CN1266308C - Film formation method for semiconductor processing - Google Patents

Film formation method for semiconductor processing Download PDF

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Publication number
CN1266308C
CN1266308C CNB038009137A CN03800913A CN1266308C CN 1266308 C CN1266308 C CN 1266308C CN B038009137 A CNB038009137 A CN B038009137A CN 03800913 A CN03800913 A CN 03800913A CN 1266308 C CN1266308 C CN 1266308C
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gas
treatment chamber
film
coated
mounting table
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CN1547624A (en
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横井裕明
善光哲
芦泽宏明
桥本毅
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Tokyo Electron Ltd
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Tokyo Electron Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—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
    • C23C16/34—Nitrides
    • 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
    • C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
    • C23C16/4404—Coatings or surface treatment on the inside of the reaction chamber or on parts thereof

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Electrodes Of Semiconductors (AREA)

Abstract

A film formation method for semiconductor processing includes a pre-coat step for coating a placing table (32) by a pre-coat before conveying a substrate (W) to be processed into a processing chamber and a step for conveying the substrate (W) to be processed into the processing chamber (21) after the pre-coat step and forming a main film on the substrate (W) to be processed. The pre-coat step repeats a first and a second step a plurality of times so that a plurality of segment films are superimposed to form a pre-coat. In the first step, a first and a second processing gas are supplied into a processing chamber (21) and a segment film containing a metal element is formed on the placing table (32). In the second step, a second processing gas not containing a metal element is supplied into the processing chamber (21) and a byproduct other than the component to form the segment film generated in the first step is removed from the processing chamber (21) by exhaust of air.

Description

The film that semiconductor processes is used
Technical field
The present invention relates to the film that a kind of semiconductor processes is used, particularly a kind of method that on the processed substrate of semiconductor wafer etc., forms the film that comprises metallic element by CVD (chemical vapour deposition).And, here, the meaning of semiconductor processes is: by form semiconductor layer, insulation layer, conductive layer etc. with predetermined pattern on processed substrates such as semiconductor wafer or LCD substrate, be used to make semiconductor element or comprise the various processing of the structure of the wiring that is connected with semiconductor element, electrode etc. on this processed substrate.
Background technology
The semiconductor element that forms multi-layer circuit structure carries out repeatedly pattern etching and makes by for example film forming on the surface of the semiconductor wafer of silicon substrate etc.For example, the connecting portion of the wiring layer on silicon substrate and its perhaps at the connecting portion of wiring layer up and down, is peeled off in order to prevent lower floor, the phase mutual diffusion of the material between perhaps suppressing up and down, and form screen layer.As this screen layer, for example use the TiN film that forms by hot CVD.As the counterdie of TiN film, have by plasma CVD and form the situation of thin Ti film and situation about not forming.
Figure 11 is the sketch chart that expression is used to form the existing C VD device of screen layer.For example, this device has the vacuum processing chamber 1 that is formed by aluminium.On the bottom surface of treatment chamber 1, form venting port 11.In the inside of treatment chamber 1, be provided for mounting table 13 with the horizontal mounting of semiconductor wafer W.Mounting table 13 is made of for example aluminium nitride, internal heater 12.Set to supply with and handle the shower nozzle 15 that gas is used, make relative with mounting table 13.Below shower nozzle 15, form a plurality of gas squit holes 14 in the position relative with the wafer W of mounting on mounting table 13.When film forming, when utilizing well heater 12 to heat the wafer W that is positioned on the mounting table 13, provide as the TiCl that handles gas from shower nozzle 15 4And NH 3At this moment, produce the reaction of following formula (1), on the whole surface of wafer W, form the TiN film.
…(1)
Handle if a plurality of wafer W are repeated such film forming, TiN also is attached on the wall in the vacuum processing chamber 1.Particularly, around the higher mounting table 13 of temperature, for example, as shown in figure 12, slowly add up this dirt settling 16.The surface heat radiant ratio of mounting table 13 changes thus, even design temperature is identical, the surface temperature of mounting table 13 also produces difference, and the homogeneity of the thickness between wafer surface reduces.For fear of this problem, wafer W is being carried out before film forming handles, for example, carry out on the whole surface of mounting table 13 pre-coated that (above, below and side) be pre-formed the TiN film and handle.For handle by this pre-coated the TiN film that forms (pre-coated: pre-coating), can be clear, for example,, just avoided the problems referred to above if thickness is more than the 0.5 μ m.In addition, by this pre-coated, when carrying out film forming on the wafer W, also suppressed by the aluminum that constitutes treatment chamber 1 and constitute the stupalith of mounting table 13, the metallic impurity such as Al among for example AlN pollute this wafer W.
As described below the carrying out of existing pre-coated operation.At first, in vacuum processing chamber 1, carry out in the vacuum exhaust mounting table temperature being heated to 600～700 ℃.As the temperature-stable of mounting table 13, then the pressure in the vacuum processing chamber 1 is 40Pa (0.3Torr).By flowing in advance behind the stabilizing gas flow, will be as the TiCl that handles gas 4Gas is with the flow of for example 30～50sccm, with NH 3Gas provides in vacuum processing chamber 1 with the flow of for example 400sccm simultaneously.After the supply of carrying out two kinds of processing gases about 15 minutes～20 minutes, handle (post nitride) for follow-up nitriding, stop TiCl 4The supply of gas is only supplied with NH with for example flow about 1000sccm 3Gas carries out the specified time simultaneously, for example the vacuum exhaust in the vacuum processing chamber about tens seconds 1.By like this,, form for example TiN film (pre-coated) about 0.5～2.0 μ m on the surface of mounting table 13.Afterwards, mounting wafer W on the mounting table 13 of pre-coated becomes embrane method on the surface of this wafer W by each, forms for example Ti film 18 and TiN film 19 (with reference to Figure 13).
But in the one-tenth embrane method of above-mentioned TiN film, in the pre-coated operation from TiCl 4Decompose in the gas or subsidiary muriate that produces and the metal reaction in the vacuum processing chamber 1, produce metal chloride.This metal oxide evaporates in film formation process, is pooled on the film of wafer W.If in this film, sneak into unscheduled metal, will produce baneful influence to the electrical specification of element, reduce yield rate.For this reason, must control the mixed volume of metal as much as possible.The tolerance limit of metal mixed volume is strict all the more along with the progress of the filming of element.
Summary of the invention
The objective of the invention is in the film that semiconductor processes is used, after the mounting table in the processing vessel being carried out the pre-coated processing, reduce the total amount of the metal impurities in the main film that on processed substrate, forms.
The 1st viewpoint of the present invention is to be used at the processed substrate of mounting on the mounting table of gastight treatment chamber, forms the film that the semiconductor processes of the film that comprises metallic element is used, and comprising:
(a) before moving into described processed substrate in the described treatment chamber, utilize pre-coated to apply the pre-coated operation of described mounting table;
(b) after described pre-coated operation, described processed substrate is moved in the described treatment chamber, on described processed substrate, form the film formation process of main film,
Wherein, described pre-coated operation comprises:
The 1st operation, in the described mounting table of heating on one side with described treatment chamber in exhaust, the 1st processing gas that will contain the unstripped gas that comprises described metallic element on one side is supplied in the described treatment chamber, forms arc (segment) film that comprises described metallic element on described mounting table;
The 2nd operation, in the described mounting table of heating on one side with described treatment chamber in exhaust, the 2nd processing gas that will not contain the unstripped gas that comprises metallic element on one side is supplied in the described treatment chamber, by exhaust, will in described the 1st operation, from described treatment chamber, remove by by-product biology that produce, except the composition that forms described arc film; And
By repeatedly repeating the described the 1st and the 2nd operation, stacked a plurality of arc films form the operation of described pre-coated,
Wherein, described film formation process comprises:
Described processed substrate is moved in the described treatment chamber operation of mounting on the described mounting table;
In the described mounting table of heating on one side with described treatment chamber in exhaust, on one side will the described the 1st and the 2nd handle gas and be supplied in the described treatment chamber, formation comprises the operation of the described main film of described metallic element on described processed substrate.
The 2nd viewpoint of the present invention is the CVD method, in order on the processed substrate on the mounting table of mounting in the gastight treatment chamber, to form the film that comprises metallic element, supply with the 1st processing gas that comprises described metallic element to described treatment chamber on one side, handle gas with the 2nd of the decomposition of assisting described the 1st processing gas, on described processed substrate, form the film that comprises described metallic element on one side, comprising:
(a) before moving into described processed substrate in the described treatment chamber, utilize pre-coated to apply the pre-coated operation of described mounting table;
(b) after described pre-coated operation, described processed substrate is moved in the described treatment chamber, on described processed substrate, form the film formation process of main film,
Wherein, described pre-coated operation comprises:
The 1st operation, in the described mounting table of heating on one side with described treatment chamber in exhaust, on one side will the described the 1st and the 2nd handle gas and be supplied in the described treatment chamber, formation comprises the arc film of described metallic element on described mounting table;
The 2nd operation, stop the described the 1st and handle gas, on the other hand, in the described mounting table of heating on one side with described treatment chamber in exhaust, handling gas with the described the 2nd on one side is supplied in the described treatment chamber, make by the decomposition of described the 1st processing gas or the intermediate and the described the 2nd of reaction generation and handle gas reaction, produce secondary resultant, described secondary resultant is removed from described treatment chamber by exhaust; And
By repeatedly repeating the described the 1st and the 2nd operation, stacked a plurality of arc films form the operation of described pre-coated,
Here, in the described the 1st and the 2nd operation, use general in fact treatment temp and processing pressure, described secondary resultant distils under this treatment temp and processing pressure,
Wherein, described film formation process comprises:
Described processed substrate is moved in the described treatment chamber operation of mounting on the described mounting table; And
In the described mounting table of heating on one side with described treatment chamber in exhaust, on one side will the described the 1st and the 2nd handle gas and be supplied in the described treatment chamber, formation comprises the operation of the described main film of described metallic element on described processed substrate.
Description of drawings
Fig. 1 is the longitudinal section of the CVD device of expression the present invention l embodiment.
Fig. 2 A～C is the figure that represents the film of the 1st embodiment according to process sequence.
Fig. 3 is illustrated in the supply cut-out of gas during employed pre-coated is handled in the film of the 1st embodiment and the control chart of pressure chronologically.
Fig. 4 is illustrated in the supply cut-out of gas during employed pre-coated is handled in the film of variation of the 1st embodiment and the control chart of pressure chronologically.
Fig. 5 is the figure of the relevant test-results of the film of expression the 1st embodiment.
Fig. 6 is the longitudinal section of the CVD device of expression the present invention the 2nd embodiment.
Fig. 7 is the figure of the treatment condition of each operation during employed pre-coated is handled in the film of representing in the 2nd embodiment.
Fig. 8 is the figure of the relation of the multiplicity of pre-coated order in the film of expression the 2nd embodiment and Fe concentration.
Fig. 9 is the figure of the treatment condition of each operation during unloaded (the stopping for a long time) after of expression is handled.
Figure 10 is the figure of the test-results of expression purifying treatment shown in Figure 9.
Figure 11 is the sketch chart of expression existing C VD device.
Figure 12 is the figure that is used to illustrate prior art problems.
Figure 13 is the figure that is used to illustrate prior art problems.
Embodiment
Inventors of the present invention in performance history of the present invention, study the problem points of utilizing the existing film that CVD device shown in Figure 11 carries out.As a result, obtain discovery as described below.
In the film forming of TiN film is handled, the surface of the internal surface of treatment chamber 1 and shower nozzle 15 etc., compare temperature with mounting table 13 lower, so the TiN film is non-cohesive or non-cohesive substantially.But, on shower nozzle 15, with the distance of mounting table 13 more in short-term, the situation of coherent film is also arranged.In the film forming of TiN film is handled, 15～20 minutes the long-time TiCl that flows for example 4Gas or TiCl 4Gas and NH 3The mixed gas of gas.In this case, because TiCl 4The thermolysis of gas is perhaps by TiCl 4Gas and NH 3The reaction of gas and produce hydrogenchloride (HCl).The surface reaction of the metal part of HCl and treatment chamber 1 etc. produces more metal chloride.This metal chloride spreads when the wafer W film forming, converges in the film on the wafer W, becomes the major cause that the metallic pollution amount increases.
Produce metallic compound when pre-coated, for this reason, the problem of compiling foreign metal on wafer W in the film forming film also exists outside the film process of TiN film.For example, PET (five ethoxy-tantalum) and O 2Gas reaction forms Ta 2O 5Under the situation of film, also on the surface of mounting table, form pre-coated.In this case, stable metal chloride and the processing gas reaction in the pre-coated operation become unsettled material in the treatment chamber, spread in treatment chamber.And, consider ClF by in matting, using 3The surface portion of the metal part of gas and treatment chamber 1 etc. reacts, and generates the situation of this metal chloride.
Below, with reference to the embodiments of the present invention of description of drawings based on this discovery formation.And, in the following description,, give identical symbol for composed component with roughly the same function and formation, only carry out repeat specification in the case of necessary.
The 1st embodiment
Fig. 1 is the sketch chart of the CVD device of expression the present invention the 1st embodiment.This device has the vacuum processing chamber cylindraceous 1 that for example is made of aluminium.The bottom surface central authorities of vacuum processing chamber 21 form the recess that constitutes exhaust chest 23.The side of exhaust chest 23 is by vapor pipe 24, is connected with the vacuum exhaust portion 25 that is used for treatment chamber 21 is maintained in vacuum pressure.Sidewall at treatment chamber 21 is provided for the sluice valve 26 that taking out of of wafer W moved into.
In the inside of treatment chamber 21, the discoideus mounting table (pedestal) 32 of supporting its downside by the pillar 31 that extends upward from the bottom surface of exhaust chest 23 is set.Mounting table 32 is by stupalith, and for example aluminium nitride (AlN) constitutes.It is big slightly to form the wafer W that likens to processed substrate above the mounting table 32, and can approximate horizontal ground mounting wafer W.In the outer edge of mounting table 32, be provided with by for example aluminum oxide (Al 2O 3) guide ring 33 that constitutes, it carries out the guiding of wafer W simultaneously from the last surface that covers mounting table 32 towards the side.
In the inside of mounting table 32, bury the well heater 34 that constitutes by for example resistance heater underground.The power feeding section 35 of well heater 34 by for example being provided with outside treatment chamber 21 carried out temperature control corresponding to each purposes.By like this, in the film formation process that can describe in the back heated up equably in the whole surface of wafer W, perhaps in the pre-coated operation, the mounting table surface is warmed up to the temperature of regulation.
On mounting table 32, be configured in the stripper pin 36 (in fact, for example having 3) that carries out the handing-over of wafer W between the carrying arm (not shown) that can enter by sluice valve 26.Stripper pin 36 relative mounting tables 32 are capable of expansion and contraction.The lifting of stripper pin 36 is by the holding components 37 of supporting their bottoms, utilizes the motion of hoisting appliance 38 to carry out.
Top at treatment chamber 21 is provided with shower nozzle 4 by insulating material 41.Shower nozzle 4 forms within it that portion prevents that the gas of two systems from mixing mutually, and the structure of each column mixed type that provides equably to mounting table 32 independently (post mix tape).3 tabular parts that shower nozzle 4 is formed by aluminium or nickel (top 4a, middle part 4b, bottom 4c) overlap formation up and down.The 1st stream 42 that is connected with the 1st gas supply pipe 5a and the 2nd stream 43 that is connected with the 2nd gas supply pipe 5b are by cutting apart formation on each parts 4a, 4b, 4c.Between each parts, the diffusion space of gas is set, be communicated with respectively with the gas squit hole 44,45 that below the 4c of bottom, forms by this space.
Gas supply to the 1st and the 2nd gas supply pipe 5a, 5b is undertaken by the gas supply mechanism 50 that is arranged on each upstream side.On gas supply mechanism 50, purge gas supply source 51, film forming gas supply source the 52, the 1st vector gas supply source 53, ammonia supply source the 54, the 2nd vector gas supply source 55 are set.Purge gas supply source 51 provides purge gas, for example ClF 3Film forming gas supply source 52 provides as the titanium tetrachloride (TiCl that contains the processing gas of the Ti that becomes film forming component 4) gas.The 1st vector gas supply source 53 is provided at TiCl 4The gas that uses as carrier when gas is supplied with, for example, nitrogen (N 2) wait rare gas element.Ammonia supply source 54 provides ammonia (NH 3).The 2nd vector gas supply source 55 provides supplies with NH 3The time vector gas that uses, for example, provide N 2Gas.
In the pipeline of gas supply mechanism 50, valve V1～V10, mass flow controller M1～M5 are set.For not by treatment chamber 21 and to vapor pipe 24 direct deflated by-pass line 5c from the 1st gas supply source 5a branch.By switch valve Va, Vc, gas stream is to treatment chamber 21 or by-pass line 5c.
And, described rearwards such, in pre-coated is handled, NH 3Gas uses as " arc film forms the processing gas of usefulness ", simultaneously, also uses as " being used to remove the processing gas of metal chloride ".In addition, TiCl 4Gas also is equivalent to any in " comprising the processing gas of metallic compound " and " as the processing gas of the compound that comprises metal and halogen ".
Shower nozzle 4 connects RF (high frequency) power supply unit 47 by matching box 46.RF power supply unit 47 offers the film forming gas plasma of wafer W when film forming is handled, promote film formation reaction.The adjusting of the extraction flow of the driving control of hoisting appliance 38, the output control of power feeding section 35, vacuum exhaust portion 25 and the gas of gas supply mechanism 50 are supplied with and are cut off and Flow-rate adjustment etc. constitutes the adjustment of each parts of film deposition systems, control by the control part (not shown) that is made of computer etc.Their control is according to carrying out in the pre-prepd method of control part.
Below, be example with the film forming situation of carrying out titanium nitride (TiN) film on the surface of wafer W, illustrate that with reference to Fig. 2 A～C and Fig. 3 the use said apparatus carries out film forming method.Omitted the diagram of the guide ring 33 among Fig. 2 A～C for convenience.
Before carrying out film forming operation, use TiCl to wafer W 4Gas and NH 3Gas forms the pre-coated operation of TiN film to the surface of mounting table 32.Because this pre-coated operation is to form for example TiN film on the whole surface of mounting table 32, so carry out at the state of wafer W not being moved in the treatment chamber 21.
At first, by vacuum exhaust portion 25 pressure control valve is all opened, to vacuum exhaust in the treatment chamber 21.Provide rare gas element by the 1st and the 2nd vector gas supply source 53,55 flows, for example N with for example 500sccm 2Gas.By well heater 34 mounting table 32 is heated to the temperature of regulation, about for example 600 ℃～700 ℃.In addition, in the pillar 31 of mounting table 32, provide as the N that encapsulates gas with for example flow about 300sccm from gas supply mechanism (not shown) 2Gas.To form malleation in the pillar 31 by encapsulation gas, make to handle gas and do not enter in the pillar 31 of the lead-out wiring that disposes the well heater 34 that is embedded in the mounting table 32, and make that wiring in the pillar 31 and terminal etc. are not corroded.The supply of this encapsulation gas is proceeded in the back.
Fig. 3 is illustrated in the film of the 1st embodiment chronologically, the supply cut-out of gas and the control chart of pressure during employed pre-coated is handled.
If, carry out the temperature-stable in the treatment chamber 21 by above-mentioned operation, begin respectively to supply with TiCl from the 1st gas supply pipe 5a in the supply that moment t1 two handles gas 4Gas and N 2Gas is supplied with NH from the 2nd gas supply pipe 5b 3Gas.When these handle the supply of gas, continue the vacuum exhaust of treatment chamber 21.In order to stablize TiCl 4Gas gas supplied flow at first, since moment t1, for example, carried out 1～60 second, was 10 seconds here, by treatment chamber 21, was not undertaken flowing in advance to the exhaust side mobile by by-pass line 5c.Afterwards, scanning valve Va, Vb, the path direction of switching gas, up to moment t2, with for example 5～90 seconds, the time that is 30 seconds here was with TiCl 4Gas provides in treatment chamber 21.On the other hand, NH 3The supply of gas be from moment t1 to t2, for example 10～120 seconds is 40 second time here, supplies with in treatment chamber 21 continuously.Thereby with TiCl 4Gas and NH 3Gas is supplied with 5～120 seconds, preferably 10～60 seconds simultaneously in this treatment chamber 21.
By above-mentioned such TiCl 4Gas and NH 3The supply of gas shown in Fig. 2 A, forms the pre-coated film (arc film) (the 1st operation: arc film forms operation) of 1TiN on the whole surface of mounting table 32.Here the pressure from moment t1 to moment t2 treatment chamber 21 maintains for example 13.3～133.3Pa (0.1～1.0Torr).The scope of gas flow for example is, TiCl 4Gas is 5～100sccm, preferably about 30～80sccm, and NH 3Gas is 50～1000sccm, preferably about 200～800sccm.Treatment temp is for example about 300～700 ℃, preferably about 400～600 ℃.
In this operation, TiCl 4Gas and NH 3Gas reacts according to above-mentioned formula (1), forms the TiN film on the surface of mounting table 32.On the other hand, the surface temperature of the inwall of treatment chamber 21 and shower nozzle 4 etc. is lower than treatment temp.For this reason, on these parts, the reaction of formula (1) does not take place in fact, two handle gas simultaneously in the vaporized state exhaust, do not pile up the TiN film.Then, stop TiCl at moment t2 4Gas and NH 3The supply of gas is with vacuum exhaust in the treatment chamber 21.At this moment, for example, also can supply with N 2Gas.
Afterwards, shown in Fig. 2 B, stop TiCl 4The supply of gas with the flow of for example 500～2000sccm, was carried out for example 1～60 second, and preferably 5～20 seconds is 30 seconds NH here 3The supply of gas (the 2nd operation: the operation of removing metal chloride).And, in detail, at NH 3In also increase N as vector gas 2Gas.At this moment, proceed the vacuum exhaust of treatment chamber 21.By like this, the pressure in the treatment chamber 21 is formed for example 133.3～666.5Pa (1～5Torr).Then, stop NH 3Supply, to carrying out vacuum exhaust in the treatment chamber 21, remove residual NH in this treatment chamber 21 3Gas.At this moment, for example, also can supply with N 2Gas.At the time point of due in t3, finish one-period in the above.
Afterwards, the cycle of the operation of t1～t3 repeats repeatedly constantly, for example, repeats 10 more than the cycle, preferably repeats 30 more than the cycle.Thus, the stack arc film forms pre-coated.And, for this cycle life, suitably adjust according to the thickness of the film that in one-period, forms.
Like this, in pre-coated is handled, during forming operation, arc film only supplies with NH 3Gas is removed from treatment chamber 21 at arc film and is formed the muriate composition that produces in the operation.Here, it is as described below to remove the mechanism of the chlorine component in the treatment chamber 21.That is, in the reaction of formula (1) from TiCl 4The unreacted reactant of the TiClx (x is any natural number) that decomposes and as the muriate and the reaction of the metal parts in the treatment chamber of secondary resultant, generation metal chloride.This metal chloride passes through NH 3Gas reduction, HCl that in this reduction reaction, produces and NH 3Reaction generates ammonium chloride (NH 4Cl).Because HCl, NH 4Unreacted reactants such as secondary resultant such as Cl and TiClx etc. distil in above-mentioned treatment temp, thus non-cohesive on inner-wall surface of treatment chamber 2 etc., discharged by former state.
By utilizing top operation on the whole surface of mounting table 32, to carry out pre-coated (so-called cycle pre-coated), on mounting table 32, form for example TiN film of 0.7 μ m left and right sides thickness.Afterwards, by well heater 34 with the temperature maintenance of mounting table 32 about 400～700 ℃, to carrying out vacuum exhaust in the treatment chamber 21, simultaneously, the valve 26 that opens the sluices is moved into wafer W in the treatment chamber 21 by carrying arm (not shown).Then, the cooperation by this carrying arm and stripper pin 36 is wafer W mounting (on precoating coating) above mounting table 32, and closed shutter valve 26 forwards to and carries out film forming handle (film formation process) on wafer W.
In film formation process, shown in Fig. 2 C, treatment chamber 21 is carried out vacuum exhaust, provide TiCl to the wafer W that is positioned on the mounting table 32 simultaneously 4Gas and NH 3Gas.At this moment, use about 400～700 ℃ treatment temp, the processing pressure about 100～1000Pa.Continue this processing up to the TiN film that obtains wishing thickness.Specifically, treatment temp is made as 680 ℃, pressure is made as 667Pa, because thickness and film formation time are proportional, so suitably set film formation time corresponding to target film thickness.In addition, this moment is reactive in order to improve corresponding to needs, and the frequency of 450kHz～60MHz, preferred 450kHz～13.56MHz also can be provided from RF power supply 47,200～1000W, preferably the RF electric power of 200～500W will be handled gaseous plasmaization, carry out film forming.Treatment temp in this case is about 300～700 ℃, preferably 400～600 ℃.
After the wafer W surface forms the end of TiN film, stop TiCl 4And NH 3Two kinds of supplies of handling gases for example, are carried out roughly the purification in 10 seconds the treatment chamber 21.Then, with NH 3Gas and as the N of vector gas 2In treatment chamber 21, provide simultaneously, on wafer W, carry out the follow-up nitriding on TiN film surface and handle.Like this, the wafer W of regulation number being repeated identical operation carries out film forming and handles.
After the wafer W of the batch of handling specified quantity, in order to remove the unwanted film forming matter that adheres in the treatment chamber 21, the temperature of mounting table 32 is set at 200 ℃, in this treatment chamber 21, provide ClF 3Gas cleans.By like this, also remove the pre-coated that on the surface of mounting table 32, forms.Afterwards, the wafer W of regulation number is being carried out once more under the situation of film formation process each operation that begins to have described from pre-coated operation once more.
As by present embodiment, the result of Miao Shuing can be clear and definite from behind, and the metal that can suppress parts uses such as treatment chamber 21 and shower nozzle 4 greatly converges in the TiN film that forms on the wafer W.
In existing pre-coated, continuously long-time continuous flow action is for handling the TiCl of gas 4Gas and NH 3Gas.For this reason, by TiCl 4Decomposition and the unreacted reactant of the TiClx that generates and as HCl, the NH of secondary resultant 4The muriate of Cl etc. be present in the treatment chamber 21 and pre-coated in.Metal partial reaction in these muriates and the treatment chamber 21 generates metal chloride, can infer, and the situation in the film on the wafer W of entering is arranged when film formation process.
Relative therewith, in the present embodiment, with TiCl 4Gas and NH 3Gas provides in treatment chamber 21, forms thin pre-coated (arc film) on mounting table 32, then makes NH 3Gas flow becomes HCl or NH with metal chloride 4Cl gas is removed.Two such operations as 1 circulation, are carried out tens circulations their formation is had the pre-coated of wishing thickness.For this reason, suppress the growing amount of the metal chloride in the treatment chamber 21, reduced the amount of metal of sneaking in the wafer W film.
In other words, in the present embodiment, do not carry out the long-time continuous film forming, the film forming of the arc film that constitutes by the operation that repeats by the short period of time and muriatic removing (purify, exhaust) form pre-coated.Therefore, suppress the muriatic generation of each operation, muriate residual in treatment chamber 21 also reduces.
By test, relatively in existing method and the present invention when pre-coated finishes the concentration of the muriatic chlorine of conduct in the treatment chamber 21.The result of this test, in the conventional method, the concentration of chlorine probably is 2～3 atom %, and is higher.In the present embodiment, the concentration of chlorine reduces to general 0.1 atom %.That is, by present embodiment, affirmation can suppress the growing amount of metal chloride.
In pre-coated is handled, NH 3The supply of gas not necessarily will be carried out off and on.In pre-coated is handled, N 2The supply of gas can not continue after the moment of above-mentioned embodiment t1.Fig. 4 imitates Fig. 3 to represent the figure of an example in this case.And flow is identical with above-mentioned embodiment with conditions such as pressure, so omitted explanation here.
At first, at the moment of the temperature-stable in treatment chamber 21 t1, by N 2Gas purifies.To moment t1, carry out TiCl 4Gas and NH 3The supply of gas stops N 2The supply of gas.After moment t1, supply with NH 3Gas stops to supply with N 2Gas is only supplied with TiCl off and on 4Gas.This circulation repeats stated number, for example 30 times.Even in this method, passing through NH to the t3 from moment t2 3Gas is removed the muriate in the treatment chamber or in the film.In addition, owing to repeat the film forming of pre-coated, so can access the effect identical with above-mentioned situation.
In method, enumerated in pre-coated and film forming two-step all to the film forming example of TiN film with reference to above-mentioned Fig. 3 or Fig. 4 explanation.Pre-coated and on wafer W the kind of film forming film can be the Ti film.When the film forming of carrying out the Ti film,, for example use TiCl as handling gas 4Gas and hydrogen (H 2), also increase and use as the argon gas (Ar) of plasma body with gas.Specifically, be 700 ℃ at film-forming temperature, pressure is under the state of 133Pa (1Torr), supplies with above-mentioned three kinds of gases in treatment chamber 21.By applying RF voltage,, promote TiCl with the Ar gaseous plasmaization to shower nozzle 4 4Gas and H 2The reduction reaction of gas.Thus, on the surface of mounting table 32 or wafer W, form the Ti film.This moment gas flow be, for example, TiCl 4Gas is 1～200sccm, H 2Gas is 1～2 liter/minute, and Ar gas is about 1 liter/minute.
Above-mentioned such Ti film also can be used for the pre-coated of mounting table 32 and the film forming of wafer W.For this reason, in the film forming of present embodiment applicable to the pre-coated+TiN film of for example TiN film, in the film forming of the pre-coated+TiN film of Ti film, in the film forming of the pre-coated+Ti film of TiN film, in four kinds of patterns in the film forming of the pre-coated+Ti film of Ti film.When the film forming of TiN film, before to the TiN film film forming of (when comprising pre-coated), also can form Ti film as counterdie.
Under above-mentioned any situation, the reactant gases that uses in order to remove muriate is NH 3, the operation identical with the method for reference Fig. 3 or Fig. 4 explanation repeated a plurality of circulations, can access same effect.The gas that is used to remove metal chloride is not limited to NH 3Gas also can be the gas that can generate ammonium halide.For example can use the gas that comprises nitrogen and hydrogen, for example N 2H 4Deng hydrazine gas.Also can be with N 2And H 2Gas and NH 3The gas appropriate combination provides, with its plasma bodyization.Even under any situation, can both obtain and the identical effect of method with reference to Fig. 3 or Fig. 4 explanation.
In order to confirm the effect of present embodiment, carry out in " background technology " comparison test of method of the embodiment of the existing method of explanation and present embodiment.In this test, treatment temp is 680 ℃, and processing pressure is 40Pa, TiCl 4Gas is the flow about 30～50sccm, NH 3Gas is the flow about 400sccm.In existing method, continue continuous flow in 10 minutes～15 minutes and handle gas, the film forming of carrying out simultaneously on wafer W is handled (as substituting that pre-coated is handled).In the method for present embodiment, as mentioned above, repeat a plurality of cycles, on wafer, carry out film forming and handle (as the replacement of pre-coated processing).Two kinds of methods all are made as target film thickness 0.7 μ m.
Fig. 5 is the figure that the result that the amount (atomicity of per unit area) by the metallic impurity in the TiN film of above-mentioned two kinds of methods formation compares is measured in expression.In Fig. 5, the bar of white is represented existing method, and shaded bar is represented the method for embodiment.As shown in Figure 5, in whole projects of the Al in the embodiment method, Cr, Fe, Ni, Cu, total amount, compare with existing method, the quantitative change of metallic impurity is few.Can understand by this result, if, alleviated metallic pollution according to the film of present embodiment.If the pre-coated by the present embodiment described is handled, also reduced the muriatic amount in the treatment chamber 21, so can infer that between the two has correlationship.
Present embodiment is not limited to Ti, TiN film, can use to comprise the metal that constitutes film forming component and the metal compound gas of halogen, also is applicable to other film that forms by gas reaction.For example, can be applicable to use WF 6Gas (tungsten hexafluoride) and H 2Gas (also exists and uses SiH 4The situation of gas) situation of formation W (tungsten) film.Also can be applicable to and use WF 6Gas and SiH 2Cl 2Gas (dichlorosilane) forms WSi 2The situation of (two tungsten silicides) film.In addition, also can be applicable to use TaBr 3Perhaps TaCl 3Gas and H 2Gas forms the situation of Ta film, perhaps uses TaBr 3Perhaps TaCl 3Gas and NH 3Perhaps NH 3And H 2Gas forms the situation of TaN film.
In addition, present embodiment is not limited to use the metal compound gas that comprises metal and halogen, also is applicable to the situation of using organic metal gas to form pre-coated.For example, using PET (five ethoxy-tantalum: Ta (OC 2H 5) 5) and O 2Gas forms Ta on wafer 2O 5Under the situation of (tantalum oxide) film, use PET and O 2Gas forms pre-coated.In this case, the secondary resultant that comprises the unreacted carbon compound that decomposes from PET or C (carbon) enter the treatment chamber or film (pre-coated film) in, this C surperficial trace in wafer W when handling compiles.Here in pre-coated is handled,, repeat by flow simultaneously PET and O as process shown in Figure 3 2The operation of gas and the O that only flows 2The cycle that the operation of gas constitutes.By like this, can be at the O that only flows 2During the gas, O 2The C reaction that comprises in gas and treatment chamber or described carbon compound and the secondary resultant etc. becomes carbonic acid gas, discharges C.
The 2nd embodiment
Fig. 6 is the sketch chart of the CVD device of expression the present invention the 2nd embodiment.This device constitutes and form Ta on wafer 2O 5Film.Below, illustrate in use as the PET and the O that comprise the unstripped gas of metallic element 2Gas forms pre-coated on mounting table, form Ta afterwards on wafer 2O 5Under the situation of film, reduce method to the metallic pollution of wafer.This method is, in the process that forms pre-coated, with PET and O 2Gas provides in treatment chamber simultaneously, then by rare gas element, for example N 2(nitrogen) purifying treatment chamber interior is at last with the series of processes of vacuum exhaust in the treatment chamber, with its multiple method.
In film deposition system shown in Figure 6, because PET is liquid at normal temperatures,, vaporize by vaporizer 62 so flow out with liquid form from the supply source 61 of PET, be provided in the treatment chamber 21.O 2Gas is provided by supply source 63.In order to shunt vacuum processing chamber 21, the by-pass line 5c that the downstream side is connected with vapor pipe 24 is set.By switch valve Vb and Vc, from effusive PET gas of the 2nd gas supply pipe 5b and N 2The state and walk around treatment chamber 21 deflated states between of gas in offering treatment chamber 21 switches.
Because Ta 2O 5Film is that the pyrolysis by PET generates, so be not arranged on matching box 46 and the RF power supply unit 47 that employed plasma generation is used among Fig. 1.About other parts, the symbolic representation same section identical with Fig. 1 is because to the explanation of the each several part explanation repetition with the structure of Fig. 1, so omitted explanation.
In order to heat processed substrate, can adopt known electron tube to add thermotectonics, replace the resistance heating well heater that on mounting table, is provided with.In this case, the heating source heating mounting table that constitutes by the electron tube that below mounting table, sets.In addition, under the situation that adopts the electron tube type of heating, as the material of mounting table, the SiC about thickness 7mm (carborundum) for example preferably.
The following describes the film of the 2nd embodiment.The explanatory view of the gas flow when Fig. 7 is a pre-coated operation in the film of expression in the 2nd embodiment etc.In Fig. 7, " 5a: " meaning is to flow through gas by the 1st gas supply pipe 5a." 5b: " meaning is to flow through gas by the 2nd gas supply pipe 5b." 5c: " meaning is to flow through gas by by-pass line 5c.And, among operation S1 below～S5, continue the vacuum exhaust of treatment chamber 21.
At first, in operation S1, the temperature of mounting table is heated to 445 ℃, to treatment chamber 21, supplies with N from the 1st gas supply pipe 5a 2Gas carries out the pre-coated operation.Then at operation S2, with described N 2The flow of gas reduces to 600sccm from 1000sccm, supplies with O with the flow of 400sccm in treatment chamber 21 simultaneously 2Gas.On the other hand, in operation S1 and S2, send PET gas and N in advance from the 2nd supply-pipe 5b 2Gas is not by treatment chamber 21, by by-pass line 5c exhaust.
In this case, the PET of operation S1 to supply gas with traffic management in advance be that the under meter tolerance of 90mg ± 15 (10～15) mg is carried out.On the other hand, the PET of operation S2 to supply gas with traffic management in advance be that the under meter tolerance of 90mg ± 5 (3～10) mg is carried out.Therefore, can more stably in treatment chamber, supply with PET.Supplying gas in advance of the PET of operation S2 can be for example more than 20 seconds, preferably on 30 seconds 1 specified time.
Afterwards, stop N at operation S3 (forming the operation of arc film) from the 1st gas supply pipe 5a 2The supply of gas will be flow through the PET gas and the N that supply gas in advance of the 2nd gas supply pipe 5b simultaneously 2Gas provides in treatment chamber 21.By before film forming, sending on gas like this, can begin from the zero hour of operation S3 to supply with processing gas with stable flow rate.In addition,, the gas flow in the treatment chamber 21 is made as necessarily (for example full flow is 1000sccm), can suppresses the temperature of the mounting table 32 that the variation by pressure in the treatment chamber 21 causes, the change of chip temperature by from operation S1～S3.
Here, by changing the time of operation S3 as follows, can adjust the arc film (Ta of accumulation 2O 5Film) thickness.In the present embodiment, if be 58 seconds, 71 seconds, 141 seconds, 281 seconds with the time set of operation S3, then the thickness of each arc film is roughly 5.2nm, 6.5nm, 13nm, 26nm.
And in operation S1～S3, the pressure in the treatment chamber 21 can be at 13.3～1333Pa roughly, preferred change setting in the scope at 39.9～667Pa roughly.In addition, treatment temp can be at roughly 300～800 ℃, preferred change setting in 350～500 ℃ scope roughly.
Stop PET gas and O at operation S4 afterwards 2N is only supplied with in the supply of gas 2Gas purifies.In addition, stop N at operation S5 2The supply of gas stops all gas, with vacuum exhaust in the treatment chamber.And in treatment chamber 21, import N by at least one supply-pipe among the 1st and the 2nd supply-pipe 5a, the 5b at operation S4 2Gas comes purifying exhaust gas.By carrying out above operation S1～S5, finish 1 pre-coated sequence to mounting table 32.Only repeat later the cycle of the operation S1～S5 or the operation S2～S5 of necessary number of times.By like this, the lamination arc film forms pre-coated.And, suitably adjust this cycle life according to the thickness of 1 formed film of cycle.
By top processing, utilize by Ta 2O 5The pre-coated that film constitutes covers mounting table 32.Afterwards, keep the temperature of mounting table 32 by well heater 34, one carries out vacuum exhaust in the face of in the treatment chamber 21, and simultaneously, the valve 26 that opens the sluices utilizes carrying arm (not shown) that wafer W is moved in the treatment chamber 21.Below, the work compound by this carrying arm and stripper pin 36 is wafer W mounting (pre-coated above) above mounting table 32, closed shutter valve 26, and the film forming of rotating on wafer W is handled (film formation process).
In film formation process, one in the face of treatment chamber 21 carries out vacuum exhaust, and one faces the wafer W that is positioned on the mounting table 32 provides PET and O 2Gas.By like this, on wafer W, form the Ta that wishes thickness 2O 5Film.At this moment, as treatment condition, can use the identical condition of the operation handled with above-mentioned pre-coated 3.
As according to embodiment, after carrying out the pre-coated operation, wafer is carried out film forming and handles, just have and can be reduced in the metallic pollution concentration in the film forming film on the wafer.By test, use the mounting table of pre-coated in the pre-coated cycle (sequence) of the Fig. 7 carry out stipulated number, on wafer, form Ta 2O 5Film is measured metallic pollution concentration in this film.
Fig. 8 is the graphic representation of this test-results of expression.In Fig. 8, transverse axis is represented the multiplicity of pre-coated cycle (sequence), and the longitudinal axis is represented Ta 2O 5The iron atom quantity of per unit area in the film.The target film thickness of " * " expression pre-coated is 90nm, the result the when multiplicity of pre-coated sequence is 4 times and 7 times.The target film thickness of " △ " expression pre-coated is about 210nm, the result the when multiplicity of pre-coated sequence is 8 times, 16 times and 32 times.The target film thickness of " zero " expression pre-coated is about 170nm, the result the when multiplicity of pre-coated sequence is 26 times and 32 times.
For example, about " △ " represented data, repeating under the situation of 8 described sequences, is 26nm (210nm/8) roughly by 1 film forming pre-coated thickness of sequence.Repeating under the situation of 16 described sequences, is 13nm (210nm/16) roughly by 1 film forming pre-coated thickness of sequence.Repeating under the situation of 32 described sequences, is 6.5nm (210nm/32) roughly by 1 film forming pre-coated thickness of sequence.
Result by Fig. 8 can understand, the concentration (impurity level) that enters into the iron of film is owing to the increased frequency of pre-coated sequence reduces, and with the number of times of pre-coated sequence very big correlationship arranged.The concentration of in Fig. 8, having represented iron, but same result also obtained for aluminium and copper.
It is strict that the design rule of semiconductor element (live width of pattern) becomes year-by-year, and the metallic pollution of thereupon allowing (metallic impurity) amount also must reduce.The benchmark of present metallic pollution amount is 1.0E+11 (atoms/cm 2) degree, the number of times that judge to repeat the pre-coated sequence thus preferably more than 13 times, is more preferably more than 15 times.But the benchmark of this metallic pollution amount can change according to user's requirement, as shown in Figure 8, under the number of times that repeats the pre-coated sequence is situation more than 4 times, can confirm effect significantly.
Be precoated on the above-mentioned variation of avoiding thermal emissivity rate like that, guarantee to have thickness to a certain degree on the inhomogeneity basis of the thickness of (interplanar) between wafer.For Ta 2O 5Film, its thickness is about 90nm.Therefore, for the shortest time finishes pre-coated and handles, the thickness of the arc film that forms in each pre-coated sequence is set to, with 90nm divided by multiplicity.For example, if multiplicity is 4 times, the thickness of arc film roughly is 22.5nm.In addition, if multiplicity is 15 times, the thickness of arc film is 6nm roughly.But, can set arbitrarily at the thickness of the formed arc film of each pre-coated sequence.
Reason by the metallic impurity amount in the film that repeatedly repeats described pre-coated sequence reduction wafer can followingly be considered.That is Ta, 2O 5Film is by the thermolysis film forming of PET.The O of Dao Ruing simultaneously 2Gas is assist gas, about Ta 2O 5Membranous, the speed of response of film etc. does not appear at and generates Ta 2O 5In the chemical equation of film.The following expression of this chemical equation.PET is (11) thermolysis at first by formula.
Ta(OC 2H 5) 5→Ta 2O 5+5C 2H 4+5C 2H 5OH …(11)
As carry out further thermolysis, then above-mentioned C 2H 5OH by formula (12) decomposes like that.
5C 2H 5OH→5C 2H 4+5H 2O …(12)
Below, if having metal chloride in the treatment chamber 21, FeCl for example 3, just react like that according to formula (13) with the ethanol of representing as the intermediate product in the above-mentioned formula, generate ethoxylate.
FeCl 3+3C 2H 5OH→Fe(OC 2H 5) 3+3HCl …(13)
This ethoxylate is by the discharge of vaporizing easily of the treatment temp in the treatment chamber 21.For this reason, during carrying out pre-coated, the metal chloride that becomes the reason of metallic impurity when follow-up wafer film forming can reduce.At Ta 2O 5Different being during with the pre-coated of TiN film do not generate metal chloride during the pre-coated of film in pre-coated is handled.On the other hand, in the treatment chamber termly by comprising the purge gas of halogen, for example ClF 3Gas cleans.Can infer thus, described metal chloride generates when cleaning.
Though metal ethoxylate oxidation exhaust generates during pre-coated, waft in treatment chamber 21, inevitably on the inwall attached to treatment chamber.Here as shown in Figure 7 in pre-coated sequence, the then above-mentioned reaction of operation S3 is with unreacted reactant with comprise the N of the secondary resultant of ethoxylate by operation S4 2Purify and discharge.In addition, wish in operation S5 N 2Purify the delay part and also draw away, can further reduce the metallic impurity amount.And, in operation S1～S4, owing to carry out the vacuum exhaust of treatment chamber 21 continuously, so also can not carry out operation S5.In addition, mobile gas also can be to be not limited to N in operation S3 2Gas, other rare gas element, for example Ar also can.
After handling wafer continuously, handling beginning up to next batch, is time idle situation.Should time idle situation be called zero load, and begin to handle after zero load again, it is many that the amount of impurities in the wafer film becomes.As this reason, consider from exhaust system the situation of in treatment chamber 21 counter-diffusion ethanol etc.That is, the throttling valve of pressure adjustment usefulness is set in proper order, collects unreacted reactant, the collector (trap) of secondary resultant, vacuum pump from the upstream side of the vapor pipe 24 of the exhaust system of treatment chamber 21.In the unloaded process, pass through rare gas element, for example N in the treatment chamber 21 2Gas purifies, but the counter-diffusions in treatment chamber 21 such as ethanol in the secondary resultant of collecting in the collector can generate the ethoxylate that described formula (13) is represented.
When after zero load, carrying out program once more here, if the cycle pre-coated of having described, the metallic impurity amount in the time of just can reducing this process in the film forming wafer film.In addition in this case, according to timetable shown in Figure 9, it also is resultful repeating purification and vacuum exhaust." 5a: ", " 5b: ", " 5c: " and the identical implication that has illustrated in fig. 7 in Fig. 9.And, continue the vacuum exhaust of treatment chamber 21 among operation S11 below～S15.
Operation S11 is the Ta that before entering zero load wafer is carried out 2O 5The film formation process of film.Operation S12 represent in the unloaded process time band (to should state flow moving be for example 3600 seconds).Below, enter the preparation that the batch processing for subsequently of operation S13 begins, here, with O 2Gas and N 2Gas provides in treatment chamber 21, carries out the 1st and purifies.The then N that will lack than operation S13 at operation S14 2Gas provides in treatment chamber 21, carries out the 2nd and purifies.Carry out vacuum exhaust at operation S15 afterwards.Repeat this operation S13～operation S15 as needs, the cycle of promptly carrying out stipulated number purifies, and carries out the Ta of next batch wafer afterwards 2O 5The film forming of film is handled.
And in operation S12 and operation S14, in treatment chamber 21, import N by at least one supply-pipe among the 1st and the 2nd supply-pipe 5a, the 5b 2Gas carries out purifying exhaust gas.In addition in operation S13, except PET gas, to adjust environment in the treatment chamber 21 with the identical condition when the wafer film forming is handled of operation S11.Then also carry out the artificial atmosphere (environment adjustment) of the environment in the treatment chamber 21 when the film forming of criticizing wafer is down handled.Cycle shown in Figure 9 purifies number of times, and is so ineffective in the time of time, needs at least three times.
Carry out in order to confirm the test of cycle purification effects shown in Figure 9.As the benchmark example, before unloaded, wafer is carried out Ta 2O 5The film forming of film is handled, Al, Fe after promptly operation S11 finishes in the adjustment wafer film and the concentration of Cu.As a comparative example, behind long-term no cargo conditions, carry out same processing, similarly adjust the described concentration of metal in the film of wafer in the finish time of operation S12.As embodiment, after zero load, repeat the operation (cycle purification) (5 minutes time) of 5 operation S13 shown in Figure 9～operation S15, carry out same processing afterwards, similarly regulate the described concentration of metal in the wafer film.
Figure 10 is the data of this test-results of expression.According to this result, the metallic impurity amount of embodiment is even any among Al, Fe and the Cu all returns to unloaded preceding data substantially.As this reason, except the generation of described ethoxylate, infer the reason as other described below.That is, the pressure of the pressure in the treatment chamber 21 among the operation S13 of Fig. 9 and operation S12 before and after it and operation S13 is different greatly.By the exhaust of carrying out simultaneously with the rapid variation of this pressure, peel off and exhaust as the parts in treatment chamber 21 such as metal chloride on the basis of metallic pollution.For this reason, in the film forming of carrying out was thereafter handled, the amount of the foreign metal that compiles in film reduced.
And, in the 2nd embodiment, in the above description, illustration use the method that forms tantalum-oxide film as the 1st PET that handles gas (the 2nd handle gas be oxygen).But the 2nd embodiment also can be applicable in the film of use as the alcoxides of other organometallic sources gas, for example, is applicable to and uses Ta (OC 2H 5) 5, Si (OC 2H 5) 4As the 1st processing gas, form each Ta 2O 5Film, TEOS-SiO 2In the method for film.In these methods, can use and contain O 2, O 3, H 2The gas that contains aerobic of O etc. is handled gas as the 2nd.
As above explanation by the 1st and the 2nd embodiment, can reduce in the treatment chamber total amount at the impurity that carries out being contained in after pre-coated is handled for example metal in the film that forms etc. on processed substrate.
That is, by the 1st and the 2nd embodiment, in the 1st operation that pre-coated is handled, unreacted matters and be present in the treatment chamber or enter secondary resultant in the film etc. and in the 2nd operation, be discharged from the material that from handle gas, decomposes from treatment chamber.For this reason, improved after film formation process in the purity that constitutes of the film that on processed substrate, forms.
For example, the 2nd embodiment is applicable to and uses PET and O 2Gas is as handling the situation that gas forms tantalum-oxide film.In this case,, carry out the 2nd operation that pre-coated is handled, can remove the carbon in pre-coated and the treatment chamber by using oxygen as reactant gases according to embodiment.In addition, in the treatment chamber that is in no cargo conditions for a long time, form under the situation of tantalum-oxide film,, supply with rare gas element, can remove the metallic compound in the treatment chamber by the 2nd operation of utilizing pre-coated to handle according to embodiment.
On the other hand, according to the 1st embodiment, in the 1st operation that pre-coated is handled, unreacted halogenide that generation is decomposed from handle gas and conduct enter the halogenide of the secondary resultant in the film.These halogenide are in the 2nd operation, by for example NH 3Gas reduction, the halogenide that will decompose in this reduction reaction is discharged from treatment chamber with gaseous phase.For this reason, after film formation process in the film that on processed substrate, forms alleviated metallic pollution.
For example, carrying out under the film forming situation of TiN film, can use as the NH that handles gas 3And TiCl 4In this case, the TiClx that produces in the 1st operation and HCl etc. can be removed from treatment chamber in the 2nd operation.The result has reduced the mixed volume to the metal chloride of the TiN film that obtains in film formation process.

Claims (14)

1. the film that semiconductor processes is used is used at the processed substrate of mounting on the mounting table of gastight treatment chamber, forms the film that comprises metallic element, it is characterized in that, comprising:
(a) before moving into described processed substrate in the described treatment chamber, utilize pre-coated to cover the pre-coated operation of described mounting table;
(b) after described pre-coated operation, described processed substrate is moved in the described treatment chamber, on described processed substrate, form the film formation process of main film,
Described pre-coated operation comprises:
The 1st operation, in the described mounting table of heating on one side with described treatment chamber in exhaust, the 1st processing gas that will contain the gas that comprises described metallic element on one side at least is supplied in the described treatment chamber, forms the arc film that comprises described metallic element on described mounting table;
The 2nd operation, stop to supply with the gas that comprises described metallic element at least, on the other hand, in the described mounting table of heating on one side with described treatment chamber in exhaust, at least a gas or the rare gas element that will comprise on one side in nitrogen-atoms, hydrogen atom and the Sauerstoffatom supply in the described treatment chamber as the 2nd processing gas, by exhaust, will in described the 1st operation, from described treatment chamber, remove by by-product biology that produce, except the composition that forms described arc film; And
By repeatedly repeating the described the 1st and the 2nd operation, stacked multilayer arc film forms the operation of described pre-coated,
Described film formation process comprises:
Described processed substrate is moved in the described treatment chamber operation of mounting on the described mounting table;
In the described mounting table of heating on one side with described treatment chamber in exhaust, on one side will the described the 1st handle gas and be supplied in the described treatment chamber, formation comprises the operation of the described main film of described metallic element on described processed substrate.
2. method according to claim 1 is characterized in that, described the 1st processing gas is to contain the gas that comprises described metallic element, and is at least a gas that comprises in nitrogen-atoms, hydrogen atom and the Sauerstoffatom.
3. method according to claim 1 and 2 is characterized in that, under each treatment temp and processing pressure of the described the 1st and the 2nd operation, and described secondary resultant distillation.
4. method according to claim 1 and 2 is characterized in that, describedly comprises that the gas of metallic element is the compound of described metallic element and halogen, and the described the 2nd handles gas comprises nitrogen-atoms and hydrogen atom.
5. method according to claim 4 is characterized in that, describedly comprises that the gas of metallic element is titanium tetrachloride, and described main film is made of titanium nitride in fact.
6. method according to claim 4 is characterized in that, describedly comprises that the gas of metallic element is titanium tetrachloride and hydrogen, and described main film is made of titanium film in fact.
7. method according to claim 1 and 2, it is characterized in that, in described the 2nd operation, stop the described at least supply that comprises the gas of metallic element, on the other hand, handle gas with the described the 2nd and supply with in described treatment chamber, the secondary resultant that will be generated with described the 2nd processing gas reaction by the decomposition of the described gas that comprises metallic element or intermediate that reaction generates utilizes exhaust to remove.
8. method according to claim 1 and 2 is characterized in that, the described gas of metallic element that comprises comprises the alkoxide of described metallic element, and described the 2nd processing gas is to comprise the gas of Sauerstoffatom or be rare gas element.
9. method according to claim 8 is characterized in that, describedly comprises that the gas of metallic element is five ethoxy-tantalum, and described main film is made of tantalum-oxide film in fact.
10. method according to claim 7 is characterized in that, between described the 2nd operation and described film formation process, stops the described the 2nd and handles gas, on the other hand, also has during the deflated purification in the described treatment chamber.
11. method according to claim 10 is characterized in that, described the 2nd operation is being supplied with rare gas element during the described purification in described treatment chamber.
12. method according to claim 8, it is characterized in that, described the 1st processing gas is to generate alcoholic acid gas by thermolysis, and ethanol and the reaction of the metal halide in the described treatment chamber by being generated by the described the 1st decomposition of handling gas generate described secondary resultant.
13. method according to claim 1 is characterized in that, between batch processing, has:
On one side to exhaust in the described treatment chamber, to described treatment chamber in supply with the unloaded operation of rare gas element on one side; With right
On one side to exhaust in the described treatment chamber, to described treatment chamber in supply with 2nd 1st cleaning section of handling gas on one side;
On one side to exhaust in the described treatment chamber, to described treatment chamber in supply with operation 2nd cleaning section triplicate of rare gas element more than on one side.
14. method according to claim 12 is characterized in that, before described pre-coated operation, also has and supply with the purge gas that comprises halogen in described treatment chamber, cleans the matting of described inner treatment chamber.
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