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
  • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
  • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
  • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
  • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B08—CLEANING
  • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
  • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
  • B08B3/04—Cleaning involving contact with liquid
  • B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
  • B08B3/12—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration by sonic or ultrasonic vibrations
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/042—Acids
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
  • C11D2111/10—Objects to be cleaned
  • C11D2111/14—Hard surfaces
  • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
• • 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
  • H01L21/67028—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like
  • H01L21/6704—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing
  • H01L21/67057—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing with the semiconductor substrates being dipped in baths or vessels

Definitions

• the present invention relates to a cleaning apparatus and a cleaning method, and more particularly, to a cleaning apparatus and a cleaning method capable of performing ultra-high-purity cleaning with extremely few steps and no heating compared to the related art.
• semiconductor devices formed on semiconductor substrates have become denser and finer to the level of sub-micron openings.
• the substrate surface must be kept ultra-clean. That is, organic substances, metals, various particles, and oxides (oxide films) must be removed from the substrate surface. Therefore, the substrate surface is cleaned.
• This step removes the oxide film.
• This step removes particles.
• step (5) H is 0. Since an oxide film is formed in step (5) since the oxide film is used, the oxide film is removed in this step. (8) Ultrapure water cleaning Room temperature
• the metal is removed.
• the container for storing the cleaning liquid of the cleaning device is made of glass or quartz.
• glass or quartz reacts with HF, so in the case of cleaning liquid containing HF, it is actually necessary to use a resin container.
• washing may be performed while applying vibration to the body to be washed or the washing liquid from outside the container.
• the container is a glass container, a quartz container or a metal container
• the vibration is sufficiently transmitted to the cleaning liquid or the object to be cleaned in the container.
• the container is a resin container
• the vibration is absorbed by the resin and is attenuated, and the vibration is not sufficiently transmitted to the cleaning liquid or the object to be cleaned in the container.
• a resin container has to be used in the case of a cleaning liquid containing HF.Therefore, in the case of a cleaning liquid containing HF, there is no conventional technique for performing cleaning while applying vibration. Was.
• An object of the present invention is to provide a cleaning method in which the number of processes is extremely small, the process can be performed only at room temperature, the amount of use of chemicals-water is small, and only the use of acid is sufficient and the recovery of chemicals is easy.
• the present invention provides a method for cleaning while applying vibration even when a cleaning solution containing HF is used. It is an object of the present invention to provide a cleaning device capable of cleaning. Disclosure of the invention
• a metal fluorinated nigger layer is formed on at least the inner surface of the cleaning liquid storage section of the metal container, and a carbon layer is formed on the nickel fluoride layer.
• a vibrator is attached.
• a carbon layer is formed on at least an inner surface of a storage section of a metal container for storing a cleaning liquid, and a fluorocarbon layer is formed on the carbon layer. It is characterized in that a vibrator is attached to the outer surface of the container.
• the method of cleaning the invention the first step of cleaning with pure water containing Ozon, while applying vibration of 5 0 0 k H z or more frequencies, and HF, and H 2 0 2 and Roh or 0 3, the second step of carrying out cleaning with the cleaning liquid containing the H 2 0 and a surfactant, a third step of cleaning with pure water,
• the inventor has diligently sought a cleaning method that requires a small number of steps and can be processed only at room temperature.
• the number of large particles of 1 or more decreases, but the number of particles of 0.5 to l; cm or small particles of 0.3 to 0.5 increases To do.
• the oxide film existing before the cleaning was removed, but another oxide film was newly formed in the cleaning step.
• Fri A material has been developed in which a nickel fluoride layer is formed on top and a carbon layer is formed on the nickel fluoride layer (Japanese Patent Application No. 6-288805). This material has excellent corrosion resistance to HF. The present inventor investigated the vibration propagation characteristics of this material, and found that this material exhibited excellent vibration propagation characteristics unlike resins.
• the present invention have found that some effect be given a vibration during cleaning by attaching the material using (HFZH 2 0./H 2 OZ surfactant) constitutes a container for cleaning liquid vibrator on its outer surface I thought there might be.
• HFZH 2 0./H 2 OZ surfactant constitutes a container for cleaning liquid vibrator on its outer surface I thought there might be.
• vibration is applied to the cleaning liquid.
• the relationship with the effect is completely unknown. In other words, it was not known at all whether the cleaning effect of the cleaning liquid containing HF would be improved or worsened if the cleaning was performed by applying vibration.
• first step cleaning with ultrapure water containing ozone is performed.
• first step most of the metals and organics are removed. However, not all are eliminated.
• the second step (HF ZH 2 0 2 ZH 2 OZ surfactant) was washed while applying vibration of 5 0 0 k H z or higher frequencies with a solution, this washing, Pateiku Le, metals, organics It can be removed and the surface roughness can be reduced. Where H 20 . Or 0 3 can be used with H 2 0 2 .
• a cleaning solution containing a surfactant is used, so after the completion of the second step, cleaning (rinsing) with ultrapure water is performed to remove the surfactant from the substrate surface (third step).
• a washing step using an ozone-containing solution is appropriately performed before the next step to completely remove the surfactant.
• the chemicals used are the same as those used in the first step, so there is no need to increase the types of controlled chemicals.
• a cleaning solution containing H 2 0 2 (or O g)
• an oxide film is formed.
• the oxide film is removed. For example, it may be performed by washing with a diluted HF solution and then washing (rinsing) with ultrapure water.
• the structure of the cleaning device used in the second step may be, for example, the structure shown in FIG. In FIG. 1, 1 is a container, 2 is a vibrator, and 3 is a cleaning liquid.
• a nickel-phosphorus plating layer is formed on the surface of the metal, and then the nickel-phosphorus layer is fluorinated with fluorine, and further subjected to a heat treatment in an inert gas (eg, nitrogen gas) atmosphere to form a fluorinated Nigel layer.
• an inert gas eg, nitrogen gas
• a carbon layer is formed by bringing a hydrocarbon gas into contact with the nickel fluoride layer (referred to as carbon treatment). Depending on the reaction conditions, it is possible to leave Nigel Fluoride or replace it entirely with carbon.
• the temperature of the carbon treatment with the hydrocarbon is from room temperature to 400 ° C, preferably from 200 to 370 ° C.
• the time of carbon treatment with hydrocarbons is 1-5 hours. It is preferable that the atmosphere of the carbon treatment is used by diluting with a hydrocarbon gas alone or an inert gas as appropriate, for example, N 9 , Ar, He or the like.
• Fluorination may be performed after carbon treatment.
• the temperature of the fluorocarbon treatment is from room temperature to 300 ° C, preferably from 100 to 250 ° C.
• the duration of the fluorocarbon treatment is several minutes to 5 hours. It is preferable that the atmosphere of the fluorocarbon treatment be performed in the absence of oxygen, and therefore, fluorine alone is used. Alternatively, it is preferable to use it after appropriately diluting it with an inert gas such as N 2 , Ar, or He.
• the fluorocarbon treatment is basically carried out at normal pressure, but may be carried out under pressure if necessary. In this case, the pressure may be about 2 atm or less in gauge pressure.
• heat treatment is preferably performed in an inert gas such as N 0 , Ar, or He.
• the heat treatment is performed at 100 to 400 ° C., preferably 200 to 370 for 1 to 5 hours, so that the heat treatment is robust and dense. This forms a flow-through carbon layer that has good adhesion to metal and good corrosion resistance.
• the metal is stainless steel, nickel, aluminum, or an alloy of these with other metals, and those whose surfaces are plated with nickel-phosphorus are also used.
• the thickness of the nickel fluoride layer is 10 ⁇ ⁇ ! M1 m is preferable, and 1100-200 nm is more preferable.
• the carbon layer preferably has a thickness of 1 nm to 1 nm, more preferably 100 to 500 nm.
• the ozone-containing ultrapure water-cleaning power and the ozone concentration are preferably 2 ppm or more. At a concentration higher than 2 ppm, the variation in surface roughness after cleaning becomes significantly smaller.
• the ultrapure water has a specific resistance of 18.2 ⁇ or more, a metal portability of l ppt or less, and an impurity count of p pb or less.
• the concentration of HF in the cleaning solution used in the second step is preferably 0.5 to 10 wt%.
• the content is 0.5 wt% or more, the oxide etching rate is increased.
• the etching rate is saturated and does not increase any more. Therefore, it is meaningless to add more than that, and the amount of chemical used increases, which is economically disadvantageous.
• the concentration of H 2 0 9 is preferably 0 ⁇ 1 ⁇ 20 wt%. If it is 0.1% or more, metal can be removed more efficiently. On the other hand, even if it exceeds 20 ⁇ %, the oxidation rate does not change, and only an increase in the amount of chemicals used is economically harmful. Further, 0 3 concentration is preferably at least 5 ppm.
• any of anionic, cationic and nonionic surfactants can be used. Further, it may be a hydrocarbon-based fluorocarbon-based or the like. Particularly preferred are nonionic activators that have the function of lowering the surface tension of the solution. As described above, if the type of the surfactant used in the second step cannot be removed by the rinse in the third step, washing with ozone (o 3 ) -added ultrapure water may be performed. In this case, the number of processes is six.
• the frequency of the vibration applied in the second step is 500 kHz or more, and preferably 1 MHz to 2 MHz. In this range, the cleaning effect is particularly remarkable.
• FIG. 1 is a conceptual diagram illustrating a cleaning device according to an embodiment.
• FIG. 2 is a graph showing test results in Example 1.
• FIG. 3 is a graph showing test results in Example 2.
• FIG. 4 is a graph showing test results in Example 4.
• FIG. 5 is a graph showing test results in Example 5.
• the first step was performed by immersing the (100) plane silicon wafer (4-inch diameter) in ultrapure water having an ozone concentration of 3 ppm for 10 minutes.
• PSL polystyrene latex
• the washing time of the above 1 to 4 is 10 minutes, and the washing temperature is room temperature.
• the cleaning was performed by immersing the silicon wafer in a cleaning liquid.
• the first step was performed by immersing the (100) plane silicon wafer (8 inch diameter) in pure water containing 20 ppm of ozone for 3 minutes.
• the wafer is immersed in the cleaning solution for 10 minutes at room temperature in each of the cleaning methods (1) (Comparative example), (3) ('Comparative example), and (2) (Example) described in Example 1. Washing was carried out.
• the surface roughness after washing was as follows.
• H 2 ⁇ 2 concentration more of metal removed as boundary 1 wt% 0. is remarkably improved.
• Fig. 4 shows the results.
• Example 1 in Example 1, using 5 p pm0 3 instead H 2 0 2.
• Processing can be performed at room temperature without heating.

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• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
• Manufacturing & Machinery (AREA)
• General Physics & Mathematics (AREA)
• Physics & Mathematics (AREA)
• Computer Hardware Design (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Power Engineering (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• Inorganic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Cleaning Or Drying Semiconductors (AREA)
• Cleaning By Liquid Or Steam (AREA)

Priority Applications (1)

Applications Claiming Priority (4)

Publications (1)

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Family Applications (1)

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• 1995
  • 1995-05-02 JP JP10884095A patent/JP3923097B2/ja not_active Expired - Fee Related
• 1996
  • 1996-02-29 TW TW085102423A patent/TW303481B/zh active
  • 1996-03-05 WO PCT/JP1996/000526 patent/WO1996027898A1/ja not_active Ceased
  • 1996-03-05 KR KR1019970705927A patent/KR100422923B1/ko not_active Expired - Fee Related
  • 1996-03-05 US US08/894,996 patent/US5944907A/en not_active Expired - Lifetime

Patent Citations (1)

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