JPH04111308A - Method for removing organic material film - Google Patents
Method for removing organic material filmInfo
- Publication number
- JPH04111308A JPH04111308A JP22929790A JP22929790A JPH04111308A JP H04111308 A JPH04111308 A JP H04111308A JP 22929790 A JP22929790 A JP 22929790A JP 22929790 A JP22929790 A JP 22929790A JP H04111308 A JPH04111308 A JP H04111308A
- Authority
- JP
- Japan
- Prior art keywords
- ozone
- photoresist
- tank
- sulfuric acid
- photoresist film
- 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
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000011368 organic material Substances 0.000 title 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 68
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 19
- 239000012498 ultrapure water Substances 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000011282 treatment Methods 0.000 claims description 37
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- 238000005468 ion implantation Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 9
- 238000001020 plasma etching Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims 2
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 53
- 230000006866 deterioration Effects 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract 3
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 abstract 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229910052785 arsenic Inorganic materials 0.000 description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 101100136634 Arabidopsis thaliana PIF6 gene Proteins 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 101100408307 Schizosaccharomyces pombe (strain 972 / ATCC 24843) pil2 gene Proteins 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- SURLGNKAQXKNSP-DBLYXWCISA-N chlorin Chemical compound C\1=C/2\N/C(=C\C3=N/C(=C\C=4NC(/C=C\5/C=CC/1=N/5)=CC=4)/C=C3)/CC\2 SURLGNKAQXKNSP-DBLYXWCISA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、有機物被膜の除去方法に関し、特に半導体装
置等のフォトリソグラフィーによる製造において使用さ
れている有機高分子化合物であるフォトレジスト膜の湿
式除去方法に関するものである。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for removing an organic film, and in particular, a wet method for removing a photoresist film, which is an organic polymer compound used in the production of semiconductor devices, etc. by photolithography. This relates to a removal method.
［従来技術］
ＩＣ，ＬＳＩ等に代表される半導体装置の製造工程では
、シリコン等の半導体基板やガラス基板上に、微細な電
気的な素子や回路を形成するために基板上に、感光性の
有機高分子化合物を塗布し、所定の回路等のパターンを
形成したフォトマスクを介して紫外線等で露光した後に
フォトレジストを現像して、基板上にフォトレジストの
回路パターンを形成し、フォトレジストの形成されてい
ない基板上にＣＶＤ、スパッタリング等で成膜を行った
り、薬剤によるエツチング、ＲＩＥ （反応性イオンエ
ツチング）、不純物の元素の加熱による拡散やイオン注
入を行っている。そして、一連のの処理が終了した基板
上のフォトレジストの膜は化学的な処理によって除去さ
れるが、 ＩＣ，ＬＳＩの製造工程では、一般にこのよ
うなフォトレジストを塗布して各種の処理をした後にフ
ォトレジスト膜を除去する操作は１回にとどまらず、数
回行われる。[Prior art] In the manufacturing process of semiconductor devices such as ICs and LSIs, photosensitive materials are used on semiconductor substrates such as silicon or glass substrates in order to form minute electrical elements and circuits on the substrates. After applying an organic polymer compound and exposing it to ultraviolet light through a photomask with a predetermined circuit pattern formed thereon, the photoresist is developed to form a photoresist circuit pattern on the substrate. Films are formed on unformed substrates by CVD, sputtering, etc., etching with chemicals, RIE (reactive ion etching), diffusion of impurity elements by heating, and ion implantation. After a series of treatments, the photoresist film on the substrate is removed by chemical treatment, but in the manufacturing process of ICs and LSIs, such photoresist is generally applied and subjected to various treatments. The subsequent operation of removing the photoresist film is performed not only once but several times.
フォトレジスト膜の除去は各種の方法が採用されている
が、フォトレジストの除去が不完全であるとその後の工
程に悪影響を与えるためにフォトレジスト膜を完全に除
去することが必要である。Various methods are used to remove the photoresist film, but it is necessary to completely remove the photoresist film because incomplete removal of the photoresist will adversely affect subsequent steps.
特に、最近のように半導体装置の集積度が高まり、形成
される半導体装置の回路の線幅が細くなると、フォトレ
ジスト膜の残渣の影響は集積度の低い場合に比べて大き
な問題となるので完全に除去することが求められている
。In particular, as the degree of integration of semiconductor devices increases in recent years and the line width of the circuits of the semiconductor devices that are formed become narrower, the influence of photoresist film residue becomes a bigger problem than in the case of low degree of integration. is required to be removed.
［発明が解決しようとする課題］
フォトレジスト膜の除去には各種の方法が採用されてお
り、薬液による湿式による方法と酸素プラズマ等を使用
する乾式方法が行われている。[Problems to be Solved by the Invention] Various methods are used to remove the photoresist film, including a wet method using a chemical solution and a dry method using oxygen plasma or the like.
フォトレジスト膜の湿式による除去方法では、通常は硫
酸が使用されており、硫酸の酸化能力を高めるために過
酸化水素を混合することが行われている。In a wet method for removing a photoresist film, sulfuric acid is usually used, and hydrogen peroxide is mixed in to increase the oxidizing ability of the sulfuric acid.
硫酸と過酸化水素を混合した液を使用してフォトレジス
ト膜の除去を行う場合には、 フォトレジスト膜の除去
を行った後に付着している硫酸などの薬液を除去し、更
に残渣を除去するために超純水で洗浄することが広く行
われている。When removing a photoresist film using a mixture of sulfuric acid and hydrogen peroxide, remove the attached chemical solution such as sulfuric acid after removing the photoresist film, and then remove the residue. Therefore, cleaning with ultrapure water is widely practiced.
通常の湿式による有機物被膜の除去は、第６図（Ａ）に
示すように、有機物被膜２１が形成されたウェハ２２を
複数枚収容したウェハカセット２３を硫酸と過酸化水素
との混合液のような処理液２４を満たした処理槽２５に
所定の時間浸漬した後に、 リンス槽２６において超純
水中に浸漬して基板に付着した薬液やフォトレジスト膜
の残渣の除去を行っていた。リンス槽には各種のものが
あるが、オーバーフロー形式のものが多く使用されてお
り、 リンス槽には超純水の供給口２７と液の出口２８
が設けられている。As shown in FIG. 6(A), the conventional wet method for removing an organic film is to remove a wafer cassette 23 containing a plurality of wafers 22 on which an organic film 21 is formed using a mixed solution of sulfuric acid and hydrogen peroxide. After being immersed in a processing tank 25 filled with a processing solution 24 for a predetermined time, the substrate is immersed in ultrapure water in a rinsing tank 26 to remove chemical solution and photoresist film residues adhering to the substrate. There are various types of rinsing tanks, but overflow type ones are often used, and the rinsing tank has an ultrapure water supply port 27 and a liquid outlet 28.
is provided.
硫酸と過酸化水素水の混合液によるフォトレジスト膜の
除去は、過酸化水素が分解して発生する発生期の酸素に
よるフォトレジスト膜の酸化分解作用が大きな役割を果
たしているために、この混合液の酸化能力を維持するた
めには、フォトレジスト膜の酸化分解によって消費され
て濃度が薄くなった硫酸および過酸化水素水を取り出し
て新しい液を補充することが必要となる。The removal of a photoresist film using a mixture of sulfuric acid and hydrogen peroxide relies on the oxidation and decomposition of the photoresist film caused by the nascent oxygen generated when hydrogen peroxide decomposes. In order to maintain the oxidizing ability of the photoresist film, it is necessary to take out the sulfuric acid and hydrogen peroxide solution that have become diluted in concentration due to oxidative decomposition of the photoresist film, and replenish the solution with new solution.
そこで、フォトレジスト膜の除去能力が低下した廃液の
処理や液の補充の操作という作業を行わなくても同等の
効果を得るために、硫酸にオゾンを供給してフォトレジ
スト膜の除去を行う方法が特公昭５２−１２０６３号と
して提案されている。Therefore, in order to obtain the same effect without having to process the waste liquid whose ability to remove the photoresist film has decreased or replenish the liquid, there is a method of removing the photoresist film by supplying ozone to sulfuric acid. has been proposed as Special Publication No. 52-12063.
しかしながら、一般のフォトレジスト膜の場合にはこの
ような硫酸中ヘオゾンを導入する方法によってもフォト
レジスト膜を除去することが可能である。が、反応性イ
オンエツチングを行ったり。However, in the case of a general photoresist film, it is also possible to remove the photoresist film by such a method of introducing heozone in sulfuric acid. However, reactive ion etching is performed.
半導体への不純物のドーピングを砒素などを高濃度にイ
オン注入した場合にはフォトレジスト膜が完全には除去
されずに残渣が残る場合が発生している。イオン注入工
程等のエネルギーの高いイオンで処理した場合にはフォ
トレジスト膜はイオン注入に使用された砒素等がフォト
レジストと化学反応をしてフォトレジスト膜が酸化を受
けにくい物質に変質しているものとみらね その結果処
理液によって酸化分解を受けにくくなったものと考えら
れる。When a semiconductor is doped with impurities such as arsenic by ion implantation at a high concentration, the photoresist film may not be completely removed and a residue may remain. When a photoresist film is treated with high-energy ions such as in an ion implantation process, the arsenic used in the ion implantation chemically reacts with the photoresist, turning the photoresist film into a substance that is less susceptible to oxidation. It is thought that as a result, it became less susceptible to oxidative decomposition by the treatment liquid.
また、フォトレジスト膜の処理に使用する硫酸は濃度が
高いので、フォ・トレジスト膜の処理液中の水の比率は
少ないが、硫酸への溶解度が極めて小さいオゾンを水の
比率の少ない硫酸中へ導入しても処理液中への溶解量は
少ないので、処理液中へオゾンを導入しても十分にオゾ
ンが利用されないことになる。したがって、硫酸中にオ
ゾンを導入してもオゾンによる酸化能力が有効に利用さ
れないことがおこる。In addition, since the sulfuric acid used to process photoresist films has a high concentration, the proportion of water in the processing solution for photoresist films is small, but ozone, which has extremely low solubility in sulfuric acid, can be transferred into sulfuric acid, which has a small proportion of water. Even if ozone is introduced, the amount dissolved in the processing liquid is small, so even if ozone is introduced into the processing liquid, the ozone will not be fully utilized. Therefore, even if ozone is introduced into sulfuric acid, the oxidizing ability of ozone is not effectively utilized.
［問題点を解決するための手段］
本発明者らは、従来の方法では除去が困難である反応性
イオンエツチングや高濃度のイオン注入等のイオンによ
る処理を受けて変質したフォトレジスト膜を除去する方
法について検討し、本発明に想到した。[Means for Solving the Problems] The present inventors removed a photoresist film that has undergone deterioration due to ion treatment such as reactive ion etching or high-concentration ion implantation, which is difficult to remove using conventional methods. The present invention was conceived after studying methods for doing so.
すなわち、通常の湿式によるフォトレジスト膜の除去方
法である硫酸と過酸化水素水の混合液中に浸漬してフォ
トレジスト膜を除去した後に、超純水中にオゾンを導入
してオゾンを溶解した液によって洗浄することにより、
オゾンの強力な酸化作用によって、通常の湿式による方
法では除去することができないで残渣として残っている
イオン注入工程等の工程を経たフォトレジスト膜を除去
することが可能であることを見いだしたものである。That is, after removing the photoresist film by immersing it in a mixture of sulfuric acid and hydrogen peroxide, which is the usual wet method for removing a photoresist film, ozone was introduced into ultrapure water to dissolve the ozone. By cleaning with liquid,
It was discovered that the strong oxidizing effect of ozone makes it possible to remove photoresist films that have gone through processes such as ion implantation processes and remain as residues that cannot be removed using normal wet methods. be.
本発明の方法で除去することができるフォトレジスト膜
はポジ型、ネガ型のいずれのフォトレジスト膜も可能で
ある。The photoresist film that can be removed by the method of the present invention can be either a positive type photoresist film or a negative type photoresist film.
オゾンによる処理は、超純水中へオゾン含有気体を供給
することによって得られる処理水によって行うが、超純
水中へのオゾンの供給は、無声放電式の発生装置から得
られる気体のオゾンに限らず、気体のオゾンをあらかじ
め超純水中に溶解させた高濃度のオゾン水や二酸化鉛電
極を陽極とし、フッ素樹脂系の陽イオン交換膜を固体高
分子電解質として使用した水の電気分解装置から得られ
る高濃度のオゾン水を使用しても良い。Ozone treatment is performed using treated water obtained by supplying ozone-containing gas to ultrapure water, but ozone is supplied to ultrapure water using gaseous ozone obtained from a silent discharge generator. Water electrolysis equipment that uses highly concentrated ozonated water in which gaseous ozone is dissolved in ultrapure water in advance, or a lead dioxide electrode as an anode and a fluororesin-based cation exchange membrane as a solid polymer electrolyte. Highly concentrated ozonated water obtained from
無声放電式のオゾン発生装置において高濃度のオゾンを
得るためには、オゾン発生装置には純酸素等の酸素濃度
の高い気体を供給することが好ましい。In order to obtain high concentration ozone in a silent discharge type ozone generator, it is preferable to supply a gas with a high oxygen concentration such as pure oxygen to the ozone generator.
また、オゾンによる処理はオゾンが分解した際に発生す
る発生期の酸素の強力な酸化作用によってフォトレジス
ト膜を酸化分解しているので、オゾンの酸化分解を促進
するために、オゾンによる処理槽中の超純水の温度を高
めてオゾンを注入することにより処理を促進することが
可能である・この場合には、オゾン処理槽の温度は４０
’Ｃないし１００’Ｃの範囲とすることが好ましい。In addition, in ozone treatment, the photoresist film is oxidized and decomposed by the strong oxidizing action of the nascent oxygen that is generated when ozone decomposes. It is possible to accelerate the treatment by increasing the temperature of ultrapure water and injecting ozone. In this case, the temperature of the ozone treatment tank is 40℃.
Preferably, the range is from 'C to 100'C.
オゾン処理槽中に供給するオゾン含有気体の濃度は、高
濃度になるほど洗浄効果が大きい。オゾンの超純水中へ
の導入部には、微細な穴を多数有するガラスフィルター
等から噴出させて、微細な気泡を形成して超純水との接
触を高めることによって、オゾン含有気体の超純水中へ
の溶解を促進することにより、オゾンによる処理を促進
することが可能である。The higher the concentration of the ozone-containing gas supplied into the ozone treatment tank, the greater the cleaning effect. At the point where ozone is introduced into the ultrapure water, the ozone-containing gas is ejected from a glass filter with many fine holes to form fine bubbles and increase contact with the ultrapure water. By promoting dissolution in pure water, it is possible to accelerate treatment with ozone.
また、オゾンはきわめて大きな酸化力を有し、人体等に
も悪影響を及ぼすので、オゾン処理槽には、排出される
オゾンを分解するオゾン分解装置を設けてオゾンを酸素
に分解する必要がある。Further, since ozone has an extremely large oxidizing power and has an adverse effect on the human body, it is necessary to install an ozone decomposition device in the ozone treatment tank to decompose the ozone into oxygen.
［作用コ
本発明は、有機物被膜の湿式による除去方法において、
硫酸と過酸化水素水によって処理をした後にオゾンを含
む超純水によって処理するもので、硫酸と過酸化水素水
の混合液によっては完全には除去できなかった砒素など
をイオン注入した有機物被膜であっても完全に除去する
ことができる。[Function] The present invention provides a wet method for removing an organic film,
It is treated with sulfuric acid and hydrogen peroxide solution, and then treated with ultrapure water containing ozone.It is an organic film with ions implanted with arsenic and other substances that could not be completely removed by a mixture of sulfuric acid and hydrogen peroxide solution. Even if there is, it can be completely removed.
［実施例コ
以下に図面を参照しつつ本発明の実施例について説明す
る。[Embodiments] Examples of the present invention will be described below with reference to the drawings.
第１図は本発明の除去方法に使用する装置を示す図面で
あるが、第１図（Ａ）に示すようにフォトレジスト膜１
が形成された基板２を複数枚収容したカセット３を硫酸
と過酸化水素水との混合液のような処理液を満たした湿
式処理槽４に所定の時間浸漬して湿式によってフォトレ
ジストの除去の処理をした後に、カセットを第１図（Ｂ
）で示すオゾン処理槽５に浸漬して処理をするものであ
る。オゾン処理槽には超純水の供給管６とオゾン発生装
置７で発生するオゾンを供給するオゾン供給管８、およ
び液の排出管９が設けられている。FIG. 1 is a diagram showing an apparatus used in the removal method of the present invention. As shown in FIG. 1(A), a photoresist film 1
A cassette 3 containing a plurality of substrates 2 on which a photoresist is removed is immersed for a predetermined time in a wet processing tank 4 filled with a processing solution such as a mixture of sulfuric acid and hydrogen peroxide. After processing, the cassette is shown in Figure 1 (B
) The treatment is carried out by immersing it in an ozone treatment tank 5 shown in FIG. The ozone treatment tank is provided with an ultrapure water supply pipe 6, an ozone supply pipe 8 for supplying ozone generated by the ozone generator 7, and a liquid discharge pipe 9.
また、オゾン処理槽内の液温はヒータ１０と温度調整装
置１１によって所望の温度に調整することが行われる。Further, the temperature of the liquid in the ozone treatment tank is adjusted to a desired temperature by a heater 10 and a temperature adjustment device 11.
オゾン処理槽から、オゾンが排出されて作業環境を悪化
することを防止するために、オゾン分解装置１２を設け
て、オゾンの環境中への排出を防止する。In order to prevent ozone from being discharged from the ozone treatment tank and worsening the working environment, an ozone decomposition device 12 is provided to prevent ozone from being discharged into the environment.
実施例１
直径６インチのシリコンのウェハー上にポジ型フォトレ
ジスト（東京応化工業（株）製０ＦＰＲ−８００）を１
．５μｍを塗布し、露先 現像を行った後、砒素の注入
濃度をｌＸｌ０”７ｃｍ”ないし３×１０′ｓ／Ｃｍ２
の濃度でイオン注入を行ったものを、濃度９０％の硫酸
と濃度３５％の過酸化水素水とを４対１の割合で混合し
た処理液に５分間浸漬した後に、超純水中に供給するオ
ゾン含有気体の濃度を変えて、室温にて５分間浸漬処理
をした後に超純水の流水中において５分間リンス処理を
した。Example 1 One layer of positive photoresist (0FPR-800 manufactured by Tokyo Ohka Kogyo Co., Ltd.) was placed on a silicon wafer with a diameter of 6 inches.
．． After applying a 5μm film and developing the exposed area, the arsenic injection concentration was adjusted to 1X10"7cm" to 3x10's/Cm2.
After ion implantation at a concentration of After changing the concentration of ozone-containing gas, immersion treatment was performed at room temperature for 5 minutes, followed by rinsing treatment for 5 minutes in running ultrapure water.
フォトレジスト膜の除去はウェハ面から一様に行われる
のではなく、フォトレジスト面に形成されているパター
ンによっても影響を受けるので、本発明者らはフォトレ
ジスト膜の除去の評価方法について検討し、次のような
方法によって評価を行った。Since the removal of the photoresist film is not performed uniformly from the wafer surface, but is also affected by the pattern formed on the photoresist surface, the present inventors investigated a method for evaluating the removal of the photoresist film. The evaluation was carried out using the following method.
パターンの形状や線幅、面積等によって剥離のされ方が
異なり、線幅、面積の大きい部分はど剥離しにくいため
、パターンを識別記号等が描かれた部分、パッド訊す−
ド龜 配線部と剥離しにくい順に４つの部分に分けて観
察し、配線部は更に配線の上面と配線の周囲に分けて観
察を行った。Peeling differs depending on the shape, line width, area, etc. of the pattern, and parts with large line widths and areas are difficult to peel off.
The wiring part was divided into four parts in order of ease of peeling, and the wiring part was further divided into the upper surface of the wiring and the periphery of the wiring.
その結果を第２図に、完全に剥離したものを○、少し残
るものを△、全く除去できなかったものを×で表すと共
に、完全な除去が行われた場合をｌｏＯとして数値でも
比較した
実施例２
オゾン処理槽に供給するオゾン含有気体に代えてあらか
じめオゾンを溶存させた超純水を用いて実施例１と同様
にして処理を行い、実施例１と同様の方法で評価した結
果を第３図に示す。The results are shown in Figure 2, where those that were completely removed are shown as ○, those that remained slightly are shown as △, and those that were not removed at all are shown as ×, and the results were also compared numerically, with loO representing complete removal. Example 2 Treatment was carried out in the same manner as in Example 1 using ultrapure water in which ozone was dissolved in advance in place of the ozone-containing gas supplied to the ozone treatment tank. Shown in Figure 3.
実施例３
オゾン処理槽中の超純水の液温を変化させて、オゾン含
有気体を注入した点を除いて実施例１と同様の方法で処
理を行った結果を第４図に示す。Example 3 FIG. 4 shows the results of a treatment carried out in the same manner as in Example 1, except that the temperature of the ultrapure water in the ozone treatment tank was changed and ozone-containing gas was injected.
比較例１
硫酸と過酸化水素水の混合液による処理のみでオゾンに
よる処理を行わなかった場合についてのフォトレジスト
の除去の状態を実施例１と同様の方法で評価した結果を
第５図に示す。Comparative Example 1 Figure 5 shows the results of evaluating the state of photoresist removal in the same manner as in Example 1 in the case of treatment with a mixture of sulfuric acid and hydrogen peroxide without ozone treatment. .
［発明の効果コ
本発明の方法により、フォトレジスト膜の通常の湿式処
理である硫酸と過酸化水素水による処理では除去するこ
とが困難であった高濃度のイオン注入処理や反応性イオ
ンエツチング等のイオンによる処理で変質したフォトレ
ジスト膜の完全な除去が可能となるので、製造工程の短
縮やの半導体装置の製造における不良品率を低下させる
ことができる。[Effects of the Invention] The method of the present invention eliminates the effects of high-concentration ion implantation, reactive ion etching, etc. that are difficult to remove with the usual wet treatment of photoresist films, such as treatment with sulfuric acid and hydrogen peroxide. Since it is possible to completely remove the photoresist film that has been altered in quality by the treatment with ions, it is possible to shorten the manufacturing process and reduce the defective product rate in the manufacturing of semiconductor devices.
第１図（Ａ）および（Ｂ）は本発明の有機物被膜の除去
方法に使用する装置を示す図、第２図は、イオン注入し
たフォトレジストの本発明の方法によって除去した場合
のイオン注入量と除去の程度を示す説明図、第３図はオ
ゾン水をオゾン処理槽に供給した場合のイオン注入量と
フォトレジスト膜の除去の関係を示す説明図、第４図は
オゾン処理槽の液温とフォトレジスト膜の除去の関係を
示す説明図、第５図は硫酸と過酸化水素水による湿式処
理のみの場合のイオン注入量とフォトレジスト膜の除去
の関係を示す説明図、第６図（Ａ）および（Ｂ）は従来
の湿式処理方法に使用する装置を示す図である。
の供給管、 ７・・・オゾン発生装置、 ８・・・オゾ
ン供給管、 ９・・・液の排出管、 １０・・・ヒータ
、 １１・・・温度調整装置、 １２・・・オゾン分解
装置、 ２１・・・有機物波Ｕ ２２・・・ウェハ、
２３・・・ウェハカセット、 ２４・・・処理液、２
５・・・処理槽、２６・・・リンス槽、２７・・・供給
味 ２８・・・液出口
特許出願人 クロリンエンジニアズ株式会社代理人 弁
理士 米 澤 明 （外７名）１・・・フォトレジス
トＰＩＬ２・・・基板、 ３・・・カセット、４・・・
湿式処理槽、５・・・オゾン−処理槽、６・・・超純水
第３図
第４図
（Ａ）
第６図
（Ｂ）Figures 1 (A) and (B) are diagrams showing the apparatus used in the organic film removal method of the present invention, and Figure 2 shows the amount of ion implantation when removing ion-implanted photoresist by the method of the present invention. Figure 3 is an explanatory diagram showing the relationship between the amount of ions implanted and the removal of the photoresist film when ozonated water is supplied to the ozone treatment tank, and Figure 4 is the temperature of the liquid in the ozone treatment tank. Figure 5 is an explanatory diagram showing the relationship between ion implantation amount and photoresist film removal in the case of only wet treatment with sulfuric acid and hydrogen peroxide solution, and Figure 6 ( A) and (B) are diagrams showing an apparatus used in a conventional wet processing method. supply pipe, 7... ozone generator, 8... ozone supply pipe, 9... liquid discharge pipe, 10... heater, 11... temperature adjustment device, 12... ozone decomposition device , 21... Organic matter wave U 22... Wafer,
23... Wafer cassette, 24... Processing liquid, 2
5... Processing tank, 26... Rinse tank, 27... Supply taste 28... Liquid outlet Patent applicant Chlorin Engineers Co., Ltd. Representative Patent attorney Akira Yonezawa (7 others) 1... Photoresist PIL2...Substrate, 3...Cassette, 4...
Wet treatment tank, 5... Ozone treatment tank, 6... Ultrapure water Figure 3 Figure 4 (A) Figure 6 (B)
Claims (4)
機物を酸化剤からなる処理液中に浸漬して処理をした後
に、超純水中にオゾンを導入したオゾン処理槽に浸漬し
て処理することを特徴とする有機物被膜の除去方法。(1) In a method of removing an organic substance film from a substrate, the organic substance is treated by immersing it in a treatment liquid consisting of an oxidizing agent, and then immersing it in an ozone treatment bath containing ozone introduced into ultrapure water. A method for removing an organic film, characterized by:
入処理を受けたものであることを特徴とする請求項１記
載の有機物被膜の除去方法。(2) The method for removing an organic film according to claim 1, wherein the organic film has been subjected to reactive ion etching or ion implantation treatment.
を特徴とする請求項１記載の有機物被膜の除去方法。(3) The method for removing an organic film according to claim 1, wherein the oxidizing agent is a mixture of sulfuric acid and hydrogen peroxide.
求項１記載の有機物被膜の除去方法。(4) The method for removing an organic film according to claim 1, further comprising heating the liquid in the ozone treatment tank.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22929790A JP3101307B2 (en) | 1990-08-30 | 1990-08-30 | How to remove organic film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22929790A JP3101307B2 (en) | 1990-08-30 | 1990-08-30 | How to remove organic film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04111308A true JPH04111308A (en) | 1992-04-13 |
| JP3101307B2 JP3101307B2 (en) | 2000-10-23 |
Family
ID=16889931
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22929790A Expired - Lifetime JP3101307B2 (en) | 1990-08-30 | 1990-08-30 | How to remove organic film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3101307B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997037853A1 (en) * | 1996-04-11 | 1997-10-16 | Citizen Watch Co., Ltd. | Ink-jet head and method for manufacturing the same |
| JP2001330969A (en) * | 2000-05-23 | 2001-11-30 | Sekisui Chem Co Ltd | Apparatus for removing photoresist |
| US6790783B1 (en) * | 1999-05-27 | 2004-09-14 | Micron Technology, Inc. | Semiconductor fabrication apparatus |
| JP2005303000A (en) * | 2004-04-12 | 2005-10-27 | Matsushita Electric Ind Co Ltd | Evaluating method of resist removing capability, and manufacturing method of electronic device |
| JP2008205048A (en) * | 2007-02-16 | 2008-09-04 | Seiko Epson Corp | Manufacturing method of piezoelectric element, and manufacturing method of liquid jetting head |
-
1990
- 1990-08-30 JP JP22929790A patent/JP3101307B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997037853A1 (en) * | 1996-04-11 | 1997-10-16 | Citizen Watch Co., Ltd. | Ink-jet head and method for manufacturing the same |
| US6790783B1 (en) * | 1999-05-27 | 2004-09-14 | Micron Technology, Inc. | Semiconductor fabrication apparatus |
| JP2001330969A (en) * | 2000-05-23 | 2001-11-30 | Sekisui Chem Co Ltd | Apparatus for removing photoresist |
| JP2005303000A (en) * | 2004-04-12 | 2005-10-27 | Matsushita Electric Ind Co Ltd | Evaluating method of resist removing capability, and manufacturing method of electronic device |
| JP4526857B2 (en) * | 2004-04-12 | 2010-08-18 | パナソニック株式会社 | Method for evaluating resist removal capability and method for manufacturing electronic device |
| JP2008205048A (en) * | 2007-02-16 | 2008-09-04 | Seiko Epson Corp | Manufacturing method of piezoelectric element, and manufacturing method of liquid jetting head |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3101307B2 (en) | 2000-10-23 |
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