JP5636833B2 - Method of analyzing nitric acid in mixed acid solution containing nitric acid - Google Patents
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Description
本発明は硝酸含有混酸液中の硝酸分析方法に関する。 The present invention relates to a method for analyzing nitric acid in a mixed acid solution containing nitric acid.
薄膜トランジスタ駆動液晶表示装置（ＴＦＴ−ＬＣＤ）の製造における配線材料としては、Ａｌ合金及びＭｏ合金との積層膜が使用されている。積層金属配線のエッチング液には、例えば、燐酸・硝酸・酢酸・水を含む混酸液が使用される。積層金属配線のエッチングにおいては、エッチング形状を良好に保つため、エッチング液の各成分量を０．３重量％の範囲でコントロールしている。したがって、積層金属配線のエッチング液には、安定した液組成での供給が求められる。そのため、各成分を高い精度で分析することが要求され、分析の誤差範囲は±０．１重量％であることが必要とされている。 As a wiring material in manufacturing a thin film transistor driving liquid crystal display device (TFT-LCD), a laminated film of an Al alloy and a Mo alloy is used. For example, a mixed acid solution containing phosphoric acid, nitric acid, acetic acid, and water is used as the etching solution for the laminated metal wiring. In the etching of the laminated metal wiring, the amount of each component of the etching solution is controlled in the range of 0.3% by weight in order to keep the etching shape good. Therefore, it is required to supply the etching solution for the laminated metal wiring with a stable liquid composition. Therefore, it is required to analyze each component with high accuracy, and the error range of analysis is required to be ± 0.1% by weight.
金属エッチングプロセスに用いる混酸液の定量分析方法として、硝酸の濃度は紫外吸光光度法によって定量し、リン酸の濃度は混酸液のドライアップ後の中和滴定法によって定量し、酢酸の濃度は合計酸当量からの硝酸当量とリン酸当量の差し引き法によって算出する方法が提案されている（特許文献１）。 As a quantitative analysis method of the mixed acid solution used in the metal etching process, the concentration of nitric acid is determined by ultraviolet absorption photometry, the concentration of phosphoric acid is determined by neutralization titration after dry-up of the mixed acid solution, and the acetic acid concentration is the total There has been proposed a method of calculating by subtracting the nitric acid equivalent and the phosphoric acid equivalent from the acid equivalent (Patent Document 1).
しかしながら、不純物としてＭｏイオンを含む硝酸含有混酸液の場合、硝酸の濃度は紫外吸光光度法によっては精度よく定量することが出来ない。 However, in the case of a nitric acid-containing mixed acid solution containing Mo ions as impurities, the concentration of nitric acid cannot be accurately quantified by ultraviolet absorption photometry.
本発明は、上記実情に鑑みなされたものであり、その目的は、Ｍｏイオンを含む硝酸含有混酸液の場合であっても硝酸を十分な精度で分析することが出来る、硝酸含有混酸液中の硝酸分析方法を提供することにある。 The present invention has been made in view of the above circumstances, and its purpose is to be able to analyze nitric acid with sufficient accuracy even in the case of a nitric acid-containing mixed acid solution containing Mo ions. It is to provide a method for analyzing nitric acid.
本発明者は、鋭意検討を重ねた結果、中和滴定を特定の溶媒の存在下で行うことにより上記の目的を達成し得るとの知見を得た。 As a result of intensive studies, the present inventor has found that the above-described object can be achieved by performing neutralization titration in the presence of a specific solvent.
すなわち、本発明の要旨は、硝酸含有混酸液中の硝酸分析方法であって、脂肪族アルコールと脂肪族ケトンとの混合溶媒に試料を溶解してアルカリで中和滴定することを特徴とする硝酸含有混酸液中の硝酸分析方法に存する。 That is, the gist of the present invention is a method for analyzing nitric acid in a mixed acid solution containing nitric acid, wherein a sample is dissolved in a mixed solvent of an aliphatic alcohol and an aliphatic ketone, and neutralized titration with an alkali. The method lies in a method for analyzing nitric acid in a mixed acid solution.
本発明によれば前記の課題が達成される。 According to the present invention, the above-described problems are achieved.
以下、本発明を詳細に説明する。本発明の分析対象となる混酸液は、硝酸とリン酸と酢酸とを含み、必要に応じて界面活性剤などの添加剤を含む水溶液であり、水を含む上記の必須成分基準の一般的な組成の一例は、次の通りである。すなわち、硝酸濃度は、通常０．１〜２０重量％、好ましくは０．５〜１２重量％、更に好ましくは３〜８重量％、リン酸濃度は、通常５０〜８０重量％、好ましくは７０〜８０重量％、酢酸濃度は、通常２〜２０重量％、好ましくは２〜１０重量％、水濃度１〜２０重量である。また、添加剤としては、界面活性剤の他、フッ化アンモニウム、錯化剤などが挙げられ、これらの濃度は、通常０．００１〜１重量％、好ましくは０．０１〜１重量％、更に好ましくは０．２〜０．５重量％である。上記の混酸液は積層金属配線のエッチング液として使用され、そして、エッチング液の各成分量が定量され、その結果に基づいて濃度コントローが行われる。
Hereinafter, the present invention will be described in detail. The mixed acid solution to be analyzed in the present invention is an aqueous solution containing nitric acid, phosphoric acid and acetic acid, and optionally containing an additive such as a surfactant. An example of the composition is as follows. That is, the nitric acid concentration is usually 0.1 to 20% by weight, preferably 0.5 to 12% by weight, more preferably 3 to 8% by weight, and the phosphoric acid concentration is usually 50 to 80% by weight, preferably 70 to 80% by weight and acetic acid concentration are usually 2 to 20% by weight, preferably 2 to 10% by weight, and
本発明の硝酸分析方法は、アルカリによる中和滴定法であり、その特徴は脂肪族アルコールと脂肪族ケトンとの混合溶媒の存在下に中和滴定を行う点にある。 The nitric acid analysis method of the present invention is a neutralization titration method using an alkali, and is characterized in that neutralization titration is performed in the presence of a mixed solvent of an aliphatic alcohol and an aliphatic ketone.
脂肪族アルコールとしては、例えば、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール等の炭素数が通常６以下の低級アルコールが使用され、脂肪族ケトンとしては、例えは、アセトン、メチルエチルケトン、ジエチルケトン等の炭素数が通常６以下の低級ケトンが使用される。これらの中では特にメタノールとアセトンとの混合溶媒が好ましい。また、脂肪族アルコール／脂肪族ケトンの比率は、通常３／１〜１／２であり、好ましくは２／１〜１／１である。そして、中和滴定法において、試料としての硝酸含有混酸液の使用量は通常０．５〜２ｇであり、混合溶媒の使用量は通常５０〜１００ｍｌである。 As the aliphatic alcohol, for example, a lower alcohol having usually 6 or less carbon atoms such as methanol, ethanol, propanol, isopropanol, and butanol is used. As the aliphatic ketone, for example, carbon such as acetone, methyl ethyl ketone, and diethyl ketone. A lower ketone having a number of usually 6 or less is used. Among these, a mixed solvent of methanol and acetone is particularly preferable. The ratio of aliphatic alcohol / aliphatic ketone is usually from 3/1 to 1/2, and preferably from 2/1 to 1/1. And in the neutralization titration method, the usage-amount of the nitric acid containing mixed acid liquid as a sample is 0.5-2g normally, and the usage-amount of a mixed solvent is 50-100 ml normally.
中和滴定法は、市販の自動滴定装置、例えば、三菱化学アナリテック社製の自動的滴定装置「ＧＴ−１００型」を使用して行うことが出来、滴定用アルカリとしては通常１ｍｏｌ／Ｌの苛性ソーダ水溶液が使用される。自動滴定装置の場合、測定結果の中和点は表示装置上にピークとして表示される。 The neutralization titration method can be performed using a commercially available automatic titration apparatus, for example, an automatic titration apparatus “GT-100 type” manufactured by Mitsubishi Chemical Analytech Co., Ltd. An aqueous caustic soda solution is used. In the case of an automatic titrator, the neutralization point of the measurement result is displayed as a peak on the display device.
本発明の硝酸分析方法によれば、特定の混合溶媒の存在下に中和滴定することにより、Ｍｏイオンを含む硝酸含有混酸液の場合であっても、分析のバラツキ３σは０．２以下、分析精度は±０．１ｗｔ％以内の結果が得られる。 According to the nitric acid analysis method of the present invention, by performing neutralization titration in the presence of a specific mixed solvent, even in the case of a nitric acid-containing mixed acid solution containing Mo ions, the analysis variation 3σ is 0.2 or less, The analysis accuracy is within ± 0.1 wt%.
なお、硝酸含有混酸液中のリン酸の定量分析は、例えば、特開２００２−３０３６１９号公報の方法、すなわち、混酸液のドライアップ後の中和滴定法によって行うことが出来、また、酢酸のの定量分析は、イオンクロマト装置やＴＯＣ計を利用した公知の方法によって行うことが出来る。 The quantitative analysis of phosphoric acid in the nitric acid-containing mixed acid solution can be performed, for example, by the method of JP-A-2002-303619, that is, neutralization titration after dry-up of the mixed acid solution. The quantitative analysis can be performed by a known method using an ion chromatograph or a TOC meter.
以下、本発明を参考例および実施例により更に詳細に説明するが、本発明は、その要旨を超えない限り、以下の実施例に限定されるものではない。なお、以下の諸例においては、中和滴定装置として三菱化学アナリテック社製の自動的滴定装置「ＧＴ−１００型」を使用し、滴定用アルカリとして１ｍｏｌ／Ｌの苛性ソーダ水溶液を使用した。 EXAMPLES Hereinafter, although a reference example and an Example demonstrate this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded. In the following examples, an automatic titration device “GT-100” manufactured by Mitsubishi Chemical Analytech Co., Ltd. was used as a neutralization titration device, and a 1 mol / L aqueous caustic soda solution was used as a titration alkali.
参考例１：
硝酸濃度１４．８重量％、リン酸濃度５９．９重量％、酢酸濃度５．０重量％の混酸液（残余は水）を調製した。この混酸液０．９ｇをそのまま試料として中和滴定を行った。図１に測定結果のチャートを示す。図１中のピーク（１）は硝酸＋酢酸＋リン酸（第１変曲点）に相当し、ピーク（２）はリン酸（第２変曲点＋第３変曲点）に相当する。この結果から、混酸液をそのまま中和滴定しても硝酸の単独ピークは得られないことが分かる。
Reference example 1:
A mixed acid solution having a nitric acid concentration of 14.8% by weight, a phosphoric acid concentration of 59.9% by weight, and an acetic acid concentration of 5.0% by weight (the balance being water) was prepared. Neutralization titration was performed using 0.9 g of this mixed acid solution as a sample. FIG. 1 shows a measurement result chart. The peak (1) in FIG. 1 corresponds to nitric acid + acetic acid + phosphoric acid (first inflection point), and the peak (2) corresponds to phosphoric acid (second inflection point + third inflection point). From this result, it is understood that a single peak of nitric acid cannot be obtained even if neutralization titration of the mixed acid solution is performed as it is.
参考例２：
参考例１において、混酸液にＭｏ濃度として２，０００ｐｐｍとなるようにＭｏを溶解し、これを試料として使用した以外は参考例１と同じように中和滴定を行った。図２に測定結果のチャートを示す。図２中のピーク（１）及びピーク（２）は図１中のものと実質的に同じであり、この結果から、混酸液の中和滴定はＭｏによって何ら影響されないことが分かる。
Reference example 2:
In Reference Example 1, neutralization titration was performed in the same manner as in Reference Example 1 except that Mo was dissolved in the mixed acid solution so that the Mo concentration was 2,000 ppm and this was used as a sample. FIG. 2 shows a measurement result chart. Peak (1) and peak (2) in FIG. 2 are substantially the same as those in FIG. 1, and it can be seen from this result that neutralization titration of the mixed acid solution is not affected at all by Mo.
参考例３：
リン酸濃度５９．９重量％の酸液を調製した。この酸液０．８ｇにメタノールとアセトン（１：１容量比）の混合溶媒５０ｍｌを添加したものを試料として中和滴定を行った。図３に測定結果のチャートを示す。図３中のピーク（１）はリン酸（第１変曲点）に相当し、ピーク（２）はリン酸（第２変曲点＋第３変曲点）に相当する。
Reference Example 3:
An acid solution having a phosphoric acid concentration of 59.9% by weight was prepared. Neutralization titration was carried out using a sample obtained by adding 50 ml of a mixed solvent of methanol and acetone (1: 1 volume ratio) to 0.8 g of this acid solution. FIG. 3 shows a measurement result chart. The peak (1) in FIG. 3 corresponds to phosphoric acid (first inflection point), and the peak (2) corresponds to phosphoric acid (second inflection point + third inflection point).
参考例４：
リン酸濃度５９．９重量％、酢酸濃度５．０重量％の混酸液（残余は水）を調製した。この混酸液０．８ｇにメタノールとアセトン（１：１容量比）の混合溶媒５０ｍｌを添加したものを試料として中和滴定を行った。図４に測定結果のチャートを示す。図４中のピーク（１）は酢酸＋リン酸（第１変曲点）に相当し、ピーク（２）はリン酸（第２変曲点＋第３変曲点）に相当する。
Reference example 4:
A mixed acid solution having a phosphoric acid concentration of 59.9% by weight and an acetic acid concentration of 5.0% by weight (the balance being water) was prepared. Neutralization titration was performed using 0.8 g of the mixed acid solution and 50 ml of a mixed solvent of methanol and acetone (1: 1 volume ratio) as a sample. FIG. 4 shows a chart of measurement results. The peak (1) in FIG. 4 corresponds to acetic acid + phosphoric acid (first inflection point), and the peak (2) corresponds to phosphoric acid (second inflection point + third inflection point).
実施例１：
硝酸濃度１４．８重量％、リン酸濃度５９．９重量％の混酸液（残余は水）を調製した。この混酸液０．８ｇにメタノールとアセトン（１：１容量比）の混合溶媒５０ｍｌを添加したものを試料として中和滴定を行った。図５に測定結果のチャートを示す。図５中のピーク（１）は硝酸に相当し、ピーク（２）はリン酸（第１変曲点）に相当する。参考例１と比較すると、メタノールとアセトン（１：１容量比）の混合溶媒の存在下の中和滴定によるならば、混酸液中の硝酸は単独ピークとして検出されることが分かる。
Example 1:
A mixed acid solution having a nitric acid concentration of 14.8% by weight and a phosphoric acid concentration of 59.9% by weight (the balance being water) was prepared. Neutralization titration was performed using 0.8 g of the mixed acid solution and 50 ml of a mixed solvent of methanol and acetone (1: 1 volume ratio) as a sample. FIG. 5 shows a measurement result chart. The peak (1) in FIG. 5 corresponds to nitric acid, and the peak (2) corresponds to phosphoric acid (first inflection point). Compared with Reference Example 1, it can be seen that nitric acid in the mixed acid solution is detected as a single peak by neutralization titration in the presence of a mixed solvent of methanol and acetone (1: 1 volume ratio).
実施例２：
硝酸濃度５．０重量％、リン酸濃度７２．０重量％、酢酸濃度５．０重量％の混酸液（残余は水）を調製した。この混酸液０．８ｇにメタノールとアセトン（１：１容量比）の混合溶媒５０ｍｌを添加したものを試料として中和滴定を行った。図６に測定結果のチャートを示す。図６中のピーク（１）は硝酸に相当し、ピーク（２）は酢酸＋リン酸（第１変曲点）に相当し、ピーク（３）はリン酸（第２変曲点＋第３変曲点）に相当する。参考例１と比較すると、メタノールとアセトン（１：１容量比）の混合溶媒の存在下の中和滴定によるならば、混酸液中の硝酸は単独ピークとして検出されることが分かる。困に、上記と同一操作による中和滴定を１０回繰り返して行うことにより求めた分析のバラツキ３σは０．２以下であり、分析精度は±０．１重量％以内であった。
Example 2:
A mixed acid solution having a nitric acid concentration of 5.0% by weight, a phosphoric acid concentration of 72.0% by weight, and an acetic acid concentration of 5.0% by weight (the balance being water) was prepared. Neutralization titration was performed using 0.8 g of the mixed acid solution and 50 ml of a mixed solvent of methanol and acetone (1: 1 volume ratio) as a sample. FIG. 6 shows a chart of measurement results. 6 corresponds to nitric acid, peak (2) corresponds to acetic acid + phosphoric acid (first inflection point), and peak (3) corresponds to phosphoric acid (second inflection point + third inflection point). It corresponds to the inflection point. Compared with Reference Example 1, it can be seen that nitric acid in the mixed acid solution is detected as a single peak by neutralization titration in the presence of a mixed solvent of methanol and acetone (1: 1 volume ratio). The frame, the variation 3σ in the analysis was determined by performing 10 times a medium Kazushizukujo by the same operation is 0.2 or less, the analysis accuracy was within 0.1% ±.
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