JPH0426116A - Etching method for oxide of substrate and cleaning method for substrate - Google Patents
Etching method for oxide of substrate and cleaning method for substrateInfo
- Publication number
- JPH0426116A JPH0426116A JP13037890A JP13037890A JPH0426116A JP H0426116 A JPH0426116 A JP H0426116A JP 13037890 A JP13037890 A JP 13037890A JP 13037890 A JP13037890 A JP 13037890A JP H0426116 A JPH0426116 A JP H0426116A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- oxygen
- nfo
- etching
- laser
- 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
- 239000000758 substrate Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims description 27
- 238000005530 etching Methods 0.000 title claims description 25
- 238000004140 cleaning Methods 0.000 title claims description 5
- 239000007789 gas Substances 0.000 claims abstract description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000001301 oxygen Substances 0.000 claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 25
- 150000002927 oxygen compounds Chemical class 0.000 claims abstract description 12
- 230000001678 irradiating effect Effects 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052681 coesite Inorganic materials 0.000 abstract description 5
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 5
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 5
- 229910052682 stishovite Inorganic materials 0.000 abstract description 5
- 229910052905 tridymite Inorganic materials 0.000 abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000605 extraction Methods 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 230000010355 oscillation Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 239000012048 reactive intermediate Substances 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000010408 film Substances 0.000 description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- 241000257465 Echinoidea Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Drying Of Semiconductors (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、基板に形成された酸化絶縁膜にサブミクロン
以下の微細加エバターンをエツチングするのに好適な方
法及び基板をクリーニングするのに好適な方法に関する
。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides a method suitable for etching a fine pattern of submicron size or less into an oxide insulating film formed on a substrate, and a method suitable for cleaning the substrate. Concerning methods.
［従来技術及びその問題点コ
超ＬＳＩ製造プロセスでは、５ｉｎ２やＡｔ２０、など
の絶縁膜を微細加工することにより、プロセスのスルー
ブツトを向上するようにしている。[Prior art and its problems] In the VLSI manufacturing process, the throughput of the process is improved by microfabrication of insulating films such as 5in2 and At20.
従来の加工技術では、５ｉｎ２などの酸化絶縁膜に対し
、フッ酸（ＨＦ）によるウェットエツチング、ＣＦ４＋
Ｈ２によるプラズマエツチング、ＮＦ３ガスにＦ２を混
入させてＩＦの働きでＳｉを引抜く方法、ＣＣρ２ Ｆ
２ ＣＣｆ’ ３ ＦＳＣＢｒ２ Ｆ２ 、ＣＢｒＦ
３などのフロンガスをマイクロ波又は光によって分解し
、それによって生成したＣＦ２やＣＦ３ラジカルによっ
てエツチングする方法などがある。Conventional processing techniques include wet etching using hydrofluoric acid (HF) and CF4+ for oxide insulating films such as 5in2.
Plasma etching with H2, method of mixing F2 into NF3 gas and extracting Si by the action of IF, CCρ2 F
2 CCf' 3 FSCBr2 F2 , CBrF
There is a method in which a fluorocarbon gas such as No. 3 is decomposed by microwaves or light, and the resulting CF2 or CF3 radicals are used for etching.
しかし、フッ酸（ＨＦ）によるウェットエツチングでは
、エツチング液の表面張力により細部まで液が浸透しに
くい。このため、この方法では、ＩＣの集積度を向上し
たサブミクロン以下の微細回路パターンをエツチングす
ることが難しい問題がある。However, in wet etching using hydrofluoric acid (HF), the surface tension of the etching solution makes it difficult for the solution to penetrate into the fine details. Therefore, with this method, there is a problem in that it is difficult to etch fine circuit patterns of submicron size or less that improve the degree of integration of ICs.
また、プラズマエツチングでは、半導体基板表面を加速
電子で叩くため、基板にダメージが発生し、欠陥発生の
確率が大きくなる問題がある。Furthermore, in plasma etching, the surface of a semiconductor substrate is hit with accelerated electrons, which causes damage to the substrate and increases the probability of defect generation.
ＣＦ２やＣＦ、ラジカルによってエツチングする方法は
、上述のように、ＣＣρ２Ｆ２ＣＣ１）＊ Ｆ、ＣＢｒ
ｚ Ｆ２、ＣＢｒＦｉなどのフロンガスを原料として使
用するため、環境破壊の問題がある。As mentioned above, the etching method using CF2, CF, and radicals is as follows: CCρ2F2CC1)*F, CBr
z Since fluorocarbon gas such as F2 and CBrFi is used as a raw material, there is a problem of environmental destruction.
ＮＦ３ガスの熱分解によるエツチングでは、ＮＦ、ガス
をＣＯ□レーザーやヒーター等で１０００℃以上に加熱
し、Ｆ２とＮ２に分解させるが、高温のため半導体基板
に悪影響を与える。In etching by thermal decomposition of NF3 gas, NF and gas are heated to 1000° C. or higher using a CO□ laser or a heater to decompose them into F2 and N2, but the high temperature adversely affects the semiconductor substrate.
マイクロ波によってＮＦ３を分解して、これによりエツ
チングする方法は、マイクロ波励起によってＮＦ、をＦ
２とＮ２に分解し、また、混入させた水素により、ＨＦ
を形成させる。この方法では、微量の酸素が混入しても
、反応が進行して、中間生成物のＮＦＯから最終生成物
のＮ ０２が容品に形成されてしまう。この結果良好な
エツチングがおこないがたい。The method of decomposing NF3 using microwaves and etching it is based on the method of decomposing NF3 by microwave excitation.
2 and N2, and the mixed hydrogen causes HF
to form. In this method, even if a trace amount of oxygen is mixed in, the reaction proceeds and the final product N 02 is formed from the intermediate product NFO in the container. As a result, it is difficult to perform good etching.
また、真空蒸着、電子ビーム蒸着、スパッタリング蒸着
、イオンビーム蒸芒などの手段により、基板に金属薄膜
や誘電体薄膜を付ける場合、基板表面に吸着している酸
素分子が問題になる。Further, when a metal thin film or dielectric thin film is attached to a substrate by means such as vacuum evaporation, electron beam evaporation, sputtering evaporation, or ion beam evaporation, oxygen molecules adsorbed on the substrate surface become a problem.
［発明が解決しようとする技術的課題］本発明は上記事
情に鑑みてなされたもので、その目的とするところは、
水素を添加することなく高速で５ｉｎ２などの酸化絶縁
膜をエツチングし、しかも基板への悪影響のない酸化物
のエツチング方法を提供するものである。[Technical problem to be solved by the invention] The present invention has been made in view of the above circumstances, and its purpose is to:
The present invention provides an oxide etching method that etches a 5in2 oxide insulating film at high speed without adding hydrogen and has no adverse effect on the substrate.
また本発明は、基板表面に吸着している酸素分子を良好
に除去して、基板表面を効果的にクリーニングできる方
法を提供するものである。The present invention also provides a method that can effectively clean the substrate surface by effectively removing oxygen molecules adsorbed on the substrate surface.
［課題を解決する手段］
すなわち本発明の酸化物のエツチング方法は、微量の酸
素又は酸素化合物を混入したＮＦ、ガス雰囲気中に、酸
化絶縁膜を形成した基板を配置し、上記ガス雰囲気中に
、ＡｒＦレーザーなどの発信波長２００ｎｍ以下のレー
ザーを照射してＮＦＯを形成し、形成されたＮＦＯの酸
素引抜力を用いて基板の酸化絶縁膜を高速でエツチング
することを特徴とする。[Means for Solving the Problems] That is, the oxide etching method of the present invention involves placing a substrate on which an oxide insulating film is formed in an NF or gas atmosphere mixed with a trace amount of oxygen or an oxygen compound, and then placing the substrate on which an oxide insulating film is formed in the gas atmosphere. The method is characterized in that NFOs are formed by irradiating a laser with an emission wavelength of 200 nm or less, such as an ArF laser, and the oxide insulating film of the substrate is etched at high speed using the oxygen extraction force of the formed NFOs.
また本発明は、ＮＦ、ガス雰囲気中に基板を配置し、Ａ
ｒＦレーザー光を照射して、基板に吸着している酸素を
脱離させて、基板をクリーニングする方法である。Further, the present invention places the substrate in an NF and gas atmosphere, and
This method cleans the substrate by irradiating it with rF laser light to remove oxygen adsorbed on the substrate.
以下、本発明の詳細な説明する。まず表面にＳｉＯ□、
Ａｌ２Ｏ５、ＴｉＯ２などの酸化絶縁膜を形成した基板
（シリコンウニｌ〜等）を用意する。そしてこの基板を
微量の酸素（０□）又は酸素化合物を混入したＮＦ、ガ
ス雰囲気中に配置する。ガス雰囲気に混入する酸素化合
物としては、Ｎｏ、Ｎ、０１ＮＯ２が挙げられる。この
状態で、ＡｒＦエキシマレーザ−など発信波長２００ｎ
ｍ以下のレーザーを照射する。ＮＦ３ガスは、第１図の
符号ａに示すように、２００ｎｍ以下の光に吸収を呈す
る。また、Ｎｏ、Ｎ２０，０２等も、同様に、２００ｎ
ｍ以下の光を吸収して分解する。The present invention will be explained in detail below. First, SiO□ on the surface,
A substrate (silicon sea urchin, etc.) on which an oxide insulating film of Al2O5, TiO2, etc. is formed is prepared. Then, this substrate is placed in an NF or gas atmosphere mixed with a trace amount of oxygen (0□) or an oxygen compound. Examples of oxygen compounds mixed in the gas atmosphere include No, N, and 01NO2. In this state, the emission wavelength is 200n, such as ArF excimer laser.
Irradiate with a laser of less than m. NF3 gas exhibits absorption of light of 200 nm or less, as shown by reference numeral a in FIG. In addition, No., N20, 02, etc. are also 200n
It absorbs and decomposes light with a wavelength of less than m.
一般にＮ Ｆ ３は、熱、マイクロ波、又は光によって
分解し、Ｎ２とＦ２とに遊離するが、Ｎ０１Ｎ２０．Ｎ
Ｏ２，０２等の存在下で、ＡｒＦレザー光を入射すると
、第１図の符号すに示すように、反応中間体であるＮＦ
Ｏが形成される。ＡｒＦエキシマレーザ−は、光子エネ
ルギーがガス分子を構成する結合エネルギーに近く（発
信波長１９３ｎｍ）、またレーザーのパルス幅が１０ナ
ノ秒と極く短い。このため、光反応が連鎖的に起こるこ
とがなく、反応中間物（Ｎ Ｆ Ｏ）を生成されるのに
都合がよい。このＮＦＯは、酸素を引抜く力が大きく、
酸化絶縁膜上の酸素を引抜いて、高速で酸化絶縁膜をエ
ツチングする。In general, NF3 is decomposed by heat, microwaves, or light and liberated into N2 and F2, but N01N20. N
When ArF laser light is incident in the presence of O2,02, etc., the reaction intermediate NF
O is formed. In the ArF excimer laser, the photon energy is close to the binding energy of gas molecules (emission wavelength: 193 nm), and the laser pulse width is extremely short, 10 nanoseconds. Therefore, a photoreaction does not occur in a chain manner, which is convenient for producing a reaction intermediate (N F O). This NFO has a large ability to extract oxygen,
Oxygen on the oxide insulating film is extracted and the oxide insulating film is etched at high speed.
酸素、酸素化合物を微量とする理由は、酸素又は酸素化
合物の量が多すぎると、形成されたＮＦＯが酸素又は酸
素化合物と結合して、ＮＯ２を形成してしまい（第１図
の符号Ｃ参照）、この結果、５ｊ０２から酸素を引抜く
ことができなくなるためである。従って、本発明の目的
を達成するために、酸素又は酸素化合物の混入量は、通
常０．１％以内が好ましく、特に０．００１〜０．０５
％程度が好適である。The reason why the amount of oxygen and oxygen compounds is so small is that if the amount of oxygen or oxygen compounds is too large, the formed NFO will combine with oxygen or oxygen compounds to form NO2 (see symbol C in Figure 1). ), as a result, oxygen cannot be extracted from 5j02. Therefore, in order to achieve the object of the present invention, the amount of oxygen or oxygen compound mixed is preferably within 0.1%, particularly 0.001 to 0.05%.
% is suitable.
なお、中間生成物のＮＦＯを酸化絶縁膜にさらすと、Ｎ
Ｏ２が生成され、ＮＦＯが消滅し、ガスの色が褐色にな
っていく。しかし、再度ＡｒＦレーザー光を照射すると
、ＮＯ２が減少し、褐色も消える。そしてＮＦＯが再び
作られる。すなわち、ガス雰囲気の初期に微量な酸素、
酸素化合物と多量のＮＦ、が存在していれば、初期のレ
ーザー照射によってＮＦＯを作り、これによってＳｆＯ
。Note that when the intermediate product NFO is exposed to an oxide insulating film, NFO
O2 is produced, NFO disappears, and the color of the gas becomes brown. However, when ArF laser light is irradiated again, NO2 decreases and the brown color disappears. And the NFO will be re-created. In other words, at the beginning of the gas atmosphere, a small amount of oxygen,
If oxygen compounds and a large amount of NF are present, the initial laser irradiation will create NFO, which will lead to SfO
.
をエツチングしＮＯ２が形成される。レーザー光の照射
を停止すれば、ＮＦＯの形成が止るため、存在するＮＦ
Ｏによってのみ５ｉ０２のエツチングが進み、次第にＮ
ＦＯがなくなり、Ｓ Ｉ Ｏ２のエツチングが止るが、
再度この系にＡｒＦレーザー光を照射すれば、形成され
ているＮＯ□を分解し、ＮＦ３と反応して、ＮＦＯを作
る。この結果、再び５ｉｎ２のエツチングが出来る（第
２図参照）従来ＮＦ、を使ってＳ】０２をエツチングす
るには、水素は不可欠であるといわれていたが、本発明
によれば、水素を用いないでも５ｉ０２がエツチングさ
れる。etching and NO2 is formed. If the laser beam irradiation is stopped, the formation of NFOs will stop, so the existing NFs will be
Etching of 5i02 progresses only by O, and gradually N
FO disappears and etching of SIO2 stops, but
When this system is irradiated with ArF laser light again, the formed NO□ is decomposed and reacts with NF3 to form NFO. As a result, 5in2 etching can be performed again (see Figure 2).It was said that hydrogen was indispensable for etching S]02 using conventional NF, but according to the present invention, hydrogen can be used. 5i02 is etched even if it is not there.
［実施例］ 以下本発明の実験例および実施例を説明する。[Example] Experimental examples and examples of the present invention will be explained below.
実験例１
（１）０２ガスを０．１容量％混入させたＮＦ３ガスを
チャンバー内に入れてＡｒＦレーザー光を入射させた場
合、（２）Ｎ２０ガスを０．１容量％混入させたＮＦ、
ガスをチャンバー内に入れてＡｒＦレーザー光を入射さ
せた場合、又は（３）Ｎｏガスを０．１容量％混入させ
たＮＦ、ガスガスをチャンバー内に入れてＡｒＦレーザ
ー光を入射させた場合について、それぞれ紫外線吸収特
性を測定した。Experimental Example 1 (1) When NF3 gas mixed with 0.1% by volume of 02 gas was placed in the chamber and ArF laser light was incident, (2) NF3 gas mixed with 0.1% by volume of N20 gas,
When gas is put into the chamber and ArF laser light is made incident, or (3) when NF or gas mixed with 0.1% by volume of No gas is put into the chamber and ArF laser light is made incident, The ultraviolet absorption characteristics of each were measured.
その結果を第３図（ａ）、（ｂ）、（ｃ）にそれぞれ示
す。The results are shown in FIGS. 3(a), (b), and (c), respectively.
実験例２
ＣＩ） 〜（３）について（Ａ ｒ Ｆレーザーを１０
ＰＰＳで照射しつづけた場合）、それぞれ、５ｉ０２を
入れた時と入れない時とで、ＮＯ□発生量を比較した。Experimental Example 2 CI) Regarding (3) (A r F laser at 10
When irradiation with PPS was continued), the amount of NO□ generated was compared when 5i02 was added and when 5i02 was not added.
ＮＯ２の発生量の比較結果を第４図に、エッチレートを
第５図に示す。ここでは、効果的にＳｉＯ２をエツチン
グするために、アルゴン、ヘリウム、又は高純度のＮ２
ガスでチャン／（−内を大気圧に保ち、外部から大気中
の空気が入り込まないようにしておく。The comparison results of the amount of NO2 generated are shown in FIG. 4, and the etch rate is shown in FIG. Here, in order to effectively etch SiO2, argon, helium, or high-purity N2 is used.
Keep the inside at atmospheric pressure and prevent atmospheric air from entering from outside.
実施例ｌ
５ｉ０２表面に弗素系レジストを塗布し、露光後、ウェ
ット現像し、これを（１）、 （２） 、 （３）のガ
ス雰囲気中でΔｒＦレーザー光を試料に対して水平方向
から入射し、露光された５ｉＯｚ面のみをエツチングし
た。Example 1 A fluorine-based resist was applied to the surface of 5i02, exposed to light, wet developed, and ΔrF laser light was applied horizontally to the sample in the gas atmosphere of (1), (2), and (3). Then, only the exposed 5iOz surface was etched.
実施例２
第６図のブロック図に示す工程に基づき、第７図の装置
を用いて、リソグラフィーのオールドライ化し、（１，
） 、 （２） 、 （３）のガス雰囲気中でＡｒＦレ
ーザー光を試料に対して水平方向から入射し、露光され
た５ｉ０２面のみをエツチングした。すなわち、熱酸化
シリコンウニ／へ−表面にＰＭＭＡレジストをスピンコ
ーティングし、これをＮＦ３ガスの満たされたセルの中
に入れ、ＡｒＦレーザーによって回路パターンを縮小投
影する。これによってレジストの露光部分のみ低分子量
化する。それと同時に、その界面近傍のＮＦ、が光分解
されドライ現象をおこなわせる。さらに、このレーザー
露光を続けるか、または水平方向からのレーザー光を入
射すると、ＮＦＯが形成され、下地の５ｉｎ２と光によ
って活性化されたＮＦＯとが反応して脱酸素反応がおき
、熱酸化５ｉｎ２のエツチングが完了する。以上のよう
に、露光工程のみでレジストの現像及び基板のエツチン
グも完了するためプロセス時間が大いに短縮される。こ
の方法でエツチングされた酸化絶縁膜のエツチング状況
を第８図の走査型顕微鏡写真に示す。Example 2 Based on the steps shown in the block diagram of FIG. 6, the apparatus of FIG. 7 was used to carry out all-dry lithography.
), (2), and (3), ArF laser light was applied horizontally to the sample in the gas atmosphere, and only the exposed 5i02 surface was etched. That is, a PMMA resist is spin-coated on the thermally oxidized silicon surface, placed in a cell filled with NF3 gas, and a circuit pattern is reduced and projected using an ArF laser. As a result, only the exposed portions of the resist are reduced in molecular weight. At the same time, NF near the interface is photodecomposed and a dry phenomenon occurs. Furthermore, when this laser exposure is continued or laser light is incident from the horizontal direction, NFO is formed, and the underlying 5in2 reacts with the NFO activated by the light to cause a deoxidation reaction, resulting in thermal oxidation 5in2. The etching is completed. As described above, development of the resist and etching of the substrate are completed by only the exposure step, so the process time is greatly shortened. The etching state of the oxide insulating film etched by this method is shown in the scanning micrograph of FIG.
なお、ＳｉＯ２のエツチングに関しては、ＮＦＯの形成
後、ＡｒＦレーザーの照射を止めても、ＮＦＯによるＯ
の引抜反応があるため、エツチングは進行する。Regarding etching of SiO2, even if the ArF laser irradiation is stopped after the formation of NFO, the O
Etching progresses because of the pull-out reaction.
実施例３
上記第７図に示した装置を用いて、ＮＦ、ガス中でｓｉ
裏表面レジストレスエツチングを行ない、その後Ｓｔ裏
表面下面のＳｉＯ２面が露出すると、微量の酸素又は酸
素化合物を混入させ、ＡｒＦレーザー光を照射し、ＮＦ
Ｏを作り、これにより下面のＳｉＯ□をエツチングした
。このＳｉのみのエッチレートを第５図に示す。Example 3 Using the apparatus shown in FIG. 7 above, Si
After performing resistless etching on the back surface, when the SiO2 surface on the lower surface of the St back surface is exposed, a trace amount of oxygen or an oxygen compound is mixed in, irradiated with ArF laser light, and NF
The SiO □ on the lower surface was etched using this. The etch rate of this Si alone is shown in FIG.
実施例４
Ｓｉ基板上の自然酸化絶縁膜のクリーニング：Ｓｉ基板
のＣＶＤを行なう前に、基板に対して（１）、（２）、
（３）のガス雰囲気中でＡｒＦレーザー光を照射した。Example 4 Cleaning of native oxide insulating film on Si substrate: Before performing CVD on the Si substrate, (1), (2),
ArF laser light was irradiated in the gas atmosphere of (3).
この結果、ＮＦＯにより基板をクリーニングがなされ、
基板上の自然酸化絶縁膜のクリニングがなされ、以下の
エツチング工程後において、得られたＳｔのパターンＣ
ＶＤのコントラストが向上した。As a result, the substrate is cleaned by NFO,
The natural oxide insulating film on the substrate is cleaned, and after the following etching process, the resulting St pattern C
The contrast of VD has improved.
実施例５
また、本発明のクリーニング方法は、蒸着される基板を
チャンバー内に配置し、このチャンバー内にＮＦ、ガス
を入れ、このガス雰囲気中で基板に直接ＡｒＦレーザー
光を照射すると、脱酸素作用が起こり、基板がクリーニ
ングされる。そしてこの処理を行った後、蒸着を行うと
、膜の付着力が強くなり、従来法では８５〜９０％内外
のＡｇ蒸着膜の反射率であったのが、この処理を施すこ
とにより９８％に向上した。Example 5 In addition, in the cleaning method of the present invention, a substrate to be vapor-deposited is placed in a chamber, NF and gas are placed in the chamber, and the substrate is directly irradiated with ArF laser light in this gas atmosphere to remove oxygen. Action occurs and the substrate is cleaned. When vapor deposition is performed after this treatment, the adhesion of the film becomes stronger, and the reflectivity of the Ag vapor deposited film was around 85-90% with the conventional method, but with this treatment, the reflectance of the Ag vapor-deposited film was 98%. improved.
［発明の効果］
以上説明したように、本発明によれば、ＮＦＯの強力な
酸素引抜力を利用することにより、基板に損傷を与える
ことなく、酸化絶縁膜にサブミクロン以下の微細加エバ
ターンを高速でエツチングするすることができる。[Effects of the Invention] As explained above, according to the present invention, by utilizing the strong oxygen extraction force of NFO, it is possible to form a submicron or less microscopic evaporation on an oxide insulating film without damaging the substrate. Can be etched at high speed.
第１図は、紫外線ｉ’ｊＦＪ定及び可視光線−Ｐ１定を
して、本発明のエツチングガス雰囲気中に形成された中
間生成物の分析結果を示す図である。
第２図は、紫外線ｎ１定及び可視光線測定をして、Ａｒ
Ｆレーザーの照射により、ＮＯ２が光分解され、ＮＯと
ＮＦＯが形成され、更に照射によりＮＦＯのみとなるこ
とを示す図である。
第３図（ａ）〜（ｃ）は、本発明の各エツチングガスの
紫外線吸収特性を示す図である。
第４図は、ＳｉＯ２を入れた時と５ｉ０２を入れない時
とのＮＯ２発生量の比較結果を示す図である。
第５図は、Ｓｔと５ｉｎ２のエッチレートを示す図であ
る。
第６図は、本発明方法の一例（リソグラフィーのオール
ドライ化）を示すブロック図である。
第７図は、第６図の本発明方法をおこなう装置の概略説
明図である。
第８図は、本発明方法でエツチングされた絶縁酸化膜の
粒子の構造を示す走査型顕微鏡写真である。
出願人代理人 弁理士 鈴江武彦
透通Ｔ
（’／、 ）
違遇千
造、置キ
（’１０ ）
レーサ゛−エネル久“−音度（ｍＪ／（ｍ２）第
図
第８図
手続補正書
平成２キ゛ ６足Ａ 日FIG. 1 is a diagram showing the analysis results of intermediate products formed in the etching gas atmosphere of the present invention, using ultraviolet i'j FJ constants and visible light -P1 constants. Figure 2 shows the Ar
FIG. 3 is a diagram showing that NO2 is photolyzed by F laser irradiation to form NO and NFO, and further irradiation leaves only NFO. FIGS. 3(a) to 3(c) are diagrams showing the ultraviolet absorption characteristics of each etching gas of the present invention. FIG. 4 is a diagram showing a comparison result of the NO2 generation amount when SiO2 is added and when 5i02 is not added. FIG. 5 is a diagram showing the etch rate of St and 5in2. FIG. 6 is a block diagram showing an example of the method of the present invention (all-dry lithography). FIG. 7 is a schematic illustration of an apparatus for carrying out the method of the invention shown in FIG. 6. FIG. 8 is a scanning micrograph showing the grain structure of an insulating oxide film etched by the method of the present invention. Applicant's agent Patent attorney Toruichi Suzue Takehiko T ('/, ) Senzo Senzo, Oki ('10) Laser "-Energy" - Sound intensity (mJ/(m2) Figure 8 Procedural amendment Heisei 2 keys 6 pairs A day
Claims (2)
ス雰囲気中に、酸化絶縁膜を形成した基板を配置する工
程と、 上記ガス雰囲気中に、発信波長２００ｎｍ以下のレーザ
ーを照射してＮＦＯを形成し、このＮＦＯにより基板の
酸化絶縁膜をエッチングする工程とを具備した基板の酸
化物のエッチング方法。(1) A step of placing a substrate on which an oxide insulating film is formed in an NF_3 gas atmosphere containing a trace amount of oxygen or oxygen compounds, and forming an NFO by irradiating a laser with an emission wavelength of 200 nm or less in the gas atmosphere. and a step of etching the oxide insulating film of the substrate using the NFO.
ｒＦレーザー光を照射して、基板に吸着している酸素を
脱離させ、基板をクリーニングする方法。(2) Place the substrate in an NF_3 gas atmosphere, and place A on the substrate.
A method of cleaning a substrate by irradiating it with rF laser light to remove oxygen adsorbed on the substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2130378A JP3053410B2 (en) | 1990-05-22 | 1990-05-22 | Method of etching substrate oxide and method of cleaning substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2130378A JP3053410B2 (en) | 1990-05-22 | 1990-05-22 | Method of etching substrate oxide and method of cleaning substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0426116A true JPH0426116A (en) | 1992-01-29 |
| JP3053410B2 JP3053410B2 (en) | 2000-06-19 |
Family
ID=15032914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2130378A Expired - Fee Related JP3053410B2 (en) | 1990-05-22 | 1990-05-22 | Method of etching substrate oxide and method of cleaning substrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3053410B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002025713A1 (en) * | 2000-09-25 | 2002-03-28 | Research Institute Of Innovative Technology For The Earth | Gas compositions for cleaning the interiors of reactors as well as for etching films of silicon-containing compounds |
| JP2003144905A (en) * | 2001-11-16 | 2003-05-20 | Central Glass Co Ltd | Gas cleaning method |
-
1990
- 1990-05-22 JP JP2130378A patent/JP3053410B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002025713A1 (en) * | 2000-09-25 | 2002-03-28 | Research Institute Of Innovative Technology For The Earth | Gas compositions for cleaning the interiors of reactors as well as for etching films of silicon-containing compounds |
| EP1320875A1 (en) * | 2000-09-25 | 2003-06-25 | Research Institute of Innovative Technology for the Earth | Gas compositions for cleaning the interiors of reactors as well as for etching films of silicon-containing compounds |
| EP1320875A4 (en) * | 2000-09-25 | 2008-01-23 | Tokyo Electron Ltd | Gas compositions for cleaning the interiors of reactors as well as for etching films of silicon-containing compounds |
| EP2372753A1 (en) * | 2000-09-25 | 2011-10-05 | Tokyo Electron Limited | Gas Compositions for Cleaning the Interiors of Reactors as Well as for Etching Films of Silicon-Containing Compounds |
| JP2003144905A (en) * | 2001-11-16 | 2003-05-20 | Central Glass Co Ltd | Gas cleaning method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3053410B2 (en) | 2000-06-19 |
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