1335854 九、發明說明 【發明所屬之技術領域】1335854 IX. Description of the invention [Technical field to which the invention pertains]
本發明係關於用來修整進行半導體晶圓 CMP (化學機械拋光）裝置之拋光墊的CMP 製造方法。 【先前技術】 舉例來說，專利文獻1係提出作爲此種 之物，其係在圓盤狀之基體（基底金屬）的 成複數圓柱狀之突起部，並藉由金屬電鍍結 之鑽石等之磨粒黏著於這些突起部的表面。 另外，專利文獻2係提出硬銲有鑽石磨: 利文獻3係進一步提出，在以此方式黏著有j 合相的表面上，藉由CVD或離子鍍等之汽^ 覆SiC等之陶瓷被膜一事。 在這種藉由CMP修整器來修整拋光墊的 由於在半導體晶圓等之拋光之際使用酸性或f 高的硏漿，故載持磨粒的金屬結合層會被此i 出）使得磨粒脫落，而有半導體晶圓被此脫； 而產生刮痕這樣的問題。特別是，在磨粒爲自 爲鎳等之金屬電鍍相的情況，因爲缺乏對磨3 的可濕性，故會在兩者的邊界部份（空穴）^ 隙，而硏漿從此縫隙進入而腐蝕金屬電鍍相ί 得進一步促使磨粒脫落。 等之拋光的 修整器及其 CMP修整器 面相間地形 相，使複數 :之物，而專 ;粒之金屬結 塗膜技術被 CMP裝置， 性之腐蝕性 漿腐蝕（溶 之磨粒所傷 石而結合相 之金屬電鍍 生極小之縫 結果，會變 1335854 由此點來看，如專利文獻3所記載，將陶瓷被膜被覆 於金屬結合相表面之CMP修整器，係藉由以此陶瓷被膜 保護金屬結合層來防止其腐蝕，因此亦可控制磨粒的脫落 。然而，在其另一方面，在此專利文獻3所記載之以汽相 塗膜技術來被覆陶瓷被膜的情況，由於自金屬結合相突出 的鑽石等之磨粒的表面亦會由被膜所被覆，故磨粒的鋒利 度會受損，而產生拋光墊之拋光率顯著下降這樣的問題》 另外，已知以專利文獻4〜7等所揭示之氣溶膠沉積 法來作爲在各種基材上形成陶瓷厚膜的手法。 [專利文獻1]特開2001-71269號公報 [專利文獻2]特開2002-273657號公報 [專利文獻3]特開200 1 -2 1 06 1 3號公報 [專利文獻4 ]專利3 3 4 8 1 5 4號公報 [專利文獻5 ]特開2 0 0 2 - 3 0 9 3 8 3號公報 [專利文獻6]特開2003-034003號公報 [專利文獻7]特開2004-091614號公報 [專利文獻8 ]特開2 0 0 3 - 1 8 3 8 4 8號公報 【發明內容】 [發明所欲解決之問題] 本發明是在此種背景之下所形成，其目的爲提供用於 CMP裝置之即使對於腐蝕性高的硏漿，仍可確實防止磨粒 脫落而抑制刮痕產生的CMP修整器。 -6- 1335854 [用以解決問題之手段] 可解決上述問題之與本發明有關的CMP修整器，其 構成爲：在磨石基體的一面，形成有將磨粒黏著於金屬結 合相中而成的磨粒層，至少在前述磨粒層的前述金屬結合 相表面’形成以溶膠凝膠法所製作之氧化物膜來作爲第一 保護層，並在前述第一保護層的表面，形成爲多結晶且在 前述結晶群體之界面實質上不存在由玻璃層所構成之粒界 層的氧化物厚膜來作爲第二保護層。 在此，厚膜爲具有1 μιη以上的膜厚度之膜。 最好是，前述第一保護層係形成爲：至少在前述磨粒 和前述金屬結合相的接合部附近，被覆前述金屬結合相。 這種構造可能藉由溶膠凝膠法來形成第一保護層，也 就是氧化物膜。由於溶膠凝膠法是利用溶液的氧化物膜之 形成方法，溶液會因表面張力而被吸引至磨粒的周圍，其 結果可想見在磨粒周邊部份的膜厚度會比其他部分還厚。 所形成的氧化物膜係被覆前述金屬結合相，且特別是在磨 粒周邊部份具有優異的耐蝕性。 第一保護層在除了磨粒周邊部份之其他部份的膜厚度 很薄，故無法得到安定之耐蝕性。因此，藉由在第一保護 層的表面形成第二保護層，也就是爲多結晶且在前述結晶 群體之界面實質上不存在由玻璃層所構成之粒界層的氧化 物厚膜’可得到安定之耐餓性。 最好是第二保護層不形成於磨粒的表面，而僅形成於 第一保護層的表面。因不形成於磨粒的表面，而不會產生 1335854 CMP修整器之硏磨性能變化等之缺點。 另外’第二保護層最好爲耐蝕性優異之氧化物，例如 氧化鋁。 另外’可考慮將噴射於氣體中分散有脆性材料之微粒 子的氣溶膠，使其碰撞至第一保護層上來形成氧化物厚膜 的方法，作爲第二保護層的製造方法。 上述方法也是如前述專利文獻4〜7所記載，被認知 爲氣溶膠沉積法的方法。 氣溶膠沉積法是在各種基材上形成陶瓷厚膜的手法， 其特徵爲：從噴嘴朝向基材噴射於氣體中分散有陶瓷微粒 子的氣溶膠，使微粒子碰撞金屬或玻璃、陶瓷或塑膠等之 基材，藉由此碰撞之衝撃，使微粒子產生變形或破碎而將 它們接合，在基材上直接形成由微粒子之構成材料所構成 的膜構造物，特別是不需加熱手段而可能以常溫形成構造 物，且可得到保有燒成體同等之機械性強度的構造物。用 於此方法之裝置，基本上是由產生氣溶膠的氣溶膠產生器 和朝向基材噴射氣溶膠的噴嘴所構成，在製作面積比噴嘴 的開口還大之構造物的情況，具有使基材和噴嘴相對移動 •擺動的位置控制手段，在於減壓下進行製作的情況，具 有形成構造物的腔室和真空幫浦，另外，一般係具有用於 產生氣溶膠的氣體產生源。 氣溶膠沉積法的製程溫度爲常溫，其特徵之一在於： 在比微粒子材料之融點低很多的溫度，亦即數百。C以下進 行構造物形成。 -8- 1335854 另外，所使用之微粒子係以陶瓷等之脆性材料爲主體 ，除了可單獨或混合使用同一材質之微粒子以外，還可能 混合不同種的微粒子來複合使用。另外，亦可能使用一部 份金屬材料或有機物材料等混合於陶瓷微粒子，或是塗佈 於陶瓷微粒子表面。在這些情況，構造物形成之主要物質 仍爲陶瓷。 關於藉由此手法所形成之膜構造物，在使用結晶性的 微粒子來作爲原料的情況，膜構造物是其微晶尺寸比原料 微粒子之尺寸還小的多結晶體，其結晶實質上不具有結晶 定向性的情況很多，故可說爲在陶瓷結晶群體之界面實質 上不存在由玻璃層所構成之粒界層，進而膜構造物的一部 份係有多半形成深入基材表面之錨（anchor)層這樣的特 徴。 藉由此方法所形成的膜構造物，明顯與微粒子群體因 壓力所堆集而以物理性附著來保持形態之狀態的所謂之壓 粉體不同，而保有充分之強度β 於此膜構造物形成時，微粒子發生破碎•變形一事， 可藉由以X光繞射法，測定用來作爲原料之微粒子及所形 成之膜構造物的微晶尺寸來加以判斷。 以下說明與氣溶膠沉積法有關的詞彙。 (多結晶） 在本件指的是微晶結合·積體而成的構造體。微晶係 實質上以其一者構成結晶，且其直徑通常爲5 nm以上。 -9 - 1335854 但是，微粒子未破碎便進入構造物中等之情況不常發生， 故實質上爲多結晶。 (微粒子） 在原粒子爲緻密質粒子的情況，是指以粒度分佈測定 或掃描型電子顯微鏡所辨別之平均粒徑爲10 μιη以下之物 。另外，在原粒子爲容易因衝撃而破碎之多孔質粒子的情 況，是指平均粒徑爲50μιη以下之物。 (氣溶膠） 是將前述微粒子分散於氦、氮、氬、氧、乾燥空氣， 這些混合氣體等之氣體中之物，而以分散有原粒子的狀態 爲佳，但通常係包含此原粒子所凝集之凝集粒。氣溶膠的 氣體壓力和溫度爲任意，但氣體中的微粒子之濃度，在換 算氣體壓力爲1大氣壓、溫度爲2 0°C的情況，對構造物 之形成而言，在從噴嘴噴射的時間點係以0.0003 mL/L〜5 mL/L之範圍内爲佳。 (界面） 在本件是指構成微晶群體之邊界的區域。 (粒界層） 是位於界面或是燒結體所稱之粒界的具有厚度（通常 爲數nm〜數μιη)之層，通常採用與結晶粒内之結晶構 -10- 1335854 造相異的非結晶構造，而且視情況而伴有不純物之離析。 [發明之效果] 由本發明所成之CMP修整器，由於在磨粒周邊部份 形成具有優異耐蝕性的第一保護層、和膜厚度厚且具有安 定之耐蝕性的第二保護層兩者，故可能防止因金屬結合相 腐蝕所導致之磨粒脫落，而可抑制刮痕之產生來謀求高水 準的半導體晶圓等之拋光。 【實施方式】 圖1爲與本發明有關的CMP修整器10之剖面模式圖 。CMP修整器係形成有基底金屬1〇1、與基底金屬1〇1接 觸之金屬結合相102、藉由金屬結合相102來黏著例如鑽 石磨粒等多數之磨粒105的磨粒層11，至少前述磨粒層 11的前述金屬結合相102表面係形成有以溶膠凝膠法所製 作之二氧化矽（silica)、二氧化鈦等之氧化物膜來作爲 第一保護層103 ’且前述第一保護層表面係形成有藉由氣 溶膠沉積法所製作之膜厚度1 μιη以上的氧化鋁膜來作爲 第二保護層104。 以下將就形成第一保護層的手法，亦即溶膠凝膠法加 以説明。 將修整器浸漬於混合Si (0(：2Η5) 4和乙醇所製作出 之Si〇2溶膠凝膠液或混合Ti( 〇C2H5 ) 4和乙醇所製作出 之Ti〇2溶膠凝膠液中1分鐘後，以200。C乾燥2小時， -11 -The present invention relates to a CMP fabrication method for trimming a polishing pad for performing a semiconductor wafer CMP (Chemical Mechanical Polishing) device. [Prior Art] For example, Patent Document 1 proposes such a thing as a plurality of cylindrical projections of a disk-shaped base (base metal), and a diamond plated by metal plating or the like. Abrasive particles adhere to the surface of these protrusions. Further, Patent Document 2 proposes a brazed diamond mill: In the literature 3, it is further proposed that a ceramic coating such as SiC or the like is coated by a vapor deposition or the like on the surface of the j-phase bonded in this manner. . In the case where the polishing pad is trimmed by the CMP conditioner, since the acid or f-high slurry is used for polishing the semiconductor wafer or the like, the metal bonding layer carrying the abrasive grains is caused by the abrasive grains. It falls off, and there is a problem that the semiconductor wafer is detached; and scratches are generated. In particular, in the case where the abrasive grains are electroplated with a metal such as nickel, since the wettability to the grinding 3 is lacking, the boundary portion (hole) of the both is formed, and the slurry enters from the gap. Corrosion of the metal plating phase further promotes the detachment of the abrasive particles. Waiting for the polished dresser and its CMP dresser surface phase to make the plural: the object, and the special; the metal coating film technology of the grain is etched by the CMP device, the corrosive slurry of the corrosion The result of the extremely small seam of the metal plating combined with the phase will change to 1335854. From this point of view, as described in Patent Document 3, the CMP dresser in which the ceramic film is coated on the surface of the metal bonded phase is protected by the ceramic film. The metal bonding layer is used to prevent corrosion of the abrasive grains, and therefore, the falling of the abrasive grains can be controlled. However, in another aspect, the ceramic film is coated by the vapor phase coating film technology described in Patent Document 3, since the self-metal bonding The surface of the abrasive grains such as the protruding diamonds is also covered by the film, so that the sharpness of the abrasive grains is impaired, and the polishing rate of the polishing pad is remarkably lowered. Further, Patent Documents 4 to 7 are known. The method of forming a thick film of ceramics on various substrates by the method of the aerosol deposition method disclosed in the above-mentioned Japanese Patent Laid-Open Publication No. JP-A-2002-273269 [Patent Document No. 2002-273657] [Patent Document 3] [Patent Document 4] Patent No. 3 3 4 8 1 5 4 [Patent Document 5] Special Opening 2 0 0 2 - 3 0 9 3 8 No. 3 [Patent [Patent Document 7] Japanese Laid-Open Patent Publication No. 2004-091614 (Patent Document 8) Japanese Patent Application Publication No. JP-A No. 2004-091 DISCLOSURE OF THE INVENTION The present invention has been made under such a background, and an object thereof is to provide a CMP conditioner which can reliably prevent abrasive particles from falling off and suppress scratch generation even for a highly corrosive slurry of a CMP apparatus. -6- 1335854 [Means for Solving the Problem] A CMP conditioner according to the present invention which solves the above problems is characterized in that, on one side of a grindstone substrate, an abrasive grain is adhered to the metal bonded phase. Forming an abrasive layer to form an oxide film formed by a sol-gel method on at least the surface of the metal-bonding phase of the abrasive grain layer as a first protective layer, and forming a surface on the surface of the first protective layer Polycrystalline and substantially free of intergranular layers composed of glass layers at the interface of the aforementioned crystalline population The thick film is used as the second protective layer. Here, the thick film is a film having a film thickness of 1 μm or more. Preferably, the first protective layer is formed at least in the aforesaid abrasive grain and the metal bonded phase. The metal bonding phase is coated in the vicinity of the joint portion. This configuration may form a first protective layer, that is, an oxide film, by a sol-gel method. Since the sol-gel method is a method of forming an oxide film using a solution, the solution It is attracted to the periphery of the abrasive grains due to the surface tension. As a result, it is conceivable that the film thickness in the peripheral portion of the abrasive grain is thicker than other portions. The formed oxide film covers the aforementioned metal-bonded phase, and particularly has excellent corrosion resistance in the peripheral portion of the abrasive grain. The first protective layer has a film thickness thinner than the other portions of the peripheral portion of the abrasive grains, so that stable corrosion resistance cannot be obtained. Therefore, by forming a second protective layer on the surface of the first protective layer, that is, a thick film of oxide which is polycrystalline and substantially free of the grain boundary layer composed of the glass layer at the interface of the aforementioned crystal population, Stability and tolerance to starvation. Preferably, the second protective layer is not formed on the surface of the abrasive particles, but is formed only on the surface of the first protective layer. Since it is not formed on the surface of the abrasive grain, it does not cause the defects of the honing performance change of the 1335854 CMP conditioner. Further, the second protective layer is preferably an oxide excellent in corrosion resistance such as alumina. Further, a method of forming an oxide thick film by colliding an aerosol sprayed with a fine particle of a brittle material in a gas to cause collision with the first protective layer is considered as a method of producing the second protective layer. The above method is also a method known as the aerosol deposition method as described in the above Patent Documents 4 to 7. The aerosol deposition method is a method of forming a ceramic thick film on various substrates, and is characterized in that an aerosol in which ceramic fine particles are dispersed in a gas from a nozzle toward a substrate is caused to cause the particles to collide with metal, glass, ceramic or plastic. The substrate is deformed by the collision, and the microparticles are deformed or broken to join them, and a film structure composed of a constituent material of the microparticles is directly formed on the substrate, and particularly may be formed at a normal temperature without heating means. As the structure, a structure in which the mechanical strength equivalent to that of the fired body is obtained can be obtained. The apparatus used in the method is basically composed of an aerosol generating aerosol generator and a nozzle for injecting an aerosol toward the substrate, and in the case of fabricating a structure having a larger area than the opening of the nozzle, the substrate is provided The positional control means for moving relative to the nozzle and swinging is produced under reduced pressure, and has a chamber for forming a structure and a vacuum pump, and generally has a gas generating source for generating an aerosol. The process temperature of the aerosol deposition method is normal temperature, and one of its characteristics is that it is at a temperature much lower than the melting point of the fine particle material, that is, several hundred. The formation of the structure is carried out below C. -8- 1335854 In addition, the fine particles used are mainly brittle materials such as ceramics. In addition to the use of fine particles of the same material alone or in combination, it is also possible to mix different kinds of fine particles for composite use. Alternatively, it is also possible to use a part of a metal material or an organic material to be mixed with the ceramic fine particles or coated on the surface of the ceramic fine particles. In these cases, the main substance formed by the structure is still ceramic. In the film structure formed by the method, when crystalline fine particles are used as a raw material, the film structure is a polycrystal having a crystallite size smaller than that of the raw material fine particles, and the crystal has substantially no crystal. There are many cases of orientation, so it can be said that there is substantially no grain boundary layer composed of a glass layer at the interface of the ceramic crystal group, and a part of the film structure is formed with an anchor which penetrates deep into the surface of the substrate (anchor) The layer is such a feature. The membrane structure formed by this method is distinct from the so-called compacted body in which the microparticle population is physically adhered to maintain the morphology by the pressure buildup, and sufficient strength β is maintained when the membrane structure is formed. In the case where the fine particles are broken or deformed, the crystallite size used as the raw material and the crystallite size of the formed film structure can be determined by the X-ray diffraction method. The vocabulary related to the aerosol deposition method is explained below. (Multi-crystal) This article refers to a structure in which microcrystals are combined and integrated. The microcrystalline system consists essentially of one of the crystals, and its diameter is usually 5 nm or more. -9 - 1335854 However, the fact that the fine particles are not broken and enters the structure or the like does not occur frequently, so it is substantially polycrystalline. (Microparticles) When the primary particles are dense particles, the average particle diameter determined by the particle size distribution measurement or the scanning electron microscope is 10 μm or less. Further, in the case where the original particles are porous particles which are easily broken by punching, the average particle diameter is 50 μm or less. (Aerosol) is a state in which the fine particles are dispersed in a gas such as helium, nitrogen, argon, oxygen, or dry air, or a mixed gas, and preferably dispersed in the original particles, but usually the primary particles are contained. Agglutinated aggregates. The gas pressure and temperature of the aerosol are arbitrary, but the concentration of the fine particles in the gas is at a pressure of 1 atm and the temperature is 20 ° C. For the formation of the structure, at the time of spraying from the nozzle It is preferably in the range of 0.0003 mL/L to 5 mL/L. (Interface) This part refers to the area that constitutes the boundary of the microcrystalline group. (Grain boundary layer) is a layer having a thickness (usually several nm to several μηη) located at the interface or the grain boundary of the sintered body, and is usually made of a different structure from the crystal structure of the crystal grain - 10 1335854. Crystal structure, and as the case may be accompanied by the isolation of impurities. [Effects of the Invention] The CMP conditioner formed by the present invention has both a first protective layer having excellent corrosion resistance and a second protective layer having a thick film thickness and stable corrosion resistance in a peripheral portion of the abrasive grain. Therefore, it is possible to prevent the abrasive grains from falling off due to corrosion of the metal bonded phase, and it is possible to suppress the occurrence of scratches and to polish a high-quality semiconductor wafer or the like. [Embodiment] Fig. 1 is a schematic cross-sectional view showing a CMP conditioner 10 relating to the present invention. The CMP conditioner is formed with a base metal 1〇1, a metal bonded phase 102 in contact with the base metal 1〇1, and an abrasive layer 11 of a plurality of abrasive grains 105 such as diamond abrasive grains adhered by the metal bonded phase 102, at least An oxide film of silica, titania or the like prepared by a sol-gel method is formed on the surface of the metal bond phase 102 of the abrasive grain layer 11 as the first protective layer 103' and the first protective layer As the second protective layer 104, an aluminum oxide film having a film thickness of 1 μm or more produced by an aerosol deposition method is formed on the surface. The method of forming the first protective layer, that is, the sol-gel method will be described below. The conditioner is immersed in a Ti〇2 sol-gel solution prepared by mixing Si(2,5Η5) 4 and ethanol with Si〇2 sol-gel solution or Ti(〇C2H5) 4 and ethanol. After a minute, dry at 200 ° C for 2 hours, -11 -
1335854 之後以5 Ο 0° C處理8小時來形成氧化物膜。此外， 用 Ti02、Al2〇3、Sn02、ZnO、V02、V205、M〇3 Ta05、Zn02等之溶膠凝膠液來作爲溶膠凝膠液。 亦可使用異丙醇來代替乙醇。 接著，以下將就形成第二保護層104的手法， 溶膠沉積法加以説明。 氣溶膠沉積法的特徵爲：從噴嘴朝向基材噴 中分散有脆性材料等之微粒子的氣溶膠，使微粒 屬或玻璃、陶瓷或塑膠等之基材，藉由此碰撞之 脆性材料微粒子產生變形或破碎而將它們接合， 直接形成由微粒子之構成材料所構成的構造物， 需加熱手段而可能以常溫形成構造物，且可得到 體同等之機械性強度的構造物。用於此方法之裝 上是由產生氣溶膠的氣溶膠產生器、和朝向基材 膠的噴嘴所構成，在製作面積比噴嘴的開口還大 的情況，具有使基材和噴嘴相對移動·擺動的位 段，在於減壓下進行製作的情況，具有形成構造 和真空幫浦，另外，一般係具有用於產生氣溶膠 生源。 氣溶膠沉積法的製程溫度爲常溫，其特徵之一 在比微粒子材料之融點低很多的溫度，亦即數百。C 行構造物形成。因此，可選擇的基材橫跨多種，即 融點金屬或樹脂材料在應用上亦無問題。 另外，所使用的微粒子係以陶瓷或半導體等之 >亦可使 、W〇3 ' 另外， 亦即氣 ί於氣體 1碰撞金 i撃，使 Ξ基材上 F別是不 I有燒成 [，基本 【射氣溶 :構造物 【控制手 7的腔室 !氣體產 •在於： 以下進 I使是低 .脆性材 -12- 1335854 料爲主體，除了可單獨或混合使用同一材質之微粒子以外 ’還可能混合不同種的脆性材料微粒子來複合使用。另外 ’亦可能使用一部份金屬材料或有機物材料等混合於脆性 材料微粒子，或是塗佈於脆性材料微粒子表面。在這些情 況，構造物形成之主要物質仍爲脆性材料。 關於藉由此手法所形成之構造物，在使用結晶性的脆 性材料微粒子來作爲原料的情況，構造物的脆性材料部份 是其微晶尺寸比原料微粒子之尺寸還小的多結晶體，其結 晶實質上不具有結晶定向性的情況很多，故可說爲在脆性 材料結晶群體之界面實質上不存在由玻璃層所構成之粒界 層，進而構造物的一部份係有多半形成深入基材表面之錨 層這樣的特徴。 藉由此方法所形成的構造物，明顯與微粒子群體因壓 力所堆集而以物理性附著來保持形態之狀態的所謂之壓粉 體不同，而保有充分之強度。 關於此構造物形成，脆性材料微粒子發生破碎·變形 一事，可藉由以X光繞射法，測定用來作爲原料之脆性材 料微粒子及所形成之脆性材料構造物的微晶尺寸來加以判 斷。亦即，以氣溶膠沉積法所形成的構造物之微晶尺寸係 顯示比原料微粒子之微晶尺寸更小之値。在使微粒子破碎 或變形所形成的偏移面或破面，形成原本存在於内部而成 爲與別的原子結合而成之原子露出的狀態之新生面。此高 表面能量的活性之新生面可視爲相鄰之脆性材料表面或同 樣相鄰之脆性材料的新生面，或是藉由與基板表面接合而 -13- 1335854 來改變氣溶膠碰撞位置，並藉由微粒子之碰撞，在被製膜 物208的所欲位置上形成膜狀的氧化鋁膜。 在此雖然是以真空幫浦209使陶瓷膜形成室205處於 減壓環境下，但並不一定需要成爲減壓環境，亦可能在大 氣中壓下製膜。另外，氣體亦不限於氮，可自由使用氦、 壓縮空氣等。 (實施例） 爲了檢驗與本發明有關的CMP修整器之性能，在 CMP硏漿（W2000、Cabot公司製）與3%過氧化氫溶液之 混合溶液中以5 0° C進行浸漬4 8小時，進行由觀察浸漬前 後之表面狀態而成的耐触性實驗。 製作下述CMP修整器來作爲用於耐鈾性實驗之與本 發明有關的CMP修整器：將修整器浸漬於以1 : 1混合Si 薄膜形成材料（三菱材料公司製）和乙醇所製作之溶膠凝 膠液1分鐘後，以200°C乾燥2小時，以500°C處理8小 時，在於作爲金屬結合相之Ni中黏著有作爲磨粒之鑽石 磨粒的表面，形成二氧化矽膜來作爲第一保護膜，接下來 ，以根據圖2之裝置，使用平均粒徑0.6 μπι的氧化鋁微 粒子，以氮氣7 L/min之流量產生氣溶膠，藉由噴嘴噴射 至被製膜物表面，而形成膜厚度3 ~5 μπι的氧化鋁膜來作 爲第二保護膜之CMP修整器。耐蝕性實驗之結果，沒有 因腐蝕所致之變色，而得知具有充分之耐蝕性。結果顯示 於表1。另外，表1亦合倂列出以下所示之比較例1、比 -15- 1335854 較例2的結果。 (比較例1 ) 爲了比較耐蝕性，製作僅形成實施例1之第二保護膜 的CMP修整器，進行與實施例1相同的耐蝕性實驗。耐 蝕性實驗之結果，在鑽石磨粒附近發現因腐蝕所致之變色 ，而得知有Ni溶出。 (比較例2) 爲了比較耐蝕性，製作不形成實施例1之第一保護膜 及第二保護膜的CMP修整器，進行與實施例1相同的耐 蝕性實驗。耐蝕性實驗之結果，鑽石磨粒所存在的面之整 個區域皆變色，而得知有Ni溶出。 [表1] 實施例1 比較例1 比較例2 第一保護膜 有 無 Μ y\\\ 第二保護膜 有 有 /fnT- m 〇 Δ X 耐蝕性實驗後槪觀 沒有因腐蝕 Γ在鑽石磨粒附近 整個區域皆因 所致之變色 因腐蝕而變色 腐蝕而變色After 1335854, it was treated at 5 Ο 0 ° C for 8 hours to form an oxide film. Further, a sol-gel solution of Ti02, Al2?3, Sn02, ZnO, V02, V205, M?3 Ta05, Zn02 or the like is used as the sol-gel solution. Isopropanol can also be used instead of ethanol. Next, the method of forming the second protective layer 104 will be described below by a sol deposition method. The aerosol deposition method is characterized in that an aerosol of fine particles such as a brittle material is dispersed from a nozzle toward a substrate, and the substrate of the microparticles or glass, ceramic or plastic is deformed by the particles of the brittle material colliding therewith. Alternatively, they may be joined together to form a structure composed of a constituent material of fine particles, and a structure may be formed at a normal temperature by heating means, and a structure having mechanical strength equivalent to the body may be obtained. The apparatus used in this method is composed of an aerosol generating aerosol generator and a nozzle facing the substrate glue, and has a substrate area and a nozzle relatively moved and oscillated in a case where the production area is larger than the opening of the nozzle. The segment is produced under reduced pressure, has a forming structure and a vacuum pump, and is generally used to generate an aerosol source. The process temperature of the aerosol deposition method is normal temperature, and one of its characteristics is a temperature much lower than the melting point of the fine particle material, that is, several hundred. The C line structure is formed. Therefore, the substrate can be selected across a wide variety, i.e., the melting point metal or resin material is not problematic in application. Further, the fine particles used may be ceramic or semiconductor, etc., or W〇3' may be added, that is, the gas may collide with the gas 1 to cause the F on the base material to be fired. [, Basic [Injection of Gas: Structure] [Control the chamber of hand 7! Gas production: lie below: I make it low. Brittle material -12- 1335854 is the main material, except that the same material can be used alone or in combination. It is also possible to mix different kinds of brittle material particles for composite use. In addition, it is also possible to use a part of a metal material or an organic material to be mixed with the brittle material particles or coated on the surface of the brittle material particles. In these cases, the main material from which the structure is formed remains a brittle material. In the case of the structure formed by the method, when a crystalline brittle material fine particle is used as a raw material, the brittle material portion of the structure is a polycrystal having a crystallite size smaller than that of the raw material fine particle, and the crystal thereof is crystallized. There are many cases in which crystal orientation is not substantially present, so it can be said that there is substantially no grain boundary layer composed of a glass layer at the interface of the crystal matrix of the brittle material, and thus a part of the structure is formed deep into the substrate. The characteristics of the anchor layer of the surface. The structure formed by this method is distinct from the so-called powder compact in which the microparticle group is physically adhered to maintain the morphology due to the pressure build-up, and sufficient strength is maintained. With regard to the formation of the structure, the crushing and deformation of the fine particles of the brittle material can be determined by measuring the crystallite size of the brittle material fine particles used as the raw material and the brittle material structure formed by the X-ray diffraction method. That is, the crystallite size of the structure formed by the aerosol deposition method shows a smaller size than the crystallite size of the raw material fine particles. In the offset surface or the broken surface formed by breaking or deforming the fine particles, a new surface in a state in which the atoms which are originally combined with other atoms are exposed is formed. The active surface of the high surface energy activity can be regarded as the new surface of the adjacent brittle material surface or the adjacent adjacent brittle material, or the position of the aerosol collision can be changed by bonding with the surface of the substrate - 13-135854, and by the microparticles In the collision, a film-shaped aluminum oxide film is formed at a desired position of the film-formed material 208. Here, although the ceramic membrane forming chamber 205 is placed under a reduced pressure environment by the vacuum pump 209, it is not necessarily required to be a reduced pressure environment, and it is also possible to form a film under atmospheric pressure. Further, the gas is not limited to nitrogen, and helium, compressed air, or the like can be used freely. (Example) In order to examine the performance of the CMP conditioner according to the present invention, it was immersed in a mixed solution of CMP slurry (W2000, manufactured by Cabot) and a 3% hydrogen peroxide solution at 50 ° C for 48 hours. A tentacity test was carried out by observing the surface state before and after the impregnation. The following CMP conditioner was produced as a CMP conditioner for the uranium resistance test according to the present invention: the conditioner was immersed in a sol prepared by mixing a Si film forming material (manufactured by Mitsubishi Materials Corporation) and ethanol with 1:1. After 1 minute, the gel solution was dried at 200 ° C for 2 hours and at 500 ° C for 8 hours. The surface of the diamond abrasive grains as abrasive grains was adhered to Ni as a metal bonded phase to form a ruthenium dioxide film. First protective film, next, using the apparatus according to Fig. 2, using an alumina fine particle having an average particle diameter of 0.6 μm, generating an aerosol at a flow rate of 7 L/min of nitrogen, and spraying the nozzle onto the surface of the film to be formed, An aluminum oxide film having a film thickness of 3 to 5 μm was formed as a CMP conditioner for the second protective film. As a result of the corrosion resistance test, there was no discoloration due to corrosion, and it was found to have sufficient corrosion resistance. The results are shown in Table 1. In addition, Table 1 also shows the results of Comparative Example 1 shown in the following, and the results of Comparative Example -15 - 1335854. (Comparative Example 1) In order to compare the corrosion resistance, a CMP conditioner in which only the second protective film of Example 1 was formed was produced, and the same corrosion resistance test as in Example 1 was carried out. As a result of the corrosion resistance test, discoloration due to corrosion was observed in the vicinity of the diamond abrasive grains, and it was found that Ni was eluted. (Comparative Example 2) In order to compare the corrosion resistance, a CMP conditioner which did not form the first protective film and the second protective film of Example 1 was produced, and the same corrosion resistance test as in Example 1 was carried out. As a result of the corrosion resistance test, the entire area of the surface in which the diamond abrasive grains exist was discolored, and it was found that Ni was eluted. [Table 1] Example 1 Comparative Example 1 Comparative Example 2 The first protective film had or without Μ y\\\ The second protective film had /fnT-m 〇Δ X. After the corrosion resistance test, there was no corrosion due to corrosion in the diamond abrasive grains. The entire area is discolored due to corrosion due to corrosion.
【圖式簡單說明】 圖1是顯示本發明之CMP修整器的實施形態之CMP 修整器的放大剖面圖。 圖2是顯示與本發明之CMP修整器的製造方法之一 實施形態有關的氣溶膠沉積裝置之圖。 -16- 1335854 【主要元件符號說明】 10 : CMP修整器 101 :基底金屬 102.金屬結合相 103 :第一保護層 1 04 :第二保護層 1 0 5 :磨粒 1 1 :磨粒層 20 :氣溶膠沉積裝置 201 :氮氣瓶 202 :氣體輸送管 2 03 :氣溶膠產生器 204 :氣溶膠輸送管 205 :陶瓷膜形成室 206 :噴嘴 207 : ΧΥΖΘ 平台 20 8 :被製膜物 209 :真空幫浦 -17BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an enlarged cross-sectional view showing a CMP conditioner of an embodiment of a CMP conditioner of the present invention. Fig. 2 is a view showing an aerosol deposition apparatus relating to an embodiment of a method of manufacturing a CMP conditioner of the present invention. -16- 1335854 [Description of main component symbols] 10: CMP conditioner 101: base metal 102. metal bonded phase 103: first protective layer 104: second protective layer 1 0 5 : abrasive grain 1 1 : abrasive grain layer 20 : Aerosol deposition apparatus 201 : nitrogen bottle 202 : gas delivery tube 2 03 : aerosol generator 204 : aerosol delivery tube 205 : ceramic membrane forming chamber 206 : nozzle 207 : 平台 platform 20 8 : film formed 209 : vacuum Pump -17