JPS61209910A - Production of colloidal silica for polishing - Google Patents
Production of colloidal silica for polishingInfo
- Publication number
- JPS61209910A JPS61209910A JP5166785A JP5166785A JPS61209910A JP S61209910 A JPS61209910 A JP S61209910A JP 5166785 A JP5166785 A JP 5166785A JP 5166785 A JP5166785 A JP 5166785A JP S61209910 A JPS61209910 A JP S61209910A
- Authority
- JP
- Japan
- Prior art keywords
- colloidal silica
- dispersant
- polishing
- ammonium hydroxide
- silica
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Silicon Compounds (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の技術分野〕
本発明は、半導体装置の製造工程でのシリコンウェハの
ポリッシングに使用されるコロイダルシリカの製造方法
に係わる。DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a method for manufacturing colloidal silica used for polishing silicon wafers in the manufacturing process of semiconductor devices.
近年、ＬＳＩ及び超ＬＳＩの製造において、基板となる
シリコンウェハの最終仕上げ工程である鏡面研磨では、
コロダルシリカからなるポリッシング剤が使用されてい
る。In recent years, in the manufacturing of LSI and VLSI, mirror polishing, which is the final finishing process of silicon wafers that serve as substrates, is
A polishing agent consisting of corodal silica is used.
ところで、従来よりポリッシングに使用されるコロイダ
ルシリカは、工業用水ガラス（珪酸ソーダ）を水で希釈
し、シリカ濃度で２〜３％にし、これを陽イオン交換樹
脂を通してＮａ＋等の金属イオンを除去した後、界面活
性剤やＮａ２Ｏが０．４〜０．５６％になるようにＮａ
ＯＨを添加してシリカの分散、安定化を行ない、これを
加熱、濃縮して１０％前後の濃度する方法より製造され
ている。By the way, colloidal silica conventionally used for polishing is made by diluting industrial water glass (sodium silicate) with water to give a silica concentration of 2 to 3%, and passing it through a cation exchange resin to remove metal ions such as Na+. After that, add Na so that the surfactant and Na2O are 0.4 to 0.56%.
It is produced by adding OH to disperse and stabilize silica, and then heating and concentrating it to a concentration of around 10%.
しかしながら、従来方法で製造されたコロイダルシリカ
はＮａ２Ｏを多量に含み、かつＦｅ等の金属も多く含ま
れているため、これをポリッシング剤として用いてウェ
ハの鏡面研磨を行うと、次のような問題を生じる。即ち
、ポリッシング剤中にＮａ＋イオンやＦｅイオン等の金
属イオンが含まれていると、このポリッシング剤で複数
個のＭＯ８ＬＳＩが形成されたウェハの鏡面研磨を行っ
た場合、前記金属イオンはウェハ及び酸化膜中での移動
度が大きいため、ゲート電極とウェハ（基板）との間に
電位差を与え、閾値電圧の変動を招く。特に、超ＬＳＩ
が６４にビット、２５６にビット、１メガピツト、更に
４メガビツトとなって、ＭＯＳトランジスタが微細化さ
れると、前記金属イオンによる閾値電圧の変動は特性上
非常に問題となる。このため、ポリッシング剤に適した
非常に微細（１０〜２０μｍ）で、かつ超高純度のコロ
イダルシリカが要求されている。However, colloidal silica produced by conventional methods contains a large amount of Na2O and also contains large amounts of metals such as Fe, so when using this as a polishing agent to mirror polish a wafer, the following problems occur. occurs. In other words, if the polishing agent contains metal ions such as Na + ions and Fe ions, when a wafer on which a plurality of MO8LSIs are formed is mirror-polished with this polishing agent, the metal ions will be removed from the wafer and oxidized. Since the mobility in the film is high, a potential difference is applied between the gate electrode and the wafer (substrate), causing a fluctuation in the threshold voltage. In particular, very LSI
When MOS transistors are miniaturized to 64 bits, 256 bits, 1 megabit, and then 4 megabits, the variation in threshold voltage due to the metal ions becomes a serious problem in terms of characteristics. For this reason, very fine (10 to 20 μm) and ultra-high purity colloidal silica suitable for polishing agents is required.
本発明は、金属イオンフリーで超高純度であり、かつ安
定性の優れたポリッシング用コロイダルシリカの製造方
法を提供しようとするものである。The present invention aims to provide a method for producing colloidal silica for polishing, which is metal ion-free, has ultra-high purity, and has excellent stability.
本発明は、高純度のケイ酸エステルを水酸化第四アンモ
ニウム及び分散剤の存在下にて加水分解を行うことを特
徴とするものである。かかる本発明によれば、水酸化第
四アンモニウムの存在下でケイ酸エステルを加水分解す
ることによって、該水酸化第四アンモニウムが加水分解
の触媒とシリカ生成後の安定化剤として作用し、かつ分
散剤の添加により生成したシリカを良好に分散でき、既
う
述の如く金属イオンフリーで超高純度であり、かつ安定
性の優れたポリッシング用コロイダルシリカを得ること
ができる。また、このコロイダルシリカを使用してウェ
ハのポリッシングを行うと、含有するシリカ粒子による
機械的研磨がなされると共に、水酸化第四アンモニウム
による化学的研磨がなされ、ウェハへの汚染を招（こと
なく極めて平滑な鏡面仕上げを達成できる。The present invention is characterized in that a highly purified silicate ester is hydrolyzed in the presence of quaternary ammonium hydroxide and a dispersant. According to the present invention, by hydrolyzing a silicate ester in the presence of quaternary ammonium hydroxide, the quaternary ammonium hydroxide acts as a catalyst for hydrolysis and as a stabilizer after silica formation, and By adding a dispersant, the produced silica can be dispersed well, and as mentioned above, colloidal silica for polishing that is free of metal ions, has ultra-high purity, and has excellent stability can be obtained. Furthermore, when wafers are polished using this colloidal silica, mechanical polishing is performed by the silica particles contained therein, and chemical polishing is performed by quaternary ammonium hydroxide, without contaminating the wafers. An extremely smooth mirror finish can be achieved.
上記ケイ酸エステルとしは、例えば一般式Ｓｉ （ＯＲ
）４ （但し、式中のＲは炭素数１〜４のアルキル基
を示す〕にて表わされる有機ケイ酸を挙げることができ
る。具体的には、テトラメトキシシラン、テトラエトキ
シシラン、テトラプロポキシシラン、テトラブトキシシ
ラン等を挙げることができる。こうしたケイ酸エステル
は、精製塔で精製した高純度のものを使用することが必
要である。The above-mentioned silicate ester is, for example, the general formula Si (OR
) 4 (However, R in the formula represents an alkyl group having 1 to 4 carbon atoms.) Specific examples include tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane. , tetrabutoxysilane, etc. It is necessary to use highly pure silicic acid esters purified in a purification tower.
上記水酸化第四アンモニウムとしては、一般式（但し、
式中のＲ１−Ｒ４は炭素数１〜４のアルキル基又はアル
カノール基を示す）にて表わされるものを挙げることが
できる。具体的には、水酸化テトラメチルアンモニウム
、水酸化テトラエチルアンモニウム、水酸化トリメチル
エタノールアンモニウム、水酸化トリエチルエタノール
アンモニラ云等を挙げることができる。こうした水酸化
第四アンモニウムは、最終のコロイダルシリカとした状
態で濃度０．５〜１０％、ｐＨ９〜１０の範囲となるよ
うに添加することが望ましい。この理由は、水酸化第四
アンモニウムの濃度を０．５％未満にすると、コロイダ
ルシリカの安定化作用等を充分に達成できず、かといっ
てその濃度が１０％を越えると、シリカ粒子として存在
しなくなり、ポリッシング作用を充分に達成することが
困難となる。The quaternary ammonium hydroxide mentioned above has the general formula (however,
In the formula, R1 to R4 represent an alkyl group or an alkanol group having 1 to 4 carbon atoms. Specific examples include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylethanolammonium hydroxide, and triethylethanolammonium hydroxide. It is desirable to add such quaternary ammonium hydroxide so that the final colloidal silica has a concentration of 0.5 to 10% and a pH of 9 to 10. The reason for this is that if the concentration of quaternary ammonium hydroxide is less than 0.5%, the stabilizing effect of colloidal silica cannot be sufficiently achieved, whereas if the concentration exceeds 10%, it will exist as silica particles. This makes it difficult to achieve a sufficient polishing effect.
上記分散剤としは、カチオン、アニオン、非イオン及び
両性の水溶性界面活性剤等を使用できるが、特にポリオ
キシエチレンノニールフエニール工−チル（花王社製商
品名：エマルゲン９１０〜９１５）等の非イオン界面活
性剤が望ましい。こうした水溶性界面活性剤は、最終の
コロイダルシリカとした状態で濃度０．０１〜０．００
１％の範囲で添加することが望ましい。この理由は、水
溶性界面活性剤の濃度が上記範囲を逸脱すると、該活性
剤の添加によるシリカ粒子の分散性を発揮できなくなる
恐れがある。As the above-mentioned dispersant, cationic, anionic, nonionic, amphoteric water-soluble surfactants, etc. can be used, and in particular, polyoxyethylene nonyl phenylated surfactants (product name: Emulgen 910-915, manufactured by Kao Corporation), etc. A nonionic surfactant is preferred. These water-soluble surfactants have a concentration of 0.01 to 0.00 in the final colloidal silica state.
It is desirable to add in a range of 1%. The reason for this is that if the concentration of the water-soluble surfactant deviates from the above range, there is a possibility that the dispersibility of the silica particles cannot be achieved due to the addition of the surfactant.
なお、上述した方法で加水分解することにより調製され
たシリカを含む溶液を加熱、濃縮することにより、所定
のシリカ濃度（通常５〜２０％濃度）のコロイダルシリ
カを製造する。Note that colloidal silica having a predetermined silica concentration (usually 5 to 20% concentration) is produced by heating and concentrating a solution containing silica prepared by hydrolysis using the method described above.
以下、本発明の実施例を詳細に説明する。 Examples of the present invention will be described in detail below.
実施例１
まず、テトラメトキシシラン１９０９
（１，２５ｍｏｌ ）と水酸化トリメチルエタノールア
ンモニウムの１０％水溶液５Ｑｃｃとポリオキシエチレ
ンノニールフエニールエーテルの１％水溶液１０ｃｃと
純水２３１０ｇとを、直径６ａｍ、２４段のスタティッ
クミキサにより充分に混合しながら、加水分解してシリ
カ濃度が約３％の溶液を調製した。次いで、この溶液を
６０〜７０℃の温度下にて減圧濃縮してシリカ濃度が約
１０％のコロイダルシリカを製造した。Example 1 First, tetramethoxysilane 1909 (1.25 mol), 5 Q cc of a 10% aqueous solution of trimethylethanol ammonium hydroxide, 10 cc of a 1% aqueous solution of polyoxyethylene nonyl phenyl ether, and 2310 g of pure water were placed in a tube with a diameter of 6 am and a 24 A solution having a silica concentration of about 3% was prepared by hydrolysis while thoroughly mixing with a stage static mixer. Next, this solution was concentrated under reduced pressure at a temperature of 60 to 70°C to produce colloidal silica having a silica concentration of about 10%.
実施例２
まず、テトラメトキシシラン１９０９（１，２５ｍｏｌ
）と水酸化テトラメチルアンモニウムの１０％水溶液６
０ｃｃとポリオキシエチレンノニールフエニールエーテ
ルの１％水溶液１０ＣＯと純水２３１（ｌとを、直径６
履、２４段のスタティックミキサにより充分に混合しな
がら、加水分解してシリカ濃度が約３％の溶液を調製し
た。次いで、この溶液を６０〜７０’Ｃの濃度下にて減
圧濃縮してシリカ濃度が約１０％のコロイダルシリカを
製造した。Example 2 First, tetramethoxysilane 1909 (1.25 mol
) and a 10% aqueous solution of tetramethylammonium hydroxide 6
0cc, 1% aqueous solution of polyoxyethylene nonyl phenyl ether, 10CO, and pure water 231 (l), diameter 6
A solution having a silica concentration of about 3% was prepared by hydrolysis while thoroughly mixing using a 24-stage static mixer. Next, this solution was concentrated under reduced pressure at a concentration of 60 to 70'C to produce colloidal silica having a silica concentration of about 10%.
比較例
まず、工業用水ガラス（珪酸ソーダ）を水で希釈し、シ
リカ濃度で２〜３％にし、これを陽イオン交換膜を通し
てＮａ”等の金属イオンを除去した。つづいて、この溶
液に界面活性剤やＮａ２Ｏを０．４〜０．５６％添加し
てシリカの分散、安定化を行なった後、加熱濃縮してシ
リカ温度約１０％のコロイダルシリカを製造した。Comparative Example First, industrial water glass (sodium silicate) was diluted with water to give a silica concentration of 2 to 3%, and was passed through a cation exchange membrane to remove metal ions such as Na. After dispersing and stabilizing the silica by adding an activator and Na2O in an amount of 0.4 to 0.56%, the mixture was heated and concentrated to produce colloidal silica having a silica temperature of about 10%.
しかして、本実施例１．２及び比較例により製造したコ
ロイダルシリカについて、それらの物性を下記第１表に
、不純物分析結果を下記第２表に夫々示した。The physical properties of the colloidal silica produced in Example 1.2 and Comparative Example are shown in Table 1 below, and the results of impurity analysis are shown in Table 2 below.
上記第２表から明らかなように、本実施例１．２により
得たコロイダルシリカは従来のコロイダルシリカに比べ
てＮａ５Ｆｅ等の金属が著しく少なく、超高純度のもの
であることが分る。As is clear from Table 2 above, the colloidal silica obtained in Example 1.2 contains significantly less metals such as Na5Fe than conventional colloidal silica, and is of ultra-high purity.
また、本実施例１．２のコロイダルシリカを用いてＭＯ
８ＬＳＩが複数個造られたシリコンウェハのポリッシン
グを行ったところ、ウェハ裏面を著しく平滑に鏡面仕上
げできると共に、ポリッシング中での各ＬＳＩへのＮａ
＋イオン等による汚染、閾値電圧の変動は認められなか
った。Furthermore, using the colloidal silica of Example 1.2, MO
When we polished a silicon wafer on which multiple 8LSIs were fabricated, we were able to achieve a very smooth mirror finish on the backside of the wafer, and the Na
No contamination by + ions, etc., and no variation in threshold voltage were observed.
（発明の効果）
以上詳述した如く、本発明によれば金属イオンフリーで
超高純度であり、かつ安定性の優れたポリッシング用コ
ロイダルシリカを製造でき、ひいてはこのコロイダルシ
リカを使用してシリコンウェハのポリッシングを行うこ
とによりウェハへの汚染を招くことなく、極めて平滑な
鏡面仕上げを達成できる等顕著な効果を有する。(Effects of the Invention) As detailed above, according to the present invention, it is possible to produce colloidal silica for polishing which is free of metal ions, has ultra-high purity, and has excellent stability. This polishing has remarkable effects such as achieving an extremely smooth mirror finish without contaminating the wafer.
Claims (4)
ム及び分散剤の存在下にて加水分解を行うことを特徴と
するポリッシング用コロイダルシリカの製造方法。(1) A method for producing colloidal silica for polishing, which comprises hydrolyzing a high-purity silicate ester in the presence of quaternary ammonium hydroxide and a dispersant.
にて表わされるものであることを特徴とする特許請求の
範囲第１項記載のポリッシング用コロイダルシリカの製
造方法。(2) The silicate ester has the general formula Si(OR)_4 [However, R in the formula represents an alkyl group having 1 to 4 carbon atoms]
2. A method for producing colloidal silica for polishing according to claim 1, characterized in that:
ル基又はアルカノール基を示す〕にて表わされるもので
あることを特徴とする特許請求の範囲第１項記載のポリ
ッシング用コロイダルシリカの製造方法。(3) Quaternary ammonium hydroxide is represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, R_1 to R_4 in the formula represent an alkyl group or an alkanol group having 1 to 4 carbon atoms] 2. A method for producing colloidal silica for polishing according to claim 1.
る特許請求の範囲第１項記載のポリッシング用コロイダ
ルシリカの製造方法。(4) The method for producing colloidal silica for polishing according to claim 1, wherein the dispersant is a water-soluble surfactant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5166785A JPS61209910A (en) | 1985-03-15 | 1985-03-15 | Production of colloidal silica for polishing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5166785A JPS61209910A (en) | 1985-03-15 | 1985-03-15 | Production of colloidal silica for polishing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61209910A true JPS61209910A (en) | 1986-09-18 |
| JPH0456774B2 JPH0456774B2 (en) | 1992-09-09 |
Family
ID=12893231
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5166785A Granted JPS61209910A (en) | 1985-03-15 | 1985-03-15 | Production of colloidal silica for polishing |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61209910A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000080349A (en) * | 1998-09-04 | 2000-03-21 | Speedfam-Ipec Co Ltd | Abrasive composition and processing method of silicon wafer using same |
| JP2007214173A (en) * | 2006-02-07 | 2007-08-23 | Nippon Chem Ind Co Ltd | Polishing composition for polishing semiconductor wafer, method for manufacturing the same, and polishing method |
| JP2007284341A (en) * | 2002-08-19 | 2007-11-01 | Hoya Corp | Methods for production of glass substrate for mask blank, mask blank, transfer mask, semiconductor device, glass substrate for mask blank, and mask blank and transfer mask |
| JP2008270584A (en) * | 2007-04-23 | 2008-11-06 | Nippon Chem Ind Co Ltd | Polishing composition for semiconductor wafer and polishing processing method |
| US7732101B2 (en) | 2002-08-19 | 2010-06-08 | Hoya Corporation | Method of producing a glass substrate for a mask blank by polishing with an alkaline polishing liquid that contains colloidal silica abrasive grains |
| JP2010182811A (en) * | 2009-02-04 | 2010-08-19 | Nippon Chem Ind Co Ltd | Semiconductor wafer polishing composition and method of manufacturing the same |
| JP2011219358A (en) * | 2004-02-25 | 2011-11-04 | Hoya Corp | Method for manufacturing glass substrate for mask blank, method for manufacturing mask blank, method for manufacturing exposure mask, method for manufacturing reflective mask blank and method for manufacturing reflective mask blank |
| WO2021153502A1 (en) | 2020-01-28 | 2021-08-05 | 三菱ケミカル株式会社 | Silica particles, silica sol, polishing composition, polishing method, method for manufacturing semiconductor wafer, and method for manufacturing semiconductor device |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5080061B2 (en) * | 2005-11-10 | 2012-11-21 | 多摩化学工業株式会社 | Method for producing neutral colloidal silica |
-
1985
- 1985-03-15 JP JP5166785A patent/JPS61209910A/en active Granted
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000080349A (en) * | 1998-09-04 | 2000-03-21 | Speedfam-Ipec Co Ltd | Abrasive composition and processing method of silicon wafer using same |
| JP2007284341A (en) * | 2002-08-19 | 2007-11-01 | Hoya Corp | Methods for production of glass substrate for mask blank, mask blank, transfer mask, semiconductor device, glass substrate for mask blank, and mask blank and transfer mask |
| US7732101B2 (en) | 2002-08-19 | 2010-06-08 | Hoya Corporation | Method of producing a glass substrate for a mask blank by polishing with an alkaline polishing liquid that contains colloidal silica abrasive grains |
| JP4526547B2 (en) * | 2002-08-19 | 2010-08-18 | Ｈｏｙａ株式会社 | Mask blank glass substrate manufacturing method, mask blank manufacturing method, EUV reflective mask blank manufacturing method, transfer mask manufacturing method, EUV reflective mask manufacturing method, and semiconductor device manufacturing method |
| JP2011219358A (en) * | 2004-02-25 | 2011-11-04 | Hoya Corp | Method for manufacturing glass substrate for mask blank, method for manufacturing mask blank, method for manufacturing exposure mask, method for manufacturing reflective mask blank and method for manufacturing reflective mask blank |
| JP2007214173A (en) * | 2006-02-07 | 2007-08-23 | Nippon Chem Ind Co Ltd | Polishing composition for polishing semiconductor wafer, method for manufacturing the same, and polishing method |
| JP2008270584A (en) * | 2007-04-23 | 2008-11-06 | Nippon Chem Ind Co Ltd | Polishing composition for semiconductor wafer and polishing processing method |
| JP2010182811A (en) * | 2009-02-04 | 2010-08-19 | Nippon Chem Ind Co Ltd | Semiconductor wafer polishing composition and method of manufacturing the same |
| WO2021153502A1 (en) | 2020-01-28 | 2021-08-05 | 三菱ケミカル株式会社 | Silica particles, silica sol, polishing composition, polishing method, method for manufacturing semiconductor wafer, and method for manufacturing semiconductor device |
| KR20220131926A (en) | 2020-01-28 | 2022-09-29 | 미쯔비시 케미컬 주식회사 | Silica particles, silica sol, polishing composition, polishing method, semiconductor wafer manufacturing method and semiconductor device manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0456774B2 (en) | 1992-09-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6159865A (en) | Wafer treating solution and method for preparing the same | |
| JP4643085B2 (en) | Method for producing high-purity colloidal silica for abrasives | |
| JP4712556B2 (en) | Alkali-resistant vertical colloidal silica particles and method for producing the same | |
| JP5599440B2 (en) | Deformed silica sol | |
| JPH0350112A (en) | Aqueous colloid dispersion liquid for fumed silica and manufacture thereof | |
| JP5270344B2 (en) | Silica sol and method for producing the same | |
| US5226930A (en) | Method for preventing agglomeration of colloidal silica and silicon wafer polishing composition using the same | |
| JP2009234908A (en) | Method of manufacturing fumed metal oxide dispersion | |
| JPS61209910A (en) | Production of colloidal silica for polishing | |
| JP5221517B2 (en) | Aluminum modified colloidal silica and method for producing the same | |
| TWI741116B (en) | Silica particle dispersion liquid and its manufacturing method | |
| JP4113288B2 (en) | Polishing composition and silicon wafer processing method using the same | |
| JP2005060219A (en) | Silica sol and manufacturing method therefor | |
| JPH0713956B2 (en) | How to etch silicon | |
| JP2926915B2 (en) | Elongated silica sol and method for producing the same | |
| JP4549878B2 (en) | Method for producing high-purity aqueous silica sol | |
| JP2001294417A (en) | Method of producing colloidal silica | |
| EP0371147A1 (en) | Abrasive composition for silicon wafer | |
| CN1194288A (en) | Nanometer silicon dioxide polishing agent and its preparing method | |
| US20020170237A1 (en) | Polishing slurry for the chemical-mechanical polishing of silica films | |
| JP2002338951A (en) | Hydrothermally treated colloidal silica for polishing agent | |
| JPS61209909A (en) | Production of colloidal silica for polishing | |
| CN101121520A (en) | Acidic silicon dioxide sol and its preparation method and use | |
| CN113980579A (en) | Chemical mechanical polishing slurry and preparation method thereof | |
| JPH05275406A (en) | Sulfuric acid composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |