CN1741973A - Methods for transferring supercritical fluids in microelectronic and other industrial processes - Google Patents

Abstract

A method of displacing a supercritical fluid from a pressure vessel (e.g., in a microelectronic manufacturing process), comprises the steps of: providing an enclosed pressure vessel containing a first supercritical fluid (said supercritical fluid preferably comprising carbon dioxide); adding a second fluid (typically also a supercritical fluid) to said vessel, with said second fluid being added at a pressure greater than the pressure of the first supercritical fluid, and with said second fluid having a density less than that of the first supercritical fluid; forming an interface between the first supercritical fluid and the second fluid; and displacing at least a portion of the first supercritical fluid from the vessel with the pressure of the second, preferably fluid while maintaining the interface therebetween.

Description

Shift the method for the supercutical fluid in microelectronics and other Industrial processes

Related application

It is the right of priority of the U.S. Patent application of NO.10/448474 that the application requires in the sequence number of application on May 30th, 2003;

It is the right of priority of the U.S. Provisional Patent Application of No.60/442867 that the application also requires in the sequence number of application on January 27th, 2003;

Mode by reference is applied for disclosed full contents in conjunction with above-mentioned two pieces.

The field of the invention

The present invention relates to shift the fluidic method and apparatus in the production process, described process includes but not limited to, remove and anhydrate and solute soluble in water, and from the substrate, MEMS or the photoelectron device that adopt liquid state or supercritical co, remove pollutent or process by product, described substrate is semiconductor chip for example.In addition, these technological processs include but not limited to, apply metal or metalloid precursor, polymkeric substance, monomer or small molecules in the semiconductor chip, MEMS or the photoelectron device that adopt liquid state or supercritical co.

Background of the present invention

The production of unicircuit, microelectronic device and micro electro mechanical device (MEMS) comprises a plurality of procedure of processings, and these many steps wherein adopt water to be beneficial to remove the process by product as the carrier of chemical substance or as medium.Material and technological evolution are by towards the motivating force guiding of small-feature-size more and more complicated micro device.In some cases, in these technologies that constantly develop, the employing of water has caused following problem, i.e. detrimentally affect of water and the by product that is carried by water.The unique physical character of the densified carbon dioxide of liquid state or above-critical state is subjected to special concern in preventing some above-mentioned defective.

Fine and close CO ₂A described technological process with practical application relates to and preventing because the image that surface tension or capillary force cause damages.In the water-based of the micro planographic plate printing image that adopts photo-resist was developed, it was subjected to special concern.Photo-resist is with the photaesthesia film of image transfer to substrate.The photo-resist coating is formed on the substrate, makes described photo-resist layer be exposed to the activating radiation source by photomask or other method then.Be exposed to activating radiation and make the photo-resist coating that photoinduced chemical transformation take place, thus with the design transfer of photomask (or other pattern generating apparatus) to the substrate that is coated with photo-resist.After the exposure, development of photoresist obtains space image, and described image allows substrate is carried out selectivity processing.Referring to for example United States Patent (USP) NO.6042997.

Photo-resist can be positivity effect or negative effects.For the resist of negative effects, the solvability of exposed region reduces, thereby it is still stayed on the substrate in developing process, and exposed region is not removed.For the resist of positivity effect, the solvability of exposed region in developing solution increases, thereby it is removed in development step, and exposed region is not unaffected.Positivity and negative effects anticorrosive additive material typically have following chemical functional, promptly ought be exposed to the UV light time of specific wavelength, and it changes.Described change is commonly referred to " polarity conversion ", and this is because polymer polarity increases or reduce the motivating force that the solubleness of polymkeric substance in developing solution normally changes.In the resist constituent,, help described change in conjunction with photic acid resultant (PAG) or photic alkaline resultant (PGB).Usually when being exposed to suitable source of radiation and postheating, produce acidity and basic group.Described developing solution is generally water-based, and dry to remove from the substrate before further handling usually.

Can cause resist distortion and pattern to damage when having capillary force in the water-based drying process of the resist pattern after imaging.When lithographic process trended towards having the less image node of large aspect ratio more, this problem was especially serious.Researchist suggestion will influence 130nm technology node with the dry relevant damage problem of water-based, and when aspect ratio increases, after technology in it becomes more general.

Researchist's suggestion of IBM and NTT adopts carbonic acid gas can reduce the damage of image and film in overcritical resist drying process (SRD).Referring to, for example, H.Namatsu, J.Vac.Sci.Technol.B 18 (6), 3308-3312 (2000); D.Goldfarb etc., J.Vac.Sci.Technol are (6) 3313-3317 (2000) B.18.Yet, though the CO that does not have surface tension and can reach ₂Critical temperature and pressure are considered to the positive factor of described drying process, but water low relatively solvability in supercritical phase is considered to a difficult problem, and it may need to adopt chemical additive to increase the fluidic transmission performance.The researchist of IBM and NTT is verified adopts some tensio-active agent in the auxiliary drying process of supercutical fluid.Yet described tensio-active agent adopts in the hexane of " indirectly SRD " washes in advance, and the article referring to Goldfarb for example mentioned above etc. perhaps only adopts special tensio-active agent in the carbonic acid gas of " directly SRD ".In direct and contact drying method, the selection of tensio-active agent and solubility promoter is subjected to following restriction, the compatibility problem that promptly causes resist to damage.Therefore, need new method to implement to adopt the SRD of carbonic acid gas.

It is to remove processing fully, clean or the aqueous solution of flushing usefulness that another problem of exsiccant is carried out on the surface of microelectronic substrates (for example applying the semiconductor chip, MEMS, optoelectronic equipment, photonic device, flat-panel monitor of photo-resist etc.), and not leaving resistates, described resistates is commonly referred to dry watermark.When being used for processing, cleaning or exsiccant solution when dry, solute concentrated causes above-mentioned watermark in the described aqueous solution.In many microelectronics, optics, micro-optic or MEMS structure, described watermark will have a negative impact to the final performance of output or device.Need a kind of effective means and will from the surface, remove (washing), thereby eliminate concentrating and final deposition-elimination watermark of residual solute based on the fluid of water.

The problems referred to above result from the production of MEMS device.The wet type procedure of processing is usually to clean and the drying step end.Evaporation drying makes the moisture that contains the lower concentration solute concentrate in some position, and wherein moisture compiles and forms the pond from the teeth outwards with in different little features, and described concentrating makes the surface-area maximum in pond.Therefore, these drying step can cause once the dissolved solute to concentrate, described solute next-door neighbour or be positioned on the moving portion.Character can help stiction promptly to lock described moving portion for the deposition material of organic or inorganic, thereby it can not be energized.Term in the production stage result " release stiction " is considered to derive from adhesive power and Van der Waals force and frictional force.The power that is generated by this phenomenon can make the moving portion on the MEMS device lose ability fully.

In order to resist stiction, the manufacturer of MEMS device has adopted for example solvent of short-chain alcohols, and described alcohols has reduced the surface tension in the cleaning process, helps drying process more uniformly.Yet only these steps can not be eliminated the generation of stiction.People propose to adopt supercritical CO ₂Be used for dry microstructure.(referring to Gregory T.Mulhern " SupercriticalCarbon Dioxide Drying of Micro Structures ") wherein, surface tension can cause damaging.Wherein the researchist of Texas Instruments Inc. (referring to for example U.S. Patent No. 6024801) is verified, is calming down before the step supercritical CO ₂Can clean organic and inorganic pollutant, thereby limit stiction from the MEMS device.

These adopt supercritical CO ₂The combination of technology by dry and cleaning stiction without limits, wherein remove water and solute simultaneously, thereby avoided water and solute concentrating at specific position.The technology that needs to calm down in conjunction with drying, cleaning and surface is to prevent to discharge stiction.

Other relates to the formation from deep channel of the drying of the wet procedure of processing of water and cleaning problems, and in the making of unicircuit, described deep channel is used for interlayer metallization.By well known to a person skilled in the art that the passage that method forms typically has big critical aspect ratio, the geometrical shape of its formation is difficult to resistates is therefrom removed.And when evaporation drying, for example dissolved solute has once been left in the wet processes step and the cleaning of water to adopt conventional fluid.When metallization, these solutes that are deposited on duct bottom can suppress electroconductibility, have reduced function.

The technology of need be after the wet type procedure of processing water (drying) and dissolved solute (cleaning) being removed from pipeline, thus loss reduced.

In addition, be used to produce the cleaning medium of the characteristic dimension that the appearance requirement of the porous dielectric material of unicircuit can be wetting more and more littler ideally, thereby remove the pollutent and the process by product of infringement device, and do not decrease ring structure or material.Compact fluid CO ₂Be ideal comparatively, this is because it has lower or does not have surface tension and extremely low viscosity.Yet chemical additive for example solubility promoter, tensio-active agent, oxygenant, etching reagent and stablizer must be removed after finishing cleaning requirement effectively.For having good transmission performance and as the fluid of the variable dissolution performance of temperature and pressure function, it may have very large challenge.Solvent fluctuation can cause material undesirably to be deposited in the porous substrates and on the surface, it does not effectively clean.Needed is a kind of technology, and it can not only effectively also be removed pollutent and process by product efficiently, and can also remove chemical reagent.

Brief introduction of the present invention

The invention provides a kind of method that supercutical fluid is displaced from pressurized vessel, it may further comprise the steps:

The seal-off pressure container is provided, wherein contains first supercutical fluid (described supercutical fluid preferably includes carbonic acid gas);

Add second fluid (typically, being similarly supercutical fluid) in described container, add the pressure that the second fluidic pressure is higher than first supercutical fluid, the second fluidic density is lower than first supercutical fluid;

Between first supercutical fluid and second fluid, form the interface; And

Near small part first supercutical fluid displaces the interface between keeping simultaneously from the container with second preferably fluid pressure.

One aspect of the present invention is a kind of method of cleaning microelectronic device, may further comprise the steps: substrate is provided, described substrate has surface portion to be cleaned, fine and close carbon dioxide cleaning composition is provided, described composition comprises carbonic acid gas and cleaning additive, and described cleaning additive is selected from solubility promoter, tensio-active agent, etching reagent, oxygenant, sequestrant, stablizer and combination thereof; Surface portion is immersed in the described densified carbon dioxide composition; Then described cleaning compositions is removed from surface portion; In described immersion step and described at least one of removing in the step, described cleaning compositions is maintained uniform composition simultaneously.The example of the device that can clean with the present invention includes but not limited to, contains dielectric semiconductor chip, semiconductor chip, unicircuit, micro electro mechanical device (MEM), the photoelectron device of (copper) that contain metal and the substrate that is coated with resist.

In a particular, the invention provides a kind of method of removing moisture or cleaning substrate, moisture, etching process by product, metal residue or the photo-resist that for example will have solute are removed from microelectronic device (for example semiconductor chip), MEM device or photoelectron device.Usually, this method may further comprise the steps: substrate (a) is provided, in certain embodiments, (substrate is by for example metal, semi-conductor, isolator or dielectric medium, photo-resist and constitute to be formed with pattern or feature on the described substrate, the silicon substrate in integrated circuit fabrication process for example), have the water of removing to be cleaned or other material (for example process by product, for example etch residue, etching hardened photo-resist and CMP resistates) on the substrate; (b) provide fine and close (for example liquid or overcritical) carbonic acid gas drying or cleaning compositions, but described composition comprises carbonic acid gas and the selectable additive that preferably includes, described additive is selected from solubility promoter, tensio-active agent and combination thereof; (c) surface portion is immersed in the described densified carbon dioxide cleaning/drying composition; (d) removes described drying or cleaning compositions from surface portion then.

Below different particular of the present invention further are discussed.

The method that another aspect of the present invention is a kind of cleaning microelectronic device is modulated in circulation mutually, to remove soluble material, particulate matter and/or pollutent etc.This method may further comprise the steps: the substrate with surface portion to be cleaned is provided, the densified carbon dioxide cleaning compositions is provided, described composition comprises carbonic acid gas and the cleaning additive that selectively still preferably includes, and described additive is selected from solubility promoter, tensio-active agent and combination thereof; Described surface portion is immersed in the described densified carbon dioxide composition, thus the clean surface part; Then described cleaning compositions is removed from surface portion.Preferably in the execution of the part or all of step of above-mentioned immersion/cleaning, adopt circulation modulation mutually, below will be described in greater detail.

Water cleaning system another aspect of the present invention is a kind of method of cleaning microelectronic device, may further comprise the steps: the substrate with surface portion to be cleaned is provided, the densified carbon dioxide cleaning compositions is provided, described composition comprises carbonic acid gas and water.But selectively preferably, comprise one or more cleaning additives in the described cleaning compositions, present in an amount at least sufficient to help the cleaning of article to be cleaned.Suitable cleaning additive comprises for example solubility promoter, tensio-active agent, water-soluble cleaning additive and combination thereof.Thereby the following steps of this method comprise surface portion immersed in the carbon dioxide cleaning composition of described densification and clean described article, then described cleaning compositions are removed from surface portion.

Particle cleaning another aspect of the present invention is a kind of method that solid particulate is cleaned from microelectronic device/remove, this method may further comprise the steps: the substrate with surface portion to be cleaned is provided, fine and close carbon dioxide cleaning composition is provided, described composition comprises carbonic acid gas and selectively still preferred cleaning additive, and described additive is selected from solubility promoter, tensio-active agent and combination thereof; Described surface portion is immersed in the described densified carbon dioxide composition, and its immersion time is enough to solid grain contamination is therefrom removed; Then described cleaning compositions is removed from surface portion.Can find that after the chemical mechanical planarization of for example substrate substrate has particle contamination.

The sedimentary again control of pollutent in a preferred embodiment, preferred control process parameters, thereby immersing step, removing step or immersion and remove in the step, described drying and/or cleaning compositions remain uniform composition, and do not have the deposition of dry additive or moisture solute on machinery, electricity or the optical assembly of resist coating, the feature with pattern or described device or circuit substantially.

In following drawing and description, will do more detailed explanation to the present invention.

Brief description of drawings

Accompanying drawing 1 has shown the substrate that is formed with the resist layer with pattern on it, has water on the different positions of substrate.

Accompanying drawing 2 has schematically been described the equipment of implementing the inventive method.

Accompanying drawing 3 has been described and has been mainly CO ₂The phase synoptic diagram of system, it is represented from being mainly CO ₂Supercritical mixtures transit to gas, avoided liquid phase.

Accompanying drawing 4 has schematically been described the equipment of implementing the inventive method.

Accompanying drawing 5 has schematically been described another embodiment of implementing the equipment of the inventive method.

Accompanying drawing 6 has schematically been described the substrate that is arranged in the pressure chamber, deposits a supercritical flow body thin film on the described substrate;

Accompanying drawing 7 has schematically been described the technology that forms product shown in the accompanying drawing 6.

Accompanying drawing 8 has shown that to containing pressure be that helium is added at the top of pressure chamber of the supercritical co of 2500psig, and wherein the supercritical co discharge line that is forced through the bottom, chamber is discharged from the chamber.This photo is that the high position of being omitted is taken from the viewing window of described chamber.

Accompanying drawing 9 is substantially with accompanying drawing 8, but it is the time point after a while shooting after adding helium.

Accompanying drawing 10 has shown in the pressure chamber that is full of supercritical helium and has added supercritical carbon dioxide fluid.Notice that described supercritical co shows as the bottom of falling the chamber with airflow pattern by helium.

Detailed description of the preferred embodiments

Below describe the present invention.This specification sheets is not the inventory that all possible different embodiments of the present invention maybe can add all features of the present invention.For example, the feature of describing in embodiment can be bonded to other embodiment, and the feature of describing in particular can be deleted from this embodiment.In addition, with regard to not departing from disclosure of the present invention, a large amount of changes and increase that various embodiments as herein described are carried out it will be apparent to those skilled in the art that.Therefore, below explanation is used to describe some particular of the present invention, is not that all changes, combination and change thereof are described fully.

Because the change or the difference of specific refractory power between first and second fluids, interface as herein described normally visually can observed (that is, can observe by human bore hole) or optics detectable (promptly can detect by the optical detection system).The not necessarily absolute transition in described interface can be the zone with certain depth or thickness, at described region memory at a kind of fluid to another fluidic transition.For example, in having the container of length dimension, the thickness at described interface or the degree of depth are about 5%, 10%, 15% or 20% of container length size, along described length direction first supercutical fluid is displaced (promptly, the total length of container or interior dimensions not merely are the migration distances of described technological process median surface).Described thickness can be measured as first of length dimension in the container or position first and second fluidic the mixings compositing areas extremely second or the distance of position of length dimension in the container, wherein first or position, the composition of container contents by or (for example constitute by first supercutical fluid substantially, comprise that weight percent is at least 90%, the zone of 95% or 99% first supercutical fluid), wherein second or position, the composition of container contents by or constitute by second fluid substantially and (for example, comprise that weight percent is at least 90%, the zone of 95% or 99% second supercutical fluid).Therefore, according to the size of the container of wherein implementing described technology, according to the capacity of container and the purpose of described technology, it can be less relatively or bigger, and the thickness at described interface can be for example 0.01,0.1 or 1 millimeter to 10 or 20 millimeters or higher; Thickness is 1,5 or 10 millimeter to 100,200 or 300 millimeters or higher; Thickness is 10,20 or 30 millimeters to 300,500 or 1000 millimeters or higher; Deng.It should be noted that in displacement step of the present invention, can " keep " interface, but the fluctuation of its thickness is usually located in the above-mentioned scope in described replacement process; It shall yet further be noted that and in displacement step, " to keep " described interface in only a part of process of the bigger technology of implementing specific invention described herein therein.

In various production technique, can utilize the present invention to shift or replace supercutical fluid, include but not limited to reaction process, imprint lithography, extraction process of cleaning procedure, coating process, for example polymerization process etc.

The example of the device that can clean with the present invention includes but not limited to, contains dielectric semiconductor chip, semiconductor chip, unicircuit, micro electro mechanical device (MEM), the optoelectronic equipment of (copper) that contain metal and the substrate that is coated with resist.Described resist typically comprises polymer materials, can be positivity effect resist or negative effects resist.When carrying out drying process, described resist can have pattern or not have pattern, and it can be through development or nonvisualized.

Can adopt suitable arbitrarily resist composition to implement the present invention, include but not limited to U.S. Patent No. 6042997; 5866304; 5492793; 5443690; 5071730; Described in 4980264 and 4491628.The applicant particularly points out, and the disclosed content of the United States Patent (USP) of this paper all references all by reference mode all is bonded to this paper.

The resist composition is applied on the substrate for example spin coating, dipping, roller coat or other conventional coating process according to known technology as liquid composition.When adopting spin coating, can adjust the solids content of coating solution, thus the film thickness of time that carries out based on the speed and the spin coating of the specific spin-coating equipment that is adopted, soltion viscosity, turner needing to obtain.

Suitably described resist composition is applied to relate in the technology that applies photo-resist the substrate that adopts usually.For example, described composition can be coated to the silicon substrate (can comprise one or more layers on it, for example silicon-dioxide, silicon nitride, polysiloxane and/or metal etc.) that is used to produce microprocessor and other integrated circuit package.Also can adopt aluminium-aluminum oxide, gallium arsenide, pottery, quartz or copper base.Also can suitably adopt the substrate that is used for liquid-crystal display and other flat panel display applications, for example glass substrate, be coated with the substrate of indium tin oxide etc.

After being coated to photo-resist on the surface, carry out drying, remove and desolvate by heating, preferred tack-free until described photo-resist coating.Perhaps, can carry out drying by technology described herein.Afterwards, imaging in a usual manner.Described exposure is enough to the photoactive component of effective exciting light resist system, thereby produces the image with pattern on the resist-coating layer.

After the exposure, roasting composition rete.Afterwards, with any suitable developing solution (its selection partly depends on selected specific anticorrosive additive material) of resist rete contact, thereby make film development.For example, described photographic developer can be polarity developer, for example based on the photographic developer of water, and for example mineral alkali, for example sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate, water glass, Starso; Quaternary phosphonium hydroxides ammonium solution, for example tetra-alkyl ammonium hydroxide solution; Various amine aqueous solutions, for example ethamine, Tri N-Propyl Amine, diethylamide, di-n-propylamine, triethylamine or methyl diethylamide; Hydramine, for example diethanolamine or trolamine; Cyclammonium, for example pyrrole is pressed against, pyrimidine etc.Usually, develop according to art-recognized process.After the development,, can randomly clean (for example with containing aqueous cleaning) to resist preferably by drying process as herein described, dry then.

After on-chip photo-resist coating is developed, optionally the development substrate is not handled on the zone of resist having, for example carry out chemical milling or be deposited on the substrate region that does not have resist according to technology well known in the art.For the production of microelectronic substrates, for example production silicon dioxide substrates, suitable etching reagent comprises gaseous etchant, for example based on the etching reagent of chlorine or fluorine, CF for example ₄Or CF ₄/ CHF ₃Etching reagent, it can apply with the plasma flow form according to technique known.

Below application composition further is discussed.Being used to implement carbon dioxide cleaning drying of the present invention or cleaning compositions typically comprises:

(a) be used for the equilibrated carbonic acid gas, usually at least 20%, 30%, 40%, 50% or 60%;

(b) 0%, 0.01%, 0.1%, 0.5%, 1% or 2% to 5% or 10% or more surfactant;

(c) 0%, 0.01%, 0.1%, 1% or 2% to 30%, 40% or 50% or more organic cosolvent;

(d) randomly, but be preferred in certain embodiments, 0%, 0.01% or 0.1% to 2%, 5% or 10% water; And

(e) when containing water, then comprise water-soluble cpds/cleaning additive to be allocated, present in an amount at least sufficient to help the cleaning of substrate.

Preferably, comprise at least a (for example, at least 0.01%) in tensio-active agent and/or the solubility promoter in described cleaning/drying composition, randomly, tensio-active agent and solubility promoter include in composition.According to the special cleaning applications and the character of substrate, can contain in the composition or not moisture.Except explanation is arranged in addition, the per-cent of this paper is weight percentage.

Described cleaning/drying composition can comprise cryogenic liquid for liquid or supercutical fluid.According to the application of determining, liquid and the supercritical co of this paper all is called " densification " carbonic acid gas.

Described organic cosolvent can be the mixture of a kind of compound or two or more components.Described organic cosolvent can for or comprise alcohol (comprising glycol, triol etc.), ether, amine, ketone, carbonic ether or alkane or hydrocarbon (aliphatic series or aromatic series).Organic cosolvent can be the mixture of compound, the mixture of above-mentioned alkane for example, or the mixture of one or more alkane and other compound, described compound is one or more above-mentioned alcohols (for example, 0% or 0.1% to 5% C1 to C15 alcohol (comprising glycol, triol etc.)) for example.Can adopting arbitrarily, tensio-active agent comprises containing to be connected to and dredges CO with enforcement the present invention ₂The close CO of group (for example lipophilic group) ₂The tensio-active agent of group (for example PCT application WO96/27704 described in) and do not contain close CO ₂The tensio-active agent of group (that is the tensio-active agent that, comprises the hydrophilic radical that is connected to hydrophobic (being generally lipophilic) group).Can use single tensio-active agent, maybe can adopt the combination of tensio-active agent.Those skilled in the art know a large amount of tensio-active agents.Referring to, the volume 1:Emulsifiers ﹠amp of McCutcheon for example; Detergents (1995 north-american version) (MC Publishing company, 175 Rock Road, Glen Rock, N.J.07452).The example that can be used to implement main surfactant types of the present invention comprises: alcohol, alkanolamide, alkanolamine, alkylaryl sulfomates, alkylaryl sulfonic acid, alkylbenzene, amine acetate, amine oxide, amine, sulfonated amine and sulfonation acid amides, betanin derivative, block polymer, carboxylation alcohols or alkyl phenol ethoxylate, carboxylic acid and lipid acid, the biphenyl sulfonic acid, ethoxylated alcohol, ethoxylated alkyl phenol, ethoxylated amine and/or acid amides, ethoxyquin lipid acid, ethoxylated fatty acid and oil, fatty acid ester, tensio-active agent based on fluorocarbon, glyceryl ester, glycol ester, the heterocyclic product, tetrahydroglyoxaline and imidazolidine derivatives, different thiosulphate, derivative based on lanolin, Yelkin TTS and Yelkin TTS derivative, xylogen and lignin derivative, maleic anhydride or succinyl oxide, methyl esters, monoglyceride and derivative thereof, alkene sulfonate, phosphoric acid ester, phosphorous organic derivative, polyoxyethylene glycol, polymkeric substance (polysaccharide, vinylformic acid and third rare acid amides) tensio-active agent, propoxylation and ethoxylated fatty acid alcohols or alkylphenol, based on proteinic tensio-active agent, quaternary surfactant, sarcosine derivative, tensio-active agent based on silicone, soap, the sorbitanic derivative, sucrose and glucose ester and derivative thereof, the vitriol of oil ﹠ fat acid and sulfonate, the vitriol of ethoxylated alkyl phenol and sulfonate, the vitriol of alcohols, the vitriol of ethoxyquin alcohols, the vitriol of fatty acid ester, benzene sulfonate, cumene, toluene and dimethylbenzene, condense naphthalenesulfonate, dodecyl and tridecyl benzene sulfonate, naphthalene and sulfonated alkyl naphathalene, the sulfonate of oil, sulphosuccinamate, sulfosuccinate and derivative thereof, taurate, sulfur-bearing and mercapto derivatives, tridecyl and Witco 1298 Soft Acid etc.

Accompanying drawing 1 has been described the substrate article 10 that need to be coated with by the inventive method exsiccant resist.Described article comprise substrate 11, and it can comprise silicone or other above-mentioned suitable material arbitrarily, itself can comprise one or more layers, is formed with resist coating 12 on it.Need be positioned at top surface by the water droplet 14,15 that drying is removed, and be located in the groove that forms on the resist coating.

Accompanying drawing 2 has schematically been described the equipment of implementing the inventive method.Described equipment comprises airtight drying receptacle 21, and it is suitable for receiving fluids or supercritical co, and in described container, the substrate 10 (or other microelectronic device to be cleaned) with coating is positioned on the suitable upholder 27.Described drying receptacle can comprise door, whipping appts or other device that is used to stir, viewing window, is connected with increase with described drying receptacle or reduce the compressor, heat exchanger of pressure wherein, be connected with increase with drying receptacle or reduce the well heater of the temperature of content wherein or water cooler etc.

Carbon dioxide cleaning/drying composition source of supply 22 links to each other with drying receptacle by suitable pipeline.Described cleaning/drying composition source of supply 22 itself can comprise one or more storage receptacles, pump, valve, be used for pipeline that drying is mixed into additive carbonic acid gas etc.Cleaning/drying composition in the described container can reach the level 28 that is higher than article to be cleaned 10.

According to the particular technology or the technical combinations of the control processing conditions that is adopted, described system comprises second gas source, second material and/or the additional carbonic acid gas 24 that is connected with drying receptacle 21.

If desired, developing solution source of supply 25 can link to each other with described container, thereby can carry out the development and the drying of substrate in same container 21.

Drainage system 26 preferably links to each other with container 21, thereby any composition that will wherein be contained is discharged.Described drainage system 26 itself can comprise (some assembly and above-mentioned supply combination of elements can have multiple function) such as suitable pump, valve, compressors, can comprise being used to distill and randomly reclaiming for example distiller of the component of carbonic acid gas, can also comprise that suitable pipeline, valve etc. are used for utilizing to supplying element to reclaim different compositions or constituent again.For example, can distill, thereby make carbon dioxide recovery and utilize again, perhaps it is recycled to additional carbonic acid gas source of supply as the part of drying composition to employed drying composition.

As mentioned above, method of the present invention may further comprise the steps:

(a) provide substrate, have pollutent or resistates on the substrate;

(b) provide fine and close (for example liquid or overcritical) carbonic acid gas dry composition, described cleaning compositions comprises carbonic acid gas and randomly but preferably include cleaning additive, and described cleaning additive is selected from solubility promoter, tensio-active agent and combination thereof;

(c) surface portion is immersed in the fine and close carbon dioxide cleaning composition; Then

(d) described cleaning compositions is removed from surface portion.

Can the control process parameter, thereby immersing step, removing step or immersing and removing in the step simultaneously, make described cleaning compositions remain the composition of homogeneous, and cleaning additive or pollutent are not deposited on or are deposited on the resist coating more basically.

Preferably, by mixing carbonic acid gas and one or more additives, the described step that provides is provided, thereby is obtained uniform solution, implement then to immerse step, keeping described cleaning compositions simultaneously is homogeneous solution.Described mixing can be implemented in drying composition source 22 by any appropriate means, for example stirs, injects under pressure etc.

The described step of removing of preferred enforcement, keeping described composition simultaneously is homogeneous solution.Usually, when composition when drying receptacle is discharged, the boiling by composite inhibiting is to implement above-mentioned steps.When with liquid CO ₂When discharging from container, the state that described liquid reaches is itself and CO ₂Steam reaches balance, i.e. saturated vapor pressure.Saturated in order to keep, when liquid by outlet or pump preferably when container bottom is discharged from container, described liquid phase boiling produces steam, thereby increases the vapor phase volume.Can cause vapour pressure to be lower than CO in the boiling of liquid/gas and liquid/liquid/solid interface forming core ₂Additive, described additive comprises solubility promoter and tensio-active agent and solute pollutent, is concentrating at the interface.

Spissated additive, sedimentary pollutent and because the interfacial stress that liquid/boiling of liquid/solid interface place forms can be damaged resist feature, MEMS or other has the microdevice of pattern.In the resist of imaging and development, size is easy to damage less than the feature of 130nm, aspect ratio about 3 especially.The process control that prevents above-mentioned damage is as follows.

For example, when described drying or cleaning compositions are liquid composition, from second pressurized gas (for example helium, nitrogen, air and composition thereof) of source of supply 24 closed chamber is pressurizeed by being used for, to implement removing step, the amount of described gas is enough to suppress to discharge the boiling of drying composition described in the step.Second gas preferably substantially can not be miscible in drying composition, and its saturated vapor pressure is higher than CO ₂Second gas itself can make drying or cleaning compositions discharge from container, perhaps can drying/cleaning compositions be discharged from container by pump or alternate manner, while, at the liquid-vapo(u)r interface place that clean container forms, second gas was kept overvoltage in discharge process.

Replacedly, if described drying or cleaning compositions are liquid phase,, do not need boiling just can finish the discharge step then by reaching liquid-gas equilibrium with second chamber or storage receptacle.In this case, chamber 21 is connected to storage receptacle 31 by the pipeline 32 (top) of gas side and the pipeline 33 of hydraulic fluid side.Thereby it is separated from each other or keep apart with container 21 and 31 that each pipeline contains valve 34,35.In discharging step, storage receptacle 31 contains the liquid CO that is in saturation pressure ₂Composition, described saturation pressure are equal to or greater than the saturated vapor pressure in cleaning/drying receptacle 21.The gas side of at first opening between container 21 and 31 connects 32, opens liquid then and surveys connection 33, to finish discharge.If 21 are positioned at enough tops of 31, liquid flows to storage receptacle 31 by gravity and/or by pump from cleaning vessel 21.Aforesaid liquid shifts and has avoided boiling, thereby has avoided the potential damage to resist feature or other device characteristic.

When described drying/cleaning compositions is overcritical composition, there is not liquid-vapo(u)r interface.In the case, at first in supercritical drying/cleaning compositions, add second material (for example above-mentioned solubility promoter or second gas), thereby make described composition such as above-mentioned discharge from container, to implement the described step of removing.If adopting second gas to make cleaning/drying composition is supercutical fluid when being displaced, described gas should be selected from saturated vapor pressure and be higher than CO ₂Gas.Example gases includes but not limited to, nitrogen, argon, helium, oxygen and composition thereof.

Replacedly, when described drying/cleaning compositions was positioned at supercritical state, before discharging step, the fluid that contains additive can be by adding pure supercritical CO simultaneously ₂With remove the supercritical CO that contains additive ₂Thereby, dilute fully.Carry out fully the fluid turnover and additive concentration is reduced to effectively minimum after, maintain supercritical state by making fluid, until being converted into steam state, described supercutical fluid is discharged from drying receptacle thereby avoided liquid.In discharge opeing/steps of exhausting, the pressure of critical temperature (Tc) in container that makes fluid temperature (F.T.) be higher than mixture is lower than the emergent pressure (Pc) of mixture, to implement said process.Accompanying drawing 3 has been described and has been mainly CO ₂The phase synoptic diagram of system, it is represented from being mainly CO ₂Supercritical mixtures transit to the gasiform possibility, to avoid liquid phase.Since the expansion of supercutical fluid and next residual gas be expanded to endothermic process, need be higher than critical temperature with the temperature of keeping fluid or gas to system's heating, be liquid or solid thereby avoid supercutical fluid or condensation of gas.By directly being converted into gas phase from supercritical phase, avoided liquid boiling, thus the interfacial stress of having avoided the meniscus by liquid/liquid/solid interface place retraction to cause, and avoided solute undesirable deposition on microstructure and in the microstructure.

In another embodiment, be used for diluting described drying/cleaning compositions from the other carbonic acid gas of source of supply 24, implement to remove step, during this dilution, described composition is removed from container by discharge system 23.Owing in described method, need more substantial carbonic acid gas, preferably adopt distiller that the carbonic acid gas of discharging is distilled, and adopt suitable pipeline and valve that carbonic acid gas is back to source of supply 22 or source of supply 24, be used for later utilization again.

In another embodiment, adopt second gas to replace the supercritical CO in drying/cleaning chamber ₂Or liquid and gaseous state CO ₂, its pressure range is higher than CO ₂The saturation point of gas, the major portion that makes second gas is a vapor phase.Second gas with low heat of compression can drain into normal atmosphere from chamber, thereby reduces the thermosteresis of system.By littler Joule-Thomson coefficient (μ) expression, gas causes the temperature variation of substrate or its vicinity less from high pressure to the expansion of atmospheric environment equally.(μ _CO2＞μ _x, x=second gas wherein)

μ＝(dT/dP) _H

In this embodiment, pressure cycling is when reaching high-throughput fast when needs, and second gas is very useful in avoiding thermal shocking.When having significant thermograde on the substrate, for example the substrate of silicon substrate may break or damage.Chamber and container cool off from gaseous expansion also may increase valuable process period, needs a large amount of heat inputs to carry out temperature regulation.It is minimum to adopt second gas thermosteresis and heat input can be reduced to, and can reduce cycling time and energy requirement.

Circulation is modulated as mentioned above mutually, in one embodiment, preferably modulate (CPM) mutually and implement cleaning by circulation, perhaps the phase of the cleaning compositions of circulation adjustment/change simultaneously (promptly, periodically cleaning compositions changed to gaseous state from liquid state, liquid state changes to overcritical, the overcritical gaseous state that changes to, the overcritical liquid state etc. that changes to).CPM is to CO ₂The processing controls of densification/cleaning compositions causes that resist, resist resistates, organic residue, particulate matter etc. are had (1) enhanced physical effect and (2) enhanced chemical action.About (1), liquid state and supercritical CO ₂Make the organic polymer plasticizing, thus CO ₂Penetrate into the body phase with molecular level, strengthened intermolecular and intramolecular ligation.In CPM, when fluidic density up-down adjustment, the carbonic acid gas air mass diffuses into the polymeric acceptor phase and leaves the polymeric acceptor phase.This process has applied mechanical stress and strain to mass polymer, thereby helps expansion, contraction, layering, the potential dissolving of polymer materials and finally remove from the surface.Because preferably adopt solubility promoter, tensio-active agent, reactant and adopt water to strengthen the densified carbon dioxide cleaning sometimes, therefore, described densification is necessary for the good carrier of these materials.About (2), adopt CPM control chemical additive at A) in the external phase, B) on the substrate surface and C) in for example separation in the resist resistates mutually of the body of material to be removed.

In the condition and range of temperature (T) and pressure (P), in other words be that many organic materialss can be dissolved in liquid state and/or supercritical CO in the above-mentioned external phase density range ₂In.In above-mentioned scope, material dissolves depends on concentration equally.Water and high polarity low-vapor pressure material and inorganic materials typically are insoluble to liquid state and supercritical CO ₂In.Yet show to have close CO ₂The tensio-active agent of characteristic is with these dispersion of materials and be emulsifiable in fine and close CO ₂In be very useful.And, show, do not contain and fluoridize or when with specific solubility promoter properties-correcting agent combination, can be used for fine and close CO based on the conventional surfactants of the component of silane ₂In.During CPM, when the density of external phase was adjusted, the chemical additive that dissolves, disperses or be emulsified in wherein separated between external phase and substrate surface.And, owing to CPM, be arranged in the body CO mutually of polymkeric substance and porous resistates ₂Can from described bulk material, diffuse out by different rates with additive, additive is concentrated in mutually at body.Describedly the expansion and the dissolving of resistates on kinetics, have been increased in the concentrated effect of body in mutually.For example, with regard to the organic polymer resistates that contains polarity hydrogen bonding functional group, described group has suppressed at fine and close CO ₂In expansion and dissolving.Can adopt solubility hydrogen bonding solubility promoter, itself and CO ₂Increased the expansion of mass polymer together, material is removed from substrate the most at last.Yet, the expansion of this material, dissolve or be dispersed in and be subject to additive on the kinetics at CO ₂In concentration.Adopt CPM, can regulate (T) and condition (P), external phase is separated with substrate surface, and be arranged in remaining object mutually.This technology increased additive at molecular level in resistates and lip-deep partial concn.Described concentrated effect has been represented additive at fine and close CO ₂Middle dissolving, dispersion or emulsive kinetic advantage.

In a word, the CPM with densified carbon dioxide and chemical additive has strengthened the removing of resist, resist resistates, particle and organic materials, and this is to realize by physics and the chemical action that increases these materials in the microelectronic substrates production process.

Circulation in the sample substrate cleaning course is modulated (CPM) mutually in the production of unicircuit, adopts densified carbon dioxide that semiconductor chip is cleaned after the etching step of following process accompanying drawing 4.Pressure 300 to 5000psi and-20 ℃ are to 100 ℃ temperature condition, and densified carbon dioxide is stored in the pressurized vessel (I) (50), and it further describes and is high pressure vessel.In automatic or manual mode substrate is packed in the cleaning chamber (III) (51), wherein substrate is placed on the platform (XI) (52) that is connected with the seal shaft (not shown) with chuck, thereby described platform can rotate.What be positioned at that platform supports on-chiply is jet pipe (X) (53), and it is designed for and disperses densified carbon dioxide and chemical additive stream, and substrate surface is carried out the directly basic fluidic effect that is.Through the cleaning carbonic acid gas of valve (a) (56) temperature that the pressure in the cleaning chamber (III) increases at-20 ℃ to 100 ℃ is issued to 300psi to 500psi through valve (i) (55) or from pressurized vessel (I) (50) from bulk storage tank (XII) (54).Can adopt heat exchanger (II) (60) to regulate fine and close CO ₂Temperature.In addition, can adopt to be positioned at chamber interior or outside heat exchanger, the temperature of the processing phase in the chamber (III) (51) is regulated.Adding fine and close CO ₂In the process or at the fine and close CO of adding ₂Before, add cleaning chamber (III) with adding module (VI) (61) from additive as required by valve (b) (62) through highly filtering chemical additive.Described additive adds that module is used for storing, filter, mixing and order or measure the additive material that adds cleaning chamber simultaneously.In cleaning course, fine and close CO ₂Can optionally adopt pump (VII) (63) to loop back described chamber by jet pipe (X) (53) through valve (e) (66) and through solid separation filter (VIII) (64) and valve (f) (65) from cleaning chamber.In working cycle, the speed rotation that substrate can 0 to 3000rmp.In cleaning, the density of system is periodically regulated equally.It can be finished by following order.Make pressurized vessel (I) (50) promptly contain fine and close CO ₂The pressure of high pressure vessel maintain the pressure that is significantly higher than (exceeding 50) cleaning chamber (III) (51) to 2000psi.With pressurized vessel (V) (70) is that the pressure of low pressure vessel maintains significantly the pressure that is lower than (low 50 to 3000psi) cleaning chamber (III) (51), and the temperature of each container is roughly the same.In described working cycle, at first open valve (a) (56), allow flow of matter to take place at (I) with (III), close then.Open valve (d) (71) then, allow at (III) and flow of matter (IV).Open valve (g) (72), lead to separator/minimizing module (IX) (73), for example strainer or other separator, it is used for chemical additive from CO ₂With separate in the refuse of removing.Described minimizing module also allows the CO that is removed ₂Material is added into jar (I) again through valve (h) (74), thereby finishes the flow of matter cycle.In addition, can be from the body storage with CO ₂Material adds in the pressurized vessel (I), makes the pressure in the container (I) be higher than chamber (III) once more.In given cleaning cycle, repeat this flow of matter cycle repeatedly (1 to 500), thereby circulate modulation (CPM) mutually.In CPM, can arbitrarily adopt pump (VII) and valve (e) and (f) strengthen fine and close CO ₂Circulation in cleaning chamber (III).In cleaning, by adopting variable-volume chamber (IV) (80), open valve (c) (81) in addition, can realize CPM.In this case, in given cleaning cycle, volume (IV) periodically increases and reduces, and scope is between 1 to 500 times.In this CPM, adopt pump (VII) and valve (e) and (f), thereby through cleaning chamber (III) randomly convection cell circulate.After being enough to one period cycle that pollutent is removed from substrate surface, add pure fine and close CO through valve (a) from jar (I) ₂Thereby, make fine and close CO ₂Mixture flows into container (V) from system through valve (d).This cleaning process continues to carry out, and all removes from chamber until all additives and refuse.Described fine and close CO ₂Be expelled to refuse or minimizing system from cleaning chamber (III).

Water-soluble cpds to be allocated adopts the example of the water-soluble cpds to be allocated that helps cleaning in the embodiment of water to include but not limited in above-mentioned cleaning system: acid (includes but not limited to HF, HF/NH ₄F (be also referred to as " BOE "-through buffered oxide etching or " BHF "-), H through buffered HF ₂SO ₄, HCl, HBr, H ₃PO ₄, HNO ₃, CH ₃CO ₂H, H ₂S ₂O ₈, KCN, KI etc.); Reactant (includes but not limited to H ₂O ₂, NH ₄F and NH ₄F ₂, SiCl ₄, SiHCl ₃, Si (C ₂H ₅O) ₄, Br, I, EDTA, tensio-active agent, (NH ₄) ₂SO ₄, O ₃, H ₂, SO ₃, N ₂O, NO, NO ₂, F ₂, CL ₂, Br ₂Deng); Basic metal or alkali (include but not limited to NH ₄OH, KOH, NaOH etc.); Weak base and ion pair (include but not limited to choline (CH ₃) ₃N ⁺(CH ₂CH ₂Tertiary amine etc.) and combination OHOH).

The method of controlling pollutent after microelectronic structure is carried out carbon dioxide cleaning is at ion implantation, " line rear end " (BEOL) cleaning course, " line front end " (FEOL) after cleaning course and the back CMP step, and the pollutent of removing from the surface characteristic of microelectronic substrates is in character and form remarkable different.Therefore, cleaning must adopt suitable chemical substance and solvent at these pollutents, thereby evaporates with its reaction, ionization, dissolving, expansion, dispersion, emulsification or from substrate.Like this, there are a large amount of system and dry cleansing process, thereby solved a large amount of waste materials based on water and solvent.

Yet, what all cleaning courses needed jointly is that all contaminants and additive are removed from substrate fully, make substrate not contain, not contain substantially or do not contain organic and inorganic, metal in fact or mixed waste (after for example described process finished, the amount of remaining pollutent was no more than 5%, 1%, 0.5%, 0.1%, 0.05%, 0.01%, 0.005%, 0.001% or lower (weight percent) of amount of pollutant before the cleaning course).These foreign materials that are commonly referred to the resistates that is arranged in the wet cleaning process of watermark can produce significant detrimentally affect to the final performance of unicircuit and other microelectronic device.Traditionally, carry out cleaning step by adopting a large amount of ultrapure waters and/or solvent, thus at wet cleaning and in based on the cleaning course of solvent with above-mentioned reduce to minimum.In these processes, fluid stream is taken away pollutent from substrate, thereby reduces to the deposition again of material minimum.When feature sizes of devices constantly reduces, these clean ways and cause a large amount of waste streams based on water and solvent constantly to increase.Usually also use the vapor phase siccative, for example the IPA siccative is reduced to the generation of watermark or water spots minimum.

In the production of microelectronic substrates, propose to adopt based on liquid state and supercritical CO ₂Cleaning and drying process.Need be in cleaning or afterwards effectively removal of pollutants on the surface characteristic of microelectronic substrates and the sedimentary again treatment process in inside.Technology disclosed herein can be competent at this task, and the while can also advantageously reduce to the extra usage quantity of handling washing fluid minimum, and it may come flowing and the refuse situation of self-forming pattern.Basic technology synoptic diagram in the accompanying drawing 5 is the describe, in general terms to the embodiment of the present invention.

In the carbon dioxide cleaning step, the fluid in the chamber can be supercritical state or liquid state.And, liquid CO ₂Composition can be positioned at saturation point, promptly saturated liquid CO ₂(liquids and gases coexist with a certain ratio), perhaps it can be (not the having meniscus) of compression.Each situation is described respectively for purposes of the present invention.

With supercritical CO ₂Composition and pollutent are removed from cleaning chamber, avoid the deposition again of cleaning additive and pollutent, and reduce to the washing lotion volume minimum.Adopt CO ₂Cleaning can adopt a large amount of chemical additives, comprise solubility promoter, tensio-active agent, reactant, water and some or all combination, thereby can or help quantitatively removing pollutent.These materials can suspend, dissolve, disperse or be emulsifiable in the carbonic acid gas external phase.Material suspension, dispersion, emulsion even solution are at supercritical CO ₂With the stability in the liquid be CO to a great extent ₂The function of fluid density.In general, work as CO ₂When the density of external phase reduces, the stability of suspension, dispersion liquid or emulsion also down will.Owing to the CO that removes by discharge from cleaning chamber or exhaust ₂Quality from slowly reducing to quick, so this technology causes material that undesirable damage takes place, promptly is called in on-chip deposition again for pollutent, and for additive, is called in on-chip deposition on fluid density.Consistent with conventional cleaning procedure, can adopt a large amount of ultrapure washing fluids, be CO in this case ₂, before steps of exhausting, additive and pollutent mixture are diluted, thus will deposit again reduce to minimum.Disadvantageously, it is based on required fluid volume and cycle of treatment time.

The present invention has avoided the problems referred to above shown in the accompanying drawing 5.No matter be before or after cleaning step, the first supercritical processing fluid that will contain a certain amount of pollutent and/or additive is removed, and material does not deposit or is deposited on the substrate.Chamber I (50) represents cleaning chamber.The storage of treat fluid is irritated after pressurized vessel II (51) the representative cleaning.It can be as required in conjunction with reducing or recirculation system.Subsystem III (52) representative is clean (promptly, enough totally to reach required degree of cleaning level/pollutent deposition more on substrate) source of gaseous state or overcritical component, it can be second gas, the saturation vapour pressure of described second gas is higher than carbonic acid gas, perhaps can be the carbonic acid gas of the heating that is positioned at supercritical phase or gas phase.The second exemplary gas comprises: helium, nitrogen, argon, oxygen and composition thereof.In the present invention, by second gas source through valve (b) 53 from the III52 of system is provided, contaminated supercutical fluid is removed from treatment chamber, the pressure of described second gas is greater than the pressure in the treatment chamber (I).In the almost while of opening valve (b), open the valve (c) 54 that is positioned between chamber (I) and the container (II), thereby remove CO in the mode of piston flow or discharge ₂And pollutent.Valve (b) stays open state, for chamber (I) provides successive second gas stream, is forced to from chamber (I) to discharge until all flowing materials, at this moment, valve-off (b) and (c).By this operation, the pressure in the container (II) keeps below the pressure in the chamber (I).

Replacedly, system (III) can provide the supercritical CO of heating to chamber (I) ₂The source, its pressure and temperature surpasses the treat fluid in the chamber (I).Ideally, the supercritical CO that adds from system (III) ₂Density be lower than chamber (I).In the case, flow into container (II) apace from chamber (I) by material, thereby with the CO of different densities ₂Fluid mixes.Described flushing operation is with CO ₂Remove from cleaning chamber with pollutent.This process can be used as final draining, exhaust afterwards, perhaps before last exhaust in conjunction with a series of filling and draining sequence.

With liquid CO ₂Composition and pollutent are removed from cleaning chamber, avoid cleaning the deposition again of interpolation and pollutent, reduce to the washing lotion volume minimum.Adopt the following sequence can be with liquid CO ₂Composition is removed from cleaning chamber, and does not have the deposition of additive or the deposition again of pollutent, and described sequence is in conjunction with second gas, for example helium or nitrogen or gaseous state or supercritical CO ₂Under first kind of situation, at first open the valve (b) that leads to system (III), fluid composition is removed from chamber (I), wherein contain second gas that pressure is higher than chamber (I) in the system (III).At the same time or after a while, open the valve (c) 54 that is positioned between chamber (I) and the container (II), thereby the piston flow of fluid composition is removed from chamber (I).After liquid is removed from (I) fully, valve-off (c) 54 and (b) 53.Before the exhaust or filling and the drain step sequence in, this process can be used as the last drain step of removing.Selectively, adopt identical process steps, by system (III) provide through the heating gaseous state CO ₂Or supercritical CO ₂At gaseous state CO ₂Situation under, the pressure and temperature of described gas must surpass and is arranged in chamber (I) treat fluid to be removed.At the supercritical CO that provides by system (III) ₂Situation under, the described fluidic temperature and pressure that is provided surpasses the fluid in the chamber (I), as long as described fluidic density is lower than the liquid in the chamber (I).When material flow to (I) to (II) and flows from (III) apace, by surface cleaning operation, gaseous state or supercritical CO are provided in described draining rinse step ₂Being condensed into liquid is favourable to described process.Once more, in a series of fillings and drain step before the chamber exhaust or before the exhaust in the end, this process can be used as last removing or rinse step.

Selectively, if cleaning chamber adopts the liquid CO that is positioned at saturation vapour pressure ₂Composition, described fluid composition can adopt following steps to be discharged from, thereby avoid the deposition of material on substrate surface.In the case, before discharge or rinse step, be in the liquid CO of saturation vapour pressure ₂Remain in the container (II).At first open the valve (e) 55 of the vapor phase side of connection (I) and vapor phase side (H), open the liquid survey of connection (I) and the valve (c) 54 of steam side (II) then, thereby described fluid composition is discharged from (I).By the effect of gravity, liquid flows out from (I), and the liquid in the chamber (I) does not seethe with excitement.The boiling that prevents liquid has avoided incidental material to deposit from the teeth outwards.Steam side communicate (be the vapor communication passage, allow flow of vapor) preferably is provided between two chambers.Once more, in a series of fillings and drain step before the chamber exhaust or before the exhaust in the end, this process can be used as last removing or rinse step.

Accompanying drawing 6 has schematically been described the substrate that is arranged in pressurized vessel, deposits the supercritical flow body thin film on the described substrate.Accompanying drawing 7 has schematically been described the technology that forms accompanying drawing 6 described products.Usually, pressurized vessel 111 contains substrate 112, applies the first supercutical fluid film, 114, the first supercutical fluids on the substrate and contains or carry and apply component (for example be dissolved in, dissolve or disperse wherein).Second supercutical fluid 115 is introduced pressurized vessel (for example pressure is a little more than first supercutical fluid), force first supercutical fluid to leave container (for example by the uplift pressure valve), thereby make the pressure in the container basic identical.On substrate, deposit the first supercritical flow body thin film thus.Can implement to intervene step to the coating component of supercutical fluid, for example next reactions steps can evaporate first supercutical fluid, will apply component and be deposited on the substrate surface.

In implementing process of the present invention, can typically comprise as the carbon dioxide composition of first supercutical fluid:

(a) be used for the equilibrated carbonic acid gas, typically be at least 20%, 30%, 40%, 50% or 60%;

(b) 0%, 0.01%, 0.1%, 0.5%, 1% or 2% to 5% or 10% or more surfactant;

(c) 0%, 0.01%, 0.1%, 1% or 2% to 30%, 40% or 50% or more organic cosolvent;

(d) choose 0%, 0.01% or 0.1% to 2% or 5% water wantonly; And

(e) be distributed in 0.01% in the composition, 0.1% or 1% to 2%, 5% or 10% or higher coating component (for example as solution or dispersion).

The pressure of first and second supercutical fluids in described container typically about 1000 or 1080psig between about 5000 to 10000psig, its temperature is positioned at about 30 or 31 degrees centigrade to about 150 or 250 degrees centigrade.

Can adopt composition that any appropriate density is lower than first supercutical fluid as second supercutical fluid, include but not limited to helium, argon, nitrogen, oxygen, hydrogen, ozone and composition thereof.

According to the optional composition that contains in the specific coated form that is adopted and first supercutical fluid (for example, applying component), the thickness of film changes, but is usually located at about 100 or 200 dusts to about 1 or 2 micron.

The described coating ingredients of coating ingredients can comprise following one or more:

● be dissolved in or be scattered in the CO that is prepared ₂In close CO ₂Polymkeric substance and polymer materials.Polymer materials is dielectric medium, photo-resist, lubricant, isolator, pigment etc. for example.

● described prescription comprises

● be positioned at the pure CO under the super critical condition ₂

● through the CO of solubility promoter modification ₂External phase

(employing has close CO in the microemulsion territory of polarizable medium-water ₂With thin CO ₂The surfactant composition of structure)

Aforesaid combination

● surface active material-for example may connect, in conjunction with or be bonded to the surface coating (bond to on-chip compound referring to 6287640 usefulness substrate carried out surface treatment, it is quoted herein and is used for describe, in general terms, because described technology can be used for the textiles substrate)

● pottery and glass precursor material, for example

● the silicon network precursor, for example: TEOS, hydrogen silicon sesquialter oxane (silsesquioxane) (HSQ), methyl silicon sesquialter oxane (MSQ)

● based on other semi-conductor and based on other network precursor (special list of chemical substance and material) of IV and V family metal

● be dissolved in CO through preparation ₂In atoms metal, for example copper and aluminium

● be dissolved in or be scattered in CO through preparation ₂In metal complex

● be dissolved in or be scattered in CO through preparation ₂In the metal level precursor (for example in semiconductor fabrication, form special chemical substance-tantalum, tungsten and the titanium nitride of " barrier layer " material, carbide silicide and ternary material, the material (special fluid phase chemistry material) that for example contains boron) the described coating processes of coating program form enforcement easily arbitrarily includes but not limited to: the meniscus coating that comprises all physical form (is described liquid CO in detail in 6497921 ₂Meniscus applies the method for liquid carbon dioxide, and same names 6083565, quote herein-consider that for dependency these reference are confined to liquid phase, this is because it is unique condition that can support meniscus.They also are confined to apply with polymer materials).

The spin coating that comprises all physical form (is described liquid CO in detail in 6001418 ₂The spin coating method and the equipment that are used for the liquid carbon dioxide system are quoted-consider that for dependency these reference are confined to liquid phase herein, and this is because it is unique condition that can support meniscus.They also are confined to apply with polymer materials).

Be connected by carrying out reactivity with described surface, will be from the material deposition of surface film

On substrate, (form surface film) by spin coating, meniscus coating etc.This example

Comprise:

● " hot wall " deposition ... on coated surface, carry out thermoinducible reaction.

● be specially adapted to the reduction of metal complex

● be specially adapted to bonding and/or crosslinked

● surface chemistry is bonding, and the following non-limitative example that is bonded in that for example produces the surface be used for carrying out the combinatorial chemistry analysis describes the present invention.

The comparative example 1

With the substrate of liquid carbon dioxide processing through applying

Can with CO ₂Miscible hydrophilic solvent, for example Virahol (IPA) adds in the high pressure vessel, contains the silicon substrate that a slice (PHS) applies through poly-(hydroxy styrenes) in the described container.With liquid CO ₂Add in the described high pressure vessel.As described liquid CO ₂When the meniscus of/IPA (IPA of 2% volume) mixture surpasses substrate surperficial, can observe damage to substrate.After system mixes 15 minutes, with liquid CO ₂/ IPA mixture is discharged from the bottom of high pressure vessel.As IPA during, observe substrate is more damaged in the boiling of liquid/gas/substrate interface.

Embodiment 1

With the substrate of liquid carbon dioxide processing through applying

With liquid CO ₂Add in the high pressure vessel, contain the silicon substrate that a slice applies through PHS in the described container, until described substrate fully by liquid CO ₂Submergence.To contain liquid CO ₂And the mixture of IPA (IPA of 2% volume) (selectively, any and CO ₂Miscible hydrophilic solvent, or hydrophilic arbitrarily/close CO ₂Tensio-active agent) add in the described high pressure vessel, in described container, the silicon substrate that is coated with PHS is by liquid CO ₂Submergence.Do not observe damage to substrate.System was mixed 15 minutes.To substrate still not infringement.The top that second gas (helium or nitrogen) is added high pressure vessel.Under second gaseous tension, discharge liquid CO ₂/ IPA mixture prevents to seethe with excitement in liquid/gas/substrate interface.After system is with the second gas expel liquid, to not infringement of substrate.With pure liquid CO ₂Cleaning system is then as above-mentioned expel liquid.To not infringement of substrate.

Embodiment 2

With the substrate of liquid carbon dioxide processing through applying

To be in the liquid CO of saturation vapour pressure ₂Add in the high pressure vessel, contain the silicon substrate that a slice applies through PHS in the described container, until described substrate fully by liquid CO ₂Submergence.To contain liquid CO ₂And the mixture of IPA (IPA of 2% volume) (selectively, any and CO ₂Miscible hydrophilic solvent, or hydrophilic arbitrarily/close CO ₂Tensio-active agent) add in the described high pressure vessel, in described container, the silicon substrate that is coated with PHS is by liquid CO ₂Submergence.Do not observe damage to substrate.With described liquid CO ₂Mixture enters to another from high pressure vessel and mainly contains the liquid CO that is positioned at saturation vapour pressure ₂High pressure vessel, method is at first to open the valve of the steam end that connects two containers, opens the valve of the liquid end that connects two containers then.When first container fully was positioned at second container top, the effect expel liquid by gravity was discharged it fully.Do not observe infringement.With pure liquid CO ₂Add as washing lotion and to contain in the segmental container of substrate, then expel liquid in the above described manner.Once more, do not observe infringement.

Embodiment 3

With liquid and overcriticalCO ₂ The substrate of processing through applying

With liquid CO ₂Add in the high pressure vessel, contain the silicon substrate that a slice applies through PHS in the described container, until described substrate fully by liquid CO ₂Submergence.To contain liquid CO ₂And the mixture of IPA (IPA of 2% volume) (selectively, any and CO ₂Miscible hydrophilic solvent, or submitted the CO of water to ₂The tensio-active agent of supporting capacity) add in the described high pressure vessel, in described container, the silicon substrate that is coated with PHS is by liquid CO ₂Submergence.Do not observe damage to substrate.Be enough to most of water after the time that substrate surface is removed through one section, with pure liquid CO ₂Dilute described liquid mixture, thereby liquid is through about 5 turnovers in dry chamber.Liquid towards CO then ₂Apply heat, be converted into supercritical phase.The temperature of keeping described fluid and gas is higher than CO ₂Critical temperature, the described chamber that contains substrate is carried out expel liquid and exhaust, thereby has avoided liquid phase.Substrate is shifted out from chamber, without any infringement.

Embodiment 4

With the substrate of supercritical carbon dioxide treatment through applying

With supercritical CO ₂Add in the high pressure vessel, contain the silicon substrate that a slice applies through PHS in the described container.To contain supercritical CO ₂And the mixture of IPA (IPA of 2% volume) (selectively, any and CO ₂Miscible hydrophilic solvent, or improved the CO of water ₂The tensio-active agent of supporting capacity) adds in the described high pressure vessel, contain the silicon substrate and the supercritical CO that are coated with PHS in the described container ₂Do not observe damage to substrate.Described system was mixed 15 minutes.Substrate is not still damaged.Second gas (helium or nitrogen) is added the top of high pressure vessel, become subcritically until described system, form meniscus.Under the pressure of second gas, discharge described liquid CO ₂/ IPA mixture prevents liquid/gas/substrate interface place boiling.System does not cause damage to substrate with after the second gas expel liquid.With pure liquid CO ₂Cleaning system, expel liquid as mentioned above then.Substrate is not damaged.

Comparative example B

With liquid carbon dioxide with water solvation from the substrate through applying

Water droplet is dropped on the silicon substrate that PHS applies.The substrate that will contain described water droplet is placed in the high pressure observation ward.With pure liquid CO ₂Add as in the high pressure vessel.System was mixed 15 minutes.Sapphire window vision by observation ward is determined liquid CO ₂Not with whole water droplet solvations.

Embodiment 5

With liquid carbon dioxide and solubility promoter with water solvation from the substrate through applying

Water droplet is dropped on the silicon substrate that PHS applies.The substrate that will contain described water droplet is placed in the high pressure observation ward.In the high pressure vessel of the silicon substrate that PHS applies, add liquid CO to containing ₂, until described substrate fully by liquid CO ₂Submergence.To contain liquid CO ₂And the mixture of IPA (IPA of 2% volume) (selectively, any and CO ₂Miscible hydrophilic solvent) add in the described high pressure vessel, in described container, the silicon substrate that is coated with PHS is by liquid CO ₂Submergence.Do not observe infringement to substrate.Mixed described system 15 minutes.Water droplet is by complete solvation.To substrate still not infringement.The top that second gas (helium or nitrogen) is added high pressure vessel.Under the pressure of second gas, discharge described liquid CO ₂/ IPA mixture prevents liquid/gas/substrate interface place boiling.System does not cause damage to substrate with after the second gas expel liquid.With pure liquid CO ₂Cleaning system, expel liquid as mentioned above then.Substrate is not damaged.

Embodiment 6

With liquid and supercritical co and solubility promoter with water from through coating

Solvation on the substrate

" substrate through PHS applies is put in this substrate in the dry chamber of prototype, and this substrate can be arranged in back water-based developing process with water-wet whole 5.Be full of liquid carbon dioxide in the described chamber.Described prototype system comprises second high pressure vessel, wherein contains liquid CO ₂With volume be 2% IPA (selectively, arbitrarily and CO ₂Miscible hydrophilic solvent, or the CO of raising water ₂The tensio-active agent of supporting capacity).With the liquid CO of blended ₂/ IPA adds the dry chamber by pump from second high pressure vessel.Mixed described system 15 minutes.Use neat liquid CO ₂Wash described liquid CO ₂/ IPA mixture carries out the turnover of 5 liquid, thereby makes the concentration of IPA reduce to some parts of previous concentration several.At CO ₂Do not form meniscus in the flushing process.CO ₂After the flushing, with liquid CO ₂Be heated to 35 ℃, fluid is converted into supercritical phase.When heating make fluid and after the temperature of gas be higher than CO ₂Critical temperature the time, with supercritical CO ₂Discharge from container/emit.When chamber is discharged gas fully, substrate is shifted out, it is exsiccant and not damage.

Embodiment 7

WithCO ₂ With chemical additive with water from imaging and after water-based is developed, be coated with resist

Substrate on drying remove

With of 5 inch silicon substrate imagings and the development of 0.238 normal Tetramethylammonium hydroxide, use washed with de-ionized water to being coated with PHS photo-resist and PAG.Described wet substrate is transferred in the dry chamber of high pressure, wherein adds a spot of liquid CO that is positioned at saturation vapour pressure ₂Add other in advance with hydrophilic/close CO ₂The tensio-active agent blended is positioned at the liquid CO of saturation vapour pressure ₂, and cycle through chamber, water is cemented out and removes from substrate surface and resist pattern characteristics.After blink, liquid drained into contain a small amount of liquid CO ₂Second storage receptacle in, method is that the steam side of two containers is communicated, and opens the valve that connects bottom the drying receptacle bottom and second storage receptacle then.Second storage receptacle fully is positioned at the below of dry chamber, thereby most of liquid is discharged from dry chamber.In dry chamber, be full of pure liquid CO then as washing lotion ₂, discharge by mode as mentioned above.Repeat, be actually zero with the concentration of guaranteeing additive.With a small amount of remaining liquid CO in the dry chamber ₂Be heated above its stagnation point, 35 ℃, with CO ₂Discharge, keep the fluids/gases temperature to be higher than critical temperature simultaneously, thereby avoid forming meniscus.Take out from chamber through imaging, development and exsiccant substrate described then, lucifuge and moistureproof the preservation are adopted scanning electronic microscope analysis then.Described displaing micro picture shown, the feature through developing that has less than line/space pattern of 120nm structurally is consistent, is not subjected to CO ₂The influence of drying process.

Embodiment 8

Remove water and the pollutent of MEM

In the production of the MEM device that contains a series of electrostatic actuators, adopt hydrofluoric acid aqueous solution to remove the oxide skin of will be sacrificed, the revolving fragment of series of parallel in substrate surface exposed.After ensuing cleaning step, described device is transferred to based on high pressure CO ₂Dry chamber in, wherein add the liquid CO be positioned at saturation vapour pressure ₂Described liquid CO ₂Contain close CO ₂/ hydrophilic tensio-active agent, described tensio-active agent in advance with CO ₂Mix, thereby guarantee to be uniform composition.After circulation for some time, in chamber, add pure liquid CO ₂, because liquid CO ₂, tensio-active agent and the solute that carries remove from container with constant pressure.Then, with remaining liquid CO in the chamber ₂Be heated to more than the critical temperature, fluid is converted into above-critical state.Then, the supercutical fluid that will be arranged in treatment chamber enters storage tank, guarantees that the temperature of fluids/gases mixture is higher than CO ₂Critical temperature.It has guaranteed to avoid occurring liquid state, meniscus and relevant surface tension in discharge/aeration step.Sem analysis to the MEM device shows that revolving fragment is basically parallel to substrate surface, does not have evidence to show and discharges stiction.

Embodiment 9

Clean behind the CMP

Adopt following processing step behind CMP, to remove polishing fluid, polishing resistates and particulate matter.The semiconductor chip that substrate is promptly had metal or dielectric surface is put into pressurized vessel.To be positioned at liquid CO ₂Aqueous hydrogen peroxide solution in the emulsion (concentration in water is 30%) is introduced under 1200psi and room temperature, contains highly purified close CO in the described emulsion ₂-b-hydrophilic surfactant.Adopt circulation to modulate mutually emulsion is condensed to substrate surface, carry out reemulsification afterwards.It realizes that by the effective volume that increases cleaning chamber it makes the pressure 1200psi that is positioned under the room temperature reduce to about 15 ℃ 790psi.Adopt automatic variable volume cylinder and suitable valve to increase volume.As liquid CO ₂When density reduces, clean aqueous solution is condensed to one blink of substrate surface.Then by reducing container volume, pressure boost, with the pressure recovery in the cleaning chamber to 1200psi.Repeat this circulation 20 times.By second cleaning soln first solution is replaced away from container then, described second solution comprises and is positioned at CO ₂Fluoride aqueous solution in the emulsion, described emulsion have highly purified close CO ₂-b-hydrophilic surfactant.Pressure 20 times are regulated in circulation as mentioned above then.Afterwards, be positioned at the supercritical CO of 1800psi and 40 ℃ ₂And the high purity surfactant container of flowing through, help removing any remaining particulate matter.Then by in container, adding pure CO ₂, finish supercritical CO ₂Clean.For the last time system is carried out exhaust, shift out substrate.

Embodiment 10

Adopt following processing step behind CMP, to remove polishing fluid, polishing resistates and particulate matter.The semiconductor chip that substrate is promptly had metal or dielectric surface is put into pressurized vessel.To be positioned at liquid CO ₂Aqueous hydrogen peroxide solution in the emulsion is introduced under 1200psi and room temperature, contains highly purified close CO in the described emulsion ₂-b-hydrophilic surfactant.Employing is connected to the chamber of the volume-variable of cleaning vessel, described clean aqueous solution is condensed to one blink of surface of substrate.By reducing the container volume pressure boost, thus with pressure recovery to initial value.Repeat described cycle 20 times.By second cleaning soln first solution is replaced away from container then, described second solution is by being positioned at CO ₂Aqueous fluoride in the emulsion is formed, and described emulsion has highly purified close CO ₂-b-hydrophilic surfactant.Adopt the chamber of volume-variable, regulate pressure more than 20 times.Contain and dissolve in CO on a small quantity ₂The supercritical CO of sequestrant (ethylenediamine tetraacetic acid (EDTA)) ₂The container of flowing through helps removing the metal ion of any remnants.Supercritical CO with highly purified tensio-active agent ₂Thereby the container of flowing through helps removing any remaining particulate matter.In container, add pure CO ₂, finish supercritical CO ₂Clean.For the last time system is carried out exhaust, shift out substrate.

Embodiment 11

Adopt photo-resist to make substrate form pattern, carry out ion implantation.The photo-resist that will be used for this process according to following steps is removed.With substrate is that semi-conductor after ion implantation is packed in the pressurized vessel.In container, add the supercritical CO be positioned at 3000psi and 35 ℃ ₂Work as supercritical CO ₂When cycling through container, add by the cosolvent mixtures of trolamine and N-methyl-2-pyrrolidone, contain close CO ₂The cosolvent mixtures of forming with the tensio-active agent of hydrophilic component and water.The weight ratio of described blend compositions is 7: 2: 1: 1, and the total concn of the additive of adding is the 2.5%w/v of described fluid system.Adopt the chamber of volume-variable and the pressure that suitable valve reduces container, the treat fluid in the cleaning chamber is expanded, thereby the enriched mixture of additive agent mixture is condensed to substrate surface.In expansion process, the temperature of mixture is reduced to below the Tc, causes being converted into liquid CO ₂Adopt the chamber and the interior heater of volume-variable, to system's pressurization, fluid mixture is heated to more than the Tc once more again.Repeat this cycle 20 times, use pure supercritical CO then ₂Clean.To this system's emission gases, shift out substrate.

Embodiment 12

Adopt following procedure of processing, after active-ion-etch,, polymkeric substance photo-resist and resist resistates are removed by the structure of test substrate.To be positioned at supercritical CO ₂In amine and high purity surfactant (2%w/v amine, 1%w/v tensio-active agent) under 3000psi and 60 ℃ add in the container, have close CO in the described tensio-active agent ₂And lipophilic ingredient.Described fluid mixture cycles through container.The pressure of fluid mixture is reduced to 1500psi fast, thereby additive is condensed to substrate surface.Then pressure is increased to 3000psi fast, all chemical additives are disperseed again.Adopt the chamber of volume-variable to repeat this circulation 20 times.Adopt interior heater that chamber is heated, as far as possible with temperature maintenance at about 60 ℃.Then, when the valve that is positioned at cavity bottom when waste chamber is opened, adding pressure in cleaning chamber is the helium of 3500psi.The pressurized pure helium of treat fluid washes from chamber apace and replaces away.After closing helium, use pure supercritical CO ₂Clean cleaning vessel.In cleaning vessel, add second cleaning soln and be positioned at 3000psi and 60 ℃ CO ₂, described second solution is by solubility promoter (2,4-diacetylmethane, total amount is 3%w/v) and high purity surfactant (1%w/v).Regulation system pressure is 20 times as mentioned above, adopts interior heater that the fluidic temperature is maintained near 60 ℃ as far as possible simultaneously.Adopt helium as second gas, discharge cleaning fluid as mentioned above.At last, use pure supercritical CO ₂Clean, adopt helium system's expel liquid to be discharged gas then, shift out substrate as second gas.

Embodiment 13

Between supercritical helium and supercritical co, form the interface

Being full of temperature in the high pressure observation ward and being about 55 degrees centigrade, pressure is the supercritical co of about 2800spig.Contain volume percent in the described supercritical co and be lower than about 4% solubility promoter N-methyl pyrrolidone.By uplift pressure setter expel liquid, thereby make the pressure in the observation ward approaching constant.Accompanying drawing 8 has shown that adding pressure to the observation ward top is approximately 2900psig, the temperature supercritical helium with supercritical co.This photo is taken in slightly high position through the viewing window of observation ward.Supercritical helium is positioned at the top of chamber, and supercritical co is positioned at the bottom of chamber, and described supercritical co is forced to discharge described chamber through the discharge line that is positioned at the bottom, chamber.Observe between two supercutical fluids and form the interface, be i.e. black border between the observation ward upper and lower.After for some time, and after adding other helium, find out in accompanying drawing 9 that extra supercritical co is forced to leave from the discharge line that is positioned at the bottom, chamber.The supercritical co thin layer with and in any coating ingredients of carrying adhere to view port, the substrate of its expression through applying.

Accompanying drawing 10 has shown added supercritical co in the pressure chamber, is full of about 2900psig and about 55 degrees centigrade supercritical helium in the pressure chamber, and the pressure that carbonic acid gas adds is slightly high, approximately 2950psig.Notice that supercritical co is fallen the bottom, chamber in the mode of air-flow by helium.The interface between supercritical co and the supercritical helium is represented on the border of the air-flow of described whereabouts, and the coating component that allows to be carried by supercritical co is deposited on the substrate by supercritical co, and in this embodiment, described substrate is the bottom of observation ward.Notice that the carbonic acid gas that is positioned at the bottom can be discharged by the bottom, chamber by the uplift pressure setter mutually, thereby the pressure in the observation ward is kept near constant.

Embodiment 14

Apply with the polymkeric substance in the supercutical fluid

To be coated on solid substrate polymkeric substance or other material dissolves in supercutical fluid 1 (SF1), its concentration makes mixture have proper density and viscosity (DEN1 and VIS1).SF1 can also contain suitable additive, makes material to be coated reach required solubleness, or reaches required density and viscosity.Can prepare second supercutical fluid 2 (SF2) by pure fluid or the pure fluid with additive, thereby the second fluidic density and viscosity are respectively DEN2 and VIS2.Some when the stagnation point separately of SF1 and SF2 is higher than them and is preferably very solution uniformly.

SF1 and SF2 are immiscible under the temperature and pressure of critical temperature that is higher than solution separately and pressure substantially.That is to say that if DEN1＞DEN2, then two fluids show stable interface, two fluids are separated come.Even SF1 and SF2 part each other are solvable, material to be coated or any component of being dissolved among the SF1 therefrom significantly or in large quantities are precipitated out but the solvability of SF2 in SF1 is not enough.In other words, SF2 and its component can not be the contrary solvents of SF2 and component thereof.Similarly, SF1 can not be the contrary solvent of SF2 and component thereof.Under these conditions, SF2 can be suspended in stable device on the SF1, and SF2 can be used for SF2 is cemented out from said vesse.If the viscosity of SF1 and SF2 makes viscous fingering and other wild effect can not cause SF2 to move in SF1 because of gravity, natural convection or other arbitrary surfaces or body force, then it also is preferred.

Need dissociating by high pressure, (free menicus coatingprocess, FMC) object of Tu Fuing can be immersed among the SF1 meniscus coating processes fully, has contained coated polymer or other material among the SF1.Coating procedure SF2 is introduced the top that applies chamber, thereby it begins to replace SF1 at the beginning.Because SF1 is used for wetting and adheres to substrate to be coated, the SF1 film will adhere on the solid.The thickness of film depends on the viscosity (VIS1 and VIS2) of replacement rate (speed of SF2), two solution and the density (DEN1 and DEN2) of two solution.When SF2 cements out SF1,, two solvents can be evaporated away from chamber by reducing the pressure in the chamber.The increase that it may cause coating solution viscosity causes coating to be deposited on the surface.The thickness of film and coating depends on vaporator rate.Can also not reduce pressure or do not evaporate finishing said process, it causes forming the single layer coating material membrane on substrate.

The object that applies by the high pressure spin coating proceeding can be put on the rotating chuck.The solution S F1 of fixed volume can be put in the center of object, can slowly inject SF2 in the chamber, thereby SF1 is not interfered.At this moment, the speed of rotation of chuck makes SF1 solution begin to flow to the edge of object, obtains thin film.Simultaneously, fluid SF2 is because the power that the chuck rotation produces begins outwards mobile.Carry out in the process at it, by the minimizing of cavity indoor pressure, two solvents may start vaporizer.When evaporative process is carried out, the viscosity of SF1 will increase, and produce the liquid or solid coating on substrate.The thickness of film depends on the viscosity of two solution VIS1 and VIS2, and the density of two solution (DEN1 and DEN2).The thickness of film also depends on speed of rotation and vaporator rate.

Embodiment 15

The multilayer deposition

Form technology thick or multilayer film according to following enforcement: 1) Organometallic precursor with Cu is dissolved in the CO that is arranged in the high-pressure chamber of containing substrate ₂In.2) helium is added in the pressurized vessel, thereby replace CO lentamente ₂Fluid mixture forms the organo-metallic film that contains solute on substrate.3) pressure with system reduces 10atm, helps CO ₂Evaporate from surface film, and 4) H of adding 10atm in pressurized vessel ₂Gas is reduced to Cu (0) with metallics from oxidation state Cu (II), obtains metallic membrane.5) make again and be full of CO in the pressure chamber ₂/ organo-metallic mixture is with displacement helium/H ₂Gas, afterwards 6) displacement and 7 of the helium that slows down) H ₂Reduction.Repeat this process for several times.

Above invention has been described, but can not be interpreted as limitation of the present invention.Invention is defined by the following claims, in the equivalent of described claim is also included within.

Claims (22)

1. method that supercutical fluid is cemented out from pressurized vessel, it may further comprise the steps:

The seal-off pressure container is provided, wherein contains supercutical fluid, described supercutical fluid comprises carbonic acid gas;

Add second fluid in described container, wherein the pressure of second fluid interpolation is higher than the pressure of described supercutical fluid, and the second fluidic density is lower than described supercutical fluid;

Between the described supercutical fluid and second fluid, form the interface;

Under the described second fluidic pressure, the described supercutical fluid of near small part cements out from container, keeps interface therebetween simultaneously.

2. the method for claim 1, wherein said interface is visible interface.

3. the method for claim 1, wherein said interface is that optics can detect the interface.

4. the method for claim 1, wherein said supercutical fluid comprises that weight percent is at least 50% carbonic acid gas.

5. the method for claim 1, wherein said second fluid comprises supercutical fluid.

6. the method for claim 1, wherein said second fluid comprises that weight percent is at least 50% helium.

7. the method for claim 1, wherein said second fluid is made of helium substantially.

8. the method for claim 1, wherein said container contains article to be cleaned, and described supercutical fluid further comprises sanitising agent.

9. the method for claim 1, wherein said container contains article to be coated, and described supercutical fluid further comprises the coating component.

10. the method for claim 1, wherein said container is an aggregation container, described supercutical fluid further comprises polymkeric substance.

11. the method for claim 1, wherein said container contains composition, contains at least a compound to be extracted in the said composition, and described supercutical fluid further comprises at least a compound that extracts from described compound.

12. the method that supercutical fluid is cemented out from pressurized vessel may further comprise the steps:

The airtight pressurized vessel that contains supercutical fluid is provided, and described supercutical fluid comprises carbonic acid gas;

Second fluid is added described container, and the pressure that described second fluid adds is higher than the pressure of described supercutical fluid, and the second fluidic density is lower than the density of described supercutical fluid;

Form the interface between the described supercutical fluid and second fluid, wherein said container has length dimension, and along this length dimension, described supercutical fluid is displaced, and the thickness at wherein said interface is no more than about 10% of described length dimension; With

Under the described second fluidic pressure, the described supercutical fluid of near small part cements out from container, the interface between keeping simultaneously.

13. method as claimed in claim 12, wherein said interface are visible interface.

14. being optics, method as claimed in claim 12, wherein said interface can detect the interface.

15. method as claimed in claim 12, wherein said supercutical fluid comprise that weight percent is at least 50% carbonic acid gas.

16. method as claimed in claim 12, wherein said second fluid comprises supercutical fluid.

17. method as claimed in claim 12, wherein said second fluid comprises that weight percent is at least 50% helium.

18. method as claimed in claim 12, wherein said second fluid is made of helium substantially.

19. method as claimed in claim 12, wherein said container contains article to be cleaned, and described supercutical fluid further comprises sanitising agent.

20. method as claimed in claim 12, wherein said container contains article to be coated, and described supercutical fluid further comprises the coating component.

21. method as claimed in claim 12, wherein said container are aggregation container, described supercutical fluid further comprises polymkeric substance.

22. method as claimed in claim 12, wherein said container contains composition, contains at least a compound to be extracted in the said composition, and described supercutical fluid further comprises at least a compound that extracts from described compound.

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