CN1352703A - Methods for wet processing electronic components having copper containing surfaces - Google Patents

Methods for wet processing electronic components having copper containing surfaces Download PDF

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CN1352703A
CN1352703A CN00807855A CN00807855A CN1352703A CN 1352703 A CN1352703 A CN 1352703A CN 00807855 A CN00807855 A CN 00807855A CN 00807855 A CN00807855 A CN 00807855A CN 1352703 A CN1352703 A CN 1352703A
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electronic devices
components
copper
solution
oxidation liquid
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史蒂文·维尔哈维尔贝克
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CFMT Inc
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CFMT Inc
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
    • H01L21/02052—Wet cleaning only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors

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

Abstract

The present invention provides methods of wet processing electronic components having surfaces containing copper. In the methods of the present invention, copper containing electronic components are contacted with a copper oxidizing solution containing an oxidizing agent, and subsequently contacted with an etching solution. The methods of the present invention are particularly useful for cleaning copper containing components.

Description

Wet treatment method with electronic devices and components of copper containing surfaces
The cross reference of related application
The 60/135th, No. 267 U.S. Provisional Patent Application that the application requires right of priority to submit to based on May 21st, 1999, all citation is for reference here.
Technical field
The present invention relates to having the method that the copper containing surfaces electronic devices and components carry out wet processing.Method of the present invention especially can be used to clean this cupric electronic devices and components.
Background technology
In the manufacturing processed of unicircuit, extensively adopt the electronic devices and components such as semiconductor wafer, flat board and other electronic devices and components parent are carried out wet processing.In order to prepare electronic devices and components, need carry out wet processing, for example, treatment step comprises: diffusion, ion implantation, epitaxy, chemical gaseous phase deposition and semispherical silicon particle growth, perhaps their combined treatment process.During wet processing, electronic devices and components contact with a series of treatment soln.For example, treatment soln can be used to carry out: burn into is removed photo-resist, cleaning or flushing electronic devices and components.Please refer to the 4th, 577, No. 650, the 4th, 740, No. 249, the 4th, 738, No. 272, the 4th, 856, No. 544, the 4th, 633, No. 893, the 4th, 778, No. 532, the 4th, 917, No. 123 United States Patent (USP)s and authorize 0233 No. 184 patent of EP of commonly-assigned us, and the Handbook of Semiconductor Wafer Cleaning Technology that writes by people such as Burkman (Wemer Kern edits, by Noyes Publication Parkridge, New Jersey publishes in 1993) in the 111st page to the 151st page Wet Chemical Processes-AqueousCleaning Processes, all quote for reference here.
The system that can be used to carry out wet processing has multiple.For example, in to single container of environment sealing (for example: the Full-Flow that CFMT technology company provides TMSystem), in the single container open to environment or a plurality of opening groove system with a plurality of work nests to atmosphere opening (for example: wet drawing), electronic devices and components are handled.
After the treating processes, usually electronic devices and components are carried out drying.Can utilize the whole bag of tricks that semiconducter substrate is carried out drying, target is to guarantee not produce pollution in the drying treatment process.Drying means comprises and utilizes method of evaporating, the centrifugal force method in the rotation washer-drier, and the dry disk of vaporization method or chemical process, for example, the 4th, 778, No. 532 and the 4th, 911, No. 761 United States Patent (USP)s disclose these method and apparatus.
For the wet treatment method that electronic devices and components are cleaned, having paid many effort seeks and is suitable for mainly by silicon with on a small quantity such as aluminium, silicon oxide, silicon nitride, titanium or such as the titanium-containing compound of titanium nitride or titanium silicide, tungsten or such as Tungstenic compound, the cobalt silicide of tungsten silicide, perhaps the electronic devices and components of other composition manufacturing of their combination carry out the method for clean.
The meaning of " cleaning " is the method for removing pollutent, and pollutent can be particle, and organism such as wax, remaining rumbling compound or grease or other adhere to the oxide skin pollutent on electronic devices and components surface.
For siliceous electronic devices and components, before any sputtering of metals step to the electronic devices and components spraymetal, have been found that in cleaning siliceous electronic devices and components process, electronic devices and components are contacted with " SC1 solution " earlier, make electronic devices and components contact very effective then with " SC2 solution ".In addition,, siliceous electronic devices and components are contacted with the aqueous solution that contains hydrofluoric acid, can improve cleaning performance by with before SC1 solution contacts.
SC1 solution is a kind of aqueous solution that contains hydrogen peroxide and ammonium hydroxide, H 2O: H 2O 2: NH 4The volume density scope of OH is usually between about 5: 1: 1 to about 200: 1: 1.Can think that SC1 soln using surface oxidation mechanism/mechanism of corrosion is cleaned.For example, can think that hydrogen peroxide produces zone of oxidation on the surface of siliceous electronic devices and components, and ammonium hydroxide is from the oxide compound of surface corrosion or removing generation.At last, grow simultaneously on the surface and corrode and produce one deck and arrive steady state during the zone of oxidation of thin (for example: be about 1nm).Oxide growth and corrosion can cause that to stick particle and other pollutant loose.In case, just can remove from the surface of electronic devices and components with sticking particle and other pollutant by loose.
With after the SC1 solution that contains hydrogen peroxide contacts, the SC2 solution that siliceous electronic devices and components contacted contains hydrogen peroxide, hydrochloric acid and water.H in the SC2 solution 2O: H 2O 2: the volume density scope of HCl is usually about 5: 1: 1 to 1000: 0: 1.SC2 is used to remove any precipitated metal thing (for example: iron, aluminium and copper throw out) that produces during electronic devices and components contact SC1 solution.Owing to improved the purity of chemicals in the SC2 solution,, therefore usually omitted the SC2 solution treatment steps so what problem the precipitated metal thing no longer has been now.
If the surface of electronic devices and components is handled to contain the metal such as aluminium, then can reduce the usage quantity of the wet processing aqueous solution in a large number.Can heavy corrosion when for example, being aqueous solution contact such as many metals of aluminium.Therefore, utilize solvent to replace the aqueous solution usually, the containing metal electronic devices and components are carried out wet processing.Yet, utilize solvent unsatisfactory, because such as relating to the environmental issue that solvent is handled and reclaimed, and improved such as flammable security risk.
Recently, electronic devices and components manufacturers begins to utilize the copper substitution of Al in electronic devices and components.Wish to utilize the copper substitution of Al mainly to be because the resistance of copper is low.The advantage of copper also is to have good erosion resistance.Yet, know little about it to how utilizing the aqueous solution that the cupric electronic devices and components are cleaned.
Authorize the 4th of Malladi (hereinafter to be referred as " Malladi "), 714, No. 517 United States Patent (USP)s etc. have disclosed a kind of method of utilizing band volitional check semiconductor device to clean copper part, the Malladi treating processes comprises: copper part is immersed in the etching tank, utilize then such as the organic acid of citric acid, tartrate etc. copper part is handled so that passivation is carried out on the surface.Yet Malladi is not provided at the method for the copper corrosion process being controlled during the cleaning.
The invention provides other method of the electronic devices and components with copper containing surfaces being carried out wet processing.According to the preferential traditional solution that when the silicon electronic devices and components are carried out wet processing, uses that adopts of wet treatment method of the present invention.The method according to this invention is specially adapted to the surperficial eliminating particle shape pollutant from the cupric electronic devices and components, can control the copper corrosion amount on the electronic devices and components simultaneously.
The present invention's general introduction
The invention provides the method for the electronic devices and components with copper containing surfaces being carried out wet processing.The method according to this invention comprises: the surface of electronic devices and components is contacted with copper oxidation liquid; The surface of electronic devices and components contacts with etching solution in second duration of contact subsequently.It is 5 or lower and contain etching reagent and be less than 5, the dissolved oxygen of 000ppb or suspension oxygen that etching solution keeps moisture pH value.The surface of electronic devices and components contacts with etching solution and pollutant can be removed from the surface of electronic devices and components with copper oxidation liquid.Utilize above-mentioned two steps, can be to controlling at removing amount and/or etching extent to the metal during the wet processing of cupric electronic devices and components.
In a preferred embodiment, the invention provides a kind of method that electronic devices and components with copper containing surfaces are carried out wet processing, this method comprises: one or more electronic devices and components are put into a container; The copper oxidation liquid that will contain oxygenant injects in this container; Electronic devices and components are contacted with copper oxidation liquid; And in container, remove copper oxidation liquid.Subsequently, this method also comprises: will contain have the pH value be 5 or hydrofluoric acid lower and that have the solution that is less than 5000ppb dissolved oxygen or suspension oxygen inject in this container; Electronic devices and components are contacted with the solution that contains hydrofluoric acid; And in container, remove the solution that contains hydrofluoric acid, wherein the surface of electronic devices and components contacts with the solution that contains hydrofluoric acid and pollutant can be removed from the surface of electronic devices and components with copper oxidation liquid.
Brief description of drawings
Fig. 1 illustrates the histogram according to comparative example 1 to 4 and 5 pairs of processed electronic devices and components clearance of particles per-cents with copper containing surfaces of example.
Detailed description of the present invention
The invention provides the method for the electronic devices and components with copper containing surfaces being carried out wet processing.For example, the method according to this invention is specially adapted to clean electronic devices and components, (for example: particle), organic compound, rumbling compound, grease or oxide skin is attached on the lip-deep pollutant of electronic devices and components with removing.
The method according to this invention can be used for requirement any wet process that the electronic devices and components with copper containing surfaces clean is handled." wet processing " means that electronic devices and components contact in the mode that requires with one or more liquid (hereinafter to be referred as " treatment solution ") electronic devices and components are handled.For example, require electronic devices and components are handled with surface cleaning, corrosion or removing photo-resist from electronic devices and components.Also require between these treatment steps, electronic devices and components to be washed.Wet processing also comprises step: electronic devices and components with contact such as gas, steam or with other fluid of steam or gas blended liquid or their combination.As used herein, term " fluid " comprises liquid, gas, gas phase liquid or their combination.Usually, carry out this wet processing process to utilize the sub-components and parts of copper power backup, treatment step comprises dielectric chemical gaseous phase deposition, plasma etching or reactance ion etching, perhaps their combination.
The treatment solution that the wet processing process is used has multiple.Usually, the most frequently used treatment solution that wet processing process is used has: chemical pretreatment solution or chemical treatment fluid and washing fluid or flush fluid.As used herein, " chemical pretreatment solution " or " chemical treatment fluid " is to react to change any liquid or the fluid of its surface composition with the surface of electronic devices and components in some way.For example, chemical pretreatment solution or chemical treatment fluid have to remove and are attached on or are bonded in the lip-deep pollutant of electronic devices and components () activity for example: particulate matter, metallic substance, photo-resist or organic substance with chemical process, perhaps have the corrosive activity is carried out on the surface of electronic devices and components, perhaps have activity in the surface growth zone of oxidation of electronic devices and components.The chemical treatment fluid of Shi Yonging contains one or more chemical reaction agents and realizes the surface treatment that requires in the present invention.According to the weight of chemical pretreatment solution, the concentration of these chemical active agents is preferentially greater than 1000ppm and more preferably greater than 10,000ppm.Chemical pretreatment solution can also contain one or more chemical reaction agents of 100%.Below will the example of the chemical pretreatment solution that uses in the inventive method be described in more detail.
Just as used in this, " washing fluid " or " flush fluid " refers to be used to remove DI water or some other liquid or fluid, chemical reaction by-product and/or the chemical treatment step release or loose particle or other pollutant of electronic devices and components and/or the residual chemical pretreatment solution of container.Washing fluid or flush fluid can also prevent that the particle or the pollutant that loosen are deposited on electronic devices and components or the container again.Below will be in more detail the example of the washing fluid that uses be in the methods of the invention described.
As used herein, " chemical treatment step " or " wet processing step " instigates each electronic devices and components to contact chemical treatment fluid or treat fluid respectively.
" electronic devices and components with copper containing surfaces " refer to that preferentially have an appointment at least 0.1% total surface area of electronic devices and components is covered by copper.The thickness of copper preferentially is at least about 0.1 micron and more preferably be about 0.5 micron to about 5 microns on the surface.Therefore, electronic devices and components are covered by copper at least in part.Under the part coverage condition, can the conventional figure overlay electronic of copper components and parts.Example with electronic devices and components of copper containing surfaces comprises: be used to make electronic devices and components (for example: electronic devices and components parent unicircuit), for example: semiconductor wafer, flat board and other parts; CD ROM disk; Hard disk; Or multi-chip module.
In wet treatment method according to the present invention, the electronic devices and components with copper containing surfaces contact with copper oxidation liquid, then with contain the etching solution that is less than 5000ppb dissolved oxygen and suspension oxygen and contact.Limit although have no idea in theory, (for example: can believe copper oxidation liquid from Cu to copper containing surfaces 0+To Cu 2+) carry out oxidation to form the combination of thin copper oxide (for example :) or different cupric oxide approximately less than 1.0nm.Believe that etching solution can controlled ratio corrode this copper oxide.
The copper oxidation liquid of electronic devices and components contact is can be to being positioned at any liquid that the lip-deep copper of electronic devices and components carries out oxidation.Copper oxidation liquid also should preferentially not comprise the solvent that can corrode copper.Copper oxidation liquid preferentially keeps the pH value to be about 7 or bigger at least, more preferably keeps the pH value to be about 8 to avoid corroding copper at least.In order to make copper oxidation liquid remain on this pH value, copper oxidation liquid preferentially can not contain its quantity can make the pH value be lower than 7 acid (for example: HCl, HF, nitric acid).
For example, suitable copper oxidation liquid comprises the solution that contains such as the oxygenant of hydrogen peroxide, ozone, ferric cyanide or their combination.Oxygenant preferentially is a hydrogen peroxide.These oxygenant optimum solvations or be suspended in any compatible liquid, for example: water, alkaline aqueous solution or such as the non-oxide organic solvent of hydrofluoric ether or their combination.Oxygenant can also be such solution, and promptly it needs not to be oxygenant is dissolved into solution in the solution.Preferentially with oxygenant dissolving or be dispersed in the water.
The concentration of oxygenant in copper oxidation liquid depends on selected oxygenant.Usually, the oxygenant that copper oxidation liquid contains with respect to overall solution volume preferentially between about 0.1 volume percent to 100 volume percent, more preferably in about 10 volume percent to percent of about 70 volume.For hydrogen peroxide, with respect to the cumulative volume of copper oxidation liquid, the concentration of the hydrogen peroxide in the copper oxidation liquid preferentially in about 0.1 volume percent between about 10 volume percent, more preferably in about 0.2 volume percent between about 1.0 volume percent.For ozone, the concentration of the ozone in the copper oxidation liquid preferentially at about 10ppm between about 50ppm, more preferably at about 10ppm extremely between about 40ppm.
In a preferred embodiment of the invention, copper oxidation liquid is SC1 solution, in SC1 solution, and according to volume, H 2O: H 2O 2: NH 4Preferentially between about 5: 1: 1 to 200: 1: 1, more preferably between about 50: 1: 1 to 150: 1: 1, override is between about 90: 1: 1 to about 110: 1: 1 for the ratio of OH.
In order to improve the wet processing process, except oxygenant, copper oxidation liquid can also contain other promoting agent.For example, can also contain tensio-active agent, inhibitor or add any other the conventional promoting agent that is used to clean in the wet processing liquid usually in the copper oxidation liquid.The quantity of adding these promoting agents in the copper oxidation liquid to preferentially is lower than 5.0 volume percent, and more preferably in about 0.01 volume percent between about 1.0 volume percent.
If require to contain tensio-active agent at copper oxidation liquid, then with respect to the cumulative volume of copper oxidation liquid, the quantity of the tensio-active agent in the copper oxidation liquid preferentially is lower than 1 volume percent, and more preferably is lower than 0.5 volume percent.For example, the tensio-active agent that can adopt comprises: anion surfactant, nonionogenic tenside, cats product and amphoterics, for example, at Kirk-Othber Concise Encyclopedia of ChemicalTechnology, John Wiley ﹠amp; Sons publishes, NY, 1985,1142-1144 page or leaf and McCutcheon ' s Detergents and Emulsifiers, 1981 North American Edition, MC Publishing Company, Glen Rock, N.J.1981 discloses them, all quotes for reference here.The preferred surfactant that the present invention uses comprises basic surface promoting agent and VALTRON Tensio-active agent, for example: Valtech Corporation of Pughtown, the VALTRON that PA provides SP2275 and SP2220, the NCW601A that Wako Company provides.
If require to contain inhibitor at copper oxidation liquid, then with respect to the gross weight of copper oxidation liquid, the quantity of adding the inhibitor in the copper oxidation liquid at about 0.1 weight percent between about 1.0 weight percents.The inhibitor example that for example, can adopt comprises benzotriazole.
Electronic devices and components preferentially contact copper oxidation liquid in certain duration of contact, are enough to guarantee form on whole wafer even copper oxide, can be because the dissolution process of copper oxidising process and cupric oxide produces the particle of an a little removing.As used herein " duration of contact " refer to that electronic devices and components are exposed to the time in the treatment solution.For example, comprise duration of contact: during during treatment solution is injected container or with electronic devices and components, immersing treatment solution, the time that electronic devices and components expose treatment solution; Electronic devices and components are immersed in the time in the treatment solution; And when in container, removing treatment solution or electronic devices and components are taken out in container, the time that electronic devices and components expose treatment solution.Actual selection depends on these factors during duration of contact, i.e. oxygenant, the concentration of oxygenant and the temperature of copper oxidation liquid of adding in the copper oxidation liquid.Yet, preferentially be at least duration of contact 30 seconds and be no more than 10 minutes.
Period of contact, the temperature of copper oxidation liquid is such, promptly can avoid the oxygenant in the copper oxidation liquid to decompose.The temperature prioritised of copper oxidation liquid is lower than 60 ℃, and more preferably between about 20 ℃ to about 40 ℃.
Can utilize any known wet processing technology that electronic devices and components are contacted with copper oxidation liquid, this mainly depends on the wet processing system of selection.For example, can immerse one or more electronic devices and components in the groove that contain copper oxidation liquid and spur.On the other hand, electronic devices and components can be placed in the container, then copper oxidation liquid be passed across container and fill with this container to realize contact.Can be under dynamic condition (for example: the container that solution is passed across put into electronic devices and components), under static conditions (for example: electronic devices and components are immersed in this solution), or (for example: solution passes across certain time cycle of container, makes electronic devices and components be immersed in another time cycle in the solution then) realizes contact under the combined situation of both of these case.Below will be in more detail the suitable wet processing system of the sub-components and parts of contact electricity be described.
Electronic devices and components make electronic devices and components contact with etching solution with after copper oxidation liquid contacts.Etching solution is any solution that contains etching reagent that can corrosion oxidation copper.Etching solution (for example: acid that can cupric oxide), thereby keep the pH value of etching solution to be about 5 or lower preferentially contains one or more non-oxidizing acids.The quantity of the etching reagent in the etching solution preferentially is such amount, promptly keeping the pH value of etching solution to be about 5 or lower, more preferably is such amount, promptly keeps the pH value of etching solution to be about 4 or lower, override is such amount, promptly keeps the pH value of etching solution to be about 3 or lower.The example of the anaerobic voltinism acid that the present invention uses comprises: hydrochloric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, such as acetate, citric acid or tartaric organic acid, perhaps their combination.The solution of dissolving or dispersion etching reagent preferentially is water, but also can be organic solvent, for example: ethylene glycol, propylene carbonate, methyl alcohol, or their combination.
In a preferred embodiment according to the present invention, etching solution is the solution that contains hydrofluoric acid.The solution that contains hydrofluoric acid can contain hydrofluoric acid, buffered hydrofluoric acid, Neutral ammonium fluoride or can produce any other material of hydrofluoric acid in solution, or their combination.Hydrofluoric acid in the hydrofluoric acid solution preferentially is such volume ratio, that is: H 2O: HF is about 5: 1 to about 1000: 1, more preferably is such volume ratio, that is: H 2O: HF is about 100: 1 to about 800: 1, and override is such volume ratio, that is: H 2O: HF is about 200: 1 to about 600: 1.
Have been found that according to the present invention preferably to keep etching solution like this, promptly help to produce slow controlled corrosion speed (for example: the speed of corrosion copper is lower than about per minute 10nm, and more preferably is lower than about per minute 1nm).Preferably with controlled corrosion speed corrosion copper at a slow speed, therefore clean the minimum number of the copper that electronic devices and components need remove.The factor that influences copper corrosion speed comprises: the pH value of the concentration of etching reagent, etching solution, dissolved oxygen or the quantity of suspension oxygen or other oxygenant and the temperature of etching solution in the etching solution in the etching solution.For example,, improve the temperature of pH value and reduction solution, can reduce the corrosion speed of copper by reducing the concentration of etching reagent, dissolved oxygen or suspension oxygen and other copper oxidant in the etching solution.In influencing the above-mentioned factor of copper corrosion speed, the quantity of dissolved oxygen or suspension oxygen or other copper oxidant perhaps is the main factor that influences copper corrosion speed in the etching solution.This is because the oxygen that reacts with copper or other copper oxidant form cupric oxide, and with this pH value of etching solution corrosion oxidation copper easily.
With respect to the gross weight of etching solution, the dissolved oxygen in the etching solution or the concentration of suspension oxygen preferentially keep below 5000ppb, more preferably keep below 100ppb, and override ground keeps low as far as possible.In addition, and other copper oxidant (for example: the copper oxidant that in copper oxidation liquid, uses, for example: H 2O 2) concentration preferentially keep below 5000ppb, more preferably keep below 100ppb, and override ground keeps low as far as possible.As mentioned above, thus the corrosion speed that dissolved oxygen or suspension oxygen or other copper oxidant keep low like this concentration can reduce copper corrosion is controlled.
As mentioned above, the pH value of etching solution preferential maintenance, be approximately equal to or less than 5, more preferably is approximately equal to or less than 4, and override be approximately equal to or less than 3.Except etching reagent, can also add buffer reagent to etching solution, thereby help to make the pH value to remain in the above-mentioned scope.The quantity of the buffer reagent that adds preferentially is enough to make pH to remain in the above-mentioned preferable range.According to the gross weight of etching solution, the quantity of the buffer reagent in the etching solution preferentially at about 0.01 weight percent between about 5.0 weight percents, and more preferably at about 0.05 weight percent between about 0.5 weight percent.
In a preferred embodiment according to the present invention, etching solution contains hydrofluoric acid and hydrochloric acid.Select for use hydrochloric acid to be because, it helps to reduce pH value and guarantees surperficial Z-current potential for just, thus particle repels mutually.For 1 volume part of hydrofluoric acid, the H of the hydrochloric acid in the etching solution 2Preferentially between about 50: 1 to about 1000: 1, more preferably between about 500: 1 to about 500: 10, and override ground is between about 500: 3 to about 500: 7 for the volume ratio of O: HCl.
Except etching reagent, can also contain other additive in the etching solution to improve the wet processing process.For example, can contain tensio-active agent, inhibitor or add any conventional additive in the wet processing liquid that is used to clean usually in the etching solution.The quantity of these additives in the etching solution is preferentially identical with above-mentioned quantity to the record of copper oxidation liquid.
Preferentially be enough to remove the oxide compound that during electronic devices and components contact copper oxidation liquid, produces the duration of contact of the preferential contact etch liquid of electronic devices and components.Depend on these factors when selecting duration of contact: etching reagent and the concentration of dissolved oxygen or suspension oxygen, the pH value of etching solution and the type of temperature and employed etching reagent in the etching solution.Yet, preferentially be at least duration of contact 30 seconds and be no more than 2 minutes.
The temperature of period of contact etching solution is high like this, promptly can control corrosion process, and realize slow corrosion speed (for example: the about 10nm of per minute corrosion or still less).The temperature prioritised of etching solution is lower than 50 ℃, and more preferably between about 20 ℃ to about 30 ℃.
Utilization is used to make the above-mentioned wet processing technology of electronic devices and components contact copper oxidation liquid can make electronic devices and components contact etch liquid.For example, can immerse one or more electronic devices and components in the groove that contain etching solution and spur it.On the other hand, electronic devices and components can be placed in the container, and make etching solution pass across container to fill with container to realize contact.In addition, can under current intelligence, under quiescent conditions or under the combined situation of both of these case, realize contact.
In a preferred embodiment according to the present invention, be reduced in the minimum process in the concentration of making great efforts dissolved oxygen or suspension oxygen, this moment, electronic devices and components and etching solution and source of oxygen were isolated under (for example: with air insulated) environment, made electronic devices and components contact etch liquid.In the system airtight (below do be described in more detail), perhaps in by rare gas element or the system that rare gas surrounded, realize this isolation processes such as argon gas such as nitrogen to environment.
In addition, because utilizing after etching solution handles, copper is easily by oxidation again, so with after etching solution contacts, any fluid of contact electronic devices and components (no matter carry out chemical treatment or wash) (for example: the copper oxidant that uses) should contain minimal amounts of dissolved oxygen or suspension oxygen or copper oxidant in copper oxidation liquid.According to the fluidic gross weight, dissolved oxygen that these fluids contain or suspension oxygen preferentially are less than 500ppb approximately, more preferably are less than 50ppb, and override is few as much as possible.Other copper oxidant that this fluid contains preferentially is less than 500ppb, more preferably is less than 50ppb, and override does not contain other copper oxidant.Owing to contain minimal amounts of dissolved oxygen or suspension oxygen and a little copper oxygenant at these fluids, so utilizing after etching solution handles, the surface of electronic devices and components is obviously reduced by the risk of oxidation again.
Except making electronic devices and components contact copper oxidation liquid and etching solution, electronic devices and components also contact the result of several other chemical treatment fluids (for example: gas, liquid, steam or their arbitrary combination) to realize requiring.For example, electronic devices and components can contact the chemical treatment fluid that is used to corrode (hereinafter to be referred as corrosive fluids), growth zone of oxidation (hereinafter to be referred as the oxidation growth fluid), elimination photo-resist (removing fluid hereinafter to be referred as photo-resist), improvement cleaning process (hereinafter to be referred as washing fluid) or their combination.In wet treatment method, can utilize flush fluid at any time electronic devices and components to be washed.Chemical treatment fluid and flush fluid preferentially are liquid.
Those of skill in the art in the present technique field recognize that operable treat fluid has multiple during wet processing.At " Chemical Etching " by Werner Kern et al., in ThinFilm Processes, edited by John L. Vosser et al., published by AcademicPress, NY 1978, examples of gases to operable treat fluid during wet processing in the pages 401-496 discloses, and all quotes for reference at this.
Electronic devices and components also contact flush fluid except the contact chemical treatment fluid.As mentioned above, flush fluid is used to clean residual chemical treatment fluid, chemical reaction by-product and/or the chemical treatment step release or loose particle or other pollutant of electronic devices and components and/or container.Flush fluid can also be used to prevent that the particle or the pollutant that loosen are deposited to electronic devices and components or container again.
Can select realizing the effective any flush fluid of above-mentioned effect.In selecting the process of flush fluid, the factor that should consider comprises: the surface properties of electronic devices and components to be washed, be dissolved in the character of the pollutant in the chemical treatment fluid and the character of chemical treatment fluid to be washed.In addition, the flush fluid of being advised should with the material compatible (chemical reaction does not promptly take place) of the structure of contacting with fluid.For example, operable flush fluid comprises: the mixture of water, organic solvent, organic solvent or their combination.Preferred organic solvent is the anhydrous organic solvent of following explanation, for example: C 1To C 10Alcohol, and be preferably C 1To C 6Alcohol.Flush fluid preferentially is liquid and contains a small amount of oxygen (for example: preferentially be less than 5000ppb, more preferably be less than 500ppb, and override be less than 100ppb).In most preferred embodiment, flush fluid is a deionized water.
Flush fluid can also be selected to contain a small amount of chemical active agent and improve developing result.For example, in flush fluid, can use tensio-active agent and/or inhibitor.The concentration of these additives is very low in the flush fluid.For example, with respect to the gross weight of flush fluid, calculate by weight, this concentration preferentially is no more than 1000ppm, more preferably is no more than 100ppm.
Those of skill in the art in the present technique field understand, wet processing result as requested selects chemical treatment fluid and chemical treatment fluid sequence.For example, before or after a step or multistep chemical treatment step, electronic devices and components contact with flush fluid.On the other hand, it is another chemical treatment step after a chemical treatment step that some other wet treatment method requires, and need not to make between two chemical treatment steps electronic devices and components contact flush fluid (promptly not carrying out the flushing at intermittence).For example, in the 08/684th, No. 543 U.S. Patent application of submitting on July 19th, 1996, this continuous wet processing process of not carrying out intermittently flushing is disclosed, all quote for reference at this.
In addition, for example, in according to one embodiment of present invention, before electronic devices and components contact copper oxidation liquid, preferably make the surface of the flush fluid of electronic devices and components contact such as water earlier with moistening electronic devices and components.In this wet processing step, flush fluid temperature prioritised about between 20 ℃ to 60 ℃ and more effectively between 20 ℃ to 40 ℃.Also require preferentially tensio-active agent to be added in this flush fluid with the above-mentioned consumption that is used for copper oxidation liquid.
In according to another embodiment of the invention, after making electronic devices and components contacts copper oxidation liquid, but at described electronic devices and components with before etching solution contacts, make electronic devices and components contact flush fluid.Flush fluid preferentially is that temperature is at about 20 ℃ to 60 ℃ deionized water.Such just as described in this, flush fluid also preferentially has a small amount of oxygen.The particle or other pollutant that discharge when being enough to the duration of contact that electronic devices and components preferentially contact flush fluid remove residual chemicals, chemical reaction by-product and/or contact copper oxidation liquid.Yet, can also after make electronic devices and components contact copper oxidation liquid, directly make electronic devices and components contact etch liquid, and need not between these two chemical treatment steps, to insert rinse step.
After making electronic devices and components contact etch liquid, electronic devices and components preferentially contact the deionized water rinsing fluid of temperature between about 20 ℃ to about 60 ℃ in the present invention.Preferentially carry out release particles or other pollutant of this rinse step to remove residual chemicals, chemical reaction by-product and after electronic devices and components contact etch liquid, to remain in container or electronic devices and components surface.The flush fluid that this step is used preferentially contains minimal amounts of dissolved oxygen or suspension oxygen (as mentioned above) is reduced to minimum with the risk that copper is oxidized again.
As mentioned above, require in the treatment solution that the present invention uses, to add tensio-active agent.Preferentially (comprise copper oxidation liquid, etching solution or washing fluid) in treatment solution and comprise one or more tensio-active agents, electronic devices and components are exposed to liquid-vapo(u)r interface.For example, during the pulling, electronic devices and components are exposed to liquid-vapo(u)r interface in electronic devices and components are immersed in treatment solution or in treatment solution.During treatment solution was injected container, electronic devices and components also were exposed to liquid-vapo(u)r interface.Have been found that tensio-active agent helps to reduce solids precipitation in many ways or stick.For example, can be in the liquid at liquid-vapo(u)r interface place (being liquid level) enrichment tensio-active agent, thereby the particle at liquid level place is discharged.Reduce to the minimum possibility that can reduce the particle contact electronic devices and components at liquid level place by particle with the liquid level place.In addition, tensio-active agent also provides the electrochemistry potential barrier to avoid occurring particle again to stick.For example, tensio-active agent will concentrate on liquid level, thereby solid surface or other surface help to reduce its total energy, comprise particle and electronic devices and components.Because electronic devices and components and particle are all surrounded by tensio-active agent in each side, so the electric charge of the total charge of particle/tensio-active agent and semiconducter substrate/tensio-active agent and tensio-active agent is approaching.Because particle and semiconducter substrate and tensio-active agent have with a kind of electric charge, do not attract each other the opposite charges so they can not resemble, thereby avoided during immersing, sticking other particle.According to wet processing step option table surface-active agent.For example, the pH value of tensio-active agent should (for example: preferentially use the basic surface promoting agent in copper oxidation liquid, and acid, non-oxidizable tensio-active agent are used for etching solution) pH value be compatible with chemical pretreatment solution.
In most preferred embodiment according to the present invention, electronic devices and components contacted as SC1 liquid, temperature about 25 ℃ about 3 minutes of the copper oxidation liquid or the duration of contact of shorter time.According to the volume of copper oxidation liquid, it is respectively 100: 1: 1 water, ammonium hydroxide and hydrogen peroxide that this SC1 liquid preferentially contains volume ratio, and the tensio-active agent that by volume is less than 1%.Then, preferentially use about 25 ℃ about 5 minutes duration of contact of deionized water rinsing electronic devices and components.After the flushing, electronic devices and components preferentially contact the solution that temperature is about 25 ℃ hydrofluoric acid containing and are less than 2 minutes duration of contact approximately.The solution of hydrofluoric acid containing preferentially contains water, hydrofluoric acid and the hydrochloric acid that volume ratio is about 500: 1: 5 respectively.Utilize temperature to be about 25 ℃ about 5 minutes of deionized water rinsing electronic devices and components again, utilize temperature to be about 25 ℃ dry about 1 minute of Virahol then.
In according to a further advantageous embodiment of the invention, except copper oxidation liquid contains the water and hydrogen peroxide that volume ratio is about 100: 1 respectively, realize this wet processing process according to above-mentioned most preferred embodiment.Copper oxidation liquid also preferentially contains the tensio-active agent of above-mentioned quantity, but does not contain ammonium hydroxide.
Therefore, have multiple according to the inventive method to the mode that electronic devices and components carry out wet processing.For example, during electronic devices and components contacts treatment solution, can utilize acoustic energy (for example in loud energy range, for example: at about 500kHz extremely between about 1MHz) to carry out wet processing and improve cleaning performance.In addition, method for example also is included in the 5th, 383, the 08/684th of No. 484 United States Patent (USP)s, submission on July 19th, 1999,543,09/209 of submission on December 10th, 1998, submit in No. 101 and on February 19th, 1999 09/253, the 60/087th of No. 157 U.S. Patent applications and submission on June 2nd, 1998, the 60/111st of No. 758 U.S. Provisional Patent Application and submission on December 8th, 1998, the wet processing technology that discloses in No. 350 U.S. Provisional Patent Application is all quoted for reference at this.
In a word, (for example, comprising: realize the inventive method in the multiple-grooved system (for example: wet drawing), single containment system (to environment open or to the environment sealing)) at any wet processing apparatus.Please refer to for example Chapter 1:Overview and Evolution of SemiconductorWafer Contamination and Cleaning Technology by Werner Kern andChapter 3:Aqueous Cleaning Processes by Con C.Burkman, Donald Deal, Donald C.Grant, and Charlie A.Peterson in Handbook of SemiconductorWafer Cleaning Technology (edited by Werner Kern, Published by NoyesPublication Parkridge, New Jersey 1993), and Wet Etch Cleaning byHiroyuki Horiki and Takao Nakazawa in Ultraclean Technology Handbook, Volume 1, (edited by Tadahiro Ohmi published by Marcel Dekker) all quotes for reference at this.
In a preferred embodiment according to the present invention, electronic devices and components are packed in single containment system.The single containment system of preferential employing, for example the 4th, 778, No. 532, the 4th, 917, No. 123, the 4th, 911, No. 761, the 4th, 795, No. 497, the 4th, 899, No. 767, the 4th, 984, No. 597, the 4th, 633, No. 893, the 4th, 917, No. 123, the 4th, 738, No. 272, the 4th, 577, No. 650, the 5th, 571, No. 337 and the 5th, 569, single containment system of No. 330 United States Patent (USP) disclosures is all quoted for reference at this.Preferred commercially available single containment system is Full-Flow TMContainer, for example Full-Flow of CFMTechnologies manufacturing TMContainer, the FL820L that Poseidon that Steag makes and Dainippon Screen make.Preferred these systems be because they oxygen quantity is controlled easier.
In most preferred embodiment according to the present invention, in can sealing the wet processing system, electronic devices and components are carried out wet processing with the time of minimizing electronic devices and components to oxygen exposure, thereby be reduced to the surperficial quilt of the electronic devices and components that the are cleaned risk of oxidation again minimum.Can seal the wet processing system and preferentially receive different treatment liquid with various orders.The preferred method that treatment solution is input in the container is that a kind of liquid is directly replaced by another kind of liquid.The Full-Flow that CFM Technologies company makes TMThe wet processing system is an example by direct replacement input liquid.
Can seal in the preferred method of single container adopting, one or more electronic devices and components be put into processing vessel and environment is sealed according to the present invention.Before making electronic devices and components contact copper oxidation liquid, the treat fluid that can select to make electronic devices and components contact flush fluid or any other requirement is earlier carried out pre-treatment to electronic devices and components.Thereby fill with the residual fluid of airborne all gases of processing vessel or previous steps and be sealed in and considerably lessly in the container realize this contact process by this fluid being passed across processing vessel.Can make fluid continue to pass across container disposable and fill with container, soak the time that requires thereby perhaps stop the fluid flow electronic devices and components.After this pre-treatment step,, then copper oxidation liquid is injected container so that electronic devices and components contact copper oxidation liquid with the fluid amount discharge container that is currently located in the container.After the contact copper oxidation liquid, can select electronic devices and components are washed, contact with etching solution then such as the solution of hydrofluoric acid containing.After the contact etch liquid, can select electronic devices and components are washed or handle with any alternate manner that requires.
In can sealing single container, utilize another kind of treat fluid to remove a kind of treat fluid and can realize in many ways.For example, can be with the treat fluid full scale clearance in the processing vessel (promptly discharge), then, during ejection or after discharging, will descend a kind of treat fluid to inject in the container.In another embodiment, the treat fluid in the container can be by down a kind of treat fluid replacement, and as the 4th, 779, No. 532 United States Patent (USP) is disclosed.
After utilizing chemical treatment fluid and flush fluid to carry out wet processing, preferentially electronic devices and components are carried out drying." drying " or " carrying out drying " refers to preferentially basically the drop on the electronic devices and components be removed.By during drying removing drop, when drop was evaporated, the impurity in the drop just can not be retained on the surface of semiconducter substrate.These undesirable impurity can (for example: watermark) or other resistates stay trace at semiconductor substrate surface.Yet, it is also contemplated that the drying process touch upon, utilize drying fluid stream or utilize known other method of those of skill in the art in the present technique field to remove treat fluid or flush fluid.
Can adopt any drying means or dehumidification system.For example, suitably drying means comprises: method of evaporating, the centrifugal force drying in the rotation washer-drier, steam drying or chemical seasoning or their combination.
Preferred drying means adopts drying fluid stream directly to replace the treatment solution (hereinafter to be referred as " directly replacing drying process ") of the last contact of electronic devices and components before carrying out drying.For example, the 4th, 778, No. 532, the 4th, 795, No. 497, the 4th, 911, No. 761, the 4th, 984, No. 597, the 5th, 571, No. 337 and the 5th, 569, in No. 330 United States Patent (USP)s direct replacement exsiccant proper method and system are disclosed.Other that can adopt directly replaced siccative the Marangoni type siccative that is provided by the manufacturers such as Steag, Dainippon and YieldUp is provided.Override adopts the 4th, 911, and the system and method for No. 761 United States Patent (USP) disclosures carries out drying to electronic devices and components.
Drying fluid flows priority section or all is made of the dry liquid of vaporization.For example, drying fluid stream can be the steam of ultrahigh-temperature and the mixture of mixtures of liquids, saturation steam or steam and uncondensable gas.
Select to constitute the dry liquid of drying fluid stream preferential with container in the last treatment solution that uses compatible and and not with electronic devices and components surface generation chemical reaction.Dry liquid also preferentially has the boiling point of reduction, and this helps to carry out drying.For example, preferentially in being lower than the organic compound of 140 degree Celsius, its boiling point under barometric point selects.The example of the dry liquid that can adopt comprises: steam, such as methyl alcohol, ethanol, 1-propyl alcohol, Virahol, n-butanols, sec-butyl alcohol, the trimethyl carbinol or tertiary amyl alcohol, acetone, acetonitrile, Perfluoroacetone, Nitromethane 99Min., acetic acid, propionic acid, ethylene glycol monomethyl ether, C2H4F2 C2H4F2, ethyl acetate, isopropyl acetate, 1,1,2-three chloro-1,2,2-Halothane, 1, the alcohol of 2-ethylene dichloride, trichloroethane, perfluor-2-butyl tetrahydrofuran, perfluor 1,4-dimethyl cyclohexane or their combination.Dry liquid is preferably C 1To C 6Alcohol, for example methyl alcohol, ethanol, 1-propyl alcohol, Virahol, n-butanols, sec-butyl alcohol, the trimethyl carbinol, tertiary amyl alcohol, amylalcohol, hexanol or their combination.
In a preferred embodiment according to the present invention, the dry liquid of selection is compatible with the treatment solution that carries out existing at that time in the processing vessel before dry and form the minimum azeotrope azeotropic mixture with treatment solution.Because water is the solvent of most convenient, the most frequently used chemical treatment fluid or flush fluid, so dry liquid is especially preferential and water forms the minimum azeotrope azeotropic mixture.
In order to reduce electronic devices and components, preferentially in single container, carry out wet processing and drying, and need not in container, to take out electronic devices and components by oxidation and the risk that produces pollutant again.For example, the suitable wet processing system that realizes wet processing process and drying process in single container comprises: the Full Flow that CFM Technologies makes TMThe FL820L that Poseidon that wet processing system, Steag make and Dainippon Sereen make.
After the drying process, take out electronic devices and components in the drying receptacle and further handle in the mode that requires.
The electronic devices and components that utilize the inventive method to obtain can roughly be eliminated the particle contaminant thing." roughly eliminate " and refer to that semiconducter substrate is at every cm 2The particle that contains preferentially is less than 0.05, and more preferably is less than 0.016.The particulate diameter that remains on the semiconducter substrate preferentially is equal to or less than 0.3 μ m, and more preferably less than 0.12 μ m, as KLA Tencor SPI particulate scan device measuring.Preferentially utilize the particle of the inventive method removing greater than 0.3 μ m.
The method according to this invention is specially adapted to remove non-metallic particle from the surface of electronic devices and components.For example, non-metallic particle comprises: SiO 2, Si 3N 4, organic substance or their combination.Example
The method according to this invention is used for the semiconductor wafer with copper containing surfaces is carried out wet processing.In all examples, the cupric disk is by silicon and silicon oxide is made and the copper layer of whole plating 400nm.After carrying out wet processing, utilize and the particle on the disk is analyzed available from the Tencor SPI scanner of KLA Tencor.Comparative example 1 to 3
The Full Flow that makes in CFM Technologies company TMFill the cupric disk in the 8100 wet processing systems.With the speed of 12 gallons of per minutes, use 120 seconds injection length altogether, with in the table 1 chemical pretreatment solution shown in the comparative example 1 is filled container.The temperature of chemical pretreatment solution is 30 ℃.After container is filled with, again disk is immersed in the chemical pretreatment solution 120 seconds.During disk contact chemical pretreatment solution, disk exposes about 1 minute to the high acoustic energy of about 650KHz frequency.
Then, directly with temperature be 30 ℃, the deionized water rinsing liquid that contains 100ppb oxygen at least replaces chemical pretreatment solution.With the speed of 24g/m, with 60 seconds times, deionized water is introduced in the processing vessel, the speed with 12g/m circulated 60 seconds then.Repeat the resistance that the deionized water of this working cycle in processing vessel has 5 megohms.After reaching this resistance, utilize extra time, make to continue in the round-robin deionized water inflow processing vessel.Total flush time is greater than 3 minutes and between flush period, and disk is exposed to high acoustic energy.
After the flushing, utilize Virahol gas drying fluid stream that disk is carried out drying.Under the pressure of 1.5psig,,, make Virahol gas pass across processing vessel with 9 fens clock times at 45 ℃.
Can utilize 3 bouts altogether in the above described manner, other two batches of disks are handled.
Then, utilize 6mm edge exclusion (edge exclusion), on 3 disks in every batch of disk, the size analyze at 18 microns to 400 microns particle contaminant thing.Average result is shown in table 2.
Each comparative chemistry treatment solution shown in the his-and-hers watches 1 repeats said process.For each comparative example, except comparative example 3, treating processes is same as described above, with the speed of 18g/m chemical pretreatment solution is injected in the container, then, after injection is finished, is not having under the high acoustic energy situation, and electronic devices and components were soaked 1 minute.In addition, except the temperature of washing fluid is that 45 ℃ and total flush time are about 2 minutes,, the electronic devices and components in the comparative example 3 are washed according to the process that comparative example 1 adopts.
Table 1: the composition of chemical pretreatment solution
Example The composition of chemical pretreatment solution (share by volume)
H 2O ?H 2O 2 ?NH 4OH ?HF ?HCl ?Surf 1
Example 1 (only utilizing copper oxidation liquid to handle) 100 ????1.3 ??2.2 ?0.0 ?0.0 ?0.6
Example 2 2(only utilize the NH that does not contain oxygenant or HF 4OH handles) 100 ????0.0 ??2.2 ?0.0 ?0.0 ?0.6
Example 3 2(only utilizing the solution that contains HF to handle) 100 ????0.0 ??0.0 ?0.2 ?1.0 ?0.0
1Tensio-active agent, the VALTRON that Valtech company provides SP2200.
2Contained oxygen is less than 100ppb comparative example 4-and utilizes the NH that does not contain oxygenant earlier 4OH handles, and utilizes then to contain HF solution and handle
Pile the cupric disk in the Full Flow container that comparative example 1 to 3 uses.First chemical pretreatment solution is injected in the container, and the temperature of first chemical pretreatment solution is 30 ℃, and by volume, its composition share is 100: 2.2: 0.6 H 2O: NH 4OH: tensio-active agent and the oxygen that is less than 100ppb.With the speed of 12g/m,, first chemical pretreatment solution is injected in the container with 120 seconds time.After injecting container, disk soaked 120 seconds in first chemical pretreatment solution again.During disk contacted first chemical pretreatment solution, disk was exposed in the high acoustic energy of about 650KHz.
Then, according to the treating processes that comparative example 1 adopts, directly use deionized water washing fluid (content of oxygen is lower than 100ppb) to replace first chemical pretreatment solution.Then, directly replace washing fluid with second chemical pretreatment solution, the temperature of second chemical pretreatment solution is 30 ℃, and by volume, its composition share is 100: 0.2: 1 H 2O: HF: HCl and the oxygen that is lower than 100ppb.With the speed of 18g/m, use 120 seconds injection length altogether, second chemical pretreatment solution is injected in the container.After injecting in the container, disk (does not have high acoustic energy) again and soaked 120 seconds in second chemical pretreatment solution.
Then, according to the treating processes that comparative example 3 adopts, the deionized water rinsing liquid that is less than about 100ppb with oxygen level is directly replaced second chemical pretreatment solution.After washing,, disk is carried out drying according to the treating processes that comparative example 1 to 3 adopts.
Utilize 3 bouts altogether, in the above described manner, other two batches of disks are handled.
Utilize the edge exclusion of 6mm, on 3 disks in every batch of disk, the size analyze at 18 microns to 400 microns particle contaminant thing.Average result is shown in table 2.Example 5-utilizes copper-containing solution to handle earlier, utilizes then to contain HF solution and handle
Except H in first chemical pretreatment solution 2O: NH 4OH: the component content of tensio-active agent is the treating processes that repeats comparative example 4 outside 100: 2.2: 0.6 volumes.
Utilize 3 bouts altogether, in the above described manner, other two batches of disks are handled.
Utilize the edge exclusion of 6mm, on 3 disks in every batch of disk, the size analyze at 18 microns to 400 microns particle contaminant thing.Average result is shown in table 2.
Table 2: the particle that is eliminated
Example Average LPD number 1
Before the processing After the processing Difference Remove per-cent
Comparative example 1 ????11841 ????1984 ??-9857 ????83
Comparative example 2 ????10002 ????1951 ??-8051 ????80
Comparative example 3 ????2115 ????291 ??-1824 ????86
Comparative example 4 ????10002 ????1943 ??-8059 ????81
Example 5 ????5334 ????3 ??-5331 ????99.9
1Average flaw spot number
Data in the table 2 are illustrated in the mean value of detected granule number on 3 disks.Before " before handling " is listed in and carries out wet processing, average grain number on the disk, " handle the back " and be listed in after the wet processing, the average grain number on the disk, " difference " listed before the wet processing and the particulate mean range on the disk between after the wet processing.Negative " difference " is illustrated in during the wet processing, is eliminated granule number." removing per-cent " lists the particulate average percent that is eliminated according to the granule number on disk before the wet processing process.
Data declaration in the table 2, the inventive method can effectively reduce the pollutant particle during the cupric electronic devices and components are carried out wet processing.For example, in example 5,, make the disk contact contain the solution of hydrofluoric acid and hydrochloric acid subsequently, can remove 99.9% particle by making cupric electronic devices and components contact SC1 solution.When comparing with comparative example, the results were quite startling and be difficult to the imagination for these.For example, when making cupric disk contact SC1 solution (comparative example 1), solution of ammonium hydroxide (comparative example 2), hydrofluoric acid/hydrochloric acid soln (comparative example 3) or contact the combination of hydrofluoric acid/hydrochloric acid soln (comparative example 4) after ammonium hydroxide, the per-cent of eliminating particle is not higher than 86%.These results schematically are shown among Fig. 1.Fig. 1 illustrates the histogram according to the eliminating particle per-cent of comparative example 1 to 4 and example 5.From as Fig. 1 as can be seen, the cupric disk of handling according to the inventive method is better unexpectedly than comparative example 1 to 4.
Although describe the present invention according to certain preferred embodiment,, obviously,, can carry out multiple conversion and adjustment to these preferred embodiments for the those of skill in the art in the present technique field.Above-mentioned explanation only has descriptive sense and does not have restricted meaning the present invention.

Claims (20)

1. method that the electronic devices and components with copper containing surfaces are carried out wet processing, this method comprises:
(a) make the surface of electronic devices and components contact copper oxidation liquid in first duration of contact; And
(b) subsequently, make the surperficial contact etch liquid of electronic devices and components in second duration of contact, wherein to keep water pH value be 5 or lower and contain etching reagent and be less than 5 to etching solution, the dissolved oxygen of 000ppb or suspension oxygen, and wherein the surface of electronic devices and components contacts with etching solution and pollutant can be removed from the surface of electronic devices and components with copper oxidation liquid.
2. method according to claim 1, wherein copper oxidation liquid comprises the oxygenant of selecting from the group of being made up of hydrogen peroxide, ozone, ferric cyanide or their combination.
3. method according to claim 2, wherein selective oxidation agent from the group of forming by hydrogen peroxide, ozone or their combination.
4. method according to claim 3, wherein copper oxidation liquid comprise water, according to the cumulative volume of copper oxidation liquid hydrogen peroxide at least about 0.1 volume percent, and to keep the pH value be 7 or bigger.
5. method according to claim 1, wherein copper oxidation liquid comprises water, hydrogen peroxide and ammonium hydroxide.
6. method according to claim 5, wherein copper oxidation liquid contains water, hydrogen peroxide and ammonium hydroxide, volume ratio H 2O: H 2O 2: NH 4OH is between about 5: 1: 1 to about 200: 1: 1.
7. method according to claim 1 is wherein selected etching reagent from the group of being made of hydrochloric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetate, citric acid, tartrate and their combination.
8. method according to claim 1, wherein etching solution is the solution that contains hydrofluoric acid, the solution that contains hydrofluoric acid comprises hydrofluoric acid and deionized water, volume ratio H 2O: HF is between about 5: 1 to about 1000: 1.
9. it is 3 or lower that method according to claim 8, the pH value that wherein contains the solution of hydrofluoric acid are maintained at about.
10. method according to claim 9, the solution that wherein contains hydrofluoric acid further comprises hydrochloric acid, volume ratio H 2O: HF: HCl is between about 50: 1: 1 to about 1000: 1: 1.
11. method according to claim 10, the solution that wherein contains hydrofluoric acid comprises dissolved oxygen or the suspension oxygen of about 100ppb at least.
12. method according to claim 1 wherein after making electronic devices and components contacts copper oxidation liquid, and before making electronic devices and components contact etch liquid, is utilized to comprise that the washing fluid of deionized water washes electronic devices and components.
13. method according to claim 1, wherein one of copper oxidation liquid or etching solution comprise tensio-active agent, inhibitor or their combination at least.
14. method according to claim 1 is wherein carried out wet processing to electronic devices and components in one or more containers.
15. method according to claim 1 is wherein handled electronic devices and components in single container.
16. method according to claim 15 wherein behind electronic devices and components contact copper oxidation liquid, is directly replaced copper oxidation liquid with washing fluid or etching solution.
17. method according to claim 1, wherein the pH value of copper oxidation liquid is at least about 7 or higher.
18. the method that the electronic devices and components with copper containing surfaces are carried out wet processing, this method comprises:
(a) one or more electronic devices and components with copper containing surfaces are placed in single container;
(b) the copper oxidation liquid that will comprise oxygenant injects in the container;
(c) make electronic devices and components contact copper oxidation liquid in first duration of contact, in container, discharge copper oxidation liquid then;
(d) with the pH value be 5 or hydrofluoric acid containing solution lower, that have 5000ppb dissolved oxygen or suspension oxygen at least inject in the container; And
(e) make electronic devices and components connect hydrofluoric acid containing solution in second duration of contact, discharge hydrofluoric acid containing solution then from container, wherein the surface of electronic devices and components contact copper oxidation liquid and hydrofluoric acid containing solution can be removed pollutant from the surface of electronic devices and components.
19. method according to claim 18 wherein by utilizing another kind of treatment solution to replace, is discharged copper oxidation liquid and hydrofluoric acid containing solution in container.
20. the method that the electronic devices and components with copper containing surfaces are carried out wet processing, this method comprises:
(a) make the surface of electronic devices and components contact copper oxidation liquid in first duration of contact, wherein the pH value of copper oxidation liquid is at least about 7 or higher; And
(b) subsequently, make the surperficial contact etch liquid of electronic devices and components in second duration of contact, wherein to keep water pH value be 5 or lower and contain etching reagent and be less than 5 to etching solution, the dissolved oxygen of 000ppb or suspension oxygen or other copper oxidant, and wherein the surface of electronic devices and components contacts with etching solution and pollutant can be removed from the surface of electronic devices and components with copper oxidation liquid.
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CN105802747B (en) * 2016-04-15 2018-11-09 林淑录 The cleaning agent of cleaning after a kind of solar-energy photo-voltaic cell silicon wafer wool making
CN115558931A (en) * 2022-10-26 2023-01-03 广东华智芯电子科技有限公司 Refining method of copper surface crystal flower, corrosion liquid combination and application thereof

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TW466728B (en) 2001-12-01
WO2000071782A1 (en) 2000-11-30

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