JP2600476B2 - Pure water production apparatus and semiconductor substrate pure water treatment method - Google Patents
Pure water production apparatus and semiconductor substrate pure water treatment methodInfo
- Publication number
- JP2600476B2 JP2600476B2 JP2289164A JP28916490A JP2600476B2 JP 2600476 B2 JP2600476 B2 JP 2600476B2 JP 2289164 A JP2289164 A JP 2289164A JP 28916490 A JP28916490 A JP 28916490A JP 2600476 B2 JP2600476 B2 JP 2600476B2
- Authority
- JP
- Japan
- Prior art keywords
- pure water
- semiconductor substrate
- resin
- production apparatus
- water treatment
- 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
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Description
【発明の詳細な説明】 〔概要〕 純水製造装置および半導体基板の純水処理方法に関
し， 全有機カーボン（TOC）値が1ppb以下の純水の製造装
置および半導体基板表面に清浄な自然酸化膜を形成する
方法の提供を目的とし， 源水供給側から主純水装置を経て，マイクロポーラス
型樹脂，紫外線酸化装置，ゲル型樹脂がこの順に配置さ
れた構成を含み，水のTOC値を低下させ，且つ半導体基
板に対して吸着性を有する有機物を除去する純水製造装
置により構成する。DETAILED DESCRIPTION OF THE INVENTION [Summary] The present invention relates to a pure water production apparatus and a pure water treatment method for a semiconductor substrate, and to a pure water production apparatus having a total organic carbon (TOC) value of 1 ppb or less and a clean natural oxide film on the surface of the semiconductor substrate. In order to provide a method for forming water, the system includes a microporous resin, an ultraviolet oxidizer, and a gel resin arranged in this order from the source water supply side through the main pure water system, and reduces the TOC value of water. And a pure water producing apparatus for removing organic substances having an adsorptivity to the semiconductor substrate.
また、半導体基板を上記純水製造装置によって製造し
た純水に浸漬する半導体基板の純水処理方法により構成
する。Further, the semiconductor substrate is immersed in pure water produced by the above-mentioned pure water producing apparatus, and the semiconductor substrate is constituted by a pure water treatment method.
本発明は純水製造装置および半導体基板の純水処理方
法に関する。The present invention relates to a pure water production apparatus and a method for treating a semiconductor substrate with pure water.
近年，半導体デバイスの微細化，高密度化が進む中
で，それに供する純水の高清浄化は極めて重要になって
きている。そのため，純水中の全有機カーボン（TOC:To
tal Organic Carbon）値を低下させる必要がある。2. Description of the Related Art In recent years, as semiconductor devices have become finer and higher in density, it has become extremely important to purify pure water for use therein. Therefore, all organic carbon in pure water (TOC: ToC)
tal Organic Carbon) value must be reduced.
また，半導体基板を極めて清浄な純水で処理すること
が要求されている。Further, it is required to treat a semiconductor substrate with extremely clean pure water.
第３図は従来の純水製造装置の構成例で,1は主純水装
置,16はカートリッジポリッシャー,15は紫外線殺菌装
置,11はウルトラフィルタを表す。FIG. 3 shows a configuration example of a conventional pure water producing apparatus, wherein 1 is a main pure water apparatus, 16 is a cartridge polisher, 15 is an ultraviolet sterilizer, and 11 is an ultra filter.
主純水装置１は前処理装置，逆浸透装置，イオン交換
装置，紫外線酸化装置等からなる。The main pure water apparatus 1 includes a pretreatment device, a reverse osmosis device, an ion exchange device, an ultraviolet oxidation device, and the like.
イオン交換樹脂は，ゲル型樹脂あるいはマイクロポー
ラス型樹脂を使用する。マイクロポーラス型樹脂はその
機械的強度と吸着特性においてゲル型樹脂より優れてい
るが，一方，樹脂の重合が不十分なことにより有機物が
溶出するという欠点がある。それゆえ，有機物の溶出が
問題となる所では，溶出が少ないゲル型樹脂を使用する
のが一般的である。イオン交換処理を行った水は紫外線
殺菌装置15を通り，さらにウルトラフィルタ11でろ過さ
れてユースポイントに供給される。As the ion exchange resin, a gel resin or a microporous resin is used. Microporous resins are superior to gel resins in mechanical strength and adsorption properties, but have the drawback that organic substances are eluted due to insufficient polymerization of the resin. Therefore, where the elution of organic matter is a problem, it is common to use a gel-type resin with little elution. The water subjected to the ion exchange treatment passes through the ultraviolet sterilizer 15 and is further filtered by the ultrafilter 11 and supplied to the use point.
また，最近では紫外線殺菌装置15に加えて紫外線酸化
装置を用いることにより,TOC値を低下させることも行わ
れるようになった。このメカニズムは紫外線照射によ
り，溶出した有機物が分解し,CO2,COOH-,H2CO3 --等を生
じさせ，それを除去するものと言われている。Recently, the use of an ultraviolet oxidizer in addition to the ultraviolet sterilizer 15 has also been used to lower the TOC value. The mechanism by ultraviolet irradiation, eluted organic substances decomposed, CO 2, COOH -, H 2 CO 3 - causing the like, are said to eliminate it.
しかし，従来の純水製造装置においてはイオン交換樹
脂や供給配管から溶出するTOCを完全に除去するのは困
難であった。それゆえ，従来に優るTOC除去技術の開発
が望まれる。However, it was difficult to completely remove TOC eluted from the ion exchange resin and the supply pipe with the conventional pure water production equipment. Therefore, development of TOC removal technology that is superior to conventional technology is desired.
さらに，従来，半導体基板の洗浄は，基板を親水性状
態にするため，薬液処理を行い，その後，純水による洗
浄を行っている。その時，基板表面に極く薄い自然酸化
膜が形成され，それが純水中の不純物の種類や量によっ
てはいわゆる汚い膜となり，その後その上に形成される
酸化膜の欠陥になるという問題があった。Further, conventionally, in cleaning of a semiconductor substrate, a chemical solution treatment is performed to make the substrate hydrophilic, and thereafter, cleaning with pure water is performed. At that time, there is a problem that an extremely thin natural oxide film is formed on the substrate surface, which becomes a so-called dirty film depending on the type and amount of impurities in pure water, and then becomes a defect of the oxide film formed thereon. Was.
本発明は，極めてTOC値が小さく，且つ半導体基板に
対して吸着性を有する有機物を除去した純水を供給する
純水製造装置を提供することを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a pure water producing apparatus for supplying pure water having a very small TOC value and removing organic substances having an adsorptivity to a semiconductor substrate.
さらに，半導体基板表面に極めて清浄な自然酸化膜を
形成する純水処理方法を提供することを目的とする。Another object of the present invention is to provide a pure water treatment method for forming an extremely clean natural oxide film on a semiconductor substrate surface.
第１図は純水製造装置の構成例、第２図は半導体基板
の純水処理を説明するための図である。FIG. 1 is a diagram illustrating a configuration example of a pure water producing apparatus, and FIG. 2 is a diagram illustrating pure water treatment of a semiconductor substrate.
上記課題は、源水供給側から主純水装置を経て，マイ
クロポーラス型樹脂，紫外線酸化装置，ゲル型樹脂がこ
の順に配置された構成を含み、水の全有機カーボン（TO
C）値を低下させ，且つ半導体基板に対して吸着性を有
する有機物を除去する純水製造装置、ならびに、半導体
基板を上記純水製造装置によって製造した純水に浸漬す
る半導体基板の純水処理方法によって解決される。The above problems include a configuration in which a microporous resin, an ultraviolet oxidizer, and a gel resin are arranged in this order from a source water supply side through a main pure water apparatus, and the total organic carbon (TO
C) A pure water producing apparatus for lowering the value and removing an organic substance having an adsorptive property to the semiconductor substrate, and a pure water treatment of the semiconductor substrate by immersing the semiconductor substrate in pure water produced by the pure water producing apparatus. Solved by the method.
本発明の純水処理装置の構成例では，源水供給側から
主純水装置１を経て，その後にマイクロポーラス型樹脂
2,紫外線酸化装置3,ゲル型樹脂４がこの順に配置された
構成を含んでいるので，マイクロポーラス型樹脂２とゲ
ル型樹脂４が相補的に作用する。即ち，マイクロポーラ
ス型樹脂２は吸着能力に優れており，源水供給側から主
純水装置１を経て残留する有機物を吸着のメカニズムで
更に除去する。しかし，イオン交換樹脂そのものが溶出
する欠点があり，その点に関しては，紫外線酸化装置３
によりイオン交換樹脂から溶出した有機物を専用に分解
した後，ゲル型樹脂４で吸着する。その結果,TOC値の極
めて低い，例えば,TOC値が1ppb以下で，且つ半導体基板
に対して吸着性を有する有機物を含まない純水を製造す
ることができる。In the configuration example of the pure water treatment apparatus of the present invention, the microporous resin is supplied from the source water supply side through the main pure water apparatus 1 and thereafter.
Since the ultraviolet oxidizing device 3 and the gel type resin 4 include a configuration arranged in this order, the microporous type resin 2 and the gel type resin 4 act complementarily. That is, the microporous resin 2 has excellent adsorption ability, and further removes organic substances remaining from the source water supply side through the main pure water apparatus 1 by an adsorption mechanism. However, there is a drawback that the ion exchange resin itself is eluted.
After the organic matter eluted from the ion exchange resin is decomposed for exclusive use, the gel-type resin 4 adsorbs the organic matter. As a result, pure water having an extremely low TOC value, for example, a TOC value of 1 ppb or less and containing no organic substance having an adsorptive property to a semiconductor substrate can be produced.
また，半導体基板13をTOC値が1ppb以下の極めて純度
の高い純水に浸漬すれば，半導体基板13表面に極めて清
浄な自然酸化膜が形成される。このような清浄な自然酸
化膜の上に成長する酸化膜は，耐圧性や電荷の熱安定性
に優れることがわかった。If the semiconductor substrate 13 is immersed in extremely pure water having a TOC value of 1 ppb or less, an extremely clean natural oxide film is formed on the surface of the semiconductor substrate 13. It has been found that the oxide film grown on such a clean natural oxide film is excellent in pressure resistance and thermal stability of electric charge.
なお，現段階において,TOC値評価装置の測定限界は1p
pbであるため，上記の1ppb以下というのは測定で検出さ
れない程度と解すべきである。At this stage, the measurement limit of the TOC value evaluation device is 1p.
Since it is pb, the above 1 ppb or less should be understood as a level that is not detected by measurement.
第１図は本発明による純水製造装置の構成例であり,1
は主純水装置,2はマイクロポーラス型樹脂,3は紫外線酸
化装置,4はゲル型樹脂,5はウルトラフィルタを表す。主
純水装置１は，前処理装置，逆浸透装置，イオン交換装
置，紫外線酸化装置等からなる。FIG. 1 shows an example of the configuration of a pure water production apparatus according to the present invention.
Is a main water purifier, 2 is a microporous resin, 3 is an ultraviolet oxidizer, 4 is a gel resin, and 5 is an ultra filter. The main pure water device 1 includes a pretreatment device, a reverse osmosis device, an ion exchange device, an ultraviolet oxidation device, and the like.
源水側から供給された水は，主純水装置１を通過した
後，マイクロポーラス型樹脂2,紫外線酸化装置3,ゲル型
樹脂で処理されて,TOC値が1ppb以下となる。その後，ウ
ルトラフィルタ５で微粒子がろ過され，ユースポイント
に供給される。After the water supplied from the source water side passes through the main pure water device 1, it is treated with the microporous resin 2, the ultraviolet oxidizing device 3, and the gel resin, and the TOC value becomes 1 ppb or less. Thereafter, the fine particles are filtered by the ultrafilter 5 and supplied to the use point.
マイクロポーラス型樹脂２としては，特に吸着特性に
優れた樹脂，例えばMR・Ｉ等を使用するのが効果的であ
る。As the microporous resin 2, it is effective to use a resin having particularly excellent adsorption characteristics, for example, MR / I.
第２図は本発明による半導体基板の純水処理を説明す
るための図であり,12は純水処理槽,13は半導体基板,14
は半導体基板処理キャリアを表す。純水処理槽12中の純
水はTOC値が1bbp以下の純水で，さらに半導体基板に吸
着するような不純物は極力除去されている。その純水中
に半導体基板13を浸漬する。この時，半導体基板13表面
には極く薄い自然酸化膜が形成される。この膜は極めて
清浄で，その後，この自然酸化膜の上に成長する酸化膜
の膜質が向上し，耐圧や電荷の熱安定性が従来の自然酸
化膜上に成長した酸化膜に比較して，はるかに良好とな
る。FIG. 2 is a diagram for explaining pure water treatment of a semiconductor substrate according to the present invention, wherein 12 is a pure water treatment tank, 13 is a semiconductor substrate,
Represents a semiconductor substrate processing carrier. The pure water in the pure water treatment tank 12 is pure water having a TOC value of 1 bbp or less, and impurities that are adsorbed on the semiconductor substrate are removed as much as possible. The semiconductor substrate 13 is immersed in the pure water. At this time, an extremely thin natural oxide film is formed on the surface of the semiconductor substrate 13. This film is extremely clean. After that, the quality of the oxide film grown on the natural oxide film is improved, and the breakdown voltage and the thermal stability of the charge are higher than those of the conventional oxide film grown on the natural oxide film. Will be much better.
この半導体基板の純水処理用の純水として，前述の純
水製造装置の構成例により製造した,TOC値1ppb以下で，
半導体基板に吸着する有機物が極力除去された純水を採
用することができる。As pure water for treating the semiconductor substrate with pure water, a TOC value of 1 ppb or less, manufactured by the above-described configuration example of the pure water manufacturing apparatus, was used.
Pure water from which organic substances adsorbed on the semiconductor substrate have been removed as much as possible can be employed.
なお，半導体基板をTOC値が1ppbより大きい純水に浸
漬する時は，成長する酸化膜の膜質の向上が十分でな
い。When the semiconductor substrate is immersed in pure water having a TOC value higher than 1 ppb, the quality of the grown oxide film is not sufficiently improved.
以上説明したように，本発明によれば,TOC値が1ppb以
下で半導体基板に吸着する有機物を極力減少させた純水
を供給する純水製造装置を提供することができる。As described above, according to the present invention, it is possible to provide a pure water producing apparatus that supplies pure water with a TOC value of 1 ppb or less and an organic substance adsorbed on a semiconductor substrate reduced as much as possible.
また，このようなTOC値の低い純水により半導体基板
を処理する時は，その後半導体基板上に極めて膜質のよ
い絶縁膜を形成することができ，半導体装置の性能向上
に寄与する効果を奏する。Further, when the semiconductor substrate is treated with such pure water having a low TOC value, an insulating film having a very good film quality can be formed on the semiconductor substrate thereafter, which has an effect of improving the performance of the semiconductor device.
第１図は純水製造装置の構成例、 第２図は半導体基板の純水処理を説明するための図、 第３図は従来の純水製造装置の構成例 である。 図において， １は主純水装置， ２はマイクロポーラス型樹脂， ３は紫外線酸化装置， ４はゲル型樹脂， ５はフィルタであってウルトラフィルタ， 11はフィルタであってウルトラフィルタ， 12は純水処理槽， 13は半導体基板， 14は半導体基板処理キャリア 15は紫外線殺菌装置， 16はカートリッジポリッシャー を表す。 FIG. 1 is a configuration example of a pure water production apparatus, FIG. 2 is a diagram for explaining pure water treatment of a semiconductor substrate, and FIG. 3 is a configuration example of a conventional pure water production apparatus. In the figure, 1 is a main pure water device, 2 is a microporous resin, 3 is an ultraviolet oxidizing device, 4 is a gel resin, 5 is a filter and an ultra filter, 11 is a filter and an ultra filter, and 12 is a pure filter. A water treatment tank, 13 is a semiconductor substrate, 14 is a semiconductor substrate processing carrier, 15 is an ultraviolet sterilizer, and 16 is a cartridge polisher.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 前田 昭彦 神奈川県川崎市中原区上小田中1015番地 富士通株式会社内 (72)発明者 米塚 寿生 神奈川県川崎市中原区上小田中1015番地 富士通株式会社内 (56)参考文献 特開 平２−261594（ＪＰ，Ａ) 特開 昭57−178327（ＪＰ，Ａ) 特開 昭63−150925（ＪＰ，Ａ) 特開 平１−241824（ＪＰ，Ａ) ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Akihiko Maeda 1015 Uedanaka, Nakahara-ku, Kawasaki-shi, Kanagawa Prefecture Inside Fujitsu Limited (72) Inventor Toshio Yonezuka 1015 Kamikodanaka, Nakahara-ku, Kawasaki-shi, Kanagawa Fujitsu Limited ( 56) References JP-A-2-261594 (JP, A) JP-A-57-178327 (JP, A) JP-A-63-150925 (JP, A) JP-A-1-241824 (JP, A)
Claims (2)
マイクロポーラス型樹脂（２），紫外線酸化装置
（３），ゲル型樹脂（４）がこの順に配置された構成を
含み、水の全有機カーボン（TOC）値を低下させ，且つ
半導体基板に対して吸着性を有する有機物を除去するこ
とを特徴とする純水製造装置。(1) From a source water supply side through a main pure water device (1),
The microporous resin (2), the ultraviolet oxidizer (3), and the gel resin (4) are arranged in this order to reduce the total organic carbon (TOC) value of water, An apparatus for producing pure water, which removes organic substances having adsorptivity.
造装置によって製造した純水に浸漬することを特徴とす
る半導体基板の純水処理方法。2. A method of treating a semiconductor substrate with pure water, comprising immersing the semiconductor substrate (13) in pure water produced by the pure water producing apparatus according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2289164A JP2600476B2 (en) | 1990-10-26 | 1990-10-26 | Pure water production apparatus and semiconductor substrate pure water treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2289164A JP2600476B2 (en) | 1990-10-26 | 1990-10-26 | Pure water production apparatus and semiconductor substrate pure water treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04161290A JPH04161290A (en) | 1992-06-04 |
| JP2600476B2 true JP2600476B2 (en) | 1997-04-16 |
Family
ID=17739593
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2289164A Expired - Fee Related JP2600476B2 (en) | 1990-10-26 | 1990-10-26 | Pure water production apparatus and semiconductor substrate pure water treatment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2600476B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5744597B2 (en) * | 2011-03-31 | 2015-07-08 | Hoya株式会社 | Mask blank glass substrate manufacturing method, mask blank manufacturing method, transfer mask manufacturing method, and semiconductor device manufacturing method |
| WO2020241476A1 (en) * | 2019-05-30 | 2020-12-03 | オルガノ株式会社 | Ultrapure water production system and ultrapure water production method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57178327A (en) * | 1981-04-27 | 1982-11-02 | Hitachi Ltd | Washer |
| JPS63150925A (en) * | 1986-12-15 | 1988-06-23 | Mitsubishi Electric Corp | Washing tank |
| JPH0724264B2 (en) * | 1988-03-23 | 1995-03-15 | 日本電気株式会社 | Semiconductor substrate washing equipment |
| JPH02261594A (en) * | 1989-03-31 | 1990-10-24 | Japan Organo Co Ltd | Device for producing ultra pure water |
-
1990
- 1990-10-26 JP JP2289164A patent/JP2600476B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04161290A (en) | 1992-06-04 |
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| LAPS | Cancellation because of no payment of annual fees |