CN1114937C - Method of forming dielectric films with reduced metal contamination - Google Patents
Method of forming dielectric films with reduced metal contamination Download PDFInfo
- Publication number
- CN1114937C CN1114937C CN96198872A CN96198872A CN1114937C CN 1114937 C CN1114937 C CN 1114937C CN 96198872 A CN96198872 A CN 96198872A CN 96198872 A CN96198872 A CN 96198872A CN 1114937 C CN1114937 C CN 1114937C
- Authority
- CN
- China
- Prior art keywords
- gas
- flow
- ozone
- cvd
- reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 71
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 68
- 239000002184 metal Substances 0.000 title claims abstract description 68
- 238000011109 contamination Methods 0.000 title abstract 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 134
- 239000007789 gas Substances 0.000 claims abstract description 124
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 82
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000001301 oxygen Substances 0.000 claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 24
- 238000010790 dilution Methods 0.000 claims abstract description 8
- 239000012895 dilution Substances 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims description 58
- 239000003085 diluting agent Substances 0.000 claims description 49
- 239000000758 substrate Substances 0.000 claims description 25
- 238000000151 deposition Methods 0.000 claims description 24
- 230000008021 deposition Effects 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- 238000006385 ozonation reaction Methods 0.000 claims description 20
- 229910052786 argon Inorganic materials 0.000 claims description 16
- 229910052734 helium Inorganic materials 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- 239000001307 helium Substances 0.000 claims description 10
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 6
- 239000002019 doping agent Substances 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 description 23
- 230000008569 process Effects 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 210000000056 organ Anatomy 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- GDFCWFBWQUEQIJ-UHFFFAOYSA-N [B].[P] Chemical compound [B].[P] GDFCWFBWQUEQIJ-UHFFFAOYSA-N 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000559 atomic spectroscopy Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000673 graphite furnace atomic absorption spectrometry Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940110728 nitrogen / oxygen Drugs 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Images
Classifications
-
- 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
- C23C16/44—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 method of coating
- C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
- C23C16/4402—Reduction of impurities in the source gas
-
- 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
- C23C16/44—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 method of coating
- C23C16/448—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 method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
- C23C16/452—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 method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by activating reactive gas streams before their introduction into the reaction chamber, e.g. by ionisation or addition of reactive species
-
- 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
- H01L21/02104—Forming layers
- 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]
-
- 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
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02551—Group 12/16 materials
- H01L21/02554—Oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
-
- 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
- H01L21/02104—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
- H01L21/02164—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 being a silicon oxide, e.g. SiO2
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- General Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Plasma & Fusion (AREA)
- Chemical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
Abstract
A method of forming dielectric layers having reduced metal atom concentration by Chemical Vapor Deposition (CVD). The CVD system includes an ozone system and a CVD reactor. Oxygen and a nitrogen free dilution gas are introduced into the ozone system where a gas stream including ozone is produced. The gas stream is delivered through metal conduits to the CVD reactor, whereby corrosive vapors which would corrode the conduits are not substantially formed, thereby providing gases which are substantially free of metal contamination which react and deposits layers having reduced metal contamination.
Description
Invention field
The application is the part continuation application (CIP) of No. the 08/573.318th, the U.S. Patent application submitted to December 15 nineteen ninety-five.
Present invention relates in general to formation, more particularly, relate to a kind of method that forms dielectric layer by chemical vapour deposition (CVD) (CVD, chemical vapor deposition) with low metal pollutant at the on-chip film of semiconductor and IC.
Background technology
In the semiconductor and IC manufacture process,, deposit various material layers for forming the semiconductor and IC device.Dielectric layer is generally used for isolating each conductive layer and realizes useful interconnection between these conductive layer.
Form dielectric layer through chemical vapor deposition (CVD) commonly used.Thereby CVD technology is to deposit a kind of material by some gas precursors being transferred on the surface and producing reaction on this surface.The CVD reactor has various ways.Low pressure chemical vapor deposition system (LPCVD, Low pressure CVD) and atmospheric pressure cvd system (APCVD, atmospheric pressure) move according to the hot CVD principle.The chemical substance that helps to be used to react with plasma in plasma-enhanced CVD system (PECVD, plasma enhanced CVD) is decomposed.
Because CVD deposits the component of described pioneer's chemical substance, therefore this precursor has high-purity and (or title pollutant free from foreign meter substantially, contaminants) be very important, because these impurity can produce reaction and be deposited in the formed film, the impurity in the film can destroy the function of device on the wafer and reduce device yield.
The more important thing is the metal impurities in the oxide skin(coating), it is a difficult problem in the semi-conductor industry.The CVD system comprises various metal assemblies, and potential metal impurities source is difficult to determine and eliminate.A kind of CVD technology utilization tetraethyl orthosilicate (TEOS) of extensive use and ozone react and deposit a silicon oxide film.In order to produce the ozone precursor, CVD system traditional in the semi-conductor industry utilizes the plasma discharge unit, high purity oxygen and small amount of nitrogen (typical weight percentage is 1%～5%) this unit of flowing through.When giving this discharge cell power supply,, plasma forms ozone (O thereby quickening the reaction of oxygen and nitrogen
3), usually at oxygen (O
2) the middle O that contains 5.5wt% that forms
3Mixture.Nitrogen is as catalyst for reaction, helps to produce one to be stabilized in ± 1.4% ozone with high concentration.
The inventor in the ozone generating process, causes serious metal impurities owing to form nitric acid in ozonation system by a large amount of discovering.Fog is impurity main in the device.Nitrogen in the ozonation system and fog produce nitric acid when running into oxygen and plasma discharge.These nitric acid influence the CVD system in many aspects.A kind of situation is, these nitric acid accumulate in the aperture of low flow velocity, and for example used mass flow controller (MFC) is surveyed in the organ pipe in the CVD system, will cause that like this MFC surveys the obstruction of organ pipe, and finally cause flow control to be lost efficacy.
Even more serious is to have been found that nitric acid can destroy metal tubes and CVD system component.Especially, nitric acid destroys stainless steel tube road surfaces hydroxide layer, causes being discharged in the air-flow such as the metal impurities of volatility chromated oxide class.These impurity are deposited in the film as impurity along with ozone is sent on the semiconductor chip.
Brief summary of the invention
Therefore, need provide a kind of method, be reduced in the entire CVD system in the ozone delivery process formation of this type of impurity and deposit a kind of film with low metal impurities and required film quality.
An object of the present invention is to provide a kind of improving one's methods of dielectric layer that be used to form.
More specifically, an object of the present invention is to provide a kind of method that is used for reducing chemical vapour deposition (CVD) dielectric layer metal impurities.
In addition, an object of the present invention is to provide a kind of method that in streams of ozone, forms metal impurities that is suitable for reducing.
Another object of the present invention provides a kind of method, and by comprising the device transmission of metal tubes, ozone does not wherein contain corrosive impurity substantially the ozone of ozone generator.
Described purpose of the present invention and other purpose reach by the method that discloses below, according to an aspect of the present invention, provide a kind of and have the method for the oxide skin(coating) of low metallic atom concentration in substrate surface deposition with chemical gas-phase deposition system, described chemical gas-phase deposition system comprises an ozone generating-device, and comprise metal tubes and a CVD (Chemical Vapor Deposition) reactor, this method may further comprise the steps:
In described ozone generating-device, introduce an Oxygen Flow;
Introducing comprises the no nitrogen dilution gas of argon gas, helium and carbon dioxide with one in described ozone generating-device, and produces an air-flow, and this air-flow comprises that ozone and this air-flow do not react with metal tubes basically;
By described metal tubes described air-flow is delivered to described CVD (Chemical Vapor Deposition) reactor, to carry the air-flow of containing metal impurity not substantially; With
In described CVD (Chemical Vapor Deposition) reactor, make the reaction of described air-flow and a kind of reactant gas, with at described substrate surface deposition one layer of containing metal atom not substantially.
According to a further aspect in the invention, provide a kind of being used for will comprise that by an ozonation system reactant gas of low metallic atom impurity is transported to the method for the CVD (Chemical Vapor Deposition) reactor that comprises metal tubes, this method may further comprise the steps:
In described ozonation system, introduce Oxygen Flow;
Introducing one comprises the no nitrogen inert gas of argon gas, helium and carbon dioxide in described ozonation system;
With described oxygen and described inert gas ozonisation, thereby produce a kind of reactive flow that comprises ozone and be substantially free of the acid of energy attack metal; With
Carry described reactive flow by the metal tubes that is included in the described ozonation system, wherein, described reactive flow does not react with metal tubes basically, thereby has reduced the formation of metallic atom impurity in described reactive flow.
According to another aspect of the invention, a kind of ozonation system that is used for carrying from an ozone generator by metal tubes the gas that comprises ozone is provided, introduce oxygen and the diluent gas that comprises argon gas, helium and carbon dioxide in this ozone generator, described diluent gas is nonnitrogenous, thereby do not form substantially and can corrode corrosion of pipe steam, thereby the not gas of containing metal impurity is provided substantially.
Method of the present invention comprises step: the gas ozoniferous that comes from an ozone generator is transmitted by metal tubes, introduced oxygen and diluent gas in this ozone generator.Nonnitrogenous in the diluent gas, corrosion corrosion of pipe steam can not form basically, so the gas that is provided is substantially free of metal impurities.
Another embodiment of the present invention provides a kind of and had the method for the oxide skin(coating) of lower metallic atom concentration a substrate surface deposition in a chemical vapor deposition (CVD) device.This CVD system comprises an ozone generating-device and a CVD reactor.Oxygen and a kind of diluent gas do not comprise nitrogen, introduce in the described ozone generating-device, and here face forms an air-flow that comprises ozone.This air communication is crossed metal tubes and is sent to described CVD reactor.This air-flow is substantially free of corrosive elements, and gas does not react with metal tubes basically during the whole device of this airflow passes, has therefore eliminated the metallic atom pollutant in the air-flow basically.Described air-flow and a kind of reacting gas are transmitted respectively by a syringe, they come out to enter described CVD reactor from syringe, wherein, described gas interacts and is substantially free of the material layer of metal impurities at the surface deposition near the wafer of described syringe.
Brief description of drawings
With reference to the accompanying drawings, by following detailed, other purpose of the present invention and advantage will be more obvious.Wherein:
Fig. 1 is the broken section sketch that can be used for realizing a chemical vapor deposition (CVD) device of the method for the invention;
Fig. 2 is the sketch according to the ozone generator that is suitable for delivery air of one embodiment of the present of invention formation;
The table of Fig. 3 shown proposed in the example 1 according to a preferred embodiment of the invention the level of the metal impurities that can reach;
The table of Fig. 4 shown provided in the example 3 according to another embodiment of the invention the level of the metal impurities that can reach;
Fig. 5 A and 5B are the scanning electron microscopy (SEM according to the cross section of a dielectric layer of method formation of the present invention, Scanning Electron Mioroscope) photo has shown the gap filling and the step coverage condition that can reach according to method of the present invention;
Fig. 6 is the figure of a demonstration according to the SIMS curve of Cr content in the film that the present invention deposited.
Detailed description of preferred embodiment
With reference to accompanying drawing, wherein, assembly is roughly the same represented with label roughly the same.Fig. 1 and Fig. 2 have shown that schematically the method according to this invention is used for carrying the device of the air-flow that comprises low metal impurities.Fig. 1 has shown the spendable chemical vapour deposition (CVD) of method of the present invention (CVD, chemical vapordeposition) device 10.Device 10 comprises that generally can produce an ozone generator 15 that comprises ozone and other gas chemistry air-flow.Air communication crosses metal tubes 16 and mass flow controller 17 is delivered to a CVD reactor 20.Shown in CVD reactor 20 are a conveyor type atmospheric pressure cvd (APCVD) type reactors, in U.S. Patent No. 4,834, it is described in detail in 020, quote herein and be used as reference.Although should be noted that what illustrate is an APCVD reactor here,, method of the present invention also can be with the CVD reactor of other type, for example low pressure chemical vapor deposition (LPCVD, low pressure CVD) and plasma-enhanced CVD (PECVD, plasma enhancedCVD) reactor.APCVD reactor 20 shown in Figure 1 typically comprises: a sleeve (muffle) 31, the syringe 30 in a plurality of a plurality of stages of formation (for simplicity, only showing a syringe 30 and a stage) and a conveyer belt 34.Typically, this reactor 20 comprises four-stage, and each stage is basic identical.In sleeve 31, in syringe 30 both sides a plurality of curtains 32 are set on every side, with isolated zone, and form zone, a settling chamber 33 betwixt.Curtain 32 comprises that a plurality of inert gases feed member (plenum) 36, and it flows inert gas downwards and along conveyer belt 34, therefore assists zone, isolated settling chamber 33.
For deposition one material layer on the surface of semiconductor device, a substrate 35 is placed on the conveyer belt 34 and is sent to sleeve 31 and enters zone, settling chamber 33 again.In zone, settling chamber 33, gas chemistry is delivered to zone near substrate 35 surfaces by syringe 30, and here, the gas chemistries qualitative response is deposition one material layer on the surface of substrate 35 also.
Gas chemistry is delivered to reactor 20 by air transporting arrangement 39, and wherein, described all gases chemical substance is delivered to syringe 30 respectively by gas delivery pipeline 16,26 and 27.In an one exemplary embodiment, by gas delivery pipeline 16,26 with 27 gases of carrying be respectively: ozone/oxygen mixture, TEOS and nitrogen/oxygen mixture (separate N
2).In this embodiment, TEOS and ozone reaction form silicon dioxide layer (SiO on substrate 35 surfaces
2), when gas reacted in zone, settling chamber 33, accessory substance and unreacted chemical material were removed by exhaust line 37 by the direction shown in the arrow usually.
For the layer in certain required composition of substrate 35 surface depositions and purity, key is that the impurity in the CVD system is dropped to minimum level, especially is present in the impurity in the air-flow of delivering to substrate.The present invention is substantially free of the deposition of this required film of method improvement of the streams of ozone of metal impurities by conveying.With reference to figure 2, described method describes in detail with reference to ozonation system shown here.With reference to top described, the inventor finds that through after a large amount of research and analysis most important metal impurities source is because the corrosive impurity steam that is present in the streams of ozone of ozone generator generation produces in the deposited film.Metal tubes in these corrosive impurity steam erosion devices causes metallic atom, especially the release of Cr atom.These Cr atoms are along with streams of ozone flows through device.And be sent to described CVD system.Here the Cr atom finally is deposited in the film as metal impurities.In order to reduce this metal impurities, method of the present invention has been utilized special diluent gas in ozone generator, to produce streams of ozone.A kind of existing dull and stereotyped discharge ozone generator 40 has been shown among Fig. 2.This ozone generator 40 comprises that generally two are separated from each other and discharge electrode 41 and 42 staggered relatively, constitute a region of discharge 47.Scribble a kind of dielectric material 43 on the discharge electrode 41 and 42.On a discharge electrode 41, apply high pressure 48, simultaneously, another discharge electrode 42 ground connection.One heat exchanger 49 contacts with 42 with discharge electrode 41 heat that produces with in the technical process of scattering and disappearing is installed.In order to produce ozone, oxygen and a kind of diluent gas are introduced via pipe 12 and 14 respectively, and then, gas mixes and delivers to ozone generator via pipe 18, and by between the pole plate 41 and 42.In the former process unit, high purity oxygen and be introduced into ozone generator 40 as the nitrogen (typically percentage by weight is 1%～5%) of diluent gas on a small quantity.Apply voltage, activated plasma in gas by power supply 48 to ozone generator.Thereby the plasma accelerated reaction makes oxygen (O
2) formation ozone (O
3).Nitrogen is as catalyst for reaction, the assist in generating ozone with high concentration.Typically, the streams of ozone that is produced is a kind of at O
2Contain percentage by weight in the gas and be 5.5% O
3O
3And O
2Mixture.This streams of ozone comprises ozone, oxygen and diluent gas, and described air communication is crossed pipe 16 discharge ozone generators.
On the contrary, method of the present invention uses different diluent gass to produce streams of ozone, it is characterized in that this streams of ozone be substantially free of can attack metal corrosive impurity steam, keep acceptable ozone concentration and stability simultaneously.With reference to figure 2, as diluent gas, diluent gas is introduced by gas line 14 with helium, argon gas or carbon dioxide in the present invention again.Oxygen is introduced by gas line 12.These gases are by managing 18 mixing and being introduced into ozone generator 40.Apply voltage through discharge electrode 41, produce plasma discharge at region of discharge 47.Plasma and outgas body assist oxygen to become the reaction of ozone.Streams of ozone flows out ozone generator by gas line 16, and this air-flow is for being included in oxygen (O usually
2) in account for about 2～5.5wt%O
3Mixture.With reference now to Fig. 1,, streams of ozone is carried by whole air transporting arrangement 39, here, described air-flow arrives mass flow controller 17 through metal tube 16, then, enter syringe 30 through another metal tube 16, here, streams of ozone flows out the zone, settling chamber 33 that syringe 30 enters close substrate 35 surfaces.Streams of ozone forms a material layer with the reacting gas reaction of flowing out syringe 30 and on the surface of substrate 35.One of them outstanding advantage is, in the process of whole air transporting arrangement of flowing through, streams of ozone basically with metal tubes and assembly reaction, institute is so that streams of ozone is substantially free of metal impurities in conveying.And, the nitric acid of being found in the device before this streams of ozone is substantially free of that can hinder the MFC sensor tube and finally cause MFC to lose efficacy.Streams of ozone is being equal to or less than every liter of gas of 0.07ng metallic atom through the level that will contain metal impurities after the conveying device in the exit of penetrating syringe 30, is preferably less than or equals every liter of gas 0.02ng metallic atom.The film that low like this metallic atom impurity concentration level causes being deposited on the substrate 35 in settling chamber 33 in the streams of ozone has and is less than or equal to 1 * 10
15Metallic atom/cm
3, preferably be less than or equal to 1 * 10
14Metallic atom/cm
3Metals content impurity, this value is lower than the impurity concentration value that device is damaged.
Although top description is carried out with reference to pole plate discharge type ozone generator, the common people that are familiar with this technology can understand that method of the present invention can realize with the ozone generator of other type.In addition, method of the present invention can be used any one diluent gas recited above, i.e. Ar, He or CO for various types of ozone generators
2In the described below preferred embodiment, in a known ASTeX type ozone generator, use CO
2As diluent gas.This ASTeX type ozone generator is water-cooled all-metal, closed cell plasma discharge type ozone generator.
The preferred embodiments different to the present invention have carried out several experiments.In following three examples, the method according to this invention is utilized device shown in Figure 2, operates three kinds of different ozone generators and produces air-flow.First experiment that method of the present invention is carried out is to use an existing oil cooling discharge type ozone generator to carry out as device shown in Figure 2 40.Second experiment is to use an existing water-cooled four-mode ozone generator.An ASTeX ozone generator is used in the 3rd experiment, respectively every speciogenesis device has been carried out the experiment of various diluent gass, and the metallic atom impurity concentration is analyzed.Described experiment illustrates that all the metallic atom impurity in the streams of ozone has dropped to a required level.To describe described experiment in detail below.
Example 1
In this embodiment, used an oil cooling discharge type ozone generator, carried out two independently experiments, each has all used different gas (Ar and He) as diluent gas.Table 1 provides the model experiment parameter.
Table 1 oil cooling discharge type ozone generator operating parameter
| Diluent gas | Ar | He |
| The diluent gas flow rate | 210sccm (standard cubic centimeter) | 528sccm |
| Diluent gas concentration | 3.5vol% (percent by volume) | 8.8vol％ |
| O 2Flow rate | 6slm | 6slm |
| O 3Concentration | 124g/m 3(O 2In contain the O of 4.74wt% 3) | 128g/m 3(O 2In contain the O of 4.89wt% 3) |
| The power of ozone generator (taking the percentage of power) | 52％ | 52％ |
With reference to figure 2,, press the listed flow velocity of table 1 by gas line 44 and introduce oxygen for each experiment.Introduce Ar and He by gas line 45 respectively by table 1 listed flow velocity and concentration.As shown in table 1, the concentration of diluent gas and flow velocity depend on employed gas, will find in the example below also to change according to the type of used ozone generator.Therefore, the common people that are familiar with this technology will understand, except three types described here, method of the present invention can also realize with many ozone generators and corresponding technological parameter.
In order to produce ozone, apply voltage for pole plate 41 by power supply 48, thereby produce plasma at region of discharge 47.At region of discharge 47, the oxygen formation ozone that reacts is created in O
2Account for about 2～5.5wt% (percentage by weight) O in the gas
3Air-flow and carry by the pipeline 16 of giving vent to anger.For each experiment, ozone concentration is all within required requirement in the air-flow as shown in table 1.
Have been found that the concentration and the stability of ozone in the streams of ozone that ratios affect produced of the diluent gas of introducing ozone generator and oxygen.Carried out some experiments to determine optimum ratio, when using Ar as diluent gas, the percent by volume (vol%) of preferred Ar is about 3.5%～9.4%, and when making diluent gas with He, the preferred volume percentage of He is about 8.8%～18%.
(bench test) measures the metal impurities in the streams of ozone with a platform experiment, and the mensuration process is as follows: select basically as shown in Figure 1 ozone generator 40 and CVD system 20 for use.One single wafer sampling apparatus 38 is installed in the ozone gas pipeline 16 between MFC 21 and the syringe 30, as shown in Figure 1.Device 38 is used for measuring the impurity level of streams of ozone, carries out described mensuration by wafer is exposed certain hour in the streams of ozone of certain specific flow velocity and ozone concentration after.Typical location parameter is: at O
2Account for 4.0～4.5wt%O in the gas
3Streams of ozone flow velocity 6slm, 15 minutes time.In order to measure, a wafer produces streams of ozone in ozone generator 40 in device 38, carry this air-flow by pipeline 16, then it is sprayed onto the top of device 38 and makes it arrive the upper surface of wafer.The air-flow that flows out is derived device 38 and is entered syringe 30, and air-flow is discharged from then.Through behind the certain hour, wafer is shifted out from device.Like this, wafer surface just contains streams of ozone impurity, can measure.Remove described impurity with known HF gas-phase decomposition (Hydro-fluoric Vapor PhaseDecomposition) technology.Analyze resulting chemical substance with existing sampling Graphite Furnace Atomic Absorption spectrometry (Graphite Furnace Atomic Spectroscopy) or inductively coupled plasma mass spectrometry method (Inductively Coupled Plasma Mass Spectromety) then, in streams of ozone, expose the contained metal impurities in back with quantitative wafer surface.In order to compare, the wafer that the streams of ozone that the existing method of making diluent gas with nitrogen is produced makes is also measured.Described bench test measurement result is shown in Fig. 3.As can be seen, the method according to this invention greatly reduces the content of Cr impurity as diluent gas with Ar or He.
Example 2
In another experiment,, used an existing water-cooled four-mode discharge ozone generator to produce streams of ozone according to one second embodiment of the present invention.According to the table technological parameter that 2A gave, use Ar and He to carry out two independently experiments respectively as diluent gas.
Table 2A-water-cooled four-mode ozone generator
| Diluent gas | Ar | He |
| The diluent gas flow rate | 1.26slm | 1.32slm |
| Diluent gas concentration | 5.25vol％ | 5.5vol％ |
| O 2Flow rate | 24slm | 24slm |
| O 3Concentration | 107g/m 3 | 107g/m 3 |
| The power of ozone generator (taking the percentage of power) | 62％ | 62％ |
With basically as described in Example 1 method produce a streams of ozone.In order to measure the impurity content in the streams of ozone, on substrate, deposit a dielectric layer as precursor with streams of ozone.Substrate is placed in the zone, settling chamber 33, under the syringe 20 in CVD reactor 20, as shown in Figure 1.Particularly, according to the operating condition relevant among the table 2A with Ar test, in order to Ar as streams of ozone dielectric layer that diluent gas produced.Carry out the CVD deposition according to the table parameter that 2B gave.
Table 2B-CVD process conditions
| The flow rate of syringe 1 (slm) | The flow rate of syringe 2 (slm) | The flow rate of syringe 2/3 (slm) | The flow rate of syringe 3 (slm) | The flow rate of syringe 4 (slm) | |
| O 2/O 3 | 4.87 | 4.85 | -- | 4.83 | 4.86 |
| Dilution N 2 | 2.09 | 2.07 | -- | 2.07 | 2.03 |
| Separator N 2 | 9.98 | 9.97 | -- | 9.95 | 9.89 |
| Liquid source-dopant dilution N 2 | 3.39 | -- | 6.79 | -- | 3.89 |
| Si source N 2 | 1.898 | -- | 3.781 | -- | 1.895 |
| Depositing temperature | 550℃ | ||||
| Belt speed | 3 "/minute | ||||
| Constant pressure | 1.18”H 2O | ||||
As show shown in the 2B, make a substrate 35 through 4 four stages of syringe and corresponding sedimentary chamber region 33 independently with CVD reactor 20, dielectric layer in this one exemplary embodiment, is delivered to 4 syringes by the gas flow rate that table 2 is given with streams of ozone.Dilution N
2Offer each syringe, the A point in Fig. 1 is connected on the streams of ozone pipe usually.Because nitrogen is introduced the downstream of the air-flow that ozone generator produced, therefore formation nitric acid and corresponding metal impurity problem that described existing technology exists can not take place.Shown in label among Fig. 1 27, separator N
2Be sent to each a certain position in 4 syringe stages.Liquid source diluting nitrogen (N
2) (Liquid Source Dilution N
2) flow velocity represent the introducing of dopant such as boron or phosphorus, nitrogen is as carrier gas.This class dopant can be used to deposit a kind of boron phosphorus silicate glass (BPGS) oxidation film.Do carrier gas with nitrogen and introduce TEOS, as Si source N among the table 2B by pipe 24
2Shown in the delegation.The flow velocity of liquid source diluting nitrogen and Si source nitrogen is shown in " syringe 2/3 flow velocity " row of table 2B, because all use a common feed tube for every kind of gas of two syringes.
Example 3
In the 3rd experiment, one the 3rd embodiment according to the present invention uses an existing ASTeX ozone generator to produce streams of ozone.According to the technological parameter that table 3A provides, use Ar, He and CO respectively
2Three independently experiments have been carried out as diluent gas.Still produce a streams of ozone by described method.According to the experiment of being carried out, realize that preferable methods of the present invention is, use the ASTeX generator, with CO
2Make diluent gas, best, CO
2Percentage by weight substantially between 2～3.6wt%.Adopt several different methods to measure the impurity concentration that exists in the different streams of ozone.At first, to CO
2For the streams of ozone that diluent gas produces is carried out a platform experiment.The experiment of being carried out in this contrast experiment and the previous examples 1 is similar, as shown in Figure 1, the sampling apparatus 38 of a single wafer is installed in the ozone gas pipeline 16 between MFC21 and syringe 30.Usually, the wafer that is placed in the device 38 is 6slm through flow velocity, at O
2In to contain concentration be 4.0～4.5wt%O
3Streams of ozone sprayed 15 minutes.Platform experiment the results are shown in Fig. 4, and the result shows: with use N
2Compare as the wafer mensuration that diluent gas carries out,, use CO according to the present invention
2Greatly reduce the contents level of Cr impurity as diluent gas, see Fig. 4.
Table 3A-ASTeX ozone generator
| Diluent gas | Ar | ?He | ?CO 2 |
| The diluent gas flow rate | 4.62slm | ?9.30slm | ?900sccm |
| Diluent gas concentration | 18.9vol％ | ?38vol％ | ?3.6vol％ |
| O 2Flow rate | 24slm | ?24slm | ?24slm |
| O 3Concentration (reality) | 48.6g/m 3 | ?46.4g/m 3 | ?107g/m 3 |
| The power of ozone generator (taking the percentage of power) | 100％ | ?100％ | ?52％ |
Except described platform experiment, also the method according to this invention has deposited dielectric layer on substrate.This rete has required lower metal impurities.Especially, according to the technological parameter that following table 3B provides, use basically APCVD reactor dielectric layer as shown in Figure 1.
Table 3B-CVD process conditions
| The flow rate of syringe 1 (slm) | The flow rate of syringe 2 (slm) | The flow rate of syringe 2/3 (slm) | The flow rate of syringe 3 (slm) | The flow rate of syringe 4 (slm) | |
| O 2/O 3 | 5.96 | 5.99 | -- | 5.97 | 5.97 |
| Dilution N 2 | 0.98 | 0.98 | -- | 0.98 | 1.00 |
| Separator N 2 | 9.96 | 9.92 | -- | 9.95 | 9.96 |
| Liquid source diluting N 2 | 3.88 | -- | 3.96 | -- | 3.88 |
| Si source N 2 | 0.867 | -- | 1.728 | -- | 0.868 |
| Depositing temperature | 500℃ | ||||
| Belt speed | 3.75 "/minute | ||||
| Constant pressure | 1.11”H 2O | ||||
Be placed on 6 ＂ silicon chips 35 on the conveyer belt 34 and make it through each of described 4 stages, thus on silicon chip the deposition dielectric film that 4800 dusts～7000 dusts are thick.In each stage, process under the syringe 30 of substrate 35 in the crystallizing field 33.Reacting gas O
3And TEOS, and other gas, come out to react from syringe, and form a material layer on this surface on surface near substrate 35.
Each film has all been carried out metal impurities mensuration, and film quality has been evaluated.Particularly, use existing analytical technology, more specifically, with secondary ion mass spectroscopy (SIMS) (Secondary Ion MassSpectrometry) technology the metals content impurity in the substrate is measured, as shown in Figure 6, standard SIM S the analysis showed that the content of Metal Cr is less than 1 * 10 in the film of the upper surface deposition of the substrate of placing under the syringe 30 in zone, settling chamber 33
14Metallic atom/cm
3, with reference to figure 6, having provided the Cr content in the film, this film is it to be deposited through CVD system 20 shown in Figure 1 obtain by transmitting a wafer 35.In this embodiment, device 20 comprises 4 settling chamber's 33 stages of zone, and each settling chamber 33 comprises a syringe 30, and described film deposits its twice process device 20 by transmitting wafer.When wafer pass sleeve 31 through the syringe 30 of 4 separation under the time dielectric film deposition on wafer, each syringe 30 each stage in zone, 4 settling chambers 33 is carried reactive pioneer's chemical substance.When wafer was conveyed through sleeve 31 by conveyer belt, wafer also passed an inlet nitrogen curtain (not shown), nitrogen curtain 32 and an outlet nitrogen curtain (not shown) between syringe.With reference to figure 6, each settling chamber is represented by an alphabetical A to H in 33 stages of zone again.Letter A-D represents and passes through for the first time 4 settling chambers' 33 stages of zone, and letter e-H represents for the second time by 4 settling chamber's 33 stages of zone.Make diluent gas with He and produce streams of ozone 16 in ozone generator 15, the parameter operation that CVD system 20 provides according to table 3B usually is to deposit described film.
Come with reference to figure 6, this figure shows Cr content (Cr atom/cm again
3) be the function of the thickness (μ m) that is deposited on the film on the silicon chip.When wafer when the device 20, Cr is deposited on the wafer, according to the quantity difference of the different Cr in position of wafer.Shown in an A-H, the content of Cr is lower than 1 * 10 in the film that is deposited under each zone, settling chamber 33 inner injector 30
14Metallic atom/cm
3The value of zone C r is higher than 1 * 10 outside settling chamber 33
14, injection areas generation gas phase Cr assembles in this is so-called, but these regional Cr content are 10 at standard deviation value still
15Within the scope, this value is the desired value that can satisfy the demand that the semiconductor industry is striven to find.
An outstanding advantage is that method of the present invention can realize that good step covers and fill in the gap.Can observe the quality of this film from Fig. 5 a and 5b, Fig. 5 a and 5b show certain a part of SEM photo of the cross section of the wafer of the dielectric film of two preferred embodiment formation according to the present invention.In Fig. 5 a, comprise the aluminum steel 51 and 52 that is formed on the substrate 35 in the wafer.Line 51 and 52 is at a distance of 1 μ m.The aspect ratio in the gap between the line 51 and 52 (aspectratio) is that 0.4 μ m height ratio, 1.0 μ m are wide.With ozone and TEOS as precursor gases online 51 and 52 and substrate 35 within silicon dioxide dielectric layers 53 of deposition.Streams of ozone is according to the operating parameter shown in the table 2A, produces with water-cooled four-mode ozone generator as diluent gas with Ar.The CVD deposition is to carry out according to the table operating parameter that 2B gave.Shown in Fig. 5 a, dielectric layer has been filled the gap of described 1 μ m equably, does not have any cavity, hillock and other defective.
Fig. 5 b is a SEM photo of the cross section of a wafer and the dielectric layer that forms according to a preferred embodiment of the invention.Wafer comprises the aluminum steel 55 and 56 that is formed at substrate 35 surfaces, and they are at a distance of 1.5 μ m.The aspect ratio in the gap between the line 55 and 56 is that 0.4 μ m height ratio, 1.0 μ m are wide.With ozone and TEOS as precursor gases depositing silicon oxide dielectric layer 57.In the preferred embodiment, streams of ozone is the operating parameter CO that provides according to table 3A
2Produce as diluent gas.The CVD deposition is to carry out according to the operating parameter that table 3B provides.Come the 5b with reference to figure again, dielectric layer has been filled described one micron gap equably, does not have cavity, hillock and other defective.
Described description to concrete preferred embodiment is in order to describe and to explain.They are not exhaustive or limit the present invention with the concrete form that discloses, obviously, can carry out many modifications and variations to the present invention, provide more embodiment according to described instruction.Scope of the present invention will be limited by back appending claims and equivalent thereof.
Claims (24)
1. method that has the oxide skin(coating) of low metallic atom concentration with chemical gas-phase deposition system in substrate surface deposition, described chemical gas-phase deposition system comprises an ozone generating-device, and comprise metal tubes and a CVD (Chemical Vapor Deposition) reactor, this method may further comprise the steps:
In described ozone generating-device, introduce an Oxygen Flow;
Introducing comprises the no nitrogen dilution gas of argon gas, helium and carbon dioxide with one in described ozone generating-device, and produces an air-flow, and this air-flow comprises that ozone and this air-flow do not react with metal tubes basically;
By described metal tubes described air-flow is delivered to described CVD (Chemical Vapor Deposition) reactor, to carry the air-flow of containing metal impurity not substantially; With
In described CVD (Chemical Vapor Deposition) reactor, make the reaction of described air-flow and a kind of reactant gas, with at described substrate surface deposition one layer of containing metal atom not substantially.
2. method according to claim 1, wherein, described diluent gas is an argon gas.
3. method according to claim 1, wherein, described diluent gas is a helium.
4. method according to claim 1, wherein, described diluent gas is a carbon dioxide.
5. method according to claim 1, wherein, described air-flow has the metallic atom concentration that is approximately equal to or less than every liter of gas 0.05ng metallic atom greatly.
6. method according to claim 1, wherein, described layer has and is approximately equal to or less than 1 * 10 greatly
15Metallic atom/cm
3Metallic atom concentration.
7. method according to claim 1, wherein, described CVD (Chemical Vapor Deposition) reactor is an aumospheric pressure cvd reactor, it comprises: a sleeve; At least one chemical vapor deposition reaction chamber zone in this sleeve; At least one is used for gas is sent to the syringe in described at least one chemical vapor deposition reaction chamber zone; With a conveyer belt that is used for mobile wafer by described reative cell and described sleeve.
8. method according to claim 1, wherein, described CVD (Chemical Vapor Deposition) reactor comprises that one is used to carry described reactant gas and described air-flow describedly to have one and be less than or equal to 1 * 10 haply to deposit
14Metallic atom concentration the layer syringe.
9. method according to claim 1, wherein, described CVD (Chemical Vapor Deposition) reactor is a pressure chemical vapor deposition reactor.
10. method according to claim 1, wherein, described CVD (Chemical Vapor Deposition) reactor is a pecvd reactor.
11. one kind is used for will comprising that by an ozonation system reactant gas of low metallic atom impurity is transported to the method for the CVD (Chemical Vapor Deposition) reactor that comprises metal tubes, this method may further comprise the steps:
In described ozonation system, introduce Oxygen Flow;
Introducing one comprises the no nitrogen inert gas of argon gas, helium and carbon dioxide in described ozonation system;
With described oxygen and described inert gas ozonisation, thereby produce a kind of reactive flow that comprises ozone and be substantially free of the acid of energy attack metal; With
Carry described reactive flow by the metal tubes that is included in the described ozonation system, wherein, described reactive flow does not react with metal tubes basically, thereby has reduced the formation of metallic atom impurity in described reactive flow.
12. method according to claim 11, wherein, described reactive flow has the metallic atom concentration that is equal to or less than every liter of gas 0.05ng metallic atom.
13. method according to claim 11, wherein, described no nitrogen inert gas is an argon gas.
14. method according to claim 11, wherein, described no nitrogen inert gas is a helium.
15. method according to claim 11, wherein, described no nitrogen inert gas is a carbon dioxide.
16. ozonation system that is used for carrying from an ozone generator gas that comprises ozone by metal tubes, introduce oxygen and diluent gas in this ozone generator, it is characterized in that, described diluent gas comprises argon gas, helium and carbon dioxide, and it is nonnitrogenous, thereby do not form substantially and can corrode corrosion of pipe steam, thereby the not gas of containing metal impurity is provided substantially.
17. ozonation system according to claim 16, wherein, described diluent gas is an argon gas.
18. ozonation system according to claim 16, wherein, described diluent gas is a helium.
19. ozonation system according to claim 16, wherein, described diluent gas is a carbon dioxide.
20. ozonation system according to claim 16, wherein, the feature of described gas is that also the metal impurities in the described gas are equal to or less than every liter of gas 0.05ng metallic atom haply.
21. method according to claim 1, wherein, described layer has and is equal to or less than 1 * 10 haply
14Metallic atom/cm
3Metallic atom concentration.
22. method according to claim 1, wherein, the flow velocity of described air-flow that is delivered to CVD (Chemical Vapor Deposition) reactor is greatly about the scope of 4.0-10.0slm.
23. method according to claim 1, wherein, the flow velocity of described reactive flow that is delivered to CVD (Chemical Vapor Deposition) reactor is greatly about the scope of 1.0～5.0slm.
24. method according to claim 1, wherein, described reactant gas comprises a kind of siliceous gas and a kind of gas that contains dopant, every kind of gas is all sent into described CVD (Chemical Vapor Deposition) reactor respectively, the flow velocity of described silicon-containing gas is greatly about the scope of 1.0～5.0slm, and the flow velocity of the described gas that contains dopant is greatly about the scope of 3.0～8.0slm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US57331895A | 1995-12-15 | 1995-12-15 | |
| US08/573,318 | 1995-12-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1204418A CN1204418A (en) | 1999-01-06 |
| CN1114937C true CN1114937C (en) | 2003-07-16 |
Family
ID=24291490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96198872A Expired - Fee Related CN1114937C (en) | 1995-12-15 | 1996-12-11 | Method of forming dielectric films with reduced metal contamination |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0867037A1 (en) |
| JP (1) | JP2000502212A (en) |
| KR (1) | KR100373434B1 (en) |
| CN (1) | CN1114937C (en) |
| AU (1) | AU1288197A (en) |
| WO (1) | WO1997022992A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11288893A (en) | 1998-04-03 | 1999-10-19 | Nec Corp | Semiconductor manufacturing apparatus and manufacture of semiconductor device |
| KR100330749B1 (en) * | 1999-12-17 | 2002-04-03 | 서성기 | Thin film deposition apparatus for semiconductor |
| JP5175414B2 (en) * | 2001-06-27 | 2013-04-03 | アプライド マテリアルズ インコーポレイテッド | Film forming method and apparatus |
| CN1326638C (en) * | 2002-07-19 | 2007-07-18 | 上海华虹（集团）有限公司 | Method for removing excessive metal in preapring silicide |
| EP3173377B1 (en) | 2011-03-24 | 2020-08-19 | Toshiba Mitsubishi-Electric Industrial Systems Corporation | Ozone gas supply system |
| US10113229B2 (en) * | 2015-12-21 | 2018-10-30 | Varian Semiconductor Equipment Associates, Inc. | Techniques for controlling ion/neutral ratio of a plasma source |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4845054A (en) * | 1985-06-14 | 1989-07-04 | Focus Semiconductor Systems, Inc. | Low temperature chemical vapor deposition of silicon dioxide films |
| US5000113A (en) * | 1986-12-19 | 1991-03-19 | Applied Materials, Inc. | Thermal CVD/PECVD reactor and use for thermal chemical vapor deposition of silicon dioxide and in-situ multi-step planarized process |
| JPH06244426A (en) * | 1993-02-04 | 1994-09-02 | Toagosei Chem Ind Co Ltd | Production of glass board for thin film formation |
-
1996
- 1996-12-11 JP JP09522910A patent/JP2000502212A/en not_active Ceased
- 1996-12-11 AU AU12881/97A patent/AU1288197A/en not_active Abandoned
- 1996-12-11 KR KR10-1998-0704363A patent/KR100373434B1/en not_active IP Right Cessation
- 1996-12-11 CN CN96198872A patent/CN1114937C/en not_active Expired - Fee Related
- 1996-12-11 EP EP96943723A patent/EP0867037A1/en not_active Withdrawn
- 1996-12-11 WO PCT/US1996/019819 patent/WO1997022992A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| WO1997022992A1 (en) | 1997-06-26 |
| KR100373434B1 (en) | 2003-05-16 |
| JP2000502212A (en) | 2000-02-22 |
| AU1288197A (en) | 1997-07-14 |
| EP0867037A1 (en) | 1998-09-30 |
| CN1204418A (en) | 1999-01-06 |
| KR20000064378A (en) | 2000-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8227346B2 (en) | Method of producing semiconductor device | |
| EP0387403B1 (en) | Deposition of silicon oxide films using alkylsilane liquid sources | |
| US6955836B2 (en) | Silicon oxide film formation method | |
| EP1612856B1 (en) | Device for cleaning cvd device and method of cleaning cvd device | |
| JPH0831454B2 (en) | Method for manufacturing semiconductor device | |
| CN1868041A (en) | Low temperature deposition of silicon oxides and oxynitrides | |
| CN101061255A (en) | Low temperature SiN deposition methods | |
| CN1114937C (en) | Method of forming dielectric films with reduced metal contamination | |
| WO2001004942A1 (en) | Chemical vapor deposition of silicon oxide films using alkylsiloxane oligomers with ozone | |
| US5324539A (en) | Method for forming CVD thin glass films | |
| KR900008970B1 (en) | Process vapor growth of phosphosilicate glass coating | |
| US7105059B2 (en) | Reaction apparatus for atomic layer deposition | |
| JPH066789B2 (en) | Deposition method of borophosphosilicate glass | |
| JPH1012601A (en) | Cvd apparatus and cvd film formation method | |
| JPS60150624A (en) | Low voltage chemical deposition diffusing dopant source for semiconductor | |
| US20030037723A9 (en) | High throughput epitaxial growth by chemical vapor deposition | |
| CN1783423A (en) | High-rate etching using high pressure F2 plasma with argon diluent | |
| RU2100477C1 (en) | Process of deposition of films of hydrogenized silicon | |
| GB2132637A (en) | Process for depositing dielectric films in a plasma glow discharge | |
| Jarek et al. | Hazards of dichlorosilane exhaust deposits from the high-temperature oxide process as determined by FT-ICR mass spectrometry | |
| Manory et al. | A comparative study of silicon deposition from SiCl4 in cold plasma using argon, H2 or Ar+ H2 | |
| TW311238B (en) | Method of forming dielectric films with reduced metal contamination | |
| Morosanu et al. | Thin film preparation by plasma and low pressure CVD in a horizontal reactor | |
| CN1732285A (en) | Protective shield and system for gas distribution | |
| US20020012749A1 (en) | Method and apparatus for coating and/or treating substrates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| CB02 | Change of applicant information |
Applicant after: Semiconductor Equipment Group Co Ltd Applicant before: Watkins-Johnson Co. |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: WATKINS JOHNSON + JOHNSON TO: SEMICONDUCTOR EQUIPMENT GROUP CO.,LTD. |
|
| C53 | Correction of patent for invention or patent application | ||
| CB02 | Change of applicant information |
Applicant after: Sealy Con Valli group Applicant after: Heat Systems Inc Applicant before: Semiconductor Equipment Group Co Ltd |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: SEMICONDUCTOR EQUIPMENT GROUP CO.,LTD. TO: SILICON VALLEY GROUP |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |