JP4499559B2 - 三フッ化塩素の製造装置を備えた半導体基板のエッチングプラントおよび三フッ化塩素の製法 - Google Patents
三フッ化塩素の製造装置を備えた半導体基板のエッチングプラントおよび三フッ化塩素の製法 Download PDFInfo
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Description
DE19919469A1または特開2001−684422号公報(JP2001684422A)から、シリコンがガス状の三フッ化塩素(ClF3)により自然にエッチングされることが公知であり、その際、この化合物がシリコン表面に吸着された後、フッ素ラジカルの遊離が生じ、これが接近可能なシリコン表面のシリコン原子と反応して自然に揮発性のフッ化ケイ素化合物になる。その際、エッチング速度はClF3の分圧の上昇に伴い加速し、相応する高い圧力および十分な物質量の供給において開削速度(abtragrate)は数μm/分以上である。しかしながら、このガスの欠点は、これが特に液状で非常に危険な物質である、ということである。
本発明による装置は従来技術に対して、ClF3−ベースのエッチング工程において、特にシリコン基板のエッチングにおいて三フッ化塩素を、その物自体として貯蔵する必要なしに、使用可能であるという利点を有する。むしろ、ClF3を高密度プラズマ中で著しく効率的なプラズマ反応により製造し、こうして製造後にプラズマ発生装置に設けられたプロセス室に直接供給することができ、このClF3がプロセス室中で、そこに存在する半導体基板上に作用する。更に、ClF3を、効率的な反応のために、数100sccm(sccm=常圧におけるガス流1cm3/分)〜slm(slm=常圧におけるガス流1dm3/分)の大量のガス流量で、エッチングの際に使用すること、もしくは本発明によるClF3の製造装置から取り出すことが可能である。
本発明を図面および以降の説明により更に詳細に説明する。図1は誘導プラズマ励起で三フッ化塩素を製造するための装置を備える半導体基板をエッチングするためのプラントの原理を示す図である。図2はマイクロ波でプラズマ励起を行う三フッ化塩素製造装置を有する半導体基板をエッチングするためのもう1つのプラントの原理を示す図である。
その際反応は次のように進行する:Cl2 → 2Cl*およびF2 → 2F*、F2*
こうして全体としては次のものを得る:Cl*+F*、F2、F2* → ClF3
誘導高周波励起もしくはマイクロ波励起により小さいプラズマ体積中で達成可能である高いプラズマ励起密度、すなわち1cm3あたり励起された粒子少なくとも1011、特に1cm3あたり励起された粒子少なくとも1012個のラジカルまたは反応性種の密度を有する高密度プラズマ105の製造は、Cl2対F2のガス流の比を1:3の値に調節する際に、前駆ガスCl2およびF2のClF3へのほぼ完全な変換が達せられる。
プラズマ発生装置100中ではClF3は次の反応により形成される:
SF6 → SF4+2F*
Cl2+F* → ClF+Cl*
ClF+2F* → ClF3
Cl*+F2、F* → ClF3
全体では:3SF6+Cl2 → 3SF4+2ClF3
である。
NF3 ← →NFx (*)+(3−x)F* x=1、2、3
これとは反対に、高い励起密度もしくはプラズマ密度においてはフッ素ラジカルおよびN2が最終生成物として優先的に生じる。この場合、プラズマ中のNF3は完全に開裂し、このことは高い効率でのフッ素ラジカルおよび窒素分子の形成に導き、この際窒素分子はその高い化学的安定性のために更に考慮する必要はない。特に、安定なN2分子の形成により出発物質の方向への逆反応でのフッ素ラジカルのその後の捕獲反応は阻止される、すなわち再結合反応への傾向はSF6の場合と同様に、安定な最終生成物N2により非常に僅かである。生じたClF3とシリコンの反応の場合にも窒素の存在は無視することができる。高いプラズマ密度におけるプラズマ中での反応は次のように進行する:
2NF3 → N2+6F*
Cl2+6F* → 2ClF3
2NF3+Cl2 → 2ClF3+N2
最適な化学量論的な変換はNF3:Cl2=2:1のガス流の最適比で生じる。
4NF3+3HCl → 3ClF3+3HF+2N2
化学量論量での反応のためにはガス流NF3:HClが4:3の比であるのが最適である。生じた三フッ化塩素は僅かな窒素とHFを最終生成物として含有している。無水(乾燥)HFは一般にシリコンでのClF3のエッチング反応において妨害せず、水分が存在しない場合酸化物も攻撃しないし、もしくは金属面を腐蝕しないので、この随伴ガスは一般に許容される。ガス成分としてHFが不所望である場合、これをプラズマ発生装置中で生じるガスから選択的に好適なフィルターを用いて、例えばアルカリ金属フッ化物または金属フッ化物での吸着により(NaF+HF → NaHF2)除去することができる。
Claims (21)
- プラズマ発生装置(100)およびプラズマ発生装置(100)の内部で高密度プラズマ(105)を発生可能であるプラズマ発生手段(110、120、130、150、155、160、170、180)を有し、高密度プラズマ(105)の影響下にプラズマ発生装置(100)中で相互に反応し三フッ化塩素を形成する、プラズマ励起下に簡単に大量のフッ素ラジカルを遊離する第1ガスおよびプラズマ励起下に簡単に塩素ラジカルを遊離する、Cl2、HClおよびガスからなる群から選択された第2ガスをプラズマ発生装置(100)に供給可能にしているガス供給手段(21、25、22、26)が設けられており、かつ生じた三フッ化塩素をプラズマ発生装置(100)から取り出すことを可能にしているガス出口(20)が設けられている、三フッ化塩素の製造装置(6)を備えた、半導体基板をエッチングするためのプラント。
- 半導体基板がシリコンウェハである、請求項1記載のプラント。
- 第1ガスとしてNF3またはSF6が使用されている、請求項1記載のプラント。
- プラズマ発生手段がコイル(110)、整合回路網(120)および高周波発生装置(130)を包含する、請求項1記載のプラント。
- プラズマ発生手段がマイクロ波導波管(150)、同調要素(155)、マグネトロン(170)、サーキュレーター(160)並びに導波管終端(180)を包含する、請求項1または4記載のプラント。
- プラズマ発生装置(100)が石英管または中空石英体、またはセラミック管または中空セラミック体を包含する、請求項1記載のプラント。
- プラズマ発生装置(100)が研磨された内壁を有する石英管または中空石英体を包含する、請求項6記載のプラント。
- プラズマ発生装置(100)が研磨された内壁を有するセラミック管または中空セラミック体を包含する、請求項6記載のプラント。
- プラズマ発生装置(100)が酸化アルミニウムからなるセラミック管または中空セラミック体を包含する、請求項6または8記載のプラント。
- ガス供給手段(21、22、25、26)がプラズマ発生装置(100)に供給される第1のガスの量を調節可能である第1の流量制御装置(22)およびプラズマ発生装置(100)に供給される第2のガスの量を調節可能である第2の流量制御装置(26)を包含する、請求項1記載のプラント。
- ガス出口(20)を介してプラズマ発生装置(100)と連結しているプロセス室(10)が装置(6)に対応配置されており、その際、半導体基板(30)がプロセス室(10)中に配置されており、三フッ化塩素を製造するための装置(6)から製造されたガス状三フッ化塩素に曝されている、請求項1から10までのいずれか1項に記載のプラント。
- プラズマ発生装置(100)中で高密度プラズマ(105)を発生させ、かつこの際プラズマ発生装置(100)にプラズマ発生装置(100)中で高密度プラズマ(105)の影響下に相互に反応して三フッ化塩素を形成する、プラズマ励起下に簡単に大量のフッ素ラジカルを遊離する第1のガスおよびプラズマ励起下に簡単に塩素ラジカルを遊離する、Cl2、HClおよびガスからなる群から選択された第2のガスを供給する、請求項1から11までのいずれか1項に記載の装置(6)中での三フッ化塩素の製法。
- 第1ガスとしてNF3またはSF6が使用される、請求項12記載の方法。
- 高密度プラズマ(105)が誘導高周波励起またはマイクロ波励起により発生する、請求項12または13記載の製法。
- プラズマ発生装置(100)またはプラズマ発生装置(100)に後接したプロセス室(10)にその他のガスとして酸素を供給する、請求項12から14までのいずれか1項記載の製法。
- 生じた三フッ化塩素を、プラズマ発生装置(100)に後接したフィルターにより、その他のガス成分から分離する、請求項12から15までのいずれか1項記載の製法。
- その他のガス成分がフッ化水素である、請求項16記載の製法。
- 第1のガスおよび第2のガスをプラズマ発生装置(100)に、高密度プラズマ(105)中にフッ素原子および塩素原子が、3:1の比で存在するように供給する、請求項12から17までのいずれか1項記載の製法。
- 第1のガスおよび第2のガスをプラズマ発生装置(100)に、高密度プラズマ(105)中にフッ素原子および塩素原子が、ラジカルまたは反応性種の形で、3:1の比で存在するように供給する、請求項18記載の製法。
- 1cm3あたり粒子少なくとも1011個のラジカルまたは反応性種の密度を有する高密度プラズマ(105)を発生させる、請求項12から19までのいずれか1項記載の製法。
- 1cm3あたり粒子少なくとも1012個のラジカルまたは反応性種の密度を有する高密度プラズマ(105)を発生させる、請求項20記載の製法。
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PCT/DE2003/001014 WO2004002882A1 (de) | 2002-06-28 | 2003-03-27 | Vorrichtung und verfahren zur erzeugung von chlortrifluorid und anlage zu ätzung von halbleitersubstraten mit dieser vorrichtung |
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JP2000036488A (ja) * | 1998-07-21 | 2000-02-02 | Speedfam-Ipec Co Ltd | ウエハ平坦化方法及びそのシステム |
US6190507B1 (en) | 1998-07-24 | 2001-02-20 | The United States Of America As Represented By The Department Of Energy | Method for generating a highly reactive plasma for exhaust gas aftertreatment and enhanced catalyst reactivity |
JP2000133494A (ja) | 1998-10-23 | 2000-05-12 | Mitsubishi Heavy Ind Ltd | マイクロ波プラズマ発生装置及び方法 |
DE60040443D1 (de) * | 1999-03-04 | 2008-11-20 | Surface Technology Systems Plc | Chlortrifluorid- gasgeneratorsystem |
DE19919469A1 (de) | 1999-04-29 | 2000-11-02 | Bosch Gmbh Robert | Verfahren zum Plasmaätzen von Silizium |
JP4321925B2 (ja) | 1999-08-24 | 2009-08-26 | 純一 半那 | 半導体基材の製造方法 |
US6783627B1 (en) * | 2000-01-20 | 2004-08-31 | Kokusai Semiconductor Equipment Corporation | Reactor with remote plasma system and method of processing a semiconductor substrate |
JP2001267241A (ja) * | 2000-03-10 | 2001-09-28 | L'air Liquide | クリーニング方法及び装置並びにエッチング方法及び装置 |
-
2002
- 2002-06-28 DE DE10229037A patent/DE10229037A1/de not_active Ceased
-
2003
- 2003-03-27 WO PCT/DE2003/001014 patent/WO2004002882A1/de active Application Filing
- 2003-03-27 EP EP03720246A patent/EP1519895A1/de not_active Withdrawn
- 2003-03-27 US US10/519,724 patent/US8382940B2/en not_active Expired - Fee Related
- 2003-03-27 JP JP2004516435A patent/JP4499559B2/ja not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
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WO2004002882A1 (de) | 2004-01-08 |
US20060006057A1 (en) | 2006-01-12 |
DE10229037A1 (de) | 2004-01-29 |
US8382940B2 (en) | 2013-02-26 |
EP1519895A1 (de) | 2005-04-06 |
JP2005531479A (ja) | 2005-10-20 |
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