JP2013226477A - Method of processing exhaust gas including nitrogen-containing compound - Google Patents
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Description
本発明は、含窒素化合物を含む排ガスの処理方法に関する。含窒素化合物を含む排ガスの処理は、環境や人体への影響を与えるガス成分の除去、例えば、大気中への異臭放出を防ぐ手段となりうる。 The present invention relates to a method for treating exhaust gas containing a nitrogen-containing compound. The treatment of exhaust gas containing nitrogen-containing compounds can be a means for removing gas components that affect the environment and the human body, for example, preventing the release of off-flavors to the atmosphere.
近年、環境問題が深刻化しており、工業的製造過程で排出されるガスのうち、地球的規模で環境に影響を与えるガス成分、人体に影響を与えるガス成分などの排出については、厳しく制限されている。その中でも、例えば、半導体や電子部品等への成膜材料の使用により、環境や人体に影響を与えるガスが発生する場合も珍しくない。
そこで、大気中への排ガスを効率的に処理する方法が望まれており、いくつかの提案もなされている（例えば、特許文献１参照）。
In recent years, environmental problems have become serious, and among the gases emitted in the industrial manufacturing process, the emission of gas components that affect the environment on a global scale and gas components that affect the human body are severely restricted. ing. Among them, for example, it is not uncommon for gases that affect the environment and the human body to be generated due to the use of film forming materials for semiconductors and electronic parts.
Thus, a method for efficiently treating exhaust gas into the atmosphere is desired, and some proposals have been made (for example, see Patent Document 1).
しかしながら、既存の化合物から発生するガス成分ならばともかく、新規な材料に起因するガス成分の場合には、既存の手段が適用されるとは限られないという問題があった。そのため、材料に整合した排ガス中のガス成分の処理が有効に行われる必要があった。 However, there is a problem that existing means are not always applied in the case of a gas component originating from a new material, regardless of a gas component generated from an existing compound. For this reason, it is necessary to effectively treat the gas component in the exhaust gas that matches the material.
本発明の課題は、即ち、上記問題点を解決し、簡便な方法によって、排ガス中の多種多様な含窒素化合物（ガス成分）を処理して、大気中に有害なガスを放出させることがない、含窒素化合物を含む排ガスの処理方法を提供するものである。 The object of the present invention is to solve the above-mentioned problems and to treat a wide variety of nitrogen-containing compounds (gas components) in the exhaust gas by a simple method so that no harmful gas is released into the atmosphere. The present invention provides a method for treating exhaust gas containing a nitrogen-containing compound.
本発明の課題は、アミン化合物、イミン化合物、複数種のアミン化合物が結合した化合物、及び１又は複数のアミン化合物と１又は複数のイミン化合物とが結合した化合物からなる群より選ばれる少なくとも１種の含窒素化合物を含む排ガスを、金属酸化物を主成分とする処理剤と接触させることを特徴とする、含窒素化合物を含む排ガスの処理方法によって解決される。 An object of the present invention is at least one selected from the group consisting of an amine compound, an imine compound, a compound in which a plurality of types of amine compounds are bonded, and a compound in which one or a plurality of amine compounds and one or a plurality of imine compounds are bonded. The exhaust gas containing a nitrogen-containing compound is brought into contact with a treatment agent containing a metal oxide as a main component, which is solved by a method for treating an exhaust gas containing a nitrogen-containing compound.
本発明により、含窒素化合物を含む排ガスの処理方法を提供することができる。 According to the present invention, a method for treating exhaust gas containing a nitrogen-containing compound can be provided.
（含窒素化合物を含む排ガス）
本発明の含窒素化合物を含む排ガスとは、アミン化合物、イミン化合物、複数種のアミン化合物が結合した化合物、及び１又は複数のアミン化合物と１又は複数のイミン化合物とが結合した化合物からなる群より選ばれる少なくとも１種の含窒素化合物を含む排ガスであり、アミン化合物とは「窒素と炭素の結合」が少なくとも１つ存在する化合物であり、イミン化合物とは「窒素と炭素の二重結合」が少なくとも１つ存在する化合物である。
複数種のアミン化合物が結合した化合物とは、「窒素と炭素の化合物」が２つ以上存在する化合物であり、１又は複数のアミン化合物と１又は複数のイミン化合物とが結合した化合物とは、「窒素と炭素の結合」が少なくとも１つ存在し、かつ「窒素と炭素の二重結合」が少なくとも１つ以上存在する化合物である。
(Exhaust gas containing nitrogen-containing compounds)
The exhaust gas containing a nitrogen-containing compound of the present invention includes an amine compound, an imine compound, a compound in which a plurality of types of amine compounds are combined, and a group in which one or more amine compounds and one or more imine compounds are combined. It is an exhaust gas containing at least one nitrogen-containing compound selected from the above, the amine compound is a compound having at least one “nitrogen-carbon bond”, and the imine compound is “nitrogen-carbon double bond” Is a compound in which at least one is present.
A compound in which a plurality of types of amine compounds are bonded is a compound in which two or more “nitrogen and carbon compounds” exist, and a compound in which one or more amine compounds and one or more imine compounds are bonded. A compound having at least one “nitrogen-carbon bond” and at least one “nitrogen-carbon double bond”.
本発明の含窒素化合物を含む排ガスにおける「含窒素化合物」とは、１又は複数個の窒素を含む配位子を有する金属錯体の反応、分解、及び反応後の分解により生じる含窒素化合物から群より選ばれる少なくとも１種の含窒素化合物を含む排ガスが好適に用いられる。 The “nitrogen-containing compound” in the exhaust gas containing the nitrogen-containing compound of the present invention is a group consisting of nitrogen-containing compounds generated by reaction, decomposition, and decomposition after reaction of a metal complex having a ligand containing one or more nitrogen. An exhaust gas containing at least one nitrogen-containing compound selected from the above is preferably used.
（１又は複数個の窒素を含む配位子を有する金属錯体）
そのような金属錯体としては、一般式（１）
(Metal complex having a ligand containing one or more nitrogen atoms)
As such a metal complex, the general formula (1)
（式中、Ｍは、金属原子を示す。Ｒ１は炭素原子数１〜６の直鎖状、分岐状又は環状のアルキル基を示し、Ｒ２及びＲ３は同一又は異なっていても良く、炭素原子数１〜３の直鎖状又は分岐状のアルキル基を示す。なお、Ｒ２及びＲ３は互いに結合して環を形成しても良い。Ｚは炭素原子数０〜５の直鎖状又は分岐状のアルキレン基を示す。ｎは配位子の数を示す。）
で示される１又は複数個の窒素を含む配位子を有する金属錯体が好適に使用される。なお、当該金属錯体は新規な化合物である（未公開；ＰＣＴ／ＪＰ２０１１／７５３４７号）。
(In the formula, M represents a metal atom. R 1 represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and R 2 and R 3 may be the same or different, A linear or branched alkyl group having 1 to 3 carbon atoms, wherein R 2 and R 3 may be bonded to each other to form a ring, and Z is a straight chain having 0 to 5 carbon atoms. And represents a branched or branched alkylene group, and n represents the number of ligands.)
A metal complex having a ligand containing one or a plurality of nitrogens represented by the formula is preferably used. Note that the metal complex is a novel compound (unpublished; PCT / JP2011 / 75347).
前記金属錯体から「含窒素化合物を含む排ガス」が発生する場合としては、常圧又は減圧下にて、当該金属錯体を半導体成膜装置内の加熱した成膜対象物に水素源とともに送り込み、ＣＶＤ法やＡＬＤ法にてマンガン含有薄膜を蒸着させるのと同時に起こりうる。なお、水素源の非存在下、熱分解でマンガン含有薄膜を蒸着させるのと同時にも起こりうる。 When “exhaust gas containing a nitrogen-containing compound” is generated from the metal complex, the metal complex is sent together with a hydrogen source to a heated film-forming target in a semiconductor film-forming apparatus under atmospheric pressure or reduced pressure. This may occur simultaneously with the deposition of the manganese-containing thin film by the ALD method or the ALD method. Note that this may occur simultaneously with the deposition of the manganese-containing thin film by thermal decomposition in the absence of a hydrogen source.
具体的には、一般式（２）〜（５）で示されるアミン化合物、一般式（６）〜（８）で示されるイミン化合物、一般式（９）で示される複数種のアミン化合物が結合した化合物、一般式（１０）で示される１又は複数のアミン化合物と１又は複数のイミン化合物とが結合した化合物が、含窒素化合物を含む排ガスの成分として挙げられる。 Specifically, amine compounds represented by general formulas (2) to (5), imine compounds represented by general formulas (6) to (8), and a plurality of types of amine compounds represented by general formula (9) are bonded. And a compound in which one or a plurality of amine compounds represented by the general formula (10) and one or a plurality of imine compounds are combined can be cited as an exhaust gas component containing a nitrogen-containing compound.
本発明の金属錯体は、前記の一般式（１）において示される。その一般式（１）において、Ｒ１はメチル基、エチル基、ｎ−プロピル基、イソプロピル基、シクロプロピル基、ｔ−ブチル基、シクロブチル基、ｔ−ペンチル基、ネオペンチル基等の炭素原子数１〜６の直鎖状、分岐状又は環状のアルキル基を示す。 The metal complex of the present invention is represented by the general formula (1). In the general formula (1), R 1 has 1 carbon atom such as methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, t-butyl group, cyclobutyl group, t-pentyl group, neopentyl group and the like. -6 linear, branched or cyclic alkyl groups are shown.
Ｒ２及びＲ３は同一又は異なっていても良く、メチル基、エチル基、プロピル基、イソプロピル基等の炭素原子数１〜３の直鎖状又は分岐状のアルキル基を示す。なお、Ｒ２及びＲ３は互いに結合して環を形成しても良い。 R 2 and R 3 may be the same or different and each represents a linear or branched alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, or an isopropyl group. R 2 and R 3 may be bonded to each other to form a ring.
又、Ｚはメチレン基、エチレン基、トリメチレン基、メチルエチレン基、テトラエチレン基、２−メチルトリメチレン基、ヘキサメチレン基等の炭素原子数０〜６の直鎖状又は Z is a straight chain having 0 to 6 carbon atoms such as methylene group, ethylene group, trimethylene group, methylethylene group, tetraethylene group, 2-methyltrimethylene group, hexamethylene group or the like;
（金属酸化物）
本発明の金属酸化物を主成分とする処理剤の「金属酸化物」としては、例えば、酸化鉄、酸化亜鉛、チタニア、シリカ、アルミナ、ゼオライト、ジルコニア、スピネルなどが使用される。
(Metal oxide)
Examples of the “metal oxide” of the treatment agent mainly composed of the metal oxide of the present invention include iron oxide, zinc oxide, titania, silica, alumina, zeolite, zirconia, spinel and the like.
金属酸化物を主成分とする処理剤の使用量は、含窒素化合物が含まれる排ガスの量や濃度に依存するが、十分に含窒素化合物が処理できる量ならば特に制限されないが、処理剤の劣化を考慮して、過剰分の処理剤を使用するのが望ましい。 The amount of the treatment agent containing a metal oxide as a main component depends on the amount and concentration of the exhaust gas containing the nitrogen-containing compound, but is not particularly limited as long as the nitrogen-containing compound can be sufficiently treated. In consideration of deterioration, it is desirable to use an excess amount of the treatment agent.
前記の方法で処理された排ガスから含窒素化合物が除去されたことを確認するための手段としては、例えば、処理済み排ガスの有機化合物定性・定量分析、排ガスの塩基性度の分析、処理剤の劣化や重量変化、色彩変化などにより行える。 Means for confirming that nitrogen-containing compounds have been removed from the exhaust gas treated by the above method include, for example, organic compound qualitative / quantitative analysis of treated exhaust gas, basicity analysis of exhaust gas, treatment agent It can be done by deterioration, weight change, color change, etc.
本発明においては、１又は複数個の窒素を含む配位子を有する金属錯体を用いた金属薄膜の製造と、その際に発生する含窒素化合物を含む排ガスの処理を同時に行うことができるシステムをも提供することができる。 In the present invention, a system capable of simultaneously producing a metal thin film using a metal complex having a ligand containing one or a plurality of nitrogen and treating exhaust gas containing a nitrogen-containing compound generated at that time. Can also be provided.
次に、実施例を挙げて本発明を具体的に説明するが、本発明の範囲はこれらに限定されるものではない。 Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto.
参考例１（１−イソプロピルアミノ−２−ジメチルアミノエタンの合成） Reference Example 1 (Synthesis of 1-isopropylamino-2-dimethylaminoethane)
攪拌装置、温度計及び滴下漏斗を備えた内容積５０ｍｌのフラスコに、イソプロピルアミン６．０ｇ（０．１０ｍｏｌ）及び水５ｍｌを加えた後、２−（ジメチルアミノ）エチルクロリド塩酸塩５．０ｇ（３５ｍｍｏｌ）の水溶液１０ｍｌを、液温が３０〜５０℃の範囲になるようにしながらゆるやかに滴下して２時間攪拌した。次いで、水酸化ナトリウム２．８ｇ（７０ｍｍｏｌ）の水溶液１０ｍｌを、氷浴下でゆるやかに滴下して１０分間反応させた。反応終了後、反応液をヘキサン２５ｍｌで２回抽出し、ヘキサン層を減圧下で濃縮した。濃縮物を減圧蒸留（６５℃、４．０ｋＰａ）して、１−イソプロピルアミノ−２−ジメチルアミノエタン１．４ｇを得た（単離収率；３１％）。 After adding 6.0 g (0.10 mol) of isopropylamine and 5 ml of water to a flask having an internal volume of 50 ml equipped with a stirrer, a thermometer and a dropping funnel, 5.0 g of 2- (dimethylamino) ethyl chloride hydrochloride ( 10 ml of an aqueous solution of 35 mmol) was gently dropped while stirring so that the liquid temperature was in the range of 30 to 50 ° C., and stirred for 2 hours. Next, 10 ml of an aqueous solution of 2.8 g (70 mmol) of sodium hydroxide was slowly dropped in an ice bath and allowed to react for 10 minutes. After completion of the reaction, the reaction solution was extracted twice with 25 ml of hexane, and the hexane layer was concentrated under reduced pressure. The concentrate was distilled under reduced pressure (65 ° C., 4.0 kPa) to obtain 1.4 g of 1-isopropylamino-2-dimethylaminoethane (isolation yield; 31%).
参考例２（（１−イソプロピルアミド−２−ジメチルアミノエタン−Ｎ，Ｎ’）リチウムの合成） Reference Example 2 (Synthesis of (1-Isopropylamido-2-dimethylaminoethane-N, N ') lithium)
攪拌装置、温度計及び滴下漏斗を備えた内容積５０ｍｌのフラスコに、アルゴン雰囲気にて、１−イソプロピルアミノ−２−ジメチルアミノエタン２．１ｇ（１６ｍｍｏｌ）とヘキサン１５ｍｌを加えた。次いで、液温を０℃に保ちながら、１．６ｍｏｌ／ｌのｎ−ブチルリチウム・へキサン溶液１０ｍｌ（１６ｍｍｏl）をゆるやかに滴下し、攪拌しながら同温度で３０分間、２０℃で２時間反応させた。反応終了後、反応液を減圧下で濃縮した後、濃縮物を真空下で乾燥し、（１−イソプロピルアミド−２−ジメチルアミノエタン−Ｎ，Ｎ’）リチウム２．１ｇを得た（単離収率；９４％）。
なお、（１−イソプロピルアミド−２−ジメチルアミノエタン−Ｎ，Ｎ’）リチウムの物性値は以下の通りであった。
In an argon atmosphere, 2.1 g (16 mmol) of 1-isopropylamino-2-dimethylaminoethane and 15 ml of hexane were added to a flask having an internal volume of 50 ml equipped with a stirrer, a thermometer and a dropping funnel. Next, while maintaining the liquid temperature at 0 ° C., 10 ml (16 mmol) of a 1.6 mol / l n-butyllithium hexane solution was slowly added dropwise, and the reaction was continued at the same temperature for 30 minutes and at 20 ° C. for 2 hours with stirring. I let you. After completion of the reaction, the reaction solution was concentrated under reduced pressure, and then the concentrate was dried under vacuum to obtain 2.1 g of (1-isopropylamido-2-dimethylaminoethane-N, N ′) lithium (isolation). Yield; 94%).
The physical properties of (1-isopropylamido-2-dimethylaminoethane-N, N ′) lithium were as follows.
１Ｈ−ＮＭＲ（テトラヒドロフラン−ｄ８，δ（ｐｐｍ））；２．９５（２Ｈ，ｔ，６．０Ｈｚ）、２．９１（１Ｈ，ｑｕｉｎｔ，６．２Ｈｚ）、２．４４（２Ｈ，ｔ，６．０Ｈｚ）、２．１８（６Ｈ，ｓ）、０．９９（６Ｈ，ｄ，６．２Ｈｚ） 1 H-NMR (tetrahydrofuran-d 8 , δ (ppm)); 2.95 (2H, t, 6.0 Hz), 2.91 (1H, quint, 6.2 Hz), 2.44 (2H, t, 6.0 Hz), 2.18 (6 H, s), 0.99 (6 H, d, 6.2 Hz)
実施例１（ビス（１−イソプロピルアミド−２−ジメチルアミノエタン−Ｎ，Ｎ’）マンガン（ＩＩ）の合成） Example 1 (Synthesis of bis (1-isopropylamido-2-dimethylaminoethane-N, N ') manganese (II))
攪拌装置、温度計及び滴下漏斗を備えた内容積５０ｍｌのフラスコに、アルゴン雰囲気にて、塩化マンガン（ＩＩ）（予め乾燥させた無水物）０．４８ｇ（３．８ｍｍｏｌ）及びテトラヒドロフラン１０ｍｌを混合して２時間攪拌させた。次いで、液温を０℃に保ちながら、参考例２と同様な方法で得られた１−イソプロピルアミド−２−ジメチルアミノエタン−Ｎ，Ｎ’）リチウム１．０ｇ（７．６ｍｍｏl）のテトラヒドロフラン溶液１０ｍｌをゆるやかに滴下した。その後、攪拌しながら２０℃で６時間反応させた。反応終了後、反応液を減圧下で濃縮し、濃縮物にヘキサン５０ｍｌを加えて攪拌させた。濾過後、得られた濾液を減圧下で濃縮した後、濃縮物を減圧下で蒸留（８０℃、１３．３Ｐａ）し、淡褐色液体として、（ビス（１−イソプロピルアミド−２−ジメチルアミノエタン−Ｎ，Ｎ’）マンガン（ＩＩ）１．０ｇを得た（単離収率；８４％）。
なお、ビス（１−イソプロピルアミド−２−ジメチルアミノエタン−Ｎ，Ｎ’）マンガン（ＩＩ）は、以下の物性値で示される新規な化合物であった。
In an argon atmosphere, 0.48 g (3.8 mmol) of manganese (II) chloride (preliminarily dried anhydride) and 10 ml of tetrahydrofuran were mixed in a 50-ml flask equipped with a stirrer, thermometer and dropping funnel in an argon atmosphere. And stirred for 2 hours. Next, a tetrahydrofuran solution of 1.0 g (7.6 mmol) of 1-isopropylamido-2-dimethylaminoethane-N, N ′) lithium obtained by the same method as in Reference Example 2 while maintaining the liquid temperature at 0 ° C. 10 ml was dripped gently. Then, it was made to react at 20 degreeC for 6 hours, stirring. After completion of the reaction, the reaction solution was concentrated under reduced pressure, and 50 ml of hexane was added to the concentrate and stirred. After filtration, the obtained filtrate was concentrated under reduced pressure, and then the concentrate was distilled under reduced pressure (80 ° C., 13.3 Pa) to obtain (bis (1-isopropylamido-2-dimethylaminoethane) as a light brown liquid. -N, N ') Manganese (II) 1.0g was obtained (isolation yield; 84%).
Note that bis (1-isopropylamido-2-dimethylaminoethane-N, N ′) manganese (II) was a novel compound represented by the following physical property values.
誘導結合プラズマ（ＩＣＰ）分析によるマンガン含有量；１７．７質量％
（計算値；１７．５質量％）
Manganese content by inductively coupled plasma (ICP) analysis; 17.7% by mass
(Calculated value: 17.5% by mass)
実施例２（ビス（１−（ｔ−ブチルアミド）−２−ジメチルアミノエタン−Ｎ，Ｎ’）マンガンの合成）
参考例１において、イソプロピルアミンをｔ−ブチルアミン７．３ｇ（０．１０ｍｏｌ）に変更し、１−（ｔ−ブチルアミノ）−２−ジメチルアミノエタン１．８ｇを減圧蒸留（６０℃、２．４ｋＰａ）により得て（単離収率；３６％）、更に、参考例２において１−イソプロピルアミノ−２−ジメチルアミノエタンを１−（ｔ−ブチルアミノ）−２−ジメチルアミノエタン２．３（１６ｍｍｏｌ）に変更し、１−（ｔ−ブチルアミノ）−２−ジメチルアミノエタン−Ｎ，Ｎ’）リチウム２．４ｇを得て（単離収率；９６％）、最後に実施例１の１−イソプロピルアミド−２−ジメチルアミノエタン−Ｎ，Ｎ’）リチウムのテトラヒドロフラン溶液を、１−（ｔ−ブチルアミノ）−２−ジメチルアミノエタン−Ｎ，Ｎ’）リチウム１．１ｇ（７．６ｍｍｏl）のテトラヒドロフラン溶液１０ｍｌに変更して実施例１と同様に反応を行い、濃縮後、減圧下で昇華（９０℃、１３Ｐａ）させた。その結果、淡緑褐色色固体として、ビス（１−（ｔ−ブチルアミド）−２−ジメチルアミノエタン−Ｎ，Ｎ’）マンガン１．１ｇを得た（単離収率；８５％）。
なお、ビス（（１−（ｔ−ブチルアミド）−２−ジメチルアミノエタン−Ｎ，Ｎ’）マンガン（ＩＩ）は、以下の物性値で示される新規な化合物であった。
Example 2 (Synthesis of bis (1- (t-butylamido) -2-dimethylaminoethane-N, N ′) manganese)
In Reference Example 1, isopropylamine was changed to 7.3 g (0.10 mol) of t-butylamine, and 1.8 g of 1- (t-butylamino) -2-dimethylaminoethane was distilled under reduced pressure (60 ° C., 2.4 kPa). In addition, in Reference Example 2, 1-isopropylamino-2-dimethylaminoethane was converted to 1- (t-butylamino) -2-dimethylaminoethane 2.3 (16 mmol). ) To obtain 2.4 g of 1- (t-butylamino) -2-dimethylaminoethane-N, N ′) lithium (isolation yield; 96%), and finally 1- A solution of isopropylamido-2-dimethylaminoethane-N, N ′) lithium in tetrahydrofuran was added 1.1 g (7. tert-butylamino) -2-dimethylaminoethane-N, N ′) lithium. Change in tetrahydrofuran 10ml of mmol) was reacted in the same manner as in Example 1, after concentration, sublimation (90 ° C. under reduced pressure to 13 Pa). As a result, 1.1 g of bis (1- (t-butylamido) -2-dimethylaminoethane-N, N ′) manganese was obtained as a pale green brown solid (isolated yield; 85%).
Note that bis ((1- (t-butylamido) -2-dimethylaminoethane-N, N ′) manganese (II) was a novel compound represented by the following physical property values.
融点；７０〜７１℃
誘導結合プラズマ（ＩＣＰ）分析によるマンガン含有量；１６．５質量％
（計算値；１６．１質量％）
Melting point: 70-71 ° C
Manganese content by inductively coupled plasma (ICP) analysis; 16.5% by mass
(Calculated value: 16.1% by mass)
実施例３（蒸着実験及び排ガス処理）
実施例２で得られたマンガン錯体を用いて、擬似的なＣＶＤ法による蒸着実験を行い、含窒素化合物を含む排ガスを発生させ、その処理能力について評価した。
評価試験には、図１に示す装置を使用した。気化装置にあるマンガン錯体を、加熱して気化させ、常圧下にて、水素とともに３００℃に加熱された被蒸着基板に送った。基板の表面上で還元されてマンガン含有薄膜が形成されるとともに、含窒素化合物を含む排ガスが発生した。当該ガスを「ゼオライトを充填した除害カラム」を通過・接触させ、含窒素化合物を含む排ガス中の含窒素化合物の処理を行った。
（蒸着条件１）
マンガン錯体；（ビス（１−（ｔ−ブチルアミド）−２−ジメチルアミノエタン−Ｎ，Ｎ’）マンガン（ＩＩ）
気化温度；１００℃
Ｈｅキャリアー流量；１００ｓｃｃｍ
水素流量；１０ｓｃｃｍ
基板材料；Ｓｉウェハー
基板温度；３００℃
反応系内圧力；１００ｋＰａ
蒸着時間；８時間
Example 3 (deposition experiment and exhaust gas treatment)
Using the manganese complex obtained in Example 2, a vapor deposition experiment by a pseudo CVD method was performed, an exhaust gas containing a nitrogen-containing compound was generated, and the treatment capability was evaluated.
The apparatus shown in FIG. 1 was used for the evaluation test. The manganese complex in the vaporizer was heated and vaporized, and sent to a deposition substrate heated to 300 ° C. with hydrogen under normal pressure. While being reduced on the surface of the substrate to form a manganese-containing thin film, exhaust gas containing nitrogen-containing compounds was generated. The gas was passed through and contacted with a “detoxification column filled with zeolite” to treat the nitrogen-containing compound in the exhaust gas containing the nitrogen-containing compound.
(Vapor deposition conditions 1)
Manganese complex; (bis (1- (t-butylamido) -2-dimethylaminoethane-N, N ′) manganese (II)
Evaporation temperature: 100 ° C
He carrier flow rate: 100 sccm
Hydrogen flow rate: 10 sccm
Substrate material; Si wafer substrate temperature; 300 ° C
Reaction system pressure: 100 kPa
Deposition time: 8 hours
（膜特性（ＸＰＳ-ｄｅｐｔｈ測定））
ＸＰＳ分析；マンガン膜
(Membrane characteristics (XPS-depth measurement))
XPS analysis; Manganese film
（除害カラムの形状及び充填剤）
形状；円筒
カラム内径；１．６ｃｍ
カラムの長さ；１２．５ｃｍ
充填剤；ゼオライト（東ソー製）
充填量；１５ｇ
(The shape and packing material of the abatement column)
Shape; cylindrical column inner diameter; 1.6cm
Column length; 12.5cm
Filler: Zeolite (Tosoh)
Filling amount: 15g
（主要含窒素成分の同定）
予めコールドトラップ（−７８℃）で捕集して確認されていた、
１−（ｔ−ブチルアミノ）−２−ジメチルアミノエタン
Ｎ−（２−（ジメチルアミノ）エチリデン）−２−メチルプロパン−２−アミン
について、それらが除害されたかどうか確認した。
化合物の同定は１Ｈ−ＮＭＲ、ＭＳ（ＥＩ）を用いて行った。
(Identification of main nitrogen-containing components)
It was confirmed by collecting with a cold trap (-78 ° C) in advance.
It was confirmed whether 1- (t-butylamino) -2-dimethylaminoethane N- (2- (dimethylamino) ethylidene) -2-methylpropan-2-amine was detoxified.
The compound was identified using 1 H-NMR and MS (EI).
１−（ｔ−ブチルアミノ）−２−ジメチルアミノエタン
１Ｈ−ＮＭＲ（テトラヒドロフラン−ｄ８，δ（ｐｐｍ））；２．５７（２Ｈ，ｔ，５．８Ｈｚ）、２．２９（２Ｈ，ｔ，５．８Ｈｚ）、２．１２（６Ｈ，ｓ）、１．１１（1Ｈ，ｂｒ）、１．０３（９Ｈ，ｓ）
ＭＳ（ＥＩ） ｍ／ｚ １４４（Ｍ＋）
1- (t-butylamino) -2-dimethylaminoethane
1 H-NMR (tetrahydrofuran-d8, δ (ppm)); 2.57 (2H, t, 5.8 Hz), 2.29 (2H, t, 5.8 Hz), 2.12 (6H, s), 1.11 (1H, br), 1.03 (9H, s)
MS (EI) m / z 144 (M +)
Ｎ−（２−（ジメチルアミノ）エチリデン）−２−メチルプロパン−２−アミン
１Ｈ−ＮＭＲ（テトラヒドロフラン−ｄ８，δ（ｐｐｍ））；７．５７（１Ｈ，ｔ，４．７Ｈｚ）、２．９２（２Ｈ，ｄ，４．７Ｈｚ）、２．３８（６Ｈ，ｓ）、１．１２（９Ｈ，ｓ）
ＭＳ（ＥＩ） ｍ／ｚ １４２（Ｍ＋）
N- (2- (dimethylamino) ethylidene) -2-methylpropan-2-amine
1 H-NMR (tetrahydrofuran-d8, δ (ppm)); 7.57 (1H, t, 4.7 Hz), 2.92 (2H, d, 4.7 Hz), 2.38 (6H, s), 1.12 (9H, s)
MS (EI) m / z 142 (M +)
（含窒素成分の除害の確認方法）
ガス中のアミン化合物を検知する機器（アミン用検知管（ガステック製））
(Confirmation method for removing nitrogenous components)
Equipment for detecting amine compounds in gas (amine detector tube (made by Gastec))
その結果、先に示したようにマンガン含有薄膜が形成されるとともに、排ガス中に含まれる前記の含窒素化合物が除去されていた。 As a result, a manganese-containing thin film was formed as described above, and the nitrogen-containing compound contained in the exhaust gas was removed.
以上の結果から、本発明により、良質な金属含有薄膜を形成できるとともに、含窒素化合物を含む排ガスを処理することができることが分かった。なお、コバルト又は鉄を中心金属とする金属錯体においても同様に良質な金属含有薄膜を形成と排ガス処理ができる。 From the above results, it was found that the present invention can form a high-quality metal-containing thin film and can treat exhaust gas containing a nitrogen-containing compound. It should be noted that a metal complex thin film containing cobalt or iron as a central metal can be similarly formed with a high-quality metal-containing thin film and subjected to exhaust gas treatment.
本発明は、含窒素化合物を含む排ガスの処理方法に関する。含窒素化合物を含む排ガスの処理は、環境や人体への影響を与えるガス成分の除去、例えば、大気中への異臭放出を防ぐ手段となりうる。 The present invention relates to a method for treating exhaust gas containing a nitrogen-containing compound. The treatment of exhaust gas containing nitrogen-containing compounds can be a means for removing gas components that affect the environment and the human body, for example, preventing the release of off-flavors to the atmosphere.
１ 気化器
２ 成膜装置
３ 除害装置
４ ガス検知管
DESCRIPTION OF SYMBOLS 1
Claims (7)
である請求項２記載の含窒素化合物を含む排ガスの処理方法。 A metal complex having a ligand containing one or more nitrogen atoms has the general formula (1)
The method for treating an exhaust gas containing a nitrogen-containing compound according to claim 2.
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| JP2009001896A (en) * | 2007-04-16 | 2009-01-08 | Air Products & Chemicals Inc | Metal precursor solution for chemical vapor deposition |
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| KR102000572B1 (en) | 2016-11-21 | 2019-07-16 | 한국화학연구원 | Manganese aminoamide amidinate precursors, preparation method thereof and process for the formation of thin film using the same |
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