CN1662676A - Method for forming ultra low k films using electron beam - Google Patents

Method for forming ultra low k films using electron beam Download PDF

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Publication number
CN1662676A
CN1662676A CN038146177A CN03814617A CN1662676A CN 1662676 A CN1662676 A CN 1662676A CN 038146177 A CN038146177 A CN 038146177A CN 03814617 A CN03814617 A CN 03814617A CN 1662676 A CN1662676 A CN 1662676A
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China
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film
electron beam
dielectric constant
low dielectric
flow velocity
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CN038146177A
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CN100400707C (en
Inventor
费尔哈德·D·穆加达姆
赵军
蒂莫西·韦德曼
里克·J·罗伯茨
夏立群
亚历山德罗斯·T·迪莫斯
文·H·朱
黄楚范
李丽华
埃利·Y·易
郑毅
斯里尼瓦斯·D·内曼尼
埃里克·霍拉
亦康苏
源松文
莱斯特·A·德克鲁埃
特洛伊·金
戴安·苏吉阿托
彼得·韦曼·李
希沙姆·穆萨德
梅利沙·M·塔姆
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Applied Materials Inc
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Applied Materials Inc
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Priority claimed from US10/302,375 external-priority patent/US20040101632A1/en
Priority claimed from US10/302,393 external-priority patent/US7060330B2/en
Priority claimed from US10/409,887 external-priority patent/US20030211244A1/en
Application filed by Applied Materials Inc filed Critical Applied Materials Inc
Publication of CN1662676A publication Critical patent/CN1662676A/en
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Publication of CN100400707C publication Critical patent/CN100400707C/en
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    • H—ELECTRICITY
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment
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    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02211—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound being a silane, e.g. disilane, methylsilane or chlorosilane
    • H—ELECTRICITY
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    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02214—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen
    • H01L21/02216—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
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    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H01L21/02345—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to radiation, e.g. visible light
    • H01L21/02351—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to radiation, e.g. visible light treatment by exposure to corpuscular radiation, e.g. exposure to electrons, alpha-particles, protons or ions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/60—Deposition of organic layers from vapour phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/068—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using ionising radiations (gamma, X, electrons)
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/31058—After-treatment of organic layers

Abstract

A method for depositing a low dielectric constant film on a substrate. The method includes depositing a low dielectric constant film comprising silicon, carbon, oxygen and hydrogen in a chemical vapor deposition chamber. The method further includes exposing the low dielectric constant film to an electron beam at conditions sufficient to increase the hardness of the low dielectric constant film.

Description

Method with the electron beam forming ultra low k films
Technical field
Embodiments of the invention relate to the manufacturing of unicircuit.More particularly, embodiments of the invention relate to the method for dielectric layer on substrate.
Background technology
Unicircuit, significantly descends on geometrical dimension after being introduced first decades ago from it.From then on, unicircuit is generally followed size every two years and is reduced the rule (being commonly referred to More's law) of half, this means that the quantity of device is every two years just doubled on the chip.Current preparation facility generates the device with 0.13 μ m even 0.1 μ m characteristic dimension routinely, and facility from now on has the more device of small-feature-size with producing very soon.
The continuing of device geometries reduces to have caused the demand to the film with lower k value, because the condenser coupling between the adjacent wires must be lowered further to reduce size of devices on the unicircuit.Specifically, have less than the isolator of about 4.0 low-k (k) and expect.Example with isolator of low-k comprises spin-coating glass, undoped silicon glass (USG), mixes fluorine silex glass (FSG) and polytetrafluoroethylene (PTFE), and these all can be buied on market.
A kind of effective ways that reduce the k value are to introduce the hole in film.The result is, low-k film has low physical strength (for example hardness) usually, and this may hinder film is integrated in the manufacturing of device.The physical strength of current use plasma aftertreatment increasing low-k film.But Cement Composite Treated by Plasma causes the increase of k value.
Therefore, need a kind of method that is used to increase the physical strength of low-k film and does not increase the k value.
Summary of the invention
Embodiments of the invention relate generally to the method for deposit low dielectric constant films on substrate.This method is included in and deposits the film having low dielectric constant that comprises silicon, carbon, oxygen and hydrogen in the CVD (Chemical Vapor Deposition) chamber.This method also is included under the condition of the hardness that is enough to increase film having low dielectric constant film having low dielectric constant is exposed in the electron beam.
Description of drawings
Therefore, reference is illustrated embodiment in the accompanying drawings, has provided the mode that can at length understand above-mentioned feature of the present invention, and to the more detailed description of the invention of simplified summary in the above.But, be noted that accompanying drawing just illustrates general embodiment of the present invention, therefore can not think limitation of the scope of the invention, because the present invention can allow other to be equal to effective embodiment.
Fig. 1 is the cross-sectional view of the exemplary CVD reactor that disposes according to the use of the embodiments described herein.
Fig. 2 is the electron beam chamber according to the embodiment of the invention.
Fig. 3 is the part figure according to the electron beam chamber of the embodiment of the invention.
Fig. 4 illustrates the electron beam chamber with feedback control circuit according to the embodiment of the invention.
Embodiment
To provide concrete description now.Here employed various terms define below.Do not provide the situation of definition below for the term that uses in the claims, the generalized that this term should be given this term that the person skilled in the relevant gives defines, as reflecting in printed publication and granted patent.Embodiments of the invention all provide remarkable and unexpected improvement to hardness, fracture threshold value and the electric property (for example leakage current and damage voltage) of ultralow dielectric film.In one embodiment, be enough to form under the condition of ultralow dielectric film (k is less than 2.5), deposition comprises the film of silicon, carbon, oxygen and hydrogen on substrate surface.Then, the ultralow dielectric film is carried out the electron beam aftertreatment.
According to one or more embodiment of the present invention, one or more film properties have been improved by electron beam (" e-beam ") processing, such as but not limited to mechanical property, thermostability, specific inductivity, etching selection, anti-isotropy tape handling (strip process) (for example, non-cross-linked polymer can be with the tape handling of isotropy downstream plasma and etching easily) and copper diffusion obstruction characteristic.We think that electron beam treatment provides such improvement at least in one aspect, because it is crosslinked (promptly that electron beam treatment has been carried out dehydrogenation to film, we think that the effect of electron beam treatment is preferentially to remove hydrogen bond, thereby make the carbon bond can be crosslinked), thus make film fine and close and increase surface hardness and Young's modulus.We also think, can realize this effect at least and do not change its most composition basically under most of situation.
According to one or more embodiment of the present invention, in the first step of producing the low-k dielectric film method, use CVD depositing operation (in the mode of describing in detail below) deposition low-k dielectric film, wherein low-k dielectric film can have predetermined porosity.Usually, the film that deposits of this CVD is very soft and comprise metastable grain and plant (species).When this CVD deposited film during by thermal annealing, metastable grain is planted and is removed, and film shrinks---and this film may have 2.6 k value., use plasma-annealing technology to reduce the time of thermal annealing by film is exposed in the plasma environment.But the plasma-annealing process efficiency is low, because its influence is limited to the surface of film.Next, according to this embodiment of the invention, in second step of producing low-k dielectric film, on the sedimentary film of CVD, carry out electron beam treatment (comprising heating film simultaneously) to be converted into hard, highly cross-linked film.At last, according to this embodiment of the invention, in the optional third step of producing low-k dielectric film, can carry out thermal annealing to the film of electron beam treatment.Its advantage is, strengthened the structure of film with the sedimentary film of electron beam treatment CVD, removed metastable grain simultaneously and planted preventing and shrink.
Be used to deposit an embodiment of the method for the film having low dielectric constant that comprises silicon, oxygen and carbon, need to use the presoma of forming based on organosilyl compound by one or more cyclic.In addition, this embodiment need mix one or more cyclic based on organosilyl compound and one or more acyclic silicoorganic compound.On the one hand, cyclic silicoorganic compound, acyclic silicoorganic compound and hydrocarbon polymer be enough to form k less than the condition of 2.5 film having low dielectric constant under with reacted.The cyclic silicoorganic compound comprise at least one silicon-carbon bonds.Acyclic silicoorganic compound comprise, such as but not limited to si-h bond or siloxane bond.Hydrocarbon polymer can be linear or cyclic, and can comprise carbon-carbon double bond or triple bond.According to one or more embodiment of the present invention,, may not need oxidizing gas so if at least a organosilicon gas comprises oxygen.
Cvd film comprises-network forming of Si-O-Si-ring junction, and described structure and one or more linear organic compound are crosslinked.Because crosslinked, produced the reactive stable net that between ring texture, has bigger spacing, therefore, sedimentary film have bigger porosity.
The ultralow dielectric film generally forms by mixing one or more precursor gas, and described precursor gas can comprise cyclic silicoorganic compound, fatty compounds, hydrocarbon polymer and oxygenated compound.The cyclic silicoorganic compound can comprise the ring texture with three or more Siliciumatoms, and this ring texture may further include one or more Sauerstoffatoms.The cyclic silicoorganic compound that can buy on the market comprise silicone atom alternative ring, and one or more alkyl linked to Siliciumatom.For example, the cyclic silicoorganic compound can comprise one or more in the following compound:
1,3,5-three silylation-2,4,6-trimethylene, (SiH 2-CH 2-) 3-(ring-type)
1,3,5,7-tetramethyl-ring tetrasiloxane (TMCTS), (SiH (CH 3)-O-) 4-(ring-type)
Octamethylcyclotetrasiloxane (OMCTS), (Si (CH 3) 2-O-) 4-(ring-type)
1,3,5,7,9-pentamethyl-D5, (SiH (CH 3)-O-) 5-(ring-type)
1,3,5,7-tetrasilane base-2,6-dioxy-4,8-dimethylene, (SiH 2-CH 2-SiH 2-O-) 2-(ring-type)
Hexamethyl cyclotrisiloxane, (Si (CH 3) 2-O-) 3-(ring-type)
Fatty compounds comprises linear or branched (the being acyclic) silicoorganic compound with one or more Siliciumatoms and one or more carbon atoms, and the linear or branched hydrocarbon polymer with at least one unsaturation carbon bond.Described structure can also comprise oxygen.The aliphatics silicoorganic compound that can buy on the market are included in and do not wrap oxygen containing organosilane between Siliciumatom and the oxygen containing organo-siloxane of bag between two or more Siliciumatoms.For example, the aliphatics silicoorganic compound can comprise one or more in the following compound:
Methyl-monosilane CH 3-SiH 3
Dimethylsilane (CH 3) 2-SiH 2
Trimethyl silane (CH 3) 3-SiH
Diethoxymethyl silane (DEMS) CH 3-SiH-(O-CH 2-CH 3) 2
Dimethyldimethoxysil,ne (DMDMOS) (CH 3O) 2-Si-(CH 3) 2
Dimethyldimethoxysil,ne (CH 3) 2-Si-(O-CH 3) 2
Ethylsilane CH 3-CH 2-SiH 3
Disilane methylmethane SiH 3-CH 2-SiH 3
Two (methyl-monosilane base) methane CH 3-SiH 2-CH 2-SiH 2-CH 3
1,2-disilane base ethane SiH 3-CH 2-CH 2-SiH 3
1,2-two (methyl-monosilane base) ethane CH 3-SiH 2-CH 2-CH 2-SiH 2-CH 3
2,2-disilane base propane SiH 3-C (CH 3) 2-SiH 3
1,3-dimethyl sily oxide CH 3-SiH 2-O-SiH 2-CH 3
1,1,3,3-tetramethyl disiloxane (TMDSO) (CH 3) 2-SiH-O-SiH-(CH 3) 2
Hexamethyldisiloxane (HMDS) (CH 3) 3-Si-O-Si-(CH 3) 3
1,3-two (silylation methylene radical) sily oxide (SiH 3-CH 2-SiH 2-) 2-O
Two (1-methyl disiloxanyl-) methane (CH 3-SiH 2-O-SiH 2-) 2-CH 2
2,2-two (1-methyl disiloxanyl-) propane (CH 3-SiH 2-O-SiH 2-) 2-C (CH 3) 2
Hexa methoxy sily oxide (HMDOS) (CH 3-O) 3-Si-O-Si-(O-CH 3) 3
Diethylsilane (C 2H 5) 2SiH 2
Propyl silane C 3H 7SiH 3
Vinyl methyl-monosilane CH 2=CH-SiH 2-CH 3
1,1,2,2-tetramethyl-disilane (CH 3) 2-SiH-SiH-(CH 3) 2
Hexamethyldisilane (CH 3) 3-Si-Si-(CH 3) 3
1,1,2,2,3,3-hexamethyl three silane (CH 3) 2-SiH-Si (CH 3) 2-SiH-(CH 3) 2
1,1,2,3,3-pentamethyl-three silane (CH 3) 2SiH-SiH (CH 3)-SiH (CH 3) 2
Dimethyl disilane base ethane CH 3-SiH 2-(CH 2) 2-SiH 2-CH 3
Dimethyl disilane base propane CH 3-SiH-(CH 2) 3-SiH-CH 3
Tetramethyl-disilane base ethane (CH 3) 2-SiH-(CH 2) 2-SiH-(CH 3) 2
Tetramethyl-disilane base propane (CH 3) 2-SiH-(CH 2) 3-Si-(CH 3) 2
Hydrocarbon polymer has 1 to about 20 adjacent carbon atoms.Hydrocarbon polymer can comprise the adjacent carbons of bonding by singly-bound, two key and triple-linked arbitrary combination.For example, organic compound can comprise having 2 alkene and alkylene to about 20 carbon atoms, for example ethene, third rare, acetylene, divinyl, tertiary butyl ethene, 1,1,3,3-tetramethyl butyl benzene, tertbutyl ether, methyl methacrylate (MMA) and tertiary butyl furfuryl group ether.
Silicoorganic compound also comprise the silicoorganic compound of the hydrocarbon composition with one or more unsaturated carbon carbon bonds, and described unsaturated carbon carbon bond is carbon-carbon double bond, carbon carbon triple bond or aryl for example.For example, the silicoorganic compound with hydrocarbon composition of one or more unsaturated carbon carbon bonds can comprise one or more in the following compound:
Vinyl methyl-monosilane CH 2=CHSiH 2CH 3
Dimethoxymethylvinylchlane (DMMVS) (CH 3O) 2-Si (CH 3)-CH=CH 2
Trimethyl silyl acetylene (CH 3) 3Si-C ≡ CH
1-(trimethyl silyl)-1,3-butadiene (CH 3) 3Si-HC ≡ CH-HC ≡ CH 2
Trimethyl silyl cyclopentadiene (CH 3) 3Si-C 5H 5
Trimethyl silyl acetic ester (CH 3) 3Si-O (C=O) CH 3
Two-tert.-butoxy diacetoxyl silane ((CH 3) 3(C=O)) 2-Si-((C=O) (CH 3) 3) 2
In one embodiment, be enough under the condition of deposit low dielectric constant films on the substrate, have one or more silicoorganic compound and one or more reacted of the hydrocarbon composition that comprises one or more unsaturated carbon carbon bonds, and be sent to substrate surface.
In another embodiment, be enough under the condition of deposit low dielectric constant films on the substrate, one or more silicoorganic compound and one or more aliphatic hydrocarbons and one or more reacted, and be sent to substrate surface.The aliphatic hydrocarbon compounds can comprise 1 to about 20 adjacent carbons.Hydrocarbon compound can comprise the adjacent carbons of bonding by singly-bound, two key and triple-linked arbitrary combination.Preferably, the aliphatic hydrocarbon compounds comprises at least one unsaturated carbon carbon bond.For example, fatty compounds can comprise having 2 alkene, alkylene and diolefine to about 20 carbon atoms, for example ethene, propylene, iso-butylene, acetylene, propine, ethylacetylene, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and m-pentadiene.
In another embodiment, the present invention includes by being enough to form under the condition of pre-treatment film net, mix one or more compounds with at least one cyclic group, one or more silicoorganic compound and optional oxidizing gas, significantly and unexpectedly reduced to contain the specific inductivity of the film of silicon, oxygen and carbon.On the one hand, to be enough to the amount of deposit low dielectric constant films on semiconducter substrate, have one or more organic compound and one or more silicoorganic compound and the reacted of at least one cyclic group.
Can carry out in the treatment chamber of chemical vapor deposition (CVD), using plasma body to assist can deposited film.Use pulsed RF, high-frequency RF, double frequency, two-phase RF or any other known, can produce plasma body maybe with the plasma generation technology of finding.After the film deposition, use the electron beam cured film, to remove organic side group (pendant organic groups), for example in deposition process, be attached to the cyclic group of the organic compound in the film web frame.
Cure step provides energy to the film web frame, and at least a portion cyclic group with in volatilization and the removal film web frame has the more more porous film net of low-k and stay.Under most of situation, the hardened film with compare according to the sedimentary unhardened film of embodiment described here, demonstrate and exceed the hardness of twice at least, can exceed 600% at most.Use the k value of the film of electron-beam curing to reduce unexpectedly, hardness increases unexpectedly, and this can't realize by traditional hardening technique.Typically, the hardened film has about 2.5 or littler specific inductivity, is preferably about 2.2 or littler, and hardness is greater than about 0.6GPa.
About having one or more compounds of at least one cyclic group, used here " cyclic group " means ring texture.This ring texture can include as few as three atom.These atoms for example can comprise carbon, silicon, nitrogen, oxygen, fluorine and their arbitrary combination.Cyclic group can comprise one or more singly-bounds, two key, triple bond and their arbitrary combination.For example, cyclic group can comprise one or more aromatic hydrocarbons, aryl, phenyl, hexanaphthene, cyclohexadiene, cycloheptadiene and their combination.Cyclic group can also be dicyclo or three rings.In addition, cyclic group preferably is bonded to linear or branched functional group.Linear or branched functional group preferably comprises alkyl or vinyl alkyl group, and has 1 to 20 carbon atom.Linear or branched functional group can also comprise Sauerstoffatom, for example ketone, ether and ester.Some exemplary compounds with at least one cyclic group comprise α terpinene (ATP), vinyl cyclohexane (VCH) and acetoxyphenyl group ester, just list here.
In the above-mentioned presoma some comprise oxygen, therefore can not need extra oxygenant.But, in any embodiment of Miao Shuing, can use one or more oxidizing gases here.Under the situation of one or more oxidizing gases of needs or liquid, they can comprise oxygen (O 2), ozone (O 3), nitrous oxide (N 2O), carbon monoxide (CO), carbonic acid gas (CO 2), water (H 2O), hydrogen peroxide (H 2O 2), oxygen-containing organic compound or their combination.In one embodiment, oxidizing gas is an oxygen.In another embodiment, oxidizing gas is an ozone.When using ozone as oxidizing gas, ozonizer accounts for weight in the gas of source 6% to 20%, generally is about 15% oxygen and is transformed into ozone, and remaining generally be oxygen.But,, can increase or reduce ozone concn according to the ozone consumption of expectation and the type of employed ozonizer.In reaction gas mixtures, add one or more oxidizing gases, with the carbon content that improves reactivity and in sedimentary film, obtain to expect.
The deposition of ultralow dielectric film can be carried out in single sediment chamber or discontinuous carrying out continuously.Perhaps, can be in two or more sediment chambers deposited film sequentially, for example as the Producer that can obtain from the Applied Materials of California Santa Clara TMCarry out in such combination tool (cluster tool).
The carbon content of institute's deposited film is not about 5 to (comprising hydrogen atom) between about 30 atomic percents, preferably about 5 between about 20 atomic percents.The carbon content of institute's deposited film is meant and does not become the membrane structure of key hydrocarbon polymer to carry out atom analysis in a large number to generally not comprising.Carbon content is represented by the per-cent of carbon atom in the deposited film, side by side except being difficult to quantized hydrogen atom.For example, the film that on average has a Siliciumatom, a Sauerstoffatom, a carbon atom and two hydrogen atoms contains the carbon of 20 atomic percents of having an appointment (in per 5 atoms a carbon atom being arranged), perhaps is about the carbon (in per three atoms except hydrogen atom a carbon atom being arranged) of 33 atomic percents under the situation of getting rid of hydrogen atom.
Can use any treatment chamber that can carry out chemical vapor deposition (CVD) to come deposited film.Referring now to Fig. 1, illustrate the vertical cross-section of parallel plate CVD treatment chamber 10.Chamber 10 comprises high vacuum region 15 and gas distribution manifold 11, and gas distribution manifold 11 has and is used for will handling gas dispersion to the perforation (not shown) of substrate by it.Substrate is placed on substrate support plate or the pedestal 12.Pedestal 12 is installed on the support bar 13, and support bar 13 is connected to pedestal 12 and promotes engine 14.Promote engine 14 and raise between position and the lower substrate loading position and reduce pedestal 12 handling, make that pedestal 12 (and be supported on pedestal 12 upper surfaces substrate) can be in lower load/unload position with controllably mobile between near the higher processing position of manifold 11.When pedestal 12 and substrate were positioned at the high processing position, isolator 17 was round them.
The gas that is incorporated into manifold 11 radially is evenly distributed to the surface of substrate.Vacuum pump 32 control with throttling valve by manifold 24 from the chamber 10 deflated speed.Deposition gases and carrier gas (if necessary) flow into hybrid system 19 by gas pipeline 18, arrive manifold 11 then.Usually, each is handled gas supply line 18 and comprises: (i) safety cut-off valve (not shown), it can cut off the processing entraining air stream of inlet chamber automatically or manually, and (ii) mass flow controller (also not shown), and it is used to measure the gas flow by gas supply pipe 18.When using toxic gas in the technology, in traditional configuration, on each gas supply pipe 18 several safety cut-off valves are set all.
In deposition process, the mixture and the reacted of one or more cyclic organosilicon compounds and one or more fatty compoundss are to form ultralow k film on substrate.Cyclic organosilicon compounds can combine with at least a aliphatics silicoorganic compound and at least a aliphatic hydrocarbon.For example, it is that about 5 to about 80 one or more cyclic organosilicon compounds, volume percent are one or more aliphatics silicoorganic compound of about 5 to about 15 that mixture comprises volume percent, and volume percent is one or more aliphatic hydrocarbons of about 5 to about 45.It is one or more oxidizing gases of about 5 to about 20 that mixture also comprises volume percent.Perhaps, it is one or more cyclic organosilicon compounds of about 45 to about 60 that mixture can comprise volume percent, volume percent is one or more aliphatics silicoorganic compound of about 5 to about 10, and volume percent is one or more aliphatic hydrocarbons of about 5 to about 35.
Generally with about 100 to about 10,000sccm, be preferably the flow velocity of about 520sccm with one or more cyclic organosilicon compounds introducing mixing systems 19.With about 100 to about 1,000sccm, be preferably the flow velocity of about 600sccm with one or more aliphatics silicoorganic compound introducing mixing systems 19.With about 100 to about 10,000sccm, be preferably the flow velocity of about 2000sccm with one or more aliphatic hydrocarbons introducing mixing systems 19.The flow velocity of oxygen-containing gas is about 100 between about 6000sccm, be preferably about 1,000sccm.Can be with about 100sccm to about 10, the flow velocity of 000sccm will comprise one or more silicoorganic compound of the alkyl composition with one or more unsaturated carbon carbon bonds and introduce mixing systems 19.Preferably, cyclic organosilicon compounds is 1,3,5,7-tetramethyl-ring tetrasiloxane, octamethylcyclotetrasiloxane or their mixing, and the aliphatics silicoorganic compound are trimethyl silanes, 1,1,3,3-tetramethyl disiloxane or their mixture.Aliphatic hydrocarbon is preferably ethene.
On the other hand, aliphatic hydrocarbon comprises one or more metastable presomas.To about 5, the amount of 00sccm adds one or more metastable presomas with about 100sccm.Preferably, metastable presoma is a tertbutyl ether.
Depositing treatment can be thermal treatment or plasma enhancement process.In the plasma enhancement process, apply RF power by use RF power source 25 to gas distribution manifold 11 usually, and form controlled plasma at the adjacent substrate place.Perhaps, can provide RF power to pedestal 12.To the RF of sediment chamber power can be the cycle or pulse, reducing the heating of substrate, and promote the bigger porosity of the sedimentary film formation of institute.For the substrate of 300mm, the power density of plasma body is at about 0.014W/cm 2With about 2.8W/cm 2Between, it is corresponding to the RF power level of about 10W to about 2000W.Preferably, the RF power level arrives between about 1700W at about 300W.
RF power source 25 can be provided in the single-frequency RF power between about 0.01MHz and the 300MHz.Perhaps, can use blended while frequency to transmit RF power, be incorporated into the decomposition of the reaction species of high vacuum region 15 with enhancing.In one embodiment, mixing is the lower frequency of about 12KHz and the upper frequency of about 13.56MHz.In another embodiment, lower frequency can be at about 400KHz in the scope of about 14MHz, and upper frequency can be in about 20MHz arrives the scope of about 100MHz.On the other hand, lower frequency can be at about 300Hz in the scope of about 100KHz, and upper frequency can be in about 5MHz arrives the scope of about 50MHz.
In deposition process, substrate is maintained at about between-20 ℃ to about 500 ℃, preferably under the temperature between about 100 ℃ to about 400 ℃.Deposition pressure generally arrives between about 20Torr at about 0.5Torr, preferably arrives between about 8Torr at about 2Torr.Sedimentation velocity is generally between about 5,000 /min and about 20,000 /min.
Current looking in the distance during journey disassociation oxidizing gas can use optional microwave office 28 before gas enters treatment chamber 10, arrive at about 50W to the oxidizing gas input about 6, the power between the 000W.Additional microwave power can avoid silicoorganic compound with reacted before excessively disassociation takes place.When oxidizing gas applies microwave power, the gas distribution plate (not shown) with the autonomous channel that is used for silicoorganic compound and oxidizing gas is preferred.
Usually, any one of the lining of chamber, distributing manifold 11, pedestal 12 and various other reactor hardware or whole all made by the material of for example aluminium or anodised aluminium.The example of this CVD reactor is being authorized people such as Wang and is being transferred as the title of assignee of the present invention's the Applied Materials U.S. Patent No. 5 for " A Thermal CVD/PECVD Reactor and Use for Thermal ChemicalVapor Deposition of Silicon Dioxide and In-situ Multi-step PlanarizedProcess ", 000, describe to some extent in 113, here by keeping in consistent with the present invention content of quoting this patent is included in.
Central controller 34 control engine 14, gas mixing system 19 and high frequency power sources 25, they are connected to controller 34 by control line 36.The activity of central controller 34 control CVD reactors, and generally comprise hard drive, disk drive and plug-in card guide rail (card rack).The plug-in card guide rail comprises single board computer (SBC), analog-and digital-input/output board, interface board and stepping engine controller plate.Central controller 34 meets VME (Versa ModularEuropeans) standard, the size and the type of this standard code plate, cage and junctor.The VME standard also stipulates to have the bus structure of 16 bit data bus and 24 bit address buses.
The pre-treatment and the method that are used to form pretreatment layer of the present invention are not limited to any specific device or any specific plasma body Activiation method.Top CVD system description is mainly used in illustrative purposes, and can use other CVD equipment, the RF high-density plasma CVD equipment or the similar devices of for example electrode cyclotron resonance (ECR) plasma CVD equipment, jigger coupling.In addition, the various variations of said system all are possible as change and other changes of substrate supports foundation design, heater design, power link position.For example, substrate can be by the substrate supports base supports and the heating of resistive heating.
Among any embodiment of Miao Shuing, after deposit low dielectric constant films, preferably use electron beam (e-beam) to handle film here.Electron beam treatment generally has at every square centimeter about 50 to about 2000 microcoulombs (μ c/cm under about 20 kiloelectron-volts (KeV) about 1 2) between dosage.Carried out for example about 2 minutes electron beam treatment about 1 minute to about 15 minutes under the general temperature between about room temperature is to about 450 ℃.Preferably, under about 400 ℃, carry out about 2 minutes electron beam treatment.On the one hand, the electron beam treatment condition is included in the 4.5KV under 400 ℃, 1.5mA and 500 μ c/cm 2In the electron beam treatment process, can there be argon or hydrogen.Though can use any electron beam equipment, a kind of exemplary apparatus is the EBK chamber, and it can obtain from Applied Materials.After deposit low dielectric constant films, with electron beam this film having low dielectric constant is handled, with at least some organic group volatilizations that make in the film, thereby in film, form hole.Organic group that can be volatilized for example comprises the alkyl composition or the aliphatic hydrocarbon described herein of the silicoorganic compound of the alkyl composition with one or more unsaturated carbon carbon bonds from the organic composition of presoma described herein.We think in film and to form the specific inductivity that hole can reduce film.Preferably, greater than 150 ℃ temperature deposit film, because we think that higher temperature will hinder volatilized organic group is fully entered in the film.
Will be further described below the details of exemplary electron beam chamber and processing.Can transmit substrate down in vacuum breaking or in vacuum (promptly without any vacuum breaking).Fig. 2 illustrates the electron beam chamber 200 according to the embodiment of the invention.Electron beam chamber 200 comprise vacuum chamber 220, large area cathode 222, the target plate 230 in no electric field region 238 and be positioned at target plate 230 and large area cathode 222 between grid anode 226.Electron beam chamber 200 also comprises makes grid anode 226 and large area cathode 222 insulating high voltage insulators 224, the negative electrode that is positioned at vacuum chamber 220 outsides covers isolator 228, be used to control the adjustable leak valve 232 of vacuum chamber 220 internal pressures, be connected to the adjustable high voltage power supply 229 of large area cathode 222, and the adjustable low-voltage power supply 231 that is connected to grid anode 226.
Thereby the chamber can also comprise the lamp of irradiation and heated substrate (not shown) watch-keeping cubicle temperature.Lamp can be positioned at target plate 230 below.Because substrate is in the vacuum environment, and adiabatic, so substrate can be by radiation heating or cooling.If lamp is extinguished, substrate will peripherad surface emissivity warm so, and cooling gradually.In whole process, substrate can shine by the lamp heating and by electron beam simultaneously.For example, according to an embodiment, infrared quartz lamp one is heading straight for, and reaches the processing service temperature up to substrate temperature.Afterwards, turn off and turn on the light, come the control wafer temperature with the space factor that changes.Substrate accumulated enough dosage up to, and substrate is processed by the electronics Continuous irradiation.Use this technology, can such as but not limited on the sclerosis substrate in less than 10 minutes than thick-layer.
According to another embodiment of the invention, do not use the infrared lamp heated substrate.According to this embodiment, use electron beam to shine and heated substrate.In this case, the power that the product of beam current and beam voltage (power=electric current * voltage) falls greater than the substrate radiation, so substrate is heated by electron beam.According to another embodiment of the invention, can use coolship to cool off substrate.This can remain on substrate near under the preset temperature.
In operation, the substrate (not shown) that will be exposed to electron beam is placed on the target plate 230.Vacuum chamber 220 is bled, make it drop to the pressure to about 200mTorr scope at about 1mTorr from normal atmosphere.Accurate pressure is by 232 controls of variable-ratio leak valve, and it can be accurate to pressure-controlling about 0.1mTorr.Electron beam generally produces under the sufficiently high voltage being applied on the large area cathode 222 by high-voltage power supply 229.Described voltage can approximately-500 volts in about 30,000 volts or higher scope.High-voltage power supply 229 can be the Bertan Model #105-30R that is made by the Bertan of Hickville in New York, or the Spellman Model #SL30N-1200X 258 that is made by the Spellman HighVoltage electronics, inc. of New York Hauppauge.Adjustable low-voltage power supply 231 applies voltage to grid anode 226, this voltage with respect to the voltage that imposes on large area cathode 222 for just.Use this voltage to control from the electron emission of large area cathode 222.Adjustable low-voltage power supply 231 can be the Acopian Model #150PT12 power supply that obtains from Pennsylvanian Acopian of Easton.
For the excitation electron emission, the gas in the no electric field region 238 between grid anode 226 and target plate 230 must become ionized, and this can produce by abiogenous gamma ray.Can also be by the high tension spark crack at vacuum chamber 220 inner artificial excitation's electron emission.In case this initial ionization has taken place, the negative a little voltage (about 0 to about-200 volts of magnitudes) that positively charged ion 342 (shown in Figure 3) is applied in to grid anode 226 is attracted to grid anode 226.These positively charged ions 342 enter the accelerating field zone 236 that is arranged between large area cathode 222 and the grid anode 226, and owing to the high pressure that imposes on large area cathode 222 is accelerated to large area cathode 222 motions.After bump large area cathode 222, these energetic ions promptly produce secondary electron 344, and they are accelerated returns grid anode 226.Be generally perpendicular to some the bump grid anode 226 in these electronics 344 of cathode surface motion, but the many electronics in these electronics 344 all pass grid anode 226 and to target plate 230 motions.Grid anode 226 preferably is placed on distance less than the mean free path place by 222 emitting electrons of large area cathode, and for example, grid anode 226 preferably is placed on and the position of large area cathode 222 distances less than about 4mm.Since between grid anode 226 and the large area cathode 222 than short range, in the accelerating field zone 236 between grid anode 226 and large area cathode 222 ionization can not take place, also be few even perhaps have.
In traditional gas discharge device, electronics will further produce positively charged ion in the accelerating field zone, and positively charged ion will attracted to large area cathode 222, thereby produce even more electron emission.Discharge is easier to snowslide and becomes unsettled high-voltage breakdown.But, according to embodiments of the invention, can be at the grid anode 226 outside ions 342 that produce by the voltage control that imposes on grid anode 226 (repelling or attraction).In other words, electron emission can be by the voltage on the change grid anode 226 by Sustainable Control.Perhaps, electron emission can be by adjustable leak valve 232 controls, and adjustable leak valve 232 is configured for the quantity of molecule in the ionization region that increases or reduce between target plate 230 and large area cathode 222.Can apply positive voltage by giving grid anode 226, promptly the voltage of grid anode surpasses the energy of any positively charged ion grain kind that produces in the space between grid anode 226 and target plate 230, stops electron emission fully.
Fig. 4 illustrates the electron beam chamber 200 with feedback control circuit 400.In some applications, under different beam energies, provide constant beam current to expect.For example, may expect to expose or be hardened in the upper strata of the film that forms on the substrate, and not comprise bottom.This can be by reducing beam energy, makes most of electronics all be absorbed in the upper strata of film and realize.After the sclerosis upper strata, may expect the full depth of cured film.This can realize to see through film fully by the acceleration voltage of rising electron beam.Feedback control circuit 400 is configured for keeps the constant beam current, makes it not rely on the change of acceleration voltage.Feedback control circuit 400 comprises integrator 466.Beam current detects resistance 490 between target plate 230 and integrator 466 by detecting resistance 490 samplings.Beam current can also be sampled when a part of electron beam is intercepted at grid anode 226 places there.Two identical gain voltage follower 492 bufferings are passed through to detect the signals that resistance 490 obtains, and it is fed to the amplifier 496 that has variable resistor 494.Voltage on the output control grid grid anode 226 of this amplifier makes the increase of beam current will cause the decline of bias voltage on the grid anode 226 and from the decline of the beam current of large area cathode 222.By the gain of variable resistor 494 resonance-amplifiers 496, make and all to be offset, thereby remain on the constant beam current at target place by the change of bias voltage by any change of the beam current that change caused of acceleration voltage.Perhaps, the output terminal of amplifier 496 can be connected to voltage-controlled variable-ratio leak valve 298, with the change of offsetting beam current by the pressure in increase or the reduction ionization region 238.In addition, by using the feedback signal of variable-ratio leak valve 298 and grid anode 226, can provide the beam current control of wider scope.Authorizing William R.Livesay and be transferred to the U.S. Patent No. 5 of the exercise question of Electron Vision Corporation (it is owned by transferee of the present invention now) for " Large-Area Uniform Electron Source ", 003, other details of electron beam chamber 200 have been described, in by reference will the part consistent being included in 178 here with the present invention.
Be the processing condition of electron beam treatment below.Pressure in the chamber can be about 10 -5To about 10 2Change in the scope of Torr, and preferably from about 10 -3To 10 -1In the scope of Torr.Distance between substrate and the grid anode should be enough to satisfy electronics produces ion when transmitting between grid anode and substrate surface.The temperature of wafer can change in about 1050 ℃ scope at about 0 ℃.Beam energy can change in about scope of 0.1 to about 100KeV.The total dose of electronics can be about 1 to about 100,000 μ C/cm 2Scope in change.Selected dosage and energy should be proportional with pending thickness.Environmental gas in the e-beam tool device can be following arbitrarily gas: the arbitrary combination of nitrogen, oxygen, hydrogen, argon gas, helium, ammonia, silane, xenon or these gases.Electron beam current can change in about scope of 0.1 to about 100mA.Preferably, use the big beam electrons from uniform large area electron electron gun to carry out electron beam treatment, described uniform large area electron electron gun covers the surf zone of pending film.In addition, for thicker film, electron-beam dose can be assigned in the step that reduces voltage, and this provides uniform dosage to handle, and wherein material is upwards hardened by the bottom.Like this, in treatment process, the degree of depth of electron beam infiltration can change.The time length of handling can be at about 0.5 minute in about 120 minutes scope.Will readily appreciate that as those of skill in the art, the time length of electron beam treatment can be decided by one or more in the parameter of above-mentioned sign, and this specific parameter set according to detailed description given here and not the too much experiment of needs just can determine routinely.
In another embodiment, the temperature of electron beam chamber 200 work can arrive in about 600 ℃ scope, for example at about 200 ℃ to about 400 ℃ at about-200 ℃.Beam energy is in about 0.5KeV arrives the scope of about 30KeV.Exposure dose is at about 1 μ c/cm 2To about 400 μ c/cm 2In the scope, and more preferably about 50 to about 200 μ c/cm 2Between, for example about 70 μ c/cm 2Electron beam generally produces under the pressure of about 100mTorr at about 1mTorr.Environmental gas in the electron beam chamber 220 can be any following gas: the arbitrary combination of the mixed gas of nitrogen, oxygen, hydrogen, argon gas, hydrogen and nitrogen, ammonia, xenon or these gases.Electron beam current in the scope of about 40mA, and more preferably arrives about 20mA at about 5mA at about 1mA.Electron beam can cover from about 4 square inches to about 700 square inches area.
The following examples have illustrated to have the low dielectric film that improves hardness.This film is to use the plasma reinforced chemical vapour deposition chamber sedimentary.Specifically, it is sedimentary that this film is to use " Producer " system that can obtain from the Applied Materials of California Santa Clara.
Film having low dielectric constant is under the constant pressure of about 5.75Torr and about 400 ℃ underlayer temperature, is deposited on by following reactant gases on the substrate of 300mm.
Octamethylcyclotetrasiloxane (OMCTS), the about 520sccm of flow velocity;
Trimethyl silane (TMS), the about 600sccm of flow velocity;
Ethene, flow velocity is about 2,000sccm;
Oxygen, flow velocity is about 1,000sccm; And
Helium, flow velocity is about 1,000sccm.
Substrate is placed on apart from gas distribution showerhead 1,050 Mill and locates.Apply the power level that frequency is about 800W of 13.56MHz to gas distribution manifold, be used for the plasma-enhanced deposition of film.Film is with the speed of about 12,000 /min deposition, and records its specific inductivity (k) be about 2.54 under 0.1MHz.
Then, under the condition that is described below, use the electron beam device of for example above-mentioned electron beam chamber 200 and so on that film was handled about 90 seconds.In last handling process, the temperature of chamber is about 400 ℃, and beam energy is about 4KeV, and electron beam current is about 3mA.The exposure dose of electron beam is about 70 μ c/cm 2In whole hardening treatment process, in the speed flowed into chamber of argon gas with about 150sccm.After aftertreatment, the specific inductivity of film remains roughly the same, and promptly about 2.54.The hardness of film is increased to about 1.40GPa from about 0.66GPa, and the modulus of film is increased to about 8.3GPa from about 4.2GPa.The thickness fracture threshold value of mould is increased to about 24,000 from about 8000 .The leakage current of film reduces at least one the order of magnitude, for example from about 3.46 * 10 -10A/cm 2Be reduced to about 5.72 * 10 -11A/cm 2(at about 1MV/cm).The voltage breakdown of film is increased to about 4.7MV from about 4.2MV.
Other embodiment of the present invention need be manufactured on the low-k dielectric film that is called formula I I here.When making this film, wherein presoma is octamethylcyclotetrasiloxane (" OMCTS "), trimethyl silane ((CH 3) 3-SiH), oxygen, ethene and as the helium of thinner.According to such embodiment, processing condition are: for the flow velocity of the about 5000mgm of OMCTS; Flow velocity for the about 600sccm of trimethyl silane; Flow velocity for the about 1000sccm of oxygen; Flow velocity for the about 2000sccm of ethene; Flow velocity for the about 1000sccm of helium; The constant pressure of about 5.75Torr; About 400 ℃ wafer base temperature; The spacing from the wafer to the shower nozzle of about 1050 Mills; And the RF power of about 800W.Other useful deposition process conditions can be definite routinely according to detailed description given here by those of ordinary skill in the art, and do not need too much experiment.
After deposited film, it is carried out electron beam treatment.Processing condition are: about 100 μ C/cm 2Treatment dosage carried out about 2 minutes, for the constant pressure of the about 15mTorr of environmental gas (argon gas), the voltage of about 4.5KeV, the electronic current of about 3mA, and about 400 ℃ chip temperature.The film that obtains like this, its hardness and Young's modulus are increased to about 1.414GPa and about 9.563GPa of the wafer of electron beam treatment respectively from about 0.699GPa of control wafer (promptly not having electron beam treatment) and about 4.902GPa, specific inductivity keeps constant substantially simultaneously, the k value that is control wafer is for about 2.52, and the k value of the wafer of electron beam treatment is about 2.49.Thickness becomes about 4889.3 of the wafer of electron beam treatment from the nominal value of about 5000 (5292.1 ) of control wafer.These results are more important, because they show that electron beam treatment has increased film strength (otherwise the physical strength of film is weak), and relatively do not change other performances.The more weak film of physical strength be used for Production Example such as logical circuit have perhaps the multiwalled unicircuit time may have problems because the stress that produces owing to the use of the more weak material of physical strength may cause the stress cracking on upper strata.
For the formula I I of electron beam treatment, except that above-mentioned improvement, the wetting angle of the wafer of electron beam treatment reduces; Thereby the film that shows electron beam treatment becomes hydrophilic.Specifically, wetting angle from being higher than of control wafer about 80 the degree value become electron beam treatment wafer be lower than about 40 the degree values.This is very important, because many photoresist materials can not deposit on hydrophobic surface.
Other embodiment of the present invention need use oxygenant (such as but not limited to H 2O 2, O 3Deng) and stable silicon precursor (such as but not limited to trimethyl silane (" TMS "), or tetramethylsilane), or have the presoma of built-in metastable functional group, such as but not limited to 1,3,5,7-tetramethyl-ring tetrasiloxane (TMCTS) is made low-k dielectric film.For example, can use the front, under lower temperature, carry out the CVD deposition, but be not limited thereto with reference to the chamber that Fig. 2 describes.For example, according to one embodiment of present invention, for a kind of use TMS and O 3The technical recipe that such heat deposition is handled needs: the constant pressure of about 100Torr, about 100 ℃ wafer keeps temperature, for O 3The flow velocity of about 4000sccm, for flow velocity such as but not limited to about 8000sccm of the thinner of helium, and the flow velocity of about 125sccm of TMS.Next, film is carried out electron beam treatment (comprising heating film simultaneously).
According to one or more embodiment of the present invention, make the film that comprises metastable group.According to one or more such embodiment, presoma comprises vinyl cyclohexane (" VCH "), octamethylcyclotetrasiloxane (" OMCTS ") and as the helium of thinner, and make the chamber that the embodiment of this film describes with reference to Fig. 2 above using.According to such embodiment, processing condition are: for the flow velocity of the about 500mgm of OMCTS; Flow velocity for the about 500mgm of VCH; Flow velocity for the about 1000sccm of helium; The constant pressure of about 5Torr; About 100 ℃ wafer base temperature; The distance from the wafer to the shower nozzle of about 800 Mills; The RF power (13.56MHz) of about 300W; And the low frequency power of about 100W (356KHz).The sedimentation rate of this film is about 12,000 /min.Other useful deposition process conditions can be definite routinely according to detailed description given here by those of ordinary skill in the art, and do not need too much experiment.After this film was deposited, it had and equals about 1.47 specific refractory power (" RI "), and the specific inductivity k that equals about 2.77.Film in stove under 440 ℃ by about 30 minutes of thermal annealing.After thermal annealing, it is about 1.37 that RI equals, and k equals about 2.45.
After this film is annealed, it is carried out electron beam treatment.Processing condition are: about 200 μ C/cm 2Treatment dosage carried out about 2 minutes, for the constant pressure of the about 15mTorr of environmental gas (argon gas), the voltage of about 4KeV, the electronic current of about 3mA, and about 400 ℃ chip temperature.The film that obtains like this has and equals about 1.43 RI, equal about 2.46 k, and the hardness and the Young's modulus that have increased.
According to this method, other embodiment comprise using provides metastable grain to plant the presoma of (such as but not limited to hexanaphthene in the film or phenyl), and the presoma that silicon is provided.According to one or more such embodiment, the presoma that provides metastable grain to plant comprises such as but not limited to norbornadiene and divinyl, and provides the presoma of silicon to comprise that (singly bound is to H, CH such as but not limited to OMCTS, TMCTS, DMDMOS and DEMS 3(OC 2H 5) 2Si) in one or more.According to this method, other embodiment comprise and use such presoma, and wherein metastable functional group can be connected to for example organic compound of VCH, and perhaps it can be built in the silicon precursor of tertiary butyl TMCTS for example.
Other embodiment of the present invention need carry out a plurality of treatment step circulations (that is heat deposition/electron beam treatment processing step circulation).At last, and alternatively, the film that obtains is carried out thermal annealing.According to such embodiment, electron beam treatment step is shorter, thereby minimizing contraction and acquisition are less than 2.5 k value.
According to another embodiment of the invention, in the above-described embodiments any one, before optional thermal anneal step and/or afterwards, can be further processed technology, with further sclerosis based on organosilyl film.Can comprise the relative inertness plasma body that is exposed to helium for example or hydrogen gas plasma such as but not limited to, this further treatment process.But, do not penetrate at more high-octane electronics under the situation of film, for example these effects of hardened may be main with cause that the surface component change is relevant because ion sputters away organic composition, and with think that the crosslinking Treatment that works has nothing to do in the electron beam treatment process.But for the sufficiently high extremely thin barrier film of carbon content, it still can be favourable using this technology.According to one or more such embodiment of the present invention, Cement Composite Treated by Plasma can be carried out in traditional PECVD or plasma etching hardware.
Example:
Ideal case 1
Under the constant pressure of about 6Torr and about 100 ℃ underlayer temperature, by following reactant gases deposit low dielectric constant films on the substrate of 200mm.
Octamethylcyclotetrasiloxane (OMCTS), the about 520sccm of flow velocity;
Ethene, flow velocity is about 2,000sccm;
Oxygen, flow velocity is about 1,000sccm; And
Helium, flow velocity is about 1,000sccm.
Substrate is placed on apart from gas distribution showerhead 1,050 Mill and locates.Apply the power level that frequency is about 1200W of 13.56MHz to shower nozzle, be used for the plasma-enhanced deposition of film.After deposit low dielectric constant films, in the EBK chamber, under about 400 ℃, substrate is exposed to about 50C/cm 2Dosage in come it is carried out electron beam treatment.Speed with about 200sccm is introduced argon gas in the chamber.Constant pressure is maintained at about 35mTorr.
Ideal case 2
Under the constant pressure of about 14Torr and about 125 ℃ underlayer temperature, by following reactant gases deposit low dielectric constant films on the substrate of 200mm.
Octamethylcyclotetrasiloxane (OMCTS), the about 210sccm of flow velocity;
Diethoxymethyl silane, the about 600sccm of flow velocity;
1,3-butadiene, flow velocity is about 1,000sccm;
Oxygen, the about 600sccm of flow velocity; And
Helium, the about 800sccm of flow velocity.
Substrate is placed on apart from gas distribution showerhead 1,050 Mill and locates.Apply the power level that frequency is about 1200W of 13.56MHz to shower nozzle, be used for the plasma-enhanced deposition of film.After deposit low dielectric constant films, in the EBK chamber, under about 400 ℃, substrate is exposed to about 50 μ C/cm 2Dosage in come it is carried out electron beam treatment.Speed with about 200sccm is introduced argon gas in the chamber.Constant pressure is maintained at about 35mTorr.
Ideal case 3
Under the constant pressure of about 6Torr and about 125 ℃ underlayer temperature, by in the following reactant gases on the substrate of 200mm deposit low dielectric constant films.
Octamethylcyclotetrasiloxane (OMCTS), the about 520sccm of flow velocity;
Propylene, flow velocity is about 2,000sccm;
Oxygen, flow velocity is about 1,000sccm; And
Helium, flow velocity is about 1,000sccm.
Substrate is placed on apart from gas distribution showerhead 1,050 Mill and locates.Apply the power level that frequency is about 800W of 13.56MHz to shower nozzle, be used for the plasma-enhanced deposition of film.After deposit low dielectric constant films, under the temperature between about 200 ℃ to about 400 ℃ with about 30 minutes of substrate annealing.With about 100 to about 10, the speed of the 000sccm for example nonreactive gas of helium, hydrogen, nitrogen or its mixed gas is introduced in the chamber.Constant pressure is maintained at about 2Torr between about 10Torr.RF power under the frequency of about 13.56MHz at about 200W to about 1, between the 000W, and preferred substrate spacing in about 300 Mills between about 800 Mills.
Ideal case 4
Under the constant pressure of about 6Torr and about 100 ℃ underlayer temperature, by following reactant gases deposit low dielectric constant films on the substrate of 200mm.
1,3,5,7-tetramethyl-ring tetrasiloxane (TMCTS), the about 700sccm of flow velocity;
Diethoxymethyl silane, the about 600sccm of flow velocity;
2,3-dimethyl-1,3-butadiene, flow velocity is about 2,000sccm;
Oxygen, flow velocity is about 1,000sccm; And
Helium, flow velocity is about 1,000sccm.
Substrate is placed on apart from gas distribution showerhead 1,050 Mill and locates.Apply the power level that frequency is about 800W of 13.56MHz to shower nozzle, be used for the plasma-enhanced deposition of film.After deposit low dielectric constant films, under the temperature between about 200 ℃ to about 400 ℃ with about 30 minutes of substrate annealing.With 100 to about 10, the speed of the 000sccm for example nonreactive gas of helium, hydrogen, nitrogen or its mixed gas is introduced in the chamber.Constant pressure is maintained at about 2Torr between about 10Torr.RF power under the frequency of about 13.56MHz at about 700W to about 1, between the 000W, and preferred substrate spacing in about 300 Mills between about 800 Mills.
Ideal case 5
Under the constant pressure of about 6Torr and about 130 ℃ underlayer temperature, by following reactant gases deposit low dielectric constant films on substrate.
The vinyl methyl-monosilane, the about 600sccm of flow velocity;
Oxygen, the about 800sccm of flow velocity; And
Carbonic acid gas, flow velocity is about 4,800sccm.
Substrate is placed on apart from gas distribution showerhead 1,050 Mill and locates.Apply the power level that frequency is about 1200W of 13.56MHz to shower nozzle, be used for the plasma-enhanced deposition of film.After deposit low dielectric constant films, in the EBK chamber, under about 400 ℃, substrate is exposed to about 50 μ C/cm 2Dosage in come it is carried out electron beam treatment.Speed with about 200sccm is introduced argon gas in the chamber.Constant pressure is maintained at about 35mTorr.
Ideal case 6
Under the constant pressure of about 6Torr and about 130 ℃ underlayer temperature, by following reactant gases deposit low dielectric constant films on the substrate of 300mm.
Octamethylcyclotetrasiloxane (OMCTS), the about 483sccm of flow velocity;
Ethene, flow velocity is about 1,600sccm;
Carbonic acid gas, flow velocity is about 4,800sccm;
Oxygen, the about 800sccm of flow velocity; And
Argon gas, flow velocity is about 1,600sccm.
Substrate is placed on apart from gas distribution showerhead 1,050 Mill and locates.Apply the power level that frequency is about 800W of 13.56MHz to shower nozzle, be used for the plasma-enhanced deposition of film.After deposit low dielectric constant films, in the EBK chamber, under about 400 ℃, 1.5mA, substrate is exposed to about 70 μ C/cm 2Dosage in come it is carried out electron beam treatment.
Following example has illustrated low dielectric film of the present invention.This film is to use as the CVD (Chemical Vapor Deposition) chamber of the part of integrated processing platform sedimentary.Specifically, it is sedimentary that this film is to use the Producer  system that can obtain from the Applied Materials of California Santa Clara.
Example 1
Under the constant pressure of about 6Torr and about 400 ℃ underlayer temperature, by following reactant gases deposit low dielectric constant films on the substrate of 200mm.
Octamethylcyclotetrasiloxane (OMCTS), the about 520sccm of flow velocity;
Trimethyl silane (TMS), the about 200sccm of flow velocity;
Ethene, flow velocity is about 2,000sccm;
Oxygen, flow velocity is about 1,000sccm; And
Helium, flow velocity is about 1,000sccm.
Substrate is placed on apart from gas distribution showerhead 1,050 Mill and locates.Apply the power level that frequency is about 800W of 13.56MHz to shower nozzle, be used for the plasma-enhanced deposition of film.Film is with the speed of about 12,000 /min deposition, and records its specific inductivity (k) be about 2.54 under 0.1MHz.
Example 2
Under the constant pressure of about 6Torr and about 400 ℃ underlayer temperature, by following reactant gases deposit low dielectric constant films on the substrate of 200mm.
Octamethylcyclotetrasiloxane (OMCTS), the about 520sccm of flow velocity;
Trimethyl silane (TMS), the about 400sccm of flow velocity;
Ethene, flow velocity is about 2,000sccm;
Oxygen, flow velocity is about 1,000sccm; And
Helium, flow velocity is about 1,000sccm.
Substrate is placed on apart from gas distribution showerhead 1,050 Mill and locates.Apply the power level that frequency is about 800W of 13.56MHz to shower nozzle, be used for the plasma-enhanced deposition of film.Film is with the speed of about 12,000 /min deposition, and records its specific inductivity (k) be about 2.51 under 0.1MHz.
Example 3
Under the constant pressure of about 6Torr and about 400 ℃ underlayer temperature, by following reactant gases deposit low dielectric constant films on the substrate of 200mm.
Octamethylcyclotetrasiloxane (OMCTS), the about 520sccm of flow velocity;
Trimethyl silane (TMS), the about 600sccm of flow velocity;
Ethene, flow velocity is about 2,000sccm;
Oxygen, flow velocity is about 1,000sccm; And
Helium, flow velocity is about 1,000sccm.
Substrate is placed on apart from gas distribution showerhead 1,050 Mill and locates.Apply the power level that frequency is about 800W of 13.56MHz to shower nozzle, be used for the plasma-enhanced deposition of film.Film is with the speed of about 12,000 /min deposition, and records its specific inductivity (k) be about 2.47 under 0.1MHz.
Example 4
Under the constant pressure of about 6Torr and about 400 ℃ underlayer temperature, by following reactant gases deposit low dielectric constant films on the substrate of 200mm.
Octamethylcyclotetrasiloxane (OMCTS), the about 520sccm of flow velocity;
Trimethyl silane (TMS), the about 800sccm of flow velocity;
Ethene, flow velocity is about 2,000sccm;
Oxygen, flow velocity is about 1,000sccm; And
Helium, flow velocity is about 1,000sccm.
Substrate is placed on apart from gas distribution showerhead 1,050 Mill and locates.Apply the power level that frequency is about 800W of 13.56MHz to shower nozzle, be used for the plasma-enhanced deposition of film.Film is with the speed of about 12,000 /min deposition, and records its specific inductivity (k) be about 2.47 under 0.1MHz.
Example 5
Under the constant pressure of about 6Torr and about 400 ℃ underlayer temperature, by following reactant gases deposit low dielectric constant films on the substrate of 200mm.
Octamethylcyclotetrasiloxane (OMCTS), the about 520sccm of flow velocity
Trimethyl silane (TMS), the about 900sccm of flow velocity;
Ethene, flow velocity is about 2,000sccm;
Oxygen, flow velocity is about 1,000sccm; And
Helium, flow velocity is about 1,000sccm.
Substrate is placed on apart from gas distribution showerhead 1,050 Mill and locates.Apply the power level that frequency is about 800W of 13.56MHz to shower nozzle, be used for the plasma-enhanced deposition of film.Film is with the speed of about 12,000 /min deposition, and records its specific inductivity (k) be about 2.48 under 0.1MHz.
Example 6
Under the constant pressure of about 14Torr and about 350 ℃ underlayer temperature, by following reactant gases deposit low dielectric constant films on substrate.
Octamethylcyclotetrasiloxane (OMCTS), the about 210sccm of flow velocity;
Trimethyl silane (TMS), the about 400sccm of flow velocity;
Oxygen, the about 600sccm of flow velocity; And
Helium, the about 800sccm of flow velocity.
Substrate is placed on apart from gas distribution showerhead 450 Mills and locates.Apply the power level that frequency is about 800W of 13.56MHz to shower nozzle, be used for the plasma-enhanced deposition of film.The specific inductivity (k) of institute's deposited film records under 0.1MHz and is about 2.67.
Example 7
Under the constant pressure of about 6Torr and about 400 ℃ underlayer temperature, by following reactant gases deposit low dielectric constant films on substrate.
Octamethylcyclotetrasiloxane (OMCTS), the about 520sccm of flow velocity;
Ethene, flow velocity is about 2,000sccm;
Oxygen, flow velocity is about 1,000sccm; And
Helium, flow velocity is about 1,000sccm.
Substrate is placed on apart from gas distribution showerhead 1,050 Mill and locates.Apply the power level that frequency is about 800W of 13.56MHz to shower nozzle, be used for the plasma-enhanced deposition of film.The specific inductivity (k) of institute's deposited film records under 0.1MHz and is about 2.55.
Example 8
Under the constant pressure of about 6Torr and about 130 ℃ underlayer temperature, by following reactant gases deposit low dielectric constant films on substrate.
Octamethylcyclotetrasiloxane (OMCTS), the about 483sccm of flow velocity;
Ethene, flow velocity is about 3,200sccm;
Oxygen, the about 800sccm of flow velocity; And
Carbonic acid gas, flow velocity is about 4,800sccm.
Substrate is placed on apart from gas distribution showerhead 1,050 Mill and locates.Apply the power level that frequency is about 1200W of 13.56MHz to shower nozzle, be used for the plasma-enhanced deposition of film.After deposit low dielectric constant films, in the EBK chamber, under about 400 ℃, substrate is exposed to about 50 μ C/cm 2Dosage in come it is carried out electron beam treatment.Speed with about 200sccm is introduced argon gas in the chamber.Constant pressure is maintained at about 35mTorr.
Example 9
Under the constant pressure of about 5Torr and about 400 ℃ underlayer temperature, by following reactant gases deposit low dielectric constant films on the substrate of about 300mm.
Octamethylcyclotetrasiloxane (OMCTS), the about 302sccm of flow velocity;
Trimethyl silane, the about 600sccm of flow velocity;
Oxygen, the about 600sccm of flow velocity;
Ethene, the about 1000sccm of flow velocity; And
Helium, the about 1200sccm of flow velocity.
Substrate is placed on apart from gas distribution showerhead 350 Mills and locates.The power level and the frequency that apply frequency and be about 800W of 13.56MHz are the power level of about 250W of 356KHz, are used for the plasma-enhanced deposition of film.After deposit low dielectric constant films, substrate is carried out aftertreatment with helium.Film deposits with the speed of 13,000 /min, and has about 2.97 to about 3.06 average dielectric constant.Mean refractive index is 1.453.The hardness of film is about 2.2GPa, and uniformity coefficient is less than 2%.Modulus is about 13.34.Leakage current is about 4.55 * 10 under 1MV/cm -10Amp/cm 2Leakage current is about 2.68 * 10 under 2MV/cm -9Amp/cm 2Voltage breakdown is about 5.93MV/cm.Stress is about 4.00 * 10 8Dynes/cm 2, the fracture threshold value is greater than 7 μ m.
Example 10
Under the constant pressure of about 4.5Torr and about 400 ℃ underlayer temperature, by following reactant gases deposit low dielectric constant films on the substrate of 200mm.
Octamethylcyclotetrasiloxane (OMCTS), the about 151sccm of flow velocity;
Trimethyl silane, the about 300sccm of flow velocity;
Oxygen, the about 300sccm of flow velocity;
Ethene, the about 500sccm of flow velocity; And
Helium, the about 600sccm of flow velocity.
Substrate is placed on apart from gas distribution showerhead 350 Mills and locates.The power level and the frequency that apply frequency and be about 400W of 13.56MHz are the power level of about 150W of 356KHz, are used for the plasma-enhanced deposition of film.After deposit low dielectric constant films, substrate is carried out aftertreatment with hydrogen.Film deposits with the speed of 10,000 /min, and has about 2.96 to about 3.01 average dielectric constant.Mean refractive index is 1.454.The hardness of film is about 2.03 to about 2.08GPa, and uniformity coefficient is 2.2%.Modulus is about 12.27.Leakage current is about 4.27 * 10 under 1MV/cm -10Amp/cm 2Leakage current is about 1.88 * 10 under 2MV/cm -9Amp/cm 2Voltage breakdown is about 4.31MV/cm.Stress is about 5.40 * 10 8Dynes/cm 2, the fracture threshold value is greater than 7 μ m.
Though example 9 and 10 uses helium as carrier gas, also can use argon gas as carrier gas.We think, use argon gas to improve the porosity of institute's deposited film as carrier gas, and have reduced the specific inductivity of institute's deposited film.We think, use argon gas and mixing RF power to increase the sedimentation velocity of film by the dissociation efficiency that improves presoma.In addition, we think that use argon gas and mixing RF power have increased the hardness and the modulus intensity of film, and do not increase the specific inductivity of film.In addition, we think and use argon gas and mixing RF power to reduce the inclined deposition that material may take place at edges of substrate.
We find that very surprisingly in example 1 to 5, specific inductivity is along with the flow velocity of TMS significantly reduces to the increase between about 600sccm at about 200sccm.The ratio of aliphatic hydrocarbon and aliphatics silicoorganic compound can obtain low specific inductivity between about 15: 1 to about 1: 1 the time.As in example 6, explaining, in cyclic organic and aliphatics silicoorganic compound, add the specific inductivity that aliphatic hydrocarbon provided of capacity, the specific inductivity that obtains than not adding aliphatic hydrocarbon hangs down 7% at least.In addition, in cyclic organic and aliphatic hydrocarbon, add the specific inductivity that the aliphatics silicoorganic compound of capacity are provided, than shown in the example 7 do not add the aliphatics silicoorganic compound and the specific inductivity that obtains at least about low 3%.
Below instance interpretation low dielectric film of the present invention.Use CVD (Chemical Vapor Deposition) chamber, " Producer DxZ " system that can obtain for example, deposited film on the substrate of 200mm from the Applied Materials of California Santa Clara.
Example 11
Under about 8Torr and about 200 ℃ temperature, deposit low dielectric constant films on each in the substrate of three 200mm.Processing gas and flow velocity below using:
α terpinene (ATP), flow velocity 3,000mgm;
Diethoxymethyl silane (DEMS), flow velocity 800mgm; And
Carbonic acid gas, flow velocity 1,000sccm.
Each substrate all is placed on apart from gas distribution showerhead 300 Mills and locates.Apply the power level that frequency is about 600W of 13.56MHz, be used for the plasma-enhanced deposition of film.Each film is all with the speed of about 2,700 /min deposition, and uses SSM 5100Hg CV survey instrument under 0.1MHz, records film and has about 5.4 specific inductivity (k).Each film all demonstrates the hardness of about 0.1GPa.
Thermal annealing:
First deposited film is carried out thermal anneal process.Anneal was carried out 4 hours under the pressure of about 425 ℃ temperature, about 10Torr in inert gas environment approximately.Shorter annealing time causes higher k value.Minimum k value through the film of thermal annealing is about 2.1, and hardness is about 0.2GPa.
Electron beam treatment under 400 ℃:
Under about 400 ℃, about 4.5KeV and 1.5mA, use about 300 μ C/cm 2Dosage, second deposited film is carried out high-temperature electronic bundle (e-beam) handles.Electron beam treatment continues about 2 minutes.After electron beam treatment, film demonstrates about 2.1 specific inductivity, and this specific inductivity than unhardened film is approximately little by 60%, and with approaching through the Schwellenwert of thermal annealing film.The electron beam film also demonstrates the hardness of about 0.7GPa, and this compares with unhardened film 600% increase approximately, 250% increase is arranged with comparing through the thermal annealing film.
Electron beam treatment at room temperature:
Under about 35 ℃, about 4.5KeV and 1.5mA, use about 300 μ C/cm 2Dosage the 3rd deposited film carried out cryotronics bundle (e-beam) handle.Electron beam treatment continues about 2 minutes.After electron beam treatment, film demonstrates about 2.3 specific inductivity, and this specific inductivity than unhardened film is approximately little by 57%.The electron beam film also demonstrates the hardness of about 0.5GPa, and this compares 400% the increase of having an appointment with unhardened film, 150% increase is arranged with comparing through the thermal annealing film.
Example 12
Under about 8Torr and about 225 ℃ temperature, deposit low dielectric constant films on each in three substrates.Processing gas and flow velocity below using:
α terpinene (ATP), flow velocity 3,000mgm;
Diethoxymethyl silane (DEMS), flow velocity 800mgm;
Carbonic acid gas, flow velocity 1,500sccm; And
Oxygen, flow velocity 100sccm.
Each substrate all is placed on apart from gas distribution showerhead 300 Mills and locates.Apply the power level that frequency is about 600W of 13.56MHz to shower nozzle, be used for the plasma-enhanced deposition of film.Each film is with the speed of about 1,800 /min deposition, and uses SSM 5100Hg CV survey instrument under 0.1MHz, records film and has about 2.85 specific inductivity (k).Each film all demonstrates the hardness of about 0.23GPa.
Thermal annealing:
First deposited film is carried out thermal anneal process.Anneal was carried out 30 minutes under the pressure of about 450 ℃ temperature, about 10Torr in inert gas environment approximately.Shorter annealing time causes higher k value.Film through thermal annealing has about 1.29 specific refractory power (RI), about 2.08 minimum k value, and the hardness of about 0.23GPa.
At 400 ℃ and 200 μ C/cm 2 Under electron beam treatment:
Under about 400 ℃, about 4.5KeV and 1.5mA, use about 200 μ C/cm 2Dosage second deposited film carried out high-temperature electronic bundle (e-beam) handle.Electron beam treatment continues about 100 seconds.After electron beam treatment, film demonstrates about 2.07 specific inductivity, and this is approximately littler by 27% than unhardened film, and with approaching through the Schwellenwert of thermal annealing film.The electron beam film also demonstrates the hardness of about 0.42GPa, this with unhardened film with compare 80% the increase of having an appointment through the thermal annealing film.
At 400 ℃ and 500 μ C/cm 2 Under electron beam treatment:
Under about 35 ℃, about 4.5KeV and 1.5mA, use about 500 μ C/cm 2Dosage the 3rd deposited film carried out cryotronics bundle (e-beam) handle.Electron beam treatment continues about 250 seconds.After electron beam treatment, film demonstrates about 2.14 specific inductivity, and this specific inductivity than unhardened film is approximately little by 25%.The electron beam film also demonstrates the hardness of about 0.74GPa, this with unhardened film with compare 220% the increase of having an appointment through the thermal annealing film.
Example 13
Under about 8Torr and about 225 ℃ temperature, deposit low dielectric constant films on each in two substrates.Processing gas and flow velocity below using:
α terpinene (ATP), flow velocity 4,000mgm;
Octamethylcyclotetrasiloxane (OMCTS), flow velocity 200mgm;
Oxygen, flow velocity 200sccm; And
Carbonic acid gas, flow velocity 2,000sccm.
Each substrate all is placed on apart from gas distribution showerhead 300 Mills and locates.Apply the power level that frequency is about 500W of 13.56MHz to shower nozzle, be used for the plasma-enhanced deposition of film.Each film is all with the speed of about 1,000 /min deposition, and uses SSM 5100Hg CV survey instrument under 0.1MHz, records film and has about 4.0 specific inductivity (k).Each film also demonstrates the hardness of about 0.1GPa.
At 400 ℃ and 120 μ C/cm 2 Under electron beam treatment:
Under about 400 ℃, about 4.5KeV and 1.5mA, use about 120 μ C/cm 2Dosage first deposited film carried out high-temperature electronic bundle (e-beam) handle.Electron beam treatment continues about 30 seconds.After electron beam treatment, film demonstrates about 1.9 specific inductivity, and this is approximately littler by 52% than unhardened film.The electron beam film also demonstrates the hardness of about 0.5GPa, and this compares 400% the increase of having an appointment with unhardened film.
At 400 ℃ and 600 μ C/cm 2 Under electron beam treatment:
Under about 400 ℃, about 4.5KeV and 1.5mA, use about 600 μ C/cm 2Dosage second deposited film carried out cryotronics bundle (e-beam) handle.Electron beam treatment continues about 150 seconds.After electron beam treatment, film demonstrates about 2.2 specific inductivity, and this specific inductivity than unhardened film is approximately little by 45%.The electron beam film also demonstrates the hardness of about 0.8GPa, and this compares 700% the increase of having an appointment with unhardened film.
Example 14
Under about 8Torr and about 225 ℃ temperature, deposit low dielectric constant films on substrate.Processing gas and flow velocity below using:
ATP, flow velocity 3,000mgm;
TMS, flow velocity 500sccm;
DEMS, flow velocity 600mgm;
Oxygen, flow velocity 100sccm; And
Carbonic acid gas, flow velocity 1,500sccm.
Substrate is placed on apart from place, about 300 Mills of gas distribution showerhead.Apply the power level that frequency is about 600W of 13.56MHz, be used for the plasma-enhanced deposition of film.Film is with the speed of about 2,000 /min deposition, and uses SSM 5100Hg CV survey instrument to record film under 0.1MHz to have about 4.3 specific inductivity (k).Film also demonstrates the hardness of about 0.1GPa.
At 400 ℃ and 200 μ C/cm 2 Under electron beam treatment:
Under about 400 ℃, about 4.5KeV and 1.5mA, use about 200 μ C/cm 2Dosage sedimentary film carried out high-temperature electronic bundle (e-beam) handle.Electron beam treatment continues about 30 seconds.After electron beam treatment, film demonstrates about 2.2 specific inductivity, and this is approximately littler by 50% than unhardened film.The electron beam film also demonstrates the hardness of about 0.7GPa, and this compares 600% the increase of having an appointment with unhardened film.
Example 15
Under about 8Torr and about 225 ℃ temperature, deposit low dielectric constant films on substrate.Processing gas and flow velocity below using:
ATP, flow velocity 4,000mgm;
TMS, flow velocity 1,000sccm;
OMCTS, flow velocity 200mgm;
Oxygen, flow velocity 100sccm; And
Carbonic acid gas, flow velocity 1,500sccm.
Substrate is placed on apart from place, about 300 Mills of gas distribution showerhead.Apply the power level that frequency is the 500W of 13.56MHz to shower nozzle, be used for the plasma-enhanced deposition of film.Film is with the speed of about 1,600 /min deposition, and uses SSM 5100Hg CV survey instrument to record film under 0.1MHz to have about 4.5 specific inductivity (k).Film also demonstrates the hardness of about 0.1GPa.
At 400 ℃ and 200 μ C/cm 2 Under electron beam treatment:
Under about 400 ℃, about 4.5KeV and 1.5mA, use about 200 μ C/cm 2Dosage sedimentary film carried out high-temperature electronic bundle (e-beam) handle.Electron beam treatment continues about 30 seconds.After electron beam treatment, film demonstrates about 2.3 specific inductivity, and this is approximately littler by 50% than unhardened film.The electron beam film also demonstrates the hardness of about 0.7GPa, and this compares 600% the increase of having an appointment with unhardened film.
Though described embodiments of the invention above, can design other embodiment of the present invention and do not break away from base region of the present invention, and the scope of the invention is indicated in the appended claims.

Claims (20)

1. the method for a deposit low dielectric constant films on substrate comprises:
Deposition comprises the film having low dielectric constant of silicon, carbon, oxygen and hydrogen in CVD (Chemical Vapor Deposition) chamber; And
Under the condition of the hardness that is enough to increase described film having low dielectric constant, described film having low dielectric constant is exposed in the electron beam.
2. method according to claim 1, wherein, described CVD (Chemical Vapor Deposition) chamber is the plasma reinforced chemical vapour deposition chamber.
3. method according to claim 1, wherein, described deposition step comprises:
In described plasma reinforced chemical vapour deposition chamber, introduce gaseous mixture, described gaseous mixture comprises one or more compounds, and this compound is selected from the group of being made up of cyclic organosilicon compounds, aliphatics silicoorganic compound, hydrocarbon polymer and oxidizing gas; And
Make described gaseous mixture reaction on described substrate, to form described film having low dielectric constant.
4. method according to claim 1, wherein, described condition is included in about 1mA to the interior electron beam current of about 15mA scope.
5. method according to claim 1, wherein, the exposure dose of described electron beam is at about 50 μ c/cm 2To about 400 μ c/cm 2Between.
6. method according to claim 1 comprises that also the speed with about 150sccm makes argon gas stream through described film having low dielectric constant.
7. method according to claim 1, wherein, described silicoorganic compound comprise at least one silicon-carbon bonds and at least one si-h bond.
8. method according to claim 1, wherein, described hydrocarbon polymer comprises the unsaturated carbon carbon bond.
9. the method for a deposit low dielectric constant films comprises:
Be enough to deposit under the mode of deposition of non-cured film, to comprise that one or more hydrocarbon polymers with at least one cyclic group and the gaseous mixture of one or more silicoorganic compound are sent to substrate surface, described non-cured film comprises described at least one cyclic group and has hardness less than about 0.3GPa on described substrate surface; And
Under being enough to provide, use electron beam from described non-cured film, to remove described at least one cyclic group basically less than 2.5 specific inductivity and curing condition greater than the hardness of 0.5GPa.
10. method according to claim 9, wherein, the ratio of oxygen and silicon was at least 2: 1 in described one or more silicoorganic compound.
11. method according to claim 9, wherein, described at least one cyclic group is the fractional saturation ring of five or six carbon atom.
12. method according to claim 9, wherein, described one or more compounds with at least one cyclic group comprise the α terpinene.
13. method according to claim 9, wherein, described curing condition comprises from about 200 electron-beam doses to every square centimeter of about 400 microcoulomb.
14. the method for a deposit low dielectric constant films comprises:
Be enough to deposit under the mode of deposition of non-cured film, to comprise one or more silicoorganic compound, have one or more hydrocarbon polymers of at least one cyclic group and the gaseous mixture of two or more oxidizing gases is sent to substrate surface, described non-cured film comprises described at least one cyclic group and has hardness less than 0.3GPa on described substrate surface; And
Under being enough to provide, use electron beam from described non-cured film, to remove described at least one cyclic group basically less than 2.2 specific inductivity and curing condition greater than the hardness of 0.4GPa.
15. method according to claim 14, wherein, described two or more oxidizing gases comprise oxygen and carbonic acid gas.
16. a deposition has about 3.0 or the method for the film having low dielectric constant of littler specific inductivity, comprising:
Make the gaseous mixture reaction, described gaseous mixture comprises:
One or more silicoorganic compound;
One or more aliphatic hydrocarbons, it has one or more unsaturated carbon carbon bonds; And
One or more oxidizing gases;
Be enough under the condition of the described film having low dielectric constant of deposition on the substrate surface, to transmit described gaseous mixture to described substrate surface; And
With electron beam described film having low dielectric constant is carried out aftertreatment, to reduce the specific inductivity of described film.
17. method according to claim 16, wherein, described one or more silicoorganic compound comprise at least one silicon-carbon bonds and at least one si-h bond.
18. method according to claim 16, wherein, described aliphatic hydrocarbon comprises two or more unsaturated carbon carbon bonds.
19. method according to claim 16, wherein, described condition comprises that frequency is that 13.56MHz and frequency are the mixing radio frequency power of 356KHz.
20. method according to claim 16, wherein, described gaseous mixture also comprises argon gas.
CNB038146177A 2002-05-08 2003-05-08 Method for forming ultra low k films using electron beam Expired - Fee Related CN100400707C (en)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US37879902P 2002-05-08 2002-05-08
US60/378,799 2002-05-08
US10/302,375 US20040101632A1 (en) 2002-11-22 2002-11-22 Method for curing low dielectric constant film by electron beam
US10/302,393 2002-11-22
US10/302,393 US7060330B2 (en) 2002-05-08 2002-11-22 Method for forming ultra low k films using electron beam
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