JP3445765B2 - Substrate surface treatment method for semiconductor element formation - Google Patents
Substrate surface treatment method for semiconductor element formationInfo
- Publication number
- JP3445765B2 JP3445765B2 JP36792399A JP36792399A JP3445765B2 JP 3445765 B2 JP3445765 B2 JP 3445765B2 JP 36792399 A JP36792399 A JP 36792399A JP 36792399 A JP36792399 A JP 36792399A JP 3445765 B2 JP3445765 B2 JP 3445765B2
- Authority
- JP
- Japan
- Prior art keywords
- ozone
- treatment
- substrate
- water
- semiconductor element
- 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.)
- Expired - Fee Related
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- Cleaning Or Drying Semiconductors (AREA)
- Cleaning By Liquid Or Steam (AREA)
Description
【0001】[0001]
【発明の属する技術分野】本発明は半導体素子形成用基
板表面処理方法に関し、詳しくは半導体素子形成に用い
られる半導体素子形成用基板上に素子形成工程や構造形
成工程において塗布され所定に処理された後の有機化合
物等を除去する基板表面処理方法に関する。特に、基板
にダメージを与えることなく且つ周辺環境への悪影響物
を排出することなく酸化分解除去処理後の残留微小異物
及び処理後の付着微小異物を簡便に洗浄除去する半導体
素子形成用基板表面処理方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating a surface of a substrate for forming a semiconductor element, and more specifically, it is applied on a substrate for forming a semiconductor element used for forming a semiconductor element in a step of forming an element or a step of forming a structure and then subjected to predetermined treatment. The present invention relates to a substrate surface treatment method for removing an organic compound or the like afterwards. Particularly, the surface treatment of the substrate for forming a semiconductor element for easily cleaning and removing the residual fine foreign matter after the oxidative decomposition removal treatment and the adhered fine foreign matter after the treatment without damaging the substrate and discharging the adverse substances to the surrounding environment Regarding the method.
【0002】[0002]
【従来の技術】基板上に微細な電気的素子や回路を形成
する場合、一般にフォトレジストを塗布し任意の回路等
のパターンを塗布表面に形成し、それをエッチング等で
処理して素子パターンを形成する。素子パターンを形成
した後、基板上のフォトレジストや有機物等の異物を除
去する。半導体素子形成において、基板上に付着した有
機物やフォトレジストの除去が完全でない場合、その後
の微細な電気的素子形成の工程で不都合が生じることが
よく知られており、基板上の有機物系異物は完全に除去
する必要がある。フォトレジストの除去は、従来、硫酸
やオゾン(O3)等の酸化力の強い物質が使用され、フ
ォトレジストの種類やその塗布特性又は素子形成条件等
により乾式処理と湿式処理のいずれか又は双方が採用さ
れている。前者は酸素を主たるプロセスガスとして用
い、真空下、酸素プラズマ等の活性状態で酸化分解して
除去する方法である。乾式処理は、通常、拡散工程にお
いてイオン注入量が約1×1015atoms/cm2
以上の場合に行われることが多い。一方、後者の湿式処
理は多くの場合、硫酸と過酸化水素を超純水に混合溶解
した混合溶液又はO3を超純水に溶解させたO3溶液を
用い酸化処理して除去する方法である。2. Description of the Related Art Generally, when a fine electric element or circuit is formed on a substrate, a photoresist is applied to form a pattern such as an arbitrary circuit on the applied surface, and the element pattern is processed by etching or the like. Form. After forming the element pattern, foreign substances such as photoresist and organic substances on the substrate are removed. It is well known that, in the formation of semiconductor elements, if the removal of the organic substances and the photoresist adhered to the substrate is not complete, inconvenience will occur in the subsequent fine electrical element formation process, Must be completely removed. To remove the photoresist, conventionally, a substance having a strong oxidizing power such as sulfuric acid or ozone (O 3 ) is used, and either dry treatment or wet treatment may be performed depending on the type of photoresist, its coating characteristics, element forming conditions and the like. Has been adopted. The former is a method in which oxygen is used as a main process gas and is oxidized and decomposed in an active state such as oxygen plasma under vacuum to remove the oxygen. In the dry process, the ion implantation amount is usually about 1 × 10 15 atoms / cm 2 in the diffusion process.
This is often done in the above cases. On the other hand, the latter wet processing often a way of removing by oxidizing using O 3 solution of a mixed solution or O 3 were mixed and dissolved sulfuric acid and hydrogen peroxide in ultrapure water to ultrapure water is there.
【0003】乾式処理した後に、更に湿式処理すること
もしばしば行われる。フォトレジストの乾式処理酸化分
解後に、残留カーボンを主成分とする異物、シリコン系
異物又はフォトレジスト除去処理の後に付着した浮遊異
物等が残留することが知られている。基板上に残留する
有機物系異物は、有機物を主成分とした微小粒子や薄膜
の状態で残留し、その後の種々の素子形成工程において
不都合を生じさせる。このような有機物系異物は、従
来、上記した湿式酸化洗浄処理、特に、超純水に硫酸と
過酸化水素を溶解した溶液で洗浄処理して除去される。
また、イオン注入量が多くフォトレジストを強いベーク
処理する等により乾式酸化分解処理でも除去が困難で残
存する若干のレジストは湿式酸化洗浄処理して除去され
る。更に、簡単な有機物は超純水にオゾンガスを溶解さ
せたオゾン水で洗浄して除去される。例えば、特開平9
−255998号公報では、基板上に残留する有機物系
微小異物を除去するためオゾンガスの存在下で紫外線照
射する方法が提案されている。更にまた、デバイス構造
を形成するエッチング工程、特に、ドライエッチング工
程及びその後の酸素等のプラズマによる酸化分解処理工
程を経た後、装置等の金属材料由来と考えられる金属コ
ンタミが残存することがあるが、これらの金属不純物も
硫酸による酸化処理により同時に除去され得る。After the dry treatment, a wet treatment is often performed. It is known that after dry-process oxidative decomposition of a photoresist, foreign matter containing residual carbon as a main component, silicon-based foreign matter, or floating foreign matter adhered after the photoresist removal treatment remains. The organic foreign matter remaining on the substrate remains in the form of fine particles or a thin film containing an organic material as a main component, which causes inconvenience in various device forming steps thereafter. Such organic foreign matter is conventionally removed by the above-described wet oxidative cleaning treatment, particularly, a cleaning treatment with a solution of sulfuric acid and hydrogen peroxide dissolved in ultrapure water.
Further, some resist which is difficult to remove even by dry oxidative decomposition treatment due to a large amount of ion implantation and strong baking of the photoresist is removed by wet oxidation cleaning treatment. Further, simple organic substances are removed by washing with ozone water in which ozone gas is dissolved in ultrapure water. For example , JP-A-9
In -255998 discloses, Ru Tei is proposed a method of UV irradiation in the presence of ozone gas for the removal of organic type fine foreign matter remaining on the substrate. Furthermore, after passing through an etching step for forming a device structure, particularly a dry etching step and a subsequent oxidative decomposition treatment step by plasma such as oxygen, metal contamination that is considered to be derived from a metal material of the device may remain. However, these metal impurities can be simultaneously removed by the oxidation treatment with sulfuric acid.
【0004】上記したようなデバイス製造においては、
フォトレジスト除去工程は種々の段階で繰返される。例
えば、シリコン及びメタルのエッチングやソース/ドレ
インの拡散工程では必ずフォトレジストが基板上に存在
しフォトレジスト除去工程が行われる。従来のフォトレ
ジスト除去工程の一般的シーケンスは、フォトレジスト
の状態によっても異なるが次のような構成からなる。即
ち、(1)上記乾式酸化分解処理→(2)硫酸と過酸化
水素を超純水に混合溶解した混合溶液による上記の湿式
処理→(3)アンモニアと過酸化水素を超純水に混合溶
解した溶液による酸化・還元湿式洗浄処理→(4)次工
程からなるシーケンスが採用される。In manufacturing the device as described above,
The photoresist removal process is repeated at various stages. For example, in the etching process of silicon and metal and the diffusion process of source / drain, the photoresist is always present on the substrate and the photoresist removal process is performed. The general sequence of the conventional photoresist removing process has the following configuration, although it varies depending on the state of the photoresist. That is, (1) the above-mentioned dry oxidative decomposition treatment → (2) the above-mentioned wet treatment with a mixed solution prepared by mixing and dissolving sulfuric acid and hydrogen peroxide in ultrapure water → (3) mixing and dissolving ammonia and hydrogen peroxide in ultrapure water Oxidation / reduction wet cleaning treatment with the above solution → (4) A sequence of the following steps is adopted.
【0005】次工程への移行に先立ち、例えば(CVD
等の成膜工程以前の)基板に構造を形成するためにフォ
トレジストを再塗布する工程等に先立ち、基板上に残存
する微小な異物(以下、単にパーティクルとする)を除
去するため洗浄処理、所謂リンス処理が行われる。この
リンス処理は、一般にアンモニア、過酸化水素水及び超
純水を混合したアルカリ性混合溶液が用いられる。パー
ティクルは、超純水に還元性のアンモニアと酸化性の過
酸化水素を混合した混合溶液により、静電的に又は基板
表面のライトエッチング(リフトオフ)によって除去で
きるためである。また、特開平10−41262号公報
は炭酸水や超純水に水素ガスを溶解した水素水を用いて
金属配線等の腐食を小さくして金属パーティクルを除去
できることを提案する。また、特開平10−12825
3号公報では0.05ppm以上水素ガスを超純水に溶
解した水素水を用いて基板を超音波照射して洗浄・リン
ス処理することが提案されている。Prior to the transition to the next process, for example, (CVD
Prior to the step of re-applying a photoresist to form a structure on the substrate (before the film forming step such as), a cleaning process for removing minute foreign matters (hereinafter, simply referred to as particles) remaining on the substrate, So-called rinse processing is performed. This rinsing treatment generally uses an alkaline mixed solution in which ammonia, hydrogen peroxide solution, and ultrapure water are mixed. This is because the particles can be removed electrostatically or by light etching (lift-off) on the substrate surface with a mixed solution in which reducing ammonia and oxidizing hydrogen peroxide are mixed with ultrapure water. Further, Japanese Patent Laid-Open No. 10-41262 proposes that metal particles can be removed by using hydrogen water obtained by dissolving hydrogen gas in carbonated water or ultrapure water to reduce corrosion of metal wiring and the like. In addition, JP-A-10-12825
Japanese Patent Laid-Open No. 3 proposes cleaning and rinsing treatment by ultrasonically irradiating the substrate with hydrogen water obtained by dissolving hydrogen gas in ultrapure water of 0.05 ppm or more.
【0006】[0006]
【発明が解決しようとする課題】しかしながら、上記し
たフォトレジスト除去工程の一般的シーケンスにおける
(1)乾式酸化分解処理、(2)湿式処理、(3)酸化
・還元湿式洗浄処理及び(4)次工程への移行前のリン
ス処理で従来採用されている各種洗浄処理にはそれぞれ
下記のような問題がある。即ち、従来の乾式処理は、酸
素プラズマを用いフォトレジストの酸化分解することが
一般的であり、酸素プラズマ等のプラズマ状態は高エネ
ルギー状態で活性であるため、しばしば半導体素子の微
細な配線や回路、その他構造を形成する材料にダメージ
を与えることがある。特に昨今、構造材料として銅(C
u)等の化学的に反応活性材を用いる傾向があり、これ
らの活性材料を酸化することが問題となっている。更
に、プラズマ状態は常圧下で得ることはできないため、
プロセスチャンバー内を真空に保つ必要があり、基板を
物理的に苛酷な環境下に置かねばならない。また、プラ
ズマにより処理装置自体がダメージを受け装置の構成
材、例えばステンレス系材料が基板に付着する等の問題
がある。However, in the general sequence of the photoresist removing process described above, (1) dry oxidative decomposition treatment, (2) wet treatment, (3) oxidation / reduction wet cleaning treatment, and (4) next The various cleaning processes conventionally used in the rinse process before shifting to the process have the following problems, respectively. That is, in the conventional dry processing, it is general to oxidize and decompose the photoresist using oxygen plasma, and the plasma state such as oxygen plasma is active in a high energy state, so that fine wiring and circuit of a semiconductor element are often used. , Others may damage the material forming the structure. Especially recently, copper (C
There is a tendency to use chemically reactive activators such as u), and oxidation of these activators is a problem. Furthermore, since the plasma state cannot be obtained under normal pressure,
The process chamber must be vacuumed and the substrate must be physically harsh. Further, there is a problem that the processing apparatus itself is damaged by the plasma and a constituent material of the apparatus, for example, a stainless material is attached to the substrate.
【0007】また、従来の湿式処理は、上記のように硫
酸と過酸化水素とを超純水に混合溶解した溶液が用いら
れ、溶液は酸化還元電位(以下、単にORPとする)が
酸性領域にあり、酸化分解したフォトレジスト等の液中
に含まれるパーティクルやフォトレジストが分解された
微小破片等がゼータポテンシャルの関係から基板に再付
着するという問題がある。また、前記のようにAlSi
Cu、Al、Cu等の化学的に反応活性な配線材のメタ
ルパターンを形成後に残留するフォトレジストの除去に
は上記溶液を使用できない。更に、上記溶液は通常10
0℃以上に加温して用いるため、昨今問題とされるクリ
ーンルーム内の化学汚染物であるSOxを排出するおそ
れがある。更にまた、硫酸は他の洗浄処理薬液と比べて
コストが高く、また薬液ライン等の腐食や取扱いが難し
い等安全面でも問題がある。硫酸系物質は総じて除去が
難しく、薬液のリンス等に大量の超純水を用いることに
もなり廃液処理等にも問題がある。Further, the conventional wet treatment uses a solution in which sulfuric acid and hydrogen peroxide are mixed and dissolved in ultrapure water as described above, and the solution has an oxidation-reduction potential (hereinafter, simply referred to as ORP) in an acidic region. However, there is a problem in that particles contained in a liquid such as photoresist that has been oxidatively decomposed and minute fragments that are decomposed from the photoresist are reattached to the substrate due to the zeta potential. In addition, as described above, AlSi
The above solution cannot be used for removing the photoresist remaining after forming a metal pattern of a chemically reactive wiring material such as Cu, Al or Cu. Further, the above solution is usually 10
Since it is used after being heated to 0 ° C. or higher, SOx, which is a chemical contaminant in a clean room, which has become a problem these days, may be discharged. Furthermore, sulfuric acid has a higher cost than other cleaning treatment chemicals, and there is a problem in terms of safety such as corrosion of chemical liquid lines and the like, and handling is difficult. Sulfuric acid-based substances are generally difficult to remove, a large amount of ultrapure water is used for rinsing chemicals, and there is a problem in waste liquid treatment.
【0008】前記特開平9−255998号公報提案の
オゾンの存在下で紫外線照射する方法では、有機物系微
小異物に対応するものでありフォトレジスト剥離工程に
は適用できない。また、アンモニアと過酸化水素を超純
水に混合溶解した還元・酸化溶液洗浄処理は、アンモニ
アは一般に鉄分(Fe)濃度が比較的高く、半導体素子
形成に用いられる基板にFeが特異吸着することも知ら
れ、Feはデバイス特性に悪影響を与えることが懸念さ
れており除去されるべき不純物であることから好ましい
洗浄処理でない。また、還元・酸化溶液は、例えば70
℃以上に加温して使用することから基板や構造を形成す
る薄膜等表面をエッチングし、基板上に好ましくない凹
凸を与え表面粗さ(ラフネス)を悪化させるおそれがあ
る。更に、Al等の配線材も腐食するおそれがあり、昨
今問題とされているクリーンルーム内のアンモニア汚染
を起こすおそれもある。また、アンモニア過水洗浄にお
いては過酸化水素水が基板上を酸化して好ましくない酸
化膜を与えて素子の電気特性を損なうおそれがある。更
に、前記特開平10−128253号公報で提案される
0.05ppm以上水素ガスを超純水に溶解した水素水
に基板を浸漬し超音波照射する方法は、リンス処理に関
するものであり、本発明において目的とする有機化合物
系異物の除去や乾式酸化分解後の残渣の除去については
何も開示せず、また、示唆もしていない。[0008] In the method of UV irradiation in the presence of a pre Kitoku No. 9-255998 JP proposal ozone, which corresponds to the organic type fine foreign matter can not be applied to the photoresist stripping process. In addition, in the reduction / oxidation solution cleaning process in which ammonia and hydrogen peroxide are mixed and dissolved in ultrapure water, ammonia generally has a relatively high iron (Fe) concentration, and Fe is specifically adsorbed on the substrate used for semiconductor element formation. It is also known that Fe is an impurity that should be removed because it is feared that Fe will adversely affect the device characteristics, so Fe is not a preferable cleaning treatment. Further, the reducing / oxidizing solution is, for example, 70
Since the substrate is heated to a temperature of not less than 0 ° C. and used, the surface of the substrate or a thin film forming a structure may be etched to give undesired irregularities on the substrate to deteriorate the surface roughness. Further, the wiring material such as Al may also be corroded, and ammonia contamination in the clean room, which has been a problem these days, may occur. Further, in the washing with ammonia-hydrogen, the hydrogen peroxide solution may oxidize the substrate to give an undesired oxide film, which may impair the electrical characteristics of the device. To a further <br/>, before Kitoku method of 0.05ppm or more hydrogen gas proposed in Unexamined 10-128253 JP immersed ultrasonic irradiation the substrate to hydrogen water, dissolved in ultrapure water to a rinse treatment However, it does not disclose or suggest the removal of the organic compound-based foreign matter or the residue after the dry oxidative decomposition, which is the object of the present invention.
【0009】本発明は、半導体素子形成に用いられる半
導体素子形成用基板上に存在する有機化合物(フォトレ
ジスト)の除去処理及びその除去処理後に残留する有機
化合物を主成分とする微小異物を除去する従来の洗浄処
理が、上記したように未だ十分でない現状に鑑み、従来
法の種々の問題を解消し基板表面や構造にダメージを与
えることなくフォトレジストの除去及び残存する有機物
化合物やパーティクル等微小異物を効果的に除去し、そ
の後の素子形成工程や成膜工程で半導体素子特性に悪影
響を与えない半導体素子形成用基板表面処理方法の開発
を目的とする。発明者らは、上記目的のため従来の洗浄
方法について、種々見直すと同時に改めて洗浄方式につ
いて鋭意検討した。その結果、乾式処理として基板等に
ダメージを与え操作性にも問題のあるプラズマ酸化方式
に替えて所定の加温状態でオゾンガスを用いて処理し、
更に、オゾン水及び/又は超音波活性水素水による湿式
処理により、最終的に素子特性が優れる素子形成基板が
得られると共に、装置への影響も少なく操作性もよい半
導体素子形成用基板の表面処理方法を見出し本発明を完
成した。The present invention removes an organic compound (photoresist) existing on a semiconductor element forming substrate used for forming a semiconductor element, and removes a minute foreign substance containing an organic compound as a main component after the removal processing. In view of the fact that the conventional cleaning process is still not sufficient as described above, the removal of the photoresist and the remaining small amount of foreign matter such as organic compounds and particles without damaging the substrate surface or structure by solving various problems of the conventional method are solved. It is an object of the present invention to develop a method for treating the surface of a substrate for forming a semiconductor element, which effectively removes the impurities and does not adversely affect the characteristics of the semiconductor element in the subsequent element forming step and film forming step. For the above-mentioned purpose, the inventors reviewed various conventional cleaning methods and, at the same time, earnestly examined the cleaning method again. As a result, as a dry process, instead of the plasma oxidation method which causes damage to the substrate etc. and has a problem in operability, the ozone gas is processed in a predetermined heating state,
Furthermore, by wet treatment with ozone water and / or ultrasonic active hydrogen water, an element formation substrate having excellent element characteristics is finally obtained, and the surface treatment of the semiconductor element formation substrate has little influence on the device and has good operability. A method was found and the present invention was completed.
【0010】[0010]
【課題を解決するための手段】本発明によれば、半導体
素子形成に用いられる半導体素子形成用基板上に存在す
るレジストの除去処理及びその除去処理後に残留する有
機化合物を主成分とする微小異物を除去する方法であ
り、被処理基板を(1)直接的又は間接的に室温以上に
加温し、乾燥雰囲気下にてオゾン含有ガスで処理するオ
ゾンガス処理工程、(2)オゾン含有ガスを超純水に溶
解したオゾン水で処理するオゾン水処理工程、及び
(3)超音波により活性化され且つ水素含有ガスを超純
水に溶解した水素水により処理する水素水処理工程の各
工程を(1)(2)(3)の順序で実施し、且つ上記
(2)のオゾン水処理工程で、20〜60ppmのオゾ
ン濃度のオゾン水を用いることを特徴とする半導体素子
形成用基板表面処理方法が提供される。According to the present invention, a resist existing on a semiconductor element forming substrate used for forming a semiconductor element is removed, and a minute foreign matter containing an organic compound as a main component remaining after the removal processing. Is a method of removing the ozone, and (1) an ozone gas treatment step of directly or indirectly heating the substrate to room temperature or higher and treating it with an ozone-containing gas in a dry atmosphere; Each of an ozone water treatment step of treating with ozone water dissolved in pure water, and (3) a hydrogen water treatment step of treating hydrogen-containing gas activated by ultrasonic waves with hydrogen water dissolved in ultrapure water
Substrates for forming a semiconductor element, wherein the steps (1), (2), and (3) are performed in the order , and ozone water having an ozone concentration of 20 to 60 ppm is used in the ozone water treatment step (2). A surface treatment method is provided.
【0011】上記本発明の半導体素子形成用基板表面処
理方法において、前記オゾンガス処理工程におけるオゾ
ン含有ガスのオゾン濃度が4〜8容量%であり、加温温
度が300〜350℃であることが好ましい。前記オゾ
ンガス処理工程で処理したオゾンガス処理基板を前記オ
ゾン水処理工程で処理することを1又は2回以上繰返し
た後に、前記水素水処理工程で処理することが好まし
い。前記オゾン水処理工程で処理したオゾン水処理基板
を前記オゾンガス処理工程で処理した後、前記水素水処
理工程で処理することが好ましい。更に、前記オゾンガ
ス処理工程で処理したオゾンガス処理基板を前記水素水
処理工程で処理した後、前記オゾン水処理工程で処理
し、更に前記水素水処理工程で処理することが好まし
く、また、前記オゾンガス処理工程並びにオゾン水処理
工程及び/又は水素水処理工程を含む一連の表面処理を
連続的に2回以上繰返して処理することが好ましく、ま
た、前記オゾンガス処理工程並びにオゾン水処理工程及
び/又は水素水処理工程を含む一連の表面処理におい
て、各工程を2回以上繰返して処理することが好まし
い。In the method for treating the surface of a substrate for forming a semiconductor element of the present invention, it is preferable that the ozone concentration of the ozone-containing gas in the ozone gas treatment step is 4 to 8% by volume and the heating temperature is 300 to 350 ° C. . It is preferable to treat the ozone gas treated substrate treated in the ozone gas treating step in the ozone water treating step one or more times, and then treat it in the hydrogen water treating step. It is preferable that the ozone water treatment substrate treated in the ozone water treatment step is treated in the ozone gas treatment step and then in the hydrogen water treatment step. Furthermore, it is preferable that after the ozone gas treatment substrate treated in the ozone gas treatment step is treated in the hydrogen water treatment step, it is further treated in the ozone water treatment step, and further in the hydrogen water treatment step. Step and a series of surface treatments including an ozone water treatment step and / or a hydrogen water treatment step are preferably continuously repeated two or more times, and the ozone gas treatment step and the ozone water treatment step and / or hydrogen water are also preferable. In a series of surface treatments including treatment steps, each step is preferably repeated twice or more.
【0012】 上記本発明の半導体素子形成用基板表面処
理方法は、前記半導体素子形成用基板がドーパントの拡
散工程又はエッチング工程における基板に適用でき、ま
た、Al、W、Cuなど化学的に反応しやすい材料を含
む基板にも適用できる。また、本発明の半導体素子形成
用基板表面処理方法は、要すれば、前記オゾン水処理工
程に用いるオゾン水に塩酸等の酸成分を100ppm以
下、好ましくは10ppm程度、及び/又は前記水素水
処理工程に用いる水素水にアンモニア等のアルカリ成分
を100ppm以下、好ましくは10ppm程度含有さ
せて処理することができる。[0012] Substrate surface treatment for semiconductor element formation of the present invention
According to the method of processing, the substrate for forming a semiconductor element is spread on the dopant.
It can be applied to the substrate in the diffusion process or etching process.
In addition, it contains materials that are chemically reactive such as Al, W, and Cu.
It can also be applied to substrates. Further, the semiconductor element formation of the present invention
The substrate surface treatment method for the
100ppm or less of acid components such as hydrochloric acid in ozone water used
Lower, preferably about 10 ppm, and / or the hydrogen water
Alkaline components such as ammonia in hydrogen water used in the treatment process
Content of 100 ppm or less, preferably about 10 ppm
Can be processed.
【0013】本発明は上記のよう構成され、オゾンガス
処理工程として半導体素子形成用基板をオゾンガス等オ
ゾン含有ガスで乾式酸化分解処理することから、従来の
酸素プラズマ処理と異なり基板又は基板上の微細な電気
的回路や配線、素子構造、構成材にダメージを与えるこ
となく基板上の有機化合物を酸化分解できる。例えば、
化学的に活性なAl、W、Cu等の材料を用いた素子基
板においても、オゾンガスはチッ化シリコンなどの保護
膜を透過せず、配線材にダメージを与えずに基板上の有
機化合物を酸化分解処理できる。特に、従来の乾式オゾ
ン処理と異なり基板表面上の温度を300℃程度に加温
すると共に、従来に比し高オゾン濃度のオゾン含有ガス
を用いることから効果的にレジストを除去できる。ま
た、プラズマを用いないことから処理チャンバー内を真
空にする必要もなく、基板を常圧の緩やかな条件下で処
理でき基板へのストレスを軽減でき、装置構成材料への
ダメージも軽減できる。更に、要すれば、オゾンガス耐
性を有する表面処理を行い装置の損傷を未然に防止する
こともできる。Since the present invention is configured as described above and the substrate for semiconductor element formation is subjected to the dry oxidative decomposition treatment with the ozone-containing gas such as ozone gas as the ozone gas treatment step, unlike the conventional oxygen plasma treatment, the substrate or the fine substrate on the substrate is finely divided. The organic compound on the substrate can be decomposed by oxidation without damaging the electric circuit, wiring, element structure, and constituent materials. For example,
Even in a device substrate made of a chemically active material such as Al, W, and Cu, ozone gas does not pass through a protective film such as silicon nitride and oxidizes an organic compound on the substrate without damaging the wiring material. Can be decomposed. Particularly, unlike the conventional dry ozone treatment, the temperature on the substrate surface is heated to about 300 ° C. and the ozone-containing gas having a higher ozone concentration than that of the conventional one is used, so that the resist can be effectively removed. Further, since the plasma is not used, it is not necessary to make the inside of the processing chamber vacuum, the substrate can be processed under a moderate condition of normal pressure, stress on the substrate can be reduced, and damage to the material constituting the device can be reduced. Further, if necessary, surface treatment having ozone gas resistance can be performed to prevent damage to the device.
【0014】オゾン水処理工程であるオゾン水による湿
式処理は、乾式オゾンガス処理工程で用いた同様のオゾ
ン含有ガスを超純水に溶解させて酸化力を有するオゾン
水とし、オゾンガス処理工程の乾式酸化分解処理後の残
渣又は乾式処理後に残留する若干のレジストである有機
化合物の酸化分解を行なう。オゾン水は、硫酸等酸性溶
液に比してAl等のメタル材へのダメージは僅かであ
り、配線材の腐食を最小限にして残渣又は有機化合物を
効率よく除去できる。また、従来の硫酸と過酸化水素の
超純水混合溶液による処理が100℃以上の高温で処理
されているのに対して、本発明のオゾン水処理は基本的
には常温で処理可能であり、昨今問題とされるクリーン
ルーム内の化学汚染物であるSOxを排出しない。ま
た、処理後の廃液はオゾンガスと水に直ちに分離され、
オゾンガスはフレア法、UVランプ法を用いることによ
り水と酸素に分解でき、従来の硫酸を用いる処理に比し
廃液処理コストが低減できる。処理に用いるオゾン水は
基本的に水であり、従来の硫酸を用いる湿式酸化法に比
し超純水によるリンスの使用量も低減できる。なお、本
発明のオゾン水処理工程においては、要すれば塩酸等の
酸成分を約100ppm、好ましくは10ppm添加し
てもよい。金属汚染物の除去のためである。In the wet treatment with ozone water, which is the ozone water treatment step, the same ozone-containing gas used in the dry ozone gas treatment step is dissolved in ultrapure water to obtain ozone water having oxidizing power, and dry oxidation in the ozone gas treatment step is carried out. Oxidative decomposition of the residue after the decomposition treatment or a small amount of the organic compound which is the resist remaining after the dry treatment is performed. Ozone water causes less damage to a metal material such as Al than an acidic solution such as sulfuric acid, and can effectively remove a residue or an organic compound while minimizing corrosion of a wiring material. Further, whereas the conventional treatment with the ultrapure water mixed solution of sulfuric acid and hydrogen peroxide is conducted at a high temperature of 100 ° C. or higher, the ozone water treatment of the present invention can be basically conducted at room temperature. It does not emit SOx, which is a chemical pollutant in the clean room, which has become a problem these days. In addition, the waste liquid after treatment is immediately separated into ozone gas and water,
Ozone gas can be decomposed into water and oxygen by using the flare method and the UV lamp method, and the waste liquid treatment cost can be reduced as compared with the conventional treatment using sulfuric acid. The ozone water used for the treatment is basically water, and the amount of rinse used with ultrapure water can be reduced as compared with the conventional wet oxidation method using sulfuric acid. In the ozone water treatment step of the present invention, if necessary, an acid component such as hydrochloric acid may be added in an amount of about 100 ppm, preferably 10 ppm. This is for removing metal contaminants.
【0015】本発明の水素水処理工程による処理は、水
素ガス含有ガスを超純水に溶解させた水素水を用いるこ
とから、従来の湿式酸化処理のように多量のアンモニア
を使用せずFe汚染レベルを低減でき、また、問題とさ
れているクリーンルーム内のアンモニア汚染も生じな
い。更に、超音波照射して活性化することから異物を有
効に除去できる。従来のアンモニアと過酸化水素の超純
水混合溶解液による処理が上記したように70℃以上で
処理するのに対し、本発明の水素水処理は、基本的には
常温で処理できエッチング等による表面粗化が軽減され
る。また、上記オゾン水処理工程と同様に、水素水は基
本的に水であり超純水によるリンス使用量が低減され
る。なお、本発明の水素水処理工程においては、要すれ
ばアンモニア等のアルカリ成分を約100ppm、好ま
しくは10ppm添加してもよい。微粒子除去の効率を
向上させるためである。Since the hydrogen water treatment step of the present invention uses hydrogen water in which a hydrogen gas-containing gas is dissolved in ultrapure water, it does not use a large amount of ammonia as in the conventional wet oxidation treatment and Fe contamination. The level can be reduced, and ammonia contamination in the clean room, which is a problem, does not occur. Further, since ultrasonic waves are activated and activated, foreign substances can be effectively removed. Whereas the conventional treatment with a mixed solution of ammonia and hydrogen peroxide in ultrapure water is performed at 70 ° C. or higher as described above, the hydrogen water treatment of the present invention can be performed basically at room temperature by etching or the like. Surface roughening is reduced. Further, as in the ozone water treatment step, hydrogen water is basically water, and the amount of rinse used by ultrapure water is reduced. In the hydrogen water treatment step of the present invention, if necessary, an alkaline component such as ammonia may be added in an amount of about 100 ppm, preferably 10 ppm. This is to improve the efficiency of removing fine particles.
【0016】更に、本発明の半導体素子形成用基板表面
処理法は、上記オゾンガス処理工程、オゾン水処理工程
及び水素水処理工程を含むようにシーケンスを設定して
一連の連続処理として行うことができる。この場合、オ
ゾンガス処理工程は基本的に必須工程であり、通常、第
1工程として採用される。しかし、例えば、オゾン水処
理工程を行った後にオゾンガス処理工程を行うこともで
き、この場合はオゾン水処理後の表面水分を触媒的に利
用してオゾンガス酸化分解を開始させ、最終的には乾式
オゾン酸化分解を行うものである。また、オゾンガス処
理工程と水素水処理工程の2工程のみで処理することも
できる。例えば、基板材料から酸化についてそれ程おそ
れずに処理できる場合は、オゾンガス処理を強度に行い
レジスト及び有機物化合物をほぼ完全に酸化分解し、オ
ゾン水処理を省略することができる。更にまた、本発明
の半導体素子形成用基板表面処理法は、特に、オゾン水
処理工程及び水素水処理工程による洗浄処理を同一洗浄
装置を用いて連続処理が可能であり、処理時間及び処理
コストが従来に比し大幅に削減できる。即ち、基板上の
フォトレジストや微細異物を洗浄処理して除去する従来
法は、乾式酸化分解処理後の各洗浄ステップが分離され
ており、それらの処理槽も完全分離していることから、
次ステップへ移行する前に超純水による中間リンスが必
要であり処理時間及び処理コストが嵩んでいたのに対す
る。Further, the semiconductor element forming substrate surface treatment method of the present invention can be carried out as a series of continuous treatments by setting a sequence so as to include the ozone gas treatment step, the ozone water treatment step and the hydrogen water treatment step. . In this case, the ozone gas treatment step is basically an essential step and is usually adopted as the first step. However, for example, the ozone gas treatment step can be performed after the ozone water treatment step. In this case, the ozone water oxidative decomposition is initiated by catalytically utilizing the surface water content after the ozone water treatment, and finally the dry type is used. It performs ozone oxidation decomposition. Further, it is also possible to perform the treatment only in two steps of the ozone gas treatment step and the hydrogen water treatment step. For example, if the substrate material can be treated without fear of oxidation, ozone gas treatment can be intensively performed to almost completely oxidize and decompose the resist and organic compounds, and the ozone water treatment can be omitted. Furthermore, in the semiconductor element forming substrate surface treatment method of the present invention, particularly, the cleaning treatment by the ozone water treatment step and the hydrogen water treatment step can be continuously performed by using the same cleaning apparatus, and the treatment time and the treatment cost can be reduced. It can be significantly reduced compared to the past. That is, in the conventional method of cleaning and removing the photoresist and fine foreign matter on the substrate, each cleaning step after the dry oxidative decomposition treatment is separated, and the processing tanks thereof are also completely separated,
On the other hand, intermediate rinsing with ultrapure water was required before moving to the next step, which increased processing time and processing cost.
【0017】[0017]
【発明の実施の形態】本発明について更に詳しく説明す
る。本発明において、表面処理する被処理基板は、半導
体素子即ち微細な電気的な素子や回路を有す基板であ
り、シリコン(Si)等の半導体基板、ガラス等の絶縁
基板等の各種半導体素子形成用基板であって、特に、半
導体素子の製造工程において微小な電気的素子と回路の
形成又は局所的にドーパント拡散又はエッチング処理を
行った後の基板である。本発明は、主に上記の基板表面
上に残留するフォトレジストの酸化分解とその後の残存
異物の洗浄処理からなる表面処理方法である。即ち、第
1はオゾンガスを用いる乾式酸化分解処理であり、第2
はその後に主に残存する有機系異物をオゾン水で処理
し、第3は次いで残存パーティクルを水素水で処理する
ことを組合わせて処理するものである。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail. In the present invention, the substrate to be surface-treated is a semiconductor element, that is, a substrate having a fine electric element or circuit, and various semiconductor element formation such as a semiconductor substrate such as silicon (Si) or an insulating substrate such as glass. In particular, it is a substrate for use after formation of minute electric elements and circuits or local dopant diffusion or etching treatment in a semiconductor element manufacturing process. The present invention is a surface treatment method mainly consisting of oxidative decomposition of the photoresist remaining on the surface of the substrate and subsequent cleaning treatment of residual foreign matters. That is, the first is a dry oxidative decomposition process using ozone gas, and the second is
After that, mainly the remaining organic foreign matter is treated with ozone water, and the third is a treatment in which residual particles are then treated with hydrogen water in combination.
【0018】本発明のオゾンガス処理工程であるオゾン
ガス乾式酸化分解処理は、従来の乾式酸化分解で用いる
酸素プラズマを使用することなく、被処理基板を室温以
上、好ましくは300〜350℃に加温して、酸素無声
放電により得られる約4〜8容量%のオゾン含有ガスを
装置の処理チャンバー内に導入することにより行うこと
ができる。本発明のオゾンガス処理工程では、例えば、
図1の模式説明図に示したような枚葉式の酸化分解処理
装置を用いることができる。図1において、酸化分解装
置10のチャンバー11は自動開閉されるようになって
おり、チャンバー11内部には半導体素子形成用基板1
2を3点保持する機構の石英製サセプター13を有す
る。チャンバー開閉と連動して半導体素子形成用基板の
送出入及び石英サセプター13への静置ができる。チャ
ンバー11はオゾンガスによる酸化分解処理前に密閉さ
れ基板12はサセプター13を介してヒーター14にて
裏面側より加温される。一方、オゾン含有ガスは、空
気、酸素等の酸素含有ガスの無声放電式や電解式のオゾ
ン発生器により得て用いることができる。図1におい
て、酸化分解装置10に、例えば無声放電によるオゾン
発生器15を設置し酸素含有ガスをフィルター16を経
て無声放電式オゾン発生器15に送入し濃度約4〜8容
量%のオゾン含有ガスを発生させてチャンバー11に配
設された拡散器17に導入される。オゾン含有ガスは拡
散器17によりチャンバー11内で効率よく拡散され
る。オゾン酸化分解処理後は、窒素ガスを酸素含有ガス
と同様にフィルターを経てチャンバー11内に導入し処
理雰囲気のオゾンを速やかに置換パージする。このとき
オゾンガスを大気開放しないためにパージ排気ガスは、
排気ライン18からオゾン分解処理装置(図示せず)に
送入してオゾンガスを酸素ガスとして装置外に排気す
る。なお、オゾン発生器15からのオゾン含有ガス及び
パージ用窒素ガスは、それぞれ送入ラインに配置された
流量(質量)調節計により流量制御されチャンバー11
に送入される。また、チャンバー11下方にはスピンモ
ータ19が配置されサセプター13を回転しその上に載
置された基板を回転させる。In the ozone gas dry oxidative decomposition treatment which is the ozone gas processing step of the present invention, the substrate to be processed is heated to room temperature or higher, preferably 300 to 350 ° C., without using oxygen plasma used in the conventional dry oxidative decomposition. Then, an ozone-containing gas of about 4 to 8% by volume obtained by the silent oxygen discharge is introduced into the processing chamber of the apparatus. In the ozone gas treatment step of the present invention, for example,
A single-wafer oxidative decomposition treatment apparatus as shown in the schematic explanatory view of FIG. 1 can be used. In FIG. 1, the chamber 11 of the oxidative decomposition apparatus 10 is designed to be automatically opened and closed, and the semiconductor element forming substrate 1 is provided inside the chamber 11.
It has a susceptor 13 made of quartz that holds 2 points at 3 points. The semiconductor element forming substrate can be fed in and out and allowed to stand still on the quartz susceptor 13 in conjunction with opening and closing of the chamber. The chamber 11 is hermetically sealed before the oxidative decomposition treatment with ozone gas, and the substrate 12 is heated from the back side by the heater 14 via the susceptor 13. On the other hand, the ozone-containing gas can be obtained by using a silent discharge type or electrolytic type ozone generator of an oxygen-containing gas such as air or oxygen. In FIG. 1, for example, an ozone generator 15 by silent discharge is installed in an oxidative decomposition apparatus 10, and an oxygen-containing gas is sent to a silent discharge ozone generator 15 through a filter 16 to contain ozone having a concentration of about 4 to 8% by volume. A gas is generated and introduced into the diffuser 17 arranged in the chamber 11. The ozone-containing gas is efficiently diffused in the chamber 11 by the diffuser 17. After the ozone oxidative decomposition treatment, nitrogen gas is introduced into the chamber 11 through the filter in the same manner as the oxygen-containing gas, and ozone in the treatment atmosphere is promptly replaced and purged. At this time, the purge exhaust gas is
The ozone gas is sent from the exhaust line 18 to an ozone decomposition treatment device (not shown) and the ozone gas is exhausted outside the device as oxygen gas. The flow rate of the ozone-containing gas from the ozone generator 15 and the purging nitrogen gas are controlled by a flow rate (mass) controller arranged in the feed line, respectively, and the chamber 11 is controlled.
Sent to. A spin motor 19 is arranged below the chamber 11 to rotate the susceptor 13 and rotate the substrate placed thereon.
【0019】本発明において、通常上記オゾンガス処理
工程後になされるオゾン水処理工程は、オゾン水による
湿式洗浄処理であり、オゾン水中のオゾン濃度は約20
〜60ppmが好ましい。オゾン水の酸化力は溶存オゾ
ン濃度に依存し、被処理基板の性状に応じて上記オゾン
濃度範囲で適宜選択することができる。例えば、ガス状
有機物による汚染物や酸化分解処理後残渣であれば、約
20〜30ppmの中程度の濃度でよく、また、イオン
注入量が多い場合や加熱処理されたレジストで酸化分解
処理によっても残留した有機化合物の除去は約50〜6
0ppmの高濃度が好適である。本発明のオゾン水は、
加圧溶解により溶解オゾン濃度を高濃度化して用いるこ
とにより上記のような残存有機化合物の酸化分解が可能
である。本発明において、オゾン含有ガスとしては、上
記オゾン含有ガス処理と同様に酸素等の無声放電による
オゾン含有ガスを用いることができる外、電解式のオゾ
ン発生器で得られるオゾン含有ガスを用いることができ
る。発生されたオゾン含有ガスは加圧して高濃度オゾン
水として用いることでフォトレジストアッシング後に残
留する強固な有機物残渣やアッシング後に残留するレジ
ストをオゾン水処理で除去できる。一方、従来の基板の
湿式オゾン洗浄で用いられるオゾン溶解水液は一般に2
0ppm程度の溶解レベルであり、このようなオゾン溶
解液では上記のアッシング後の有機物残渣やレジストを
除去することはできなかった。また、本発明のオゾン水
処理工程の湿式処理システムは、従来の開放系で行われ
る湿式処理と異なり加圧処理のため閉鎖系で行うことか
ら安全の面でも危険が回避される。更に、オゾン水はオ
ゾン発生器からの発生オゾン含有ガスを用いて調製して
使用し薬液槽に貯溜しないため液性状が安定し、処理後
の基板性状のばらつきも少ない。In the present invention, the ozone water treatment step usually performed after the ozone gas treatment step is a wet cleaning treatment with ozone water, and the ozone concentration in the ozone water is about 20.
-60 ppm is preferable. The oxidizing power of ozone water depends on the dissolved ozone concentration, and can be appropriately selected within the above ozone concentration range depending on the properties of the substrate to be treated. For example, if it is a pollutant due to a gaseous organic substance or a residue after oxidative decomposition treatment, it may have a medium concentration of about 20 to 30 ppm, or if a large amount of ion implantation is performed or a heat-treated resist is subjected to oxidative decomposition treatment. Removal of residual organic compounds is about 50-6
A high concentration of 0 ppm is suitable. The ozone water of the present invention is
By increasing the concentration of dissolved ozone by pressure dissolution and using it, oxidative decomposition of the above-mentioned residual organic compound is possible. In the present invention, as the ozone-containing gas, an ozone-containing gas obtained by a silent discharge of oxygen or the like can be used as in the ozone-containing gas treatment, and an ozone-containing gas obtained by an electrolytic ozone generator can be used. it can. The generated ozone-containing gas is pressurized to be used as high-concentration ozone water, whereby a strong organic residue remaining after photoresist ashing and a resist remaining after ashing can be removed by ozone water treatment. On the other hand, the ozone-dissolved water liquid used in the conventional wet ozone cleaning of the substrate is generally 2
The dissolution level was about 0 ppm, and it was not possible to remove the organic residue and the resist after the above ashing with such an ozone solution. Further, the wet treatment system of the ozone water treatment step of the present invention is different from the conventional wet treatment performed in an open system, and since it is performed in a closed system because it is a pressure treatment, danger can be avoided in terms of safety. Further, since the ozone water is prepared by using the ozone-containing gas generated from the ozone generator and is not stored in the chemical liquid tank, the liquid property is stable, and the substrate property after the treatment has little variation.
【0020】本発明における水素水処理工程は、上記の
オゾン水処理工程と同様に湿式洗浄処理であり水素水に
より洗浄処理するものである。本発明においては、少な
くとも1ppm以上の水素ガスを超純水に溶解した水素
水を用いて超音波照射して洗浄する。前記したように特
開平10−128253号公報で提案される水素ガス
0.05ppm以上溶解した水素水に基板を浸漬し超音
波照射する方法は、洗浄・リンス処理について開示する
ものであり、特に、本発明において目的とするオゾン含
有ガスによる基板上のフォトレジストの乾式酸化分解後
に残存する有機物系残渣や有機物系化合物に端を発する
微細異物の除去、即ち、レジストをアッシングした後に
残留する微細異物を除去することについては何ら開示し
ていない。しかも、これらを実用的に洗浄除去するため
の好適な水素溶解濃度は少なくとも1ppm以上であ
り、好ましくは1.2〜2.0ppmであり、これらは
発明者らにより初めて確認されたものである。水素水処
理工程において用いる水素含有ガスも、オゾン水処理工
程のオゾン含有ガスと同様に電解方式で得られる水素ガ
スを用いることができる。また、水素水のORP値は、
約−550mVであり粒子と基板上の表面電位が同じ負
にチャージするため静電的な反発によっても効率的に除
去される。また、超音波によるキャビテーションの効果
によって物理的にもパーティクルは除去され、且つ、水
素や水酸基等のラジカルが発生するために極めて薄い有
機膜等の分解が行われる。また、水素水は基本的に静電
的な反発力を利用するため、化学的除去方法に対してパ
ーティクルの組成にあまり影響されず、イオン注入され
る物質の種類にあまり影響されないThe hydrogen water treatment step in the present invention is a wet cleaning treatment similar to the above ozone water treatment step, and is a cleaning treatment with hydrogen water. In the present invention, cleaning is performed by ultrasonic irradiation using hydrogen water in which at least 1 ppm or more of hydrogen gas is dissolved in ultrapure water. As described above, the method of immersing a substrate in hydrogen water having a hydrogen gas content of 0.05 ppm or more and irradiating ultrasonic waves proposed in JP-A-10-128253 discloses a cleaning / rinsing treatment, and in particular, In the present invention, the removal of fine foreign matters originating from the organic residue and organic compounds remaining after the dry oxidative decomposition of the photoresist on the substrate by the ozone-containing gas targeted in the present invention, that is, the fine foreign matters remaining after ashing the resist, It does not disclose any removal. Moreover, a suitable hydrogen dissolution concentration for practically washing and removing these is at least 1 ppm or more, preferably 1.2 to 2.0 ppm, which were first confirmed by the inventors. As the hydrogen-containing gas used in the hydrogen water treatment step, the hydrogen gas obtained by the electrolysis method can be used similarly to the ozone-containing gas in the ozone water treatment step. Also, the ORP value of hydrogen water is
It is about −550 mV, and the surface potentials on the particles and the substrate are negatively charged, so that they are efficiently removed by electrostatic repulsion. Further, particles are physically removed by the effect of cavitation by ultrasonic waves, and radicals such as hydrogen and hydroxyl groups are generated, so that an extremely thin organic film or the like is decomposed. In addition, since hydrogen water basically uses electrostatic repulsion, the composition of particles is less affected by the chemical removal method, and the type of ion-implanted material is less affected.
【0021】本発明において、上記オゾン水処理工程及
び水素水処理工程の湿式洗浄処理は必要に応じて同一装
置を用いて行うことができ、オゾン水処理工程及び水素
水処理工程の湿式洗浄処理を連続的に一括して行うこと
ができる。これら湿式洗浄処理は、例えば、図2の模式
説明図に示したような湿式洗浄処理装置を用いることが
できる。なお、図2の湿式洗浄処理装置20における構
成部材で上記図1に示した装置と同様の構成部材につい
ては同一符号を付し説明を省略する。図2において、被
処理基板12はチャンバー11のカップ21内でバキュ
ーム式チャック22で保持される。チャック方式はバキ
ューム式及び側面保持式があり、いずれの方式でもよ
い。一方、湿式洗浄処理装置20にはオゾン水調製器2
3及び水素水調製器24が設置され、オゾン水及び水素
水はそれぞれ濃度等を調整され流量(質量)調節計で流
量制御されて流入ラインを経由してチャンバーカップ2
1内に流入される。チャック22に保持された基板12
に対し、オゾン水はノズル(図示せず)を介して放出さ
れ、水素水は可動式の超音波発生器付ディスペンサー2
5から放出される。また、湿式洗浄処理装置20は、酸
成分供給器26及びアルカリ成分供給器27を設置し、
必要に応じて、金属汚染除去のためオゾン水中に微量、
例えば10ppm添加する塩酸、硫酸等の酸成分や、微
粒子除去の効率を向上するため水素水中に同様に微量、
10ppm添加するアンモニア等のアルカリ成分を、オ
ゾン水若しくは水素水と同時に/又はオゾン水若しくは
水素水に混入させてチャンバーカップ21内に注入でき
るようになっている。更に、超純水(DIW)供給機構
28を配設し、各溶液洗浄処理後の基板を洗浄するため
チャンバーカップ21内の上方及び下方からノズルを介
して超純水を流出できる。各薬液で湿式洗浄処理後、超
純水にてリンス洗浄処理した基板は3000rpmで回
転させいわゆるスピンドライ方式によって乾燥する。ま
た、高濃度化オゾン水等を流入させることから洗浄装置
内から溶存オゾンガスが大気中に放出しないように、適
宜、筐体排気設備(図示せず)を配設する。更に、高濃
度オゾンガスが直接排気されないように、上記図1の酸
化分解装置10と同様に排気ライン18から熱分解処理
装置又はUVランプ分解処理装置(図示せず)に送入し
てオゾンガスを酸素ガスとして装置外に排気する。下記
する実施例では熱分解処理装置を用い分解し排出した。In the present invention, the wet cleaning treatment of the ozone water treatment step and the hydrogen water treatment step can be carried out by using the same apparatus as needed, and the wet cleaning treatment of the ozone water treatment step and the hydrogen water treatment step can be performed. It can be done continuously and collectively. For these wet cleaning treatments, for example, a wet cleaning treatment apparatus as shown in the schematic explanatory view of FIG. 2 can be used. The same components as those of the apparatus shown in FIG. 1 among the components of the wet cleaning apparatus 20 of FIG. 2 are designated by the same reference numerals and the description thereof will be omitted. In FIG. 2, the substrate 12 to be processed is held in the cup 21 of the chamber 11 by the vacuum chuck 22. The chuck method includes a vacuum method and a side holding method, and any method may be used. On the other hand, the wet cleaning treatment device 20 includes an ozone water preparation device 2
3 and a hydrogen water preparation device 24 are installed, the concentration of ozone water and hydrogen water are adjusted, and the flow rate is controlled by a flow rate (mass) controller.
1 is flowed into. Substrate 12 held by chuck 22
On the other hand, ozone water is discharged through a nozzle (not shown), and hydrogen water is a movable ultrasonic wave generator-equipped dispenser 2
Emitted from 5. Further, the wet cleaning processing apparatus 20 is provided with an acid component supplier 26 and an alkaline component supplier 27,
If necessary, trace amount in ozone water to remove metal contamination,
For example, acid components such as hydrochloric acid and sulfuric acid added at 10 ppm, and a trace amount in hydrogen water to improve the efficiency of removing fine particles,
An alkaline component such as ammonia added at 10 ppm can be injected into the chamber cup 21 simultaneously with ozone water or hydrogen water and / or by being mixed with ozone water or hydrogen water. Further, an ultrapure water (DIW) supply mechanism 28 is provided so that the ultrapure water can flow out from above and below the inside of the chamber cup 21 through the nozzle to wash the substrate after each solution washing process. After the wet cleaning treatment with each chemical, the substrate rinsed with ultrapure water is rotated at 3000 rpm and dried by a so-called spin dry method. Further, a casing exhaust facility (not shown) is appropriately arranged so that the dissolved ozone gas is not released into the atmosphere from the inside of the cleaning device due to the inflow of highly concentrated ozone water or the like. Further, in order to prevent the high-concentration ozone gas from being directly exhausted, the ozone gas is sent to the thermal decomposition treatment device or the UV lamp decomposition treatment device (not shown) from the exhaust line 18 similarly to the oxidation decomposition device 10 of FIG. Exhaust out of the device as gas. In the examples described below, a thermal decomposition treatment apparatus was used to decompose and discharge.
【0022】本発明において、例えば、オゾン水処理工
程後にオゾンガス処理工程で処理する場合は、3工程を
同一装置で行ってもよい。このため表面処理操作が簡便
化される外、一連の処理による設備費及び処理時間が従
来の方法に比し低減され好ましい。但し、設計条件や操
作条件等により各湿式洗浄処理を別々の装置を用いて行
ってもよい。本発明の湿式洗浄処理を行うための装置
は、オゾン水を発生させる装置、又は、オゾン含有ガス
と超純水を気液接触してオゾン水とする機構を有す部位
と接続することによりオゾン水を供給できる。また、水
素水も同様である。オゾン水又は水素水による処理は、
全て例えば25℃の常温で行うことができ、要すれば適
宜加温して行ってもよい。更に、上記したようにオゾン
含有ガス及び水素ガスは、いずれも電解式オゾン発生装
置において得ることができることから、本発明の半導体
素子用基板表面処理方法と電解式オゾン発生装置とを組
合わせ、陽極より発生するオゾン含有ガスをオゾンガス
処理工程及びオゾン水処理工程に用い、陰極より発生す
る水素ガスを水素水処理工程に用いることにより、各処
理工程に要するオゾン含有ガス、オゾン水及び水素水を
効率的に製造でき、装置が簡略化でき且つ操作も簡便と
なる。In the present invention, for example, when the ozone gas treatment step is followed by the ozone gas treatment step, the three steps may be carried out by the same apparatus. Therefore, the surface treatment operation is simplified, and the equipment cost and treatment time for a series of treatments are reduced as compared with the conventional method, which is preferable. However, each wet cleaning process may be performed using different devices depending on design conditions, operating conditions, and the like. The apparatus for performing the wet cleaning treatment of the present invention is an apparatus for generating ozone water, or ozone by connecting to a portion having a mechanism for making ozone water by gas-liquid contact of ozone-containing gas and ultrapure water. Can supply water. The same applies to hydrogen water. Treatment with ozone water or hydrogen water
All can be performed at room temperature, for example, 25 ° C., and may be appropriately heated if necessary. Further, as described above, since both the ozone-containing gas and the hydrogen gas can be obtained in the electrolytic ozone generator, the method for treating the substrate surface of the semiconductor element of the present invention and the electrolytic ozone generator are combined to produce an anode. By using the ozone-containing gas generated from the ozone gas treatment step and the ozone water treatment step and using the hydrogen gas generated from the cathode in the hydrogen water treatment step, the ozone-containing gas, ozone water and hydrogen water required for each treatment step can be efficiently used. Manufacture, the device can be simplified, and the operation is simple.
【0023】[0023]
【実施例】以下、本発明を実施例に基づき更に詳細に説
明する。但し、本発明は下記実施例に制限されるもので
ない。
(試料作成)試料として8インチ(8”)CZ法(チョ
クラルスキー法)により調製されたシリコン(Si)ウ
ェハを、ウェット浸漬型洗浄装置にてNH3と過酸化水
素を超純水に混合溶解した溶解液(NH3:超純度過酸
化水素:超純水=1:1:8)に浸漬し、70℃で超音
波照射処理した。処理したウェハは乾燥後、i線(36
5nm)感光有機化合物を枚葉式スピンコーターにて膜
厚が約12000Åになるように塗布し、i線で25秒
間全面露光を行いフォトレジストを感光させた。感光後
に窒素(N2)気流中にてウェハをベークした。また、
チャンバー内を約10−3Torrに吸引減圧しCF4
乾式エッチングを40秒行ない、試料Aを得た。また、
上記と同様に有機化合物を塗布、感光後、BF2又はA
sをイオン注入した試料を用意した。BF2のドーズ量
が5.0×1013atoms/cm2(加速電圧:1
5keV)を試料B、Asのドーズ量が8.0×10
13atoms/cm2(加速電圧:30keV)を試
料C、BF2のドーズ量が3.0×1015atoms
/cm2(加速電圧:20keV)を試料D、Asのド
ーズ量が2.0×1015atoms/cm2(加速電
圧:40keV)を試料Eとした。試料作成条件を表1
にまとめて示した。各試料は何れも光干渉型膜厚測定装
置にて有機化合物膜厚を測定し、表1に併せて示した。EXAMPLES The present invention will be described in more detail based on the following examples. However, the present invention is not limited to the following examples. (Sample preparation) A silicon (Si) wafer prepared by the 8-inch (8 ") CZ method (Czochralski method) as a sample is dissolved by dissolving NH3 and hydrogen peroxide in ultrapure water with a wet immersion type cleaning device. Was immersed in a solution (NH3: ultrapure hydrogen peroxide: ultrapure water = 1: 1: 8) and subjected to ultrasonic irradiation at 70 ° C. The treated wafer was dried and then subjected to i-line (36
(5 nm) A photosensitive organic compound was applied by a single-wafer spin coater to a film thickness of about 12,000 Å, and the whole surface was exposed to i-line for 25 seconds to expose the photoresist. After exposure, the wafer was baked in a nitrogen (N 2 ) gas stream. Also,
The inside of the chamber is suctioned and depressurized to about 10 −3 Torr and CF 4 is added.
Dry etching was performed for 40 seconds to obtain sample A. Also,
Similarly to the above, after applying an organic compound and exposing, BF 2 or A
A sample in which s was ion-implanted was prepared. The dose amount of BF 2 is 5.0 × 10 13 atoms / cm 2 (accelerating voltage: 1
5 keV) is the sample B and the dose amount of As is 8.0 × 10.
13 atoms / cm 2 (accelerating voltage: 30 keV) was used as the sample C and the dose amount of BF 2 was 3.0 × 10 15 atoms.
/ Cm 2 (accelerating voltage: 20 keV) was used as sample D, and the dose amount of As was 2.0 × 10 15 atoms / cm 2 (accelerating voltage: 40 keV) as sample E. Table 1 shows sample preparation conditions
Are summarized in. For each sample, the film thickness of the organic compound was measured by a light interference type film thickness measuring device and is also shown in Table 1.
【0024】[0024]
【表1】 [Table 1]
【0025】実施例1
オゾンガス処理工程(乾式オゾン酸化分解処理)→オゾ
ン水処理工程(オゾン濃度:20ppm)→水素水処理
工程のシーケンスで試料A、B及びCをそれぞれ順次処
理した。上記図1と同様に構成された酸化分解装置10
を用いて、サセプター13上でオゾンガス処理工程の処
理前に約60秒間各試料の加温を行なった。試料Aは、
温度300℃で72秒間オゾン濃度4容量%のオゾン含
有酸素ガスを流量10リットル/分で流通させ処理し
た。試料Bは温度300℃で180秒間オゾン濃度容量
5%のオゾン含有酸素ガスを流量12リットル/分で流
通させ処理した。試料Cは温度350℃で200秒間オ
ゾン濃度5容量%のオゾン含有酸素ガスを流量14リッ
トル/分で流通させ処理した。試料は何れも光干渉型膜
厚測定装置にてフォトレジスト厚を測定し結果を表2に
示した。この結果、オゾン含有ガス酸化分解処理で基板
上のフォトレジストはほぼ完全に除去され、残留は確認
されないことが分かった。このため、オゾンガス処理工
程後の基板上のパーティクルをレーザー光散乱型パーテ
ィクルカウンターで粒子サイズ0.2μm以上のものを
測定した。その結果によれば基板上にフォトレジスト自
体は残存しないが、オゾンガス処理後の残渣が残存する
ことが分った。また、基板表面には若干のフォトレジス
ト片等も確認された。これらはカーボン、シリコンの酸
化化合物を主成分とした異物であった。更に、比較的サ
イズの大きな粒子が残留することも確認された。Example 1 Samples A, B and C were sequentially treated in the sequence of ozone gas treatment step (dry ozone oxidative decomposition treatment) → ozone water treatment step (ozone concentration: 20 ppm) → hydrogen water treatment step. Oxidation / decomposition device 10 having the same structure as that of FIG.
Was used to heat each sample on the susceptor 13 for about 60 seconds before the ozone gas treatment step. Sample A is
Ozone-containing oxygen gas having an ozone concentration of 4% by volume was circulated at a temperature of 300 ° C. for 72 seconds at a flow rate of 10 l / min for treatment. Sample B was treated at a temperature of 300 ° C. for 180 seconds by flowing an ozone-containing oxygen gas having an ozone concentration capacity of 5% at a flow rate of 12 liters / minute. Sample C was treated by flowing ozone-containing oxygen gas having an ozone concentration of 5% by volume at a temperature of 350 ° C. for 200 seconds at a flow rate of 14 l / min. The thickness of each of the samples was measured with an optical interference type film thickness measuring device, and the results are shown in Table 2. As a result, it was found that the photoresist on the substrate was almost completely removed by the ozone-containing gas oxidative decomposition treatment, and no residue was confirmed. Therefore, the particles on the substrate after the ozone gas treatment step were measured with a laser light scattering type particle counter to have a particle size of 0.2 μm or more. According to the result, it was found that the photoresist itself did not remain on the substrate, but the residue after the ozone gas treatment remained. Also, some photoresist pieces and the like were confirmed on the substrate surface. These were foreign substances containing carbon and silicon oxide compounds as main components. Further, it was confirmed that relatively large particles remained.
【0026】[0026]
【表2】 [Table 2]
【0027】次に、上記のようにオゾンガス処理工程に
て酸化分解処理した各試料を上記図2と同様に構成され
た装置を用いてオゾン水にて洗浄処理した。オゾン水は
装置20のノズルから吐出し、各試料を共に1000r
pmで回転させ、試料Aは30秒、試料Bは45秒、試
料Cは60秒それぞれ同様に処理した。処理前後の0.
2μm以上のパーティクルをレーザー光散乱型パーティ
クルカウンターで測定し、その結果を表2に示した。オ
ゾン水処理工程後はカウントされるパーティクル数は減
少し、かつ粒子サイズのピークは約5μmから約1μm
にシフトし、残留していたフォトレジスト片等の比較的
大きな異物がオゾン水処理によって酸化分解されること
が分かる。Next, each sample subjected to the oxidative decomposition treatment in the ozone gas treatment step as described above was washed with ozone water using the apparatus having the same structure as that shown in FIG. Ozone water is discharged from the nozzle of the device 20, and each sample is 1000 r
The sample A was rotated for 30 seconds, the sample B was processed for 45 seconds, and the sample C was processed for 60 seconds. 0 before and after processing.
Particles of 2 μm or more were measured with a laser light scattering type particle counter, and the results are shown in Table 2. After the ozone water treatment process, the number of particles counted is reduced, and the particle size peak is about 5 μm to about 1 μm.
It can be seen that the relatively large foreign matter such as the photoresist pieces, which has been shifted to, is oxidized and decomposed by the ozone water treatment.
【0028】次いで、上記オゾン水処理工程で処理した
各試料に残留する微小なパーティクルを除去するため水
素水で処理した。各試料A、B及びCを共に1000r
pmで回転させて水素水を装置20の超音波発生器付デ
ィスペンサー25から放出して20秒間処理した。この
時の超音波の周波数は1.5MHzであった。レーザー
光散乱型パーティクルカウンターで同様に処理前後のパ
ーティクルを測定し結果を表2に示した。これらの結果
から本実施例の処理後に残留するパーティクル数は、従
来法に匹敵又はそれ以上に低減されることが明らかであ
る。Next, in order to remove fine particles remaining in each sample treated in the above ozone water treatment step, the sample was treated with hydrogen water. 1000r for each sample A, B and C
It was rotated at pm and hydrogen water was discharged from the dispenser 25 with an ultrasonic generator of the apparatus 20 and treated for 20 seconds. The frequency of ultrasonic waves at this time was 1.5 MHz. Particles before and after the treatment were similarly measured with a laser light scattering type particle counter, and the results are shown in Table 2. From these results, it is clear that the number of particles remaining after the treatment of this example is reduced to a level comparable to or higher than that of the conventional method.
【0029】実施例2
オゾンガス処理工程→オゾン水処理工程(オゾン濃度:
60ppm)→水素水処理工程のシーケンスで上記試料
A、D及びEををそれぞれ順次処理した。第1のオゾン
ガス処理工程での処理前に約60秒間各試料の加温を行
なった。試料Aは、温度300℃で72秒間オゾン濃度
4容量%のオゾン含有酸素ガスを流量10リットル/分
で流通させ処理した。試料Dは温度350℃で180秒
間オゾン濃度容量5%のオゾン含有酸素ガスを流量14
リットル/分で流通させ処理した。試料Eは温度350
℃で200秒間オゾン濃度6容量%のオゾン含有酸素ガ
スを流量16リットル/分で流通させ処理した。試料は
何れも光干渉型膜厚測定装置にてフォトレジスト厚を測
定し結果を表3に示した処理した。また、酸化分解処理
後はフォトレジストが各試料の基板中央部に残留してい
たためパーティクルは測定しなかった。Example 2 Ozone gas treatment step → ozone water treatment step (ozone concentration:
Samples A, D and E were sequentially treated in the sequence of 60 ppm) → hydrogen water treatment step. Each sample was heated for about 60 seconds before the treatment in the first ozone gas treatment step. Sample A was treated at a temperature of 300 ° C. for 72 seconds by flowing an ozone-containing oxygen gas having an ozone concentration of 4% by volume at a flow rate of 10 l / min. Sample D has a flow rate of ozone-containing oxygen gas of 5% at an ozone concentration capacity of 5% for 180 seconds at a temperature of 350 ° C.
It was circulated and processed at a rate of 1 liter / minute. Sample E has a temperature of 350
Ozone-containing oxygen gas having an ozone concentration of 6% by volume was flowed at a flow rate of 16 l / min for 200 seconds at 0 ° C. for processing. For each sample, the photoresist thickness was measured with an optical interference type film thickness measuring device, and the results were treated as shown in Table 3. In addition, since the photoresist remained in the center of the substrate of each sample after the oxidative decomposition treatment, particles were not measured.
【0030】[0030]
【表3】 [Table 3]
【0031】次いで、オゾンガス処理工程にて酸化分解
処理した各試料を実施例1と同様にしてオゾン水にて洗
浄処理した。各試料を共に1000rpmで回転させ、
試料Aは30秒、試料Dは90秒、試料Eは120秒そ
れぞれオゾン水をノズルから吐出して処理した。処理前
後の0.2μm以上のパーティクルをレーザー光散乱型
パーティクルカウンターで測定し、その結果を表3に示
した。オゾン水処理後の各試料には、フォトレジスト片
と思われる異物は殆ど確認されず残存フォトレジストが
完全に除去されていた。パーティクルの殆どは、カーボ
ン、シリコン系であると判断できた。Then, each sample subjected to the oxidative decomposition treatment in the ozone gas treatment step was washed with ozone water in the same manner as in Example 1. Rotate each sample together at 1000 rpm,
Sample A was processed for 30 seconds, sample D for 90 seconds, and sample E for 120 seconds by ejecting ozone water from the nozzle. Particles of 0.2 μm or more before and after the treatment were measured with a laser light scattering type particle counter, and the results are shown in Table 3. In each of the samples after the ozone water treatment, almost no foreign matter, which is considered to be a photoresist piece, was confirmed, and the residual photoresist was completely removed. Most of the particles could be determined to be carbon or silicon.
【0032】次に、上記オゾン水処理工程で処理した各
試料に残留するパーティクルを除去するため水素水で処
理した。各試料A、D及びEを共に1000rpmで回
転させて実施例1と同様にして水素水を超音波発生器付
ディスペンサー25から放出して20秒間処理した。こ
の時の超音波の周波数は1.5MHzであった。レーザ
ー光散乱型パーティクルカウンターで同様に処理前後の
パーティクルを測定し結果を表3に示した。Next, in order to remove particles remaining in each sample treated in the above-mentioned ozone water treatment step, the sample was treated with hydrogen water. Each sample A, D and E was rotated at 1000 rpm and hydrogen water was discharged from the dispenser 25 with an ultrasonic generator and treated for 20 seconds in the same manner as in Example 1. The frequency of ultrasonic waves at this time was 1.5 MHz. Particles before and after the treatment were similarly measured with a laser light scattering type particle counter, and the results are shown in Table 3.
【0033】これらの結果から、上記シーケンスにおけ
る基板処理は、オゾン水処理工程でオゾン濃度約60p
pmの高濃度オゾン水を使用することから有機物の除去
だけではなくフォトレジスト剥離も可能であることが明
らかである。従って、特に、酸化分解処理を可能な限り
避けたい場合に有効であり、例えばイオン注入の条件に
よっては乾式処理をある程度の処理に止めて、従来の酸
化分解処理後の硫酸と過酸化水素の超純水混合溶液での
処理と同等に適用することができる。これによりオゾン
ガス処理工程で酸化分解をある程度のフォトレジスト除
去に留め、次のオゾン水処理でフォトレジストと有機物
を同時に除去できることも明らかとなった。本実施例2
の処理後に残留するパーティクル数も、実施例1と同様
に従来法に匹敵又はそれ以上に低減されることが明らか
である。From these results, the substrate treatment in the above sequence is performed with the ozone water treatment step at an ozone concentration of about 60 p.
It is apparent that the use of pm high-concentration ozone water enables not only removal of organic substances but also photoresist stripping. Thus, in particular, is effective when it is desired to avoid as much as possible oxidative degradation treatment, for example, depending on the conditions of the ion implantation stop dry processing a certain processing, after conventional oxidation decomposition treatment of sulfuric acid and hydrogen peroxide It can be applied in the same manner as the treatment with the ultrapure water mixed solution. As a result, it became clear that in the ozone gas treatment step, the oxidative decomposition can be limited to the photoresist removal to some extent, and the next ozone water treatment can simultaneously remove the photoresist and the organic matter. Example 2
It is clear that the number of particles remaining after the treatment (1) is reduced to a level comparable to or more than that of the conventional method as in the first embodiment.
【0034】[0034]
【発明の効果】本発明は、半導体素子を形成する基板の
各種素子構造を形成後の不要なフォトレジストを除去す
る基板表面処理方法であり、オゾン含有ガス、高濃度オ
ゾン水と水素水を使用することから、基板上の有機物除
去のために硫酸やアンモニア等の酸成分やアルカリ成分
及び有機溶剤を用いる従来法に比し、環境負荷が小さく
且つ素子構造にダメージを与えることなく低コストとな
り、工業的に実用性に優れる。また、上記従来法で用い
た酸成分、アルカリ成分及び有機溶剤を用いないため、
半導体素子の構造や配線材料を著しく腐食することなく
ダメージを軽減する。また、デバイスの電気特性低下を
最小限にすることができ、素子性能の信頼性を向上させ
電気抵抗の低下、消費電力の低減、素子性能の高速化が
図れると同時に、製造歩留まりが向上し、且つ、半導体
製造装置のランニングコストの低減と安全性の向上も図
ることができる。The present invention is a substrate surface treatment method for removing unnecessary photoresist after forming various element structures of a substrate for forming a semiconductor element, using an ozone-containing gas, high-concentration ozone water and hydrogen water. Therefore, compared with the conventional method using an acid component such as sulfuric acid or ammonia or an alkaline component and an organic solvent for removing organic substances on the substrate, the environmental load is small and the cost is low without damaging the element structure, It has excellent industrial utility. Further, since the acid component, the alkali component and the organic solvent used in the above conventional method are not used,
Damage is reduced without significantly corroding the structure of semiconductor elements and wiring materials. In addition, it is possible to minimize the deterioration of the electrical characteristics of the device, improve the reliability of the element performance, reduce the electric resistance, reduce the power consumption, speed up the element performance, and at the same time improve the manufacturing yield. In addition, it is possible to reduce the running cost and improve the safety of the semiconductor manufacturing apparatus.
【0035】また、半導体素子形成用基板の処理として
オゾンガスを用いた乾式酸化分解反応、オゾン水、水素
水等いわゆる機能水による処理は従来から多くの報告が
なされている。しかし、本発明はプラズマ等の高エネル
ギー状態の物質や高純度の従来の薬液を一切使用しない
ことから半導体素子構造や形成材料へのダメージを軽減
することができ、かつ乾式、湿式処理を組み合わせるこ
とにより、より効率的に基板の処理を可能とした。オゾ
ンガスは酸化力が強く且つプラズマのように高エネルギ
ー状態ではないため構造を透過する等の問題を生じるこ
となく基板上の主に有機化合物を除去できる。オゾン水
等の処理も多数の報告があるが、本発明は高濃度オゾン
水と高温でのオゾンガスを用い、除去し難かったフォト
レジスト等の多量の有機化合物を直接剥離することを可
能にし、乾式酸化分解処理後の洗浄処理用として高濃度
オゾン水を用いることや、高温でのオゾン含有ガス処理
と高濃度オゾン水処理を組合わせることは、本発明にお
いて初めて提案するものである。Many reports have hitherto been made on the treatment of semiconductor element forming substrates, such as dry oxidative decomposition reaction using ozone gas and treatment with so-called functional water such as ozone water and hydrogen water. However, the present invention can reduce damage to the semiconductor element structure and the forming material because it does not use high-energy substances such as plasma or high-purity conventional chemicals, and combines dry and wet treatments. This makes it possible to process the substrate more efficiently. Since ozone gas has a strong oxidizing power and is not in a high energy state like plasma, mainly organic compounds on the substrate can be removed without causing problems such as permeation through the structure. Although there are many reports on the treatment of ozone water and the like, the present invention enables high-concentration ozone water and ozone gas at high temperature to directly peel off a large amount of organic compounds such as photoresist, which is difficult to remove, and a dry method. It is the first proposal in the present invention to use high-concentration ozone water for cleaning treatment after oxidative decomposition treatment, or to combine high-temperature ozone-containing gas treatment and high-concentration ozone water treatment.
【0036】更に、水素水を超音波活性化して用いる処
理は、微小な異物を除去することが可能であるとされて
いるが、本発明は前記オゾン水処理を組合わせることに
より、高純度硫酸等の薬液を使用することなく、例えば
フォトレジスト等の有機化合物の剥離からその後の洗浄
までの一連の工程を連続的に一括して行うことができ
る。従来法で用いたプラズマ等の高エネルギー物質や硫
酸等の薬液を用いない乾式処理と湿式処理を組合わせた
ことにより、危険な薬液との接触を回避できる等のメリ
ットにより操作が簡便となり工業的に有用性が向上す
る。更に、薬液の不使用によりトータルコストの軽減や
削減に貢献することから工業的に有用である。Further, it is said that the treatment using hydrogen water after ultrasonic activation can remove minute foreign matters. In the present invention, high purity sulfuric acid can be obtained by combining the ozone water treatment. For example, a series of processes from the peeling of the organic compound such as photoresist to the subsequent cleaning can be continuously and collectively performed without using a chemical solution such as. The combination of dry and wet processes that do not use high-energy substances such as plasma and chemicals such as sulfuric acid used in the conventional method makes it easy to operate because of the merit of avoiding contact with dangerous chemicals. To improve the usefulness. Further, it is industrially useful because it contributes to the reduction or reduction of the total cost by not using the chemical liquid.
【図1】本発明のオゾンガス処理工程用の酸化分解処理
装置の一例を示す模式説明図FIG. 1 is a schematic explanatory view showing an example of an oxidative decomposition treatment apparatus for an ozone gas treatment process of the present invention.
【図2】本発明のオゾン水処理工程及び水素水処理工程
用の湿式洗浄処理装置の一例を示す模式説明図FIG. 2 is a schematic explanatory view showing an example of a wet cleaning treatment apparatus for the ozone water treatment process and the hydrogen water treatment process of the present invention.
10 酸化分解処理装置 11 チャンバー 12 半導体素子形成用基板 13 サセプター 14 ヒーター 15 オゾン発生器 16 フィルター 17 ガス拡散器 18 排気ライン 19 スピンモータ 20 湿式洗浄処理装置 21 チャンバーカップ 22 チャック 23 オゾン水調製器 24 水素水調製器 25 超音波発生器付ディスペンサー 26 酸成分供給器 27 アルカリ成分供給器 28 超純水供給機構 10 Oxidative decomposition treatment equipment 11 chambers 12 Semiconductor element forming substrate 13 Susceptor 14 heater 15 Ozone generator 16 filters 17 Gas diffuser 18 Exhaust line 19 Spin motor 20 Wet cleaning equipment 21 chamber cup 22 chuck 23 Ozone water preparation device 24 Hydrogen water preparation device 25 Ultrasonic Generator Dispenser 26 Acid component feeder 27 Alkaline component feeder 28 Ultrapure water supply mechanism
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7,DB名) H01L 21/304 B08B 3/08 ─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. 7 , DB name) H01L 21/304 B08B 3/08
Claims (5)
形成用基板上に存在するレジストの除去処理及びその除
去処理後に残留する有機化合物を主成分とする微小異物
を除去する方法であり、被処理基板を(1)直接的又は
間接的に室温以上に加温し、乾燥雰囲気下にてオゾン含
有ガスで処理するオゾンガス処理工程、(2)オゾン含
有ガスを超純水に溶解したオゾン水で処理するオゾン水
処理工程、及び(3)超音波により活性化され且つ水素
含有ガスを超純水に溶解した水素水により処理する水素
水処理工程の各工程を(1)(2)(3)の順序で実施
し、且つ上記(2)のオゾン水処理工程で、20〜60
ppmのオゾン濃度のオゾン水を用いることを特徴とす
る半導体素子形成用基板表面処理方法。1. A method for removing a resist existing on a substrate for forming a semiconductor element used for forming a semiconductor element, and a method for removing minute foreign matters containing an organic compound as a main component after the removal processing. (1) an ozone gas treatment step of directly or indirectly heating to room temperature or higher and treating with ozone-containing gas in a dry atmosphere, (2) treating ozone-containing gas with ozone water dissolved in ultrapure water Steps (1), (2) and (3) of the ozone water treatment step and the hydrogen water treatment step of (3) treating with hydrogen water activated by ultrasonic waves and dissolving hydrogen-containing gas in ultrapure water In the ozone water treatment step of (2) above, 20 to 60
A substrate surface treatment method for semiconductor element formation, which comprises using ozone water having an ozone concentration of ppm.
るオゾン含有ガスのオゾン濃度が4〜8容量%であり、
加温温度が300〜350℃である請求項1記載の半導
体素子形成用基板表面処理方法。2. The ozone concentration of the ozone-containing gas in the ozone gas treatment step (1) is 4 to 8% by volume,
The substrate surface treatment method for forming a semiconductor element according to claim 1, wherein the heating temperature is 300 to 350 ° C.
解濃度が1.2〜2.0ppmの水素水を用いる請求項
1又は2記載の半導体素子形成用基板表面処理方法。3. The substrate surface treatment method for forming a semiconductor element according to claim 1, wherein hydrogen water having a hydrogen dissolution concentration of 1.2 to 2.0 ppm is used in the hydrogen water treatment step (3).
したオゾンガス処理基板を前記(2)のオゾン水処理工
程で処理することを2回以上繰返した後に、前記(3)
の水素水処理工程で処理する請求項1〜3のいずれか1
項記載の半導体素子形成用基板表面処理方法。4. The ozone gas treatment substrate treated in the ozone gas treatment step of (1) is treated twice or more in the ozone water treatment step of (2), and then the (3).
The hydrogen water treatment process according to any one of claims 1 to 3.
A method for treating a surface of a substrate for forming a semiconductor element according to the item.
トの拡散工程又はエッチング工程終了後の基板である請
求項1〜4のいずれか1項に記載の半導体素子形成用基
板表面処理方法。Wherein said semiconductor element forming substrate, the semiconductor element formation substrate surface treatment method according to any one of claims 1 to 4, which is a diffusion process or the substrate after the etching step is completed the dopant.
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JP36792399A JP3445765B2 (en) | 1999-12-24 | 1999-12-24 | Substrate surface treatment method for semiconductor element formation |
US09/742,423 US6743301B2 (en) | 1999-12-24 | 2000-12-22 | Substrate treatment process and apparatus |
US10/827,352 US6983756B2 (en) | 1999-12-24 | 2004-04-20 | Substrate treatment process and apparatus |
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JP36792399A JP3445765B2 (en) | 1999-12-24 | 1999-12-24 | Substrate surface treatment method for semiconductor element formation |
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JP3445765B2 true JP3445765B2 (en) | 2003-09-08 |
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JP2002261062A (en) * | 2001-03-05 | 2002-09-13 | Texas Instr Japan Ltd | Method and device for removing particle on semiconductor wafer |
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JP4076365B2 (en) | 2002-04-09 | 2008-04-16 | シャープ株式会社 | Semiconductor cleaning equipment |
JP2005217262A (en) | 2004-01-30 | 2005-08-11 | Matsushita Electric Ind Co Ltd | Method for manufacturing compound semiconductor device |
JP4555729B2 (en) * | 2005-05-17 | 2010-10-06 | 積水化学工業株式会社 | Resist removing method and resist removing apparatus |
WO2007017939A1 (en) * | 2005-08-10 | 2007-02-15 | Fujitsu Limited | Process for producing semiconductor device |
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