WO1993001133A1 - System for supplying pure water and cleaning method therefor - Google Patents
System for supplying pure water and cleaning method therefor Download PDFInfo
- Publication number
- WO1993001133A1 WO1993001133A1 PCT/JP1992/000838 JP9200838W WO9301133A1 WO 1993001133 A1 WO1993001133 A1 WO 1993001133A1 JP 9200838 W JP9200838 W JP 9200838W WO 9301133 A1 WO9301133 A1 WO 9301133A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pure water
- nitrogen
- water
- oxygen
- cleaning
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/0073—Degasification of liquids by a method not covered by groups B01D19/0005 - B01D19/0042
- B01D19/0078—Degasification of liquids by a method not covered by groups B01D19/0005 - B01D19/0042 by vibration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/0005—Degasification of liquids with one or more auxiliary substances
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/0031—Degasification of liquids by filtration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/04—Non-contaminated water, e.g. for industrial water supply for obtaining ultra-pure water
Definitions
- the present invention relates to a pure water supply system and a cleaning method, and more particularly to, for example, a pure water supply system and a silicon substrate cleaning method used in a cleaning step of an LSI manufacturing process.
- the conventional technology will be described by taking a cleaning step of an LSI manufacturing process as an example.
- an insulating film is formed on a silicon wafer, a predetermined pattern of windows is opened in the insulating film, and then washed, and p-type or n-type elements are introduced according to the purpose. Then, the step of diffusing or annealing the above impurities into silicon in a thermal diffusion furnace is repeated to form an element.
- the cleaning step is very important for manufacturing high-performance devices, and it is necessary to completely remove dirt on silicon.
- pure water from which dissolved oxygen in deionized water has been degassed may be used so that an oxide film is not formed on the silicon surface.
- the main component of air is nitrogen
- pure water saturated with nitrogen cannot absorb air remaining in the holes opened in the windows, so trace impurities remain on the silicon surface without being washed. Of device characteristics No further improvement or reduction in variation could be achieved.
- the present invention provides pure water by degassing nitrogen and oxygen dissolved in water, and further by improving the wettability of water on the surface of a substrate, particularly the surface of a silicon wafer from which an insulating film has been removed.
- the present invention aims to provide a washing method and a pure water supply system for completely washing and removing even a trace amount of impurities on silicon by contacting the silicon surface.
- a first gist of the present invention is a pure water supply system characterized in that a means for degassing nitrogen and oxygen gas in water is provided in the middle of a pipe for supplying pure water to a use point.
- a second aspect of the present invention resides in a substrate cleaning method characterized in that a substrate is washed using pure water supplied by the pure water supply system according to the first aspect.
- the pure water of the present invention is, for example, low-purity water used in a washing step of a semiconductor manufacturing process.
- low-purity water used in a washing step of a semiconductor manufacturing process.
- pure water from which impurities have been removed is used. (table 1 )
- FIG. 1 One configuration example of the pure water supply system of the present invention is shown in FIG. 1, and an example of a supply method will be described with reference to the drawing.
- the pressure is increased to about 15 kcm 2 by a high-pressure pump 2 and sent to a reverse osmosis device 3.
- the permeated water from which about 95% of ions have been removed by the reverse osmosis device 3 is stored in the permeated water tank 4. Concentrated water containing high-concentration ion is discharged out of the system.
- the permeated water is sent to the first ion exchange tower 6-1 by the pump 5, where it is converted into pure water having a specific resistance of about 16 to 18 ⁇ ⁇ cm and stored in the water storage tank 7.
- the water in the water storage tank 7 is sent to the use point 14 by the circulation pump 8 through the circulation pipe, and is returned to the water storage tank 7 again.
- a sterilizing means 9, a deaerator 10, an ion exchange tower 6-2, and an ultrafilter 11 are arranged.
- the specific resistance of pure water is 18 ⁇ ⁇ cm or more.
- the sterilizing means 9 is for preventing the generation of bacteria in pure water, and includes, for example, an ozone injecting device and an ultraviolet lamp, but of course, other methods may be used.
- the ultrafilter 11 is provided in order to remove minute suspended substances, dead bodies of bacteria killed by the sterilizing means 9, and the like.
- any method can be used as long as it can degas dissolved nitrogen and oxygen in water.
- a membrane degassing method, a vacuum degassing method or a nitrogen degassing method can be used.
- a bubbling method using a gas not containing oxygen can be used.
- a gaseous membrane for example, a Teflon-based hollow fiber membrane or a spiral membrane is filled in a housing that can withstand vacuum, water is introduced into the inside of the membrane, and the outside of the membrane is 10 to 50, for example.
- the vacuum deaeration method is based on disposing a filler in a vacuum vessel, supplying water to the filler from the top of the vessel while reducing the pressure to, for example, 10 to 50 torr, and dissolving dissolved nitrogen in the water and Degas oxygen.
- the dissolved oxygen concentration in pure water is reduced to 50 to 100 ppb, and nitrogen is reduced to 100 to 200 ppb.
- Pure water obtained by the above method absorbs air easily, so even if air remains in holes with a high aspect ratio, pure water and silicon come in contact with each other because they absorb air in pure water. Can be removed by washing.
- the pure water obtained by the above film degassing or vacuum degassing method is further bubbled with a gas that does not contain nitrogen and oxygen, such as Ar gas, so that a dissolved oxygen concentration of 5 ppb or less and a nitrogen concentration of 1 It is preferable to use pure water of O ppb or less.
- the catalyst holding means 12 and the microwave generating means 13 are provided between the above-mentioned circulating fiber and the use point 14 ′, and the silicon is irradiated by the microwave while contacting the catalyst with pure water.
- the result of washing with pure water against the above dirt is further improved.
- the wettability of pure water to the silicon wafer changes, and pure water that has not wetted the silicon wafer wets the entire wafer. The reason for this is not clear, but by irradiating a microwave in the presence of a catalyst, hydrogen bonds between water molecules are broken and the water molecules that existed as macromolecules act as molecules of smaller units. As a result, it is assumed that the silicon wafer can be wetted.
- the catalyst holding means 12 used in the present invention is capable of holding the catalyst by microwaves. Any suitable one can be used, for example, as shown in FIG. 2, a Teflon container 15 having an inner diameter larger than the pure water inlet 16 and outlet 17; A plurality of 1 mm-thick sheet filters made of Teflon with a small hole of about 5 ⁇ m are inserted perpendicularly to the direction of pure water flow, and a catalyst is inserted between these Teflon filters. To form a catalyst layer.
- the catalyst for example, Pd, Pt and the like are used, and the particle size is preferably 1 to 1 from the viewpoint of reactivity.
- the width of the catalyst is preferably small to suppress induction heating by microwaves, for example, about 1 mm.
- the microwave is introduced parallel to the Teflon sheet and the catalyst layer (that is, perpendicular to the flow direction of pure water).
- any suitable means can be used as long as it can generate microwaves having a frequency of 1 to 10 GHz, but in order to cut hydrogen bonds of water efficiently, a magnetron type is used. Are preferred. The output depends on the amount of pure water used, but about 1 KW is used.
- pure water containing no nitrogen and oxygen absorbs residual air. Therefore, pure water can be brought into contact with the silicon surface, and trace impurities on silicon can be removed.
- an extremely small amount of impurities attached to the silicon surface can be completely removed, and the performance of the device can be improved.
- FIG. 1 is a diagram showing one configuration example of a pure water it device of the present invention.
- FIG. 2 is a schematic sectional view showing an example of the catalyst holding means.
- Fig. 3 is a graph showing the variation in the MOS transistor and the mutual inductance characteristics.
- (A) shows the case where the conventional pure water was used in the washing step, and (b) used the pure water of the example in the washing step. Is the case.
- Pure water was prepared using the pure water supply system shown in Fig. 1.
- a membrane degassing method and a publishing method using Ar gas were used in combination.
- the dissolved oxygen in pure water was measured using Orbissphere 2713 dissolved oxygen meter.
- the dissolved oxygen was measured by fabricating the N 0 gas monitor had use of gas chromatography TC D detector (Temperature Conduction Detector).
- the respective concentrations were 550 ppb of nitrogen and 280 ppb of oxygen after degassing the membrane, 9 ppb of nitrogen and 4 ppb of oxygen after Ar gas coupling.
- the catalyst holding means 12 shown in FIG. 2 was arranged between the pure water circulation path and the use point 14 ', and microwaves were applied to the pure water.
- the filter 19 of the catalyst holding means 12 a filter made of Teflon (a product name of polyfluorinated polyethylene fiber of du Pont, the same applies hereinafter) having a hole diameter of 2 / zm and a thickness of 1 mm was used. It was inserted into a single container. Pd powder having a diameter of 5 to 6 zm was put between the filters to form five catalyst layers.
- the catalyst holding means 12 was attached to the resonator 20 of the microwave generator 13, and a microwave of 2.45 GHz and 700 W was applied to the catalyst via the microwave waveguide 21.
- the flow rate of pure water was set at 21 min by providing a pump upstream of the holding means 12.
- degassed pure water (1) and degassed and microwave-treated pure water (2) were produced.
- the channel length is 0.5 m
- the channel width is 1.5 ⁇ m
- the contact hole of source and drain is 1 mx 1 yum, 0.6 ⁇ .mx 0.6 111 and 0.3 mx 0.3 m.
- Figure 3 shows the evaluation results.
- Figures 3 (a) and 3 (b) show the results when using the conventional pure water (3) and degassed pure water (1) in the final cleaning, respectively. Evaluation was performed for the number 10 to 100 or so transistors in each condition, showing the measured values of g m by a value normalized by a mean value g m * of each female population.
- the cleaning of the silicon wafer becomes more complete and it can be removed with conventional pure water As a result of the removal of trace impurities that could not be achieved, it is possible to manufacture high-performance devices with higher characteristics.
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP19920914383 EP0598124A4 (en) | 1991-07-02 | 1992-07-02 | PURE WATER SUPPLY SYSTEM AND CLEANING METHOD. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3/188146 | 1991-07-02 | ||
JP18814691A JP3235621B2 (ja) | 1991-07-02 | 1991-07-02 | 純水供給システム及び洗浄方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1993001133A1 true WO1993001133A1 (en) | 1993-01-21 |
Family
ID=16218556
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1992/000838 WO1993001133A1 (en) | 1991-07-02 | 1992-07-02 | System for supplying pure water and cleaning method therefor |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0598124A4 (ja) |
JP (1) | JP3235621B2 (ja) |
WO (1) | WO1993001133A1 (ja) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2611182B2 (ja) * | 1994-06-07 | 1997-05-21 | 工業技術院長 | 脱入気装置 |
DE4446270C1 (de) * | 1994-12-23 | 1996-02-29 | Hewlett Packard Gmbh | Basisstruktur für einen Flüssigkeitschromatographie-Entgaser |
US6348157B1 (en) | 1997-06-13 | 2002-02-19 | Tadahiro Ohmi | Cleaning method |
JP4135780B2 (ja) * | 1997-08-29 | 2008-08-20 | ユーシーティー株式会社 | 薬液定量注入装置および方法 |
US6021791A (en) * | 1998-06-29 | 2000-02-08 | Speedfam-Ipec Corporation | Method and apparatus for immersion cleaning of semiconductor devices |
JP2000265945A (ja) * | 1998-11-10 | 2000-09-26 | Uct Kk | 薬液供給ポンプ、薬液供給装置、薬液供給システム、基板洗浄装置、薬液供給方法、及び基板洗浄方法 |
CN102257434B (zh) | 2008-12-18 | 2013-04-24 | 旭化成电子材料株式会社 | 烧蚀层、感光性树脂结构体、使用了该感光性树脂结构体的凸版印刷版的制造方法 |
JP5342264B2 (ja) * | 2009-02-13 | 2013-11-13 | 株式会社荏原製作所 | めっき装置及びめっき方法 |
KR101255895B1 (ko) * | 2009-12-10 | 2013-04-17 | 가부시키가이샤 코아테크노로지 | 포화 가스 함유 나노 버블수의 제조 방법 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6146290A (ja) * | 1984-08-13 | 1986-03-06 | Toshiba Corp | 流体処理装置 |
JPS63270590A (ja) * | 1987-04-28 | 1988-11-08 | Matsushita Electric Ind Co Ltd | 浄水器 |
JPH03154601A (ja) * | 1989-11-10 | 1991-07-02 | Ebara Infilco Co Ltd | 水中の溶存酸素の除去方法 |
JPH0418977A (ja) * | 1990-05-11 | 1992-01-23 | Mitsubishi Electric Corp | 溶存気体除去装置 |
JPH04190803A (ja) * | 1990-11-26 | 1992-07-09 | Nomura Micro Sci Kk | 純水または超純水中の溶存酸素の除去方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5258096A (en) * | 1975-11-10 | 1977-05-13 | Central Glass Co Ltd | Method for prduction of high purity hydrogen gas |
JPS58139706A (ja) * | 1982-02-15 | 1983-08-19 | Daido Steel Co Ltd | 脱ガス法 |
JPH02126992A (ja) * | 1988-11-05 | 1990-05-15 | Kyodo Sanso Kk | 超純水製造における殺菌および脱気方法 |
-
1991
- 1991-07-02 JP JP18814691A patent/JP3235621B2/ja not_active Expired - Fee Related
-
1992
- 1992-07-02 WO PCT/JP1992/000838 patent/WO1993001133A1/ja not_active Application Discontinuation
- 1992-07-02 EP EP19920914383 patent/EP0598124A4/en not_active Withdrawn
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6146290A (ja) * | 1984-08-13 | 1986-03-06 | Toshiba Corp | 流体処理装置 |
JPS63270590A (ja) * | 1987-04-28 | 1988-11-08 | Matsushita Electric Ind Co Ltd | 浄水器 |
JPH03154601A (ja) * | 1989-11-10 | 1991-07-02 | Ebara Infilco Co Ltd | 水中の溶存酸素の除去方法 |
JPH0418977A (ja) * | 1990-05-11 | 1992-01-23 | Mitsubishi Electric Corp | 溶存気体除去装置 |
JPH04190803A (ja) * | 1990-11-26 | 1992-07-09 | Nomura Micro Sci Kk | 純水または超純水中の溶存酸素の除去方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP0598124A4 * |
Also Published As
Publication number | Publication date |
---|---|
JPH057705A (ja) | 1993-01-19 |
JP3235621B2 (ja) | 2001-12-04 |
EP0598124A4 (en) | 1994-11-30 |
EP0598124A1 (en) | 1994-05-25 |
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