発明の研磨パッド用重合体のショ
アーＤ硬度を前記好ましい範囲とするために、例えば、
硬度の大きい外殻から形成される中空の分散体が分散さ
れた研磨パッド用重合体組成物を得ることもできる。し
かし、このような研磨パッド用重合体組成物からは被研
磨面に接触する面が十分に平坦な研磨パッドを得ること
が困難となり、好ましくない。In order to set the Shore D hardness of the polymer for a polishing pad of the present invention within the above-mentioned preferred range, for example,
It is also possible to obtain a polishing pad polymer composition in which a hollow dispersion formed from an outer shell having high hardness is dispersed. However, it is difficult to obtain a polishing pad having a sufficiently flat surface in contact with the surface to be polished from such a polishing pad polymer composition, which is not preferable.
【００１８】また、この分散体は熱可塑性重合体中にど
のような形状で分散されていてもよいが、鱗片状及び繊
維状を除く形状、例えば、球状及び方形状等であること
が好ましい。また、この分散体の平均粒径は０．０１〜
１０００μｍ（より好ましくは０．１〜５００μｍ、更
には１〜３００μｍ）であることが好ましい。この平均
粒径が０．０１μｍ未満であると研磨効果を十分に得る
ことのできる研磨パッドが得られ難くなる。一方、この
粒径が１０００μｍを超えると強度及び研磨速度が十分
な研磨パッドが得られ難くなる。尚、この平均粒径は分
散体の最長長さの平均値であるものとする。The dispersion may be dispersed in the thermoplastic polymer in any shape. However, it is preferable that the dispersion has a shape other than a scale and a fiber, such as a sphere and a square. The average particle size of the dispersion is 0.01 to
It is preferably 1000 μm (more preferably 0.1 to 500 μm, further preferably 1 to 300 μm). When the average particle size is less than 0.01 μm, it becomes difficult to obtain a polishing pad capable of sufficiently obtaining a polishing effect. On the other hand, if the particle size exceeds 1000 μm, it becomes difficult to obtain a polishing pad with sufficient strength and polishing rate. The average particle size is an average value of the longest length of the dispersion.
【００１９】更に、第５発明のように水溶性物質は、熱
可塑性重合体の加工温度において固体であることが好ま
しい。水溶性物質を熱可塑性重合体中に分散させる方法
は限定されないが、通常、水溶性物質、熱可塑性重合体
及びその他の添加剤等を混練することにより得ることが
できる。この混練において熱可塑性重合体は加工し易い
ように加熱されて混練されるが、この時の温度において
水溶性物質は固体であることが好ましい。固体であるこ
とにより、熱可塑性重合体との相溶性の大きさに関わら
ず水溶性物質を前記の好ましい形状及び平均粒径を呈す
る分散体として分散させ易くなる。従って、使用する熱
可塑性重合体の加工温度により、水溶性物質を選択する
ことが好ましい。Further, as in the fifth invention, the water-soluble substance is preferably solid at the processing temperature of the thermoplastic polymer. The method for dispersing the water-soluble substance in the thermoplastic polymer is not limited, but it can be usually obtained by kneading the water-soluble substance, the thermoplastic polymer and other additives. In this kneading, the thermoplastic polymer is heated and kneaded so as to be easily processed. At this temperature, the water-soluble substance is preferably a solid. By being solid, it becomes easy to disperse the water-soluble substance as a dispersion having the above-mentioned preferred shape and average particle size, regardless of the degree of compatibility with the thermoplastic polymer. Therefore, it is preferable to select a water-soluble substance depending on the processing temperature of the thermoplastic polymer to be used.
【００２０】本発明の研磨パッド用重合体組成物におい
ては、熱可塑性重合体と水溶性物質との親和性、及び熱
可塑性重合体に対する水溶性物質の分散性を制御するた
め、相溶化剤を配合することができる。相溶化剤として
は、酸無水物基、カルボキシル基、ヒドロキシル基、エ
ポキシ基、オキサゾリン基及びアミノ基等により変性さ
れた重合体、ブロック共重合体、並びにランダム共重合
体、更に、種々のノニオン系界面活性剤、カップリング
剤等を挙げることができる。また、硬度及び靭性を調整
するためにゴム等を配合することもできる。In the polymer composition for a polishing pad of the present invention, a compatibilizer is used in order to control the affinity between the thermoplastic polymer and the water-soluble substance and the dispersibility of the water-soluble substance in the thermoplastic polymer. Can be blended. Examples of the compatibilizer include polymers modified with acid anhydride groups, carboxyl groups, hydroxyl groups, epoxy groups, oxazoline groups and amino groups, block copolymers, random copolymers, and various nonionics. Surfactants, coupling agents and the like can be mentioned. Further, rubber or the like can be blended to adjust hardness and toughness.
【００２１】また、必要に応じて、充填材、軟化剤、酸
化防止剤、紫外線吸収剤、帯電防止剤、滑剤、可塑剤等
の各種の添加剤を添加することができる。このうち充填
剤としては、炭酸カルシウム、炭酸マグネシウム、タル
ク、クレー等を挙げることができる。これらの充填材を
添加することにより剛性を向上させることができる。更
に、シリカ、アルミナ、セリア、ジルコニア、酸化チタ
ン、酸化ジルコニウム、二酸化マンガン、三酸化二マン
ガン、炭酸バリウム等の研磨性能を有する砥粒も充填材
として使用することができる。Further, if necessary, various additives such as a filler, a softener, an antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, and a plasticizer can be added. Examples of the filler include calcium carbonate, magnesium carbonate, talc, clay and the like. The rigidity can be improved by adding these fillers. Further, abrasives having polishing performance such as silica, alumina, ceria, zirconia, titanium oxide, zirconium oxide, manganese dioxide, dimanganese trioxide, and barium carbonate can also be used as the filler.
【００２２】本発明の研磨パッド用重合体組成物の製造
方法は特に限定されない。混練工程を有する場合は公知
の混練機等により混練を行うことができる。例えば、ロ
ール、ニーダー、バンバリーミキサー、押出機（単軸、
多軸）等の混練機を挙げることができる。尚、混練され
た研磨パッド用重合体組成物は、プレス成形、押出成
形、射出成形等を行うことによりシート状、ブロック状
又はフィルム状等の所望の形状に加工することができ
る。また、これを所望の大きさに加工することにより研
磨パッドを得ることができる。The method for producing the polymer composition for a polishing pad of the present invention is not particularly limited. In the case of having a kneading step, kneading can be performed by a known kneader or the like. For example, roll, kneader, Banbury mixer, extruder (single screw,
Kneaders such as polyaxial). The kneaded polymer composition for a polishing pad can be processed into a desired shape such as a sheet, block, or film by performing press molding, extrusion molding, injection molding, or the like. Further, by processing this into a desired size, a polishing pad can be obtained.
【００２３】本第６発明の研磨パッドは、第１乃至第５
発明のうちのいずれか１項に記載の研磨パッド用重合体
組成物からなることを特徴とする。本発明の研磨パッド
を半導体ウエハの研磨に使用する場合、そのショアーＤ
硬度は３５以上（通常１００以下、より好ましくは５０
〜９０、更には６０〜８５）とすることが好ましい。こ
のショアーＤ硬度が３５未満であると、研磨時に被研磨
体に加えることのできる圧力が十分でなくなることがあ
り、研磨速度が低下し易く、また研磨平坦性が十分でな
くなることがある。The polishing pad according to the sixth aspect of the present invention comprises the first to fifth polishing pads.
A polishing pad comprising the polymer composition for a polishing pad according to any one of the inventions. When the polishing pad of the present invention is used for polishing a semiconductor wafer, its shore D
Hardness is 35 or more (usually 100 or less, more preferably 50 or less)
To 90, more preferably 60 to 85). If the Shore D hardness is less than 35, the pressure that can be applied to the object to be polished during polishing may not be sufficient, and the polishing rate may be easily reduced, and the polishing flatness may not be sufficient.
【００２４】また、特に、水と接触し、分散体が遊離し
た後に形成されるポアの大きさは０．０１〜１０００μ
ｍ（より好ましくは０．１〜５００、更には１〜３００
μｍ）であることが好ましい。このポアの大きさが０．
０１μｍ未満であるとスラリー中に含まれる砥粒の粒径
より小さくなることがあるため、その保持力が低下し、
十分な研磨効果が得られ難くなる。一方、ポアの大きさ
が１０００μｍを超えると、この大きさが過大となり強
度、研磨速度において十分でなくなることがある。In particular, the size of the pore formed after contact with water and release of the dispersion is 0.01 to 1000 μm.
m (more preferably 0.1 to 500, furthermore 1 to 300
μm). The size of this pore is 0.
If it is less than 01 μm, it may be smaller than the particle size of the abrasive grains contained in the slurry, so its holding power is reduced,
It becomes difficult to obtain a sufficient polishing effect. On the other hand, if the size of the pores exceeds 1000 μm, the size may be too large and the strength and the polishing rate may not be sufficient.
【００２５】本発明の研磨パッド用重合体組成物は、発
泡ウレタン系樹脂のように内部に気泡を有さない。即
ち、水溶性物質からなる水分散体によりポアとなる空隙
が充填されているため十分な押し込み硬さを有する。ま
た、加工時に添加する水溶性物質の量及び熱可塑性樹脂
との相溶性等を調整することにより、研磨パッド用重合
体組成物内に形成される分散体の大きさ及び数を調節す
ることができる。このため、この研磨パッド用重合体組
成物から形成される研磨パッドは、その押し込み硬さ及
びポアの大きさ及び数が所望のものを得ることができ
る。The polymer composition for a polishing pad of the present invention does not have bubbles inside unlike the urethane foam resin. In other words, since the pores are filled with the water dispersion of the water-soluble substance, it has sufficient indentation hardness. Further, by adjusting the amount of the water-soluble substance added at the time of processing and the compatibility with the thermoplastic resin, the size and number of the dispersion formed in the polymer composition for the polishing pad can be adjusted. it can. For this reason, a polishing pad formed from the polymer composition for a polishing pad can have a desired indentation hardness and a desired size and number of pores.
【００２６】[0026]
【発明の実施の形態】以下、実施例により本発明を具体
的に説明する。 （１）研磨パッド用重合体組成物の調製 表１に示す温度に保持した小型ニーダーに、表１に示す
成分を、表１に示す配合割合で混練し、研磨パッド用重
合体組成物を得た。尚、表１における実施例４ではエポ
キシ官能性シランの１０％メタノール溶液を噴霧分散し
た後、１２０℃で３時間乾燥させた水溶性物質を使用し
た。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically with reference to examples. (1) Preparation of Polymer for Polishing Pad The components shown in Table 1 were kneaded in a small kneader maintained at the temperature shown in Table 1 at the compounding ratio shown in Table 1 to obtain a polymer composition for polishing pad. Was. In Example 4 in Table 1, a 10% methanol solution of epoxy-functional silane was spray-dispersed and then dried at 120 ° C. for 3 hours.
【００２７】[0027]
【表１】 [Table 1]
【００２８】尚、表１における各成分は以下のものであ
る。 熱可塑性重合体 ＴＰＥＥ；熱可塑性ポリエステルエラストマー、東洋紡
績株式会社製、商品名「ペルプレン Ｓ−２００１」 ＴＰＡＥ；熱可塑性ポリアミドエラストマー、エルフア
トケム・ジャパン社製、商品名「ペバックス ７０３３
ＳＡ」 ＴＰＵ；熱可塑性ポリウレタンエラストマー、大日精化
工業株式会社製、商品名「レザミン Ｐ４２５０」 ＡＢＳ；ＡＢＳ樹脂、テクノポリマー株式会社製、商品
名「テクノ ＡＢＳ３５０」 ＥＶＯＨ；エチレン−ビニルアルコール共重合体、株式
会社クラレ製、商品名「エバール ＥＰ−Ｇ１１０」The components in Table 1 are as follows. Thermoplastic polymer TPEE; thermoplastic polyester elastomer, manufactured by Toyobo Co., Ltd., trade name "Perprene S-2001"TPAE; thermoplastic polyamide elastomer, manufactured by Elphatochem Japan Ltd., trade name "PEBAX 7033"
SA "TPU; thermoplastic polyurethane elastomer, manufactured by Dainichi Seika Kogyo Co., Ltd., trade name" Rezamin P4250 "ABS; ABS resin, manufactured by Techno Polymer Co., Ltd., trade name" Techno ABS350 "EVOH; ethylene-vinyl alcohol copolymer, Product name “EVAL EP-G110” manufactured by Kuraray Co., Ltd.
【００２９】水溶性物質 β−ＣＤ；β−シクロデキストリン、横浜国際バイオ研
究所製、商品名「デキシーパール」 Ｋ2ＳＯ4；硫酸カリウム、大塚化学株式会社製、商品名
「硫酸カリウム大塚一級」 ＰＶＡ；ポリビニルアルコール、株式会社クラレ製、商
品名「ポバール ＣＰ−１０００」 ＰＥＯ；ポリエチレンオキサイド、明成化学工業社製、
商品名「アルコックスＲ−１０００」 添加剤 エポキシ官能性シラン、信越シリコーン株式会社製、商
品名「ＫＢＭ−４０３」Water-soluble substance β-CD; β-cyclodextrin, manufactured by Yokohama International Bio-Laboratory, trade name “Dexy Pearl” K 2 SO 4 ; potassium sulfate, manufactured by Otsuka Chemical Co., Ltd., trade name “potassium sulfate Otsuka first grade” PVA: polyvinyl alcohol, manufactured by Kuraray Co., Ltd., trade name “Poval CP-1000” PEO: polyethylene oxide, manufactured by Meisei Chemical Industry Co., Ltd.
Brand name "Alcox R-1000" Additive Epoxy-functional silane, brand name "KBM-403" manufactured by Shin-Etsu Silicone Co., Ltd.
【００３０】（２）体積膨張率の測定 得られた９種類の研磨パッド用重合体組成物をプレス成
形し、厚さ２ｍｍの成形板を得た。この成形板より２０
ｃｍ×２５ｍｍの試験片を切り出した。ＪＩＳＫ ６２
５８に従い、２３℃の蒸留水に７２時間浸漬した。この
ときの試験片の浸漬前後の大気中重量及び浸漬前後の水
中重量を測定し、体積膨張率を算出した。この結果を表
２に示す。(2) Measurement of Volume Expansion Coefficient The obtained nine types of polymer compositions for polishing pads were press-molded to obtain a molded plate having a thickness of 2 mm. 20 from this molded plate
A test piece of cm × 25 mm was cut out. JISK 62
According to No. 58, it was immersed in distilled water at 23 ° C. for 72 hours. At this time, the weight of the test piece in the air before and after immersion and the weight in water before and after immersion were measured, and the volume expansion coefficient was calculated. Table 2 shows the results.
【００３１】[0031]
【表２】 尚、表２において＊は第１発明の範囲外であることを示
す。また、＊＊は第２発明の範囲外であることを示す。[Table 2] In Table 2, * indicates that the value is outside the scope of the first invention. In addition, ** indicates that it is outside the scope of the second invention.
【００３２】（３）浸漬によるショアーＤ硬度変化の測
定 また、（２）と同様にして得られた試験片の浸漬前のシ
ョアーＤ硬度をＡＳＴＭ Ｄ２２４０に従い測定した。
その後、２３℃の蒸留水に７２時間浸漬し、試験片のシ
ョアーＤ硬度を再度測定した。このようにして得られた
ショアーＤ硬度の変化量を表２に併記する。(3) Measurement of Shore D Hardness Change by Dipping Shore D hardness of the test piece obtained in the same manner as in (2) before dipping was measured according to ASTM D2240.
Thereafter, the test piece was immersed in distilled water at 23 ° C. for 72 hours, and the Shore D hardness of the test piece was measured again. The change in Shore D hardness thus obtained is also shown in Table 2.
【００３３】（４）研磨パッドの作成 （１）で得られた研磨パッド用重合体組成物をモールド
プレスし、直径３０ｃｍ、厚さ３ｍｍの円盤体を得た。
フライス盤により、この円盤体の表面に切削平坦化加工
を施した。その後、更にフライス盤により深さ１ｍｍ、
幅１ｍｍの溝を、その間隔が６．５ｍｍとなるように形
成して研磨パッドを得た。尚、この研磨パッドの表面に
形成された溝は研磨パッドの表面積の２５％であった。(4) Preparation of polishing pad The polymer composition for a polishing pad obtained in (1) was subjected to mold pressing to obtain a disc having a diameter of 30 cm and a thickness of 3 mm.
The surface of the disk was cut and flattened by a milling machine. After that, 1 mm deep with a milling machine,
Grooves having a width of 1 mm were formed so that the interval was 6.5 mm, to obtain a polishing pad. The groove formed on the surface of the polishing pad was 25% of the surface area of the polishing pad.
【００３４】（５）研磨 （４）で得られた各研磨パッドを研磨装置（ラップマス
ターＳＦＴ社製、型式「ラップマスター ＬＭ−１
５」）の定盤に貼り付けた。このパッド上に、スラリー
（キャボット社製、商品名「Ｗ−２０００」）を５０ｃ
ｃ／分の流量で供給した。また、被研磨材としてタング
ステン膜が施されたウエハを４×４ｃｍ角に切り出し、
定盤に固定した。研磨装置の定盤の回転数を６６ｒｐｍ
にして３分間研磨を行った。(5) Polishing Each polishing pad obtained in (4) is polished by a polishing apparatus (Lappmaster LM-1 manufactured by Lappmaster SFT).
5)). On this pad, a slurry (trade name “W-2000”, manufactured by Cabot Corporation) was applied for 50 c.
It was supplied at a flow rate of c / min. In addition, a wafer having a tungsten film as a material to be polished is cut into 4 × 4 cm squares,
It was fixed on the surface plate. The rotation speed of the platen of the polishing machine is 66 rpm
And polished for 3 minutes.
【００３５】（６）研磨速度の算出 （５）で各研磨パッドを使用して研磨したウエハの表面
を抵抗率測定機（ＮＰＳ社製、型式「Σ−５」）により
直流４探針法で測定し、研磨前のウエハの表面抵抗値と
比較し、研磨速度として算出した。この結果を表２の各
々の研磨パッドを形成した研磨パッド用重合体組成物の
欄に併記する。尚、タングステン膜の厚さ（Å）＝［表
面抵抗値（Ω／ｃｍ2）×タングステンの抵抗率（Ω／
ｃｍ）］×１０8である。(6) Calculation of Polishing Rate The surface of the wafer polished by using each polishing pad in (5) is measured by a direct current four-probe method using a resistivity measuring machine (NPS, model “製 -5”). It was measured and compared with the surface resistance value of the wafer before polishing, and was calculated as a polishing rate. The results are also shown in Table 2 in the column of the polymer composition for a polishing pad on which each polishing pad was formed. The thickness of the tungsten film (Å) = [surface resistance value (Ω / cm 2 ) × resistivity of tungsten (Ω /
cm)] × 10 8 .
【００３６】（７）形状の変化 （５）の研磨を行った後のパッドを目視にて、その形状
がどの程度変化しているかを観察した。そり及び亀裂等
の変化が見て取れない場合は○、それ以外の場合は×と
表２に併記した。(7) Change in Shape The degree of change in the shape of the pad after the polishing of (5) was visually observed. In the case where no change such as a warp or a crack can be seen, the results are shown in Table 2 as "O", and in other cases, "X".
【００３７】表２の結果より、実施例１〜６では、いず
れも体積膨張率が０．１〜３．４％と小さい。また、シ
ョアーＤ硬度低下も０〜５と小さい。このため、研磨パ
ッドの形状を十分に維持することができ、研磨速度も１
６７〜２４３ｎｍ／分（特に、２０８〜２４３ｎｍ／
分）と十分な値を得ることができる。また、これらの研
磨パッドでは、水溶性物質を２０〜７０重量％と幅広い
範囲で配合することができる。特に、実施例４では硫酸
カリウムをカップリング処理することで、水に浸漬した
場合であってもその溶出を適度に抑制することができ、
適度な押し込み硬度を有する研磨パッドとすることがで
きる。このため、水溶性物質の配合量は７０重量％と非
常に多くすることができる。From the results shown in Table 2, the volume expansion coefficients of Examples 1 to 6 are as small as 0.1 to 3.4%. Also, the decrease in Shore D hardness is as small as 0 to 5. For this reason, the shape of the polishing pad can be sufficiently maintained, and the polishing rate can be reduced to one.
67 to 243 nm / min (particularly, 208 to 243 nm /
Min) and a sufficient value can be obtained. In these polishing pads, a water-soluble substance can be blended in a wide range of 20 to 70% by weight. In particular, in Example 4, by performing a potassium sulfate coupling treatment, even when immersed in water, the elution thereof can be appropriately suppressed,
A polishing pad having appropriate indentation hardness can be obtained. For this reason, the compounding amount of the water-soluble substance can be as large as 70% by weight.
【００３８】これに対して、比較例１では、ショアーＤ
硬度低下が１４と大きいために、十分な研磨速度が得ら
れない。また、比較例２では、体積膨潤率及びショアー
Ｄ硬度低下のいずれも測定不可能な位大きく、比較例３
では、体積膨潤率が３１％、ショアーＤ硬度低下が２４
と大きい。このため、いずれにおいても研磨することが
できず、また、研磨パッドの形状を保持することもでき
ない。比較例４では、ショアーＤ硬度低下が１１と大き
いために、十分な研磨速度が得られない。これは、実施
例４と同様な組成及び配合割合であるがカップリング処
理を行っていないために硫酸カリウムが過度に溶出し、
ショアーＤ硬度の低下を抑制することができないためで
ある。On the other hand, in Comparative Example 1, Shore D
Since the decrease in hardness is as large as 14, a sufficient polishing rate cannot be obtained. In Comparative Example 2, both the volume swelling ratio and the decrease in Shore D hardness were so large that they could not be measured.
, The volume swelling ratio is 31% and the decrease in Shore D hardness is 24
And big. For this reason, any of them cannot be polished and the shape of the polishing pad cannot be maintained. In Comparative Example 4, since the decrease in Shore D hardness was as large as 11, a sufficient polishing rate could not be obtained. This is the same composition and compounding ratio as in Example 4, but potassium sulfate is excessively eluted because the coupling treatment is not performed,
This is because a decrease in Shore D hardness cannot be suppressed.
【００３９】[0039]
【発明の効果】本第１発明によると、押し込み硬さが大
きく、スラリーの保持性に優れ、強度が高く、研磨速度
の大きな研磨パッドが得られる研磨パッド用重合体組成
物を得ることができる。本第２発明によると、第１発明
と同様な優れた研磨パッドが得られる研磨パッド用重合
体組成物を得ることができる。本第３乃至第５発明によ
ると特に優れた研磨パッドが得られる研磨パッド用重合
体組成物を得ることができる。第６発明によると、押し
込み硬さが大きく、スラリーの保持性に優れ、強度が高
く、研磨速度の大きな研磨パッドを得ることができる。According to the first aspect of the present invention, it is possible to obtain a polishing pad polymer composition which has a large indentation hardness, excellent slurry holding properties, high strength and a high polishing rate. . According to the second aspect of the present invention, a polymer composition for a polishing pad that can provide the same excellent polishing pad as the first aspect of the invention can be obtained. According to the third to fifth aspects of the present invention, it is possible to obtain a polymer composition for a polishing pad capable of obtaining a particularly excellent polishing pad. According to the sixth invention, it is possible to obtain a polishing pad having high indentation hardness, excellent slurry retention, high strength, and a high polishing rate.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 栗原 文夫 東京都中央区築地２丁目11番24号 ジェイ エスアール株式会社内 Ｆターム(参考） 3C058 AA09 AA14 CB03 CB10 DA17 4F071 AA08 AA09 AA15 AA20 AA21 AA22 AA29 AA32 AA33 AA51 AA54 AA75 DA17 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Fumio Kurihara Inventor F-term (reference) 3-11-24 Tsukiji 2-chome, Chuo-ku, Tokyo JSR Corporation 3C058 AA09 AA14 CB03 CB10 DA17 4F071 AA08 AA09 AA15 AA20 AA21 AA22 AA29 AA32 AA33 AA51 AA54 AA75 DA17
Claims (6)
性重合体中に分散された水溶性物質とを含み、温度２３
℃の水に７２時間浸漬した場合の体積膨潤率が２０％以
下であることを特徴とする研磨パッド用重合体組成物。1. A thermoplastic resin comprising a water-insoluble thermoplastic polymer and a water-soluble substance dispersed in the thermoplastic polymer.
A polymer composition for a polishing pad, which has a volume swelling ratio of not more than 20% when immersed in water at 72 ° C. for 72 hours.
性重合体中に分散された水溶性物質とを含み、温度２３
℃の水に７２時間浸漬した場合のショアーＤ硬度の低下
が１０以下であることを特徴とする研磨パッド用重合体
組成物。2. A composition comprising a water-insoluble thermoplastic polymer and a water-soluble substance dispersed in the thermoplastic polymer, and having a temperature of 23.
A polymer composition for a polishing pad, wherein a decrease in Shore D hardness when immersed in water at 72 ° C. for 72 hours is 10 or less.
と上記水溶性物質との合計量の１０重量％以上である請
求項１又は２記載の研磨パッド用重合体組成物。3. The polishing pad polymer composition according to claim 1, wherein the amount of the water-soluble substance is 10% by weight or more of the total amount of the thermoplastic polymer and the water-soluble substance.
ており、該分散体は中空でない請求項１乃至３のうちの
いずれか１項に記載の研磨パッド用重合体組成物。4. The polishing pad polymer composition according to claim 1, wherein the water-soluble substance is dispersed as a dispersion, and the dispersion is not hollow.
て、上記水溶性物質は固体である請求項１乃至４のうち
のいずれか１項に記載の研磨パッド用重合体組成物。5. The polishing pad polymer composition according to claim 1, wherein the water-soluble substance is a solid at the processing temperature of the thermoplastic polymer.
記載の研磨パッド用重合体組成物からなることを特徴と
する研磨パッド。6. A polishing pad comprising the polymer composition for a polishing pad according to any one of claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22388199A JP3880028B2 (en) | 1999-08-06 | 1999-08-06 | Polymer composition for polishing pad and polishing pad using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22388199A JP3880028B2 (en) | 1999-08-06 | 1999-08-06 | Polymer composition for polishing pad and polishing pad using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001047355A true JP2001047355A (en) | 2001-02-20 |
| JP3880028B2 JP3880028B2 (en) | 2007-02-14 |
Family
ID=16805181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22388199A Expired - Lifetime JP3880028B2 (en) | 1999-08-06 | 1999-08-06 | Polymer composition for polishing pad and polishing pad using the same |
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|---|---|
| JP (1) | JP3880028B2 (en) |
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| WO2003043071A1 (en) * | 2001-11-13 | 2003-05-22 | Toyo Boseki Kabushiki Kaisha | Grinding pad and method of producing the same |
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