CN102446728A - Method of modifying insulating film - Google Patents
Method of modifying insulating film Download PDFInfo
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- CN102446728A CN102446728A CN2011103036957A CN201110303695A CN102446728A CN 102446728 A CN102446728 A CN 102446728A CN 2011103036957 A CN2011103036957 A CN 2011103036957A CN 201110303695 A CN201110303695 A CN 201110303695A CN 102446728 A CN102446728 A CN 102446728A
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- oxidized silicon
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- 238000000034 method Methods 0.000 title claims abstract description 214
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 243
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 150
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 150
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 124
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 90
- 230000003647 oxidation Effects 0.000 claims abstract description 88
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims description 167
- 238000012545 processing Methods 0.000 claims description 124
- 239000007789 gas Substances 0.000 claims description 119
- 238000000137 annealing Methods 0.000 claims description 96
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- 229910052760 oxygen Inorganic materials 0.000 claims description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 32
- 239000001301 oxygen Substances 0.000 claims description 32
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 15
- 230000005855 radiation Effects 0.000 description 15
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- 239000010703 silicon Substances 0.000 description 15
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- 238000002834 transmittance Methods 0.000 description 13
- 229910052721 tungsten Inorganic materials 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
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- 239000010937 tungsten Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000010453 quartz Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 9
- 229910007991 Si-N Inorganic materials 0.000 description 8
- 229910006294 Si—N Inorganic materials 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
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- 238000010792 warming Methods 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
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- 239000004411 aluminium Substances 0.000 description 3
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- 230000015572 biosynthetic process Effects 0.000 description 3
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- 239000000377 silicon dioxide Substances 0.000 description 3
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
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- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229920006361 Polyflon Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
- H01L21/02321—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment introduction of substances into an already existing insulating layer
- H01L21/02329—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment introduction of substances into an already existing insulating layer introduction of nitrogen
- H01L21/02332—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment introduction of substances into an already existing insulating layer introduction of nitrogen into an oxide layer, e.g. changing SiO to SiON
-
- 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
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
- H01L21/02337—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a gas or vapour
- H01L21/0234—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a gas or vapour treatment by exposure to a plasma
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
- H01L21/28158—Making the insulator
- H01L21/28167—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation
- H01L21/28202—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation in a nitrogen-containing ambient, e.g. nitride deposition, growth, oxynitridation, NH3 nitridation, N2O oxidation, thermal nitridation, RTN, plasma nitridation, RPN
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
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- Microelectronics & Electronic Packaging (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Plasma & Fusion (AREA)
- Formation Of Insulating Films (AREA)
- Insulated Gate Type Field-Effect Transistor (AREA)
Abstract
The invention aims to restrain nitrogen concentration reduction in a film caused by N dropping of an oxidized silicon nitride film formed through plasma nitridation treatment and minimize nitrogen concentration fluctuation in treated members and treated groups. In a method for modifying an insulating film, the following steps are performed: a nitridation treatment step of performing plasma nitridation treatment on a silicon oxide film which is exposed from the surface of the treated member for forming the oxidized silicon nitride film; and a modifying step of performing oxidation treatment on the surface of the oxidized silicon nitride film, wherein vacuum atmosphere is kept at the time period after the nitridation treatment step and before the modifying step. Additionally, when the nitrogen concentration of the oxidized silicon nitride film on which the nitridation treatment is just finished is set to NC0, and a target value of the nitrogen concentration of the oxidized silicon nitride film after the modifying step is set to NCT, plasma nitridation treatment is performed for causing NC0>NCT.
Description
Technical field
The method of modifying of the dielectric film that for example the present invention relates in the manufacturing of the device of MOS structure, to utilize.
Background technology
Be in the semiconductor device of representative with MOSFET,, using oxidized silicon nitride (SiON) film as gate insulating film in order to prevent the penetration phenomenon of so-called boron.In addition, follow the miniaturization of semiconductor device in recent years, the requirement of high performance, the filmization of gate insulating film is gradually near the limit.With silica (SiO
2) during the film film, the leakage current that is caused by direct Tunneling is the exponential function formula to be increased, consumes electric power increases.Therefore, from the purpose that reduces leakage current, also can use the oxidized silicon nitride film as gate insulating film.
The oxidized silicon nitride film can be through to for example by the formed SiO of method of thermal oxidation etc.
2The plasma of membrane interaction nitrogen and forming.And through the formed oxidized silicon nitride film of plasma nitridation process, in order to prevent membranous deterioration, (patent documentation 1～3) handled in the modification that has also proposed to carry out thermal annealing etc. for like this.
The prior art document
Patent documentation
Patent documentation 2 TOHKEMY 2006-156995
Patent documentation 3 International Publication WO2008/081724
Summary of the invention
Invent problem to be solved
To SiO
2Film carry out the formed oxidized silicon nitride film of plasma nitridation process along with nitrogen treatment after the passage of time, nitrogen-atoms discharges (so-called " N obscission ") to the outside from film.If the N obscission takes place; Even carry out plasma nitridation process at the same terms; According to the difference of stand-by period of the next operation of distance, the result who be formed between semiconductor wafer, fluctuation takes place the nitrogen concentration between group in the oxidized silicon nitride film, the quality management difficulty of final products.For example, when utilizing the oxidized silicon nitride film,, cause the worry that reliability reduces or rate of finished products reduces of device because then there is the effect change that penetrates or suppress leakage current of boron in the fluctuation of nitrogen concentration as transistorized gate insulating films such as MOSFET.
Therefore; The object of the present invention is to provide a kind of oxidized silicon nitride film; In this film; Suppressed the come off reduction of nitrogen concentration the film that causes, the fluctuation of the nitrogen concentration between handled object, between group has been dropped to Min., the nitrogen concentration in the film is stable to a certain degree from N through the formed oxidized silicon nitride film of plasma nitridation process.
Be used to solve the method for problem
The method of modifying of dielectric film of the present invention comprises that the silicon oxide film to exposing on the surface of handled object carries out plasma nitridation process, forms the nitrogen treatment operation of oxidized silicon nitride film; With the modified process that the surface of above-mentioned oxidized silicon nitride film is carried out oxidation processes, above-mentioned nitrogen treatment operation is still kept vacuum atmosphere after finishing, and then begins above-mentioned modified process.
In the method for modifying of dielectric film of the present invention, preferably nitrogen concentration is made as N in the film of the oxidized silicon nitride film after the nitrogen treatment operation has just been finished
C0, the desired value of nitrogen concentration in the film of the oxidized silicon nitride film behind the modified process is made as N
CTThe time, carry out above-mentioned plasma nitridation process and make N
C0＞N
CT
In the method for modifying of dielectric film of the present invention; Preferred above-mentioned modified process comprises the plasma oxidation processing that utilizes plasma processing apparatus, and this gas ions processing unit imports microwave through the flat plane antenna with a plurality of holes and produces the plasma of handling gas in container handling.At this moment, preferably in the same container handling of above-mentioned plasma treatment appts, a handled object is carried out above-mentioned plasma nitridation process and the processing of above-mentioned plasma oxidation continuously.At this moment, preferably after above-mentioned plasma nitridation process, before above-mentioned plasma oxidation handles, remove nitrogen residual in above-mentioned container handling through vacuumizing or clean to handle.In addition, preferably also be included in after above-mentioned plasma oxidation handles,, in oxidizing atmosphere, handled object carried out the operation of annealing in process with the temperature in the scope more than 800 ℃, below 1100 ℃ as the part of above-mentioned modified process.
In addition, in the method for modifying of dielectric film of the present invention, in the scope of processing pressure more than 67Pa, below the 1333Pa that preferred above-mentioned plasma oxidation is handled.
In addition, in the method for modifying of dielectric film of the present invention, preferred above-mentioned plasma oxidation is handled and in the scope more than 0.1%, below 20%, is carried out with respect to the volume flow ratio of whole processing gases at oxygen.
In addition, in the method for modifying of dielectric film of the present invention, the treatment temperature that preferred above-mentioned plasma oxidation is handled is in the scope more than 200 ℃, below 600 ℃.
In addition, in the method for modifying of dielectric film of the present invention, the processing time that preferred above-mentioned plasma oxidation is handled is in the scope more than 1 second, below 90 seconds.
In addition; In the method for modifying of dielectric film of the present invention; Preferably utilize plasma treatment appts to carry out above-mentioned nitrogen treatment operation; This plasma processing unit imports microwave through the flat plane antenna with a plurality of holes and produces the plasma of handling gas in container handling, utilize annealing device to carry out above-mentioned modified process, and this annealing device is through carrying out annealing in process with the temperature in the scope more than 800 ℃, below 1100 ℃ to handled object in oxidizing atmosphere.At this moment, the processing time of preferred above-mentioned annealing in process is in the scope below 50 seconds more than 10 seconds.In addition, preferably carry out from of the handover of above-mentioned plasma processing apparatus to the handled object of above-mentioned annealing device at vacuum state.
In addition, in the method for modifying of dielectric film of the present invention, the gate insulating film that preferred above-mentioned oxidized silicon nitride film is the MOS structure devices.
The effect of invention
According to the present invention, through after plasma nitridation process, maintaining vacuum atmosphere, then begin modified process, can improve the membranous of oxidized silicon nitride film, suppress the minimizing (N comes off) of the nitrogen concentration by the time of oxidized silicon nitride film.Therefore; Through for example in the modification of the gate insulating film of the MOS structure devices of MOSFET etc., utilizing the method for modifying of dielectric film of the present invention; Can effectively suppress the increase of leakage current or penetrating of boron; And the fluctuation of nitrogen concentration of the gate insulating film between the inhibition wafer, between group improves the reliability and the rate of finished products of semiconductor device.
Description of drawings
Fig. 1 is the summary section of an example of the expression plasma processing apparatus that can in the 1st execution mode of the present invention, use.
Fig. 2 is the figure of the structure of expression flat plane antenna.
Fig. 3 is the key diagram of the structure example of expression control part.
Fig. 4 is the flow chart of summary of step of the method for modifying of the relevant dielectric film of expression the 1st execution mode of the present invention.
Fig. 5 is the key diagram of the 1st execution mode ionic medium body nitrogen treatment operation.
Fig. 6 is the key diagram of the 1st execution mode ionic medium body oxidation processes operation.
Fig. 7 is the key diagram of the oxidized silicon nitride film after modification is handled in the 1st execution mode.
Fig. 8 is the summary section of an example of the expression annealing in process device that can in the 2nd execution mode of the present invention, use.
Fig. 9 is the vertical view of the schematic configuration of the expression base plate processing system that can in the 2nd execution mode of the present invention, use.
Figure 10 is the flow chart of summary of step of the method for modifying of the relevant dielectric film of expression the 2nd execution mode of the present invention.
Figure 11 is the key diagram of the 2nd execution mode ionic medium body nitrogen treatment operation.
Figure 12 is the key diagram of oxidizing annealing operation in the 2nd execution mode.
Figure 13 is the key diagram of the oxidized silicon nitride film after modification is handled in the 2nd execution mode.
Figure 14 is the flow chart of summary of step of the method for modifying of the relevant dielectric film of expression the 3rd execution mode of the present invention.
Figure 15 is the key diagram of the 3rd execution mode ionic medium body nitrogen treatment operation.
Figure 16 is the key diagram of the 3rd execution mode ionic medium body oxidation processes operation.
Figure 17 is the key diagram of oxidizing annealing operation in the 3rd execution mode.
Figure 18 is the key diagram of the oxidized silicon nitride film after modification is handled in the 3rd execution mode.
Figure 19 is nitrogen concentration and the figure of the relation in elapsed time in the SiON film behind the expression Test Example 1 ionic medium body nitrogen treatment.
Figure 20 is through the figure of the relation of the slip of the nitrogen concentration in the SiON film after 1 hour and nitrogen concentration after expression Test Example 1 ionic medium body nitrogen treatment operation finishes.
Figure 21 representes respectively after the plasma nitridation process through the N concentration of the SiON film after 16 hours with through the figure of the difference (longitudinal axis) of the N concentration of the SiON film after 1 hour according to treatment conditions.
Figure 22 is the figure of the collection of illustrative plates of the XPS analysis of the nitrogen-atoms in the SiON film and oxygen atom before and after the expression plasma oxidation is handled.
Figure 23 is the nitrogen concentration of the SiON film after expression has just finished with respect to plasma nitridation process, through the slip (longitudinal axis) of the nitrogen concentration after 100 hours and the figure of the relation of the condition of annealing in process.
Embodiment
[the 1st execution mode]
Below, with reference to accompanying drawing, specify execution mode of the present invention.The method of modifying of the dielectric film of this execution mode comprises silicon oxide film is carried out plasma nitridation process, forms the operation of oxidized silicon nitride film and this oxidized silicon nitride film is carried out the modified process that plasma oxidation is handled.
Fig. 1 is the profile that schematically shows the schematic configuration of the plasma processing apparatus 100 that in the method for modifying of the relevant dielectric film of the 1st execution mode of the present invention, uses.Fig. 2 is the vertical view of flat plane antenna of the plasma processing apparatus 100 of presentation graphs 1.Fig. 3 is the figure of structure example of control part of the plasma processing apparatus 100 of expression control chart 1.
The flat plane antenna in the hole of plasma processing apparatus 100 through having a plurality of slit-shaped is especially through RLSA (Radial Line Slot Antenna; Radial line slot antenna), in container handling, imports microwave, as the RLSA microwave plasma processing apparatus of the microwave excited plasma that can produce high density and low electron temperature and constitute.In plasma processing apparatus 100, can utilize to have 1 * 10
10～5 * 10
12/ cm
3Plasma density and the plasma with low electron temperature of 0.7～2eV handle.Therefore, plasma processing apparatus 100 can be used in the purpose of plasma nitridation process, plasma oxidation processing suitably in the manufacture process of various semiconductor devices.
In the plasma processing apparatus 100; As primary structure; Comprise: the container handling 1 that air-tightness constitutes; The gas supply device 18 of supply gas in container handling 1 possesses and is used for carrying out the exhaust apparatus of the vacuum pump 24 that decompression exhaust handles in the container 1, be arranged at the top of container handling 1, to container handling 1 in the importing microwave microwave introduction device 27 and control the control part 50 of each structural portion of these plasma processing apparatus 100.
In the inside of container handling 1, the level that is provided for supports the carrying of W of semiconductor wafer (below, only be called " wafer ") of handled object to put platform 2.Carry put platform 2 by the high material of heat conductivity for example pottery such as AlN constitute.Putting platform 2 this year is supported by the holding components cylindraceous 3 that the bottom central from exhaust chamber 11 extends to the top.Holding components 3 for example is made up of potteries such as AlN.
In addition, put platform 2 and be provided for covering this its outer edge, the cover ring 4 of guiding wafer W carrying.This cover ring 4 is by for example quartz, AlN, Al
2O
3, the endless member that constitutes of material such as SiN.Cover ring 4 preferred coverings are carried and are put the surperficial and surperficial of platform 2.Thus, can prevent metallic pollution etc.
In addition, put platform 2 and bury resistance heating type heater 5 underground carrying as thermoregulation mechanism.This heater 5 heats to carry and puts platform 2 through by heater power source 5a power supply, heats equably with this heat to be processed substrate wafer W.
In addition, put platform 2 and be equipped with thermocouples (TC) 6 carrying.Through carrying the temperature survey of putting platform 2, can the heating-up temperature of wafer W for example be controlled at scope from room temperature to 900 ℃ by this thermocouple 6.
In addition, carrying the wafer anchor (not diagram) of putting platform 2 and being provided for supporting wafer W.Each wafer anchor is set to can be prominent to carrying the surface of putting platform 2.
Interior all liners cylindraceous 7 that constitutes by quartz that is provided with at container handling 1.In addition, carrying the outer circumferential side put platform 2, the baffle plate 8 of quartzy system is set annularly, it has and is used for carrying out a large amount of steam vent 8a of even exhaust in the container handling 1.This baffle plate 8 is supported by a plurality of pillars 9.
At the summary central portion of the diapire 1a of container handling 1, form circular peristome 10.The exhaust chamber 11 that is communicated with this peristome 10, gives prominence to downwards is set at diapire 1a.Connect blast pipe 12 at this exhaust chamber 11, be connected with vacuum pump 24 through this blast pipe 12.
Be equipped with the cover 13 of the ring-type of central portion opening on the top of container handling 1.The interior week of opening to the inside (container handling in space) outstanding, form the 13a of support sector of ring-type.
Sidewall 1b at container handling 1 is provided with the importing portion 15 that forms ring-type.This gas importing portion 15 is connected with supply nitrogenous gas, oxygen-containing gas or the plasma exciatiaon gas supply device 18 with gas.In addition, gas importing portion 15 also can be set to nozzle-like or shower shape.
In addition, the sidewall 1b of container handling 1 be provided for carrying out plasma processing apparatus 100 and therewith between the inlet side carrying room 103 of adjacency wafer W move into moving into of taking out of take out of mouthfuls 16 and switch this move into and take out of mouthfuls 16 gate valve G1.
Gas supply device 18 (for example has the gas supply source; Inactive gas supply source 19a, nitrogenous gas supply source 19b, oxygen-containing gas supply source 19c), pipe arrangement (for example; Gas pipeline 20a, 20b, 20c), volume control device (for example; Mass flow controller 21a, 21b, 21c) and valve (for example, switch valve 22a, 22b, 22c).In addition, in the gas supply device 18, as the illustrated gas supply source that do not have beyond above-mentioned, the cleaning gas supply source that uses in the time of for example also can having in replacement Treatment container 1 atmosphere etc.
As inactive gas, for example can use N
2Gas or rare gas etc.As rare gas, for example can use Ar gas, Kr gas, Xe gas, He gas etc.Among these, especially preferably using Ar gas aspect the economy excellence.As the nitrogenous gas that is used for plasma nitridation process, for example can use N
2, NO, NO
2, NH
3Deng.In addition, as being used for the oxygen-containing gas that plasma oxidation is handled, can use for example oxygen (O
2), steam (H
2O), nitric oxide (NO), nitrous oxide (N
2O) etc.
Inactive gas, nitrogenous gas and oxygen-containing gas are from inactive gas supply source 19a, nitrogenous gas supply source 19b and the oxygen-containing gas supply source 19c of gas supply device 18; Arrive gas importing portion 15 through piping 20a, 20b, 20c respectively, in container handling 1, import from gas importing portion 15.Switch valve 22a, 22b, the 22c of 1 group of mass flow controller 21a, 21b, 21c and front and back thereof are set at each the pipeline 20a, 20b, the 20c that connect each gas supply source.Through the structure of such gas supply device 18, can carry out the control of switching and the flow etc. of gas supplied.
Exhaust apparatus possesses vacuum pump 24.Vacuum pump 24 for example is made up of high speed vacuum pump of turbomolecular pump etc. etc.Vacuum pump 24 is connected with the exhaust chamber 11 of container handling 1 through blast pipe 12.Gas in the container handling 1 evenly flows in the 11a of the space of exhaust chamber 11, and further through operation vacuum pump 24,11a process blast pipe 12 is to outside exhaust from the space.Thus, can be with rapid decompression to specified vacuum degree in the container handling 1,0.133Pa for example reduces pressure.
The structure of microwave introduction device 27 then, is described.In the microwave introduction device 27,, possess transmittance plate 28, flat plane antenna 31, slow wave material 33, coating member 34, waveguide pipe 37, match circuit 38 and microwave generating apparatus 39 as primary structure.
The transmittance plate 28 of microwave transmission is provided in the cover 13 on the side-prominent 13a of support sector of interior week.Transmittance plate 28 is made up of dielectric, for example by quartz or Al
2O
3, pottery such as AlN constitutes.Between this transmittance plate 28 and the 13a of support sector, hermetic seal via seal member 29.Therefore, keep air-tightness in the container handling 1.
As shown in Figure 2, each microwave radiation hole 32 for example is elongated rectangle (slit-shaped).And typically the microwave radiation hole 32 of adjacency is configured to " T " word shape.In addition, further dispose with concentric circles as a whole with the microwave radiation hole 32 of shape (for example T word shape) combining and configuring of regulation like this.
The length in microwave radiation hole 32 or arrangement pitch can be according to wavelength (λ g) decisions of microwave.For example, the interval in microwave radiation hole 32 is with λ g/4～λ g configuration.In addition, in Fig. 2, the interval each other, microwave radiation hole 32 that forms the adjacency of concentric circles is represented by Δ r.In addition, the shape in microwave radiation hole 32 can be toroidal, other shape such as circular-arc.In addition, the configuration mode in microwave radiation hole 32 is not special to be limited, and except concentric circles, for example also can be configured to helical form, radial etc.
On flat plane antenna 31, setting has the slow wave material 33 greater than permittivity of vacuum.Because the wavelength of microwave is elongated in a vacuum, this slow wave material 33 has the wavelength that shortens microwave and the function of adjusting plasma.As the material of slow wave material 33, for example can use quartz, polyflon, polyimide resin etc.
In addition, between flat plane antenna 31 and transmittance plate 28, in addition, between slow wave material 33 and flat plane antenna 31, can contact respectively also and can separate, but preferred contact.
On the top of container handling 1, coating member 34 is set, make it cover these flat plane antennas 31 and slow wave material 33.Coating member 34 is for example formed by aluminium or stainless steel and other metal materials.Form flat guided wave path by this coating member 34 with flat plane antenna 31.The upper end of cover 13 and coating member 34 are by seal member 35 sealings.In addition, form cooling water stream 34a in the inside of coating member 34.Through the cooling water that in this cooling water stream 34a, circulates, can cool off coating member 34, slow wave material 33, flat plane antenna 31 and transmittance plate 28.In addition, coating member 34 ground connection.
Central authorities at the upper wall (top) of coating member 34 form peristome 36, connect waveguide pipe 37 at this peristome 36.Distolateral at another of waveguide pipe 37, connect the microwave generating apparatus 39 that produces microwaves via match circuit 38.
Waveguide pipe 37 has the coaxial waveguide pipe 37a of the section toroidal that extends to the top from the peristome 36 of above-mentioned coating member 34, the rectangular wave guide 37b of extension in the horizontal direction that is connected through mode converter 40 with upper end at this coaxial waveguide pipe 37a.Mode converter 40 has the function that in rectangular conduit ripple 37b, is transformed to the TEM pattern with the microwave of TE mode propagation.
Inner wire 41 is extended at center at coaxial waveguide pipe 37a.This inner wire 41, its bottom is connected and fixed on the center of flat plane antenna 31.Through such structure; Microwave is efficiently propagated to the flat guided wave path that is formed by coating member 34 and flat plane antenna 31 with radial via the inner wire 41 of coaxial waveguide pipe 37a equably; Microwave radiation hole (slit) 32 by flat plane antenna 31 imports in container handling, generates plasma.
Through the microwave introduction device 27 of such formation, propagate to flat plane antenna 31 via waveguide pipe 37 at the microwave that microwave generating apparatus 39 produces, import in container handling 1 via transmittance plate 28 again.In addition,, for example preferably use 2.45GHz, also can use 8.35GHz, 1.98GHz etc. in addition as the frequency of microwave.
Each structural portion of plasma processing apparatus 100 is connected with control part 50 and is controlled.Control part 50 has electronic computer, and is for example as shown in Figure 3, possesses the process controller 51 of CPU, user interface 52 and the storage part 53 that is connected with this process controller 51.Process controller 51 is in plasma processing apparatus 100; The control appliance of each structural portion that Comprehensive Control is for example relevant with the process conditions of temperature, pressure, gas flow, microwave output etc. (for example, heater power source 5a, gas supply device 18, vacuum pump 24, microwave generating apparatus 39 etc.).
Like this; As required, through according to accessing scheme arbitrarily from storage part 53, it is carried out at process controller 51 places from instruction of user interface 52 etc.; Under the control of process controller 51, in the container handling 1 of plasma processing apparatus 100, carry out required processing.In addition; The scheme of above-mentioned control program or treatment conditions data etc. can be utilized and be accommodated in the storage medium that electronic computer can read; The scheme of the state in CD-ROM, hard disk, floppy disk, flash memory, DVD, the Blu-ray Disc etc. for example; Perhaps also can be device, for example transmit and the scheme of online utilization at any time via special circuit from other.
In the plasma device 100 that constitutes like this, can carry out that basalis etc. not have the Cement Composite Treated by Plasma damaged at the low temperature below 600 ℃.In addition, therefore plasma device 100 for example also can realize the uniformity of processing owing to the excellent in uniformity of plasma in the face of wafer W to the for example above large-scale wafer W in 300mm footpath.
The method of modifying of the dielectric film that in plasma device 100, carries out then, is described with reference to Fig. 4～Fig. 7.Fig. 4 is the flow chart of expression as the flow process of the modification procedure of the silicon oxide film of dielectric film, and Fig. 4～Fig. 7 is the process chart of its master operation of explanation.
The method of modifying of the dielectric film of this execution mode is for example implemented according to the step from step S1 to step S4 shown in Fig. 4.At first, in the step S1 of Fig. 4, move into wafer W as process object to plasma device 100.
Here, at the near surface of wafer W, form silicon layer 301 and silica (SiO above that
2) film 303.Then, as shown in Figure 5 in step S2, use plasma device 100, the silicon oxide film 303 of wafer W is carried out plasma nitridation process.Through plasma nitridation process, silicon oxide film 303 is modified as oxidized silicon nitride (SiON) film 305 by nitrogenize.In this plasma nitrogen treatment, prediction after plasma oxidation treatment process (step S3) in the minimizing of nitrogen concentration, carry out nitrogen treatment, make nitrogen concentration N
C0Than final objective nitrogen concentration N
CTFor example high by about 1～3%.The condition of the plasma nitridation process of step S2 is as long as can realize nitrogen concentration N
C0Get final product, not special the qualification can be carried out with condition arbitrarily.
Then, as shown in Figure 6 in step S3, use the surface of 100 pairs of oxidized silicon nitride films 305 of plasma processing apparatus to carry out the plasma oxidation processing.The viewpoint that comes off from the oxidation that suppresses oxidized silicon nitride film 305 and N; The plasma oxidation of step S3 is handled after the plasma nitridation process of step S2 finishes; Then in container handling 1, atmosphere is still maintained vacuum; Finish in back 180 seconds in plasma nitridation process, preferably at 60 seconds with interior enforcement.In this operation, the scope plasma oxidation with about the for example depth direction 0.5～1.0nm on the top layer of oxidized silicon nitride film 305 is modified as the high oxidized silicon nitride film 305B of oxygen concentration.Thus, as shown in Figure 7, on silicon layer 301,, form the rich oxygen containing oxidized silicon nitride film 305B of oxidized silicon nitride film 305A and modification above that as oxidized silicon nitride film 305.
[plasma oxidation processed steps]
Plasma oxidation processed steps and the condition of step S3 are as follows.At first; Carry out decompression exhaust in the container handling 1 of limit article on plasma body device 100; The limit is from inactive gas supply source 19a, the oxygen-containing gas supply source 19c of gas supply device 18, and for example the flow with regulation imports Ar gas, O via gas importing portion 15 respectively in container handling 1
2Gas.Operation like this is with the pressure that is adjusted to regulation in the container handling 1.
Then, the assigned frequency that produces with microwave generating apparatus 39 is that the microwave of for example 2.45GHz conducts to waveguide pipe 37 via match circuit 38.The microwave of conduction is supplied with via 41 pairs of flat plane antennas of inner wire 31 in order through rectangular wave guide 37b and coaxial waveguide pipe 37a in waveguide pipe 37.That is, microwave transmits with the TE pattern in rectangular wave guide 37b, and the microwave of this TE pattern converts the TEM pattern at mode converter 40, transmits to the flat guided wave path that is made up of coating member 34 and flat plane antenna 31 via coaxial waveguide pipe 37a.And the superjacent air space via the wafer W of transmittance plate 28 to container handling 1 in radiates microwave from the microwave radiation hole 32 that connects the slit-shaped that forms at flat plane antenna 31.The microwave output of this moment for example during the wafer W more than handling the 200mm diameter, can be selected in the scope below the above 5000W of 1000W according to purpose.
Through the microwave that radiates to container handling 1 through transmittance plate 28 from flat plane antenna 31, in container handling 1, form electromagnetic field, Ar gas and O
2Gas is plasmaization respectively.This plasma that excites is through microwave 32 radiation from a large amount of microwave radiation hole of flat plane antenna 31, has roughly 1 * 10
10～5 * 10
12/ cm
3High density, and have the roughly low electron temperature below the 1.2eV near the wafer W.To form the plasma damage that is caused by ion etc. of the basad film of plasma few in operation like this.And, through the reactive specy O in the plasma
2 +Ion or O (
1D
2) effect of free radical, wafer W is carried out plasma oxidation handle.That is, the surface of the oxidized silicon nitride film 305 through oxidation wafer W as thin as a wafer replaces Si-N key or the free N of labile state on the top layer of film, forms the Si-O key, thereby forms rich oxygen containing oxidized silicon nitride film 305B.Thus, the nitrogen in the oxidized silicon nitride film forms shielded state, does not come off, and can nitrogen concentration be maintained certain and stable status.
[plasma oxidation treatment conditions]
As the processing gas that plasma oxidation is handled, the preferred gas that contains rare gas and oxygen-containing gas that uses.Preferably use Ar gas as rare gas, preferably use O as oxygen-containing gas
2Gas.At this moment, the viewpoint that the timeliness of the nitrogen concentration from suppress oxidized silicon nitride film 305 effectively reduces, O
2Gas is with respect to the volume flow ratio (O of whole processing gases
2Throughput/all the handle percentage of gas flow) preferably in the scope more than 0.1%, below 20%, more preferably in the scope more than 1%, below 15%, is desirably in the scope more than 10%, below 15%.In plasma oxidation is handled, for example set in the scope of flow more than 500mL/min (sccm), below the 5000mL/min (sccm) of Ar gas O
2In the scope of the flow of gas more than 5mL/min (sccm), below the 1000mL/min (sccm), form above-mentioned flow-rate ratio.
In addition; The viewpoint that the timeliness of the nitrogen concentration from suppress oxidized silicon nitride film 305 effectively reduces; In the for example preferred scope more than 67Pa, below the 1333Pa of processing pressure; More preferably in the scope more than 133.3Pa, below the 1333Pa, be desirably in that 333Pa is above, in the scope of 1333Pa.If processing pressure is less than 67Pa in plasma oxidation is handled; Then owing to the ion component as the oxidation activity kind in the plasma forms leading; Therefore oxidation rate increases, and the nitrogen concentration on the surface of nitriding and oxidizing silicon fiml 303 resulting oxidized silicon nitride films 305 reduces.
In addition, the reactive specy O from effective generation plasma
2 +Ion or O (
1D
2) viewpoint of free radical sets out, the power density of microwave is preferably at 0.51W/cm
2More than, 2.56W/cm
2Below scope in, for the surface with as thin as a wafer thickness sox/nox silicon fiml 305, energy of plasma is little more excellent, therefore more preferably at 0.51W/cm
2More than, 1.54W/cm
2Scope in.In addition, the power density of microwave is meant the unit are 1cm to projection plate 28
2The microwave power of being supplied with (below identical).For example during the wafer W more than handling the 200mm diameter, microwave power is preferably in the scope more than 1000W, below the 5000W.
In addition, the heating-up temperature of wafer W, as carrying the temperature of putting platform 2, for example preferred in the scope more than 200 ℃, below 600 ℃, more preferably in the scope more than 400 ℃, below 600 ℃.
In addition, the viewpoint on the top layer from sox/nox silicon fiml 305 only, the processing time that plasma oxidation is handled is for example preferably more than 1 second, below 90 seconds, more preferably in the scope more than 1 second, below 60 seconds.Like this, through in the short time Cement Composite Treated by Plasma, can be with the surface of as thin as a wafer thickness sox/nox silicon fiml 305.In addition; When in same container handling 1, carrying out the plasma oxidation processing with plasma nitridation process; After silicon oxide film carried out plasma nitridation process,, or vacuumize and supply with Ar gas etc. and carry out exhaust rapidly preferably to the residual nitrogen vacuumizing and exhausting in the container handling 1.
Above condition is stored in the storage part 53 of control part 50 as scheme.Then; Process controller 51 reads this scheme; To each structural portion of plasma processing apparatus 100 for example gas supply device 18, vacuum pump 24, microwave generating apparatus 39, heater power source 5a etc. see control signal off, carry out plasma oxidation with required condition thus and handle.
With after 305 modifications of oxidized silicon nitride film, in step S4,, finish processing as stated to 1 piece of wafer W through wafer W being taken out of plasma processing apparatus 100.
In this execution mode, in the oxidized silicon nitride film 305B of modification, through plasma oxidation, the unsettled nitrogen-atoms in the oxidized silicon nitride film 305 is substituted by oxygen atom, outside film, emits.Therefore, the nitrogen concentration N among the oxidized silicon nitride film 305B
C1Be lower than the nitrogen concentration N of the oxidized silicon nitride film 305 after the firm plasma nitridation process
C0(N
C0＞N
C1).In addition, handle the nitrogen concentration N of oxidized silicon nitride film 305A in the deep of modification through plasma oxidation
C2With the nitrogen concentration N after the firm plasma nitridation process
C0Be almost equal value.Therefore, preferably carry out the plasma nitridation process of step S2 and the plasma oxidation of step S3 and handle the nitrogen concentration N of the feasible final oxidized silicon nitride film 305A that forms
C2Nitrogen concentration N with oxidized silicon nitride film 305B
C1Average and target nitrogen concentration N
CTApproaching.
In this execution mode, can in the identical container handling of plasma processing apparatus 100, carry out the plasma nitridation process of step S2 and the plasma oxidation of step S3 continuously and handle.Therefore, after the plasma nitridation process, the nitrogen concentration in oxidized silicon nitride film 305 does not take place through the time change (reducing naturally) during, carry out the plasma oxidation processing, can realize the stabilisation of the nitrogen concentration in the oxidized silicon nitride film 305.In addition, in this execution mode, also can use with after the unit equipment of the identical multi-cavity cell structure of the base plate processing system 200 (Fig. 9) stated, in different container handlings, carry out the plasma nitridation process of step S2 and the plasma oxidation of step S3 and handle.
[the 2nd execution mode]
Then, to Figure 13, the method for modifying of the dielectric film that the 2nd execution mode of the present invention is relevant is described with reference to Fig. 8.The method of modifying of the dielectric film of this execution mode can comprise silicon oxide film is carried out plasma nitridation process, forms the operation of oxidized silicon nitride film and this oxidized silicon nitride film is carried out the modified process that oxidizing annealing is handled.Here, the plasma nitridation process in this execution mode can use with the 1st execution mode in the identical plasma processing apparatus 100 that uses (Fig. 1～Fig. 3) implements.
Oxidizing annealing is handled and can be utilized annealing in process device for example shown in Figure 8 101 to carry out.This annealing in process device 101 is controlled good, devices that can heat the short time; For example can use as carrying out RTP (rapid thermal treatment, the Rapid Thermal Process) device that oxidizing annealing handles to the film that on wafer W, forms etc. in the high-temperature area short time about with 800～1100 ℃ under the oxidizing gas atmosphere.
In Fig. 8, symbol 71 is container handlings cylindraceous, below this container handling 71, releasably is provided with bottom heat-generating units 72; In addition; Above container handling 71, releasably be provided with top heat-generating units 74, make itself and bottom heat-generating units 72 opposed.Heat-generating units 72 in the bottom, on cooling water jecket 73, have the tungsten lamp 76 as firing equipment of a plurality of arrangements.Likewise, heat-generating units 74 on top, have cooling water jecket 75 and the tungsten lamp 76 as firing equipment of a plurality of arrangements below it.In addition, as lamp, being not limited to tungsten lamp 76, for example also can be halogen lamp, Xe lamp, mercury vapor lamp, photoflash lamp etc.Like this, in container handling 71 mutually each tungsten lamp 76 of being equipped with of subtend with do not have illustrated power supply to join, through the electric power quantity delivered that control part 50 is regulated from power supply, can control caloric value.In addition, the structure of control part 50 identical with the 1st execution mode (with reference to Fig. 3).
Between bottom heat-generating units 72 and top heat-generating units 74, be provided for supporting the support sector 77 of wafer W.The liner that the state that this support sector 77 has a processing space that is used in remaining in container handling 71 is supported the wafer anchor 77a of wafer W and is supported in the hot liner 78 of the temperature that is used to measure wafer W in the processing is provided with the 77b of portion.In addition, support sector 77 is not connected with there being illustrated whirligig, makes support sector 77 as a whole around vertical axle rotation.Thus, wafer W is rotated with fixing speed in processing, realizes heat treated homogenizing.
Below container handling 71, configuration pyrometer 81 through port 81a and optical fiber 81b, is measured the hot line that comes self-heating liner 78 in the heat treatment through pyrometer 81, can grasp the temperature of wafer W indirectly.In addition, also can directly measure the temperature of wafer W.
In addition, below hot liner 78, clamping is equipped with quartz member 79 between the tungsten lamp 76 of bottom heat-generating units 72, and as shown in the figure, above-mentioned port 81a is arranged at this quartz member 79.In addition, also can be equipped with a plurality of port 81a.In addition, above wafer W, between the tungsten lamp 76 of top heat-generating units 74 also clamping be equipped with quartz member 80a.In addition, also set quartz member 80b with mode at the inner peripheral surface of container handling 71 around wafer W.In addition, the lifter pin that is used to support wafer W to make its up-down (not diagram) connects hot liner 78 and is provided with, and is used for moving into of wafer W and takes out of.
At clamping seal member (not diagram) respectively between bottom heat-generating units 72 and the container handling 71 and between top heat-generating units 74 and the container handling 71, form airtight conditions in the container handling 71.In addition,, be equipped with the gas supply device 83 that is connected with gas introduction tube 82, can in the processing space of handling space 71, do not import for example O through there being illustrated volume control device at the sidepiece of container handling 71
2Gas, NO, N
2O, H
2O is (by O
2And H
2Produce through the steam generator) etc. oxidizing gas, or further import the inactive gas etc. of rare gas etc. as required.In addition,, blast pipe 84 is set in the bottom of container handling 71, through there not being the exhaust apparatus of illustrated vacuum pump etc., can be to reducing pressure in the container handling 71.
Each structural portion of annealing in process device 101 is also identical with plasma processing apparatus 100, is connected with control part 50 and is controlled.And according to accessing scheme arbitrarily from the instruction of user interface 52 etc. from storage part 53, through carrying out at process controller 51, under the control of process controller 51, the oxidizing annealing that carries out in the annealing in process device 101 is handled.For example, through utilizing the electric power quantity delivered of process controller 51 control setting heat-generating units 72 and each tungsten lamp 76 of top heating power supply 74, can regulate the firing rate and the heating-up temperature of wafer W in the bottom.In addition, can regulate the flow and the ratio of the oxidizing gas of in container handling 71, supplying with from gas supply device 83.
Fig. 9 is the base plate processing system 200 of plasma nitridation process and oxidizing annealing processing is for example carried out in expression continuously with vacuum condition to wafer W a summary construction diagram.This base plate processing system 200 is as the unit equipment of multi-cavity cell structure and constitute.
As main composition; Base plate processing system 200 possesses 4 technical module 100a, 100b, 101a and 101b that wafer W carried out various processing; These technical modules 100a, 100b, 101a and 101b are passed through the inlet side carrying room 103 that gate valve G1 is connected; At 2 load lock 105as, the 105b of this inlet side carrying room 103, with the loading unit 107 that these two load lock 105a, 105b are connected through gate valve G3 through gate valve G2 connection.
4 technical module 100a, 100b, 101a and 101b can carry out the processing of same content to wafer W, also can carry out the processing of different content respectively.In this execution mode; Can be in technical module 100a, 100b, the silicon of wafer W is carried out plasma nitridation process, form the oxidized silicon nitride film; In technical module 101a, 101b, further the oxidized silicon nitride film that forms through plasma nitridation process is carried out oxidizing annealing and handle.
In the inlet side carrying room 103 that can vacuumize, the Handling device 109 as the 1st substrate transfer apparatus of the handing-over of technical module 100a, 100b, 101a and 101b and load lock 105a, 105b being carried out wafer W is set.This Handling device 109 has a pair of carrying arm 111a, the 111b of mutual subtend configuration.Each carries arm 111a, 111b is the center with identical rotating shaft, can bend and stretch and rotate.In addition, the front end at each carrying arm 111a, 111b is provided for carrying fork 113a, the 113b that puts the maintenance wafer W respectively.Handling device 109 is to upload the state that is equipped with wafer W at these forks 113a, 113b; Between technical module 100a, 100b, 101a and 101b, perhaps carry out the carrying of wafer W between technical module 100a, 100b, 101a and 101b and load lock 105a, the 105b.
In load lock 105a, 105b, be provided with to carry respectively and put carrying of wafer W and put platform 106a, 106b.Load lock 105a, 105b can switch vacuum state and atmosphere opening state.Put platform 106a, 106b through carrying of this load lock 105a, 105b, between inlet side carrying room 103 and atmospheric side carrying room 119 (afterwards stating), carry out the handing-over of wafer W.
Atmospheric side carrying room 119 possesses the recycle unit (omitting diagram) that nitrogen or clean air are flowed downward, and keeps cleaning ambient.Atmospheric side carrying room 119 is the shape of overlooking rectangle, along its length direction guide rail 123 is set.Handling device 117 is supported with the mobile mode of can sliding on this guide rail 123.That is, Handling device 117 can not move to directions X along guide rail 123 through there being illustrated drive unit.This Handling device 117 has and is configured to up and down 2 sections a pair of carrying arm 125a, 125b.Each carries arm 125a, 125b constitutes with the mode that can bend and stretch and rotate.Front end at each carrying arm 125a, 125b is provided with the fork 127a, the 127b that put and keep the holding member of wafer W as carrying respectively.Handling device 117 carries out the carrying of wafer W to upload the state that is equipped with wafer W at these forks 127a, 127b between wafer case CR, load lock 105a, 105b and the position indicator 121 of load port LP.
Load port LP constitutes can carry the mode of putting wafer case CR.Wafer case CR carries with the same intervals multistage and puts and take in many pieces of wafer W.
[step of processing of wafers]
In base plate processing system 200, wafer W is carried out plasma nitridation process and oxidizing annealing processing with following step.At first, use the fork 127a of the Handling device 117 of atmospheric side carrying room 119, any of 127b,, behind position indicator 121 adjustment positions, move into load lock 105a (or 105b) through 1 piece of wafer W of wafer case CR taking-up of load port LP.Wafer W is carried and is placed the load lock 105a (or 105b) that carries the state of putting platform 106a (or 106b), closing gate valve G3, and inner pressure relief is vented to vacuum state.Afterwards, open gate valve G2, fork 113a, 113b through the Handling device 109 in the inlet side carrying room 103 transport wafer W from load lock 105a (or 105b).
Through the wafer W that Handling device 109 transports from load lock 105a (or 105b), at first, move into any of technical module 100a, 100b, behind the closing gate valve G1 wafer W is carried out plasma nitridation process.
Then, open above-mentioned gate valve G1, the wafer W that is formed with oxidized silicon nitride film 305 is moved into the arbitrary side who keeps vacuum state technical module 101a, 101b by Handling device 109 from technical module 100a (or 100b).Then, behind the closing gate valve G1 wafer W being carried out oxidizing annealing handles.
Then, open above-mentioned gate valve G1, the wafer W that is formed with the oxidized silicon nitride film 305 of modification is taken out of from technical module 101a (or 101b) through Handling device 109 with remaining in vacuum state, moves into load lock 105a (or 105b).Then, with above-mentioned opposite step, in the wafer case CR of load port LP, take in the wafer W that disposes, finish processing to 1 piece of wafer W in the base plate processing system 200.In addition, the configuration of each processing unit in base plate processing system 200 can be any configuration structure so long as the configuration that can handle efficiently gets final product.And the quantity of the technical module in the base plate processing system 200 is not limited to 4, also can be more than 5.
Figure 10 is the flow chart of expression as the flow process of the modification procedure of the silicon oxide film of dielectric film, and the engineering drawing of its master operation is explained in Figure 11～13rd.
The method of modifying of the dielectric film of this execution mode is for example implemented through the step from step S11 to step S15 that Figure 10 representes.Here, can implement equally with step S1, the S2 of the 1st execution mode until the operation of step S11, S12.At first, in the step S11 of Figure 10,, will move into plasma processing apparatus 100 ( technical module 100a or 100b) as the wafer W of process object through the Handling device 109 in the inlet side carrying room 103.Here,, form silicon layer 301, form silica (SiO above that at the near surface of wafer W
2) film 303.Then, shown in figure 11 in step S12, the silicon oxide film 303 of wafer W is carried out plasma nitridation process.Through plasma nitridation process, silicon oxide film 303 is formed oxidized silicon nitride film (SiON) film 305 by nitrogenize.In this plasma nitrogen treatment, prediction after the minimizing of nitrogen concentration of oxidizing annealing treatment process (step S14), carry out nitrogen treatment, make formation than target nitrogen concentration N
CTFor example high about 1～3% nitrogen concentration N
C0The condition of the plasma nitridation process of step S12 is as long as can realize nitrogen concentration N
C0Get final product, have no restriction, can carry out with condition arbitrarily.
Then, in step S13, wafer W is transferred to annealing in process device 101 ( technical module 101a or 101b) from plasma processing apparatus 100 ( technical module 100a or 100b).This is transferred through the Handling device 109 in the inlet side carrying room 103 and implements at vacuum state.
Then, shown in figure 12 in step S14, use annealing in process device 101, oxidizing annealing is carried out on the surface of oxidized silicon nitride 305 handle.From surface oxidation that suppresses oxidized silicon nitride 305 and the viewpoint that N comes off; Oxidizing annealing is handled after the plasma nitridation process of step S12 finishes; Keep vacuum state; Wafer W is moved into annealing in process device 101, from plasma nitridation process finish 180 seconds with interior, preferably at 60 seconds with interior enforcement.In this operation, the for example scope oxidation about depth direction 0.5～1.0nm of top layer with oxidized silicon nitride film 303 is modified as the high oxidized silicon nitride film 305B of oxygen concentration.Thus, shown in figure 13, on silicon layer 301,, form the rich oxygen containing oxidized silicon nitride film 305B of oxidized silicon nitride film 305A and the modification on it as oxidized silicon nitride film 305.
[oxidizing annealing processed steps]
At first, in annealing in process device 101, after the support sector 77 in container handling 71 is provided with wafer W, form airtight space.Then; Under the control of process controller 51; Never illustrated power supply is supplied with the electric power of regulation and is made as the state of opening (access) to the heater (omitting diagram) of each tungsten lamp 76 of bottom heat-generating units 72 and top heat-generating units 74; The heating of each heater, the hot line of generation arrives wafer W through quartz member 79 with quartz member 80a, based on the condition (programming rate, heating-up temperature, gas flow etc.) of scheme from heated chip W rapidly up and down.One side heated chip W is on one side from the flow importing O of gas supply device 83 with regulation
2The oxygen-containing gas of gas etc., operation does not simultaneously have illustrated exhaust apparatus, carries out exhaust from blast pipe 84, makes the oxidizing atmosphere that forms decompression state in the container handling 71 thus.
During oxidizing annealing is handled, do not make support sector 77 as a whole around vertical axle rotation through there being illustrated rotating mechanism, promptly horizontal direction is for example rotated with the rotary speed of 80rpm, thereby makes the wafer W rotation.Its result can guarantee the uniformity to the heat supplied of wafer W.In addition, in heat treatment,, can measure the temperature of wafer W indirectly through the temperature of the hot liner 78 of pyrometer 81 mensuration.The temperature data of measuring through pyrometer 81 feeds back to process controller 51, when between the design temperature of scheme, having difference, regulates to the electric power of tungsten lamp 76 and supplies with.
After heat treatment finishes; The tungsten lamp 76 of turning off (cut-out) bottom heat-generating units 72 and top heat-generating units 74; And in container handling 71 through there not being illustrated cleaning port continue to flow into the cleaning gas of nitrogen etc., and from blast pipe 84 exhausts, with taking out of after the wafer W cooling.
In addition, oxidizing annealing is handled preferred as following illustration is divided into enforcement of a plurality of stages (for example 3 stages) heating process.
At first, in the 1st temperature rise period, the emissivity that wafer W is warming up to wafer W reaches the 1st maximum temperature.Here, the emissivity of wafer W is set according to the oxidized silicon nitride film that forms in wafer W.
Then, in the 2nd temperature rise period, wafer W is reached the 1st maximum temperature from the emissivity of wafer W be warming up to the 2nd temperature that is lower than treatment temperature.Here, the 2nd temperature X is defined as the temperature of the relational expression below satisfying
3≤(T-X)/Y≤7
Wherein, T representes treatment temperature, and Y is illustrated in intensification temperature amplitude per 1 second in the 3rd programming rate.
In the above-mentioned relation formula, less than 3 o'clock,, produce overshoot (overshoot) at (T-X)/Y because the relation of the 3rd temperature rise period and its heating rate is too short, high in the possibility of wafer W generation warpage or slip, so not preferred.On the contrary, in the above-mentioned relation formula, surpass at 7 o'clock,, processing flux is descended, so not preferred because the relation of the 3rd temperature rise period and its heating rate is long at (T-X)/Y.It is 85%～95% temperature that the 2nd temperature X for example preferably is made as with respect to treatment temperature T.
In the 3rd temperature rise period, will be processed substrate and be warming up to from the 2nd temperature and reach treatment temperature.Then, at treatment temperature (for example 800 ℃～1100 ℃), implement the oxidizing annealing of constant temperature and handle, the processing of stipulated time finishes the back descends the temperature of wafer W through the rate of temperature fall with regulation, finishes heat treatment.
From 3 temperature rise periods of the 1st temperature rise period to the, it is high to make the heating rate of the 2nd temperature rise period be higher than the heating rate of the 3rd temperature rise period.Mainly, in the 2nd temperature rise period, preferably improve heating rate as far as possible from improving the viewpoint of output.But, be warming up to treatment temperature with high heating rate, overshoot takes place, cause by rapid variations in temperature that firing rate becomes inhomogeneous, is being processed the slip that substrate applies thermal stress (deformation), warpage or crystal defect take place in being processed the face of substrate.Therefore,, prevent overshoot, make the firing rate in the face that is processed substrate even, prevent to be processed the warpage of substrate or the generation of slippage through after the 2nd temperature rise period, being provided with the 3rd temperature rise period than its low heating rate.
In addition, the heating rate of the 3rd temperature rise period is preferably more than the heating rate of the 1st temperature rise period.In the 1st temperature rise period, reach maximum temperature (the 1st temperature) though be warming up to the emissivity of wafer W, arrive in the process of the 1st temperature being processed substrate and be easy to generate warpage.Therefore, if the heating rate in the 1st temperature rise period is too high, the interior firing rate of face that then is processed substrate becomes inhomogeneous, is being processed substrate generation warpage, or is producing slip etc.Therefore, the heating rate in the 1st temperature rise period is preferably set to below the heating rate of the 3rd temperature rise period, in the programming rate of 3 steps, is preferably set to minimum.
Handle through oxidizing annealing, the surface of the oxidized silicon nitride film 305 of oxidation wafer W as thin as a wafer, the Si-N key of the most surperficial labile state of replacement film or free N form the Si-O key, thereby form rich oxygen containing oxidized silicon nitride film 305B.Thus, the nitrogen in the oxidized silicon nitride film forms shielded state, does not come off, and can nitrogen concentration be maintained certain and stable status.
[condition that oxidizing annealing is handled]
Oxygen-containing gas as oxidizing annealing is handled gets final product so long as can in container handling 71, form the gas of oxidizing atmosphere, not special restriction, for example preferred O
2Gas, NO gas, N
2O gas, H
2O (steam) etc. also can sneak into rare gas or the N of Ar as inactive gas etc. in these
2Deng.Use O
2Gas and N
2During the mist of gas, in order to improve modified effect, preferably with O
2Gas flow: N
2The volume ratio of the gas flow for example mode in 10: 1～1: 2 scope mixes.In mode of the present invention, the viewpoint that reduces in time of the nitrogen concentration from suppress the oxidized silicon nitride film is effectively especially preferably used O
2The oxidizing annealing of gas is handled.At this moment, the flow of oxygen-containing gas can be set in the scope that 0.5mL/min (sccm) is above, 2000mL/min (sccm) is following.
In addition, the viewpoint that reduces in time of the nitrogen concentration from suppress the oxidized silicon nitride film, processing pressure are preferably in the scope more than 10Pa, below the 15000Pa, more preferably in the scope more than 133Pa, below the 10000Pa.
In addition, the heating-up temperature of wafer W, as the measurement temperature of pyrometer 81, for example preferred in the scope more than 800 ℃, below 1100 ℃, more preferably in the scope more than 900 ℃, below 1100 ℃.
In addition, the viewpoint on the top layer from sox/nox silicon fiml 305 only, the processing time that oxidizing annealing is handled is for example preferred in the scope more than 10 seconds, below 50 seconds, more preferably in the scope more than 10 seconds, below 30 seconds.Through carrying out oxidizing annealing with such short time, can be with the surface of as thin as a wafer thickness sox/nox silicon fiml 305.That in addition, can suppress oxidized silicon nitride film 305 increases film (increase of electric thickness (EOT)).
Above condition is stored in the storage part 53 of control part 50 as scheme.Then; Process controller 51 reads this scheme; To each structural portion of annealing in process device 101 for example gas supply device 83, exhaust apparatus (not diagram), bottom heat-generating units 72 and top heat-generating units 74 (tungsten lamp 76) wait and see control signal off, carry out the oxidizing annealing processing with required condition thus.
As stated to after 305 modifications of oxidized silicon nitride film; In step S15; Handling device 109 through in the vacuum carrying chamber 103 is taken out of the wafer W that disposes from annealing in process device 101 ( technical module 101a or 101b), be accommodated in above-mentioned steps among the wafer case CR of load port LP.
In this execution mode, in the oxidized silicon nitride film 305B of modification, to handle through oxidizing annealing, the unsettled nitrogen-atoms in the oxidized silicon nitride film 305 is substituted by oxygen atom, outside film, emits.Therefore, the nitrogen concentration N among the oxidized silicon nitride film 305B
C1Be lower than the nitrogen concentration N of the oxidized silicon nitride film 305 after plasma nitridation process has just finished
C0(N
C0＞N
C1).In addition, handle the nitrogen concentration N of oxidized silicon nitride film 305A in the deep of modification through oxidizing annealing
C2Nitrogen concentration N after almost just having finished with plasma nitridation process
C0Be the value that equates.Therefore, preferably carry out the plasma nitridation process of step S12 and the oxidizing annealing of step S14 and handle the nitrogen concentration N of the feasible final oxidized silicon nitride film 305A that forms
C2With the nitrogen concentration N among the oxidized silicon nitride film 305B
C1Average and target nitrogen concentration N
CTApproaching.
In this execution mode, can in processing substrate system 200, keep vacuum condition to carry out the plasma nitridation process of step S12 and the oxidizing annealing processing of step S14 continuously.Therefore, after the plasma nitridation process, the nitrogen concentration in oxidized silicon nitride film 305 does not take place through the time change (reducing naturally) during, carry out plasma nitridation process, can realize the stablizing of nitrogen concentration in the oxidized silicon nitride film 305.
Other structures in this execution mode are identical with the 1st execution mode with effect.
[the 3rd execution mode]
Then, with reference to Figure 14～Figure 18, the method for modifying of the dielectric film that the 3rd execution mode of the present invention is relevant is described.The method of modifying of the dielectric film of this execution mode can comprise silicon oxide film is carried out plasma nitridation process, forms the operation of oxidized silicon nitride film; This oxidized silicon nitride film is carried out the 1st modified process of plasma nitridation process; With the 2nd modified process that the oxidized silicon nitride film is carried out the oxidizing annealing processing.Here, the plasma nitridation process in this execution mode and plasma oxidation handle can use with the 1st execution mode in the identical plasma processing apparatus 100 (Fig. 1～Fig. 3) implement of employed device.Oxidizing annealing is handled and for example can be utilized annealing in process device shown in Figure 8 101 to carry out.In addition, more than handle can with the composite set of the multi-cavity cell structure of base plate processing system 200 same structures shown in Figure 9 in carry out.
Figure 14 is the flow chart of expression as the flow process of the modification procedure of the silicon oxide film of dielectric film, and Figure 15～Figure 18 is the process chart of its master operation of explanation.
The method of modifying of the dielectric film of this execution mode is for example implemented through the step from step S21 to step S26 that Figure 14 representes.Wherein, the operation of step S21～S23 can likewise be implemented with the step S1～S3 of the 1st execution mode.At first, in the step S21 of Figure 14, will move into plasma processing apparatus 100 (technical module 100a or 100b) as the wafer W of process object through the Handling device 109 in the inlet side carrying room 103.Wherein, at the near surface of wafer W, form silicon layer 301 and silica (SiO above that
2) film 303.Then, shown in figure 15 in step S22, the silicon oxide film 303 of wafer W is carried out plasma nitridation process.Through plasma nitridation process, silicon oxide film 303 is formed oxidized silicon nitride (SiON) film 305 by nitrogenize.In this plasma nitrogen treatment, prediction after plasma oxidation treatment process (step S23) and oxidizing annealing handle the minimizing of the nitrogen concentration of (step S25), carry out nitrogen treatment, feasible formation is than final goal nitrogen concentration N
CTFor example high about 1～3% nitrogen concentration N
C0As long as the condition of the plasma nitridation process of step S22 can realize nitrogen concentration N
C0Get final product, not special restriction can be carried out with condition arbitrarily.
Then, shown in figure 16 in step S23, use the surface of 100 pairs of oxidized silicon nitride films 305 of plasma processing apparatus to carry out the plasma oxidation processing.The viewpoint that comes off from the oxidation that suppresses oxidized silicon nitride film 305 and N; After the plasma nitridation process of step S22 finishes; Then in container handling 1, atmosphere is maintained at vacuum, finishes to handle with interior enforcement plasma oxidation with interior, preferred 60 seconds in back 180 seconds in plasma nitridation process.In this operation,, be modified as the high oxidized silicon nitride film 305B of oxygen concentration with the top layer of the oxidized silicon nitride film 305 scope plasma oxidation about depth direction 0.5～1.0nm for example.Thus, shown in figure 17, on silicon layer 301, form the rich oxygen containing oxidized silicon nitride film 305B of oxidized silicon nitride film 305A and the modification on it.The condition of plasma nitridation process is identical with the step S13 of the 1st execution mode.
Then, in step S24, wafer W is transferred to annealing in process device 101 ( technical module 101a or 101b) from plasma processing apparatus 100 ( technical module 100a or 100b).This is transferred through the Handling device 109 in the inlet side carrying room 103 and implements at vacuum state.
Then, shown in figure 17 in step S25, use annealing in process device 101, oxidizing annealing is carried out on the surface of oxidized silicon nitride film 305 handle.In this operation, the for example scope oxidation about depth direction 0.5～1.0nm of top layer with oxidized silicon nitride film 305 is modified as the high oxidized silicon nitride film 305B of oxygen concentration.Thus, shown in figure 18, on silicon layer 301,, form the rich oxygen containing oxidized silicon nitride film 305B of oxidized silicon nitride film 305A and modification above that as oxidized silicon nitride film 305.The condition that oxidizing annealing is handled is identical with the step S14 of the 2nd execution mode.
After as stated oxidized silicon nitride film 305 being carried out modification; In step S26; Through the Handling device 109 in the inlet side carrying room 103; The wafer W that disposes is taken out of annealing in process device 101 ( technical module 101a or 101b), be accommodated in above-mentioned steps among the wafer case CR of load port LP.
In this execution mode; Through the combination that plasma oxidation is handled and oxidizing annealing is handled; The surface of the oxidized silicon nitride film 305 of oxidation wafer W as thin as a wafer; The Si-N key of the most surperficial labile state of replacement film or free N form the Si-O key, thereby form rich oxygen containing oxidized silicon nitride film 305B.Thus, the nitrogen in the oxidized silicon nitride film forms shielded state, does not come off, and can nitrogen concentration be maintained certain and stable status.
In this execution mode, in the oxidized silicon nitride film 305B of modification, through the combination that plasma oxidation is handled and oxidizing annealing is handled, the unsettled nitrogen-atoms in the oxidized silicon nitride film 305 is substituted by oxygen atom, outside film, emits.Therefore, the nitrogen concentration N among the oxidized silicon nitride film 305B
C1Be lower than the nitrogen concentration N of the oxidized silicon nitride film 305 after plasma nitridation process has just finished
C0(N
C0＞N
C1).In addition, handle the nitrogen concentration N with the oxidized silicon nitride film 305A in the deep of oxidizing annealing processing modification through plasma oxidation
C2Nitrogen concentration N after almost just having finished with plasma nitridation process
C0Be the value that equates.Therefore, preferably carry out the plasma nitridation process of step S22, the plasma oxidation processing of step S23 and the oxidizing annealing of step S25 and handle the nitrogen concentration N of the feasible final oxidized silicon nitride film 305A that forms
C2With the nitrogen concentration N among the oxidized silicon nitride film 305B
C1Average and target nitrogen concentration N
CTApproaching.
In this execution mode, can in base plate processing system 200, keep vacuum condition to carry out the plasma nitridation process of step S22, the plasma oxidation processing of step S23 and the oxidizing annealing of step S25 continuously and handle.Therefore, after the plasma nitridation process, the nitrogen concentration in oxidized silicon nitride film 305 does not take place through the time change (reducing naturally) during, carry out plasma oxidation and handle and the oxidizing annealing processing, can realize the stablizing of nitrogen concentration in the oxidized silicon nitride film 305.
In addition, in this execution mode, shown in figure 14; After the plasma nitridation process of step S22, carry out the plasma oxidation of step S23 and handle, afterwards; Carrying out the oxidizing annealing of step S25 handles; But also can after the plasma nitridation process of step S22, at first carry out oxidizing annealing and handle, then carry out plasma oxidation and handle.In addition, the plasma oxidation of the plasma nitridation process of step S22 and step S23 is handled and also can be changed container handling and carry out.For example, plasma nitridation process that can step S22 is carried out in technical module 100a, and the plasma oxidation of step S23 is handled and in technical module 100b, carried out.
Other structures in this execution mode are identical with the 1st and the 2nd execution mode with effect.
[effect]
In the oxidized silicon nitride film after the plasma nitridation process silicon oxide film just finishes, contain the Si-N key and the nitrogen-atoms of labile state.These nitrogen-atoms are along with effluxion is emitted (N break-off) to the outside lentamente from the oxidized silicon nitride film.Inventor of the present invention thinks, after the plasma nitridation process, the nitrogen concentration in the oxidized silicon nitride film through the time N break-off that reduces be because the Si-N key cuts off easily, replace in this, the oxygen atom in the atmosphere is ingested in the film, is replaced into the cause of Si-O key.Therefore; Reverse thinking; Back through just having finished in plasma nitridation process (for example in 180 seconds) continue to keep vacuum atmosphere; Implement to comprise that the modification that plasma oxidation is handled and/or oxidizing annealing is handled of short time handles on the top layer of oxidized silicon nitride film, convert the Si-N key of this top layer part into the Si-O key by the strong hand, and promote the nitrogen-atoms of free state outside film, to emit.Handle through modification, near the top layer of oxidized silicon nitride film, form thin layer richness oxygen containing (densification of S-O key) modified layer.This modified layer is brought into play a kind of barrier functionality, and the effect of emitting of nitrogen-atoms in the deep of the modified layer of inhibition from the oxidized silicon nitride film is arranged.Therefore, handle, can prevent the reduction (N break-off) of lasting for a long time nitrogen concentration through modification.In addition; During modification is handled,, predict the minimizing amplitude in advance though follow the minimizing of nitrogen concentration of the near surface degree of oxidized silicon nitride film; Through in the plasma nitridation process operation, adding slightly many nitrogen, can the oxidized silicon nitride film behind the modified process be controlled at the target nitrogen concentration.
Then, the experimental data that forms basis of the present invention is described.
Test Example 1:
SiO to the thickness 3.2nm through the dry type oxidation process film forming
2Film; The plasma processing apparatus of plasma processing apparatus 100 same structures of representing among use and Fig. 1; Carry out plasma nitridation process with following condition, form thus 4 grades of different N concentrations (nitrogen concentration: high, in-Gao, in-low, low) the SiON film.
[plasma nitridation process condition]
Ar gas flow: 500 or 1000mL/min (sccm)
N
2Gas flow: 200mL/min (sccm)
Processing pressure: 35Pa (260mTorr)
Carry the temperature of putting platform: 400 ℃
Microwave power: 1900W
Processing time: 5 seconds, 30 seconds, 115 seconds or 300 seconds
In 27 ℃ of atmosphere, place each SiON film, through the time ground measure nitrogen concentration in the film.Its result of expression in Figure 19.The longitudinal axis of Figure 19 is represented the nitrogen concentration in the SiON film, and transverse axis is represented the elapsed time.According to this result, the nitrogen concentration at initial stage is low more, and then the minimizing of nitrogen concentration tendency is more little in the film, and the high more then tendency of the nitrogen concentration at initial stage is big more.Can think this be since on SiON film surface the Si-N key for a long time because easily by the oxidation of the oxygen of outside institute, so the Si-N key is changed to the Si-O key, nomadic nitrogen is discharged into the outer result of film.
Then; To the nitrogen concentration among Figure 19 is the SiON film of " in-Gao "; The plasma processing apparatus of plasma processing apparatus 100 same structures of representing among use and Fig. 1; Implement plasma oxidations with following two kinds of conditions and handle, estimate the initial stage nitrogen concentration of nitrogen concentration after with respect to plasma nitridation process through the time slip.Wherein, plasma oxidation is handled and in same container handling, was implemented with interior at 180 seconds after the plasma nitridation process.Its result of expression in Figure 20.The longitudinal axis of Figure 20 representes to finish from plasma nitridation process the slip (%) of the nitrogen concentration of beginning, and transverse axis is represented to finish through the nitrogen concentration (%) after 1 hour from plasma nitridation process.In addition, Figure 21 representes respectively after the plasma nitridation process through the N concentration of the SiON film after 16 hours with through the difference (longitudinal axis) of the N concentration of the SiON film after 1 hour according to treatment conditions.In addition, " standard " among Figure 20 and Figure 21 is meant that not carrying out plasma oxidation handles, and only carries out the situation that plasma nitridation process is placed.
[condition 1: high oxidization rate]
Ar gas flow: 2000mL/min (sccm)
O
2Gas flow: 20mL/min (sccm)
Flow percentage (O
2/ Ar+O
2): about 1%
Processing pressure: 127Pa (950mTorr)
Carry the temperature of putting platform: 400 ℃
Microwave power: 2750W
Microwave Power Density: 0.97W/cm
2(the every 1cm of the area of transmittance plate
2)
Processing time: 3 seconds
[condition 2: low oxidation rate]
Ar gas flow: 2000mL/min (sccm)
O
2Gas flow: 300mL/min (sccm)
Flow percentage (O
2/ Ar+O
2): about 13%
Processing pressure: 333Pa (2500mTorr)
Carry the temperature of putting platform: 400 ℃
Microwave power: 2750W
Microwave Power Density: 0.97W/cm
2(the every 1cm of the area of transmittance plate
2)
Processing time: 3 seconds
Can confirm film from Figure 20 and Figure 21, when carrying out plasma oxidation, compare that the minimizing of nitrogen concentration all is suppressed with the situation that does not have plasma oxidation to handle with arbitrary condition of the condition 2 of condition of high oxidization rate 1 and low oxidation rate to SiON.That is, handle through the SiON film being carried out plasma oxidation, suppressed nitrogen concentration through the time reduce.Be the volume flow ratio of 333Pa, oxygen when being 13% condition 2 especially in processing pressure, even through the identical time, the position of point in Figure 20 above also demonstrate significantly and change.Therefore, handle at the plasma oxidation that is used for modification treatment S iON film, confirmed that processing pressure is preferably more than the 127Pa, more preferably more than the 333Pa, the oxygen flow of all handling in the gas is made as more than 1% than preferably, more preferably is made as more than 13%.
In addition, Figure 22 representes the result that the XPS (x-ray photoelectron power spectrum) in the SiON film of plasma oxidation before and after handling analyzes.The longitudinal axis of Figure 22 represent with film in the nitrogen concentration intensity relevant with oxygen concentration, transverse axis is represented the degree of depth in the film.Can know from this Figure 22, handle, increase at the degree of depth oxygen concentration below the extremely shallow 0.5nm in film surface through plasma oxidation, on the contrary, the nitrogen concentration minimizing.
Test Example 2
SiO to the thickness 6nm through the dry type oxidation process film forming
2Film, the plasma processing apparatus of plasma processing apparatus 100 same structures of representing among use and Fig. 1 carries out plasma nitridation process with following condition, forms the SiON film.
[plasma nitridation process condition]
Ar gas flow: 1000mL/min (sccm)
N
2Gas flow: 200mL/min (sccm)
Processing pressure: 35Pa (260mTorr)
Carry the temperature of putting platform: 400 ℃
Microwave power: 1900W
Processing time: 115 seconds
To this SiON film, carry out annealing in process with the condition of following expression.Wherein, annealing in process is followed plasma nitridation process, the wafer W that will be formed with the SiON film move into continue to keep vacuum with Fig. 8 in the device of annealing in process device 101 represented with spline structure, at 180 seconds with interior enforcement.
[annealing conditions 1:O
2Annealing]
O
2Gas flow: 2L/min (s1m)
[annealing conditions 2:O
2N
2Annealing]
O
2Gas flow: N
2Gas flow ratio: 1: 1
O
2Gas flow: 1L/min (s1m)
N
2Gas flow: 1mL/min (sccm)
[annealing conditions 3:N
2Annealing]
N
2Gas flow: 2mL/min (sccm)
[common condition]
Processing pressure: 133Pa (1Torr), 667Pa (5Torr) or 9998Pa (75Torr)
Treatment temperature: 900 ℃, 1050 ℃ or 1100 ℃
15 seconds processing times
The nitrogen concentration of the SiON film after Figure 23 representes just to have finished with respect to plasma nitridation process is through the slip (longitudinal axis) of the nitrogen concentration after 100 hours and the relation of annealing in process condition.In addition, " standard " among Figure 23 is meant that not carrying out annealing in process only carries out the situation that plasma nitridation process is placed.Can know, for the slip with nitrogen concentration suppresses for below 1% of desired value, with the N of annealing conditions 3
2Annealing is compared, the O of preferred annealing conditions 1
2The O of annealing or annealing conditions 2
2N
2Annealing.In addition, confirmed the O of annealing conditions 1
2In the annealing, processing pressure and treatment temperature be high more, and then to suppress the effect of minimizing of nitrogen concentration big more.
As stated, confirmed to carry out plasma oxidation processing or oxidizing annealing processing, can improve the membranous of oxidized silicon nitride film, can suppress N and come off through the SiON film behind the article on plasma body nitrogen treatment.In addition, be appreciated that also that according to The above results SiON film after can article on plasma body nitrogen treatment carries out that plasma oxidation is handled and oxidizing annealing is handled both.
The method of modifying of dielectric film of the present invention for example through in the modification of the gate insulating film of the MOS constructional device of MOSFET etc., utilizing, can suppress the increase of leakage current or penetrating of boron effectively, can improve the reliability and the rate of finished products of semiconductor device.
More than, execution mode of the present invention has been described, but the present invention is not limited to above-mentioned execution mode, various distortion can be arranged.For example; In the above-described embodiment; Though in plasma oxidation is handled, used the microwave plasma processing apparatus of RLSA mode, can use the for example plasma processing apparatus of other modes of ICP plasma mode, ecr plasma mode, surface echo plasma mode, magnetron plasma mode etc.In addition, handle about oxidizing annealing, also be not limited to piece annealing in process device of leaf formula mode, the annealing in process device that also can use other modes is batch-wise thermal oxidation furnace etc. for example.
Symbol description
1 ... Container handling; 2 ... Carry and put platform; 3 ... Holding components; 5 ... Heater; 12 ... Blast pipe; 15 ... Gas importing portion; 16 ... Move into and take out of mouth; 18 ... Gas supply device; 19a ... The inactive gas supply source; 19b ... The nitrogenous gas supply source; 19c ... The oxygen-containing gas supply source; 24 ... Vacuum pump; 28 ... Transmittance plate; 29 ... Seal member; 31 ... Flat plane antenna; 32 ... The microwave radiation hole; 37 ... Waveguide pipe; 37a ... Coaxial waveguide pipe; 37b ... Rectangular wave guide; 39 ... Microwave generating apparatus; 50 ... Control part; 51 ... Process controller; 52 ... User interface; 53 ... Storage part; 100 ... Plasma processing apparatus; 101 ... The annealing in process device; 200 ... Base plate processing system; 301 ... Silicon layer; 303; 305 ... Silicon oxide film; W ... Semiconductor wafer (substrate)
Claims (14)
1. the method for modifying of a dielectric film is characterized in that, comprising:
Silicon oxide film to exposing on the surface of handled object carries out plasma nitridation process, forms the nitrogen treatment operation of oxidized silicon nitride film; With
The modified process of oxidation processes is carried out on the surface of said oxidized silicon nitride film,
Said nitrogen treatment operation is still kept vacuum atmosphere after finishing, and then begins said modified process.
2. the method for modifying of dielectric film as claimed in claim 1 is characterized in that:
Nitrogen concentration is made as N in the film of the oxidized silicon nitride film after said nitrogen treatment operation has just been finished
C0, the desired value of nitrogen concentration in the film of the oxidized silicon nitride film behind the said modified process is made as N
CTThe time, carry out above-mentioned plasma nitridation process and make N
C0＞N
CT
3. the method for modifying of dielectric film as claimed in claim 1 is characterized in that:
Said modified process comprises the plasma oxidation processing that utilizes plasma processing apparatus, and said plasma processing apparatus imports microwave through the flat plane antenna with a plurality of holes and produces the plasma of handling gas in container handling.
4. the method for modifying of dielectric film as claimed in claim 3 is characterized in that:
To a handled object, in the same container handling of said plasma processing apparatus, carry out said plasma nitridation process and said plasma oxidation continuously and handle.
5. the method for modifying of dielectric film as claimed in claim 4 is characterized in that:
After said plasma nitridation process, before said plasma oxidation handles, remove nitrogen residual in said container handling through vacuumizing or clean to handle.
6. like the method for modifying of claim 4 or 5 described dielectric films, it is characterized in that:
Also be included in after said plasma oxidation handles,, in oxidizing atmosphere, handled object carried out the operation of annealing in process with the temperature in the scope more than 800 ℃, below 1100 ℃ as the part of said modified process.
7. like the method for modifying of each described dielectric film in the claim 3～5, it is characterized in that: in the scope of processing pressure more than 67Pa, below the 1333Pa that said plasma oxidation is handled.
8. like the method for modifying of each described dielectric film in the claim 3～5, it is characterized in that: said plasma oxidation is handled and in the scope more than 0.1%, below 20%, is carried out with respect to the volume flow ratio of whole processing gases at oxygen.
9. like the method for modifying of each described dielectric film in the claim 3～5, it is characterized in that: the treatment temperature that said plasma oxidation is handled is in the scope more than 200 ℃, below 600 ℃.
10. like the method for modifying of each described dielectric film in the claim 3～5, it is characterized in that: the processing time that said plasma oxidation is handled is in the scope more than 1 second, below 90 seconds.
11. the method for modifying of dielectric film according to claim 1 or claim 2 is characterized in that:
Utilize plasma processing apparatus to carry out said nitrogen treatment operation, said plasma processing apparatus imports microwave through the flat plane antenna with a plurality of holes and produces the plasma of handling gas in container handling,
Utilize annealing device to carry out said modified process, said annealing device is through carrying out annealing in process with the temperature in the scope more than 800 ℃, below 1100 ℃ to handled object in oxidizing atmosphere.
12. the method for modifying of dielectric film as claimed in claim 11 is characterized in that:
The processing time of said annealing in process is in the scope more than 10 seconds, below 50 seconds.
13. the method for modifying of dielectric film as claimed in claim 12 is characterized in that:
Under vacuum state, carry out from of the handover of said plasma processing apparatus to the handled object of said annealing device.
14. the method for modifying like each described dielectric film in the claim 1～5 is characterized in that: said oxidized silicon nitride film is the gate insulating film of MOS structure devices.
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| JP6040609B2 (en) * | 2012-07-20 | 2016-12-07 | 東京エレクトロン株式会社 | Film forming apparatus and film forming method |
| CN112005344B (en) * | 2018-04-27 | 2023-11-17 | 东京毅力科创株式会社 | Substrate processing system and substrate processing method |
| JP6983322B2 (en) * | 2018-08-02 | 2021-12-17 | 株式会社Fuji | Atmospheric pressure plasma generator |
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| JP5425404B2 (en) * | 2008-01-18 | 2014-02-26 | 東京エレクトロン株式会社 | Method for processing amorphous carbon film and method for manufacturing semiconductor device using the same |
| KR20090080606A (en) * | 2008-01-22 | 2009-07-27 | 주식회사 하이닉스반도체 | Method of manufacturing a flash memory device |
| KR20100012482A (en) * | 2008-07-29 | 2010-02-08 | 주식회사 하이닉스반도체 | Method of forming a tunnel dielectric layer in a flash memory device |
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| KR20120034016A (en) | 2012-04-09 |
| KR101270875B1 (en) | 2013-06-05 |
| JP2012079785A (en) | 2012-04-19 |
| TW201234480A (en) | 2012-08-16 |
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