JPS614232A - Cleaning method of semiconductor substrate - Google Patents
Cleaning method of semiconductor substrateInfo
- Publication number
- JPS614232A JPS614232A JP12576084A JP12576084A JPS614232A JP S614232 A JPS614232 A JP S614232A JP 12576084 A JP12576084 A JP 12576084A JP 12576084 A JP12576084 A JP 12576084A JP S614232 A JPS614232 A JP S614232A
- Authority
- JP
- Japan
- Prior art keywords
- ozone
- semiconductor substrate
- acid
- cleaning
- substrate
- 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.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02052—Wet cleaning only
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
Description
【発明の詳細な説明】 〔技術分野〕 、本発明は半導体基板の洗浄方法に関するものである。[Detailed description of the invention] 〔Technical field〕 The present invention relates to a method for cleaning a semiconductor substrate.
ＬＳＩ製造において、ウェハの洗浄工程は各プロセス間
にゴミ、汚れを除去する数多くの処理回数を必要とし、
製品の歩留シ向上に重要な技術となっている。この洗浄
工程で使われている生な液としてはアルカリ系と酸系に
大別される。公知の洗浄液としてはアンモニア水−過酸
化水素系、又は塩酸−過酸化水素系（通称ＲＣＡ洗浄と
もいう）。In LSI manufacturing, the wafer cleaning process requires numerous processing times to remove dust and dirt between each process.
This is an important technology for improving product yield. The raw liquids used in this cleaning process are broadly divided into alkaline and acidic liquids. Known cleaning solutions include ammonia water-hydrogen peroxide system or hydrochloric acid-hydrogen peroxide system (also commonly referred to as RCA cleaning).
さらに、硫酸−過酸化水素系、硫酸−硝酸系等の混酸溶
液が用いられている。溶液は通常６０〜１５０℃に加温
され、時には超音波を併用することもある。Furthermore, mixed acid solutions such as sulfuric acid-hydrogen peroxide type and sulfuric acid-nitric acid type are used. The solution is usually heated to 60 to 150°C, and sometimes ultrasonic waves are also used.
しかしながら、アンモニア−過酸化水素系や塩酸−過酸
化水素系では、過酸化水素がすぐにＨ２Ｏと発生期のＯ
に分解してしまうので、酸化力が劣化し、洗浄力が持続
せず間欠的に過酸化水素を補充する必要があり、工程と
しては繁雑になる。硫酸−過酸化水素系も同じ理由で不
利である。この硫酸−過酸化水素系や硫酸−硝酸系等は
廃液として処理する場合の問題がある。それは硫酸を廃
棄する場合、水と反応して１００℃以上な９安全上危険
があり、このため大量の水を必要とし、又硝酸を使う場
合は、窒素酸、化物等が発生し公害上規制される等、大
量に使うことはできないという不利な点がある。すなわ
ち、処理費用が高くなる。However, in ammonia-hydrogen peroxide systems and hydrochloric acid-hydrogen peroxide systems, hydrogen peroxide quickly becomes H2O and nascent O2.
As the oxidizing power deteriorates, the cleaning power does not last long and it is necessary to replenish hydrogen peroxide intermittently, making the process complicated. The sulfuric acid-hydrogen peroxide system is also disadvantageous for the same reason. This sulfuric acid-hydrogen peroxide system, sulfuric acid-nitric acid system, etc. have problems when disposed of as waste liquid. When disposing of sulfuric acid, it reacts with water to over 100 degrees Celsius, which poses a safety hazard, and requires a large amount of water. Also, when nitric acid is used, nitrogen acids, compounds, etc. are generated, and pollution regulations are in place. It has the disadvantage that it cannot be used in large quantities, such as when it is damaged. In other words, processing costs increase.
又上記の酸−過酸化水素系に代る処理方法としての公知
例として特公昭５２−０１２０６３号の半導体基板のレ
ジスト膜除去方法がある。この方法は硫酸を用いて過酸
化水素の代りにオゾンを用いる方法であるが、この方法
では硫酸を廃液処理するのに大量の水（〜ｌＯ倍希釈）
を必要とする等、安全上、費用の点で問題があった。A known example of a processing method in place of the above-mentioned acid-hydrogen peroxide system is a method for removing a resist film from a semiconductor substrate, disclosed in Japanese Patent Publication No. 52-012063. This method uses sulfuric acid and ozone instead of hydrogen peroxide, but in this method, a large amount of water (~10 times dilution) is required to treat the sulfuric acid as waste liquid.
There were problems in terms of safety and cost.
本発明は安全上を高め、かつ低順な処理を行なうことが
できるようにした処理方法を提供するものである。The present invention provides a processing method that increases safety and allows processing to be performed in a low order manner.
本発明は有機酸を洗浄液として、槽内にオゾン／酸素を
バブルしてシリコンウェハの表面汚れを除去することを
特徴とする半導体基板の洗浄方法である。The present invention is a method for cleaning a semiconductor substrate, which includes using an organic acid as a cleaning liquid and bubbling ozone/oxygen in a tank to remove surface stains from a silicon wafer.
有機酸のうちギ酸は強酸で、還元性をもっている。一方
、酢酸は弱酸であり、それぞれ重金属（Ｍ）と反応して
−ＣＯＯＨ基のＨを置換し、−ＣＯＯＭなる金属塩を作
る。Among organic acids, formic acid is a strong acid and has reducing properties. On the other hand, acetic acid is a weak acid, and reacts with a heavy metal (M) to replace H in the -COOH group, producing a metal salt called -COOM.
−又オゾンをバブルすることによシ、有機汚染物質をオ
ゾンにより酸化し、分解除去することができる。-Also, by bubbling ozone, organic pollutants can be oxidized by ozone and decomposed and removed.
すなわち、水金明毎半導体基板（ウエノ為）上の重金属
はギ酸塩、又は酢酸塩を作り有機汚染物質はオゾンで分
解することにより、洗浄を行おうとするものである。That is, the heavy metals on the semiconductor substrate (Ueno-made) are made to form formate or acetate, and the organic contaminants are decomposed by ozone to be cleaned.
次に本発明と従来例とを比較しながら説明する。 Next, the present invention will be explained while comparing it with a conventional example.
以下に本発明の一実施例について説明する。An embodiment of the present invention will be described below.
本発明は洗浄槽に有機酸（例えばギ酸、酢酸）を入れ、
これを加温（１００〜１５０℃）し、この液内に半導体
基板を浸漬し、槽底部よりオゾン／酸素をバブルして該
基板にあてて洗浄を行うものである。In the present invention, an organic acid (for example, formic acid, acetic acid) is placed in a cleaning tank,
This is heated (100 to 150° C.), a semiconductor substrate is immersed in this solution, and ozone/oxygen is bubbled from the bottom of the tank and applied to the substrate for cleaning.
本発明で用いた洗浄槽はテフロン製のものを用い、液温
は投込型石英ヒーターで加熱・制御した。The cleaning tank used in the present invention was made of Teflon, and the liquid temperature was heated and controlled with an immersion type quartz heater.
又オゾン／酸素は槽底部よりパイレックス製ガス分配器
によりバブルして行った。同型槽を用いて従来のＲＣＡ
洗浄液のＮＨａＯＨＨａＯ□−Ｈ２０Ｃ１：１：５）で
、液温〜８０℃、１０分間洗浄を行った。Further, ozone/oxygen was bubbled from the bottom of the tank using a Pyrex gas distributor. Conventional RCA using the same type of tank
Cleaning was performed with a cleaning solution of NHaOHHaO□-H20C (1:1:5) at a temperature of ~80° C. for 10 minutes.
さらに本発明による方法では、前記の同じ槽を用いて同
一ロットのウェハを用いて該ウェハをギ酸又は酢酸溶液
に浸漬する。このとき、この溶液を１００〜１５０℃に
加温する。さらに槽底部よりオゾン／酸素をバブルして
〜ｌＯ分間洗浄を行った。Furthermore, the method according to the invention uses the same bath and the same lot of wafers to immerse the wafers in a formic acid or acetic acid solution. At this time, this solution is heated to 100-150°C. Furthermore, ozone/oxygen was bubbled from the bottom of the tank to perform cleaning for ~10 minutes.
従来法のＮＨ４ＯＨ−Ｈ２０□−Ｈ，Ｏ系溶液で洗浄し
たウェハと、本発明によるギ酸−オゾン−０２系溶液で
洗浄したウェハとをスチーム処理（９５０℃、１０分Ｈ
，−０２雰囲気）を行い、非接触法によるライフタイム
を測定した結果と、ＭＯＳ Ｃ−Ｖ法によシ評価したＶ
ＦＲ（フラットバンド電圧）とを表−１に示す。Wafers cleaned with a conventional NH4OH-H20□-H,O-based solution and wafers cleaned with a formic acid-ozone-02-based solution according to the present invention were steam-treated (950°C, 10 min.
, -02 atmosphere) and measured the lifetime by the non-contact method, and the V evaluated by the MOS C-V method.
FR (flat band voltage) is shown in Table-1.
表−１
〔発明の効果〕
第１表に示したように本発明による洗浄方法は従来のＲ
ＣＡ洗浄液に比べて、再結合ライフタイムの値が〜３倍
となシ、洗浄効果が優れている事を示している。又ＭＯ
８Ｃ−Ｖ法より求めたＶＦＲ（フラットハンド電圧）は
従来法のものと大きな違いはなく、−１，ＯＶであった
。Table 1 [Effects of the Invention] As shown in Table 1, the cleaning method according to the present invention is superior to the conventional R
Compared to the CA cleaning solution, the recombination lifetime value is ~3 times that of the CA cleaning solution, indicating that the cleaning effect is excellent. Also MO
The VFR (flat hand voltage) determined by the 8C-V method was -1.OV, which was not much different from that of the conventional method.
以上のように本発明の洗浄方法は従来法との洗浄効果と
比較して同等以上であり、充分に目的が達成される。As described above, the cleaning method of the present invention has a cleaning effect equal to or better than that of the conventional method, and the purpose is fully achieved.
又本発明は硫酸、硝酸等が水と反応して発熱する問題が
生じたり、公害上問題になることは少い・それはギ酸、
酢酸は高温（〜１５０°Ｃ）でｃｏ、 ｃｏ２゜Ｈ２Ｏ
等に分解し易ことと、オゾンによりさ′らに分解を促進
されるためである。とのため、本発明によれば、廃液す
るときには水にも容易に溶け、問題はなく、工業上安全
、且つ合理的に作業をすることができるばかシでなく、
処理に要する費用を削減することができる効果を有する
ものである。In addition, the present invention is less likely to cause problems such as sulfuric acid, nitric acid, etc. reacting with water and generate heat, or cause pollution problems.
Acetic acid becomes co, co2°H2O at high temperature (~150°C)
This is because it is easy to decompose, and ozone further promotes decomposition. Therefore, according to the present invention, when disposing of liquid as waste, it is easily soluble in water, there is no problem, it is industrially safe, and it is not a fool that can be operated rationally.
This has the effect of reducing processing costs.
Claims (1)
溶液中に浸漬し、処理することを特徴とする半導体基板
の洗浄方法。(1) A method for cleaning a semiconductor substrate, which comprises immersing the semiconductor substrate in a solution containing an organic acid and bubbles of ozone/oxygen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12576084A JPS614232A (en) | 1984-06-19 | 1984-06-19 | Cleaning method of semiconductor substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12576084A JPS614232A (en) | 1984-06-19 | 1984-06-19 | Cleaning method of semiconductor substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS614232A true JPS614232A (en) | 1986-01-10 |
Family
ID=14918138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12576084A Pending JPS614232A (en) | 1984-06-19 | 1984-06-19 | Cleaning method of semiconductor substrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS614232A (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0259985A2 (en) * | 1986-09-02 | 1988-03-16 | Arrowhead Industrial Water, Inc. | Integrated circuit manufacturing process |
| JPS63274700A (en) * | 1987-04-03 | 1988-11-11 | ワッカー・ジルトロニク・ゲゼルシャフト・フュア・ハルブライターマテリアリエン・ミット・ベシュレンクテル・ハフツング | Method of removing slice sawing accessory means residual piece and remover |
| EP0536752A2 (en) * | 1991-10-11 | 1993-04-14 | Air Products And Chemicals, Inc. | Process for cleaning integrated circuits during the fabrication |
| EP0867924A2 (en) * | 1997-02-14 | 1998-09-30 | Interuniversitair Micro-Elektronica Centrum Vzw | Method for removing organic contaminants from a semiconductor surface |
| WO1998054759A1 (en) * | 1997-05-29 | 1998-12-03 | Memc Electronic Materials, Inc. | Process for the removal of copper and other metallic impurities from silicon |
| WO1998054758A1 (en) * | 1997-05-29 | 1998-12-03 | Memc Electronic Materials, Inc. | Process for the removal of copper from polished boron doped silicon wafers |
| US6174817B1 (en) | 1998-08-26 | 2001-01-16 | Texas Instruments Incorporated | Two step oxide removal for memory cells |
| EP1088603A1 (en) * | 1999-09-30 | 2001-04-04 | Purex Co.Ltd. | Method of removing contamination adhered to surfaces and apparatus used therefor |
| US6551409B1 (en) | 1997-02-14 | 2003-04-22 | Interuniversitair Microelektronica Centrum, Vzw | Method for removing organic contaminants from a semiconductor surface |
| US6701941B1 (en) | 1997-05-09 | 2004-03-09 | Semitool, Inc. | Method for treating the surface of a workpiece |
| US6830628B2 (en) | 1997-05-09 | 2004-12-14 | Semitool, Inc. | Methods for cleaning semiconductor surfaces |
| US6837252B2 (en) | 1997-05-09 | 2005-01-04 | Semitool, Inc. | Apparatus for treating a workpiece with steam and ozone |
| US6867148B2 (en) * | 2001-05-16 | 2005-03-15 | Micron Technology, Inc. | Removal of organic material in integrated circuit fabrication using ozonated organic acid solutions |
| US7264680B2 (en) | 1997-05-09 | 2007-09-04 | Semitool, Inc. | Process and apparatus for treating a workpiece using ozone |
| US7378355B2 (en) | 1997-05-09 | 2008-05-27 | Semitool, Inc. | System and methods for polishing a wafer |
| US7404863B2 (en) | 1997-05-09 | 2008-07-29 | Semitool, Inc. | Methods of thinning a silicon wafer using HF and ozone |
| US7767586B2 (en) | 2007-10-29 | 2010-08-03 | Applied Materials, Inc. | Methods for forming connective elements on integrated circuits for packaging applications |
-
1984
- 1984-06-19 JP JP12576084A patent/JPS614232A/en active Pending
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0259985A2 (en) * | 1986-09-02 | 1988-03-16 | Arrowhead Industrial Water, Inc. | Integrated circuit manufacturing process |
| JPS63274700A (en) * | 1987-04-03 | 1988-11-11 | ワッカー・ジルトロニク・ゲゼルシャフト・フュア・ハルブライターマテリアリエン・ミット・ベシュレンクテル・ハフツング | Method of removing slice sawing accessory means residual piece and remover |
| EP0536752A2 (en) * | 1991-10-11 | 1993-04-14 | Air Products And Chemicals, Inc. | Process for cleaning integrated circuits during the fabrication |
| JPH06260463A (en) * | 1991-10-11 | 1994-09-16 | Air Prod And Chem Inc | Detergent for removing metal- containing contaminant and contaminant cleaning |
| EP0867924A3 (en) * | 1997-02-14 | 1999-09-01 | Interuniversitair Micro-Elektronica Centrum Vzw | Method for removing organic contaminants from a semiconductor surface |
| EP0867924A2 (en) * | 1997-02-14 | 1998-09-30 | Interuniversitair Micro-Elektronica Centrum Vzw | Method for removing organic contaminants from a semiconductor surface |
| US6551409B1 (en) | 1997-02-14 | 2003-04-22 | Interuniversitair Microelektronica Centrum, Vzw | Method for removing organic contaminants from a semiconductor surface |
| US6837252B2 (en) | 1997-05-09 | 2005-01-04 | Semitool, Inc. | Apparatus for treating a workpiece with steam and ozone |
| US7264680B2 (en) | 1997-05-09 | 2007-09-04 | Semitool, Inc. | Process and apparatus for treating a workpiece using ozone |
| US7404863B2 (en) | 1997-05-09 | 2008-07-29 | Semitool, Inc. | Methods of thinning a silicon wafer using HF and ozone |
| US6701941B1 (en) | 1997-05-09 | 2004-03-09 | Semitool, Inc. | Method for treating the surface of a workpiece |
| US6817370B2 (en) | 1997-05-09 | 2004-11-16 | Semitool, Inc. | Method for processing the surface of a workpiece |
| US6830628B2 (en) | 1997-05-09 | 2004-12-14 | Semitool, Inc. | Methods for cleaning semiconductor surfaces |
| US6843857B2 (en) | 1997-05-09 | 2005-01-18 | Semitool, Inc. | Methods for cleaning semiconductor surfaces |
| US7378355B2 (en) | 1997-05-09 | 2008-05-27 | Semitool, Inc. | System and methods for polishing a wafer |
| US6869487B1 (en) | 1997-05-09 | 2005-03-22 | Semitool, Inc. | Process and apparatus for treating a workpiece such as a semiconductor wafer |
| WO1998054758A1 (en) * | 1997-05-29 | 1998-12-03 | Memc Electronic Materials, Inc. | Process for the removal of copper from polished boron doped silicon wafers |
| WO1998054759A1 (en) * | 1997-05-29 | 1998-12-03 | Memc Electronic Materials, Inc. | Process for the removal of copper and other metallic impurities from silicon |
| US6174817B1 (en) | 1998-08-26 | 2001-01-16 | Texas Instruments Incorporated | Two step oxide removal for memory cells |
| US6699330B1 (en) * | 1999-09-30 | 2004-03-02 | Nomura Micro Science Co., Ltd. | Method of removing contamination adhered to surfaces and apparatus used therefor |
| EP1088603A1 (en) * | 1999-09-30 | 2001-04-04 | Purex Co.Ltd. | Method of removing contamination adhered to surfaces and apparatus used therefor |
| US6867148B2 (en) * | 2001-05-16 | 2005-03-15 | Micron Technology, Inc. | Removal of organic material in integrated circuit fabrication using ozonated organic acid solutions |
| US7767586B2 (en) | 2007-10-29 | 2010-08-03 | Applied Materials, Inc. | Methods for forming connective elements on integrated circuits for packaging applications |
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