JP2005217360A - Metal polishing solution and polishing method - Google Patents
Metal polishing solution and polishing method Download PDFInfo
- Publication number
- JP2005217360A JP2005217360A JP2004025448A JP2004025448A JP2005217360A JP 2005217360 A JP2005217360 A JP 2005217360A JP 2004025448 A JP2004025448 A JP 2004025448A JP 2004025448 A JP2004025448 A JP 2004025448A JP 2005217360 A JP2005217360 A JP 2005217360A
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- Prior art keywords
- polishing
- metal
- acid
- polishing liquid
- copper
- Prior art date
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 106
- 239000002184 metal Substances 0.000 title claims abstract description 106
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- 239000002002 slurry Substances 0.000 claims description 15
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Abstract
Description
本発明は、特に半導体デバイスの配線形成工程の研磨に使用される金属用研磨液及び研磨方法に関する。 The present invention relates to a metal polishing liquid and a polishing method used particularly for polishing in a wiring formation process of a semiconductor device.
近年、半導体集積回路（以下ＬＳＩと記す）の高集積化、高性能化に伴って新たな微細加工技術が開発されている。化学機械研磨（以下ＣＭＰと記す）法もその一つであり、ＬＳＩ製造工程、特に多層配線形成工程における層間絶縁膜の平坦化、金属プラグ形成、埋め込み配線形成において頻繁に利用される技術である。この技術は、例えば、特許文献１に開示されている。 In recent years, new microfabrication techniques have been developed along with higher integration and higher performance of semiconductor integrated circuits (hereinafter referred to as LSIs). The chemical mechanical polishing (hereinafter referred to as CMP) method is one of them, and is a technique frequently used in the LSI manufacturing process, particularly in the multilayer wiring formation process, planarization of the interlayer insulating film, metal plug formation, and buried wiring formation. . This technique is disclosed in Patent Document 1, for example.
また、最近はＬＳＩを高性能化するために、配線材料として銅及び銅合金の利用が試みられている。しかし、銅及び銅合金は従来のアルミニウム合金配線の形成で頻繁に用いられたドライエッチング法による微細加工が困難である。そこで、あらかじめ溝を形成してある絶縁膜上に銅或いは銅合金薄膜を堆積して埋め込み、溝部以外の銅或いは銅合金薄膜をＣＭＰにより除去して埋め込み配線を形成する、いわゆるダマシン法が主に採用されている。この技術は、例えば、特許文献２に開示されている。 Recently, in order to improve the performance of LSIs, attempts have been made to use copper and copper alloys as wiring materials. However, copper and copper alloys are difficult to finely process by the dry etching method frequently used in the formation of conventional aluminum alloy wiring. Therefore, a so-called damascene method is mainly used in which a copper or copper alloy thin film is deposited and embedded on an insulating film in which a groove is formed in advance, and the copper or copper alloy thin film other than the groove is removed by CMP to form a buried wiring. It has been adopted. This technique is disclosed in Patent Document 2, for example.
銅及び銅合金等の金属ＣＭＰの一般的な方法は、円形の研磨定盤（プラテン）上に研磨パッドを貼り付け、研磨パッド表面を金属用研磨液で浸し、基板の金属膜を形成した面を押し付けて、その裏面から所定の圧力（以下研磨圧力と記す）を加えた状態で研磨定盤を回し、研磨液と金属膜の凸部との機械的摩擦によって凸部の金属膜を除去するものである。
ＣＭＰに用いられる金属用研磨液は、一般には酸化剤及び砥粒からなっており必要に応じてさらに酸化金属溶解剤、保護膜形成剤が添加される。まず酸化剤によって金属膜表面を酸化し、その酸化層を砥粒によって削り取るのが基本的なメカニズムと考えられている。凹部の金属表面の酸化層は研磨パッドにあまり触れず、砥粒による削り取りの効果が及ばないので、ＣＭＰの進行とともに凸部の金属層が除去されて基板表面は平坦化される。この詳細については、非特許文献１に開示されている。
A general method of metal CMP such as copper and copper alloy is a surface on which a polishing pad is attached on a circular polishing platen (platen), the surface of the polishing pad is immersed in a metal polishing liquid, and a metal film of a substrate is formed. Is pressed and a polishing surface plate is rotated with a predetermined pressure (hereinafter referred to as polishing pressure) applied from the back surface, and the metal film on the convex portion is removed by mechanical friction between the polishing liquid and the convex portion of the metal film. Is.
The metal polishing liquid used in CMP is generally composed of an oxidizing agent and abrasive grains, and a metal oxide dissolving agent and a protective film forming agent are further added as necessary. First, it is considered that the basic mechanism is to oxidize the surface of a metal film with an oxidizing agent and scrape the oxidized layer with abrasive grains. Since the oxide layer on the metal surface of the recess does not touch the polishing pad so much and the effect of scraping off by the abrasive grains does not reach, the metal layer of the projection is removed and the substrate surface is flattened with the progress of CMP. This detail is disclosed in Non-Patent Document 1.
ＣＭＰによる研磨速度を高める方法として酸化金属溶解剤を添加することが有効とされている。砥粒によって削り取られた金属酸化物の粒を研磨液に溶解（以下エッチングと記す）させてしまうと砥粒による削り取りの効果が増すためと解釈できる。 As a method for increasing the polishing rate by CMP, it is effective to add a metal oxide dissolving agent. It can be interpreted that if the metal oxide particles scraped by the abrasive grains are dissolved in the polishing liquid (hereinafter referred to as etching), the effect of scraping by the abrasive grains increases.
配線の銅或いは銅合金等の下層には、層間絶縁膜中への銅拡散防止及び層間絶縁膜との密着性向上のためにバリア層として、タンタルやタンタル合金及び窒化タンタルやその他のタンタル化合物等が形成される。したがって、銅或いは銅合金を埋め込む配線部分以外では、露出したバリア層をＣＭＰにより取り除く必要がある。しかし、これらのバリア層導体は、銅或いは銅合金に比べ硬度が高いために、銅或いは銅合金用の研磨材料の組み合わせでは十分な研磨速度が得られず、かつ平坦性が悪くなる場合が多い。そこで、銅或いは銅合金を研磨する第１工程と、バリア層導体を研磨する第２工程からなる２段研磨方法が検討されている。 In the lower layer of copper or copper alloy, etc. of the wiring, tantalum, tantalum alloy, tantalum nitride, other tantalum compounds, etc. as a barrier layer for preventing copper diffusion into the interlayer insulating film and improving adhesion with the interlayer insulating film Is formed. Therefore, it is necessary to remove the exposed barrier layer by CMP except for the wiring portion in which copper or a copper alloy is embedded. However, since these barrier layer conductors have higher hardness than copper or copper alloys, a combination of polishing materials for copper or copper alloys cannot provide a sufficient polishing rate, and flatness often deteriorates. . Therefore, a two-step polishing method is being studied which includes a first step of polishing copper or a copper alloy and a second step of polishing the barrier layer conductor.
バリア層導体を研磨する第２工程において、バリア金属用研磨液には、バリア層の研磨速度を向上させるために、例えば砥粒の粒径を大きくして研磨を行うことがあるが、銅或いは銅合金や酸化膜に異物が発生して電気特性不良の原因になるという問題がある。また、このような電気特性不良は、ＣＭＰ後の洗浄不足により発生するといった問題があった。 In the second step of polishing the barrier layer conductor, the barrier metal polishing liquid may be polished by increasing the grain size of the abrasive grains in order to improve the polishing rate of the barrier layer. There is a problem that foreign matters are generated in the copper alloy or the oxide film, resulting in poor electrical characteristics. In addition, such an electrical characteristic defect has a problem that it occurs due to insufficient cleaning after CMP.
請求項１記載の発明は、バリア層の研磨速度が大きいため、平坦性が高い金属用研磨液を提供するものであり、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性が高く、低コストの半導体デバイスに好適である。
請求項２記載の発明は、請求項１記載の発明の効果に加え、さらにバリア層の研磨速度が大きいいため、平坦性が高く、生産性の良い金属用研磨液を提供するものであり、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性が高く、低コストの半導体デバイスに好適である。
請求項３記載の発明は、請求項１〜２記載の発明の効果に加え、さらにバリア層の研磨速度の面内均一性に優れるため、平坦性が高く、生産性の良い金属用研磨液を提供するものであり、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性が高く、低コストの半導体デバイスに好適である。
請求項４記載の発明は、請求項１〜３記載の発明の効果に加え、さらに研磨後の洗浄性に優れるため、平坦性が高く、生産性の良い金属用研磨液を提供するものであり、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性が高く、低コストの半導体デバイスに好適である。
請求項５記載の発明は、請求項１〜４記載の発明の効果に加え、さらにバリア層金属の研磨速度の研磨速度を高めるため平坦性が高く、生産性の良い金属用研磨液を提供するものであり、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性が高く、低コストの半導体デバイスに好適である。
請求項６記載の発明は、請求項１〜５記載の発明の効果に加え、さらに研磨異物を抑制した金属用研磨液を提供するものであり、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性が高く、低コストの半導体デバイスに好適である。
請求項７記載の発明は、請求項１〜６記載の発明の効果に加え、さらに銅或いは銅合金配線の研磨速度を調整できる金属用研磨液を提供するものであり、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性が高く、低コストの半導体デバイスに好適である。
請求項８記載の発明は、請求項１〜７記載の発明の効果に加え、さらに銅或いは銅合金配線の研磨速度を調整でき銅残渣を取り除ける金属用研磨液を提供するものであり、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性が高く、低コストの半導体デバイスに好適である。
請求項９記載の発明は、請求項１〜８記載の発明の効果に加え、さらに銅或いは銅合金配線、バリア層金属の研磨均一性に優れる金属用研磨液を提供するものであり、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性が高く、低コストの半導体デバイスに好適である。
請求項１０記載の発明は、請求項１〜９記載の発明の効果に加え、さらに銅或いは銅合金配線、バリア層金属の研磨均一性に優れる金属用研磨液を提供するものであり、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性が高く、低コストの半導体デバイスに好適である。
請求項１１記載の発明は、タンタル、窒化タンタル、タンタル合金、その他のタングステン化合物、チタン、窒化チタン、チタン合金、その他のチタン化合物、タングステン、窒化タングステン、タングステン合金、その他のタングステン化合物から選ばれるバリア層用として請求項１〜1１記載の発明の効果を有する金属用研磨液を提供するものであり、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性が高く、低コストの半導体デバイスに好適である。
請求項１２記載の発明は、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性が高く、低コストの半導体デバイスの製造における研磨方法を提供するものである。
The invention according to claim 1 provides a metal polishing liquid having high flatness due to the high polishing rate of the barrier layer, and is excellent in miniaturization, thinning, dimensional accuracy, electrical characteristics, and high reliability. It is suitable for a low-cost semiconductor device.
The invention described in claim 2 provides a metal polishing liquid having high flatness and good productivity because the barrier layer has a high polishing rate in addition to the effect of the invention described in claim 1, and is fine. It is suitable for low-cost semiconductor devices with excellent reliability, thinness, dimensional accuracy, and electrical characteristics, high reliability, and low cost.
In addition to the effects of the inventions of claims 1 and 2, the invention described in claim 3 is excellent in in-plane uniformity of the polishing rate of the barrier layer, so that a metal polishing liquid with high flatness and good productivity is obtained. It is provided and is excellent in miniaturization, thin film formation, dimensional accuracy, electrical characteristics, high reliability, and suitable for a low-cost semiconductor device.
In addition to the effects of the inventions of claims 1 to 3, the invention described in claim 4 provides a metal polishing liquid with high flatness and good productivity because of excellent cleaning properties after polishing. Therefore, it is excellent in miniaturization, thinning, dimensional accuracy, and electrical characteristics, high reliability, and suitable for low-cost semiconductor devices.
In addition to the effects of the first to fourth aspects of the invention, the fifth aspect of the invention provides a metal-polishing liquid having high flatness and good productivity in order to increase the polishing speed of the barrier layer metal. Therefore, it is excellent in miniaturization, thinning, dimensional accuracy, and electrical characteristics, high reliability, and suitable for a low-cost semiconductor device.
In addition to the effects of the inventions of claims 1 to 5, the invention of claim 6 provides a metal-polishing liquid that further suppresses polishing foreign matters, and is made finer, thinner, dimensional accuracy, and electrical characteristics. It is excellent in reliability, high reliability and low cost semiconductor devices.
The invention described in claim 7 provides a metal polishing liquid capable of adjusting the polishing rate of copper or copper alloy wiring, in addition to the effects of the inventions described in claims 1 to 6. It has excellent dimensional accuracy and electrical characteristics, is highly reliable, and is suitable for low-cost semiconductor devices.
The invention described in claim 8 provides a metal polishing liquid capable of adjusting the polishing rate of copper or copper alloy wiring and removing copper residues in addition to the effects of the inventions described in claims 1 to 7, and miniaturizing It is suitable for semiconductor devices with excellent thinness, dimensional accuracy and electrical characteristics, high reliability and low cost.
In addition to the effects of the inventions described in claims 1 to 8, the invention described in claim 9 provides a metal-polishing liquid excellent in polishing uniformity of copper or copper alloy wiring and barrier layer metal. It is suitable for semiconductor devices with excellent thinness, dimensional accuracy and electrical characteristics, high reliability and low cost.
The invention described in claim 10 provides a metal polishing liquid excellent in polishing uniformity of copper or copper alloy wiring and barrier layer metal in addition to the effects of the inventions described in claims 1 to 9, and is miniaturized. It is suitable for semiconductor devices with excellent thinness, dimensional accuracy and electrical characteristics, high reliability and low cost.
The invention according to claim 11 is a barrier selected from tantalum, tantalum nitride, tantalum alloy, other tungsten compounds, titanium, titanium nitride, titanium alloys, other titanium compounds, tungsten, tungsten nitride, tungsten alloys, and other tungsten compounds. A metal polishing liquid having the effects of the invention according to claims 1 to 11 is provided for use in a layer, and is excellent in miniaturization, thinning, dimensional accuracy, electrical characteristics, high reliability, and low cost. It is suitable for.
The invention described in claim 12 provides a polishing method in the manufacture of a semiconductor device that is excellent in miniaturization, thinning, dimensional accuracy, electrical characteristics, high reliability, and low cost.
本発明は、酸化金属溶解剤、砥粒、砥粒を沈降させない界面活性剤及び水を含有することを特徴とする金属用研磨液に関する。
本発明は、酸化金属溶解剤が、有機酸、有機酸エステル、有機酸のアンモニウム塩及び硫酸から選ばれる少なくとも１種である金属用研磨液に関する。
本発明は、砥粒を含有する上記記載の金属用研磨液に関する。
本発明は、砥粒が、シリカ、アルミナ、セリア、チタニア、ジルコニア、ゲルマニアから選ばれる少なくとも１種である金属用研磨液に関する。
本発明は、金属の酸化剤を含むことを特徴とする金属用研磨液に関する。
本発明は、金属の酸化剤が、過酸化水素、硝酸、過ヨウ素酸カリウム、次亜塩素酸及びオゾン水から選ばれる少なくとも１種である上記記載の金属用研磨液に関する。
本発明は、有機溶媒を含むことを特徴とする金属用研磨液に関する。
本発明は、有機溶媒が０．１〜９５重量％含有することを特徴とする金属用研磨液に関する。
本発明は、有機溶媒がグリコールモノエーテル類、アルコール類、カーボネート類から選ばれる少なくとも1種である金属用研磨液に関する。
本発明は、研磨される金属が、銅、銅合金のバリア層である金属用研磨液に関する。
本発明は、バリア層がタンタル、窒化タンタル、タンタル合金、その他のタングステン化合物、チタン、窒化チタン、チタン合金、その他のチタン化合物、タングステン、窒化タングステン、タングステン合金、その他のタングステン化合物から選ばれる少なくとも１種を含む金属用研磨液に関する。
本発明は、研磨定盤の研磨布上に金属用研磨液を供給しながら、被研磨膜を有する基板を研磨布に押圧した状態で研磨定盤と基板を相対的に動かすことによって被研磨膜を研磨する研磨方法に関する。
The present invention relates to a metal-polishing liquid characterized by containing a metal oxide solubilizer, abrasive grains, a surfactant that does not precipitate abrasive grains, and water.
The present invention relates to a metal polishing slurry in which the metal oxide solubilizer is at least one selected from organic acids, organic acid esters, ammonium salts of organic acids, and sulfuric acid.
The present invention relates to the above-described metal-polishing liquid containing abrasive grains.
The present invention relates to a metal polishing slurry wherein the abrasive is at least one selected from silica, alumina, ceria, titania, zirconia, and germania.
The present invention relates to a metal-polishing liquid characterized by containing a metal oxidizing agent.
The present invention relates to the above metal polishing slurry, wherein the metal oxidizing agent is at least one selected from hydrogen peroxide, nitric acid, potassium periodate, hypochlorous acid, and ozone water.
The present invention relates to a metal-polishing liquid comprising an organic solvent.
The present invention relates to a metal-polishing liquid characterized by containing an organic solvent in an amount of 0.1 to 95% by weight.
The present invention relates to a metal polishing slurry in which the organic solvent is at least one selected from glycol monoethers, alcohols, and carbonates.
The present invention relates to a metal-polishing liquid in which the metal to be polished is a barrier layer of copper or a copper alloy.
In the present invention, the barrier layer is at least one selected from tantalum, tantalum nitride, tantalum alloy, other tungsten compounds, titanium, titanium nitride, titanium alloys, other titanium compounds, tungsten, tungsten nitride, tungsten alloys, and other tungsten compounds. The present invention relates to a metal polishing slurry containing seeds.
The present invention provides a film to be polished by relatively moving the polishing platen and the substrate while pressing the substrate having the film to be polished against the polishing cloth while supplying the metal polishing liquid onto the polishing cloth of the polishing surface plate. The present invention relates to a polishing method for polishing a metal.
本発明により、金属の研磨速度が大きくエッチング速度が小さいため、生産性が高く、ディッシング及びエロージョンが小さい金属用研磨液が得られた。この金属用研磨液は、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性の高い半導体デバイス及び機器に好適である。
本発明により、層間絶縁膜の研磨速度が大きく平坦性が高い金属用研磨液が得られた。この金属用研磨液は微細化、薄膜化、寸法精度、電気特性に優れ、信頼性が高く、低コストの半導体デバイスに好適である。
本発明により、上記の発明の効果に加え、さらにバリア層金属の研磨速度を低下させずに層間絶縁膜の研磨速度を維持するため、平坦性が高く、生産性の良い金属用研磨液が得られた。この金属用研磨液は、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性が高く、低コストの半導体デバイスに好適である。
本発明により、上記の発明の効果に加え、さらに研磨後の洗浄性に優れるため、平坦性が高く、生産性の良い金属用研磨液が得られた。この金属用研磨液は、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性が高く、低コストの半導体デバイスに好適である。
本発明により、上記の発明の効果に加え、さらにバリア層金属の研磨速度及び層間絶縁膜の研磨速度を高めるため平坦性が高く、生産性の良い金属用研磨液が得られた。この金属用研磨液は、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性が高く、低コストの半導体デバイスに好適である。
本発明により、上記の発明の効果に加え、さらに研磨異物を抑制した金属用研磨液が得られた。この金属用研磨液は、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性が高く、低コストの半導体デバイスに好適である。
本発明により、上記の発明の効果に加え、さらに蒸留水のみで洗浄が可能な金属用研磨液が得られた。この金属用研磨液は、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性が高く、低コストの半導体デバイスに好適である。
本発明により、上記の発明の効果に加え、さらに銅或いは銅合金配線の研磨速度を調整できる金属用研磨液が得られた。この金属用研磨液は、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性が高く、低コストの半導体デバイスに好適である。
本発明により、上記の発明の効果に加え、さらに銅或いは銅合金配線の研磨速度を調整でき銅残渣を取り除ける金属用研磨液が得られた。この金属用研磨液は、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性が高く、低コストの半導体デバイスに好適である。
本発明により、上記の発明の効果に加え、さらに銅或いは銅合金配線、バリア層金属、層間絶縁膜の研磨均一性に優れる金属用研磨液が得られた。この金属用研磨液は、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性が高く、低コストの半導体デバイスに好適である。
本発明により、上記の発明の効果に加え、さらに銅或いは銅合金配線、バリア層金属、層間絶縁膜の研磨均一性に優れる金属用研磨液が得られた。この金属用研磨液は、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性が高く、低コストの半導体デバイスに好適である。
本発明により、銅或いは銅合金のバリア層用として上記の効果を有する金属用研磨液を微細化、薄膜化、寸法精度、電気特性に優れ、信頼性が高く、低コストの半導体デバイスに好適である。
本発明により、タンタル、窒化タンタル、タンタル合金、その他のタングステン化合物、チタン、窒化チタン、チタン合金、その他のチタン化合物、タングステン、窒化タングステン、タングステン合金、その他のタングステン化合物から選ばれるバリア層用としての金属用研磨液が得られた。この金属用研磨液は、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性が高く、低コストの半導体デバイスに好適である。
本発明により、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性が高く、低コストの半導体デバイスの製造における研磨方法が得られた。
According to the present invention, a metal polishing liquid having high productivity and low dishing and erosion was obtained because the metal polishing rate was high and the etching rate was low. This metal polishing liquid is excellent in miniaturization, thinning, dimensional accuracy, and electrical characteristics, and is suitable for highly reliable semiconductor devices and equipment.
According to the present invention, a metal polishing liquid having a high polishing rate for the interlayer insulating film and high flatness was obtained. This metal polishing liquid is excellent in miniaturization, thinning, dimensional accuracy, and electrical characteristics, has high reliability, and is suitable for a low-cost semiconductor device.
According to the present invention, in addition to the effects of the above invention, the polishing rate of the interlayer insulating film is maintained without lowering the polishing rate of the barrier layer metal, so that a metal polishing liquid with high flatness and good productivity can be obtained. It was. This metal polishing liquid is excellent in miniaturization, thinning, dimensional accuracy, and electrical characteristics, has high reliability, and is suitable for a low-cost semiconductor device.
According to the present invention, in addition to the effects of the above-described invention, since the cleaning property after polishing is further excellent, a metal polishing slurry having high flatness and good productivity was obtained. This metal polishing liquid is excellent in miniaturization, thinning, dimensional accuracy, and electrical characteristics, has high reliability, and is suitable for a low-cost semiconductor device.
According to the present invention, in addition to the effects of the above-described invention, the polishing rate for the barrier layer metal and the polishing rate for the interlayer insulating film are further increased, so that a metal polishing liquid with high flatness and good productivity was obtained. This metal polishing liquid is excellent in miniaturization, thinning, dimensional accuracy, and electrical characteristics, has high reliability, and is suitable for a low-cost semiconductor device.
By this invention, in addition to the effect of said invention, the metal polishing liquid which suppressed the foreign material for grinding | polishing further was obtained. This metal polishing liquid is excellent in miniaturization, thinning, dimensional accuracy, and electrical characteristics, has high reliability, and is suitable for a low-cost semiconductor device.
According to the present invention, in addition to the effects of the above-described invention, a metal polishing liquid that can be cleaned only with distilled water is obtained. This metal polishing liquid is excellent in miniaturization, thinning, dimensional accuracy, and electrical characteristics, has high reliability, and is suitable for a low-cost semiconductor device.
According to the present invention, in addition to the effects of the above invention, a metal polishing liquid capable of adjusting the polishing rate of copper or copper alloy wiring is obtained. This metal polishing liquid is excellent in miniaturization, thinning, dimensional accuracy, and electrical characteristics, has high reliability, and is suitable for a low-cost semiconductor device.
According to the present invention, in addition to the effects of the above-described invention, a metal-polishing liquid capable of adjusting the polishing rate of copper or copper alloy wiring and removing the copper residue was obtained. This metal polishing liquid is excellent in miniaturization, thinning, dimensional accuracy, and electrical characteristics, has high reliability, and is suitable for a low-cost semiconductor device.
According to the present invention, in addition to the effects of the above-described invention, a metal polishing liquid excellent in polishing uniformity of copper or copper alloy wiring, barrier layer metal, and interlayer insulating film was obtained. This metal polishing liquid is excellent in miniaturization, thinning, dimensional accuracy, and electrical characteristics, has high reliability, and is suitable for a low-cost semiconductor device.
According to the present invention, in addition to the effects of the above-described invention, a metal polishing liquid excellent in polishing uniformity of copper or copper alloy wiring, barrier layer metal, and interlayer insulating film was obtained. This metal polishing liquid is excellent in miniaturization, thinning, dimensional accuracy, and electrical characteristics, has high reliability, and is suitable for a low-cost semiconductor device.
According to the present invention, the metal polishing liquid having the above-mentioned effects for the barrier layer of copper or copper alloy is excellent in miniaturization, thinning, dimensional accuracy, electrical characteristics, high reliability, and low cost. is there.
According to the present invention, as a barrier layer selected from tantalum, tantalum nitride, tantalum alloy, other tungsten compounds, titanium, titanium nitride, titanium alloys, other titanium compounds, tungsten, tungsten nitride, tungsten alloys, and other tungsten compounds. A metal polishing liquid was obtained. This metal polishing liquid is excellent in miniaturization, thinning, dimensional accuracy, and electrical characteristics, has high reliability, and is suitable for a low-cost semiconductor device.
According to the present invention, a polishing method in manufacturing a semiconductor device having excellent miniaturization, thinning, dimensional accuracy, electrical characteristics, high reliability, and low cost has been obtained.
本発明においては、層間絶縁膜上にバリア層及び銅或いは銅合金を含む金属膜を形成・充填する。この基板をまず銅或いは銅合金／バリア層の研磨速度比が十分大きい銅及び銅合金用の研磨液を用いてＣＭＰすると、基板の凸部のバリア層が表面に露出し、凹部に銅或いは銅合金膜が残された所望の導体パタ−ンが得られる。この得られたパターン基板が本発明における被研磨物に当たる。 In the present invention, a barrier layer and a metal film containing copper or a copper alloy are formed and filled on the interlayer insulating film. When this substrate is first CMPed using a polishing solution for copper and copper alloy having a sufficiently high polishing rate ratio of copper or copper alloy / barrier layer, the barrier layer on the convex portion of the substrate is exposed on the surface, and the copper or copper in the concave portion is exposed. A desired conductor pattern in which the alloy film remains is obtained. The obtained pattern substrate corresponds to the object to be polished in the present invention.
本発明の金属用研磨液は、酸化金属溶解剤、砥粒、砥粒を沈降させない界面活性剤を含有する研磨液である。有機溶媒、金属の酸化剤、重量平均分子量が５００以上のポリマまたは金属防食剤を添加してもよい。 The metal polishing liquid of the present invention is a polishing liquid containing a metal oxide solubilizer, abrasive grains, and a surfactant that does not precipitate the abrasive grains. An organic solvent, a metal oxidizing agent, a polymer having a weight average molecular weight of 500 or more, or a metal anticorrosive may be added.
本発明の酸化金属溶解剤は、特に制限はないが、ギ酸、酢酸、プロピオン酸、酪酸、吉草酸、２−メチル酪酸、ｎ−ヘキサン酸、３，３−ジメチル酪酸、２−エチル酪酸、４−メチルペンタン酸、ｎ−ヘプタン酸、２−メチルヘキサン酸、ｎ−オクタン酸、２−エチルヘキサン酸、安息香酸、グリコ−ル酸、サリチル酸、グリセリン酸、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、マレイン酸、フタル酸、リンゴ酸、酒石酸、クエン酸等の有機酸、これらの有機酸エステル及びこれら有機酸のアンモニウム塩等が挙げられる。また塩酸、硫酸、硝酸等の無機酸、これら無機酸のアンモニウム塩類、例えば過硫酸アンモニウム、硝酸アンモニウム、塩化アンモニウム等、クロム酸等が挙げられる。これらの中では、実用的なＣＭＰ速度を維持しつつ、エッチング速度を効果的に抑制できるという点でギ酸、マロン酸、リンゴ酸、酒石酸、クエン酸が銅、銅合金及び銅又は銅合金の酸化物から選ばれた少なくとも１種の金属層を含む積層膜に対して好適である。これらは１種類単独で、もしくは２種類以上混合して用いることができる。 The metal oxide solubilizer of the present invention is not particularly limited, but formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4 -Methylpentanoic acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutar Examples thereof include organic acids such as acid, adipic acid, pimelic acid, maleic acid, phthalic acid, malic acid, tartaric acid, and citric acid, organic acid esters thereof, and ammonium salts of these organic acids. Further, inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and ammonium salts of these inorganic acids such as ammonium persulfate, ammonium nitrate and ammonium chloride, chromic acid and the like can be mentioned. Among these, formic acid, malonic acid, malic acid, tartaric acid, and citric acid are copper, copper alloy, and copper or copper alloy oxidation in that the etching rate can be effectively suppressed while maintaining a practical CMP rate. It is suitable for a laminated film including at least one metal layer selected from those. These can be used alone or in combination of two or more.
本発明の金属用研磨液の砥粒としては、シリカ、アルミナ、ジルコニア、セリア、チタニア、炭化珪素等の無機物砥粒、ポリスチレン、ポリアクリル、ポリ塩化ビニル等の有機物砥粒のいずれでもよいが、研磨液中での分散安定性が良く、ＣＭＰにより発生する研磨傷（スクラッチ）の発生数の少ない、平均粒径が７０ｎｍ以下のコロイダルシリカ、コロイダルアルミナが好ましく、平均粒径が４０nm以下のコロイダルシリカ、コロイダルアルミナがより好ましい。一次粒子が平均２粒子未満しか凝集していない粒子が好ましく、一次粒子が平均１．２粒子未満しか凝集していない粒子がより好ましい。また、平粒度分布の標準偏差が１０nm以下であることが好ましく、平粒度分布の標準偏差が５nm以下であることがより好ましい。コロイダルシリカはシリコンアルコキシドの加水分解または珪酸ナトリウムのイオン交換による製造方法が知られており、コロイダルアルミナは硝酸アルミニウムの加水分解による製造方法が知られている。 As abrasive grains of the metal polishing liquid of the present invention, any of inorganic abrasive grains such as silica, alumina, zirconia, ceria, titania, silicon carbide, and organic abrasive grains such as polystyrene, polyacryl, polyvinyl chloride, Colloidal silica and colloidal alumina having an average particle size of 40 nm or less are preferred, with good dispersion stability in the polishing liquid and a small number of polishing scratches (scratches) generated by CMP. Colloidal alumina is more preferable. Particles in which primary particles are aggregated with an average of less than 2 particles are preferable, and particles in which primary particles are aggregated with an average of less than 1.2 particles are more preferable. Further, the standard deviation of the flat particle size distribution is preferably 10 nm or less, and the standard deviation of the flat particle size distribution is more preferably 5 nm or less. Colloidal silica is known for its production by hydrolysis of silicon alkoxide or ion exchange of sodium silicate, and colloidal alumina is known for its production by hydrolysis of aluminum nitrate.
コロイダルシリカは、粒径制御性やアルカリ金属不純物の点で、シリコンアルコキシドの加水分解による製造方法によるものが最も利用される。シリコンアルコキシドとしては、TEMS（テトラメトキシシラン）又はTEOS（テトラエトキシシラン）が一般に用いられる。アルコール溶媒中で加水分解する方法において、粒径に影響するパラメータとしては、シリコンアルコキシドの濃度、触媒として用いられるアンモニア濃度とｐH、反応温度、アルコール溶媒の種類（分子量）及び反応時間などがある。これらのパラメータを調整することによって、所望の粒径及び凝集度のコロイダルシリカ分散液を得ることができる。 Colloidal silica is most often used in terms of particle size controllability and alkali metal impurities by a production method by hydrolysis of silicon alkoxide. As the silicon alkoxide, TEMS (tetramethoxysilane) or TEOS (tetraethoxysilane) is generally used. In the method of hydrolysis in an alcohol solvent, parameters affecting the particle size include the concentration of silicon alkoxide, the concentration and pH of ammonia used as a catalyst, the reaction temperature, the type (molecular weight) of the alcohol solvent, and the reaction time. By adjusting these parameters, a colloidal silica dispersion having a desired particle size and agglomeration degree can be obtained.
本発明のＣＭＰ用研磨液における砥粒を沈降させない界面活性剤としては、特に制限はないが、アルカリ金属を含まないものが好ましく、例えば、ポリエチレングリコール型非イオン性界面活性剤、グリコール類、グリセリン脂肪酸エステル、ソルビット脂肪酸エステル、脂肪酸アルカノールアミド、アルコール硫酸エステル塩、アルキルエーテル硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルリン酸エステルから選ばれる少なくとも1種であることが好ましい。また、例えば好ましい界面活性剤としてラウリル硫酸、ラウリル硫酸トリエタノールアミン、塩化ラウリルトリメチルアンモニウム、塩化ベンザルコニウム液、ヒドロキシエタンジホスホン酸等が挙げられる。 The surfactant that does not precipitate abrasive grains in the polishing slurry for CMP of the present invention is not particularly limited, but preferably does not contain an alkali metal. For example, polyethylene glycol type nonionic surfactants, glycols, glycerin Preferably, the fatty acid ester, sorbite fatty acid ester, fatty acid alkanolamide, alcohol sulfate ester salt, alkyl ether sulfate ester salt, alkylbenzene sulfonate salt, and alkyl phosphate ester are used. Also, for example, preferred surfactants include lauryl sulfate, lauryl sulfate triethanolamine, lauryl trimethyl ammonium chloride, benzalkonium chloride solution, hydroxyethane diphosphonic acid and the like.
発明における金属用研磨液の有機溶媒としては特に制限はないが、例えばエチレンカーボネート、プロピレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート等のカーボネート化合物、ブチロラクトン、プロピロラクトン等のラクトン化合物、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、トリプロピレングリコール等のグリコール化合物、エチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、トリエチレングリコールモノメチルエーテル、トリプロピレングリコールモノメチルエーテルやエチレングリコールモノエチルエーテル、プロピレングリコールモノエチルエーテル、ジエチレングリコールモノエチルエーテル、ジプロピレングリコールモノエチルエーテル、トリエチレングリコールモノエチルエーテル、トリプロピレングリコールモノエチルエーテルやエチレングリコールモノプロピルエーテル、プロピレングリコールモノプロピルエーテル、ジエチレングリコールモノプロピルエーテル、ジプロピレングリコールモノプロピルエーテル、トリエチレングリコールモノプロピルエーテル、トリプロピレングリコールモノプロピルエーテルやエチレングリコールモノブチルエーテル、プロピレングリコールモノブチルエーテル、ジエチレングリコールモノブチルエーテル、ジプロピレングリコールモノブチルエーテル、トリエチレングリコールモノブチルエーテル、トリプロピレングリコールモノブチルエーテルやエチレングリコールジメチルエーテル、プロピレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、ジプロピレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテル、トリプロピレングリコールジメチルエーテルやエチレングリコールジエチルエーテル、プロピレングリコールジエチルエーテル、ジエチレングリコールジエチルエーテル、ジプロピレングリコールジエチルエーテル、トリエチレングリコールジエチルエーテル、トリプロピレングリコールジエチルエーテルやエチレングリコールジプロピルエーテル、プロピレングリコールジプロピルエーテル、ジエチレングリコールジプロピルエーテル、ジプロピレングリコールジプロピルエーテル、トリエチレングリコールジプロピルエーテル、トリプロピレングリコールジプロピルエーテルやエチレングリコールジブチルエーテル、プロピレングリコールジブチルエーテル、ジエチレングリコールジブチルエーテル、ジプロピレングリコールジブチルエーテル、トリエチレングリコールジブチルエーテル、トリプロピレングリコールジブチルエーテル、テトラヒドロフラン、ジオキサン、ジメトキシエタン、ポリエチレンオキサイド、エチレングリコールモノメチルアセテート、ジエチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート等のエーテル化合物、メタノール、エタノール、プロパノール、n-ブタノール、n-ペンタノール、n-ヘキサノール、イソプロパノール、等のアルコール化合物、アセトン、メチルエチルケトン等のケトン化合物、その他フェノール、ジメチルホルムアミド、n-メチルピロリドン、酢酸エチル、乳酸エチル、スルホラン等が挙げられる。 The organic solvent for the metal polishing liquid in the invention is not particularly limited. For example, carbonate compounds such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate, lactone compounds such as butyrolactone and propyrolactone, ethylene glycol , Glycol compounds such as propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, tripropylene Glycol monomethyl ether and ethylene Glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, tripropylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monopropyl ether, diethylene glycol Monopropyl ether, dipropylene glycol monopropyl ether, triethylene glycol monopropyl ether, tripropylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, triethyl Glycol monobutyl ether, tripropylene glycol monobutyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol diethyl ether, diethylene glycol diethyl ether , Dipropylene glycol diethyl ether, triethylene glycol diethyl ether, tripropylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol dipropyl ether, diethylene glycol dipropyl ether, dip Lopylene glycol dipropyl ether, triethylene glycol dipropyl ether, tripropylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dibutyl ether, diethylene glycol dibutyl ether, dipropylene glycol dibutyl ether, triethylene glycol dibutyl ether, tripropylene glycol di Ether compounds such as butyl ether, tetrahydrofuran, dioxane, dimethoxyethane, polyethylene oxide, ethylene glycol monomethyl acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methanol, ethanol, propanol, n-butanol, n-pentanol, n- Hexano Le, isopropanol, alcohol compounds such as acetone, ketone compounds such as methyl ethyl ketone, other phenols, dimethylformamide, n- methyl pyrrolidone, ethyl acetate, ethyl lactate, sulfolane.
本発明の金属の酸化剤としては、過酸化水素（Ｈ２Ｏ２）、硝酸、過ヨウ素酸カリウム、次亜塩素酸、オゾン水等が挙げられ、その中でも過酸化水素が特に好ましい。これらは１種類単独で、もしくは２種類以上混合して用いることができる。基体が集積回路用素子を含むシリコン基板である場合、アルカリ金属、アルカリ土類金属、ハロゲン化物などによる汚染は望ましくないので、不揮発成分を含まない酸化剤が望ましい。但し、オゾン水は組成の時間変化が激しいので過酸化水素が最も適している。但し、適用対象の基体が半導体素子を含まないガラス基板などである場合は不揮発成分を含む酸化剤であっても差し支えない。 Examples of the metal oxidizing agent of the present invention include hydrogen peroxide (H 2 O 2 ), nitric acid, potassium periodate, hypochlorous acid, ozone water, etc. Among them, hydrogen peroxide is particularly preferable. These may be used alone or in combination of two or more. When the substrate is a silicon substrate including an integrated circuit element, contamination by alkali metal, alkaline earth metal, halide, etc. is not desirable, so an oxidizing agent that does not contain a nonvolatile component is desirable. However, hydrogen peroxide is most suitable because ozone water has a severe compositional change over time. However, when the substrate to be applied is a glass substrate or the like that does not include a semiconductor element, an oxidizing agent that includes a nonvolatile component may be used.
本発明の重量平均分子量が５００以上のポリマとしては、重量平均分子量が５００以上であれば特に制限はなく、例えばアルギン酸、ペクチン酸、カルボキシメチルセルロ−ス、寒天、カ−ドラン及びプルラン等の多糖類；ポリアスパラギン酸、ポリグルタミン酸、ポリリシン、ポリリンゴ酸、ポリメタクリル酸、ポリメタクリル酸アンモニウム塩、ポリメタクリル酸ナトリウム塩、ポリアミド酸、ポリマレイン酸、ポリイタコン酸、ポリフマル酸、ポリ（ｐ−スチレンカルボン酸）、ポリアクリル酸、ポリアクリルアミド、アミノポリアクリルアミド、ポリアクリル酸アンモニウム塩、ポリアクリル酸ナトリウム塩、ポリアミド酸、ポリアミド酸アンモニウム塩、ポリアミド酸ナトリウム塩及びポリグリオキシル酸等のポリカルボン酸及びその塩；ポリビニルアルコ−ル、ポリビニルピロリドン及びポリアクロレイン等のビニル系ポリマ等が挙げられる。但し、適用する基体が半導体集積回路用シリコン基板などの場合はアルカリ金属、アルカリ土類金属、ハロゲン化物等による汚染は望ましくないため、酸もしくはそのアンモニウム塩が望ましい。基体がガラス基板等である場合はその限りではない。その中でもペクチン酸、寒天、ポリリンゴ酸、ポリメタクリル酸、ポリアクリル酸アンモニウム塩、ポリアクリルアミド、ポリビニルアルコール及びポリビニルピロリドン、それらのエステル及びそれらのアンモニウム塩が好ましい。 The polymer having a weight average molecular weight of 500 or more of the present invention is not particularly limited as long as the weight average molecular weight is 500 or more. For example, there are many polymers such as alginic acid, pectic acid, carboxymethyl cellulose, agar, cardran and pullulan. Sugars; polyaspartic acid, polyglutamic acid, polylysine, polymalic acid, polymethacrylic acid, polymethacrylic acid ammonium salt, polymethacrylic acid sodium salt, polyamic acid, polymaleic acid, polyitaconic acid, polyfumaric acid, poly (p-styrenecarboxylic acid) Polyacrylic acid, polyacrylamide, amino polyacrylamide, polyacrylic acid ammonium salt, polyacrylic acid sodium salt, polyamic acid, polyamic acid ammonium salt, polyamic acid sodium salt and polyglyoxylic acid Salts; polyvinyl alcohol - le, vinyl polymers such as polyvinyl pyrrolidone and acrolein and the like. However, when the substrate to be applied is a silicon substrate for a semiconductor integrated circuit or the like, contamination with an alkali metal, an alkaline earth metal, a halide, or the like is not desirable, so an acid or an ammonium salt thereof is desirable. This is not the case when the substrate is a glass substrate or the like. Among these, pectinic acid, agar, polymalic acid, polymethacrylic acid, ammonium polyacrylate, polyacrylamide, polyvinyl alcohol and polyvinylpyrrolidone, esters thereof and ammonium salts thereof are preferable.
また、本発明の金属用研磨液に金属防食剤を添加しても良い。例えば、２−メルカプトベンゾチアゾ−ル、１，２，３−トリアゾ−ル、１，２，４−トリアゾ−ル、３−アミノ−１Ｈ−１，２，４−トリアゾ−ル、ベンゾトリアゾ−ル、１−ヒドロキシベンゾトリアゾ−ル、１−ジヒドロキシプロピルベンゾトリアゾ−ル、２，３−ジカルボキシプロピルベンゾトリアゾ−ル、４−ヒドロキシベンゾトリアゾ−ル、４−カルボキシル（−１Ｈ−）ベンゾトリアゾ−ル、４−カルボキシル(−１Ｈ−)ベンゾトリアゾ−ルメチルルエステル、４−カルボキシル(−１Ｈ−)ベンゾトリアゾ−ルブチルエステル、４−カルボキシル(−１Ｈ−)ベンゾトリアゾ−ルオクチルエステル、５−ヘキシルベンゾトリアゾ−ル、[１，２，３−ベンゾトリアゾリル−１−メチル][１，２，４−トリアゾリル−１−メチル][２−エチルヘキシル]アミン、トリルトリアゾ−ル、ナフトトリアゾ−ル、ビス[（１−ベンゾトリアゾリル）メチル]ホスホン酸等が挙げられる。また、ピリミジン骨格を有する化合物としてピリミジン、1,2,4-トリアゾロ[1,5-a] ピリミジン、1,3,4,6,7,8-ヘキサハイドロ-2H-ピリミド[1,2-a] ピリミジン、1,3-ジフェニル-ピリミジン-2,4,6-トリオン、1,4,5,6-テトラハイドロピリミジン、2,4,5,6-テトラアミノピリミジンサルフェイト、2,4,5-トリハイドロキシピリミジン、2,4,6-トリアミノピリミジン、2,4,6-トリクロロピリミジン、2,4,6-トリメトキシピリミジン、2,4,6-トリフェニルピリミジン、2,4-ジアミノ-6-ヒドロキシルピリミジン、2,4-ジアミノピリミジン、2-アセトアミドピリミジン、2-アミノピリミジン、2-メチル-5,7-ジフェニル-(1,2,4)トリアゾロ(1,5-a) ピリミジン、2-メチルサルファニル-5,7-ジフェニル-(1,2,4)トリアゾロ(1,5-a) ピリミジン、2-メチルサルファニル-5,7-ジフェニル-4,7-ジヒドロ-(1,2,4)トリアゾロ(1,5-A) ピリミジン、4-アミノピラゾロ[3,4,-d] ピリミジン等が挙げられ、これらは１種類単独で、もしくは２種類以上混合して用いることができる。 Moreover, you may add a metal anticorrosive to the metal polishing liquid of this invention. For example, 2-mercaptobenzothiazol, 1,2,3-triazole, 1,2,4-triazole, 3-amino-1H-1,2,4-triazole, benzotriazole 1-hydroxybenzotriazole, 1-dihydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzotriazole, 4-carboxyl (-1H-) Benzotriazole, 4-carboxyl (-1H-) benzotriazole methyl ester, 4-carboxyl (-1H-) benzotriazole butyl ester, 4-carboxyl (-1H-) benzotriazol octyl ester, 5-hexylbenzo Triazol, [1,2,3-benzotriazolyl-1-methyl] [1,2,4-triazolyl-1-methyl] [2-e Hexyl] amine, Torirutoriazo - le, Nafutotoriazo - le, bis [(1-benzotriazolyl) methyl] phosphonic acid. Further, as compounds having a pyrimidine skeleton, pyrimidine, 1,2,4-triazolo [1,5-a] pyrimidine, 1,3,4,6,7,8-hexahydro-2H-pyrimido [1,2-a ] Pyrimidine, 1,3-diphenyl-pyrimidine-2,4,6-trione, 1,4,5,6-tetrahydropyrimidine, 2,4,5,6-tetraaminopyrimidine sulfate, 2,4,5 -Trihydroxypyrimidine, 2,4,6-triaminopyrimidine, 2,4,6-trichloropyrimidine, 2,4,6-trimethoxypyrimidine, 2,4,6-triphenylpyrimidine, 2,4-diamino- 6-hydroxylpyrimidine, 2,4-diaminopyrimidine, 2-acetamidopyrimidine, 2-aminopyrimidine, 2-methyl-5,7-diphenyl- (1,2,4) triazolo (1,5-a) pyrimidine, 2 -Methylsulfanyl-5,7-diphenyl- (1,2,4) triazolo (1,5-a) pyrimidine, 2-methylsulfanyl-5,7-diphenyl-4,7-dihydro- (1,2 , 4) Triazolo ( 1,5-A) Pyrimidine, 4-aminopyrazolo [3,4, -d] pyrimidine and the like can be mentioned, and these can be used alone or in combination of two or more.
本発明の酸化金属溶解剤の配合量は、酸化金属溶解剤、砥粒を沈降させない界面活性剤、砥粒、及び水の総量１００ｇに対して、０．００１〜２０ｇとすることが好ましく、０．００２〜１５ｇとすることがより好ましく、０．００５〜１５ｇとすることが特に好ましい。配合量が ０．００１ｇ未満では、研磨速度が低く、２０ｇを超えるとエッチングの抑制が困難となり研磨面に荒れが生じる傾向がある。 The compounding amount of the metal oxide solubilizer of the present invention is preferably 0.001 to 20 g with respect to 100 g of the total amount of the metal oxide solubilizer, the surfactant that does not precipitate the abrasive grains, the abrasive grains, and the water. It is more preferable to set it as 0.002-15g, and it is especially preferable to set it as 0.005-15g. If the blending amount is less than 0.001 g, the polishing rate is low, and if it exceeds 20 g, it is difficult to suppress etching and the polished surface tends to be rough.
本発明の砥粒の配合量は、酸化金属溶解剤、砥粒を沈降させない界面活性剤、砥粒、及び水の総量１００ｇに対して、０〜５０ｇとすることが好ましく、０．００１〜４５ｇとすることがより好ましく、０．００２〜４０ｇとすることが特に好ましい。配合量が４０ｇを超えると異物が多く発生する傾向にある。 The compounding amount of the abrasive grains of the present invention is preferably 0 to 50 g with respect to 100 g of the total amount of the metal oxide solubilizer, the surfactant that does not precipitate the abrasive grains, the abrasive grains, and the water, and 0.001 to 45 g. It is more preferable to set it as 0.002 to 40 g. When the amount exceeds 40 g, a large amount of foreign matter tends to be generated.
本発明の砥粒を沈降させない界面活性剤の配合量は、酸化金属溶解剤、砥粒を沈降させない界面活性剤、砥粒、及び水の総量１００ｇに対して、０．０００１〜１０ｇとすることが好ましく、０．２〜６０ｇとすることがより好ましく、０．０００５〜８ｇとすることが特に好ましい。配合量が ０．０００１ｇ未満では、研磨液の基板に対する濡れ性が低く、１０ｇを超えると異物が多く発生する傾向にある。 The blending amount of the surfactant that does not settle the abrasive grains of the present invention is 0.0001 to 10 g with respect to 100 g of the total amount of the metal oxide dissolving agent, the surfactant that does not settle the abrasive grains, the abrasive grains, and the water. Is preferable, 0.2 to 60 g is more preferable, and 0.0005 to 8 g is particularly preferable. If the blending amount is less than 0.0001 g, the wettability of the polishing liquid to the substrate is low, and if it exceeds 10 g, a large amount of foreign matter tends to be generated.
本発明の有機溶媒の配合量は、酸化金属溶解剤、砥粒を沈降させない界面活性剤、砥粒、及び水の総量１００ｇに対して、０．０１〜８０ｇとすることが好ましく、０．２〜６０ｇとすることがより好ましく、０．０５〜７０ｇとすることが特に好ましい。配合量が ０．０１ｇ未満では、研磨液の基板に対する濡れ性が低く、６０ｇを超えると引火する可能性があり危険である。 The blending amount of the organic solvent of the present invention is preferably 0.01 to 80 g with respect to 100 g of the total amount of the metal oxide solubilizer, the surfactant that does not precipitate the abrasive grains, the abrasive grains, and the water, 0.2 It is more preferable to set it to -60g, and it is especially preferable to set it as 0.05-70g. If the blending amount is less than 0.01 g, the wettability of the polishing liquid to the substrate is low, and if it exceeds 60 g, there is a possibility of catching fire, which is dangerous.
本発明の金属の酸化剤の配合量は、酸化金属溶解剤、砥粒を沈降させない界面活性剤、砥粒、及び水の総量１００ｇに対して、０〜５０ｇとすることが好ましく、０．００１〜４５ｇとすることがより好ましく、０．００２〜４０ｇとすることが特に好ましい。配合量が５０ｇを超えると、研磨面に荒れが生じる傾向がある。 The compounding amount of the metal oxidizer of the present invention is preferably 0 to 50 g with respect to 100 g of the total amount of metal oxide solubilizer, surfactant that does not precipitate abrasive grains, abrasive grains, and water, 0.001 It is more preferable to set it to -45g, and it is especially preferable to set it as 0.002-40g. When the amount exceeds 50 g, the polished surface tends to be rough.
本発明の水溶性ポリマの配合量は、酸化金属溶解剤、砥粒を沈降させない界面活性剤、砥粒、及び水の総量１００ｇに対して０〜１０ｇとすることが好ましく、０．０１〜８ｇとすることがより好ましく、０．０２〜５ｇとすることが特に好ましい。この配合量が１０ｇを超えると研磨速度が低下する傾向がある。 The blending amount of the water-soluble polymer of the present invention is preferably 0 to 10 g with respect to 100 g of the total amount of metal oxide solubilizer, surfactant that does not precipitate abrasive grains, abrasive grains, and water, and 0.01 to 8 g. Is more preferable, and 0.02 to 5 g is particularly preferable. If this amount exceeds 10 g, the polishing rate tends to decrease.
水溶性ポリマの重量平均分子量は５００以上とすることが好ましく、１５００以上とすることがより好ましく５０００以上とすることが特に好ましい。重量平均分子量の上限は特に規定するものではないが、溶解性の観点から５００万以下である。重量平均分子量が５００未満では高い研磨速度が発現しない傾向にある。本発明では、重量平均分子量が５００以上である少なくとも１種以上の水溶性ポリマを用いることが好ましい。 The weight average molecular weight of the water-soluble polymer is preferably 500 or more, more preferably 1500 or more, and particularly preferably 5000 or more. The upper limit of the weight average molecular weight is not particularly specified, but is 5 million or less from the viewpoint of solubility. When the weight average molecular weight is less than 500, a high polishing rate tends not to be exhibited. In the present invention, it is preferable to use at least one water-soluble polymer having a weight average molecular weight of 500 or more.
本発明の金属防食剤の配合量は、酸化金属溶解剤、砥粒を沈降させない界面活性剤、砥粒、及び水の総量１００ｇに対して０〜１０ｇとすることが好ましく、０．００１〜８ｇとすることがより好ましく、０．００２〜５ｇとすることが特に好ましい。この配合量が１０ｇを超えると研磨速度が低くなってしまう傾向がある。 The compounding amount of the metal anticorrosive of the present invention is preferably 0 to 10 g with respect to 100 g of the total amount of metal oxide solubilizer, surfactant that does not precipitate abrasive grains, abrasive grains, and water, 0.001 to 8 g. More preferably, it is particularly preferably 0.002 to 5 g. If this amount exceeds 10 g, the polishing rate tends to be low.
本発明の金属用研磨液には、上述した材料のほかに界面活性剤、ビクトリアピュアブルー等の染料、フタロシアニングリーン等の顔料等の着色剤を含有させてもよい。 In addition to the materials described above, the metal polishing slurry of the present invention may contain a surfactant, a dye such as Victoria Pure Blue, and a colorant such as a pigment such as phthalocyanine green.
本発明を適用する銅、銅合金及び銅又は銅合金の酸化物（以下銅合金という）膜としては、公知のスパッタ法、メッキ法により成膜できる。 The copper, copper alloy, and copper or copper alloy oxide (hereinafter referred to as copper alloy) film to which the present invention is applied can be formed by a known sputtering method or plating method.
本発明を適用する金属としては、タングステン、窒化タングステン、タングステン合金、その他のタングステン化合物、チタン、窒化チタン、チタン合金、その他のチタン化合物、タンタル、窒化タンタル、タンタル合金、その他のタンタル化合物、から選ばれた少なくとも１種の金属バリア層を含む積層膜である。 The metal to which the present invention is applied is selected from tungsten, tungsten nitride, tungsten alloys, other tungsten compounds, titanium, titanium nitride, titanium alloys, other titanium compounds, tantalum, tantalum nitride, tantalum alloys, and other tantalum compounds. A laminated film including at least one metal barrier layer.
本発明を適用する層間絶縁膜としては、シリコン系皮膜や有機ポリマ膜が挙げられる。シリコン系皮膜としては、二酸化ケイ素、フルオロシリケートグラス、トリメチルシランやジメトキシジメチルシランを出発原料として得られるオルガノシリケートグラス、シリコンオキシナイトライド、水素化シルセスキオキサン等のシリカ系皮膜や、シリコンカーバイド及びシリコンナイトライドが挙げられる。また、有機ポリマ膜としては、全芳香族系低誘電率層間絶縁膜が挙げられる。これらの膜は、ＣＶＤ法、スピンコート法、ディップコート法、またはスプレー法によって成膜される。 Examples of the interlayer insulating film to which the present invention is applied include a silicon-based film and an organic polymer film. Silicon-based coatings include silicon dioxide, fluorosilicate glass, organosilicate glass obtained using trimethylsilane and dimethoxydimethylsilane as starting materials, silicon oxynitride, silica-based coatings such as silsesquioxane hydride, silicon carbide and A silicon nitride is mentioned. Examples of the organic polymer film include a wholly aromatic low dielectric constant interlayer insulating film. These films are formed by a CVD method, a spin coating method, a dip coating method, or a spray method.
本発明の研磨方法は、研磨定盤の研磨パッド上に前記の金属用研磨液を供給しながら、被研磨膜を有する基板を研磨パッドに押圧した状態で研磨定盤と基板を相対的に動かすことによって被研磨膜を研磨する研磨方法である。研磨する装置としては、半導体基板を保持するホルダと研磨パッドを貼り付けた（回転数が変更可能なモータ等を取り付けてある）定盤を有する一般的な研磨装置が使用できる。研磨パッドとしては、一般的な不織布、発泡ポリウレタン、多孔質フッ素樹脂などが使用でき、特に制限がない。研磨条件には制限はないが、定盤の回転速度は基板が飛び出さないように２００ｒｐｍ以下の低回転が好ましい。被研磨膜を有する半導体基板の研磨パッドへの押し付け圧力が１〜１００ｋPaであることが好ましく、ＣＭＰ速度のウエハ面内均一性及びパターンの平坦性を満足するためには、５〜５０ｋPaであることがより好ましい。研磨している間、研磨パッドには金属用研磨液をポンプ等で連続的に供給する。この供給量に制限はないが、研磨パッドの表面が常に研磨液で覆われていることが好ましい。研磨終了後の半導体基板は、流水中でよく洗浄後、スピンドライ等を用いて半導体基板上に付着した水滴を払い落としてから乾燥させることが好ましい。 The polishing method of the present invention moves the polishing platen and the substrate relatively while pressing the substrate having the film to be polished against the polishing pad while supplying the metal polishing liquid onto the polishing pad of the polishing platen. This is a polishing method for polishing the film to be polished. As a polishing apparatus, a general polishing apparatus having a surface plate with a holder for holding a semiconductor substrate and a polishing pad attached (a motor or the like whose rotation speed can be changed) is attached. As the polishing pad, a general nonwoven fabric, foamed polyurethane, porous fluororesin, or the like can be used, and there is no particular limitation. The polishing conditions are not limited, but the rotation speed of the surface plate is preferably a low rotation of 200 rpm or less so that the substrate does not jump out. The pressure applied to the polishing pad of the semiconductor substrate having the film to be polished is preferably 1 to 100 kPa, and 5 to 50 kPa in order to satisfy the uniformity in the wafer surface of the CMP rate and the flatness of the pattern. Is more preferable. During polishing, a polishing liquid for metal is continuously supplied to the polishing pad with a pump or the like. Although there is no restriction | limiting in this supply amount, it is preferable that the surface of a polishing pad is always covered with polishing liquid. The semiconductor substrate after completion of polishing is preferably washed in running water and then dried after removing water droplets adhering to the semiconductor substrate using spin drying or the like.
以下、実施例により本発明を説明する。本発明はこれらの実施例により制限されるものではない。 Hereinafter, the present invention will be described by way of examples. The present invention is not limited by these examples.
（研磨液作製方法）
表1に示すような配合で材料を混合し実施例１〜１２及び比較例１〜２で用いる金属用研磨液を作製した。
（研磨条件）
ブランケット基板：トリメチルシランを出発原料としてＣＶＤ法で成膜されたオルガノシリケート(厚さ：１０００nm)を形成したシリコン基板
：厚さ１０００nmの二酸化ケイ素を形成したシリコン基板
：厚さ２００nmのタンタル膜を形成したシリコン基板
：厚さ１６００nmの銅膜を形成したシリコン基板
パターン基板：トリメチルシランを出発原料としてＣＶＤ法で成膜されたオルガノシリケート、または二酸化ケイ素中に公知の方法を用いて深さ０．５〜１００μｍの溝を形成して、公知のスパッタ法によってバリア層として厚さ２００nmのタンタル膜を形成し、同様にスパッタ法により銅膜を１．０μｍ形成した基板を公知の方法で突出した銅膜だけ研磨した基板。
研磨パッド：ＩＣ１０００（ロデ−ル社製）
研磨圧力：２１０ｇ／ｃｍ２
基体と研磨定盤との相対速度：３６ｍ／ｍｉｎ
（洗浄条件A）
Ontrack製半導体ウエハ用洗浄機を用いて薬液を用いてブラシ洗浄を30秒間行い、スピン乾燥した。
（洗浄条件B）
Ontrack製半導体ウエハ用洗浄機を用いて蒸留水を用いてブラシ洗浄を30秒間行い、スピン乾燥した。
（評価項目）
研磨速度：各種ブランケット基板を６０秒研磨することで求めた。
オルガノシリケート及び二酸化ケイ素の研磨速度は研磨前後での膜厚差を大日本スクリーン社製ラムダエースを用いて測定し求めた。また、タンタル膜及び銅の研磨速度は研磨前後での膜厚差を電気抵抗値から換算して求めた。
研磨速度の面内均一性：上記研磨速度の標準偏差を平均値に対して１００分率（％）で
表した。
エッチング速度：攪拌した金属用研磨液（２５℃、攪拌１００ｒｐｍ）への浸漬前後の銅膜厚差を電気抵抗値から換算して求めた。
平坦性（ディッシング量）：上記層間絶縁膜にオルガノシリケートまたは二酸化ケイ素を用いたパターン基板を、上記金属用研磨液で９０秒間研磨を行った。次に、触針式段差計で配線金属部幅１００μｍ、絶縁膜部幅１００μｍが交互に並んだストライプ状パターン部の表面形状から、絶縁膜部に対する配線金属部の膜減り量を求めた。
平坦性（エロージョン量）：上記金属用研磨液で９０秒間研磨を行ったパターン基板に
形成された配線金属部幅４．５μｍ、絶縁膜部幅０．５μｍが交互に並んだ総幅２．５mmのストライプ状パターン部の表面形状を触針式段差計により測定し、ストライプ状パターン周辺の絶縁膜フィールド部に対するパターン中央付近の絶縁膜部の膜減り量を求めた。
配線抵抗値：上記金属用研磨液で９０秒間研磨を行ったパターン基板を用いて、配線抵抗値の測定を行った。ディッシング量測定部の幅１００μｍ銅配線パターンにおいて、配線長さ１mmの配線抵抗値を測定した。また、エロージョン量測定部の幅４．５μｍ銅配線パターンにおいて、配線長さ１mmの配線抵抗値を測定した。
洗浄性：上記金属用研磨液で９０秒間研磨を行ったパターン基板の研磨カスの量をＳＥＭを用いて観察し、１ｃｍ２当たりの個数で評価した。
研磨異物：上記金属用研磨液で９０秒間研磨を行ったパターン基板の研磨キズの量をＫＬＡ Ｔｅｎｃｏｒ２１３８を用いて測定し、１ウエハ当たりの個数で評価した。
実施例１〜１２及び比較例１〜２のＣＭＰによるオルガノシリケートグラス、二酸化ケイ素、タンタル、及び銅の研磨速度、並びにエッチング速度、ディッシング量、エロージョン量、及び配線抵抗値、洗浄性、及び研磨異物の評価結果を表２に示した。
(Polishing liquid preparation method)
The metal polishing liquid used by Examples 1-12 and Comparative Examples 1-2 was produced by mixing materials with the composition shown in Table 1.
(Polishing conditions)
Blanket substrate: Silicon substrate on which organosilicate (thickness: 1000 nm) is formed by CVD using trimethylsilane as a starting material: Silicon substrate on which silicon dioxide with a thickness of 1000 nm is formed: Tantalum film with a thickness of 200 nm is formed Silicon substrate: silicon substrate on which a copper film having a thickness of 1600 nm is formed Pattern substrate: organosilicate formed by a CVD method using trimethylsilane as a starting material, or a depth of 0.5 using a known method in silicon dioxide A copper film in which a groove having a thickness of ˜100 μm is formed, a tantalum film having a thickness of 200 nm is formed as a barrier layer by a known sputtering method, and a substrate on which a copper film is similarly formed by a sputtering method is formed by a known method Only polished substrate.
Polishing pad: IC1000 (Rodel)
Polishing pressure: 210 g / cm 2
Relative speed between substrate and polishing surface plate: 36 m / min
(Cleaning condition A)
Using Ontrack semiconductor wafer cleaner, brush cleaning was performed for 30 seconds using a chemical solution, followed by spin drying.
(Cleaning condition B)
Brush cleaning was performed for 30 seconds with distilled water using an Ontrack semiconductor wafer washer and spin-dried.
(Evaluation item)
Polishing speed: Determined by polishing various blanket substrates for 60 seconds.
The polishing rate of organosilicate and silicon dioxide was determined by measuring the difference in film thickness before and after polishing using Lambda Ace manufactured by Dainippon Screen. The polishing rate of the tantalum film and copper was obtained by converting the film thickness difference before and after polishing from the electric resistance value.
In-plane uniformity of polishing rate: The standard deviation of the polishing rate was expressed in terms of 100 minutes (%) with respect to the average value.
Etching rate: The difference in copper film thickness before and after immersion in a stirred metal polishing liquid (25 ° C., stirring 100 rpm) was calculated from the electrical resistance value.
Flatness (dishing amount): A patterned substrate using organosilicate or silicon dioxide as the interlayer insulating film was polished for 90 seconds with the metal polishing liquid. Next, the film reduction amount of the wiring metal part with respect to the insulating film part was obtained from the surface shape of the stripe pattern part in which the wiring metal part width of 100 μm and the insulating film part width of 100 μm were alternately arranged with a stylus step meter.
Flatness (Erosion amount): A total width of 2.5 mm in which wiring metal part width 4.5 μm and insulating film part width 0.5 μm are alternately arranged on a pattern substrate polished for 90 seconds with the above metal polishing liquid. The surface shape of the stripe pattern portion was measured with a stylus type step meter, and the amount of film reduction of the insulating film portion near the center of the pattern with respect to the insulating film field portion around the stripe pattern was determined.
Wiring resistance value: The wiring resistance value was measured using a pattern substrate polished for 90 seconds with the above metal polishing liquid. A wiring resistance value with a wiring length of 1 mm was measured in a copper wiring pattern with a width of 100 μm in the dishing amount measuring section. Moreover, the wiring resistance value of 1 mm in wiring length was measured in the 4.5 μm wide copper wiring pattern of the erosion amount measuring part.
Detergency: The amount of polishing residue of the pattern substrate polished for 90 seconds with the above metal polishing solution was observed using SEM and evaluated by the number per 1 cm 2 .
Polishing foreign matter: The amount of polishing scratches on the patterned substrate polished for 90 seconds with the above metal polishing solution was measured using KLA Tencor 2138, and evaluated by the number per wafer.
Polishing rate of organosilicate glass, silicon dioxide, tantalum, and copper by CMP of Examples 1 to 12 and Comparative Examples 1 to 2, etching rate, dishing amount, erosion amount, wiring resistance value, cleaning property, and polishing foreign matter The evaluation results are shown in Table 2.
比較例１及び比較例２では、オルガノシリケートグラスの研磨速度が小さく、研磨速度の面内均一性が大きいためにディッシング及びエロージョンが大きく配線抵抗値が増加している。また、比較例１及び比較例２では、洗浄性及び研磨異物が悪化した。それに対し実施例１〜１２では、研磨カスの量及び研磨キズの量が少なく良好である。
In Comparative Examples 1 and 2, since the polishing rate of the organosilicate glass is low and the in-plane uniformity of the polishing rate is large, dishing and erosion are large and the wiring resistance value is increased. Moreover, in Comparative Example 1 and Comparative Example 2, the detergency and abrasive foreign matter deteriorated. In contrast, in Examples 1 to 12, the amount of polishing residue and the amount of polishing scratches are small and good.
Claims (12)
While supplying the metal polishing liquid according to claim 1 to the polishing cloth of the polishing surface plate, by relatively moving the polishing surface plate and the substrate while pressing the substrate having the film to be polished against the polishing cloth. A polishing method for polishing a film to be polished.
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| JP2007088379A (en) * | 2005-09-26 | 2007-04-05 | Fujifilm Corp | Aqueous polishing liquid and chemical mechanical polishing method |
| WO2007116770A1 (en) * | 2006-04-03 | 2007-10-18 | Jsr Corporation | Aqueous dispersion for chemical mechanical polishing, chemical mechanical polishing method, and kit for preparing aqueous dispersion for chemical mechanical polishing |
| JP2009507659A (en) * | 2005-09-09 | 2009-02-26 | サン−ゴバン セラミックス アンド プラスティクス，インコーポレイティド | Conductive hydrocarbon fluid |
| WO2012133591A1 (en) | 2011-03-30 | 2012-10-04 | 株式会社 フジミインコーポレーテッド | Polishing composition, polishing method using same, and method for producing semiconductor device |
| WO2016127424A1 (en) * | 2015-02-15 | 2016-08-18 | Acm Research (Shanghai) Inc. | Method for optimizing metal planarization process |
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| JP2009507659A (en) * | 2005-09-09 | 2009-02-26 | サン−ゴバン セラミックス アンド プラスティクス，インコーポレイティド | Conductive hydrocarbon fluid |
| JP2007088379A (en) * | 2005-09-26 | 2007-04-05 | Fujifilm Corp | Aqueous polishing liquid and chemical mechanical polishing method |
| WO2007116770A1 (en) * | 2006-04-03 | 2007-10-18 | Jsr Corporation | Aqueous dispersion for chemical mechanical polishing, chemical mechanical polishing method, and kit for preparing aqueous dispersion for chemical mechanical polishing |
| JPWO2007116770A1 (en) * | 2006-04-03 | 2009-08-20 | Jsr株式会社 | Chemical mechanical polishing aqueous dispersion, chemical mechanical polishing method, and kit for preparing chemical mechanical polishing aqueous dispersion |
| KR101406642B1 (en) | 2006-04-03 | 2014-06-11 | 제이에스알 가부시끼가이샤 | An aqueous dispersion for chemical mechanical polishing, a chemical mechanical polishing method, and a kit for producing an aqueous dispersion for chemical mechanical polishing |
| WO2012133591A1 (en) | 2011-03-30 | 2012-10-04 | 株式会社 フジミインコーポレーテッド | Polishing composition, polishing method using same, and method for producing semiconductor device |
| US9150758B2 (en) | 2011-03-30 | 2015-10-06 | Fujimi Incorporated | Polishing composition, polishing method using same, and method for producing semiconductor device |
| WO2016127424A1 (en) * | 2015-02-15 | 2016-08-18 | Acm Research (Shanghai) Inc. | Method for optimizing metal planarization process |
| CN120941265A (en) * | 2025-10-16 | 2025-11-14 | 江苏中科智芯集成科技有限公司 | Grinding control methods and systems applicable to ultra-thin wafer thinning |
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