WO2009099138A1 - Method for cleaning semiconductor wafer and device for cleaning semiconductor wafer - Google Patents
Method for cleaning semiconductor wafer and device for cleaning semiconductor wafer Download PDFInfo
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- WO2009099138A1 WO2009099138A1 PCT/JP2009/051952 JP2009051952W WO2009099138A1 WO 2009099138 A1 WO2009099138 A1 WO 2009099138A1 JP 2009051952 W JP2009051952 W JP 2009051952W WO 2009099138 A1 WO2009099138 A1 WO 2009099138A1
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- microbubbles
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- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31127—Etching organic layers
- H01L21/31133—Etching organic layers by chemical means
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
-
- 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
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67017—Apparatus for fluid treatment
- H01L21/67063—Apparatus for fluid treatment for etching
- H01L21/67075—Apparatus for fluid treatment for etching for wet etching
- H01L21/67086—Apparatus for fluid treatment for etching for wet etching with the semiconductor substrates being dipped in baths or vessels
Definitions
- the present invention relates to a cleaning method and a cleaning apparatus for removing organic substances such as resist, contaminants, residual chemicals and the like on the surface of a semiconductor wafer.
- the semiconductor manufacturing process consists of a circuit design process, mask manufacturing process, wafer manufacturing process, wafer processing process, assembly process, inspection process, and waste processing process.
- cleaning is an important technology especially in the wafer processing process. It is positioned as.
- the wafer processing process includes a wafer polishing process, a substrate process, a wiring process, and the like, and is performed by cleaning, etching, resist removal, and the like.
- the ratio of the number of cleaning processes to the total number of processes in semiconductor manufacturing accounts for about 30%. Under such circumstances, an RCA cleaning method has been developed and has greatly contributed to wafer cleaning.
- the RCA cleaning method is a cleaning method based on hydrogen peroxide (H 2 O 2 ), removing organic substances with sulfuric acid hydrogen peroxide (SPM), removing particles with ammonia hydrogen peroxide (APM), and hydrochloric acid peroxidation. It consists of metal impurity removal with hydrogen water (HPM), natural oxide film and thermal oxide film removal with dilute hydrofluoric acid (DHF), and final cleaning with ultrapure water.
- the treatment using sulfuric acid / hydrogen peroxide solution is performed by combining sulfuric acid and hydrogen peroxide solution, and is mainly used to remove organic substances, but also has an effect of removing metal impurities, and is about 130 to 150 ° C.
- the treatment using ammonia hydrogen peroxide solution is performed by combining ammonia and hydrogen peroxide solution, and is performed at a temperature of about 30 to 70 ° C. in order to remove particles and organic substances.
- the treatment using hydrochloric acid and hydrogen peroxide is performed by combining hydrochloric acid and hydrogen peroxide, and is performed at a temperature of about 30 ° C. to remove metal impurities.
- the treatment using dilute hydrofluoric acid is used to remove oxide films and metal impurities, and is usually performed at about 25 ° C. at room temperature.
- Ozone water has an effect of removing organic substances, and by adopting a single wafer type, it can be expected that the wafer is not subject to self-contamination in the process of removing the object to be removed, and that the cleaning effect can be improved.
- a method of increasing the temperature of the ozone water must be employed (Patent Document 1).
- Patent Document 1 a method of increasing the temperature of the ozone water must be employed.
- Patent Document 1 has a problem of loss of energy and time associated with heating.
- an object of the present invention is to provide a semiconductor wafer cleaning method and apparatus using ozone that are effective even at room temperature and are environmentally friendly.
- the present inventor has obtained water containing micro-order microbubbles containing ozone having a predetermined bubble characteristic, generated by a two-phase flow swirl method or a pressure dissolution method. It has been found that (ozone microbubble water) is effective for cleaning semiconductor wafers.
- the method for cleaning a semiconductor wafer of the present invention based on the above knowledge is as described in claim 1, wherein the pH is obtained by adding an acid to pure water having an electric conductivity of 1 ⁇ S / cm or less or to the pure water.
- the particle size is 50 ⁇ m or less, which is generated in an aqueous solution with a maximum reduced to 1, and has a particle size peak at 10 to 15 ⁇ m when measured with a laser light blocking liquid particle counter. This is characterized in that water containing fine bubbles containing ozone and having a number in the region of 1000 / mL or more is brought into contact with the surface of the semiconductor wafer.
- the cleaning method according to claim 2 is the cleaning method according to claim 1, wherein the semiconductor wafer is immersed in water containing microbubbles containing ozone, or water containing microbubbles containing ozone is used as a semiconductor. It is characterized by being performed by placing on a wafer. Further, according to the semiconductor wafer cleaning apparatus of the present invention, the pH is lowered to 1 at the maximum by adding acid to pure water having an electric conductivity of 1 ⁇ S / cm or less, or to the pure water. The particle size is 50 ⁇ m or less, and the particle size peak is 10 to 15 ⁇ m as measured with a laser light blocking liquid particle counter, and the number in the peak region is 1000. At least means for producing water containing microbubbles containing ozone, and at least means for bringing the water containing microbubbles containing ozone produced into contact with the surface of the semiconductor wafer It is characterized by that.
- FIG. 6 is a basic configuration diagram of another example.
- 2 is a spectrum showing generation of hydroxyl radicals measured by an electron spin resonance method in Example 1. 2 is a photograph of the semiconductor wafer before (left) and after (right) removal of resist.
- the method for cleaning a semiconductor wafer of the present invention was produced in pure water having an electric conductivity of 1 ⁇ S / cm or less or in an aqueous solution having a pH lowered to 1 at maximum by adding an acid to the pure water.
- the water containing ozone-containing microbubbles used in the present invention can be produced, for example, using a microbubble generator using a known two-phase flow swirling method or pressure dissolution method.
- a vortex with a radius of 10 cm or less is forcibly generated using a rotor, etc., and a gas-liquid mixture containing ozone in obstacles such as wall surfaces or fluids with different relative velocities.
- the gas component containing ozone acquired in the vortex is dispersed along with the disappearance of the vortex, so that a large amount of microbubbles containing the desired ozone can be generated.
- microbubbles containing the desired ozone are generated by diffusing gaseous components containing ozone in water toward these bubble nuclei along with supersaturation conditions and growing the bubble nuclei.
- the bubbles generated by these methods are microbubbles having a particle size of 50 ⁇ m or less, and have a particle size peak at 10 to 15 ⁇ m when measured with a laser light blocking liquid particle counter.
- the number of microbubbles in the region is 1000 / mL or more (see JP 2000-51107 A, JP 2003-265938 A, etc. if necessary).
- the pH of pure water whose electric conductivity for generating microbubbles containing ozone is 1 ⁇ S / cm or less is not particularly limited. However, a high alkali condition in which the pH exceeds 10 is not preferable because most of the ozone decomposes before ozone contacts the surface of the semiconductor wafer. On the other hand, under weakly alkaline to strongly acidic conditions (for example, pH 1 to 10), a sufficiently strong cleaning effect can be exhibited in the decomposition and removal of resists and organic substances. It should be noted that acidic conditions are more preferable for the purpose of removing metal contamination such as oxide film and metal impurities, but pure water that has not been adjusted for pH (pH is about 7) in consideration of environmental pollution by drainage and ease of handling. Is preferably used.
- the method of bringing water containing ozone-containing microbubbles into contact with the surface of the semiconductor wafer is not particularly limited.
- the semiconductor wafer is immersed in water containing ozone-containing microbubbles or ozone is used. It can be performed by applying water containing fine bubbles to the semiconductor wafer.
- a semiconductor wafer is immersed in water containing microbubbles containing ozone, the semiconductor wafer is placed in flowing water, or water containing microbubbles containing ozone is injected into the semiconductor wafer in water.
- Examples of a method of applying water containing fine bubbles containing ozone to a semiconductor wafer include a flowing water method, a spray method, and a shower method.
- the cleaning may be performed in a batch mode, but it is preferable to perform the cleaning in a single wafer mode in that the wafer can be prevented from being subjected to self-contamination in the process of removing the object to be removed.
- FIG. 1 is a basic configuration diagram of an example of an apparatus for performing cleaning by immersing a semiconductor wafer in water containing microbubbles containing ozone.
- the apparatus shown in FIG. 1 has a particle size generated in pure water having an electric conductivity of 1 ⁇ S / cm or less or an aqueous solution in which the pH is lowered to 1 at maximum by adding an acid to the pure water. It has a particle size peak of 10 to 15 ⁇ m when measured with a laser light blocking liquid particle counter at 50 ⁇ m or less, and the number in the peak region is 1000 / mL or more.
- an ozone generator and a microbubble generator are provided, and ozone is used as means for bringing the water containing fine bubbles containing ozone into contact with the surface of the semiconductor wafer.
- a water injection nozzle containing microbubbles contained therein is provided.
- the semiconductor wafer is placed in a treatment tank filled with water containing microbubbles containing ozone by fixing means (not shown), and water containing microbubbles containing ozone is sprayed onto the semiconductor wafer from above in water. It is configured to be.
- FIG. 2 is a basic configuration diagram of an example of an apparatus for performing cleaning by applying water containing fine bubbles containing ozone to a semiconductor wafer.
- the apparatus shown in FIG. 2 is configured such that a semiconductor wafer is placed above a water receiving tank by a fixing means (not shown), and water containing microbubbles containing ozone is sprayed onto the semiconductor wafer from above. 1 is different from the apparatus shown in FIG. 1 (other configurations are the same as those of the apparatus shown in FIG. 1).
- microbubbles By bringing water containing ozone-containing microbubbles into contact with the surface of the semiconductor wafer, microbubbles (its zeta) that rapidly shrinks and disappears due to physical and chemical stimuli at and near the interface with the object to be removed.
- the potential measured by electrophoresis is +20 to -120 mV depending on the pH of the water, and is positively charged under strong acidic conditions and negatively charged under other conditions).
- the concentrated hydroxyl ions are released to the surrounding space at a stretch, and at that time, ozone molecules existing inside and around the bubbles are decomposed to generate active species containing at least hydroxyl radicals.
- the material is strongly decomposed or solubilized, and the removal target is urged to be detached from the surface of the semiconductor wafer.
- Example 1 For example, pure water having an electric conductivity of 1 ⁇ S / cm or less is prepared at room temperature under a high pressure of 4 atm according to a method using a pressure dissolution method described in JP-A-2003-265938, and an inhalation gas After the ozone was dissolved, microbubbles containing ozone having a particle size distribution of 1 ⁇ m to 50 ⁇ m were generated in pure water from the supersaturated condition of the dissolved ozone generated by opening the ozone to atmospheric pressure. The microbubbles had a particle size peak at 10 to 15 ⁇ m as measured by a laser light blocking liquid particle counter, and the number of microbubbles in the peak area was 1000 / mL or more.
- the zeta potential of the microbubbles was about ⁇ 20 mV (measured by electrophoresis).
- the pure water containing the released microbubbles was mixed in a beaker containing about 5000 mL of pure water, and the pure water in the beaker was again sucked into the microbubble generator. Under this condition, a wafer (silicon wafer) coated with a resist was placed at a position 5 cm away from the outlet of pure water containing microbubbles. The wafer had a diameter of about 12.5 cm, and a novolac resin was applied to the surface with a thickness of 1300 nm. Under these conditions, pure water containing microbubbles was allowed to collide with the wafer surface for 20 minutes.
- FIG. 3 shows the results of measuring the hydroxyl radical generated in water by electron spin resonance using DMPO (5,5-dimethyl-1-pyrroline-N-oxide), which is a spin trapping agent.
- FIG. 4 shows a photograph of an unprocessed wafer and a processed wafer. In addition, when the surface of the wafer before and after the processing was analyzed with an energy dispersive X-ray fluorescence analyzer, Si was 98.817% and S was 1.183% before the processing.
- Si was 100% and S was 0%. Further, from the infrared absorption spectrum analysis of FT-IR, absorption such as benzene ring and C ⁇ O, C—O, C—H, etc., recognized before the treatment was not recognized after the treatment. In addition, after sampling the water in the treatment tank after processing, it is analyzed whether it contains novolak resin coated on the wafer as a resist and phenol, cresol, and dimethylphenol known as degradation products. As a result, the presence of these organic substances was not recognized. This was considered due to the fact that the novolac resin was decomposed very effectively to carbon dioxide and water.
- Example 2 Using a microbubble generator known per se (see Japanese Patent Application Laid-Open No. 2003-265938 if necessary), the particle size distribution is 50 ⁇ m or less, and the measurement with a laser light blocking type particle counter in liquid is 10 A microbubble containing ozone having a particle size peak at ⁇ 15 ⁇ m and the number of microbubbles in the peak area of 1000 / mL or more in pure water having an electric conductivity of 1 ⁇ S / cm or less. While being continuously generated, this water was poured in a flowing state on a wafer having a diameter of 8 inches in which a novolak resin was applied to the surface with a thickness of 1300 nm. The distance from the water outlet to the wafer was about 5 cm.
- the water spilled from the wafer was collected in a beaker containing about 3000 L of water, and then circulated by being sucked again by the microbubble generator.
- pure water at room temperature electrical conductivity is 1 ⁇ S / cm or less
- the experiment was continued for 20 minutes under these conditions.
- Si was 98.767% and S was 1.233% before processing, but Si after processing was Si. At 100%, S was 0%.
- Comparative Example 1 A cleaning test was performed on a semiconductor wafer coated with a resist using ozone water, which is a conventional method. Ozone was released at room temperature using a diffuser tube into pure water with a conductivity of 1 ⁇ S / cm or less filled in a 5000 mL beaker. The ozone generator used had an ozone amount of 5 g / L and a gas amount of 2 L / min. In Examples 1 and 2, about half of this amount of gas was used, but in this test, all of the amount of gas generated from the device was released from the diffuser.
- the present invention has industrial applicability in that it can provide a semiconductor wafer cleaning method and cleaning apparatus using ozone that is effective even at about room temperature and is environmentally friendly.
Abstract
Disclosed are a method for cleaning a semiconductor wafer using ozone, which is effective even at a temperature around room temperature and is environmentally friendly, and a device for cleaning semiconductor wafer. The method for cleaning a semiconductor wafer is characterized in that water containing ozone-containing microbubbles is brought into contact with the surface of a semiconductor wafer and the ozone-containing microbubbles have been produced in pure water having an electric conductivity of not more than 1 μS/cm or an aqueous solution having a pH value lowered to 1 at the maximum by the addition of an acid to the pure water, have a particle diameter of not more than 50 μm, and have a peak of particle diameters of 10 to 15 μm as measured with a submerged particle counter in a laser beam cutoff system, the number of the ozone-containing microbubbles in the peak region being not less than 1000 particles/mL. The device for cleaning a semiconductor wafer is characterized by comprising at least means for producing the water containing ozone-containing microbubbles and means for bringing the water containing ozone-containing microbubbles thus produced into contact with the surface of the semiconductor wafer.
Description
本発明は、半導体ウエハの表面の、レジストなどの有機物、汚染物質、残存薬液などの除去のための洗浄方法および洗浄装置に関する。
The present invention relates to a cleaning method and a cleaning apparatus for removing organic substances such as resist, contaminants, residual chemicals and the like on the surface of a semiconductor wafer.
半導体の製造工程は、回路設計工程、マスク製造工程、ウエハ製造工程、ウエハ処理工程、組立工程、検査工程および排出物処理工程などから成り立っており、その中でも特にウエハ処理工程では洗浄が重要な技術として位置づけられている。ウエハ処理工程は、ウエハの研磨工程、基板工程および配線工程などからなり、洗浄、エッチング、レジスト除去などによって実施される。半導体の製造では工程毎に洗浄が繰り返されるため、半導体製造の全工程数における洗浄工程数の比率は約３０％を占めると言われている。
この様な中にあって、ＲＣＡ洗浄法が開発され、ウエハ洗浄に大きく貢献してきた。ＲＣＡ洗浄法は、過酸化水素（Ｈ２Ｏ２）をベースとした洗浄法であり、硫酸過酸化水素水（ＳＰＭ）による有機物除去、アンモニア過酸化水素水（ＡＰＭ）による粒子除去、塩酸過酸化水素水（ＨＰＭ）による金属不純物除去、希フッ酸（ＤＨＦ）による自然酸化膜および熱酸化膜除去、および超純水による最終洗浄で構成される。
硫酸過酸化水素水を用いた処理は、硫酸と過酸化水素水を組み合わせて行うものであり、主に有機物を除去するために利用されるが、金属不純物除去効果もあり、１３０～１５０℃程度の温度で実施される。アンモニア過酸化水素水を用いた処理は、アンモニアと過酸化水素水を組み合わせて行うものであり、粒子や有機物を除去するために３０～７０℃程度の温度で実施される。塩酸過酸化水素水を用いた処理は、塩酸と過酸化水素水を組み合わせて行うものであり、３０℃程度の温度で、金属不純物を除去するために実施される。希フッ酸を用いた処理は、酸化膜や金属不純物を除去するために利用され、通常は室温の２５℃程度で実施される。また、これらと合わせて、１ＭＨｚ程度の超音波（メガソニック）などを併用することで、化学作用と物理作用の相乗効果を利用する場合もある。
今日、半導体製造を取り巻く状況としては、大きな流れとして超微細構造への推移と環境への配慮がある。このことから、より高度な清浄技術の要求と共に、現在の薬液中心の洗浄方法からの脱却が要望されている。その様な流れの中で、オゾンを水中でバブリングさせて製造される、機能水としてのオゾン水の利用が注目されている。オゾン水には有機物に対する除去効果があり、また、枚葉式を採用することで、除去対象物の除去過程でウエハが自己汚染を受けることを回避でき、洗浄効果を向上させることが期待できる。しかしながら、基本的にオゾン水によるウエハの洗浄効果は優れているとは言えないため、例えば、オゾン水の温度を上げるなどの方法を採用しなければならない（特許文献１）。けれども、このような方法には、加熱することに伴うエネルギーや時間のロスの問題がある。また、ウエハとオゾン水との間に温度差があった場合、ウエハの熱変形により基板が破壊してしまうといった問題がある。
特開２００４－３１９７２号公報
The semiconductor manufacturing process consists of a circuit design process, mask manufacturing process, wafer manufacturing process, wafer processing process, assembly process, inspection process, and waste processing process. Among them, cleaning is an important technology especially in the wafer processing process. It is positioned as. The wafer processing process includes a wafer polishing process, a substrate process, a wiring process, and the like, and is performed by cleaning, etching, resist removal, and the like. In semiconductor manufacturing, since cleaning is repeated for each process, it is said that the ratio of the number of cleaning processes to the total number of processes in semiconductor manufacturing accounts for about 30%.
Under such circumstances, an RCA cleaning method has been developed and has greatly contributed to wafer cleaning. The RCA cleaning method is a cleaning method based on hydrogen peroxide (H 2 O 2 ), removing organic substances with sulfuric acid hydrogen peroxide (SPM), removing particles with ammonia hydrogen peroxide (APM), and hydrochloric acid peroxidation. It consists of metal impurity removal with hydrogen water (HPM), natural oxide film and thermal oxide film removal with dilute hydrofluoric acid (DHF), and final cleaning with ultrapure water.
The treatment using sulfuric acid / hydrogen peroxide solution is performed by combining sulfuric acid and hydrogen peroxide solution, and is mainly used to remove organic substances, but also has an effect of removing metal impurities, and is about 130 to 150 ° C. At a temperature of The treatment using ammonia hydrogen peroxide solution is performed by combining ammonia and hydrogen peroxide solution, and is performed at a temperature of about 30 to 70 ° C. in order to remove particles and organic substances. The treatment using hydrochloric acid and hydrogen peroxide is performed by combining hydrochloric acid and hydrogen peroxide, and is performed at a temperature of about 30 ° C. to remove metal impurities. The treatment using dilute hydrofluoric acid is used to remove oxide films and metal impurities, and is usually performed at about 25 ° C. at room temperature. In addition, in combination with these, there is a case where a synergistic effect of a chemical action and a physical action is used by using an ultrasonic wave (megasonic) of about 1 MHz.
As for the situation surrounding semiconductor manufacturing today, transition to ultrafine structure and environmental considerations are a major trend. For this reason, with the request of more advanced cleaning technology, there is a demand for a departure from current chemical-centered cleaning methods. In such a flow, the use of ozone water as functional water produced by bubbling ozone in water is drawing attention. Ozone water has an effect of removing organic substances, and by adopting a single wafer type, it can be expected that the wafer is not subject to self-contamination in the process of removing the object to be removed, and that the cleaning effect can be improved. However, since it cannot be said that the cleaning effect of the wafer with ozone water is basically excellent, for example, a method of increasing the temperature of the ozone water must be employed (Patent Document 1). However, such a method has a problem of loss of energy and time associated with heating. Further, when there is a temperature difference between the wafer and the ozone water, there is a problem that the substrate is destroyed due to thermal deformation of the wafer.
JP 2004-31972 A
この様な中にあって、ＲＣＡ洗浄法が開発され、ウエハ洗浄に大きく貢献してきた。ＲＣＡ洗浄法は、過酸化水素（Ｈ２Ｏ２）をベースとした洗浄法であり、硫酸過酸化水素水（ＳＰＭ）による有機物除去、アンモニア過酸化水素水（ＡＰＭ）による粒子除去、塩酸過酸化水素水（ＨＰＭ）による金属不純物除去、希フッ酸（ＤＨＦ）による自然酸化膜および熱酸化膜除去、および超純水による最終洗浄で構成される。
硫酸過酸化水素水を用いた処理は、硫酸と過酸化水素水を組み合わせて行うものであり、主に有機物を除去するために利用されるが、金属不純物除去効果もあり、１３０～１５０℃程度の温度で実施される。アンモニア過酸化水素水を用いた処理は、アンモニアと過酸化水素水を組み合わせて行うものであり、粒子や有機物を除去するために３０～７０℃程度の温度で実施される。塩酸過酸化水素水を用いた処理は、塩酸と過酸化水素水を組み合わせて行うものであり、３０℃程度の温度で、金属不純物を除去するために実施される。希フッ酸を用いた処理は、酸化膜や金属不純物を除去するために利用され、通常は室温の２５℃程度で実施される。また、これらと合わせて、１ＭＨｚ程度の超音波（メガソニック）などを併用することで、化学作用と物理作用の相乗効果を利用する場合もある。
今日、半導体製造を取り巻く状況としては、大きな流れとして超微細構造への推移と環境への配慮がある。このことから、より高度な清浄技術の要求と共に、現在の薬液中心の洗浄方法からの脱却が要望されている。その様な流れの中で、オゾンを水中でバブリングさせて製造される、機能水としてのオゾン水の利用が注目されている。オゾン水には有機物に対する除去効果があり、また、枚葉式を採用することで、除去対象物の除去過程でウエハが自己汚染を受けることを回避でき、洗浄効果を向上させることが期待できる。しかしながら、基本的にオゾン水によるウエハの洗浄効果は優れているとは言えないため、例えば、オゾン水の温度を上げるなどの方法を採用しなければならない（特許文献１）。けれども、このような方法には、加熱することに伴うエネルギーや時間のロスの問題がある。また、ウエハとオゾン水との間に温度差があった場合、ウエハの熱変形により基板が破壊してしまうといった問題がある。
Under such circumstances, an RCA cleaning method has been developed and has greatly contributed to wafer cleaning. The RCA cleaning method is a cleaning method based on hydrogen peroxide (H 2 O 2 ), removing organic substances with sulfuric acid hydrogen peroxide (SPM), removing particles with ammonia hydrogen peroxide (APM), and hydrochloric acid peroxidation. It consists of metal impurity removal with hydrogen water (HPM), natural oxide film and thermal oxide film removal with dilute hydrofluoric acid (DHF), and final cleaning with ultrapure water.
The treatment using sulfuric acid / hydrogen peroxide solution is performed by combining sulfuric acid and hydrogen peroxide solution, and is mainly used to remove organic substances, but also has an effect of removing metal impurities, and is about 130 to 150 ° C. At a temperature of The treatment using ammonia hydrogen peroxide solution is performed by combining ammonia and hydrogen peroxide solution, and is performed at a temperature of about 30 to 70 ° C. in order to remove particles and organic substances. The treatment using hydrochloric acid and hydrogen peroxide is performed by combining hydrochloric acid and hydrogen peroxide, and is performed at a temperature of about 30 ° C. to remove metal impurities. The treatment using dilute hydrofluoric acid is used to remove oxide films and metal impurities, and is usually performed at about 25 ° C. at room temperature. In addition, in combination with these, there is a case where a synergistic effect of a chemical action and a physical action is used by using an ultrasonic wave (megasonic) of about 1 MHz.
As for the situation surrounding semiconductor manufacturing today, transition to ultrafine structure and environmental considerations are a major trend. For this reason, with the request of more advanced cleaning technology, there is a demand for a departure from current chemical-centered cleaning methods. In such a flow, the use of ozone water as functional water produced by bubbling ozone in water is drawing attention. Ozone water has an effect of removing organic substances, and by adopting a single wafer type, it can be expected that the wafer is not subject to self-contamination in the process of removing the object to be removed, and that the cleaning effect can be improved. However, since it cannot be said that the cleaning effect of the wafer with ozone water is basically excellent, for example, a method of increasing the temperature of the ozone water must be employed (Patent Document 1). However, such a method has a problem of loss of energy and time associated with heating. Further, when there is a temperature difference between the wafer and the ozone water, there is a problem that the substrate is destroyed due to thermal deformation of the wafer.
そこで本発明は、室温程度で行っても効果的であって、しかも環境にやさしい、オゾンを用いた半導体ウエハの洗浄方法および洗浄装置を提供することを目的とする。
Accordingly, an object of the present invention is to provide a semiconductor wafer cleaning method and apparatus using ozone that are effective even at room temperature and are environmentally friendly.
本発明者は上記の点に鑑みて鋭意研究を重ねた結果、二相流旋回方式や加圧溶解方式によって生成させた、所定の気泡特性を有するオゾンを含有するマイクロオーダーの微小気泡を含む水（オゾンマイクロバブル水）が、半導体ウエハの洗浄に効果的であることを見出した。
As a result of intensive research in view of the above points, the present inventor has obtained water containing micro-order microbubbles containing ozone having a predetermined bubble characteristic, generated by a two-phase flow swirl method or a pressure dissolution method. It has been found that (ozone microbubble water) is effective for cleaning semiconductor wafers.
以上の知見に基づいてなされた本発明の半導体ウエハの洗浄方法は、請求項１記載の通り、電気伝導度が１μＳ／ｃｍ以下である純水中または前記純水に酸を添加することでｐＨを最大で１まで低下させた水溶液中において生成させた、粒径が５０μｍ以下で、レーザー光遮断方式の液中パーティクルカウンターによる計測において１０～１５μｍに粒径のピークを有しており、そのピークの領域における個数が１０００個／ｍＬ以上である、オゾンを含有する微小気泡を含む水を、半導体ウエハの表面に接触させて行うことを特徴とする。
また、請求項２記載の洗浄方法は、請求項１記載の洗浄方法において、オゾンを含有する微小気泡を含む水中に半導体ウエハを浸漬させるか、または、オゾンを含有する微小気泡を含む水を半導体ウエハにかけることで行うことを特徴とする。
また、本発明の半導体ウエハの洗浄装置は、請求項３記載の通り、電気伝導度が１μＳ／ｃｍ以下である純水中または前記純水に酸を添加することでｐＨを最大で１まで低下させた水溶液中において生成させた、粒径が５０μｍ以下で、レーザー光遮断方式の液中パーティクルカウンターによる計測において１０～１５μｍに粒径のピークを有しており、そのピークの領域における個数が１０００個／ｍＬ以上である、オゾンを含有する微小気泡を含む水を製造するための手段と、製造されたオゾンを含有する微小気泡を含む水を半導体ウエハの表面に接触させるための手段を少なくとも有することを特徴とする。 The method for cleaning a semiconductor wafer of the present invention based on the above knowledge is as described in claim 1, wherein the pH is obtained by adding an acid to pure water having an electric conductivity of 1 μS / cm or less or to the pure water. The particle size is 50 μm or less, which is generated in an aqueous solution with a maximum reduced to 1, and has a particle size peak at 10 to 15 μm when measured with a laser light blocking liquid particle counter. This is characterized in that water containing fine bubbles containing ozone and having a number in the region of 1000 / mL or more is brought into contact with the surface of the semiconductor wafer.
The cleaning method according to claim 2 is the cleaning method according to claim 1, wherein the semiconductor wafer is immersed in water containing microbubbles containing ozone, or water containing microbubbles containing ozone is used as a semiconductor. It is characterized by being performed by placing on a wafer.
Further, according to the semiconductor wafer cleaning apparatus of the present invention, the pH is lowered to 1 at the maximum by adding acid to pure water having an electric conductivity of 1 μS / cm or less, or to the pure water. The particle size is 50 μm or less, and the particle size peak is 10 to 15 μm as measured with a laser light blocking liquid particle counter, and the number in the peak region is 1000. At least means for producing water containing microbubbles containing ozone, and at least means for bringing the water containing microbubbles containing ozone produced into contact with the surface of the semiconductor wafer It is characterized by that.
また、請求項２記載の洗浄方法は、請求項１記載の洗浄方法において、オゾンを含有する微小気泡を含む水中に半導体ウエハを浸漬させるか、または、オゾンを含有する微小気泡を含む水を半導体ウエハにかけることで行うことを特徴とする。
また、本発明の半導体ウエハの洗浄装置は、請求項３記載の通り、電気伝導度が１μＳ／ｃｍ以下である純水中または前記純水に酸を添加することでｐＨを最大で１まで低下させた水溶液中において生成させた、粒径が５０μｍ以下で、レーザー光遮断方式の液中パーティクルカウンターによる計測において１０～１５μｍに粒径のピークを有しており、そのピークの領域における個数が１０００個／ｍＬ以上である、オゾンを含有する微小気泡を含む水を製造するための手段と、製造されたオゾンを含有する微小気泡を含む水を半導体ウエハの表面に接触させるための手段を少なくとも有することを特徴とする。 The method for cleaning a semiconductor wafer of the present invention based on the above knowledge is as described in claim 1, wherein the pH is obtained by adding an acid to pure water having an electric conductivity of 1 μS / cm or less or to the pure water. The particle size is 50 μm or less, which is generated in an aqueous solution with a maximum reduced to 1, and has a particle size peak at 10 to 15 μm when measured with a laser light blocking liquid particle counter. This is characterized in that water containing fine bubbles containing ozone and having a number in the region of 1000 / mL or more is brought into contact with the surface of the semiconductor wafer.
The cleaning method according to claim 2 is the cleaning method according to claim 1, wherein the semiconductor wafer is immersed in water containing microbubbles containing ozone, or water containing microbubbles containing ozone is used as a semiconductor. It is characterized by being performed by placing on a wafer.
Further, according to the semiconductor wafer cleaning apparatus of the present invention, the pH is lowered to 1 at the maximum by adding acid to pure water having an electric conductivity of 1 μS / cm or less, or to the pure water. The particle size is 50 μm or less, and the particle size peak is 10 to 15 μm as measured with a laser light blocking liquid particle counter, and the number in the peak region is 1000. At least means for producing water containing microbubbles containing ozone, and at least means for bringing the water containing microbubbles containing ozone produced into contact with the surface of the semiconductor wafer It is characterized by that.
本発明によれば、室温程度で行っても効果的であって、しかも環境にやさしい、オゾンを用いた半導体ウエハの洗浄方法および洗浄装置を提供することができる。
According to the present invention, it is possible to provide a semiconductor wafer cleaning method and apparatus using ozone, which is effective even at about room temperature and is environmentally friendly.
本発明の半導体ウエハの洗浄方法は、電気伝導度が１μＳ／ｃｍ以下である純水中または前記純水に酸を添加することでｐＨを最大で１まで低下させた水溶液中において生成させた、粒径が５０μｍ以下で、レーザー光遮断方式の液中パーティクルカウンターによる計測において１０～１５μｍに粒径のピークを有しており、そのピークの領域における個数が１０００個／ｍＬ以上である、オゾンを含有する微小気泡を含む水を、半導体ウエハの表面に接触させて行うことを特徴とするものである。
The method for cleaning a semiconductor wafer of the present invention was produced in pure water having an electric conductivity of 1 μS / cm or less or in an aqueous solution having a pH lowered to 1 at maximum by adding an acid to the pure water. Ozone with a particle size of 50 μm or less, having a particle size peak at 10 to 15 μm as measured by an in-liquid particle counter using a laser light blocking method, and having a number in the peak area of 1000 / mL or more. It is characterized in that it is carried out by bringing water containing microbubbles contained into contact with the surface of the semiconductor wafer.
本発明において使用する、オゾンを含有する微小気泡を含む水は、例えば、自体公知の二相流旋回方式や加圧溶解方式による微小気泡発生装置を利用して製造することができる。二相流旋回方式を採用する場合、回転子などを利用して半径が１０ｃｍ以下の渦流を強制的に生じせしめ、壁面などの障害物や相対速度の異なる流体にオゾンを含んだ気液混合物を打ち当てることにより、渦流中に獲得したオゾンを含んだ気体成分を渦の消失とともに分散させることで、所望のオゾンを含んだ微小気泡を大量に発生させることができる。また、加圧溶解方式を採用する場合、２気圧以上の高圧下でオゾンを含んだ気体を水中に溶解させた後、これを大気圧に開放することにより生じたオゾンを含んだ溶解気体の過飽和条件からオゾンを含んだ気泡を発生させることができる。この場合、圧力の開放部位において、水流と障害物を利用して半径が１ｍｍ以下の渦を多数発生させ、渦流の中心域における水の分子揺動を起因として多量の気相の核（気泡核）を形成させるとともに、過飽和条件に伴ってこれらの気泡核に向かって水中のオゾンを含んだ気体成分を拡散させ、気泡核を成長させることにより、所望のオゾンを含んだ微小気泡を大量に発生させることができる。なお、これらの方法によって発生した気泡は、粒径が５０μｍ以下の微小気泡で、レーザー光遮断方式の液中パーティクルカウンターによる計測において１０～１５μｍに粒径のピークを有しており、そのピークの領域における微小気泡の個数は１０００個／ｍＬ以上である（必要であれば特開２０００－５１１０７号公報や特開２００３－２６５９３８号公報などを参照のこと）。
The water containing ozone-containing microbubbles used in the present invention can be produced, for example, using a microbubble generator using a known two-phase flow swirling method or pressure dissolution method. When the two-phase flow swirl method is adopted, a vortex with a radius of 10 cm or less is forcibly generated using a rotor, etc., and a gas-liquid mixture containing ozone in obstacles such as wall surfaces or fluids with different relative velocities. By striking, the gas component containing ozone acquired in the vortex is dispersed along with the disappearance of the vortex, so that a large amount of microbubbles containing the desired ozone can be generated. In addition, when the pressure dissolution method is adopted, supersaturation of dissolved gas containing ozone generated by dissolving ozone-containing gas in water under high pressure of 2 atm or higher and then releasing it to atmospheric pressure. Bubbles containing ozone can be generated from the conditions. In this case, a large number of vortices having a radius of 1 mm or less are generated at the pressure release site using water flow and obstacles, and a large amount of gas phase nuclei (bubble nuclei due to water molecular fluctuations in the central region of the vortex flow. ) And a large amount of microbubbles containing the desired ozone are generated by diffusing gaseous components containing ozone in water toward these bubble nuclei along with supersaturation conditions and growing the bubble nuclei. Can be made. The bubbles generated by these methods are microbubbles having a particle size of 50 μm or less, and have a particle size peak at 10 to 15 μm when measured with a laser light blocking liquid particle counter. The number of microbubbles in the region is 1000 / mL or more (see JP 2000-51107 A, JP 2003-265938 A, etc. if necessary).
オゾンを含んだ微小気泡を発生させる電気伝導度が１μＳ／ｃｍ以下である純水のｐＨは特段限定されるものではない。しかしながら、ｐＨが１０を超えるような高アルカリ条件は、オゾンが半導体ウエハの表面に接触する前に大部分が分解してしまうため好ましくない。一方、弱アルカリ性から強酸性の条件（例えばｐＨ１～１０）においては、レジストや有機物の分解、除去において十分に強力な洗浄効果を発揮することができる。なお、酸化膜や金属不純物などの金属汚染を除去する目的では酸性条件がより好ましいが、排水による環境汚染や取扱の容易さを考えれば、ｐＨ調整を行っていない純水（ｐＨは約７）の利用が好ましい。
The pH of pure water whose electric conductivity for generating microbubbles containing ozone is 1 μS / cm or less is not particularly limited. However, a high alkali condition in which the pH exceeds 10 is not preferable because most of the ozone decomposes before ozone contacts the surface of the semiconductor wafer. On the other hand, under weakly alkaline to strongly acidic conditions (for example, pH 1 to 10), a sufficiently strong cleaning effect can be exhibited in the decomposition and removal of resists and organic substances. It should be noted that acidic conditions are more preferable for the purpose of removing metal contamination such as oxide film and metal impurities, but pure water that has not been adjusted for pH (pH is about 7) in consideration of environmental pollution by drainage and ease of handling. Is preferably used.
本発明において、オゾンを含有する微小気泡を含む水を半導体ウエハの表面に接触させる方法は、特段限定されず、例えば、オゾンを含有する微小気泡を含む水中に半導体ウエハを浸漬させたり、オゾンを含有する微小気泡を含む水を半導体ウエハにかけたりすることで行うことができる。オゾンを含有する微小気泡を含む水中に半導体ウエハを浸漬させる場合、流動する水中に半導体ウエハを設置したり、水中の半導体ウエハに対してオゾンを含有する微小気泡を含む水を噴射したりすることで、水中に分散させた多数のオゾンを含む微小気泡がウエハの表面に衝突して作用するようにすることが好ましい。オゾンを含有する微小気泡を含む水を半導体ウエハにかける方法としては、流水方式、噴霧方式、シャワー方式などが挙げられる。洗浄は、バッチ式で行ってもよいが、枚葉式で行うことが、除去対象物の除去過程でウエハが自己汚染を受けることを回避できる点において好ましい。
In the present invention, the method of bringing water containing ozone-containing microbubbles into contact with the surface of the semiconductor wafer is not particularly limited. For example, the semiconductor wafer is immersed in water containing ozone-containing microbubbles or ozone is used. It can be performed by applying water containing fine bubbles to the semiconductor wafer. When a semiconductor wafer is immersed in water containing microbubbles containing ozone, the semiconductor wafer is placed in flowing water, or water containing microbubbles containing ozone is injected into the semiconductor wafer in water. Thus, it is preferable that microbubbles containing a large number of ozone dispersed in water collide with the surface of the wafer to act. Examples of a method of applying water containing fine bubbles containing ozone to a semiconductor wafer include a flowing water method, a spray method, and a shower method. The cleaning may be performed in a batch mode, but it is preferable to perform the cleaning in a single wafer mode in that the wafer can be prevented from being subjected to self-contamination in the process of removing the object to be removed.
図１は、オゾンを含有する微小気泡を含む水中に半導体ウエハを浸漬させて洗浄を行うための装置の一例の基本構成図である。図１に示す装置は、電気伝導度が１μＳ／ｃｍ以下である純水中または前記純水に酸を添加することでｐＨを最大で１まで低下させた水溶液中において生成させた、粒径が５０μｍ以下で、レーザー光遮断方式の液中パーティクルカウンターによる計測において１０～１５μｍに粒径のピークを有しており、そのピークの領域における個数が１０００個／ｍＬ以上である、オゾンを含有する微小気泡を含む水を製造するための手段として、オゾン発生装置とマイクロバブル発生装置を備え、製造されたオゾンを含有する微小気泡を含む水を半導体ウエハの表面に接触させるための手段として、オゾンを含有する微小気泡を含む水の噴射ノズルを備える。半導体ウエハは図略の固定手段によってオゾンを含有する微小気泡を含む水が満たされた処理槽内に設置され、水中でその上方からオゾンを含有する微小気泡を含む水が半導体ウエハに対して噴射されるように構成されている。半導体ウエハの洗浄中に発生する浮遊物は、処理槽からのオゾンを含有する微小気泡を含む水のオーバーフローによって極めて効果的に除去され、一定の処理時間が経過した後の処理槽内の水は、廃棄されるかオゾンを含有する微小気泡を含む水を製造するための水として再利用される（後述する実施例から明らかなように半導体ウエハの洗浄に使用した後の水であってもオゾンを含有する微小気泡の作用によってそこに含まれる有機物は皆無または皆無に等しいので再利用を図っても半導体ウエハに対する有機物の再付着はない）。図２は、オゾンを含有する微小気泡を含む水を半導体ウエハにかけて洗浄を行うための装置の一例の基本構成図である。図２に示す装置は、水受けタンクの上方に半導体ウエハが図略の固定手段によって設置され、その上方からオゾンを含有する微小気泡を含む水が半導体ウエハに対して噴射されるように構成されている点が図１に示す装置と異なる（その他の構成は図１に示す装置の構成と同じである）。
FIG. 1 is a basic configuration diagram of an example of an apparatus for performing cleaning by immersing a semiconductor wafer in water containing microbubbles containing ozone. The apparatus shown in FIG. 1 has a particle size generated in pure water having an electric conductivity of 1 μS / cm or less or an aqueous solution in which the pH is lowered to 1 at maximum by adding an acid to the pure water. It has a particle size peak of 10 to 15 μm when measured with a laser light blocking liquid particle counter at 50 μm or less, and the number in the peak region is 1000 / mL or more. As means for producing water containing bubbles, an ozone generator and a microbubble generator are provided, and ozone is used as means for bringing the water containing fine bubbles containing ozone into contact with the surface of the semiconductor wafer. A water injection nozzle containing microbubbles contained therein is provided. The semiconductor wafer is placed in a treatment tank filled with water containing microbubbles containing ozone by fixing means (not shown), and water containing microbubbles containing ozone is sprayed onto the semiconductor wafer from above in water. It is configured to be. The suspended matter generated during the cleaning of the semiconductor wafer is extremely effectively removed by the overflow of water containing microbubbles containing ozone from the processing tank, and the water in the processing tank after a certain processing time has passed. , Which is discarded or reused as water for producing water containing microbubbles containing ozone (even if the water is used for cleaning semiconductor wafers, as will be clear from the examples described later) The organic matter contained therein is completely or completely absent by the action of the microbubbles containing, so that even if reuse is attempted, the organic matter does not reattach to the semiconductor wafer). FIG. 2 is a basic configuration diagram of an example of an apparatus for performing cleaning by applying water containing fine bubbles containing ozone to a semiconductor wafer. The apparatus shown in FIG. 2 is configured such that a semiconductor wafer is placed above a water receiving tank by a fixing means (not shown), and water containing microbubbles containing ozone is sprayed onto the semiconductor wafer from above. 1 is different from the apparatus shown in FIG. 1 (other configurations are the same as those of the apparatus shown in FIG. 1).
オゾンを含有する微小気泡を含む水を半導体ウエハの表面に接触させることで、除去対象物との界面やその近傍において、物理的および化学的な刺激によって急激に縮小し消滅する微小気泡（そのゼータ電位を電気泳動法によって測定すると水のｐＨに応じて＋２０～－１２０ｍＶであり、強い酸性条件下ではプラス帯電でその他の条件下ではマイナス帯電である）が、その消滅の過程で気液界面に濃縮した水酸基イオンなどを周辺空間に一気に開放し、その際に、気泡の内部や周辺に存在するオゾン分子を分解して少なくとも水酸基ラジカルを含む活性種を生成させ、生成した活性種が、除去対象物を強力に分解乃至可溶化し、また、除去対象物の半導体ウエハの表面からの離脱を促す。従って、オゾンを含有する微小気泡を含む水が室温程度（例えば１０～４０℃）であっても、優れた洗浄効果を発揮する。なお、従来から知られているオゾンを水中でバブリングさせて製造されるオゾン水を利用した洗浄方法の場合、生成する気泡は、水中を浮上して水面で破壊されてしまう、主たる粒径が約１ｍｍ程度のものであり、バブリングによってオゾンを水中に単に溶解させているだけであることから、水中で気泡が消滅することによって活性種が生成するといったことはなく、よって、洗浄効果は、水中に溶解したオゾンによる作用に過ぎない。この相違が、本発明による洗浄方法と従来の洗浄方法との効果の相違に反映されている。
By bringing water containing ozone-containing microbubbles into contact with the surface of the semiconductor wafer, microbubbles (its zeta) that rapidly shrinks and disappears due to physical and chemical stimuli at and near the interface with the object to be removed. The potential measured by electrophoresis is +20 to -120 mV depending on the pH of the water, and is positively charged under strong acidic conditions and negatively charged under other conditions). The concentrated hydroxyl ions are released to the surrounding space at a stretch, and at that time, ozone molecules existing inside and around the bubbles are decomposed to generate active species containing at least hydroxyl radicals. The material is strongly decomposed or solubilized, and the removal target is urged to be detached from the surface of the semiconductor wafer. Therefore, even if the water containing ozone-containing microbubbles is about room temperature (for example, 10 to 40 ° C.), an excellent cleaning effect is exhibited. In addition, in the case of a cleaning method using ozone water that is produced by bubbling ozone that is conventionally known in the water, the bubbles that are generated float about in the water and are destroyed on the surface of the water. Since the ozone is simply dissolved in water by bubbling, active species are not generated by the disappearance of bubbles in the water. It is only the effect of dissolved ozone. This difference is reflected in the difference in effect between the cleaning method of the present invention and the conventional cleaning method.
以下、本発明を実施例によって詳細に説明するが、本発明は以下の記載に限定して解釈されるものではない。
Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not construed as being limited to the following description.
実施例１：
例えば、特開２００３－２６５９３８号公報に記載の加圧溶解方式による方法に従って、４気圧の高圧下で、常温にて電気伝導度が１μＳ／ｃｍ以下である純水を調製し、かつ、吸入気体としてオゾンを溶解させた後、これを大気圧に開放することにより生じた溶解オゾンの過飽和条件から粒径分布が１μｍ～５０μｍのオゾンを含む微小気泡を純水中に発生させた。この微小気泡は、レーザー光遮断方式の液中パーティクルカウンターによる計測において１０～１５μｍに粒径のピークを有しており、そのピークの領域における微小気泡の個数は１０００個／ｍＬ以上であった。また、微小気泡のゼータ電位は約－２０ｍＶであった（電気泳動法による測定）。放出した微小気泡を含む純水は約５０００ｍＬの純水を含むビーカー中で混合され、そのビーカー中の純水は再び微小気泡の発生装置に吸引させた。この条件において、微小気泡を含む純水の排出口から５ｃｍ離れた位置にレジストを塗布したウエハ（シリコンウエハ）を設置した。ウエハは直径が約１２．５ｃｍであり、表面にノボラック樹脂を１３００ｎｍの厚さで塗布したものとした。この条件で、２０分間連続して微小気泡を含む純水をウエハの表面に衝突させた。処理開始時の水温は約２０℃であり、終了時の温度は約２８℃であった。また、処理終了時のｐＨはオゾンなどの影響で弱い酸性を示しており５．４７であった。水中で発生した水酸基ラジカルを、スピントラップ剤であるＤＭＰＯ（５，５－ジメチル－１－ピロリン－Ｎ－オキサイド）を用いて電子スピン共鳴法で測定した結果を図３に示す。また、未処理のウエハと処理後のウエハの写真を図４に示す。また、処理前と処理後のウエハの表面をエネルギー分散型蛍光Ｘ線分析装置で解析したところ、処理前はＳｉが９８．８１７％でＳが１．１８３％であったものが、処理後ではＳｉが１００％でＳが０％となった。また、ＦＴ－ＩＲの赤外吸収スペクトル分析からは処理前に認められたベンゼン環やＣ＝Ｏ、Ｃ－Ｏ、Ｃ－Ｈなどの吸収が処理後では認められなくなった。さらに、処理後の処理槽の水をサンプリングし、高速液体クロマトグラフィーを用いて、レジストとしてウエハに塗布したノボラック樹脂およびその分解産物として知られているフェノール、クレゾール、ジメチルフェノールが含まれているか分析した結果、これらの有機物の存在は認められなかった。このことは、ノボラック樹脂が炭酸ガスと水にまで極めて効果的に分解されたことによるものと考察された。なお、このような結果は、処理前において純水に塩酸を加えてｐＨを１．６５に低下させた場合においても、また、水温を５０℃以上に高めた場合においても、さらに両者を同時に行った場合においても同様に認められた。 Example 1:
For example, pure water having an electric conductivity of 1 μS / cm or less is prepared at room temperature under a high pressure of 4 atm according to a method using a pressure dissolution method described in JP-A-2003-265938, and an inhalation gas After the ozone was dissolved, microbubbles containing ozone having a particle size distribution of 1 μm to 50 μm were generated in pure water from the supersaturated condition of the dissolved ozone generated by opening the ozone to atmospheric pressure. The microbubbles had a particle size peak at 10 to 15 μm as measured by a laser light blocking liquid particle counter, and the number of microbubbles in the peak area was 1000 / mL or more. The zeta potential of the microbubbles was about −20 mV (measured by electrophoresis). The pure water containing the released microbubbles was mixed in a beaker containing about 5000 mL of pure water, and the pure water in the beaker was again sucked into the microbubble generator. Under this condition, a wafer (silicon wafer) coated with a resist was placed at a position 5 cm away from the outlet of pure water containing microbubbles. The wafer had a diameter of about 12.5 cm, and a novolac resin was applied to the surface with a thickness of 1300 nm. Under these conditions, pure water containing microbubbles was allowed to collide with the wafer surface for 20 minutes. The water temperature at the start of the treatment was about 20 ° C., and the temperature at the end of the treatment was about 28 ° C. The pH at the end of the treatment was 5.47, indicating weak acidity due to the influence of ozone and the like. FIG. 3 shows the results of measuring the hydroxyl radical generated in water by electron spin resonance using DMPO (5,5-dimethyl-1-pyrroline-N-oxide), which is a spin trapping agent. Further, FIG. 4 shows a photograph of an unprocessed wafer and a processed wafer. In addition, when the surface of the wafer before and after the processing was analyzed with an energy dispersive X-ray fluorescence analyzer, Si was 98.817% and S was 1.183% before the processing. Si was 100% and S was 0%. Further, from the infrared absorption spectrum analysis of FT-IR, absorption such as benzene ring and C═O, C—O, C—H, etc., recognized before the treatment was not recognized after the treatment. In addition, after sampling the water in the treatment tank after processing, it is analyzed whether it contains novolak resin coated on the wafer as a resist and phenol, cresol, and dimethylphenol known as degradation products. As a result, the presence of these organic substances was not recognized. This was considered due to the fact that the novolac resin was decomposed very effectively to carbon dioxide and water. In addition, such a result is carried out at the same time even when the pH is lowered to 1.65 by adding hydrochloric acid to pure water before the treatment or when the water temperature is increased to 50 ° C. or higher. In the case of the case, it was similarly recognized.
例えば、特開２００３－２６５９３８号公報に記載の加圧溶解方式による方法に従って、４気圧の高圧下で、常温にて電気伝導度が１μＳ／ｃｍ以下である純水を調製し、かつ、吸入気体としてオゾンを溶解させた後、これを大気圧に開放することにより生じた溶解オゾンの過飽和条件から粒径分布が１μｍ～５０μｍのオゾンを含む微小気泡を純水中に発生させた。この微小気泡は、レーザー光遮断方式の液中パーティクルカウンターによる計測において１０～１５μｍに粒径のピークを有しており、そのピークの領域における微小気泡の個数は１０００個／ｍＬ以上であった。また、微小気泡のゼータ電位は約－２０ｍＶであった（電気泳動法による測定）。放出した微小気泡を含む純水は約５０００ｍＬの純水を含むビーカー中で混合され、そのビーカー中の純水は再び微小気泡の発生装置に吸引させた。この条件において、微小気泡を含む純水の排出口から５ｃｍ離れた位置にレジストを塗布したウエハ（シリコンウエハ）を設置した。ウエハは直径が約１２．５ｃｍであり、表面にノボラック樹脂を１３００ｎｍの厚さで塗布したものとした。この条件で、２０分間連続して微小気泡を含む純水をウエハの表面に衝突させた。処理開始時の水温は約２０℃であり、終了時の温度は約２８℃であった。また、処理終了時のｐＨはオゾンなどの影響で弱い酸性を示しており５．４７であった。水中で発生した水酸基ラジカルを、スピントラップ剤であるＤＭＰＯ（５，５－ジメチル－１－ピロリン－Ｎ－オキサイド）を用いて電子スピン共鳴法で測定した結果を図３に示す。また、未処理のウエハと処理後のウエハの写真を図４に示す。また、処理前と処理後のウエハの表面をエネルギー分散型蛍光Ｘ線分析装置で解析したところ、処理前はＳｉが９８．８１７％でＳが１．１８３％であったものが、処理後ではＳｉが１００％でＳが０％となった。また、ＦＴ－ＩＲの赤外吸収スペクトル分析からは処理前に認められたベンゼン環やＣ＝Ｏ、Ｃ－Ｏ、Ｃ－Ｈなどの吸収が処理後では認められなくなった。さらに、処理後の処理槽の水をサンプリングし、高速液体クロマトグラフィーを用いて、レジストとしてウエハに塗布したノボラック樹脂およびその分解産物として知られているフェノール、クレゾール、ジメチルフェノールが含まれているか分析した結果、これらの有機物の存在は認められなかった。このことは、ノボラック樹脂が炭酸ガスと水にまで極めて効果的に分解されたことによるものと考察された。なお、このような結果は、処理前において純水に塩酸を加えてｐＨを１．６５に低下させた場合においても、また、水温を５０℃以上に高めた場合においても、さらに両者を同時に行った場合においても同様に認められた。 Example 1:
For example, pure water having an electric conductivity of 1 μS / cm or less is prepared at room temperature under a high pressure of 4 atm according to a method using a pressure dissolution method described in JP-A-2003-265938, and an inhalation gas After the ozone was dissolved, microbubbles containing ozone having a particle size distribution of 1 μm to 50 μm were generated in pure water from the supersaturated condition of the dissolved ozone generated by opening the ozone to atmospheric pressure. The microbubbles had a particle size peak at 10 to 15 μm as measured by a laser light blocking liquid particle counter, and the number of microbubbles in the peak area was 1000 / mL or more. The zeta potential of the microbubbles was about −20 mV (measured by electrophoresis). The pure water containing the released microbubbles was mixed in a beaker containing about 5000 mL of pure water, and the pure water in the beaker was again sucked into the microbubble generator. Under this condition, a wafer (silicon wafer) coated with a resist was placed at a position 5 cm away from the outlet of pure water containing microbubbles. The wafer had a diameter of about 12.5 cm, and a novolac resin was applied to the surface with a thickness of 1300 nm. Under these conditions, pure water containing microbubbles was allowed to collide with the wafer surface for 20 minutes. The water temperature at the start of the treatment was about 20 ° C., and the temperature at the end of the treatment was about 28 ° C. The pH at the end of the treatment was 5.47, indicating weak acidity due to the influence of ozone and the like. FIG. 3 shows the results of measuring the hydroxyl radical generated in water by electron spin resonance using DMPO (5,5-dimethyl-1-pyrroline-N-oxide), which is a spin trapping agent. Further, FIG. 4 shows a photograph of an unprocessed wafer and a processed wafer. In addition, when the surface of the wafer before and after the processing was analyzed with an energy dispersive X-ray fluorescence analyzer, Si was 98.817% and S was 1.183% before the processing. Si was 100% and S was 0%. Further, from the infrared absorption spectrum analysis of FT-IR, absorption such as benzene ring and C═O, C—O, C—H, etc., recognized before the treatment was not recognized after the treatment. In addition, after sampling the water in the treatment tank after processing, it is analyzed whether it contains novolak resin coated on the wafer as a resist and phenol, cresol, and dimethylphenol known as degradation products. As a result, the presence of these organic substances was not recognized. This was considered due to the fact that the novolac resin was decomposed very effectively to carbon dioxide and water. In addition, such a result is carried out at the same time even when the pH is lowered to 1.65 by adding hydrochloric acid to pure water before the treatment or when the water temperature is increased to 50 ° C. or higher. In the case of the case, it was similarly recognized.
実施例２：
自体公知の微小気泡発生装置（必要であれば特開２００３－２６５９３８号公報を参照のこと）を使用して、粒径分布が５０μｍ以下で、レーザー光遮断方式の液中パーティクルカウンターによる計測において１０～１５μｍに粒径のピークを有しており、そのピークの領域における微小気泡の個数が１０００個／ｍＬ以上のオゾンを含む微小気泡を、電気伝導度が１μＳ／ｃｍ以下である純水中に連続的に発生させながら、表面にノボラック樹脂を１３００ｎｍの厚さで塗布した直径８インチのウエハに対して、この水を流水状態で掛け流した。水の排出口からウエハまでの距離は約５ｃｍとした。ウエハからこぼれ落ちた水は約３０００Ｌの水を含むビーカーに溜めた後、再度、微小気泡発生装置に吸引させることで循環して利用した。なお、循環水としては室温条件の純水（電気伝導度は１μＳ／ｃｍ以下）を利用した。この条件で実験を２０分間継続した。処理前と処理後のウエハの表面をエネルギー分散型蛍光Ｘ線分析装置で解析したところ、処理前はＳｉが９８．７６７％でＳが１．２３３％であったものが、処理後ではＳｉが１００％でＳが０％となった。なお、このような結果は、処理前において純水に塩酸を加えてｐＨを１．６２に低下させた場合においても、また、水温を５０℃以上に高めた場合においても、さらに両者を同時に行った場合においても同様に認められた。 Example 2:
Using a microbubble generator known per se (see Japanese Patent Application Laid-Open No. 2003-265938 if necessary), the particle size distribution is 50 μm or less, and the measurement with a laser light blocking type particle counter in liquid is 10 A microbubble containing ozone having a particle size peak at ˜15 μm and the number of microbubbles in the peak area of 1000 / mL or more in pure water having an electric conductivity of 1 μS / cm or less. While being continuously generated, this water was poured in a flowing state on a wafer having a diameter of 8 inches in which a novolak resin was applied to the surface with a thickness of 1300 nm. The distance from the water outlet to the wafer was about 5 cm. The water spilled from the wafer was collected in a beaker containing about 3000 L of water, and then circulated by being sucked again by the microbubble generator. As the circulating water, pure water at room temperature (electric conductivity is 1 μS / cm or less) was used. The experiment was continued for 20 minutes under these conditions. When the surface of the wafer before processing and after processing was analyzed with an energy dispersive X-ray fluorescence spectrometer, Si was 98.767% and S was 1.233% before processing, but Si after processing was Si. At 100%, S was 0%. In addition, such a result is carried out at the same time both when the hydrochloric acid is added to pure water and the pH is lowered to 1.62 before the treatment, and when the water temperature is increased to 50 ° C. or higher. In the case of the case, it was similarly recognized.
自体公知の微小気泡発生装置（必要であれば特開２００３－２６５９３８号公報を参照のこと）を使用して、粒径分布が５０μｍ以下で、レーザー光遮断方式の液中パーティクルカウンターによる計測において１０～１５μｍに粒径のピークを有しており、そのピークの領域における微小気泡の個数が１０００個／ｍＬ以上のオゾンを含む微小気泡を、電気伝導度が１μＳ／ｃｍ以下である純水中に連続的に発生させながら、表面にノボラック樹脂を１３００ｎｍの厚さで塗布した直径８インチのウエハに対して、この水を流水状態で掛け流した。水の排出口からウエハまでの距離は約５ｃｍとした。ウエハからこぼれ落ちた水は約３０００Ｌの水を含むビーカーに溜めた後、再度、微小気泡発生装置に吸引させることで循環して利用した。なお、循環水としては室温条件の純水（電気伝導度は１μＳ／ｃｍ以下）を利用した。この条件で実験を２０分間継続した。処理前と処理後のウエハの表面をエネルギー分散型蛍光Ｘ線分析装置で解析したところ、処理前はＳｉが９８．７６７％でＳが１．２３３％であったものが、処理後ではＳｉが１００％でＳが０％となった。なお、このような結果は、処理前において純水に塩酸を加えてｐＨを１．６２に低下させた場合においても、また、水温を５０℃以上に高めた場合においても、さらに両者を同時に行った場合においても同様に認められた。 Example 2:
Using a microbubble generator known per se (see Japanese Patent Application Laid-Open No. 2003-265938 if necessary), the particle size distribution is 50 μm or less, and the measurement with a laser light blocking type particle counter in liquid is 10 A microbubble containing ozone having a particle size peak at ˜15 μm and the number of microbubbles in the peak area of 1000 / mL or more in pure water having an electric conductivity of 1 μS / cm or less. While being continuously generated, this water was poured in a flowing state on a wafer having a diameter of 8 inches in which a novolak resin was applied to the surface with a thickness of 1300 nm. The distance from the water outlet to the wafer was about 5 cm. The water spilled from the wafer was collected in a beaker containing about 3000 L of water, and then circulated by being sucked again by the microbubble generator. As the circulating water, pure water at room temperature (electric conductivity is 1 μS / cm or less) was used. The experiment was continued for 20 minutes under these conditions. When the surface of the wafer before processing and after processing was analyzed with an energy dispersive X-ray fluorescence spectrometer, Si was 98.767% and S was 1.233% before processing, but Si after processing was Si. At 100%, S was 0%. In addition, such a result is carried out at the same time both when the hydrochloric acid is added to pure water and the pH is lowered to 1.62 before the treatment, and when the water temperature is increased to 50 ° C. or higher. In the case of the case, it was similarly recognized.
比較例１：
従来法であるオゾン水を利用してレジストを塗布した半導体ウエハの洗浄試験を実施した。５０００ｍＬのビーカー中に満たした電気伝導度が１μＳ／ｃｍ以下である純水中に、散気管を利用して室温条件下でオゾンを放出した。使用したオゾン発生装置はオゾン量が５ｇ／Ｌであり、気体量は２Ｌ／分とした。実施例１と実施例２ではこの気体量の約半分を利用したが、この試験では装置から発生した気体量の全てを散気管から放出した。試験はビーカー内のオゾンが飽和状態になったのを確認した後に半導体ウエハをビーカー内に設置して、オゾンを連続的に供給しながら２０分間試験を継続した。処理前と処理後のウエハの表面をエネルギー分散型蛍光Ｘ線分析装置で解析したところ、処理前はＳｉが９８．８７８％でＳが１．２２２％であったものが、処理後ではＳｉが９８．９４７％でＳが１．０５３％となり、レジストを完全に除去することができなかった。実施例１と比較例１の結果から、本発明の洗浄方法は、従来法であるオゾン水を用いた方法に比べて７倍以上の洗浄能力を持つことがわかった。 Comparative Example 1:
A cleaning test was performed on a semiconductor wafer coated with a resist using ozone water, which is a conventional method. Ozone was released at room temperature using a diffuser tube into pure water with a conductivity of 1 μS / cm or less filled in a 5000 mL beaker. The ozone generator used had an ozone amount of 5 g / L and a gas amount of 2 L / min. In Examples 1 and 2, about half of this amount of gas was used, but in this test, all of the amount of gas generated from the device was released from the diffuser. In the test, after confirming that the ozone in the beaker became saturated, the semiconductor wafer was placed in the beaker, and the test was continued for 20 minutes while supplying ozone continuously. When the surface of the wafer before and after the processing was analyzed with an energy dispersive X-ray fluorescence spectrometer, Si was 98.878% and S was 1.222% before the processing. At 98.947%, S was 1.053%, and the resist could not be completely removed. From the results of Example 1 and Comparative Example 1, it was found that the cleaning method of the present invention has a cleaning capability of 7 times or more compared with the conventional method using ozone water.
従来法であるオゾン水を利用してレジストを塗布した半導体ウエハの洗浄試験を実施した。５０００ｍＬのビーカー中に満たした電気伝導度が１μＳ／ｃｍ以下である純水中に、散気管を利用して室温条件下でオゾンを放出した。使用したオゾン発生装置はオゾン量が５ｇ／Ｌであり、気体量は２Ｌ／分とした。実施例１と実施例２ではこの気体量の約半分を利用したが、この試験では装置から発生した気体量の全てを散気管から放出した。試験はビーカー内のオゾンが飽和状態になったのを確認した後に半導体ウエハをビーカー内に設置して、オゾンを連続的に供給しながら２０分間試験を継続した。処理前と処理後のウエハの表面をエネルギー分散型蛍光Ｘ線分析装置で解析したところ、処理前はＳｉが９８．８７８％でＳが１．２２２％であったものが、処理後ではＳｉが９８．９４７％でＳが１．０５３％となり、レジストを完全に除去することができなかった。実施例１と比較例１の結果から、本発明の洗浄方法は、従来法であるオゾン水を用いた方法に比べて７倍以上の洗浄能力を持つことがわかった。 Comparative Example 1:
A cleaning test was performed on a semiconductor wafer coated with a resist using ozone water, which is a conventional method. Ozone was released at room temperature using a diffuser tube into pure water with a conductivity of 1 μS / cm or less filled in a 5000 mL beaker. The ozone generator used had an ozone amount of 5 g / L and a gas amount of 2 L / min. In Examples 1 and 2, about half of this amount of gas was used, but in this test, all of the amount of gas generated from the device was released from the diffuser. In the test, after confirming that the ozone in the beaker became saturated, the semiconductor wafer was placed in the beaker, and the test was continued for 20 minutes while supplying ozone continuously. When the surface of the wafer before and after the processing was analyzed with an energy dispersive X-ray fluorescence spectrometer, Si was 98.878% and S was 1.222% before the processing. At 98.947%, S was 1.053%, and the resist could not be completely removed. From the results of Example 1 and Comparative Example 1, it was found that the cleaning method of the present invention has a cleaning capability of 7 times or more compared with the conventional method using ozone water.
本発明は、室温程度で行っても効果的であって、しかも環境にやさしい、オゾンを用いた半導体ウエハの洗浄方法および洗浄装置を提供することができる点において産業上の利用可能性を有する。
The present invention has industrial applicability in that it can provide a semiconductor wafer cleaning method and cleaning apparatus using ozone that is effective even at about room temperature and is environmentally friendly.
Claims (3)
- 電気伝導度が１μＳ／ｃｍ以下である純水中または前記純水に酸を添加することでｐＨを最大で１まで低下させた水溶液中において生成させた、粒径が５０μｍ以下で、レーザー光遮断方式の液中パーティクルカウンターによる計測において１０～１５μｍに粒径のピークを有しており、そのピークの領域における個数が１０００個／ｍＬ以上である、オゾンを含有する微小気泡を含む水を、半導体ウエハの表面に接触させて行うことを特徴とする半導体ウエハの洗浄方法。 Generated in pure water with an electric conductivity of 1 μS / cm or less or an aqueous solution whose pH has been lowered to 1 by adding an acid to the pure water. Water containing fine bubbles containing ozone, which has a particle size peak of 10 to 15 μm in the measurement with a liquid particle counter of the method, and the number in the peak area is 1000 / mL or more, A method for cleaning a semiconductor wafer, which is performed by contacting the surface of the wafer.
- オゾンを含有する微小気泡を含む水中に半導体ウエハを浸漬させるか、または、オゾンを含有する微小気泡を含む水を半導体ウエハにかけることで行うことを特徴とする請求項１記載の洗浄方法。 The cleaning method according to claim 1, wherein the cleaning is performed by immersing the semiconductor wafer in water containing ozone-containing microbubbles or by applying water containing ozone-containing microbubbles to the semiconductor wafer.
- 電気伝導度が１μＳ／ｃｍ以下である純水中または前記純水に酸を添加することでｐＨを最大で１まで低下させた水溶液中において生成させた、粒径が５０μｍ以下で、レーザー光遮断方式の液中パーティクルカウンターによる計測において１０～１５μｍに粒径のピークを有しており、そのピークの領域における個数が１０００個／ｍＬ以上である、オゾンを含有する微小気泡を含む水を製造するための手段と、製造されたオゾンを含有する微小気泡を含む水を半導体ウエハの表面に接触させるための手段を少なくとも有することを特徴とする半導体ウエハの洗浄装置。 Generated in pure water with an electric conductivity of 1 μS / cm or less or an aqueous solution whose pH has been lowered to 1 by adding an acid to the pure water. In this method, water containing fine bubbles containing ozone having a particle size peak of 10 to 15 μm in the measurement by a particle counter in liquid and having a number in the peak region of 1000 / mL or more is produced. And a semiconductor wafer cleaning apparatus characterized by comprising at least means for bringing the water containing fine bubbles containing ozone into contact with the surface of the semiconductor wafer.
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| JP2011050931A (en) * | 2009-09-04 | 2011-03-17 | Reo Laboratory Co Ltd | Method for generating hydroxyl radical in water |
| JP2011132080A (en) * | 2009-12-25 | 2011-07-07 | Mitsubishi Materials Corp | Cleaning method of silicon surface |
| JP2012089679A (en) * | 2010-10-20 | 2012-05-10 | National Institute Of Advanced Industrial & Technology | Method of cleaning semiconductor wafer |
| WO2012090815A1 (en) * | 2010-12-28 | 2012-07-05 | シャープ株式会社 | Resist removal device and resist removal method |
| CN102640256A (en) * | 2009-11-30 | 2012-08-15 | 朗姆研究公司 | Method and apparatus for surface treatment using a mixture of acid and oxidizing gas |
| JP2012176353A (en) * | 2011-02-25 | 2012-09-13 | Shibaura Mechatronics Corp | Substrate washing system, substrate washing method, apparatus for manufacturing display device, and method for manufacturing display device |
| WO2014118862A1 (en) * | 2013-01-29 | 2014-08-07 | 信越半導体株式会社 | Cleaning method using ozonated water and cleaning apparatus |
| CN106471602A (en) * | 2014-03-31 | 2017-03-01 | 独立行政法人产业技术综合研究所 | Method for making semiconductor and the cleaning method of wafer substrates |
| JP2021118235A (en) * | 2020-01-23 | 2021-08-10 | 国立大学法人東北大学 | Wafer substrate cleaning method |
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| JP2011050931A (en) * | 2009-09-04 | 2011-03-17 | Reo Laboratory Co Ltd | Method for generating hydroxyl radical in water |
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| JP2012176353A (en) * | 2011-02-25 | 2012-09-13 | Shibaura Mechatronics Corp | Substrate washing system, substrate washing method, apparatus for manufacturing display device, and method for manufacturing display device |
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| JP2014146693A (en) * | 2013-01-29 | 2014-08-14 | Shin Etsu Handotai Co Ltd | Cleaning method and cleaning device using ozone water |
| CN106471602A (en) * | 2014-03-31 | 2017-03-01 | 独立行政法人产业技术综合研究所 | Method for making semiconductor and the cleaning method of wafer substrates |
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| US20170125240A1 (en) * | 2014-03-31 | 2017-05-04 | National Institute Of Advanced Industrial Science And Technology | Method for manufacturing semiconductor and method for cleaning wafer substrate |
| US11107705B2 (en) | 2018-07-30 | 2021-08-31 | Samsung Electronics Co., Ltd. | Cleaning solution production systems and methods, and plasma reaction tanks |
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| JP2021118235A (en) * | 2020-01-23 | 2021-08-10 | 国立大学法人東北大学 | Wafer substrate cleaning method |
| JP7426620B2 (en) | 2020-01-23 | 2024-02-02 | 国立大学法人東北大学 | How to clean wafer substrate |
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| JP5540351B2 (en) | 2014-07-02 |
| KR20100119783A (en) | 2010-11-10 |
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| CN101939826A (en) | 2011-01-05 |
| JPWO2009099138A1 (en) | 2011-05-26 |
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