WO2006028844A1 - Method to deposit functionally graded dielectric films via chemical vapor deposition using viscous precursors - Google Patents
Method to deposit functionally graded dielectric films via chemical vapor deposition using viscous precursors Download PDFInfo
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- WO2006028844A1 WO2006028844A1 PCT/US2005/030956 US2005030956W WO2006028844A1 WO 2006028844 A1 WO2006028844 A1 WO 2006028844A1 US 2005030956 W US2005030956 W US 2005030956W WO 2006028844 A1 WO2006028844 A1 WO 2006028844A1
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- Prior art keywords
- flow rate
- silicon
- containing gas
- carbon containing
- gas
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 78
- 239000002243 precursor Substances 0.000 title description 5
- 238000005229 chemical vapour deposition Methods 0.000 title description 2
- 239000007789 gas Substances 0.000 claims abstract description 135
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000012159 carrier gas Substances 0.000 claims abstract description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 230000000903 blocking effect Effects 0.000 claims abstract description 7
- 230000004888 barrier function Effects 0.000 claims description 32
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 15
- 230000007423 decrease Effects 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 238000009792 diffusion process Methods 0.000 claims description 3
- 238000000151 deposition Methods 0.000 description 28
- 230000008021 deposition Effects 0.000 description 26
- 229910052751 metal Inorganic materials 0.000 description 20
- 239000002184 metal Substances 0.000 description 20
- 239000000758 substrate Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 235000012431 wafers Nutrition 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052581 Si3N4 Inorganic materials 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000000443 aerosol Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 239000008246 gaseous mixture Substances 0.000 description 4
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical group N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004590 computer program Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 2
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 2
- 229910020776 SixNy Inorganic materials 0.000 description 1
- 238000012387 aerosolization Methods 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
- H01L21/31604—Deposition from a gas or vapour
- H01L21/31633—Deposition of carbon doped silicon oxide, e.g. SiOC
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
- C23C16/029—Graded interfaces
-
- 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
- C23C16/44—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
- C23C16/455—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 introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
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- 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
- H01L21/02126—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
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- 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
- H01L21/02205—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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- 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]
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- 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
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
- H01L21/02304—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment formation of intermediate layers, e.g. buffer layers, layers to improve adhesion, lattice match or diffusion barriers
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- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
Definitions
- IC device fabrication includes etching patterns of gaps into a metal layer such as aluminum. The gaps may then be filled with dielectric materials such as silicon dioxide. More recently, IC device fabricators are switching from aluminum to copper and other more conductive metals to take advantage of the lower resistance of these metals to electric current. In the case of copper, the metal's higher resistance to etching than aluminum is encouraging a switch to damascene processes where dielectric layers are deposited to form an integrated stack that are etched to create gaps for a subsequent metal gap-fill.
- IMD intermetal dielectric
- IMD layers typically include a barrier layer to prevent the diffusion of the metal into the adjacent dielectric layers.
- a barrier layer is silicon nitride (Si x N y ), which is also commonly used as an etch stop material for the formation of the damascene structures.
- barrier layers have been developed from materials with lower dielectric constants.
- Silicon-carbon based barrier layers e.g., silicon oxycarbide (SiOCH) barrier layers
- SiOCH silicon oxycarbide
- One such layer for example, is the BLOKTM (Barrier Low K) developed by Applied Materials, Inc. of Santa Clara, California.
- BLOKTM Barrier Low K
- TMS trimethylsilane
- silicon oxycarbide and other silicon-carbon based low- ⁇ barrier layers have improved dielectric constants, they often have poor adherence to other low- ⁇ silicon-carbon materials that make up the bulk dielectric portion of the IMD layer.
- Oxide films such as silicon dioxide (SiO 2 ) adhere much better to the silicon-carbon based low-/c barrier layers, but also have higher K values that raise the overall dielectric constant of the IMD layer.
- SiO 2 silicon dioxide
- Embodiments of the present invention include a method of forming a graded dielectric layer on an underlying layer.
- the method includes the step of flowing a mixture of a silicon-carbon containing gas, an oxygen containing gas and a carrier gas through a showerhead comprising a blocking plate and a faceplate to form an oxide rich portion of the graded dielectric layer, where the silicon-carbon containing gas has an initial flow rate.
- the method also includes the step of flowing the silicon-carbon containing gas at a first intermediate flow rate for about 0.5 seconds or longer, where the first intermediate flow rate is higher than the initial flow rate.
- the method may also include the step of flowing the silicon-carbon containing gas at a fastest flow rate higher than the first intermediate flow rate to form a carbon rich portion of the graded dielectric layer.
- Other embodiments of the invention include a method of forming a graded dielectric layer on an underlying layer, where the method includes the step of flowing a mixture of a silicon-carbon containing gas, an oxygen containing gas and a carrier gas through a showerhead comprising a blocking plate and a faceplate to form an oxide rich portion of the graded dielectric layer, wherein the silicon-carbon containing gas has an initial flow rate.
- the method also includes the step of increasing the silicon-carbon containing gas to a fastest flow rate to form a carbon rich portion of the graded dielectric layer, where the carrier gas has a carrier gas flow rate that stays constant until after the silicon-carbon containing gas reaches the fastest flow rate.
- Additional embodiments of the invention include a system for forming a graded dielectric layer on an underlying layer.
- the system includes a showerhead that includes a blocking plate and a face plate, wherein the showerhead is coupled to a gas supply inlet through which a process gas comprising a silicon-carbon containing gas, an oxygen containing gas and a carrier gas is introduced into the showerhead.
- the system also includes a liquid flow meter to control a flow rate of the silicon-carbon containing gas to the showerhead, where the liquid flow meter is programmed to flow the silicon-carbon containing gas at an initial flow rate during the formation of an oxygen rich portion of the graded dielectric layer, then increasing the silicon-carbon containing gas flow rate from the initial flow rate to an intermediate flow rate, and maintaining the intermediate flow rate for about 0.5 seconds or longer, and then further increasing the silicon-carbon containing gas flow rate from the intermediate flow rate to a fastest flow rate to form a carbon rich portion of the graded dielectric layer.
- Figs. IA and IB show a barrier layer and functionally graded dielectric layer formed on a metal filled trench according to embodiments of the methods of the present invention
- FIG. 2 shows a simplified cross-sectional view of an integrated circuit device that includes functionally graded dielectric layer formed according to embodiments of the methods of the present invention
- FIG. 3 shows a flowchart of steps for forming a graded dielectric layer according to embodiments of the methods of the present invention
- Fig. 4 shows a flowchart of steps for forming a graded dielectric layer according to additional embodiments of the methods of the present invention
- Fig. 5 plots the flow rate of a silicon-carbon containing gas as a function of time for a conventional dielectric layer deposition and a deposition according to an embodiment of the methods of the present invention
- Fig. 6 shows a sectional view of a showerhead that may be used with embodiments of the present invention.
- FIG. 7 shows a simplified cross-sectional diagram of an exemplary plasma CVD deposition chamber used with embodiments of the systems and methods of the present invention.
- Embodiments of the present invention include methods of forming a low- ⁇ , functionally graded film layer that includes an oxide rich portion for better adherence to an underlying layer (e.g., a silicon oxycarbide barrier layer) and a carbon-rich portion (e.g., the bulk dielectric) having a lower K value.
- the method includes flowing a mixture of silicon- carbon containing gas and oxygen containing gas at an initial flow rate favoring a high oxygen to silicon flow rate ratio to deposit a thin (e.g., about IOA to about 8 ⁇ A thick) oxide rich portion of the functionally graded dielectric layer.
- flow rate for the silicon- carbon containing gas may be increased (and oxygen containing gas may be decreased) to boost the silicon-carbon concentration in the bulk dielectric portion of the functionally graded dielectric layer. Because the oxide-rich portion is relatively small, it has a small effect on the overall K value of the layer.
- the silicon-carbon gases used with the present invention are often organo-silicon compounds such as octamethylcyclotetrasiloxane (“OMCTS”) [((CEb) 2 SiO) 4 ].
- OMCTS octamethylcyclotetrasiloxane
- Compounds like OMCTS are viscous liquids at room temperature, which when heated (e.g., about 350°C) produce vapors that may be carried by a carrier gas to a deposition chamber where the functionally graded dielectric is formed.
- the blocker plate can also introduce a drop in the pressure of the gas mixture across the plate, which can result in condensation of the silicon-carbon around passages through the blocker plate and face plate.
- the condensate in these passages, as well as the formation of organo-silicon aerosol particles in the reaction chamber, can lead to increased numbers of infilm adders (e.g., about 10,000 or more adders) falling on the substrate.
- the problem is exacerbated by the fact that the adders are not uniformly distributed on the substrate, but instead tend to concentrate in the area below the center of the showerhead faceplate.
- Embodiments of the present invention reduce condensation of the silicon-carbon vapor and the infilm adders through a number of techniques, including modulating the change in the flow rate of the silicon-carbon containing gas, and maintaining a high carrier gas flow rate until after an increase in the flow rate of the silicon-carbon containing gas has occurred.
- These techniques and others, used alone or in combination, can reduce the number of infilm adders from the tens of thousands to the order of about 10 or less.
- Fig. IA shows an example of a layers upon which a barrier layer and a functionally graded dielectric layer formed according to embodiments of the present invention.
- the layers include a dielectric layer 104 containing trench 106 filled with a conductive material (e.g., copper).
- the dielectric layer 104 and trench 106 may be formed on an underlying support layer 102.
- Support layer 102 may be a silicon substrate, a metal film layer (e.g. a copper or aluminum layer), a salicide layer formed on top of a source, drain or gate electrode, or a dielectric layer (e.g., a IMD layer), among other kinds of layers.
- barrier layer 108 may be formed from silicon-carbon based materials (e.g., silicon oxycarbide) that have lower K values than conventional oxide and nitride based barrier layers (e.g., silicon nitride).
- the K value of barrier layer 108 formed from silicon-carbon based materials depends on the ratio of carbon to silicon atoms in the layer.
- the C:Si ratio in the gaseous mixture is greater than 1 : 1 (e.g., about 3 : 1 to about 8:1).
- the higher the substrate temperature the lower the C:Si ratio in the deposited layer Relatively high C:Si ratios in the gaseous mixture may be desirable when depositing the barrier layer 108 at high substrate temperatures.
- Functionally graded dielectric (“FGD”) layer 110 may be formed on the underlying barrier layer 108 according to embodiments of the methods of the invention described below.
- the FGD layer 110 may include an oxide-rich portion that is in contact with the underlying barrier layer 108, and a carbon-rich portion (Le., the bulk dielectric portion) that is further away from barrier layer 108.
- the oxide-rich portion of the layer may comprise silicon (Si) 3 oxygen (O) and carbon (C) where the ratio of silicon to oxygen is lower than average to reflect the higher than average concentration of oxygen present in the layer.
- the oxide-rich portion of the FGD layer 110 may be in a range from about 10 A to about 100 A thick (e.g., about 70 A to 80 A thick).
- the carbon-rich, bulk dielectric portion of FGD layer 110 may have a C:Si ratio substantially similar to barrier layer 108 (e.g., about 55:45 to about 65:35).
- the bulk dielectric portion may be from about 5000 A to about 10,000 A thick, and provide FGD layer with an overall K value of about 3.5 or less (e.g., from about 3.3 to about 3.0).
- Fig. 2 illustrates a simplified cross-sectional view of an integrated circuit 200 that includes functionally graded inter-metal dielectric (FGIMD) layers 240, 242, 244 formed according to embodiments of the present invention.
- Integrated circuit 200 includes NMOS and PMOS transistors 203 and 206, which are separated and electrically isolated from each other by a field oxide region 220 formed by local oxidation of silicon (LOCOS), or other technique.
- transistors 203 and 206 may be separated and electrically isolated ' from each other by a shallow trench isolation (STI) technique (not shown) when transistors 203 and 206 are both NMOS or both PMOS.
- STI shallow trench isolation
- Each transistor 203 and 206 comprises a source region 212, a drain region 215 and a gate region 218.
- a premetal dielectric (PMD) layer 221 separates transistors 203 and 206 from metal layer 240 with connections between metal layer 240 and the transistors made by contacts 224.
- Metal layer 240 is one of four metal layers, 240, 242, 244 and 246, included in integrated circuit 200. Each metal layer 240, 242, 244, and 246 is separated from adjacent metal layers by respective barrier layers and FGIMD layers 227, 228, or 229. Adjacent metal layers are connected at selected openings by vias 226. Deposited over metal layer 246 are planarized passivation layers 230.
- simplified integrated circuit 200 is for illustrative purposes.
- One of ordinary skill in the art could implement use of the present invention in relation to fabrication of other integrated circuits such as microprocessors, application specific integrated circuits (ASICs), memory devices, and the like.
- the present invention maybe applied to PMOS, NMOS, CMOS, bipolar, or BiCMOS, among other devices.
- a flowchart is shown illustrating the step of a method of forming a graded dielectric layer according to embodiments of the invention.
- the method may start by flowing a gas mixture at an initial flow rate 302 through a gas showerhead to deposit an oxide-rich portion of the graded dielectric layer 304 on an underlying layer (e.g., a low- ⁇ barrier layer).
- the gas mixture may include a silicon-carbon containing gas (e.g., OMCTS), an oxygen containing gas (e.g., O 2 ) and a carrier gas (e.g., He).
- the silicon containing gas may be a viscous liquid at room temperature and the flow rate of its gas vapors measured in milligrams per minute (mgm).
- the silicon-carbon containing gas is OMCTS
- its initial flow rate may be for example, 500 mgm in a He carrier gas flowing at a rate of about 4800 seem and O 2 flowing at about 500 seem during the deposition of the oxide-rich portion of the graded dielectric layer.
- the relative amounts of the gas mixture components are changed to form portions of the dielectric layer with a higher carbon to silicon ratio (i.e., carbon-rich portions of the graded dielectric layer).
- These changes may include increasing the flow of the carbon-silicon gas to a first intermediate rate (e.g., increasing the flow rate of OMCTS from about 500 mgm to about 1000 mgm) and maintaining that rate for about 0.5 seconds or longer (e.g., from about 0.5 seconds to about 2.5 seconds).
- the silicon-carbon containing gas is increased to a second intermediate flow rate 308 (e.g., from about 1000 mgm to about 1750 mgm) for 0.5 seconds or longer before increasing to a final, fastest flow rate.
- a second intermediate flow rate 308 e.g., from about 1000 mgm to about 1750 mgm
- Other embodiments have the silicon-carbon gas flow rate stop for a period of time at additional intermediate flow rates (not shown) before reaching the fastest flow rate.
- the flow rates for the oxygen containing gas and/or carrier gas may be continuously decreasing.
- the O 2 flow rate may drop from about 500 seem to about 160 seem and the He gas flow rate may drop from about 4800 seem to about 1000 seem.
- the flow rates for one or more of the gases other than the silicon-carbon gas may decrease continuously from an initial flow rate to a final flow rate without stopping at any intermediate steps. For example, following the deposition of the oxide-rich layer, the flow rate for these gases may drop at a constant and continuous rate (without having an intermediate rate plateau) until reaching a final flow rate for the rest of the deposition.
- an OMCTS flow rate may increase from the second intermediate rate (e.g., about 1750 mgm) to a fastest flow rate (e.g., about 2500 mgm) where the fastets flow rate may be maintained for 45 seconds or longer during the deposition of the carbon-rich portion of the graded dielectric layer 312.
- Fig. 4 shows a flowchart illustrating other embodiments for forming a graded dielectric layer according to methods of the invention. Ih these embodiments, the flow rate of the silicon-carbon containing gas increases continuously from an initial rate to a final, fastest rate without pausing at an intermediate step. Condensation and/or aerosolization of the silicon-carbon containing gas is avoided, however, by maintaining the flow rate of the carrier gas at a high initial rate until after the silicon-carbon containing gas is close to (or reaches) its fastest flow rate.
- the method may start by flowing a gas mixture at an initial flow rate 402 through a gas showerhead to deposit an oxide-rich portion of the graded dielectric layer 404 on an underlying layer (e.g., a low-/c barrier layer).
- the gas mixture may include a silicon-carbon containing gas (e.g., OMCTS), an oxygen containing gas (e.g., O 2 ) and a carrier gas (e.g., He).
- the silicon carbon containing gas is increased in step 406 from the initial flow rate (e.g., about 500 mgm) to a fastest flow rate (e.g., about 2500 mgm) without pausing at an intermediate flow rate.
- the increase in the silicon-carbon containing gas flow rate may be, for example, about 1350 mgm/sec, such that the flow rate continuously increases from the initial flow rate to the final flow rate in about 1.5 seconds.
- the flow rate of the carrier gas may be reduced to a final flow rate 408 for the deposition of the carbon-rich portion of the graded dielectric layer 410.
- a carrier gas that includes helium (He) may maintain an initial He flow rate of about 4800 seems while the OMCTS flow rate increases from about 500 mgm to about 2500 mgm.
- He helium
- the oxygen containing gas may drop while the silicon-carbon containing gas is increasing to its fastest flow rate. In other embodiments, the oxygen containing gas may maintain its initial flow rate with the carrier gas until the silicon- containing gas approaches or reaches its fastest flow rate. For example, the flow rate for O 2 may decrease from about 500 seem to about 160 seem while the flow rate for OMCTS increases from 500 mgm to 2500 mgm.
- Fig. 5 plots the flow rate of a silicon-containing gas over the course of a dielectric deposition using a conventional method (dashed line) and a method according to an embodiment of the invention (solid line).
- the conventional method increases the flow rate of the silicon-carbon gas from an initial rate of 500 mgm to a fastest flow rate of 2500 mgm in as short a time as possible (e.g., about 0.2 seconds). While the silicon-carbon gas is increasing, the carrier gas (not shown) is rapidly decreasing, and there is a high probability of forming a lot (e.g., about 1000 or more) of infilm adders on the underlying layers (e.g., the barrier layer).
- the plot of the increase in flow rate for the silicon-carbon containing gas according to the present invention shows the gas going through two intermediate flow rate plateaus, with each plateau lasting about 2 seconds.
- the intermediate steps reduce the chances of the precursor condensing in the passages of the showerhead, and/or forming aerosol droplets that deposit on the underlying layer.
- FIG. 6 illustrates a sectional view of the structure a showerhead 600 that may be used with embodiments of the present invention.
- a blocker plate 602 having a plurality of through-holes 604 is disposed between a face plate 606 of a shower head 600 and a connecting portion of a gas supply inlet 608. With the blocker plate 602, gas delivered from the gas supply inlet 608 is temporarily stored in a baffle space 610 on the upstream side of the blocker plate 602.
- Fig. 7 illustrates an embodiment of a parallel-plate plasma enhanced chemical vapor deposition (PECVD) system 10 that may be used in conjunction with embodiments of the methods and systems of the present invention.
- System 10 includes a vacuum chamber 15 in which one or more layers may be deposited on a substrate (not shown).
- System 10 contains a gas distribution showerhead 11 for dispersing process gases through perforated holes in the face plate of showerhead 11 to a substrate (e. g., a 200 mm wafer, 300 mm wafer, etc.) positioned on susceptor 12.
- a substrate e. g., a 200 mm wafer, 300 mm wafer, etc.
- Susceptor 12 is thermally responsive and is mounted on supports 13 such that the susceptor 12 (and the substrate) can be controllably moved between a lower loading/off-loading position and an upper processing position 14, which is in proximity to showerhead IL
- a center board (not shown) includes sensors for providing information on the position of the substrate.
- susceptor 12 and substrate are in processing position 14, they are surrounded by baffle plate 17 having a plurality of spaced holes 23 which exhaust into an annular vacuum manifold 24.
- Deposition and carrier gases are supplied through supply lines 18 into a mixing system 19 where they are combined and then sent to showerhead 11.
- Supply lines 18 for each of the process gases may include (i) safety shut-off valves (not shown) that can be used to automatically or manually shut-off the flow of process gas into the chamber, and (ii) mass flow controllers 20 that measure the flow of gas or liquid through the supply lines.
- the several safety shut-off valves are positioned on each gas supply line in conventional configurations.
- the rate at which deposition and carrier gases are supplied to gas mixing system 19 is controlled by liquid or gas mass flow controllers 20 and/or by valves.
- gas supplied to showerhead 11 is vented toward and uniformly distributed radially across the surface of the wafer in a laminar flow as indicated by arrows 21.
- An exhaust system then exhausts the gas via ports 23 into the circular vacuum manifold 24 and out an exhaust line 31 by a vacuum pump system (not shown).
- the rate at which gases are released through exhaust line 31 is controlled by a throttle valve 32.
- a controlled plasma may be formed adjacent to the substrate by RF energy applied to showerhead 11 from RF power supply 25.
- showerhead 11 may also act as an RF electrode, while susceptor 12 is grounded.
- RF power supply 25 may supply single or mixed frequency RF power (or other desired variations) to showerhead 11 to enhance the decomposition of reactive species introduced into chamber 15.
- the mixed frequency RF power is generated by a high frequency RF generator 40 (RFl) and corresponding match circuit 42 and a low frequency RF generator 44 (RF2) and corresponding match circuit 46.
- a high frequency filter 48 prevents voltage generated by high frequency generator 40 from damaging the low frequency generator.
- External lamp heater module 26 provides a collimated annular pattern of light 27 through a quartz window 28 onto an annular outer peripheral portion of susceptor 12. Such heat distribution compensates for the natural heat loss pattern of susceptor 12 and provides rapid thermal and uniform susceptor and substrate heating for effecting deposition.
- the chamber lining, showerhead face plate, supports 13, and other system hardware may be made out of materials such as aluminum or anodized aluminum.
- An example of such an apparatus is described in U.S. Patent No. 5,000,113 entitled “Thermal CVD/PECVD Reactor and Use for Thermal Chemical Vapor Deposition of Silicon Dioxide and In situ Multi-step Planarized Process,” issued to Wang et al, an assigned to Applied Materials, Inc., the assignee of the present invention, the entire contents of which is herein incorporated by reference.
- a motor raises and lower susceptor 12 between a processing position 14 and a lower, substrate-loading position.
- Motors and optical sensors are used to move and determine the position of movable mechanical assemblies such as throttle valve 32 and susceptor 12.
- the heater, motors, valves and flow controllers 20 connected to supply lines 18, gas delivery system, throttle valve 32, RF power supply 25, and lamp magnet drivers are all controlled by a system controller 34 over control lines 36, some of which are shown in Fig. 7.
- System controller 34 controls activities of the apparatus.
- the system controller executes system control software, which is a computer program stored in a computer- readable medium such as a memory 38.
- memory 38 may be a hard disk drive, but memory 38 may also be other kinds of memory.
- the computer program includes sets of instructions that dictate, for example, the timing, mixture of gases, chamber pressure, chamber temperature, RF power levels, susceptor position, and other parameters of a process.
- Other computer programs e.g., one stored on another memory device such as a floppy disk or other program storage media
- the system controller may include a hard disk drive (memory 38), floppy disk drive and card rack, among other elements.
- the card rack contains a single board computer (SBC) processor 37, analog and digital input/output boards, interface boards and stepper motor controller boards.
- SBC single board computer
- Various parts of system 10 may conform to the Versa Modular European (VME) standard that defies board, card cage, and connector dimensions and types.
- VME Versa Modular European
- the VME standard also defines the bus structure having a 16-bit data bus and 24-bit address bus.
- the wafers having graded dielectric layers formed according to methods of the present invention had barely detectable numbers of infilm adders exceeding 0.16 ⁇ m in size (i.e., less than 10 adders). Similarly low numbers of infilm adders (9 and 16 adders) were counted for a method that included three intermediate flow rate steps between the initial and final flow rates for the OMCTS component.
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Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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JP2007530308A JP2008511758A (en) | 2004-09-01 | 2005-08-29 | Functionally graded dielectric layer deposition method by chemical vapor deposition using viscous precursors |
EP05792661A EP1794784A1 (en) | 2004-09-01 | 2005-08-29 | Method to deposit functionally graded dielectric films via chemical vapor deposition using viscous precursors |
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US10/931,609 US7166544B2 (en) | 2004-09-01 | 2004-09-01 | Method to deposit functionally graded dielectric films via chemical vapor deposition using viscous precursors |
US10/931,609 | 2004-09-01 |
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PCT/US2005/030956 WO2006028844A1 (en) | 2004-09-01 | 2005-08-29 | Method to deposit functionally graded dielectric films via chemical vapor deposition using viscous precursors |
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EP (1) | EP1794784A1 (en) |
JP (1) | JP2008511758A (en) |
KR (1) | KR20070054201A (en) |
CN (1) | CN100477115C (en) |
TW (1) | TWI317543B (en) |
WO (1) | WO2006028844A1 (en) |
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Also Published As
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KR20070054201A (en) | 2007-05-28 |
US7166544B2 (en) | 2007-01-23 |
TW200620534A (en) | 2006-06-16 |
US20060046520A1 (en) | 2006-03-02 |
US7802538B2 (en) | 2010-09-28 |
CN101065835A (en) | 2007-10-31 |
EP1794784A1 (en) | 2007-06-13 |
JP2008511758A (en) | 2008-04-17 |
US20070079753A1 (en) | 2007-04-12 |
CN100477115C (en) | 2009-04-08 |
TWI317543B (en) | 2009-11-21 |
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