CN106971937B - The film build method of TiON film - Google Patents

The film build method of TiON film Download PDF

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Publication number
CN106971937B
CN106971937B CN201610847749.9A CN201610847749A CN106971937B CN 106971937 B CN106971937 B CN 106971937B CN 201610847749 A CN201610847749 A CN 201610847749A CN 106971937 B CN106971937 B CN 106971937B
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film
gas
tion
supply
build method
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CN106971937A (en
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石坂忠大
小泉正树
佐野正树
洪锡亨
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Tokyo Electron Ltd
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Tokyo Electron Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
    • H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
    • H01L21/02186—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing titanium, e.g. TiO2
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/308—Oxynitrides
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition

Abstract

Problem of the present invention is that providing a kind of film build method of the TiON film of superior TiON film of flatness that can form a film.Its solution is, in film forming initial stage, alternative supply X1 times rear, supply oxidant circulation for repeating gas containing Ti and nitriding gas is subjected to Y1 circulation, in text message later, alternative supply X2 times rear, supply oxidant circulation for repeating gas containing Ti and nitriding gas is subjected to Y2 circulation until as required film thickness.At this point, the repeat number X1 of film forming initial stage and the repeat number X2 of text message later are set to X1 > X2.

Description

The film build method of TiON film
Technical field
The present invention relates to the film build methods of TiON film.
Background technique
Recently, semiconductor equipment is being miniaturize for the purpose of improving equipment performance.In addition, semiconductor equipment is being examined Consider application to mobile device or in view of the influence to environment, is required to reduce consumption electric power.As for corresponding to these One of method imported the high-k film as made of high dielectric constant (high-k) material and metal gate in a mosfet Combination.In addition, also using high-k film in capacitor unit to improve the capacity of DRAM.
HfO has been used in high-k film2And ZrO2, lamination have Al2O3With ZrO2Material etc. oxide material, but by this When being used for semiconductor equipment a bit, oxygen therein is detached from, and occurs the defect of oxygen in high-k film sometimes.If having in high-k film The defect of oxygen forms dipole at the interface of the metal gate adjacent with high-k film, electrode, since dipole is enabled with curved Song reduces effective work function.As a result, electronics becomes easy flowing, increase leakage current.
As the technology for solving such problems, a kind of technology is disclosed in patent document 1 and non-patent literature 1, is led to It crosses and adds oxygen into the TiN film used as metal gate, electrode being formed on high-k film, make the oxygen defect in high-k film It reduces.Specifically, passing through after forming TiN film by PVD (physical vapour deposition (PVD), Physical Vapor Deposition) Implement annealing or oxygen plasma treatment based on oxygen-containing gas, oxygen is added into TiN film.
However, the development of the miniaturization with semiconductor equipment, when forming film, it is desirable that the high stepcoverage of fine pattern Rate, while the controlling of film is also required, when forming TiN film, sufficient step coverage rate cannot be obtained by above-mentioned PVD, Even if using the good CVD of step coverage rate ratio PVD (chemical vapor deposition, Chemical Vapor is considered Deposition), the controlling of film is also insufficient.In addition, in above patent document 1 or the method for non-patent literature 1, for The additive amount of the oxygen of TiN film is limited, can not add required oxygen sometimes.
Then, inquire into can by TiN film with good step coverage rate and with excellent controlling form a film such as lower section Method: to pass through the TiCl as the gas containing Ti4Gas and NH as nitriding gas3The alternative supply of gas is come the TiN film that carries out Film build method (such as patent document 2) based on, oxygen-containing gas is periodically passed through in film forming or it is made to be exposed to oxygen etc. Under gas ions, to form TiON film.Thereby, it is possible to ensure good step coverage rate, filming control, and can be into film Add an adequate amount of oxygen.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Application Publication 2015-506097 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2003-077864 bulletin
Non-patent literature
Non-patent literature 1:E.Cartier, et al., Appl.Phys.Lett., Vol.95,2009, p.042901
Summary of the invention
Problems to be solved by the invention
However it has been found that passing through TiCl4Gas and NH3The alternative supply of gas is come in the film forming of the TiN film carried out, the period Property supply oxygen-containing gas, oxygen plasma etc. oxidant method in, due to film forming initial stage oxidant supply, sometimes The flatness of film is caused to be deteriorated.
In addition, the development of the miniaturization with equipment, if the opening of the capacitor arrangement of such as DRAM narrows, depth-width ratio It gets higher, the TiCl at through-hole bottom (cylinder bottom)4Reduction become inadequate sometimes.Restore it is insufficient in the case where, according to Under the reaction of (1) chlorine occurs from TiCl4In disengaging, still, the nitridation that there is the Ti of the reaction by (2) below cannot The worry sufficiently carried out.
(1)TiCl4+NH3→Ti?The disengaging of+Cl chlorine
(2)Ti?+NH3→ TiN nitridation
Although having in TiN film before oxidation outstanding in the case where the reaction that the reaction of above-mentioned (1) but (2) occurs is insufficient Dead key exists.Since dangling bonds is active, even also easily being reacted with the oxygen in high-k film in film forming, There is oxygen defect in high-k film.Therefore, even if adjacently forming TiON film with high-k film, it is also difficult to fully improve and set Standby characteristic.
Further, it was found that merely with TiCl is being passed through4Gas and NH3The alternative supply of gas and in the film forming that carries out periodically When ground supplies the method for the oxidant of oxygen-containing gas, oxygen plasma etc., chlorine (Cl) residual of 0.7at.% or so is had, sometimes It goes wrong in flatness etc..
Also, in the case where high through-hole of depth-width ratio etc. forms TiON film, there is also be difficult to by above method oxygen The case where up to through-hole bottom, in this case, it is desirable that improve oxidation efficiency.
Therefore, problem of the present invention is that, with by the alternative supply of gas containing Ti and nitriding gas carry out at Premised on the film build method for supplying oxidant in film, a kind of be difficult to happen caused by the oxidant supply due to initial stage smoothly is provided The film build method of the TiON film of the deterioration of property.
Other projects of the invention are, to carry out by the alternative supply of gas containing Ti and nitriding gas Premised on the film build method for supplying oxidant in the film forming of TiN film, a kind of TiN film being able to suppress before oxidant supply is provided The film build method of the TiON film of middle the phenomenon that generating dangling bonds.
The other other projects of the present invention are, to pass through the TiCl as the gas containing Ti4Gas and nitriding gas Alternative supply and premised on supplying the film build method of oxidant in the film forming of TiN film that carries out, providing one kind can reduce chlorine The film build method of the TiON film of content.
Other project of the invention is, to pass through the TiCl as the gas containing Ti4The friendship of gas and nitriding gas Premised on the film build method for supplying oxidant in the film forming of the TiN film carried out for supply, providing one kind can be improved oxidation effect The film build method of the TiON film of rate.
The method used for solving the problem
In order to solve the above problems, the first viewpoint of the invention provides a kind of film build method of TiON film, which is characterized in that It, will with defined treatment temperature by substrate reception processed in process container, making holding decompression state in above-mentioned process container For the following multiple circulations of circulating repetition to form TiON film, above-mentioned circulation is as follows: will contain Ti gas and nitriding gas to above-mentioned processing Alternative supply in container after forming unit TiN film, supplies oxidant in Xiang Shangshu process container and makes above-mentioned unit TiN film oxygen Change, wherein in film forming initial stage, will repeat alternative supply X1 time of above-mentioned gas containing Ti and nitriding gas afterwards, for oxygen supply The circulation of agent carries out Y1 circulation, in text message later, will repeat the alternative supply X2 of gas containing Ti and nitriding gas After secondary, the circulation progress Y2 circulation of oxidant is supplied until becoming required film thickness, the repeat number of above-mentioned film forming initial stage X1 and it is above-mentioned after the repeat number X2 of text message be set to X1 > X2.
Above-mentioned X1 is preferably in the range of 10≤X1≤60, and above-mentioned X2 is preferably in the range of 1≤X2≤25.In addition, above-mentioned X1 3 times or more of preferably above-mentioned X2.Above-mentioned Y1 is preferably in the range of 1≤Y1≤5.
Second viewpoint of the invention provides a kind of film build method of TiON film, which is characterized in that by substrate reception processed It is with defined treatment temperature, following circulating repetition is multiple in process container, making to keep decompression state in above-mentioned process container For circulation to form TiON film, above-mentioned circulation is as follows: the alternative supply into above-mentioned process container of Ti gas and nitriding gas will be contained, from And after forming unit TiN film, carry out into above-mentioned process container supply nitriding gas rear ventilation (Port ス ト Off ロ ー) processing and The processing for supplying oxidant into above-mentioned process container and aoxidizing above-mentioned unit TiN film.
In above-mentioned second viewpoint, above-mentioned rear ventilation treatment is also possible to the supply of nitriding gas and cleans gas The processing that supply is repeated as many times.In addition, the supply of above-mentioned oxidant can also be carried out intermittently repeatedly.
Third viewpoint of the invention provides a kind of film build method of TiON film, which is characterized in that by substrate reception processed It is with defined treatment temperature, following circulating repetition is multiple in process container, making to keep decompression state in above-mentioned process container Circulation is to form a film, and later, implements argon ion processing to above-mentioned film surface, above-mentioned circulation is as follows: by the gas containing Ti containing chlorine Cleaning between body and nitriding gas across above-mentioned process container is alternately supply, and after forming unit TiN film, is supplied oxidant and is made Above-mentioned unit TiN film oxidation.
In above-mentioned third viewpoint, the processing of above-mentioned argon ion can by generating argon plasma, by argon ion therein Substrate processed is introduced to carry out.In addition, above-mentioned argon ion processing can carry out above-mentioned film surface by the shock of argon ion Processing.
Above-mentioned film forming can be carried out from the processing of above-mentioned argon ion in different devices.In this case, carry out it is above-mentioned at The device of film and the device for carrying out above-mentioned argon ion processing are preferably mounted in have can transport substrate processed in a vacuum In the processing system of conveyer, above-mentioned film forming and the processing of above-mentioned argon ion are carried out continuously in the case where not destroying vacuum. Above-mentioned film forming and the processing of above-mentioned argon ion can also carry out in same process container.
4th viewpoint of the invention provides a kind of film build method of TiON film, which is characterized in that by substrate reception processed It is with defined treatment temperature, following circulating repetition is multiple in process container, making to keep decompression state in above-mentioned process container For circulation to form TiON film, above-mentioned circulation is as follows: will contain the alternative supply into above-mentioned process container of Ti gas and nitriding gas, shape After unit TiN film, intermittently repeatedly supply oxidant into above-mentioned process container and aoxidize above-mentioned unit TiN film Processing.
In above-mentioned 4th viewpoint, above-mentioned oxidant can be supplied with pulse type.Alternatively, it is also possible in above-mentioned oxidant After supply, to cleaning in above-mentioned process container, the cleaning in supply and above-mentioned process container by above-mentioned oxidant is carried out Multiple circulations.
From above-mentioned first viewpoint into the 4th viewpoint, above-mentioned gas containing Ti is preferably TiCl4Gas, above-mentioned nitriding gas are excellent It is selected as NH3Gas.As above-mentioned oxidant, it is able to use selected from O2Gas, O3Gas, H2O、NO2In oxygen-containing gas or will be upper State oxygen-containing gas carry out it is plasmarized obtained from substance.Above-mentioned treatment temperature is preferably 300~500 DEG C.
In addition, the 5th viewpoint of the invention provides a kind of storage medium, which is characterized in that its be work on computers, And be stored with the storage medium of the program for controlling film formation device, above procedure when being executed, make computer control it is above-mentioned at Film device makes above-mentioned film formation device carry out the film build method of the above-mentioned first~the 4th viewpoint.
The effect of invention
First viewpoint according to the present invention will repeat above-mentioned gas containing Ti and nitriding gas in film forming initial stage After alternative supply X1 times, the circulation of supply oxidant carry out Y1 circulation, in text message later, will repeat gas containing Ti with After alternative supply X2 times of nitriding gas, the circulation progress Y2 circulation of oxidant is supplied until becoming required film thickness, at this In kind film forming process, above-mentioned X1 and above-mentioned X2 are set to X1 > X2.Thereby, it is possible to almost without at the beginning of the film forming of film growth Phase keeps the frequency of the supplying step of oxidant low, therefore, is able to suppress the amount of oxidation at film forming initial stage, inhibits film forming initial stage due to oxygen The phenomenon that influence of agent causes the flatness of TiON film surface to be deteriorated, the good TiON film of flatness can be obtained.
Second viewpoint according to the present invention, after forming unit TiN film, in the processing for carrying out making above-mentioned unit TiN film oxidation Before, the rear ventilation treatment of nitriding gas is carried out, so can prevent from forming dangling bonds in unit TiN film, can be prevented In the film forming of TiON film, the oxygen in high-k film is taken away by TiN film.Therefore, it can more be prevented securely from and be produced in high-k film The phenomenon that raw oxygen defect, it can reduce leakage current.
Third viewpoint according to the present invention, by between gas containing Ti and nitriding gas containing chlorine across above-mentioned process container It cleans after being alternately supply, forming unit TiN film, circulating repetition that supply oxidant aoxidizes above-mentioned unit TiN film is multiple follows Ring, to form a film, later, therefore implementing argon ion processing to above-mentioned film surface can be removed by the energy of argon ion Cl in film can reduce the Cl concentration in film.In addition, carrying out argon ion processing in this way, surface smoothness can be obtained High TiON film.
4th viewpoint according to the present invention will carry out stating upwards after film forming unit TiN film intermittently more in process container The multiple circulations of circulating repetition of the secondary processing for supplying oxidant and making above-mentioned unit TiN film oxidation, so that TiON film is formed, because This, can be improved oxidation efficiency.
Detailed description of the invention
Fig. 1 is the film forming dress for showing the film build method of TiON film involved in first embodiment for carrying out the present invention The summary section of an example set.
Fig. 2 is the film forming for being shown as the premise of the film build method of TiON film involved in first embodiment of the invention The time diagram of an example of the process of method.
Fig. 3 is the film forming for being shown as the premise of the film build method of TiON film involved in first embodiment of the invention The flow chart of an example of the process of method.
Fig. 4 is the schematic diagram for showing the film-forming state when forming TiON film with the process of Fig. 2, Fig. 3.
Fig. 5 is the circulation shown in the case where being set as X=6 in becoming the film build method of premise of present embodiment Several figures with the relationship of film thickness.
Fig. 6 be show an example of the process of the film build method of TiON film involved in an embodiment of the invention when Between scheme.
Fig. 7 is to show the TiON film formed by the technique for keeping X fixed and pass through the work that changes X according to present embodiment The figure of the relationship for the film thickness and mist degree in TiON film that skill is formed.
Fig. 8 is to show to find out the TiON film formed by the technique for keeping X fixed and according to present embodiment by changing X Technique formed TiON film film in oxygen concentration result figure.
(a) is in the case where generating dangling bonds in the TiN film shown before oxidation, in adjacent high-k film in Fig. 9 There is the figure of the mechanism of oxygen defect, is (b) the rear ventilation shown through nitriding gas, oxygen does not occur in adjacent high-k film The figure of the mechanism of defect.
Figure 10 is show the detailed process of the film build method of TiON film involved in second embodiment of the present invention one The time diagram of example.
Figure 11 is show the detailed process of the film build method of TiON film involved in second embodiment of the present invention one The flow chart of example.
Figure 12 be show the argon of the film build method of TiON film involved in third embodiment for carrying out the present invention from The sectional view of an example of sub-processing unit.
Figure 13 is the figure for showing the film composition of the TiON film to form a film by method shown in Fig. 2.
Figure 14 is the SEM photograph on the surface of the TiON film to be formed a film by method shown in Fig. 2.
Figure 15 is an example for showing the process of the film build method of TiON film involved in third embodiment of the present invention Flow chart.
Figure 16 is the figure of the Cl concentration in the TiON film before and after showing Ar ion processing.
Figure 17 is the figure of the film composition of the TiON film before and after showing Ar ion processing.
Figure 18 is the SEM photograph on the surface of the TiON film before and after Ar ion processing.
Figure 19 is the figure of the film thickness of the TiON film before and after showing Ar ion processing.
Figure 20 is the schematic diagram for showing an example of processing system of the film forming and Ar ion processing that are able to carry out TiON film.
Figure 21 be show the film process and Ar ion processing that TiON film can be carried out continuously in same cavity at The sectional view of film device.
Figure 22 be show the film build method of TiON film involved in the 4th embodiment of the invention detailed process one The time diagram of example.
Figure 23 be show the film build method of TiON film involved in the 4th embodiment of the invention detailed process one The flow chart of example.
Figure 24 is shown in the 4th embodiment of the invention, the figure for the supply example that oxidant is supplied with pulse type.
Figure 25 is in order to illustrate the figure of the effect of the 4th embodiment of the invention.
Figure 26 is an example for showing detailed process when the 4th embodiment of the invention to be applied to second embodiment Time diagram.
The explanation of symbol
1 ... cavity
2 ... pedestals
5 ... heaters
10 ... spray heads
20 ... gas supply members
21…TiCl4Gas supply source
23…NH3Gas supply source
25、29…N2Gas supply source
27 ... oxidant supply sources
50 ... control units
52 ... storage units
52a ... storage medium
61 ... Ar gas supply sources
65 ... high frequency electric sources
100,100 ' ... film formation devices
101 ... unit TiN films
200 ... argon ion processing units
201 ... cavitys
207 ... gas supply members
210 ... platforms
High frequency electric source is used in 215 ... biasings
222 ... induction coils
High frequency electric source is used in the generation of 223 ... plasmas
300 ... processing systems
310 ... vacuum carrying rooms
311,332 ... wafer transfer components
320 ... road lock chambers
330 ... atmosphere carrying rooms
340 ... vehicles
W ... semiconductor wafer
Specific embodiment
Hereinafter, embodiments of the present invention are specifically described referring to attached drawing.
In the following description, the unit of the flow of gas uses mL/min, but since gas is because of temperature and body due to air pressure Big variation occurs for product, so using the value for being converted into standard state.In addition, being scaled the flow of standard state usually with sccm (sccm, Standerd Cubic Centimeter per Minutes) label, therefore together by sccm Label.Standard state described herein refers to, 0 DEG C of temperature (273.15K), the state of air pressure 1atm (101325Pa).
< first embodiment >
Fig. 1 is the film forming dress for showing the film build method of TiON film involved in first embodiment for carrying out the present invention The summary section of an example set.
The film formation device 100 has, generally cylindrical cavity 1.It is configured in the inside of cavity 1 and is made of AlN Pedestal 2, said base 2 is as horizontally supporting the platform of the wafer W as substrate processed, and by pedestal 2 is arranged in Central lower the state configuration that supports of cylindric support member 3.The peripheral part of pedestal 2 is provided with for guide wafer W Guide ring 4.In addition, be embedded with the heater 5 being made of the refractory metal of molybdenum etc. in pedestal 2, the heater 5 by by Heater power source 6 is powered, and the wafer W as substrate processed is heated to defined temperature.
In the roof 1a of cavity 1, it is provided with spray head 10.Spray head 10 has basic components 11 and shower plate 12, in shower plate 12 peripheral part passes through bolt (not shown) via the intermediate member 13 annular in shape for preventing from attaching, with basic components 11 It is fixed.Shower plate 12 has been formed in the interior thereof recess portion, has formed gas diffusion between basic components 11 and shower plate 12 in flange shape Space 14.Basic components 11 are formed with flange part 11a in its periphery, and flange part 11a is installed on the roof 1a of cavity 1. It is formed with multiple gas discharges hole 15 in shower plate 12, there are two gas introducing ports 16 and 17 in the formation of basic components 11.
Gas supply member 20 includes the TiCl supplied as the gas containing Ti4The TiCl of gas4Gas supply source 21 and Supply the NH as nitriding gas3The NH of gas3Gas supply source 23.TiCl4Gas supply source 21 and TiCl4Gas feed line Road 22 is connected, the TiCl4Gas feed line road 22 is connected with first gas entrance hole 16.NH3Gas supply source 23 and NH3 Gas feed line road 24 is connected, the NH3Gas feed line road 24 is connected with second gas entrance hole 17.
TiCl4Gas feed line road 22 and N2Gas feed line road 26 is connected, and is configured to N2Gas as delivery gas or Gas is cleaned from N2Gas supply source 25 is to the N2The structure that gas feed line road 26 supplies.
NH3Gas feed line road 24 is connected with oxidant supply lines 28, is configured to O2Gas, O3Gas, H2O、NO2Deng The structure that oxygen-containing gas is supplied as oxidant from oxidant supply source 27 to the oxidant supply lines 28.It can also will be oxygen-containing It is used after gas progress is plasmarized as oxidant.At this point, both can will be in advance to oxygenous from oxidant supply source 27 Body carry out it is plasmarized obtained from substance as oxidant supply, oxygen-containing gas can also be carried out in spray head 10 etc. from Daughter.In addition, NH3Gas feed line road 24 and N2Gas feed line road 30 is connected, and is configured to N2Gas is as delivery gas Or gas is cleaned from N2Gas supply source 29 is to the N2The structure that gas feed line road 30 supplies.
In addition, gas supply member 20 also has ClF of the supply as purge gas3The ClF of gas3Gas supply source 31, ClF3Gas supply source 31 and ClF3Gas feed line road 32a is connected.The ClF3Gas feed line road 32a and TiCl4Gas supplies It is connected to route 22.In addition, being equipped with from ClF3Gas feed line road 32a branch and and NH3What gas feed line road 24 was connected ClF3Gas feed line road 32b.
In TiCl4Gas feed line road 22, NH3Gas feed line road 24, oxidant route 28, N2Gas feed line road 26, 30、ClF3Gas feed line road 32a equipped with mass flow controller 33 and clips two valves of mass flow controller 33 34.In addition, in ClF3In the 32b of gas feed line road, it is equipped with valve 34.
Therefore, TiCl is come from4The TiCl of gas supply source 214Gas and come from N2The N of gas supply source 252Gas via TiCl4Gas feed line road 22 reaches the gas diffusion space 14 in spray head 10 from the first gas entrance hole 16 of spray head 10, separately Outside, NH is come from3The NH of gas supply source 233Gas, the oxidant for carrying out autoxidator supply source 27 and come from N2Gas supply The N in source 292Gas is via NH3Gas feed line road 24 reaches the gas in spray head 10 from the second gas entrance hole 17 of spray head 10 Diffusion space 14, these gases spue from the gas discharge hole 15 of shower plate 12 into cavity 1.
In addition, spray head 10 is also possible to TiCl4Gas and NH3Gas is independently supplied to rear hybrid in cavity 1.
In addition, as gas containing Ti, in addition to TiCl4In addition, additionally it is possible to use four (isopropoxy) titaniums (TTIP), tetrabormated Titanium (TiBr4), titanium tetra iodide (TiI4), tetrem vlmethyl titanium (TEMAT), four dimethylamino titaniums (TDMAT), four diethyls Base amino titanium (TDEAT) etc..In addition, as nitriding gas, in addition to NH3In addition, additionally it is possible to use monomethyl hydrazine (MMH).In addition, As the N for being used as delivery gas and cleaning gas2The substitution of gas is also able to use other torpescence gas such as Ar gas Body.
The heater 45 for heating spray head 10 is equipped in the basic components 11 of spray head 10.The heater 45 and heater Power supply 46 is connected, and spray head 10 is heated to required temperature by powering from heater power source 46 to heater 45.? The recess portion on the top of basic components 11 is formed in equipped with the heat insulating member 47 for improving the heating efficiency of heater 45.
It is formed with circular hole 35 in the central portion of the bottom wall 1b of cavity 1, is equipped with the side to cover the hole 35 in bottom wall 1b The exhaust chamber 36 that formula is protruded downwards.It is connected with exhaust pipe 37 in the side of exhaust chamber 36, the exhaust pipe 37 and exhaust apparatus 38 It is connected.And it is configured to by making the exhaust apparatus 38 work that will be decompressed to defined vacuum degree in cavity 1.
In pedestal 2, it is used to support wafer W and makes three (only illustrating two) wafer support needles 39 of wafer W lifting with energy Enough to be arranged relative to the surface protrusion of pedestal 2 or the mode of embedment, these wafer support needles 39 are supported the support of plate 40.Also, Wafer support needle 39 is gone up and down by the drive member 41 of cylinder etc. via support plate 40.
Side wall in cavity 1 is equipped with: for carrying out between cavity 1 and adjacent setting and wafer transfer room (not shown) The carrying-in/carrying-out mouth 42 of the carrying-in/carrying-out of wafer W and gate valve 43 for being opened and closed the carrying-in/carrying-out mouth 42.
Heater power source 6 and 46, valve 34, mass flow controller 33, the driving structure of constituting portion as film formation device 100 Part 41 etc., be set as being connected with the control unit 50 for having microprocessor (computer) and the composition that is controlled.In addition, controlling Portion 50 is also connected with user interface 51, and the user interface 51 is by carrying out order to allow operator to manage film formation device 100 Keyboard, the display that the working condition of film formation device 100 is visualized and indicated etc. of input operation etc. form.Moreover, controlling Portion 50 processed is connected with storage unit 52, is stored in the storage unit 52: for the various processing executed in film formation device 100 to be passed through control Portion 50 processed controls the program realized and for making each constituting portion of film formation device 100 execute processing according to treatment conditions Program, i.e. processing scheme.Processing scheme is stored in the storage medium 52a in storage unit 52.Storage medium can be hard disk Deng fixed medium, it is also possible to the medium of the mobilitys such as CDROM, DVD.Furthermore it is also possible to from other devices, such as through Processing scheme is suitably transmitted by special circuit.Then, according to needs, by instruction from user interface 51 etc. will arbitrarily from Reason scheme is recalled from storage unit 52, make control unit 50 execute, as a result, under the control of control unit 50, in film formation device 100 into The required processing of row.
Then, the film build method of TiON film involved in the present embodiment to above film formation device 100 is illustrated.
Firstly, making to become the state for being evacuated to vacuum in cavity 1 by exhaust apparatus 38, on one side from N225 He of gas supply source 29 by N2Gas will be preheated to film-forming temperature in cavity 1 via in the importing cavity 1 of spray head 10, on one side by heater 5, in temperature At the time of degree is stablized, pass through TiCl4Gas and NH3Gas, in the chamber of 1 inner wall of cavity, 36 inner wall of exhaust chamber and spray head 10 etc. Internal parts surface precoats TiN film.
After precoating treatment, gate valve 43 is opened, from wafer transfer room by carrying device (not shown) via removing Enter to move out mouth 42 and move in wafer W into cavity 1, and loads on the base 2.Later, wafer W is preferably added by heater 5 The predetermined temperature of the range of heat to 300~500 DEG C supplies N into cavity 12The preheating of gas progress wafer W.In chip At the time of temperature is almost stable, start the film forming of TiON film.
In the film build method of TiON film involved in present embodiment, it will recycle and be recycled as one as follows, by this The film build method of the multiple circulations of circulating repetition (Y circulation) is as premise, above-mentioned circulation are as follows: by the TiCl as the gas containing Ti4 The supply of gas and NH as nitriding gas3The supply of gas across cavity 1 cleaning and be alternately repeated as many times (X times) Afterwards, oxidant is supplied, cleans cavity 1 later.
For the time diagram and Fig. 3 of an example reference Fig. 2 of the process of the film build method of the premise as present embodiment Flow chart be illustrated.
As shown in these figures, initially, from TiCl4Gas supply source 21 is by TiCl4Gas is supplied to cavity 1, makes TiCl4Gas Body is adsorbed (step S1), next, stopping TiCl4The supply of gas, utilizes N2Gas will clean (step S2) in cavity 1, connect Get off, from NH3Gas supply source 23 is by NH3Gas is supplied to cavity 1, makes itself and adsorbed TiCl4It reacts and forms TiN (step Rapid S3), next, stopping NH3Gas utilizes N2Gas will clean (step S4) in cavity 1, these steps S1~S4 is repeated X It is secondary.Later, from oxidant supply source 27 by oxidant (such as O2Gas) it is supplied to cavity 1 to carry out oxidation processes (step S5), next (step S6) will be cleaned in cavity 1.This circulation is formed into institute by being repeated Y circulation as a circulation It is required that thickness TiON film.
Film-forming state at this time is shown in Fig. 4.As shown in the drawing, by repeating step S1~S4 X times, regulation film is formed Thick unit TiN film 101 aoxidizes unit TiN film 101 by carrying out the oxidation processes of step S5 later.Using this as one Circulation carries out Y circulation, the TiON film of regulation film thickness is consequently formed.According to the X at this time as the number of repetition of step S1~S4, The oxygen amount of TiON film can be adjusted.That is, the frequency aoxidized if reducing X increases, therefore the amount of pulling in of the oxygen in film increases, phase Instead, the oxygen amount of pulling in if increasing X in film is reduced.In addition, can follow according to repeating to carry out step S5, S6 after step S1~S4 The recurring number Y of ring adjusts film thickness.
Using device shown in FIG. 1, X=6 is such to be set as definite value for the value of X, real by above-mentioned basic film build method Border on oxidation film formed TiON film as a result, recurring number and the relationship of film thickness are as shown in Figure 5.Recurring number herein is X and Y Product.As shown in Figure 5 it is found that the state that do not grow up at film forming initial stage there are film (film forming is slow).Therefore, if X is set as definite value, At film forming initial stage, amount of oxidation is superfluous for actual film-forming amount.In addition, when the amount of oxidation at so film forming initial stage is more, bottom Film is influenced by oxidant, and there are the worries that the flatness of TiON film surface is deteriorated.
Here, the stage in present embodiment, after being more than the number of repetition of step S1~S4 of film forming initial stage Step S1~S4 number of repetition.That is, being set as X1 times by the number of repetition of the step S1~S4 at the initial stage of forming a film, step later In the case that the number of repetition of rapid S1~S4 is set as X2, it is set as X1 > X2.
Specifically, as shown in the time diagram of Fig. 6, in film forming initial stage, it is bigger than usually that step S1~S4 will be repeated X1 times of value after, carry out the step S5 as oxidant supplying step and the circulation as the step S6 for cleaning step carries out Y1 Circulation after repeating step S1~S4 ratio X1 few X2 times, is carried out as oxidant supplying step in text message later Step S5 and as clean step step S6 circulation carry out Y2 circulation.That is, making the weight of step S1~S4 forming a film on the way Again X variation is counted.Later by the total of Y1 circulation and Y2 circulation, the film thickness of TiON film is determined.
In this way, it can reduce the supplying step of the oxidant of the step S5 at the film forming initial stage hardly grown up in film Frequency, therefore it is able to suppress the amount of oxidation at film forming initial stage, it is able to suppress caused by the influence as oxidant at film forming initial stage The phenomenon that flatness of TiON film surface is deteriorated, can obtain the good TiON film of flatness.In addition, hardly grow up from film When film forming A-stage becomes film forming as stable state, by the way that the repeat number of step S1~S4 is reduced to X2 from X1, it can make Amount of oxidation relative to film-forming amount becomes required value.In addition, the oxygen concentration of TiON film entirety can also pass through oxidation processes Time, oxidant flow be adjusted.
In this case, the number of repetition X2 of step S1~S4 in stable state is set to make the oxidation in TiON film Measuring (oxygen concentration) becomes required value, the preferably range of 1≤X2≤25.In addition, step S1~S4 in A-stage Number of repetition X1 is preferably 3 times of X2 or more, preferably the range in 10≤X1≤60.The recurring number Y1 at film forming initial stage is set as can Make up film forming that film is not grown up it is slow during, the range preferably in 1≤Y1≤5.Recurring number Y2 can be according to needing to form a film The film thickness of TiON film be appropriately configured.
After forming TiON film in this way, it will be evacuated to vacuum in cavity 1, wafer W is moved out.
In addition, using TiCl as Ti unstrpped gas4Gas uses NH as nitriding gas3Gas, as delivery gas Body cleans gas and uses N2Gas uses O as oxidant2In the case where gas, the preferred scope of membrance casting condition is as follows.
Treatment temperature (base-plate temp): 300~500 DEG C
Cavity internal pressure: 13.33~1333Pa (0.1~10Torr)
TiCl4Gas flow: 10~200mL/min (sccm)
NH3Gas flow: 1000~10000mL/min (sccm)
N2Gas flow: 1000~30000mL/min (sccm)
The primary service time of step 1~4: 0.01~3sec
O2Gas flow: 10~3000mL/min (sccm)
O2Gas supplying time: 0.1~60sec
Next, for the TiON film formed by the technique (X technique for fixing) for keeping X fixed and according to present embodiment The TiON film that the technique (X variation technique) for changing X is formed, compares the flatness on surface.Here, as Ti raw material Gas uses TiCl4Gas uses NH as nitriding gas3Gas uses N as delivery gas cleaning gas2Gas is made O is used for oxidant2Gas is set as X=6 in X technique for fixing with the membrance casting condition in above range, adjusts film by Y Thickness forms TiON film, is set as X1=30, Y1=1, X2=6 in X variation technique, adjusts film thickness by Y2, form TiON Film.Film-forming temperature is set as 430 DEG C.In addition, surface smoothness is evaluated by mist degree (Haze).Mist degree is, from diffusion The index for indicating light scattering that transmitted light is acquired relative to the ratio of full light transmitted light, is value relevant to surface roughness. The more low then surface smoothness of haze value is the better, and the more high then surface smoothness of haze value is poorer.
It the results are shown in Fig. 7.Fig. 7 is to show the TiON film formed by X technique for fixing and formed by X variation technique TiON film in film thickness and mist degree relationship figure.As shown in the drawing, change technique in film forming initial stage, X technique for fixing and X Haze value does not have a difference, but when film thickness becomes 10nm, and haze value when X changes technique is small.It can confirm, by according to this reality The mode of applying changes X, and compared with the situation for keeping X fixed, the flatness of TiON film becomes good.
Next, influence of the oxidation frequency for oxygen concentration in film to film forming initial stage is investigated.Here, passing through X Ray photoelectron spectroscopic analysis (XPS) acquires the oxygen concentration at the nine of chip, acquires using its average value as the oxygen concentration in film. The results are shown in Fig. 8.As shown in the drawing it has been confirmed that in the X technique for fixing for keeping X fixed and the X of present embodiment variation technique Film in oxygen concentration almost without difference.
< second embodiment >
Next, being illustrated for second embodiment of the present invention.In the present embodiment, using the film forming of Fig. 1 Device 100 forms TiON film by the method for enhancing nitridation than first embodiment.
Hereinafter, being illustrated for an example of the film build method of the TiON film of present embodiment.
Firstly, opening gate valve 43 after being carried out similarly precoating treatment with first embodiment, pass through from wafer transfer room Carrying device (not shown) moves in wafer W into cavity 1 via carrying-in/carrying-out mouth 42, and mounting is on the base 2.Later, lead to The predetermined temperature that wafer W is heated to preferably 300~500 DEG C of range by heater 5 is crossed, supplies N into cavity 12Gas, into The preheating of row wafer W.At the time of the temperature of chip is almost stable, start the film forming of TiON film.
In the film forming of TiON film, with the development of the miniaturization of equipment, such as the opening of capacitor arrangement of DRAM becomes TiCl when narrow, depth-width ratio is got higher, in the process of Fig. 2 of the premise as first embodiment, at through-hole bottom (cylinder bottom)4 Reduction it is sometimes insufficient.In the case where restoring insufficient, chlorine is occurred from TiCl by the reaction of (1) below4Disengaging, But the worry that the nitridation that there is the Ti of reaction by (2) below cannot be carried out sufficiently.
(1)TiCl4+NH3→Ti?The disengaging of+Cl chlorine
(2)Ti?+NH3→ TiN nitridation
In the case where although the reaction that the reaction of above-mentioned (1) but (2) occurs is insufficient, as shown in Fig. 9 (a), before oxidation TiN film in generate the dangling bonds of Ti not in conjunction with N.Since dangling bonds is active, though in film forming, also easily with , there is oxygen defect (Vo) in high-k film in oxygen (Ox) reaction in adjacent high-k film.If occurring in high-k film Oxygen defect (Vo), the then caused leakage electricity of PF (Poole-Frankel, the Poole-Frenkel) conduction occurred via defect Stream increases.
Here, in the present embodiment, after forming unit TiN film, before carrying out oxidation processes, having added supply NH3Gas The step of body.As a result, as shown in Fig. 9 (b), it can prevent from forming dangling bonds in unit TiN film, prevent the film forming in TiON film In, the oxygen in high-k film is taken away by TiN film.
0 time diagram and the flow chart of Figure 11 are illustrated specific process example referring to Fig.1.
As shown in these, initially, in the same manner as step S1~S4 of first embodiment, from TiCl4Gas supply source 21 By TiCl4Gas is supplied to cavity 1, makes to adsorb TiCl4Gas (step S11), next, stopping TiCl4The supply of gas, benefit Use N2Gas will clean (step S12) in cavity 1, next, from NH3Gas supply source 23 is by NH3Gas is supplied to cavity 1, is made Itself and adsorbed TiCl4It reacts and forms TiN (step S13), next, stopping NH3Gas utilizes N2Gas will be in cavity 1 It cleans (step S14), these steps S11~S14 is repeated X times.Later, from NH3Gas supply source 23 is by NH3Gas is to cavity 1 It supplies and carries out NH3The rear ventilation (step S15) of gas, next, stopping NH3Gas uses N2Gas will clean in cavity 1 (step S16), later, from oxidant supply source 27 by oxidant (such as O2Gas) it is supplied to cavity 1, carry out oxidation processes (step S17) next will clean (step S18) in cavity 1.It is recycled above circulation as one, by being repeated Y Circulation forms the TiON film of required thickness.
At this point, the oxygen amount of TiON film can be adjusted by the repeat number X of step S11~S14.That is, if reducing repeat number X The frequency of oxidation increases, therefore the oxygen amount of pulling in film increases, on the contrary, the oxygen amount of pulling in film subtracts if increasing repeat number X It is few.In addition, film thickness can be adjusted by recurring number Y.In addition, the oxygen concentration of TiON film can not only by adjusting step S11~ The number of repetition of S14 is adjusted, and can be also adjusted by adjusting the time of oxidation processes, the flow of oxidant.
After being thusly-formed TiON film, it will be evacuated to vacuum in cavity 1, wafer W is moved out.
In this way, due to the NH of step 15 additional before the oxidation processes of step 173The rear ventilation of gas, so can prevent Dangling bonds only is formed in unit TiN film, can be prevented in forming TiON film, the oxygen in high-k film is taken away by TiN film.Cause This, can more be prevented securely from high-k film and the phenomenon that oxygen defect occur, can reduce leakage current.Such effect is right In as the DRAM capacitor of extremely fine construction, only pass through the NH of common alternative supply3Then there is hardly possible in gas supply So that through-hole bottom (cylinder bottom) sufficiently restore worry the case where be particularly effective, but present embodiment is not limited only to this feelings Condition can be applied to all situations that TiON film is adjacently formed with high-k film.
In the present embodiment, as oxidant, O can be used2Gas, O3Gas, H2O、NO2Deng oxygen-containing gas, Oxygen-containing gas can be carried out it is plasmarized after use as oxidant.In addition, as gas containing Ti, in addition to TiCl4In addition, Four (isopropoxy) titaniums (TTIP), titanium tetrabromide (TiBr can also be used4), titanium tetra iodide (TiI4), tetrem vlmethyl titanium (TEMAT), four dimethylamino titaniums (TDMAT), four diethylamino titaniums (TDEAT) etc..In addition, as nitriding gas, in addition to NH3In addition, monomethyl hydrazine (MMH) can also be used.In addition, as being used as delivery gas and cleaning the N of gas2Gas replaces In generation, is also able to use other inactive gas such as Ar gas.
In addition, using TiCl as Ti unstrpped gas4Gas uses NH as nitriding gas3Gas, as delivery gas Body cleans gas and uses N2Gas uses O as oxidant2The preferred scope of membrance casting condition in the case where gas is as follows.
Treatment temperature (base-plate temp): 300~500 DEG C
Cavity internal pressure: 13.33~1333Pa (0.1~10Torr)
TiCl4Gas flow: 10~200mL/min (sccm)
NH3Gas flow: 1000~10000mL/min (sccm)
N2Gas flow: 1000~30000mL/min (sccm)
The primary service time of step 11~16: 0.01~3sec
O2Gas flow: 10~3000mL/min (sccm)
O2Gas supplying time: 0.1~60sec
In addition, in above-mentioned example, NH3The rear ventilation of gas is only set to once but it is also possible to be by NH3Gas ventilation and Clean the supply form of the number more than being repeated twice in a pulsed fashion.
The first embodiment party can also apply to by the rear ventilation of nitriding gas before oxidation processes in present embodiment The film build method of TiON film involved in formula, can also play same effect in this case.
< third embodiment >
Next, being illustrated to third embodiment of the present invention.
In the present embodiment, using the film formation device of Fig. 1 100, pass through Fig. 2's of the premise as first embodiment After process carries out the film forming of TiON film, argon ion processing is implemented to film surface.
Figure 12 is the sectional view for showing an example for the device for implementing argon ion processing.
ICP (inductively coupled plasma body, Inductively Coupled Plasma) type plasma is splashed here, showing The example that injection device is used as argon ion processing unit.
As shown in figure 12, which has the cavity 201 of the ground connection as made of the metals such as aluminium, in chamber The bottom of body 201 is equipped with exhaust outlet 202 and gas introduction port 203.Exhaust outlet 202 is connected with exhaust pipe 204, exhaust pipe 204 It is connected with the throttle valve and the exhaust component 205 as made of vacuum pump etc. for carrying out pressure adjustment.In addition, gas introduction port 203 Be connected with gas supplying tubing 206, gas supplying tubing 206 with for supplying argon (Ar) gas and N2Other gases such as gas Gas supply member 207 be connected.Platform 210 is made of conductive material, is grounded via pillar 211.
It is provided in cavity 201 for loading the platform 210 as the wafer W of substrate processed.It is equipped with and is used in platform 210 Adsorb the electrostatic chuck of chip and the temperature adjustment component (not shown) for carrying out temperature adjustment to chip.In below the platform 210 Centre is equipped with cylindrical pillar 211.The lower part of pillar 211 is penetratingly formed at inserting for the central part of the bottom of process container 201 Through-hole 212, extends downward.Pillar 211 can be gone up and down by lift component (not shown), thus go up and down platform 210.In platform Between 210 and the bottom of cavity 201, bellows 213 is equipped in a manner of around pillar 211.Platform 210 is connected with supply lines 214 It connects, supply lines 214 is extended downward by the inside of pillar 211.Supply lines 214 is connected with biasing high frequency electric source 215, from Biasing applies the high-frequency bias of such as 13.56MHz with high frequency electric source 215 via platform 210 to wafer W.
It is vertical upwards to be equipped with such as three (only illustrating two) support needles 216 in the bottom of cavity 201, support needle 216 Insert is in the needle insertion hole (not shown) that platform 210 is arranged in, and when having dropped platform 210, becomes the upper of support needle 216 The state of end support wafer W, makes it possible the conveying of wafer W.
It is equipped in the lower sides of cavity 201 in order to by the carrying-in/carrying-out mouth 217 of wafer W carrying-in/carrying-out, carrying-in/carrying-out mouth 217 are opened and closed by gate valve 218.
On the other hand, at the top of cavity 201, transmitting plate 220 as made of dielectric are hermetically equipped with, in the transmitting plate The upper surface of 220 sides, equipped with the plasma-generating source for generating Ar gaseous plasma for the processing space S in cavity 201 221.Plasma-generating source 221 have the induction coil 222 being arranged along the upper surface of transmitting plate 220 and with the induction coil The 222 plasma generation high frequency electric sources 223 being connected.Also, by from plasma generation with high frequency electric source 223 to sense It answers coil 222 to apply the RF power of such as 13.56MHz, forms induction field in processing space S via transmitting plate 220.
The top of cavity 201 becomes rake 201a, is equipped on the inside of it in section inclined cyclic annular (butt inwardly Circular cone is shelly-shaped) target, in addition, be equipped with to target apply DC voltage DC power supply and be located at target peripheral side magnetite ( It is not shown), but in the case where being used as argon ion processing unit, due to these It is not necessary to, so omitting the description.
Argon ion processing unit 200 also has control unit (not shown) same as the control unit 50 of film formation device 100, respectively Constituting portion is connected with control unit and is controlled.
In such argon ion processing unit 200, Ar gas is supplied into cavity 201 from gas supply member 207, from High frequency electric source 223 applies RF power to induction coil 222, and the processing space S in cavity 201 generates Ar plasma as a result, Ar ion is introduced wafer W by body, also, the RF power by applying biasing from biasing with high frequency electric source 215 to platform 210, Ar ion processing is implemented to wafer W surface.
Next, being illustrated to an example of the film build method of the TiON film of present embodiment.
It is known in the film forming of TiON film, only by as shown in Figure 2, TiCl will be passed through4Gas and NH3The alternating of gas supplies The film forming and oxidation processes later for the unit TiN film given as a circulation and by the method for the multiple circulations of the circulating repetition, Then can be as shown in figure 13, there are the generations such as flatness as shown in figure 14 in the chlorine (Cl) for remaining 0.7at.% or so in film The case where.This is because the TiCl as unstrpped gas4It is not completely reduced, Cl can be remained in film.In addition, Figure 13 is to show The figure for the result that the film composition of TiON film is measured using x-ray photoelectron spectroscopy (XPS) device, Figure 14 is the surface of TiON film Scan microscope (SEM) photo.
Here, after forming TiON film by process as shown in Figure 2, argon ion processing is carried out in present embodiment, thus Make to remain Cl reduction.
For specific process, the flow chart based on Figure 15 is illustrated.
Firstly, in the same manner as first embodiment, in the cavity 1 after the precoating treatment for having carried out film formation device 100, warp Wafer W is moved in by carrying-in/carrying-out mouth 42, mounting is on the base 2.Later, wafer W is heated to preferably 300 by heater 5 The predetermined temperature of~500 DEG C of range supplies N into cavity 12Gas carries out the preheating of wafer W, keeps the temperature of wafer W steady Fixed (step S21).
Next, in the same manner as step S1~S4 of first embodiment, from TiCl4Gas supply source 21 is by TiCl4Gas It is supplied to cavity 1, makes TiCl4Gas is adsorbed (step S22), next, stopping TiCl4The supply of gas, uses N2Gas will (step S23) is cleaned in cavity 1, next, from NH3Gas supply source 23 is by NH3Gas is supplied to cavity 1, is made it and is adsorbed TiCl4It reacts and forms TiN (step S24), next, stopping NH3Gas uses N2Gas will clean (step in cavity 1 S25), these steps S22~S25 is repeated into stipulated number.Later, from oxidant supply source 27 by oxidant (such as O2Gas) It supplies, carries out oxidation processes (step S26) to cavity 1, next will clean (step S27) in cavity 1.It regard this circulation as one A circulation forms the TiON film of required thickness by providing to recycle the circulating repetition.
At this point, the oxygen amount of TiON film can be adjusted according to the number of repetition of step S22~S25.That is, if reducing repetition time Number, then the frequency aoxidized increases, so the oxygen amount of pulling in film increases, if increasing number of repetition on the contrary, the oxygen in film is drawn Enter amount reduction.In addition, also film thickness can be adjusted according to recurring number.In addition, the oxygen concentration of TiON film can not only pass through step The number of repetition of S22~S25 is adjusted, additionally it is possible to is adjusted by the flow of the time of oxidation processes, oxidant.
After TiON film is consequently formed, it will be evacuated to vacuum in cavity 1, wafer W is moved out into (step S28) from cavity 1.
Next, the wafer W for being formed with TiON film is moved in the cavity 201 of argon ion processing unit 200, it is positioned in platform On 210 (step S29).Later, cavity 201 is evacuated to 10-6After the high vacuum of Pa magnitude, Ar gas is supplied into cavity 201 It adjusts to authorized pressure, by applying RF power from high frequency electric source 223 to induction coil 222, the processing in cavity 201 is empty Between S generate Ar plasma.It later, will by applying the RF power of biasing from biasing with high frequency electric source 215 to platform 210 Ar ion introduces wafer W, implements Ar ion processing (step S30) to wafer W surface.
After Ar ion processing, it will be evacuated to vacuum in cavity 201, wafer W is moved out into (step S31) from cavity 201.
In the present embodiment, plasma is generated in cavity 201, and the Ar ion in plasma is introduced into crystalline substance Wafer W is handled in piece W, therefore, the Cl in TiON film can be removed by the energy of Ar ion, can reduce in film Cl concentration.I.e., it is contemplated that Cl combines state that can be weak to exist in TiON film, passes through shock (bombardment effect) energy of Ar ion It is enough to be fully detached from it from film, it can extremely efficient reduce the Cl in film.Therefore, the TiON of purity is high can be obtained Film.In addition, can not sputter to film by Ar ion processing, and improve surface smoothness.
In the present embodiment, it as gas containing Ti, is able to use if it contains Cl.In addition, as oxidant, energy Enough use O2Gas, O3Gas, H2O、NO2Equal oxygen-containing gas can also carry out oxygen-containing gas plasmarized rear as oxidation Agent uses.Moreover, as nitriding gas, in addition to NH3In addition, additionally it is possible to use monomethyl hydrazine (MMH).In addition, as fortune is used as Gas carrier and the N for cleaning gas2The substitution of gas is also able to use other inactive gas such as Ar gas.
In addition, using TiCl as Ti unstrpped gas4Gas uses NH as nitriding gas3Gas, as delivery gas Body cleans gas and uses N2Gas uses O as oxidant2The preferred scope of membrance casting condition in the case where gas and first Embodiment is identical.
In addition, the Ar ion processing of the device for having used Figure 12, may be exemplified following condition.
Plasma generates the power for using high frequency electric source (13.56MHz): 1kW
The biasing power of high frequency electric source (13.56MHz): 1kW
Cavity internal pressure: 0.33Pa (2.5mTorr)
Ar gas flow；55mL/min(sccm)
Handle the time: 3sec
Next, comparing the Cl concentration implemented before and after Ar ion processing to TiON film.Here, film-forming temperature is set as 430 DEG C, step S22~S25 is repeated 14 times processing that is rear, carrying out step S26, S27 as one and is recycled, this circulation is carried out 33 circulations, to form TiON film, Ar ion processing is with the progress of foregoing illustrative condition.Cl concentration is by XPS to chip It is measured at nine, is acquired by its average value.It the results are shown in Figure 16.As shown in the drawing, the Cl before Ar ion processing is dense Degree is 0.7at.%, but is reduced to 0.1at.% by Ar ion processing.Thus result is it has been confirmed that by Ar ion processing, Residual Cl can be effectively removed.
Next, carrying out the group to the TiON film before above-mentioned TiON film implementation Ar ion processing and after implementing by XPS At analysis.The results are shown in Figure 17.As shown in the drawing it has been confirmed that the film composition of TiON film is certainly several before and after Ar ion processing Do not change, only the Cl in film is detached from.
Figure 18 (a), (b) are the surfaces of the TiON film before implementing Ar ion processing for above-mentioned TiON film and after implementing SEM photograph.It has been confirmed that the film surface after Ar ion processing is higher than flatness before processing as shown in these SEM photographs.
Figure 19 is the figure for showing the film thickness to the TiON film before above-mentioned TiON film implementation Ar ion processing and after implementing.? This, acquires the film thickness at the nine of chip, shows its average value.As shown in the drawing, it has been confirmed that TiON before and after Ar ion processing The film thickness difference of film is small (~0.5nm), does not sputter, and by the effect of the shock of Ar ion, makes its smoothing.
Film formation device 100 and argon ion processing unit 200 can be entirely different device (out of the ordinary), but it is preferable to use these It is connected by same conveyer, so as to carry out the film forming of TiON film and the system of Ar ion processing with not destroying vacuum.
Figure 20 is the schematic diagram for showing an example of processing system of the film forming and Ar ion processing that are able to carry out TiON film.It should The vacuum carrying room 310 that processing system 300 has flat shape hexagonal, film formation device 100 and argon ion processing unit 200 It is connected in a manner of opposite one another with vacuum carrying room 310 via gate valve G.In addition, there are two being connected in vacuum carrying room 310 Road lock chamber (ロ ー De ロ ッ Network) 320.
Defined vacuum atmosphere is maintained as in vacuum carrying room 310, in the wafer transfer for being wherein provided with conveying wafer W Component 311.Wafer transfer component 311 is carried out for 200, two film formation device 100, argon ion processing unit road lock chambers 320 Chip conveying.
On road, lock chamber 320 is provided with atmosphere carrying room 330, road lock chamber 320 with 310 opposite side of vacuum carrying room It is connected with atmosphere carrying room 330 via gate valve G.Atmosphere carrying room 330 is connected with the vehicle 340 of storage wafer W.Separately Outside, in atmosphere carrying room 330, it is equipped with guide rail 331 along the orientation of vehicle 340, being equipped with can be on the guide rail 331 Mobile wafer transfer component 332.In addition, being equipped with the alignment room for carrying out the alignment of wafer W in the side of atmosphere carrying room 330 333。
According to such processing system 300, transported by wafer transfer component 332 from the wafer W that vehicle 340 takes out Into road lock chamber 320, after road lock chamber 320 remains vacuum, the wafer W of road lock chamber 320 is by vacuum carrying room 310 Interior wafer transfer component 311 picks up.Later, wafer W is being transported to film formation device 100 film forming for carrying out TiON film first Afterwards, it is transported to argon ion processing unit 200 and carries out argon ion processing.Later, after being handled by wafer transfer component 311 Wafer transfer to road lock chamber 320, road lock chamber 320 is restored to atmospheric pressure, by wafer transfer component 332 by wafer W It send and returns to vehicle 340.
By above method, the film forming of TiON film and Ar ion processing can be connected in the case where not destroying vacuum It is continuous to carry out.
In addition, can be carried out continuously in same cavity if Ar ion processing function is arranged in film formation device The film process and Ar ion processing of TiON film.Figure 21 is the sectional view for showing such film formation device.The film formation device 100 ' substantially have basically same structure with the film formation device of Fig. 1 100, but attached Ar gas in film formation device 100 Functions of physical supply and Ar plasma systematic function.That is, the gas supply member 20 of film formation device 100 ' is attached with the confession of Ar gas The Ar gas feed line road 62 of Ar gas, Ar gas feed line road 62 and N are supplied to source 61 and from Ar gas supply source 612Gas Supply lines 30 are connected.In Ar gas feed line road 62, equipped with mass flow controller 33 and mass flow control is clipped Two valves 34 of device 33.Ar gas can be supplied to cavity 1 as a result,.
In addition, being equipped with electrode 63 in pedestal 2, electrode 63 is connected via supply lines 64 with high frequency electric source 65.By from High frequency electric source 65 generates high-frequency electric field between electrode 63 and spray head 10, supplies into cavity 1 to 63 supply high frequency electric power of electrode Such high-frequency electric field is generated in the state of Ar gas to having, and thus generates the plasma of Ar gas.In addition, from high frequency electric source The RF power of 65 supplies also introduces the high-frequency bias of Ar ion as the wafer W on pedestal 2 and functions.Therefore, energy After enough forming TiON film as described above in cavity 1, continue to generate Ar plasma in cavity 1, Ar ion is introduced into wafer W Ar ion processing is implemented to wafer W.
In this way, wafer W is maintained on the pedestal 2 in cavity 1, through the above steps S22 by film formation device 100 ' After~S27 forms TiON film, the Ar ion processing that step 30 is carried out in cavity 1 can continue to, therefore handling capacity pole can be made It is high.
In addition, Ar ion can be supplied to wafer W by carrying out the device of Ar ion processing, it is not limited to above illustration.
Ar ion processing in present embodiment can also apply to TiON involved in first and second embodiment The film build method of film can also play same effect in that case.
The 4th embodiment > of <
Next, being illustrated for the 4th embodiment of the invention.
Method in present embodiment, using the film formation device 100 of Fig. 1, by enhancing oxidation than first embodiment Form TiON film.
Hereinafter, being illustrated for an example of the film build method of the TiON film of present embodiment.
Firstly, opening gate valve 43 after being carried out similarly precoating treatment with first embodiment, pass through from wafer transfer room Carrying device (not shown) moves in wafer W to cavity 1 via carrying-in/carrying-out mouth 42, is placed in pedestal 2.Later, pass through Wafer W is heated to the predetermined temperature of preferably 300~500 DEG C of range by heater 5, supplies N into cavity 12Gas carries out The preheating of wafer W.When the temperature of chip is almost stable, start the film forming of TiON film.
In the film forming of TiON film, in the process of Fig. 2 of the premise as first embodiment, oxidation efficiency occurs not Abundant situation.Specifically, the development of the miniaturization with equipment, such as the opening of capacitor arrangement of DRAM narrows, is high When width is than getting higher, in the process of Fig. 2 of the premise as first embodiment, no normal direction through-hole bottom (cylinder bottom) supply is abundant Oxygen, thus oxidation it is sometimes insufficient.
Here, in present embodiment, in forming the oxidation processes after unit TiN film, by oxidant (such as O2Gas) Intermittently, it repeatedly supplies.Thus it enables that the supply of oxidant improves, to improve oxidation efficiency.In particular, energy Enough through-hole bottoms high for depth-width ratio can also supply oxidant, prevent from aoxidizing insufficient.This is considered as intermittently supplying When oxidant, during closing valve, not supplying oxidant, the oxidant of high pressure is saved bit by bit in piping, open valve when Carve the reason that can supply the oxidant of high pressure.
Specific process example is illustrated referring to the time diagram of Figure 22 and the flow chart of Figure 23.
It is initially, same as step S1~S4 of first embodiment as shown in these, from TiCl4Gas supply source 21 will TiCl4Gas is supplied to cavity 1, makes TiCl4Gas is adsorbed (step S41), next, stopping TiCl4The supply of gas, benefit Use N2Gas will clean (step S42) in cavity 1, next, from NH3Gas supply source 23 is by NH3Gas is supplied to cavity 1, is made Itself and adsorbed TiCl4It reacts and forms TiN (step S43), next, stopping NH3Gas utilizes N2Gas will be in cavity 1 It cleans (step S44), these steps S41~S44 is repeated X times.Later, by oxidant (such as O2Gas) it is supplied from oxidant Supply (step S45) of the source 27 into cavity 1 and the cleaning (step S46) in cavity 1 is repeated into N circulation, passes through intermittence Ground carries out oxidation processes for oxygen supply.It is recycled above circulation as one, by the way that this is repeated Y circulation, required by formation Thickness TiON film.
At this point, oxidant (such as O2Gas) supply preferably as shown in figure 24, be set as pulse type.In addition, oxidant Primary service time can be set as 0.05~30sec, preferably 0.05~5sec, more preferably 0.05~3sec.One Secondary service time is total oxidization time multiplied by the value of recurring number.Oxidation efficiency reduces certain journey with by primary service time Spend and increase cycle-index N and there is the tendency risen, if but primary service time it is too short, be difficult to supply oxidant.
At this point, the oxygen amount of TiON film can be adjusted according to the repeat number X of step S41~S44.That is, if reducing repeat number X The frequency of oxidation increases, therefore the oxygen amount of pulling in film can be made to increase, on the contrary the oxygen amount of pulling in if increasing repeat number X in film It reduces.In addition, film thickness can be adjusted according to recurring number Y.In addition, the oxygen concentration of TiON film can not only be by adjusting step S41 The number of repetition of~S44 is adjusted, additionally it is possible to is adjusted according to the flow of the time of oxidation processes, oxidant.
After being thusly-formed TiON film, it will be evacuated to vacuum in cavity 1, wafer W is moved out.
In this way, repeating the supply of the oxidant of step 45 and the cleaning of step 46, oxidant is intermittently supplied, Oxidation processes are carried out, therefore can be improved oxidation efficiency, can also be sufficiently fed oxidant at the high through-hole bottom of depth-width ratio, it can It is sufficiently carried out oxidation.
In the present embodiment, O can be used as oxidant2Gas, O3Gas, H2O、NO2Equal oxygen-containing gas, can also Using by oxygen-containing gas carry out it is plasmarized after use as oxidant.In addition, as gas containing Ti, in addition to TiCl4In addition, also It is able to use four (isopropoxy) titaniums (TTIP), titanium tetrabromide (TiBr4), titanium tetra iodide (TiI4), tetrem vlmethyl titanium (TEMAT), four dimethylamino titaniums (TDMAT), four diethylamino titaniums (TDEAT) etc..In addition, as nitriding gas, in addition to NH3In addition, additionally it is possible to use monomethyl hydrazine (MMH).In addition, as being used as delivery gas and cleaning the N of gas2Gas replaces In generation, is also able to use other inactive gas such as Ar gas.
In addition, using TiCl as Ti unstrpped gas4Gas uses NH as nitriding gas3Gas, as delivery gas Body cleans gas and uses N2Gas uses O as oxidant2The preferred scope of other membrance casting conditions in the case where gas It is as follows.
Treatment temperature (base-plate temp): 300~500 DEG C
Cavity internal pressure: 13.33~1333Pa (0.1~10Torr)
TiCl4Gas flow: 10~200mL/min (sccm)
NH3Gas flow: 1000~10000mL/min (sccm)
N2Gas flow: 1000~30000mL/min (sccm)
The primary service time of step 41~44: 0.01~3sec
O2Gas flow: 10~3000mL/min (sccm)
Total O2Gas supplying time: 0.1~60sec
Next, being illustrated for the confirmation result of the effect of present embodiment.
Here, using TiCl as Ti unstrpped gas4Gas uses NH as nitriding gas3Gas, as delivery gas Body cleans gas and uses N2Gas uses O as oxidant2Gas, is set as X=6, Y=50, O when oxidation processes2Gas The supply method of body changes in condition A, B, C described below, and keeps the oxidization time in Y circulation consistent and form TiON Film determines oxygen concentration in film.O2The supply method of gas is condition A: the continuous supply of flow 1400sccm, condition B: stream The continuous supply of 300sccm is measured, condition C: the pulse supply of flow 300sccm.In the pulse supply of condition C, by primary O2 The supply of gas is set as 0.2sec, adjusts oxidization time by recurring number N.The relationship of oxidization time and recurring number N at this time As follows.
The relationship of oxygen concentration is shown in Figure 25 in oxidization time and film at this time.Compare as the condition A and item continuously supplied Part B is it has been confirmed that under identical oxidization time, O2Oxygen concentration is high in the film in condition A more than gas flow.In addition, comparing phase Same O2The condition B and condition C of gas flow it has been confirmed that under identical oxidization time, oxygen in the condition C of pulse supply The amount of pulling in (oxygen concentration in film) increases.In addition, comparison condition A and condition C, although the O of the condition C of pulse supply2Gas flow For 300sccm, however under identical oxidization time, there is the oxygen amount of pulling in being equal with the condition A of continuous supply, 1400sccm (oxygen concentration in film), whereby it was confirmed that, by by O2Gas pulses supply, can be improved oxidation efficiency.
The supply of intermittent oxidant in present embodiment can also apply to involved by first~third embodiment And TiON film film build method, can also play in this case when forming TiON film improve oxidation efficiency effect.
In particular, it is outstanding to prevent from being formed in unit TiN film to play reinforcing nitridation by being applied to second embodiment Dead key and can be big as oxidation efficiency by be improved later based on the oxidation processes of intermittent oxidant supply Effect.
So time when present embodiment will be applied to be illustrated in Figure 26 in this second embodiment.Figure 26 is in Figure 24 institute Show in method, further increases NH3The rear ventilation (step S47) of gas and utilize N2Cleaning (step in the cavity 1 of gas Rapid S48) method.That is, after being repeated X times by the formation of the unit TiN film of step 41~44, by NH3The rear ventilation of gas (step S47) and utilize N2The cleaning (step S48) of gas carries out primary or repeats, next, by oxidant (such as O2Gas) cleaning (step S46) in supply (step S45) and cavity 1 into cavity 1 repeat N circulation carry out it is intermittent Oxidation processes are recycled above circulation as one, by the way that this is repeated Y circulation, form the TiON film of required thickness. Dangling bonds is few thereby, it is possible to obtaining, and the TiON film that oxidation efficiency is high.
< others application >
More than, embodiments of the present invention are illustrated, but the present invention is not limited to above embodiment, at this Various modifications are able to carry out in the range of the technical idea of invention.For example, the film formation device of Fig. 1 used in above embodiment It only illustrates, is not limited to the device of Fig. 1.In addition, instantiating semiconductor wafer, but the principle of the present invention as substrate processed On, it is not limited to this, can also be such as using base plate for liquid crystal display device as others base the FPD substrate of representative Plate, this is self-evident.

Claims (17)

1. a kind of film build method of TiON film, it is characterised in that:
This method is by substrate reception processed in process container, making holding decompression state in the process container, with regulation Treatment temperature, by the multiple circulations of following circulating repetition come the methods that form TiON film, the circulation is as follows: will contain Ti gas with Nitriding gas alternative supply into the process container, after forming unit TiN film, supply oxidant in Xiang Suoshu process container and The unit TiN film is aoxidized,
In film forming initial stage, alternative supply X1 times rear, supply oxidant of the gas containing Ti and nitriding gas will be repeated Circulation carry out Y1 circulation,
It is rear, supply oxidant by alternative supply X2 times of repetition gas containing Ti and nitriding gas in text message later Circulation carries out Y2 circulation, until become required film thickness,
The repeat number X1 of the film forming initial stage and it is described after the repeat number X2 of text message be set to X1 > X2.
2. the film build method of TiON film as described in claim 1, it is characterised in that:
Range of the X1 in 10≤X1≤60, range of the X2 in 1≤X2≤25.
3. the film build method of TiON film as claimed in claim 1 or 2, it is characterised in that:
The X1 is 3 times of the X2 or more.
4. the film build method of TiON film as claimed in claim 1 or 2, it is characterised in that:
Range of the Y1 in 1≤Y1≤5.
5. a kind of film build method of TiON film, it is characterised in that:
By substrate reception processed in process container, making holding decompression state in the process container, with defined processing temperature The multiple circulations of following circulating repetition are formed TiON film by degree, and the circulation is as follows: will contain Ti gas and nitriding gas to described Alternative supply in process container after forming unit TiN film, supply into the process container at the rear ventilation of nitriding gas It manages and supplies oxidant into the process container and make the processing of the unit TiN film oxidation, it, will in the rear ventilation treatment The supply of nitriding gas and the supply for cleaning gas are repeated as many times.
6. the film build method of TiON film as claimed in claim 5, it is characterised in that:
The supply of the oxidant intermittently carries out repeatedly.
7. the film build method of TiON film as claimed in claim 1 or 5, it is characterised in that:
After the film forming, argon ion processing is implemented to the film surface.
8. the film build method of TiON film as claimed in claim 7, it is characterised in that:
The argon ion processing is carried out by generating argon plasma, argon ion therein being introduced substrate processed.
9. the film build method of TiON film as claimed in claim 7, it is characterised in that:
The argon ion processing carries out the film surface processing by the shock of argon ion.
10. the film build method of TiON film as claimed in claim 7, it is characterised in that:
The film forming and argon ion processing are carried out in different devices.
11. the film build method of TiON film as claimed in claim 10, it is characterised in that:
The device for carrying out the film forming and the device for carrying out the argon ion processing are mounted in have can transport quilt in a vacuum The processing system for handling the conveyer of substrate connects the film forming and argon ion processing in the case where not destroying vacuum It is continuous to carry out.
12. the film build method of TiON film as claimed in claim 7, it is characterised in that:
The film forming and argon ion processing carry out in same process container.
13. a kind of film build method of TiON film, it is characterised in that:
By substrate reception processed in process container, making holding decompression state in the process container, with defined processing temperature The multiple circulations of following circulating repetition are formed TiON film by degree, and the circulation is as follows: will contain Ti gas and nitriding gas to described Alternative supply in process container after forming unit TiN film, alternately repeatedly carries out the supply of oxidant in Xiang Suoshu process container With the supply for cleaning gas and make the processing of unit TiN film oxidation.
14. the film build method of TiON film as claimed in claim 13, it is characterised in that:
The oxidant is supplied with pulse type.
15. the film build method of the TiON film as described in any one of claim 1,5 and 13, it is characterised in that:
The gas containing Ti is TiCl4Gas, the nitriding gas are NH3Gas.
16. the film build method of the TiON film as described in any one of claim 1,5 and 13, it is characterised in that:
As the oxidant, can be used selected from O2Gas, O3Gas, H2O、NO2In oxygen-containing gas or will be described oxygen-containing Plasma obtained from gaseous plasma.
17. the film build method of the TiON film as described in any one of claim 1,5 and 13, it is characterised in that:
The treatment temperature is 300~500 DEG C.
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