CN1767154A - Method for removing carbon-containing residues from a substrate - Google Patents
Method for removing carbon-containing residues from a substrate Download PDFInfo
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- CN1767154A CN1767154A CN 200510098056 CN200510098056A CN1767154A CN 1767154 A CN1767154 A CN 1767154A CN 200510098056 CN200510098056 CN 200510098056 CN 200510098056 A CN200510098056 A CN 200510098056A CN 1767154 A CN1767154 A CN 1767154A
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Abstract
A process for removing carbon-containing residues from a substrate is described herein. In one aspect, there is provided a process for removing carbon-containing residue from at least a portion of a surface of a substrate comprising: providing a process gas comprising an oxygen source, a fluorine source, an and optionally additive gas wherein the molar ratio of oxygen to fluorine contained within the process gas ranges from about 1 to about 10; activating the process gas using at least one energy source to provide reactive species; and contacting the surface of the substrate with the reactive species to volatilize and remove the carbon-containing residue from the surface.
Description
The cross reference of related application
The application is with the U.S. Provisional Application No.60/590 of application on July 23rd, 2004, and 628 is priority.
Background of invention
At semiconductor integrated circuit (IC), opto-electronic device, and in the manufacturing of microelectromechanical systems (MEMS), carry out the multistep thin film deposition, thus on monolithic substrate or wafer, construct some closed circuits (chip) and device.Common with each wafer of various thin film depositions, such as but not limited to, as the diffusion impervious layer of binary and/or this class of transition metal ternary compound; Conductive film for example, but is not limited to, tungsten, copper and aluminium; Semiconductive thin film for example, but is not limited to, mixes and unadulterated polysilicon (poly-Si), and doping and unadulterated (intrinsic) amorphous silicon (a-Si); Dielectric film for example, but is not limited to, silicon dioxide (SiO
2), unadulterated silex glass (USG), boron doped silex glass (BSG), the silex glass (PSG) of phosphorus doping, boron phosphorus silicate glass (BPSG), silicon nitride (Si
3N
4) and silicon oxynitride (SiON); Low-k (low-k) dielectric film for example, but is not limited to, the organic silicate glass (OSG) that the silicate glass (FSG) that fluorine mixes, silica or carbon mix; Light actuating resisting corrosion film; With the antireflecting coating that constitutes by the organic or inorganic material (ARC) film.
The material that is particularly suitable for semi-conductor industry is a composite organic hydrochlorate film.The global density of known reduction material can reduce the dielectric constant (k) of this material.A kind of method that reduces density of material is by introducing hole.By chemical vapor deposition (CVD) technology or alternate manner, use contains the precursor mixture that a kind of pore-creating precursor or pore generating agent (typically being one or more carbon compounds) and a kind of structure form precursor (typically being organosilan and/or organosiloxane), can produce the composite organic hydrochlorate film of porous.In some example, carbon-containing residue is owing to the deposition that structure forms precursor and pore-creating precursor forms.For example in U.S. Patent number 6,846,525; 6,716,770; 6,583,048 and be disclosed in U.S. Patent Publication No. 2004/0241463; 2004/0197474; 2004/0175957; 2004/0175501; 2004/0096672; Provide in 2004/0096593 to finish to be configured to and/or the example of pore-creating precursor, here it all is incorporated herein by reference.In case deposited composite organic hydrochlorate film, just must remove at least a portion of this pore-creating precursor, thereby one deck porous membrane is provided.
The example that structure forms the thing precursor comprises silicon-containing compound, for example organosilan and organosiloxane.The organosilan and the organosiloxane that are fit to comprise, for example: (a) formula R
1 nSiR
2 4-nThe alkyl silane of expression, wherein n is the integer of 1-3; R
1And R
2Be the C of side chain or straight chain independently of one another
1-C
8Alkyl group (for example, methyl, ethyl), C
3-C
8Replacement or the group of naphthene base (for example, cyclobutyl, cyclohexyl) of non-replacement, C
3-C
10The undersaturated alkyl group of part (for example, acrylic, butadienyl), C
6-C
12Replacement or the aromatic yl group (for example, phenyl, tolyl) of non-replacement, corresponding line style, side chain, ring-type, the undersaturated alkyl of part, or contain alkoxy grp (for example, methoxyl group, ethyoxyl, phenoxy group at least a in) the aryl, and R
2Selectively be hydride (for example, methyl-monosilane, dimethylsilane, trimethyl silane, tetramethylsilane, phenyl silane, aminomethyl phenyl silane, cyclohexyl silane, t-butylsilane, ethylsilane, diethylsilane, tetraethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysil,ne, dimethylethoxysilane, methyl triethoxysilane, methyldiethoxysilane, triethoxysilane, trimethyl phenoxysilane and phenoxy group silane); (b) formula R
1(R
2 2SiO)
nSiR
2 3The line style organosiloxane of expression, wherein n is the integer of 1-10, or formula (R
1R
2SiO)
nThe expression cyclic organic siloxane, wherein n is the integer of 2-10, and R
1And R
2Be group as defined above (for example, 1,3,5,7-tetramethyl-ring tetrasiloxane, octamethylcy-clotetrasiloxane, hexamethyl cyclotrisiloxane, HMDO, 1,1,2,2-tetramethyl disiloxane and octamethyltrisiloxane); (c) formula R
2(SiR
1R
2)
nR
2The line style organosilan oligomer of expression, wherein n is the integer of 2-10, or formula (SiR
1R
2)
nThe cyclic organic alkane of expression, wherein n is the integer of 3-10, and R
1And R
2For group as defined above (for example, 1,2-dimethyl disilane, 1,1,2,2-tetramethyl disilane, 1,2-dimethyl-1,1,2,2-dimethoxy silane, hexamethyldisilane, prestox three silane, 1,2,3,4,5,6-hexaphenyl six silane, 1,2-dimethyl-1,2-diphenyl disilane and 1,2-diphenyl disilane).In certain embodiments, this organosilan/organosiloxane is a cyclic alkyl silane, the cyclic alkyl siloxanes, cyclic alkoxy silane or between a pair of Si atom, contain at least one alkoxyl or alkyl bridged bond, for example 1,2-disilane alcohol ethane, 1,3-disilane alcohol propane, dimethyl-silicon heterocycle butane, 1, two (trimethylsiloxy) cyclobutane of 2-, 1,1-dimethyl-1-sila-2,6-dioxane, 1,1-dimethyl-1-sila-2-oxinane, 1, two (trimethylsiloxy) ethane of 2-, 1, two (dimetylsilyl) benzene of 4-, prestox Fourth Ring siloxanes (OMCTS) or 1,3-(dimetylsilyl) cyclobutane.In certain embodiments, this organosilan/organosiloxane contains active lateral group, and this survey base is selected from by the cyclic group of epoxides, carboxylate, alkynes, diene, phenylacetylene base, strain and the C that can spatially hinder or strain this organosilan/organosiloxane
4-C
10The group that group constituted, for example trimethyl silyl acetylene, 1-(trimethyl silyl)-1,3-butadiene, trimethyl silyl cyclopentadiene, trimethyl silyl acetate and two-tert-butoxy diacetoxy silane.
This hole forms precursor can be hydrocarbon compound, preferably has 1-13 carbon atom.The example of these compounds comprises, but be not limited thereto, α-terpinenes, limonene, cyclohexane, γ-terpinenes, amphene, dimethyl hexadiene, ethylo benzene, norbornadiene, epoxy pentane, 1,2,4-trimethyl-cyclohexane, 1,5-dimethyl-1, the diene of 5-cyclo-octadiene, amphene, adamantane, 1,3-butadiene, replacement, australene, nopinene and decahydronaphthalene.The example that the hole forms the thing precursor can also comprise the decomposability organic group.Some examples that contain the compound of decomposability organic group are included in U.S. Patent No. 6,171, and disclosed those compounds in 945 are all introduced here as a reference.Other example that the hole forms the thing precursor also can be the decomposability polymer.This decomposability polymer can be a RADIATION DECOMPOSITION.Special provision only content, otherwise employed here term " polymer " ", also comprise term oligomer and/or copolymer.The RADIATION DECOMPOSITION polymer is to be exposed to resolvent polymer under the ray, for example, and ultraviolet light, X-ray, electron beam or the like.The example of these polymer comprises having a kind of polymer that the structural system of three-dimensional structure can be provided, and for example, but is not limited thereto block copolymer, i.e. diblock, three blocks and segmented copolymer; Star block copolymer; The star diblock copolymer; The grafting diblock copolymer; The cograft copolymer; The dendroid graft copolymer; The tapered block copolymer; And the composition of these structural systems.The example of degradable polymer also is disclosed in U.S. Patent No. 6,204, in 202, all introduces as a reference here.
In some example, a kind of independent compound can play structure simultaneously and form thing and hole formation thing in porous OSG film.In other words, structure forms the thing precursor and needs not to be different compounds with hole formation thing precursor, and in certain embodiments, it is the part (for example, covalent bonding) that this structure forms the thing precursor that this hole forms thing.
When depositing operation when being desirably in substrate (typically being silicon wafer) and go up forming film, form on the surface that the reaction of these films exposed in process chamber also unproductively and produce, thereby on the downstream of the fore line of locular wall, nozzle and this process chamber, stay the abundant residues thing.These residues typically contain carbon, are called carbon-containing residue here.In addition the material that also may exist comprises, for example, and from the silicon of precursor mixture and/or from being exposed to the fluorinated gas plasma that is used to clean and/or the fluorine of fluorine-containing precursor.The accumulation of carbon-containing residue can cause particle detachment in the process chamber, the decline of deposition uniformity and influence the processing deviation of ensuing deposition.Defective and equipment failure in the structure that these influences can cause being deposited.Therefore, need be to the periodic purge of this process chamber, the chamber of being also referred to as is cleaned.Thereby must remove these residues and guarantee the integrality (uniformity, component purity, reproducibility) of this synthesizing organo-silicon hydrochlorate film of deposition subsequently.In some example, carbon-containing residue can occur with the form of oligomer and polymer, makes that therefore the removing of residue is complicated more.
Use the plasma cleaning of fluorinated gas plasma to be often used in cleaning process room between the deposition.The fluorinated gas that the typical case uses comprises NF
3, C
2F
6, CF
4, CHF
3, F
2And the material in various fluorine atom (F) sources that other can be provided convenience in the clean of chamber.The fluorinated gas of some types is relatively easy processing because these gas non-corrosivenesss and under external condition not with building material or air source gas reaction.The typical case uses a kind of C
2F
6/ O
2Or NF
3Plasma etch process comes cleaning process room.Yet, have been found that the plasma that wherein contains fluorinated gas can not remove all carbon-containing residue that are deposited on this process chamber inner surface effectively during above-mentioned needs produce the codeposition technology of synthesizing organo-silicon silicate material.
Brief overview of the present invention
The technology of removing carbon-containing residue from the substrate surface that is coated with carbon-containing residue to small part will be described here.On the one hand, a kind of technology that is used for removing from substrate surface carbon-containing residue is provided, comprises: provide a kind of, the fluorine source by oxygen source, randomly add the processing gas that gas constitutes, wherein the contained oxygen and the molar ratio range of fluorine are about 1 to about 10 in this processing gas; Use one or more energy sources (energysources) to activate this processing gas so that reactive materials to be provided; And the surface of substrate is contacted, with this reactive materials to volatilize from this surface and to remove carbon-containing residue.
On the other hand, a kind of technology that is used for removing from the surface of process chamber carbon-containing residue is provided, wherein this process chamber is used to deposit composite organic hydrochlorate film, and described technology comprises: process chamber is provided, and wherein this chamber comprises the surface that is coated with carbon-containing residue to small part; Provide a kind of by oxygen source, fluorine source and randomly add the processing gas that gas constitutes, wherein the contained oxygen and the molar ratio range of fluorine are about 1 to about 10 in this processing gas; Use one or more energy sources to activate this processing gas so that reactive materials to be provided; Residue is contacted, to form at least a volatile products, wherein in 5 holders (Torr) or littler pressure this contact procedure of execution down with this reactive materials; And remove these at least a volatile products from this process chamber.
On the other hand, a kind of technology that is used for removing from the surface of process chamber carbon-containing residue is provided, wherein this process chamber is used to deposit composite organic hydrochlorate film, and described technology comprises: process chamber is provided, and wherein this chamber comprises the surface that is coated with carbon-containing residue to small part; Provide a kind of by oxygen source, fluorine source and randomly add the processing gas that gas constitutes, wherein the contained oxygen and the molar ratio range of fluorine are about 1 to about 10 in this processing gas; By using a kind of energy source to activate this processing gas, to form reactive materials, wherein the first of this processing gas activates and introduces in this process chamber outside this process chamber, and the second portion of this processing gas activates in this process chamber; Residue is contacted, to form at least a volatile products with this reactive materials; And remove these at least a volatile products from this process chamber.
Remain on the other hand, a kind of technology that is used for removing from the surface of process chamber carbon-containing residue is provided, wherein this process chamber is used to deposit composite organic hydrochlorate film, and described technology comprises: process chamber is provided, and wherein this chamber comprises the surface that is coated with carbon-containing residue to small part; Provide a kind of by oxygen source, fluorine source and randomly add the processing gas that gas constitutes, wherein the contained oxygen and the molar ratio range of fluorine are about 1 to about 10 in this processing gas; By using a kind of energy source to activate this processing gas, to form reactive materials, wherein the first of this processing gas activates and introduces in this process chamber outside this process chamber, and the second portion of this processing gas activates in this process chamber; Residue is contacted with this reactive materials,, wherein under 5Torr or littler pressure, carry out this contact procedure to form at least a volatile products; And remove these at least a volatile products from this process chamber.
Brief description of the drawings
Fig. 1 provides by fourier-transform infrared (FTIR) spectrometer record, the NF that carries out under 2.5Torr pressure
3The curve chart of the material concentration that is flowed out during remote (remote) (anaerobic) plasma of/Ar cleans.
Fig. 2 a is by quadrupole mass spectrometer (QMS) record, at 2.5Torr pressure and O
2/ NF
3Than the NF that carries out under=4.0 conditions
3/ O
2The curve chart of the material concentration that is flowed out during the remote plasma of/Ar cleans.
Fig. 2 b is by fourier-transform infrared (FTIR) spectrometer record, at 2.5Torr pressure and O
2/ NF
3Than the NF that carries out under=4.0 conditions
3/ O
2The curve chart of the material concentration that is flowed out during the remote plasma of/Ar cleans.
Fig. 3 a is by quadrupole mass spectrometer (QMS) record, the NF that carries out under 2.5Torr pressure
3The curve chart of the material concentration that is flowed out during remote plasma cleaning of/Ar (anaerobic) and RF (original position) power supply (power) are auxiliary.
Fig. 3 b is by fourier-transform infrared (FTIR) spectrometer record, the NF that carries out under 2.5Torr pressure
3The curve chart of the material concentration that is flowed out during remote plasma cleaning of/Ar (anaerobic) and RF (original position) power supply are auxiliary.
Fig. 4 a is by quadrupole mass spectrometer (QMS) record, at 2.0Torr pressure and O
2/ NF
3Than the NF that carries out under=3.0 conditions
3/ O
2The curve chart of the material concentration that/He original position plasma is flowed out during cleaning.
Fig. 4 b is by fourier-transform infrared (FTIR) spectrometer record, at 2.0Torr pressure and O
2/ NF
3Than the NF that carries out under=3.0 conditions
3/ O
2The curve chart of the material concentration that/He original position plasma is flowed out during cleaning.
Fig. 5 a has shown under the 750sccm helium flow speed as O
2/ NF
3The CO of the function of ratio and constant pressure
2Discharge.
Fig. 5 b has shown under the 2.5Torr chamber pressure as O
2/ NF
3The CO of the function of ratio and helium flow speed
2Discharge.
Fig. 5 c has shown under the 750sccm helium flow speed as O
2/ NF
3The SiF of the function of ratio and constant pressure
4Discharge.
Fig. 5 d has shown under the 2.5Torr chamber pressure as O
2/ NF
3The SiF of the function of ratio and helium flow speed
4Discharge.
Fig. 5 e is by quadrupole mass spectrometer (QMS) record, at 2.0Torr pressure and O
2/ NF
3Than the NF that carries out under=4.0 conditions
3/ O
2The curve chart of the material concentration that/He original position plasma is flowed out during cleaning.
Fig. 5 f is by fourier-transform infrared (FTIR) spectrometer record, at 2.0Torr pressure and O
2/ NF
3Than the NF that carries out under=4.0 conditions
3/ O
2The curve chart of the material concentration that/He original position plasma is flowed out during cleaning.
Fig. 5 g has shown under the 750sccm argon flow rate as O
2/ NF
3The CO of the function of ratio and constant pressure
2Discharge.
Fig. 5 h has shown under the 2.5Torr chamber pressure as O
2/ NF
3The CO of the function of ratio and argon flow rate
2Discharge.
Fig. 5 i has shown under the 750sccm argon flow rate as O
2/ NF
3The SiF of the function of ratio and constant pressure
4Discharge.
Fig. 5 j has shown under the 2.5Torr chamber pressure as O
2/ NF
3The SiF of the function of ratio and argon flow rate
4Discharge.
Fig. 5 k is by quadrupole mass spectrometer (QMS) record, at 2.0Torr pressure and O
2/ NF
3Than the NF that carries out under=4.0 conditions
3/ O
2The curve chart of the material concentration that/Ar original position plasma is flowed out during cleaning.
Fig. 5 l is by fourier-transform infrared (FTIR) spectrometer record, at 2.0Torr pressure and O
2/ NF
3Than the NF that carries out under=4.0 conditions
3/ O
2The curve chart of the material concentration that/Ar original position plasma is flowed out during cleaning.
Fig. 6 a is by quadrupole mass spectrometer (QMS) record, at 2.0Torr pressure and O
2/ NF
3Than the NF that carries out under=4.0 conditions
3/ O
2The curve chart of the material concentration that is flowed out during the remote plasma of/Ar cleans.
Fig. 6 b is by fourier-transform infrared (FTIR) spectrometer record, at 2.0Torr pressure and O
2/ NF
3Than the NF that carries out under=4.0 conditions
3/ O
2The curve chart of the material concentration that is flowed out during the remote plasma of/Ar cleans.
The detailed description of invention
Technique disclosed herein is used for removing carbon-containing residue from least part of surface of substrate. In a specific embodiment, this technique is removed nonvolatile matter from least part of surperficial supernatant in process chamber and any fixture wherein, and for example carbon-containing residue is also wanted simultaneously so that infringement is minimum. The material that is cleaned and removes from this surface is transformed into by the solid non-volatile materials and has more high-volatile material, and it can easily be removed by the vavuum pump in the process chamber or miscellaneous equipment. Unlike Mechanical Method, wet etching and/or other cleaning, this technique disclosed herein needn't require from production line and/or between the exposure period of this chamber process chamber and fixture thereof be moved to the liquid chemical solvent.
In a specific embodiment, technique disclosed herein is removed carbon-containing residue at least part of surface in process chamber, this process chamber is used at least one surface such as the substrate of this class of silicon wafer, in for example chemical vapour deposition (CVD) (CVD) of composite organic hydrochlorate film, ald (ALD), spray pyrolysis (spray pyrolysis) and/or the vacuum moulding machine. Thereby by making this carbon-containing residue contact with this substance reaction with reactive materials and forming volatile products, this carbon-containing residue can be removed from the one or more surfaces in this process chamber and any fixture wherein. Term used herein " volatile products " relates to carbon-containing residue and contains by activation that reaction obtains product and accessory substance between the reactive materials that the processing gas in oxygen source and fluorine source forms.
This reactive materials makes the processing gas that contains oxygen source and fluorine source activate and form by at least one energy source. Oxygen in this processing gas and the mol ratio of fluorine are higher with respect to the relatively cleaning example of the chemical substance that adopts so far. Find unexpectedly that also oxygen in this technique can affect the removing of carbon-containing residue significantly on the mol ratio of fluorine. In certain embodiments, for example, find that unexpectedly oxygen can promote the removing of carbon-containing residue to the mol ratio of fluorine significantly greater than the unified value in this technique (unity), and the damage of the substrate that wherein exposes is minimized.
By the processing gas that this carbon-containing sediment is exposed to activation with its removing. This processing gas comprises oxygen source, fluorine source and at least a interpolation gas optionally. In these embodiments, contained oxygen and the mol ratio of fluorine can be 1-10 or 2-8 or 3-6 in this processing gas. The example of oxygen source includes, but are not limited to this, oxygen (O2), ozone (O3), carbon monoxide (CO), carbon dioxide (CO2), nitrogen dioxide (NO2), nitrous oxide (N2O), nitric oxide (NO), water (H2O), and composition thereof. This content of processing oxygen source in gas can be the 20%-90% of the whole volume of processing gas.
This processing gas contains the fluorine source.The example that is suitable for the fluorine source gas of technology described here comprises: HF (hydrofluoric acid), F
2(fluorine gas), NF
3(Nitrogen trifluoride), SF
6(sulphur hexafluoride), FNO (nitrosyl fluoride), C
3F
3N
3(cyanuric fluoride), C
2F
2O
2(oxalyl fluoride), perfluocarbon be CF for example
4, C
2F
6, C
3F
8, C
4F
8Or the like, hydrogen fluorine carbide is CHF for example
3And C
3F
7H or the like, the fluorine oxycarbide is C for example
4F
8O (perfluoro oxolane) (perfluorotetrahydrofuran) or the like, the hydrogen fluorine carbide of oxidation is hydrogen fluorine ether (for example, methyl trifluoro methyl ether (CH for example
3OCF
3)), Fluorine monohydroxide ester (hypofluorites) is CF for example
3-OF (fluorine oxo fluoroform (FTM)) and FO-CF
2-OF (two-difluoro oxo-difluoromethane (BDM)), or the like, the fluoro peroxide is CF for example
3-O-O-CF
3(two-three fluoridize-methyl-peroxide (BTMP)), F-O-O-F or the like, the fluoro trioxide is CF for example
3-O-O-O-CF
3Deng, amine fluoride is CF for example
5N (perfluorinate methylamine), fluoridize for example C of nitrile
2F
3N (perfluoro acetonitrile), C
3F
6N (perfluorinate propionitrile) and CF
3NO (three fluoridize nitrosyl radical methane) and COF
2(carbonyl fluoride).This fluorine source can provide with various means, for example, but is not limited thereto conventional cylinder, safe delivery system, vacuum conveying system and/or set up the solid-state or liquid generator in fluorine source in use.This content of handling fluorine source in gas can be the 10%-35% of the whole volume of handling gas.
In certain embodiments, at least a of oxygen source and fluorine source is same compound.Thus, by using one or more fluorine sources of also containing suitable high-load oxygen, the mol ratio in oxygen source and fluorine source can be overlapping in this processing gas.Thus, these fluorine source compounds can be handled at this and play difunctional dose in admixture of gas, and for example except independently using the oxygen source compound in order to replace.Also contain quite high oxygen content and can comprise for example CF of Fluorine monohydroxide ester with the example in these embodiments suitable fluorine source
3-OF (fluorine oxo fluoroform (FTM)) and FO-CF
2-OF (two-difluoro oxo-difluoromethane (BDM)), or the like, the fluoro peroxide is CF for example
3-O-O-CF
3(two-three fluoridize-methyl-peroxide (BTMP)), F-O-O-F or the like, the fluoro trioxide is CF for example
3-O-O-O-CF
3Deng.
In certain embodiments, the gas of one or more interpolations can be joined in this processing gas.The example of the gas that adds comprises hydrogen, nitrogen, helium, neon, argon gas, krypton gas, xenon, and composition thereof.In certain embodiments, the gas of this interpolation is hydrogen.The gas of believing this interpolation can improve plasma characteristics and cleaning better to be suitable for some concrete application.This interpolation gas also can help out when oxygen source and/or fluorine source are transferred to substrate or process chamber.In certain embodiments, handle the content that adds gas in the gas and can be the 0%-80% of the whole volume of handling gas.
Technology disclosed herein is used in the process chamber and the surface of the wherein contained various fixtures that have is removed carbon-containing residue and its damage is minimized, and this fixture for example but is not limited thereto, fluid issuing and inlet, nozzle, work piece platform, or the like.The example of process chamber comprises CVD and/or the ALD process chamber that is used for deposition low-k dielectric material on the surface of substrate.The surface of this chamber and wherein contained fixture can be made of various material, comprise metal, as titanium, aluminium, stainless steel, nickel, or the alloy that constitutes by same material, and/or insulating material, as pottery, for example, quartz or Al
2O
3
This processing gas can activate by one or more energy sources, for example, but be not limited thereto, original position plasma, remote plasma, remote heat/catalyzing activation, the heating of original position heat (thermal heating), electron attachment and photoactivation, thus form reactive materials.These sources can be used singly or in combination, and for example use series system.
Heat or plasma-activated and/or enhancing can influence the etching and the cleaning efficiency of carbon-containing residue significantly.In hot heat activation, be heated by resistive device or strong illumination device and heat this process chamber and the wherein contained fixture that has.Handle the gas thermal decomposition for making the reactive free radical and the atom of carbon-containing residue volatilization subsequently.This energy source also can provide high temperature, to overcome the reacting activation potential barrier and to improve reaction rate.For hot activation, this substrate can be heated at least 100 ℃, or at least 300 ℃, or at least 500 ℃.Pressure can arrive 760Torr for 10mTorr, or 1Torr is to 760Torr.
Among the embodiment of Ji Huoing, for example original position RF plasma is used for activating and handles gas in position, and this handles oxygen contained in the gas and fluorine molecule can divide to form reactive materials, as reactive ion and free radical by discharge.Fluoride ion and free radical and oxygen-carrying ion and free radical can react with carbon-containing residue, can be by the volatile materials of vacuum pump from the process chamber removing thereby form.
In the embodiment that uses the original position plasma-activated, this original position plasma can produce and/or with 1W/cm at least with the 13.56MHzRF power supply
2, or 5W/cm at least
2, or 10W/cm at least
2The RF power strength produces.Selectively, this original position plasma energy is lower than under the 13.56MHz in the RF frequency to be operated, with the cleaning of the locular wall that strengthens ground connection and/or wherein contained fixture.Operating pressure can for 2.5mTorr to 100Torr, or 5mTorr is to 50Torr, or 10mTorr is to 20Torr.In a specific embodiment, under 5Torr or lower pressure, handle.In these embodiments, an original position energy source, for example original position RF plasma can make up with heat and/or remote energy source.This specific embodiment has guaranteed plasma stability and can ignore damage to this process chamber and wherein contained fixture.
Remote energy source for example, but is not limited thereto, by the remote plasma source that RF activates, and microwave, or ICP activation, remote heat shock work-source, remote catalytic activation of source, or the far-away sources of heat and catalyzing activation combination can be used to produce volatile products.In remote plasma cleaned, gas was handled in activation, to form reactive materials in the outside, settling chamber, this material is imported process chamber make carbon-containing residue volatilize.In remote hot activation, handle at first the flow through heating region of process chamber outside of gas.Thereby decomposing this gas by high temperature contact in the container outside process chamber cleans.Selectable mode comprises uses remote catalyst resolution process gas, or heat heating and catalytic pyrolysis make up to promote the activation of oxygen and fluorine source in this processing gas.
In certain embodiments, can activate/strengthen the reactive materials of remote plasma generation and the reaction between the carbon-containing residue by reactor heating.Reactive materials that remote plasma produces and the reaction between the carbon-containing residue can activate by the temperature that reactor is heated to the oxygen that contains in the source contained in this processing gas of enough decomposition and fluorine and/or strengthen.Thereby the cleaning reaction between this requirement energy activated material depends on the prescription of handling gas with the actual temp of its removing.
In a specific embodiment, adopt the isoionic combination of remote plasma and original position as energy source, handle gas to form reactive materials thereby activate.In this embodiment, activate the first that handles gas in the zone of process chamber outside, it introduces this process chamber after activating.With the arbitrary portion of the first activation gas, in process chamber, activate the second portion that this handles gas, the reactive materials of wherein having recombinated.
In alternate embodiments, in photon, oxygen and fluorine source molecule in the energy resolution process gas are to form reactive materials by heavy exposure.For example, ultraviolet light, extreme ultraviolet light (deep ultraviolet) and vacuum ultraviolet can be assisted the fracture of strong chemical bond in the carbon-containing residue, and the oxygen and the fluorine source of handling in the gas are decomposed, thereby improve the clearance rate of carbon-containing residue.The mode that also can adopt other that cleaning described here is activated and strengthens.For example, can use the photon of induced chemical reaction to produce reactive materials and strengthen this etching/cleaning reaction.
In certain embodiments, process chamber can keep similar substantially operating condition (pressure and temperature) during the cleaning operation with during the electroless copper deposition operation.For example, be used for the embodiment of CVD, stop the inflow of deposition gases and discharge from reactor and pipeline at process chamber.If desired, the temperature of reactor can become optimum value; Yet in a preferred embodiment, the temperature of process chamber remains under the condition of depositing operation.Processing gas flows in the process chamber and is activated, so that reactive materials to be provided.This reactive materials converts carbon-containing residue to the volatile products of removing from this chamber.After stipulated time, or after the concentration of judging the formed volatile products that flow out this chamber is lower than acceptable level, stop to handle the inflow of gas, and preferably discharge from this chamber and pipeline.Restart the inflow of deposition gases then and continue the CVD depositing operation.
In a further embodiment, technology described here can be used for a plurality of fields of the semiconductor manufacturing industry except the chamber is cleaned, and for example removes etched carbonaceous material from substrate.In these embodiments, operable suitable substrate includes, but not limited to for example GaAs (" GaAs ") of semi-conducting material, boron nitrogen (" BN ") silicon and contain silicon composition, for example polysilicon, poly-silicon, amorphous silicon, epitaxial silicon, silicon dioxide (" SiO
2"), carborundum (" SiC "), silicon oxide carbide (" SiOC "), silicon nitride (" SiN "), carbonitride of silicium (" SiCN "), organic silicate glass (" OSG "), organic fluorinated silicate glass (" OFSG "), fluorinated silicate glass (" FSG ") and other substrate or its mixture that is fit to.Substrate may further include such as the various layers that scribble this class of film on it, for example, antireflecting coating, photoresist, organic polymer, porous is organic and inorganic material, metal such as copper and aluminium and/or disperse barrier layer, for example binary and/or transition metal ternary compound.Wet method removing traditionally and/or plasma etching are used for these semiconductor fabrication process.
To describe this technology in more detail with reference to following embodiment, but should be understood that method described here is not limited thereto.
Embodiment
Next be to use comparative technology and technology described here to remove the experimental example of carbon-containing residue from process chamber.In ensuing all embodiment, the surface of CVD chamber all is covered with the carbon-containing residue that deposits composite organic hydrochlorate film and produce on silicon wafer.The mixture that the hole of 80 weight % forms the structure formation precursor diethoxymethyl silane (DEMS) of precursor limonene (LIMO) and 20 weight % is used at PECVD process chamber deposit film.Measure the film thickness of each film, and find to be approximately 1000nm (1 micron).Table 1a provides the technological parameter of handling the component of gas and being used for each embodiment.
Use Applied Materials P-5000 PECVD reactor or have the process chamber that remote plasma source (MKS Astron-Ex, from Wilmington, the MKS of MA obtains) invests wherein and implement these embodiment.This process chamber comprises baseline platform or hearth electrode, is connecting the top electrode of RF power supply, is used to flow into the gas access of handling gas, and is being connected the vacuum delivery side of pump.Locular wall be ground connection and remain on 75 ℃, and this chamber interior, for example pedestal remains on 300 ℃.After deposition composite organic hydrochlorate film, silicon wafer is removed and is carried out the cleaning of the carbon-containing residue of this chamber from the PECVD chamber.
For the embodiment that uses original position plasma cleaning formulation, this chamber is stabilized in constant pressure 1.5-3.0Torr, handles gas and can guarantee under the condition of the ratio of showing oxygen-containing gas shown in the 1a and fluoro-gas in this chamber of introducing at gas flow rate.Top electrode is by 13.56MHz RF power supply energize then.Handle gas and charge into this chamber, and use vacuum pump that the volatile products and the reactant gas of reaction are removed from this chamber by the gas access.
Use Applied Materials P-5000 DxZ PECVD chamber to implement remote plasma washing test, this chamber is the improvement thing of the remote plasma source of Astron-Ex of MKS company.After the organic silicate thin film of deposition, silicon wafer is removed and is carried out the cleaning of the carbon-containing residue of this chamber from the PECVD chamber.Repeat this technology.Make after this reactor exhaust, will handle gas and introduce the remote plasma generator of this Astron-Ex.Stablize constant pressure then and open and have the far-away sources of 6kW RF power supply.Believe that this strong plasma energy makes the branch quantum splitting of handling gas, wherein this processing gas flows into the downstream by the metal tube that is communicated with and enters this chamber by nozzle then, and reacts with the carbon-containing residue of this chamber surface.To remove from this reactor by the formed volatile compound of reaction between reactive materials and the residue by vacuum port.
Remote and original position plasma (remote+RF the is auxiliary) washing test that uses Applied Materials P-5000 DxZ PECVD chamber to make up, this chamber is the improvement thing of the remote plasma source of Astron-Ex of MKS company.Deposition composite organic hydrochlorate film is removed silicon wafer then from the PECVD chamber.Make after this reactor exhaust, will handle gas and introduce the remote plasma generator of this Astron-Ex.Stablize constant pressure then and open and have the far-away sources of 6kW RF power supply.Believe that this strong plasma energy makes the branch quantum splitting of handling gas, wherein this processing gas enters this chamber by nozzle.Top electrode is by 13.56MHzRF power supply energize then.Remote and the combination of original position plasma is activated reactive materials and the reaction of on-chip synthesizing organo-silicon hydrochlorate film.To remove from this reactor by the formed volatile compound of reaction between reactive materials and the carbon-containing residue by vacuum port.
After the deposition of each use various treatment formulations that Table I provided and parameter, clean the about 240-420 of this process chamber second.Afterwards, carry out this chamber and the wherein range estimation of fixture in the deposition (each 1000nm) of a series of (about 15-20) and clean cycle (about 200-420 second) at every turn.Visual observation is listed in the Table II, and below detailed results will be discussed.
Table I. formulation parameter
| Embodiment # | Figure # | Fluoro-gas | Oxygen-containing gas | Add gas | O 2/NF 3Mol ratio | Pressure (Torr) | Far-away sources | Former potential source | Original position power supply (w) |
| Comparative example 1 | 1 | NF 3 | Do not have | Argon | Do not have | 2.5 | Be | Not | Do not have |
| Comparative example 2 | 2a，2b | NF 3 | O 2 | Argon | 4.0 | 2.5 | Be | Not | Do not have |
| Comparative example 3 | 3a-3b | NF 3 | Do not have | Argon | Do not have | 2.5 | Be | Be | 1000.0 |
| Comparative example 4 | 4a，4b | NF 3 | O 2 | Helium | 3.0 | 2.0 | Not | Be | 1750.0 |
| Embodiment 1a | 5a-5d | NF 3 | O 2 | Helium | 2.0-4.0 | 2.0-3.0 | Not | Be | 1750.0 |
| Embodiment 1b | 5e，5f | NF 3 | O 2 | Helium | 4.0 | 2.0 | Not | Be | 1750.0 |
| Embodiment 2a | 5g-5j | NF 3 | O 2 | Argon | 3.0-6.0 | 2.0 | Not | Be | 1750.0 |
| Embodiment 2b | 5k，5l | NF 3 | O 2 | Argon | 4.0 | 2.0 | Not | Be | 1750.0 |
| Embodiment 3a | Do not have | NF 3 | O 2 | Argon | 2.0-4.0 | 1.5-2.5 | Be | Be | 750.0-1750.0 |
| Embodiment 3b | 6a，6b | NF 3 | O 2 | Argon | 3.0-5.0 | 2.0 | Be | Be | 1250.0 |
Table II. performance formula: range estimation and result
| Embodiment # | Washer jet? | Clean locular wall? | Clean throttle orifice? | The nozzle damage? |
| Comparative example 1 | Do not remove | Do not remove | Do not remove | Do not remove |
| Comparative example 2 | Do not remove.There is thick brown residue | Do not remove; There is residue | Do not remove; Be coated with the brown residue on every side | Not damaged |
| Comparative example 3 | Do not remove.On nozzle, there are yellow, powdery layer | Do not remove; There is the brown residue | Do not remove; Be coated with the brown residue on every side | Not damaged |
| Comparative example 4 | Remove | Do not remove; Exist the band brown striped and the brown of drop, many pores, the sclerosis residue | Do not remove.The thick-layer brown residue that has shelly | Form some electric arcs; Flashing-off |
| Embodiment 1a | The residue of ceramic ring outside is removed to minimum | Brown maculiform residue; At some zone crust | Brown shelly residue is arranged around the throttle orifice | Not damaged |
| Embodiment 1b | The residue of ceramic ring outside is removed to minimum | The yellow cord shape residue that has some brown spots | Some brown spots are around throttle orifice | Not damaged |
| Embodiment 2a | Except that having brown/yellow spotting shape residue, the outside, edge removes | Brown striated liquid residue | Do not remove.Thin brown residue is arranged around at the edge | Less (pin hole) flashing-off |
| Embodiment 2b | Remove | Remove | Remove | Not damaged |
| Embodiment 3a | Remove | The small residue of insignificant brown | The spot shape brown/yellow residue at edge is minimum | Not damaged |
| Embodiment 3b | Remove | Remove | Remove | Not damaged |
The example of chamber cleaning is monitored in the CVD chamber in pump exhaust place and quadrupole mass spectrometer (QMS) by Fourier transformation infrared spectrometer (FTIR).This industrial analysis is used to the accessory substance that the chamber of identification is cleaned, and measure and handle emission, and definite scavenging period.
Use a HgCdTe detector and a 0.01m air chamber that has heated in the downstream of handling pump, carry out the measurement of emission by the FTIR spectrum analysis (MKS Multigas, model 2010) of emission.In pump exhaust place, by 1/4 inch compression set sampling.The gas of being discharged thereby pass through N
2Pump purges (50-70slm) and dilutes.Use metal diaphragm pump from the pump effluent, to extract the technology effluent.Sample wire is to be heated to 1/8 inch about 100 ℃ stainless steel tube.Before vented exhaust, pass the FTIR unit and extract sample gas out with pump.The temperature and pressure of air chamber is controlled at 150 ℃ and 1.0 atmospheric pressure respectively.The concentration that is write down is corrected for temperature and pressure during measuring.At 0.5cm
-1Collect absorption spectrum under the resolution, on average surpass 8 scannings (scans).This analytical method summary that is used for measurement of concetration is in Table III.
Table III. be used for the analytic approach that FTIR measures
| Compound | Absorption region (cm -1) | Benchmark concentration (ppm.min) |
| NF 3 | 870-930 | 5，9，16，33，63，100 |
| SiF 4 | 1000-1044 | 140 |
| CF 4 | 1245-1290 | 6，28，53，112，280，1120 |
| COF 2 | 1880-1980；771-777；934-990； 1200-1280 | 50，80，125，200，300，500，800，1250， 2000，3000，5000 |
| HF | 3982-4364，3405-3982 | 1，5，10，15，20，25，50，75，100，250， 500，750，1000 |
Use Baizers quadrupole mass spectrometer (QMS) monitoring CVD chamber.This QMS is a feature with the ion source of one 200 an atomic mass unit massenfilter and a sealing.Sampling provides high sensitivity to 40 microns apertures for 1-10Torr.QMS uses flexible 1/4 inch stainless steel tube in the sampling of CVD chamber, and is positioned apart from the about 24 inches places of process chamber.N is used in quality location (m/e)
2(14,28 and 42 atomic mass unit) and NF
3(71 and 52 atomic mass unit) proofreaied and correct.Do not proofread and correct the QMS of quantitative measurment.For quick sampling, the QMS inlet extracts for differential, that is, the QMS response time must be shorter than the variation of gas component.Use the vacuum port draws sample gas of turbomolecular pump from the CVD chamber.The point that is used for the dividing potential drop monitoring is: NF
3(52 atomic mass unit), SiF
4(85 atomic mass unit), F
2(38 atomic mass unit), COF
2(66 atomic mass unit) CO
2(44 atomic mass unit), CF
4(69 atomic mass unit).Outflow the results are shown in the Table IV.This table is quantified the accessory substance (SiF in the effluent stream of every kind of prescription
4, CO
2, COF
2, CF
4, and HF) volume, and list in the Table IV for the analysis result of part embodiment.
Table IV. the effluent of different formulations
| Embodiment # | O 2/NF 3Mol ratio | Pressure (Torr) | Far-away sources | Former potential source | Original position power supply (w) | Average SiF 4 (scc) | Average CO 2 (scc) | Average HF (scc) | Average CF 4 (scc) | Average COF 2 (scc) |
| Comparative example 1 | Do not have | 2.5 | Be | Not | Do not have | 7.29 | 12.28 | 310.51 | 6.17 | 1.94 |
| Comparative example 2 | 4.0 | 2.5 | Be | Not | Do not have | 9.0 | 46.8 | 344.81 | 0.3 | 48.0 |
| Comparative example 3 | Do not have | 2.5 | Be | Be | 1000.0 | 25.40 | Do not have | 1111.34 | 413.00 | 28.86 |
| Comparative example 4 | 3.0 | 2.0 | Not | Be | 1750.0 | 20.75 | 181.43 | 890.42 | 2.45 | 73.17 |
| Embodiment 1b | 4.0 | 2.0 | Not | Be | 1750.0 | 20.66 | 198.03 | 916.74 | 1.20 | 57.83 |
| Embodiment 2b | 4.0 | 2.0 | Not | Be | 1750.0 | 33.26 | 287.48 | 1234.29 | 1.60 | 113.62 |
| Embodiment 3b | 3.0-5.0 | 2.0 | Be | Be | 1250.0 | 31.60 | 380.74 | 1164.54 | 8.06 | 175.01 |
Comparing embodiment 1:NF
3The remote plasma of/Ar cleans
Be used to assess remote NF as the CVD chamber of cleaning carbon-containing residue
3The isoionic process conditions of/Ar are as follows: the NF of per minute 700 standard cubic centimeters (sccm)
3Flow velocity; The argon flow rate of 1400sccm; With the 2.0-2.5Torr pressure limit.Other technological parameter and condition are listed in the Table I.All clean and all to use remote plasma source (that is, Astron opens) and remain in the CVD chamber (that is, do not adopt the RF power supply or do not have former potential source) without any plasma.Introduce argon gas and make after the pressure stability of this chamber, produce remote plasma by power supply being acted on the Astron plasma source.In case this argon plasma has been stablized, when keeping these ion energies, introduce NF
3Use remote NF
3/ Ar plasma cleaned this chamber 250 seconds.
FTIR distribution curve during the exemplary chamber cleaning has been shown among Fig. 1.The accessory substance that the chamber is cleaned is SiF
4, CO
2, CF
4, F
2, and HF, and list in the Table IV.These measurements show that silicon composition in the CVD residue is with SiF
4Form remove, and carbon component is mainly with CF
4Form is secondly with CO
2Form remove.Carbon residue comprises that also considerable hydrogen composition and itself and fluorine reaction generate HF.Although oxygen is not included in the composition of handling in the gas, yet oxygen also is the composition of CVD residue and is etch byproducts.Believe that thereby oxygen can produce CO with the carbon component and the fluorine plasma reaction of CVD residue
2Accessory substance.Fluorine gas (F
2) by remote NF
3The regrouping of F atom that plasma produced and producing.
With reference to Fig. 1, introduce NF
3Afterwards, SiF
4, CF
4, and the concentration of HF rapid growth is arranged.About 15-30 CF after second
4, HF and SiF
4Accessory substance reaches maximum.This chamber is exposed to active the processing in the gas after about 250 seconds, the CF that measures by FTIR
4, CO
2And SiF
4The concentration of accessory substance returns to baseline values.This distribution map typically represented etching be completely and locular wall removed the CVD residue.HF concentration has also reached the relatively stable value of about 800ppm.SiF
4, CF
4, and the HF distribution map clean after all showing about 200 seconds and be exposed to remote NF fully and again
3Plasma is invalid.
With reference to Table IV, respectively by the CO in the effluent stream
2Measured with the HF volume, the shared content of whole hydrocarbon residues that the processing gas of use embodiment 3b and parameter are removed is about 3% and 25%.By the SiF in the effluent stream
4Volume is measured, and the shared content of silicon residue that the processing gas of use embodiment 3b and parameter are removed is about 22%.By with CF
4, COF
2And CO
2The molal quantity of the carbon that form is removed is measured, and the carbon that the processing gas of use embodiment 3b and parameter are removed is removed the shared content of thing and is about 4%.
Comparing embodiment 1 proof, when the CVD chamber of the polymer residues of cleaning carbon containing, silicon, fluorine and hydrogen, remote NF
3Plasma is invalid.
Comparing embodiment 2:NF
3/ O
2The remote plasma of/Ar cleans
Be used to assess remote NF as the CVD chamber of cleaning carbon-containing residue
3/ O
2The isoionic process conditions summary of/Ar is in Table V.Finish ten depositions and 13 cleanings successively.Employed process parameters range is as follows: NF
3Flow velocity (0-300sccm), O
2: NF
3Than (0.0-4.0), pressure (2.5-3.0Torr).All clean and all to use remote plasma source (that is, Astron opens) and remain on without any plasma and (that is, not adopt the RF power supply) in the CVD chamber, described in Table I.Introduce argon gas and make after the pressure stability of this chamber, produce remote plasma by power supply being acted on the Astron plasma source.In case this argon plasma has been stablized, just when keeping these ion energies, introduce and contain NF
3And O
2The processing admixture of gas.Use remote NF then
3/ O
2/ Ar plasma cleans this chamber 130-250 second.
Table V. be used for comparing embodiment 2 (remote NF
3/ O
2/ Ar plasma) cleans the process conditions of testing
| Operation | Scavenging period (s) | Ar (sccm) | Pressure (Torr) | NF 3 (sccm) | O 2 (sccm) | O 2/NF 3Ratio | RF (W) | Astro n | | |
| 1 | 250.0 | 500 | 2.5 | 300.0 | 1200.0 | 4.0 | Do not have | | Stable | |
| 2 | 250.0 | 500 | 2.5 | 300.0 | 1200.0 | 4.0 | Do not have | | Stable | |
| 3 | 250.0 | 500 | 2.5 | 300.0 | 1200.0 | 4.0 | Do not have | | Stable | |
| 4 | 250.0 | 500 | 2.5 | 300.0 | 1200.0 | 4.0 | Do not have | | Stable | |
| 5 | 250.0 | 500 | 2.5 | 300.0 | 1200.0 | 4.0 | Do not have | | Stable | |
| 6 | Do not clean | Do not clean | Do not clean | Do not clean | Do not clean | Do not clean | Do not have | Open | Do not clean | |
| 7 | 250.0 | 500 | 2.5 | 300.0 | 1200.0 | 4.0 | Do not have | Open | Stable | |
| 8 | 250.0 | 500 | 2.5 | 300.0 | 1200.0 | 4.0 | Do not have | Open | Stable | |
| 9 | 250.0 | 500 | 2.5 | 300.0 | 1200.0 | 4.0 | Do not have | | Stable | |
| 10 | 250.0 | 500 | 2.5 | 0.0 | 1200.0 | No NF 3 | Do not have | | Stable | |
| 11 | 0.0 | 500 | 2.5 | 300.0 | 1200.0 | 4.0 | Do not have | Open | Not enough | |
| 12 | 130.0 | 1400 | 3.0 | 700.0 | 0.0 | 0.0 | Do not have | | Stable | |
| 13 | 250.0 | 500 | 2.5 | 300.0 | 1200.0 | 4.0 | Do not have | Open | Stable |
QMS during the exemplary chamber cleaning (operation #5) and FTIR distribution map are respectively as shown in Fig. 2 a and 2b.The accessory substance that the chamber is cleaned is SiF
4, CO
2, COF
2, F
2, and HF.These measurements show that silicon composition in the CVD residue is with SiF
4Form remove, and carbon component is with CO
2And COF
2Form volatilization.Carbon residue comprises that also considerable hydrogen composition and itself and fluorine reaction generate HF.Most silicon and carbon are with SiF
4, CO
2Form volatilization with HF.
With reference to figure 2a and 2b, introducing contains NF
3And O
2Processing gas after, SiF
4, CO
2With the concentration of HF rapid growth is arranged.The concentration of these accessory substances reaches maximum after about 30 seconds, reduces then.Carry out after this cleaned about 120 seconds, by QMS (Fig. 2 a) or FTIR (Fig. 2 b) record these by-product concentrations a little variation arranged.(Fig. 2 a) records F by QMS in the time of the decay of these etch byproducts
2Divide and be pressed with rapid growth.F
2Surface typically be good terminal monitor.NF
3/ O
2Generation fluorine atom in the plasma passes through etch consumption during the chamber is cleaned.In case etch processes is finished, then fluorine atom is with F
2Form regroups.SiF
4, CO
2, HF and F
2Distribution map all show and clean fully, and further be exposed to NF
3/ O
2Plasma is invalid.In fact, for cleaning, Room 13 of each comparing embodiment 2 produce sizable etching of crossing.
Finish after the deposition/clean cycle shown in the Table V range estimation CVD chamber interior.Although be the deposition and the PDEMS chemistry consumption (31 gram) of relatively small amount, yet can see considerable carbon residue at the CVD chamber surface.Result's summary of range estimation is in Table II.Thick brown residue appear on the nozzle and the throttle orifice periphery around.Locular wall also is covered with thin residue layer.This nozzle does not damage.
With reference to Table IV, respectively by the CO in the effluent stream
2Measured with the HF volume, the shared content of whole hydrocarbon residues that the technological parameter of use embodiment 3b is removed is about 13% and 30%.By the SiF in the effluent stream
4Volume is measured, and the shared content of silicon residue that the technological parameter of use embodiment 3b is removed is about 28%.By with CF
4, COF
2And CO
2The molal quantity of the carbon that form is removed is measured, and the carbon that the technological parameter of use embodiment 3b is removed is removed the shared content of thing and is about 17%.
Comparing embodiment 2 proves when the CVD chamber of the polymer residues of cleaning carbon containing, silicon, fluorine and hydrogen, remote NF
3/ O
2/ Ar plasma is invalid.
The NF that comparing embodiment 3: original position RF is auxiliary
3The remote plasma of/Ar cleans
Be used to assess NF as the remote and former bit combination of the CVD chamber of cleaning carbon-containing residue
3The isoionic process conditions summary of/Ar is in Table VI.Finishing ten times successively deposits and ten secondary cleaning (Table VI).The process parameters range of each operation is as follows: NF
3Flow velocity (700sccm), O
2: NF
3Than (0.0), pressure (2.5Torr), RF power supply (1000W).Handle in the gas during the chamber is cleaned and do not comprise oxygen (O
2).All clean and all adopt remote plasma source (that is, Astron opens) and the combination that remains on the original position plasma source of (that is the RF power supply of 1000W) in the CVD chamber.Introduce argon gas and make after the pressure stability of this chamber, produce remote plasma by power supply being acted on the Astron plasma source.In case this argon plasma has been stablized, just when keeping these ion energies, introduce NF
3In case remote NF
3/ Ar plasma is stablized (15 seconds), just the RF power supply is acted on injector electrode, at the indoor generation plasma of CVD (that is original position plasma).Use remote and original position NF then
3This chamber 210-360 second is cleaned in the combination of/Ar plasma.
Table VI. the remote NF that original position RF is auxiliary
3/ Ar plasma process condition
| Operation | Scavenging period (second) | Ar flow velocity (sccm) | Pressure (Torr) | NF 3Flow velocity (sccm) | Astron | Plasma stability | RF power supply (W) | |
| 1 | 250.0 | 1400 | 2.5 | 700.0 | Open | | No RF | |
| 2 | 250.0 | 1400 | 2.5 | 700.0 | Open | Stable | 1000.0 | |
| 3 | 250.0 | 1400 | 2.5 | 700.0 | Open | Stable | 1000.0 | |
| 4 | 210.0 | 1400 | 2.5 | 700.0 | Open | Stable | 1000.0 | |
| 5 | 360.0 | 1400 | 2.5 | 700.0 | Open | Stable | 1000.0 | |
| 6 | 330.0 | 1400 | 2.5 | 700.0 | Open | Stable | 1000.0 | |
| 7 | 300.0 | 1400 | 2.5 | 700.0 | Open | Stable | 1000.0 | |
| 8 | 300.0 | 1400 | 2.5 | 700.0 | Open | Stable | 1000.0 | |
| 9 | 300.0 | 1400 | 2.5 | 700.0 | Open | Stable | 1000.0 | |
| 10 | 300.0 | 1400 | 2.5 | 700.0 | Open | Stable | 1000.0 | |
| 11 | 300.0 | 1400 | 2.5 | 700.0 | Open | Stable | 1000.0 | |
| 12 | 300.0 | 1400 | 2.5 | 700.0 | Open | Stable | 1000.0 |
Show QMS and FTIR distribution map during the cleaning of exemplary chamber among Fig. 3 a and the 3b respectively.The accessory substance that the chamber is cleaned is SiF
4, CF
4, F
2, and HF.These measurements show that silicon composition in the CVD residue is with SiF
4Form remove, and carbon component is mainly with CF
4Form volatilization.Carbon residue comprises that also considerable hydrogen composition and itself and fluorine reaction generate HF.Most silicon and carbon are with SiF
4, CF
4And the form of HF volatilization.Also measure number of C OF
2And CO
2(Fig. 3 b).Although do not comprise O in the processing gas
2But oxygen is still the component of CVD residue and is etch byproducts.Infer that thereby oxygen may produce CO with carbon component and the fluorine plasma reaction in the CVD residue
2And COF
2Accessory substance.A large amount of F
2By remote NF
3The regrouping of F atom that plasma produced and producing.CF in the comparing embodiment 3
4Concentration shows thus that far above comparing embodiment 2 carbon is mainly with CF
4Form rather than with CO
2Or COF
2Form remove because the oxygen in the purge gas mixture is limited amount.
Introduce NF
3Afterwards, SiF
4, CF
4And the concentration of HF has rapid growth (Fig. 3 a and 3b).After about 30 seconds, HF and SiF
4The concentration of accessory substance reaches maximum, and after about 120 seconds, CF
4Peak concentration just produce.Carry out after this cleaned about 200 seconds, by QMS (Fig. 3 a) or FTIR (Fig. 3 b) record these by-product concentrations and return to baseline values.This distribution map shows that normally etching is complete, and locular wall has been eliminated the CVD residue.SiF
4, CF
4Clean after all showing about 200 seconds with the distribution map of HF and finish, and be exposed to the NF of combination again
3Plasma is invalid.In fact, for cleaning, Room 12 of each comparing embodiment 3 comprise sizable etching of crossing.
With reference to Table IV, measured by the HF volume in the effluent stream, the shared content of whole hydrocarbon residues that the technological parameter of use embodiment 3b is removed is about 95%.By the SiF in the effluent stream
4Volume is measured, and the shared content of silicon residue that the technological parameter of use embodiment 3b is removed is about 80%.By with CF
4, COF
2And CO
2The molal quantity of the carbon that form is removed is measured, and the carbon that the technological parameter of use embodiment 3b is removed is removed the shared content of thing and is about 77%.
Finish after the deposition/clean cycle shown in the Table VI range estimation CVD chamber interior.Although be the deposition and the PDEMS chemistry consumption (44 gram) of relatively small amount, yet can see considerable carbon residue at the CVD chamber surface.Result's summary of range estimation is in Table II.Yellow powdery residue covers on nozzle and the locular wall, and nozzle periphery is covered with the brown residue.Throttle orifice is covered with thick brown residue.There is not tangible plasma damage for nozzle.These observationses are consistent with the effluent distribution map, and this shows that main carbon back residue is residual time after second at cleaning this chamber 210-360.
The auxiliary remote NF of comparing embodiment 3 proof original position RF power supplys
3/ Ar plasma is not exclusively effectively when cleaning contains the CVD chamber of polymerism residue of carbon, silicon, fluorine and hydrogen.Although they have removed most of SiF
4Residue, but can not remove the carbon-based polymer residue fully.
Comparing embodiment 4:O
2/ NF
3NF than=3.0
3/ O
2/ He original position plasma
Be used to assess O as the CVD chamber of cleaning carbon-containing residue
2/ NF
3Than the NF that equals 3.0
3/ O
2The isoionic process conditions summary of/He original position is in Table I.Finish 16 times successively and deposit and clean, the parameter of these operations is listed in the Table VII.The effluent distribution map of #15 is as shown in Figs. 4a and 4b, and wash result has been discussed in Table II.This effluent distribution map shows that main outflow material is COF
2, CO
2, F
2, SiF
4And HF.In this effluent stream, also measure for example CF of other material
4And COF.First double fluid goes out product (COF
2And CO
2) mainly be when free oxygen and fluorine atom combine with the alkyl deposition residues, to form, and HF mainly is by the formation that reacts to each other from the hydrogen of hydro carbons and fluorine.The unreacted fluorine atom formation fluorine gas that regroups, its formed SiF during with silicon residue reaction in fluorine atom and this chamber
4From the chamber, discharge together.
Table VII .O
2/ NF
3Original position NF than=3
3/ O
2The process conditions that/He plasma cleans
| Operation | Scavenging period (s) | Pressure (Torr) | NF 3Flow velocity (sccm) | O 2Flow velocity (sccm) | He flow velocity (sccm) | RF power supply (W) | |
| 1 | 240.0 | 2.0 | 300.0 | 900.0 | 2000.0 | 1750 | Unstable |
| 2 | 240.0 | 2.0 | 300.0 | 900.0 | 2000.0 | 1750 | Unstable |
| 3 | 240.0 | 2.0 | 300.0 | 900.0 | 2000.0 | 1750 | Unstable |
| 4 | 260.0 | 2.0 | 300.0 | 900.0 | 2000.0 | 1750 | Unstable |
| 5 | 260.0 | 2.0 | 300.0 | 900.0 | 1000.0 | 1750 | Unstable |
| 6 | 225.0 | 2.0 | 300.0 | 900.0 | 1000.0 | 1750 | |
| 7 | 220.0 | 2.0 | 300.0 | 900.0 | 1000.0 | 1750 | Stable |
| 8 | 210.0 | 2.0 | 300.0 | 900.0 | 1000.0 | 1750 | Stable |
| 9 | 220.0 | 2.0 | 300.0 | 900.0 | 1000.0 | 1750 | |
| 10 | 220.0 | 2.0 | 300.0 | 900.0 | 1000.0 | 1750 | |
| 11 | 220.0 | 2.0 | 300.0 | 900.0 | 1000.0 | 1750 | |
| 12 | 220.0 | 2.0 | 300.0 | 900.0 | 1000.0 | 1750 | |
| 13 | 220.0 | 2.0 | 300.0 | 900.0 | 1000.0 | 1750 | Stable |
| 14 | 220.0 | 2.0 | 300.0 | 900.0 | 1000.0 | 1750 | Stable |
| 15 | 220.0 | 2.0 | 300.0 | 900.0 | 1000.0 | 1750 | Stable |
| 16 | 220.0 | 2.0 | 300.0 | 900.0 | 1000.0 | 1750 | Stable |
Introduce NF
3Afterwards, SiF
4, CO
2With the concentration of HF rapid growth (Fig. 4 a and 4b) is arranged.Approximately 30-45 is after second, SiF
4And CO
2The concentration of accessory substance reaches maximum, and approximately 90-120 is after second, and the peak concentration of HF just produces.SiF
4, CO
2Be respectively 200/1000000ths (ppm), 1000ppm and 4700ppm with the peak concentration of HF.Carry out to clean 210-260 after second, (Fig. 4 a) or the measured SiF of FTIR (Fig. 4) by QMS
4Concentration returns to baseline values.CO
2Although with HF by-product concentration-not in baseline values-also demonstrate downward trend.(Fig. 4 a) records F by QMS
2These etch byproducts decay are followed in the rapid growth of dividing potential drop.F
2Peak value appear at the about 150-180 that cleans after the beginning and locate second, and its appearance is typical good terminal monitor.NF
3/ O
2The fluorine atom that is produced in the plasma passes through etch consumption during the chamber is cleaned.In case etch processes is complete, then fluorine atom reconfigures and is F
2SiF
4, CO
2, HF and F
2Distribution map all show and be exposed to NF
3/ O
2After/He plasma surpasses 240 seconds, all be invalid aspect any residue that remains on the locular wall of removing.
With reference to Table IV, respectively by the CO in the effluent stream
2Measured with the HF volume, the shared content of whole hydrocarbon residues that the technological parameter of use embodiment 3b is removed is about 48% and 76%.By the SiF in the effluent stream
4Volume is measured, and the shared content of silicon residue that the technological parameter of use embodiment 3b is removed is about 65%.By with CF
4, COF
2And CO
2The molal quantity of the carbon that form is removed is measured, and the carbon that the technological parameter of use embodiment 3b is removed is removed the shared content of thing and is about 46%.
This chamber of carrying out after a series of tests in Table II and the range estimation of nozzle show that the original position cleaning formulation that is used for these tests has successfully been removed all residues of nozzle, yet cause some small nozzle damages.Yet this prescription can not clean locular wall, and even after clean repeatedly the many pores of still residual embrown and residue that hardened.Also can observe liquid striped of brown and drop liquid along the some parts of locular wall.Throttle orifice find thick brown, the shelly residue.These visual observation are consistent with the calculated value that the total hydro carbons that calculates from the effluent distribution map is removed thing.
Comparing embodiment 4 proof O
2With NF
3Ratio be 3 original position NF
3/ O
2/ He plasma can not clean the CVD chamber of the polymerism residue that contains carbon, silicon, fluorine and hydrogen fully.After scavenging period is the 210-260 repeatedly cleaning of second, still residual a large amount of carbon back residue.
Embodiment 1a: the NF of experimental study
3/ O
2/ He original position plasma cleans design
Use NF
3/ O
2The process conditions that/He original position plasma is carried out a series of deposition and clean cycle as shown in Table VIII.Finishing 20 times successively deposits and 20 secondary cleaning.CO in the effluent stream
2Content (volume) is as pressure, NF
3Flow velocity and O
2/ NF
3The function of ratio is shown among Fig. 5 a and the 5b.Cleaning characteristics result sketches in Table II.Contour plot among Fig. 5 a and the 5b shows, works as O
2/ NF
3Than increasing to 4.0 from 2.0, when pressure is reduced to 2.0Torr from 3.0Torr, and when the flow velocity of interpolation gas (helium) when 500 increase to 2000sccm, the CO in the effluent stream
2Content increases.Contour plot among Fig. 5 c and the 5d shows, works as O
2/ NF
3Than from 2.0 increase to 4.0 and pressure when 3.0Torr is reduced to 2.0Torr, the SiF in the effluent stream
4Content also increases, but only is a small amount of.When helium flow speed increases, SiF in the effluent stream
4Constancy of volume, the removing that therefore shows the silicon residue is completely basically and does not rely on the flow velocity that adds gas.
Table VIII. the NF of experimental study
3/ O
2/ He original position plasma cleans the test condition of design
| Operation | Helium flow speed (sccm) | O 2/NF 3Ratio | NF 3Flow velocity (sccm) | O 2Flow velocity (sccm) | Pressure (Torr) | Scavenging period (s) | RF power supply (W) | Plasma stability |
| 1 | 1000 | 4.0 | 300.0 | 1200 | 2.0 | 200.0 | 1750 | Stable |
| 2 | 1000 | 4.0 | 300.0 | 1200 | 2.0 | 200.0 | 1750 | Stable |
| 3 | 1000 | 4.0 | 300.0 | 1200 | 2.0 | 200.0 | 1750 | Stable |
| 4 | 750 | 3.0 | 300.0 | 900 | 2.0 | 200.0 | 1750 | Stable |
| 5 | 500 | 2.0 | 300.0 | 600 | 2.0 | 200.0 | 1750 | Stable |
| 6 | 500 | 3.0 | 300.0 | 900 | 2.5 | 200.0 | 1750 | Stable |
| 7 | 500 | 2.0 | 300.0 | 600 | 3.0 | 200.0 | 1750 | Unstable |
| 8 | 1000 | 4.0 | 300.0 | 1200 | 2.0 | 200.0 | 1750 | Stable |
| 9 | 1000 | 3.0 | 300.0 | 900 | 2.5 | 200.0 | 1750 | Stable |
| 10 | 500 | 4.0 | 300.0 | 1200 | 2.0 | 200.0 | 1750 | Stable |
| 11 | 1000 | 4.0 | 300.0 | 1200 | 3.0 | 200.0 | 1750 | Stable |
| 12 | 750 | 2.0 | 300.0 | 600 | 2.5 | 200.0 | 1750 | Stable |
| 13 | 750 | 3.0 | 300.0 | 900 | 2.5 | 200.0 | 1750 | Stable |
| 14 | 750 | 4.0 | 300.0 | 1200 | 2.5 | 200.0 | 1750 | Stable |
| 15 | 500 | 4.0 | 300.0 | 1200 | 3.0 | 200.0 | 1750 | Stable |
| 16 | 750 | 3.0 | 300.0 | 900 | 3.0 | 200.0 | 1750 | Stable |
| 17 | 1000 | 2.0 | 300.0 | 600 | 2.0 | 200.0 | 1750 | Stable |
| 18 | 750 | 3.0 | 300.0 | 900 | 2.5 | 200.0 | 1750 | Stable |
| 19 | 750 | 3.0 | 300.0 | 900 | 2.5 | 200.0 | 1750 | Stable |
| 20 | 1000 | 2.0 | 300.0 | 600 | 3.0 | 200.0 | 1750 | Stable |
| 21 | 750 | 3.0 | 300.0 | 900 | 2.5 | 200.0 | 1750 | Stable |
| 22 | 750 | 4.0 | 300.0 | 1200 | 2.0 | 200.0 | 1750 | Stable |
With reference to Table II, this chamber of carrying out after a series of tests and the range estimation of nozzle show, except the outer lip outside at the ceramic ring of nozzle has occurred the micro residue thing, this nozzle has been removed totally.There is not the nozzle damage.Some housings that occur moth patch shape residue on the locular wall.Brown shelly residue has also appearred around throttle orifice.
Embodiment 1b:O
2/ NF
3The NF of ratio=4.0 and P=2.0Torr
3/ O
2/ He original position plasma cleans
Be used to assess original position NF as the CVD chamber of cleaning carbon-containing residue
3/ O
2The isoionic process conditions summary of/He is in Table I X.Finish 20 primary depositing and cleaning successively.Fig. 5 e and 5f provide operation #15 (P=2.0Torr and O
2/ NF
3Ratio=4.0) effluent distribution map, and Table II has been discussed wash result.The effluent distribution map shows that main outflow material is COF
2, CO
2, F
2, SiF
4And HF.First double fluid goes out product (COF
2And CO
2) mainly be when free oxygen and fluorine atom combine with the alkyl deposition residues, to form, and HF mainly to be hydrogen by hydro carbons and fluorine react to each other formation.In effluent stream, also monitor other material, for example CF
4And COF.The unreacted fluorine atom formation fluorine gas that regroups, its formed SiF during with silicon residue reaction in fluorine atom and this chamber
4From the chamber, discharge together.
Table I X.O
2/ NF
3The NF of ratio=4.0 and P=2.0Torr
3/ O
2The test condition that/He original position plasma cleans
| Operation | Helium flow speed (sccm) | O 2/NF 3Ratio | Pressure (Torr) | NF 3Flow velocity (sccm) | O 2Flow velocity (sccm) | Plasma stability | RF power supply (W) | Scavenging period (second) |
| 1 | 1500 | 3.0 | 2.0 | 300.0 | 900.0 | Unstable | 1750 | Variable |
| 2 | 1500 | 3.0 | 2.0 | 300.0 | 900.0 | Unstable | 1750 | Variable |
| 3 | 1500 | 3.0 | 2.0 | 300.0 | 900.0 | Unstable | 1750 | 220.0 |
| 4 | 1500 | 5.0 | 2.0 | 300.0 | 1500.0 | Unstable | 1750 | 220.0 |
| 5 | 1000 | 5.0 | 2.0 | 300.0 | 1500.0 | Unstable | 1750 | 220.0 |
| 6 | 1000 | 4.0 | 2.0 | 300.0 | 1200.0 | Unstable | 1750 | 220.0 |
| 7 | 1000 | 4.0 | 2.0 | 300.0 | 1200.0 | Stable | 1750 | 240.0 |
| 8 | 1000 | 4.0 | 2.0 | 300.0 | 1200.0 | Stable | 1750 | 225.0 |
| 9 | 1000 | 4.0 | 2.0 | 300.0 | 1200.0 | Stable | 1750 | 200.0 |
| 10 | 1000 | 4.0 | 2.0 | 300.0 | 1200.0 | Stable | 1750 | 200.0 |
| 11 | 1000 | 4.0 | 2.0 | 300.0 | 1200.0 | Stable | 1750 | 200.0 |
| 12 | 1000 | 4.0 | 2.0 | 300.0 | 1200.0 | Stable | 1750 | 200.0 |
| 13 | 1000 | 4.0 | 2.0 | 300.0 | 1200.0 | Stable | 1750 | 200.0 |
| 14 | 1000 | 4.0 | 2.0 | 300.0 | 1200.0 | Stable | 1750 | 200.0 |
| 15 | 1000 | 4.0 | 2.0 | 300.0 | 1200.0 | Stable | 1750 | 200.0 |
| 16 | 1000 | 4.0 | 2.0 | 300.0 | 1200.0 | Stable | 1750 | 200.0 |
| 17 | 1000 | 4.0 | 2.0 | 300.0 | 1200.0 | Stable | 1750 | 200.0 |
| 18 | 1000 | 4.0 | 2.0 | 300.0 | 1200.0 | Stable | 1750 | 200.0 |
| 19 | 1000 | 4.0 | 2.0 | 300.0 | 1200.0 | Stable | 1750 | 200.0 |
| 20 | 1000 | 4.0 | 2.0 | 300.0 | 1200.0 | Stable | 1750 | 180.0 |
| 21 | 1000 | 4.0 | 2.0 | 300.0 | 1200.0 | Stable | 1750 | 180.0 |
Introduce NF
3Afterwards, SiF
4, CO
2With the concentration of HF rapid growth (Fig. 5 e and 5f) is arranged.About 30-45 SiF after second
4And CO
2The concentration of accessory substance reaches maximum, and approximately 90-120 after second the peak concentration of HF just produce.SiF
4, CO
2Be respectively 200 (ppm), 1000ppm and 4700ppm with the peak concentration of HF.Carry out this cleaning 210-260 after second, by QMS (Fig. 5 e) or FTIR (Fig. 5 f)) SiF that records
4Concentration returns to baseline values.CO
2Although with HF by-product concentration-not in baseline values-also demonstrate downward trend.Record at F by QMS (Fig. 5 e)
2The sharp increase of dividing potential drop is these etch byproducts decay simultaneously.F
2Peak value appear at the about 150-180 that cleans after the beginning and locate second, and its appearance is typical good terminal monitor.NF
3/ O
2The fluorine atom that is produced in the plasma passes through etch consumption during the chamber is cleaned.In case etch processes is complete, then fluorine atom regroups and is F
2SiF
4, CO
2, HF and F
2Distribution map all show and be exposed to NF
3/ O
2After/He plasma surpasses 240 seconds, all be invalid aspect any residue that remains on the locular wall of removing.
With reference to Table IV, respectively by the CO in the effluent stream
2Measured with the HF volume, the shared content of whole hydrocarbon residues that the technological parameter of use embodiment 3b is removed is about 52% and 79%.By the SiF in the effluent stream
4Volume is measured, and the shared content of silicon residue that the technological parameter of use embodiment 3b is removed is about 65%.By with CF
4, COF
2And CO
2The molal quantity of the carbon that form is removed is measured, and the carbon that the technological parameter of use embodiment 3b is removed is removed the shared content of thing and is about 46%.
With reference to Table II, this chamber of carrying out after a series of test and the range estimation of nozzle show that the original position cleaning formulation that is used for these tests has successfully been removed residue from nozzle, and without any the nozzle damage.Yet this prescription can not clean locular wall fully, and even after cleaning repeatedly still residual the yellow cord shape residue that has some brown spots.Around throttle orifice, also can observe some brown spots.These visual observation are consistent with the calculated value that the total hydro carbons that calculates from the effluent distribution map is removed thing.
Embodiment 1b proves about 240 seconds scavenging period and high O
2/ NF
3Guarantee whole basically siliceous residues and above half the removing of alkyl residue than (among this embodiment than=4.0) and low-pressure (being lower than 3.0Torr among this embodiment) binding energy.
Embodiment 2a:NF
3/ O
2/ Ar original position plasma cleans
A series of use NF
3/ O
2The process conditions summary that/Ar original position plasma is carried out is in Table X.Finish 19 depositions and 20 cleanings successively.CO in the effluent stream
2Content (volume) is as pressure, NF
3Flow velocity and O
2/ NF
3The function of ratio is shown among Fig. 5 g and the 5h.Cleaning characteristics result sketches in Table II.Contour plot among Fig. 5 g and the 5h shows, works as O
2/ NF
3Than increasing to the CO in the effluent stream at 5.0 o'clock from 3.0
2Content increases, but does not have big variation when pressure when 2.0Torr is reduced to 1.5Torr.Yet when the flow velocity that adds gas (argon) increases number of C O when 1000 reduce to 500sccm
2Remove thing.Contour plot among Fig. 5 i and the 5j shows, works as O
2/ NF
3Than increasing to the SiF in the effluent stream at 5.0 o'clock from 3.0
4It is about 15% that content increases, but do not have big variation when pressure when 2.0Torr is reduced to 1.5Torr.
Table X .NF
3/ O
2The test condition that/Ar original position plasma cleans
| Operation | Scavenging period (s) | Argon flow rate (sccm) | O 2/NF 3Ratio | Pressure (Torr) | NF 3Flow velocity (sccm) | O 2Flow velocity (sccm) | Plasma stability | RF power supply (W) |
| 1 | 240.0 | 1000 | 4.0 | 2.0 | 300.0 | 1200.0 | Stable | 1750 |
| 2 | 120.0 | 1000 | 4.0 | 2.0 | 300.0 | 1200.0 | Stable | 1750 |
| 3 | 200.0 | 500 | 3.0 | 2.0 | 300.0 | 900.0 | Stable | 1750 |
| 4 | 200.0 | 500 | 5.0 | 2.0 | 300.0 | 1500.0 | Stable | 1750 |
| 5 | 200.0 | 1000 | 5.0 | 2.0 | 300.0 | 1500.0 | Stable | 1750 |
| 6 | 200.0 | 1000 | 3.0 | 2.0 | 300.0 | 900.0 | Stable | 1750 |
| 7 | 200.0 | 1000 | 3.0 | 1.5 (1.64) | 300.0 | 900.0 | Unstable | 1750 |
| 8 | 200.0 | 500 | 3.0 | 1.5 | 300.0 | 900.0 | Unstable | 1750 |
| 9 | 200.0 | 500 | 5.0 | 2.0 | 200.0 | 1000.0 | Unstable | 1750 |
| 10 | 200.0 | 1000 | 5.0 | 2.0 | 200.0 | 1000.0 | Unstable | 1750 |
| 11 | 200.0 | 1000 | 4.0 | 2.0 | 250.0 | 1000.0 | Stable | 1750 |
| 12 | 220.0 | 1000 | 5.0 | 2.0 | 250.0 | 1250.0 | Stable | 1750 |
| 13 | 220.0 | 750 | 5.0 | 2.0 | 250.0 | 1250.0 | Stable | 1750 |
| 14 | 220.0 | 500 | 5.0 | 2.0 | 250.0 | 1250.0 | Stable | 1750 |
| 15 | 200.0 | 500 | 6.0 | 2.0 | 250.0 | 1500.0 | Stable | 1750 |
| 16 | 200.0 | 500 | 5.0 | 2.0 | 300.0 | 1500.0 | Stable | 1750 |
| 17 | 200.0 | 500 | 5.0 | 2.0 | 300.0 | 1500.0 | Stable | 1750 |
| 18 | 200.0 | Mechanical breakdown | Mechanical breakdown | Mechanical breakdown | Mechanical breakdown | Mechanical breakdown | Mechanical breakdown | Mechanical breakdown |
| 19 | 200.0 | 500 | 5.0 | 2.0 | 300.0 | 1500.0 | Stable | 1750 |
| 20 | 200.0 | 500 | 5.0 | 2.0 | 300.0 | 1500.0 | Stable | 1750 |
With reference to Table II, this chamber of carrying out after a series of tests and the range estimation of nozzle show, except little brown-yellow, spot shape residue that the outside at ring occurs, this nozzle has been removed totally.This nozzle has less (pin hole) flashing-off (burn mark), and the chances are is caused by unsettled plasma under the low pressure for it.The brown residue that the striated similar liquids is arranged on the locular wall, and thin brown residue is arranged around the ring of throttle orifice.These residues are that the wide region owing to process conditions used in this research produces; That is, some test conditions are suitable for the erase residual thing unlike shown in the embodiment 3b.
Embodiment 2b:0
2/ NF
3The NF of ratio=4.0 and P=2.0Torr
3/ O
2/ Ar original position plasma cleans
The tentative test condition that is used for this embodiment is shown in following Table X I.Operation #20 (P=2.0 and O
2/ NF
3Than=4.0) the effluent distribution map shown in Fig. 5 k and 5l and wash result is discussed in Table II.The effluent distribution map shows that main outflow material is COF
2, CO
2, F
2, SiF
4And HF.First double fluid goes out product (COF
2And CO
2) mainly be when free oxygen and fluorine atom combine with the alkyl deposition residues, to form, and HF mainly to be hydrogen by hydro carbons and fluorine react to each other formation.In effluent stream, also monitor other material, for example CF
4And COF
2The unreacted fluorine atom formation fluorine gas that regroups, its formed SiF during with silicon residue reaction in fluorine atom and this chamber
4From the chamber, discharge together.
Table X I.O
2/ NF
3The NF of ratio=4.0 and P=2.0Torr
3/ O
2The test condition that/Ar original position plasma cleans
| Operation | Scavenging period (s) | Argon flow rate (sccm) | Pressure (Torr) | NF 3Flow velocity (sccm) | O 2Flow velocity (sccm) | O 2/NF 3Ratio | Plasma stability | RF power supply (W) |
| 1 | 360.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | Stable | 1750.0 |
| 2 | 360.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | Stable | 1750.0 |
| 3 | 360.0 | 500 | 2.0 | 300.0 | 1800.0 | 6.0 | Stable | 1750.0 |
| 4 | 360.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | Stable | 1750.0 |
| 5 | 360.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | Stable | 1750.0 |
| 6 | 360.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | Stable | 1750.0 |
| 7 | 360.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | Stable | 1750.0 |
| 8 | 360.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | Stable | 1750.0 |
| 9 | 360.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | Stable | 1750.0 |
| 10 | 360.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | Stable | 1750.0 |
| 11 | 360.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | Stable | 1750.0 |
| 12 | 360.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | Stable | 1750.0 |
| 13 | 360.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | Stable | 1750.0 |
| 14 | 360.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | Stable | 1750.0 |
| 15 | 360.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | Stable | 1750.0 |
| 16 | 420.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | Stable | 1750.0 |
| 17 | 420.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | Stable | 1750.0 |
| 18 | 420.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | Stable | 1750.0 |
| 19 | 420.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | Stable | 1750.0 |
| 20 | 420.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | Stable | 1750.0 |
Introduce NF
3Afterwards, SiF
4, CO
2With the concentration of HF rapid growth (Fig. 5 k and 5l) is arranged.Begin to clean about 90 seconds SiF afterwards
4Concentration reach the maximum of about 400ppm, and HF and CO
2Just early the generation after about 30 and 60 seconds respectively of the peak value of concentration.CO
2Be respectively 2500ppm and 9000ppm with the peak concentration of HF.QMS (Fig. 5 k) or FTIR (Fig. 5 l) record about 4 minutes SiF afterwards
4Concentration reaches baseline values, and after about 6 minutes CO
2Reach baseline values with the concentration of HF.
Record at F by QMS (Fig. 5 k)
2The dividing potential drop sharp increase is these etch byproducts decay simultaneously.F
2Peak value appear at the about 180-240 that cleans after the beginning and locate second, and its appearance is typical good terminal monitor.NF
3/ O
2The fluorine atom that is produced in the plasma passes through etch consumption during the chamber is cleaned.In case etch processes is complete, then fluorine atom regroups and is F
2F after 4 minutes
2The concentration profile level that becomes, in fact therefore about 3-4 minute mistake etching period be provided.
With reference to Table II, this chamber of carrying out after a series of test and the range estimation of nozzle show that nozzle, locular wall and throttle orifice all clean up.Although nozzle itself does not demonstrate any structure damage, independent flashing-off is arranged on nozzle.
With reference to Table IV, respectively by the CO in the effluent stream
2Measured with the HF volume, the shared content of whole hydrocarbon residues that the technological parameter of use embodiment 3b is removed is about 76% and 100%.By the SiF in the effluent stream
4Volume is measured, and the shared content of silicon residue that the technological parameter of use embodiment 3b is removed is about 100%.By with CF
4, COF
2And CO
2The molal quantity of the carbon that form is removed is measured, and the carbon that the technological parameter of use embodiment 3b is removed is removed the shared content of thing and is about 72%.
These observed results show, use sufficiently long scavenging period when (300-420 second), and the original position cleaning formulation that is used for these tests has successfully been removed silicon and hydro carbons residue.These observed results are consistent with the effluent distribution map, after it shows that cleaning finishes (420 seconds), the HF of trace only arranged, negligible CO
2And COF
2, and do not have SiF
4Or CF
4
The NF that embodiment 3a. original position RF is auxiliary
3/ O
2The remote plasma of/Ar cleans: DOE research
Be used to assess remote and original position NF as the combination of the CVD chamber of cleaning carbon-containing residue
3/ O
2The isoionic process conditions summary of/Ar is in Table X II.Finish whole 49 depositions and 50 secondary cleaning successively.The process parameters range that research obtains is as follows: NF
3Flow velocity (400-1600sccm), O
2: NF
3Than (2.0-4.0), pressure (1.75-2.50Torr), RF power supply (750-1750W).All clean and adopt remote plasma source (that is, Astron opens) and remain on the plasma combination of (that is, adopting the RF power supply of 750-1750W) in the CVD chamber.
Introduce argon gas and make after the pressure stability of this chamber, produce remote plasma by power supply being acted on the Astron plasma source.In case this argon plasma has been stablized, when keeping these ion energies, introduce and contain NF
3And O
2Processing gas.In case remote NF
3/ O
2/ Ar plasma is stablized (15 seconds), just the RF power supply is acted on injector electrode, thereby at the indoor generation plasma of CVD (that is original position plasma).Use remote and original position NF then
3This chamber 320-420 second is cleaned in the combination of/Ar plasma.Next each process conditions of sketching in Table X II are carried out auxiliary (the crossing etching) of following condition and are cleaned: NF
3=400sccm, O
2=1600sccm, Ar=500sccm, pressure=2.0Torr, Astron=opens, RF power supply=1000W, time=60-180s.This purpose of crossing the etching cleaning is, after the tentative processing that each Table X II is sketched, removes any residual carbon residue.
Reference table XII finishes after deposition/clean cycle, range estimation CVD chamber interior.Although be a large amount of deposition and PDEMS chemistry consumptions (190 gram), yet only see few carbon residue at the CVD chamber surface.Nozzle has been removed any CVD residue fully.Locular wall is almost completely to clean up, and only sees and can ignore the brown watermark residue of not remembering.Minimum spot shape brown/yellow residue is arranged around the ring of throttle orifice.Nozzle does not have the vestige of plasma damage, and all plasmas are stable.
Remote and the original position NF of embodiment 3a proof combination
3/ O
2/ Ar plasma is effective when cleaning contains the CVD chamber of polymerism residue of carbon, silicon, fluorine and hydrogen.
The NF that Table X II. original position RF is auxiliary
3/ O
2The remote plasma of/Ar cleans
| Operation | Scavenging period (s) | Ar ?(sccm) | Pressure (Torr) | NF 3Flow velocity (sccm) | O 2Flow velocity (sccm) | O 2/NF 3Ratio | RF (W) | Astron | Plasma stability |
| 1 | 420 | 500 | 2.0 | 400 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 2 | 420 | 500 | 2.0 | 400 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 3 | 420 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 4 | 420 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 5 | 420 | 500 | 2.5 | 200.0 | 400.0 | 2.0 | 1750.0 | Open | Stable |
| 6 | 420 | 500 | 2.5 | 200.0 | 400.0 | 2.0 | 750.0 | Open | Stable |
| 8 | 420 | 500 | 1.5 | 200.0 | 800.0 | 4.0 | 1750.0 | Open | Stable |
| 9 | 420 | 500 | 1.5 | 200.0 | 400.0 | 2.0 | 1750.0 | Open | Stable |
| 10 | 420 | 500 | 2.0 | 300.0 | 900.0 | 3.0 | 1250.0 | Open | Stable |
| 11 | 420 | 500 | 2.5 | 300.0 | 900.0 | 3.0 | 1250.0 | Open | Stable |
| 12 | 420 | 500 | 2.5 | 400.0 | 800.0 | 2.0 | 750.0 | Open | Stable |
| 13 | 420 | 500 | 1.5 | 200.0 | 400.0 | 2.0 | 750.0 | Open | Stable |
| 14 | 420 | 500 | 2.0 | 300.0 | 900.0 | 3.0 | 750.0 | Open | Stable |
| 15 | 420 | 500 | 1.5 | 200.0 | 800.0 | 4.0 | 750.0 | Open | Stable |
| 16 | 420 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 17 | 420 | 500 | 2.5 | 400.0 | 800.0 | 2.0 | 1750.0 | Open | Stable |
| 18 | 420 | 500 | 2.0 | 200.0 | 600.0 | 3.0 | 1250.0 | Open | Stable |
| 19 | 420 | 500 | 1.5 | 400.0 | 1600.0 | 4.0 | 1750.0 | Open | Stable |
| 20 | 320 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1750.0 | Open | Stable |
| 21 | 320 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 22 | 320 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 23 | 320 | 500 | 2.0 | 300.0 | 900.0 | 3.0 | 1250.0 | Open | Stable |
| 24 | 320 | 500 | 2.0 | 300.0 | 900.0 | 3.0 | 1250.0 | Open | Stable |
| 25 | 320 | 500 | 1.5 | 300.0 | 900.0 | 3.0 | 1250.0 | Open | Stable |
| 26 | 320 | 500 | 2.0 | 400.0 | 1200.0 | 3.0 | 1250.0 | Open | Stable |
| Operation | Scavenging period (s) | Ar (sccm) | Pressure (Torr) | NF 3Flow velocity (sccm) | O 2Flow velocity (sccm) | O 2/NF 3Ratio | RF (W) | Astron | Plasma stability |
| 27 | 320 | 500 | 1.5 | 400.0 | 800.0 | 2.0 | 750.0 | Open | Stable |
| 28 | 320 | 500 | 2.0 | 300.0 | 1200.0 | 4.0 | 1250.0 | Open | Stable |
| 29 | 320 | 500 | 1.5 | 400.0 | 800.0 | 2.0 | 1750.0 | Open | Stable |
| 30 | 320 | 500 | 1.5 | 400.0 | 1600.0 | 4.0 | 750.0 | Open | Stable |
| 31 | 320 | 500 | 1.5 | 400.0 | 800.0 | 2.0 | 1750.0 | Open | Stable |
| 32 | 320 | 500 | 2.5 | 400.0 | 1600.0 | 4.0 | 1750.0 | Open | Stable |
| 33 | 320 | 500 | 2.0 | 300.0 | 900.0 | 3.0 | 1750.0 | Open | Stable |
| 34 | 420 | 500 | 1.6 | 300 | 900 | 3.0 | 1250 | Open | Stable |
| 35 | 420 | 500 | 1.6 | 300 | 900 | 3.0 | 1250 | Open | Stable |
| 36 | 420 | 500 | 1.6 | 300 | 900 | 3.0 | 1250 | Open | Stable |
| 37 | 420 | 500 | 1.75 | 300 | 900 | 3.0 | 1250 | Open | Stable |
| 38 | 420 | 500 | 2.5 | 200 | 800 | 4.0 | 750 | Open | Stable |
| 39 | 420 | 500 | 2.5 | 200 | 800 | 4.0 | 1750 | Open | Stable |
| 40 | 420 | 500 | 2 | 300 | 600 | 2.0 | 1250 | Open | Stable |
| 41 | 420 | 500 | 2.5 | 400 | 1600 | 4.0 | 750 | Open | Stable |
| 42 | 360 | 500 | 2.5 | 200 | 800 | 4.0 | 1750 | Open | Stable |
| 43 | 360 | 500 | 1.75 | 300 | 1200 | 4.0 | 1250 | Open | Stable |
| 44 | 360 | 500 | 1.75 | 300 | 1200 | 4.0 | 1250 | Open | Stable |
| 45 | 360 | 500 | 1.75 | 300 | 1200 | 4.0 | 1250 | Open | Stable |
| 46 | 360 | 500 | 1.75 | 300 | 1200 | 4.0 | 1250 | Open | Stable |
| 47 | 360 | 500 | 1.75 | 300 | 1200 | 4.0 | 1250 | Open | Stable |
| 48 | 360 | 500 | 1.75 | 300 | 1200 | 4.0 | 1250 | Open | Stable |
| 49 | 360 | 500 | 1.75 | 300 | 1200 | 4.0 | 1250 | Open | Stable |
| 50 | 360 | 500 | 2.00 | 400 | 1600 | 4.0 | 1250 | Open | Stable |
| 51 | 360 | 500 | 2.00 | 400 | 1600 | 4.0 | 1250 | Open | Stable |
| 52 | 360 | 500 | 2.00 | 400 | 1600 | 4.0 | 1250 | Open | Stable |
| Operation | Scavenging period (s) | Ar (sccm) | Pressure (Torr) | ?NF 3Flow velocity (sccm) | O 2Flow velocity (sccm) | O 2/NF 3Ratio | RF (W) | Astron | Plasma stability |
| 53 | 360 | 500 | 2.00 | 400 | 1600 | 4.0 | 1250 | Open | Stable |
| 54 | 360 | 500 | 2.00 | 400 | 1600 | 4.0 | 1250 | Open | Stable |
The NF that embodiment 3b. original position RF is auxiliary
3/ O
2The remote plasma of/Ar cleans
Be used to prove auxiliary NF as the original position RF of the CVD chamber of cleaning carbon-containing residue
3/ O
2The process conditions of the remote isoionic effect of/Ar are as follows: NF
3Flow velocity=400sccm, O
2: NF
3Than=4.0, argon flow rate=500sccm, pressure=2.0Torr, Astron opens, RF power supply=1250W.Assess preferred embodiment by finishing 20 (20) inferior depositions/cleaning (Table II) successively.All clean and adopt remote plasma source (that is, Astron opens) and remain on the original position plasma source combination of (that is, adopting the RF power supply of 1250W) in the CVD chamber.
The pressure stability of introducing argon gas (500sccm) and making this chamber produces remote plasma by power supply being acted on the Astron plasma source after 2.0Torr.In case this argon plasma has been stablized, keeping these ion energies to introduce NF simultaneously
3(400sccm) and O
2(1600sccm).In case remote NF
3/ O
2/ Ar plasma is stablized (15 seconds), just the RF power supply is acted on injector electrode, at the indoor generation plasma of CVD (that is original position plasma).Use the remote and original position NF of combination then
3/ Ar plasma cleaned this chamber 360 seconds.Ensuing deposition and preferred chamber cleaning formulation did not have etching to clean.
The NF that Table X III. original position RF is auxiliary
3/ O
2The remote plasma of/Ar cleans
| Operation | Scavenging period (s) | Ar (sccm) | Pressure (Torr) | NF 3Flow velocity (sccm) | O 2Flow velocity (sccm) | O 2/NF 3Ratio | RF (W) | Astron | Plasma stability |
| 1 | 240.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 2 | 240.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 3 | 240.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 4 | 300.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 5 | 300.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 6 | 300.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 7 | 300.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 8 | 300.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 9 | 300.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 10 | 300.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 11 | 240.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 12 | 240.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 13 | 240.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 14 | 240.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 15 | 300.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 16 | 300.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 17 | 360.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 18 | 360.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 19 | 360.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 20 | 360.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 21 | 360.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
| 22 | 360.0 | 500 | 2.0 | 400.0 | 1600.0 | 4.0 | 1250.0 | Open | Stable |
QMS during exemplary chamber cleaning (operation #20) and FTIR distribution map are respectively shown in Fig. 6 a and 6b.The accessory substance that the chamber is cleaned is SiF
4, CF
4, F
2, HF, COF
2And CO
2These measurements show that silicon composition in the CVD residue is with SiF
4Form remove, and carbon component is mainly with CO
2, COF
2And CF
4Form volatilization.Carbon residue comprises that also considerable hydrogen composition and itself and fluorine reaction generate HF.Most silicon is converted into SiF
4, and most hydrocarbon residue is converted into CO
2COF
2CF
4And HF.A large amount of F
2By remote NF
3The reconfiguring of F atom that plasma produced and producing.
Introduce NF
3And O
2Afterwards, the concentration of all accessory substances all has rapid growth: SiF
4, CF
4, CO
2, COF
2And HF (Fig. 6 a and 6b).Cleaning beginning back CF in the time of about 10 seconds
4The concentration of accessory substance reaches maximum, and other accessory substance (CO
2, SiF
4And HF) concentration about 45-60 after drawing the original position plasma reaches maximum during second.Approximately 240-300 distribution curve second reaches their stable state value after drawing the original position plasma, show thus etching fully and locular wall removed the CVD residue.SiF
4, CF
4, CO
2, COF
2Clean fully after all showing about 240 seconds with the distribution map of HF, and be exposed to the NF of combination again
3/ O
2/ Ar plasma is unnecessary.In fact, for cleaning, the Room 20 of each embodiment 3b comprise sizable etching of crossing.
With reference to Table II, finish after deposition/clean cycle range estimation CVD chamber interior.Although be a large amount of deposition and PDEMS chemistry consumptions, yet CVD chamber surface former state.Nozzle, locular wall and throttle orifice have been removed any CVD residue fully.Nozzle does not have the vestige of plasma damage, and all plasmas are stable.These observed results and the CO that passes through in the effluent stream
2HF and SiF
4The hydrocarbon of the measured removing of volume consistent with the total content of silicon residue.With reference to Table IV, by with CF
4, COF
2And CO
2The measured result of molal quantity of the carbon that form is removed is maximum with the carbon remote and that original position plasma prescription is removed that makes up.
Remote and the original position NF of embodiment 3b proof combination
3/ O
2/ Ar plasma is effective when cleaning contains the CVD chamber of polymerism residue of carbon, silicon, fluorine and hydrogen.
Claims (20)
1, a kind of technology that is used for removing carbon-containing residue from least a portion of substrate surface, this technology comprises:
A kind of processing gas that is made of oxygen source, fluorine source and optional interpolation gas is provided, and wherein should handle the contained oxygen of gas and the molar ratio range of fluorine is from about 1 to about 10;
Use at least a energy source to activate this processing gas, thereby reactive materials is provided; With
This substrate surface is contacted with this reactive materials, thus volatilization and remove carbon-containing residue from this surface.
2, the technology of claim 1, at least a portion of wherein said activation step takes place in the position of the outside, place of carrying out contact procedure.
3, the technology of claim 1, wherein said activation step and described contact procedure take place in same place.
4, the technology of claim 1, wherein said oxygen source comprise and are selected from least a in oxygen, ozone, nitric oxide, nitrous oxide, nitrogen dioxide, carbon monoxide, carbon dioxide, water and composition thereof.
5, the technology of claim 1, wherein said activation step are used a kind of remote plasma energy source.
6, the technology of claim 5, wherein said activation step is used the original position plasma.
7, the technology of claim 1, wherein the fluorine source comprises and is selected from F
2, HF, NF
3, SF
6, COF
2, NOF, C
3F
3N
3, C
2F
2O
2, perfluocarbon, hydrogen fluorine carbide, fluorine oxycarbide, oxidation hydrogen fluorine carbide, hydrogen fluorine ether, Fluorine monohydroxide ester, fluoro peroxide, fluoro trioxide, amine fluoride, fluoridize at least a in nitrile and composition thereof.
8, the technology of claim 1, wherein at least a described oxygen source is identical compound with the fluorine source.
9, the technology of claim 8, wherein said identical compound are to be selected from least a in Fluorine monohydroxide ester, fluoro peroxide, fluoro trioxide and composition thereof.
10, the technology of claim 1, wherein said processing gas comprises interpolation gas.
11, the technology of claim 10, wherein said interpolation gas is to be selected from H
2, N
2, He, Ne, Kr, Xe, Ar, and composition thereof in a kind of.
12, a kind of technology that is used for removing carbon-containing residue from chamber surfaces, wherein this process chamber is used to deposit the composite organic silicate material, and this technology comprises:
Process chamber is provided, and wherein this chamber comprises the surface that is covered with carbon-containing residue to small part;
A kind of processing gas that is made of oxygen source, fluorine source and optional interpolation gas is provided, and wherein should handle the contained oxygen of gas and the molar ratio range of fluorine is from about 1 to about 10;
Use at least a energy source to activate this processing gas, thereby form reactive materials;
Described residue is contacted with this reactive materials, thereby form at least a volatile products; With
Remove described at least a volatile products from this process chamber.
13, the technology of claim 12, at least a portion of wherein said activation step takes place in the position of the outside, place of carrying out contact procedure.
14, the technology of claim 13, wherein said contact procedure is carried out under 5Torr or littler pressure.
15, a kind of technology that is used for removing carbon-containing residue from chamber surfaces, wherein this process chamber is used to deposit the composite organic silicate material, and this technology comprises:
Process chamber is provided, and wherein this chamber comprises the surface that is covered with carbon-containing residue to small part;
A kind of processing gas that is made of oxygen source, fluorine source and optional interpolation gas is provided, and wherein should handle the contained oxygen of gas and the molar ratio range of fluorine is from about 1 to about 10;
Use at least a energy source to activate this processing gas, to form reactive materials, wherein at least a portion of this processing gas activates in this process chamber, and should handle the position activation of another part at least outside this process chamber of gas;
Described residue is contacted with this reactive materials, thereby form at least a volatile products; With
Remove described at least a volatile products from this process chamber.
16, a kind of technology that is used for removing carbon-containing residue from chamber surfaces, wherein this process chamber is used to deposit the composite organic silicate material, and this technology comprises:
Process chamber is provided, and wherein this chamber comprises the surface that is covered with carbon-containing residue to small part;
A kind of processing gas that is made of oxygen source, fluorine source and optional interpolation gas is provided, and wherein should handle the contained oxygen of gas and the molar ratio range of fluorine is from about 1 to about 10;
Use at least a energy source to activate this processing gas, to form reactive materials, wherein the first of this processing gas activates and is incorporated in this process chamber in this process chamber outside, and the second portion of this processing gas activates in this process chamber;
Described residue is contacted with this reactive materials, thereby form at least a volatile products, wherein this contact procedure is carried out under 5Torr or littler pressure; With
Remove described at least a volatile products from this process chamber.
17, the technology of claim 16, wherein said composite organic hydrochlorate film are formed with holes the deposition of precursor and structure formation precursor and produce.
18, the technology of claim 17, wherein said hole forms precursor and is selected from α-terpinenes, limonene, cyclohexane, 1,2,4-trimethyl-cyclohexane, 1,5-dimethyl-1, at least a in the diene of 5-cyclo-octadiene, amphene, adamantane, 1,3-butadiene, replacement, decahydronaphthalene and composition thereof.
19, the technology of claim 17, wherein said structure forms precursor and is selected from diethoxymethyl silane, dimethoxy-methyl silane, the diisopropoxy methyl-monosilane, two tert-butoxy methyl-monosilanes, methyl triethoxysilane, methyltrimethoxy silane, methyl three isopropoxy silane, methyl three tert-butoxy silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyl diisopropoxy silane, dimethyl two tert-butoxy silane, 1,3,5, the 7-tetramethyl-ring tetrasiloxane, at least a in octamethylcy-clotetrasiloxane and the tetraethoxysilane.
20, a kind of technology that is used for deposition one deck composite organic hydrochlorate film on substrate, this technology comprises:
Described substrate is placed in the process chamber;
Use a kind of hole form precursor and a kind of structure form precursor deposition composite organic hydrochlorate film on this substrate and on this at least one indoor surface the deposited carbon-containing residue, wherein this deposition step is carried out by the technology that is selected from chemical vapour deposition (CVD), ald, vacuum moulding machine, spray pyrolysis and combination thereof;
A kind of processing gas that is made of oxygen source, fluorine source and optional interpolation gas is provided, and wherein should handle the contained oxygen of gas and the molar ratio range of fluorine is from about 1 to about 10;
Use at least a energy source to activate this processing gas, to form reactive materials;
Described residue is contacted with this reactive materials, thereby form at least a volatile products; With
Thereby remove described at least a volatile materials from reactor and clean this reactor.
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|---|---|---|---|
| US59062804P | 2004-07-23 | 2004-07-23 | |
| US60/590628 | 2004-07-23 | ||
| US11/178545 | 2005-07-12 |
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