WO2005015622A1 - 成膜方法 - Google Patents
成膜方法 Download PDFInfo
- Publication number
- WO2005015622A1 WO2005015622A1 PCT/JP2004/007554 JP2004007554W WO2005015622A1 WO 2005015622 A1 WO2005015622 A1 WO 2005015622A1 JP 2004007554 W JP2004007554 W JP 2004007554W WO 2005015622 A1 WO2005015622 A1 WO 2005015622A1
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- WO
- WIPO (PCT)
- Prior art keywords
- film
- plasma
- metal
- gas
- forming
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 79
- 239000010936 titanium Substances 0.000 claims abstract description 82
- 229910021341 titanium silicide Inorganic materials 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims description 121
- 239000002184 metal Substances 0.000 claims description 121
- 229910021332 silicide Inorganic materials 0.000 claims description 50
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims description 50
- 230000008569 process Effects 0.000 claims description 28
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 16
- 239000010703 silicon Substances 0.000 claims description 15
- 229910004339 Ti-Si Inorganic materials 0.000 claims description 11
- 229910010978 Ti—Si Inorganic materials 0.000 claims description 11
- 238000009832 plasma treatment Methods 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 238000009616 inductively coupled plasma Methods 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- -1 o1y-Si Substances 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 218
- 210000002381 plasma Anatomy 0.000 description 103
- 239000013078 crystal Substances 0.000 description 53
- 229910008484 TiSi Inorganic materials 0.000 description 35
- 230000015572 biosynthetic process Effects 0.000 description 23
- 239000010410 layer Substances 0.000 description 22
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 230000001965 increasing effect Effects 0.000 description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 238000005229 chemical vapour deposition Methods 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 7
- 229910010066 TiC14 Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 229910008479 TiSi2 Inorganic materials 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- DFJQEGUNXWZVAH-UHFFFAOYSA-N bis($l^{2}-silanylidene)titanium Chemical compound [Si]=[Ti]=[Si] DFJQEGUNXWZVAH-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 241001122767 Theaceae Species 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000005121 nitriding Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 4
- 241001191378 Moho Species 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- LLQHSBBZNDXTIV-UHFFFAOYSA-N 6-[5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-4,5-dihydro-1,2-oxazol-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC1CC(=NO1)C1=CC2=C(NC(O2)=O)C=C1 LLQHSBBZNDXTIV-UHFFFAOYSA-N 0.000 description 1
- WKEMJKQOLOHJLZ-UHFFFAOYSA-N Almogran Chemical compound C1=C2C(CCN(C)C)=CNC2=CC=C1CS(=O)(=O)N1CCCC1 WKEMJKQOLOHJLZ-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 241000282994 Cervidae Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000287463 Phalacrocorax Species 0.000 description 1
- 241000287462 Phalacrocorax carbo Species 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229960002133 almotriptan Drugs 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
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 230000000763 evoking effect Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- H01L21/28518—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 the conductive layers comprising silicides
-
- 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
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/08—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal halides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/42—Silicides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
Definitions
- the present invention relates to a film forming method for forming a metal silicide film by plasma processing on an object to be processed, for example, an Si-containing portion such as a surface of a Si substrate or a metal silicide layer.
- A1 Aligninum
- W Diamond
- alloys based on these are generally used.
- a Ti film is formed inside a contact hole or a via hole prior to embedding them. Are formed, and a TiN film is formed as a barrier layer.
- Such a metal film is formed on a base prior to the film forming process in order to obtain a good contact resistance.
- ⁇ -A treatment is performed to remove the natural oxide film.
- Such a natural oxide film is generally removed by dilute hydrofluoric acid.
- hydrogen gas and argon as described in Patent Document 2 below are used as a device for removing a natural oxide film.
- invitation using gas i ⁇ 3 ⁇ 4r? [5] A type that forms palladium plasma has been proposed.
- the Si 2 crystal becomes more non-uniform.
- the TiSi 2 crystal in the non-uniform state is relatively sparse, the specific resistance is high and the contact between the TiSi 2 film and the base is not uniform. And Therefore, the contact resistance increases.
- the Si diffusion layer becomes shallower with the miniaturization of the device, the Ti Si at the bottom of the contact hole becomes smaller.
- the thickness of the two films has become thinner, and the demand for the best Moho in the field between the Si diffusion layer and the TiSi 2 film has been required.
- Patent Document 1 Japanese Patent Application Laid-Open No.
- Patent Document 2 Japanese Patent Application Laid-Open No. Hei 4-336642 (FIG. 2 and its description).
- the present invention has been made in view of such circumstances, and the invention When forming a metal silicide film such as a titanium silicide film on the si-containing part of the body, the metal silicide has a lower resistance than before without increasing the film formation temperature. It is an object to provide a film formation method capable of forming a film. It is another object of the present invention to provide a film formation method capable of forming a metal silicide film having a uniform diameter, particularly a titanium silicide film.
- a first aspect of the present invention provides a film forming method for forming a metal silicide film on a Si-containing portion of an object to be processed, the method comprising: Treating the portion with plasma using high frequency, and supplying a metal-containing source gas containing the metal in the metal silicide to be formed on the Si-containing portion treated with the plasma. And forming a metal film made of the metal by plasma and forming a metal silicide film by a reaction between the metal film and Si in the Si-containing portion.
- a film forming method characterized in that the treatment of the Si-containing portion with plasma is performed while applying a DC bias voltage (V dc) having an absolute value of 20 OV or more to the object to be processed. I do.
- V dc DC bias voltage
- a DC bias voltage (V dc) having an absolute value as high as 2 OOV or more is applied to the object to be processed.
- ions in the plasma act more strongly on the surface of the object than in the conventional case of removing a native oxide film.
- the underlying Si-containing layer is converted into a monoreflection as a whole, but on the other hand, forms a water-soluble state (in the case of Si, the surface state has more unbonded Si than in the Si single crystal).
- the temperature of the object to be processed is lower than before.
- the Si-containing portion may be a Si plate or an oly-Si metal substrate, and may be formed on a single-crystal Si substrate (Si wafer).
- Ru can and rows cormorant this by using an inductively coupled bra Zuma.
- it can be performed using parallel plate type plasma or micro wave plasma.
- the step of forming the metal silicide film is performed by supplying a metal-containing raw material gas and using plasma.
- the reduction of the metal-containing source gas by supplying the reducing gas may be repeated a plurality of times, so that the film can be formed at a lower temperature.
- the above-mentioned metals include NiC N PtMo ⁇ aHfZr in addition to Ti described above. These metals are usually It can form a metal silicide crystal structure with low resistance at high temperatures.
- a step of forming a metal silicide film on the Si-containing portion of the object from which the natural oxide film has been removed, wherein the step of forming the metal silicide film comprises: First, a metal-containing source gas containing a metal in the metal silicide to be deposited without generating plasma is supplied at a predetermined time to generate a metal-silicon bond, and then the metal-containing source gas is discharged. Plasma is generated while being supplied to form a metal film made of the metal, and a metal silicide film is formed by a reaction between the metal film and the Si-containing portion at that time.
- a film formation method for forming a metal silicide film on a Si-containing portion of an object to be processed, wherein the natural oxide film on the Si-containing portion is removed.
- a film forming method for forming a titanium side and a film on a Si-containing portion of an object to be processed is provided.
- the Ti-containing source gas is supplied for a predetermined period of time without generating plasma to generate a Ti—Si bond, and then the Ti-containing source gas is supplied.
- a film forming method characterized in that a Ti film is formed by generating plasma, and a titanium silicide film is formed by a reaction between the Ti film and a Si-containing portion at that time.
- the formation of TiSi 2 crystals having a non-uniform grain size is conventionally caused by the simultaneous supply of the ⁇ i -containing raw material gas and the formation of plasma.
- sufficient T i containing source gas into the processing surface plasma is formed in the ftu supplied, co Ntaku T at T i one S i bonds is small state on S i containing layer surface is collected by a bottom i S i 2 It was found that this was to start crystal growth. Specifically, when the T 1 -S i bond is small, its existence is non-uniform and it is highly reactive with the active S i surface.
- T i C 1 X The reaction of T i C 1 X occurs rapidly.
- An inhomogeneous crystal is formed on the bottom surface of the contact hole depending on the number of T i — S i bonds. That is, relatively T i one S i bonds often co down relatively dense grain size of uniform T i S i 2 crystals in data click Tohoru portion is formed relatively T i one S i bonds A relatively sparse large TiSi 2 crystal is formed in the contact hole where there is little.
- T isi reaction system and this varying crystallinity of T i S i 2 (orientation) is affected by the initial reaction of T isi 2 are known.
- the metal-containing source gas when forming the metal silicide film, is supplied for a predetermined time without first generating plasma, and the third aspect is the second aspect.
- Titanium In this method, Ti-containing source gas is supplied for a predetermined time without first generating plasma to generate Ti-Si bonds. As a result, a bond between the metal and the silicon is uniformly formed on the Si-containing portion before the metal silicide starts crystal growth. If Chita Nshiri rhino de is, T i S i 2 crystals is sufficient T i one S i coupled before starting the growth occurring on S i containing moiety.
- a metal-silicon bond such as a Ti—Si bond causes uniform crystal growth by the subsequent plasma generation, and the crystal grains and crystallinity (orientation) become uniform.
- the metal silicide (titanium silicide) itself has a low resistance, and the contact between the metal silicide (titanium silicide) and the base becomes uniform, thereby reducing the contact resistance. Can be lowered.
- the metal-containing source gas is first supplied for a predetermined time without generating plasma to generate a metal-silicon bond. It is preferable to generate As a result, a metal silicide film having a thinner and lower resistance than before can be obtained without raising the film forming temperature, and a metal silicide film having a uniform crystal grain size can be obtained. The effect of being able to obtain is added.
- the time for supplying the Ti-containing source gas without first generating plasma be 2 seconds or more, and more preferably 5 seconds or more.
- the Si-containing portion include a Si substrate, po1y-Si or a metal silicide, and contact diffusion formed on a single-crystal Si (Si wafer). Layers can be mentioned as typical examples.
- Single crystal silicon is Including B, P, As doped.
- the step of removing the ⁇ white natural oxide film, a high frequency can and this performing Ri by the Burazuma with, the third aspect of the configuration is effective when Do you this Yo in Japanese dice ⁇ o 0
- the removal of the natural oxide film by plasma using high frequency is preferably performed by using inductively coupled plasma or by using remote plasma.
- a self-bias voltage (V dc) having an absolute value of 200 V or more is applied to the object to be processed. Is preferred.
- the Ti-containing source gas when plasma is generated, the Ti-containing source gas can be kept flowing.o
- the titanium silicide film In the process of forming Ti, first, a Ti-containing raw material gas is supplied for a predetermined time without generating plasma to generate a Ti-Si bond, and thereafter, when the plasma is generated, the Ti-containing material gas is generated. By stopping the source gas, flowing the source gas, reducing the Ti-containing source gas with the plasma and the reducing gas, and continuously supplying the Ti-containing source gas and supplying the plasma and the reducing gas. May be repeated several times.
- a film forming method for forming a metal silicide film on a Si-containing portion of an object to be processed comprising: A metal-containing source gas containing a metal in the metal silicide to be deposited on the portion is supplied for a predetermined time to generate a metal-silicon bond, and then the metal-containing source gas is supplied. While generating plasma A second step of forming a metal film made of the metal, and forming a metal silicide film by a reaction between the metal film and the Si-containing portion at that time.
- a deposition method characterized by first supplying a metal-containing raw material gas at a low flow rate and then supplying it at a high flow rate.
- a film forming method for forming a titanium silicide film on a Si-containing portion of an object to be processed comprising: The Ti-containing source gas is supplied onto the i-containing portion for a predetermined time to generate Ti Si bond.
- Plasma is generated while supplying the Ti-containing source gas in one step and then a Ti film is formed, and the titanium silicide film is formed by a reaction between the Ti film and the Si-containing portion at that time.
- a second step of forming provides a film formation method characterized by first supplying a Ti-containing source gas at a low flow rate, and then supplying it at a high flow rate.
- a metal-containing source gas is supplied at a high flow rate from the beginning when a plasma is generated and a metal film is formed, the morphology of the interface between the metal silicide and the Si-containing portion will deteriorate. There is a risk.
- the metal is T i
- a raw material gas containing T i is supplied at a high flow rate from the beginning, the reaction with S i proceeds rapidly, and T i S i 2 crystals with a large particle size are formed.
- the morphology at the interface between the TiS12 layer and the Si-containing portion may be degraded.
- film formation According to the variation in parameters and the plasma incident distribution of the Si-containing part,
- the Ti-metal-containing source gas is supplied for a predetermined period of time without generating plasma to generate a bond between the metal and silicon, and then when generating plasma, the metal is first generated.
- the raw material gas is supplied at a low flow rate and then at a high flow rate.
- a fifth aspect is that the fourth aspect is applied to the formation of a titanium silicide film, and a Ti-containing source gas is supplied for a predetermined time without first forming a plasma to produce a Ti_S i bonds to form enough ⁇ i before the Ti Si 2 crystal begins to grow.
- a low-flow Ti-containing source gas is first supplied to supply a Ti flow.
- the reaction with i proceeds slowly.
- uniform metal silicide crystals having a small particle size are formed.
- a uniform TiSi 2 crystal having a small particle size is formed. Therefore, even when the deposition rate is increased by the subsequent supply of a high flow rate gas, uniform crystal growth can be produced, and as a result, a metal cylinder having fine and uniform crystal grains can be obtained. Since a film can be formed, the surface morphology can be improved.
- the third aspect when a plasma is generated to form a T i film, it is preferable to first supply the T i -containing source gas at a low flow rate and then supply it at a high flow rate.
- the T i -containing source gas when generating plasma and forming a T 1 film, the ⁇ i -containing source gas is supplied at a low flow rate first, and then at a high flow rate.
- the low flow rate is in the range of 0.005 to 0.012 L / min,
- the 13 ⁇ 4 flow rate in the range of 0.004 to 0.020 L / min.
- the T i film is formed by T i C 14 gas, H 2 gas, and
- the process can be performed by supplying Ar gas, and the step of forming the titanium silicide film is performed by setting the temperature of the stage on which the object to be processed is mounted in a range of 350 to 700 ° C. It is preferable to do it.
- the metal in addition to Ti described above, Ni, Co, Pt, Mo, Ta,
- H f or Z r can be mentioned.
- the object to be processed has a DC bias voltage (V dc ) Is applied, the deposition 9
- a metal-containing silicon gas is generated by supplying a metal-containing source gas for a predetermined time without first generating plasma, so that the crystal is formed.
- a uniform metal silicon K film can be formed.
- a metal-containing source gas is supplied for a predetermined time without generating a plasma to generate a metal-silicon bond, and a low-flow metal-containing source gas is supplied first. While plasm Since a uniform metal silicide crystal having a small grain size is formed by forming the metal silicide, a good metal silicide film having the same interface homologue can be formed.
- FIGS. 1A to 1D are cross-sectional views illustrating each step of a film forming method according to a first embodiment of the present invention.
- FIG. 2 is a cross-sectional view showing a schematic configuration of an apparatus for treating the surface of a Si wafer by plasma using high frequency.
- FIG. 3 is a cross-sectional view illustrating a schematic configuration of a Ti film forming apparatus.
- 4A to 4D are cross-sectional views illustrating each step of a film forming method according to a second embodiment of the present invention.
- FIG. 5 is a chart showing the timing of gas supply and plasma generation in a TiSi 2 film formation process according to the second embodiment of the present invention.
- FIG. 6 is a chart showing the timing of gas supply and plasma generation in a TiSi 2 film forming process according to a third embodiment of the present invention.
- FIG. 7A is a diagram schematically showing a cross section of a TiSi 2 crystal when a gas is supplied at a high flow rate from the beginning when a plasma is generated to form a Ti film.
- FIG. 7B is a diagram schematically showing a cross section of a TiSi 2 crystal formed according to the third embodiment of the present invention.
- FIG. 8 is a view showing an X-ray diffraction profile of the TiSi 2 film manufactured according to the first embodiment of the present invention.
- FIG. 9 shows a scanning electron microscope (SEM) image of a cross section of the TiSi 2 film manufactured according to the first embodiment of the present invention.
- FIG. 10 is a view showing an X-ray diffraction profile of a TiSi 2 film manufactured according to the second embodiment of the present invention.
- FIG. 11 is a diagram showing a scanning electron microscope (SEM) image of a cross section of a TiSi 2 film manufactured according to the second embodiment of the present invention.
- SEM scanning electron microscope
- FIG. 12 shows the X-ray diffraction profile of the TiSi 2 film manufactured according to the first embodiment of the present invention, and Vdc are normal values.
- FIG. 3 is a diagram showing a comparison between the X-ray diffraction profile file of FIG.
- Figure 13 shows a scanning electron microscope (SEM) image of a cross section of a TiSi2 film manufactured by a conventional method.
- FIGS. 1A to 1D are process diagrams for explaining a film forming method according to a first embodiment of the present invention.
- An interlayer insulating film 2 is formed on a Si wafer 1 and etched.
- the surface of the Si wafer 1 is processed by plasma using high frequency while applying a DC bias voltage of V or more.
- FIG. 2 is a cross-sectional view illustrating a schematic configuration of a plasma processing apparatus that performs the processing of FIG. 1B.
- This device uses an inductively coupled plasma (I)
- CP CP
- the first embodiment not only the removal of the native oxide film but also the application of RF bias to the si wafer 1 i Attract ions into the surface of wafer 1 and perform ion treatment.
- the plasma processing clothing la The plasma processing clothing la.
- Reference numeral 10 denotes a substantially cylindrical chamber 11 and a substantially cylindrical bell gear 12 which is provided above the chamber 11 and is continuous with the chamber 11. .
- a susceptor 13 made of ceramics, such as AIN, for horizontally supporting the Si wafer 1 as an object to be processed is supported by a cylindrical support member 14.
- a clamp 15 for clamping the Si wafer 1 is provided at the outer edge of the susceptor 13 6
- a heater 16 for heating the Si quencher 1 is embedded in the susceptor 13.
- Venoreja 1 2 is an example X. If quartz, sera,
- RF power supply 18 is 300 kHz
- 660 MHz Preferably, it has a frequency of 450 kHz.
- an induction electromagnetic field is formed in the bell jar 12.
- the gas supply mechanism 20 is used to supply gas for processing Pfuzuma to the chamber.
- a gas introduction nozzle 27 is provided on the side wall of the channel 11, and a pipe 21 extending from the gas supply mechanism 20 is connected to the gas introduction nozzle 27. Is introduced into the channel 11 through the gas introduction nozzle 27. ⁇ The valley and mass ⁇ -1n controller of each pipe are not shown. Is controlled by
- Examples of the plasma processing gas include Ar, Ne, and He, and each of them can be used alone.
- An exhaust pipe 28 is connected to the bottom wall of the channel 11, and an exhaust device 29 including a vacuum pump is connected to the exhaust pipe 28. Then, by operating the exhaust device 29, it is possible to reduce the pressure inside the chamber 11 and the bell jar 12 to a predetermined degree of vacuum.
- a gate valve 30 is provided on the side wall of the chamber 11.
- the susceptor 13 contains, for example, tungsten or a metal.
- An electrode 32 made by braiding V-banden wire or the like in a mesh shape is embedded, and a high-frequency power supply 31 is connected to the electrode 32 so that a negative DC bias can be applied.
- the gate valve 30 is opened and the channel is opened.
- the susceptor 13 is supplied with high-frequency power from the high-frequency power supply 31 and the si bias 1 is supplied with a negative bias voltage, that is, a Dc noise voltage (Vdc).
- Vdc Dc noise voltage
- the application of the Vdc causes the ions in the plasma to be drawn into the Si wafer 1.
- V d c during normal oxide film removal is —100 to
- V dc a higher V dc is applied than in the case of ordinary removal of a white oxide film.
- V dc ions in the plasma act more strongly on the surface of the Si wafer 1 than in the case of removing a native oxide film. For this reason, the surface of the Si wafer 1 as a film forming base is entirely converted into an amorphous state and becomes a highly reactive state, and as described later, the Ti Si 2 film is thereafter formed. When formed, the contact resistance can be further reduced, and as a result, a large number of TiSi2 of the structure C54 can be formed.
- the absolute value of V dc is preferably 25 OV, more preferably 30 OV or more.
- the processing conditions at this time include, for example, a pressure of 0.01 to 13.3 Pa, preferably 0.04 to 2.7 Pa, a wafer temperature of room temperature to 500 ° C, and a gas flow rate.
- a pressure of 0.01 to 13.3 Pa preferably 0.04 to 2.7 Pa
- a wafer temperature of room temperature to 500 ° C preferably 0.04 to 2.7 Pa
- a gas flow rate There is also a r you and H 2:. 0 0 0 1 ⁇ 0 0 2 L / min, the frequency of the high frequency power supply 1 8 for ICP 4 5 9
- FIG. 3 is a cross-sectional view showing a schematic configuration of the Ti film forming apparatus.
- This film-forming apparatus 40 is a close-packed, substantially cylindrical channel.
- a susceptor 42 for horizontally supporting the Si wafer 1 as an object to be processed is arranged in a state supported by a cylindrical support member 43.
- The-* susceptor 42 is composed of a ceramic such as A 1 N, for example.
- the outer periphery of the susceptor 42 is provided with a guiding 44 for guiding the Si wafer W.
- This gay drilling 4 This gay drilling 4
- the susceptor 42 is embedded with a resistance heating type heater 45 made of molybdenum, tungsten wire, or the like.
- the heater 45 is powered by a heater power supply 46 to be covered. Processing object
- the Si wafer 1 is heated to a predetermined temperature. Note that the delivery of the Si wafer 1 to the susceptor 42 is performed while the Si wafer 1 is lifted by three lift pins provided to be able to protrude and retract therein.
- the insulators ⁇ 1 to K 50 are provided through insulating members 49.
- the upper block 50 is composed of an upper block 50a, a middle block ⁇ , a solid block 50b, and a lower block 50c. And the lower block Discharge holes 57 and 58 for discharging gas are alternately formed in the body 50c.
- a first gas inlet 51 and a second gas inlet 52 are formed on the upper surface of the upper block ⁇ body 50a.
- a gas passage 55 is formed in the middle block body 50b where a large number of gas passages 53 branch off from the first gas inlet 51.
- the gas passage 53 communicates with these gas passages 55.
- the gas passage 55 communicates with the discharge hole 57 of the lower block body 50.
- a gas passage 56 is formed in the middle book body 50b.
- the gas supply mechanism 60 is a C 1 F gas supply source 61 for supplying C 1 F gas, which is a cleaning gas, and a Ti-containing gas.
- T i C 1 4 for supplying gas T i C 1 gas supply source 6 2
- a r gas A r gas supply source 6 3 instead H 2 gas supplying H 2 gas which is the original gas supplies a plug Zumagasu the source 6 4, NH 3 gas and a NH 3 gas supply source 71 supplies.
- C 1 F to the gas supply source 61 is a gas La Lee emissions 6 5, T i C 1 4 gas supply source 6 gas line 6 6 in 2, to A r gas supply source 6 3 gas line 6 7, gas line 6-8 in H 2 gas supply source 6 4, gas line 7 9 it in the NH 3 gas supply source 71 2 Connected.
- Each line is provided with a valve 69, a valve 77 and a mass flow controller 70.
- a gas line 66 extending from a TiC 14 gas supply source 62 has an exhaust device 7.
- Gas line 80 connected to 6 is connected via valve 78.
- the first is a gas inlet port 5 1 T i C 1 4 Ri gas supply source 6 2 from Ru extending gas line 6 6 is connected Contact, this is a gas line 6 6 C 1 F 3 gas supply
- a gas line 65 extending from a source 61 and a gas line 67 extending from an Ar gas supply 63 are connected.
- a gas line 68 extending from the H 2 gas supply source 64 and a gas line 79 extending from the NH 3 gas supply source 71 are connected to the second gas inlet 52.
- the TiC14 gas from the TiC14 gas supply source 62 is carried by the Ar gas, and is transferred to the gas line 66 via the gas line 66.
- the first gas inlet P51 of the nozzle 50 into the shaft 50, and is discharged from the discharge hole 57 through the gas passages 53, 55 into the chamber 41.
- the second gas inlet port 5 2 force of head 5 0 H 2 gas from the H 2 gas supply source 6 4 and through a gas line 6 8 to sheet catcher Wa primary, et Shah Wae' de The gas is discharged into the chamber 41 through the discharge holes 58 through the gas passages 54 and 56.
- the high-frequency power supply is connected to the
- High frequency power is supplied to the high frequency lightning source 73 3, so that the high frequency power source is supplied to the low frequency power source 50.
- the gas supplied into the chamber through the chamber 41 is converted into a plasma, whereby the film forming reaction proceeds and ⁇ o.
- As a shield head functioning as an electrode to which the high-frequency power is supplied as a counter electrode of 50, for example, a molybdenum wire or the like is meshed on the upper part of the susceptor 42; A pole 74 of ⁇ is buried.
- a high frequency power supply 82 is connected to the electrode 74 via a matching unit 81 so that a high frequency voltage for obtaining a bias voltage is applied.
- An exhaust pipe 75 is connected to the bottom wall 41 b of the chamber 41, and an exhaust pipe 76 including a vacuum pump is connected to the>-exhaust pipe 75.
- the inside of the chamber 41 is 500 to 7
- the inside of the chan-no-41 is evacuated by the exhaust device 76 to a predetermined vacuum state, and Ar gas and H 2 gas are supplied at a predetermined flow ratio.
- a gas is 0.1 to 5 L / min,
- H 3 gas is introduced into the chamber 41 at, for example, 0.1 to 3 L / min to generate plasma and to stabilize the pre-coated Ti film by nitriding.
- a gutter tool (not shown) is opened, a Si wafer is loaded into the chamber 41 from a port and a lock chamber (not shown), and the Si wafer 1 is placed on the susceptor 42 and discharged.
- the chamber W is heated by the heater 45 while the inside of the channel 41 is watched by the device 76, and the H2 gas is heated to 0 • 5 to 10.0 L / min. , Preferably 0.55.0 L / in, Ar gas between 0.1 and 5 L / in.
- the heating temperature (susceptor temperature) of the Si wafer 1 by the heater 45 is set to about 500 to 700 ° C., preferably.
- a high-frequency power supply 73 to a shower head 50 to 300 kHz to 60 MHz, preferably 400 to 450 kHz. at a frequency of z, 200-; LOOOW, preferably 200-500 W Supply high-frequency power to generate plasma in chamber 41 and form T i film in plasma gas
- the Ti film sucks up the underlying Si ⁇ ⁇ 1 1 1 Si and reacts with ⁇ i and Si to form the Ti i 2 A film is formed.
- the Si wafer 1 since the absolute value of 200 V is applied to the surface of Si wafer 1, which is much higher than that in the case of removing the native oxide film, the Si wafer 1 is applied.
- the Si wafer 1 On the surface of the silicon wafer 1, not only the natural oxide film is removed but also the ions in the plasma act more strongly on the surface of the silicon wafer 1, and the entire surface of the Si wafer 1 on which the film is to be formed is completely mono-reflective.
- the unbonded Si (the part where the bond is broken) is larger than that of the Si single crystal, and a state of high reactivity is formed.
- the temperature for forming the same film as the conventional TiSi 2 film is set to 50 to The temperature can be as low as 100 ° C.
- the Ti film is formed by supplying TiC 14 gas and H
- TiC14 gas is supplied for a short time to generate an adsorption reaction of Ti film (reaction between Ti and Si).
- T i Cl 4 gas A process in which a T i film is formed by H 2 gas, Ar gas, and plasma generation, a process of repeating the process of introducing H 2 gas and Ar gas + plasma generation several times, for example, ALD (Atomic Layered Deposition) process.
- ALD Atomic Layered Deposition
- a film can be formed even with c.
- ⁇ i C 14 gas is supplied for a predetermined time prior to plasma generation.
- a Ti-Si bond may be generated on the Si wafer, and then a plasma may be generated.
- the resistance of the titanium silicide film can be further reduced.
- the surface of the TiC 12 film 4 is nitrided.
- the temperature of the susceptor 42 is reduced to 350 to 70 °.
- Ar gas and H 2 gas are allowed to flow immediately, and plasma can be generated by applying a high frequency to perform processing.
- the chamber pressure, temperature, plasma generation conditions, Ar gas flow rate, and H 2 gas flow rate during nitriding are the same as those during Ti film formation.
- 1 F 3 gas supply source 6 1 Cara supplies C 1 F 3 gas and cleans the inside of the chamber.
- FIGS. 4D to 4D are cross-sectional views illustrating each step of the film forming method according to the second embodiment of the present invention. In the second embodiment, as shown in FIG.
- the i-containing source gas is supplied for a predetermined time to generate Ti-Si bonding, and then plasma is generated. Thereafter, if necessary, as shown in FIG. 4D, the same processing as in FIG. 1D is performed, and the surface of the TiSi 2 film 4 is subjected to plasma nitriding.
- the voltage can be set to about 180 V, and the other conditions can be processed in the same way as the above conditions. However, also in this embodiment, it is effective to perform the processing with the absolute value of Vdc not less than 200 V.
- the following film forming process of the TiSi 2 film shown in FIG. 4C is performed under basically the same film forming conditions by the apparatus shown in FIG. 3 described above. supplying T i C 1 4 without Zuma form, performs followed by forming a plasma treatment. Specifically, after placing Si wafer 1 on susceptor 42, heater While heating the wafer W by 45, the inside of the chamber 41 is evacuated by the exhaust device 76 to make the inside of the chamber 41 the above-mentioned predetermined pressure, and the timing is shown in FIG.
- T i C 1 4 gas of the predetermined maintaining these flow A T-second flow is performed at a flow rate to generate T i -S i bonding on the S i wafer 1, and then the predetermined high frequency power is supplied from the high frequency power supply 73 to generate plasma in the chamber 41.
- the plasma generation before T i C 1 4 gas supply time T is more than 2 seconds, is set favored properly is 2-3 0 seconds, for example, 1 0 seconds.
- T i containing feed gas at a T i C 1 4 gas supply and flop plasma formation and at the same time, plasma before sufficient T i C 1 4 gas is supplied to the surface of the S i wafer 1 Are formed, and T i Si i 2 starts abrupt crystal growth in a state where the number of T i -S i bonds on the surface of the Si wafer 1 which is the bottom of the contact is small. Depending on the number of i-Si bonds, heterogeneous crystals were formed due to abnormal growth.
- the diameter is relatively large, about 50 nm, several TiSi 2 crystals are formed on the Si contact surface of the SO 2, and if the diameter is relatively small, about 10 nm, it is 10 nm. ⁇ 2 0 pieces of T i S i 2 crystal is made form.
- the contact resistance has increased due to this.
- the Ti-containing raw material gas, TiC14 gas is first generated without generating plasma. Supplied for a predetermined time to gradually generate Ti-Si bonds over the entire surface of Si wafer 1. Ri by the and this makes, T i S i 2 occurs have enough T i one S i bound to before starting the crystal growth.
- the supply of the TiC 14 gas and the supply of the H 2 gas as the reducing gas + the generation of plasma are performed alternately in the ⁇ i film formation. be able to.
- the supply of the first T i C l 4 corresponds to the pre-flow.
- a contact hole is formed on the Si wafer 1 in the same manner as in FIGS. 4A and 4B, and the surface of the Si wafer is formed by plasma using a high frequency. Remove the oxide film.
- the step of forming the T i S i 2 film is similar to FIG. 4 C and basically, this Kodewa, T i C 1 4 gas is the first T i containing source gas without generating a plasma Is supplied for a predetermined time to generate Ti-Si bonds, and then, when a plasma is generated to form a Ti film, the Ti-containing raw material gas, TiC14 gas, is first discharged.
- the reaction with Si proceeds slowly.
- the flow rate of the TiC 14 gas is increased to a high flow rate F 2, and the deposition rate is increased to form a film.
- the low flow rate F1 is 0.001 to 0.012 L / min
- the high flow rate F2 is 0.012. 00.020 L / min
- the low flow rate F1 is set to 0.005 to 0.004 LZmin
- the high flow rate F2 is set to 0.004 to 0.00 Ol OL / min.
- the supply time T 1 of the T i C 1 4 prior to the plasma generation for example, 1 to 3 0 seconds feed time T 2 of the T i C 1 4 at low flow F 1, for example 5-6 0 Seconds, preferably set to 5 to 30 seconds.
- a method of improving the field 1 ⁇ morphology by generating plasma while supplying T 1 C 14 at a low flow rate to form a T i film is particularly effective in such a case.
- the high-frequency power supply 18 has a power of 500 W and the bias high-frequency power supply 3 1 Dimension 3
- the power was set to 800 W and the Vdc power was set to 53 V. Then, using the device shown in Fig. 3, the susceptor temperature
- Processing was performed at 640 ° C. and a wafer temperature of 620 ° C. for 31 seconds to form a thick TiSi 2 film.
- Figure 8 shows the X-ray diffraction profile at that time.
- the TiSi 2 film formed according to the first embodiment has a strong peak strength of TiSi 2 having a crystal structure C 54 as shown in FIG. It was confirmed that a force S of about 70% was formed.
- Figure 9 shows an SEM image of the cross section of the hole in the sample.
- Fig. 9 shows the result of working with hydrofluoric acid.
- the portion where the ⁇ i Si 2 film was present was thin ⁇ uniform and the crystal grain size was uniform. It is estimated.
- the T i S i 2 film of 2 7 nm was formed.
- FIG. 10 The X-ray diffraction profile at that time is shown in FIG. As shown in Fig. 10, a peak of TiSi2 of crystal structure C54 was observed.
- Figure 11 shows an SEM image of the cross section of the hole in the sample. Note that Fig. 11 is etched with hydrofluoric acid, and the TiSi 2 film is removed by etching. As shown in the figure, it is presumed that also in this case, the portion where the TiSi 2 film was present was thin and uniform, and the crystal grain size was uniform.
- FIG. 12 shows the X-ray diffraction profile (A) of another part of the sample manufactured according to the first embodiment and VdC3 ⁇ 4 ”after plasma treatment under the conditions of normal natural oxide film removal.
- the X-ray diffraction profile of the sample formed (B) is shown in comparison with the X-ray diffraction profile (C) of the sample formed without such a plasma treatment.
- Figure 12 shows the X-ray diffraction profile (A) of another part of the sample manufactured according to the first embodiment and VdC3 ⁇ 4 ”after plasma treatment under the conditions of normal natural oxide film removal.
- the X-ray diffraction profile of the sample formed (B) is shown in comparison with the X-ray diffraction profile (C) of the sample formed without such a plasma treatment.
- FIG. 13 shows an SEM image of a cross section of a hole portion of a conventional sampnolet without performing the processing of the present invention.
- the etching was performed with hydrofluoric acid, and the ⁇ i Si 2 film was removed by etching. As shown in FIG. 13, it is presumed that the portion where the TiSi 2 film was present was thick and non-uniformly removed, and the crystal grain size was uneven.
- the present invention is not limited to the above embodiment, and can be variously modified within the scope of the concept of the present invention.
- a high frequency performed before the formation of the TiSi 2 film is used.
- the plasma treatment was performed using IC-plasma, but the present invention is not limited to this, and a parallel plate plasma (capacitively-coupled plasma) may be used, and a microwave is introduced directly into the chamber. Occasionally, microwave plasma may be used. O However, it is preferable because there is little concern that the ICP plasma may give unnecessary damage to the object to be processed. Further, in the case of removing a natural oxide film as in the second embodiment, a remote plasma with small damage to the substrate can be suitably used.
- Et al is has been shown for example using the S i wafer as the base of the T i S i 2 film, P o 1 is not limited thereto y - may be filed by S i, not only the S i It may be a metal silicide. Further, the case where TiCl4 gas is used as a source gas has been described as an example, but the present invention is not limited to this, and any Ti-containing source gas may be used. For example, TD for organic titanium
- M A ⁇ dimethylamine
- TDEAT getyla, sangitan
- the present invention is not limited to this.
- metal-containing source gases such as Co, Pt, Mo, Ta, Hf, and Zr.
- the Ti-containing source gas is supplied for a predetermined time without generating plasma, and then the Ti-containing source gas is initially supplied at a low flow rate. form T i S i 2 film and then supplies a high is to generate al plasma
- a method of forming a TiSi 2 film can also be applied when a native oxide film is not removed. In this case, the effect that the crystal grain size of the TiSi 2 film can be reduced can be maintained, and as a result, the interface morphology can be improved. it can.
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US7981794B2 (en) * | 2006-10-30 | 2011-07-19 | Tokyo Electron Limited | Film forming method and substrate processing apparatus |
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US20040224504A1 (en) * | 2000-06-23 | 2004-11-11 | Gadgil Prasad N. | Apparatus and method for plasma enhanced monolayer processing |
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KR101139165B1 (ko) * | 2006-10-19 | 2012-04-26 | 도쿄엘렉트론가부시키가이샤 | Ti계 막의 성막 방법 및 기억 매체 |
JP4931716B2 (ja) * | 2007-07-18 | 2012-05-16 | 東京エレクトロン株式会社 | プラズマ処理装置及びプラズマ生成室 |
JP5213594B2 (ja) * | 2008-09-04 | 2013-06-19 | 東京エレクトロン株式会社 | 熱処理装置 |
CN102245802A (zh) * | 2008-12-12 | 2011-11-16 | 东京毅力科创株式会社 | 成膜方法、成膜装置和存储介质 |
JP4676567B1 (ja) * | 2010-07-20 | 2011-04-27 | 三井造船株式会社 | 半導体基板熱処理装置 |
JP5063755B2 (ja) * | 2010-08-09 | 2012-10-31 | 三井造船株式会社 | 誘導加熱装置および誘導加熱方法 |
KR101978966B1 (ko) | 2013-03-12 | 2019-05-16 | 엘에스산전 주식회사 | 랜드마크 센서를 통한 위치 기반 서비스 시스템 및 그의 제어 방법 |
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US11430661B2 (en) * | 2018-12-28 | 2022-08-30 | Applied Materials, Inc. | Methods and apparatus for enhancing selectivity of titanium and titanium silicides during chemical vapor deposition |
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-
2004
- 2004-05-26 KR KR1020077023634A patent/KR100884852B1/ko not_active IP Right Cessation
- 2004-05-26 KR KR1020067002771A patent/KR100822493B1/ko not_active IP Right Cessation
- 2004-05-26 CN CN2004800104700A patent/CN1777977B/zh not_active Expired - Fee Related
- 2004-05-26 WO PCT/JP2004/007554 patent/WO2005015622A1/ja active Application Filing
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2006
- 2006-02-10 US US11/350,799 patent/US20060127601A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH0689873A (ja) * | 1992-07-24 | 1994-03-29 | Nippon Steel Corp | 化学気相成長による金属薄膜形成方法 |
WO1999009586A2 (en) * | 1997-08-21 | 1999-02-25 | Micron Technology, Inc. | Method for forming titanium silicide and titanium by cvd |
JP2002124485A (ja) * | 2000-10-16 | 2002-04-26 | Matsushita Electric Ind Co Ltd | 半導体装置の製造方法 |
JP2003055767A (ja) * | 2001-08-14 | 2003-02-26 | Tokyo Electron Ltd | 金属シリサイド膜の成膜方法 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7981794B2 (en) * | 2006-10-30 | 2011-07-19 | Tokyo Electron Limited | Film forming method and substrate processing apparatus |
Also Published As
Publication number | Publication date |
---|---|
KR100822493B1 (ko) | 2008-04-16 |
KR100884852B1 (ko) | 2009-02-23 |
KR20060041306A (ko) | 2006-05-11 |
US20060127601A1 (en) | 2006-06-15 |
CN1777977A (zh) | 2006-05-24 |
CN1777977B (zh) | 2010-07-07 |
KR20070108952A (ko) | 2007-11-13 |
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