US20020081844A1 - Method of manufacturing a barrier metal layer using atomic layer deposition - Google Patents
Method of manufacturing a barrier metal layer using atomic layer deposition Download PDFInfo
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- US20020081844A1 US20020081844A1 US10/084,193 US8419302A US2002081844A1 US 20020081844 A1 US20020081844 A1 US 20020081844A1 US 8419302 A US8419302 A US 8419302A US 2002081844 A1 US2002081844 A1 US 2002081844A1
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- barrier metal
- metal layer
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 146
- 239000002184 metal Substances 0.000 title claims abstract description 144
- 230000004888 barrier function Effects 0.000 title claims abstract description 136
- 238000000231 atomic layer deposition Methods 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- 239000004065 semiconductor Substances 0.000 claims abstract description 63
- 239000000758 substrate Substances 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 50
- 239000012535 impurity Substances 0.000 claims abstract description 38
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 24
- 239000007789 gas Substances 0.000 claims description 219
- 238000010926 purge Methods 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 230000002045 lasting effect Effects 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000006227 byproduct Substances 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000003870 refractory metal Substances 0.000 claims description 4
- 238000000151 deposition Methods 0.000 abstract description 25
- 230000008021 deposition Effects 0.000 abstract description 24
- 230000007246 mechanism Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 description 18
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 13
- 229910003074 TiCl4 Inorganic materials 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910010037 TiAlN Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000008646 thermal stress Effects 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- QRDJMFAGNINQFN-UHFFFAOYSA-N CC[Ti](N)CC Chemical compound CC[Ti](N)CC QRDJMFAGNINQFN-UHFFFAOYSA-N 0.000 description 1
- QDGMSMUNXGCWRA-UHFFFAOYSA-N C[Ti](C)N Chemical compound C[Ti](C)N QDGMSMUNXGCWRA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910004491 TaAlN Inorganic materials 0.000 description 1
- 229910004535 TaBN Inorganic materials 0.000 description 1
- 229910004200 TaSiN Inorganic materials 0.000 description 1
- 229910010060 TiBN Inorganic materials 0.000 description 1
- 229910010421 TiNx Inorganic materials 0.000 description 1
- 229910008482 TiSiN Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
Images
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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/20—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy
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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
- C23C16/44—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
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45531—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making ternary or higher compositions
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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
- C23C16/44—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
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—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 System
- 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 System by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
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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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—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 System
- 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 System by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
- H01L21/28562—Selective deposition
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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
- H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric
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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
- H01L21/7685—Barrier, adhesion or liner layers the layer covering a conductive structure
Definitions
- the present invention relates to a method of manufacturing semiconductor devices. More particularly, the present invention relates to a method of manufacturing a barrier metal layer using atomic layer deposition.
- a barrier metal layer (for example, a TiN layer, a TaN layer, a WN layer) may be formed between adjacent material layers in order to prevent mutual diffusion or a chemical reaction from occurring between the adjacent material layers.
- barrier metal layers are typically interposed between a lower electrode of a capacitor and a contact plug, between a dielectric layer of a capacitor and an upper electrode of the capacitor, between a conductive line and an insulating layer, and between a via contact and an insulating layer.
- CVD chemical vapor deposition
- a precursor including a halogen, such as Cl is used as a typical metal source gas.
- the manufacturing process of a CVD barrier metal layer has an advantage in that the barrier metal is deposited rapidly, and a drawback in that the halogen of the precursor fails to fall out of the barrier metal layer and remains as an impurity within the barrier metal layer.
- the halogen remaining within the barrier metal layer as described above may cause an adjacent material layer (for example, an aluminum conductive line) to erode, and may increase the resistivity of the barrier metal layer.
- the amount of halogen remaining within the barrier metal layer must be reduced so as to decrease the resistivity of the barrier metal layer.
- the CVD barrier metal layer manufacturing process must be performed at a high temperature.
- a deposition temperature of at least 675° C. is required to obtain a resistivity of 200 ⁇ -cm or less.
- a barrier metal layer is fabricated at a deposition temperature of 600° C. or greater, the thermal budget of an underlayer formed below the barrier metal layer is quite high, and secondary problems such as the generation of thermal stress are created.
- a CVD barrier metal layer must be formed over an Si contact or a via contact at a deposition temperature of 500° C. or less if the Si contact or via contact are not to be unduly thermally stressed. That is, the CVD barrier metal layer manufacturing process must be performed at a low temperature.
- a method of adding methylhydrazine (MH) to a metal source gas TiCl 4 can be used to facilitate the deposition of the barrier metal at a low temperature.
- this technique has a drawback in that the step coverage of the barrier metal layer is compromised.
- the problems in the CVD barrier metal layer manufacturing process posed by using a metal source gas such as TiCL 4 as a precursor can be overcome by a technique of flushing the entire surface of a semiconductor substrate with an impurity-removing gas after the barrier metal layer is formed.
- the rate at which the impurity-removing gas must flow to flush the surface of the semiconductor substrate is several tens to several hundreds of times greater than that at which the reaction gas flows into the reaction chamber. Accordingly, this technique requires controlling the process conditions prevailing in the reaction chamber, such as the pressure of the chamber and the like. Effecting such a control takes time and thus, increases the total time of the manufacturing process.
- ALD atomic layer deposition
- the conventional barrier metal layer forming method using ALD has an advantage in that it can be performed at a low temperature while minimizing the content of Cl in the barrier metal layer.
- the mechanism by which the barrier metal is deposited in ALD is chemical adsorption. Therefore, the conventional barrier metal layer forming method using ALD has a drawback in that the deposition rate is too slow for use in manufacturing semiconductor devices.
- the deposition rate of a typical CVD process used to form a TiN layer is approximately several hundreds of ⁇ /min.
- the deposition rate at which a TiN layer can be formed using the conventional ALD process is less than 100 ⁇ /min, which is very slow compared to when the CVD process is used.
- a first object of the present invention is to provide a method of manufacturing a barrier metal layer that makes use of atomic layer deposition (ALD) but in which the deposition rate is not too slow.
- ALD atomic layer deposition
- a second object of the present invention is to provide a method of manufacturing a barrier metal layer using ALD, and by which the deposition rate at which the ALD occurs can be increased without an accompanying increase in the amount of impurities being left in the barrier metal layer.
- the present invention provides a method of manufacturing a barrier metal layer including: (a) supplying a first source gas onto the entire surface of a semiconductor substrate in the form of a pulse having a duration lasting from a point in time A 1 to a point in time A 2 , and (b) supplying a second source gas, which reacts with the first source gas, onto the entire surface of the semiconductor substrate in the form of a pulse having a duration lasting from a point in time A 3 to a point in time A 4 , wherein A 3 is at least as early in time as A 1 and no later in time than A 2 .
- point in time A 4 is no earlier than point in time A 2 .
- points in time the pulse of the first source gas begins and ends can be the same as those at which the pulse of the second source gas begins and ends. That is, point in time A 1 can coincide with point in time A 3 , and point in time A 2 can coincide with point in time A 4 .
- a purge gas can be used to discharge by-products of the reaction between the first and second source gases.
- the purge gas is supplied onto the entire surface of the semiconductor substrate beginning at a point in time that is earlier than or that coincides with point in time A 1 .
- the purge gas can be supplied onto the entire surface of the semiconductor substrate beginning at a point in time that is later than point in time A 1 and is no later than point in time A 3 .
- An impurity-removing gas can be additionally used to free any impurities that have managed to become trapped within the barrier metal layer.
- the method includes a step (c) of supplying an impurity-removing gas onto the entire surface of the semiconductor substrate for a predetermined period of time, after point in time A 4 and while the purge gas is still being supplied.
- the gas supply scheme comprising the steps (a), (b) and (c) constitutes a cycle of operation, and the cycle can be repeated at least once to increase the thickness of the barrier metal layer a desired amount.
- the first source gas can include a gas of the halogen element family and a refractory metallic element, and the second source gas can include nitrogen.
- the purge gas can be an inert gas such as argon.
- the impurity removing gas can be NH 3 .
- the present invention provides a method of manufacturing a barrier metal layer, including: (a) supplying a first source gas onto the entire surface of a semiconductor substrate in the form of a pulse having a duration lasting from a point in time B 1 to a point in time B 2 , (b) supplying a second source gas, which reacts with the first source gas, onto the entire surface of the semiconductor substrate in the form of a pulse having a duration lasting from a point in time B 3 to a point in time B 4 , whereby a barrier metal layer is formed, and (c) supplying an impurity-removing gas onto the entire surface of the semiconductor substrate in the form of a pulse having a duration lasting from a point in time B 5 to a point in time B 6 to remove impurities from the barrier metal layer, wherein B 3 is later in time than B 2 , and B 5 is later in time than B 4 .
- a purge gas can also be supplied onto the entire surface of the semiconductor substrate, beginning at a point in time that is earlier than or coincides with point in time B 1 , or that is later than B 1 and no later than point in time B 2 , to remove all of the first source gas that is physically adsorbed at the surface of the semiconductor substrate before the second source gas is supplied and/or to discharge by-products of the reaction between the first and second source gases.
- FIG. 1 is a timing diagram of the gas supply scheme of a first embodiment of a method of fabricating a barrier metal layer using atomic layer deposition (ALD) according to the present invention
- FIG. 2 is a timing diagram of an alternative gas supply scheme of the first embodiment of a method of fabricating a barrier metal layer using atomic layer deposition (ALD) according to the present invention.
- FIG. 3 is a timing diagram of the gas supply scheme of a second embodiment of a method of fabricating a barrier metal layer using atomic layer deposition (ALD) according to the present invention.
- ALD atomic layer deposition
- a semiconductor substrate is loaded into a processing chamber of an ALD apparatus.
- the semiconductor substrate may have a feature having a predetermined aspect ratio.
- the feature may be a word line, a conductive line such as a bit line, a contact plug, a via contact, a capacitor upper electrode, or the like.
- first and second source gases and a purge gas are supplied to the chamber according to the scheme shown in FIG. 1 to form a barrier metal layer on a prescribed feature of the semiconductor substrate.
- the barrier metal layer is typically formed of a binary or larger compound including a refractory metal and nitrogen.
- TiN is representative of the material of the barrier metal layer. Therefore, the first embodiment will be described in connection with the formation of a Ti-containing layer as a barrier metal layer.
- a first source gas is pulsed onto the surface of a semiconductor substrate for a duration lasting from a point in time A 1 to a point in time A 2 .
- the pulse of the first source gas is chemically and physically adsorbed by the entire surface of the semiconductor substrate according to the surface topology thereof.
- some of the first source gas that has been physically adsorbed is then removed by the purge gas because the purge gas is being directed onto the entire surface of the semiconductor substrate while the first source gas is being physically adsorbed.
- the purge gas and the source gas entrained therein are discharged to the outside of the processing chamber.
- FIG. 1 shows that the continuous supplying of the purge gas is initiated at point in time A 1 .
- the continuous supplying of the purge gas can be initiated before point in time A 1 , or at a point in time A 3 that is as early as point in time A 1 but no later than point in time A 2 .
- the purge gas is an inert gas, such as argon.
- a gas comprising a refractory metal is used as the first source gas.
- Ti a refractory metal
- TiCl 4 is used as the first source gas.
- other source gases containing the barrier metal and capable of reacting with a second source gas can be used.
- a metallo-organic gas such as tetrakis diethyl amino titanium (TDEAT) or tetrakis dimethyl amino titanium (TDMAT) can be used as the first source gas.
- a pulse of the second source gas is directed onto the surface of the semiconductor substrate for a duration lasting from point in time A 3 to a point in time A 4 , and while the purge gas continues to be supplied onto the entire surface of the semiconductor substrate. Note, at point in time A 3 some of the first source gas is still being supplied and thus, not all of the first source gas physically adsorbed at the surface of the semiconductor substrate has been removed at this time by the purge gas.
- a 4 is a point in time that occurs no earlier than point in time A 2 but occurs some time after point in time A 3 .
- the points in time under which the scheme of the gas supply is established are related as follows: (A 1 ⁇ A 3 ⁇ A 2 , A 2 ⁇ A 4 , A 1 ⁇ A 2 , and A 3 ⁇ A 4 ).
- point in time A 1 can coincide with point in time A 3
- point in time A 2 can coincide with point in time A 4
- the first and second source gases would be pulsed beginning at the same time and continuing for the same duration.
- the pulsing of the second source gas is initiated before or at the same time the pulsing of the first source gas terminates.
- the pulse of the second source gas terminates after or at the same time the pulsing of the first source gas terminates.
- the purge gas is supplied along the entire surface of the semiconductor substrate for a duration lasting from point in time A 4 to a point in time A 5 , thereby discharging by-products of the reaction of the first and second source gases.
- a gas including a non-metallic element (N) of the barrier metal layer (TiN) is used as the second source gas.
- N non-metallic element
- TiN barrier metal layer
- NH 3 is used as the second source gas.
- other gases which react with the first source gas and contain nitrogen, such as N 2 can be used as the second source gas.
- the mechanism by which the barrier metal (TiN) is deposited no longer consists of ALD because the first source gas physically adsorbed at the surface of the semiconductor substrate has not been completely removed by the purge gas. Accordingly, the second source gas reacts with not only that part of the first source gas that has been chemically adsorbed at the surface of the semiconductor substrate but also that part of the first source gas that has been physically adsorbed.
- ALD results from the reaction between that part of the first source gas chemically adsorbed at the surface of the semiconductor substrate and the second source gas
- CVD results from the reaction between that part of the first source gas physically adsorbed and the second source gas. Consequently, the ALD that takes place provides a 100% step coverage and the CVD that takes place provides a high deposition rate.
- impurities (Cl) are present in a barrier metal layer (TiN) when the barrier metal layer is formed by CVD.
- impurity-containing gases HCl and TiCl x generated as by-products are discharged from the processing chamber by flushing the entire surface of the semiconductor substrate with an inert gas while the first and second source gases react with each other (A 3 -A 4 ) and for a predetermined period of time (that is, for a duration of A 4 -A 5 ) after the pulse of the second source gas terminates. Consequently, impurities (Cl) are prevented from being entrapped within the deposited material.
- the method of the present invention can be performed at a low temperature (for example, 450 to 500° C.) without producing a high level of impurities in the barrier metal layer because the present invention also employs ALD.
- the present invention also suppresses thermal stress and thereby decreases the thermal budget of the layer (underlayer) beneath the barrier metal layer.
- the duration of A 1 , to A 5 is a cycle T 1 , and a barrier metal layer can be formed to a desired thickness by repeating the cycle T 1 a predetermined number of times.
- the method can also comprise a step of pulsing an impurity-removing gas to further ensure that impurities (Cl) are prevented from being trapped within the barrier metal layer (TiN).
- the thickness of the TiN layer formed after one cycle is established by the process recipe under which the first and second source gases, and the purge gas (and impurity-removing gas) are supplied into the processing chamber.
- the impurity-removing gas can be supplied for a duration beginning at point in time A 6 and ending at point in time A 7 , while the purge gas is being directed onto the surface of a semiconductor substrate and after the pulse of the second source gas terminates.
- the impurity-removing gas reacts with impurities trapped in the barrier metal layer during the reaction of the first and second source gases, and frees the impurities from the barrier metal layer.
- the impurity-removing gas reduces the impurities to their constituent elements.
- the impurity-removing gas can easily diffuse into the metal barrier layer and thereby react with the impurities because the thickness of the barrier metal layer formed during the time period from A 1 to A 4 is very thin (about 10 to 20 ⁇ ).
- the technique of the present invention in which impurity-removing gas is supplied after one of a plurality of cycles can remove impurities (Cl) from the barrier metal layer using only a tiny flow of the impurity-removing gas.
- NH 3 can be used as the impurity-removing gas.
- the processing apparatus does not need a separate gas supply line dedicated to the impurity-removing gas because the impurity-removing gas and the second source gas are the same. Rather, another pulse of the second source gas can be supplied from the time period A 6 -A 7 (see reference character I).
- gases other than NH 3 can be used as the impurity-removing gas. In these cases, a separate gas supply line dedicated to the impurity-removing gas is required.
- the impurity-removing gas is NH 3
- the impurity-removing gas diffuses into the barrier metal layer that was formed during the time period of from A 1 to A 4 and reacts with impurities (Cl) within the layer according to the following chemical equation, and frees the impurities (Cl) from the barrier metal layer in the form of gas (HCl).
- the second embodiment of the present invention can also reduce the amount of impurities remaining in a barrier metal layer to a greater extent than the conventional ALD method without seriously compromising the deposition rate.
- the second embodiment will also be described as applied to the forming of a TiN barrier metal layer.
- a semiconductor substrate is loaded into a processing chamber of an ALD apparatus.
- a first source gas is supplied in the form of a pulse, beginning at a point in time B 1 and terminating at a point in time B 2 , while a purge gas is being continuously supplied onto the entire surface of the semiconductor substrate.
- the first source gas is chemically and physically adsorbed at the surface of the semiconductor substrate according to the topology of the surface.
- FIG. 3 shows that the flow of purge gas is initiated at the point in time B 1 .
- the flow of the purge gas can be initiated prior to the point in time B 1 , or from any point in time as early as B 1 and no later than B 2 .
- the physically-adsorbed part of the first source gas is removed by the purge gas from the point in time B 2 to a point in time B 3 .
- the second source gas is supplied in the form of a pulse beginning from the point in time B 3 and terminating at the point in time B 4 while the purge gas continuous to be supplied onto the entire surface of the semiconductor substrate.
- the purge gas is supplied, whereby by-products generated by the reaction of the first and second source gases are discharged from the chamber.
- the impurity-removing gas is supplied in the form of a pulse beginning from the point in time B 5 and terminating at a point in time B 6 while the purge gas continuous to be supplied onto the entire surface of the semiconductor substrate.
- the first and second source gases and the impurity-removing gas can be the same as those used in the first embodiment.
- the impurity-removing gas and the second source gas can be of the same type, whereby the processing apparatus does not require a separate gas supply line dedicated to the impurity-removing gas. That is, another pulse of the second source gas can be supplied during the time period of B 5 -B 6 (see reference character II).
- a separate gas supply line dedicated to the impurity-removing gas is required.
- impurities formed during the period of time from B 1 to B 4 are removed from the barrier metal layer by the impurity-removing gas. Thereafter, from the point in time B 6 to a point in time B 7 , the purge gas discharges by-products of the reaction between the impurity-removing gas and the impurities.
- the time period of B 1 to B 7 represents a cycle T 2 , and the barrier metal layer can be formed to a desired thickness by repeating the cycle T 2 .
- the impurity-removing gas is supplied after the supply of the second source gas is terminated, so that fewer impurities remain within the barrier metal layer than when the prior art method is used.
- the deposition rate of the barrier metal in ALD can be typically controlled by adjusting the process recipe under which the first and second source gases are supplied. That is, the deposition rate of the barrier metal can be increased by controlling the supply of the first and second source gases.
- increasing the deposition rate of the barrier metal in this way is normally accompanied by a corresponding increase in the amount of impurities within the barrier metal layer. That is, there is a limit to ALD in changing the process recipe to increase the deposition rate of the barrier metal.
- the use of the impurity-removing gas allows the process recipe under which the first and second source gases are supplied to be adjusted for increasing the deposition rate of the barrier metal without giving rise to a corresponding increase in the amount of impurities remaining within the barrier metal layer.
- the second embodiment provides a significant degree of freedom in adjusting the process recipe under which the first and second source gases are supplied.
- first and second embodiments of the present invention are applied to the manufacture of a binary barrier metal layer (TiN) will now be described in detail.
- the present invention is not limited to the manufacture of a TiN binary metal layer. Rather, the present invention is also applicable to the manufacture of other binary barrier metal layers such as a TaN layer, a WN layer, an AlN layer, a CrN layer and a BN layer.
- the type of first and second source gases and impurity-removing gas to be used when manufacturing barrier metal layers other than the TiN barrier layer will be readily apparent to those of ordinary skill in the art.
- the barrier metal layer is formed of AlN
- an AlClx gas can be used as the first source gas
- NH 3 can be used as the second source gas and as the impurity-removing gas.
- the present invention is not applicable only to the manufacture of binary barrier metal layers, but can also be applied to the manufacture of barrier metal layers formed of larger compounds.
- the present invention can also be applied to the manufacture of a TiBN layer, a TaBN layer, a TiAlN layer, a TaAlN layer, a TiSiN layer, a TaSiN layer, a TiCN layer, a WBN layer, and the like.
- a first source gas for example, TiCl 4
- a second source gas for example, trimethyl aluminum (TMA)
- a third source gas for example, NH 3
- the duration of the pulse of the first source gas is from a point in time C 1 to a point in time C 2
- the duration of the pulse of the second source gas is from a point in time C 3 to a point in time C 4
- the duration of the pulse of the third source gas is from a point in time C 5 to a point in time C 6 .
- the purge gas is directed onto the entire surface of the semiconductor substrate for a predetermined period of time, thereby completing the cycle.
- the cycle is repeated a predetermined number of times to form a barrier metal layer (TiAlN) having a desired thickness.
- the barrier metal layer of TiAlN can also be formed using the second embodiment of the present invention, under the schemes set forth above.
- the deposition mechanism includes CVD along with ALD.
- the second embodiment will also exhibit a higher deposition rate than the prior art.
- the purge gas is continuously supplied onto the entire surface of the semiconductor substrate while the source gases are being supplied.
- the amount of impurities remaining within the barrier metal layer are minimal even though the process is carried at a temperature as low as that used to carry out the conventional ALD process.
- an impurity-removing gas can be supplied in the form of a pulse after the first through third source gases are suppled, as in the first embodiment, thereby reducing the amount of impurities within the barrier metal layer.
- the barrier metal layer is formed by ALD and CVD, so that the deposition rate of the barrier metal is greater than if the barrier metal layer were formed only through ALD. Also, a purge gas is continuously supplied onto the entire surface of the semiconductor substrate during the manufacture of the barrier metal layer, so that the amount of impurities remaining within the barrier metal layer is minimized despite the fact that the method is carried out at a low temperature suitable for ALD.
- the barrier metal layer is formed only through ALD.
- an impurity-removing gas is supplied during the process to free impurities that have been trapped in the barrier metal layer. Therefore, the process recipe for the source gases has a high degree of freedom, can be changed to a great extent to increase the deposition rate of the barrier metal. Therefore, even though the barrier metal layer is formed only through ALD, the barrier metal can be deposited at higher and higher rates without corresponding increases in the impurity content of the barrier metal layer.
Abstract
A method of manufacturing a barrier metal layer uses atomic layer deposition (ALD) as the mechanism for depositing the barrier metal. The method includes supplying a first source gas onto the entire surface of a semiconductor substrate in the form of a pulse, and supplying a second source gas, which reacts with the first source gas, onto the entire surface of the semiconductor substrate in the form of a pulse. In a first embodiment, the pulses overlap in time so that the second source gas reacts with part of the first source gas physically adsorbed at the surface of the semiconductor substrate to thereby form part of the barrier metal layer by chemical vapor deposition whereas another part of the second source gas reacts with the first source gas chemically adsorbed at the surface of the semiconductor substrate to thereby form part of the barrier metal layer by atomic layer deposition. Thus, the deposition rate is greater than if the barrier metal layer were only formed by ALD. In the second embodiment, an impurity-removing gas is used to remove impurities in the barrier metal layer. Thus, even if the gas supply scheme is set up to only use ALD in creating the barrier metal layer, the deposition rate can be increased without the usual accompanying increase in the impurity content of the barrier metal layer.
Description
- 1. Field of the Invention
- The present invention relates to a method of manufacturing semiconductor devices. More particularly, the present invention relates to a method of manufacturing a barrier metal layer using atomic layer deposition.
- 2. Description of the Related Art
- In the manufacture of semiconductor devices, a barrier metal layer (for example, a TiN layer, a TaN layer, a WN layer) may be formed between adjacent material layers in order to prevent mutual diffusion or a chemical reaction from occurring between the adjacent material layers. For example, in the manufacture of a semiconductor memory device having a capacitor over bit-line (COB) structure, barrier metal layers are typically interposed between a lower electrode of a capacitor and a contact plug, between a dielectric layer of a capacitor and an upper electrode of the capacitor, between a conductive line and an insulating layer, and between a via contact and an insulating layer.
- However, as the integration density of semiconductor devices increases, the topography of the surface on which a barrier metal layer is to be deposited becomes more rugged. When a barrier metal layer is formed on a rugged surface by a physical deposition process such as sputtering, the step coverage of the barrier metal layer is poor. Accordingly, a process providing excellent step coverage must be used to form a barrier metal layer on a deposition surface having a rugged topography. To this end, chemical vapor deposition (CVD) has been proposed. Hereinafter, a barrier metal layer formed by CVD will be referred to as a CVD barrier metal layer.
- In the process of manufacturing a CVD barrier metal layer, a precursor including a halogen, such as Cl, is used as a typical metal source gas. The manufacturing process of a CVD barrier metal layer has an advantage in that the barrier metal is deposited rapidly, and a drawback in that the halogen of the precursor fails to fall out of the barrier metal layer and remains as an impurity within the barrier metal layer. The halogen remaining within the barrier metal layer as described above may cause an adjacent material layer (for example, an aluminum conductive line) to erode, and may increase the resistivity of the barrier metal layer. Thus, the amount of halogen remaining within the barrier metal layer must be reduced so as to decrease the resistivity of the barrier metal layer. In order to achieve this, the CVD barrier metal layer manufacturing process must be performed at a high temperature.
- For example, in a CVD barrier metal layer manufacturing process using TiCl 4 as a metal source gas, a deposition temperature of at least 675° C. is required to obtain a resistivity of 200 μΩ-cm or less. However, when a barrier metal layer is fabricated at a deposition temperature of 600° C. or greater, the thermal budget of an underlayer formed below the barrier metal layer is quite high, and secondary problems such as the generation of thermal stress are created. For instance, a CVD barrier metal layer must be formed over an Si contact or a via contact at a deposition temperature of 500° C. or less if the Si contact or via contact are not to be unduly thermally stressed. That is, the CVD barrier metal layer manufacturing process must be performed at a low temperature. A method of adding methylhydrazine (MH) to a metal source gas TiCl4 can be used to facilitate the deposition of the barrier metal at a low temperature. However, this technique has a drawback in that the step coverage of the barrier metal layer is compromised.
- The above-described problem of thermal stress, prevailing in the method of forming a CVD barrier metal layer manufacturing using a metal source gas such as TiCl 4 as a precursor, can be overcome by using an organometallic precursor such as tetrakis diethylamino Ti (TDEAT) or tetrakis dimethylamino Ti (TDMAT). That is, this so-called MOCVD barrier metal layer manufacturing process can be performed at a low temperature compared to the CVD barrier metal layer manufacturing process. However, a MOCVD barrier metal layer includes a large quantity of carbon impurities and therefore, exhibits a high resistivity. Also, the MOCVD barrier metal layer has worse step coverage than a barrier metal layer that is formed using a metal source gas such as TiCl4 as a precursor.
- Alternatively, the problems in the CVD barrier metal layer manufacturing process posed by using a metal source gas such as TiCL 4 as a precursor can be overcome by a technique of flushing the entire surface of a semiconductor substrate with an impurity-removing gas after the barrier metal layer is formed. However, the rate at which the impurity-removing gas must flow to flush the surface of the semiconductor substrate is several tens to several hundreds of times greater than that at which the reaction gas flows into the reaction chamber. Accordingly, this technique requires controlling the process conditions prevailing in the reaction chamber, such as the pressure of the chamber and the like. Effecting such a control takes time and thus, increases the total time of the manufacturing process.
- Also, a method of forming a barrier metal layer using an atomic layer deposition (ALD) process has been used in an attempt to overcome the problems posed by the use of Cl in the CVD barrier metal layer manufacturing process. The conventional barrier metal layer forming method using ALD has an advantage in that it can be performed at a low temperature while minimizing the content of Cl in the barrier metal layer. However, the mechanism by which the barrier metal is deposited in ALD is chemical adsorption. Therefore, the conventional barrier metal layer forming method using ALD has a drawback in that the deposition rate is too slow for use in manufacturing semiconductor devices. As a comparison, the deposition rate of a typical CVD process used to form a TiN layer is approximately several hundreds of Å/min. On the other hand, the deposition rate at which a TiN layer can be formed using the conventional ALD process is less than 100 Å/min, which is very slow compared to when the CVD process is used.
- A first object of the present invention is to provide a method of manufacturing a barrier metal layer that makes use of atomic layer deposition (ALD) but in which the deposition rate is not too slow.
- A second object of the present invention is to provide a method of manufacturing a barrier metal layer using ALD, and by which the deposition rate at which the ALD occurs can be increased without an accompanying increase in the amount of impurities being left in the barrier metal layer.
- To achieve the first above object, the present invention provides a method of manufacturing a barrier metal layer including: (a) supplying a first source gas onto the entire surface of a semiconductor substrate in the form of a pulse having a duration lasting from a point in time A 1 to a point in time A2, and (b) supplying a second source gas, which reacts with the first source gas, onto the entire surface of the semiconductor substrate in the form of a pulse having a duration lasting from a point in time A3 to a point in time A4, wherein A3 is at least as early in time as A1 and no later in time than A2. Preferably, point in time A4 is no earlier than point in time A2. Moreover, the points in time the pulse of the first source gas begins and ends can be the same as those at which the pulse of the second source gas begins and ends. That is, point in time A1 can coincide with point in time A3, and point in time A2 can coincide with point in time A4.
- A purge gas can be used to discharge by-products of the reaction between the first and second source gases. The purge gas is supplied onto the entire surface of the semiconductor substrate beginning at a point in time that is earlier than or that coincides with point in time A 1. Alternatively, the purge gas can be supplied onto the entire surface of the semiconductor substrate beginning at a point in time that is later than point in time A1 and is no later than point in time A3.
- An impurity-removing gas can be additionally used to free any impurities that have managed to become trapped within the barrier metal layer. In this case, the method includes a step (c) of supplying an impurity-removing gas onto the entire surface of the semiconductor substrate for a predetermined period of time, after point in time A 4 and while the purge gas is still being supplied.
- The gas supply scheme comprising the steps (a), (b) and (c) constitutes a cycle of operation, and the cycle can be repeated at least once to increase the thickness of the barrier metal layer a desired amount.
- The first source gas can include a gas of the halogen element family and a refractory metallic element, and the second source gas can include nitrogen. The purge gas can be an inert gas such as argon. The impurity removing gas can be NH 3.
- To achieve the second object, the present invention provides a method of manufacturing a barrier metal layer, including: (a) supplying a first source gas onto the entire surface of a semiconductor substrate in the form of a pulse having a duration lasting from a point in time B 1 to a point in time B2, (b) supplying a second source gas, which reacts with the first source gas, onto the entire surface of the semiconductor substrate in the form of a pulse having a duration lasting from a point in time B3 to a point in time B4, whereby a barrier metal layer is formed, and (c) supplying an impurity-removing gas onto the entire surface of the semiconductor substrate in the form of a pulse having a duration lasting from a point in time B5 to a point in time B6 to remove impurities from the barrier metal layer, wherein B3 is later in time than B2, and B5 is later in time than B4.
- A purge gas can also be supplied onto the entire surface of the semiconductor substrate, beginning at a point in time that is earlier than or coincides with point in time B 1, or that is later than B1 and no later than point in time B2, to remove all of the first source gas that is physically adsorbed at the surface of the semiconductor substrate before the second source gas is supplied and/or to discharge by-products of the reaction between the first and second source gases.
- The above and other objects, features and advantages of the present invention will become more apparent from the following detailed description of the preferred embodiments thereof made with reference to the attached drawings, of which:
- FIG. 1 is a timing diagram of the gas supply scheme of a first embodiment of a method of fabricating a barrier metal layer using atomic layer deposition (ALD) according to the present invention;
- FIG. 2 is a timing diagram of an alternative gas supply scheme of the first embodiment of a method of fabricating a barrier metal layer using atomic layer deposition (ALD) according to the present invention; and
- FIG. 3 is a timing diagram of the gas supply scheme of a second embodiment of a method of fabricating a barrier metal layer using atomic layer deposition (ALD) according to the present invention.
- The preferred embodiments of the present invention will now be described in detail with reference to the attached drawings.
- <First Embodiment>
- In the first embodiment of a method of fabricating a barrier metal layer according to the present invention, first, a semiconductor substrate is loaded into a processing chamber of an ALD apparatus. The semiconductor substrate may have a feature having a predetermined aspect ratio. The feature may be a word line, a conductive line such as a bit line, a contact plug, a via contact, a capacitor upper electrode, or the like. After the semiconductor substrate is loaded into the processing chamber, first and second source gases and a purge gas are supplied to the chamber according to the scheme shown in FIG. 1 to form a barrier metal layer on a prescribed feature of the semiconductor substrate.
- The barrier metal layer is typically formed of a binary or larger compound including a refractory metal and nitrogen. TiN is representative of the material of the barrier metal layer. Therefore, the first embodiment will be described in connection with the formation of a Ti-containing layer as a barrier metal layer.
- Referring now to FIG. 1, while a purge gas is continuously directed onto the entire surface of the semiconductor substrate, a first source gas is pulsed onto the surface of a semiconductor substrate for a duration lasting from a point in time A 1 to a point in time A2. The pulse of the first source gas is chemically and physically adsorbed by the entire surface of the semiconductor substrate according to the surface topology thereof. However, some of the first source gas that has been physically adsorbed is then removed by the purge gas because the purge gas is being directed onto the entire surface of the semiconductor substrate while the first source gas is being physically adsorbed. The purge gas and the source gas entrained therein are discharged to the outside of the processing chamber.
- Note, FIG. 1 shows that the continuous supplying of the purge gas is initiated at point in time A 1. However, the continuous supplying of the purge gas can be initiated before point in time A1, or at a point in time A3 that is as early as point in time A1 but no later than point in time A2. Also, the purge gas is an inert gas, such as argon.
- On the other hand, a gas comprising a refractory metal (in this case, Ti) is used as the first source gas. For example, TiCl 4 is used as the first source gas. However, other source gases containing the barrier metal and capable of reacting with a second source gas can be used. For instance, considering the present example of a Ti-containing barrier metal layer, a metallo-organic gas such as tetrakis diethyl amino titanium (TDEAT) or tetrakis dimethyl amino titanium (TDMAT) can be used as the first source gas.
- Next, a pulse of the second source gas is directed onto the surface of the semiconductor substrate for a duration lasting from point in time A 3 to a point in time A4, and while the purge gas continues to be supplied onto the entire surface of the semiconductor substrate. Note, at point in time A3 some of the first source gas is still being supplied and thus, not all of the first source gas physically adsorbed at the surface of the semiconductor substrate has been removed at this time by the purge gas. A4 is a point in time that occurs no earlier than point in time A2 but occurs some time after point in time A3. Thus, the points in time under which the scheme of the gas supply is established are related as follows: (A1≦A3≦A2, A2≦A4, A1≠A2, and A3≠A4). Under this scheme, point in time A1 can coincide with point in time A3, and point in time A2 can coincide with point in time A4, in which case the first and second source gases would be pulsed beginning at the same time and continuing for the same duration.
- In any case, the pulsing of the second source gas is initiated before or at the same time the pulsing of the first source gas terminates. The pulse of the second source gas terminates after or at the same time the pulsing of the first source gas terminates. After the pulse of the second source gas terminates, only the purge gas is supplied along the entire surface of the semiconductor substrate for a duration lasting from point in time A 4 to a point in time A5, thereby discharging by-products of the reaction of the first and second source gases.
- A gas including a non-metallic element (N) of the barrier metal layer (TiN) is used as the second source gas. For example, NH 3 is used as the second source gas. However, other gases which react with the first source gas and contain nitrogen, such as N2, can be used as the second source gas.
- Now, in ALD, that part of the first source gas that has been chemically adsorbed reacts with the second source gas. However, from point in time A 3 to point in time A4, i.e. the duration of the pulse of the second source gas, the mechanism by which the barrier metal (TiN) is deposited no longer consists of ALD because the first source gas physically adsorbed at the surface of the semiconductor substrate has not been completely removed by the purge gas. Accordingly, the second source gas reacts with not only that part of the first source gas that has been chemically adsorbed at the surface of the semiconductor substrate but also that part of the first source gas that has been physically adsorbed. Thus, although ALD results from the reaction between that part of the first source gas chemically adsorbed at the surface of the semiconductor substrate and the second source gas, CVD results from the reaction between that part of the first source gas physically adsorbed and the second source gas. Consequently, the ALD that takes place provides a 100% step coverage and the CVD that takes place provides a high deposition rate.
- Moreover, as was described above, a large amount of impurities (Cl) are present in a barrier metal layer (TiN) when the barrier metal layer is formed by CVD. However, in the present invention, impurity-containing gases HCl and TiCl x generated as by-products are discharged from the processing chamber by flushing the entire surface of the semiconductor substrate with an inert gas while the first and second source gases react with each other (A3-A4) and for a predetermined period of time (that is, for a duration of A4-A5) after the pulse of the second source gas terminates. Consequently, impurities (Cl) are prevented from being entrapped within the deposited material. That is, even though the present invention employs the deposition mechanism of CVD, namely a process in which a high temperature is required to suppress the level of impurities in the barrier metal layer, the method of the present invention can be performed at a low temperature (for example, 450 to 500° C.) without producing a high level of impurities in the barrier metal layer because the present invention also employs ALD. Thus, the present invention also suppresses thermal stress and thereby decreases the thermal budget of the layer (underlayer) beneath the barrier metal layer.
- In the first embodiment, the duration of A 1, to A5 is a cycle T1, and a barrier metal layer can be formed to a desired thickness by repeating the cycle T1 a predetermined number of times. Also, the method can also comprise a step of pulsing an impurity-removing gas to further ensure that impurities (Cl) are prevented from being trapped within the barrier metal layer (TiN). The thickness of the TiN layer formed after one cycle is established by the process recipe under which the first and second source gases, and the purge gas (and impurity-removing gas) are supplied into the processing chamber.
- As shown in FIG. 2, the impurity-removing gas can be supplied for a duration beginning at point in time A 6 and ending at point in time A7, while the purge gas is being directed onto the surface of a semiconductor substrate and after the pulse of the second source gas terminates. The impurity-removing gas reacts with impurities trapped in the barrier metal layer during the reaction of the first and second source gases, and frees the impurities from the barrier metal layer. For example, the impurity-removing gas reduces the impurities to their constituent elements. Also, the impurity-removing gas can easily diffuse into the metal barrier layer and thereby react with the impurities because the thickness of the barrier metal layer formed during the time period from A1 to A4 is very thin (about 10 to 20 Å). Accordingly, in contrast with the conventional technique of flushing the barrier metal layer with an impurity-removing gas after the barrier metal layer has been completed, the technique of the present invention in which impurity-removing gas is supplied after one of a plurality of cycles can remove impurities (Cl) from the barrier metal layer using only a tiny flow of the impurity-removing gas.
- NH 3 can be used as the impurity-removing gas. In this case, the processing apparatus does not need a separate gas supply line dedicated to the impurity-removing gas because the impurity-removing gas and the second source gas are the same. Rather, another pulse of the second source gas can be supplied from the time period A6-A7 (see reference character I). On the other hand, gases other than NH3 can be used as the impurity-removing gas. In these cases, a separate gas supply line dedicated to the impurity-removing gas is required.
- When the impurity-removing gas is NH 3, the impurity-removing gas diffuses into the barrier metal layer that was formed during the time period of from A1 to A4 and reacts with impurities (Cl) within the layer according to the following chemical equation, and frees the impurities (Cl) from the barrier metal layer in the form of gas (HCl).
- [Chemical equation]
- TiNxCly(S)+NH3(g)→TiN(s)+HCl(g)
- <Second Embodiment>
- Next, a second embodiment of a method of forming a barrier metal layer will be described. Like the first embodiment, the second embodiment of the present invention can also reduce the amount of impurities remaining in a barrier metal layer to a greater extent than the conventional ALD method without seriously compromising the deposition rate. For the sake of convenience, the second embodiment will also be described as applied to the forming of a TiN barrier metal layer.
- Referring to FIG. 3, in the second embodiment of the present invention, first, a semiconductor substrate is loaded into a processing chamber of an ALD apparatus. Next, a first source gas is supplied in the form of a pulse, beginning at a point in time B 1 and terminating at a point in time B2, while a purge gas is being continuously supplied onto the entire surface of the semiconductor substrate. The first source gas is chemically and physically adsorbed at the surface of the semiconductor substrate according to the topology of the surface.
- FIG. 3 shows that the flow of purge gas is initiated at the point in time B 1. However, the flow of the purge gas can be initiated prior to the point in time B1, or from any point in time as early as B1 and no later than B2. Then, the physically-adsorbed part of the first source gas is removed by the purge gas from the point in time B2 to a point in time B3. Thereafter, the second source gas is supplied in the form of a pulse beginning from the point in time B3 and terminating at the point in time B4 while the purge gas continuous to be supplied onto the entire surface of the semiconductor substrate. Then, from the point in time B4 to a point in time B5 only the purge gas is supplied, whereby by-products generated by the reaction of the first and second source gases are discharged from the chamber. Then, the impurity-removing gas is supplied in the form of a pulse beginning from the point in time B5 and terminating at a point in time B6 while the purge gas continuous to be supplied onto the entire surface of the semiconductor substrate. Note, the first and second source gases and the impurity-removing gas can be the same as those used in the first embodiment.
- Also, similar to the first embodiment, the impurity-removing gas and the second source gas can be of the same type, whereby the processing apparatus does not require a separate gas supply line dedicated to the impurity-removing gas. That is, another pulse of the second source gas can be supplied during the time period of B 5-B6 (see reference character II). On the other hand, when gases other than NH3 are used as the impurity-removing gas, a separate gas supply line dedicated to the impurity-removing gas is required.
- In this embodiment, impurities formed during the period of time from B 1 to B4 are removed from the barrier metal layer by the impurity-removing gas. Thereafter, from the point in time B6 to a point in time B7, the purge gas discharges by-products of the reaction between the impurity-removing gas and the impurities.
- The time period of B 1 to B7 represents a cycle T2, and the barrier metal layer can be formed to a desired thickness by repeating the cycle T2. In the second embodiment, the impurity-removing gas is supplied after the supply of the second source gas is terminated, so that fewer impurities remain within the barrier metal layer than when the prior art method is used.
- Consideration of the content of impurities within the barrier metal layer aside, the deposition rate of the barrier metal in ALD can be typically controlled by adjusting the process recipe under which the first and second source gases are supplied. That is, the deposition rate of the barrier metal can be increased by controlling the supply of the first and second source gases. However, increasing the deposition rate of the barrier metal in this way is normally accompanied by a corresponding increase in the amount of impurities within the barrier metal layer. That is, there is a limit to ALD in changing the process recipe to increase the deposition rate of the barrier metal. However, in the second embodiment of the present invention, the use of the impurity-removing gas allows the process recipe under which the first and second source gases are supplied to be adjusted for increasing the deposition rate of the barrier metal without giving rise to a corresponding increase in the amount of impurities remaining within the barrier metal layer. In other words, the second embodiment provides a significant degree of freedom in adjusting the process recipe under which the first and second source gases are supplied.
- A case in which the first and second embodiments of the present invention are applied to the manufacture of a binary barrier metal layer (TiN) will now be described in detail. However, the present invention is not limited to the manufacture of a TiN binary metal layer. Rather, the present invention is also applicable to the manufacture of other binary barrier metal layers such as a TaN layer, a WN layer, an AlN layer, a CrN layer and a BN layer. The type of first and second source gases and impurity-removing gas to be used when manufacturing barrier metal layers other than the TiN barrier layer will be readily apparent to those of ordinary skill in the art.
- For example, when the barrier metal layer is formed of AlN, an AlClx gas can be used as the first source gas, and NH 3 can be used as the second source gas and as the impurity-removing gas.
- Also, the present invention is not applicable only to the manufacture of binary barrier metal layers, but can also be applied to the manufacture of barrier metal layers formed of larger compounds. For example, the present invention can also be applied to the manufacture of a TiBN layer, a TaBN layer, a TiAlN layer, a TaAlN layer, a TiSiN layer, a TaSiN layer, a TiCN layer, a WBN layer, and the like.
- For example, when the barrier metal layer is formed of TiAlN using the first embodiment of the present invention, a first source gas (for example, TiCl 4), a second source gas (for example, trimethyl aluminum (TMA)) and a third source gas (for example, NH3) can be supplied according to the following schemes. Note, in these schemes, the duration of the pulse of the first source gas is from a point in time C1 to a point in time C2, the duration of the pulse of the second source gas is from a point in time C3 to a point in time C4, and the duration of the pulse of the third source gas is from a point in time C5 to a point in time C6.
- [first scheme]
- C1≦C3≦C2 and C1≦C5≦C2
- [second scheme]
- C1≦C3≦C2 and C3≦C5≦C4
- After the first through third source gases are supplied according to any one of the above schemes, the purge gas is directed onto the entire surface of the semiconductor substrate for a predetermined period of time, thereby completing the cycle. The cycle is repeated a predetermined number of times to form a barrier metal layer (TiAlN) having a desired thickness.
- The barrier metal layer of TiAlN can also be formed using the second embodiment of the present invention, under the schemes set forth above. In this case, the deposition mechanism includes CVD along with ALD. Thus, the second embodiment will also exhibit a higher deposition rate than the prior art. Also, the purge gas is continuously supplied onto the entire surface of the semiconductor substrate while the source gases are being supplied. Thus, the amount of impurities remaining within the barrier metal layer are minimal even though the process is carried at a temperature as low as that used to carry out the conventional ALD process. Furthermore, in the second embodiment, an impurity-removing gas can be supplied in the form of a pulse after the first through third source gases are suppled, as in the first embodiment, thereby reducing the amount of impurities within the barrier metal layer.
- According to one aspect of the present invention, the barrier metal layer is formed by ALD and CVD, so that the deposition rate of the barrier metal is greater than if the barrier metal layer were formed only through ALD. Also, a purge gas is continuously supplied onto the entire surface of the semiconductor substrate during the manufacture of the barrier metal layer, so that the amount of impurities remaining within the barrier metal layer is minimized despite the fact that the method is carried out at a low temperature suitable for ALD.
- According to another aspect of the present invention, the barrier metal layer is formed only through ALD. However, an impurity-removing gas is supplied during the process to free impurities that have been trapped in the barrier metal layer. Therefore, the process recipe for the source gases has a high degree of freedom, can be changed to a great extent to increase the deposition rate of the barrier metal. Therefore, even though the barrier metal layer is formed only through ALD, the barrier metal can be deposited at higher and higher rates without corresponding increases in the impurity content of the barrier metal layer.
- Although the present invention has been described with reference to the preferred embodiments thereof, various modifications thereof will be apparent to those of ordinary skill in the art. All such modifications are seen to be within the true spirit and scope of the invention as defined by the appended claims.
Claims (17)
1. A method of manufacturing a barrier metal layer, comprising the steps of:
loading a semiconductor substrate into a processing chamber;
supplying a first source gas, containing a metal, onto the entire surface of the semiconductor substrate in the form of a pulse having a duration lasting from a point in time A1 to a point in time A2, whereby the first source gas is chemically and physically adsorbed at the surface; and
supplying a second source gas, that is reactive with the first source gas to form the barrier metal, onto the entire surface of the semiconductor substrate in the form of a pulse having a duration lasting from a point in time A3 to a point in time A4, wherein said point in time A3 is no earlier than said point in time A1 and no later than said point in time A2, whereby one portion of the second source gas reacts with that part of the first source gas physically adsorbed at the surface of the semiconductor substrate to thereby form the barrier metal layer by chemical vapor deposition whereas another part of the second source gas reacts with that part of the first source gas chemically adsorbed at the surface of the semiconductor substrate to thereby form the barrier metal layer by atomic layer deposition.
2. The method of claim 1 , wherein said point in time A4 is no later in time than said point in time A2.
3. The method of claim 1 , and further comprising supplying a purge gas onto the entire surface of the semiconductor substrate beginning at a point in time that is no later than said point in time A1.
4. The method of claim 1 , and further comprising supplying a purge gas onto the entire surface of the semiconductor substrate beginning at a point in time that is later than said point in time A1 and no later than said point in time A3.
5. The method of claim 1 , wherein the first source gas includes an element of the halogen family and a refractory metal, and the second source gas includes nitrogen.
6. The method of claim 1 , and further comprising supplying a purge gas onto the entire surface of the semiconductor substrate for a predetermined period of time after said point in time A4 to discharge by-products of the reaction between the first and second source gases.
7. The method of claim 6 , wherein said steps of supplying the first source gas in the form of a pulse, supplying the second source gas in the form of a pulse, and supplying the purge gas for a predetermined period of time are repeated at least once to increase the thickness of the barrier metal layer.
8. The method of claim 1 , wherein the reaction of the first and second source gases produces an impurity trapped in the barrier metal layer, and further comprising supplying a purge gas onto the entire surface of the semiconductor substrate, and supplying an impurity-removing gas, capable of reacting with the impurity, onto the entire surface of the semiconductor substrate for a predetermined period of time beginning after point in time A4 and while the purge gas is being supplied, in order to remove impurities from the barrier metal layer.
9. The method of claim 8 , wherein the impurity removing-gas is NH3.
10. The method of claim 8 , wherein said steps of supplying the first source gas in the form of a pulse, supplying the second source gas in the form of a pulse, and supplying the impurity-removing gas are repeated at least once to increase the thickness of the barrier metal layer.
11. The method of claim 11 , wherein said point in time A1 coincides with said point in time A3, and said point in time A2 coincides with said point in time A4.
12. A method of manufacturing a barrier metal layer, comprising the steps of:
loading a semiconductor substrate into a processing chamber;
supplying a first source gas, containing a metal, onto the entire surface of the semiconductor substrate in the form of a pulse having a duration lasting from a point in time B1 to a point in time B2, whereby the first source gas is chemically and physically adsorbed at the surface;
supplying a second source gas, that is reactive with the first source gas to form the barrier metal, onto the entire surface of the semiconductor substrate in the form of a pulse having a duration lasting from a point in time B3 to a point in time B4, whereby part of the second source gas reacts with that part of the first source gas chemically adsorbed at the surface of the semiconductor substrate to thereby form the barrier metal layer by atomic layer deposition; and
supplying an impurity-removing gas onto the entire surface of the semiconductor substrate in the form of a pulse having a duration lasting from a point in time B5 that is later than said point in time B4, to a point in time B6 to thereby remove impurities from the barrier metal layer.
13. The method of claim 12 , wherein said point in time B3 is later in time than said point in time B2, and further comprising supplying a purge gas onto the entire surface of the semiconductor substrate beginning at a point in time that is no later than said point in time B1 to purge the substrate of the first source gas physically adsorbed at the surface thereof before the second source gas is supplied.
14. The method of claim 12 , wherein said point in time B3 is later in time than said point in time B2, and further comprising supplying a purge gas onto the entire surface of the semiconductor substrate beginning at a point in time that is later than said point in time B1 and is no later than aid point in time B2 to purge the substrate of the first source gas physically adsorbed at the surface thereof before the second source gas is supplied.
15. The method of claim 12 , wherein the first source gas includes an element of the halogen family and a refractory metal, and the second source gas includes nitrogen.
16. The method of claim 12 , wherein said steps of supplying the first source gas in the form of a pulse, supplying the second source gas in the form of a pulse, and supplying the impurity-removing gas in the form of a pulse are repeated at least once to increase the thickness of the barrier metal layer.
17. The method of claim 12 , wherein the impurity-removing gas is NH3.
Priority Applications (1)
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| US10/084,193 US20020081844A1 (en) | 2000-04-20 | 2002-02-28 | Method of manufacturing a barrier metal layer using atomic layer deposition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020000020996A KR100363088B1 (en) | 2000-04-20 | 2000-04-20 | Method of manufacturing barrier metal layer using atomic layer deposition method |
| KR2000-20996 | 2000-04-20 | ||
| US09/826,946 US6399491B2 (en) | 2000-04-20 | 2001-04-06 | Method of manufacturing a barrier metal layer using atomic layer deposition |
| US10/084,193 US20020081844A1 (en) | 2000-04-20 | 2002-02-28 | Method of manufacturing a barrier metal layer using atomic layer deposition |
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| US09/826,946 Division US6399491B2 (en) | 2000-04-20 | 2001-04-06 | Method of manufacturing a barrier metal layer using atomic layer deposition |
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| US10/084,193 Abandoned US20020081844A1 (en) | 2000-04-20 | 2002-02-28 | Method of manufacturing a barrier metal layer using atomic layer deposition |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2001303251A (en) | 2001-10-31 |
| US20010034123A1 (en) | 2001-10-25 |
| US6399491B2 (en) | 2002-06-04 |
| KR20010097163A (en) | 2001-11-08 |
| KR100363088B1 (en) | 2002-12-02 |
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