JPH07330357A - Quartz glass material for microwave plasma equipment - Google Patents
Quartz glass material for microwave plasma equipmentInfo
- Publication number
- JPH07330357A JPH07330357A JP11978394A JP11978394A JPH07330357A JP H07330357 A JPH07330357 A JP H07330357A JP 11978394 A JP11978394 A JP 11978394A JP 11978394 A JP11978394 A JP 11978394A JP H07330357 A JPH07330357 A JP H07330357A
- Authority
- JP
- Japan
- Prior art keywords
- glass material
- quartz glass
- microwave
- silica glass
- value
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/14—Other methods of shaping glass by gas- or vapour- phase reaction processes
- C03B19/1453—Thermal after-treatment of the shaped article, e.g. dehydrating, consolidating, sintering
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/02—Pure silica glass, e.g. pure fused quartz
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/02—Pure silica glass, e.g. pure fused quartz
- C03B2201/03—Impurity concentration specified
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/02—Pure silica glass, e.g. pure fused quartz
- C03B2201/03—Impurity concentration specified
- C03B2201/04—Hydroxyl ion (OH)
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/07—Impurity concentration specified
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/20—Doped silica-based glasses doped with non-metals other than boron or fluorine
- C03B2201/23—Doped silica-based glasses doped with non-metals other than boron or fluorine doped with hydroxyl groups
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Thermal Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Glass Melting And Manufacturing (AREA)
- Glass Compositions (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Chemical Vapour Deposition (AREA)
- Drying Of Semiconductors (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はマイクロ波プラズマ装置
用の石英ガラス材料に関し、より詳細にはマイクロ波を
使用して発生させたプラズマを利用する半導体デバイス
製造用のエッチング装置、アッシング装置またはＣＶＤ
装置等に配設されたマイクロ波導入窓、観測窓、ベルジ
ャ、ウエハ支持部品等を形成するのに用いられるマイク
ロ波プラズマ装置用の石英ガラス材料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a quartz glass material for a microwave plasma apparatus, and more particularly to an etching apparatus, an ashing apparatus or a CVD apparatus for manufacturing a semiconductor device utilizing plasma generated by using microwaves.
TECHNICAL FIELD The present invention relates to a quartz glass material for a microwave plasma device used for forming a microwave introduction window, an observation window, a bell jar, a wafer supporting component, etc. arranged in the device or the like.
【０００２】[0002]
【従来の技術】真空近くに減圧した容器内に反応ガスと
マイクロ波とを導入し、ガス放電を起こさせてプラズマ
を発生させ、このプラズマをウエハ表面に導いてエッチ
ング、アッシング（レジスト除去）あるいはＣＶＤ（Ce
mical Vapor Deposition）等の処理を行なわせるマイク
ロ波プラズマ装置は、高集積半導体素子等の製造に欠く
ことができないものとなってきている。2. Description of the Related Art A reaction gas and a microwave are introduced into a container whose pressure is reduced to near vacuum, a gas discharge is caused to generate plasma, and the plasma is guided to the wafer surface to perform etching, ashing (resist removal) or CVD (Ce
Microwave plasma devices that perform processing such as mical vapor deposition) have become indispensable for manufacturing highly integrated semiconductor elements and the like.
【０００３】図２は従来のこの種マイクロ波プラズマ装
置の一例を模式的に示した断面図であり、図中１１は略
中空直方体形状の反応器を示している。反応器１１はス
テンレス鋼等の金属を用いて形成され、その周囲壁は２
重構造となっており、この内部は冷却水流通室１８が形
成されている。そして冷却水流通室１８に冷却水を通す
ことにより、反応器１１が冷却されるようになってい
る。反応器１１上部はプラズマ生成室２０となってお
り、プラズマ生成室２０上部はマイクロ波導入窓２２に
より気密状態に封止されており、マイクロ波導入窓２２
は誘電損失が小さく、かつ耐熱性を有する石英ガラス材
料等を用いて略板形状に形成されている。またプラズマ
生成室２０の下方にはメッシュ構造を有する仕切り板１
７を挟んで反応室２１が形成されており、反応室２１内
におけるマイクロ波導入窓２２と対向する箇所には、試
料Ｓを載置するための試料台２３が配設されている。ま
た反応室２０の下部壁には排気装置（図示せず）に接続
された排気口１４が形成されており、プラズマ生成室２
０の一側壁には反応器１１内に所要の反応ガスを供給す
るためのガス供給管１３が接続されている。FIG. 2 is a sectional view schematically showing an example of a conventional microwave plasma apparatus of this type, and 11 in the figure shows a reactor having a substantially hollow rectangular parallelepiped shape. The reactor 11 is made of a metal such as stainless steel, and its surrounding wall is 2
It has a heavy structure, and a cooling water flow chamber 18 is formed inside this. The reactor 11 is cooled by passing cooling water through the cooling water flow chamber 18. The upper part of the reactor 11 is a plasma generation chamber 20, and the upper part of the plasma generation chamber 20 is hermetically sealed by a microwave introduction window 22.
Is formed in a substantially plate shape using a quartz glass material or the like having a small dielectric loss and heat resistance. A partition plate 1 having a mesh structure is provided below the plasma generation chamber 20.
A reaction chamber 21 is formed with the sample 7 sandwiched therebetween, and a sample table 23 for mounting the sample S is arranged at a position facing the microwave introduction window 22 in the reaction chamber 21. An exhaust port 14 connected to an exhaust device (not shown) is formed on the lower wall of the reaction chamber 20.
A gas supply pipe 13 for supplying a required reaction gas into the reactor 11 is connected to one side wall of the reactor 0.
【０００４】一方、反応器１１の上方にはＡｌ（アルミ
ニウム）等を用いて形成された枠体１２ａが配設され、
枠体１２ａ下面には誘電体層１２ｂがボルト（図示せ
ず）等を用いて固定されている。誘電体層１２ｂは誘電
損失の小さいフッ素樹脂、ポリエチレンあるいはポリス
チレン等を用いて形成されており、これら枠体１２ａ、
誘電体層１２ｂ等により誘電体線路１２が構成されてい
る。さらに誘電体線路１２には導波管１５を介してマイ
クロ波発振器１６が接続されており、マイクロ波発振器
１６からのマイクロ波が導波管１５を通って誘電体線路
１２に導入されるようになっている。On the other hand, a frame body 12a made of Al (aluminum) or the like is arranged above the reactor 11.
A dielectric layer 12b is fixed to the lower surface of the frame body 12a using bolts (not shown) or the like. The dielectric layer 12b is formed by using fluororesin, polyethylene, polystyrene or the like having a small dielectric loss.
The dielectric layer 12b and the like constitute the dielectric line 12. Further, a microwave oscillator 16 is connected to the dielectric line 12 via a waveguide 15, and microwaves from the microwave oscillator 16 are introduced into the dielectric line 12 through the waveguide 15. Has become.
【０００５】このように構成されたマイクロ波プラズマ
装置を用い、試料台２３上に載置された試料Ｓ表面に、
例えばアッシング処理やエッチング処理を施す場合、ま
ず排気口１４から排気を行ない、その後ガス供給管１３
からＣｌ2 、ＨＢｒ、Ｏ2 等の反応ガスをプラズマ生成
室２０内に供給して反応器１１内を所要の真空度に設定
する。また装置の作動中、冷却水流通室１８に冷却水を
流して反応器１１周辺を冷却する。次にマイクロ波発振
器１６を作動させてマイクロ波を発振させ、このマイク
ロ波を導波管１５を介して誘電体線路１２に導入する
と、誘電体線路１２下方に電界が形成され、この電界が
石英ガラス材料等を用いて形成されたマイクロ波導入窓
２２を透過してプラズマ生成室２０内に導入される。す
るとガス供給管１３を介してプラズマ生成室２０内に供
給された反応ガスがこの電界によりプラズマ化される。
このプラズマのうち主として電気的に中性の活性ガス種
がメッシュ状の仕切り板１７を透過して反応室２１内に
均一に拡がり、試料台２３上に載置された試料Ｓ表面に
到達してアッシング処理やエッチング処理等が行なわれ
る。Using the microwave plasma device thus constructed, the surface of the sample S placed on the sample table 23 is
For example, when performing an ashing process or an etching process, exhaust is first performed from the exhaust port 14, and then the gas supply pipe 13 is used.
To supply a reaction gas such as Cl 2 , HBr, and O 2 into the plasma generation chamber 20 to set the inside of the reactor 11 to a required vacuum degree. Further, during the operation of the apparatus, the cooling water is supplied to the cooling water flow chamber 18 to cool the periphery of the reactor 11. Next, the microwave oscillator 16 is operated to oscillate a microwave, and when this microwave is introduced into the dielectric line 12 through the waveguide 15, an electric field is formed below the dielectric line 12, and this electric field is formed by quartz. It is introduced into the plasma generation chamber 20 through the microwave introduction window 22 formed of a glass material or the like. Then, the reaction gas supplied into the plasma generation chamber 20 through the gas supply pipe 13 is turned into plasma by this electric field.
Of this plasma, mainly electrically neutral active gas species permeate through the mesh-shaped partition plate 17 to spread uniformly in the reaction chamber 21, and reach the surface of the sample S mounted on the sample table 23. Ashing processing, etching processing, etc. are performed.
【０００６】また図示しない別のマイクロ波プラズマ装
置には、石英ガラス材料等により形成された部品として
観測窓、ウエハ支持治具、ベルジャ等が配設されてい
る。Further, another microwave plasma device (not shown) is provided with an observation window, a wafer supporting jig, a bell jar, etc. as parts made of quartz glass material or the like.
【０００７】ところで、上記したマイクロ波導入窓２
２、観測窓、ウエハ支持具、ベルジャ等を形成する石英
ガラス材料は、原料及び製造方法により溶融石英ガラス
材料と気相合成石英ガラス材料との２種類に大別され
る。溶融石英ガラス材料は原料として天然の結晶質石英
粉末を用い、真空状態下の電気抵抗加熱炉、または酸素
−水素火炎の熱により溶融・形成したものであり、原料
等からの不純物を比較的多く含んでいる一方、耐熱性が
高いという特性を有している。また気相合成石英ガラス
材料はＳｉＣｌ4 等のＳｉ化合物を酸素−水素火炎中で
加水分解することにより気相合成したもので、含有する
不純物濃度は数１０ｐｐｂ以下であり、非常に高純度で
ある。そして上記した従来のマイクロ波導入窓２２等の
部品には、主として比較的耐熱性が高い溶融石英ガラス
材料が用いられていた。By the way, the microwave introduction window 2 described above is used.
2. The quartz glass materials forming the observation window, the wafer support, the bell jar, etc. are roughly classified into two types, that is, fused quartz glass materials and vapor-phase synthetic quartz glass materials, depending on the raw material and the manufacturing method. The fused silica glass material uses natural crystalline quartz powder as a raw material and is melted and formed by the heat of an electric resistance heating furnace in a vacuum state or an oxygen-hydrogen flame. On the other hand, it has the property of high heat resistance. Further, the vapor-phase synthetic quartz glass material is obtained by vapor-phase synthesis by hydrolyzing a Si compound such as SiCl 4 in an oxygen-hydrogen flame, and has an impurity concentration of tens of ppb or less, which is extremely high purity. . A fused silica glass material having a relatively high heat resistance is mainly used for the above-mentioned conventional microwave introduction window 22 and other parts.
【０００８】[0008]
【発明が解決しようとする課題】しかし、上記した溶融
石英ガラス材料を用いて形成されたマイクロ波導入窓２
２等の部品は使用中に穴が開くというトラブルが発生し
易く、寿命が短いという問題があった。However, the microwave introduction window 2 formed by using the above fused silica glass material.
Parts such as 2 are apt to have a problem that a hole is opened during use and have a problem of a short service life.
【０００９】また前記溶融石英ガラス材料を用いて形成
されたマイクロ波導入窓２２等の部品にはＮａ、Ｋ、Ｆ
ｅ、Ａｌ等の不純物が全体で数ｐｐｍ〜２０ｐｐｍ程度
含有されており、プラズマ処理中にこれらがハロゲン化
して試料Ｓ表面に付着し、ウエハの品質に悪影響を及ぼ
すという問題があった。Further, parts such as the microwave introduction window 22 formed by using the fused silica glass material are Na, K, F.
There is a problem in that impurities such as e and Al are contained in the total of several ppm to 20 ppm, and these are halogenated during the plasma processing and adhere to the surface of the sample S, which adversely affects the quality of the wafer.
【００１０】一方、前記気相合成石英ガラス材料を用い
て形成されたマイクロ波導入窓２２等の部品は高純度で
あり、組織が比較的均一であることから、ハロゲン系の
活性ガス種による侵食が比較的均一に行なわれ、穴が開
くトラブルの発生は少ない。また近年、電子回路等の高
集積化に伴い、試料ＳとしてのＳｉウエハに対する不純
物汚染防止の要求が一層高くなっており、前記溶融石英
ガラス材料よりも純度の高い前記気相合成石英ガラス材
料の使用が求められてきている。On the other hand, parts such as the microwave introduction window 22 formed by using the above-mentioned vapor phase synthetic quartz glass material are of high purity and have a relatively uniform structure, so that they are eroded by the halogen-based active gas species. Is performed relatively uniformly, and there are few troubles in which holes are formed. Further, in recent years, with the high integration of electronic circuits and the like, the demand for preventing the impurity contamination of the Si wafer as the sample S has become higher, and the vapor phase synthetic quartz glass material having a higher purity than the fused silica glass material has been demanded. It is required to be used.
【００１１】しかしながら従来の前記気相合成石英ガラ
ス材料を用いて形成されたマイクロ波導入窓２２等の部
品は、マイクロ波を用いたプラズマ処理中に破損が生じ
易く、前記プラズマ処理を安定して行なうのが難しいと
いう課題があった。However, the conventional components such as the microwave introduction window 22 formed by using the above-mentioned vapor-phase synthetic quartz glass material are likely to be damaged during the plasma treatment using the microwave, and the plasma treatment is stabilized. There was a problem that it was difficult to do.
【００１２】本発明はこのような課題に鑑みなされたも
のであり、マイクロ波を用いるプラズマ装置の部品とし
て使用しても、ウエハの不純物汚染を生じさせず、また
プラズマ処理中に穴が開くことも破損することもなく、
寿命を長くすることができるとともに、プラズマ処理を
安定的に行なわせることができるマイクロ波プラズマ装
置用の石英ガラス材料を提供することを目的としてい
る。The present invention has been made in view of the above problems, and does not cause impurity contamination of a wafer even when it is used as a component of a plasma apparatus using microwaves, and a hole is opened during plasma processing. Without any damage,
An object of the present invention is to provide a quartz glass material for a microwave plasma device, which can have a long life and can stably perform plasma treatment.
【００１３】[0013]
【課題を解決するための手段】上記目的を達成するため
に本発明に係るマイクロ波プラズマ装置用の石英ガラス
材料は、気相化学反応により合成された石英ガラス材料
であって、含有されるＯＨ基濃度が１３０ｐｐｍ以下で
あり、ＧＨｚ周波数帯域におけるＦＱ値（周波数×Ｑ
値）が１０００００以上であることを特徴としている。In order to achieve the above object, a quartz glass material for a microwave plasma device according to the present invention is a quartz glass material synthesized by a gas phase chemical reaction and contains OH. The basic concentration is 130 ppm or less, and the FQ value in the GHz frequency band (frequency × Q
The value) is 100,000 or more.
【００１４】[0014]
【作用】本発明者等はマイクロ波プラズマ装置用の石英
ガラス材料について検討した結果、該石英ガラス材料中
にＮａ、Ｋ、Ｌｉ、Ｆｅ、Ａｌ等の不純物元素がそれぞ
れ１ｐｐｍ以上含有されると（すなわち溶融石英ガラス
の場合）、脈理と称される耐食性に劣る不均一組織が発
生し易くなり、この不均一組織がハロゲン系の活性ガス
種により選択的に侵食され、穴が開くトラブルが発生し
易くなることを突き止めた。The present inventors have studied quartz glass materials for microwave plasma devices and found that the quartz glass materials each contain 1 ppm or more of impurity elements such as Na, K, Li, Fe, and Al ( That is, in the case of fused silica glass), a heterogeneous structure called striae, which is inferior in corrosion resistance, is likely to occur, and this inhomogeneous structure is selectively eroded by the halogen-based active gas species, causing a problem of opening holes I found that it would be easier to do.
【００１５】またプラズマ処理中、マイクロ波電力が石
英ガラス材料に吸収され、該石英ガラス材料が発熱する
と、このとき発生する熱応力により破損が生じることも
突き止められた。Further, it was also found that when the quartz glass material absorbs microwave power during the plasma treatment and the quartz glass material generates heat, the thermal stress generated at this time causes damage.
【００１６】周波数と誘電体損失（ｔａｎδ）の逆数で
あるＱ値との積が前記ＦＱ値であり、マイクロ波による
誘電体損失が格子振動の減衰項に起因しているとき、前
記ＦＱ値は一定になることが知られており、したがって
該ＦＱ値を材料固有の値として評価し得る。そして前記
マイクロ波電力が石英ガラス材料に吸収され易いか否か
は前記石英ガラス材料の前記ＦＱ値に依存し、マイクロ
波領域での前記ＦＱ値が１０００００以上になると、前
記石英ガラス材料への前記マイクロ波電力の吸収が抑制
され、前記石英ガラス材料の発熱が少なくなり、該発熱
・昇温に伴う熱応力の発生が抑制され、したがって前記
石英ガラス材料の破損が生じ難くなることが明らかとな
った。The product of the frequency and the Q value which is the reciprocal of the dielectric loss (tan δ) is the FQ value. When the dielectric loss due to microwaves is caused by the attenuation term of the lattice vibration, the FQ value is It is known to be constant, so the FQ value can be evaluated as a material-specific value. Whether or not the microwave power is easily absorbed by the quartz glass material depends on the FQ value of the quartz glass material. When the FQ value in the microwave region is 100000 or more, It has been clarified that absorption of microwave power is suppressed, heat generation of the quartz glass material is reduced, generation of thermal stress due to the heat generation and temperature rise is suppressed, and thus damage of the quartz glass material is less likely to occur. It was
【００１７】またマイクロ波領域における前記ＦＱ値と
前記石英ガラス材料に含有される前記不純物及びＯＨ基
の濃度との関係について調査した結果、前記不純物濃度
が低く、かつ前記ＯＨ基濃度が１３０ｐｐｍ以下の石英
ガラス材料の場合、前記ＦＱ値を１０００００以上に高
められることが明らかとなった。前記ＯＨ基濃度は、前
記石英ガラス材料の仮焼時における温度と時間とを調整
することにより制御し得る。As a result of investigating the relationship between the FQ value in the microwave region and the concentrations of the impurities and OH groups contained in the quartz glass material, the impurity concentration is low and the OH group concentration is 130 ppm or less. It has been clarified that the FQ value can be increased to 100,000 or more in the case of a quartz glass material. The OH group concentration can be controlled by adjusting the temperature and time during calcination of the quartz glass material.
【００１８】従来の気相合成石英ガラス材料を用いた場
合、前記不純物濃度は低いにも拘らず前記ＯＨ基濃度が
１３０ｐｐｍを超えており、したがってシラノール結合
で存在する前記ＯＨ基またはガラスの網目構造中に溶存
する水分子の回転による損失が生じ、前記ＦＱ値が１０
００００未満となり、前記破損が発生すると考えられ
る。When the conventional vapor-phase synthetic quartz glass material is used, the OH group concentration exceeds 130 ppm despite the low impurity concentration. Therefore, the OH group present in silanol bond or the glass network structure. Loss due to rotation of water molecules dissolved therein causes the FQ value to be 10
It is less than 0000, and it is considered that the damage occurs.
【００１９】本発明に係るマイクロ波プラズマ装置用の
石英ガラス材料によれば、気相化学反応により合成され
た石英ガラス材料であるため、含有されるＮａ、Ｋ、Ｌ
ｉ、Ｆｅ、Ａｌ等の不純物量を少なくし得るとともに、
前記ＯＨ基濃度が低く、前記ＦＱ値も所定値以上に高い
ため、前記石英ガラス材料にマイクロ波電力が吸収され
るのを抑制し得ることとなる。この結果、前記石英ガラ
ス材料製の構成部品が配設された装置を用い、マイクロ
波を利用して試料にプラズマ処理を施す際、前記構成部
品による前記マイクロ波電力の吸収が抑制され、前記構
成部品の発熱を少なくして熱応力の発生を減少させ得る
こととなり、前記構成部品が前記熱応力により破損する
のを防止し得ることとなる。また脈理の発生に伴う侵食
も阻止され、穴が開くトラブルも生じなくなる。Since the quartz glass material for the microwave plasma device according to the present invention is a quartz glass material synthesized by a vapor phase chemical reaction, it contains Na, K and L.
The amount of impurities such as i, Fe, and Al can be reduced, and
Since the OH group concentration is low and the FQ value is higher than a predetermined value, it is possible to suppress the microwave power from being absorbed by the quartz glass material. As a result, when the apparatus in which the constituent parts made of the quartz glass material are arranged is used and the sample is subjected to the plasma treatment using the microwave, the absorption of the microwave power by the constituent parts is suppressed, The heat generation of the component can be reduced to reduce the generation of thermal stress, and the component can be prevented from being damaged by the thermal stress. In addition, the erosion due to the occurrence of striae is prevented, and the trouble of opening holes does not occur.
【００２０】[0020]
【実施例及び比較例】以下、本発明に係るマイクロ波プ
ラズマ装置用の石英ガラス材料を用いた実施例を図面に
基づいて説明する。なお、従来例と同一の機能を有する
構成部品には同一の符号を付すこととする。図２は、実
施例に係る石英ガラス材料製のマイクロ波導入窓が組み
込まれたマイクロ波プラズマ装置を摸式的に示した断面
図であり、図中３２はマイクロ波導入窓を示している。
マイクロ波導入窓３２用の石英ガラス材料を製造する場
合、まずＶＡＤ（Vapor-phase Axial Deposition) 法と
呼ばれるＳｉＣｌ4 ガスを用いた酸素−水素火炎中での
気相合成法により、合成石英ガラス多孔体を作製する。
次にこの合成石英ガラス多孔体を所定温度で所定時間仮
焼した後、約１５００℃で焼結させて透明化し、石英ガ
ラス材料（ロッド）を作製する。そしてこの石英ガラス
材料に熱加工を施すことにより、長さが約４００ｍｍ×
幅が約４００ｍｍ×厚さが約３０ｍｍの板形状を有する
マイクロ波導入窓３２を形成する。なお、前記石英ガラ
ス材料に含有されるＯＨ基量は、前記仮焼工程における
温度及び時間を調整することにより制御する。その他の
構成及び、このマイクロ波プラズマ装置を用いてアッシ
ング処理やエッチング処理を施す方法は従来の場合と同
様であるので、ここではその詳細な説明は省略する。EXAMPLES AND COMPARATIVE EXAMPLES Examples using a quartz glass material for a microwave plasma device according to the present invention will be described below with reference to the drawings. It should be noted that components having the same functions as those of the conventional example are designated by the same reference numerals. FIG. 2 is a schematic cross-sectional view of a microwave plasma device in which a microwave introduction window made of a quartz glass material according to an embodiment is incorporated, in which 32 denotes a microwave introduction window.
When manufacturing a quartz glass material for the microwave introduction window 32, first, a synthetic quartz glass porous material is produced by a vapor phase synthesis method in an oxygen-hydrogen flame using SiCl 4 gas called VAD (Vapor-phase Axial Deposition) method. Make a body.
Next, this synthetic quartz glass porous body is calcined at a predetermined temperature for a predetermined time, and then sintered at about 1500 ° C. to be transparent, and a quartz glass material (rod) is produced. And by subjecting this quartz glass material to thermal processing, the length is about 400 mm ×
A microwave introduction window 32 having a plate shape with a width of about 400 mm and a thickness of about 30 mm is formed. The amount of OH groups contained in the quartz glass material is controlled by adjusting the temperature and time in the calcination step. The other configurations and the method of performing the ashing process and the etching process using this microwave plasma device are the same as those in the conventional case, and therefore the detailed description thereof is omitted here.
【００２１】次に、上記構成のマイクロ波プラズマ装置
を用いて試料ＳとしてのＳｉウエハに繰り返しフォトレ
ジスト膜のアッシング処理を施し、処理したＳｉウエハ
の枚数と実施例に係る石英ガラス材料製のマイクロ波導
入窓３２における破損状態との関係を調査した結果につ
いて説明する。なお比較例としては従来のＯＨ基濃度が
高い気相合成石英ガラス材料を用いて形成されたマイク
ロ波導入窓２２を使用した。Next, the Si wafer as the sample S was repeatedly subjected to the ashing treatment of the photoresist film by using the microwave plasma apparatus having the above-mentioned structure, and the number of the treated Si wafers and the quartz glass material-based microwave according to the embodiment were used. The result of investigating the relationship with the damage state in the wave introducing window 32 will be described. As a comparative example, the microwave introduction window 22 formed by using the conventional vapor-phase synthetic quartz glass material having a high OH group concentration was used.
【００２２】図１は本発明に係るマイクロ波プラズマ装
置用の石英ガラス材料を用いた実施例１〜４のものと、
従来の気相合成石英ガラス材料を用いた比較例１〜３
（ただし、比較例３は図示せず）のものとに関し、それ
ぞれのＦＱ値とＯＨ基濃度との関係について調査した結
果を示した曲線図である。ＯＨ基濃度は赤外線吸収法
（J.P.Williams et al:Ceramics Bulletin;vol.63,No1
1,p1408(1984)) により測定し、実施例１のものはＯＨ
基濃度が５ｐｐｍ、実施例２は２０ｐｐｍ、実施例３は
５０ｐｐｍ、実施例４は１００ｐｐｍ、比較例１は１５
０ｐｐｍ、比較例２は２００ｐｐｍ、比較例３は３００
ｐｐｍであった。この場合のＦＱ値は、前記ロッド等か
ら直径が約２０ｍｍ、厚さが約７ｍｍの試験片を形成
し、ネットワークアナライザを用いてＧＨｚ領域におい
て測定した。なお実施例１〜４及び比較例１〜３のもの
の不純物元素についてはプラズマ発光分析法、原子吸光
分析法により分析を行い、Ａｌ、Ｎａ、Ｋ、Ｌｉ、Ｆ
ｅ、Ｃｒ及びＮｉ等の総量がそれぞれ１ｐｐｍ以下であ
ることを確認した。FIG. 1 shows one of Examples 1 to 4 using a quartz glass material for a microwave plasma device according to the present invention,
Comparative Examples 1 to 3 using a conventional vapor-phase synthetic quartz glass material
(However, Comparative Example 3 is not shown) is a curve diagram showing the results of an investigation on the relationship between the FQ value and the OH group concentration of each. Infrared absorption method (JPWilliams et al: Ceramics Bulletin; vol.63, No1)
1, p1408 (1984)), and that of Example 1 is OH
The group concentration is 5 ppm, Example 2 is 20 ppm, Example 3 is 50 ppm, Example 4 is 100 ppm, and Comparative Example 1 is 15 ppm.
0 ppm, Comparative Example 2 is 200 ppm, Comparative Example 3 is 300
It was ppm. The FQ value in this case was measured in the GHz range using a network analyzer by forming a test piece having a diameter of about 20 mm and a thickness of about 7 mm from the rod or the like. The impurity elements of Examples 1 to 4 and Comparative Examples 1 to 3 were analyzed by plasma emission spectrometry and atomic absorption spectrometry, and Al, Na, K, Li and F were analyzed.
It was confirmed that the total amount of e, Cr, Ni, etc. was 1 ppm or less.
【００２３】図１及び下記の表１から明らかなように、
ＯＨ基濃度が１３０ｐｐｍを超える比較例１〜３のもの
ではいずれもＧＨｚ領域におけるＦＱ値が１０００００
未満となる一方、ＯＨ基濃度が１３０ｐｐｍ以上の実施
例１〜４のものではいずれもＧＨｚ領域におけるＦＱ値
が１０００００以上になっている。As is apparent from FIG. 1 and Table 1 below,
In each of Comparative Examples 1 to 3 in which the OH group concentration exceeds 130 ppm, the FQ value in the GHz region is 100,000.
On the other hand, in each of Examples 1 to 4 in which the OH group concentration is 130 ppm or more, the FQ value in the GHz region is 100,000 or more.
【００２４】また実施例１〜４のものと比較例１〜３の
ものとを使用した際における、それぞれの破損状況を調
査した結果を下記の表１に併せて示した。実験は酸素プ
ラズマを１０分間印加するという、通常の処理よりも厳
しい条件下で行った。Further, Table 1 below shows the results of investigations of the damage conditions of Examples 1 to 4 and Comparative Examples 1 to 3 respectively. The experiment was conducted under a severer condition than the usual treatment, in which oxygen plasma was applied for 10 minutes.
【００２５】[0025]
【表１】 [Table 1]
【００２６】表１から明らかなように、ＯＨ基濃度が１
３０ｐｐｍを超えるとともにＧＨｚ領域におけるＦＱ値
が１０００００未満の比較例１〜３のものでは、Ｓｉウ
エハを１０〜６０枚処理すると破損したが、ＯＨ基濃度
が１３０ｐｐｍ以下であり、ＧＨｚ領域におけるＦＱ値
が１０００００以上である実施例１〜４のものでは、Ｓ
ｉウエハの処理枚数が２５０枚になっても異状がなかっ
た。As is clear from Table 1, the OH group concentration is 1
In Comparative Examples 1 to 3 having an FQ value of more than 30 ppm and a GHz value of less than 100,000, the Si wafer was damaged when 10 to 60 Si wafers were processed, but the OH group concentration was 130 ppm or less and the FQ value in the GHz area was low. In Examples 1 to 4 of 100,000 or more, S
Even if the number of processed i-wafers reached 250, there was no abnormality.
【００２７】上記結果から明らかなように、実施例に係
るマイクロ波プラズマ装置用の石英ガラス材料では、含
有されるＮａ、Ｋ、Ｌｉ、Ｆｅ、Ａｌ等の不純物を少な
くすることができるとともに、前記ＯＨ基濃度が低く、
前記ＦＱ値も所定値以上に高いため、前記石英ガラス材
料によるマイクロ波電力の吸収を抑制することができ
る。この結果、前記石英ガラス材料製のマイクロ波導入
窓３２が配設された装置を用い、マイクロ波を利用して
試料Ｓにアッシング処理を施す際のマイクロ波導入窓３
２の発熱を抑えて熱応力の発生を減少させ、マイクロ波
導入窓３２が前記熱応力により破損するのを防止するこ
とができる。したがって修理等により生じる工程の中断
をなくすことができるため、プラズマ処理を安定的に行
なわせることができる。As is clear from the above results, in the quartz glass material for the microwave plasma device according to the embodiment, the impurities such as Na, K, Li, Fe and Al contained can be reduced, and Low OH group concentration,
Since the FQ value is also higher than the predetermined value, the absorption of microwave power by the quartz glass material can be suppressed. As a result, the microwave introduction window 3 when the sample S is subjected to the ashing process by using the microwave by using the apparatus in which the microwave introduction window 32 made of the quartz glass material is provided.
It is possible to suppress the heat generation of No. 2 and reduce the generation of thermal stress, and prevent the microwave introduction window 32 from being damaged by the thermal stress. Therefore, the interruption of the process caused by repair or the like can be eliminated, so that the plasma treatment can be stably performed.
【００２８】なお、上記した実施例では、石英ガラス材
料をＳｉウエハ上に形成されたフォトレジスト膜にアッ
シング処理を施すマイクロ波プラズマ装置のマイクロ波
導入窓３２の形成に用いた場合について説明したが、Ｓ
ｉウエハ上に形成されたポリＳｉ、Ｓｉ酸化膜、あるい
はＡｌ合金膜にエッチング処理を施す装置のマイクロ波
導入窓にも同様に適用することができる。In the above-mentioned embodiment, the case where the quartz glass material is used for forming the microwave introduction window 32 of the microwave plasma device for ashing the photoresist film formed on the Si wafer has been described. , S
It can be similarly applied to a microwave introduction window of an apparatus for etching a poly-Si, Si oxide film or Al alloy film formed on an i-wafer.
【００２９】さらには、上記した実施例に係る石英ガラ
ス材料は、ポリＳｉ膜の形成等の際に使用するマイクロ
波を利用したＣＶＤ装置に配設されたマイクロ波導入
窓、ウエハ支持具、観測窓、ベルジャ等、マイクロ波を
利用する装置の構成部材の形成に用いることができる。Furthermore, the quartz glass materials according to the above-mentioned examples are used for microwave introduction windows arranged in a CVD apparatus using a microwave used for forming a poly-Si film, a wafer support, and an observation device. It can be used to form constituent members of a device utilizing microwaves, such as windows and bell jars.
【００３０】[0030]
【発明の効果】以上詳述したように本発明に係るマイク
ロ波プラズマ装置用の石英ガラス材料にあっては、気相
化学反応により合成された石英ガラス材料であって、含
有されるＯＨ基濃度が１３０ｐｐｍ以下であり、ＧＨｚ
周波数域におけるＦＱ値が１０００００以上であるの
で、含有されるＮａ、Ｋ、Ｌｉ、Ｆｅ、Ａｌ等の不純物
量を少なくすることができるとともに、前記ＯＨ基濃度
が低く、前記ＦＱ値も所定値以上に高いため、前記石英
ガラス材料にマイクロ波電力が吸収されるのを抑制する
ことができる。この結果、前記石英ガラス材料製の構成
部品が配設された装置を用い、マイクロ波を利用して試
料にプラズマ処理を施す際、前記構成部品による前記マ
イクロ波電力の吸収を抑制することができ、前記構成部
品の発熱を少なくして熱応力の発生を減少させることが
でき、前記構成部品が前記熱応力により破損するのを防
止することができる。また、脈理の発生に伴う侵食も阻
止することができ、穴が開くトラブルの発生もなくすこ
とができる。したがって修理等により生じる工程の中断
をなくすことができ、プラズマ処理を安定的に行なわせ
ることができる。As described above in detail, the quartz glass material for the microwave plasma device according to the present invention is a quartz glass material synthesized by a vapor phase chemical reaction, and the concentration of OH group contained therein is high. Is 130 ppm or less, GHz
Since the FQ value in the frequency range is 100,000 or more, the amount of impurities such as Na, K, Li, Fe, and Al contained can be reduced, the OH group concentration is low, and the FQ value is also a predetermined value or more. Since it is extremely high, it is possible to suppress the microwave power from being absorbed by the quartz glass material. As a result, it is possible to suppress the absorption of the microwave power by the component when the plasma treatment is performed on the sample by using the microwave using the device in which the component made of the quartz glass material is arranged. The heat generation of the component can be reduced to reduce the generation of thermal stress, and the component can be prevented from being damaged by the thermal stress. In addition, it is possible to prevent erosion due to the occurrence of striae, and it is possible to prevent the occurrence of the trouble of opening a hole. Therefore, it is possible to eliminate the interruption of the process caused by repair or the like, and it is possible to stably perform the plasma processing.
【図１】マイクロ波プラズマ装置用石英ガラス材料にお
ける本発明に係る実施例のものと、比較例のものとに関
し、それぞれのＦＱ値とＯＨ基濃度との関係について調
査した結果を示した曲線図である。FIG. 1 is a curve diagram showing the results of investigating the relationship between the FQ value and the OH group concentration of a quartz glass material for a microwave plasma apparatus according to an example of the present invention and a comparative example. Is.
【図２】実施例及び従来例に係る石英ガラス材料製のマ
イクロ波導入窓がそれぞれ組み込まれたマイクロ波プラ
ズマ装置をひとつの図により示した摸式的断面図であ
る。FIG. 2 is a schematic cross-sectional view showing a microwave plasma device in which a microwave introduction window made of a quartz glass material according to each of the example and the conventional example is incorporated.
３２ マイクロ波導入窓 32 microwave introduction window
Claims (1)
ス材料であって、含有されるＯＨ基濃度が１３０ｐｐｍ
以下であり、ＧＨｚ周波数帯域におけるＦＱ値（周波数
×Ｑ値）が１０００００以上であることを特徴とするマ
イクロ波プラズマ装置用の石英ガラス材料。1. A quartz glass material synthesized by a gas phase chemical reaction, wherein the concentration of OH group contained is 130 ppm.
A quartz glass material for a microwave plasma device, which has an FQ value (frequency x Q value) in the GHz frequency band of 100,000 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06119783A JP3116723B2 (en) | 1994-06-01 | 1994-06-01 | Quartz glass material for microwave plasma equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06119783A JP3116723B2 (en) | 1994-06-01 | 1994-06-01 | Quartz glass material for microwave plasma equipment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07330357A true JPH07330357A (en) | 1995-12-19 |
| JP3116723B2 JP3116723B2 (en) | 2000-12-11 |
Family
ID=14770118
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06119783A Expired - Lifetime JP3116723B2 (en) | 1994-06-01 | 1994-06-01 | Quartz glass material for microwave plasma equipment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3116723B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002047034A (en) * | 2000-07-31 | 2002-02-12 | Shinetsu Quartz Prod Co Ltd | Quartz glass jig for process equipment using plasma |
| JP2008223123A (en) * | 2007-03-15 | 2008-09-25 | Rohm Co Ltd | Radical generator |
| WO2019093182A1 (en) * | 2017-11-07 | 2019-05-16 | Ａｇｃ株式会社 | Silica glass for high-frequency devices, and high-frequency device |
| CN110544613A (en) * | 2018-05-28 | 2019-12-06 | 东京毅力科创株式会社 | Plasma processing apparatus and plasma processing method |
| WO2021172232A1 (en) | 2020-02-28 | 2021-09-02 | Ａｇｃ株式会社 | Silica glass, high frequency device using silica glass, and silica glass production method |
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-
1994
- 1994-06-01 JP JP06119783A patent/JP3116723B2/en not_active Expired - Lifetime
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002047034A (en) * | 2000-07-31 | 2002-02-12 | Shinetsu Quartz Prod Co Ltd | Quartz glass jig for process equipment using plasma |
| JP2008223123A (en) * | 2007-03-15 | 2008-09-25 | Rohm Co Ltd | Radical generator |
| WO2008114719A1 (en) * | 2007-03-15 | 2008-09-25 | Rohm Co., Ltd. | Radical generating apparatus and zno thin film |
| WO2019093182A1 (en) * | 2017-11-07 | 2019-05-16 | Ａｇｃ株式会社 | Silica glass for high-frequency devices, and high-frequency device |
| CN111263736A (en) * | 2017-11-07 | 2020-06-09 | Ａｇｃ株式会社 | Quartz glass for high frequency devices and high frequency devices |
| US20200255324A1 (en) * | 2017-11-07 | 2020-08-13 | AGC Inc. | Silica glass for radio-frequency device and radio-frequency device technical field |
| JPWO2019093182A1 (en) * | 2017-11-07 | 2020-11-26 | Ａｇｃ株式会社 | Silica glass for high frequency devices and high frequency devices |
| US11912617B2 (en) | 2017-11-07 | 2024-02-27 | AGC Inc. | Silica glass for radio-frequency device and radio-frequency device technical field |
| US11362405B2 (en) | 2018-01-15 | 2022-06-14 | AGC Inc. | Filter |
| CN110544613A (en) * | 2018-05-28 | 2019-12-06 | 东京毅力科创株式会社 | Plasma processing apparatus and plasma processing method |
| CN110544613B (en) * | 2018-05-28 | 2023-05-26 | 东京毅力科创株式会社 | Plasma processing apparatus and plasma processing method |
| WO2021172232A1 (en) | 2020-02-28 | 2021-09-02 | Ａｇｃ株式会社 | Silica glass, high frequency device using silica glass, and silica glass production method |
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| Publication number | Publication date |
|---|---|
| JP3116723B2 (en) | 2000-12-11 |
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