CN1789487A - Method of depositing a metal compound layer and apparatus for depositing a metal compound layer - Google Patents
Method of depositing a metal compound layer and apparatus for depositing a metal compound layer Download PDFInfo
- Publication number
- CN1789487A CN1789487A CNA2005101369870A CN200510136987A CN1789487A CN 1789487 A CN1789487 A CN 1789487A CN A2005101369870 A CNA2005101369870 A CN A2005101369870A CN 200510136987 A CN200510136987 A CN 200510136987A CN 1789487 A CN1789487 A CN 1789487A
- Authority
- CN
- China
- Prior art keywords
- source gas
- metal compound
- flow velocity
- compound layer
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000002736 metal compounds Chemical class 0.000 title claims abstract description 334
- 238000000034 method Methods 0.000 title claims abstract description 138
- 238000000151 deposition Methods 0.000 title claims abstract description 121
- 239000007789 gas Substances 0.000 claims abstract description 914
- 239000000758 substrate Substances 0.000 claims abstract description 202
- 230000008569 process Effects 0.000 claims abstract description 70
- 239000000463 material Substances 0.000 claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 claims abstract description 49
- 239000002184 metal Substances 0.000 claims abstract description 49
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 16
- 150000002367 halogens Chemical class 0.000 claims abstract description 16
- 239000002905 metal composite material Substances 0.000 claims description 83
- 230000008021 deposition Effects 0.000 claims description 68
- 238000010926 purge Methods 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 239000007921 spray Substances 0.000 claims description 43
- 238000006557 surface reaction Methods 0.000 claims description 28
- 230000015572 biosynthetic process Effects 0.000 claims description 23
- 238000012546 transfer Methods 0.000 claims description 22
- 208000005189 Embolism Diseases 0.000 claims description 8
- 230000004888 barrier function Effects 0.000 claims description 7
- 230000001360 synchronised effect Effects 0.000 claims 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 175
- 238000005516 engineering process Methods 0.000 description 60
- 238000012545 processing Methods 0.000 description 35
- 238000007598 dipping method Methods 0.000 description 22
- 239000007788 liquid Substances 0.000 description 19
- 229910052801 chlorine Inorganic materials 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 239000000460 chlorine Substances 0.000 description 17
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 16
- 238000004140 cleaning Methods 0.000 description 16
- 239000006227 byproduct Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 13
- 238000005137 deposition process Methods 0.000 description 12
- 239000010936 titanium Substances 0.000 description 10
- 229910052719 titanium Inorganic materials 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 238000000231 atomic layer deposition Methods 0.000 description 9
- 238000005229 chemical vapour deposition Methods 0.000 description 9
- 230000008646 thermal stress Effects 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 238000005530 etching Methods 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000006298 dechlorination reaction Methods 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 239000006200 vaporizer Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000003321 amplification Effects 0.000 description 3
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- 241000588731 Hafnia Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- -1 Titanium nitride Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- VKJLWXGJGDEGSO-UHFFFAOYSA-N barium(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Ba+2] VKJLWXGJGDEGSO-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- XRFHCHCLSRSSPQ-UHFFFAOYSA-N strontium;oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[O-2].[Ti+4].[Sr+2] XRFHCHCLSRSSPQ-UHFFFAOYSA-N 0.000 description 1
Images
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
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having 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
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
- H01L21/28158—Making the insulator
- H01L21/28167—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation
- H01L21/28202—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation in a nitrogen-containing ambient, e.g. nitride deposition, growth, oxynitridation, NH3 nitridation, N2O oxidation, thermal nitridation, RTN, plasma nitridation, RPN
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
- Electrodes Of Semiconductors (AREA)
Abstract
In a method and an apparatus for depositing a metal compound layer, a first source gas and a second source gas may be provided onto a substrate to deposit a first metal compound layer on the substrate. The first source gas may include a metal and halogen elements, and the second source gas may include a first material capable of being reacted with the metal and a second material capable of being reacted with the halogen element. The first and the second source gases may be provided at a first flow rate ratio. A second metal compound layer may be deposited on the first metal compound layer by providing the first and the second source gases with a second flow rate ratio different from the first flow rate ratio. The apparatus may include a process chamber configured to receive a substrate, a gas supply system, and a flow rate control device.
Description
Prioity claim
According to 35USC § 119, require the right of priority of Korean Patent Application No. 2004-104741 that applied on December 13rd, 2004 and the Korean Patent Application No. 2005-49565 that applied on June 10th, 2005, at this its content all is incorporated herein by reference.
Technical field
Example embodiment of the present invention relates to a kind of method and apparatus that is used for the depositing metal compound layer.More specifically, example embodiment of the present invention relates to the method and apparatus that is used for deposit titanium nitride layer on substrate.
Background technology
Semiconductor memory can be made by for example carrying out a series of multiple cell processes on the silicon wafer at substrate.Cell processes can comprise deposition process, oxidation operation, photo-mask process and smooth operation.For form layers on substrate, can carry out deposition process.For at the layer that forms on the substrate on oxide skin or the oxidation substrate, can carry out oxidation operation.In addition, in order on substrate, to form the figure of wishing, can carry out photo-mask process by the layer on the etched substrate.Layer in order to form on the smooth substrate can carry out smooth operation.
By several depositing technics, for example, chemical vapor deposition (CVD) technology, physical vapor deposition (PVD) technology and atomic layer deposition (ALD) technology can form each layer on substrate.For example, can form the silicon oxide layer that can be used as gate insulation layer, insulating intermediate layer or medium layer by CVD technology.Can form silicon nitride layer by CVD technology, silicon nitride layer can be used as mask, etching stop layer or partition.In addition, can form various metal compound layers by CVD technology, PVD technology or ALD technology, this metal compound layer can be used to form metal line, electrode or the embolism of semiconducter device.
In semiconducter device, can adopt usually metal composite layer for example titanium nitride layer form embolism, this embolism is electrically connected to unit elements the electrode or the metal line of electrical condenser.Metal composite layer also can be used as metal barrier, to prevent the diffusion of atoms metal.Titanium nitride layer typically can form by CVD technology, PVD technology or ALD technology.
Titanium nitride layer can pass through titanium chloride (TiCl under about 680 ℃ temperature
4) gas and ammonia (NH
3) between reaction form.Can reduce chlorine (Cl) atomic quantity remaining in the titanium nitride layer by increasing treatment temp, to form titanium nitride layer.But if treatment temp is lowered, titanium nitride layer can have improved step coverage so.In addition, if treatment temp increases,, comprise that so the beneath structure of layer and/or figure may be by the thermal stress damage that produces in the forming process of titanium nitride layer to reduce the chlorine atom in the titanium nitride layer.
Recently, because the area of the elementary cell of semiconducter device is reduced widely, developed various technologies and made highly integrated semiconducter device.For example, can use height-k material to form the medium layer of transistorized gate insulation layer or electrical condenser.In addition, can use low-k material to form insulating intermediate layer, to reduce the parasitic capacitance between insulating intermediate layer and the metal line thus.Height-k examples of material can comprise yttrium oxide (Y
2O
3), hafnia (HfO
2), zirconium white (ZrO
2), niobium oxides (Nb
2O
5), titanium oxide barium (BaTiO
3) and strontium titanium oxides (SrTiO
3).
If form titanium nitride layer by CVD technology comprising on hafnia or the zirconic medium layer, the reaction by medium layer and source gas such as titanium chloride inter gas may produce byproduct of reaction so, for example, and hafnium chloride (HfCl
4) or zirconium chloride (ZrCl
4).This byproduct of reaction may damage the dielectric medium and/or the electrical property of medium layer.Byproduct of reaction may increase the leakage current by medium layer.Byproduct of reaction may increase the ratio resistance (specificresistance) of medium layer, and this may increase the contact resistance of electrical condenser.
In order to improve the problems referred to above, can advantageously use ALD technology to form titanium nitride layer, but titanium nitride layer is to be used as medium layer or gate insulation layer.If form titanium nitride layer by ALD technology, so because titanium nitride layer can form being less than about under 600 ℃ the treatment temp, so titanium nitride layer can have improved step coverage.In addition, by alternately providing the source gas that forms titanium nitride layer can reduce the quantity of the chlorine atom in the titanium nitride layer.But, if form titanium nitride layer, compare with CVD technology so by ALD technology, can reduce the manufacturing turnout of titanium nitride layer.
Continuous flow deposit (SFD) technology can be with solving the problems referred to above relevant with the formation of conventional titanium nitride layer.SFD technology can comprise by providing on the substrate of reactant gases in reaction chamber and form titanium nitride layer that at first dechlorination atom, cleaning reaction chamber are once more removed from titanium nitride layer in the cleaning reaction chamber.Although compare with ALD technology, SFD technology can provide the manufacturing turnout of higher titanium nitride layer, and SFD technology may provide the manufacturing turnout of the titanium nitride layer that still is lower than CVD technology.
Summary of the invention
In exemplary embodiments of the present invention, a kind of method of depositing metal compound layer can comprise, the first source gas and the second source gas are provided on substrate, with first metal compound layer of deposit on substrate, the first source gas comprises metal, the second source gas comprise can with the material of this metal reaction, wherein provide the first and second source gases with first-class speed ratio, wherein the deposition rate of first metal compound layer of the surface reaction by the first and second source inter gas is higher than the deposition rate of first metal compound layer of the mass transfer by the first and second source inter gas fully, and provide the first and second source gases with second velocity ratio, second velocity ratio is different from first-class speed ratio, with deposit second metal compound layer on first metal compound layer, and wherein the first and second source gases are removed undesirable material from first and second metal compound layers simultaneously.
In another exemplary embodiments of the present invention, a kind of method of depositing metal compound layer can comprise, the first source gas and the second source gas are provided on substrate, with first metal compound layer of deposit on substrate, the first source gas comprises metal, the second source gas comprises the material that can react with this metal, wherein provide the first and second source gases with first-class speed ratio, wherein the deposition rate of first metal compound layer of the surface reaction by the first and second source inter gas is higher than the deposition rate of first metal compound layer of the mass transfer by the first and second source inter gas fully, provide the first and second source gases with second velocity ratio that is different from first-class speed ratio, with deposit second metal compound layer on first metal compound layer, provide the first and second source gases with the 3rd velocity ratio that is different from first-class speed ratio, with deposit the 3rd metal compound layer on second metal compound layer, to cause the surface reaction of the first and second source inter gas, and provide the first and second source gases with the 4th velocity ratio that is different from the 3rd velocity ratio, with deposit the 4th metal compound layer on the 3rd metal compound layer.
In exemplary embodiments of the present invention, a kind of equipment of depositing metal compound layer can comprise, be made as the treatment chamber of accommodating substrates, be made as the airing system that the first source gas and the second source gas are provided on substrate, wherein the first source gas comprises that the metal and the second source gas comprise the material that can react with this metal, and be made as the flow velocity of adjusting the first and second source gases current velocity controller with first metal compound layer of deposit on substrate, wherein provide the first and second source gases with first-class speed ratio, and the flow velocity that also is made as the adjustment first and second source gases, with deposit second metal compound layer on first metal compound layer, remove undesirable material from first and second metal compound layers simultaneously, wherein provide the first and second source gases with second velocity ratio that is different from first-class speed ratio.
Description of drawings
Detailed description by its exemplary embodiments will make the present invention become clearer with reference to the accompanying drawings, wherein:
Fig. 1 is the sectional view that explanation exemplary embodiments according to the present invention is made as the equipment of depositing metal compound layer;
Fig. 2 is the amplification profile of first air supply unit of explanation equipment shown in Figure 1;
Fig. 3 is the method for equipment depositing metal compound layer shown in Figure 1 is used in explanation according to an exemplary embodiments of the present invention schema;
Fig. 4 illustrates the sequential chart of the time of presenting of the source gas in the method shown in Figure 3;
Fig. 5 is that explanation exemplary embodiments metal compound layer according to the present invention is with respect to TiCl
4The graphic representation of the treatment temp of gas and the deposition rate of flow velocity;
Fig. 6 be the explanation exemplary embodiments according to the present invention under about 500 ℃ treatment temp metal compound layer with respect to TiCl
4The graphic representation of the processing pressure of gas and the deposition rate of flow velocity;
Fig. 7 be the explanation exemplary embodiments according to the present invention under about 700 ℃ treatment temp metal compound layer with respect to TiCl
4The graphic representation of the processing pressure of gas and the deposition rate of flow velocity;
Fig. 8 A, 8B and 8C are the electron microscopic pictures of the titanium nitride layer that forms under the pressure of about 700 ℃ temperature and about 5Torr of the velocity ratio of explanation exemplary embodiments according to the present invention by change source inter gas;
Fig. 9 A, 9B and 9C are the electron microscopic pictures of the titanium nitride layer that forms under the pressure of about 500 ℃ temperature and about 2Torr of the velocity ratio of explanation exemplary embodiments according to the present invention by change source inter gas;
Figure 10 A and 10B illustrate the sequential chart of the time of presenting of the first source gas in the method shown in Figure 3;
Figure 11 is the sectional view that explanation another exemplary embodiments according to the present invention is used for the equipment of depositing metal compound layer;
Figure 12 is the method for equipment depositing metal compound layer shown in Figure 11 is used in explanation according to an exemplary embodiments of the present invention schema;
Figure 13 illustrates the sequential chart of the time of presenting of the source gas in the method shown in Figure 12;
The sequential chart of the time of presenting of the first source gas that provides on substrate is provided in method shown in Figure 12 Figure 14;
Figure 15 shows in continuous flow deposit (SFD) technology titanium nitride layer with respect to the graphic representation of the deposition rate of number of cycles;
Figure 16 shows at TiCl
4Titanium nitride layer is with respect to the graphic representation of the deposition rate of number of cycles in pulsed deposition (TPD) technology;
The every equipment of Figure 17 unit of showing hour (UPEH) is with respect to the graphic representation of the ratio resistance of the titanium layer that uses SFD and TPD technology to form;
Figure 18 is the sectional view of explanation according to the equipment of another exemplary embodiments depositing metal compound layer of the present invention;
Figure 19 is equipment method of depositing metal compound layer on substrate shown in Figure 180 is used in explanation according to an exemplary embodiments of the present invention schema;
Figure 20 illustrates the sequential chart of the time of presenting of the source gas that uses in the method shown in Figure 19;
Figure 21 is the sectional view that explanation exemplary embodiments according to the present invention is used for the equipment of depositing metal compound layer;
Figure 22 is equipment method of depositing metal compound layer on substrate shown in Figure 21 is used in explanation according to an exemplary embodiments of the present invention schema;
Figure 23 illustrates the sequential chart of the time of presenting of the source gas that uses in the method shown in Figure 22;
Figure 24 is the sectional view that explanation exemplary embodiments according to the present invention is used for the equipment of depositing metal compound layer;
Figure 25 is equipment method of depositing metal compound layer on substrate shown in Figure 24 is used in explanation according to an exemplary embodiments of the present invention schema;
Figure 26 illustrates the sequential chart of the time of presenting of the source gas that uses in the method shown in Figure 25;
Figure 27 is the sectional view that explanation another exemplary embodiments according to the present invention is used for the equipment of depositing metal compound layer;
Figure 28 is equipment method of depositing metal compound layer on substrate shown in Figure 27 is used in explanation according to an exemplary embodiments of the present invention schema;
Figure 29 illustrates the sequential chart of the time of presenting of the source gas that uses in the method shown in Figure 28; And
Figure 30 is the sectional view of explanation according to the semiconducter device of exemplary embodiments manufacturing of the present invention.
Embodiment
Describe the present invention more completely referring now to accompanying drawing, wherein show exemplary embodiments of the present invention.But the present invention can embody with many different forms, should not be regarded as being limited to exemplary embodiments set forth herein.On the contrary, these exemplary embodiments are provided as the processing example.In the drawings, can amplification layer and regional size and relative dimension in order to know.
Be to be understood that, when an element or layer be called another element or layer " on ", " being connected to " or " being coupled to " another element or when layer, it can be directly on another element or layer, connect or be coupled to another element or layer, maybe can have insertion element or layer.On the contrary, when an element be called as directly another element or layer " on " or " being directly connected to " during to another element or layer, do not have insertion element or layer.In entire chapter, identical numeral refers to components identical.As used herein term " and/or " comprise one or more relevant list arbitrarily and all combinations.
Although should be appreciated that at this and can use the term first, second, third, etc. to describe each element, assembly, zone, layer and/or part, these elements, assembly, zone, layer and/or part should not limited by these terms.These terms only are to be used for making an element, assembly, layer or part and the difference mutually of other zone, layer or part.Therefore, under the condition that does not break away from instruction of the present invention, first element of discussing below, assembly, zone, layer or part can be called second element, assembly, zone, layer or part.
Element or parts other element to that indicated in the drawings or the relation of parts for convenience of description can the usage space relative terms at this, for example, " ... beneath ", " ... following ", D score, " ... on ", " on " etc.Be to be understood that the space relative terms is the different orientation of device in the use that is used for comprising the direction of describing or in the operation in figure.For example, if the device among the figure is reversed, be described as so other elements or parts " below " or at other elements or parts " beneath " then element will be oriented in other elements or parts " on ".Therefore, exemplary term " ... following " can comprise " and ... on " and " ... under " two kinds of orientations.Device can by in addition directed (revolve turn 90 degrees or with other directions) with explain the relative descriptor in space as used herein thus.
Specialized vocabulary is only to be used to describe certain embodiments rather than restriction the present invention as used herein.Singulative as used herein " a ", " an " and " the " is same to plan to comprise plural form, unless context clearly illustrates that in addition.It should also be understood that, when using in this manual, term " comprises " and/or " comprising " illustrate the existence of parts, integral body, step, operation, element and/or the assembly of statement, but do not get rid of existence or increase one or more miscellaneous parts, integral body, step, operation, element, assembly and/or its group.
Figure has described exemplary embodiments of the present invention at this reference section, and sectional view is the synoptic diagram of idealized embodiment of the present invention (and intermediate structure).Like this, should envision because for example variation of the legend shape of the variation of manufacturing process and/or tolerance.Therefore, exemplary embodiments of the present invention should not be regarded as being limited to the specified shape in zone shown here but the shape that comprises gained for example by the deviation of making.For example, be illustrated as the orthogonal injection region and usually will have slick and sly or crooked feature and/or have the gradient of implantation concentration, rather than the binary from the injection region to non-injection region changes at its edge.Equally, can cause buried regions and some injection take place by injecting the buried regions that forms by zone between its surface of injecting.Therefore, the zone shown in the figure is schematically in essence, and their shape is not planned to illustrate the true form of device area and do not planned to limit the scope of the invention.
Unless otherwise defined, all terms (comprising technology and scientific terminology) have equivalent by the those of ordinary skill common sense of the technical field under the present invention as used herein.It should also be understood that term, as those terms that in normally used dictionary, define, should be interpreted as having the meaning in the environment that meets correlation technique and do not explained or form perception exceedingly, unless clearly limited at this by idealized.
Fig. 1 is the sectional view that explanation exemplary embodiments according to the present invention is used for the equipment of depositing metal compound layer on substrate.Fig. 2 is the amplification profile of first air supply unit of the equipment in the explanatory view 1.
With reference to Fig. 1 and 2, equipment 100 can be set as the depositing metal compound layer, and the deposition process that can be used for for example forming on silicon (SOI) substrate on silicon wafer or the isolator at substrate 10 the metal composite layer (not shown).For example, equipment 100 can be used for forming metal compound layer on substrate 10, for example titanium nitride layer.Metal compound layer can refer to the single metal compound layer, and metal composite layer can refer to the complex metal compound layer of minimum two metal compound layers.
Equipment 100 can comprise treatment chamber 102, Stage microscope 104 and airing system 120.
Treatment chamber 102 can provide enclosed space, wherein can form the deposition process of metal composite layer.Stage microscope 104 can be disposed in the treatment chamber 102, and support substrates 10 in deposition process.Treatment chamber 102 can be connected to vacuum system 110, with discharging byproduct of reaction, residual gas, Purge gas and/or purge gas.
Provide source gas on the substrate 10 that airing system 120 can load in treatment chamber 102, on substrate 10, to form metal composite layer.Airing system 120 can additionally provide Purge gas in treatment chamber 102, so that before the formation of metal composite layer and/or afterwards, and the inside of cleaning processing chamber 102.
Spray header 106 can be arranged in top at treatment chamber 102, so that source gas and Purge gas are ejected in the treatment chamber 102 equably.Spray header 106 can be connected to airing system 120.In exemplary embodiments of the present invention, Purge gas can be used as voltage-controlled gas, with adjustment/control treatment chamber 102 pressure inside.
Airing system 120 can be provided to the first source gas and the second source gas in the treatment chamber 102, forms metal composite layer thus on substrate 10.The first source gas can comprise metal and haloid element.The second source gas can comprise first material that can react with the metal of the first source gas.In addition, the second source gas can comprise second material that can react with the haloid element of the first source gas.If form titanium nitride layer on substrate 10, the first source gas and the second source gas can comprise titanium chloride (TiCl respectively so
4) gas and ammonia (NH
3).
Airing system 120 can comprise first air supply unit 130, second air supply unit 140 and the 3rd air supply unit 150.First source gas (for example, the TiCl is provided on the substrate 10 that first air supply unit 130 can load in treatment chamber 102
4Gas) and first vector gas.Second air supply unit 140 can provide second source gas (for example, the NH on substrate 10
3Gas) and second vector gas.The 3rd air supply unit 150 can be provided to Purge gas in the treatment chamber 102.Airing system 120 can be connected to spray header 106 (following detailed description) by a plurality of connection lines.
As shown in Figure 2, first air supply unit 130 can comprise first reservoir 132, encloses container 134 and dipping (immersed) pipeline 136.First reservoir 132 can be stored first vector gas therein.Encloses container 134 can receive first liquid source (for example, the TiCl of liquid phase
4), to produce the first source gas.Dipping pipeline 136 can extend to encloses container 134 from first reservoir 132.The first end of dipping pipeline 136 can be coupled to first reservoir (reservoir) 132, and the second end of dipping pipeline 136 can be dipped in first liquid source of storage in the encloses container 134.By making first liquid that provides by dipping pipeline 136 produce bubble, can obtain the first source gas from first liquid source.
In exemplary embodiments of the present invention, first air supply unit 130 can comprise vaporizer.Vaporizer can direct heating first liquid source (for example, the TiCl of liquid phase
4), to produce first source gas (for example, the TiCl thus
4Gas).In addition, vaporizer can obtain first liquid source and change it into the mist phase, and vaporizer can produce the first source gas by heating mist-phase liquid source.
Second air supply unit 140 can comprise second reservoir 142 and the second source gas tank 144.Second reservoir 142 can be stored second vector gas therein.Second source gas (for example, the NH is provided on the substrate 10 that the second source gas tank 144 can be loaded in treatment chamber 102
3Gas).The 3rd air supply unit 150 can comprise the 3rd reservoir (not shown), so that Purge gas is provided in the treatment chamber 102.
Can arrange the spray header 106 that is connected to airing system 120 on the top of treatment chamber 102, so that the first and second source gases are provided on substrate 10.
Spray header 106 can comprise a plurality of first nozzles and a plurality of second nozzle.First nozzle can provide the first source gas equably on substrate 10.Second nozzle can be injected in second gas on the substrate 10 equably.The first source gas should not mix with the second source gas in spray header 106.The first and second source gases should be provided on the substrate 10 independently.If first gas source comprises TiCl
4The gas and the second source gas comprise NH
3Gas can pass through TiCl so
4Gas and NH
3The reaction of inter gas forms titanium nitride layer on substrate 10.
The spray header 106 of first air supply unit 130 and encloses container 134 can interconnect by the first connection line 170a, first fen pipeline (divided line) 172a and second fen pipeline 172b.First and second fens pipeline 172a and 172b can divide out branch from the first connection line 170a.The spray header 106 of second air supply unit 140 and the second source gas tank 144 can interconnect by the second connection line 170b, the 3rd fen pipeline 172c and the 4th fen pipeline 172d.Third and fourth fen pipeline 172c and 172d can divide out branch from the second connection line 170b.The 3rd air supply unit 150 can be connected to the first connection line 170a by the 3rd connection line 170c.Second reservoir 142 of second air supply unit 140 can be connected to the second connection line 170b by the 4th connection line 170d.
Airing system 120 can also comprise the 4th air supply unit 160, is connected to the 3rd connection line 170c by the 5th connection line 170e.The 4th air supply unit 160 can provide purge gas in treatment chamber 102, with the inside of cleaning process room 102.
In exemplary embodiments of the present invention, can Purge gas be provided in the spray header 106, as shown in Figure 1 by the 3rd connection line 170c and the first connection line 170a.In another exemplary embodiments of the present invention, the 3rd connection line 170c can be connected to the second connection line 170b, so that Purge gas is introduced in the spray header 106.
Therebetween, the first bypass line 174a, the second bypass line 174b, the 3rd bypass line 174c and the 4th bypass line 174d can be connected respectively to first fen pipeline 172a, second minute pipeline 172b, the 3rd fen pipeline 172c and the 4th fen pipeline 172d.
The first gate valve 176a and the second gate valve 176b can be installed respectively in the first connection line 170a and the second connection line 170b.In the 3rd connection line 170c and the 4th connection line 170d, can arrange the first flow control valve 178a and the second flowrate control valve 178b respectively.In addition, in the 5th connection line 170e and dipping pipeline 136, the 3rd flowrate control valve 178c and the 4th flowrate control valve 178d can be installed respectively.
In first minute pipeline 172a, the first bypass line 174a, second fen pipeline 172b and the second bypass line 174d, the first interlock valve 180a, the second interlock valve 180b, the 3rd interlock valve 180c and the 4th interlock valve 180d can be installed respectively.In addition, in the 3rd minute pipeline 172c, the 3rd bypass line 174c, the 4th fen pipeline 172d and the 4th bypass line 174d, can arrange the 5th interlock valve 180e, the 6th interlock valve 180f, the 7th interlock valve 180g and the 8th interlock valve 180h respectively.
At first minute the first mass flow control device 182a can be installed among the pipeline 172a, be adjusted into first flow with flow velocity with the first source gas.At the 3rd minute the second mass flow control device 182b can be installed among the pipeline 172c, be adjusted into second flow velocity that sets in advance with flow velocity the second source gas.In addition, can arrange among the pipeline 172b at second minute and be adjusted into the 3rd flow velocity with flow velocity by the 3rd mass flow control device 182c the first source gas.Can arrange the 4th mass flow control device 182d among the pipeline 172d at the 4th minute, be the 4th flow velocity with the flow velocity of adjusting the second source gas.
In exemplary embodiments of the present invention, can represent the flow velocity of the blended first source gas and first vector gas by the first and the 3rd flow velocity of the first and the 3rd mass flow control device 182a and 182c adjustment.In the mixed gas through the first and the 3rd mass flow control device 182a and 182c, the velocity ratio between the first source gas and first vector gas can be about 1.0: 1.0.
For the flow with first and second gases becomes its laminar flow, can provide first to fourth 4th bypass line 174a, 174b, 174c and 174d.For example, before forming metal composite layer on the substrate 10, first to fourth bypass line 174a, 174b, 174c and 174d can be opened, with at first to fourth fen pipeline 172a, 172b, the laminar flow that respectively flow of the first and second source gases is changed among 172c and the 172d.
When on substrate 10, providing the first source gas and the second source gas respectively with first flow velocity and second flow velocity, so that on substrate 10 during deposit first metal compound layer, the first and the 5th interlock valve 180a and 180e can be opened, and the second and the 6th interlock valve 180b and 180f can be closed.Simultaneously, for the third and fourth flow velocity bypass, the first and second source gases, the 3rd and the 7th interlock valve 180c and 180g can be closed, and the 4th and the 8th interlock valve 180d and 180h can be opened.
On the contrary, when can the first and second source gases being introduced respectively in the treatment chamber 102 with third and fourth flow velocity, so that on first metal compound layer during deposit second metal compound layer, the the 3rd and the 7th interlock valve 180c and 180g can open, and the 4th and the 8th interlock valve 180d and 180h can be closed.Simultaneously, in order to use the first and second flow velocity bypass, the first and second source gases respectively, the first and the 5th interlock valve 180a and 180e can be closed, but the second and the 6th interlock valve 180b and 180f can be opened.As a result, can be on first metal compound layer deposit second metal compound layer continuously, and can remove undesirable material from first and second metal compound layers, for example, chlorine.By chlorine and the second source gas reaction that provides with the 4th flow velocity are provided, can remove the chlorine that may be contained in first and second metal compound layers.For example, chlorine can react with the second source gas, produces the hydrogenchloride (HCl) that can easily remove from first and second metal compound layers thus.
Valve control unit 190 can be controlled first to the 8th interlock valve 180a, 180b, 180c, 180d, 180e, 180f, the operation of 180g and 180h.Valve control unit 190 can further be controlled the operation of the first and second gate valve 176a and 176b and control first to fourth flowrate control valve 178a, 178b, the operation of 178c and 178d.
First vector gas, second vector gas and Purge gas (purging gas) can comprise rare gas element respectively, for example, and argon (Ar) gas or nitrogen (N
2) gas.In exemplary embodiments of the present invention, first reservoir 132, second reservoir 142 and the 3rd reservoir can be stored the first source gas, second source gas and the Purge gas respectively.In another exemplary embodiments of the present invention, can provide the first source gas, second source gas and the Purge gas from the single reservoir (not shown) of airing system 120.
In dipping pipeline 136, can arrange the primary heater (not shown), so that first vector gas that provides from first reservoir 132 to be provided.Primary heater can increase from first liquid source (for example, the TiCl of liquid phase
4) first source gas (for example, the TiCl
4Gas) vaporization efficiency.Primary heater may provide heat to first vector gas, so that first vector gas can reach the temperature of the boiling point that is higher than first liquid source fully.Primary heater can heat first vector gas to about 100 ℃ to about 180 ℃ temperature range.For example, the temperature of first vector gas can be about 150 ℃.
At the first connection line 170a, first fen pipeline 172a with respectively the heating jacket (not shown) can be installed among the pipeline 172b in second minute, to prevent first source gas condensation in each connection line.
Secondary heater 184 can be coupled to encloses container 134, with heating encloses container 134, increases the vaporization efficiency from the first source gas of first liquid source thus.Secondary heater 184 can comprise resistance coil, and this resistance coil can surround encloses container 134.
In Stage microscope 104, can further provide Stage microscope well heater 108, so that substrate 10 is heated to treatment temp.Stage microscope well heater 108 also can comprise resistance coil.In addition, Stage microscope well heater 108 can comprise a plurality of lamp (not shown).For example, Stage microscope well heater 108 can comprise a plurality of halogen lamps (halogen lamp), and halogen lamp can comprise lamp housing and lamp assembly.The useful to irradiation of rays that lamp housing can comprise halogen lamp and produce on Stage microscope 104 by halogen lamp.The lamp assembly can comprise the transparent window of arranging between Stage microscope 104 and the halogen lamp.
Sidewall at treatment chamber 102 can provide gate 186.Substrate 10 can be loaded into treatment chamber 102 neutralizations from treatment chamber 102 unloadings by gate 186.
By the vacuum system 110 that is coupled to treatment chamber 102, can remove byproduct of reaction and the residual gas that the forming process of metal composite layer, produces from treatment chamber 102.Vacuum system 110 can comprise vacuum pump 112, vacuum pipeline 114 and segregaion valve 116.
Fig. 3 is equipment method of depositing metal compound layer on substrate shown in Figure 1 is used in explanation according to an exemplary embodiments of the present invention schema.Fig. 4 is the sequential chart of the time of presenting of source gas in the explanation method shown in Figure 4.
Referring to figs. 1 to 4, in S100, by the first source gas and the second source gas are provided on substrate 10, can be on substrate 10 deposit first metal compound layer.The first source gas can comprise metal and haloid element.The second source gas can comprise first material that can react with the metal in the first source gas, and can comprise second material that can react with the haloid element in the first source gas.For example, the first source gas can comprise TiCl
4Gas, and the second source gas can comprise NH
3Gas.Substrate 10 can be loaded onto in the treatment chamber 102.The first and second source gases may be provided on the substrate 10, with deposit first metal compound layer on substrate 10.
In the forming process of first metal compound layer, the flow velocity that the first and second mass flow control device 182a and 182b can adjust the first and second source gases is first-class speed ratio.First-class speed ratio can be in about 1.0: 0.5 to about 1.0: 10 scope.For example, first-class speed ratio can be about 1.0: 1.0.In other words, first-class speed ratio can be in about 0.1: 1.0 to about 2.0: 1.0 scope.For example, first flow velocity of the first source gas can be about 30sccm, and second flow velocity of the second source gas can be about 30sccm.
When first flow velocity is less than about 0.1 with respect to the velocity ratio of second flow velocity, first metal compound layer of deposit correctly on substrate 10.When velocity ratio is approximately higher than 2.0, although on substrate 10 deposit first metal compound layer continuously, the efficient of the first source gas may be reduced unfriendly.
In S110, by the first source gas and the second source gas are provided on substrate 10, can be on first metal compound layer deposit second metal compound layer.Simultaneously, can remove undesirable material from first and second metal compound layers.The first and second source gases can provide with second velocity ratio that is different from first-class speed ratio basically.Specifically, can provide the first source gas, and provide the second source gas with the 4th flow velocity that is higher than second flow velocity fully with the 3rd flow velocity that is lower than first flow velocity fully.The 3rd mass flow control device 182c and the 4th mass flow control device 182d can adjust the 3rd flow velocity of the first source gas and the 4th flow velocity of the second source gas respectively.Second velocity ratio between the 4th flow velocity of the 3rd flow velocity of the first source gas and the second source gas can be in about 1.0: 100 to about 1.0: 1, in 000 the scope, to remove undesirable material fully from first and second metal compound layers.In other words, second velocity ratio between the 3rd flow velocity and the 4th flow velocity can be in about 0.001: 1.0 to about 0.01: 1.0 scope.In addition, second flow velocity of second gas and the 3rd velocity ratio between the 4th flow velocity can be in about 1.0: 10 to about 1.0: 100 scope.That is the 3rd velocity ratio between the second and the 4th flow velocity of second gas can be in about 0.01: 1.0 to about 0.1: 1.0 scope.For example, in the forming process of second metal compound layer, the 3rd flow velocity of the first source gas is about 2sccm, and the 4th flow velocity of the second source gas is about 1,000sccm.
In exemplary embodiments of the present invention, can use the first source gas that provides with the 3rd flow velocity, the second source gas that provides with the 4th flow velocity and the residue first source gas that may be present in the treatment chamber 102 forms second metal compound layer.After the formation of first metal compound layer, in treatment chamber 102, may stay the remaining first source gas.As mentioned above, can remove the chlorine that may be contained in first and second metal compound layers by the second source gas that provides with high flow velocities.
In S120, has the metal composite layer (for example, first and second metal compound layers) of wishing thickness by repeating the operation of S100 and S110, can on substrate 10, forming.That is, carry out first operation of deposit first metal compound layer and second operation of deposit second metal compound layer continuously, have the metal composite layer of wishing thickness so that can on substrate 10, form.
As shown in Figure 4, the first period t1 can carry out first operation of deposit first metal compound layer, and the second period t2 can carry out second operation of deposit second metal compound layer.First and second operations can be performed several seconds to about tens seconds approximately respectively.For example, first and second metal compound layers can be deposited about 6 seconds respectively.
Owing to can remove dechlorination fully from first and second metal compound layers, therefore can under lower temperature, carry out first and second operations.Thus, metal composite layer can have the step coverage of increase.In exemplary embodiments of the present invention, can to about 600 ℃ temperature and at about 0.1Torr, to the pressure of about 2.5Torr, form metal composite layer at about 400 ℃.
The chlorination titanium layer is with respect to the treatment temp of source gas and the deposition rate of flow velocity
In order to estimate the deposition rate of metal compound layer according to the treatment temp of source gas and flow velocity,, measure deposition rate at the titanium nitride layer on the substrate under about 550 ℃ temperature and under about 700 ℃ temperature by changing the flow velocity of source gas.
Fig. 5 is that explanation exemplary embodiments metal compound layer according to the present invention is with respect to TiCl
4The graphic representation of the treatment temp of gas and the deposition rate of flow velocity.
By changing TiCl
4First deposition rate of velocity measurement first titanium nitride layer of gas; Under the first about 550 ℃ temperature in treatment chamber load substrates; And under the flow velocity of about 60sccm, provide NH
3Gas.In addition, by changing TiCl
4Second deposition rate of velocity measurement second titanium nitride layer of gas; Under the second about 700 ℃ temperature in treatment chamber load substrates; And under the flow velocity of about 60sccm, provide NH
3Gas.In two experiments, treatment chamber is in the pressure of about 5Torr.
Measuring result has been shown among Fig. 5.With reference to figure 5, work as TiCl
4Gas is with respect to NH
3The velocity ratio of gas was approximately higher than 0.5: 1.0 o'clock, and second deposition rate of second titanium nitride layer has saturation value.In addition, work as TiCl
4Gas is with respect to NH
3The velocity ratio of gas was less than about 0.5: 1.0 o'clock, and second deposition rate of second titanium nitride layer has peak value.Work as TiCl
4Gas is with respect to NH
3The velocity ratio of gas was approximately higher than 0.17: 1.0 o'clock, and first deposition rate of first titanium nitride layer is constant basically.
As TiCl under about 700 ℃ treatment temp
4When the flow velocity of gas was approximately higher than 30sccm, second deposition rate of second titanium nitride layer had the value of the substantially constant of about 6.1 /seconds.Work as TiCl
4When the flow velocity of gas was approximately higher than 14sccm, second deposition rate of second titanium nitride layer was about for 10.6 /seconds.On the contrary, as TiCl under about 550 ℃ treatment temp
4When the flow velocity of gas was approximately higher than 30sccm, first deposition rate of first titanium nitride layer had the value of the substantially constant of about 3.8 /seconds.Work as TiCl
4When the flow velocity of gas was less than about 30sccm, first deposition rate of first titanium nitride layer did not change basically.
As mentioned above, work as TiCl
4Gas is with respect to NH
3The velocity ratio of gas was less than about 0.5: 1.0 o'clock, under the second about 700 ℃ temperature, and deposit titanium nitride layer undesirably on substrate.Work as TiCl
4Gas is with respect to NH
3The velocity ratio of gas was approximately higher than 0.5: 1.0 o'clock, because source gas TiCl for example
4Gas and NH
3The surface reaction of inter gas can desirably form titanium nitride layer on substrate.But, work as TiCl
4Gas is with respect to NH
3The velocity ratio of gas was less than about 0.5: 1.0 o'clock, and the formation of titanium nitride layer may depend primarily on TiCl
4Gas and NH
3The mass transfer of inter gas, rather than TiCl
4Gas and NH
3The surface reaction of inter gas, the titanium nitride layer of deposit may have poor step coverage thus.Mass transfer means that wherein the first and second source gases in being provided to treatment chamber react to each other on substrate after, a kind of phenomenon of titanium nitride deposit brokenly on substrate.Surface reaction means after the surface portion that the first and second source gases are adjacent to substrate reacts to each other, and can form the another kind of phenomenon of the continuous nitride titanium layer with uniform thickness on substrate.
If the formation of titanium nitride layer depends primarily on mass transfer rather than surface reaction, titanium nitride layer may have poor step coverage so.But if the formation of titanium nitride layer depends primarily on surface reaction rather than mass transfer, titanium nitride can have the step coverage that increases widely so.
As shown in Figure 5, if under the first about 550 ℃ temperature, form titanium nitride, can guarantee TiCl more fully so
4Gas and NH
3The process allowance of the velocity ratio of inter gas.If TiCl
4Gas is with respect to NH
3The velocity ratio of gas was approximately higher than 0.5: 1.0, and the deposition rate of titanium nitride layer can be very even so.If TiCl4 gas is with respect to NH
3The velocity ratio of gas is in about 0.17: 1.0 to about 0.5: 1.0 scope, and the deposition rate of titanium nitride layer may increase a little so, because at TiCl
4Gas is with respect to NH
3Mass transfer may take place under the low velocity ratio of gas.Because difference is little between the saturation value of deposition rate and the peak value, for example, about 0.9 /second, the therefore TiCl under the first about 550 ℃ temperature
4Gas and NH
3The process allowance of the velocity ratio of inter gas can be fully greater than the TiCl under the second about 700 ℃ temperature
4Gas and NH
3The process allowance of the velocity ratio of inter gas.Therefore, when the velocity ratio of the first and second source inter gas is in about 0.17: 1.0 to about 0.5: 1.0 scope, the formation of titanium nitride layer may depend primarily on the surface reaction of the first and second source inter gas, rather than the mass transfer of source inter gas.In addition, if form titanium nitride layer according to the surface reaction of source inter gas, titanium nitride layer can have the step coverage that increases widely so.
As mentioned above, when forming titanium nitride layer under lower temperature, titanium nitride layer can have the step coverage that increases widely, and TiCl
4Gas and NH
3The inter gas velocity ratio can increase.And, because under lower temperature, form titanium nitride layer, so in the formation of titanium nitride layer, comprise that the beneath structure of layer and/or figure can have the thermal stresses that reduces widely.
Titanium nitride layer is with respect to the processing pressure of source gas and the deposition rate of flow velocity
Deposition rate in order to estimate titanium nitride layer according to the processing pressure and the flow velocity of source gas forms on substrate in the process of titanium nitride layer by the flow velocity that changes source gas, measures the deposition rate of titanium nitride layer under the processing pressure of 2Torr and about 3Torr.
Fig. 6 be the explanation exemplary embodiments according to the present invention under about 500 ℃ treatment temp titanium nitride layer with respect to TiCl
4The graphic representation of the processing pressure of gas and the deposition rate of flow velocity.
In exemplary embodiments of the present invention, provide NH by flow velocity with about 60sccm
3Gas and by changing TiCl
4The flow velocity of gas, the 3rd deposition rate of measurement the 3rd titanium nitride layer under first processing pressure of about 2Torr.Provide NH by flow velocity with about 60sccm
3Gas and by changing TiCl
4The flow velocity of gas, the 4th deposition rate of measurement tetrazotization titanium layer under second processing pressure of about 3Torr.Measuring result has been shown among Fig. 6.Third and fourth titanium nitride layer forms under about 500 ℃ treatment temp.
Fig. 7 be exemplary embodiments according to the present invention under about 700 ℃ treatment temp titanium nitride layer with respect to TiCl
4The graphic representation of the processing pressure of gas and the deposition rate of flow velocity.
In exemplary embodiments of the present invention, provide NH by flow velocity with about 60sccm
3Gas and by changing TiCl
4The flow velocity of gas, the 5th deposition rate of measurement the 5th titanium nitride layer under the 3rd processing pressure of about 2Torr.Provide NH by flow velocity with about 60sccm
3Gas and by changing TiCl
4The flow velocity of gas is managed the 6th deposition rate of measuring the 6th titanium nitride layer under the pressure everywhere at the of about 5Torr.Measuring result has been shown among Fig. 7.The the 5th and the 6th titanium nitride layer forms under about 700 ℃ treatment temp.
As shown in Figure 6, if TiCl
4Gas is with respect to NH
3The velocity ratio of gas is about 1.0: 1.0, and third and fourth deposition rate of third and fourth titanium nitride layer can be saturated under second pressure of first pressure of about 2Torr and about 3Torr so.But, the 4th deposition rate of the tetrazotization titanium layer that under the 3rd deposition rate of the 3rd titanium nitride layer that forms under first pressure of about 2Torr is higher than second pressure at about 3Torr fully, forms.Therefore, when processing pressure was low, titanium nitride layer can have the step coverage of increase.
With reference to figure 7, titanium nitride layer can be similar to the deposition rate variation of titanium nitride layer with respect to treatment temp with respect to the deposition rate variation of processing pressure.If treatment chamber is under the 3rd pressure of about 2Torr, can use TiCl so
4Gas and NH
3Velocity ratio deposit the 5th titanium nitride layer of the broad of inter gas.The 5th deposition rate of the 5th titanium nitride layer can be similar under about 550 ℃ temperature and the deposition rate of first titanium nitride layer that forms under the pressure of about 5Torr, as shown in Figure 5.Therefore, by control treatment temp and processing pressure at least one, titanium nitride layer can have the step coverage of increase.
Fig. 8 A, 8B and 8C are the electron microscope pictures of the titanium nitride layer that forms under the pressure of about 700 ℃ temperature and about 5Torr of the velocity ratio of explanation exemplary embodiments according to the present invention by change source inter gas.Fig. 9 A, 9B and 9C are the electron microscope pictures of the titanium nitride layer that forms under the pressure of about 500 ℃ temperature and about 2Torr of the velocity ratio of explanation exemplary embodiments according to the present invention by change source inter gas.
With reference to figure 8A, 8B and 8C, provide NH by flow velocity with about 60sccm
3Gas and provide TiCl by the flow velocity with about 10sccm respectively
4Gas (referring to Fig. 8 A), the flow velocity of about 30sccm provides TiCl
4Gas (referring to Fig. 8 B), and the flow velocity of about 60sccm provides TiCl
4Gas (referring to Fig. 8 C) under the pressure of about 700 ℃ temperature and about 5Torr, can for example form titanium nitride layer on the cylindricality lower electrode at electrical condenser.When the flow velocity with about 10sccm provides TiCl
4During gas, because the deposition rate of titanium nitride layer may depend primarily on TiCl
4Gas and NH
3The mass transfer of inter gas may be irregularly formed titanium nitride layer very much on lower electrode.When the flow velocity with about 30sccm provides TiCl
4During gas,, on lower electrode, may be irregularly formed titanium nitride layer a little, shown in Fig. 8 B although on the lower electrode of electrical condenser, form titanium nitride layer more continuously.But, when the flow velocity with about 60sccm provides TiCl
4During gas, can be formed uniformly very much titanium nitride layer on lower electrode, this flow velocity is substantially equal to NH
3The flow velocity of gas.
With reference to figure 9A, 9B and 9C, by providing NH under the flow velocity with about 60sccm
3Gas and provide TiCl by the flow velocity with about 10sccm respectively
4Gas (referring to Fig. 9 A), the flow velocity of about 30sccm provides TiCl
4Gas (referring to Fig. 9 B) and the flow velocity of about 60sccm provide TiCl
4Gas (referring to Fig. 9 C) under the pressure of about 500 ℃ temperature and about 2Torr, can for example form titanium nitride layer on the cylindricality lower electrode at electrical condenser.Shown in Fig. 9 A to 9C, if form titanium nitride layer at a lower temperature, on the cylindricality lower electrode, can be formed uniformly very much all titanium nitride layers so, so that each titanium nitride layer can have the step coverage of increase.
As mentioned above, by depositing metal compound layer under lesser temps and lower pressure, for example, titanium nitride layer can advantageously generate metal composite layer.Therefore, metal composite layer can have excellent step coverage and be applied under the thermal stresses of structure can be reduced widely.In exemplary embodiments of the present invention,, can reduce leakage current so widely from titanium nitride layer if on the lower electrode of electrical condenser or on the metal barrier of the grid structure in the transistor, form titanium nitride layer.
Figure 10 A and 10B are the sequential charts that the time of presenting of the first source gas in according to the method for exemplary embodiments of the present invention is described.Figure 10 A shows when the operation that is used for the depositing metal compound layer is repeated twice, is used for first of the first source gas and presents time A.Figure 10 B shows when the operation that is used for the depositing metal compound layer is repeated four times, is used for second of the first source gas and presents time B.
With reference to figure 3,10A and 10B, first quantity of presenting the first source gas that time A provides can be fully greater than second quantity of presenting the first source gas that time B provides, because when the S110 operation is carried out, in treatment chamber 102, may stay some the first source gas that provides among the S100.In other words, if comprise that for the treatment desired time number of cycles of first and second operations increases, the quantity of the first source gas can increase so.Thus, can correctly control the deposition rate of metal compound layer by the number of cycles of adjusting first and second operations, the equipment 100 by Fig. 1 increases the manufacturing turnout thus.And, according to the number of cycles that increases, can remove the chlorine that may be included in the metal compound layer effectively from metal compound layer, so that metal compound layer can have the ratio resistance that reduces widely.
Figure 11 is the sectional view that explanation another exemplary embodiments according to the present invention is used for the equipment of depositing metal compound layer.
With reference to Figure 11, on substrate 10, can use the equipment 200 of depositing metal compound layer in the deposition process process of formation metal composite layer such as titanium nitride layer.
Equipment 200 can comprise treatment chamber 202, Stage microscope 204, vacuum system 210 and airing system 220.
Stage microscope 204 can be disposed in the treatment chamber 202, and support substrates 10 in the deposition process process.Vacuum system 210 can produce pressure in the inside of treatment chamber 202.
Airing system 220 can be provided at the first source gas and the second source gas on the substrate 10, to form metal composite layer on substrate 10.Airing system 220 can be connected to spray header 206, and spray header 206 is arranged in the top of treatment chamber 202.
Spray header 206 can comprise a plurality of first nozzles and a plurality of second nozzle, so that first and second sources are injected on the substrate 10.
Airing system 220 can provide the first and second source gases on substrate 10, to form metal composite layer on substrate 10.If form titanium nitride layer on substrate 10, the first source gas can comprise titanium and chlorine so, and the second source gas can comprise nitrogen and hydrogen.For example, the first source gas and the second source gas can comprise TiCl respectively
4Gas and NH
3Gas.
The first source gas and the second source gas can be introduced in the treatment chamber 202 with first vector gas and second vector gas respectively.
Airing system 220 can provide Purge gas in treatment chamber 202, with the inside of cleaning processing chamber 202.Purge gas can be used as voltage-controlled gas again, with control/adjustment treatment chamber 202 pressure inside.In exemplary embodiments of the present invention, airing system 220 can also provide purge gas in treatment chamber 202, with the inside of cleaning process room 202.
Airing system 220 can comprise first air supply unit 230, second air supply unit 240, the 3rd air supply unit 250 and the 4th air supply unit 260.Airing system 220 can be connected to spray header 206 by a plurality of connection lines.First source gas (for example, the TiCl is provided on the substrate 10 that first air supply unit 230 can load in treatment chamber 202
4Gas) and first vector gas.Second air supply unit 240 can provide second source gas (for example, the NH on substrate 10
3Gas) and second vector gas.The 3rd air supply unit 250 can provide Purge gas in treatment chamber 202, and the 4th air supply unit 260 can be introduced purge gas in the treatment chamber 202.
First air supply unit 230 can comprise first reservoir 232, encloses container 234 and dipping pipeline 236.First reservoir 232 can be stored first vector gas therein.Encloses container 234 can receive first liquid source (for example, the TiCl of liquid phase
4), to produce the first source gas.Dipping pipeline 236 can extend to encloses container 234 from first reservoir 232.By making first vector gas that provides by dipping pipeline 236 produce bubble, can obtain the first source gas from first liquid source.In exemplary embodiments of the present invention, first air supply unit 230 can comprise vaporizer.
Second air supply unit 240 can comprise second reservoir 242 and the second source gas tank 244.Second reservoir 242 can be stored second vector gas therein, and the second source gas tank 244 can provide second source gas (for example, the NH
3Gas) in treatment chamber 202.
The first connection line 270a can be connected to spray header 206 encloses container 234 of first air supply unit 230.Spray header 206 can be connected to the second source gas tank 244 of second air supply unit 240 by the second connection line 270b.In addition, spray header 206 can be connected to 244, the first fens pipeline 272a of the second source gas tank and second fen pipeline 272b can divide out branch from the second connection line 270b by first fen pipeline 272a and second fen pipeline 272b.
The 3rd connection line 270c can be connected to the first connection line 270a with the 3rd gas supply line 250.Second reservoir 242 of second air supply unit 240 can be connected to the second connection line 270b by the 4th connection line 270d.
The 4th air supply unit 260 can be connected to the 3rd connection line 270c by the 5th connection line 270e, so that purge gas is provided in the treatment chamber 202.
The first bypass line 274a, the second bypass line 274b and the 3rd bypass line 274c can be coupled to the first connection line 270a, first fen pipeline 272a and second fen pipeline 272b respectively.
In the first connection line 270a and the second connection line 270b, can arrange the first gate valve 276a and the second gate valve 276b respectively.In the 3rd connection line 270c, the 4th connection valve 270d, the 5th connection valve 270e and dipping pipeline 236, first flow control valve 278a, the second flowrate control valve 278b, the 3rd flowrate control valve 278c and the 4th flowrate control valve 278d can be installed respectively.
In the first connection line 270a, the first bypass line 274a, first minute pipeline 272a, the second bypass line 274b, second fen pipeline 272b and the 3rd bypass line 274c, can arrange the first interlock valve 280a, the second interlock valve 280b, the 3rd interlock valve 280c, the 4th interlock valve 280d, the 5th interlock valve 280e and the 6th interlock valve 280f respectively.
Can arrange the first mass flow control device 282a in the first connection line 270a, be first flow velocity with the flow velocity of adjusting the first source gas.The second mass flow control device 282b can be installed among the pipeline 272a at first minute, was second flow velocity with the flow velocity of adjusting the second source gas.The 3rd mass flow control device 282c can be installed among the pipeline 272b at second minute, was the 3rd flow velocity with the flow velocity of adjusting the 3rd source gas.
When on substrate 10, providing the first source gas and the second source gas with first flow velocity and second flow velocity respectively, so that on substrate 10 during deposit first metal compound layer, the first and the 3rd interlock valve 280a and 280c can be opened, and the second and the 4th interlock valve 280b and 280d can be closed.In addition, for the 3rd flow velocity bypass second source gas, the 5th interlock valve 280e can be closed, but the 6th interlock valve 280f can be opened.
After deposit first metal compound layer, the 5th interlock valve 280e can be opened on substrate 10, and the 6th interlock valve 280f can be closed, and can provide the second source gas on first metal compound layer with the 3rd flow velocity simultaneously.Simultaneously, the first and the 3rd interlock valve 280a and 280c can be closed, and the second and the 4th interlock valve 280b and 280d can be opened, so that use the first and second flow velocity bypass, the first and second source gases respectively.Thus, after the formation of first metal compound layer, can be on first metal compound layer deposit second metal compound layer continuously, and, can remove dechlorination from first and second metal compound layers according to the reaction of the residue first source inter gas in second source gas that provides with the 3rd flow velocity and the treatment chamber 202.
Valve control unit 290 can be controlled the operation of first to the 6th interlock valve 280a, 280b, 280c, 280d, 280e and 280f.Valve control unit 290 can also be adjusted the operation of the first and second gate valve 276a and 276b and the performance of first to fourth flowrate control valve 278a, 278b, 278c and 278d.
Stage microscope 204 can comprise well heater 208, so that substrate 10 is heated to the treatment desired temperature.Gate 286 can be disposed in the sidewall of treatment chamber 202, substrate 10 is loaded into treatment chamber 202 neutralizations from treatment chamber 202 unloading substrates 10.By the vacuum system 110 that is connected to treatment chamber 202, can remove byproduct of reaction and the residual gas that the forming process of metal composite layer, produces from treatment chamber 202.
Figure 12 is the schema that uses equipment method of depositing metal compound layer on substrate shown in Figure 11 according to exemplary embodiments of the present invention.Figure 13 is the sequential chart of the time of presenting of source gas in the explanation method shown in Figure 12, and Figure 14 is the sequential chart that the time of presenting of the first source gas that provides on substrate in the method shown in Figure 12 is described.
With reference to figures 11 to 14, in S200, can be by on substrate 10, providing the first source gas and the second source gas, deposit first metal compound layer on substrate 10.The first source gas can comprise metal and haloid element.The second source gas can comprise first material that can react with the metal in the first source gas, and can comprise second material that can react with the haloid element in the first source gas.Provide the first and second source gases with first-class speed ratio on the substrate 10 that in treatment chamber 202, loads.For example, the first source gas can comprise TiCl
4Gas, and the second source gas can comprise NH
3Gas.
In the forming process of first metal compound layer, the first mass flow control device 282a can adjust first flow velocity of the first source gas, and the second mass flow control device 282b can adjust second flow velocity of the second source gas.In exemplary embodiments of the present invention, first source gas (for example, the TiCl
4Gas) first flow velocity and second source gas (for example, the NH
3Gas) the first-class speed ratio between second flow velocity can be in about 1.0: 0.5 to about 1.0: 10 scope.First-class speed ratio can be about 1.0: 1.0, with surface reaction deposit first metal compound layer on substrate 10 by the first and second source inter gas.
In S210, after the supply that stops the first source gas, can the second source gas be introduced in the treatment chamber 202 with the flow velocity that increases, so that by the second source gas that provides with the flow velocity that increases and the reaction of the residue first source inter gas in the treatment chamber 202, can be on first metal compound layer deposit second metal compound layer.The second source gas can be provided on the substrate 10 with the 3rd flow velocity.Although can be on first metal compound layer deposit second metal compound layer continuously, can remove undesirable material (for example, chlorine) from first and second metal compound layers.
The 3rd mass flow control device 282c can adjust the 3rd flow velocity of the second source gas, to form second metal compound layer and to remove haloid element.The 3rd flow velocity of the second source gas can be higher than second flow velocity fully.In exemplary embodiments of the present invention, second velocity ratio between second flow velocity and the 3rd flow velocity can be in about 1.0: 10 to about 1.0: 100 scope.
In S220, has the metal composite layer of wishing thickness by repeating operation S200 and S210, can on substrate 10, forming.That is, can carry out first operation of deposit first metal compound layer and second operation of deposit second metal compound layer continuously, have the metal composite layer of wishing thickness so that can on substrate 10, form.
As shown in figure 13, the first period t1 can provide the first source gas with first flow velocity on substrate 10, and for the first period t1 in S200, can provide second operation on first metal compound layer with second flow velocity.In S210, can stop the supply of the first source gas, and, can on substrate 10, provide the second source gas with the 3rd flow velocity that increases for the second period t2.Although in S210, can not provide the first source gas, but because after the S200 that forms first metal compound layer, in treatment chamber 202, may be left the first source gas, therefore the remaining first source gas can react with the second source gas, thus deposit second metal compound layer continuously on first metal compound layer.For example, in S200, first and second source gas (for example, the TiCl
4Gas and NH
3Gas) can be introduced in the treatment chamber 202 with the flow velocity of about 60sccm respectively.In S210, can be with for example about 1, the flow velocity of 000sccm provides second gas on substrate 10.
In S210, the first interlock valve 280a can be closed, to stop the supply of the first source gas.But, as shown in figure 14,, on substrate 10, can provide the residue in the treatment chamber 202 the first source gas continuously although can stop the supply of the first source gas by the first interlock valve 280a.Therefore, the flow velocity of the first source gas of the residue among the S210 can be lower than first flow velocity of the first source gas among the S200 fully.In the formation of second metal compound layer,, can little by little reduce the supply of the residue first source gas, with the remaining first source gas of completely consumed by making the remaining first source gas and the second source gas reaction.If the second period t2 of the second source gas was shorter than fully from the time of the treatment chamber 202 dischargings first source gas, in S210, can little by little reduce the flow velocity of the first source gas so.If the second period t2 of the second source gas is long fully, the flow velocity of the first source gas can little by little be reduced so, and in S210, the remaining first source gas can be by completely consumed.
In S200 and S210, substrate 10 can have about 400 to about 600 ℃ treatment temp, and treatment chamber 202 can have about processing pressure of 0.1 to about 2.5Torr.For example, substrate 10 can have about 500 ℃ treatment temp, and treatment chamber 202 can have the processing pressure of about 2.0Torr.
In exemplary embodiments of the present invention, the aforesaid method of deposit titanium layer can be called as TiCl
4Pulsed deposition (TPD) technology.If form titanium nitride layer by the TPD technology according to exemplary embodiments of the present invention on substrate, titanium nitride layer can have so increases electrical property widely, is higher than the conventional titanium nitride layer that forms by SFD technology.
The evaluation of the performance of the titanium nitride layer that forms by SFD technology and TPD technology
Can on substrate, form the 6th titanium nitride by above-mentioned SFD technology.Can be respectively on substrate, provide TiCl with the flow velocity of about 60sccm
4Gas and NH
3About 6 seconds of gas to form titanium nitride layer on substrate, can use the nitrogen purge treatment chamber about 3 seconds.Can be on the 6th titanium nitride layer with about 1, the flow velocity of 000sccm provides NH
3About 6 seconds of gas is to remove the chlorine that may be present in the titanium nitride layer.Nitrogen can be introduced into treatment chamber about 3 seconds, with cleaning processing chamber.These operations that form titanium nitride layer can be repeated about 24 times.That is the number of cycles that comprises above-mentioned operation can be about 24.In SFD technology, substrate can have about 500 ℃ temperature, and treatment chamber can have the pressure of about 3Torr.
TPD technology by exemplary embodiments of the present invention can form the 7th titanium nitride layer on substrate.Can be respectively on substrate provide TiCl with the flow velocity of about 60sccm
4Gas and NH
3About 6 seconds of gas forms first titanium nitride layer on the substrate that loads thus in treatment chamber.Stopping TiCl
4After the supply of gas, can be on first titanium nitride layer with about 1, the flow velocity of 000sccm provides NH
3About 6 seconds of gas forms second titanium nitride layer thus continuously, and removes the chlorine that may be contained in first and second titanium nitride layers simultaneously on first titanium nitride layer.The circulation that comprises the above-mentioned operation that forms first and second titanium nitride layers can be repeated about 24 times.That is, the number of cycles that forms first and second nitride layers can be about 24.In TPD technology, substrate can have about 500 ℃ temperature, and treatment chamber can have the pressure of about 2Torr.
The 6th titanium nitride layer that forms by SFD technology can have the ratio resistance of about 329 μ Ω cm, and can have the ratio resistance of about 283 μ Ω cm by the 7th titanium nitride layer that TPD technology forms.The 6th titanium nitride layer can have about 12.1% thickness evenness, and the 7th titanium nitride layer can have about 6.0% thickness evenness.As a result, compare with the 6th titanium nitride layer that forms by SFD technology, the titanium nitride layer that forms by TPD technology can have the lower ratio resistance and the thickness evenness of increase.In addition, the treatment time of using TDP technology to form the 7th titanium nitride layer can be considerably shorter than uses SFD technology to form the treatment time of the 6th titanium nitride layer, uses TPD technology to increase the manufacturing turnout that forms titanium nitride layer widely thus.
Figure 15 is the graphic representation of titanium nitride layer with respect to the deposition rate of the number of cycles in the SFD technology.Figure 16 is the graphic representation of titanium nitride layer with respect to the deposition rate of the number of cycles in the TPD technology.Figure 17 shows the graphic representation of the every equipment in unit hour (UPEH) with respect to the ratio resistance of the titanium layer that uses SFD and TPD technology to form.
In conventional SFD technology,, can provide TiCl by the flow velocity with about 60sccm respectively for first period
4Gas and NH
3Form titanium nitride layer on the substrate that gas loads in treatment chamber.For second period, can be with about 1, the flow velocity of 000sccm is provided to nitrogen in the treatment chamber, with the inside of cleaning processing chamber.For the 3rd period, can be with about 1, the flow velocity of 000sccm provides NH on titanium nitride layer
3Gas, so that remove dechlorination, and for the 4th period from titanium nitride layer, can be with about 1, the flow velocity of 000sccm is introduced nitrogen in the treatment chamber.Above-mentioned operation can be repeated, to form the titanium nitride layer with about 150 thickness thus.As shown in figure 15, comprise that the number of cycles of above-mentioned operation can be adjusted, to obtain to be used for the deposition rate of titanium nitride layer by conventional SFD operation.In conventional SFD operation, substrate can have about 500 ℃ treatment temp and treatment chamber can have the processing pressure of about 3Torr.The first, second, third and the 4th period can be about 6 seconds respectively, about 3 seconds, about 6 seconds and about 3 seconds.
With reference to Figure 15, in conventional SFD technology, the number of cycles that forms titanium nitride layer can not influence the deposition rate of titanium nitride layer, because the nitrogen that provides by second period can be removed the first source gas that first period provided fully from treatment chamber.In other words, may increase although form the number of cycles of titanium nitride layer, the total amount that forms the first source gas of titanium nitride layer can not change.Therefore, in conventional SFD technology, when the number of cycles that forms titanium nitride layer increased, the deposition rate of titanium nitride layer can be a constant basically.
In the TPD technology of exemplary embodiments of the present invention,, can be respectively on substrate, provide TiCl with the flow velocity of about 60sccm for first period
4Gas and NH
3Gas forms first titanium layer thus on substrate.Can on first titanium nitride layer, can provide TiCl
4Gas and NH
3Gas is to form second titanium nitride layer and to remove dechlorination from first and second titanium nitride layers simultaneously on first titanium nitride layer.The circulation that comprises above-mentioned operation can repeatedly be carried out, to form the titanium nitride layer with about 150 thickness on substrate.As shown in figure 16, number of cycles can comprise above-mentioned operation and can be adjusted, with the deposition rate of the titanium nitride layer that obtains to form by the TPD technology according to exemplary embodiments of the present invention.In TPD technology, substrate can have about 500 ℃ treatment temp and treatment chamber can have the processing pressure of about 2Torr.First and second periods can be about 6 seconds respectively and about 6 seconds.In addition, the TiCl that provides when second period
4When the flow velocity of gas can be about 3.5sccm and about 5sccm, can measure the deposition rate of titanium nitride layer, as shown in figure 16.
With reference to Figure 16, work as TiCl
4The flow velocity of gas can be (a) about 2sccm, (b) about 3.5sccm and (c) during about 5sccm, and according to the increase of the number of cycles that comprises the above-mentioned operation that forms titanium nitride layer, the deposition rate of titanium nitride layer can little by little increase.The TiCl that provides by first period
4Gas and NH
3The surface reaction of inter gas can form first titanium nitride layer on substrate, and by surface reaction and the NH that provides with high flow velocities
3Residue TiCl in gas, the treatment chamber
4Gas and the TiCl that provides with low flow velocity in second period
4Mass transfer in the middle of the gas can form second titanium nitride layer continuously on first titanium nitride layer.Therefore, when number of cycles increased, the deposition rate of titanium nitride layer can little by little increase.
Although in the forming process of second titanium nitride layer because TiCl
4Gas and NH
3Mass transfer may take place in the change in flow of gas, but the step coverage of titanium nitride layer can not be damaged, because the TiCl that provides of second period
4The flow velocity of gas can be markedly inferior to NH
3Gas, and on substrate, can form first and second titanium nitride layers.In addition, because treatment temp and processing pressure can be lower, therefore can suppress TiCl
4Gas and NH
3The mass transfer of inter gas is so that titanium nitride layer can keep good step coverage.As a result, when TiCl can temporarily be provided
4During gas, can increase the deposition rate of titanium nitride layer widely, and not damage the step coverage of titanium nitride layer.
Therebetween, by adjusting the TiCl that second period provided
4Gas and NH
3The velocity ratio of inter gas can increase the deposition rate of titanium nitride layer, and is irrelevant with treatment temp and treatment time.In exemplary embodiments of the present invention, work as TiCl
4Gas and NH
3The inter gas velocity ratio can be in about 1.0: 100 to about 1.0: 1, and in the time of in 000 the scope, the deposition rate of the titanium nitride layer by mass transfer can be substantially equal to the deposition rate by the titanium nitride layer of surface reaction.
With reference to Figure 15 because when in conventional SFD technology when the treatment desired time, the internal recycle number increased, because the deposition rate of titanium nitride layer can be a constant basically, so the manufacturing turnout of titanium nitride layer can be consistent.But, as shown in figure 17, work as NH
3The time of presenting of gas may increase when reducing the ratio resistance of titanium nitride layer, and the UPEH of conventional SFD technology can be reduced widely, reduces the manufacturing turnout of titanium nitride layer of the unit equipment of time per unit and deposit titanium nitride layer thus significantly.
On the contrary, as shown in figure 16, when in according to the TPD technology of exemplary embodiments of the present invention when the treatment desired time, the internal recycle number can increase because the deposition rate of titanium nitride layer increases, the manufacturing turnout of titanium nitride layer can increase.In addition, as shown in figure 17, work as NH
3The time of presenting of gas can be increased so that when reducing the ratio resistance of titanium nitride layer, and the UPEH of TPD technology can not be changed basically, keeps time per unit thus basically and is used for the manufacturing turnout of titanium nitride layer of the unit equipment of deposit titanium nitride layer.
Figure 18 is the sectional view that explanation another exemplary embodiments according to the present invention is used for the equipment of depositing metal compound layer.
With reference to Figure 18, on substrate 10, form metal composite layer, for example, in the deposition process process of titanium nitride layer, can adopt the equipment 300 of depositing metal compound layer.
Equipment 300 can comprise treatment chamber 302, Stage microscope 304, vacuum system 310 and airing system 320.
Stage microscope 304 can be in treatment chamber 302 support substrates 10, and vacuum system 310 can keep the pressure in the inside of treatment chamber 302.
Airing system 320 can provide the first source gas and the second source gas on substrate 10, to form metal composite layer on substrate 10.Airing system 320 can be connected to spray header 306, and spray header 306 is disposed in the top of treatment chamber 302.Spray header 306 can comprise a plurality of first nozzles and a plurality of second nozzle, the first and second source gases are injected in equably on the substrate 10 that loads on the Stage microscope 304.
Airing system 320 can provide the first and second source gases on substrate 10, to form metal composite layer on substrate 10.The first source gas can comprise metal and haloid element.The second source gas can comprise nitrogen and hydrogen.In order to form titanium nitride layer on substrate 10, the first source gas can comprise TiCl
4The gas and the second source gas can comprise NH
3Gas.The first source gas and the second source gas can be introduced in the treatment chamber 302 by first vector gas and second vector gas respectively.
Airing system 320 can also provide Purge gas and purge gas in treatment chamber 302, so that the inside of purification and cleaning process room 302.Purge gas can also be used as voltage-controlled gas, with control/adjustment treatment chamber 302 pressure inside.
Airing system 320 can comprise provides first source gas (for example, the TiCl
4Gas) and first air supply unit 330 of first vector gas, provide second source gas (for example, the NH
3Gas) and second air supply unit 340 of second vector gas, the 4th air supply unit 360 that the 3rd air supply unit 350 of Purge gas is provided and purge gas is provided.Airing system 320 can be connected to spray header 306 by a plurality of connection lines.
First air supply unit 330 can comprise first reservoir 332, reception first liquid source (for example, the TiCl of liquid phase that stores first vector gas
4) encloses container 334 and extend to dipping pipeline 336 encloses container 334 from first reservoir 332.By making first vector gas that provides by dipping pipeline 336 produce bubble, can obtain the first source gas from first liquid source.In exemplary embodiments of the present invention, first air supply unit 330 can comprise vaporizer.
Second air supply unit 340 can comprise second reservoir 342 of storing second vector gas and second source gas (for example, the NH is provided
3Gas) the second source gas tank 344.
The spray header 306 of first air supply unit 330 and encloses container 334 can interconnect by the first connection line 370a, first fen pipeline 372a and second fen pipeline 372b.First and second fens pipeline 372a and 372b can divide out branch from the first connection line 370a.The spray header 306 of second air supply unit 340 and the second source gas tank 344 can interconnect by the second connection line 370b.The 3rd air supply unit 350 can be connected to the first connection line 370a by the 3rd connection line 370c.Second reservoir 342 of second air supply unit 340 can be connected to the second connection line 370b by the 4th connection line 370d.The 4th air supply unit 360 can be connected to the 3rd connection line 370c by the 5th connection line 370e, so that the 4th air supply unit 360 can introduce purge gas in the treatment chamber 302, with the inside of cleaning process room 302.
The first bypass line 374a, the second bypass line 374b and the 3rd bypass line 374c can be connected to first fen pipeline 372a, second fen pipeline 372b and the first connection line 370a respectively.
The first gate valve 376a and the second gate valve 376b can be installed respectively in the first connection line 370a and the second connection line 370b.In the 3rd connection line 370c, the 4th connection line 370d, the 5th connection line 370e and dipping pipeline 336, can arrange first flow control valve 378a, the second flowrate control valve 378b, the 3rd flowrate control valve 378c and the 4th flowrate control valve 378d respectively.
At first minute pipeline 372a, the first bypass line 374a, can arrange the first interlock valve 380a, the second interlock valve 380b, the 3rd interlock valve 380c, the 4th interlock valve 380d, the 5th interlock valve 380e and the 6th interlock valve 380f respectively among pipeline 372b, the second bypass line 374d, the second connection line 370b and the 3rd bypass line 374c in second minute.
Can arrange the first mass flow control device 382a among the pipeline 372a at first minute, be first flow velocity so that adjust the flow velocity of the first source gas.The second mass flow control device 382b can be installed in the second connection line 370b, is second flow velocity with the flow velocity of adjusting the second source gas.In addition, the 3rd mass flow control device 382c can be installed among the pipeline 372b at second minute, be the 3rd flow velocity so that adjust the flow velocity of the first source gas.
When can on substrate 10, providing the first source gas and the second source gas with first flow velocity and second flow velocity respectively, so that on substrate 10 during deposit first metal compound layer, the first and the 5th interlock valve 380a and 380e can be opened, and the second and the 6th interlock valve 380b and 380f can be closed.Simultaneously, for the 3rd flow velocity bypass first source gas, the 3rd interlock valve 380c can be closed, but the 4th interlock valve 380d can be opened.
On substrate 10, form after first metal compound layer, the the 3rd and the 5th interlock valve 380c and 380e can be opened, and the 4th and the 6th interlock valve 380d and 380f can be closed, and can with the 3rd flow velocity and second flow velocity first source gas and the second source gas be introduced in the treatment chamber 302 respectively simultaneously.Simultaneously, the first interlock valve 380a can be closed with the second interlock valve 380b and can be opened, so that with the first flow velocity bypass, the first source gas.Therefore, can be on first metal compound layer deposit second metal compound layer continuously, and after the formation of first metal compound layer, the first source gas that provides according to the second source gas that provides with second flow velocity, with the 3rd flow velocity and the reaction of the residue first source inter gas in the treatment chamber 302 remove dechlorination from first and second metal compound layers simultaneously.
Valve control unit 390 can be adjusted first to the 6th interlock valve 380a, 380b, 380c, 380d, the operation of the operation of 380e and 380f, the first and second gate valve 376a and 376b and first to fourth flowrate control valve 378a, 378b, the performance of 378c and 378d.
Stage microscope 304 can comprise well heater 308, so that substrate 10 is heated to the treatment desired temperature.Sidewall at treatment chamber 302 can provide gate 386, substrate 10 is loaded into treatment chamber 302 neutralizations from treatment chamber 302 unloading substrates 10.By the vacuum system 310 that is coupled to treatment chamber 302, can remove byproduct of reaction and the residual gas that the forming process of metal composite layer, produces from treatment chamber 302.
Figure 19 is the schema that uses equipment method of depositing metal compound layer on substrate shown in Figure 180 according to exemplary embodiments of the present invention.Figure 20 is the sequential chart that the time of presenting of the source gas that uses in the method shown in Figure 19 is described.
Referring to figs. 18 to 20, in S300, by the first source gas and the second source gas are provided on substrate 10, can be at substrate 10 deposit first metal compound layer on the silicon wafer for example.On substrate 10, can provide the first and second source gases with first-class speed ratio.The first source gas can comprise metal and haloid element.The second source gas can comprise first material that can react with the metal in the first source gas, and can comprise second material that can react with the haloid element in the first source gas.For example, the first source gas can comprise TiCl
4Gas, the second source gas can comprise NH
3Gas.
In the forming process of first metal compound layer, the first and second mass flow control device 382a and 382b can adjust the flow velocity of the first and second source gases.For example, the first-class speed ratio between second flow velocity of first flow velocity of the first source gas and the second source gas can be in about 1.0: 0.5 to about 1.0: 10 scope.First-class speed ratio can be about 1.0: 1.0, with surface reaction deposit first metal compound layer by the first and second source inter gas.For example, first flow velocity of the first source gas can be about 60sccm, and second flow velocity of the second source gas can be about 60sccm.
In S310, by the first source gas and the second source gas are provided on substrate 10, can be on first metal compound layer deposit second metal compound layer.Simultaneously, can remove undesirable material from first and second metal compound layers.The first and second source gases can provide with second velocity ratio that is different from first-class speed ratio fully.Specifically, the first source gas can provide with the 3rd flow velocity that is lower than first flow velocity fully, and the flow velocity of the second source gas can keep consistently.That is the second source gas can provide with second flow velocity.In exemplary embodiments of the present invention, the velocity ratio between second flow velocity of the 3rd flow velocity of the first source gas and the second source gas can be approximately higher than 1.0: 100.The 3rd mass flow control device 382c can adjust the 3rd flow velocity of the first source gas.
In S320, has the metal composite layer of wishing thickness by repeating S30 and S310, can on substrate, forming.That is, can carry out first operation of deposit first metal compound layer and second operation of deposit second metal compound layer, on substrate 10, form metal composite layer thus.
As shown in figure 20, in S300,, can on substrate 10, provide the first source gas, and, can on substrate 10, introduce the second source gas with second flow velocity for the first period t1 with first flow velocity for the first period t1.In S310, for the second period t2, can on first metal compound layer, provide the first source gas, and, can on first metal compound layer, introduce the second source gas with second flow velocity for the second period t2 with the 3rd flow velocity.
In S300 and S310, substrate 10 can have about 400 ℃ to about 600 ℃ treatment temp, and treatment chamber 302 can have the processing pressure of the about 2.5Torr of about 0.1Torr.For example, substrate 10 can have about 500 ℃ treatment temp and treatment chamber 302 can have the processing pressure of about 2.0Torr.
Figure 21 is the sectional view that explanation another exemplary embodiments according to the present invention is used for the equipment of depositing metal compound layer.
With reference to Figure 21, on substrate 10, form metal composite layer, for example, can use the equipment 400 of depositing metal compound layer in the deposition process process of titanium nitride layer.
First air supply unit 430 can have first reservoir 432, reception first liquid source (for example, the TiCl of liquid phase of storage first vector gas
4) encloses container 434 and extend to dipping pipeline 436 encloses container 434 from first reservoir 432.By making first vector gas that provides by dipping pipeline 436 produce bubble, can obtain the first source gas from first liquid source.In exemplary embodiments of the present invention, first air supply unit 430 can comprise vaporizer.Second air supply unit 440 can comprise second reservoir 442 of storing second vector gas and second source gas (for example, the NH is provided
3Gas) the second source gas tank 444.
The first connection line 470a can be connected to encloses container 434 with spray header 406, and the second connection line 470b can be connected to spray header 406 the second source gas tank 444.The 3rd air supply unit 450 can be connected to the first connection line 470a by the 3rd connection line 470c, and second reservoir 442 of second air supply unit 440 can be connected to the second connection line 470b by the 4th connection line 470d.The 4th air supply unit 460 can be connected to the 3rd connection line 470c by the 5th connection line 470e, providing purge gas in treatment chamber 402, and the inside of cleaning process room 402.
The first bypass line 474a and the second bypass line 474b can be connected to the first connection line 470a and the second connection line 470b respectively.
In the first connection line 470a and the second connection line 470b, can arrange the first gate valve 476a and the second gate valve 476b respectively.In the 3rd connection line 470c, the 4th connection line 470d, the 5th connection line 470e and dipping pipeline 436, first flow control valve 478a, the second flowrate control valve 478b, the 3rd flowrate control valve 478c and the 4th flowrate control valve 478d can be installed respectively.In the first connection line 470a, the first bypass line 474a, the second connection line 470b and the second bypass line 474d, can arrange the first interlock valve 480a, the second interlock valve 480b, the 3rd interlock valve 480c and the 4th interlock valve 480d respectively.
Can arrange the first mass flow control device 482a in the first connection line 470a, be first flow velocity with the flow velocity of adjusting the first source gas.The second mass flow control device 482b can be installed in the second connection line 470b, is second flow velocity with the flow velocity of adjusting the second source gas.
When can on substrate 10, providing the first source gas and the second source gas with first flow velocity and second flow velocity respectively, so that on substrate 10 during deposit first metal compound layer, the first and the 3rd interlock valve 480a and 480c can be opened, but the second and the 4th interlock valve 480b and 480d can be closed.
After forming first metal compound layer, the 3rd interlock valve 480c can be opened, and the 4th interlock valve 480d can be closed, and can stop the supply of the first source gas and can provide the second source gas on first metal compound layer with second flow velocity simultaneously.At this moment, the first interlock valve 480a can be closed, but the second interlock valve 480b can be opened, so that with the first flow velocity bypass, the first source gas.Thus, deposit second metal compound layer continuously on first metal compound layer, and, can remove dechlorination from first and second metal compound layers simultaneously according to second source gas that after the formation of first metal compound layer, provides and the first source inter gas reaction of the residue in the treatment chamber 402 with second flow velocity.
Figure 22 is the schema that uses equipment method of depositing metal compound layer on substrate shown in Figure 21 according to exemplary embodiments of the present invention.Figure 23 is the sequential chart that the time of presenting of the source gas that uses in the method shown in Figure 22 is described.
With reference to figures 21 to 23, in S400, by the first source gas and the second source gas are provided on substrate 210 with first-class speed ratio, can be at substrate 10 deposit first metal compound layer on the silicon wafer for example.The first source gas can comprise metal and haloid element, and the second source gas can comprise first material that can react with the metal in the first source gas, and can comprise second material that can react with the haloid element in the first source gas.For example, the first source gas can comprise TiCl
4Gas, the second source gas can comprise NH
3Gas.
In the forming process of first metal compound layer, the first and second mass flow control device 482a and 482b can adjust first flow velocity of the first source gas and second flow velocity of the second source gas independently.For example, first-class speed ratio can be in about 1.0: 0.5 to about 1.0: 10 scope.First-class speed ratio can be about 1.0: 1.0, so that pass through the surface reaction of the first and second source inter gas, deposit first metal compound layer.For example, first flow velocity of the first source gas can be about 60sccm, and second flow velocity of the second source gas can be about 60sccm.
In S410, can stop the supply of the first source gas, and can on first metal compound layer, provide the second source gas with second flow velocity, so that can be by the second source gas that provides with constant flow rate and the reaction of the residue first source inter gas in the treatment chamber 402, deposit second metal compound layer on first metal compound layer.Simultaneously, can remove undesirable material from first and second metal compound layers by the reaction of the second source gas and the remaining first source inter gas.
In S420,, can on substrate, form and have the metal composite layer of wishing thickness by repeating the operation of S400 and S410 continuously.That is, can carry out first operation of deposit first metal compound layer and second operation of deposit second metal compound layer, so that on substrate 10, form metal composite layer thus.
In the S400 neutralization as shown in figure 23, for the first period t1, can on substrate 10, provide the first source gas, and, can on substrate 10, introduce the second source gas with second flow velocity for the first period t1 with first flow velocity.In S410, can stop the supply of the first source gas, for the second period t2, can on first metal compound layer, provide the second source gas with second flow velocity.After the formation of first metal compound layer, the first source gas that in treatment chamber 402, can be left in S400, to provide.Reaction by remaining the first source gas and the second source inter gas can be on first metal compound layer deposit second metal compound layer continuously, the second source gas can provide with constant flow rate.In exemplary embodiments of the present invention, in operation S400 and S410, can be with the flow velocity of about 60sccm with first source gas (for example, the TiCl
4Gas) introduce intermittently in the treatment chamber 402.In addition, in operation S400 and S410, can be with the constant flow rate of about 60sccm with second source gas (for example, the NH
3Gas) introduce in the treatment chamber 402.
Specifically, although the first interlock valve 480a can stop the supply of the first source gas in S410, but the residue that provides among the S400 first source gas can react with the second source gas that provides among the S410, so as on first metal compound layer deposit second metal compound layer continuously.If the second period t2 of S410 is shorter than fully from treatment chamber 402 and discharges the time that the first source gas needs, first flow velocity of the first source gas can little by little be reduced in the formation of second metal compound layer so.If the second period t2 sufficiently long of S410, first flow velocity of the first source gas can little by little be reduced in the formation of second metal compound layer so.After the formation of second metal compound layer, the first residue source gas can be by completely consumed.
In S400 and S410, substrate 10 can have about 400 ℃ to about 600 ℃ treatment temp, and treatment chamber 402 can have the extremely processing pressure of about 2.5Torr of about 0.1Torr.For example, substrate 10 can have about 500 ℃ treatment temp, and treatment chamber 402 can have the processing pressure of about 2.0Torr.
Figure 24 is the sectional view that explanation exemplary embodiments according to the present invention is used for the equipment of depositing metal compound layer.
With reference to Figure 24, on semiconducter substrate 10, form metal composite layer, for example, can adopt the equipment 500 of depositing metal compound layer in the deposition process process of titanium nitride layer.Equipment 500 can comprise treatment chamber 502, Stage microscope 504, vacuum system 510 and airing system 520.
Provide the first source gas and the second source gas on the substrate 10 that airing system 520 can load in treatment chamber 502, so that on substrate 10, form metal composite layer.Airing system 520 can be connected to spray header 506, and spray header 506 is arranged in the top of treatment chamber 502.
If form titanium nitride layer on substrate 10, the first source gas can comprise TiCl so
4The gas and the second source gas can comprise NH
3Gas.Can use first vector gas and second vector gas that the first source gas and the second source gas are carried in the treatment chamber 502 respectively.Airing system 520 can also provide Purge gas and purge gas in treatment chamber 502, so that purify respectively and the inside of cleaning process room 502.
Airing system 520 can comprise provides first source gas (for example, the TiCl
4Gas) and first air supply unit 530 of first vector gas, provide second source gas (for example, the NH
3Gas) and second air supply unit 540 of second vector gas, the 4th air supply unit 560 that the 3rd air supply unit 550 of Purge gas is provided and purge gas is provided.Airing system 520 can be connected to spray header 506 by a plurality of connection lines.
First air supply unit 530 can have first reservoir 532, storage first liquid source (for example, the TiCl of liquid phase of storage first vector gas
4) encloses container 534 and extend to dipping pipeline 536 encloses container 534 from first reservoir 532.By making first vector gas that provides by dipping pipeline 536 produce bubble, can obtain the first source gas from first liquid source.Second air supply unit 540 can comprise second reservoir 542 of storing second vector gas and second source gas (for example, the NH is provided
3Gas) the second source gas tank 544.
Spray header 506 can be connected to the encloses container 534 of first air supply unit 530 by the first connection line 570a, first fen pipeline 572a, second fen pipeline 572b and the 3rd fen pipeline 572c.First to the 3rd fen pipeline 572a, 572b and 572c can divide out branch from the first connection line 570a.Spray header 506 can be connected to the second source gas tank 544 of second air supply unit 540 by the second connection line 570b, the 4th fen pipeline 572d, the 5th fen pipeline 572e and the 6th fen pipeline 572f.The the 4th to the 6th fen pipeline 572d, 572e and 572f can divide out branch from the second connection line 570b.The 3rd air supply unit 550 can be connected to the first connection line 570a by the 3rd connection line 570c.Second reservoir 542 of second air supply unit 540 can be connected to the second connection line 570b by the 4th connection line 570d.The 4th air supply unit 560 can be connected to the 3rd connection line 570c by the 5th connection line 570e, providing purge gas in treatment chamber 502, and the inside of cleaning process room 502.
The first bypass line 574a, the second bypass line 574b, the 3rd bypass line 574c, the 4th bypass line 574d, the 5th bypass line 574e and the 6th bypass line 574f can be connected to first minute pipeline 572a, second minute pipeline 572b, the 3rd fen pipeline 572c, the 4th minute pipeline 572d, the 5th fen pipeline 572e and the 6th fen pipeline 572f respectively.
In the first connection line 570a and the second connection line 570b, can arrange the first gate valve 576a and the second gate valve 576b respectively.In the 3rd connection line 570c, the 4th connection line 570d, the 5th connection line 570e and dipping pipeline 536, first flow control valve 578a, the second flowrate control valve 578b, the 3rd flowrate control valve 578c and the 4th flowrate control valve 578d can be installed respectively.At first fen pipeline 572a, the first bypass line 574a, second fen pipeline 572b, the second bypass line 574b, the 3rd fen pipeline 572c, the 3rd bypass line 574c, the 4th fen pipeline 572d, the 4th bypass line 574d, the 5th fen pipeline 572e, the 5th bypass line 574e, can arrange the first interlock valve 580a respectively among the 6th fen pipeline 572f and the 6th bypass line 574f, the second interlock valve 580b, the 3rd interlock valve 580c, the 4th interlock valve 580d, the 5th interlock valve 580e, the 6th interlock valve 580f, the 7th interlock valve 580g, the 8th interlock valve 580h, the 9th interlock valve 580i, the tenth interlock valve 580j, the 11 interlock valve 580k and the 12 interlock valve 580m.
In first fen pipeline 572a can be first flow velocity with the flow velocity of adjusting the first source gas arranging the first mass flow control device 582a.At the 4th minute the second mass flow control device 582b can be installed among the pipeline 572d, be second flow velocity with the flow velocity of adjusting the second source gas.Can arrange the 3rd mass flow control device 582c among the pipeline 572b at second minute, be the 3rd flow velocity with the flow velocity of adjusting the first source gas.At the 5th minute the 4th mass flow control device 582d can be installed among the pipeline 572e, be the 4th flow velocity with the flow velocity of adjusting the second source gas.Can arrange the 5th mass flow control device 582e among the pipeline 572c at the 3rd minute, be the 5th flow velocity with the flow velocity of adjusting the first source gas.At the 6th minute the 6th mass flow control device 582f can be installed among the pipeline 572f, be the 6th flow velocity with the flow velocity of adjusting the second source gas.
When can on substrate 10, providing the first source gas and the second source gas with first flow velocity and second flow velocity respectively, so that on substrate 10 during deposit first metal compound layer, the first and the 7th interlock valve 580a and 580g can be opened, and the second and the 8th interlock valve 580b and 580h can be closed.Simultaneously, the 3rd and the 5th interlock valve 580c and 580e can be closed, and the 4th and the 6th interlock valve 580d and 580f can be opened, so that with the 3rd and the 5th flow velocity bypass first source gas.In addition, for the 4th and the 6th flow velocity bypass second source gas, the 9th and the 11 interlock valve 580i and 580k can be closed, but the tenth and the 12 interlock valve 580j and 580m can be opened.
After forming first metal compound layer, the the 3rd and the 9th interlock valve 580c and 580i can be opened, and the 4th and the tenth interlock valve 580d and 580j can be closed, simultaneously can on first metal compound layer, provide the first and second source gases, so that form second metal compound layer with third and fourth flow velocity.At this moment, the first and the 5th interlock valve 580a and 580e can be closed, but the second and the 6th interlock valve 580b and 580f can be opened, so that with the first and the 5th flow velocity bypass first source gas.In addition, the 7th and the 11 interlock valve 580g and 580k can be closed, and the 8th and the 12 interlock valve 580h and 580m can be opened, so that with the second and the 6th flow velocity bypass second source gas.
After deposit second metal compound layer, the the 5th and the 11 interlock valve 580e and 580k can be opened, but the 6th and the 12 interlock valve 580f and 580m can be closed, simultaneously can on second metal compound layer, provide the first and second source gases, so that form the 3rd metal compound layer with the 5th and the 6th flow velocity.Simultaneously, the first and the 3rd interlock valve 580a and 580c can be closed, and the second and the 4th interlock valve 580b and 580d can be opened, so that with the first and the 3rd flow velocity bypass first source gas.In addition, the 7th and the 9th interlock valve 580g and 580i can be closed, but the 8th and the tenth interlock valve 580h and 580j can be opened, so that with the second and the 6th flow velocity bypass second source gas.
After forming the 3rd metal compound layer, the the 3rd and the 9th interlock valve 580c and 580i can be opened, but the 4th and the tenth interlock valve 580d and 580j can be closed, simultaneously can on the 3rd metal compound layer, provide the first and second source gases, so that on the 3rd metal compound layer, form the 4th metal compound layer with third and fourth flow velocity.Simultaneously, the first and the 5th interlock valve 580a and 580e can be closed, but the second and the 6th interlock valve 580b and 580f can be opened, so that use the first and the 5th flow velocity bypass first source gas respectively.In addition, the 7th and the 11 interlock valve 580g and 580k can be closed, and the 8th and the 12 interlock valve 580h and 580m can be opened, so that with the second and the 6th flow velocity bypass second source gas.
Valve control unit 590 can be controlled the first to the 12 interlock valve 580a, 580b, 580c, 580d, 580e, 580f, 580g, 580h, 580i, 580j, the operation of the operation of 580k and 580m, the first and second gate valve 576a and 576b and first to fourth flowrate control valve 578a, 578b, the performance of 578c and 578d.
Stage microscope 504 can comprise well heater 508, with heated substrate 10 to the treatment desired temperature.Gate 586 can be disposed in the sidewall of treatment chamber 502, so as substrate 10 can be loaded in the treatment chamber 502 by gate 586/from treatment chamber 502 unloadings.The vacuum system 510 that is coupled to treatment chamber 502 can be removed the byproduct of reaction that produces in the forming process of metal illuvium and the residual gas in the treatment chamber 502.
Figure 25 is the schema that uses equipment method of depositing metal compound layer on substrate shown in Figure 24 according to exemplary embodiments of the present invention.Figure 26 is the sequential chart that the time of presenting of the source gas that uses in the method shown in Figure 25 is described.
With reference to Figure 24 to 26, in S500, by the first source gas and the second source gas are provided on substrate 240 with first-class speed ratio, can be at substrate 10 deposit first metal compound layer on the silicon wafer for example.The first source gas can comprise metal and haloid element, and the second source gas can comprise first material that can react with the metal in the first source gas, and can comprise second material that can react with the haloid element in the first source gas.For example, the first source gas can comprise TiCl
4Gas, the second source gas can comprise NH
3Gas.
In the deposit of first metal compound layer, the first and second mass flow control device 582a and 582b can adjust first flow velocity of the first source gas and second flow velocity of the second source gas respectively independently.First-class speed ratio between second flow velocity of first flow velocity of the first source gas and the second source gas can be determined therein can be by the first and second source inter gas the surface reaction rather than the scope of mass transfer deposit first metal compound layer of the first and second source inter gas in.
In exemplary embodiments of the present invention, the first-class speed ratio between first and second flow velocitys of the first and second source gases can be in about 1.0: 2.0 to about 1.0: 10 scope.In other words, first-class speed ratio can be in about 0.1: 1.0 to about 0.5: 1.0 scope.Therefore, because second flow velocity of the second source gas can be lower than first flow velocity of the first source gas relatively, so can remove undesirable material, for example chlorine effectively from first metal compound layer.For example, first flow velocity of the first source gas can be the about 20sccm that adjusts by the first mass flow control device 582a, and second flow velocity of the second source gas can be the about 60sccm that adjusts by the second mass flow control device 582b.
In S510, can on first metal compound layer, provide the first and second source gases with second velocity ratio that is different from first flow velocity fully.Thus, by the reaction of the first and second source inter gas, can be on first metal compound layer deposit second metal compound layer, and can remove undesirable material simultaneously from first and second metal compound layers.
In exemplary embodiments of the present invention, the first source gas can be provided with the 3rd flow velocity that is lower than first flow velocity fully, and provide the second source gas under the 4th flow velocity of second flow velocity being higher than fully.The 3rd mass flow control device 582c can adjust the 3rd flow velocity of the first source gas, and the 4th mass flow control device 582d can adjust the 4th flow velocity of the second source gas.For example, second velocity ratio between the 3rd flow velocity and the 4th flow velocity can be in about 1.0: 100 to about 1.0: 1, in 000 the scope, to remove undesirable material fully from first and second metal compound layers.In other words, second velocity ratio can be in about 0.001: 1.0 to about 0.01: 1.0 scope.In the forming process of second metal compound layer, the first source gas can be provided with the 3rd flow velocity of about 2.0sccm, and can be with about 1, the flow velocity of 000sccm provides the second source gas.In exemplary embodiments of the present invention, second velocity ratio between second flow velocity and the 4th flow velocity can be in about 1.0: 10 to about 1.0: 100 scope.
In S520,, can on substrate, form and have first metal composite layer of wishing thickness by repeating the operation of S500 and S510 continuously.First metal composite layer can comprise first and second metal compound layers.
In S530, by providing the first and second source gases with the 3rd velocity ratio that is different from second velocity ratio basically, can be on first metal composite layer deposit the 3rd metal compound layer.The 5th mass flow control device 582e can adjust the 5th flow velocity of the first source gas, and the 6th mass flow control device 582f can adjust the 6th flow velocity of the second source gas.The 3rd velocity ratio between the 5th and the 6th flow velocity can be in about 1.0: 0.5 to about 1.0: 2.0 scope.In exemplary embodiments of the present invention, the 3rd velocity ratio between the 5th and the 6th flow velocity can be about 1.0: 1.0, so that deposit the 3rd metallic compound advantageously of the surface reaction by the first and second source inter gas.For example, the 5th flow velocity of the first source gas can be about 30sccm, and the 6th flow velocity of the second source gas can be about 30sccm.
In S540, by providing the first and second source gases with the 4th velocity ratio that is different from the 3rd velocity ratio basically, can be on the 3rd metal compound layer deposit the 4th metal compound layer continuously, and can remove simultaneously to be contained in and not wish material in third and fourth metal compound layer.The first source gas and the second source gas can provide with the 7th flow velocity and the 8th flow velocity respectively.
In exemplary embodiments of the present invention, the 4th velocity ratio can be substantially equal to second velocity ratio.Because the 3rd mass flow control device 582c and the 4th mass flow control device 582d can adjust the 7th flow velocity and the 8th flow velocity, the 4th velocity ratio between the 7th and the 8th flow velocity can be in about 1.0: 100 to about 1.0: 1, in 000 the scope.
In S550,, can on first metal composite layer, form and have second metal composite layer of wishing thickness by repeating the operation of S530 and S540 continuously.Second metal composite layer can comprise third and fourth metal compound layer.
In the forming process of first metal composite layer, haloid element can with the materials chemistry ground reaction that comprises in the beneath layer, the byproduct of reaction of the electrical property that produces thus under damaging layer.For under preventing layer electrical property is damaged, first flow velocity of the first source gas can be lower than second flow velocity of the second source gas that uses in the forming process of first composite bed fully.
If on first metal composite layer, form second metal composite layer, reaction between first metal composite layer material that can prevent to comprise in haloid element and the beneath layer so is so that the 5th flow velocity of the first source gas becomes fully greater than first flow velocity of the first source gas.Thus, by the surface reaction of the first and second source inter gas, can on first metal composite, be formed uniformly second metal composite layer.
In exemplary embodiments of the present invention, in the forming process of first metal composite layer, treatment temp and processing pressure can be lower.Can suppress the mass transfer of source inter gas at lower treatment temp and pressure, as illustrated in Figures 5 and 6, so that first metal composite layer can have good step coverage, and the thermal stresses of layer under can reducing to be applied to.In addition, under lower treatment temp, can suppress the reaction between the material in haloid element and the beneath layer, and the residence time that can reduce the first source gas in the treatment chamber 502, the reaction between the material in haloid element and the beneath layer suppressed thus.In the forming process of first metal composite layer, treatment temp can be in about 400 to about 600 ℃ scope, and processing pressure can be in about scope of 0.1 to about 2.5Torr.For example, treatment temp can be about 500 ℃ and processing pressure and can be about 2.0Torr.
In exemplary embodiments of the present invention, can form second metal composite layer with treatment temp and the processing pressure that is substantially similar to first metal composite layer.
In exemplary embodiments of the present invention, beneath layer can comprise the barrier oxide layer of the medium layer of electrical condenser, transistorized gate insulation layer, Nonvolatile semiconductor device etc.If beneath layer comprises height-k material, for example hafnia (HfO
2) or zirconium white (ZrO
2), comprise hafnium chloride (HfCl
4) or zirconium chloride (ZrCl
4) the generation of byproduct of reaction can be suppressed, with the resistance of layer under reducing widely thus with from the leakage current of beneath layer.
Shown in Fig. 5 and 7, when only considering the step coverage of metal composite layer, by adjusting one of treatment temp and processing pressure, metal composite layer can have the step coverage of hope.If under the higher processing pressure of about 5Torr and about 500 ℃ lower Li Wendu, form first metal composite layer, although processing pressure is higher so, first metal composite layer can have the thermal stresses that produces in excellent step coverage and the beneath layer and can be reduced.Because the residence time of the first source gas in the treatment chamber 502 can be longer relatively, in the forming process of first metal composite layer, haloid element can react with the material in the beneath layer.But by the control treatment temp, first metal composite layer can sufficiently have the step coverage of hope.
If under the lower of about 2Torr reason pressure and about 700 ℃ higher treatment temp, form first metal composite layer, although the thermal stresses that produces in the layer under cannot reducing so, first metal composite layer can sufficiently have the step coverage of hope.
As mentioned above, in the deposit of the 3rd metal compound layer the 5th flow velocity of the first source gas can be fully greater than first flow velocity of the first source gas in the deposit of first metal compound layer.On the contrary, the 6th flow velocity of the second source gas can be less than or equal to second flow velocity of the second source gas in the forming process of first metal compound layer fully in the forming process of the 3rd metal compound layer.Therefore, can be by the surface reaction of the first and second source inter gas rather than mass transfer deposit the 3rd metal compound layer of the first and second source inter gas.That is, if the 5th flow velocity is higher than first flow velocity and the 6th flow velocity is lower than second flow velocity, in the deposit of the 3rd metal compound layer, can relatively increase the velocity ratio of the first and second source inter gas so.Thus, because surface reaction rather than mass transfer, the 3rd metal compound layer can have good step coverage.
In exemplary embodiments of the present invention, etching solution and/or etching gas cannot infiltrate in the beneath layer by metal composite layer.Therefore, can prevent from effectively the etching that beneath layer and/or substrate cause is damaged.
Figure 27 is the sectional view that explanation another exemplary embodiments according to the present invention is used for the equipment of depositing metal compound layer.
With reference to Figure 27, on semiconducter substrate 10, form metal composite layer, for example, can adopt the equipment 600 of depositing metal compound layer in the deposition process process of titanium nitride layer.Equipment 600 can comprise treatment chamber 602, Stage microscope 604, vacuum system 610 and airing system 620.
Provide the first source gas and the second source gas on the substrate 10 that airing system 620 can be placed in chamber 602, so that on substrate 10, form metal composite layer.Airing system 620 can be connected to spray header 606, and spray header 606 is arranged in the top of treatment chamber 602.
If form titanium nitride layer on substrate 10, the first source gas can comprise TiCl so
4The gas and the second source gas can comprise NH
3Gas.The first source gas and the second source gas can use first vector gas and second vector gas to be carried in the treatment chamber 602 respectively.Airing system 620 can also provide Purge gas and purge gas in treatment chamber 602, so that the inside of purification and cleaning process room 602.
First air supply unit 630 can have first reservoir 632, storage first liquid source (for example, the TiCl of liquid phase of storage first vector gas
4) encloses container 634 and extend to dipping pipeline 636 encloses container 634 from first reservoir 632.Second air supply unit 640 can comprise second reservoir 642 of storing second vector gas and second source gas (for example, the NH is provided
3Gas) the second source gas tank 644.
The first bypass line 674a, the second bypass line 674b, the 3rd bypass line 674c, the 4th bypass line 674d and the 5th bypass line 574e can be connected to first minute pipeline 672a, second minute pipeline 672b, the 3rd fen pipeline 672c, the 4th minute pipeline 672d, the 5th fen pipeline 672e respectively.
In the second connection line 670a and the second connection line 670b, can arrange the first gate valve 676a and the second gate valve 676b respectively.In the 3rd connection line 670c, the 4th connection line 670d, the 5th connection line 670e and dipping pipeline 636, first flow control valve 678a, the second flowrate control valve 678b, the 3rd flowrate control valve 678c and the 4th flowrate control valve 678d can be installed respectively.At first fen pipeline 672a, the first bypass line 674a, second fen pipeline 672b, the second bypass line 674b, the 3rd fen pipeline 672c, the 3rd bypass line 674c, the 4th fen pipeline 672d, the 4th bypass line 674d, the 5th fen pipeline 672e, can arrange the first interlock valve 680a among the 5th bypass line 674e respectively, the second interlock valve 680b, the 3rd interlock valve 680c, the 4th interlock valve 680d, the 5th interlock valve 680e, the 6th interlock valve 680f, the 7th interlock valve 680h, the 8th interlock valve 680i, the 9th interlock valve 680i and the tenth interlock valve 680j.
Can arrange the first mass flow control device 682a among the pipeline 672a at first minute, be first flow velocity with the flow velocity of adjusting the first source gas.At the 3rd minute the second mass flow control device 682b can be installed among the pipeline 672c, be second flow velocity with the flow velocity of adjusting the second source gas.Can arrange the 3rd mass flow control device 682c among the pipeline 672d at the 4th minute, be the 3rd flow velocity with the flow velocity of adjusting the second source gas.The 4th mass flow control device 682d can be installed among the pipeline 672b at second minute, was the 4th flow velocity with the flow velocity of adjusting the first source gas.Can arrange the 5th mass flow control device 682e among the pipeline 672e at the 5th minute, be the 5th flow velocity with the flow velocity of adjusting the second source gas.
When can on substrate 10, providing the first source gas and the second source gas with first flow velocity and second flow velocity respectively, so that on substrate 10 during deposit first metal compound layer, the first and the 5th interlock valve 680a and 680e can be opened, and the second and the 6th interlock valve 680b and 680f can be closed.Simultaneously, the 3rd interlock valve 680c can be closed with the 4th interlock valve 680d and can be opened, so that with the 4th flow velocity bypass first source gas.In addition, for the 3rd and the 5th flow velocity bypass second source gas, the 7th and the 9th interlock valve 680g and 680i can be closed, but the 8th and the tenth interlock valve 680h and 680j can be opened.
After forming first metal compound layer, the 7th interlock valve 680g can be opened, and the 8th interlock valve 680h can be closed, stop the supply of the first source gas simultaneously and on first metallic compound, provide the second source gas, so that on first metal compound layer, form second metal compound layer with the 3rd flow velocity.At this moment, the first and the 3rd interlock valve 680a and 680c can be closed, but the second and the 4th interlock valve 680b and 680d can be opened, so that use the first and the 4th flow velocity bypass first source gas respectively.In addition, the 5th and the 9th interlock valve 680e and 680i can be closed, and the 6th and the tenth interlock valve 680f and 680h can be opened, so that with the second and the 5th flow velocity bypass second source gas.By the second source gas that provides with the 3rd flow velocity and the reaction of the residue first source inter gas in the treatment chamber 602, can be on first metal compound layer deposit second metal compound layer continuously.At this moment, by the second source gas that provides with the 3rd flow velocity, can remove the chlorine that comprises in first and second metal compound layers.
After deposit second metal compound layer, the the 3rd and the 9th interlock valve 680c and 680i can be opened, but the 4th and the tenth interlock valve 680d and 680j can be closed, simultaneously can on second metal compound layer, provide the first and second source gases, so that on second metal compound layer, form the 3rd metal compound layer with the 4th and the 5th flow velocity.Simultaneously, the first interlock valve 680a can be closed with the second interlock valve 680b and can be opened, so that with the first flow velocity bypass, the first source gas.In addition, the 5th and the 7th interlock valve 680e and 680g can be closed, but the 6th and the 8th interlock valve 680f and 680h can be opened, so that with the second and the 3rd flow velocity bypass second source gas.
After forming the 3rd metal compound layer, the 7th interlock valve 680g can be opened, the 8th interlock valve 680h can be closed, stop the supply of the first source gas simultaneously and can on the 3rd metal compound layer, provide the second source gas, so that on the 3rd metal compound layer, form the 4th metal compound layer with the 3rd flow velocity.At this moment, the first and the 3rd interlock valve 680a and 680c can be closed, but the second and the 4th interlock valve 680b and 680d can be opened, so that with the first and the 3rd flow velocity bypass first source gas.In addition, the 5th and the 9th interlock valve 680e and 680i can be closed, and the 6th and the tenth interlock valve 680f and 680h can be opened, so that with the second and the 5th flow velocity bypass second source gas.By the second source gas that provides with the 3rd flow velocity and the reaction of the residue first source inter gas in the treatment chamber 602, can be on the 3rd metal compound layer deposit the 4th metal compound layer continuously.At this moment, can remove the chlorine that comprises in third and fourth metal compound layer by the second source gas that provides with the 3rd flow velocity.
Figure 28 is the schema that uses equipment method of depositing metal compound layer on substrate shown in Figure 27 according to exemplary embodiments of the present invention.Figure 29 is the sequential chart that the time of presenting of the source gas that uses in the method shown in Figure 28 is described.
With reference to Figure 27 to 29, in S600, by the first source gas and the second source gas are provided on substrate 270 with first-class speed ratio, can be at substrate 10 deposit first metal compound layer on the silicon wafer for example.The first source gas can comprise metal and haloid element, and the second source gas can comprise first material that can react with the metal in the first source gas, and can comprise second material that can react with the haloid element in the first source gas.For example, the first source gas can comprise TiCl
4Gas, and the second source gas can comprise NH
3Gas.
In the deposition process of first metal compound layer, the first and second mass flow control device 682a and 682b can adjust first flow velocity of the first source gas and second flow velocity of the second source gas independently.First-class speed ratio between second flow velocity of first flow velocity of the first source gas and the second source gas can determine therein can be by the first and second source inter gas the surface reaction rather than the scope of mass transfer deposit first metal compound layer of the first and second source inter gas in.
In exemplary embodiments of the present invention, the first-class speed ratio between first and second flow velocitys of the first and second source gases can be in about 1.0: 2.0 to about 1.0: 10 scope.In other words, first-class speed ratio can be in about 0.1: 1.0 to about 0.5: 1.0 scope.Therefore, because second flow velocity of the second source gas can be lower than first flow velocity of the first source gas relatively, so can remove undesirable material, for example chlorine effectively from first metal compound layer.For example, by the first mass flow control device 682a, first flow velocity of the first source gas can be about 20sccm, and by the second mass flow control device 682b, second flow velocity of the second source gas can be about 60sccm.
In S610, can stop the supply of the first source gas, and can on first metal compound layer, provide the second source gas with the 3rd flow velocity, the 3rd flow velocity is fully greater than second flow velocity.Thus, by the second source gas that provides with the 3rd flow velocity and the reaction of the residue first source inter gas in the treatment chamber 602, can be on first metal compound layer deposit second metal compound layer continuously.Simultaneously, by the second source gas that under the 3rd flow velocity, provides and the reaction of the remaining first source inter gas, can remove undesirable material from first and second metal compound layers.
In exemplary embodiments of the present invention, the 3rd mass flow control device 682c can adjust the 3rd flow velocity of the second source gas.Velocity ratio between second flow velocity and the 3rd flow velocity can be in about 1.0: 100 to about 1.0: 1, in 000 the scope.For example, the 3rd flow velocity of the second source gas can be about 1,000sccm.
In exemplary embodiments of the present invention, in S610, the first and the 3rd interlock valve 680a and 680c can stop the supply of the first source gas.Because the residue first source gas that provides among the S600 can react with the second source gas that provides among the S610m, therefore can be on first metal compound layer deposit second metal compound layer continuously.If the treatment time among the S610 is sufficiently long, so in the forming process of second metal compound layer, the flow velocity of the first source gas can little by little reduce from first flow velocity, then can the remaining first source gas of completely consumed after forming second metal compound layer.Treatment time in S610, the more remaining first source gas can react with the second source gas continuously, helps the formation of second metal compound layer thus.
In S620,, can on substrate, form and have first metal composite layer of wishing thickness by repeating operation S600 and S610 continuously.First composite bed can comprise first and second metal compound layers.
In S630, by providing the first and second source gases with the 4th flow velocity and the 5th flow velocity respectively, can be on first metal composite layer deposit the 3rd metal compound layer.The 4th flow velocity can be fully greater than first flow velocity, and the 5th flow velocity can be less than or equal to second flow velocity fully.The 4th mass flow control device 682d can adjust the 4th flow velocity of the first source gas, and the 5th mass flow control device 682e can adjust the 5th flow velocity of the second source gas.Velocity ratio between the 4th and the 5th flow velocity can be in about 1.0: 0.5 to about 1.0: 2.0 scope.For example, the 4th flow velocity of the first source gas can be about 30sccm, and the 5th flow velocity of the second source gas can be about 30sccm.
In S640, deposit the 4th metal compound layer continuously on the 3rd metal compound layer, the supply by stopping the first source gas and provide the second source gas can remove the chlorine that comprises in third and fourth metal compound layer simultaneously with the 6th flow velocity that equals the 3rd flow velocity.The 3rd mass flow control device 682c can advantageously adjust the 6th flow velocity of the second source gas.The 4th metal compound layer can come deposit by identical with second metal compound layer basically operation.
In S650,, can on first composite bed, form and have second metal composite layer of wishing thickness by repeating operation S630 and S640 continuously.Second composite bed can comprise third and fourth metal compound layer.
Figure 30 is the sectional view that explanation exemplary embodiments according to the present invention comprises the semiconducter device of titanium nitride layer.
With reference to Figure 30, on semiconducter substrate 10, can form a plurality of field-effect transistors 20.On transistor 20, can form bit line structure 30, and the electrical condenser 40 that on bit line structure 30, can form the storage data.
The insulating intermediate layer 70a that said structure can be inserted into, 70b and 70c branch are opened.Those structures can form by general semiconductor fabrication basic technology.
Can form the lower electrode 42 and/or the top electrode 44 of electrical condenser 40 by the equipment of above-mentioned depositing technics and depositing metal compound layer, according to exemplary embodiments of the present invention.If medium layer 46 comprises height-k material, so because can under the Li Wendu of lower, use the TiCl that has than minimum velocity
4Gas forms lower electrode 42 and/or top electrode 44, and the reaction between haloid element and height-k material can be suppressed effectively.Therefore, can be reduced widely from the leakage current of lower electrode 42 and/or top electrode 44, and the ratio resistance of lower electrode 42 and/or top electrode 44 can increase.
At insulating intermediate layer 70a, 70b and 70c and conductive structure for example can form metal barrier 32 and 52 between bit line 30 and the metal wiring structure 50.Metal barrier 32 and 52 also can form by the above-mentioned depositing technics and the equipment of exemplary embodiments depositing metal compound layer according to the present invention.Owing to can form metal barrier 32 and 52 under the Li Wendu of lower, the thermal stresses that therefore is applied to beneath structure can be reduced, and beneath structure and the conductive structure for example resistance between bit line 30 and the metal wiring structure 50 can be reduced.
According to the present invention, can use the first source gas and second source gas deposit first metal compound layer on substrate.By controlling the flow velocity of the first and second source gases, can be on first metal compound layer deposit second metal compound layer continuously.In the formation of metal composite layer, can remove undesirable material simultaneously from first and second metal compound layers.Therefore, metal composite layer can have the resistance that reduces widely, and compares the manufacturing turnout that can increase metal composite layer significantly with conventional ALD technology or conventional SFD technology.
In addition, metal composite layer can form under lower Li Wendu and processing pressure, so that can reduce down below issuable thermal stresses in the structure, and metal compound layer can have good step coverage.If beneath structure comprises height-k material, the reaction between haloid element in the metal composite layer and height-k material can be suppressed effectively so, reduces leakage current from metal composite layer widely by beneath structure thus.
And metal composite layer can have the composite structure that comprises a plurality of metal compound layers, in the successive etching procedure by preventing that etching solution and/or etching gas from infiltrating the etching that metal composite layer can suppress beneath structure is caused fully and damaging.
Above be the explanation of exemplary embodiments of the present invention, do not think its restriction.Although described several exemplary embodiments of the present invention, the those skilled in the art will readily appreciate that under the situation that does not break away from novel teachings of the present invention and mode in itself that many improvement of exemplary embodiments are possible.Thus, all this improvement all are confirmed as comprising within the scope of the invention.In claims, device-Jia-function clause is confirmed as covering the structure described here of carrying out described function, not only the structure of structural equivalents but also covering equivalence.Therefore, be to be understood that it above is explanation of the present invention, be not regarded as being limited to disclosed specific embodiment, the improvement of disclosed embodiment and other embodiment are confirmed as comprising within the scope of the invention.
Claims (46)
1. the method for a depositing metal compound layer comprises:
The first source gas and the second source gas are provided on substrate, with first metal compound layer of deposit on substrate, the first source gas comprises metal, the second source gas comprises the material that can react with this metal, wherein provide the first and second source gases with first-class speed ratio, wherein the deposition rate of first metal compound layer of the surface reaction by the first and second source inter gas is higher than the deposition rate of first metal compound layer of the mass transfer by the first and second source inter gas fully; And
Provide the first and second source gases with second velocity ratio that is different from first-class speed ratio, with deposit second metal compound layer on first metal compound layer, wherein the first and second source gases are removed undesirable material simultaneously from first and second metal compound layers.
2. according to the process of claim 1 wherein that the first source gas comprises TiCl
4, the second source gas comprises NH
3
3. according to the process of claim 1 wherein that first-class speed ratio is in about 1.0: 0.5 to about 1.0: 10 scope, and second velocity ratio is in about 1.0: 100 to about 1.0: 1, in 000 the scope.
4. according to the process of claim 1 wherein that the flow velocity of the first source gas in the forming process of first metal compound layer is greater than the flow velocity of the first source gas in the forming process of second metal compound layer.
5. according to the process of claim 1 wherein that the flow velocity of the second source gas in the forming process of second metal compound layer is greater than the flow velocity of the second source gas in the forming process of first metal compound layer.
6. according to the method for claim 5, wherein the 3rd velocity ratio between the flow velocity of second gas in the forming process of the flow velocity of the second source gas in the forming process of first metal compound layer and second metal compound layer is in about 1.0: 10 to about 1.0: 100 scope.
According to the process of claim 1 wherein about 400 to about 600 ℃ temperature deposit first and second metal compound layers.
8. according to the process of claim 1 wherein at about pressure of 0.1 to about 2.5Torr and about 400 deposit first and second metal compound layers to about 700 ℃ temperature.
9. according to the method for claim 1, also comprise flow velocity that increases by the second source gas and the supply that reduces or stop the first source gas, wherein remain the first source gas and the second source gas reacts, with deposit second metal compound layer.
10. according to the method for claim 1, also comprise:
Supply by reducing or stop the first source gas and by using the flow velocity greater than the flow velocity of the second source gas in the forming process of first metal compound layer that the second source gas is provided is removed undesirable material from first metal compound layer; And
Supply by reducing or stop the first source gas and by using the flow velocity greater than the flow velocity of the second source gas in the forming process of second metal compound layer that the second source gas is provided is removed undesirable material from second metal compound layer.
11. the method for a depositing metal compound layer comprises:
The first source gas and the second source gas are provided on substrate, with first metal compound layer of deposit on substrate, the first source gas comprises metal, the second source gas comprises the material that can react with this metal, wherein provide the first and second source gases with first-class speed ratio, wherein the deposition rate of first metal compound layer of the surface reaction by the first and second source inter gas is higher than the deposition rate of first metal compound layer of the mass transfer by the first and second source inter gas fully;
Provide the first and second source gases with second velocity ratio that is different from first-class speed ratio, with deposit second metal compound layer on first metal compound layer;
Provide the first and second source gases with the 3rd velocity ratio that is different from first-class speed ratio, with deposit the 3rd metal compound layer on second metal compound layer, to cause the surface reaction of the first and second source inter gas; And
Provide the first and second source gases with the 4th velocity ratio that is different from the 3rd velocity ratio, with deposit the 4th metal compound layer on the 3rd metal compound layer.
12. according to the method for claim 11, wherein the first source gas comprises TiCl
4, the second source gas comprises NH
3
13. according to the method for claim 11, wherein in the forming process of first metal compound layer, the flow velocity of the first source gas is lower than the flow velocity of the second source gas.
14. according to the method for claim 13, wherein first-class speed ratio is in about 1.0: 2.0 to about 1.0: 10.0 scope.
15. according to the method for claim 11, wherein the flow velocity of the first source gas in the forming process of first metal compound layer is greater than the flow velocity of the first source gas in the forming process of second metal compound layer.
16. according to the method for claim 11, wherein the deposition rate of second metal compound layer of the surface reaction by the first and second source inter gas is similar to the deposition rate of second metal compound layer of the mass transfer by the first and second source inter gas.
17. according to the method for claim 16, wherein second velocity ratio is in about 1.0: 100 to about 1.0: 1, in 000 the scope.
18. according to the method for claim 11, wherein the flow velocity of the second source gas in the forming process of second metal compound layer is greater than the flow velocity of the second source gas in the forming process of first metal compound layer.
19. according to the method for claim 18, wherein the velocity ratio between the flow velocity of the second source gas is in about 1.0: 10 to about 1.0: 100 scope in the forming process of the flow velocity of the second source gas in the forming process of first metal compound layer and second metal compound layer.
20. according to the method for claim 11, wherein the flow velocity of the first source gas in the forming process of the 3rd metal compound layer is greater than the flow velocity of the first source gas in the forming process of first metal compound layer.
21. according to the method for claim 11, wherein the 3rd velocity ratio is in about 1.0: 0.5 to about 1.0: 2.0 scope.
22. according to the method for claim 11, wherein second velocity ratio is similar to the 4th velocity ratio.
23. according to the method for claim 22, wherein the flow velocity of the first source gas in the forming process of second metal compound layer is similar to the flow velocity of the first source gas in the forming process of the 4th metal compound layer.
24. according to the method for claim 11, wherein about 400 to about 600 ℃ temperature deposit first to fourth metal compound layer.
25. according to the method for claim 11, wherein at about pressure of 0.1 to about 2.5Torr and about 400 deposit first to fourth metal compound layer to about 700 ℃ temperature.
26. according to the method for claim 11, wherein repeat deposit first metal compound layer and deposit second metal compound layer continuously, on substrate, to form first metal composite layer.
27. according to the method for claim 26, wherein first metal composite layer is formed up to about 30 thickness to about 100 .
28. according to the method for claim 26, wherein repeat deposit the 3rd metal compound layer and deposit the 4th metal compound layer continuously, on first metal composite layer, to form second metal composite layer.
29. according to the method for claim 28, wherein first and second metal composite layers form the lower electrode or the top electrode of electrical condenser.
30. according to the method for claim 28, wherein first and second metal composite layers form metal barrier.
31. according to the method for claim 28, wherein first and second metal composite layers form and will descend structure to be connected to the embolism of structure.
32. the method for a depositing metal compound layer comprises:
The first source gas and the second source gas are provided on substrate, with first metal compound layer of deposit on substrate, the first source gas comprises metal, the second source gas comprises the material that can react with this metal, wherein provide the first and second source gases with first-class speed ratio, wherein the deposition rate of first metal compound layer of the surface reaction by the first and second source inter gas is higher than the deposition rate of first metal compound layer of the mass transfer by the first and second source inter gas fully;
Provide the second source gas and the supply that reduces or stop the first source gas on first metal compound layer with the flow velocity that increases, wherein the second source gas reacts with the residue first source gas, with deposit second metal compound layer on first metal compound layer;
Provide the first and second source gases with second velocity ratio that is different from first-class speed ratio, to cause the surface reaction of the first and second source inter gas, with deposit the 3rd metal compound layer on second metal compound layer; And
Provide the second source gas and the supply that reduces or stop the first source gas on the 3rd metal compound layer with the flow velocity that increases, wherein the second source gas reacts with the residue first source gas, with deposit the 4th metal compound layer on the 3rd metal compound layer.
33. as the method for claim 32, wherein the first source gas comprises halogen, and the second source gas comprise can with the material of this halogen reaction, with deposit first metal compound layer.
34. the method according to claim 33 also comprises:
Provide the first and second source gases with first flow velocity and second flow velocity respectively, with deposit first metal compound layer;
By providing the first source gas with the 3rd flow velocity that is lower than first flow velocity and by using the 4th flow velocity that the second source gas is provided greater than second flow velocity, remove halogen from first and second metal compound layers, and the formation of second metal compound layer and to remove halogen synchronous;
Use the 5th flow velocity greater than first flow velocity that the first source gas is provided and by providing the second source gas, with deposit the 3rd metal compound layer on second metal compound layer with the 6th flow velocity that is similar to or be lower than second flow velocity; And
By providing the first source gas with the 7th flow velocity that is similar to the 3rd flow velocity and by providing the second source gas with the 8th flow velocity that is similar to the 4th flow velocity, remove halogen from third and fourth metal compound layer, and the formation of the 4th metal compound layer and to remove halogen synchronous.
35. method according to claim 34, wherein the velocity ratio between first and second flow velocitys is in about 1.0: 2.0 to about 1.0: 10 scope, velocity ratio between third and fourth flow velocity is in about 1.0: 100 to about 1.0: 1, in 000 the scope, and the velocity ratio between the 5th and the 6th flow velocity is in about 1.0: 0.5 to about 1.0: 2.0 scope.
36. the method according to claim 34 also comprises:
Reduce or stop the supply of the first source gas and by providing the second source gas with the 3rd flow velocity greater than second flow velocity, so that the second source gas and the residue first source gas reaction, thus on first metal compound layer deposit second metal compound layer and remove halogen simultaneously;
Use the 4th flow velocity greater than first flow velocity that the first source gas is provided and provide the second source gas, with deposit the 3rd metal compound layer on second metal compound layer with the 5th flow velocity that is similar to or be lower than second flow velocity; And
Reduce or stop the supply of the first source gas and by providing the second source gas with the 6th flow velocity that is similar to the 3rd flow velocity, so that the second source gas and the residue first source gas reaction, thus on the 3rd metal compound layer deposit the 4th metal compound layer and remove halogen simultaneously.
37. the equipment of a depositing metal compound layer comprises:
Be made as the treatment chamber of accommodating substrates;
Be made as the airing system that the first source gas and the second source gas are provided on substrate, wherein the first source gas comprises that the metal and the second source gas comprise the material that can react with this metal; And
Be made as the current velocity controller of the flow velocity of the adjustment first and second source gases with first metal compound layer of deposit on substrate, wherein provide the first and second source gases with first-class speed ratio, and also be made as adjust the first and second source gases flow velocity with deposit second metal compound layer on first metal compound layer, remove undesirable material from first and second metal compound layers simultaneously, wherein provide the first and second source gases with second velocity ratio that is different from first-class speed ratio.
38. according to the equipment of claim 37, wherein this current velocity controller comprises:
First-class speed control member made comprises that being made as the flow velocity of adjusting the first and second source gases is the first mass flow control device and the second mass flow control device of first-class speed ratio; And
The second flow rate control parts comprise that being made as the flow velocity of adjusting the first and second source gases is the 3rd mass flow control device and the 4th mass flow control device of second velocity ratio.
39. according to the equipment of claim 37, wherein this current velocity controller comprises:
First-class speed control member made comprises being made as that to adjust the first source gas be the first mass flow control device of first-class speed ratio with respect to the flow velocity of the second source gas; With
The second flow rate control parts comprise being made as that to adjust the second source gas be the second mass flow control device of second velocity ratio with respect to the flow velocity of the first source gas.
40. according to the equipment of claim 37, wherein this current velocity controller comprises:
First-class speed control member made comprises being made as that to adjust the first source gas be the first mass flow control device and the 3rd mass flow control device of first-class speed ratio with respect to the flow velocity of the second source gas; With
The second flow rate control parts comprise being made as that to adjust the second source gas be the second mass flow control device of second velocity ratio with respect to the flow velocity of the first source gas.
41. according to the equipment of claim 37, wherein this current velocity controller comprises:
First-class speed control member made comprises being made as that to adjust the first source gas be the first mass flow control device of first-class speed ratio with respect to the flow velocity of the second source gas; With
The second flow rate control parts comprise being made as that to adjust the second source gas be the second mass flow control device of second velocity ratio with respect to the flow velocity of the first source gas.
42. according to the equipment of claim 37, wherein this current velocity controller comprises:
First-class speed control member made comprises the first mass flow control device of first flow velocity of adjusting the first source gas, the 3rd mass flow control device of the 3rd flow velocity of adjusting the first source gas and the 5th mass flow control device of adjusting the 5th flow velocity of the first source gas;
The second flow rate control parts comprise the second mass flow control device of second flow velocity of adjusting the second source gas, the 4th mass flow control device of the 4th flow velocity of adjusting the second source gas and the 6th mass flow control device of adjusting the 6th flow velocity of the first source gas.
43. according to the equipment of claim 37, wherein this current velocity controller comprises:
First-class speed control member made comprises first mass flow control device of first flow velocity of adjusting the first source gas and the 4th mass flow control device of the 4th flow velocity of adjusting the first source gas;
The second flow rate control parts comprise the second mass flow control device of second flow velocity of adjusting the second source gas, the 3rd mass flow control device of the 3rd flow velocity of adjusting the second source gas and the 5th mass flow control device of adjusting the 5th flow velocity of the first source gas.
44. according to the equipment of claim 37, also comprise the spray header on the top that is arranged in treatment chamber, on substrate so that the first and second source gases to be provided equably.
45. according to the equipment of claim 44, wherein this airing system comprises:
Be made as first air supply unit that the first source gas is provided; And
Be used to provide second air supply unit of the second source gas, wherein airing system is connected to spray header by a plurality of connection lines, and connection line comprises and is connected to spray header with first connection line that the first source gas is provided be connected to spray header so that second connection line of the second source gas to be provided.
46. according to the equipment of claim 45, wherein this airing system also comprises: being made as provides three air supply unit of Purge gas in the treatment chamber; And be made as four air supply unit of purge gas in the treatment chamber is provided.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20040104741 | 2004-12-13 | ||
| KR1020040104741 | 2004-12-13 | ||
| KR1020050049565 | 2005-06-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1789487A true CN1789487A (en) | 2006-06-21 |
Family
ID=36787604
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005101369870A Pending CN1789487A (en) | 2004-12-13 | 2005-12-13 | Method of depositing a metal compound layer and apparatus for depositing a metal compound layer |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR100596495B1 (en) |
| CN (1) | CN1789487A (en) |
| TW (1) | TW200619414A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101320765A (en) * | 2007-06-05 | 2008-12-10 | 株式会社半导体能源研究所 | Photoelectric conversion device and manufacturing method |
| CN108695193A (en) * | 2017-03-30 | 2018-10-23 | 株式会社日立国际电气 | Substrate processing method using same, recording medium and substrate board treatment |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5087657B2 (en) * | 2009-08-04 | 2012-12-05 | 株式会社日立国際電気 | Semiconductor device manufacturing method and substrate processing apparatus |
| JP5610438B2 (en) | 2010-01-29 | 2014-10-22 | 株式会社日立国際電気 | Substrate processing apparatus and semiconductor device manufacturing method |
| JP5722595B2 (en) * | 2010-11-11 | 2015-05-20 | 株式会社日立国際電気 | Substrate processing apparatus and semiconductor device manufacturing method |
| KR101830976B1 (en) * | 2011-06-30 | 2018-02-22 | 삼성디스플레이 주식회사 | Apparatus for atomic layer deposition |
| US20130143415A1 (en) * | 2011-12-01 | 2013-06-06 | Applied Materials, Inc. | Multi-Component Film Deposition |
| US9514933B2 (en) | 2014-01-05 | 2016-12-06 | Applied Materials, Inc. | Film deposition using spatial atomic layer deposition or pulsed chemical vapor deposition |
| KR102518932B1 (en) * | 2023-01-27 | 2023-04-06 | (주)브이아이테크 | MTS deposition gas control system of silicon carbide deposition equipment |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100363088B1 (en) * | 2000-04-20 | 2002-12-02 | 삼성전자 주식회사 | Method of manufacturing barrier metal layer using atomic layer deposition method |
| JP4528413B2 (en) | 2000-04-25 | 2010-08-18 | 日鉱金属株式会社 | Vapor growth method |
-
2005
- 2005-06-10 KR KR1020050049565A patent/KR100596495B1/en not_active IP Right Cessation
- 2005-12-08 TW TW094143330A patent/TW200619414A/en unknown
- 2005-12-13 CN CNA2005101369870A patent/CN1789487A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101320765A (en) * | 2007-06-05 | 2008-12-10 | 株式会社半导体能源研究所 | Photoelectric conversion device and manufacturing method |
| CN101320765B (en) * | 2007-06-05 | 2015-11-25 | 株式会社半导体能源研究所 | The manufacture method of photoelectric conversion device |
| CN108695193A (en) * | 2017-03-30 | 2018-10-23 | 株式会社日立国际电气 | Substrate processing method using same, recording medium and substrate board treatment |
| CN108695193B (en) * | 2017-03-30 | 2022-03-18 | 株式会社国际电气 | Substrate processing method, recording medium, and substrate processing apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100596495B1 (en) | 2006-07-04 |
| TW200619414A (en) | 2006-06-16 |
| KR20060066602A (en) | 2006-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1574231A (en) | Fabrication method of semiconductor integrated circuit device | |
| CN1036860C (en) | Process for forming metal deposited film containing aluminium as main component by use of alkly aluminium hydride | |
| CN1291461C (en) | Dielectric film and method of forming it semiconductor device nonvolatile semiconductor memory device and production method for semiconductor device | |
| CN1115720C (en) | Method for mfg. semiconductor integrated circuit device | |
| CN101032006A (en) | Method for manufacturing semiconductor device and substrate processing apparatus | |
| CN1284224C (en) | Semiconductor device and mfg. technology thereof | |
| CN1268003C (en) | Semiconductor device and methdo of manufacturing the same | |
| CN1860596A (en) | Method for producing material of electronic device | |
| CN1693537A (en) | Very low temp. chamical gas-phase deposite technology of variable component independent of conformal, stress and chamical gas-phase deposite layer | |
| CN1449045A (en) | Semiconductor device and manufacturing method thereof | |
| CN1181220C (en) | Method for producing coated workpieces, uses and installation for the method | |
| CN1670913A (en) | Insulating film forming method, insulating film forming apparatus, and plasma film forming apparatus | |
| CN1913120A (en) | Method of manufacturing a semiconductor device and the semiconductor device | |
| CN1828902A (en) | Semiconductor device and method for manufacturing the same | |
| CN1445838A (en) | Semiconductor device and manufacturing method thereof | |
| CN1789487A (en) | Method of depositing a metal compound layer and apparatus for depositing a metal compound layer | |
| CN1838387A (en) | Etching method and apparatus | |
| CN1476057A (en) | Plasma processor and variable impedance apparatus correcting method | |
| CN1340862A (en) | Semiconductor device and padding for 'semiconductor on insulator' | |
| CN100347831C (en) | Deposition method and semiconductor device | |
| CN1467812A (en) | Semiconductor device containing insulator and method for manufacturing the same | |
| CN1574353A (en) | Semiconductor device and method of manufacturing the same | |
| CN1909249A (en) | Semiconductor device with thin-film transistors and method of fabricating the same | |
| CN1787186A (en) | Semiconductor device fabrication method | |
| CN101069279A (en) | Semiconductor device and its manufacturing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20060621 |