JP2006272265A - Method and apparatus for modifying surface of article by fluorine-containing gas - Google Patents
Method and apparatus for modifying surface of article by fluorine-containing gas Download PDFInfo
- Publication number
- JP2006272265A JP2006272265A JP2005098889A JP2005098889A JP2006272265A JP 2006272265 A JP2006272265 A JP 2006272265A JP 2005098889 A JP2005098889 A JP 2005098889A JP 2005098889 A JP2005098889 A JP 2005098889A JP 2006272265 A JP2006272265 A JP 2006272265A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- gas
- zone
- chamber
- surface modification
- 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
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 161
- 239000011737 fluorine Substances 0.000 title claims abstract description 159
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 158
- 238000000034 method Methods 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 136
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims description 188
- 238000012986 modification Methods 0.000 claims description 36
- 230000004048 modification Effects 0.000 claims description 36
- 238000002715 modification method Methods 0.000 claims description 33
- 239000004743 Polypropylene Substances 0.000 claims description 18
- 229920001155 polypropylene Polymers 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000011261 inert gas Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000004891 communication Methods 0.000 claims description 8
- 150000002736 metal compounds Chemical class 0.000 claims description 8
- -1 polypropylene Polymers 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 238000003682 fluorination reaction Methods 0.000 claims description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 229910052743 krypton Inorganic materials 0.000 claims description 3
- 238000004518 low pressure chemical vapour deposition Methods 0.000 claims description 3
- 150000001247 metal acetylides Chemical class 0.000 claims description 3
- 229910001510 metal chloride Inorganic materials 0.000 claims description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910003465 moissanite Inorganic materials 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 3
- 229920005591 polysilicon Polymers 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- 229910010272 inorganic material Inorganic materials 0.000 claims description 2
- 239000011147 inorganic material Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000011368 organic material Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- 238000004381 surface treatment Methods 0.000 description 11
- 125000004429 atom Chemical group 0.000 description 10
- 238000009616 inductively coupled plasma Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910018089 Al Ka Inorganic materials 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Landscapes
- Treatments Of Macromolecular Shaped Articles (AREA)
- Silicon Compounds (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、含フッ素化合物含有ガスを減圧下で励起して活性種を生成させ、その後圧力を大気圧あるいはそれ以上へと上昇させるとともに冷却することで、生成した活性種の全てを実質的に失活させフッ素含有ガス（以下、F2ガスと言う場合がある）を発生させ、該F2ガスを物品の表面と接触させて該表面を改質する方法に関する。 The present invention excites the fluorine-containing compound-containing gas under reduced pressure to generate active species, and then raises the pressure to atmospheric pressure or higher and cools it to substantially all the generated active species. The present invention relates to a method for generating a fluorine-containing gas (hereinafter sometimes referred to as F 2 gas) by deactivation and bringing the F 2 gas into contact with the surface of an article to modify the surface.
また、本発明は、含フッ素化合物含有ガスを減圧下で励起して活性種を生成させ、その後圧力を大気圧あるいはそれ以上へと上昇させるとともに冷却することで、生成した活性種の全てを実質的に失活させF2ガスを発生させ、該F2ガスを物品の表面と接触させて表面を改質するための装置にも関する。 Further, the present invention excites the fluorine-containing compound-containing gas under reduced pressure to generate active species, and then raises the pressure to atmospheric pressure or higher and cools it to substantially all the generated active species. manner quenched to generate F 2 gas, also relates to an apparatus for modifying the surface of the F 2 gas is contacted with the surface of the article.
プラズマCVD法は、半導体デバイスの製造における薄膜形成に広く用いられている。プラズマCVD法では、NF3等のガス状の含フッ素化合物をプラズマ化し、該プラズマ活性種により半導体基板表面のエッチングやCVDチャンバーのクリーニングが行われている。その際、F2ガスも生成するが、F2ガスは排ガスとして処理されている。
例えば、F2ガスをプラズマ化し、このプラズマ活性種を用いてCVDチャンバーの内壁をクリーニングする方法としては、特許文献１のようなものが挙げられる。この場合、F2ガス自体が利用されるのではなく、F2ガスのプラズマが使用されている。
また、含フッ素化合物に由来するプラズマを用いて半導体以外の材料の表面処理を行う方法としては、金属材料やプラスチック材料の表面処理が報告されている（特許文献２及び特許文献３を参照）。しかし、この方法ではプラズマが表面処理される物品の内部に侵入し、該物質に損傷を与える可能性がある。
The plasma CVD method is widely used for thin film formation in the manufacture of semiconductor devices. In the plasma CVD method, a gaseous fluorine-containing compound such as NF 3 is converted into plasma, and the surface of the semiconductor substrate is etched and the CVD chamber is cleaned by the plasma active species. At that time, F 2 gas is also produced, but the F 2 gas is treated as exhaust gas.
For example, as a method for converting F 2 gas into plasma and cleaning the inner wall of the CVD chamber using this plasma active species, the method described in
In addition, as a method for performing surface treatment of a material other than a semiconductor using plasma derived from a fluorine-containing compound, surface treatment of a metal material or a plastic material has been reported (see
F2ガスをプラズマ化せずに用いて表面処理を行う方法も報告されている（例えば、特許文献４を参照）。しかし、このようにF2ガスを直接用いる方法には、以下の問題がある。まず、F2ガスの毒性、危険性、反応性、及び腐食性のため、F2ガスを大量に保管、輸送、及び使用することが困難である。危険性を低減するため、希釈したF2ガスを使用することもできるが、保管及び輸送コストが増加する。さらに、F2ガスが接触する部位には、非常に安定な材料を用いる必要があるため、表面処理設備のコストが高くなる。 There has also been reported a method of performing surface treatment using F 2 gas without converting it into plasma (see, for example, Patent Document 4). However, such a method using F 2 gas directly has the following problems. First, the toxicity of F 2 gas, risk, reactivity, and for corrosion resistance, mass storage of F 2 gas, transportation, and it is difficult to use. To reduce the risk, diluted F 2 gas can be used, but storage and transportation costs increase. Furthermore, since it is necessary to use a very stable material for the portion where the F 2 gas comes into contact, the cost of the surface treatment equipment increases.
また、ハロゲン化合物を、大気圧又はその近傍の圧力下で低周波電圧を印加することにより励起して分解し、ハロゲン又はハロゲン化水素を発生させ、物品の表面を処理する方法が提案されている（特許文献５を参照）。大気圧又はその近傍の圧力下という条件で実施できることは、操作上簡易で安全な方法という利点をもつ。しかし、この方法では分解効率が低く、発生させ得るハロゲン又はハロゲン化水素の濃度はかなり希薄なレベルのものであって、その後の利用に供するのに充分な濃度や量を確保するのは容易なことでない。
本発明は、上記のような事情に鑑みなされたものであり、簡便な装置において安全で容易にF2ガスによる表面改質を行う方法を提供する。本発明は、安全で容易にF2ガスによる表面改質を行うことができる装置も提供する。 The present invention has been made in view of the above circumstances, and provides a method for performing surface modification with F 2 gas safely and easily in a simple apparatus. The present invention also provides an apparatus that can perform surface modification with F 2 gas safely and easily.
本発明者らは、これらの課題を解決すべく鋭意検討を進めた結果、F2ガスよりも取り扱いが容易な含フッ素化合物を含有するガスを供給し、表面改質前に該含フッ素化合物をF2ガスに変換することにより、安全で容易にF2ガスによる表面改質を行うことができることを発見し、特には、含フッ素化合物を減圧状態で励起して活性種を生成させ、その後圧力を大気圧あるいはそれ以上に上昇させるとともに冷却することで、生成した活性種の全てを実質的に失活させることにより、含フッ素化合物からＦ２ガスを効率良く、充分な濃度と量とで発生させることができることを見出し、本発明を完成させた。 As a result of diligent investigations to solve these problems, the present inventors have supplied a gas containing a fluorine-containing compound that is easier to handle than F 2 gas, and the fluorine-containing compound is not subjected to surface modification. It was discovered that surface modification with F 2 gas can be performed safely and easily by converting to F 2 gas, and in particular, the fluorine-containing compound is excited under reduced pressure to generate active species, and then the pressure the by cooling with increasing atmospheric pressure or more, the by substantially inactivate all of the generated active species efficiently F 2 gas from the fluorine-containing compound, generated in a sufficient concentration and amount The present invention has been completed.
本発明によれば、含フッ素化合物から表面改質に必要とされる量のF2ガスを製造して表面改質に使用できるため、大量のF2ガスを予め準備・保管する必要がない。 According to the present invention, since an amount of F 2 gas required for surface modification can be produced from a fluorine-containing compound and used for surface modification, it is not necessary to prepare and store a large amount of F 2 gas in advance.
即ち、本発明は、以下のものを提供する。
[Ａ]（１）第１のゾーン中で、含フッ素化合物含有ガスに減圧下でエネルギーを付与することにより、含フッ素化合物含有ガス中の少なくとも１つの含フッ素化合物を励起し、それにより発生した活性種を含む励起含フッ素化合物含有ガスを生成し、
（２）生成した励起含フッ素化合物含有ガスを、第１のゾーンと連通した第２のゾーンに輸送する間に、輸送系内の圧力を大気圧または大気圧以上へと上昇させるとともに輸送系を冷却することにより、活性種の全てを実質的に失活させ、フッ素ガスに変換して、フッ素含有ガスを生成し、
（３）第２のゾーン中で、フッ素含有ガスと物品の表面とを減圧、大気圧または大気圧以上の圧力下で接触させ、該物品の表面を改質する、
表面改質方法。
[Ｂ]（１）第１のゾーン中で、含フッ素化合物含有ガスに減圧下でエネルギーを付与することにより、含フッ素化合物含有ガス中の少なくとも１つの含フッ素化合物を励起し、それにより発生した活性種を含む励起含フッ素化合物含有ガスを生成し、
（２）第１のゾーン中の圧力を大気圧あるいは大気圧以上へと上昇させるとともに冷却することにより、活性種の全てを実質的に失活させ、フッ素ガスに変換して、フッ素含有ガスを生成し、
（３）生成したフッ素含有ガスを、第１のゾーンと連通した第２のゾーンに輸送し、
（４）第２のゾーン中で、フッ素含有ガスを物品の表面と減圧、大気圧または大気圧以上の圧力下で接触させ、該物品の表面を改質する、
表面改質方法。
[Ｃ]第１のゾーンが第１の反応チャンバーであり、第２のゾーンが第２の反応チャンバーである、[Ａ]〜[Ｂ]の何れかに記載の表面改質方法。
[Ｄ]含フッ素化合物含有ガスにエネルギーを付与してから表面改質される物品と接触させるまでの間に、不活性ガスを導入する工程をさらに含む、[Ａ]〜[Ｃ]の何れかに記載の表面改質方法。
[Ｅ]エネルギーを付与する工程が含フッ素化合物含有ガスのプラズマ化を含む、[Ａ]〜[Ｄ]の何れかに記載の表面改質方法。
[Ｆ]含フッ素化合物が、ＮＦ3、Ｃ2Ｆ6、ＣＯＦ2、またはこれらの組み合わせから選択される、[Ａ]〜[Ｅ]の何れかに記載の表面改質方法。
[Ｇ]含フッ素化合物含有ガスが、不活性ガス及び／または酸素を含む、[Ａ]〜[Ｆ]の何れかに記載の表面改質方法。
[Ｈ]不活性ガスが、Ｈｅ、Ｎｅ、Ａｒ、Ｘｅ、Ｋｒ、Ｎ2、またはこれらの組み合わせである、[Ｇ]に記載の表面改質方法。
[Ｉ]含フッ素化合物が、Ｃ2Ｆ6、ＣＯＦ2、またはこれら混合物のとき、酸素の存在下でプラズマ化される、[Ａ]〜[Ｈ]の何れかに記載の表面改質方法。
[Ｊ]表面改質が、物品表面のフッ素化によって行われる、[Ａ]〜[Ｉ]の何れかに記載の表面改質方法。
[Ｋ]表面改質される物品が、金属及び／または金属化合物及び／またはポリマーである、[Ａ]〜[Ｊ]の何れかに記載の表面改質方法。
[Ｌ]ポリマーが、ポリプロピレンを主成分とする物品である、[Ｋ]に記載の表面改質方法。
[Ｍ]金属化合物が、金属酸化物、金属窒化物、金属炭化物、金属水酸化物及び金属塩化物の群から選択される１種以上である、[Ｋ]に記載の表面改質方法。
[Ｎ]金属化合物がＳｉを主成分とする化合物である、[Ｋ]に記載の表面改質方法。
[Ｏ]Ｓｉを主成分とする化合物が、Ｓｉ、ＳｉＯ2、Ｓｉ3Ｎ4、ＳｉＣ、ポリシリコン、アモルファスシリコン、またはこれらの組み合わせである、[Ｎ]に記載の表面改質方法。
[Ｐ]Ｓｉを主成分とする化合物が、ＬＰＣＶＤ装置で成膜されたものである、[Ｎ]に記載の表面改質方法。
[Ｑ]（１）含フッ素化合物含有ガスを減圧下でプラズマ化する手段を備えた、第１のゾーンと、
（２）該第１のゾーンと連通し、内部に表面改質される物品を有するとともに、該第１のゾーンから輸送する間に、輸送系内の圧力を大気圧あるいはそれ以上に調整するとともに輸送系を冷却する手段を備え、発生したフッ素含有ガスと該物品の表面とを減圧、大気圧または大気圧以上の圧力下で接触させて、該物品の表面を改質する手段を備えた、第２のゾーンと、
を備えた表面改質装置。
[Ｒ]（１）含フッ素化合物含有ガスを減圧下でプラズマ化し、その後圧力を大気圧あるいはそれ以上に調整するとともに冷却することによりフッ素含有ガスを発生する手段を備えた、第１のゾーンと、
（２）該第１のゾーンと連通し、内部に表面改質される物品を有するとともに、発生したフッ素含有ガスと該物品の表面とを減圧、大気圧または大気圧以上の圧力下で接触させて、該物品の表面を改質する手段を備えた、第２のゾーンと、
を備えた表面改質装置。
[Ｓ]（１）含フッ素化合物含有ガスを減圧下でプラズマ化する手段を備えた、第１のチャンバーと、
（２）該第１のチャンバーと連通し、圧力を大気圧あるいはそれ以上に調整するとともに冷却することでフッ素含有ガスを発生する手段を備えた輸送路と、
（３）該輸送路と連通し、内部に表面改質される物品を有するとともに、発生したフッ素含有ガスと該物品の表面とを減圧、大気圧または大気圧以上の圧力下で接触させて、該物品の表面を改質する手段を備えた、第２のチャンバーと、
を備えた表面改質装置。
[Ｔ]第１のチャンバーの後ろに真空ポンプが、さらに第２のチャンバーの前及び／または後に、コンプレッサー若しくは真空ポンプが設置される、[Ｑ]〜[Ｓ]の何れかに記載の表面改質装置。
[Ｕ]第１のチャンバー、真空ポンプ、第２のチャンバー、及び真空ポンプが順に連通し、さらに、第１のチャンバーと真空ポンプ、第２のチャンバーと真空ポンプが、それぞれ独立して連通する、[Ｑ]〜[Ｓ]の何れかに記載の表面改質装置。
[Ｖ]第１のチャンバー、真空ポンプ、コンプレッサー、及び第２のチャンバーが順に連通し、さらに、第１のチャンバーと真空ポンプ、コンプレッサーと第２のチャンバーが、それぞれ独立して連通する、[Ｑ]〜[Ｓ]の何れかに記載の表面改質装置。
[Ｗ][Ｑ]〜[Ｖ]の何れかに記載の装置を、有機及び／または無機材料の直接フッ素化反応に用いる表面改質方法。
That is, the present invention provides the following.
[A] (1) In the first zone, by applying energy to the fluorine-containing compound-containing gas under reduced pressure, at least one fluorine-containing compound in the fluorine-containing compound-containing gas is excited and generated thereby Producing an excited fluorine-containing compound-containing gas containing active species,
(2) While transporting the generated excited fluorine-containing compound-containing gas to the second zone communicating with the first zone, the pressure in the transport system is increased to atmospheric pressure or higher and the transport system is By cooling, substantially all of the active species are deactivated and converted to fluorine gas, producing a fluorine-containing gas,
(3) In the second zone, the fluorine-containing gas and the surface of the article are brought into contact under reduced pressure, atmospheric pressure or a pressure higher than atmospheric pressure to modify the surface of the article.
Surface modification method.
[B] (1) In the first zone, by applying energy to the fluorine-containing compound-containing gas under reduced pressure, at least one fluorine-containing compound in the fluorine-containing compound-containing gas was excited and generated thereby Producing an excited fluorine-containing compound-containing gas containing active species,
(2) By raising the pressure in the first zone to atmospheric pressure or above atmospheric pressure and cooling it, substantially all of the active species are deactivated and converted to fluorine gas. Generate and
(3) transporting the generated fluorine-containing gas to a second zone communicating with the first zone;
(4) In the second zone, the fluorine-containing gas is brought into contact with the surface of the article under reduced pressure, atmospheric pressure or a pressure higher than atmospheric pressure to modify the surface of the article.
Surface modification method.
[C] The surface modification method according to any one of [A] to [B], wherein the first zone is a first reaction chamber and the second zone is a second reaction chamber.
[D] The method according to any one of [A] to [C], further comprising a step of introducing an inert gas between the time when energy is applied to the fluorine-containing compound-containing gas and the contact with the article to be surface-modified. The surface modification method described in 1.
[E] The surface modification method according to any one of [A] to [D], wherein the step of imparting energy includes plasma formation of the fluorine-containing compound-containing gas.
[F] The surface modification method according to any one of [A] to [E], wherein the fluorine-containing compound is selected from NF 3 , C 2 F 6 , COF 2 , or a combination thereof.
[G] The surface modification method according to any one of [A] to [F], wherein the fluorine-containing compound-containing gas contains an inert gas and / or oxygen.
[H] The surface modification method according to [G], wherein the inert gas is He, Ne, Ar, Xe, Kr, N 2 , or a combination thereof.
[I] The surface modification method according to any one of [A] to [H], wherein when the fluorine-containing compound is C 2 F 6 , COF 2 , or a mixture thereof, the plasma is formed in the presence of oxygen.
[J] The surface modification method according to any one of [A] to [I], wherein the surface modification is performed by fluorination of the article surface.
[K] The surface modification method according to any one of [A] to [J], wherein the article to be surface-modified is a metal and / or a metal compound and / or a polymer.
[L] The surface modification method according to [K], wherein the polymer is an article mainly composed of polypropylene.
[M] The surface modification method according to [K], wherein the metal compound is at least one selected from the group consisting of metal oxides, metal nitrides, metal carbides, metal hydroxides, and metal chlorides.
[N] The surface modification method according to [K], wherein the metal compound is a compound containing Si as a main component.
[O] The surface modification method according to [N], wherein the compound containing Si as a main component is Si, SiO 2 , Si 3 N 4 , SiC, polysilicon, amorphous silicon, or a combination thereof.
[P] The surface modification method according to [N], wherein the compound containing Si as a main component is formed by an LPCVD apparatus.
[Q] (1) a first zone comprising means for converting the fluorine-containing compound-containing gas into plasma under reduced pressure;
(2) While having an article which is in communication with the first zone and whose surface is modified inside, and adjusting the pressure in the transport system to atmospheric pressure or higher while transporting from the first zone, A means for cooling the transport system, and a means for modifying the surface of the article by bringing the generated fluorine-containing gas into contact with the surface of the article under reduced pressure, atmospheric pressure or a pressure higher than atmospheric pressure, A second zone;
A surface modification apparatus equipped with
[R] (1) a first zone comprising means for generating a fluorine-containing gas by converting a fluorine-containing compound-containing gas into a plasma under reduced pressure and then adjusting the pressure to atmospheric pressure or higher and cooling it; ,
(2) Having an article that is surface-modified inside and communicates with the first zone, and the generated fluorine-containing gas and the surface of the article are brought into contact under reduced pressure, atmospheric pressure, or pressure higher than atmospheric pressure. A second zone comprising means for modifying the surface of the article;
A surface modification apparatus equipped with
[S] (1) a first chamber comprising means for converting the fluorine-containing compound-containing gas into plasma under reduced pressure;
(2) a transport path that communicates with the first chamber and that has means for generating a fluorine-containing gas by adjusting the pressure to atmospheric pressure or higher and cooling it;
(3) having an article which is in communication with the transport path and whose surface is modified inside, and contacting the generated fluorine-containing gas with the surface of the article under reduced pressure, atmospheric pressure or pressure higher than atmospheric pressure; A second chamber comprising means for modifying the surface of the article;
A surface modification apparatus equipped with
[T] The surface modification according to any one of [Q] to [S], wherein a vacuum pump is installed behind the first chamber, and a compressor or a vacuum pump is installed before and / or after the second chamber. Quality equipment.
[U] The first chamber, the vacuum pump, the second chamber, and the vacuum pump communicate with each other in order, and further, the first chamber and the vacuum pump, and the second chamber and the vacuum pump communicate with each other independently. [Q] to [S] The surface modifying apparatus according to any one of [S].
[V] The first chamber, the vacuum pump, the compressor, and the second chamber communicate with each other in order, and the first chamber and the vacuum pump, and the compressor and the second chamber communicate with each other independently, [Q ] To [S].
[W] A surface modification method using the apparatus according to any one of [Q] to [V] for direct fluorination reaction of organic and / or inorganic materials.
本発明において、第１のゾーンは、エネルギーを付与する手段により、含フッ素化合物含有ガスに減圧下でエネルギーが付与される空間をさし、第２のゾーンとは、表面改質される物品が設置される空間をさす。第１のゾーンと第２のゾーンとはガス連通し、含フッ素化合物含有ガスが第１のゾーンから第２のゾーンへガス連通する。 In the present invention, the first zone refers to a space where energy is imparted to the fluorine-containing compound-containing gas under reduced pressure by means for imparting energy, and the second zone refers to the article whose surface is to be modified. Refers to the installation space. The first zone and the second zone are in gas communication, and the fluorine-containing compound-containing gas is in gas communication from the first zone to the second zone.
第１のゾーン及び第２のゾーンは、同一のチャンバーであってもよいし、異なるチャンバーであってもよい。後者の場合、第１のゾーン及び第２のゾーンは、各々第１のチャンバー及び第２のチャンバーとなる。第１のチャンバー及び第２のチャンバーは、任意の公知の方法によりガス連通される。例えば、第１のチャンバー及び第２のチャンバーがガス流通によって接続され、含フッ素化合物含有ガスが該ガス流路を通じて第１のゾーンから第２のゾーンへ流通する。
また、第１のゾーンと第２のゾーンは独立して連通しており、両者の圧力を独立に
変動させることができる。第１のゾーンでは減圧下で含フッ素化合物含有ガスを励起し、第１のゾーンから第２のゾーンへの輸送過程で圧力を大気圧あるいはそれ以上に上げるとともに冷却することにより、生成した活性種の全てを実質的に失活させF2ガスに変換し、第２のゾーンで該F2ガスを物品の表面と、減圧、大気圧または大気圧以上の圧力下で接触させ、表面を改質する。ただし、F2への変換は、かかる様態に限定されるものではなく、第１のゾーン中で行われてもよい。
本発明において、第１のゾーンに供給される含フッ素化合物含有ガス中の含フッ素化合物はエネルギー付与によって励起し分解された後にF2ガスを生成し、F2ガスよりも取り扱いが容易であれば特に制限はないが、F2ガスを効率的に発生させるという点からNF3、C2F6、COF2が望ましい。これらの含フッ素化合物は、単独で使用しても、また組み合わせて使用してもよい。
The first zone and the second zone may be the same chamber or different chambers. In the latter case, the first zone and the second zone become the first chamber and the second chamber, respectively. The first chamber and the second chamber are in gas communication by any known method. For example, the first chamber and the second chamber are connected by gas flow, and the fluorine-containing compound-containing gas flows from the first zone to the second zone through the gas flow path.
Moreover, the 1st zone and the 2nd zone are connected independently, The pressure of both can be fluctuate | varied independently. In the first zone, the fluorine-containing compound-containing gas is excited under reduced pressure, and the active species generated by raising the pressure to atmospheric pressure or higher and cooling in the process of transport from the first zone to the second zone All of the above is substantially deactivated and converted to F 2 gas, and in the second zone, the F 2 gas is brought into contact with the surface of the article under reduced pressure, atmospheric pressure or a pressure higher than atmospheric pressure to modify the surface. To do. However, the conversion to F 2 is not limited to such a mode, and may be performed in the first zone.
In the present invention, the fluorine-containing compound in the fluorine-containing compound-containing gas supplied to the first zone generates F 2 gas after being excited and decomposed by applying energy, and is easier to handle than F 2 gas. Although there is no particular limitation, NF 3 , C 2 F 6 , and COF 2 are desirable in terms of efficiently generating F 2 gas. These fluorine-containing compounds may be used alone or in combination.
第１のゾーンに供給される含フッ素化合物含有ガスは、含フッ素化合物以外のガスを含有してもよい。含フッ素化合物以外のガスの種類及び流量、並びに第１のゾーンの圧力は、第１のゾーンで含フッ素化合物を励起する様態、及び、目的とする生成F2濃度に応じて選択される。第１のゾーンでプラズマを発生させる場合、含フッ素化合物以外のガスとして、不活性ガス及び／又は酸素を用いることができる。不活性ガスには、He、Ne、Ar、Xe、Kr、N2、またはそれらの組み合わせが含まれる。含フッ素化合物がC2F6あるいはCOF2を含む場合、O2が好ましい。 The fluorine-containing compound-containing gas supplied to the first zone may contain a gas other than the fluorine-containing compound. The type and flow rate of the gas other than the fluorine-containing compound and the pressure in the first zone are selected in accordance with the state of exciting the fluorine-containing compound in the first zone and the target generated F 2 concentration. When plasma is generated in the first zone, an inert gas and / or oxygen can be used as a gas other than the fluorine-containing compound. The inert gas includes He, Ne, Ar, Xe, Kr, N 2 , or combinations thereof. When the fluorine-containing compound contains C 2 F 6 or COF 2 , O 2 is preferable.
第１のゾーンにおいて、含フッ素化合物にエネルギーを付与して励起する方法としては、プラズマ化が挙げられる。プラズマ化には、任意の公知の手法を用いることができ、例えば、誘導結合プラズマ（ICP）、ヘリコン波プラズマ、及び電子サイクロトン共鳴プラズマ（ECR）が挙げられる。 In the first zone, as a method for exciting the fluorine-containing compound by applying energy, plasma formation can be mentioned. Arbitrary well-known methods can be used for plasmatization, and examples thereof include inductively coupled plasma (ICP), helicon wave plasma, and electron cyclotron resonance plasma (ECR).
第１のゾーンで励起された含フッ素化合物を含有するガスは、第２のゾーンで表面改質される物品と接触するまでの間にF2を生成する。F2は第１のゾーンで生成してもよく、第１のゾーンから第２のゾーンへ輸送する間に生成してもよい。第１のゾーン及び第２のゾーンが異なるチャンバーである場合、両者を接続するガス流路中でF2が生成してもよい。F2が生成する反応機構に制限はなく、例えば励起により生じたFラジカルの再結合が挙げられる。 The gas containing the fluorine-containing compound excited in the first zone generates F 2 until it comes into contact with the article to be surface-modified in the second zone. F 2 may be generated in the first zone or may be generated during transport from the first zone to the second zone. When the first zone and the second zone are different chambers, F 2 may be generated in the gas flow path connecting the two . There is no limitation on the reaction mechanism in which F 2 is generated, and examples thereof include recombination of F radicals generated by excitation.
含フッ素化合物含有ガスが２以上の含フッ素化合物を含有する場合、全ての種類の含フッ素化合物からF2が生成してもよく、一部の種類の含フッ素化合物のみがF2生成に寄与してもよい。なお第１のゾーンに供給される際に含フッ素化合物を含有したガスを、本明細書では「含フッ素化合物含有ガス」と表記する。第１のゾーンで励起された含フッ素化合物を含有するガスを、「励起含フッ素化合物含有ガス」と表記する。また、「励起含フッ素化合物含有ガス」中に、励起された含フッ素化合物由来のF2が含まれる場合がある。 When the fluorine-containing compound-containing gas contains two or more fluorine-containing compounds, F 2 may be generated from all types of fluorine-containing compounds, and only some types of fluorine-containing compounds contribute to F 2 generation. May be. Note that a gas containing a fluorine-containing compound when supplied to the first zone is referred to as a “fluorine-containing compound-containing gas” in this specification. The gas containing the fluorine-containing compound excited in the first zone is referred to as “excited fluorine-containing compound-containing gas”. Further, the “excited fluorine-containing compound-containing gas” may contain F 2 derived from the excited fluorine-containing compound.
本発明の方法では、表面改質に必要な量のF2ガスを第１のゾーンで含フッ素化合物を励起することにより製造し、第２のゾーンで表面改質に消費するため、予め大量のF2ガスを準備または輸送し、取り扱う必要がないという利点が得られる。つまり、表面改質を行う前はF2ガスよりも安定で取り扱いが容易な含フッ素化合物の形態で保存し、表面改質の際に当該含フッ素化合物をF2ガスに変換して利用することにより、従来のF2ガスの取り扱いに関する問題を解決することができる。 In the method of the present invention, an amount of F 2 gas necessary for the surface modification is produced by exciting the fluorine-containing compound in the first zone and consumed for the surface modification in the second zone. The advantage is that F 2 gas need not be prepared or transported and handled. In other words, it is prior to performing surface modification and stored in the form of a stable and easy to handle fluorine-containing compound than F 2 gas, using an equivalent fluorinated compound during surface modification are converted into F 2 gas Thus, it is possible to solve the problems related to the conventional handling of F 2 gas.
含フッ素化合物を励起してから表面改質される物品と接触させるまでの間に、該含フッ素化合物に別のガスを混合してもよい。これにより、発生F2ガス濃度を任意に調整することができる。混合する別のガスとしては、不活性ガスが好ましい。ここで不活性ガスとは、前述の通りである。別のガスの導入は、第１のゾーン内及び第２のゾーン内の任意の位置で行うことができる。第１のゾーン及び第２のゾーンが異なるチャンバーである場合、第１のチャンバーと第２のチャンバーとを接続するガス流路の任意の位置で行うことができる。 Another gas may be mixed with the fluorine-containing compound during the period from when the fluorine-containing compound is excited to when it is brought into contact with the article to be surface-modified. Thereby, the generated F 2 gas concentration can be adjusted arbitrarily. As another gas to be mixed, an inert gas is preferable. Here, the inert gas is as described above. The introduction of another gas can be performed at any position in the first zone and the second zone. When the first zone and the second zone are different chambers, it can be performed at an arbitrary position of the gas flow path connecting the first chamber and the second chamber.
第２のゾーンの圧力、温度及び発生F2濃度は、表面改質される物品の材質及び表面積に応じて選択される。
表面改質がなされる物品に特に制限はなく、F2ガスと接触して反応するものがあれば、何れの材質の物品でもよい。F2ガスと反応するという観点から、表面改質される物品は、金属及び／または金属化合物及び／またはポリマーであることが好ましい。金属としては、例えば、鉄、アルミニウム、チタン、亜鉛、ニッケル、スズ、銅等の単体金属や、ステンレス、真鍮等の合金が挙げられる。金属化合物としては、金属酸化物、金属窒化物、金属炭化物、金属水酸化物及び金属塩化物の群から選択される1種以上が挙げられ、例えば、Siを主成分とする化合物、即ちSi、SiO2、Si3N4、SiC、ポリシリコン、アモルファスシリコン、またはこれらの組み合わせ等が挙げられる。また、該Siを主成分とする化合物はＬＰＣＶＤ装置で成膜されたものも挙げられる。ポリマーとしては、ポリプロピレンを主成分とする物が挙げられる。
The pressure, temperature and generated F 2 concentration of the second zone are selected according to the material and surface area of the article to be surface modified.
There are no particular restrictions on the article to be surface-modified, and any article may be used as long as it reacts upon contact with F 2 gas. From the viewpoint of reacting with F 2 gas, the surface-modified article is preferably a metal and / or a metal compound and / or a polymer. Examples of the metal include simple metals such as iron, aluminum, titanium, zinc, nickel, tin, and copper, and alloys such as stainless steel and brass. Examples of the metal compound include one or more selected from the group of metal oxides, metal nitrides, metal carbides, metal hydroxides, and metal chlorides. For example, a compound containing Si as a main component, that is, Si, Examples thereof include SiO 2 , Si 3 N 4 , SiC, polysilicon, amorphous silicon, or a combination thereof. In addition, examples of the compound containing Si as a main component include those formed by an LPCVD apparatus. As a polymer, the thing which has a polypropylene as a main component is mentioned.
本発明は、第１のゾーン及び第２のゾーンを備えた表面改質装置に関し、第１のチャンバー、第２のチャンバー、及び第１のチャンバーと第２のチャンバーとを接続するガス流路を備えた表面改質装置にも関する。 The present invention relates to a surface reforming apparatus having a first zone and a second zone, and includes a first chamber, a second chamber, and a gas flow path connecting the first chamber and the second chamber. It also relates to a surface modification device provided.
第１のゾーンは減圧下でエネルギーを付与する手段を備え、含フッ素化合物含有ガスにエネルギーを付与することにより、含フッ素化合物含有ガス中の少なくとも１つの含フッ素化合物が励起される。エネルギーを付与する手段としては、プラズマ発生装置が挙げられる。プラズマ発生装置としては、ICPプラズマ装置、ECRプラズマ装置、及びヘリコン波プラズマ発生装置等が挙げられる。 The first zone includes means for applying energy under reduced pressure. By applying energy to the fluorine-containing compound-containing gas, at least one fluorine-containing compound in the fluorine-containing compound-containing gas is excited. As a means for applying energy, a plasma generator can be used. Examples of the plasma generator include an ICP plasma device, an ECR plasma device, and a helicon wave plasma generator.
第１のゾーンで含フッ素化合物を励起した後は、励起含フッ素化合物含有ガスは第２のゾーンに輸送される。第２のゾーンは、表面改質される物品を搬入する手段を備えることができる。搬入手段に特に制限はなく、移動ステージが試料搬入室を経由して搬入されてもよい。 After exciting the fluorine-containing compound in the first zone, the excited fluorine-containing compound-containing gas is transported to the second zone. The second zone can comprise means for carrying an article to be surface modified. There are no particular restrictions on the loading means, and the moving stage may be loaded via the sample loading chamber.
第１及び第２のゾーンが異なるチャンバーである場合、第１のチャンバー及び第２のチャンバーを接続するガス流路を通じて励起含フッ素化合物含有ガスが流通する。また、第１のチャンバーを減圧にするため第１のチャンバーの後ろに真空ポンプが、さらに、第２のチャンバーを表面改質される物品に応じて減圧乃至加圧にするため第２のチャンバーの前及び／または後に、コンプレッサー若しくは真空ポンプが設置される。 When the first and second zones are different chambers, the excited fluorine-containing compound-containing gas flows through the gas flow path connecting the first chamber and the second chamber. In addition, a vacuum pump is provided behind the first chamber for reducing the pressure of the first chamber, and further, a second pump is provided for reducing the pressure of the second chamber according to the article to be surface-modified. A compressor or vacuum pump is installed before and / or after.
本発明の表面改質装置は、輸送系を冷却する手段をさらに備える。冷却する温度としては１００℃以下とすることが望ましく、好ましくは５０℃以下、より好ましくは２５℃以下であり、また０℃以上が好ましい。この条件により活性種の全てを実質的に失活させ、効率的にフッ素ガスへの変換が行われるとともに、輸送系材料への腐食をも抑えることが可能となる。 The surface modification apparatus of the present invention further includes means for cooling the transport system. The cooling temperature is desirably 100 ° C. or lower, preferably 50 ° C. or lower, more preferably 25 ° C. or lower, and preferably 0 ° C. or higher. Under this condition, all of the active species are substantially deactivated, and conversion to fluorine gas is performed efficiently, and corrosion to the transport system material can be suppressed.
本発明の表面改質装置は、励起含フッ素化合物含有ガスと不活性ガスとを混合する手段をさらに備えてもよい。励起含フッ素化合物含有ガスと不活性ガスとを混合する手段に特に制限はなく、単に励起含フッ素化合物含有ガスの流路と不活性ガスの流路とが合流するよう設計されていてもよい。 The surface modification apparatus of the present invention may further include means for mixing the excited fluorine-containing compound-containing gas and the inert gas. The means for mixing the excited fluorine-containing compound-containing gas and the inert gas is not particularly limited, and it may be designed so that the flow path of the excited fluorine-containing compound-containing gas and the flow path of the inert gas simply merge.
第２のゾーンあるいは第２のチャンバーから排出されたガスにはF2や含フッ素化合物が残存する場合があるため、該排出ガスは排出ガス処理装置へ送られる。 Since F 2 and fluorine-containing compounds may remain in the gas exhausted from the second zone or the second chamber, the exhaust gas is sent to the exhaust gas processing device.
以下、含フッ素化合物含有ガスをプラズマ化により励起する本発明の実施態様について、図１を参照して説明する。 Hereinafter, an embodiment of the present invention in which a fluorine-containing compound-containing gas is excited by plasma will be described with reference to FIG.
図１の表面改質装置において、第１のチャンバーはプラズマ発生装置を備え、該第１のチャンバー後ろの真空ポンプでプラズマ発生に適した圧力まで減圧にする。減圧にした後、Ar等でプラズマを発生させる。作動条件は、供給される含フッ素化合物が励起されるよう選択される。作動条件は、含フッ素化合物の分解率が高くなるよう、好ましくは含フッ素化合物が完全に分解されるよう、選択される。好ましくは133.3Pa〜1333Paである。その後、含フッ素化合物、例えばNF3を含有するガスを第１のチャンバーに供給する。含フッ素化合物を、第１のチャンバーに供給する前に他のガス、例えばN2やArを混合してもよい。この混合を行う場合、含フッ素化合物及び別のガスを含有するガスが含フッ素化合物含有ガスとして第１のチャンバーに供給される。即ち、その供給される含フッ素化合物含有ガスは、NF3単独でもよいし、NF3とN2やArとの混合ガスであってもよい。 In the surface modification apparatus of FIG. 1, the first chamber includes a plasma generator, and the pressure is reduced to a pressure suitable for plasma generation by a vacuum pump behind the first chamber. After reducing the pressure, plasma is generated with Ar or the like. The operating conditions are selected such that the supplied fluorine-containing compound is excited. The operating conditions are selected so that the decomposition rate of the fluorine-containing compound is high, and preferably the fluorine-containing compound is completely decomposed. Preferably it is 133.3Pa-1333Pa. Thereafter, a gas containing a fluorine-containing compound, for example, NF 3 is supplied to the first chamber. Another gas such as N 2 or Ar may be mixed before supplying the fluorine-containing compound to the first chamber. When this mixing is performed, a gas containing a fluorine-containing compound and another gas is supplied to the first chamber as a fluorine-containing compound-containing gas. That is, the supplied fluorine-containing compound-containing gas may be NF 3 alone or a mixed gas of NF 3 and N 2 or Ar.
含フッ素化合物含有ガスがNF3単独の場合は、
NF3 → 1/2N2 ＋ 3/2F2
のように、NF3が完全にF2に変換されると、25%のN2ガスが発生するため、発生するF2ガスの濃度は最大75%となる。本発明の好ましい特徴の一つは、NF3の完全分解を実質的に達成できることにある。
When the fluorine-containing compound-containing gas is NF 3 alone,
NF 3 → 1 / 2N 2 + 3 / 2F 2
Thus, when NF 3 is completely converted to F 2 , 25% of N 2 gas is generated, so the concentration of the generated F 2 gas is 75% at the maximum. One preferred feature of the present invention is that substantially complete degradation of NF 3 can be achieved.
励起含フッ素化合物含有ガスは、ガス流路を通じて第１のチャンバーから第２のチャンバーに輸送される。該ガス流路中で、圧力を大気圧あるいはそれ以上へと上昇させるとともに冷却することにより、活性種の全てを実質的に失活させ、フッ素ガスへと変換する。 The excited fluorine-containing compound-containing gas is transported from the first chamber to the second chamber through the gas flow path. By raising the pressure to atmospheric pressure or higher and cooling in the gas flow path, all the active species are substantially deactivated and converted to fluorine gas.
導入可能なNF3量が、100sccm〜5000sccmであることから、発生F2ガス量は、150sccm〜7500sccmとなる。75%よりも希釈して使用したい場合は、処理室（第２のチャンバー）手前から、また、F2ガス濃度をできる限り低い濃度で取り扱いたい場合は、真空ポンプ手前から、不活性ガスを導入する。あるいはプラズマを発生させる条件に合致するのであれば、プラズマ発生装置手前より不活性ガスを導入し、任意の濃度に調節する。即ち、図中に示した３つの入口の内、１つ以上の任意の別のガスを混合することができる。あるいはまた、別のガスを全く混合しなくてもよく、含フッ素化合物に別のガスが混合された含フッ素化合物含有ガスを予め準備してもよい。この希釈F2ガスをライン下流に設けた処理室（第２のチャンバー）に導入し、物品の表面改質に用いる。大気圧（常圧）下での表面改質は図１、減圧下での表面改質は図２、加圧下での表面改質は図３に示すような構造になる。第２のチャンバーから排出されるガスは、排出処理装置に導入される。 Since the amount of NF 3 that can be introduced is 100 sccm to 5000 sccm, the amount of generated F 2 gas is 150 sccm to 7500 sccm. Introduce an inert gas from the front of the treatment chamber (second chamber) if you want to dilute it below 75%, or from the front of the vacuum pump if you want to handle the F 2 gas concentration as low as possible. To do. Alternatively, if the plasma generation conditions are met, an inert gas is introduced from the front of the plasma generation apparatus and adjusted to an arbitrary concentration. That is, one or more arbitrary other gases can be mixed among the three inlets shown in the figure. Alternatively, another gas may not be mixed at all, and a fluorine-containing compound-containing gas in which another gas is mixed with the fluorine-containing compound may be prepared in advance. This diluted F 2 gas is introduced into a processing chamber (second chamber) provided downstream of the line and used for surface modification of the article. The surface modification under atmospheric pressure (normal pressure) is as shown in FIG. 1, the surface modification under reduced pressure is as shown in FIG. 2, and the surface modification under pressure is as shown in FIG. The gas discharged from the second chamber is introduced into the discharge processing apparatus.
以下、本発明を実施例により説明するが、本発明が以下の実施例に限定されるものではない。
実施例１
図１の装置を用いて、含フッ素化合物含有ガスからF2を製造した。含フッ素化合物として、NF3を用い、またプラズマ発生装置として誘導結合プラズマ（ICP）発生装置（ASTeX社製ASTRONi）を使用した。
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to a following example.
Example 1
Using the apparatus of FIG. 1, F 2 was produced from a fluorine-containing compound-containing gas. NF 3 was used as the fluorine-containing compound, and an inductively coupled plasma (ICP) generator (ASTRONi manufactured by ASTeX) was used as the plasma generator.
まず、約25℃（20-25℃）で第１のチャンバーを１Torr（133Pa）まで減圧にした後、Arを1000sccm導入しプラズマを発生させた。次に、NF3（流量：1000 sccm）を第１のチャンバーに供給した。第１のチャンバー下流の配管を100℃以下の温度を維持するように冷却し、希釈ガス入口３で窒素（流量：48000 sccm）により希釈するとともに、含フッ素化合物含有ガスを真空ポンプ下流で大気圧下約25℃の第２のチャンバーに輸送した。
First, after reducing the pressure of the first chamber to 1 Torr (133 Pa) at about 25 ° C. (20-25 ° C.), 1000 sccm of Ar was introduced to generate plasma. Next, NF 3 (flow rate: 1000 sccm) was supplied to the first chamber. The piping downstream of the first chamber is cooled so as to maintain a temperature of 100 ° C. or lower, diluted with nitrogen (flow rate: 48000 sccm) at the
本実施例のNF3流量では、理論上、供給したNF3が完全にF2に変換すると（NF3 → 1/2N2 ＋ 3/2F2）、N2及びF2が、それぞれ500 sccm及び1500 sccm発生することになる。従って、NF3が完全に変換された場合には、窒素で再希釈した後のF2の濃度は3.0 vol.% となる。 In the NF 3 flow rate of this example, theoretically, when the supplied NF 3 is completely converted to F 2 (NF 3 → 1 / 2N 2 + 3 / 2F 2 ), N 2 and F 2 are 500 sccm and 1500 sccm will be generated. Therefore, when NF 3 is completely converted, the concentration of F 2 after re-dilution with nitrogen is 3.0 vol.%.
真空ポンプと第２のチャンバーとの間で含フッ素化合物含有ガスをサンプリングし、FT-IR測定及び10%KI水溶液を用いた滴定を行った。FT-IR測定装置には、Midac社製FT-IR IGA-2000を用いた。その結果、含フッ素化合物含有ガス中のF2の濃度は、3.10 vol.% であり、第１のチャンバーに供給したNF3の変換率は99.78%であることがわかった。 The fluorine-containing compound-containing gas was sampled between the vacuum pump and the second chamber, and FT-IR measurement and titration using a 10% KI aqueous solution were performed. The FT-IR IGA-2000 manufactured by Midac was used as the FT-IR measurement apparatus. As a result, it was found that the concentration of F 2 in the fluorine-containing compound-containing gas was 3.10 vol.%, And the conversion rate of NF 3 supplied to the first chamber was 99.78%.
次に、第２のチャンバー内でポリプロピレン板の表面処理を行った。第２のチャンバーとしては、内容積4.6LのNi製の円柱体容器を用いた。この中にポリプロピレン板（以下、PPと略すことがある。L×W×H＝20mm×20mm×2mm）を5個設置し、窒素ガスで第２のチャンバー内を置換した。その後、上記操作により得た含フッ素化合物含有ガスを、第２のチャンバー内に輸送し、約25℃で所定時間、PPの表面処理を行った。処理時間ごとのPP表面の接触角（水との接触角（単位：度））を測定した（処理前のPP接触角は、89度）。その測定結果を表１に示す（PP 5個（n=5）の平均値を算出）。
実施例２
第１のチャンバーから放出された含フッ素化合物含有ガスを希釈する窒素の流量を28000 sccm に変更した点を除き、実施例１と同様に実験を行った。なお、この条件でNF3が完全に変換する場合、常圧下の第２のチャンバーに輸送される含フッ素化合物含有ガス中のF2の濃度は、5.0 vol.% となる。
Next, the surface treatment of the polypropylene plate was performed in the second chamber. As the second chamber, a cylindrical cylinder made of Ni having an internal volume of 4.6 L was used. Five polypropylene plates (hereinafter abbreviated as PP. L × W × H = 20 mm × 20 mm × 2 mm) were placed therein, and the inside of the second chamber was replaced with nitrogen gas. Thereafter, the fluorine-containing compound-containing gas obtained by the above operation was transported into the second chamber, and the surface treatment of PP was performed at about 25 ° C. for a predetermined time. The contact angle (contact angle with water (unit: degree)) of the PP surface for each treatment time was measured (PP contact angle before treatment was 89 degrees). The measurement results are shown in Table 1 (calculating the average value of 5 PPs (n = 5)).
Example 2
The experiment was performed in the same manner as in Example 1 except that the flow rate of nitrogen for diluting the fluorine-containing compound-containing gas released from the first chamber was changed to 28000 sccm. When NF 3 is completely converted under these conditions, the concentration of F 2 in the fluorine-containing compound-containing gas transported to the second chamber under normal pressure is 5.0 vol.%.
サンプリングされた含フッ素化合物含有ガス中のF2の濃度は、5.03 vol.%であり、NF3の変換率は99.78%であることがわかった。 It was found that the concentration of F 2 in the sampled fluorine-containing compound-containing gas was 5.03 vol.%, And the conversion rate of NF 3 was 99.78%.
次に、実施例１と同様にして、PPの表面処理を行い、その接触角を測定した。その測定結果を表１に示す。
実施例３
含フッ素化合物として、C2F6を用い、またプラズマ発生装置として誘導結合プラズマ（ICP）発生装置（Landmark Technology社製Litmas Blue1200）を使用した。
まず、約25℃（20-25℃）で第１のチャンバーを１Torr（133Pa）まで減圧した。次に、C2F6（流量：40 sccm）を酸素（流量：160 sccm ）で希釈して含フッ素化合物含有ガスとして第１のチャンバーに供給した。プラズマ発生装置には、1200Wの出力を印加した。第１のチャンバーから放出される含フッ素化合物含有ガスを希釈ガス入口３で窒素（流量：100slm）により再度希釈するとともに、大気圧下約25℃の第２のチャンバーに輸送した。
Next, the surface treatment of PP was performed in the same manner as in Example 1, and the contact angle was measured. The measurement results are shown in Table 1.
Example 3
C 2 F 6 was used as the fluorine-containing compound, and an inductively coupled plasma (ICP) generator (Litmas Blue 1200 manufactured by Landmark Technology) was used as the plasma generator.
First, the first chamber was depressurized to 1 Torr (133 Pa) at about 25 ° C. (20-25 ° C.). Next, C 2 F 6 (flow rate: 40 sccm) was diluted with oxygen (flow rate: 160 sccm) and supplied to the first chamber as a fluorine-containing compound-containing gas. An output of 1200 W was applied to the plasma generator. The fluorine-containing compound-containing gas released from the first chamber was diluted again with nitrogen (flow rate: 100 slm) at the
サンプリングされた含フッ素化合物含有ガス中には、714 ppm のF2ガスが検出され、供給したC2F6の変換率はほぼ100%であった。 In the sampled fluorine-containing compound-containing gas, 714 ppm of F 2 gas was detected, and the conversion rate of the supplied C 2 F 6 was almost 100%.
次に、上記の窒素で希釈した含フッ素化合物含有ガスを使用して、ポリプロピレン板に代えて金属板を使用する以外は、実施例１と同様にし、その表面処理を行った。内容積4.6LのNi製の円柱体容器（第２のチャンバー）内に、アルミニウム板（以下、Alと略すことがある。L×W×H＝20mm×20mm×2mm）を5個設置し、窒素ガスで第２のチャンバー内を置換した。その後、上記操作により得た含フッ素化合物含有ガスを、第２のチャンバー内に輸送し、25℃で所定時間、Alの表面処理を行った。処理時間ごとのAl表面の接触角（水との接触角（単位：度））を測定した。その測定結果を表２に示す。
実施例４
含フッ素化合物含有ガスとしてC2F6に代えてCOF2を用いた点を除き、実施例３と同様にして実験を行った。
Next, the surface treatment was performed in the same manner as in Example 1 except that the fluorine-containing compound-containing gas diluted with nitrogen was used and a metal plate was used instead of the polypropylene plate. Five aluminum plates (hereinafter abbreviated as Al. L × W × H = 20mm × 20mm × 2mm) are installed in a cylindrical cylinder made of Ni (second chamber) with an internal volume of 4.6L. The inside of the second chamber was replaced with nitrogen gas. Thereafter, the fluorine-containing compound-containing gas obtained by the above operation was transported into the second chamber, and Al was surface-treated at 25 ° C. for a predetermined time. The contact angle (contact angle with water (unit: degree)) of the Al surface for each treatment time was measured. The measurement results are shown in Table 2.
Example 4
The experiment was performed in the same manner as in Example 3 except that COF 2 was used instead of C 2 F 6 as the fluorine-containing compound-containing gas.
サンプリングされた含フッ素化合物含有ガス中には、146 ppm のF2ガスが検出され、供給したCOF2の変換率は71%であった。 146 ppm of F 2 gas was detected in the sampled fluorine-containing compound-containing gas, and the conversion rate of the supplied COF 2 was 71%.
次に、実施例３と同様にして、Alに代えて銅板（Cuと略すことがある）の表面処理を行い、その接触角を測定した。なお、このときCuは、予め酸洗（Cuを0.1NのＨＣｌ溶液に入れて30 min 攪拌後、水洗3回）及び加熱処理（大気中200℃で1hr加熱後、デシケータ中で放冷）を行った。その測定結果を表２に示す。
実施例５
図１の装置を用いて、ポリプロピレンの表面改質を行った。含フッ素化合物ガスとしてNF3を用い、プラズマ発生装置として誘導結合プラズマ（ICP）発生装置（Landmark Technology社製Litmas Blue1200）を使用した。第２のチャンバーには、L×W×H＝20mm×20mm×2mmのポリプロピレン（PP）試料を設置した。
Next, in the same manner as in Example 3, a surface treatment was performed on a copper plate (sometimes abbreviated as Cu) instead of Al, and the contact angle was measured. At this time, Cu was previously pickled (Cu was added to a 0.1N HCl solution and stirred for 30 min, then washed with water three times) and heat-treated (heated at 200 ° C. for 1 hr in the air and then allowed to cool in a desiccator). went. The measurement results are shown in Table 2.
Example 5
Surface modification of polypropylene was performed using the apparatus shown in FIG. NF 3 was used as the fluorine-containing compound gas, and an inductively coupled plasma (ICP) generator (Litmas Blue1200 manufactured by Landmark Technology) was used as the plasma generator. In the second chamber, a polypropylene (PP) sample of L × W × H = 20 mm × 20 mm × 2 mm was placed.
まず、約25℃（20-25℃）で第１のチャンバーを１Torrまで減圧した。次に、NF3（流量：100 sccm ）を入口１で窒素（流量：400 sccm ）により希釈して含フッ素化合物含有ガスを作成し、該含フッ素化合物含有ガスを第１のチャンバーに供給した。プラズマ発生装置には1200Ｗの出力を印加した。第１のチャンバーから放出された含フッ素化合物含有ガスを入口３で窒素（流量：14400 sccm ）により再度希釈し、大気圧下約25℃の第２のチャンバーに導入した。この条件でNF3が完全に変換されると、第２のチャンバーに導入される含フッ素化合物含有ガス中のF2濃度は、１vol.% となる（サンプリングして分析した結果、F2濃度は、1.05vol.% であり、変換率99.84% であった）。
First, the first chamber was depressurized to 1 Torr at about 25 ° C. (20-25 ° C.). Next, NF 3 (flow rate: 100 sccm) was diluted with nitrogen (flow rate: 400 sccm) at the
第２のチャンバーでは、PP試料を大気圧下25℃で3時間、含フッ素化合物含有ガスと接触させた。 In the second chamber, the PP sample was contacted with the fluorine-containing compound-containing gas at 25 ° C. under atmospheric pressure for 3 hours.
PP試料表面を、ULVAC-PHI社製XPS PHI Quantum 2000により分析した。処理前では、試料表面における炭素の原子濃度は83 atom% であり、フッ素の原子濃度は0 atom% であったが、処理後では、炭素の原子濃度は48 atom% 、フッ素の原子濃度は45 atom% となった。このXPSの結果から、試料表面がフッ素化されたことがわかる。 The surface of the PP sample was analyzed by XPS PHI Quantum 2000 manufactured by ULVAC-PHI. Before the treatment, the atomic concentration of carbon on the sample surface was 83 atom% and the atomic concentration of fluorine was 0 atom%, but after the treatment, the atomic concentration of carbon was 48 atom% and the atomic concentration of fluorine was 45 atom%. atom%. From the XPS results, it can be seen that the sample surface was fluorinated.
なお、XPS測定条件は以下の通りである。 The XPS measurement conditions are as follows.
X-ray Source:Al Ka 1486.6eV monochromatic
X-ray Power:24.72W
X-ray Beam Diameter:100.0mm
Source Analyzer Angle:45.0°
Neutralizer Energy:1.0V
Neutralizer Current:25.0nA
Depth Profile
Sputter Ion:Ar+
Sputter Energy:3.000keV
Sputter Current:25.0nA
実施例６
NF3（流量：200 sccm ）を窒素（流量：300 sccm ）で希釈して含フッ素化合物含有ガスを作成し、第１のチャンバーから放出される含フッ素化合物含有ガスを流量9300 sccm の窒素で希釈した点を除き、実施例５と同様にPP試料の表面改質を行った。NF3が完全に変換されたと仮定すると、常圧下の第２のチャンバーに導入される含フッ素化合物含有ガス中のF2濃度は、3vol.% となる（サンプリングして分析した結果、F2濃度は、2.97 vol.% であり、変換率99.73% であった）。
X-ray Source: Al Ka 1486.6eV monochromatic
X-ray Power: 24.72W
X-ray Beam Diameter: 100.0mm
Source Analyzer Angle: 45.0 °
Neutralizer Energy: 1.0V
Neutralizer Current: 25.0nA
Depth Profile
Sputter Ion: Ar +
Sputter Energy: 3.000keV
Sputter Current: 25.0nA
Example 6
NF 3 (flow rate: 200 sccm) is diluted with nitrogen (flow rate: 300 sccm) to create a fluorine-containing compound-containing gas, and the fluorine-containing compound-containing gas released from the first chamber is diluted with nitrogen at a flow rate of 9300 sccm Except for this point, the surface modification of the PP sample was performed in the same manner as in Example 5. When NF 3 is assumed to have been completely converted, F 2 concentration of the fluorine-containing compound-containing gas introduced into the second chamber under normal pressure is, 3 vol.% And comprising (a result of the analysis by sampling, F 2 concentration Was 2.97 vol.%, And the conversion rate was 99.73%).
PP試料表面を、実施例５と同様にULVAC-PHI社製XPS PHI Quantum 2000により分析した。処理前では、試料表面における炭素の原子濃度は83 atom% であり、フッ素の原子濃度は0 atom% であったが、処理後では、炭素の原子濃度は41 atom% 、フッ素の原子濃度は52 atom% であった。この結果から、試料表面がフッ素化されたことがわかる。
実施例７
図１の装置を用いて、SiO2膜ウエハのエッチング試験を行った。内容積4.6LのNi製の円柱体容器（第２のチャンバー）内に、単結晶Si上にSiO2膜（7500Å）を成膜したウエハ（25mm×25mm）を設置した。また、この第２のチャンバーの上流に、プラズマ発生装置（第１のチャンバー）として誘導結合プラズマ（ICP）発生装置（ASTeX社製ASTRONi）を設置し、さらに第１のチャンバー下流に配管を冷却する冷却装置を設置した。
The surface of the PP sample was analyzed by XPS PHI Quantum 2000 manufactured by ULVAC-PHI as in Example 5. Before the treatment, the atomic concentration of carbon on the sample surface was 83 atom% and the atomic concentration of fluorine was 0 atom%, but after the treatment, the atomic concentration of carbon was 41 atom% and the atomic concentration of fluorine was 52 atom%. atom%. This result shows that the sample surface was fluorinated.
Example 7
An etching test of the SiO 2 film wafer was performed using the apparatus shown in FIG. A wafer (25 mm × 25 mm) in which a SiO 2 film (7500 mm) was formed on single crystal Si was placed in a cylindrical cylindrical container (second chamber) made of Ni having an internal volume of 4.6 L. An inductively coupled plasma (ICP) generator (ASTRONi manufactured by ASTeX) is installed upstream of the second chamber as a plasma generator (first chamber), and the pipe is cooled downstream of the first chamber. A cooling device was installed.
第１及び第２のチャンバー内を、窒素により置換した。その後、第２のチャンバー内を、0.5×105Paまで減圧し、所定温度（(1)260℃、並びに(2) 310℃）に加熱した。また、約25℃（20-25℃）で第１のチャンバーを１Torr（133Pa）まで減圧にした後、Arを1000sccm導入しプラズマを発生させた。次に、NF3（流量：1000 sccm）を第１のチャンバーに供給した。第１のチャンバー下流の配管を100℃以下の温度を維持するように冷却し、希釈ガス入口３で窒素（流量：5500 sccm）により希釈した。これにより、F2濃度20 vol.% の含フッ素化合物含有ガスを発生させた。この含フッ素化合物含有ガスのうち1000 sccm を、上記の0.5×105Pa 及び各々の所定温度に保ったまま第２のチャンバー内に輸送し、それぞれの温度において目的のウエハの表面処理を行った。
The inside of the first and second chambers was replaced with nitrogen. Thereafter, the pressure in the second chamber was reduced to 0.5 × 10 5 Pa and heated to predetermined temperatures ((1) 260 ° C. and (2) 310 ° C.). The first chamber was decompressed to 1 Torr (133 Pa) at about 25 ° C. (20-25 ° C.), and then Ar was introduced at 1000 sccm to generate plasma. Next, NF 3 (flow rate: 1000 sccm) was supplied to the first chamber. The piping downstream of the first chamber was cooled so as to maintain a temperature of 100 ° C. or lower, and diluted with nitrogen (flow rate: 5500 sccm) at the
処理後のウエハは、Nanometrics社製Nano Spec 3000AF-T を用いて膜厚測定を行い、各々の所定温度でのエッチングレートを求めた。その結果を表３に示す。
実施例８
図１の表面処理装置を使用して、化合物のフッ素化を行った。
The processed wafer was subjected to film thickness measurement using Nano Spec 3000AF-T manufactured by Nanometrics, and the etching rate at each predetermined temperature was determined. The results are shown in Table 3.
Example 8
The compound was fluorinated using the surface treatment apparatus of FIG.
図１の表面処理装置において、処理室の位置に捕集ボンベを置き、その後段に恒温槽を付帯した1000mlのＰＦＡ製反応器を設置した。その反応器に1,3-ジオキソラン-2-オン 517g（5.87mol）を入れ、50℃の恒温槽中で融解させた。次に、窒素ガスを200sccmの流量で反応器内に30分間吹き込みながら、溶存している空気等のガス成分を系外に追い出し、系内の窒素置換を行った。その後、含フッ素化合物含有ガスとしてNF3を用い、更にプラズマ発生装置としては誘導結合プラズマ（ICP）発生装置（ASTeX社製ASTRONi）を使用して、NF3からF2を50−100℃の温度制御のもとで発生させた。NF3:1000sccmを導入し、N2:3000sccmで希釈し30%F2を発生させた。その30%F2のうち350sccmを、先端にSUS製フィルター（細孔直径15μm、表面積 7.5cm2）を装着したガス吹き込み管を使用して反応器に導入した。回転数を約800rpmにした攪拌機によって絶えず反応液を攪拌して、一ヶ所にフッ素ガスを滞留させないようにした。反応器内の液相温度は、外部の恒温槽により50−60℃に保つようにした。同時に、反応器上部に取り付けた冷却器で、原料、生成物及び副生したフッ化水素の蒸気を凝縮・還流させながら、気相温度を35−50℃に保つようにした。未反応フッ素等の不凝縮ガスは、冷却器の後に設けた除害装置で処理した。 In the surface treatment apparatus of FIG. 1, a collection cylinder was placed at the position of the treatment chamber, and a 1000 ml PFA reactor attached with a thermostatic bath was installed at the subsequent stage. The reactor was charged with 517 g (5.87 mol) of 1,3-dioxolan-2-one and melted in a thermostatic bath at 50 ° C. Next, while nitrogen gas was blown into the reactor at a flow rate of 200 sccm for 30 minutes, dissolved gas components such as air were driven out of the system, and nitrogen substitution in the system was performed. Then, using NF3 as the fluorine-containing compound-containing gas, and using an inductively coupled plasma (ICP) generator (ASTRONi manufactured by ASTeX) as the plasma generator, temperature control from 50 to 100 ° C from NF 3 to F 2 Generated under. NF 3 : 1000 sccm was introduced and diluted with N 2 : 3000 sccm to generate 30% F 2 . 350 sccm of the 30% F 2 was introduced into the reactor using a gas blowing tube equipped with a SUS filter (pore diameter 15 μm, surface area 7.5 cm 2 ) at the tip. The reaction solution was continuously stirred by a stirrer having a rotation speed of about 800 rpm so that the fluorine gas was not retained in one place. The liquid phase temperature in the reactor was kept at 50-60 ° C. by an external thermostat. At the same time, the gas phase temperature was maintained at 35-50 ° C. while condensing and refluxing the raw material, product, and by-product hydrogen fluoride vapor with a cooler attached to the upper part of the reactor. Uncondensed gases such as unreacted fluorine were treated with a detoxifying device provided after the cooler.
フッ素の導入量が10.6mol（原料の1.8モル当量）に達した時点で反応を終了し、副生したフッ化水素を蒸留して除去した後、水（200ml）及び10%NaHCO3水溶液（100ml）で洗浄し、ジクロロメタン（500ml×6回）で抽出した。その抽出液を無水硫酸マグネシウムで乾燥した後、ジクロロメタンを留去した。得られた粗生成物590gを蒸留精製したところ、純度90%以上の4-フルオロ-1,3-ジオキソラン-2-オンが480g得られた（収率 約70%）。 The reaction was terminated when the amount of fluorine introduced reached 10.6 mol (1.8 molar equivalents of the raw material), and hydrogen fluoride produced as a by-product was removed by distillation, and then water (200 ml) and 10% aqueous NaHCO 3 solution (100 ml) ) And extracted with dichloromethane (500 ml × 6 times). The extract was dried over anhydrous magnesium sulfate and dichloromethane was distilled off. When 590 g of the obtained crude product was purified by distillation, 480 g of 4-fluoro-1,3-dioxolan-2-one having a purity of 90% or more was obtained (yield: about 70%).
純度90%の粗生成物は、15℃にて再結晶を3回繰り返したところ、純度99%以上の4-フルオロ-1,3-ジオキソラン-2-オンが約390g得られた。 The crude product having a purity of 90% was recrystallized three times at 15 ° C., and about 390 g of 4-fluoro-1,3-dioxolan-2-one having a purity of 99% or more was obtained.
Claims (23)
（２）生成した励起含フッ素化合物含有ガスを、第１のゾーンと連通した第２のゾー
ンに輸送する間に、輸送系内の圧力を大気圧または大気圧以上へと上昇させるとともに輸送系を冷却することにより、活性種の全てを実質的に失活させ、フッ素ガスに変換して、フッ素含有ガスを生成し、
（３）第２のゾーン中で、フッ素含有ガスと物品の表面とを減圧、大気圧または大気圧以上の圧力下で接触させ、該物品の表面を改質する、
表面改質方法。 (1) In the first zone, by applying energy to the fluorine-containing compound-containing gas under reduced pressure, at least one fluorine-containing compound in the fluorine-containing compound-containing gas is excited, and the activated species generated thereby Producing an excited fluorine-containing compound-containing gas,
(2) While transporting the generated excited fluorine-containing compound-containing gas to the second zone communicating with the first zone, the pressure in the transport system is increased to atmospheric pressure or higher and the transport system is By cooling, substantially all of the active species are deactivated and converted to fluorine gas, producing a fluorine-containing gas,
(3) In the second zone, the fluorine-containing gas and the surface of the article are brought into contact under reduced pressure, atmospheric pressure or a pressure higher than atmospheric pressure to modify the surface of the article.
Surface modification method.
（２）第１のゾーン中の圧力を大気圧あるいは大気圧以上へと上昇させるとともに冷却することにより、活性種の全てを実質的に失活させ、フッ素ガスに変換して、フッ素含有ガスを生成し、
（３）生成したフッ素含有ガスを、第１のゾーンと連通した第２のゾーンに輸送し、
（４）第２のゾーン中で、フッ素含有ガスを物品の表面と減圧、大気圧または大気圧以上の圧力下で接触させ、該物品の表面を改質する、
表面改質方法。 (1) In the first zone, by applying energy to the fluorine-containing compound-containing gas under reduced pressure, at least one fluorine-containing compound in the fluorine-containing compound-containing gas is excited, and the activated species generated thereby Producing an excited fluorine-containing compound-containing gas,
(2) By raising the pressure in the first zone to atmospheric pressure or above atmospheric pressure and cooling it, substantially all of the active species are deactivated and converted to fluorine gas. Generate and
(3) transporting the generated fluorine-containing gas to a second zone communicating with the first zone;
(4) In the second zone, the fluorine-containing gas is brought into contact with the surface of the article under reduced pressure, atmospheric pressure or a pressure higher than atmospheric pressure to modify the surface of the article.
Surface modification method.
改質方法。 The surface modification method according to claim 11, wherein the polymer is an article mainly composed of polypropylene.
（２）該第１のゾーンと連通し、内部に表面改質される物品を有するとともに、該第１のゾーンから輸送する間に、輸送系内の圧力を大気圧あるいは大気圧以上に調整するとともに輸送系を冷却する手段を備え、発生したフッ素含有ガスと該物品の表面とを減圧、大気圧または大気圧以上の圧力下で接触させて該物品の表面を改質する手段を備えた、第２のゾーンと、
を備えた表面改質装置。 (1) a first zone comprising means for converting the fluorine-containing compound-containing gas into plasma under reduced pressure;
(2) It has an article that is in communication with the first zone and has a surface modified inside, and adjusts the pressure in the transport system to atmospheric pressure or higher than atmospheric pressure during transportation from the first zone. And a means for cooling the transport system, and a means for modifying the surface of the article by bringing the generated fluorine-containing gas into contact with the surface of the article under reduced pressure, atmospheric pressure or a pressure higher than atmospheric pressure, A second zone;
A surface modification apparatus equipped with
（２）該第１のゾーンと連通し、内部に表面改質される物品を有するとともに、発生したフッ素含有ガスと該物品の表面とを減圧、大気圧または大気圧以上の圧力下で接触させて、該物品の表面を改質する手段を備えた、第２のゾーンと、
を備えた表面改質装置。 (1) a first zone comprising means for generating a fluorine-containing gas by converting the fluorine-containing compound-containing gas into a plasma under reduced pressure and then adjusting the pressure to atmospheric pressure or higher and cooling it;
(2) Having an article which is in communication with the first zone and whose surface is modified inside, and the generated fluorine-containing gas and the surface of the article are brought into contact under reduced pressure, atmospheric pressure or pressure higher than atmospheric pressure. A second zone comprising means for modifying the surface of the article;
A surface modification apparatus equipped with
（２）該第１のチャンバーと連通し、圧力を大気圧あるいはそれ以上に調整するとともに冷却することによりフッ素含有ガスを発生する手段を備えた輸送路と、
（３）該輸送路と連通し、内部に表面改質される物品を有するとともに、発生したフッ素含有ガスと該物品の表面とを減圧、大気圧または大気圧以上の圧力下で接触させて、該物品の表面を改質する手段を備えた、第２のチャンバーと、
を備えた表面改質装置。 (1) a first chamber comprising means for converting the fluorine-containing compound-containing gas into plasma under reduced pressure;
(2) a transport path that communicates with the first chamber, includes a means for generating a fluorine-containing gas by adjusting the pressure to atmospheric pressure or higher and cooling it;
(3) having an article that is surface-modified inside and in communication with the transport path, and contacting the generated fluorine-containing gas with the surface of the article under reduced pressure, atmospheric pressure or pressure higher than atmospheric pressure; A second chamber comprising means for modifying the surface of the article;
A surface modification apparatus equipped with
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005098889A JP4634199B2 (en) | 2005-03-30 | 2005-03-30 | Surface modification method and apparatus using fluorine-containing gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005098889A JP4634199B2 (en) | 2005-03-30 | 2005-03-30 | Surface modification method and apparatus using fluorine-containing gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006272265A true JP2006272265A (en) | 2006-10-12 |
| JP4634199B2 JP4634199B2 (en) | 2011-02-16 |
Family
ID=37207516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005098889A Active JP4634199B2 (en) | 2005-03-30 | 2005-03-30 | Surface modification method and apparatus using fluorine-containing gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4634199B2 (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008150676A (en) * | 2006-12-19 | 2008-07-03 | Air Water Inc | Method for regenerating hard film-coated metallic member |
| JP2010526986A (en) * | 2007-05-11 | 2010-08-05 | エスディーシー マテリアルズ インコーポレイテッド | Heat exchanger, cooling device and cooling method |
| WO2013145955A1 (en) * | 2012-03-28 | 2013-10-03 | セントラル硝子株式会社 | Method and apparatus for producing fluorine gas |
| US9302260B2 (en) | 2007-10-15 | 2016-04-05 | SDCmaterials, Inc. | Method and system for forming plug and play metal catalysts |
| US9308524B2 (en) | 2009-12-15 | 2016-04-12 | SDCmaterials, Inc. | Advanced catalysts for automotive applications |
| US9332636B2 (en) | 2009-12-15 | 2016-05-03 | SDCmaterials, Inc. | Sandwich of impact resistant material |
| JP2016086188A (en) * | 2007-12-21 | 2016-05-19 | ゾルファイ フルーオル ゲゼルシャフト ミット ベシュレンクテル ハフツングＳｏｌｖａｙ Ｆｌｕｏｒ ＧｍｂＨ | Process for production of microelectromechanical systems |
| US9427732B2 (en) | 2013-10-22 | 2016-08-30 | SDCmaterials, Inc. | Catalyst design for heavy-duty diesel combustion engines |
| US9433938B2 (en) | 2011-02-23 | 2016-09-06 | SDCmaterials, Inc. | Wet chemical and plasma methods of forming stable PTPD catalysts |
| US9498751B2 (en) | 2011-08-19 | 2016-11-22 | SDCmaterials, Inc. | Coated substrates for use in catalysis and catalytic converters and methods of coating substrates with washcoat compositions |
| US9511352B2 (en) | 2012-11-21 | 2016-12-06 | SDCmaterials, Inc. | Three-way catalytic converter using nanoparticles |
| US9517448B2 (en) | 2013-10-22 | 2016-12-13 | SDCmaterials, Inc. | Compositions of lean NOx trap (LNT) systems and methods of making and using same |
| US9533299B2 (en) | 2012-11-21 | 2017-01-03 | SDCmaterials, Inc. | Three-way catalytic converter using nanoparticles |
| US9586179B2 (en) | 2013-07-25 | 2017-03-07 | SDCmaterials, Inc. | Washcoats and coated substrates for catalytic converters and methods of making and using same |
| US9687811B2 (en) | 2014-03-21 | 2017-06-27 | SDCmaterials, Inc. | Compositions for passive NOx adsorption (PNA) systems and methods of making and using same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10314934A (en) * | 1997-05-20 | 1998-12-02 | Seiko Epson Corp | Surface treating method |
| JP2004075471A (en) * | 2002-08-20 | 2004-03-11 | Anelva Corp | Method for producing gaseous halogen, apparatus for producing gaseous halogen and recovery/circulation system for gaseous halogen |
-
2005
- 2005-03-30 JP JP2005098889A patent/JP4634199B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10314934A (en) * | 1997-05-20 | 1998-12-02 | Seiko Epson Corp | Surface treating method |
| JP2004075471A (en) * | 2002-08-20 | 2004-03-11 | Anelva Corp | Method for producing gaseous halogen, apparatus for producing gaseous halogen and recovery/circulation system for gaseous halogen |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9216398B2 (en) | 2005-04-19 | 2015-12-22 | SDCmaterials, Inc. | Method and apparatus for making uniform and ultrasmall nanoparticles |
| US9719727B2 (en) | 2005-04-19 | 2017-08-01 | SDCmaterials, Inc. | Fluid recirculation system for use in vapor phase particle production system |
| US9599405B2 (en) | 2005-04-19 | 2017-03-21 | SDCmaterials, Inc. | Highly turbulent quench chamber |
| JP2008150676A (en) * | 2006-12-19 | 2008-07-03 | Air Water Inc | Method for regenerating hard film-coated metallic member |
| JP2010526986A (en) * | 2007-05-11 | 2010-08-05 | エスディーシー マテリアルズ インコーポレイテッド | Heat exchanger, cooling device and cooling method |
| JP2014139509A (en) * | 2007-05-11 | 2014-07-31 | Sdc Materials Inc | Heat exchanger, cooler, and cooling method |
| US9592492B2 (en) | 2007-10-15 | 2017-03-14 | SDCmaterials, Inc. | Method and system for forming plug and play oxide catalysts |
| US9737878B2 (en) | 2007-10-15 | 2017-08-22 | SDCmaterials, Inc. | Method and system for forming plug and play metal catalysts |
| US9302260B2 (en) | 2007-10-15 | 2016-04-05 | SDCmaterials, Inc. | Method and system for forming plug and play metal catalysts |
| US9597662B2 (en) | 2007-10-15 | 2017-03-21 | SDCmaterials, Inc. | Method and system for forming plug and play metal compound catalysts |
| JP2016086188A (en) * | 2007-12-21 | 2016-05-19 | ゾルファイ フルーオル ゲゼルシャフト ミット ベシュレンクテル ハフツングＳｏｌｖａｙ Ｆｌｕｏｒ ＧｍｂＨ | Process for production of microelectromechanical systems |
| US9308524B2 (en) | 2009-12-15 | 2016-04-12 | SDCmaterials, Inc. | Advanced catalysts for automotive applications |
| US9533289B2 (en) | 2009-12-15 | 2017-01-03 | SDCmaterials, Inc. | Advanced catalysts for automotive applications |
| US9332636B2 (en) | 2009-12-15 | 2016-05-03 | SDCmaterials, Inc. | Sandwich of impact resistant material |
| US9433938B2 (en) | 2011-02-23 | 2016-09-06 | SDCmaterials, Inc. | Wet chemical and plasma methods of forming stable PTPD catalysts |
| US9498751B2 (en) | 2011-08-19 | 2016-11-22 | SDCmaterials, Inc. | Coated substrates for use in catalysis and catalytic converters and methods of coating substrates with washcoat compositions |
| WO2013145955A1 (en) * | 2012-03-28 | 2013-10-03 | セントラル硝子株式会社 | Method and apparatus for producing fluorine gas |
| US9533299B2 (en) | 2012-11-21 | 2017-01-03 | SDCmaterials, Inc. | Three-way catalytic converter using nanoparticles |
| US9511352B2 (en) | 2012-11-21 | 2016-12-06 | SDCmaterials, Inc. | Three-way catalytic converter using nanoparticles |
| US9586179B2 (en) | 2013-07-25 | 2017-03-07 | SDCmaterials, Inc. | Washcoats and coated substrates for catalytic converters and methods of making and using same |
| US9566568B2 (en) | 2013-10-22 | 2017-02-14 | SDCmaterials, Inc. | Catalyst design for heavy-duty diesel combustion engines |
| US9427732B2 (en) | 2013-10-22 | 2016-08-30 | SDCmaterials, Inc. | Catalyst design for heavy-duty diesel combustion engines |
| US9517448B2 (en) | 2013-10-22 | 2016-12-13 | SDCmaterials, Inc. | Compositions of lean NOx trap (LNT) systems and methods of making and using same |
| US9950316B2 (en) | 2013-10-22 | 2018-04-24 | Umicore Ag & Co. Kg | Catalyst design for heavy-duty diesel combustion engines |
| US9687811B2 (en) | 2014-03-21 | 2017-06-27 | SDCmaterials, Inc. | Compositions for passive NOx adsorption (PNA) systems and methods of making and using same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4634199B2 (en) | 2011-02-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4634199B2 (en) | Surface modification method and apparatus using fluorine-containing gas | |
| JP4804345B2 (en) | F2-containing gas manufacturing method and F2-containing gas manufacturing apparatus | |
| JP3855081B2 (en) | CVD apparatus equipped with fluorine gas cleaning mechanism and method of cleaning CVD apparatus with fluorine gas | |
| JP5011148B2 (en) | Semiconductor device manufacturing method, cleaning method, and substrate processing apparatus | |
| US20120285492A1 (en) | Methods of dry stripping boron-carbon films | |
| US20060016459A1 (en) | High rate etching using high pressure F2 plasma with argon dilution | |
| JP4459329B2 (en) | Method and apparatus for removing attached film | |
| JP2004146787A (en) | Method for etching high dielectric constant material, and for cleaning deposition chamber for high dielectric constant material | |
| JP2009503270A (en) | Use of NF3 to remove surface deposits | |
| TW583736B (en) | Plasma cleaning gas and plasma cleaning method | |
| TW201216355A (en) | Plasma processing method and plasma processing apparatus | |
| US20070028943A1 (en) | Method of using sulfur fluoride for removing surface deposits | |
| JP2016219786A (en) | Dry etching method, dry etching agent, and method of manufacturing semiconductor device | |
| JP2013062342A (en) | Cleaning method of film forming device | |
| JP2008060171A (en) | Method of cleaning semiconductor processing equipment | |
| TW201348136A (en) | Method and apparatus for producing fluorine gas | |
| JPWO2018181104A1 (en) | Dry etching method or dry cleaning method | |
| JP4320389B2 (en) | CVD chamber cleaning method and cleaning gas used therefor | |
| JP2019044264A (en) | Processing method of tungsten oxide, and manufacturing method for tungsten hexafluoride | |
| JP4220318B2 (en) | Cleaning method inside process chamber | |
| JP2008294121A (en) | Manufacturing method and manufacturing apparatus of semiconductor device | |
| JP2003327412A (en) | Method for generating fluorine | |
| TW202300702A (en) | Etching gas and etching method | |
| JPH10212582A (en) | Method for using chlorine trifluoride in cleaning surface of thin film forming device | |
| JP2008115473A (en) | Production device for silicon-containing film, and production method therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20071206 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100224 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100309 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100907 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100921 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20101116 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20101118 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4634199 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131126 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131126 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |