JP2020155720A - Elemental silicon polishing rate improver - Google Patents
Elemental silicon polishing rate improver Download PDFInfo
- Publication number
- JP2020155720A JP2020155720A JP2019055141A JP2019055141A JP2020155720A JP 2020155720 A JP2020155720 A JP 2020155720A JP 2019055141 A JP2019055141 A JP 2019055141A JP 2019055141 A JP2019055141 A JP 2019055141A JP 2020155720 A JP2020155720 A JP 2020155720A
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- JP
- Japan
- Prior art keywords
- polishing
- acid
- present
- silicon
- ion
- 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
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 55
- 239000010703 silicon Substances 0.000 title claims abstract description 55
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- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 37
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- -1 iron ion Chemical class 0.000 claims abstract description 13
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- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 5
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- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 3
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- 150000002500 ions Chemical class 0.000 claims description 41
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- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- RTAYJOCWVUTQHB-UHFFFAOYSA-H yttrium(3+);trisulfate Chemical compound [Y+3].[Y+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RTAYJOCWVUTQHB-UHFFFAOYSA-H 0.000 description 1
Landscapes
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
Description
本発明は、単体シリコンの研磨速度向上剤に関する。 The present invention relates to an agent for improving the polishing rate of simple substance silicon.
近年、ＬＳＩ（Ｌａｒｇｅ Ｓｃａｌｅ Ｉｎｔｅｇｒａｔｉｏｎ）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（ｃｈｅｍｉｃａｌ ｍｅｃｈａｎｉｃａｌ ｐｏｌｉｓｈｉｎｇ；ＣＭＰ）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（ダマシン配線）形成において頻繁に利用される技術である。 In recent years, new microfabrication techniques have been developed along with the high integration and high performance of LSI (Large Scale Integration). Chemical mechanical polishing (CMP) method is one of them, and is frequently used in LSI manufacturing process, especially in multilayer insulation film flattening, metal plug formation, and embedded wiring (damaching wiring) formation in the LSI manufacturing process, especially in the multilayer wiring formation process. It is a technology to be done.
当該ＣＭＰは、半導体製造における各工程に適用されてきており、その一態様として、例えばトランジスタ作製におけるゲート形成工程への適用が挙げられる。トランジスタ作製の際には、シリコン、多結晶シリコン（ポリシリコン）やシリコン窒化物（窒化ケイ素）といったＳｉ含有材料を研磨することがあり、トランジスタの構造によっては、各Ｓｉ含有材料の研磨レートを制御することが求められている。 The CMP has been applied to each process in semiconductor manufacturing, and one embodiment thereof includes application to a gate forming process in transistor manufacturing, for example. When manufacturing a transistor, Si-containing materials such as silicon, polycrystalline silicon (polysilicon) and silicon nitride (silicon nitride) may be polished, and the polishing rate of each Si-containing material is controlled depending on the structure of the transistor. Is required to do.
例えば、特許文献１〜３には、砥粒、界面活性剤等を含む研磨剤でポリシリコンを研磨する技術が開示されている。 For example, Patent Documents 1 to 3 disclose a technique for polishing polysilicon with an abrasive containing abrasive grains, a surfactant, and the like.
本発明は、ポリシリコン等の単体シリコンを研磨するに当たり、高い研磨速度で研磨することができる単体シリコンの研磨速度向上剤を提供することを目的とする。 An object of the present invention is to provide an agent for improving the polishing rate of elemental silicon, which can be polished at a high polishing rate when polishing elemental silicon such as polysilicon.
上記課題を解決すべく、本発明者は鋭意研究を積み重ねた。その結果、遷移金属イオンと、液体キャリアとを含む、単体シリコンの研磨速度向上剤により上記課題が解決されうることを見出した。 In order to solve the above problems, the present inventor has accumulated extensive research. As a result, it has been found that the above-mentioned problems can be solved by an agent for improving the polishing rate of elemental silicon, which contains transition metal ions and liquid carriers.
本発明は、ポリシリコン等の単体シリコンを研磨するに当たり、高い研磨速度で研磨することができる単体シリコンの研磨速度向上剤を提供することができる。 The present invention can provide an agent for improving the polishing rate of elemental silicon, which can be polished at a high polishing rate when polishing elemental silicon such as polysilicon.
以下、本発明を説明する。なお、本発明は、以下の実施の形態のみには限定されない。また、特記しない限り、操作および物性等の測定は室温（２０〜２５℃）／相対湿度４０〜５０％ＲＨの条件で測定する。 Hereinafter, the present invention will be described. The present invention is not limited to the following embodiments. Unless otherwise specified, the operation and physical properties are measured under the conditions of room temperature (20 to 25 ° C.) / relative humidity of 40 to 50% RH.
本発明は、遷移金属イオンと、液体キャリアとを含む、単体シリコンの研磨速度向上剤である。かかる構成によって、ポリシリコン等の単体シリコンを研磨するに当たり、高い研磨速度で研磨することができる単体シリコンの研磨速度向上剤を提供することができる。 The present invention is an agent for improving the polishing rate of elemental silicon, which contains transition metal ions and a liquid carrier. With such a configuration, it is possible to provide an agent for improving the polishing rate of elemental silicon, which can be polished at a high polishing rate when polishing elemental silicon such as polysilicon.
［研磨対象物］
本発明の一実施形態によれば、研磨対象物は、単体シリコンである。単体シリコンとしては、特に制限はないが、ポリシリコン（Ｐｏｌｙ Ｓｉ、多結晶シリコン）、単結晶シリコン、アモルファスシリコン、ドープドシリコン等が挙げられる。かかる実施形態によれば、研磨速度向上の効果を効率的に得ることができる。本発明の一実施形態において、単体シリコンの用途は制限されず、半導体基板、太陽電池の基板、液晶ディスプレイ（ＬＣＤ）のＴＦＴ等が挙げられる。また、それらのテストウェハ、モニターウェハ、搬送チェックウェハ、ダミーウェハ等にも好適である。
[Object to be polished]
According to one embodiment of the present invention, the object to be polished is elemental silicon. The single silicon is not particularly limited, and examples thereof include polysilicon (Poly Si, polycrystalline silicon), single crystal silicon, amorphous silicon, and doped silicon. According to such an embodiment, the effect of improving the polishing speed can be efficiently obtained. In one embodiment of the present invention, the use of simple substance silicon is not limited, and examples thereof include a semiconductor substrate, a solar cell substrate, and a TFT of a liquid crystal display (LCD). It is also suitable for these test wafers, monitor wafers, transfer check wafers, dummy wafers, and the like.
本発明の一実施形態によれば、研磨対象物は、単体シリコン以外の研磨対象物を含んでもよい。 According to one embodiment of the present invention, the object to be polished may include an object to be polished other than elemental silicon.
［単体シリコンの研磨速度促進剤］
（液体キャリア）
本発明の一実施形態によれば、液体キャリアとしては、有機溶媒、水（特に純水）が考えられるが、研磨対象物の汚染や他の成分の作用を阻害するという観点から、不純物をできる限り含有しない水が好ましい。具体的には、イオン交換樹脂にて不純物イオンを除去した後フィルタを通して異物を除去した純水や超純水、または蒸留水が好ましい。
[Simple silicon polishing rate accelerator]
(Liquid carrier)
According to one embodiment of the present invention, an organic solvent and water (particularly pure water) can be considered as the liquid carrier, but impurities can be formed from the viewpoint of contaminating the object to be polished and inhibiting the action of other components. Water that does not contain as much as possible is preferable. Specifically, pure water, ultrapure water, or distilled water from which impurity ions have been removed with an ion exchange resin and then foreign substances have been removed through a filter is preferable.
（遷移金属イオン）
本発明の一実施形態における、単体シリコンの研磨速度促進剤は、遷移金属イオンを含む。ここで上述の用途（特に半導体基板）においては、不純物が各種デバイスに悪影響を与え得ることが知られている。不純物としては、パーティクル、金属等がある。パーティクルは、配線パターンを正常に形成するのを妨げる。また、金属不純物は、例えば、ゲート酸化膜の耐圧劣化や、ＰＮ接合における微小の電流リーク、トランジスタ動作不安定性を引き起こす。ゆえに、かような用途における分野においては、金属は不純物になりうるとして、従前、その使用が忌避されてきた。本発明は、遷移金属イオンを敢えて積極的に組成物中に含有させるという斬新な手法を用いて単体シリコンの研磨速度を向上させるとの従来にない画期的なものである。
(Transition metal ion)
The polishing rate accelerator for elemental silicon in one embodiment of the present invention contains transition metal ions. Here, it is known that impurities can adversely affect various devices in the above-mentioned applications (particularly semiconductor substrates). Impurities include particles, metals and the like. Particles prevent the successful formation of wiring patterns. Further, metal impurities cause, for example, deterioration of the withstand voltage of the gate oxide film, minute current leakage in the PN junction, and transistor operation instability. Therefore, in the field of such applications, the use of metals has been avoided as they can be impurities. The present invention is an unprecedented epoch-making one in which the polishing rate of elemental silicon is improved by using a novel technique of intentionally actively containing transition metal ions in the composition.
本発明の一実施形態によれば、遷移金属イオンとは、遷移金属のイオンである。本発明の一実施形態において、遷移金属とは、周期表で第３族元素から第１１族元素の間に存在する元素である。 According to one embodiment of the present invention, a transition metal ion is a transition metal ion. In one embodiment of the present invention, a transition metal is an element that exists between Group 3 and Group 11 elements in the periodic table.
本発明の一実施形態によれば、前記遷移金属イオンが、第１遷移系列（スカンジウムから銅）または第２遷移系列（イットリウムから銀）であることが好ましい。本発明の一実施形態によれば、前記遷移金属イオンが、第１遷移系列の遷移元素イオンであることがより好ましい。かかる実施形態によれば、遷移金属イオンがイオンとして安定的に研磨用組成物中に存在し、研磨時に単体シリコン表面への析出を防ぐことができる効果がある。 According to one embodiment of the present invention, the transition metal ion is preferably the first transition series (scandium to copper) or the second transition series (yttrium to silver). According to one embodiment of the present invention, it is more preferable that the transition metal ion is a transition element ion of the first transition series. According to such an embodiment, the transition metal ions are stably present as ions in the polishing composition, and there is an effect that precipitation on the surface of the simple substance silicon can be prevented during polishing.
本発明の一実施形態によれば、前記遷移金属イオンが、単体金属のイオンである。かかる実施形態によれば、単体シリコン表面を除去しやすい形に変化させるのに有利と考えられる。よって、本発明の一実施形態によれば、前記遷移金属イオンが、過マンガン酸由来のイオン、クロム酸由来のイオン、二クロム酸由来のイオンおよび鉄酸由来のイオンからなる群から選択される少なくとも１種のイオンではないことが好ましい。本発明の一実施形態において、前記遷移金属イオンが、単体金属のイオン以外のイオンであると、単体シリコン表面の過剰な酸化による研磨性能の低下の虞もある。 According to one embodiment of the present invention, the transition metal ion is an ion of a simple substance metal. According to such an embodiment, it is considered advantageous to change the surface of the simple substance silicon into a form that can be easily removed. Therefore, according to one embodiment of the present invention, the transition metal ion is selected from the group consisting of an ion derived from permanganic acid, an ion derived from chromic acid, an ion derived from dichromic acid and an ion derived from iron acid. It is preferably not at least one type of ion. In one embodiment of the present invention, if the transition metal ion is an ion other than the ion of the elemental metal, there is a risk that the polishing performance may be deteriorated due to excessive oxidation of the surface of the elemental silicon.
本発明の一実施形態によれば、スカンジウム（３価イオンの形態でのみ存在）、チタン（３価イオンの形態でのみ存在）、バナジウム、クロム、マンガン、鉄、コバルト（以上、２価イオンと３価イオンが存在）、ニッケル（２価イオンの形態でのみ存在）、銅（１価イオンと２価イオンが存在）等の第１遷移系列の遷移金属イオン；イットリウム（３価の形態でのみ存在）、ジルコニウム（４価イオンでの形態で存在することが一般的）、ニオブ（５価イオンの形態で存在することが一般的）、モリブデン（２価イオンから５価イオンの形態で存在することが一般的）、ルテニウム（２価イオンと３価イオンの形態で存在）、ロジウム（１価イオンから４価イオンの形態で存在）、パラジウム（２価イオンと４価イオンの形態で存在）、銀（１価イオンから３価イオンの形態で存在）等の第２遷移系列の遷移金属イオン；およびタンタル（５価イオンの形態で存在することが一般的）、タングステン（２価イオンから５価イオンの形態で存在）、イリジウム（１価イオンから４価イオンの形態で存在）、白金（２価イオンと４価イオンの形態で存在）、金（１価イオンから３価イオンの形態で存在）等の第３遷移系列の遷移金属イオン；セリウム、プラセオジウム（３価イオンと４価イオンの形態で存在）、サマリウム、ユウロピウム（２価イオンと３価イオンの形態で存在）、テルビウム（３価イオンと４価イオンの形態で存在）、イッテルビウム（２価イオンと３価イオンの形態で存在）等の第３遷移系列のランタノイド系列のイオン；からなる群から選択されうる。本発明の一実施形態によれば、前記遷移金属イオンが、銅イオン、ニッケルイオン、鉄イオンおよびマンガンイオンからなる群から選択されうる。かかる実施形態によれば、単体シリコン表面を除去しやすい形に変化させるのに有利と考えられる。 According to one embodiment of the present invention, scandium (existing only in the form of trivalent ions), titanium (existing only in the form of trivalent ions), vanadium, chromium, manganese, iron, cobalt (above, divalent ions). Transition metal ions of the first transition series such as trivalent ions), nickel (existing only in the form of divalent ions), copper (existing monovalent and divalent ions); ittrium (only in the form of trivalents) Existence), zirconium (generally present in the form of tetravalent ions), niobium (generally present in the form of pentavalent ions), molybdenum (generally present in the form of divalent to pentavalent ions) (Generally), ruthenium (exists in the form of divalent and trivalent ions), rhodium (exists in the form of monovalent to tetravalent ions), palladium (exists in the form of divalent and tetravalent ions) , Transition metal ions of the second transition series such as silver (present in the form of monovalent to trivalent ions); and tantalum (generally present in the form of pentavalent ions), tungsten (present in the form of divalent to 5). (Exists in the form of valent ions), Iridium (exists in the form of monovalent to tetravalent ions), Platinum (exists in the form of divalent and tetravalent ions), Gold (exists in the form of monovalent to trivalent ions) Transition metal ions of the third transition series such as (existence); cerium, placeodium (existing in the form of trivalent and tetravalent ions), samarium, europium (existing in the form of divalent and trivalent ions), terbium (3) It can be selected from the group consisting of lanthanoid series ions of the third transition series such as itterbium (present in the form of divalent and trivalent ions), which exists in the form of valent ions and tetravalent ions. According to one embodiment of the present invention, the transition metal ion can be selected from the group consisting of copper ion, nickel ion, iron ion and manganese ion. According to such an embodiment, it is considered advantageous to change the surface of the simple substance silicon into a form that can be easily removed.
本発明の一実施形態によれば、前記遷移金属イオンとしては、好ましくは複数の価数を持つものであり、より好ましくは複数の価数を持つものの内、高いものがよい。かかる実施形態によれば、ポリシリコンの研磨速度向上の効果がより顕著となる。例えば、ニッケルイオンは、２価イオンの形態での形態でのみ存在し、鉄イオンは、２価イオン、３価イオンの複数の価数を有しうるため、複数の価数を持つとの観点で、鉄イオンの方が好ましい。また、鉄イオンで比較すれば、より高い価数を持つ観点で、Ｆｅ２＋よりもＦｅ３＋の方が好ましい。セリウムイオンで比較すれば、より高い価数を持つ観点で、Ｃｅ３＋よりもＣｅ４＋の方が好ましい。 According to one embodiment of the present invention, the transition metal ion preferably has a plurality of valences, and more preferably a high valence among those having a plurality of valences. According to such an embodiment, the effect of improving the polishing rate of polysilicon becomes more remarkable. For example, nickel ions exist only in the form of divalent ions, and iron ions can have a plurality of valences of divalent ions and trivalent ions, and thus have a plurality of valences. Therefore, iron ions are preferable. Further, when compared with iron ions, Fe 3+ is preferable to Fe 2+ from the viewpoint of having a higher valence. When compared with cerium ions, Ce 4+ is preferable to Ce 3+ from the viewpoint of having a higher valence.
本発明の一実施形態によれば、遷移金属イオン源としては、硫酸銅・五水和物、硫酸ニッケル・六水和物、硫酸鉄（ＩＩ）・七水和物、硫酸鉄（ＩＩＩ）・ｎ水和物、硫酸マンガン・五水和物、硫酸スカンジウム・五水和物、硫酸チタン（ＩＩＩ）、塩化バナジウム（ＩＩ）、硫酸バナジウム、硫酸クロム（ＩＩ）水和物、塩化クロム（ＩＩＩ）・六水和物、硫酸コバルト・七水和物、塩化コバルト（ＩＩＩ）、硫酸イットリウム（ＩＩＩ）・八水和物、硫酸ジルコニウム（ＩＶ）・四水和物、塩化ニオブ（Ｖ）、塩化モリブデン（ＩＩＩ）、塩化ルテニウム（ＩＩＩ）、塩化ロジウム（ＩＩＩ）、硝酸ロジウム（ＩＶ）、塩化パラジウム（ＩＩ）、四酢酸パラジウム（ＩＶ）、硝酸銀（Ｉ）、塩化タンタル（Ｖ）、塩化タングステン（Ｖ）、塩化イリジウム（ＩＩＩ）・三水和物、塩化イリジウム（ＩＶ）、塩化金（ＩＩＩ）、硝酸セリウム（ＩＩＩ）・六水和物、硝酸セリウム（ＩＶ）アンモニウム、塩化プラセオジム（ＩＩＩ）・水和物、硫酸サマリウム（ＩＩＩ）・八水和物、硫酸ユウロピウム（ＩＩＩ）・八水和物、硫酸テルビウム（ＩＩＩ）、硫酸イッテルビウム（ＩＩＩ）・八水和物等が好適である。かかる実施形態によれば、容易に水に溶解するなどのハンドリングの点で有利である。 According to one embodiment of the present invention, the transition metal ion source includes copper sulfate / pentahydrate, nickel sulfate / hexahydrate, iron (II) sulfate / heptahydrate, iron (III) sulfate, and the like. n-hydrate, manganese sulfate / pentahydrate, scandium sulfate / pentahydrate, titanium (III) sulfate, vanadium chloride (II), vanadium sulfate, chromium (II) sulfate hydrate, chromium (III) chloride・ Hexahydrate, cobalt sulfate ・ heptahydrate, cobalt chloride (III), yttrium sulfate (III) ・ octahydrate, zirconium sulfate (IV) ・ tetrahydrate, niobium chloride (V), molybdenum chloride (III), ruthenium chloride (III), rhodium (III) chloride, rhodium nitrate (IV), palladium (II) chloride, palladium (IV) tetraacetate, silver nitrate (I), tantalum chloride (V), tungsten chloride (V) ), Iridium chloride (III) / trihydrate, Iridium chloride (IV), gold chloride (III), cerium nitrate (III) / hexahydrate, cerium (IV) nitrate / ammonium chloride, placeodim (III) chloride / water Japanese products, samarium sulfate (III) / octahydrate, europium sulfate (III) / octahydrate, terbium sulfate (III), itterbium sulfate (III) / octahydrate and the like are suitable. According to such an embodiment, it is advantageous in terms of handling such as being easily dissolved in water.
本発明の一実施形態によれば、液体キャリア中に、前記遷移金属イオンが、１０ｍＭ以上含まれることが好ましく、２０ｍＭ以上含まれることがより好ましく、５０ｍＭ以上含まれることがさら好ましい。かかる下限であることによって単体シリコンの研磨速度を向上させるのに十分な金属イオン濃度を確保できる。本発明の一実施形態によれば、液体キャリア中に、前記遷移金属イオンが、１０００ｍＭ以下含まれることが好ましく、５００ｍＭ以下含まれることがより好ましく、１００ｍＭ以下含まれることがさらに好ましい。かかる上限であることによって保管時の析出を抑制する効果がある。 According to one embodiment of the present invention, the transition metal ion is preferably contained in the liquid carrier in an amount of 10 mM or more, more preferably 20 mM or more, and even more preferably 50 mM or more. By setting such a lower limit, a sufficient metal ion concentration can be secured to improve the polishing rate of the simple substance silicon. According to one embodiment of the present invention, the transition metal ion is preferably contained in the liquid carrier in an amount of 1000 mM or less, more preferably 500 mM or less, and further preferably 100 mM or less. By setting such an upper limit, there is an effect of suppressing precipitation during storage.
［研磨用組成物］
本発明の一実施形態によれば、砥粒と、上記の研磨速度向上剤と、を含む、研磨用組成物が提供される。かかる実施形態によれば、単体シリコンの研磨速度向上の効果を効率的に得ることができる。
[Polishing composition]
According to one embodiment of the present invention, there is provided a polishing composition containing abrasive grains and the above-mentioned polishing rate improver. According to such an embodiment, the effect of improving the polishing speed of the simple substance silicon can be efficiently obtained.
（砥粒）
研磨用組成物中に含まれる砥粒は、研磨対象物を機械的に研磨する作用を有し、研磨対象物である単体シリコンの研磨速度を向上させる。
(Abrasive grain)
The abrasive grains contained in the polishing composition have an action of mechanically polishing the object to be polished, and improve the polishing rate of the simple substance silicon which is the object to be polished.
本発明の一実施形態において、砥粒の具体例としては、例えば、シリカ、アルミナ、ジルコニア、チタニア等の金属酸化物からなる粒子が挙げられる。該砥粒は、単独でもまたは２種以上混合して用いてもよい。また、該砥粒は、市販品を用いてもよいし合成品を用いてもよい。これら砥粒の中でも、シリカが好ましく、ヒュームドシリカ、コロイダルシリカがより好ましく、特に好ましいのはコロイダルシリカである。コロイダルシリカの製造方法としては、ケイ酸ソーダ法、ゾルゲル法が挙げられ、いずれの製造方法で製造されたコロイダルシリカであっても、本発明の砥粒として好適に用いられる。しかしながら、高純度で製造できるゾルゲル法により製造されたコロイダルシリカが好ましい。 In one embodiment of the present invention, specific examples of the abrasive grains include particles made of metal oxides such as silica, alumina, zirconia, and titania. The abrasive grains may be used alone or in combination of two or more. Further, as the abrasive grains, a commercially available product or a synthetic product may be used. Among these abrasive grains, silica is preferable, fumed silica and colloidal silica are more preferable, and colloidal silica is particularly preferable. Examples of the method for producing colloidal silica include a sodium silicate method and a sol-gel method, and any colloidal silica produced by any of the production methods is suitably used as the abrasive grains of the present invention. However, colloidal silica produced by the sol-gel method, which can be produced with high purity, is preferable.
本発明の一実施形態において、前記砥粒は、その表面が修飾されてなる砥粒である。その表面が修飾されてない砥粒を用いると、単体シリコンの研磨速度を向上させることができない虞がある。かような砥粒は、例えば、アルミニウム、チタンまたはジルコニウム等の金属あるいはそれらの酸化物を砥粒と混合して砥粒の表面にドープすることや、有機酸やアミノ基等を固定化することにより得ることができる。そのなかでも好ましいのは、有機酸を表面に化学的に結合させたシリカである。 In one embodiment of the present invention, the abrasive grains are abrasive grains whose surface is modified. If abrasive grains whose surface is not modified are used, there is a possibility that the polishing speed of the simple substance silicon cannot be improved. For such abrasive grains, for example, a metal such as aluminum, titanium or zirconium or an oxide thereof is mixed with the abrasive grains and doped on the surface of the abrasive grains, or an organic acid, an amino group or the like is immobilized. Can be obtained by Among them, silica in which an organic acid is chemically bonded to the surface is preferable.
本発明の一実施形態において、前記有機酸は、特に制限されないが、スルホン酸、カルボン酸、リン酸等が挙げられ、好ましくはスルホン酸である。なお、有機酸を表面に固定したシリカは、シリカの表面に上記有機酸由来の酸性基（例えば、スルホ基、カルボキシル基、リン酸基等）が（場合によってはリンカー構造を介して）共有結合により固定されていることになる。ここで、リンカー構造とは、シリカの表面と、有機酸との間に介在する任意の構造を意味する。よって、有機酸を表面に固定したシリカは、シリカの表面に有機酸由来の酸性基が直接共有結合により固定されることによって形成されてもよいし、リンカー構造を介して共有結合により固定されることによって形成されていてもよい。これらの有機酸をシリカ表面へ導入する方法は特に制限されず、メルカプト基やアルキル基等の状態でシリカ表面に導入し、その後、スルホン酸やカルボン酸に酸化するといった方法の他に、上記有機酸基に保護基が結合した状態でシリカ表面に導入し、その後、保護基を脱離させるといった方法がある。 In one embodiment of the present invention, the organic acid is not particularly limited, but examples thereof include sulfonic acid, carboxylic acid, and phosphoric acid, and sulfonic acid is preferable. In silica in which an organic acid is immobilized on the surface, an acidic group derived from the organic acid (for example, a sulfo group, a carboxyl group, a phosphoric acid group, etc.) is covalently bonded to the surface of the silica (in some cases, via a linker structure). Will be fixed by. Here, the linker structure means an arbitrary structure interposed between the surface of silica and the organic acid. Therefore, the silica having the organic acid fixed on the surface may be formed by directly fixing the acidic group derived from the organic acid to the surface of the silica by a covalent bond, or is fixed by a covalent bond via a linker structure. It may be formed by. The method of introducing these organic acids into the silica surface is not particularly limited, and in addition to the method of introducing these organic acids into the silica surface in the state of a mercapto group, an alkyl group, etc. and then oxidizing to a sulfonic acid or a carboxylic acid, the above organic acids There is a method of introducing the protective group onto the surface of the silica with the protective group bonded to the acid group, and then removing the protective group.
有機酸を表面に固定したシリカの具体的な合成方法として、有機酸の一種であるスルホン酸をシリカの表面に固定するのであれば、例えば、“Ｓｕｌｆｏｎｉｃ ａｃｉｄ−ｆｕｎｃｔｉｏｎａｌｉｚｅｄ ｓｉｌｉｃａ ｔｈｒｏｕｇｈ ｑｕａｎｔｉｔａｔｉｖｅ ｏｘｉｄａｔｉｏｎ ｏｆ ｔｈｉｏｌ ｇｒｏｕｐｓ”， Ｃｈｅｍ． Ｃｏｍｍｕｎ． ２４６−２４７ （２００３）に記載の方法で行うことができる。具体的には、３−メルカプトプロピルトリメトキシシラン等のチオール基を有するシランカップリング剤をシリカにカップリングさせた後に過酸化水素でチオール基を酸化することにより、スルホン酸が表面に固定化されたシリカを得ることができる。本発明の実施例のスルホン酸が表面に修飾されているコロイダルシリカも同様にして製造している。 As a specific method for synthesizing silica in which an organic acid is fixed on the surface, if sulfonic acid, which is a kind of organic acid, is fixed on the surface of silica, for example, "Sulphonic acid-functionalized silicon thiol quantative oxidation of thiol groups". , Chem. Commun. It can be carried out by the method described in 246-247 (2003). Specifically, sulfonic acid is immobilized on the surface by coupling a silane coupling agent having a thiol group such as 3-mercaptopropyltrimethoxysilane to silica and then oxidizing the thiol group with hydrogen peroxide. Silane can be obtained. Colloidal silica in which the surface of the sulfonic acid of the example of the present invention is modified is also produced in the same manner.
カルボン酸をシリカの表面に固定するのであれば、例えば、“Ｎｏｖｅｌ Ｓｉｌａｎｅ Ｃｏｕｐｌｉｎｇ Ａｇｅｎｔｓ Ｃｏｎｔａｉｎｉｎｇ ａ Ｐｈｏｔｏ ｌａｂｉｌｅ ２−Ｎｉｔｒｏｂｅｎｚｙｌ Ｅｓｔｅｒ ｆｏｒ Ｉｎｔｒｏｄｕｃｔｉｏｎ ｏｆ ａ Ｃａｒｂｏｘｙ Ｇｒｏｕｐ ｏｎ ｔｈｅ Ｓｕｒｆａｃｅ ｏｆ Ｓｉｌｉｃａ Ｇｅｌ”， Ｃｈｅｍｉｓｔｒｙ Ｌｅｔｔｅｒｓ， ３， ２２８−２２９ （２０００）に記載の方法で行うことができる。具体的には、光反応性２−ニトロベンジルエステルを含むシランカップリング剤をシリカにカップリングさせた後に光照射することにより、カルボン酸が表面に固定化されたシリカを得ることができる。 If the carboxylic acid is to be fixed to the surface of silica, for example, "Novell Silane Coupling Agents Contining a Photolabile 2-Nitrobenzyl Ester for Introducation of a Carboxy Group Silicon It can be carried out by the method described in (2000). Specifically, silica having a carboxylic acid immobilized on the surface can be obtained by coupling silica with a silane coupling agent containing a photoreactive 2-nitrobenzyl ester and then irradiating with light.
本発明の一実施形態において、前記砥粒の平均一次粒子径が１０ｎｍ以上であることが好ましく、１５ｎｍ以上であることがより好ましく、２０ｎｍ以上であることがさらに好ましく、２５ｎｍ以上であることがよりさらに好ましく、３０ｎｍ以上であることがよりさらに好ましい。本発明の一実施形態の研磨用組成物において、前記砥粒の平均一次粒子径が６０ｎｍ以下であることが好ましく、５０ｎｍ以下であることがより好ましく、４０ｎｍ以下であることがさらに好ましい。砥粒が上記の平均一次粒子径を有することによって研磨速度を向上できる効果がある。本発明における平均一次粒子径は、実施例に記載の方法によって測定される値を採用してもよい。 In one embodiment of the present invention, the average primary particle diameter of the abrasive grains is preferably 10 nm or more, more preferably 15 nm or more, further preferably 20 nm or more, and more preferably 25 nm or more. It is more preferably 30 nm or more, and even more preferably 30 nm or more. In the polishing composition of one embodiment of the present invention, the average primary particle diameter of the abrasive grains is preferably 60 nm or less, more preferably 50 nm or less, and further preferably 40 nm or less. When the abrasive grains have the above average primary particle diameter, there is an effect that the polishing speed can be improved. For the average primary particle size in the present invention, a value measured by the method described in Examples may be adopted.
本発明の一実施形態において、前記砥粒の平均二次粒子径が４０ｎｍ以上であることが好ましく、４５ｎｍ以上であることがより好ましく、５０ｎｍ以上であることがさらに好ましく、５５ｎｍ以上であることがよりさらに好ましく、６０ｎｍ以上であることがよりさらに好ましく、６５ｎｍ以上であることがよりさらに好ましい。本発明の一実施形態において、前記砥粒の平均二次粒子径が、１００ｎｍ以下であることが好ましく、９０ｎｍ以下であることがより好ましく、８０ｎｍ以下であることがさらに好ましく、７５ｎｍ以下であることがよりさらに好ましい。砥粒が上記の平均二次粒子径を有することによって研磨速度を向上できる効果がある。本発明における平均二次粒子径は、実施例に記載の方法によって測定される値を採用してもよい。 In one embodiment of the present invention, the average secondary particle diameter of the abrasive grains is preferably 40 nm or more, more preferably 45 nm or more, further preferably 50 nm or more, and more preferably 55 nm or more. Even more preferably, it is even more preferably 60 nm or more, and even more preferably 65 nm or more. In one embodiment of the present invention, the average secondary particle diameter of the abrasive grains is preferably 100 nm or less, more preferably 90 nm or less, further preferably 80 nm or less, and 75 nm or less. Is even more preferable. When the abrasive grains have the above average secondary particle diameter, there is an effect that the polishing speed can be improved. For the average secondary particle size in the present invention, a value measured by the method described in Examples may be adopted.
本発明の一実施形態において、研磨用組成物中の砥粒における、レーザー回折散乱法により求められる粒度分布において、微粒子側から積算粒子質量が全粒子質量の９０％に達するときの粒子の直径Ｄ９０と、１０％に達するときの粒子の直径Ｄ１０との比（本明細書中、単に「Ｄ９０／Ｄ１０」とも称する）の下限は、１．３以上であることが好ましく、１．４以上であることがより好ましく、１．５以上であることがさらに好ましく、１．６以上であることがよりさらに好ましい。かかる下限であることによって研磨速度を向上できる効果がある。本発明の一実施形態において、Ｄ９０／Ｄ１０の上限は、４．０以下であることが好ましく、３．５以下であることがより好ましく、３．０以下であることがさらに好ましく、２．０以下であることがよりさらに好ましい。かかる上限であることによって研磨速度を向上できる効果がある。 In one embodiment of the present invention, in the particle size distribution of the abrasive grains in the polishing composition obtained by the laser diffraction / scattering method, the particle diameter D90 when the integrated particle mass reaches 90% of the total particle mass from the fine particle side. The lower limit of the ratio of the particles to the particle diameter D10 when reaching 10% (also simply referred to as “D90 / D10” in the present specification) is preferably 1.3 or more, preferably 1.4 or more. More preferably, it is more preferably 1.5 or more, and even more preferably 1.6 or more. By setting such a lower limit, there is an effect that the polishing speed can be improved. In one embodiment of the present invention, the upper limit of D90 / D10 is preferably 4.0 or less, more preferably 3.5 or less, further preferably 3.0 or less, and 2.0 or less. The following is even more preferable. By setting such an upper limit, there is an effect that the polishing speed can be improved.
本発明の一実施形態において、前記研磨用組成物中で、前記砥粒の含有量が、０．０１質量％以上であることが好ましく、０．０５質量％以上であることがより好ましく、０．１質量％以上であることがさらに好ましく、０．２質量％以上であることがよりさらに好ましく、０．４質量％以上であることがよりさらに好ましく、０．６質量％以上であることがよりさらに好ましく、０．８質量％以上であることがよりさらに好ましい。かかる下限であることによって研磨速度を向上できる効果がある。本発明の一実施形態において、前記研磨用組成物中で、前記砥粒の含有量が、１０質量％以下であることが好ましく、８質量％以下であることがより好ましく、６質量％以下であることがさらに好ましく、４質量％以下であることがよりさらに好ましく、２質量％以下であることがよりさらに好ましく、１．５質量％以下であることがよりさらに好ましい。かかる上限であることによって研磨用組成物を用いて研磨した後の研磨対象物の表面に欠陥が生じたり表面粗さが増大したりするのを抑えることができる。 In one embodiment of the present invention, the content of the abrasive grains in the polishing composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 0. .1% by mass or more is further preferable, 0.2% by mass or more is further preferable, 0.4% by mass or more is further preferable, and 0.6% by mass or more is preferable. Even more preferably, it is even more preferably 0.8% by mass or more. By setting such a lower limit, there is an effect that the polishing speed can be improved. In one embodiment of the present invention, the content of the abrasive grains in the polishing composition is preferably 10% by mass or less, more preferably 8% by mass or less, and 6% by mass or less. It is even more preferably 4% by mass or less, further preferably 2% by mass or less, and even more preferably 1.5% by mass or less. By setting such an upper limit, it is possible to suppress the occurrence of defects on the surface of the object to be polished and the increase in surface roughness after polishing with the polishing composition.
本発明の一実施形態によれば、研磨用組成物中に、前記遷移金属イオンが、０．１ｍＭ以上含まれることが好ましく、０．５ｍＭ以上含まれることがより好ましく、１ｍＭ以上含まれることがさらに好ましく、１．５ｍＭ以上含まれることがよりさらに好ましく、２ｍＭ以上含まれることがよりさらに好ましく、２．５ｍＭ以上含まれることがよりさらに好ましく、３ｍＭ以上含まれることがよりさらに好ましく、３．５ｍＭ以上含まれることがよりさらに好ましく、４ｍＭ以上含まれることがよりさらに好ましく、４．５ｍＭ以上含まれることがよりさらに好ましい。かかる下限であることによって単体シリコンの研磨速度向上の効果を効率的に得ることができる。本発明の一実施形態によれば、研磨用組成物中に、前記遷移金属イオンが、１００ｍＭ以下含まれることが好ましく、５０ｍＭ以下含まれることがより好ましく、２０ｍＭ以下含まれることがさらに好ましく、１０ｍＭ以下含まれることがより好ましく、９ｍＭ以下含まれることがより好ましく、８ｍＭ以下含まれることがより好ましく、７ｍＭ以下含まれることがより好ましく、６ｍＭ以下含まれることがより好ましく、５．５ｍＭ以下含まれることがより好ましい。かかる上限であることによって研磨用組成物の電気伝導度の過度な上昇を抑え、研磨用組成物の保管安定性を保つ効果がある。本発明の一実施形態によれば、研磨用組成物中に、前記遷移金属イオンが、０．５〜２０ｍＭ含まれる。かかる実施形態によれば、研磨用組成物の保管安定性を保ちつつ単体シリコンの研磨速度向上の効果を効率的に得ることができる。 According to one embodiment of the present invention, the transition metal ion is preferably contained in an amount of 0.1 mM or more, more preferably 0.5 mM or more, and more preferably 1 mM or more in the polishing composition. More preferably, it is more preferably 1.5 mM or more, further preferably 2 mM or more, further preferably 2.5 mM or more, even more preferably 3 mM or more, 3.5 mM. It is even more preferable that it is contained in an amount of 4 mM or more, and it is even more preferable that it is contained in an amount of 4.5 mM or more. By setting such a lower limit, the effect of improving the polishing speed of the simple substance silicon can be efficiently obtained. According to one embodiment of the present invention, the transition metal ion is preferably contained in the polishing composition in an amount of 100 mM or less, more preferably 50 mM or less, further preferably 20 mM or less, and 10 mM. It is more preferably contained below, more preferably 9 mM or less, more preferably 8 mM or less, more preferably 7 mM or less, more preferably 6 mM or less, and more preferably 5.5 mM or less. Is more preferable. By setting such an upper limit, there is an effect of suppressing an excessive increase in the electric conductivity of the polishing composition and maintaining the storage stability of the polishing composition. According to one embodiment of the present invention, the transition metal ion is contained in the polishing composition at 0.5 to 20 mM. According to such an embodiment, the effect of improving the polishing speed of the elemental silicon can be efficiently obtained while maintaining the storage stability of the polishing composition.
［研磨用組成物のｐＨ］
本発明の一実施形態によれば、研磨用組成物のｐＨは、７．０未満の酸性であっても、７．０の中性であっても、７．０超の塩基性であってもよいが、好ましくは、７．０未満である。一般的に、単体シリコンは、酸性領域で研磨速度を向上させ難いことが知られている。本発明によれば、かような研磨速度を向上させ難い酸性の環境下であったとしても、研磨速度を向上させることができる画期的なものである。よって、酸性領域で研磨速度が向上され易いことが知られている窒化ケイ素と、単体シリコンとを研磨する際、酸性領域へのｐＨ設計によって窒化ケイ素の研磨速度を向上させ、単体シリコンの研磨速度向上剤を含有させることによって（酸性領域で研磨速度を向上させ難い）単体シリコンの研磨速度を向上させることができ、窒化ケイ素の研磨速度と、単体シリコンの研磨速度との研磨選択比を１に近づけることができる。本発明の一実施形態において、窒化ケイ素の研磨速度と、単体シリコンの研磨選択比は、０．２〜５が好ましく、０．５〜２がより好ましく、０．８〜１．２がさらに好ましい。
[PH of polishing composition]
According to one embodiment of the present invention, the pH of the polishing composition is more than 7.0 basic, whether it is less than 7.0 acidic or 7.0 neutral. It may be, but preferably less than 7.0. In general, it is known that simple substance silicon is difficult to improve the polishing rate in an acidic region. According to the present invention, even in an acidic environment where it is difficult to improve the polishing rate, the polishing rate can be improved epoch-making. Therefore, when polishing silicon nitride and single silicon, which are known to easily improve the polishing rate in the acidic region, the polishing speed of silicon nitride is improved by designing the pH in the acidic region, and the polishing speed of the single silicon is improved. By containing an improver, the polishing speed of single silicon can be improved (it is difficult to improve the polishing speed in the acidic region), and the polishing selectivity between the polishing speed of silicon nitride and the polishing speed of single silicon is set to 1. You can get closer. In one embodiment of the present invention, the polishing rate of silicon nitride and the polishing selectivity of elemental silicon are preferably 0.2 to 5, more preferably 0.5 to 2, and even more preferably 0.8 to 1.2. ..
本発明の一実施形態によれば、研磨用組成物のｐＨは、６．０未満である。本発明の一実施形態によれば、研磨用組成物のｐＨは、５．０未満である。本発明の一実施形態によれば、研磨用組成物のｐＨは、４．０未満である。本発明の一実施形態によれば、研磨用組成物のｐＨは、３．５以下である。本発明の一実施形態によれば、研磨用組成物のｐＨは、３．０以下である。本発明の一実施形態によれば、研磨用組成物のｐＨは、２．５以下である。本発明の一実施形態によれば、研磨用組成物のｐＨは、２．３以下である。本発明の一実施形態によれば、研磨用組成物のｐＨは、２．２以下である。本発明によれば、かような強い酸性領域の下でも、研磨速度を向上させることができる。本発明の一実施形態によれば、研磨用組成物のｐＨは、１．０以上である。本発明の一実施形態によれば、研磨用組成物のｐＨは、１．２以上である。本発明の一実施形態によれば、研磨用組成物のｐＨは、１．４以上である。本発明の一実施形態によれば、研磨用組成物のｐＨは、１．６以上である。本発明の一実施形態によれば、研磨用組成物のｐＨは、１．８以上である。本発明の一実施形態によれば、研磨用組成物のｐＨは、２．０以上である。ｐＨが高くなるに伴い、単体シリコンの研磨速度を向上させることができる。本発明の一実施形態によれば、研磨用組成物のｐＨは、１〜６である。本発明によれば、かような研磨速度を向上させ難い酸性の環境下であったとしても、単体シリコンの研磨速度を向上させることができる。 According to one embodiment of the present invention, the pH of the polishing composition is less than 6.0. According to one embodiment of the present invention, the pH of the polishing composition is less than 5.0. According to one embodiment of the present invention, the pH of the polishing composition is less than 4.0. According to one embodiment of the present invention, the pH of the polishing composition is 3.5 or less. According to one embodiment of the present invention, the pH of the polishing composition is 3.0 or less. According to one embodiment of the present invention, the pH of the polishing composition is 2.5 or less. According to one embodiment of the present invention, the pH of the polishing composition is 2.3 or less. According to one embodiment of the present invention, the pH of the polishing composition is 2.2 or less. According to the present invention, the polishing rate can be improved even under such a strongly acidic region. According to one embodiment of the present invention, the pH of the polishing composition is 1.0 or higher. According to one embodiment of the present invention, the pH of the polishing composition is 1.2 or higher. According to one embodiment of the present invention, the pH of the polishing composition is 1.4 or higher. According to one embodiment of the present invention, the pH of the polishing composition is 1.6 or higher. According to one embodiment of the present invention, the pH of the polishing composition is 1.8 or higher. According to one embodiment of the present invention, the pH of the polishing composition is 2.0 or higher. As the pH increases, the polishing rate of simple substance silicon can be improved. According to one embodiment of the present invention, the pH of the polishing composition is 1-6. According to the present invention, the polishing rate of elemental silicon can be improved even in an acidic environment where it is difficult to improve the polishing rate.
本発明の一実施形態によれば、研磨用組成物は、ｐＨ調整剤を含む。本発明の一実施形態によれば、ｐＨ調整剤は酸およびアルカリのいずれであってもよく、また、無機化合物および有機化合物のいずれであってもよい。酸の具体例としては、例えば、硫酸、硝酸、ホウ酸、炭酸、次亜リン酸、亜リン酸およびリン酸等の無機酸；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、グリコール酸、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、クエン酸および乳酸等のカルボン酸、ならびにメタンスルホン酸、エタンスルホン酸およびイセチオン酸等の有機硫酸、フィチン酸、ヒドロキシエチリデンジホスホン酸等の有機リン系の酸等の有機酸等が挙げられる。アルカリの具体例としては、水酸化カリウム等のアルカリ金属の水酸化物、アンモニア、エチレンジアミンおよびピペラジン等のアミン、ならびにテトラメチルアンモニウムおよびテトラエチルアンモニウム等の第４級アンモニウム塩が挙げられる。これらｐＨ調整剤は、単独でもまたは２種以上混合しても用いることができる。 According to one embodiment of the present invention, the polishing composition comprises a pH adjuster. According to one embodiment of the present invention, the pH adjuster may be either an acid or an alkali, and may be either an inorganic compound or an organic compound. Specific examples of the acid include inorganic acids such as sulfuric acid, nitrate, boric acid, carbonic acid, hypophosphoric acid, phosphite and phosphoric acid; 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, glycol Acids, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, maleic acid, phthalic acid, malic acid, tartaric acid, carboxylic acids such as citric acid and lactic acid, and methanesulfonic acid Examples thereof include organic sulfuric acids such as ethanesulfonic acid and isethionic acid, organic acids such as phytic acid and organic phosphorus-based acids such as hydroxyethylidene diphosphonic acid. Specific examples of the alkali include hydroxides of alkali metals such as potassium hydroxide, amines such as ammonia, ethylenediamine and piperazine, and quaternary ammonium salts such as tetramethylammonium and tetraethylammonium. These pH adjusters can be used alone or in admixture of two or more.
本発明の一実施形態によれば、研磨用組成物の電気伝導度が、０．１ｍＳ／ｃｍ以上であることが好ましく、０．５ｍＳ／ｃｍ以上であることがより好ましく、１ｍＳ／ｃｍ以上であることがさらに好ましく、２ｍＳ／ｃｍ以上ことがよりさらに好ましく、３ｍＳ／ｃｍ以上ことがよりさらに好ましく、４ｍＳ／ｃｍ以上ことがよりさらに好ましい。かかる実施形態によれば、ｐＨの変動を抑えるバッファー効果を付与することができる。本発明の一実施形態によれば、研磨用組成物の電気伝導度が、２０ｍＳ／ｃｍ以下であることが好ましく、１５ｍＳ／ｃｍ以下であることがより好ましく、１０ｍＳ／ｃｍ以下であることがさらに好ましく、８ｍＳ／ｃｍ以下であることがさらに好ましく、６ｍＳ／ｃｍ以下であることがさらに好ましく、５ｍＳ／ｃｍ以下であることがさらに好ましい。かかる実施形態によれば、砥粒の凝集抑制効果がある。なお、電気伝導度の測定方法は、実施例記載の方法による。また、研磨用組成物の電気伝導度は、研磨速度向上剤の添加量の調整等によって制御することができる。 According to one embodiment of the present invention, the electrical conductivity of the polishing composition is preferably 0.1 mS / cm or more, more preferably 0.5 mS / cm or more, and 1 mS / cm or more. It is even more preferably 2 mS / cm or more, even more preferably 3 mS / cm or more, and even more preferably 4 mS / cm or more. According to such an embodiment, it is possible to impart a buffer effect that suppresses fluctuations in pH. According to one embodiment of the present invention, the electrical conductivity of the polishing composition is preferably 20 mS / cm or less, more preferably 15 mS / cm or less, and further preferably 10 mS / cm or less. It is more preferably 8 mS / cm or less, further preferably 6 mS / cm or less, still more preferably 5 mS / cm or less. According to such an embodiment, there is an effect of suppressing aggregation of abrasive grains. The method for measuring the electrical conductivity is the method described in the examples. Further, the electric conductivity of the polishing composition can be controlled by adjusting the amount of the polishing speed improver added or the like.
［他の成分］
本発明の一実施形態によれば、研磨用組成物は、金属防食剤、防腐剤、防カビ剤、水溶性高分子、難溶性の有機物を溶解するための有機溶媒等の他の成分をさらに含んでもよい。
[Other ingredients]
According to one embodiment of the present invention, the polishing composition further comprises other components such as metal anticorrosives, preservatives, fungicides, water-soluble polymers, organic solvents for dissolving sparingly soluble organics. May include.
本発明の一実施形態によれば、研磨用組成物は、実質的に、酸化剤を含まない。かかる実施形態によれば、単体シリコン表面の過剰な酸化による研磨性能の低下との技術的効果がある。本発明の一実施形態によれば、研磨用組成物は、実質的に、過酸化水素、過酸化ナトリウム、過酸化バリウム、オゾン水、過マンガン酸、クロム酸、重クロム酸、ペルオキソ二硫酸、ペルオキソリン酸、ペルオキソ硫酸、ペルオキソホウ酸、過ギ酸、過酢酸、過安息香酸、過フタル酸、次亜塩素酸、次亜臭素酸、次亜ヨウ素酸、塩素酸、亜塩素酸、過塩素酸、臭素酸、ヨウ素酸、過ヨウ素酸、過硫酸またはジクロロイソシアヌルである、酸化剤を含まない。かかる実施形態によれば、単体シリコン表面の過剰な酸化による研磨性能の低下との技術的効果がある。なお、本明細書中、「実質的に含まない」とは、研磨用組成物中に全く含まない概念の他、研磨用組成物中に、０．０５ｇ／Ｌ以下含む場合を含む。 According to one embodiment of the invention, the polishing composition is substantially free of oxidants. According to such an embodiment, there is a technical effect of reducing the polishing performance due to excessive oxidation of the surface of the simple substance silicon. According to one embodiment of the present invention, the polishing composition is substantially composed of hydrogen peroxide, sodium peroxide, barium peroxide, ozone water, permanganic acid, chloric acid, chloric acid, peroxodisulfuric acid, and the like. Peroxophosphate, peroxosulfuric acid, peroxoboric acid, pergic acid, peracetic acid, perbenzoic acid, perphthalic acid, hypochlorous acid, hypochlorous acid, hypochlorous acid, chloric acid, chloric acid, perchloric acid , Bronic acid, chlorous acid, periodic acid, persulfate or dichloroisocyanul, free of oxidants. According to such an embodiment, there is a technical effect of reducing the polishing performance due to excessive oxidation of the surface of the simple substance silicon. In addition to the concept that "substantially not contained" in the present specification is not contained in the polishing composition at all, it includes the case where the polishing composition contains 0.05 g / L or less.
［研磨用組成物の製造方法］
本発明の一実施形態によれば、研磨用組成物の製造方法は、特に制限されず、例えば、砥粒と、研磨速度向上剤と、必要に応じて他の成分とを、攪拌混合することにより得ることができる。各成分を混合する際の温度は特に制限されないが、１０〜４０℃が好ましく、溶解速度を上げるために加熱してもよい。また、混合時間も特に制限されない。
[Manufacturing method of polishing composition]
According to one embodiment of the present invention, the method for producing the polishing composition is not particularly limited, and for example, the abrasive grains, the polishing speed improver, and other components, if necessary, are stirred and mixed. Can be obtained by The temperature at which each component is mixed is not particularly limited, but is preferably 10 to 40 ° C., and may be heated to increase the dissolution rate. Further, the mixing time is not particularly limited.
［研磨方法］
本発明の一実施形態によれば、上記の研磨用組成物は、単体シリコンの研磨に好適に用いられる。よって、本発明の一実施形態によれば、研磨方法は、上記の研磨用組成物を用いて、または、上記の製造方法によって研磨用組成物を得、当該研磨用組成物を用いて、単体シリコンを含む研磨対象物を研磨することを有する、研磨方法である。
[Polishing method]
According to one embodiment of the present invention, the above polishing composition is suitably used for polishing simple substance silicon. Therefore, according to one embodiment of the present invention, the polishing method uses the above-mentioned polishing composition or the above-mentioned manufacturing method to obtain a polishing composition, and the polishing composition is used as a simple substance. It is a polishing method including polishing an object to be polished containing silicon.
研磨装置としては、研磨対象物を有する基板等を保持するホルダーと回転数を変更可能なモータ等とが取り付けてあり、研磨パッド（研磨布）を貼り付け可能な研磨定盤を有する一般的な研磨装置を使用することができる。 As a polishing device, a holder for holding a substrate or the like having an object to be polished and a motor or the like whose rotation speed can be changed are attached, and a polishing platen to which a polishing pad (polishing cloth) can be attached is generally provided. Polishing equipment can be used.
前記研磨パッドとしては、一般的な不織布、ポリウレタン、および多孔質フッ素樹脂等を特に制限なく使用することができる。研磨パッドには、研磨用組成物が溜まるような溝加工が施されていることが好ましい。 As the polishing pad, general non-woven fabric, polyurethane, porous fluororesin and the like can be used without particular limitation. The polishing pad is preferably grooved so that the polishing composition can be collected.
研磨条件にも特に制限はなく、例えば、研磨定盤の回転速度は、１０〜５００ｒｐｍが好ましく、キャリア回転速度は、１０〜５００ｒｐｍが好ましく、研磨対象物を有する基板にかける圧力（研磨圧力）は、０．１〜１０ｐｓｉが好ましい。研磨パッドに研磨用組成物を供給する方法も特に制限されず、例えば、ポンプ等で連続的に供給する方法が採用される。この供給量に制限はないが、研磨パッドの表面が常に本発明の研磨用組成物で覆われていることが好ましい。 The polishing conditions are also not particularly limited. For example, the rotation speed of the polishing surface plate is preferably 10 to 500 rpm, the carrier rotation speed is preferably 10 to 500 rpm, and the pressure (polishing pressure) applied to the substrate having the object to be polished is , 0.1 to 10 psi is preferable. The method of supplying the polishing composition to the polishing pad is also not particularly limited, and for example, a method of continuously supplying the polishing composition with a pump or the like is adopted. Although the supply amount is not limited, it is preferable that the surface of the polishing pad is always covered with the polishing composition of the present invention.
［半導体基板の製造方法］
本発明の一実施形態によれば、上記の研磨方法を有する、半導体基板の製造方法も提供される。かかる実施形態によって、半導体基板の生産効率が向上する。
[Manufacturing method of semiconductor substrate]
According to one embodiment of the present invention, there is also provided a method for manufacturing a semiconductor substrate having the above polishing method. According to such an embodiment, the production efficiency of the semiconductor substrate is improved.
本発明を、以下の実施例及び比較例を用いてさらに詳細に説明する。ただし、本発明の技術的範囲が以下の実施例のみに制限されるわけではない。なお、特記しない限り、「％」及び「部」は、それぞれ、「質量％」及び「質量部」を意味する。また、下記実施例において、特記しない限り、操作は室温（２５℃）／相対湿度４０〜５０％ＲＨの条件下で行われた。 The present invention will be described in more detail with reference to the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following examples. Unless otherwise specified, "%" and "part" mean "mass%" and "part by mass", respectively. Further, in the following examples, unless otherwise specified, the operation was performed under the conditions of room temperature (25 ° C.) / relative humidity of 40 to 50% RH.
［研磨用組成物の調製］
砥粒（スルホン酸固定コロイダルシリカ；平均一次粒子径：３５ｎｍ、平均二次粒子径：７０ｎｍ、Ｄ９０／Ｄ１０：１．７）と；遷移金属イオンおよび液体キャリア（純水）とからなる研磨速度向上剤と；ｐＨ調整剤としての６０％硫酸と；を表１に示される組成となるように攪拌混合することにより、各研磨用組成物を調製した（混合温度：約２５℃、混合時間：約１０分）。なお、各遷移金属イオンは、表１に示される遷移金属イオン源由来である。また、砥粒の平均一次粒子径は、マイクロメリテックス社製の“Ｆｌｏｗ ＳｏｒｂＩＩ ２３００”を用いて測定されたＢＥＴ法による砥粒の比表面積と、砥粒の密度とから算出した。また、砥粒の平均二次粒子径は、Ｍｉｃｒｏｔｒａｃ社製の“ＵＰＡ−ＵＴ１５１”を用いて測定された動的光散乱法により算出した。
[Preparation of polishing composition]
Abrasive grains (sulfonic acid-fixed colloidal silica; average primary particle size: 35 nm, average secondary particle size: 70 nm, D90 / D10: 1.7); improvement of polishing speed consisting of transition metal ions and liquid carriers (pure water) Each polishing composition was prepared by stirring and mixing the agent and 60% sulfuric acid as a pH adjuster so as to have the composition shown in Table 1 (mixing temperature: about 25 ° C., mixing time: about. 10 minutes). Each transition metal ion is derived from the transition metal ion source shown in Table 1. The average primary particle size of the abrasive grains was calculated from the specific surface area of the abrasive grains by the BET method measured using "Flow SorbII 2300" manufactured by Micromeritex Co., Ltd. and the density of the abrasive grains. The average secondary particle diameter of the abrasive grains was calculated by a dynamic light scattering method measured using "UPA-UT151" manufactured by Microtrac.
［研磨用組成物のｐＨ］
研磨用組成物のｐＨは、ガラス電極式水素イオン濃度指示計（株式会社堀場製作所製 型番：Ｆ−２３）を使用し、標準緩衝液（フタル酸塩ｐＨ緩衝液ｐＨ：４．０１（２５℃）、中性リン酸塩ｐＨ緩衝液ｐＨ：６．８６（２５℃）、炭酸塩ｐＨ緩衝液ｐＨ：１０．０１（２５℃））を用いて３点校正した後で、ガラス電極を研磨用組成物に入れて、２分以上経過して安定した後の値を測定することにより決定した。結果を表１に示す。
[PH of polishing composition]
For the pH of the polishing composition, a glass electrode type hydrogen ion concentration indicator (Horiba Seisakusho Co., Ltd. model number: F-23) was used, and a standard buffer solution (phthalate pH buffer solution pH: 4.01 (25 ° C.)) was used. ), Neutral phosphate pH buffer pH: 6.86 (25 ° C), carbonate pH buffer pH: 10.01 (25 ° C)), and then polish the glass electrode after three-point calibration. It was determined by putting it in the composition and measuring the value after it became stable after 2 minutes or more. The results are shown in Table 1.
［研磨用組成物の電気伝導度］
研磨用組成物調製後の電気伝導度は、卓上型電気伝導度計（株式会社堀場製作所製 型番：ＤＳ−７１）により測定した。結果を表１に示す。
[Electrical conductivity of polishing composition]
The electrical conductivity of the polishing composition after preparation was measured with a desktop electric conductivity meter (HORIBA, Ltd. model number: DS-71). The results are shown in Table 1.
［研磨試験］
実施例１〜５および比較例１〜４において、研磨対象物として、表面に厚さ５０００Åのポリシリコン膜を形成したシリコンウェーハ（３００ｍｍ、ブランケットウェーハ）を使用した。それぞれのシリコンウェーハを６０ｍｍ×６０ｍｍのチップに切断したクーポンを試験片とし、下記の条件により研磨した。
[Polishing test]
In Examples 1 to 5 and Comparative Examples 1 to 4, silicon wafers (300 mm, blanket wafers) having a 5000Å-thick polysilicon film formed on the surface were used as polishing objects. A coupon obtained by cutting each silicon wafer into chips of 60 mm × 60 mm was used as a test piece and polished under the following conditions.
（研磨装置及び研磨条件）
研磨装置：日本エンギス株式会社製ラッピングマシーン ＥＪ−３８０ＩＮ−ＣＨ
研磨圧力：３．０４ｐｓｉ（＝２０．９６ｋＰａ）
パッド：ニッタハース株式会社製 硬質ポリウレタンパッド ＩＣ１０１０
研磨定盤回転数：６０ｒｐｍ
キャリア回転数：４０ｒｐｍ
研磨用組成物の供給：掛け流し
研磨用組成物供給量：１００ｍｌ／分
研磨時間：６０秒間。
(Polishing equipment and polishing conditions)
Polishing device: Wrapping machine EJ-380IN-CH manufactured by Nippon Engis Co., Ltd.
Polishing pressure: 3.04 psi (= 20.96 kPa)
Pad: Rigid polyurethane pad IC1010 manufactured by Nitta Hearth Co., Ltd.
Polishing surface plate rotation speed: 60 rpm
Carrier rotation speed: 40 rpm
Supply of polishing composition: Free-flowing polishing composition supply amount: 100 ml / min Polishing time: 60 seconds.
（研磨速度の評価）
ポリシリコンの研磨速度は、厚みを光学式膜厚測定器（ラムダエースＶＭ−２０３０：大日本スクリーン製造株式会社製）で求め、（研磨前の厚み）−（研磨後の厚み）を研磨時間で除することにより算出した。
(Evaluation of polishing speed)
For the polishing speed of polysilicon, the thickness is determined by an optical film thickness measuring device (Lambda Ace VM-2030: manufactured by Dainippon Screen Mfg. Co., Ltd.), and (thickness before polishing)-(thickness after polishing) is the polishing time. Calculated by dividing.
結果を表１に示す。 The results are shown in Table 1.
＜考察＞
実施例の研磨用組成物は、単体シリコンの研磨速度向上剤が含まれているので、ポリシリコンの研磨速度が顕著に向上している。これに対し、比較例の研磨用組成物は、単体シリコンの研磨速度向上剤を含んでいないので、ポリシリコンの研磨速度を向上できていない。
<Discussion>
Since the polishing composition of the example contains a polishing rate improving agent for elemental silicon, the polishing rate of polysilicon is significantly improved. On the other hand, the polishing composition of the comparative example does not contain the polishing rate improving agent for elemental silicon, so that the polishing rate of polysilicon cannot be improved.
実施例の中でも研磨速度の優劣はあった。これについて考察すると、まず、遷移金属イオンとして、好ましくは複数の価数を持つものであることは上述のとおりである。２価イオンの形態でのみ存在するニッケルイオンを使用した実施例２よりも、複数の価数を持つ遷移金属イオンを使用した実施例１、３〜５の方がポリシリコンの研磨速度を向上させている。また、複数の価数を持つものの内、高いものがよいことも上述のとおりであり、Ｆｅ２＋を使用した実施例３より、Ｆｅ３＋を使用した実施例４の方がポリシリコンの研磨速度を向上させている。 Among the examples, there were superiority and inferiority in polishing speed. Considering this, first, as described above, the transition metal ion preferably has a plurality of valences. Examples 1, 3 to 5 using transition metal ions having a plurality of valences improved the polishing speed of polysilicon as compared with Example 2 using nickel ions existing only in the form of divalent ions. ing. Further, as described above, among those having a plurality of valences, the one having a higher valence is preferable, and the polishing speed of polysilicon is higher in Example 4 using Fe 3+ than in Example 3 using Fe 2+. It is improving.
またメカニズムを考察すると、遷移金属イオンは、ポリシリコン表面をより研磨させやすい（脆い）状態にするための触媒的作用を有するものと推測される。触媒として機能するために、ポリシリコン表面のＳｉ原子に遷移金属イオンが吸着または配位がなされることが必要と推測されるところ、この吸着・配位のし易さの差が触媒活性の差となり、最終的に研磨速度の差として現れているものと考えられる。 Considering the mechanism, it is presumed that the transition metal ion has a catalytic action for making the polysilicon surface more easily polished (brittle). It is presumed that transition metal ions need to be adsorbed or coordinated to Si atoms on the surface of polysilicon in order to function as a catalyst, and this difference in ease of adsorption and coordination is the difference in catalytic activity. It is considered that the difference in polishing speed finally appears.
Claims (13)
請求項１〜７のいずれか１項に記載の研磨速度向上剤と、
を含む、研磨用組成物。 Abrasive grains and
The polishing speed improver according to any one of claims 1 to 7.
A polishing composition, including.
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| JP2015127987A (en) * | 2013-12-27 | 2015-07-09 | 花王株式会社 | Manufacturing method of polishing liquid composition |
| WO2016181889A1 (en) * | 2015-05-08 | 2016-11-17 | 株式会社フジミインコーポレーテッド | Polishing composition |
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| JP2009283951A (en) * | 2002-02-11 | 2009-12-03 | Dupont Air Products Nanomaterials Llc | Free radical-forming activator attached to solid and used to enhance cmp formulation |
| JP2015127987A (en) * | 2013-12-27 | 2015-07-09 | 花王株式会社 | Manufacturing method of polishing liquid composition |
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