US20010002334A1 - Methods of forming titanium nitride composite layers using composite gases having increasing TiC14 to NH3 ratios - Google Patents
Methods of forming titanium nitride composite layers using composite gases having increasing TiC14 to NH3 ratios Download PDFInfo
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- US20010002334A1 US20010002334A1 US09/767,523 US76752301A US2001002334A1 US 20010002334 A1 US20010002334 A1 US 20010002334A1 US 76752301 A US76752301 A US 76752301A US 2001002334 A1 US2001002334 A1 US 2001002334A1
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- tin film
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- 238000000034 method Methods 0.000 title claims abstract description 129
- 239000007789 gas Substances 0.000 title claims description 186
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 title abstract description 3
- 239000002131 composite material Substances 0.000 title 2
- 229910010066 TiC14 Inorganic materials 0.000 title 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 331
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 56
- 229910003074 TiCl4 Inorganic materials 0.000 claims abstract description 47
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 47
- 238000000137 annealing Methods 0.000 claims abstract description 37
- 230000001681 protective effect Effects 0.000 claims abstract description 37
- 239000004065 semiconductor Substances 0.000 claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- 238000009792 diffusion process Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 239000010936 titanium Substances 0.000 abstract description 40
- 239000000460 chlorine Substances 0.000 description 50
- 238000000151 deposition Methods 0.000 description 13
- 230000004888 barrier function Effects 0.000 description 11
- 239000010410 layer Substances 0.000 description 5
- 239000012790 adhesive layer Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 238000005137 deposition process Methods 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000011800 void material 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
- H01L21/70—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
- H01L21/76853—Barrier, adhesion or liner layers characterized by particular after-treatment steps
- H01L21/76855—After-treatment introducing at least one additional element into the layer
- H01L21/76856—After-treatment introducing at least one additional element into the layer by treatment in plasmas or gaseous environments, e.g. nitriding a refractory metal liner
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—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
-
- 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
- H01L21/76846—Layer combinations
-
- 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
- H01L21/76853—Barrier, adhesion or liner layers characterized by particular after-treatment steps
- H01L21/76861—Post-treatment or after-treatment not introducing additional chemical elements into the layer
- H01L21/76864—Thermal treatment
Definitions
- the present invention relates to a method of manufacturing a semiconductor device, and more particularly, to a method of forming a titanium nitride film and a method of manufacturing a semiconductor device using the same.
- An adhesive layer having a Ti/TiN structure is generally employed in order to improve the poor adhesive characteristic of a metal such as tungsten (W) for filling a contact hole, when a metal contact plug required for the metal wiring of a semiconductor device is formed.
- a metal such as tungsten (W)
- a physical vapor deposition (PVD) method such as a sputtering method is used for forming the adhesive layer having the Ti/TiN structure.
- PVD physical vapor deposition
- a film having a poor step coverage is obtained. Therefore, in the case of forming a contact having a large aspect ratio, the overhang of the Ti/TiN film is severe at the entrance of the contact hole when the Ti/TiN film is used as the adhesive layer or a barrier layer. Accordingly, a large void is formed in the contact during a subsequent process of depositing a tungsten film.
- WF 6 gas used as a source gas during a subsequent process of depositing the tungsten film, and Ti of the Ti/TiN film react, thus forming a nonconductor or vaporizing some part. Accordingly, the TiN film is lifted and peeled off. If so, the Ti/TiN film cannot serve as a barrier with respect to the WF 6 gas.
- the TiN film formed by the CVD method using TiCl 4 gas as a source gas is generally used as an adhesive layer of a metal film or a barrier film when a metal contact or a capacitor is formed since it is possible to obtain a good step coverage.
- a large amount of chlorine (Cl) is included in the formed TiN film in the method of forming the TiN film by the CVD method using the TiCl 4 gas as the source gas.
- the TiN film containing a large amount of Cl shows a high resistivity. Also, since Cl permeates and damages the Ti film which is an underlayer, a high temperature rapid thermal nitration (RTN) process, or an NH 3 plasma process is required on the Ti film in order to prevent the Cl permeation.
- RTN rapid thermal nitration
- a method of forming a multilayer TiN film by a chemical vapor deposition (CVD) method on a semiconductor substrate on which an underlayer is formed In this method, an underlayer protective TiN film is formed on the underlayer. A main TiN film is formed on the underlayer protective TiN film.
- CVD chemical vapor deposition
- the underlayer is a Ti film.
- NH 3 gas may be pre-flown on the surface of the Ti film before the step (a).
- the step (a) comprises the steps of (a-1) forming a first TiN film on the underlayer to have a thickness of between 10 and 100 ⁇ using a source gas composed of a mixture of TiCl 4 gas and NH 3 gas and (a-2) annealing the first TiN film in an NH 3 gas atmosphere.
- the step (b) comprises the steps of (b-1) forming a second TiN film on the underlayer protective TiN film using a source gas formed of a mixture of TiCl 4 gas and NH 3 gas and (b-2) annealing the second TiN film in the NH 3 gas atmosphere.
- the gas flow ratio of TiCl 4 to NH 3 is between 0.02 and 0.1 in the source gas.
- the first and second TiN films are formed under a pressure of between 0.2 and 0.5 Torr and at a temperature of between 530 and 680°C.
- the steps of annealing the first TiN film and the second TiN film are respectively performed at a temperature of between 530 and 680° C.
- the step (c) of forming an oxygen diffusion preventing TiN film on the main TiN film can be further comprised after the step (b).
- the step (c) comprises the steps of (c-1) forming a third TiN film on the main TiN film using a source gas composed of a mixture of TiCl 4 gas and NH 3 gas, to have a thickness of between 10 and 100 ⁇ and (c-2) annealing the third TiN film in the NH 3 gas atmosphere.
- the third TiN film is formed under a pressure of between 0.2 and 0.5 Torr and at a temperature of between 530 and 680° C.
- a TiN film is formed on the underlayer protective TiN film to have a thickness of between 10 and 100 ⁇ using a source formed of a mixture of TiCl 4 gas and NH 3 gas.
- the TiN film is annealed in an NH 3 gas atmosphere. The above steps are repeated until the main TiN film having a desired thickness is obtained.
- a first TiN film covering the underlayer exposed on a semiconductor substrate is formed by a chemical vapor deposition (CVD) method using a source gas supplied in a first gas flow ratio having a predetermined TiCl 4 to NH 3 gas flow ratio.
- the first TiN film is annealed in an NH 3 gas atmosphere to form an underlayer protective TiN film.
- a second TiN film is formed on the underlayer protective TiN film by the CVD method, using a source gas supplied in a second gas flow ratio having a TiCl 4 to NH 3 gas flow ratio larger than the first gas flow ratio.
- the second TiN film is annealed in an NH 3 gas atmosphere to form a main TiN film.
- the first gas flow ratio and the second gas flow ratio are selected to be between 0.02 and 0.1, respectively.
- the first gas flow ratio is selected to be between 0.02 and 0.05.
- the step of forming the first TiN film and the step of forming the second TiN film are respectively performed under a pressure of between 0.2 and 0.5 Torr and at a temperature of between 530 and 680°C.
- the steps of annealing the first TiN film and the second TiN film are respectively performed at a temperature of between 530 and 680°C.
- a third TiN film is formed on the main TiN film using a source gas supplied in a third gas flow ratio having a TiCl 4 to NH 3 gas flow ratio which is smaller than the second gas flow ratio.
- the third TiN film is annealed in an NH 3 gas atmosphere.
- the third gas flow ratio is selected to be between 0.02 and 0.1.
- a first TiN film covering the underlayer exposed on a semiconductor substrate by the CVD method using a source gas supplied in a first gas flow ratio having a predetermined TiCl 4 to NH 3 gas flow ratio.
- a second TiN film is formed on the first TiN film by the CVD method, using a source gas supplied in a second gas flow ratio having a TiCl 4 to NH 3 gas flow ratio which is larger than the first gas flow ratio.
- the first TiN film and the second TiN film are annealed in a NH 3 gas atmosphere.
- an insulating film having a contact hole is formed on a semiconductor substrate.
- a Ti film is formed on the inner wall of the contact hole.
- a multilayer TiN film is formed by repeating a process of forming a TiN film on the Ti film by a CVD method using a source gas composed of a mixture of TiCl 4 gas and NH 3 gas and annealing the TiN film in an NH 3 gas atmosphere at least two times.
- a metal plug is formed on the multilayer TiN film.
- the present invention it is possible to obtain a densified multilayer TiN film sufficiently removed of the Cl component so that the device is not deteriorated.
- the multilayer TiN film according to the present invention is used as a barrier film of a metal contact, it is possible to reduce the resistance of the contact and to omit an additional process such as a high temperature rapid thermal nitration (RTN) process for protecting an underlayer.
- RTN rapid thermal nitration
- FIGS. 1A through 1F are cross sectional views for describing a method of forming a multilayer TiN film according to a first embodiment of the present invention
- FIGS. 2A and 2B are cross sectional views for describing a method of forming a multilayer TiN film according to a second embodiment of the present invention.
- FIGS. 3A through 3F are cross sectional views for describing a method of forming a multilayer TiN film according to a third embodiment of the present invention.
- FIGS. 4A through 4C are cross sectional views for describing a method of forming a multilayer TiN film according to a fourth embodiment of the present invention.
- FIG. 5 is a graph showing the resistivities of a multilayer TiN film formed according to the present invention and TiN films formed by a conventional method.
- FIGS. 6A through 6E are cross sectional views for describing a method of manufacturing a semiconductor device according to a preferred embodiment of the present invention.
- FIGS. 1A through 1F are cross sectional views showing processes of a method of forming a multilayer TiN film by a multiple step chemical vapor deposition (CVD) process according to a first embodiment of the present invention.
- CVD chemical vapor deposition
- an underlayer 10 such as a Ti film is formed on a semiconductor substrate (not shown).
- the underlayer 10 may be TaO or Pt.
- a first TiN film 22 is formed on the underlayer 10 by a chemical vapor deposition (CVD) method using a mixture of TiCl 4 gas and NH 3 gas as a source gas, to have a thickness of between 10 and 100 ⁇ in the first step of forming a multilayer TiN film by a multiple step deposition.
- the deposition process is performed at a temperature of between 530 and 680° C.
- the first TiN film 22 is formed on the underlayer 10 through thermal reduction of the TiCl 4 gas with the NH 3 gas in the source gas.
- the flow rates of the TiCl 4 gas and the NH 3 gas, each of which compose the source gas, are controlled so as to obtain a TiCl 4 to NH 3 gas flow ratio of between 0.02 and 0.1.
- the reaction pressure during the formation of the first TiN film 22 is between 0.2 and 0.5 Torr.
- an NH 3 pre-flow step of providing the NH 3 gas on the surface of the underlayer 10 may be performed before forming the first TiN film 22 .
- the NH 3 pre-flow step is performed for 60 seconds at a temperature of between 530 and 680°C. and under a pressure of 0.3 Torr.
- the first TiN film 22 is annealed in an NH 3 gas atmosphere.
- the NH 3 gas is provided on the first TiN film 22 at the temperature of between 530 and 680°C.
- a Cl component existing on the surface or the grain boundary of the first TiN film 22 is completely removed and the place from which Cl is removed is filled with an N component.
- the first TiN film 22 is densified. Therefore, an underlayer protective TiN film 22 a which contains few Cl component is formed.
- the NH 3 gas of 1,000 sccm is supplied for 60 seconds under a pressure of 3 Torr and at the temperature of between 530 and 680° C., for the NH 3 annealing.
- the underlayer protective TiN film 22 a obtained after the NH 3 annealing is sufficiently removed of the Cl component and the place from which Cl is removed is filled with the N component. Accordingly, the underlayer protective TiN film 22 a is densified. Therefore, it is difficult for the Cl component to permeate the underlayer protective TiN film 22 a from the TiCl 4 gas when a TiN film is formed using the TiCl 4 gas in a subsequent process. Therefore, it is possible to prevent the underlayer 10 from being damaged by the Cl component.
- a second TiN film 24 is formed on the underlayer protective TiN film 22 a to a predetermined thickness.
- the thickness of the second TiN film 24 is determined considering the thicknesses of the underlayer protective TiN film 22 a according to the total thickness of the multilayer TiN film to be formed.
- the deposition conditions at this time are the same as those of forming the first TiN film 22 described with reference to FIG. 1A.
- a main TiN film 24 a removed of the Cl component contained in the second TiN film 24 and having a densified structure is formed by annealing the second TiN film 24 in the NH 3 gas atmosphere by the same method as that described with reference to FIG. 1B.
- a third TiN film 26 is formed on the main TiN film 24 a by the same method as that of forming the first TiN film 22 described with reference to FIG. 1A, to have the thickness of between 10 and 100 ⁇ .
- the Cl component is removed from the third TiN film 26 by annealing the third TiN film 26 in a NH 3 gas atmosphere, and a densified oxygen diffusion preventing TiN film 26 a is formed by the same method as that described with reference to FIG. 1B.
- the multilayer TiN film 20 formed of the underlayer protective TiN film 22 a , the main TiN film 24 a , and the oxygen diffusion preventing TiN film 26 a is formed on the underlayer 10 by a multiple step CVD method.
- the multilayer TiN film is formed by a three step deposition process.
- the present invention is not restricted to this.
- FIGS. 2A and 2B are cross sectional views showing processes of the method of forming the multilayer TiN film by the multiple step CVD process according to a second embodiment of the present invention.
- an underlayer protective TiN film 62 a is formed on the underlayer 50 to have a thickness of between 10 and 100 ⁇ .
- a second TiN film 64 is formed on the underlayer protective TiN film 62 a by the same method as the method of forming the first TiN film 22 described with reference to FIG. 1A, to have a thickness of between 10 and 100 ⁇ .
- the Cl component contained in the second TiN film 64 is completely removed by annealing the second TiN film 64 in an NH 3 gas atmosphere by the same method as that describe with reference to FIG. 1B.
- a plurality of main TiN films are formed to have a desired thickness by sequentially forming a second main TiN film (not shown), a third main TiN film (not shown), . . . on the first main TiN film 64 a by repeating the step of forming the TiN film of FIG. 2A and the NH 3 annealing step of FIG. 2B as many times as required with respect to the resultant material in which the first main TiN film 64 a is formed.
- the method according to the second embodiment may require a longer process time than the method according to the first embodiment, described in FIGS. 1 A through IF.
- the TiN film obtained by the method according to the second embodiment contains less Cl component and is more dense.
- FIGS. 3A through 3F are cross sectional views showing processes of the method of forming a multilayer TiN film by the multiple step CVD process according to a third embodiment of the present invention.
- an underlayer 70 such as a Ti film is formed on the semiconductor substrate (not shown).
- a first TiN film 72 is formed on the underlayer 70 , to a thickness of between 10 and 100 ⁇ , by the CVD method under a pressure of between 0.2 and 0.5 Torr and at a temperature of between 530 and 680°C., using a source gas composed of a mixture of the TiCl 4 gas and the NH 3 gas supplied in a first gas flow ratio of TiCl 4 to NH 3 selected from a value between 0.02 and 0.1 and having a relatively low Cl content.
- the first gas flow ratio is selected from a value between 0.02 and 0.05, more preferably, from a value between 0.03 and 0.04.
- the first TiN film 72 is annealed in an NH 3 atmosphere at a temperature of between 530 and 680°C.
- the Cl component existing on the surface of the first TiN film 72 or the grain boundary in the first TiN film 72 is completely removed and the place from which Cl is removed is filled with an N component. Accordingly, the first TiN film 72 is densified. Therefore, an underlayer protective TiN film 72 a which contains a small amount of the Cl component is formed on the underlayer 70 . Also, there is a small amount of the Cl component in the interface between the underlayer protective TiN film 72 a and the underlayer 70 .
- the NH 3 gas of 1,000 sccm is supplied for 60 seconds under the pressure of 3 Torr and at the temperature of between 530 and 680° C., for the NH 3 annealing.
- the underlayer protective TiN film 72 a is obtained by depositing the first TiN film 72 using a source gas containing a relatively low content of Cl and by sufficiently removing the Cl component residing in the TiN film 72 , it is possible to contact the underlayer protective TiN film 72 a , completely removed of the Cl component, to the underlayer 70 . Also, in the underlayer protective TiN film 72 a , the place from which Cl is removed is filled with an N component by the NH 3 annealing. Accordingly the underlayer protective TiN film 72 a is densified.
- a second TiN film 74 is formed on the underlayer protective TiN film 72 a to have a predetermined thickness, by the CVD method, using a source gas supplied in a second gas flow ratio of TiCl 4 to NH 3 selected from a value between 0.02 and 0.1 and larger than the first gas flow ratio, so as to have a larger content of Cl than in the source gas supplied in the first gas flow ratio.
- the thickness of the second TiN film 74 is determined considering the thicknesses of the underlayer protective TiN film 72 a according to the total thickness of the multilayer TiN film to be formed.
- the deposition temperature and the pressure condition at this time are the same as those of forming the first TiN film 72 described with reference to FIG. 3A.
- the second TiN film 74 is annealed in the NH 3 atmosphere and the Cl component contained in the second TiN film 74 is removed by the same method as that described with reference to FIG. 3B. Accordingly, a densified main TiN film 74 a is formed.
- a third TiN film 76 is formed on the main TiN film 74 a to have a thickness of between 10 and 100 ⁇ by the same method as the method of forming the first TiN film 72 described with reference to FIG. 3A.
- a source gas supplied in a third flow ratio of TiCl 4 to NH 3 selected from a value between 0.02 and 0.1 and smaller than the second gas flow ratio so as to contain a smaller content of Cl than in the source gas supplied in the second gas flow ratio.
- a densified oxygen diffusion preventing TiN film 76 a is formed by annealing the third TiN film 76 in the NH 3 gas atmosphere and removing the Cl component from the third TiN film 76 by the same method as that described with reference to FIG. 3B.
- a multilayer TiN film 78 comprised of the underlayer protective TiN film 72 a , the main TiN film 74 a , and the oxygen diffusion preventing TiN film 76 a is formed on the underlayer 70 by the multiple step CVD method.
- the step of forming the oxygen diffusion preventing TiN film 76 a described with reference to FIGS. 3E and 3F can be omitted if necessary.
- FIGS. 4A through 4C are cross sectional views showing processes of the method of forming a multilayer TiN film by the multiple step CVD method according to a fourth embodiment of the present invention.
- an underlayer 80 for example, a Ti film is formed on a semiconductor substrate (not shown).
- a first TiN film 82 is formed on the underlayer 80 to have a thickness of between 10 and 100 ⁇ by the CVD method under a pressure of between 0.2 and 0.5 Torr and at a temperature of between 530 and 680° C., using a source gas composed of a mixture of the TiCl 4 gas and the NH 3 gas supplied in a first gas flow ratio of TiCl 4 to NH 3 selected from a value between 0.02 and 0.1 and having a relatively low Cl component.
- the first gas flow ratio is selected between 0.02 and 0.05, more preferably, from a value between 0.03 and 0.04.
- a second TiN film 84 is formed on the first TiN film 82 by the CVD method, to have a predetermined thickness, using a source gas supplied in a second gas flow ratio of TiCl 4 to NH 3 selected between 0.02 and 0.1 and larger than the first gas flow ratio so as to have a larger content of Cl than in the source gas supplied in the first gas flow ratio.
- the thickness of the second TiN film 84 is determined considering the thicknesses of the first TiN film 82 according to the total thickness of the multilayer TiN film to be formed.
- the deposition temperature and the pressure condition at this time are the same as those of forming the first TiN film 82 described with reference to FIG. 4A.
- the resultant obtained by sequentially stacking the first TiN film 82 and the second TiN film 84 is annealed in a NH 3 gas atmosphere at a temperature of 530 to 680°C.
- 1000 sccm of the NH 3 gas is supplied for 60 seconds under a pressure of 3 Torr and at the temperature of between 530 and 680° C.
- the step of NH 3 annealing the first TiN film 82 was omitted before forming the second TiN film 84 .
- the structure of the multilayer TiN film 88 in which the surface and inside thereof is completely removed of the Cl component by the above method is densified. Therefore, although the multilayer TiN film 88 is exposed to air, it is possible to prevent oxygen from permeating the multilayer TiN film 88 . Therefore, it is possible to prevent the resistivity from increasing due to the permeation of oxygen into the multilayer TiN film 88 .
- FIG. 5 is a graph showing the result of comparing the resistivity of the multilayer TiN film formed by the multiple step CVD method according to the present invention with the resistivity of the TiN film formed by the conventional method.
- FIG. 5 shows a case of a multilayer TiN film formed by a multilayer deposition method according to the present invention.
- a multilayer TiN film having a thickness of 500 ⁇ is formed by successively repeating the process of NH 3 annealing the TiN film obtained after forming the TiN film having a thickness of 50 ⁇ by the CVD method 10 times.
- the characteristics denoted by (b) and (c) show cases in which the TiN film having the thickness of 500 ⁇ is deposited in one step by the CVD method and the NH 3 gas is supplied to the TiN film.
- (b) shows a case in which 1,000 sccm of NH 3 gas is supplied at a temperature of 680° C. and under a relatively high pressure of 3 Torr.
- (c) shows a case in which 400 sccm of the NH 3 gas is supplied at a temperature of 680°C. and under a relatively low pressure of 0.3 Torr.
- the characteristic denoted by (d) shows a case in which a TiN film having a thickness of 500 ⁇ is deposited in one step by the CVD method, in which the step of providing the NH 3 gas is omitted.
- the multilayer TiN film formed by the multiple step CVD method according to the present invention contains an extremely small content of Cl and hardly undergoes increment of the resistivity due to substitution of oxygen when the multilayer TiN film is exposed to air.
- the Ti film is not damaged at all by the Cl component during the formation of the TiN film and the lifting of the TiN film is prevented by forming the multilayer TiN film on the Ti film by the multiple step CVD method according to the present invention without performing the RTN process or the NH 3 plasma process after forming the Ti film.
- FIGS. 6A through 6E are cross sectional views showing processes of a method of manufacturing a semiconductor device according to a preferred embodiment of the present invention.
- an interlayer dielectric film 110 having a contact hole for exposing a part of a conductive layer (not shown), which is formed on a semiconductor substrate 100 .
- a Ti film 120 is formed on the resultant in which the contact hole H is formed by a sputtering method or the CVD method to have a thickness of about between 300 and 900 ⁇ .
- a multilayer TiN film 130 is formed on the Ti film 120 using a source gas comprised of TiCl 4 gas and NH 3 gas.
- the multilayer TiN film 130 is obtained by forming a Ti film protective TiN film 132 , a main TiN film 134 , and an oxygen diffusion preventing TiN film 136 by the same method as that of the first embodiment.
- the main TiN film 134 can be formed of a single film formed by the single step CVD process. However, it may be formed of a multilayer film formed by the multiple step CVD process.
- the main TiN film 134 is formed of a multilayer film
- the main TiN film is 134 having a desired thickness is formed by repeating, as many times as required, the step of forming a TiN film on the Ti protecting TiN film 132 , by the CVD method to have a thickness of between 10 and 100 ⁇ and the step of NH 3 annealing the TiN film, thus removing the Cl component in the TiN film and densifying the TiN film.
- the multilayer TiN film 130 is described to be comprised of the Ti protecting TiN film 132 , the main TiN film 134 , and the oxygen diffusion preventing TiN film 136 .
- the present invention is not restricted to this.
- the oxygen diffusion preventing TiN film 136 can be omitted in order to simplify the process and to save expenses when the increase of resistivity according to the permeation of oxygen is negligible, thus not deteriorating the device.
- a metal layer 140 is formed by depositing a metal such as tungsten on the resultant in which the multilayer TiN film 130 is formed so as to fill the inside of the contact hole H.
- the upper surface of the interlayer dielectric film 110 is exposed by polishing the resultant in which the metal layer 140 is formed by a chemical mechanical polishing method, and a barrier film comprised of the Ti film 120 and the multilayer TiN film 130 and a metal plug 140 a on the barrier film are formed in the contact hole H.
- the multilayer TiN film formed by a multiple step CVD method is used as a TiN film constructing the barrier film of the Ti/TiN structure in order to form the contact of a semiconductor device, it is possible to prevent the Ti film from being damaged, to prevent the TiN film from being lifted by the multilayer TiN film which does not contain the Cl component, and to remarkably lower resistivity in the TiN film, without performing a subsequent process such as the RTN process after forming the Ti film.
- the multilayer TiN film formed by the multiple step deposition method according to the present invention does not contain the Cl component and is dense, the resistivity in the TiN film is remarkably low. Therefore, when the multilayer TiN film formed by the method according to the present invention is used as the barrier film of a contact, it is possible to reduce the resistance of the contact and to prevent voids from being formed in the contact since the step coverage of the barrier film is excellent.
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Abstract
A method of forming a multilayer titanium nitride film hardly containing any Cl component by a multiple step chemical vapor deposition method, and a method of manufacturing a semiconductor device using the same are provided. In the present invention, a multilayer TiN film is formed by multiple step chemical vapor deposition (CVD) on a semiconductor substrate on which an underlayer is formed. In order to form the multilayer TiN film, an underlayer protective TiN film is formed by forming a first TiN film on the underlayer and NH3 annealing the first TiN film. A main TiN film is formed by forming a second TiN film on the underlayer protective TiN film and NH3 annealing the second TiN film. A source gas used in order to form the first TiN film has a smaller TiCl4 to NH3 gas flow ratio than a source gas for forming the second TiN film. In order to apply the multilayer TiN film to the fabrication of the semiconductor device, an insulating film having a contact hole is formed on a semiconductor substrate. A Ti film is formed on the inner wall of the contact hole. A multilayer TiN film is formed on the Ti film by the multiple step CVD method. A metal plug is formed on the multilayer TiN film.
Description
- 1. Field of the Invention
- The present invention relates to a method of manufacturing a semiconductor device, and more particularly, to a method of forming a titanium nitride film and a method of manufacturing a semiconductor device using the same.
- 2. Description of the Related Art
- An adhesive layer having a Ti/TiN structure is generally employed in order to improve the poor adhesive characteristic of a metal such as tungsten (W) for filling a contact hole, when a metal contact plug required for the metal wiring of a semiconductor device is formed.
- In a conventional technology, a physical vapor deposition (PVD) method such as a sputtering method is used for forming the adhesive layer having the Ti/TiN structure. However, when the Ti/TiN structure is formed by the PVD method, a film having a poor step coverage is obtained. Therefore, in the case of forming a contact having a large aspect ratio, the overhang of the Ti/TiN film is severe at the entrance of the contact hole when the Ti/TiN film is used as the adhesive layer or a barrier layer. Accordingly, a large void is formed in the contact during a subsequent process of depositing a tungsten film. Also, when the Ti/TiN film is too thin on the bottom of the contact due to the poor step coverage of the Ti/TiN film, WF6 gas, used as a source gas during a subsequent process of depositing the tungsten film, and Ti of the Ti/TiN film react, thus forming a nonconductor or vaporizing some part. Accordingly, the TiN film is lifted and peeled off. If so, the Ti/TiN film cannot serve as a barrier with respect to the WF6 gas.
- Therefore, a process of forming a TiN film by a chemical vapor deposition (CVD) method has been recently developed.
- In particular, the TiN film formed by the CVD method using TiCl4 gas as a source gas is generally used as an adhesive layer of a metal film or a barrier film when a metal contact or a capacitor is formed since it is possible to obtain a good step coverage.
- A large amount of chlorine (Cl) is included in the formed TiN film in the method of forming the TiN film by the CVD method using the TiCl4 gas as the source gas. The TiN film containing a large amount of Cl shows a high resistivity. Also, since Cl permeates and damages the Ti film which is an underlayer, a high temperature rapid thermal nitration (RTN) process, or an NH3 plasma process is required on the Ti film in order to prevent the Cl permeation.
- When the high temperature RTN process or the NH3 plasma process is performed with respect to the Ti film, the following problems occur. Firstly, the number of processes increases and a semiconductor manufacturing process becomes complicated since the above process is added. Secondly, additional equipment should be introduced since the above process is added. As a result, the burden of equipment investment increases. Thirdly, shallow junctions have recently started to be realized in semiconductor devices. Therefore, the allowed thickness of the Ti film deposited as the barrier film in the contact hole is restricted. However, a considerable amount of Ti is consumed in the Ti film by the high temperature RTN process or the NH3 plasma process. As a result it is not possible to secure a stable contact resistance since the amount of residing Ti becomes small.
- To solve the above problem(s), it is an objective of the present invention to provide a method of forming a multilayer TiN film so as to lower the amount of Cl in a TiN film introduced when the TiN film is formed by a chemical vapor deposition (CVD) method such that the device does not deteriorate.
- It is another objective of the present invention to provide a method of manufacturing a multilayer TiN film by which it is possible to simplify a process by reducing the number of process steps.
- It is still another objective of the present invention to provide a method for manufacturing a semiconductor device using the TiN film formed by the above method.
- Accordingly, to achieve the first and second objectives, there is provided a method of forming a multilayer TiN film by a chemical vapor deposition (CVD) method on a semiconductor substrate on which an underlayer is formed. In this method, an underlayer protective TiN film is formed on the underlayer. A main TiN film is formed on the underlayer protective TiN film.
- The underlayer is a Ti film. At this time, NH3 gas may be pre-flown on the surface of the Ti film before the step (a).
- The step (a) comprises the steps of (a-1) forming a first TiN film on the underlayer to have a thickness of between 10 and 100 Å using a source gas composed of a mixture of TiCl4 gas and NH3 gas and (a-2) annealing the first TiN film in an NH3 gas atmosphere.
- The step (b) comprises the steps of (b-1) forming a second TiN film on the underlayer protective TiN film using a source gas formed of a mixture of TiCl4 gas and NH3 gas and (b-2) annealing the second TiN film in the NH3 gas atmosphere.
- The gas flow ratio of TiCl4 to NH3 is between 0.02 and 0.1 in the source gas.
- The first and second TiN films are formed under a pressure of between 0.2 and 0.5 Torr and at a temperature of between 530 and 680°C.
- The steps of annealing the first TiN film and the second TiN film are respectively performed at a temperature of between 530 and 680° C.
- The step (c) of forming an oxygen diffusion preventing TiN film on the main TiN film can be further comprised after the step (b).
- The step (c) comprises the steps of (c-1) forming a third TiN film on the main TiN film using a source gas composed of a mixture of TiCl4 gas and NH3 gas, to have a thickness of between 10 and 100 Å and (c-2) annealing the third TiN film in the NH3 gas atmosphere.
- The third TiN film is formed under a pressure of between 0.2 and 0.5 Torr and at a temperature of between 530 and 680° C.
- In order to form the main TiN film, a TiN film is formed on the underlayer protective TiN film to have a thickness of between 10 and 100 Å using a source formed of a mixture of TiCl4 gas and NH3 gas. The TiN film is annealed in an NH3 gas atmosphere. The above steps are repeated until the main TiN film having a desired thickness is obtained.
- Also, to achieve the above objectives, a first TiN film covering the underlayer exposed on a semiconductor substrate is formed by a chemical vapor deposition (CVD) method using a source gas supplied in a first gas flow ratio having a predetermined TiCl4 to NH3 gas flow ratio. The first TiN film is annealed in an NH3 gas atmosphere to form an underlayer protective TiN film. A second TiN film is formed on the underlayer protective TiN film by the CVD method, using a source gas supplied in a second gas flow ratio having a TiCl4 to NH3 gas flow ratio larger than the first gas flow ratio. The second TiN film is annealed in an NH3 gas atmosphere to form a main TiN film.
- The first gas flow ratio and the second gas flow ratio are selected to be between 0.02 and 0.1, respectively. The first gas flow ratio is selected to be between 0.02 and 0.05.
- The step of forming the first TiN film and the step of forming the second TiN film are respectively performed under a pressure of between 0.2 and 0.5 Torr and at a temperature of between 530 and 680°C.
- The steps of annealing the first TiN film and the second TiN film are respectively performed at a temperature of between 530 and 680°C.
- After forming the main TiN film, a third TiN film is formed on the main TiN film using a source gas supplied in a third gas flow ratio having a TiCl4 to NH3 gas flow ratio which is smaller than the second gas flow ratio. The third TiN film is annealed in an NH3 gas atmosphere.
- The third gas flow ratio is selected to be between 0.02 and 0.1.
- Also, to achieve the above objectives, in the present invention, a first TiN film covering the underlayer exposed on a semiconductor substrate by the CVD method, using a source gas supplied in a first gas flow ratio having a predetermined TiCl4 to NH3 gas flow ratio. A second TiN film is formed on the first TiN film by the CVD method, using a source gas supplied in a second gas flow ratio having a TiCl4 to NH3 gas flow ratio which is larger than the first gas flow ratio. The first TiN film and the second TiN film are annealed in a NH3 gas atmosphere.
- To achieve the third objective, in a method of manufacturing a semiconductor substrate according to the present invention, an insulating film having a contact hole is formed on a semiconductor substrate. A Ti film is formed on the inner wall of the contact hole. A multilayer TiN film is formed by repeating a process of forming a TiN film on the Ti film by a CVD method using a source gas composed of a mixture of TiCl4 gas and NH3 gas and annealing the TiN film in an NH3 gas atmosphere at least two times. A metal plug is formed on the multilayer TiN film.
- According to the present invention, it is possible to obtain a densified multilayer TiN film sufficiently removed of the Cl component so that the device is not deteriorated. When the multilayer TiN film according to the present invention is used as a barrier film of a metal contact, it is possible to reduce the resistance of the contact and to omit an additional process such as a high temperature rapid thermal nitration (RTN) process for protecting an underlayer.
- The above objectives and advantages of the present invention will become more apparent by describing in detail a preferred embodiment thereof with reference to the attached drawings in which:
- FIGS. 1A through 1F are cross sectional views for describing a method of forming a multilayer TiN film according to a first embodiment of the present invention;
- FIGS. 2A and 2B are cross sectional views for describing a method of forming a multilayer TiN film according to a second embodiment of the present invention;
- FIGS. 3A through 3F are cross sectional views for describing a method of forming a multilayer TiN film according to a third embodiment of the present invention;
- FIGS. 4A through 4C are cross sectional views for describing a method of forming a multilayer TiN film according to a fourth embodiment of the present invention;
- FIG. 5 is a graph showing the resistivities of a multilayer TiN film formed according to the present invention and TiN films formed by a conventional method; and
- FIGS. 6A through 6E are cross sectional views for describing a method of manufacturing a semiconductor device according to a preferred embodiment of the present invention.
- Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the attached drawings.
- FIGS. 1A through 1F are cross sectional views showing processes of a method of forming a multilayer TiN film by a multiple step chemical vapor deposition (CVD) process according to a first embodiment of the present invention.
- Referring to FIG. 1A, an
underlayer 10 such as a Ti film is formed on a semiconductor substrate (not shown). Theunderlayer 10 may be TaO or Pt. Afirst TiN film 22 is formed on theunderlayer 10 by a chemical vapor deposition (CVD) method using a mixture of TiCl4 gas and NH3 gas as a source gas, to have a thickness of between 10 and 100 Å in the first step of forming a multilayer TiN film by a multiple step deposition. The deposition process is performed at a temperature of between 530 and 680° C. Here, thefirst TiN film 22 is formed on theunderlayer 10 through thermal reduction of the TiCl4 gas with the NH3 gas in the source gas. - At this time, the flow rates of the TiCl4 gas and the NH3 gas, each of which compose the source gas, are controlled so as to obtain a TiCl4 to NH3 gas flow ratio of between 0.02 and 0.1. The reaction pressure during the formation of the
first TiN film 22 is between 0.2 and 0.5 Torr. - Preferably, an NH3 pre-flow step of providing the NH3 gas on the surface of the
underlayer 10 may be performed before forming thefirst TiN film 22. The NH3 pre-flow step is performed for 60 seconds at a temperature of between 530 and 680°C. and under a pressure of 0.3 Torr. - Referring to FIG. 1B, the
first TiN film 22 is annealed in an NH3 gas atmosphere. For this, the NH3 gas is provided on thefirst TiN film 22 at the temperature of between 530 and 680°C. As a result, a Cl component existing on the surface or the grain boundary of thefirst TiN film 22 is completely removed and the place from which Cl is removed is filled with an N component. Accordingly, thefirst TiN film 22 is densified. Therefore, an underlayerprotective TiN film 22 a which contains few Cl component is formed. Also, there are few Cl components in the interface between the underlayerprotective TiN film 22 a and theunderlayer 10. For example, the NH3 gas of 1,000 sccm is supplied for 60 seconds under a pressure of 3 Torr and at the temperature of between 530 and 680° C., for the NH3 annealing. - The underlayer
protective TiN film 22 a obtained after the NH3 annealing is sufficiently removed of the Cl component and the place from which Cl is removed is filled with the N component. Accordingly, the underlayerprotective TiN film 22 a is densified. Therefore, it is difficult for the Cl component to permeate the underlayerprotective TiN film 22 a from the TiCl4 gas when a TiN film is formed using the TiCl4 gas in a subsequent process. Therefore, it is possible to prevent theunderlayer 10 from being damaged by the Cl component. - Referring to FIG. 1C, a
second TiN film 24 is formed on the underlayerprotective TiN film 22 a to a predetermined thickness. The thickness of thesecond TiN film 24 is determined considering the thicknesses of the underlayerprotective TiN film 22 a according to the total thickness of the multilayer TiN film to be formed. The deposition conditions at this time are the same as those of forming thefirst TiN film 22 described with reference to FIG. 1A. - Referring to FIG. 1D, a
main TiN film 24 a removed of the Cl component contained in thesecond TiN film 24 and having a densified structure is formed by annealing thesecond TiN film 24 in the NH3 gas atmosphere by the same method as that described with reference to FIG. 1B. - It is possible to prevent the Cl component from permeating into the underlayers of the
main TiN film 24 a during the subsequent process of depositing a TiN film on themain TiN film 24 a using the TiCl4 gas since themain TiN film 24 a removed of the Cl component has a densified structure. - Referring to FIG. 1E, a
third TiN film 26 is formed on themain TiN film 24 a by the same method as that of forming thefirst TiN film 22 described with reference to FIG. 1A, to have the thickness of between 10 and 100 Å. - Referring to FIG. 1F, the Cl component is removed from the
third TiN film 26 by annealing thethird TiN film 26 in a NH3 gas atmosphere, and a densified oxygen diffusion preventingTiN film 26 a is formed by the same method as that described with reference to FIG. 1B. - The
multilayer TiN film 20 formed of the underlayerprotective TiN film 22 a, themain TiN film 24 a, and the oxygen diffusion preventingTiN film 26 a is formed on theunderlayer 10 by a multiple step CVD method. - As mentioned above, when the semiconductor substrate on which the
multilayer TiN film 20 is formed is exposed to the air for a subsequent process after forming themultilayer TiN film 20 by the CVD method, it is possible to prevent oxygen in the air from permeating themultilayer TiN film 20 by the oxygen diffusion preventingTiN film 26 a formed on the surface of themultilayer TiN film 20. Therefore, it is possible to prevent the resistivity from increasing due to the permeation of oxygen into themultilayer TiN film 20 including the oxygen diffusion preventingTiN film 26 a formed by the multiple step CVD method. - In the above embodiment, the multilayer TiN film is formed by a three step deposition process. However, the present invention is not restricted to this.
- For example, if the increase of the resistivity according to the permeation of oxygen is negligible, thus not deteriorating the device, the process of forming the oxygen diffusion preventing
TiN film 26 a can be omitted in order to simplify processes and to save expenses. - Also, it is possible to form a multilayer TiN film comprised of three or more layers by a multiple step CVD method as follows, instead of forming the multilayer TiN film by the three step deposition process as mentioned in the above embodiment.
- FIGS. 2A and 2B are cross sectional views showing processes of the method of forming the multilayer TiN film by the multiple step CVD process according to a second embodiment of the present invention.
- Referring to FIG. 2A, after forming an
underlayer 50 on a semiconductor substrate (not shown) by the same method as that described with reference to FIG. 1A, an underlayerprotective TiN film 62 a is formed on theunderlayer 50 to have a thickness of between 10 and 100 Å. Asecond TiN film 64 is formed on the underlayerprotective TiN film 62 a by the same method as the method of forming thefirst TiN film 22 described with reference to FIG. 1A, to have a thickness of between 10 and 100 Å. - Referring to FIG. 2B, the Cl component contained in the
second TiN film 64 is completely removed by annealing thesecond TiN film 64 in an NH3 gas atmosphere by the same method as that describe with reference to FIG. 1B. - Accordingly, a densified first
main TiN film 64 a is formed. - Then, a plurality of main TiN films are formed to have a desired thickness by sequentially forming a second main TiN film (not shown), a third main TiN film (not shown), . . . on the first
main TiN film 64 a by repeating the step of forming the TiN film of FIG. 2A and the NH3 annealing step of FIG. 2B as many times as required with respect to the resultant material in which the firstmain TiN film 64 a is formed. - The method according to the second embodiment, described with reference to FIGS. 2A and 2B, may require a longer process time than the method according to the first embodiment, described in FIGS.1A through IF. However, the TiN film obtained by the method according to the second embodiment contains less Cl component and is more dense.
- FIGS. 3A through 3F are cross sectional views showing processes of the method of forming a multilayer TiN film by the multiple step CVD process according to a third embodiment of the present invention.
- Referring to FIG. 3A, an
underlayer 70 such as a Ti film is formed on the semiconductor substrate (not shown). Afirst TiN film 72 is formed on theunderlayer 70, to a thickness of between 10 and 100 Å, by the CVD method under a pressure of between 0.2 and 0.5 Torr and at a temperature of between 530 and 680°C., using a source gas composed of a mixture of the TiCl4 gas and the NH3 gas supplied in a first gas flow ratio of TiCl4 to NH3 selected from a value between 0.02 and 0.1 and having a relatively low Cl content. Preferably, the first gas flow ratio is selected from a value between 0.02 and 0.05, more preferably, from a value between 0.03 and 0.04. - Referring to FIG. 3B, the
first TiN film 72 is annealed in an NH3 atmosphere at a temperature of between 530 and 680°C. As a result, the Cl component existing on the surface of thefirst TiN film 72 or the grain boundary in thefirst TiN film 72 is completely removed and the place from which Cl is removed is filled with an N component. Accordingly, thefirst TiN film 72 is densified. Therefore, an underlayerprotective TiN film 72 a which contains a small amount of the Cl component is formed on theunderlayer 70. Also, there is a small amount of the Cl component in the interface between the underlayerprotective TiN film 72 a and theunderlayer 70. For example, the NH3 gas of 1,000 sccm is supplied for 60 seconds under the pressure of 3 Torr and at the temperature of between 530 and 680° C., for the NH3 annealing. - Since the underlayer
protective TiN film 72 a is obtained by depositing thefirst TiN film 72 using a source gas containing a relatively low content of Cl and by sufficiently removing the Cl component residing in theTiN film 72, it is possible to contact the underlayerprotective TiN film 72 a, completely removed of the Cl component, to theunderlayer 70. Also, in the underlayerprotective TiN film 72 a, the place from which Cl is removed is filled with an N component by the NH3 annealing. Accordingly the underlayerprotective TiN film 72 a is densified. Therefore, it is difficult for the Cl component to permeate the underlayerprotective TiN film 72 a from the TiCl4 gas when a TiN film is formed, using the TiCl4 gas in a subsequent process, on the underlayerprotective TiN film 72 a. Therefore, it is possible to prevent theunderlayer 70 from being damaged by the Cl component. - Referring to FIG. 3C, a
second TiN film 74 is formed on the underlayerprotective TiN film 72 a to have a predetermined thickness, by the CVD method, using a source gas supplied in a second gas flow ratio of TiCl4 to NH3 selected from a value between 0.02 and 0.1 and larger than the first gas flow ratio, so as to have a larger content of Cl than in the source gas supplied in the first gas flow ratio. The thickness of thesecond TiN film 74 is determined considering the thicknesses of the underlayerprotective TiN film 72 a according to the total thickness of the multilayer TiN film to be formed. The deposition temperature and the pressure condition at this time are the same as those of forming thefirst TiN film 72 described with reference to FIG. 3A. - Referring to FIG. 3D, the
second TiN film 74 is annealed in the NH3 atmosphere and the Cl component contained in thesecond TiN film 74 is removed by the same method as that described with reference to FIG. 3B. Accordingly, a densifiedmain TiN film 74 a is formed. - Referring to FIG. 3E, a
third TiN film 76 is formed on themain TiN film 74 a to have a thickness of between 10 and 100 Å by the same method as the method of forming thefirst TiN film 72 described with reference to FIG. 3A. A source gas supplied in a third flow ratio of TiCl4 to NH3 selected from a value between 0.02 and 0.1 and smaller than the second gas flow ratio so as to contain a smaller content of Cl than in the source gas supplied in the second gas flow ratio. - Referring to FIG. 3F, a densified oxygen diffusion preventing
TiN film 76 a is formed by annealing thethird TiN film 76 in the NH3 gas atmosphere and removing the Cl component from thethird TiN film 76 by the same method as that described with reference to FIG. 3B. - A multilayer TiN film78 comprised of the underlayer
protective TiN film 72 a, themain TiN film 74 a, and the oxygen diffusion preventingTiN film 76 a is formed on theunderlayer 70 by the multiple step CVD method. - The step of forming the oxygen diffusion preventing
TiN film 76 a described with reference to FIGS. 3E and 3F can be omitted if necessary. - It is possible to prevent oxygen in the air from permeating the multilayer TiN film78, since the multilayer TiN film 78 has a densified structure, when the semiconductor substrate on which the multilayer TiN film 78 is formed is exposed to air in order to perform a subsequent process. Therefore, it is possible to prevent the resistivity from increasing due to the permeation of oxygen in the multilayer TiN film 78 formed by the multiple step CVD method.
- FIGS. 4A through 4C are cross sectional views showing processes of the method of forming a multilayer TiN film by the multiple step CVD method according to a fourth embodiment of the present invention.
- Referring to FIG. 4A, an
underlayer 80, for example, a Ti film is formed on a semiconductor substrate (not shown). Afirst TiN film 82 is formed on theunderlayer 80 to have a thickness of between 10 and 100 Å by the CVD method under a pressure of between 0.2 and 0.5 Torr and at a temperature of between 530 and 680° C., using a source gas composed of a mixture of the TiCl4 gas and the NH3 gas supplied in a first gas flow ratio of TiCl4 to NH3 selected from a value between 0.02 and 0.1 and having a relatively low Cl component. Preferably, the first gas flow ratio is selected between 0.02 and 0.05, more preferably, from a value between 0.03 and 0.04. - Referring to4B, a
second TiN film 84 is formed on thefirst TiN film 82 by the CVD method, to have a predetermined thickness, using a source gas supplied in a second gas flow ratio of TiCl4 to NH3 selected between 0.02 and 0.1 and larger than the first gas flow ratio so as to have a larger content of Cl than in the source gas supplied in the first gas flow ratio. The thickness of thesecond TiN film 84 is determined considering the thicknesses of thefirst TiN film 82 according to the total thickness of the multilayer TiN film to be formed. The deposition temperature and the pressure condition at this time are the same as those of forming thefirst TiN film 82 described with reference to FIG. 4A. - Referring to4C, the resultant obtained by sequentially stacking the
first TiN film 82 and thesecond TiN film 84 is annealed in a NH3 gas atmosphere at a temperature of 530 to 680°C. For the NH3 annealing, 1000 sccm of the NH3 gas is supplied for 60 seconds under a pressure of 3 Torr and at the temperature of between 530 and 680° C. As a result, the Cl component existing on the surfaces or the grain boundaries of the first andsecond TiN films multilayer TiN film 88 comprised of the densified underlayerprotective TiN film 82 a andmain TiN film 84 a. - In the present embodiment, the step of NH3 annealing the
first TiN film 82 was omitted before forming thesecond TiN film 84. However, the structure of themultilayer TiN film 88 in which the surface and inside thereof is completely removed of the Cl component by the above method is densified. Therefore, although themultilayer TiN film 88 is exposed to air, it is possible to prevent oxygen from permeating themultilayer TiN film 88. Therefore, it is possible to prevent the resistivity from increasing due to the permeation of oxygen into themultilayer TiN film 88. - FIG. 5 is a graph showing the result of comparing the resistivity of the multilayer TiN film formed by the multiple step CVD method according to the present invention with the resistivity of the TiN film formed by the conventional method.
- In FIG. 5, (a) shows a case of a multilayer TiN film formed by a multilayer deposition method according to the present invention. To be specific, a multilayer TiN film having a thickness of 500 Å is formed by successively repeating the process of NH3 annealing the TiN film obtained after forming the TiN film having a thickness of 50 Å by the
CVD method 10 times. The characteristics denoted by (b) and (c) show cases in which the TiN film having the thickness of 500 Å is deposited in one step by the CVD method and the NH3 gas is supplied to the TiN film. To be specific, (b) shows a case in which 1,000 sccm of NH3 gas is supplied at a temperature of 680° C. and under a relatively high pressure of 3 Torr. (c) shows a case in which 400 sccm of the NH3 gas is supplied at a temperature of 680°C. and under a relatively low pressure of 0.3 Torr. The characteristic denoted by (d) shows a case in which a TiN film having a thickness of 500 Å is deposited in one step by the CVD method, in which the step of providing the NH3 gas is omitted. - It is noted from the result of FIG. 5 that the multilayer TiN film formed by the multiple step deposition method according to the present invention has much lower resistivity than the conventional methods.
- As a result, it is noted that the multilayer TiN film formed by the multiple step CVD method according to the present invention contains an extremely small content of Cl and hardly undergoes increment of the resistivity due to substitution of oxygen when the multilayer TiN film is exposed to air.
- Also, the Ti film is not damaged at all by the Cl component during the formation of the TiN film and the lifting of the TiN film is prevented by forming the multilayer TiN film on the Ti film by the multiple step CVD method according to the present invention without performing the RTN process or the NH3 plasma process after forming the Ti film. As a result, it is possible to form a TiN film having low resistivity by forming the TiN film to have a small amount of Cl by the multiple step CVD method.
- Therefore, it is possible to reduce contact resistance when the multilayer TiN film formed by the above method is employed as a barrier film in a metal contact.
- FIGS. 6A through 6E are cross sectional views showing processes of a method of manufacturing a semiconductor device according to a preferred embodiment of the present invention.
- Referring to FIG. 6A, an
interlayer dielectric film 110 having a contact hole for exposing a part of a conductive layer (not shown), which is formed on asemiconductor substrate 100. - Referring to FIG. 6B, a
Ti film 120 is formed on the resultant in which the contact hole H is formed by a sputtering method or the CVD method to have a thickness of about between 300 and 900 Å. - Referring to FIG. 6C, a
multilayer TiN film 130 is formed on theTi film 120 using a source gas comprised of TiCl4 gas and NH3 gas. - The
multilayer TiN film 130 is obtained by forming a Ti filmprotective TiN film 132, amain TiN film 134, and an oxygen diffusion preventingTiN film 136 by the same method as that of the first embodiment. Themain TiN film 134 can be formed of a single film formed by the single step CVD process. However, it may be formed of a multilayer film formed by the multiple step CVD process. - When the
main TiN film 134 is formed of a multilayer film, the main TiN film is 134 having a desired thickness is formed by repeating, as many times as required, the step of forming a TiN film on the Ti protectingTiN film 132, by the CVD method to have a thickness of between 10 and 100 Å and the step of NH3 annealing the TiN film, thus removing the Cl component in the TiN film and densifying the TiN film. - In the present embodiment, the
multilayer TiN film 130 is described to be comprised of the Ti protectingTiN film 132, themain TiN film 134, and the oxygen diffusion preventingTiN film 136. However, the present invention is not restricted to this. - For example, the oxygen diffusion preventing
TiN film 136 can be omitted in order to simplify the process and to save expenses when the increase of resistivity according to the permeation of oxygen is negligible, thus not deteriorating the device. - Referring to FIG. 6D, a
metal layer 140 is formed by depositing a metal such as tungsten on the resultant in which themultilayer TiN film 130 is formed so as to fill the inside of the contact hole H. - Referring to FIG. 6E, the upper surface of the
interlayer dielectric film 110 is exposed by polishing the resultant in which themetal layer 140 is formed by a chemical mechanical polishing method, and a barrier film comprised of theTi film 120 and themultilayer TiN film 130 and ametal plug 140 a on the barrier film are formed in the contact hole H. - As mentioned above, when the multilayer TiN film formed by a multiple step CVD method is used as a TiN film constructing the barrier film of the Ti/TiN structure in order to form the contact of a semiconductor device, it is possible to prevent the Ti film from being damaged, to prevent the TiN film from being lifted by the multilayer TiN film which does not contain the Cl component, and to remarkably lower resistivity in the TiN film, without performing a subsequent process such as the RTN process after forming the Ti film.
- In the method for manufacturing a semiconductor device according to the present embodiment, only the case in which the method of forming the multilayer TiN film according to the first embodiment is described. However, the present invention is not restricted to this. The multilayer TiN film formed by all methods provided in the detailed description of the present invention, and methods which can be varied within the scope of the present invention by anyone skilled in the art, can be applied to the process of forming the contact of the semiconductor device.
- As mentioned above, when the multilayer TiN film is formed by the multiple step CVD method according to the present invention, it is possible to completely remove the Cl component in the TiN film and to make the TiN film dense. Therefore, it is possible to prevent the Cl component of the source gas TiCl4 from permeating into the Ti film which is the underlayer of the TiN film, during the process of depositing the TiN film on the Ti film. Accordingly, it is possible to prevent the underlayer from being damaged by the Cl component and to prevent the TiN film formed on the underlayer from being lifted.
- Also, since the multilayer TiN film formed by the multiple step deposition method according to the present invention does not contain the Cl component and is dense, the resistivity in the TiN film is remarkably low. Therefore, when the multilayer TiN film formed by the method according to the present invention is used as the barrier film of a contact, it is possible to reduce the resistance of the contact and to prevent voids from being formed in the contact since the step coverage of the barrier film is excellent.
- The present invention is not restricted to the above embodiments, and it is clearly understood that many variations are possible within the scope and spirit of the present invention by anyone skilled in the art.
Claims (36)
1. A method of forming a multilayer TiN film by a chemical vapor deposition (CVD) method on a semiconductor substrate on which an underlayer is formed, comprising the steps of:
(a) forming an underlayer protective TiN film on the underlayer; and
(b) forming a main TiN film on the underlayer protective TiN film.
2. The method of , wherein the underlayer is a Ti film.
claim 1
3. The method of , wherein NH3 gas is pre-flown on the surface of the Ti film before the step (a).
claim 2
4. The method of , wherein the step (a) comprises the steps of;
claim 1
(a-1) forming a first TiN film on the underlayer to have a thickness of between 10 and 100 Å using a source gas composed of a mixture of TiCl4 gas and NH3 gas; and
(a-2) annealing the first TiN film in an NH3 gas atmosphere, and wherein the step (b) comprises the steps of:
(b-1) forming a second TiN film on the underlayer protective TiN film using a source gas formed of a mixture of TiCl4 gas and NH3 gas; and
(b-2) annealing the second TiN film in the NH3 gas atmosphere.
5. The method of , wherein the gas flow ratio of TiCl4 to NH3 is between 0.02 and 0.1 in the source gas.
claim 4
6. The method of , wherein the first and second TiN films are formed under a pressure of between 0.2 and 0.5 Torr and at a temperature of between 530 and 680°C.
claim 4
7. The method of , wherein the steps of annealing the first TiN film and the second TiN film are respectively performed at a temperature of between 530 and 680°C.
claim 4
8. The method of , further comprising the step (c) of forming an oxygen diffusion preventing TiN film on the main TiN film after the step (b).
claim 1
9. The method of , wherein the step (c) comprises the steps of:
claim 8
(c-1) forming a third TiN film on the main TiN film using a source gas composed of a mixture of TiCl4 gas and NH3 gas, to have a thickness of between 10 and 100 Å; and
(c-2) annealing the third TiN film in the NH3 gas atmosphere.
10. The method of , wherein the gas flow ratio of TiCl4 to NH3 is between 0.02 and 0.1 in the source gas and the third TiN film is formed under a pressure of between 0.2 and 0.5 Torr and at a temperature of between 530 and 680°C.
claim 9
11. The method of , wherein the step (b) comprises the steps of:
claim 1
(b-1) forming a TiN film on the underlayer protective TiN film to have a thickness of between 10 and 100 Å using a source gas formed of a mixture of TiCl4 gas and NH3 gas;
(b-2) annealing the TiN film in an NH3 gas atmosphere; and
(b-3) repeating the steps (b-1) and (b-2) until the main TiN film having a desired thickness is obtained.
12. The method of , wherein the gas flow ratio of TiCl4 to NH3 is between 0.02 and 0.1 in the source gas and the third TiN film is formed under a pressure of between 0.2 and 0.5 Torr and at a temperature of between 530 and 680°C.
claim 11
13. A method of forming a multilayer TiN film, comprising the steps of:
(a) forming a first TiN film covering an underlayer exposed on a semiconductor substrate, by a chemical vapor deposition (CVD) method using a source gas supplied in a first gas flow ratio having a predetermined TiCl4 to NH3 gas flow ratio;
(b) annealing the first TiN film in an NH3 gas atmosphere to form an underlayer protective TiN film;
(c) forming a second TiN film on the underlayer protective TiN film by the CVD method, using a source gas supplied in a second gas flow ratio having a TiCl4 to NH3 gas flow ratio larger than the first gas flow ratio; and
(d) annealing the second TiN film in an NH3 gas atmosphere to form a main TiN film.
14. The method of , wherein the first gas flow ratio and the second gas flow ratio are selected to be between 0.02 and 0.1, respectively.
claim 13
15. The method of , wherein the first gas flow ratio is selected to be between 0.02 and 0.05.
claim 14
16. The method of , wherein the step of forming the first TiN film and the step of forming the second TiN film are respectively performed under a pressure of between 0.2 and 0.5 Torr and at a temperature of between 530 and 680° C.
claim 13
17. The method of , wherein the steps of annealing the first TiN film and the second TiN film are respectively performed at a temperature of between 530 and 680°C.
claim 13
18. The method of , wherein the first TiN film has a thickness of between 10 and 100 Å.
claim 13
19. The method of , wherein the underlayer is a Ti film.
claim 13
20. The method of , after the step (d), further comprising the steps of:
claim 13
(e) forming a third TiN film on the main TiN film using a source gas supplied in a third gas flow ratio having a TiCl4 to NH3 gas flow ratio which is smaller than the second gas flow ratio; and
(f) annealing the third TiN film in an NH3 gas atmosphere.
21. The method of , wherein the third gas flow ratio is selected to be between 0.02 and 0.1.
claim 20
22. The method of , wherein the third TiN film has a thickness of between 10 and 100 Å.
claim 20
23. The method of , wherein the step of forming the third TiN film is performed under a pressure of between 0.2 and 0.5 Torr and at a temperature of between 530 and 680°C.
claim 20
24. The method of , wherein the step of annealing the third TiN film is performed at a temperature of between 530 and 680°C.
claim 20
25. A method of forming a multilayer TiN film, comprising the steps of:
(a) forming a first TiN film covering an underlayer exposed on a semiconductor substrate by the CVD method, using a source gas supplied in a first gas flow ratio having a predetermined TiCl4 to NH3 gas flow ratio;
(b) forming a second TiN film on the first TiN film by the CVD method, using a source gas supplied in a second gas flow ratio having a TiCl4 to NH3 gas flow ratio which is larger than the first gas flow ratio; and
a (c) annealing the first TiN film and the second TiN film in a NH3 gas atmosphere.
26. The method of , wherein the underlayer is a Ti film.
claim 25
27. The method of , wherein the first gas flow ratio and the second gas flow ratio are selected to be between 0.02 and 0.1, respectively.
claim 25
28. The method of , wherein the first gas flow ratio is selected to be between 0.02 and 0.05.
claim 25
29. The method of , wherein the step of forming the first TiN film and the step of forming the second TiN film are respectively performed under a pressure of between 0.2 and 0.5 Torr and at a temperature of between 530 and 680°C.
claim 25
30. The method of , wherein the annealing step is performed at a temperature of between 530 and 680°C.
claim 25
31. The method of , wherein the first TiN film has a thickness of between 10 and 100 Å.
claim 25
32. A method of manufacturing a semiconductor substrate, comprising the steps of:
(a) forming an insulating film having a contact hole on a semiconductor substrate;
(b) forming a Ti film on the inner wall of the contact hole;
(c) forming a multilayer TiN film by repeating a process of forming a TiN film on the Ti film by a CVD method using a source gas composed of a mixture of TiCl4 gas and NH3 gas and annealing the TiN film in an NH3 gas atmosphere at least two times; and
(d) forming a metal plug on the multilayer TiN film.
33. The method of , wherein, in the step (c), the step of forming the multilayer TiN film comprises the steps of:
claim 32
forming a Ti protecting TiN film using a source gas supplied in a first gas flow ratio having a predetermined TiCl4 to NH3 gas flow ratio; and
forming a main TiN film using a source gas supplied in a second gas flow ratio having a TiCl4 to NH3 gas flow ratio which is larger than the first gas flow ratio.
34. The method of , wherein the step of forming the Ti protecting TiN film comprises the steps of:
claim 33
forming a first TiN film on the Ti film, to have a thickness of between 10 and 100 Å, using a source gas supplied in the first gas flow ratio selected to be between 0.02 and 0.05; and
annealing the first TiN film in an NH3 gas atmosphere, and the step of forming the main TiN film comprises the steps of:
forming a second TiN film on the Ti protecting TiN film using a source gas supplied in the second gas flow ratio selected to be between 0.02 and 0.1; and
annealing the second TiN film in an NH3 gas atmosphere.
35. The method of , wherein the step of forming the multilayer TiN film further comprises the step of forming an oxygen diffusion preventing TiN film on the main TiN film.
claim 33
36. The method of , wherein the step of forming the oxygen diffusion preventing TiN film comprises the steps of:
claim 35
forming a third TiN film on the main Ti film using the source gas, to have a thickness of between 10 and 100 Å; and
annealing the third TiN film in an NH3 gas atmosphere.
Priority Applications (1)
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US09/767,523 US6291342B2 (en) | 1998-07-22 | 2001-01-23 | Methods of forming titanium nitride composite layers using composite gases having increasing TiCl4 to NH3 ratios |
Applications Claiming Priority (6)
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KR98-29527 | 1998-07-22 | ||
KR19980029527 | 1998-07-22 | ||
KR1019990009184A KR100331545B1 (en) | 1998-07-22 | 1999-03-18 | Method of forming multi-layered titanium nitride film by multi-step chemical vapor deposition process and method of manufacturing semiconductor device using the same |
KR99-9184 | 1999-03-18 | ||
US09/356,928 US6207557B1 (en) | 1998-07-22 | 1999-07-19 | Method of forming multilayer titanium nitride film by multiple step chemical vapor deposition process and method of manufacturing semiconductor device using the same |
US09/767,523 US6291342B2 (en) | 1998-07-22 | 2001-01-23 | Methods of forming titanium nitride composite layers using composite gases having increasing TiCl4 to NH3 ratios |
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US09/356,928 Continuation US6207557B1 (en) | 1998-07-22 | 1999-07-19 | Method of forming multilayer titanium nitride film by multiple step chemical vapor deposition process and method of manufacturing semiconductor device using the same |
US09/356,928 Division US6207557B1 (en) | 1998-07-22 | 1999-07-19 | Method of forming multilayer titanium nitride film by multiple step chemical vapor deposition process and method of manufacturing semiconductor device using the same |
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US20010002334A1 true US20010002334A1 (en) | 2001-05-31 |
US6291342B2 US6291342B2 (en) | 2001-09-18 |
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US09/356,928 Expired - Lifetime US6207557B1 (en) | 1998-07-22 | 1999-07-19 | Method of forming multilayer titanium nitride film by multiple step chemical vapor deposition process and method of manufacturing semiconductor device using the same |
US09/767,523 Expired - Lifetime US6291342B2 (en) | 1998-07-22 | 2001-01-23 | Methods of forming titanium nitride composite layers using composite gases having increasing TiCl4 to NH3 ratios |
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Also Published As
Publication number | Publication date |
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KR100331545B1 (en) | 2002-04-06 |
US6291342B2 (en) | 2001-09-18 |
KR20000011213A (en) | 2000-02-25 |
US6207557B1 (en) | 2001-03-27 |
JP2000068232A (en) | 2000-03-03 |
JP3732048B2 (en) | 2006-01-05 |
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