JP4460440B2 - How to store hexafluoroacetylacetone - Google Patents
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- JP4460440B2 JP4460440B2 JP2004373064A JP2004373064A JP4460440B2 JP 4460440 B2 JP4460440 B2 JP 4460440B2 JP 2004373064 A JP2004373064 A JP 2004373064A JP 2004373064 A JP2004373064 A JP 2004373064A JP 4460440 B2 JP4460440 B2 JP 4460440B2
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Description
本発明は、半導体製造分野、及びクリーニング分野で使用されるヘキサフルオロアセチルアセトンの保存方法に関する。 The present invention relates to a method for storing hexafluoroacetylacetone used in the field of semiconductor manufacturing and cleaning.
ヘキサフルオロアセチルアセトン（1,1,1,5,5,5−ヘキサフルオロ−2,4−ペンタンジオン、以下、ＨｆＡｃＡｃと略す）は、数多くの種類の金属と容易に反応し錯体を形成することから、現在、半導体の成膜分野、及びクリーニング分野への応用が期待されている。これらの分野で使用するためには、わずかの不純物が成膜に悪影響を与えるため、高純度のものを使用することが要求される（特許文献１、２）。 Hexafluoroacetylacetone (1,1,1,5,5,5-hexafluoro-2,4-pentanedione, hereinafter abbreviated as HfAcAc) easily reacts with many types of metals to form complexes. Currently, application to the field of semiconductor film formation and the field of cleaning is expected. In order to use in these fields, it is required to use a high-purity one because a small amount of impurities adversely affects film formation (Patent Documents 1 and 2).
ＨｆＡｃＡｃは、一般的に樹脂、またはガラス製の容器に保存される。しかし、容器の密閉性、耐久性、接続の容易さの観点から、実際に成膜装置で使用するためには、金属製容器に入れて使用することが重要である。 HfAcAc is generally stored in a resin or glass container. However, from the viewpoint of container sealing, durability, and ease of connection, it is important to use it in a metal container in order to actually use it in a film forming apparatus.
例えば、ＨｆＡｃＡｃを汎用性の高い金属製容器であるステンレス鋼製容器に保存した場合には、容器への導入直後に表面の自然酸化膜と反応し、金属錯体が生成し、純度低下が起こるという問題点があった。また、自然酸化膜と反応した後も容器材質と反応して錯体を形成し、未反応のＨｆＡｃＡｃが完全に無くなるまで純度低下が進行するという問題点があった。 For example, when HfAcAc is stored in a stainless steel container, which is a highly versatile metal container, it reacts with a natural oxide film on the surface immediately after introduction into the container, a metal complex is formed, and purity is reduced. There was a problem. In addition, after reacting with the natural oxide film, it reacts with the container material to form a complex, and there is a problem that the purity decreases until unreacted HfAcAc is completely eliminated.
従って、本発明の課題は、純度低下が起こらないようなＨｆＡｃＡｃの金属製容器への長期保存方法を提供することである。
本発明者らは、鋭意検討の結果、ＨｆＡｃＡｃを、表面の自然酸化膜を除去する前処理を施したＡｌ製容器、Ａｌ−Ｍｇ合金製容器、Ａｌ−Ｍｇ−Ｓｉ系合金製容器に保存することで、分解を抑制できることを見出し本発明に到達した。 As a result of intensive studies, the inventors of the present invention store HfAcAc in an Al container, an Al-Mg alloy container, and an Al-Mg-Si alloy container that have been subjected to pretreatment for removing the natural oxide film on the surface. Thus, the inventors have found that the decomposition can be suppressed and have reached the present invention.
すなわち本発明は、表面の自然酸化膜を除去する前処理として、ヘキサフルオロアセチルアセトンによる洗浄処理、Ｈ ２ 雰囲気によるアニ−ル処理、またはＨ ２ によるプラズマ処理を施した、Ａｌ製容器、Ａｌ−Ｍｇ合金製容器、またはＡｌ−Ｍｇ−Ｓｉ系合金製容器に保存することを特徴とするヘキサフルオロアセチルアセトンの保存方法を提供するものである。 That is, according to the present invention, as a pretreatment for removing the natural oxide film on the surface, a cleaning treatment with hexafluoroacetylacetone, an annealing treatment with an H 2 atmosphere, or a plasma treatment with H 2 is performed. The present invention provides a storage method for hexafluoroacetylacetone, which is stored in an alloy container or an Al-Mg-Si alloy container.
以下、本発明の内容を詳細に説明する。
本発明において、前処理として、ヘキサフルオロアセチルアセトンによる洗浄処理、Ｈ ２ 雰囲気によるアニ−ル処理、またはＨ ２ によるプラズマ処理を施した、Ａｌ製容器、Ａｌ−Ｍｇ合金製容器、Ａｌ−Ｍｇ−Ｓｉ系合金製容器を使用する。Ａｌ等は、金属の中で最もＨｆＡｃＡｃ錯体を形成しにくいことによる。
Hereinafter, the contents of the present invention will be described in detail.
In the present invention, as a pretreatment, a cleaning treatment with hexafluoroacetylacetone, an annealing treatment with an H 2 atmosphere, or a plasma treatment with H 2 , an Al container, an Al-Mg alloy container, Al-Mg-Si Use an alloy-based container. Al and the like are due to the fact that HfAcAc complex is hardly formed among metals.
また、ＨｆＡｃＡｃは、Ａｌ、Ａｌ−Ｍｇ合金、Ａｌ−Ｍｇ−Ｓｉ系合金、Ｃｒ金属単体とは錯体を形成しにくいが、Ａｌ、Ａｌ−Ｍｇ合金、またはＡｌ−Ｍｇ−Ｓｉ系合金の酸化物に変化すると錯体を形成しやすくなる。表面の自然酸化膜を除去するため、本発明では前処理を施す必要がある。ここで取り扱うＡｌ、Ａｌ−Ｍｇ合金、またはＡｌ−Ｍｇ−Ｓｉ系合金とは、その組成が、Ａｌ（１００％Ａｌ）、Ａｌ−Ｍｇ合金（Ａｌ：９９．９〜９０．０％、Ｍｇ：０．１〜１０．０％）、Ａｌ−Ｍｇ−Ｓｉ系合金（Ａｌ：９９．８〜９４．０％、Ｍｇ：０．１〜５．０％、Ｓｉ：０．１〜１．０％）のものである。前処理の方法は、その一つの方法として、ＨｆＡｃＡｃによる洗浄処理がある。洗浄処理とは、まずＨｆＡｃＡｃを不活性ガスにより置換した容器内に入れて密閉し、加温した状態で一定時間保持する。この際、不活性ガスの種類については特に問わない。温度については、１０〜４００℃の温度範囲が好ましい。１０℃未満だと、十分な効果が得られず、また４００℃を超えるとＨｆＡｃＡｃが炭化し、容器表面にすすが付着するため好ましくない。次に、容器内のＨｆＡｃＡｃを廃棄し、もう一度ＨｆＡｃＡｃにより洗浄した後、不活性ガス雰囲気下で乾燥を行うものである。この際の不活性ガスの種類、条件についても特に問わない。 HfAcAc is difficult to form a complex with Al, Al—Mg alloy, Al—Mg—Si alloy, and Cr metal alone, but is an oxide of Al, Al—Mg alloy, or Al—Mg—Si alloy. When it changes to, it becomes easier to form a complex. In order to remove the natural oxide film on the surface, it is necessary to perform a pretreatment in the present invention. The Al, Al—Mg alloy, or Al—Mg—Si alloy used here has a composition of Al (100% Al), Al—Mg alloy (Al: 99.9 to 90.0%, Mg: 0.1 to 10.0%), Al—Mg—Si based alloy (Al: 99.8 to 94.0%, Mg: 0.1 to 5.0%, Si: 0.1 to 1.0%) )belongs to. As one of the pretreatment methods, there is a cleaning treatment with HfAcAc. In the cleaning treatment, first, HfAcAc is placed in a container substituted with an inert gas, sealed, and kept in a heated state for a certain period of time. At this time, the kind of the inert gas is not particularly limited. About temperature, the temperature range of 10-400 degreeC is preferable. If it is less than 10 ° C, sufficient effects cannot be obtained, and if it exceeds 400 ° C, HfAcAc is carbonized and soot adheres to the surface of the container. Next, HfAcAc in the container is discarded, washed with HfAcAc once again, and then dried in an inert gas atmosphere. In this case, the type and conditions of the inert gas are not particularly limited.
その他の方法としては、Ｈ２雰囲気によるアニール処理がある。Ｈ２によるアニール処理の温度は、１００〜５００℃の温度範囲が好ましい。Ｈ２濃度、希釈ガスの種類、圧力については、特に問わない。１００℃未満だと十分な効果が得られなく、５００℃を超えると容器の変形が起こるため好ましくない。 As another method, there is an annealing process in an H 2 atmosphere. The temperature of the annealing treatment with H 2 is preferably in the temperature range of 100 to 500 ° C. The H 2 concentration, the type of dilution gas, and the pressure are not particularly limited. When the temperature is lower than 100 ° C, a sufficient effect cannot be obtained, and when the temperature exceeds 500 ° C, the container is deformed, which is not preferable.
さらにもう一つの方法としては、Ｈ２によるプラズマ処理がある。この場合、Ｈ２濃度については、２０〜１００ｖｏｌ％の範囲が好ましい。希釈する場合には、Ａｒを８０〜０ｖｏｌ％の範囲で添加することが好ましい。次に電力密度は、０．５〜１．５ Ｗ／ｃｍ２の範囲で用いる方が効果的であり好ましい。電力密度が０．５Ｗ／ｃｍ２未満だと十分な効果が得られず、また１．５Ｗ／ｃｍ２を超えると容器自体の損傷が激しく好ましくない。温度については特に問わないが、好ましくは０〜５００ ℃の範囲で用いる方が効果的であり好ましい。０ ℃未満では装置自体の冷却が必要であり、５００ ℃を超えると装置の加熱が問題になるため実用的ではない。圧力についても特に問わないが、好ましくは０．１〜１０００ Ｐａの範囲、更に好ましくは１０〜５００ Ｐａで用いる方が効果的であり好ましい。 Yet another method is plasma treatment with H 2 . In this case, the H 2 concentration is preferably in the range of 20 to 100 vol%. When diluting, it is preferable to add Ar in the range of 80 to 0 vol%. Next, it is more effective and preferable to use the power density in the range of 0.5 to 1.5 W / cm 2 . If the power density is less than 0.5 W / cm 2 , sufficient effects cannot be obtained, and if it exceeds 1.5 W / cm 2 , the container itself is severely damaged, which is not preferable. Although it does not ask | require in particular about temperature, It is more effective and preferable to use in the range of 0-500 degreeC preferably. If it is less than 0 ° C., it is necessary to cool the device itself. Although it does not ask | require also about a pressure in particular, Preferably it is the range of 0.1-1000 Pa, More preferably, it is more effective and preferable to use in 10-500 Pa.
本発明の方法により、ＨｆＡｃＡｃの分解・反応を抑制し、純度の低下を起こさずに長期保存することができる。 According to the method of the present invention, decomposition and reaction of HfAcAc can be suppressed, and long-term storage can be performed without causing a decrease in purity.
以下、実施例により本発明を詳細に説明するが、かかる実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, it is not limited to this Example.
実施例２〜１０、比較例２〜４
Ａｌ製容器、Ａｌ−Ｍｇ合金製容器（Ａ５０５２）、Ａｌ−Ｍｇ−Ｓｉ系合金製容器（Ａ６０６３）をそれぞれ十分に洗浄した後、十分な乾燥を行った。つぎに、ＨｆＡｃＡｃによる洗浄処理を施した後（実施例２、３、４）、温度２００℃、Ｈ２濃度１００％、圧力１０３ｋＰａでＨ２アニール処理（実施例５、６、７）、及びＨ２濃度１００％、電流密度０．７５Ｗ／ｃｍ２、温度５０℃、圧力１．０ＰａでＨ２プラズマ処理（実施例８、９、１０）を施した後、フィルターにより金属パーティクルを除去したＡｒによって容器内を十分に置換した。その後、ＨｆＡｃＡｃを５００ｇ正確に測り入れ、マントルヒーターで３０℃に加熱した状態で１週間、及び２週間それぞれ放置し、容器内のＨｆＡｃＡｃ中の金属成分をＩＣＰ−ＭＳ（Ｉｎｄｕｃｔｉｖｅｌｙ Ｃｏｕｐｌｅｄ Ｐｌａｓｍａ Ｍａｓｓ Ｓｐｅｃｔｒｏｓｃｏｐｙ）を用いて分析した。
Examples 2-10, Comparative Examples 2-4
The Al container, the Al—Mg alloy container (A5052), and the Al—Mg—Si alloy container (A6063) were each thoroughly washed and then sufficiently dried. Next, after performing a cleaning process with HfAcAc (Examples 2, 3, and 4), an H 2 annealing process (Examples 5, 6, and 7) at a temperature of 200 ° C., an H 2 concentration of 100%, and a pressure of 103 kPa, and H 2 After performing H 2 plasma treatment (Examples 8, 9, and 10) at a concentration of 100%, a current density of 0.75 W / cm 2 , a temperature of 50 ° C., and a pressure of 1.0 Pa, Ar was used to remove metal particles with a filter. The inside of the container was sufficiently replaced. Thereafter, 500 g of HfAcAc was accurately measured, and left for 1 week and 2 weeks while being heated to 30 ° C. with a mantle heater, and the metal component in HfAcAc in the container was subjected to ICP-MS (Inductively Coupled Plasma Mass Spectroscopy) . And analyzed.
以上の操作で得られた結果を実験前、及び前処理を施していないＡｌ製容器、Ａｌ−Ｍｇ合金製容器（Ａ５０５２）、Ａｌ−Ｍｇ−Ｓｉ系合金製容器（Ａ６０６３）の比較例の分析結果と併せて表１に示す。前処理を施したＡｌ製容器、Ａｌ−Ｍｇ合金製容器、Ａｌ−Ｍｇ−Ｓｉ系合金製容器からは、いずれもＡｌの増加が認められていない。 The results obtained by the above operations were analyzed before the experiment and in comparative examples of an Al container, an Al—Mg alloy container (A5052), and an Al—Mg—Si alloy container (A6063) that had not been pretreated. The results are shown in Table 1 . No increase in Al was observed from the pre-treated Al container, Al—Mg alloy container, and Al—Mg—Si alloy container.
以上の結果より、Ａｌ製容器、Ａｌ−Ｍｇ合金製容器、Ａｌ−Ｍｇ−Ｓｉ系合金製容器に前処理を施した後、使用することで純度の低下がなく、ＨｆＡｃＡｃを長期保存方法することができた。 From the above results, after pre-treating an Al container, an Al—Mg alloy container, or an Al—Mg—Si alloy container, there is no decrease in purity by using it, and HfAcAc is stored for a long period of time. I was able to.
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