JP2008094649A - Surface treatment method for quartz glass substrate and hydrogen radical etching apparatus - Google Patents
Surface treatment method for quartz glass substrate and hydrogen radical etching apparatus Download PDFInfo
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Abstract
【課題】
本発明は、ＬＳＩ分野の極端紫外線（ＥＵＶ）を用いたリソグラフィ反射マスク基板などに対する要望に応えることができるようにした高平坦度（サブナノメータレベル）石英ガラス基板を得ることができるようにした石英ガラス基板の表面処理方法及びその処理方法に好適に用いられる水素ラジカルエッチング装置を提供する。
【解決手段】
石英ガラス基板の表面平坦度を制御する方法であって、石英ガラス基板を水素ラジカルエッチング装置内に載置し、前記石英ガラス基板に水素ラジカルを作用させて表面平坦度をサブナノメータレベルで制御できるようにした。
【選択図】図１【Task】
The present invention provides a quartz substrate capable of obtaining a high flatness (sub-nanometer level) quartz glass substrate capable of meeting a demand for a lithography reflection mask substrate using extreme ultraviolet rays (EUV) in the LSI field. A surface treatment method for a glass substrate and a hydrogen radical etching apparatus suitably used for the treatment method are provided.
[Solution]
A method of controlling the surface flatness of a quartz glass substrate, wherein the quartz glass substrate is placed in a hydrogen radical etching apparatus, and hydrogen radicals act on the quartz glass substrate to control the surface flatness at a sub-nanometer level. I did it.
[Selection] Figure 1
Description
本発明は、反応性の高い表面構造を付与した石英ガラス基板と原子状水素（水素ラジカル）との高反応性を利用した洗浄不要の気相化学エッチング法に関し、ＬＳＩ分野の極端紫外線（ＥＵＶ）を用いたリソグラフィ反射マスク基板などに対する要望に応えることができるようにした高平坦度（サブナノメータレベル）石英ガラス基板を得ることができる石英ガラス基板の表面処理方法及びその処理方法に好適に用いられる水素ラジカルエッチング装置に関する。 The present invention relates to a cleaning-free gas phase chemical etching method utilizing high reactivity between a quartz glass substrate provided with a highly reactive surface structure and atomic hydrogen (hydrogen radical), and extreme ultraviolet (EUV) in the LSI field. A method for treating a surface of a quartz glass substrate capable of obtaining a quartz glass substrate having a high flatness (sub-nanometer level) adapted to meet a demand for a lithographic reflection mask substrate or the like using a glass substrate and a method for treating the quartz glass substrate. The present invention relates to a hydrogen radical etching apparatus.
極端紫外線（ＥＵＶ）リソグラフィは、極めて波長の短い超紫外線を用いて、シリコンウエハに微細な回路イメージを焼き付けるリソグラフィ技術であり、電子ビームリソグラフィと並んで、次世代コンピュータチップ開発のための有望な技術とされている。現在チップ製造に用いられているのはＤＵＶ（遠紫外線）リソグラフィと呼ばれる技術だが、ＥＵＶではその２０分の１程度の波長の光線を用い、それに伴って回路も微細にすることができ、乗せられる回路の数が増えることでプロセッサの性能も向上する。このＥＵＶリソグラフィ技術の発展に伴い、ＥＵＶリソグラフィ反射マスク基板として好適に使用される高平坦度（サブナノメータレベル）石英ガラス基板が待望されているのが現状である。 Extreme ultraviolet (EUV) lithography is a lithography technology that uses ultra-ultraviolet light with a very short wavelength to burn a fine circuit image onto a silicon wafer. Along with electron beam lithography, it is a promising technology for developing next-generation computer chips. It is said that. A technology called DUV (far-ultraviolet) lithography is currently used for chip manufacturing, but EUV uses a light beam having a wavelength of about one-twentieth of that, and the circuit can be made finer accordingly. As the number of circuits increases, the performance of the processor also improves. With the development of this EUV lithography technology, a high flatness (sub-nanometer level) quartz glass substrate that is suitably used as an EUV lithography reflection mask substrate is currently being awaited.
本発明者は、上記した従来技術の問題点に鑑み、ＥＵＶリソグラフィ反射マスク基板として好適に使用される高平坦度（サブナノメータレベル）石英ガラス基板を開発すべく鋭意研究を重ねた結果、反応性の高い表面構造を付与した石英ガラス基板と原子状水素（水素ラジカル）との高反応性を利用した気相化学エッチング法を適用することによって従来にない高平坦度（サブナノメータレベル）石英ガラス基板を製造することができることを見出し、本発明を完成したものである。 In view of the above-mentioned problems of the prior art, the inventor has conducted extensive research to develop a high flatness (sub-nanometer level) quartz glass substrate that is preferably used as an EUV lithography reflection mask substrate. Highly flatness (sub-nanometer level) quartz glass substrate by applying a vapor-phase chemical etching method using high reactivity between atomic glass (hydrogen radical) and a quartz glass substrate with a high surface structure The present invention has been completed by finding that it can be produced.
本発明は、ＬＳＩ分野の極端紫外線（ＥＵＶ）を用いたリソグラフィ反射マスク基板などに対する要望に応えることができるようにした高平坦度（サブナノメータレベル）石英ガラス基板を得ることができるようにした石英ガラス基板の表面処理方法及びその処理方法に好適に用いられる水素ラジカルエッチング装置を提供することを目的とする。 The present invention provides a quartz substrate capable of obtaining a high flatness (sub-nanometer level) quartz glass substrate capable of meeting a demand for a lithography reflection mask substrate using extreme ultraviolet rays (EUV) in the LSI field. It aims at providing the surface treatment method of a glass substrate, and the hydrogen radical etching apparatus used suitably for the processing method.
上記目的を達成するために、本発明の石英ガラス基板の表面処理方法は、石英ガラス基板の表面平坦度を制御する方法であって、石英ガラス基板を水素ラジカルエッチング装置内に載置し、前記石英ガラス基板に水素ラジカルを作用させて表面平坦度をサブナノメータレベルで制御できるようにしたことを特徴とする。 In order to achieve the above object, a surface treatment method for a quartz glass substrate of the present invention is a method for controlling the surface flatness of a quartz glass substrate, wherein the quartz glass substrate is placed in a hydrogen radical etching apparatus, The present invention is characterized in that hydrogen radicals are allowed to act on a quartz glass substrate to control the surface flatness at a sub-nanometer level.
前記石英ガラス基板として、超低膨張ガラス基板が好適に用いられる。前記超低膨張ガラス基板が、チタニアを含有する石英ガラス基板であることが好ましい。 As the quartz glass substrate, an ultra-low expansion glass substrate is preferably used. The ultra-low expansion glass substrate is preferably a quartz glass substrate containing titania.
前記水素ラジカルエッチング装置としては、水素分子を水素ラジカルに分解する発熱体を具備した水素ラジカルエッチング装置が好適に用いられる。前記発熱体の設定温度は１０００〜２１００℃の範囲とするのが好ましい。前記水素ラジカルエッチング装置における前記石英ガラス基板に対する処理圧力は１００Ｐａ以下が好適であり、１〜１０Ｐａの範囲とするのがより好適である。前記基板の加熱温度は５００〜１１００℃の範囲とするのが好ましい。前記水素ラジカルエッチング装置内に設置され前記石英ガラス基板を載置するトレー部材が黒色石英材料で形成されているのが好適である。 As the hydrogen radical etching apparatus, a hydrogen radical etching apparatus having a heating element that decomposes hydrogen molecules into hydrogen radicals is preferably used. The set temperature of the heating element is preferably in the range of 1000 to 2100 ° C. The processing pressure for the quartz glass substrate in the hydrogen radical etching apparatus is preferably 100 Pa or less, and more preferably in the range of 1 to 10 Pa. The heating temperature of the substrate is preferably in the range of 500 to 1100 ° C. It is preferable that a tray member installed in the hydrogen radical etching apparatus and on which the quartz glass substrate is placed is formed of a black quartz material.
本発明の石英ガラス基板は、本発明の石英ガラス基板の表面処理方法によって表面処理された石英ガラス基板であって、サブナノメータレベルの表面平坦度を有することを特徴とする。 The quartz glass substrate of the present invention is a quartz glass substrate surface-treated by the method of treating a surface of a quartz glass substrate of the present invention, and has a surface flatness of a sub-nanometer level.
本発明の水素ラジカルエッチング装置は、本発明方法に用いられ水素ラジカルを発生させてその水素ラジカルによって石英ガラス基板の表面処理を行う装置であって、処理容器本体と、該処理容器本体内に設置されたホルダー部材と、該ホルダー部材内に設置されたヒーター部材と、該ホルダー部材の上面に設けられた石英ガラス基板を載置するトレー部材と、該処理容器本体内の上部に上下動自在に設けられた発熱体と、該処理容器本体内に水素ガスを導入する導入孔と、該処理容器本体内の廃ガスを排気する排気孔と、を含むことを特徴とする。
前記トレー部材を黒色石英材料で形成するのが好適である。
The hydrogen radical etching apparatus of the present invention is an apparatus for generating hydrogen radicals and performing surface treatment of a quartz glass substrate with the hydrogen radicals used in the method of the present invention, and is installed in a processing container body and the processing container body Holder member, a heater member installed in the holder member, a tray member on which a quartz glass substrate provided on the upper surface of the holder member is placed, and an upper part in the processing container main body, which are movable up and down. It includes a heating element provided, an introduction hole for introducing hydrogen gas into the processing container main body, and an exhaust hole for exhausting waste gas in the processing container main body.
The tray member is preferably formed of a black quartz material.
本発明の水素ラジカルエッチング装置において、前記発熱体と前記トレー部材との間に高融点金属からなる輻射シールド部材を配置することが好ましい。前記輻射シールド部材としては、複数の穴を有した複数枚の板からなり、各板の間に間隙を設け、隣り合う板の穴の位置が重ならないように配置されてなる輻射シールド部材が好適に用いられる。 In the hydrogen radical etching apparatus of the present invention, it is preferable that a radiation shield member made of a refractory metal is disposed between the heating element and the tray member. As the radiation shield member, a radiation shield member composed of a plurality of plates having a plurality of holes, provided with a gap between the plates, and arranged so that the positions of the holes of adjacent plates do not overlap each other is preferably used. It is done.
本発明の石英ガラス基板の表面処理方法によれば、表面平坦度をサブナノメータレベルで制御することができ、水素ラジカルエッチングにおける処理温度及び処理時間を調整することにより、所望の平坦化及び粗面化を達成することができる。特に、本発明の石英ガラス基板の表面処理方法によれば、ＬＳＩ分野の極端紫外線（ＥＵＶ）を用いたリソグラフィ反射マスク基板などに対する要望に応えることができるようにした高平坦度（サブナノメータレベル）石英ガラス基板を得ることができる。また、本発明の水素ラジカルエッチング装置によれば、本発明の石英ガラス基板の表面処理方法を効率よく実施できるという利点がある。 According to the surface treatment method for a quartz glass substrate of the present invention, the surface flatness can be controlled at a sub-nanometer level, and a desired flattening and rough surface can be achieved by adjusting the treatment temperature and treatment time in hydrogen radical etching. Can be achieved. In particular, according to the surface treatment method for a quartz glass substrate of the present invention, high flatness (sub-nanometer level) that can meet the demand for a lithography reflection mask substrate using extreme ultraviolet rays (EUV) in the LSI field. A quartz glass substrate can be obtained. Moreover, according to the hydrogen radical etching apparatus of this invention, there exists an advantage that the surface treatment method of the quartz glass substrate of this invention can be implemented efficiently.
以下、本発明の実施の形態について添付図面に基づいて説明するが、図示例は本発明の好ましい実施の形態を示すもので、本発明の技術思想から逸脱しない限り、種々の変形が可能であることはいうまでもない。 DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below with reference to the accompanying drawings. However, the illustrated examples show preferred embodiments of the present invention, and various modifications can be made without departing from the technical idea of the present invention. Needless to say.
図１は本発明の水素ラジカルエッチング装置の１つの実施形態を示す概略説明図である。図２は本発明の石英ガラス基板の表面処理方法における処理容器内における反応を模式的に示す説明図である。 FIG. 1 is a schematic explanatory view showing one embodiment of the hydrogen radical etching apparatus of the present invention. FIG. 2 is an explanatory view schematically showing a reaction in a processing container in the surface treatment method for a quartz glass substrate of the present invention.
図１において、１０は水素ラジカルエッチング装置で、処理容器本体１２を有している。該処理容器本体１２内にはホルダー部材１４が設置されている。該ホルダー部材１４内にはヒーター部材１６が設置されている。１８は該ホルダー部材１４の上面に設けられたトレー部材で、表面処理される石英ガラス基板２０を載置する作用を行う。２２は発熱体で、所定の高温、好ましくは１０００〜２１００℃、に設定され、処理容器本体１２内に導入される水素ガスを高効率に接触分解して水素ラジカルとする作用を果たす。該発熱体２２は、例えば、タングステン（Ｗ）等の触媒体ワイア材料で形成されている。該発熱体２２は該処理容器本体１０内の上部に上下動自在に設けられた支持部材２４に取り付けられ、該支持部材２４とともに上下動可能とされている。２５ａ及び２５ｂは該発熱体２２と該トレー部材１８との間に配置された輻射シールド部材であり、２５ａは複数の穴２７ａを有し、２５ｂは複数の穴２５ｂを有する。前記発熱体２２の輻射により石英ガラス基板２０の温度が必要以上に加熱される場合があるが、該輻射シールド部材２５ａ，２５ｂを設けることにより、これを防ぐことができ、石英ガラス基板２０の温度をホルダー部材１４のヒーター部材１６により独立に制御可能となる。一方、水素ラジカルは寿命が長く、該輻射シールド部材２５ａ，２５ｂを配置しても拡散による回り込みにより処理対象の石英ガラス基板表面へ十分に到達することができる。該輻射シールド部材は、図１に示した如く、複数の穴２７ａ，２７ｂを有した２枚以上の板２５ａ，２５ｂからなり、各板の間に間隙を設け、隣り合う板の穴２７ａ，２７ｂの位置が重ならないように配置することが好ましい。該輻射シールド部材２５ａ，２５ｂの形状及び材質は特に限定されないが、高融点金属からなることが好ましい。また、穴２７ａ，２７ｂの形状も特に限定されないが、該輻射シールド部材２５ａ，２５ｂがシャワープレート構造と同様の作用を示すように構成するのが好適である。なお、図１においては２枚の板を設けた例を示したが、３枚以上の板を設けてもよい。２６は該処理容器本体１０内に水素ガスを導入する導入孔であり、２８は該処理容器本体１０内の廃ガスを排気する排気孔である。３０は前室で、石英ガラス基板２０を処理容器本体１２内に搬入及び搬出する際に用いられる。前記トレー部材１８の材質としては、従来から熱処理装置において常用される窒化珪素等を用いることができるが、黒色石英が特に好適である。該黒色石英は、ホルダーからの輻射吸収の効率が良く、基板加熱のためのエネルギーを低減することができる。 In FIG. 1, reference numeral 10 denotes a hydrogen radical etching apparatus having a processing container main body 12. A holder member 14 is installed in the processing container main body 12. A heater member 16 is installed in the holder member 14. Reference numeral 18 denotes a tray member provided on the upper surface of the holder member 14 and performs an operation of placing the quartz glass substrate 20 to be surface-treated. Reference numeral 22 denotes a heating element, which is set to a predetermined high temperature, preferably 1000 to 2100 ° C., and serves to generate hydrogen radicals by catalytically decomposing hydrogen gas introduced into the processing vessel body 12 with high efficiency. The heating element 22 is made of, for example, a catalyst wire material such as tungsten (W). The heating element 22 is attached to a support member 24 provided in the upper part of the processing container main body 10 so as to be movable up and down, and can be moved up and down together with the support member 24. Reference numerals 25a and 25b denote radiation shield members disposed between the heating element 22 and the tray member 18. 25a has a plurality of holes 27a, and 25b has a plurality of holes 25b. Although the temperature of the quartz glass substrate 20 may be heated more than necessary due to the radiation of the heating element 22, this can be prevented by providing the radiation shield members 25 a and 25 b, and the temperature of the quartz glass substrate 20. Can be independently controlled by the heater member 16 of the holder member 14. On the other hand, hydrogen radicals have a long life, and even if the radiation shield members 25a and 25b are arranged, they can sufficiently reach the surface of the quartz glass substrate to be processed by the wraparound due to diffusion. As shown in FIG. 1, the radiation shield member is composed of two or more plates 25a and 25b having a plurality of holes 27a and 27b. A gap is provided between the plates, and the positions of the holes 27a and 27b in the adjacent plates. It is preferable to arrange them so that they do not overlap. The shape and material of the radiation shield members 25a and 25b are not particularly limited, but are preferably made of a refractory metal. Further, the shape of the holes 27a and 27b is not particularly limited, but it is preferable that the radiation shield members 25a and 25b are configured to exhibit the same action as the shower plate structure. Although FIG. 1 shows an example in which two plates are provided, three or more plates may be provided. Reference numeral 26 denotes an introduction hole for introducing hydrogen gas into the processing container main body 10, and reference numeral 28 denotes an exhaust hole for exhausting the waste gas in the processing container main body 10. A front chamber 30 is used when the quartz glass substrate 20 is carried into and out of the processing container main body 12. As the material of the tray member 18, silicon nitride or the like conventionally used in a heat treatment apparatus can be used, and black quartz is particularly suitable. The black quartz has a high efficiency of absorbing the radiation from the holder and can reduce the energy for heating the substrate.
この黒色石英は、水酸基を含むシリカ多孔質ガラス体を、ハロゲン化シランを除く揮発性珪素化合物雰囲気中で気相反応させた後、焼成して緻密なガラス体とする方法において、前記気相反応を８００℃を超え１３００℃以下の反応温度で行った後、１３００℃以上１９００℃以下で焼成することによって製造され、特に含有される炭素濃度が３００ｐｐｍを超え５００００ｐｐｍ以下かつ水酸基濃度が３０ｐｐｍ以下であるもの（特開２００４−１２３５１４公報参照）か、または２４５ｎｍの吸収係数が０．０５ｃｍ-1以上である石英ガラス体を製造する方法であって、シリカ多孔質体を還元処理及び焼成処理して緻密なガラス体とする方法において、前記シリカ多孔質体を炭素を含む気体と４００℃以上１３００℃以下で反応させる還元処理を行った後、１３００℃以上１９００℃以下で焼成して、緻密化した黒色ガラス体を得る方法によって製造され、特に含有される炭素濃度が１００ｐｐｍを超え１００００ｐｐｍ以下であるもの（ＷＯ２００４／０５０５７０公報参照）を用いることができる。 This black quartz is obtained by subjecting a porous silica glass body containing a hydroxyl group to a gas phase reaction in a volatile silicon compound atmosphere excluding a halogenated silane, followed by firing to form a dense glass body. Is carried out at a reaction temperature of more than 800 ° C. and not more than 1300 ° C., followed by firing at not less than 1300 ° C. and not more than 1900 ° C. Or a method for producing a quartz glass body having an absorption coefficient of 245 nm of 0.05 cm −1 or more, wherein the silica porous body is subjected to a reduction treatment and a firing treatment to obtain a dense In the method for forming a vitreous body, the silica porous body is reacted with a gas containing carbon at 400 ° C. or higher and 1300 ° C. or lower. After the treatment, it is produced by a method of obtaining a dense black glass body by firing at 1300 ° C. or higher and 1900 ° C. or lower, and particularly containing carbon concentration of more than 100 ppm and 10000 ppm or less (WO 2004/050570) Reference) can be used.
本発明において、表面処理される石英ガラス基板２０としては、二酸化珪素のみからなるガラス基板、及び二酸化珪素を主成分とするガラス基板が用いられ、室温（２０℃±５℃）における線膨張係数が０．０×１０-7／℃以上６．０×１０-7／℃以下である超低膨張ガラス基板が好適である。前記超低膨張ガラス基板としては、例えば、チタニアを含有する石英ガラス基板が好ましく、該チタニア濃度が２質量％以上１５質量％以下であることがより好ましい。また、前記チタニアを含有する石英ガラス基板の組成はチタニアと二酸化珪素からなることが好ましい。 In the present invention, as the quartz glass substrate 20 to be surface-treated, a glass substrate composed solely of silicon dioxide and a glass substrate mainly composed of silicon dioxide are used, and the linear expansion coefficient at room temperature (20 ° C. ± 5 ° C.) is used. An ultra-low expansion glass substrate that is 0.0 × 10 −7 / ° C. or higher and 6.0 × 10 −7 / ° C. or lower is preferable. As the ultra-low expansion glass substrate, for example, a quartz glass substrate containing titania is preferable, and the titania concentration is more preferably 2% by mass or more and 15% by mass or less. The composition of the quartz glass substrate containing titania is preferably composed of titania and silicon dioxide.
上記水素ラジカルエッチング装置１０を用いた石英ガラス基板２０に対する水素ラジカルエッチング処理について図２によって模式的に説明する。まず、処理容器本体１２内に水素ガス（Ｈ2）を導入し、高温に熱せられた発熱体２２によってその水素ガスを接触分解して水素ラジカルを発生させる（図２（ａ））。次いで、発生した水素ラジカルによって、トレー部材１８上に載置された凹凸を有する石英ガラス基板２０の表面を水素ラジカルエッチング処理し（図２（ｂ））、サブナノメータレベルの平坦度を有する石英ガラス基板２０ａを作成する（図２（ｃ））。 A hydrogen radical etching process for the quartz glass substrate 20 using the hydrogen radical etching apparatus 10 will be schematically described with reference to FIG. First, hydrogen gas (H 2 ) is introduced into the processing vessel main body 12, and the hydrogen gas is catalytically decomposed by a heating element 22 heated to a high temperature to generate hydrogen radicals (FIG. 2A). Next, the surface of the quartz glass substrate 20 having irregularities placed on the tray member 18 is subjected to hydrogen radical etching treatment by the generated hydrogen radicals (FIG. 2B), and quartz glass having a sub-nanometer level flatness. A substrate 20a is formed (FIG. 2C).
次に、平坦化処理された石英ガラス基板の表面評価手法について説明する。
処理表面におけるμｍ領域の表面状態の変化をＡＦＭ（Atomic Force Microscope：原子間力顕微鏡）やＳＴＭ（Scanning Tunneling Microscope：走査型トンネル顕微鏡）などの観察により、評価することができる。はじめに、ＡＦＭを用いてμｍ領域の表面粗さをＲa，Ｒq，Ｒz（Ｒmax）を用いて評価した。粗さ曲線の算術平均高さであるＲaは、基準長さｌ内の任意の位置ｘにおける粗さ曲線の高さＺ（ｘ）の絶対値の平均であり、以下の式（１）で表される。
Next, a method for evaluating the surface of the flattened quartz glass substrate will be described.
Changes in the surface state of the μm region on the treated surface can be evaluated by observation with an AFM (Atomic Force Microscope) or STM (Scanning Tunneling Microscope). First, the surface roughness of the μm region was evaluated using R a , R q , and R z (R max ) using AFM. Ra , which is the arithmetic average height of the roughness curve, is an average of absolute values of the height Z (x) of the roughness curve at an arbitrary position x within the reference length l. expressed.
Ｒqは粗さの２乗平均平方根高さであり、以下の式（２）で表される。 R q is the root mean square height of the roughness, and is represented by the following formula (2).
Ｒz（Ｒmax）は粗さ曲線の山の高さの最大値と谷の深さの最大値の和である。これらは、その表面粗さを数値で把握できる点で優れているが、高さの情報しか含まないため、微細な表面の状態変化の情報が含まれていない可能性がある。これに対して、得られた表面の凹凸を空間周波数領域へ変換することにより、空間周波数での振幅強度で表すパワースペクトル解析は、微細な表面形状を数値化することができる。Ｚ（ｘ，ｙ）をｘ座標、ｙ座標における高さのデータとすると、そのフーリエ変換は以下の式（３）で与えられる。 R z (R max ) is the sum of the maximum value of the peak of the roughness curve and the maximum value of the depth of the valley. These are excellent in that the surface roughness can be grasped numerically, but since only the height information is included, there is a possibility that the information on the minute surface state change is not included. On the other hand, by converting the obtained surface irregularities into the spatial frequency domain, the power spectrum analysis represented by the amplitude intensity at the spatial frequency can digitize the fine surface shape. If Z (x, y) is the height data in the x-coordinate and y-coordinate, the Fourier transform is given by the following equation (3).
ここで、Ｎx，Ｎyはｘ方向とｙ方向のデータの数である。ｕ＝０，１，２，．．．．Ｎx−１，ｖ＝０，１，２，．．．．Ｎy−１であり、このとき空間周波数ｆは、以下の式（４）で与えられる。 Here, N x and N y are the numbers of data in the x and y directions. u = 0, 1, 2,. . . . N x −1, v = 0, 1, 2,. . . . N y −1. At this time, the spatial frequency f is given by the following equation (4).
このときのパワースペクトル密度（Power Spectrum Density，ＰＳＤ）は、以下の式（５）で与えられる。 The power spectrum density (PSD) at this time is given by the following equation (5).
このパワースペクトル解析は、表面状態の変化を単純な高さの変化としてだけでなく、その空間周波数での変化として把握することができる点で優れており、原子レベルでの微視的な反応などが表面に与える影響を解析する手法として期待される。ここでは、表面処理前後のＰＳＤの差スペクトルにより、各空間周波数における変化を評価した。 This power spectrum analysis is excellent in that it can grasp the change of the surface state not only as a simple change in height but also as a change in its spatial frequency, such as microscopic reaction at the atomic level, etc. It is expected as a method for analyzing the effect of the surface on the surface. Here, the change in each spatial frequency was evaluated by the difference spectrum of PSD before and after the surface treatment.
ついで、本発明の方法を用いた実施例及びそれと対比する比較例についても示すが、本発明は、これらによって何等限定されるものではなく、特許請求の範囲の記載に基づいて把握されるものであることは勿論である。 Next, examples using the method of the present invention and comparative examples to be compared with the examples will also be shown. However, the present invention is not limited to these examples, and is understood based on the description of the scope of claims. Of course there is.
（実施例１）
実施例１では、図１に示した水素ラジカルエッチング装置を用いて、Ｈ2ガスの流量２０ｓｃｃｍで装置内の圧力を１０Ｐａとなるように排気し、発熱体の温度を１８００℃にして、水素ラジカルを生成させた。輻射シールド部材としては、φ２ｍｍの穴を２０ｍｍピッチの升目に開けたＭｏ製の２枚の板を用い、各板の穴位置が重ならないように５ｍｍの隙間を隔てて２枚の板を配置した。この装置内に、黒色石英ホルダーにのせた石英ガラス基板（ＳｉＯ2ガラス基板）を温度１０００℃にし、１時間、３時間、５時間、７時間、１０時間、１５時間の間、処理を行なった。
(Example 1)
In Example 1, the hydrogen radical etching apparatus shown in FIG. 1 was used, the H 2 gas flow rate was 20 sccm, the pressure inside the apparatus was exhausted to 10 Pa, the temperature of the heating element was set to 1800 ° C., and the hydrogen radical Was generated. As the radiation shield member, two plates made of Mo with φ2 mm holes formed in 20 mm pitch grids were used, and the two plates were arranged with a 5 mm gap so that the hole positions of each plate did not overlap. . In this apparatus, a quartz glass substrate (SiO 2 glass substrate) placed on a black quartz holder was set at a temperature of 1000 ° C., and the treatment was performed for 1, 3, 5, 7, 10, and 15 hours. .
この処理前後の石英ガラス基板の表面をＡＦＭを用いて観察し、表面粗さＲa、Ｒq及びＲzの値とともに、ＰＳＤの差スペクトルにより、表面処理による変化を解析した。 The surface of the quartz glass substrate before and after this treatment was observed using AFM, and the change due to the surface treatment was analyzed by the difference spectrum of PSD together with the values of the surface roughness Ra , Rq and Rz .
図３に処理後の１×１μｍの領域のＡＦＭ像を示した。各試料や測定場所によって、その表面の状態に差はあるものの７時間から、ＡＦＭ像に変化が生じていることがわかる。それより長い時間の処理では変化が明瞭になり、２０ｎｍ程度の凹凸が認められる。各処理時間におけるＲaとＲqの値を図４に示した。 FIG. 3 shows an AFM image of the 1 × 1 μm region after processing. It can be seen that the AFM image has changed from 7 hours although there are differences in the surface state depending on each sample and measurement location. When the treatment is performed for a longer time, the change becomes clear and irregularities of about 20 nm are observed. The values of Ra and Rq at each treatment time are shown in FIG.
図３及び４からわかるように５時間の処理では、その値がほとんど変化しないが、それ以降徐々に値が大きくなることがわかる。図の左端のデータは未処理の試料の表面を評価した値である。１時間処理におけるＲaやＲqの平均値は未処理の試料よりも低い値を示していることから、短時間処理により、ＲaやＲqの値で表される表面粗さが減少していることを示している。 As can be seen from FIGS. 3 and 4, in the process for 5 hours, the value hardly changes, but thereafter the value gradually increases. The data at the left end of the figure is a value obtained by evaluating the surface of an untreated sample. Since the average values of Ra and Rq after 1 hour treatment are lower than those of the untreated sample, the surface roughness expressed by the Ra and Rq values is reduced by short-time treatment. It shows that.
図５に１×１μｍの領域のＡＦＭ像から求めたＰＳＤの差スペクトルの処理時間による変化を示した。図５からわかるように、１時間処理では、広い周波数域で負になっている。処理時間が７時間となると、２０〜７０μｍ-1に幅広いピークが認められる。１０００℃、１０Ｐａの水素ラジカル処理では、１時間程度の短時間の処理によって、その表面の凹凸が減少する傾向があることがわかった。 FIG. 5 shows the change of the PSD difference spectrum obtained from the AFM image of the 1 × 1 μm region depending on the processing time. As can be seen from FIG. 5, in the one-hour processing, it is negative in a wide frequency range. When the treatment time is 7 hours, a broad peak is observed at 20 to 70 μm −1 . In the hydrogen radical treatment at 1000 ° C. and 10 Pa, it was found that the unevenness of the surface tends to decrease by the treatment for a short time of about 1 hour.
また、７時間以上の長時間の処理によって、１５〜５０ｎｍ程度のマイクロラフネスが生じることが示され、これは、図３の（ｅ）や（ｆ）で認められる凹凸の大きさと一致している。 Further, it is shown that a microroughness of about 15 to 50 nm is generated by a long-time treatment of 7 hours or more, which is consistent with the size of the irregularities recognized in (e) and (f) of FIG. .
処理前後の基板表面のＲzについては、１μｍ×１μｍの面積に対し処理前１．３ｎｍであったＲzが基板温度１０００℃、処理時間１時間により０．９ｎｍとなり、本発明によりサブナノメータレベルの表面平坦度を有した石英ガラス基板を実現できた。 The R z of before and after treatment of the substrate surface, 1μm × 1μm R z is a substrate temperature of 1000 ° C. was pretreated 1.3nm to area, 0.9 nm next by the processing time of 1 hour, the sub-nanometer level by the present invention A quartz glass substrate having a surface flatness of 5 mm was realized.
（実施例２）
実施例２では、図１に示した水素ラジカルエッチング装置を用いて、Ｈ2ガスの流量２０ｓｃｃｍで装置内の圧力を１０Ｐａとなるように排気し発熱体の温度を１８００℃にして、水素ラジカルを生成させた。この装置内に、黒石英ホルダーにのせた石英ガラス基板（ＳｉＯ2ガラス基板）の温度を６００℃から１０００℃まで変化させて１５時間の間、処理を行なった。
(Example 2)
In Example 2, the hydrogen radical etching apparatus shown in FIG. 1 was used, the H 2 gas flow rate was 20 sccm, the pressure inside the apparatus was exhausted to 10 Pa, the temperature of the heating element was set to 1800 ° C., and hydrogen radicals were removed. Generated. In this apparatus, the temperature of the quartz glass substrate (SiO 2 glass substrate) placed on the black quartz holder was changed from 600 ° C. to 1000 ° C., and the treatment was performed for 15 hours.
この処理前後の石英ガラス基板の表面のＡＦＭ観察を行い、表面粗さＲaとＲqの値とともに、ＰＳＤの差スペクトルにより、表面処理による変化を解析した。 Perform AFM observation of the process before and after the quartz glass substrate surface, with the surface roughness value R a and R q, the difference spectrum of the PSD, and analyze changes by surface treatment.
図６に各基板温度での処理後の１×１μｍの領域のＡＦＭ像を示した。各試料や測定場所によって、その表面の状態に差はあるものの基板温度８００℃までの処理による表面の明瞭な変化は認められなかった。また、基板温度１０００℃の処理によって表面に大きな変化が生じていることがわかった。 FIG. 6 shows an AFM image of a 1 × 1 μm region after processing at each substrate temperature. Although there was a difference in the state of the surface depending on each sample and measurement place, a clear change of the surface due to the treatment up to the substrate temperature of 800 ° C. was not recognized. Moreover, it turned out that the big change has arisen on the surface by the process of substrate temperature 1000 degreeC.
各基板温度での処理におけるＲaとＲqの値を図７に示した。図７の左端のデータは未処理の試料の表面を評価した値である。図７からわかるように基板温度６００℃では、未処理の表面粗さよりも低い粗さの値を示し、８００℃でほぼ未処理と同じ値になり、９００℃、１０００℃と温度が上昇するにしたがって、急速にその値が増加することがわかる。 The values of Ra and Rq in the treatment at each substrate temperature are shown in FIG. The data at the left end of FIG. 7 is a value obtained by evaluating the surface of an untreated sample. As can be seen from FIG. 7, when the substrate temperature is 600 ° C., the roughness value is lower than the untreated surface roughness. At 800 ° C., the roughness value is almost the same as the untreated surface, and the temperature rises to 900 ° C. and 1000 ° C. Therefore, it can be seen that the value increases rapidly.
図８に１×１μｍの領域のＡＦＭ像から求めたＰＳＤの差スペクトルの基板温度による変化を示した。図８からわかるように、基板温度が６００℃の処理では、１０〜７０μｍ-1の幅広い周波数域で負になっている。基板温度が８００℃の処理では、６０〜７０μｍ-1に、９００℃の処理では、５０μｍ-1に、１０００℃の処理では、３０〜４０μｍ-1に、ピークが認められる。基板温度を比較的低い温度で水素ラジカル処理をすることにより、その表面の凹凸が減少する傾向があることがわかった。 FIG. 8 shows the change of the PSD difference spectrum obtained from the AFM image of the 1 × 1 μm region depending on the substrate temperature. As can be seen from FIG. 8, in the processing at the substrate temperature of 600 ° C., it is negative in a wide frequency range of 10 to 70 μm −1 . In the processing of the substrate temperature is 800 ° C. is a 60～70Myuemu -1, in the processing of 900 ° C. is a 50 [mu] m -1, in the processing in 1000 ° C., to 30 to 40 .mu.m -1, a peak is observed. It was found that the surface irregularities tend to be reduced by performing hydrogen radical treatment at a relatively low substrate temperature.
（実施例３）
表面処理される石英ガラス基板として、チタニアを６．８％含有する石英ガラス（２０〜３５℃における線膨張係数：０×１０-7／℃）製の基板を用いた以外は実施例１及び２と同様に実験を行った結果、それぞれ同様の結果が得られた。
(Example 3)
Examples 1 and 2 except that a quartz glass substrate containing 6.8% titania (linear expansion coefficient at 20 to 35 ° C .: 0 × 10 −7 / ° C.) was used as the surface-treated quartz glass substrate. As a result of conducting an experiment in the same manner as above, similar results were obtained.
１０：水素ラジカルエッチング装置、１２：処理容器本体、１４：ホルダー部材、１６：ヒーター部材、１８：トレー部材、２０：石英ガラス基板、２２：発熱体、２４：支持部材、２５ａ，２５ｂ：輻射シールド部材、２６：導入孔、２７ａ，２７ｂ：輻射シールド部材の穴、２８：排気孔、３０：前室。 DESCRIPTION OF SYMBOLS 10: Hydrogen radical etching apparatus, 12: Processing container main body, 14: Holder member, 16: Heater member, 18: Tray member, 20: Quartz glass substrate, 22: Heat generating body, 24: Support member, 25a, 25b: Radiation shield Member, 26: introduction hole, 27a, 27b: hole of radiation shield member, 28: exhaust hole, 30: anterior chamber.
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