WO2000007220A2 - Procedes de traitement humide utilisant des fluides de traitement a l'ozone pour la fabrication de composants electroniques - Google Patents

Procedes de traitement humide utilisant des fluides de traitement a l'ozone pour la fabrication de composants electroniques Download PDF

Info

Publication number
WO2000007220A2
WO2000007220A2 PCT/US1999/016954 US9916954W WO0007220A2 WO 2000007220 A2 WO2000007220 A2 WO 2000007220A2 US 9916954 W US9916954 W US 9916954W WO 0007220 A2 WO0007220 A2 WO 0007220A2
Authority
WO
WIPO (PCT)
Prior art keywords
electronic components
process fluid
ozonated
ozonated process
fluid
Prior art date
Application number
PCT/US1999/016954
Other languages
English (en)
Other versions
WO2000007220A3 (fr
Inventor
Jennifer Ware Parker
Steven Verhaverbeke
Original Assignee
Cfmt, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cfmt, Inc. filed Critical Cfmt, Inc.
Priority to AU52331/99A priority Critical patent/AU5233199A/en
Priority to JP2000562934A priority patent/JP2003533865A/ja
Publication of WO2000007220A2 publication Critical patent/WO2000007220A2/fr
Publication of WO2000007220A3 publication Critical patent/WO2000007220A3/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
    • H01L21/02052—Wet cleaning only
    • 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
    • B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B2203/00—Details of cleaning machines or methods involving the use or presence of liquid or steam
    • B08B2203/005—Details of cleaning machines or methods involving the use or presence of liquid or steam the liquid being ozonated

Definitions

  • the present invention is directed to wet processing methods for the manufacture of electronic components including electronic component precursors. More specifically, this invention relates to methods of processing electronic components using ozonated process fluids.
  • wet processing is carried out to prepare the electronic components for processing steps such as diffusion, ion implantation, epitaxial growth, chemical vapor deposition, and hemispherical silicon grain growth, or combinations thereof.
  • the electronic components are contacted with a series of processing solutions.
  • the processing solutions may be used, for example, to etch, to remove photoresist, to clean, to grow an oxide layer, or to rinse the electronic components. See, e.g., U.S. Patent Nos.
  • the electronic components may be processed in a single vessel system closed to the environment (such as a Full-FlowTM system supplied by CFM Technologies, Inc.), a single vessel system open to the environment, or a multiple open bath system (e.g., wet bench) having a plurality of baths open to the atmosphere.
  • a single vessel system closed to the environment such as a Full-FlowTM system supplied by CFM Technologies, Inc.
  • a single vessel system open to the environment such as a single vessel system open to the environment, or a multiple open bath system (e.g., wet bench) having a plurality of baths open to the atmosphere.
  • the electronic components are typically dried. Drying of the semiconductor substrates can be done using various methods, with the goal being to ensure that there is no contamination created during the drying process. Methods of drying include evaporation, centrifugal force in a spin-rinser-dryer, steam or chemical drying of wafers, including the methods and apparatus disclosed in, for example, U.S. Pat. Nos. 4,778,532 and 4,911,761.
  • an important consideration for an effective wet processing method is that the electronic component produced by the process be ultraclean (i.e., with minimum particle contamination and minimum chemical residue).
  • An ultraclean electronic component is preferably free of particles, metallic contaminants, organic contaminants, and native oxides; has a smooth surface; and has a hydrogen-terminated surface.
  • U.S. Patent No. 5,464,480 issued to Matthews describes a process in which semiconductor wafers are contacted with a solution of ozone and water at a temperature of about 1°C to about 15°C.
  • Matthews discloses, for example, placing the semiconductor wafers into a tank containing deionized water, diffusing ozone into the deionized water for a time sufficient to oxidize the organic materials from the wafers, while maintaining the temperature of the water at between about 1 °C to about 15°C, and then rinsing the wafers with deionized water.
  • Matthews further discloses exposing the wafers to ultraviolet light during the process.
  • ozone gas is generated in an ozone generator and fed to an ozonator where the ozone gas is mixed with DI water.
  • the ozone gas is also simultaneously fed to the bottom of the process vessel via specially designed device that provides a uniform stream of gaseous ozone into the bath.
  • Matthews et al. Mat. Res. Soc. Symp. Proc, 1997, 477, 173-78. See also 1997 Joint Int'sMtg. of Electro. Chem. Soc'yand Int'l Soc 'y. of Electro., Abstract 1886, p.
  • ozone-injected ultrapure water ozone concentration of about 1 -2 ppm
  • the ozonated water is used to remove organic impurities.
  • the wafers are then treated with NH 4 OH and H 2 O 2 to remove organic and metal particles, followed by a treatment with HF and H 2 O 2 to remove native oxide, metal, and to improve surface smoothness.
  • the wafers are then rinsed with DI water.
  • the ozone gas is generated by electrolyzing ultra pure water.
  • the generated ozone gas is then dissolved in ultrapure water through a membrane. Ohmi et al., J. Electrochem. Soc 'y, 140, 1993, 804-10.
  • Another method uses a moist ozone gas phase.
  • a quartz container is filled with a small amount of liquid, sufficient to immerse the O 3 diffuser.
  • the liquid is DI water spiked with additives such as hydrogen peroxide or acetic acid, if appropriate.
  • a lid is placed on the container and the liquid is heated to 80°C. Wafers are placed directly above the liquid interface, they are not immersed in the liquid. Heating of the liquid in a sealed container and continuous O 3 bubbling through the liquid exposes the wafers to a moist ambient O 3 environment. DeGendtetal. Symp. VLSI Tech. Dig. Tech. Papers, 1998, 168-69.
  • the De Gendt paper further describes a method whereby a quartz tank is filled with 7 liters of liquid, an ozone diffuser is located at the bottom of the tank, and the liquid can be heated. The wafers are positioned directly above the ozone diffuser and immersed in the liquid such that O 2 /O 3 bubbles contact the wafer surfaces.
  • the De Gendt paper also reports that OH radical scavengers such as acetic acid can enhance process efficiency.
  • photoresist removal is carried out in a gas phase reactor at a temperature of between about 200-300°C.
  • additives such as N 2 O gas are mixed with the ozone gas. See Olness et al, Mat. Res. Soc'y. Symp., 135, 1993, 261-66.
  • ozone with cleaning solutions has also been investigated.
  • One such method uses a wafer cleaning sequence with a single-wafer spin using ozonated water and dilute HF to remove contaminants such as particles, metallics, and organics from the wafer surfaces.
  • the method consists of pouring ozonated water on a wafer surface for 10 seconds, followed by pouring dilute HF over the wafers for 15 seconds. This cycle is repeated until the desired results are achieved.
  • Ozone has also been used in conjunction with sulfuric acid as a means for stripping photoresist from semiconductor wafers. See, e.g., U.S. Patent Nos. 4,899,767 and 4,917,123 issued to CFM Technologies. The methods described in the CFM patents are carried out in a single vessel system and, generally, a solution of sulfuric acid is spiked with an oxidizing agent such as ozone.
  • Other systems using sulfuric acid in conjunction with ozone may employ a gas distribution system that includes a sparger plate with holes for distributing gas through a bath in the tank. See, e.g., U.S. Patent No. 5,082,518 assigned to SubMicron. SubMicron's patent describes the use of an apparatus that distributes ozone directly into the treatment tank containing the sulfuric acid.
  • Ozone ashing has also been investigated as a means for removing photoresist material from wafers.
  • photoresist is oxidized at higher temperatures (250-350°C) by two strong oxidizing gases, ozone and atomic oxygen, A small amount of excited nitrous oxide enhances the ashing rate.
  • Koizumi discloses an alternative apparatus and method using gaseous ozone for removing a photoresist film from a semiconductor wafer.
  • an apparatus is used that processes a single wafer at a time.
  • the apparatus exposes the wafer to a gas mixture containing ozone and alcohol while the wafer surface is preferably heated to a temperature of 150 °C to 250 °C to effect removal of the photoresist.
  • Another method for pre-cleaning wafers uses an O 3 /IR process as an in situ cleaning step for organic removal before oxide etching to condition the surface and to assure etch repeatability and uniformity.
  • a thin layer of oxide may be grown on the wafer surface.
  • the ozone is fed into the process chamber while the wafer is being heated by an infra red lamp to a certain temperature, after which the ozone is turned off and the wafer is cooled down by a low temperature inert gas.
  • ozone gas in conjunction with ultraviolet light for cleaning and etching wafer surfaces has also been investigated. See Semiconductor Wafer Cleaning and Surface Characterization (proceedings of the 2 nd workshop), Moon, St Wafer Cleaning Study by UV/Ozone ands In Situ Surface Analysis, 68-76; ASM Int'l, Li et al, UV/Ozone Pre- Treatment on Organic Contaminated Wafer for Complete Oxide Removal in HF Vapor Cleaning.
  • ozone has been investigated for use in wet processing techniques, there are still many drawbacks. For example, one problem associated with the use of ozone when dissolved in water is that the mass transfer rate of ozone to an electronic component is quite slow.
  • gaseous ozone has been used alone and in combination with other gaseous substances to improve the rate of processing of electronic components
  • the use of gaseous ozone has disadvantages as well.
  • gaseous ozone undesirably leaves oxidized organic by products on the electronic components which must subsequently be removed, often requiring additional apparatuses.
  • processing, especially when performed to remove photoresist is typically done at high temperatures (greater than 150 °C and more commonly greater than 250 °C). These high temperatures can lead to malfunctions in the electronic component.
  • Another disadvantage is that many systems currently used for processing electronic components with gaseous ozone process a single wafer at one time and/or are not able to perform several processing steps in one vessel.
  • the present invention provides methods of readily delivering ozone in a stable form to electronic components during wet processing. Also for example, the present invention provides methods for exposing the electronic components to gaseous ozone and other processing solutions in a series of steps in a single vessel.
  • the present invention provides, inter alia, wet processing methods for the manufacture of electronic components, including electronic component precursors such as semiconductor wafers used in integrated circuits. More specifically, this invention relates to methods of, for example, processing electronic components using wet processing techniques with ozonated process fluids.
  • the methods of the invention may be used, inter alia, to remove organic materials, such as photoresists, from electronic components and to oxidize the surfaces of the electronic components (i.e., growth of an oxide layer).
  • the methods of the present invention may also be used in pretreatment steps such as cleaning or etching.
  • a method for wet processing electronic components including contacting the surfaces of the electronic components with a wetting solution to wet the surfaces of the electronic components with the wetting solution, where the wetting solution contains water; forming an ozonated process fluid containing gaseous ozone where the ozonated process fluid is in the form of a gas, vapor, mist, or mixtures thereof; and contacting the electronic components with the ozonated process fluid in a reaction chamber for a contact time and in the presence of at least one base for at least a portion of the contact time, where the ozonated process fluid is in the temperature range of about 20 °C to about 145 °C, and the base is present in the wetting solution or the ozonated process fluid, or combinations thereof.
  • a method for wet processing electronic components that includes loading in an enclosable single vessel a plurality of electronic components; contacting the surfaces of the electronic components with a wetting solution to wet the surfaces of the electronic components with the wetting solution, where the wetting solution contains water; forming an ozonated process fluid containing gaseous ozone where the ozonated process fluid is in the form of a gas, vapor, mist, or mixtures thereof; contacting the electronic components with the ozonated process fluid in a reaction chamber for a contact time and in the presence of at least one base for at least a portion of the contact time, where the ozonated process fluid is in the temperature range of about 20 °C to about 145 °C, and the base is present in the wetting solution or the ozonated process fluid, or combinations thereof; and contacting the electronic components in the vessel with one or more processing solutions after the contacting of the electronic components with the ozonated process fluid.
  • a method for wet processing electronic components that includes contacting electronic components with a wetting solution to wet the surfaces of the electronic components with the wetting solution, where the wetting solution contains water and at least one base; contacting the wetted electronic components with an ozonated process fluid for a contact time, where the ozonated process fluid is in the form of a gas, vapor, mist, or mixtures thereof, and where the ozonated process fluid is in the temperature range of about 20 °C to about 145 °C; and contacting the electronic component with one or more processing fluids after the contacting of the electronic components with the gaseous ozone.
  • the present invention provides methods of wet processing electronic components using an ozonated process fluid.
  • the methods of the present invention are particularly useful for removing organic materials from the surfaces of electronic components using the ozonated process fluid.
  • the methods of the present invention can remove organic materials such as photoresists (ashed or unashed), plasticizers, surfactants, fluorocarbon polymers, organics from human contact or combinations thereof.
  • the methods of the invention may also be used to grow an oxide layer on the electronic component surface.
  • the methods of the invention are also contemplated to be used for pre-treatment cleaning, cleaning in between processing steps, and post-treatment cleaning and processing (e.g., oxide growth).
  • the present invention also provides methods of using an ozonated process fluid where a plurality of electronic components can be treated with the ozonated process fluid simultaneously and/or where the electronic components can be subsequently contacted with other process fluids in the same vessel.
  • wet processing means the electronic components are contacted with one or more liquids (hereinafter referred to as “process liquids” or “process solutions”) to process the electronic components in a desired manner. For example, it may be desired to treat the electronic components to clean, etch, or remove photoresist from the surfaces of the electronic components. It may also be desired to rinse the electronic components between such treatment steps.
  • wet processing may also include steps where the electronic components are contacted with other fluids, such as a gas, a vapor, or a liquid mixed with a vapor or gas, or combinations thereof.
  • process fluid includes liquids, gases, liquids in their vapor phases, or combinations thereof.
  • vapor as used herein is meant to include partially vaporized liquid, saturated vapor, unsaturated vapor, supersaturated vapor or combinations thereof.
  • mist as used herein means a spray of liquid droplets.
  • the mist may be a spray of droplets preferably ranging in size from about 10 ⁇ m to about 1500 ⁇ m, more preferably from about 50 ⁇ m or lower and most preferably from about 30 ⁇ m or lower.
  • process fluids used during wet processing there are various types of process fluids used during wet processing.
  • the most common types of process fluids used during wet processing are reactive chemical process fluids or liquids, and rinsing fluids or liquids.
  • reactive chemical process fluid or “reactive chemical process liquid” as used herein, is any liquid or fluid that reacts in some desired manner with the surfaces of the electronic components to alter the surface composition of the electronic component.
  • the reactive chemical process liquid or fluid may have activity in removing contamination adhered or chemically bound to the surfaces of the electronic components, such as particulate, metallic, photoresist, or organic materials; activity in etching the surfaces of the electronic component; or activity in growing an oxide layer on the surface of the electronic component.
  • rinsing liquid or “rinsing fluid” refers to DI water or some other liquid or fluid that removes from the electronic components and/or vessel residual reactive chemical process fluids, reaction by-products, and/or particles or other contaminants freed or loosened by the chemical treatment step.
  • the rinsing liquids or fluids may also be used to prevent redeposition of loosened particles or contaminants onto the electronic components or vessel. Examples of reactive chemical process fluids and rinsing fluids useful in the methods of the present invention are described in more detail hereinafter.
  • chemical treatment step or “wet processing step” refers to contacting the electronic components with a reactive chemical process fluid or process fluid respectively.
  • reaction chamber refers to vessels (enclosed or open to the atmosphere), baths, wet benches and other reservoirs suitable for wet processing electronic components.
  • single vessel refers to any wet processing system in which the electronic components are maintained in one vessel during the entire wet processing sequence.
  • electronic components includes for example electronic component precursors such as semiconductor wafers, flat panels, and other components used in the manufacture of electronic components (i.e., integrated circuits); CD ROM disks; hard drive memory disks; or multichip modules.
  • the electronic components are contacted with a wetting solution and an ozonated process fluid, where at least one base is present for at least a portion of the contact time that the electronic components are contacted with the ozonated process fluid.
  • the base may be present for example in the wetting solution, the ozonated process fluid, or both.
  • the base present in the wetting solution and/or ozonated process fluid enhances the reaction of ozone with the electronic components in the following manner.
  • the presence of a base enhances the formation of hydroxide ions in the presence of compounds containing hydroxide functional groups (e.g., ammonia in the presence of water) or directly provides a source of hydroxide ions (e.g., ammonium hydroxide).
  • hydroxide ions react with ozone to form hydroxyl radicals. These hydroxyl radicals are believed to be more effective in removing or oxidizing contaminants such as organic materials found on the surfaces of electronic components in comparison to ozone.
  • the hydroxyl radicals are believed to react quickly and nonselectively with the saturated and unsaturated carbon-carbon bonds typically found in organic materials to form such oxidation reaction products as CO, CO 2 , H 2 O, or combinations thereof.
  • gaseous ozone will react with organic materials, the reaction with gaseous ozone is more selective and slower.
  • the wetting solution may be any liquid that contains water that is capable of wetting the surfaces of the electronic components.
  • wet or “wetting” it is meant that the wetting solution when contacted with the electronic components preferably forms a layer of wetting solution that coats the electronic components.
  • this layer provides an effective medium for the ozone to react to form hydroxy radicals at or near the surfaces of the electronic components, and/or to react directly with the surfaces of the electronic components.
  • the layer of wetting solution is continuous so that ozone can react uniformly on the surfaces of the electronic components.
  • the thickness of the layer is relatively thin to ensure that the ozone forms hydroxyl radicals close enough to the surfaces of the electronic components for reaction (e.g., preferably about 40 ⁇ m or less).
  • the wetting solution may also contain other compounds, that are preferably water soluble, to promote the formation of hydroxyl radicals.
  • the compound may contain hydroxyl functional groups that are capable of generating hydroxyl radicals in the presence of ozone or water.
  • compounds that promote the formation of hydroxyl radicals include for example, hydrogen peroxide, bases, or combinations thereof.
  • Bases that can be present in the wetting solution include for example inorganic bases or organic bases, such as ammonia, ammonium hydroxide, alkyl ammonium hydroxides, such as trimethyl ammonium hydroxide, alkali or alkaline earth metal hydroxides such as sodium hydroxide or potassium hydroxide, organic amines, basic amino acids, or combinations thereof.
  • Preferred bases include ammonium hydroxide, alkyl ammonium hydroxides, alkali metal hydroxides, alkaline earth metal hydroxides or combinations thereof.
  • the preferred amount of such compounds in the wetting solution will depend on the compound chosen.
  • the base is added in an amount to provide a pH in the wetting solution of from about 9 to about 13.
  • hydrogen peroxide preferably hydrogen peroxide is present in the wetting solution at a concentration of from about 0.01 moles per liter to about 0.5 moles per liter, and more preferably from about 0.05 moles per liter to about 0.2 moles per liter.
  • the electronic components may be contacted with the wetting solution in any manner that wets the surfaces of the electronic components with the wetting solution.
  • the electronic components may be immersed and withdrawn from a wetting solution.
  • the electronic components may also be placed in a vessel, where the vessel is filled and then drained of the wetting solution.
  • the wetting solution may also be applied to the electronic components as a mist.
  • these methods of wetting the electronic components can be varied to adjust the thickness of the layer of wetting solution on the electronic components.
  • the temperature of the wetting solution during contact with the electronic components is preferably from about room temperature to about the condensation temperature of the wetting solution.
  • the temperature of the wetting solution may be for example from about 25 °C to about 100 °C, more preferably from about 30 °C to about 80 °C, and most preferably from about 35 °C to about 60 °C.
  • the pressure of the wetting solution during contact with the electronic components is preferably from about 0 psig to about 20 psig.
  • the electronic components in the methods of the present invention are also contacted with an ozonated process fluid.
  • the ozonated process fluid may be any fluid that contains gaseous ozone and is in the form of a gas, vapor, mist or combinations thereof.
  • the ozonated process fluid may be for example gaseous ozone, or a combination of gaseous ozone and one or more other process fluids.
  • the other process fluids present in the ozonated process fluid are in the form of a vapor, gas, mist or combinations thereof.
  • the stability of the gaseous ozone is increased in comparison to ozone dissolved in a liquid, thereby increasing the chances that the gaseous ozone will reach the surfaces of the electronic components for reaction (such as with organic materials located on the surfaces of the electronic components).
  • the concentration of ozone in the ozonated process fluid expressed as weight of ozone per volume of ozonated process fluid is from about 10 g/m 3 to about 300 g/m 3 , more preferably from about 50 g/m 3 to about 250 g/m 3 , and most preferably from about 100 g/m 3 to about 200 g/m 3 at standard temperature and pressure (25 °C, 1 atm).
  • the temperature of the ozonated process fluid that is contacted with the electronic components will depend upon the ozonated process fluid chosen, in general, the temperature of the ozonated process fluid preferably ranges from about 20 °C to about 145 °C and more preferably from about 40 °C to about 120 °C.
  • the pressure of the ozonated process fluid during contact with the electronic components is preferably from about 0 psig to about 20 psig, more preferably from about 1 psig to about 10 psig, and most preferably from about 1 psig to about 5 psig.
  • the ozonated process fluid may also contain other process fluids in addition to gaseous ozone.
  • the ozonated process fluid contains a hydroxide fluid.
  • hydroxide fluid it is meant any process fluid, in the form of a gas, vapor, mist, or combinations thereof, that promotes the formation of hydroxyl radicals alone or in combination with other reactants in the presence of ozone.
  • the hydroxide fluid may contain compounds having hydroxyl functional groups that promote the formation of hydroxyl radicals, or the hydroxide fluid may be a base, or combinations thereof.
  • Suitable hydroxide fluids include for example water; hydrogen peroxide; or bases that are capable of providing, alone or in combination with another process fluid such as water, hydroxide ions; or any combination thereof.
  • Bases useful in the present invention include inorganic bases and organic bases. Suitable bases include for example, ammonia, ammonium hydroxide, alkyl ammonium hydroxides, such as trimethyl ammonium hydroxide, alkali or alkaline earth metal hydroxides such as sodium hydroxide or potassium hydroxide; organic amines; basic amino acids; or combinations thereof.
  • Preferred bases include ammonia, ammonium hydroxide, trimethylammonium hydroxide, organic amines, or combinations thereof.
  • the most preferred hydroxide fluids useful in the methods of the present invention are water, ammonia, ammonium hydroxide, trimethylammonium hydroxide or combinations thereof.
  • the concentration of the hydroxide fluid in the ozonated process fluid will depend upon such process parameters as the type of hydroxide fluid being used.
  • the base will be added in an amount to provide a pH of from about 9 to about 13 at the surfaces of the electronic components, taking into account the water present from the wetting solution and any hydroxide fluids from the ozonated process fluid deposited on the electronic components.
  • the molar ratio of ozone to hydroxide fluid is from about 1 : 90 to about 40 : 1 , more preferably from about 1 : 10 to about 20: 1 , and most preferably from about 1 :2 to about 2:1.
  • other process fluids may be present in the ozonated process fluid.
  • other process fluids include for example alcohols, such as C, to C 20 alcohols, and more preferably C, to C 6 alcohols such as methanol, ethanol, propanol (e.g., isopropanol), butanol, pentanol, or hexanol; hydrogen chloride; hydrogen fluoride; carbon dioxide; or combinations thereof.
  • acetic acid is a hydroxyl radical scavenger
  • the reaction chamber is substantially free of acetic acid when gaseous ozone is present in the reaction chamber to prevent the scavenging of hydroxyl radicals.
  • the other process fluids may be present in the ozonated process fluid to preferably provide a molar ratio of ozone to the other process fluids in the ozonated process fluid in an amount of from about 1 :90 to about 40:1.
  • the preferred temperatures of the process fluids prior to formation of the ozonated process fluid will depend on the form of the process fluid.
  • the process fluid is a gas such as ammonia
  • the process fluid is not heated prior to formation of the ozonated process fluid.
  • the temperature of the process fluid ranges from about room temperature to the condensation temperature of the process fluid.
  • this temperature is preferably from about 20 °C to about 100 °C.
  • the process fluid is a vapor
  • the vapor is at a temperature above its condensation temperature, and more preferably at a temperature to permit condensation of the vapor on the surfaces of the electronic components.
  • the ozonated process fluid may be formed.
  • the method of formation does not significantly promote the degradation of ozone.
  • the ozonated process fluid may be formed by adding each process fluid separately into a reaction chamber containing wetted electronic components prior to or during the addition of the gaseous ozone.
  • the ozonated process fluid may also be formed by combining ozone and/or any of the process fluids together prior to addition to the reaction chamber containing the electronic components.
  • the process fluids are preferably in a form to minimize their reaction with ozone.
  • the base is a gas such as ammonia
  • the ozone is added to the reaction chamber separately from the other process fluids to form the ozonated process fluid.
  • the sequence of addition of the components of the ozonated process fluid can also be staggered to enhance the formation of hydroxyl radicals at the surfaces of the electronic components.
  • the process fluids in the ozonated process fluid are added slightly before and optionally during the addition of the gaseous ozone.
  • the electronic components can be coated with a thin layer of one or more process fluids (such as water and/or base) to facilitate the reaction of the ozone in this layer to form hydroxyl radicals.
  • process fluids such as water and/or base
  • gaseous ozone and a vapor of water may be combined under pressure to form the ozonated process fluid.
  • This ozonated process fluid can then be expanded when introduced into the reaction chamber by using, for example, a throttle valve.
  • gaseous ozone and a hydroxide fluid may be added to a reaction chamber containing electronic components from separate openings, and combined in the reaction chamber to form an ozonated process fluid.
  • the gaseous ozone and hydroxide fluid may supplied for example from opposing openings to enhance formation of hydroxyl radicals at the surfaces of the electronic components.
  • the gaseous ozone and hydroxide fluid may be combined by spraying the hydroxide fluid in the form of a mist into the reaction chamber prior to and/or during the addition of gaseous ozone to the reaction chamber so that the ozone is combined with the mist in the reaction chamber.
  • the mist can be created by any technique known to those skilled in the art such as through the use of ultrasonic or megasonic mistifiers, jets, atomizers, or spray nozzles.
  • the gaseous ozone is added at the bottom of the reaction chamber and the hydroxide fluid is added from the top of the reaction chamber.
  • the mist may be for example a deionized water mist or a mist of a base dissolved in water.
  • the mist is supplied to the reaction chamber at a temperature below the condensation temperature of the hydroxide fluid.
  • the temperature is from about 25°C to about 90 °C, and more preferably from about 30°C to about 50° C.
  • the ozone is preferably supplied to the reaction chamber at a temperature of from about 25°C to about 50 °C and a pressure of from about 1 psig to about 20 psig.
  • An advantage to using an ozonated process fluid containing a mixture of a mist of hydroxide fluid and gaseous ozone is that the gaseous ozone has a longer lifetime in a mist in comparison to ozone dissolved in bulk liquid, and even in comparison to ozone mixed with a vapor having an elevated temperature (e.g., greater than 90 °C).
  • the ozonated process fluid may be formed from ozonated water.
  • Ozonated water is formed by dissolving gaseous ozone in a solution containing water according to techniques well known to those skilled in the art. For example, the dissolving of ozone is performed at a temperature and pressure to enhance the solubility of the ozone in the water.
  • the ozonated water is then treated, for example through evaporation of the ozonated water to form an ozonated process fluid containing ozone and water vapor.
  • the ozonated water may be treated to form the ozonated process fluid.
  • the ozonated process liquid may be evaporated using heat to form an ozonated process fluid containing ozone and water vapor.
  • ozonated water is contacted with a carrier gas, such as nitrogen.
  • the carrier gas preferably "picks-up" or evaporates the gaseous ozone and water vapor to form an ozonated process fluid containing the carrier gas, ozone, and water vapor.
  • the contacting of the carrier gas with the ozonated process liquid may be carried out by any technique known to those skilled in the art such as through sparging or bubbling the carrier gas through the ozonated process liquid.
  • the carrier gas during contact with the ozonated water is preferably at a temperature below the boiling point of the ozonated water.
  • the ozonated process fluid once formed is preferably, immediately contacted with the electronic components in a reaction chamber for a time to accomplish the desired result.
  • the temperature of the electronic components during contacting is preferably at or slightly below the temperature of the ozonated process fluid.
  • contact time it is meant the time an electronic component is exposed to a process fluid.
  • the contact time will include the time an electronic component is exposed to the process fluid during filling a vessel with the process fluid or immersing the electronic component in the process fluid; the time the electronic component is soaked in the process fluid; and the time the electronic component is exposed to the process fluid while the process fluid or electronic component is being removed from the vessel.
  • the actual contact time chosen will also depend on such variables as the temperature, pressure, and composition of the ozonated process fluid, and the composition of the surfaces of the electronic components.
  • the contact time with the ozonated process fluid will be for at least 30 seconds.
  • the contacting of the ozonated process fluid is performed subsequent to wetting the electronic components with the wetting solution to ensure that there is a layer of wetting solution on the electronic components.
  • the ozonated process fluid is contacted with the electronic components in the presence of at least one base that is present in the ozonated process fluid (e.g., as a hydroxide fluid previously described herein), or is present in the wetting solution, or is present in both the ozonated process fluid and wetting solution.
  • a base is present in the ozonated process fluid
  • the base is combined with the gaseous ozone according to the methods previously described to minimize the base degrading the ozone prior to reaching the surfaces of the electronic components.
  • the electronic components are contacted with a wetting solution of water and then contacted with an ozonated process fluid containing gaseous ozone, water vapor, and a base.
  • the base is preferably a gas, vapor or combination thereof and is selected from ammonia, an alkyl ammonium hydroxide, an organic amine, or combinations thereof, and is most preferably selected from ammonia.
  • the ozonated process fluid is preferably formed by separately adding ozone, water vapor, and ammonia to the reaction chamber.
  • the deionized water vapor is preferably supplied at a pressure of from about 1 psig to about 20 psig and temperature of from about 70 °C to about 140 °C.
  • the ozone and ammonia is preferably supplied at pressures ranging from about 1 psig to about 20 psig and temperatures of from about 25 °C to about 50 °C.
  • the electronic components are contacted with a wetting solution of water and then contacted with an ozonated process fluid containing ozone and a base dissolved in an aqueous solution (e.g., the base is an aqueous solution of ammonium hydroxide, or an alkali or an alkaline earth metal hydroxide).
  • the base is preferably added to the reaction chamber as a mist in a separate stream from the ozone.
  • the electronic components are contacted with a wetting solution containing a base (hereinafter "basic solution") and contacted with an ozonated process fluid.
  • the basic solution contains ammonium hydroxide or an alkali or alkaline metal hydroxide solution.
  • the ozonated process fluid may be for example pure gaseous ozone, or a mixture of a hydroxide fluid (e.g., water and/or base) and ozone.
  • the basic solution and ozonated process fluid could be fed to the reaction chamber.
  • the basic solution could be fed to the reaction chamber in the form of a mist prior to or during the addition of the ozonated process fluid to the reaction chamber.
  • the basic solution could also be applied to the electronic components by filling the reaction chamber containing the electronic components with the basic solution.
  • the ozonated process fluid may be added to the reaction chamber during (such as through direct displacement of the basic solution with the ozonated process fluid) or after removal of the basic solution from the reaction chamber.
  • the electronic components are contacted with a wetting solution that is a mist of water and contacted with an ozonated process fluid containing ammonia and gaseous ozone during and/or after contacting the electronic components with the wetting solution.
  • the gaseous ozone and ammonia are preferably added separately to the reaction chamber in this embodiment.
  • the electronic components may be contacted with any number of other reactive chemical process fluids (e.g., gas, liquid, vapor or any combination thereof) to achieve the desired result.
  • the electronic components may be contacted with reactive chemical process fluids used to etch (hereinafter referred to as etching fluids), grow an oxide layer (hereinafter referred to as oxide growing fluids) , to remove photoresist (hereinafter referred to as photoresist removal fluids), to enhance cleaning (hereinafter referred to as cleaning fluids), or combinations thereof.
  • etching fluids reactive chemical process fluids used to etch
  • oxide growing fluids grow an oxide layer
  • photoresist removal fluids to remove photoresist
  • cleaning fluids to enhance cleaning
  • the reactive chemical process fluids useful in the present invention contain one or more chemically reactive agents to achieve the desired surface treatment.
  • concentration of such chemically reactive agents will be greater than 1000 ppm and more preferably greater than 10,000 ppm, based on the weight of the reactive chemical process fluid.
  • concentration is equal to or greater than about 10 ppm and more preferably from about 10 ppm to about 50 ppm.
  • Examples of chemically reactive agents include for example hydrochloric acid or buffers containing the same, ammonium hydroxide or buffers containing the same, hydrogen peroxide, sulfuric acid or buffers containing the same, mixtures of sulfuric acid and ozone, hydrofluoric acid or buffers containing the same, chromic acid or buffers containing the same, phosphoric acid or buffers containing the same, acetic acid or buffers containing the same, nitric acid or buffers containing the same, ammonium fluoride buffered hydrofluoric acid, deionized water and ozone, or combinations thereof.
  • the reactive chemical process fluid may contain 100% of one or more chemically reactive agents.
  • solvents such as acetone, N-methyl pyrrolidone, or combinations thereof.
  • solvents are chemically reactive agents used, for example, to remove organics or to provide other cleaning benefits.
  • Examples of preferred reactive chemical process fluids useful in the present invention include cleaning fluids, etching fluids, and photoresist removal fluids.
  • Cleaning fluids typically contain one or more corrosive agent such as an acid or base.
  • Suitable acids for cleaning include for example sulfuric acid, hydrochloric acid, nitric acid, or aqua regia.
  • Suitable bases include for example, ammonium hydroxide.
  • the desired concentration of the corrosive agent in the cleaning fluid will depend upon the particular corrosive agent chosen and the desired amount of cleaning. These corrosive agents may also be used with oxidizing agents such as ozone or hydrogen peroxide.
  • Preferred cleaning solutions are "SCI” solutions containing water, ammonia, and hydrogen peroxide, and "SC2" solutions containing water, hydrogen peroxide, and hydrochloric acid.
  • Typical concentrations for SCI solutions range from about 5:1:1 to about 200:1:1 parts by volume H 2 O : H 2 O 2 : NH 4 OH.
  • Typical concentrations for SC2 solutions range from about 5:1:1 to about 1000:0:1 parts by volume H 2 O : H 2 O 2 :HCl.
  • Suitable etching solutions contain agents that are capable of removing oxides.
  • a common etching agent used is for example hydrofluoric acid, buffered hydrofluoric acid, ammonium fluoride, or other substances which generate hydrofluoric acid in solution.
  • a hydrofluoric acid containing etching solution may contain for example from about 4:1 to about 1000: 1 parts by weight H 2 O :HF.
  • process fluids that can be used during wet processing.
  • Other examples of process fluids that can be used during wet processing are disclosed in "Chemical Etching” by Werner Kern et al., in Thin Film Processes, edited by John L. Vosser et al. , published by Academic Press, NY 1978, pages 401 -496, which is incorporated by reference in its entirety.
  • the electronic components may also be contacted with rinsing fluids during the methods of the present invention.
  • rinsing fluids are used to remove from the electronic components and/or vessel residual reactive chemical process fluids, reaction by-products, and/or particles or other contaminants freed or loosened by a chemical treatment step.
  • the rinsing fluids may also be used to prevent redeposition of loosened particles or contaminants onto the electronic components or vessel.
  • any rinsing fluid may be chosen that is capable of achieving the effects described above.
  • a rinsing fluid such factors as the nature of the surfaces of the electronic components to be rinsed, the nature of contaminants dissolved in the reactive chemical process fluid, and the nature of the reactive chemical process fluid to be rinsed should be considered.
  • the proposed rinsing fluid should be compatible (i.e., relatively nonreactive) with the materials of construction in contact with the fluid.
  • Rinsing fluids which may be used include for example water, organic solvents, mixtures of organic solvents, ozonated water, or combinations thereof.
  • Preferred organic solvents include those organic compounds useful as drying solutions disclosed hereinafter such as C j to C 10 alcohols, and preferably C, to C 6 alcohols.
  • the rinsing fluid is a liquid and more preferably is deionized water.
  • Rinsing fluids may also optionally contain low levels of chemically reactive agents to enhance rinsing.
  • the rinsing fluid may be a dilute aqueous solution of hydrochloric acid or acetic acid to prevent, for example, metallic deposition on the surface of the electronic component.
  • Surfactants, anti-corrosion agents, and/or ozone are other additives used in rinsing fluids.
  • the concentration of such additives in the rinsing fluid is minute.
  • the concentration is preferably not greater than about 1000 ppm by weight and more preferably not greater than 100 ppm by weight based on the total weight of the rinsing fluid.
  • the concentration of ozone in the rinsing fluid is 5 ppm or less.
  • the electronic components are contacted with at least one processing fluid that is a liquid (i.e., processing solution) subsequent to contact with the ozonated process fluid to aid in removal of reaction by products or residual chemicals such as oxidized organic material.
  • processing solution may be a reactive chemical process liquid or rinsing liquid or combinations thereof.
  • the electronic components after contact with an ozonated process fluid are contacted with a cleaning solution such as an
  • the electronic components may be optionally rinsed with a rinsing liquid such as deionized water.
  • a rinsing liquid such as deionized water.
  • the SCI Solution is at a temperature of from about 15 °C to about 95 °C, and more preferably from about 25 °C to about 45 °C.
  • the SC2 Solution is at a temperature of from about 15 °C to about 95 °C, and more preferably from about 25 °C to about 45 ° C.
  • the rinsing liquid is at a temperature of from about 15 ° C to about 90 ° C, and more preferably from about 25 °C to about 30°C.
  • the electronic components may be contacted with an etching solution subsequent to contact with the ozonated process fluid.
  • the etching solution contains hydrofluoric acid
  • the temperature of the hydrofluoric acid is from about 15°C to about 95 °C, and more preferably from about 35 °C to about 40°C.
  • the elctronic components may be contacted with a rinsing liquid such as deionized water.
  • the temperature of the rinsing liquid is from about 15 ° C to 90 ° C, and more preferably from about 25°C to about 30°C.
  • the electronic components after contact with an ozonated process fluid, may be contacted with an SCI solution having a concentration of about 80:3:1 parts by volume H 2 O : H 2 O 2 : NH 4 OH; an SC2 solution having a concentration of 80:1 :1 parts by volume H 2 O:H 2 O 2 :HCl; and a hydrofluoric acid solution having a concentration of about 4:1 to about 1000:1 parts by volume H 2 O:HF.
  • This method is particularly useful for cleaning and etching.
  • the order of treatment of the SCI solution, the SC2 solution, and the etching solution may also be reversed.
  • the electronic components after contact with the ozonated process fluid, are contacted with an SCI solution, and then contacted with an SC2 solution.
  • the electronic components are then preferably rinsed with deionized water and dried using an isopropanol vapor.
  • wet processing can be carried out using sonic energy (such as in the megasonic energy range) during the contacting of the electronic components with a process liquid to enhance cleaning.
  • sonic energy such as in the megasonic energy range
  • Such methods may also include wet processing techniques disclosed in for example U.S. Patent No. 5,383,484; U.S. Patent Application Ser. Nos. 08/684,543, filed July 19, 1996; 09/209,101, filed December 10, 1998; and 09/253,157, filed February 19, 1999; and U.S. Provisional Patent Application Ser. Nos. 60/087,758 filed June 2, 1998;and 60/111,350 filed December 8, 1998, the disclosures of which are all hereby incorporated by reference in their entireties.
  • the methods of the invention may be carried out in generally any wet processing equipment including for example multiple bath systems (e.g., wet bench), and single vessel systems (open or closable to the environment). See, e.g., Chapter 1 : Overview and Evolution of Semiconductor Wafer Contamination and Cleaning Technology by Werner Kern and Chapter 3: Aqueous Cleaning Processes by Don C. Burkman, Donald Deal, Donald C. Grant, and Charlie A.
  • the wet processing system will also include storage tanks for chemical reagents, such as ammonium hydroxide (NH 4 OH) or hydrofluoric acid (HF); and a system for delivering deionized water used for rinsing the electronic components and diluting the chemical reagents.
  • chemical reagents such as ammonium hydroxide (NH 4 OH) or hydrofluoric acid (HF)
  • a system for delivering deionized water used for rinsing the electronic components and diluting the chemical reagents.
  • the chemical reagents are preferably stored in their concentrated form, which is: hydrogen peroxide (H 2 O 2 ) (31%), NH 4 OH (28%), hydrochloric acid (HC1) (37%), HF (49%), and sulfuric acid (H 2 SO 4 ) (98%) (percentages represent weight percentages in aqueous solutions).
  • the storage tanks are preferably set-up so that they are in fluid communication with the reaction chamber where the electronic components are treated.
  • the gaseous ozone is preferably produced externally to the wet processing reaction chamber.
  • Ozone may be generated by any method known to those skilled in the art without departing from the spirit of the invention.
  • ozone is generated with a high capacity generator such as a TEX8200 capable of producing roughly 100 grams/hr or greater.
  • the electronic components are housed in a single vessel system.
  • single vessel systems such as those disclosed in U.S. Patent Nos.4,778,532, 4,917,123, 4,911,761, 4,795,497, 4,899,767, 4,984,597, 4,633,893, 4,917,123, 4,738,272, 4,577,650, 5,571,337 and 5,569,330, the disclosures of which are herein incorporated by reference in their entirety, are used.
  • Preferred commercially available single vessel systems are Full-FlowTM vessels such as those manufactured by CFM Technologies, Poseidon manufactured by Steag, and FL820L manufactured by Dainippon Screen. Such systems are preferred because foreign gas and contamination levels can be more readily controlled.
  • the single vessel wet processing system also preferably includes metering devices such as a control valve and/or pump for transporting chemical reagents from the storage tank area to the reaction chamber.
  • a processing control system such as a personal computer, is also typically used as a means to monitor processing conditions (e.g., flow rates, mix rates, exposure times, and temperature).
  • processing conditions e.g., flow rates, mix rates, exposure times, and temperature.
  • the processing control system can be used to program the flow rates of chemical reagents and deionized water so that the appropriate concentration of chemical reagent(s) will be present in the reactive chemical process fluid.
  • the electronic components are wet processed in an enclosable single vessel wet processing system.
  • the enclosable single vessel wet processing system is also preferably capable of receiving different process fluids in various sequences.
  • a preferred method of delivering process fluids to the vessel is by direct displacement of one fluid with another.
  • the Full FlowTM wet processing system manufactured by CFM Technologies, Inc is an example of a system capable of delivering fluids by direct displacement.
  • Such systems are preferred because they result in a more uniform treatment of the electronic components.
  • the chemicals utilized in the chemical treatment of electronic components are quite dangerous in that they may be strong acids, alkalis, or volatile solvents.
  • Enclosable single vessels minimize the hazards associated with such process fluids by avoiding atmospheric contamination and personnel exposure to the chemicals, and by making handling of the chemicals safer.
  • one or more electronic components are placed in a single vessel and closed to the environment.
  • the electronic components may optionally be contacted with one or more process fluids for pretreatment.
  • the electronic components are contacted with a wetting solution, such as a basic solution, to wet the surfaces of the electronic components.
  • a wetting solution such as a basic solution
  • Such contacting can be accomplished through directing the wetting solution into the vessel to fill the process vessel full with the wetting solution so that gases from the atmosphere or residual fluid from a previous step are not significantly trapped within the vessel.
  • the fluid can be continuously directed through the vessel once the vessel is full of the wetting solution, or the flow of wetting solution can be stopped to soak the electronic components for a desired time.
  • the wetting solution may then be removed from the vessel and the ozonated process fluid may be directed into the vessel to contact the electronic components with the ozonated process fluid.
  • a base is preferably present in the vessel for at least a portion of the time that the electronic components are contacted with the ozonated process fluid.
  • the electronic components may be optionally rinsed with a rinsing fluid and/or contacted with another process fluid such as one or more reactive chemical process fluids.
  • the removal of one process fluid with another process fluid in the enclosable single vessel can be accomplished in several ways. For example, the process fluid in the process vessel can be completely removed (i.e., drained), and then the next process fluid can be directed into the vessel during or after draining. In another embodiment, the process fluid present in the vessel can be directly displaced by the next desired process fluid as described for example in U.S. Patent No. 4,778,532.
  • the electronic components are preferably dried.
  • dry or “drying” it is meant that the electronic components are preferably made substantially free of liquid droplets.
  • impurities present in the liquid droplets do not remain on the surfaces of the semiconductor substrates when the liquid droplets evaporate. Such impurities undesirably leave marks (e.g., watermarks) or other residues on the surfaces of the semiconductor substrates.
  • drying may simply involve removing a treating, or rinsing fluid, for example with the aid of a drying fluid stream, or by other means known to those skilled in the art.
  • any method or system of drying may be used. Suitable methods of drying include for example evaporation, centrifugal force in a spin-rinser-dryer, steam or chemical drying, or combinations thereof.
  • the wet processing and drying is performed in a single vessel without removing the electronic components from the vessel.
  • a preferred method of drying uses a drying fluid stream to directly displace the last processing solution that the electronic components are contacted with prior to drying (hereinafter referred to as "direct displace drying").
  • direct displace drying Suitable methods and systems for direct displace drying are disclosed in for example U.S. Patent Nos.4,778,532, 4,795,497, 4,911,761,
  • Marangoni type dryers supplied by manufacturers such as Steag, Dainippon, and YieldUp.
  • the drying fluid stream is formed from a partially or completely vaporized drying solution.
  • the drying fluid stream may be for example superheated, a mixture of vapor and liquid, saturated vapor or a mixture of vapor and a noncondensible gas.
  • the drying solution chosen to form the drying fluid stream is preferably miscible with the last process fluid in the vessel and non-reactive with the surfaces of the electronic components.
  • the drying solution also preferably has a relatively low boiling point to facilitate drying.
  • the drying solution is preferably selected from organic compounds having a boiling point of less than about 140 degrees centigrade at atmospheric pressure.
  • drying solutions which may be employed are steam, alcohols such as methanol, ethanol, 1-propanol, isopropanol, n-butanol, secbutanol, tertbutanol, or tert-amyl alcohol, acetone, acetonitrile, hexafluoroacetone, nitromethane, acetic acid, propionic acid, ethylene glycol mono-methyl ether, difluoroethane, ethyl acetate, isopropyl acetate, l ,l ,2-trichloro-l ,2,2- trifluoroethane, 1 ,2-dichloroethane, trichloroethane, perfluoro-2-butyltetrahydrofuran, perfluoro-1 ,4-dimethylcyclohexane or combinations thereof.
  • alcohols such as methanol, ethanol, 1-propanol, isopropanol, n-but
  • the drying solution is a C, to C 6 alcohol, such as for example methanol, ethanol, 1-propanol, isopropanol, n-butanol, secbutanol, tertbutanol, tert-amyl alcohol, pentanol, hexanol or combinations thereof.
  • a C, to C 6 alcohol such as for example methanol, ethanol, 1-propanol, isopropanol, n-butanol, secbutanol, tertbutanol, tert-amyl alcohol, pentanol, hexanol or combinations thereof.
  • a drying solution is selected which is miscible with the processing solution present in the process vessel immediately before drying and forms a minimum-boiling azeotrope with the processing solution. Since water is the most convenient and commonly used solvent for chemical treatment or rinsing fluids, a drying solution which forms a minimum-boiling azeotrope with water is especially preferred.
  • the electronic components may be removed from the drying vessel and further processed in any desired manner.
  • the present invention has been described above with respect to particular preferred embodiments, it will be apparent to those skilled in the art that numerous modifications and variations can be made to those designs. The descriptions provided are for illustrative purposes and are not intended to limit the invention.

Landscapes

  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Cleaning Or Drying Semiconductors (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Weting (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne des procédés de traitement humide utilisant des fluides de traitement à l'ozone pour la fabrication de composants électroniques. Pour réaliser ces procédés, les composants électroniques sont placés au contact d'une solution mouillante et d'un fluide de traitement à l'ozone contenant de l'ozone gazeux. Le contact des composants électroniques avec un fluide de traitement à l'ozone est effectué en présence d'une base. Les procédés de l'invention sont particulièrement utiles pour éliminer des matières organiques de surfaces de composants électroniques.
PCT/US1999/016954 1998-07-29 1999-07-26 Procedes de traitement humide utilisant des fluides de traitement a l'ozone pour la fabrication de composants electroniques WO2000007220A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU52331/99A AU5233199A (en) 1998-07-29 1999-07-26 Wet processing methods for the manufacture of electronic components using ozonated process fluids
JP2000562934A JP2003533865A (ja) 1998-07-29 1999-07-26 電子構成要素の製造でオゾン含有プロセス流体を用いて電子構成要素を湿式処理する方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US9454598P 1998-07-29 1998-07-29
US60/094,545 1998-07-29
US36020699A 1999-07-23 1999-07-23
US09/360,206 1999-07-23

Publications (2)

Publication Number Publication Date
WO2000007220A2 true WO2000007220A2 (fr) 2000-02-10
WO2000007220A3 WO2000007220A3 (fr) 2007-11-22

Family

ID=26789010

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1999/016954 WO2000007220A2 (fr) 1998-07-29 1999-07-26 Procedes de traitement humide utilisant des fluides de traitement a l'ozone pour la fabrication de composants electroniques

Country Status (4)

Country Link
JP (1) JP2003533865A (fr)
AU (1) AU5233199A (fr)
TW (1) TW404853B (fr)
WO (1) WO2000007220A2 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002050634A (ja) 2000-04-28 2002-02-15 Semiconductor Energy Lab Co Ltd 半導体装置の作製方法
EP1255287A1 (fr) * 2000-09-28 2002-11-06 Mitsubishi Denki Kabushiki Kaisha Procede et appareil de traitement de substrat
EP1745864A3 (fr) * 2005-07-18 2007-04-25 DALSA Semiconductor Inc. Procédé d'élimination de résidus formés lors de la fabrication de systèmes MEMS
US7399578B2 (en) 2001-05-14 2008-07-15 Kabushiki Kaisha Toshiba Alkaline solution and manufacturing method, and alkaline solution applied to pattern forming method, resist film removing method, solution application method, substrate treatment method, solution supply method, and semiconductor device manufacturing method
US8951902B2 (en) 2000-04-28 2015-02-10 Semiconductor Energy Laboratory Co., Ltd. Methods of removing contaminant impurities during the manufacture of a thin film transistor by applying water in which ozone is dissolved

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101046287B1 (ko) 2004-03-22 2011-07-04 레나 게엠베하 기판 표면 처리 방법
JP2010226089A (ja) * 2009-01-14 2010-10-07 Rohm & Haas Electronic Materials Llc 半導体ウェハをクリーニングする方法
JP7341850B2 (ja) * 2019-10-25 2023-09-11 株式会社Ｓｃｒｅｅｎホールディングス 基板処理方法および基板処理装置

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5181985A (en) * 1988-06-01 1993-01-26 Wacker-Chemitronic Gesellschaft Fur Elektronik-Grundstoffe Mbh Process for the wet-chemical surface treatment of semiconductor wafers
US5464480A (en) * 1993-07-16 1995-11-07 Legacy Systems, Inc. Process and apparatus for the treatment of semiconductor wafers in a fluid
US5484549A (en) * 1993-08-30 1996-01-16 Ecolab Inc. Potentiated aqueous ozone cleaning composition for removal of a contaminating soil from a surface
US5853491A (en) * 1994-06-27 1998-12-29 Siemens Aktiengesellschaft Method for reducing metal contamination of silicon wafers during semiconductor manufacturing

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57204132A (en) * 1981-06-10 1982-12-14 Fujitsu Ltd Washing method for silicon wafer
JPH0199221A (ja) * 1987-10-12 1989-04-18 Nec Corp 半導体基板の洗浄方法
JP3405371B2 (ja) * 1994-10-19 2003-05-12 三菱瓦斯化学株式会社 半導体基板のオゾン洗浄方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5181985A (en) * 1988-06-01 1993-01-26 Wacker-Chemitronic Gesellschaft Fur Elektronik-Grundstoffe Mbh Process for the wet-chemical surface treatment of semiconductor wafers
US5464480A (en) * 1993-07-16 1995-11-07 Legacy Systems, Inc. Process and apparatus for the treatment of semiconductor wafers in a fluid
US5484549A (en) * 1993-08-30 1996-01-16 Ecolab Inc. Potentiated aqueous ozone cleaning composition for removal of a contaminating soil from a surface
US5853491A (en) * 1994-06-27 1998-12-29 Siemens Aktiengesellschaft Method for reducing metal contamination of silicon wafers during semiconductor manufacturing

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002050634A (ja) 2000-04-28 2002-02-15 Semiconductor Energy Lab Co Ltd 半導体装置の作製方法
US8951902B2 (en) 2000-04-28 2015-02-10 Semiconductor Energy Laboratory Co., Ltd. Methods of removing contaminant impurities during the manufacture of a thin film transistor by applying water in which ozone is dissolved
EP1255287A1 (fr) * 2000-09-28 2002-11-06 Mitsubishi Denki Kabushiki Kaisha Procede et appareil de traitement de substrat
EP1255287A4 (fr) * 2000-09-28 2008-07-09 Mitsubishi Electric Corp Procede et appareil de traitement de substrat
US7399578B2 (en) 2001-05-14 2008-07-15 Kabushiki Kaisha Toshiba Alkaline solution and manufacturing method, and alkaline solution applied to pattern forming method, resist film removing method, solution application method, substrate treatment method, solution supply method, and semiconductor device manufacturing method
EP1745864A3 (fr) * 2005-07-18 2007-04-25 DALSA Semiconductor Inc. Procédé d'élimination de résidus formés lors de la fabrication de systèmes MEMS
US8071486B2 (en) 2005-07-18 2011-12-06 Teledyne Dalsa Semiconductor Inc. Method for removing residues formed during the manufacture of MEMS devices

Also Published As

Publication number Publication date
JP2003533865A (ja) 2003-11-11
AU5233199A (en) 2000-02-21
TW404853B (en) 2000-09-11
WO2000007220A3 (fr) 2007-11-22

Similar Documents

Publication Publication Date Title
US6491763B2 (en) Processes for treating electronic components
US20020066717A1 (en) Apparatus for providing ozonated process fluid and methods for using same
US6551409B1 (en) Method for removing organic contaminants from a semiconductor surface
US6167891B1 (en) Temperature controlled degassification of deionized water for megasonic cleaning of semiconductor wafers
JP5249462B2 (ja) 水蒸気または蒸気を用いた基板の処理方法
JPH1027771A (ja) 洗浄方法及び洗浄装置
US20030205254A1 (en) Method for processing the surface of a workpiece
US6295998B1 (en) Temperature controlled gassification of deionized water for megasonic cleaning of semiconductor wafers
JP2001517365A (ja) フォトレジストの除去方法
KR100238234B1 (ko) 반도체소자용 인-시튜 세정장치 및 그를 이용한 반도체 소자의 세정방법
JP3133054B2 (ja) 基板の洗浄処理方法及び洗浄処理装置
WO2000007220A2 (fr) Procedes de traitement humide utilisant des fluides de traitement a l'ozone pour la fabrication de composants electroniques
JP3538114B2 (ja) 表面付着汚染物質の除去方法及び除去装置
JP2891578B2 (ja) 基板処理方法
JP2003045842A (ja) 表面付着異質物質の除去方法及び除去装置
US6495099B1 (en) Wet processing methods for the manufacture of electronic components
US20030093917A1 (en) Apparatus and methods for processing electronic component precursors
US6517636B1 (en) Method for reducing particle contamination during the wet processing of semiconductor substrates
JP2004104090A (ja) 表面付着汚染物質の除去方法及び除去装置
KR100228372B1 (ko) 실리콘 표면이 노출된 웨이퍼 세정 방법
KR20010041359A (ko) 통제된 기체 수준을 가진 공정 액체를 사용하는 전자부품습식 처리방법
US20070261718A1 (en) Method and apparatus for ozone-enhanced cleaning of flat objects with pulsed liquid jet
JP2004140126A (ja) 洗浄後の半導体基板の乾燥方法
KR20050101658A (ko) 기판 처리 장치 및 방법

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW SD SL SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
ENP Entry into the national phase

Ref document number: 2000 562934

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 99809243.6

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 1999937516

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWW Wipo information: withdrawn in national office

Ref document number: 1999937516

Country of ref document: EP