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CN1665609A - Fluid assisted cryogenic cleaning - Google Patents

Fluid assisted cryogenic cleaning Download PDF

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Publication number
CN1665609A
CN1665609A CN038103621A CN03810362A CN1665609A CN 1665609 A CN1665609 A CN 1665609A CN 038103621 A CN038103621 A CN 038103621A CN 03810362 A CN03810362 A CN 03810362A CN 1665609 A CN1665609 A CN 1665609A
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CN
China
Prior art keywords
described method
fluid
steam
cleaning
low temperature
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Pending
Application number
CN038103621A
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Chinese (zh)
Inventor
S·巴那基
H·F·春
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Messer LLC
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BOC Group Inc
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Publication date
Priority claimed from US10/324,221 external-priority patent/US6852173B2/en
Priority claimed from US10/403,147 external-priority patent/US6949145B2/en
Application filed by BOC Group Inc filed Critical BOC Group Inc
Publication of CN1665609A publication Critical patent/CN1665609A/en
Pending legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02101—Cleaning only involving supercritical fluids
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
    • B08B7/0064—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by temperature changes
    • B08B7/0092—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by temperature changes by cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
    • B24C1/00—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods
    • B24C1/003—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods using material which dissolves or changes phase after the treatment, e.g. ice, CO2
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • 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
    • H01L21/67051—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing using mainly spraying means, e.g. nozzles

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cleaning Or Drying Semiconductors (AREA)
  • Cleaning By Liquid Or Steam (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

The present invention is directed to fluid assisted cryogenic cleaning of a substrate surface requiring precision cleaning such as semiconductors, metals, and dielectric films. The process comprises the steps of applying a fluid selected from the group consisting of high vapor pressure liquids, reactive gases, and vapors of reactive liquids onto the substrate surface followed by or simultaneously with cryogenic cleaning of the substrate surface to remove contaminants.

Description

Fluid assisted cryogenic cleans
TECHNICAL FIELD OF THE INVENTION
The present invention relates to carry out low temperature clean in or before the method for cleaning with liquid or steam, assisting in removing needs semiconductor surface and other lip-deep foreign substance and pollutants of accurately cleaning.
Background of invention
Having or not having the cleaning and the surface preparation of the silicon wafer of various thin layers is keys of method for manufacturing integrated circuit.The particle of wafer surface and the removal of pollutant are to carry out in several key method steps in ic manufacturing process.On 0.18 μ m method node, there are 80 in 400 operations, promptly 20% manufacturing process belongs to matting.The type of film, surface configuration and the pollutant that will remove at cleaning product line front end (FEOL) and terminal (BEOL) changes the difficulty that has increased cleaning method, removes the pith that degranulation becomes this cleaning.
With regard to the manufacturing of integrated circuit zero defect, International Technology Road map forSemiconductor (ITRS) points out that critical granularity is half [1] of DRAM 1/2 pitch.Therefore, on 130nm method node, because DRAM 1/2 pitch is 130nm, critical granularity is 65nm.Therefore must remove the particle of granularity, to guarantee to make zero defect component greater than 65nm.
Because the adhesion of small size particle improves with the ratio of removal power, so little particle is difficult to remove.With regard to submicron, particle is a Van der Waals force with the initial adherence power on surface.This power depends on the distance and the Hamaker constant on size, particle and the surface of particle.The Van der Waals force of the spheric granules on the flat base material is represented with equation 1:
F ab = A 132 d p 12 Z 0 2 - - - ( 1 )
A in the formula 132For particle, surface with participate in the Hamaker constant of the system that medium constitutes; d PParticle diameter, Z 0Be the distance of particle apart from the surface.The Hamaker constant of hybrid system is represented with equation (2):
A 132＝A 12+A 33-A 13-A 23 (2)
The Hamaker constant of two kinds of different materials concerns the geometric average value representation with each Hamaker constant, i.e. Aij=(Aii*Ajj) 1/2, wherein Aii and Ajj are the Hamaker constant of material i and j.Can carry out theory with Lifshitz and London model calculates.The Hamaker constant on particle that uses in integrated circuit fabrication process and surface is listed in document [2,3], compares with air, and when the participation medium was liquid, the Hamaker constant was less.Van der Waals force is directly proportional with the Hamaker constant, reduces when therefore having liquid level between particle and surface.
Must be removed various types of organic and metal organic pollutions except being difficult to from the surface removal granule, also existing.New insulation material (dielectric constant＜3) and metal have appearred in the demand along with to big conversion speed and line function, to reduce the RC delay constant in the circuit.Selected metal, i.e. copper has increased the difficulty of process conformity scheme.Just connect in the aluminium,, carry out the method for dielectric deposition then and carry out metal pattern with the reactive ion etching (RIE) that carries out aluminium earlier.To copper elder generation deposit dielectric film and in addition etching, form passage and groove, in those etching outlines, carry out the copper deposition then.Use chemical mechanical polishing method (CMP) to remove excessive copper again, prepare against the usefulness of thin layer subsequently with flat surface.This production line end (BEOL) forms the method that connects in the copper and makes Dual Damascene method second.
After dielectric etch formed passage and groove, a large amount of fluoropolymer residues was left in wafer surface and profile inboard, as shown in Figure 1.These residues produce in etching process, and a part is used for side wall passivation in anisotropic etching.Etch residues must be removed, carry out rete deposition subsequently then: copper barrier layer Ta/TaN film, copper seed layer (seed layer), in Damascene method process, profile is carried out the electrochemistry filling at last with copper.
Usually be about 0.13 μ m in the interior connection of BOEL with the size of profile.Clean with the sidewall residue in the efficient removal profile in order to carry out low temperature, as shown in Figure 1, the granularity of cryogenic particles must be less than 0.13 μ m.These particles must arrive wafer surface with enough fast speed, so that make the sidewall residue required Momentum Transfer that comes off.
Have three kinds of mechanism to can be used to carry out surface clean: 1) cryogenic particles is carried out Momentum Transfer, to overcome the adhesion of pulp particle and wafer surface; 2) particle that will come off is removed the purge gas tractive force and 3 of usefulness from wafer surface) be dissolved with organic pollutants with liquid, these pollutants are to form on the interface of cryogenic particles and wafer surface.
At CO 2During low temperature cleaned, the air-flow of wafer surface produced a boundary layer.CO 2Cryogenic particles must be passed the contaminant particle that the boundary layer arrives wafer surface and will remove.In the motion of passing the boundary layer, owing to CO on the boundary layer 2Gas produces tractive force to contaminant particle, CO 2The speed of cryogenic particles reduces.The thickness of hypothetical boundary layer is h, and cryogenic particles must enter the boundary layer with the normal component of the speed that equals h/t at least, and wherein t arrives wafer surface institute time-consuming for passing the boundary layer.Particle passes across the border relaxation time of layer by with shown in the following formula (1):
τ = 2 a 2 ρ p C c 9 η - - - ( 1 )
In the formula:
A is a particle radius
ρ pBe grain density
η is a gas viscosity
C cBe the Cunningham slip correction factor, as the formula (2)
C c＝1+1.246(λ/a)+0.42(λ/a)exp[-0.87(a/λ)] (2)
λ is the mean free path of gas molecule in the formula.Because CO 2Low temperature cleans and to carry out under normal pressure, and granularity is become greater than the Cunningham slip correction factor the cryogenic particles of 0.1 μ m equals 1.
Therefore, in order to make CO 2Cryogenic particles has enough momentum and removes exogenous impurity on wafer surface and the profile inside, and the time of passing the boundary layer must be less than the relaxation time, and they will arrive the surface with the speed than initial velocity big 36% in this case.Equation 1 shows relaxation time reducing and reduce with granularity.Therefore, the granularity smaller particles can not arrive the surface of wafer with the required enough speed of the inwall of effective cleaning submicron passage and groove.
The method of prior art is generally used CO 2Or argon gas carries out cryogenic spray to remove the exogenous impurity on surface.For example, referring to the United States Patent (USP) 5,931,721 that is entitled as Aerosol Sueface Processing; The United States Patent (USP) 6,036,581 that is entitled as SubstrateCleaning Method and Apparatus; Be entitled as 5,853,962 of Photoresist andRedeposition Removal Using Carbon Dioxide Jet Sprary; The United States Patent (USP) 6,203,406 and the United States Patent (USP) 5,775,127 that is entitled as High DispersionCarbon Dioxide Snow Apparatus that are entitled as Aerosol Sueface Processing.In the above-mentioned prior art patent, all adopt to relate to Momentum Transfer and remove relatively exogenous impurity than even curface to the physical force of pollutant.Because the adhesion between contaminant particle and the base material is stronger, the method for prior art is to removing smaller particles, promptly＜3 μ m particle effective inadequately.In addition, this cleaning method is not enough to clean the profile that resembles the such high-aspect-ratio of passage and groove in the terminal integrated element manufacture process of production line, require to remove little submicron and the composition polymer residue that the dielectric etch deposition is produced in this operation.
The United States Patent (USP) 6,332,470 that is entitled as Aerosol Substrate Cleaner disclose only use steam or with the method for the steam purge semiconductor substrate of high pressure drop coupling.Regrettably, hydraulic shock does not resemble CO 2Solid has enough Momentum Transfer abilities like that, thereby can not resemble and use CO 2The such effective removal granularity smaller particles of solid.The United States Patent (USP) 5,908,510 that is entitled as Residue Removal by Supercritical Fluid discloses employing low temperature aerosol and supercritical fluid or liquid CO 2In conjunction with method.Because CO 2Be nonpolar molecule, the solvability of polarity exogenous impurity obviously reduces.Equally, form liquid or supercritical CO 2Need high pressure (liquid greater than 75psi, is 1080psi to supercritical liq), so apparatus expensive.United States Patent (USP) 6,231,775 suggestions utilize sulfur trioxide gas or the mode that combines with other gases is removed the organic matter that base material produces in processes such as polishing.This vapor phase cleaning method is not enough to remove the crosslinked that produces when carrying out etching in the typical dual Damascene integrated approach of the low-k materials of employing resemble the carbon doped oxide.
Therefore, need effectively and efficiently to remove semiconductor wafer, metal film and other surfaces that needs meticulous cleaning, and from the pollutant of high-aspect-ratio profile inside, comprise particle, exogenous impurity and chemical residue, and homogeneous phase and the heterogeneous contaminants formed by crosslinked and loose photoresist, post-etch residues and submicron.
Summary of the invention
Semiconductor, metal and the dielectric film etc. that the invention provides novel improved need the cleaning method of the substrate surface of meticulous cleaning.
The present invention includes the pollutant of the substrate surface of the meticulous cleaning of removal needs.Can or adopt this method before low temperature cleans simultaneously, to remove the exogenous impurity and the pollutant of substrate surface.This method adopts the fluid of the steam that is selected from high vapour pressure liquid, reactant gas or reactive fluid, and this depends on the pollutant that substrate surface will be removed.Fluid preferably keeps contacting maximum 20 minutes with the surface.It has formed a kind of environment of removing surface contaminant or minimizing and surface adhesion, thereby can remove pollutant with the low temperature cleaning method subsequently.
The accompanying drawing summary
The present invention will be described with reference to following drawing:
Figure 1 shows that the cleaning situation of back recess etch residue in two Damasecne structures.Left side figure is the SEM that has the back recess etch structure of etch residues.Right figure is the SEM of plasma and wet cleaning step after etching structure.
Figure 2 shows that standard cryogenic is cleaned and the comparison of auxiliary cleaning method granularity of liquid of the present invention and particle removal efficiency.
Figure 3 shows that traditional C O 2The schematic diagram of low temperature purging system.
Describe in detail
Auxiliary cleaning method of liquid and embodiment
The used liquid of the inventive method is high vapour pressure liquid, can reduce the Fan Dehuali between exogenous impurity and base material such as semiconductor wafer surface or the film surface etc.High vapour pressure liquid is ejected into substrate surface.The preliminary injection of liquid can reduce Fan Dehuali, thereby makes low temperature subsequently clean the exogenous impurity that is easier to remove substrate surface.If the process upstream before low temperature cleans is based on the process of water, of the United States Patent (USP) 10/215,859 of application simultaneously, this liquid also can be removed a large amount of water before low temperature cleans.In addition, high vapour pressure liquid also can be used for dissolving the organic pollution on surface.Can select concrete high vapour pressure liquid for use according to the situation of the contained organic pollution of substrate surface.It will be appreciated by those skilled in the art that the kind of liquid that can dissolve organic pollution commonly used.
Be applicable to that high vapour pressure liquid of the present invention includes but not limited to ethanol, acetone, ethanol-acetone mixture, isopropyl alcohol, methyl alcohol, methyl formate, methyl iodide, bromic ether, acetonitrile, ethyl chloride, pyrrolidines and oxolane.Yet, can use any liquid with high vapour pressure.High vapour pressure liquid is easy to come out from the surface evaporation of base material, and does not need base material heated or rotate to give drying.Liquid preferably have a low freezing point, and be polarity.Freezing point of liquid is low can be guaranteed can not freeze because of chip temperature descends at the residual any residual liquid of wafer surface when low temperature cleans, and reaches chip temperature and descend in the low temperature cleaning process.Liquid polarity helps the dissolving of the organic and inorganic pollution of wafer surface.Preferably, the vapour pressure of liquid in the time of 25 ℃ greater than 5kPa, the freezing point of liquid is lower than-50 ℃, dipole moment is greater than 1.5D.
Then, high vapour pressure liquid can be used for the substrate surface of the meticulous cleaning of any needs, and the surface comprises semiconductor surface and metal and dielectric film preferably.Therefore, no matter when use " semiconductor ", " metal film ", " dielectric film " or speech such as " wafers ", mean that same method can be applicable to other substrate surfaces at this.Other surfaces are included in hard disk media, optics, GaAs base material and the film that uses in the composite semiconductor manufacture method.At this example that provides and do not mean that qualification the present invention.
In one embodiment of the invention, under 30-50 ℃ of temperature, high vapour pressure liquid is ejected into semiconductor wafer surface.Liquid can be injected into thick film or thin layer.Bed thickness is at least the 5-10 Δ.The spray nozzle that the most handy Teflon makes sprays, and deionized water is ejected on the wafer surface.But can adopt any other used nozzle of this area.With the liquid cover wafers at least 1 minute was good, preferably maximum 10 minutes.Can spray one time liquid on the surface during this period, or spray repeatedly to guarantee that wafer surface keeps moistening.In addition, rotating speed rotation wafer that can 100rpm, simultaneously thereon atomizing of liquids to guarantee even cover wafers surface.
After this moistening stage, begin to carry out cryogenic spray.The cryogenic spray method can be used carbon dioxide, argon gas or other gas, and these are known in the field.Any known technology can be adopted, below CO will be described 2The low temperature cleaning method.The initial result of high vapour pressure liquid that uses has reduced the Hamaker constant, thereby has reduced Fan Dehuali.This method has reduced the adhesion of pollutant and wafer surface, compares with only carrying out the low temperature cleaning, is easier to remove the pollutant of wafer surface.
Perhaps, can be when low temperature cleans applicating liquid.In this case, for example, in conjunction with being used for CO 2First nozzle that low temperature cleans, second nozzle of installation atomizing of liquids.Liquid is preferably used with thin layer, can proceed CO on injecting liquid into base material 2Low temperature cleans.
Obviously improved the effect that low temperature cleans the removal particulate pollutant after using high vapour pressure liquid.Fig. 2 shown carry out that standard cryogenic is cleaned and the cleaning of liquid assisted cryogenic to the particle removal efficiency comparable situation of variable grain specification.With employing standard C O 2The low temperature cleaning method is compared, and uses liquid of the present invention to assist CO 2Low temperature cleaning method rather than standard C O 2Low temperature cleans, and the particle removal situation that granularity is lower than 0.76 μ m obviously improves.When granular size during at the 0.98-2.50 mu m range, liquid assisted cryogenic cleaning method of the present invention and standard C O 2The particle removal effect of low temperature cleaning method does not have notable difference.
Steam is auxiliary to be cleaned and embodiment
Use reactant gas or reactive fluid steam to assist in removing pollutant.Reactant gas or steam are to select according to the reactivity of the pollutant of itself and substrate surface.Reactant gas or steam generally are used to remove organic photoresist and the fluoropolymer etch residues in the profile in the substrate surface.Behind pollutant reaction, gases/vapors better produces gaseous by-product.(following for ease of reference the present invention explanation, referring to reactant gas comprise the reactive fluid steam, comprise reactant gas referring to reactive vapors.)
In the cleaning method of semiconductor wafer, the pollutant that remove not only comprises particulate pollutant, also is included in FEOL (production line front end) and BEOL operation microelectronics and makes the organic and inorganic and metal organic residue that produces in each operation.These films can not be removed with pure physical method.Need satisfy the cleaning degree requirement with the auxiliary any physics impurity-removing method of chemical method.In the present invention, the gas phase ablution is a chemical cleaning method, and wherein the low temperature cleaning is important physics cleaning method.Two kinds of methods are implemented to remove homogeneous phase or heterogeneous contaminants fully simultaneously or sequentially.
The example that can be used for the reactive vapors of the inventive method has high vapour pressure steam, comprises (but not doing to be limited to) acetone, ethanol-acetone mixture, isopropyl alcohol, methyl alcohol, methyl formate, methyl iodide and bromic ether.Can also comprise ozone, water vapour, hydrogen, nitrogen, nitrogen oxide, Nitrogen trifluoride, helium, argon gas, sulfur trioxide, oxygen, fluorine or fluorohydrocarbon gas or admixture of gas.Gas or steam should be able to react with the fluoropolymer etch residues in organic photoresist and the profile.In addition, byproduct of reaction is gaseous state preferably, so that can they be removed from the purge chamber by nitrogen stream.Preferred gas or liquid vapors comprise isopropyl alcohol, ethanol-acetone mixture, methyl alcohol, ozone, water vapour, Nitrogen trifluoride, sulfur trioxide, oxygen, fluorine or fluorohydrocarbon gas.
In after etching clean to be used, cryogenic particles can't arrive in the profile of high-aspect-ratio of passage and groove.Gas or steam must efficiently be diffused into these profiles.Gas or steam can carry out chemical reaction with polymer residues then, convert it into gaseous by-product, can remove these accessory substances with the nitrogen stream of blowing over substrate surface.Perhaps, gas or steam can be imported the purge chamber that independently keeps low pressure.In temperature this purge chamber, carry out the gases/vapors phase reaction up to 200EC.After this cleaning process, wafer transfer can be arrived second purge chamber under the normal pressure, carry out low temperature there and clean.
In this method, steam can be in the wafer surface condensation.If steam is selected for use proper, condensation can also reduce the Hamaker constant, and therefore reduces particle and surperficial adhesion.Such condensation helps to remove degranulation by the low temperature cleaning method.
Adopt radical initiator to produce the method for reactive chemical group, can also improve gas or steam and the reactivity of the pollutant that will remove as ultraviolet ray, X ray, Excimer laser, corona discharge or plasma.With freeze or low temperature aerosol physics cleaning method combines and removes non-reacted pollutant.Similar cleaning method can be referring to using the downstream MW plasma of chemical substance and generation ion to bombard the isoionic double frequency plasma of RF ablution in wet cleaning with generation and pollutant reaction.
Of the present invention one in conjunction with CO 2In the embodiment of low temperature cleaning method, the steam of liquid is installed in and CO by one 2Nozzle ejection on the same cantilever in low temperature cleaning method place.This nozzle can be small-sized stainless steel hole, and diameter is 1/4-1/2 ", or a kind of custom-designed nozzle, the corona discharge lead had vertically, so that in steam, discharge.Nozzle preferably and substrate surface into about 10-90 ° of angle.Steam can also spray by the injector head of substrate surface top, to guarantee even covering substrates surface.When steam is provided, the temperature of base material preferably and steam temperature be consistent.Make the steam condensation if desired, can make the temperature of base material remain below steam temperature, make the steam on the substrate surface be condensed into very thin liquid film.But,, can make steam have reactivity by means of radical initiator if steam is not enough to the pollutant reaction with given type.Steam preferably reaches 20 minutes at the injecting time of substrate surface.Can spray continuously or intermittently.Use one type steam preferably, but also can simultaneously or use mixed vapour to remove pollutant successively if necessary.
According to the present invention, the injection of reactant gas or steam can be cleaned with low temperature and be carried out in same purge chamber, perhaps can carry out in the purge chamber that separates.Low temperature clean can also be on using reactant gas or steam in or carry out afterwards.According to the character of used reactant gas or steam, water vapour for example need be purged the purge chamber before cleaning beginning to carry out low temperature.
Use the result of reactant gas or steam obviously to improve pollutant, especially to the removal effect of the pollutant in the etching outline on the substrate surface.This cleaning method is particularly useful for removes the homogeneous phase pollutant, as residual photoresist after residual film of after etching on the sidewall of passage and groove or the etching.
Embodiment-standard C O 2Low temperature cleans
Carry out fluid clean after or simultaneously, carry out the standard cryogenic cleaning.United States Patent (USP) 5,853,962 have described standard C O 2, in full with reference to being incorporated into this.To typical C O 2The low temperature purging system can be referring to Fig. 3.Clean container 12 provides ultra-clean, sealing or airtight cleaning zone.Clean in the zone at this, wafer 1 is fixed on the platen 2 by vacuum.The platen temperature that has wafer is controlled at the highest 100 ℃.From under the room temperature of pipeline and the CO of 850psi pressure 2Liquid at first filters through oversintering pot strainer 4, filters out very little particle from liquid stream, pure as far as possible carbon dioxide to be provided and to reduce pollutant in the liquid stream.Make CO then 2Liquid expands by a small nozzle, and nozzle diameter is preferably 0.05 " 0.15 ".The rapid expanding of liquid causes temperature to descend, and the result is at the CO that flows with about 1-3 cubic feet/min speed 2Form solid CO in the air-flow 2The snow grain.By solid and gas CO 2Form fluid and wafer surface into about 30 °-60 ° angle.Nozzle preferably is positioned at locating apart from about 0.375 " 0.5 " of wafer surface that sight line along nozzle to wafer surveys.In cleaning process, platen 2 moves forward and backward along guide rail 9 in the y direction, and the cantilever at washer jet place is at x direction upper edge guide rail 10 moving linearlies simultaneously.The result has formed grating in wafer surface and has cleaned form, and its step-length and sweep speed can preestablish as required.It is low as far as possible that the humidity of purge chamber preferably keeps, as dew point＜-40 ℃.Low humidity can prevent in cleaning process the water in the environment in the wafer surface condensation with freeze, and increases adhesion between them because of form brilliant bridge between contaminant particle and wafer surface.Can or clean flowing of dry air by nitrogen stream and keep low humidity.
In the whole cleaning process, in and the purge chamber in electrostatic charge also very important.Accomplish this point with bipolar corona discharge ionization rod 5.System also is equipped with near CO 2The polonium nozzle of nozzle back is installed in the static neutralization of the wafer on the ground connection platen with enhancing.Because CO 2The synergy of the low humidity that flow through nozzle, also is subjected in the purge chamber being kept by wafer surface has produced electrostatic charge by triple discharges.
To concrete pollutant, scrubbing mechanism is mainly CO 2The momentum of cryogenic particles shifts, to overcome the adhesion of contaminant particle in wafer surface.In case " loosening ", CO take place in particle 2The tractive force of gas is just removed its surface from wafer.The removing mechanism of organic membrane contaminant is: low temperature CO 2Percussive pressure in wafer surface causes having formed CO on the interface on organic pollution and surface 2Liquid lamella.CO then 2Liquid is dissolved with organic pollutants and it is with from wafer surface.
Mean explanation of the present invention in this used concrete scheme and embodiment, not as limiting.Can other embodiments used in this invention be understood by the professional person easily.Concrete scheme like this will be included in this
In the invention scope.
List of references
[1].International?Technology?Roadmap?for?Semiconductors?2001?Edition.
[2]Handbook?of?Semiconductor?Wafer?Cleaning?TechnologyScience，Technology?and?Applications，Edited?by?Werner?Kern，NoyesPublications，1993.
[3]Particle?Conttrol?for?Semiconductor?Manufacturing，Edited?byR.P.Donovan，Marcel?Dekker?Inc.，1990.

Claims (21)

1. remove the method for the pollutant of the substrate surface that needs meticulous cleaning, may further comprise the steps: a) at least a fluid is applied to substrate surface, fluid is selected from high vapour pressure liquid, reactant gas and reactive fluid; And b) substrate surface being carried out low temperature cleans.
2. the described method of claim 1 is characterized in that, step a) and b) carry out simultaneously.
3. the described method of claim 1 is characterized in that, step a) and b) carry out successively.
4. the described method of claim 1, it is characterized in that, at least a fluid is high vapour pressure liquid, be selected from ethanol, acetone, ethanol-acetone mixture, isopropyl alcohol, methyl alcohol, methyl formate, methyl iodide, bromic ether, acetonitrile, ethyl chloride, pyrrolidines and oxolane, and their mixture.
5. the described method of claim 1 is characterized in that, at least a fluid is the steam of reactive fluid, and described liquid is selected from ethanol, acetone, ethanol-acetone mixture, isopropyl alcohol, methyl alcohol, methyl formate, methyl iodide, bromic ether and their mixture.
6. the described method of claim 1, it is characterized in that at least a fluid is to be selected from following reactant gas: described liquid is selected from ozone, water vapour, hydrogen, nitrogen, nitrogen oxide, Nitrogen trifluoride, helium, argon gas, neon, sulfur trioxide, oxygen, fluorine, fluorohydrocarbon gas and their mixture.
7. the described method of claim 1, it is characterized in that, at least a fluid is reactant gas or steam, is selected from isopropyl alcohol, ethanol-acetone mixture, methyl alcohol, ozone, water vapour, Nitrogen trifluoride, sulfur trioxide, oxygen, fluorine and fluorohydrocarbon gas and their mixture.
8. the described method of claim 1 is characterized in that, kept in touch maximum 10 minutes on fluid and surface before beginning to carry out the low temperature cleaning.
9. the described method of claim 8 is characterized in that, kept in touch less than 2 minutes on fluid and surface before beginning to carry out the low temperature cleaning.
10. the described method of claim 1 is characterized in that, the size of pollutant is less than 0.76 μ m.
11. the described method of claim 1 is characterized in that, the size of pollutant is less than 0.13 μ m.
12. the described method of claim 1 is characterized in that, greater than about 5kPa, freezing point is lower than-50 ℃ to the vapour pressure of high vapour pressure liquid under 25 ℃.
13. the described method of claim 1 is characterized in that the dipole moment of high vapour pressure liquid is greater than about 1.5D.
14. the described method of claim 1 is characterized in that, before beginning to carry out the low temperature cleaning, the bed thickness of at least 5 Δs that keeps from the teeth outwards of high vapour pressure liquid was less than 10 minutes, most preferably less than 2 minutes.
15. the described method of claim 4 is characterized in that, this method also comprises the step of high vapour pressure liquid removal substrate surface water.
16. the described method of claim 1 is characterized in that, substrate surface is semiconductor, metal or dielectric film.
17. the described method of claim 1 is characterized in that, at least a fluid is for forming the reactant gas or the steam of volatile gaseous accessory substance with lip-deep pollutant reaction; Also be included in and begin to carry out to make before low temperature cleans reactant gas or steam and surface to keep in touch the step that reaches 20 minutes and remove gaseous by-product.
18. the described method of claim 17 is characterized in that, in low pressure and/or maximum 200EC reactant gas or steam is imported the purge chamber that base material is housed.
19. the described method of claim 18 is characterized in that, removes accessory substance and comprises that the dry air with nitrogen or cleaning purges the purge chamber.
20. the described method of claim 17 is characterized in that, in the presence of radical initiator with reactant gas or vapor applications in the surface, so that make reactant gas or steam and pollutant produce reactive chemical by-product.
21. the described method of claim 20 is characterized in that, radical initiator is ultraviolet ray, x ray, laser, corona discharge or plasma.
CN038103621A 2002-04-05 2003-04-03 Fluid assisted cryogenic cleaning Pending CN1665609A (en)

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US36985302P 2002-04-05 2002-04-05
US36985202P 2002-04-05 2002-04-05
US60/369,853 2002-04-05
US60/369,852 2002-04-05
US10/324,221 US6852173B2 (en) 2002-04-05 2002-12-19 Liquid-assisted cryogenic cleaning
US10,324,221 2002-12-19
US10/403,147 US6949145B2 (en) 2002-04-05 2003-03-31 Vapor-assisted cryogenic cleaning
US10/403,147 2003-03-31

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AU2003233485A1 (en) 2003-10-27

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