CN102090153A - Microwave plasma processing device - Google Patents
Microwave plasma processing device Download PDFInfo
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- CN102090153A CN102090153A CN2009801039491A CN200980103949A CN102090153A CN 102090153 A CN102090153 A CN 102090153A CN 2009801039491 A CN2009801039491 A CN 2009801039491A CN 200980103949 A CN200980103949 A CN 200980103949A CN 102090153 A CN102090153 A CN 102090153A
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- microwave
- processing apparatus
- plasma processing
- chamber
- penetrating plate
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
- H05H1/00—Generating plasma; Handling plasma
- H05H1/24—Generating plasma
- H05H1/46—Generating plasma using applied electromagnetic fields, e.g. high frequency or microwave energy
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/511—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using microwave discharges
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32192—Microwave generated discharge
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32192—Microwave generated discharge
- H01J37/32211—Means for coupling power to the plasma
- H01J37/3222—Antennas
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32192—Microwave generated discharge
- H01J37/32211—Means for coupling power to the plasma
- H01J37/32238—Windows
Abstract
In a microwave plasma processing device, a plane antenna (31) for radiating a microwave to form plasma is provided with a plurality of pairs of microwave radiation holes (32) that are different in direction from each other and are concentrically arranged at a central region (31a) and a circumferential region (31c) in the case where the surface of the plane antenna is concentrically divided into the central region (31a), the circumferential region (31c) and a middle region (31b); no microwave radiation hole is formed in the middle region (31b); and a microwave transmission plate (28) is formed at a concave portion (28a) of the microwave radiation surface.
Description
Technical field
The present invention relates to carry out the microwave plasma processing apparatus of the plasma treatment of oxidation processes or nitrogen treatment etc.
Background technology
Plasma treatment is an indispensable technology in the manufacturing of semiconductor equipment, recently, owing to require high integrated, the high speed of LSI, constitute the design rule miniaturization day by day of the semiconductor element of LSI, in addition, the semiconductor wafer maximization that also becomes, thereupon, even in plasma processing apparatus, also require it can tackle this miniaturization and maximization.
But, in the parallel plate-types and inductance coupling high type plasma processing apparatus used more in the past, because electron temperature is higher, therefore, in fine element, can generate plasma damage, in addition, owing to be defined the higher zone of plasma density, therefore, large-scale semiconductor wafer is carried out evenly and plasma treatment at a high speed difficulty relatively.
Therefore, a kind of can receive publicity with RLSA (Radial Line Slot Antenna (the radial line slot antenna)) microwave plasma processing apparatus that high density is formed uniformly the plasma of low electron temperature (for example, international the 2004/008519th trumpeter's volume that discloses).
The RLSA microwave plasma processing apparatus is following device, top at chamber is provided with the flat plane antenna (Radial LineSlot Antenna) that is formed with many slits (slit) with the pattern of stipulating, make the microwave of deriving slit (radiation hole) radiation from flat plane antenna from microwave generation source, and in the chamber that is retained vacuum, radiate via the microwave penetrating plate that constitutes by dielectric that is located under it, the gas that is imported in the chamber by this microwave electric field carry out plasmaization, the handled object of semiconductor wafer etc. is handled by the plasma of such formation.
In this RLSA microwave plasma processing apparatus, can realize high plasma density in the broad regions scope under antenna, can carry out uniform plasma treatment at short notice.In addition, owing to be formed with low electron temperature plasma, therefore, the damage of element is less.
This low damage of research and utilization and the high advantage of uniformity are to being suitable for of various processing such as oxidation processes and nitrogen treatment.
In such microwave plasma processing apparatus, will be formed with the flat plane antenna in many slits (radiation hole) via the waveguide pipe guiding by the microwave that microwave generating apparatus produces.And, propagate microwave from the central part of flat plane antenna to periphery, in this process, see through the microwave penetrating plate that is made of dielectric radiates the circle partial wave in chamber microwave from many slits.By the electromagnetic field that generates by this microwave that is radiated, generate the plasma that imports to the gas in the chamber.
Therefore, in described document, in order to obtain uniform plasma, form the slit of flat plane antenna in basic mode uniformly, and the microwave penetrating plate forms smooth, but, because microwave sees through the microwave penetrating plate that dielectric be made of from slit at the central part from flat plane antenna and radiates in chamber when periphery is propagated, therefore, because the influence of the reflected wave that produces during the microwave penetrating plate that microwave penetrating is made of dielectric etc., microwave can be by introduction chamber be not indoor equably, for example the electric field strength of central portion can become more high than periphery, it is inhomogeneous that electric field strength can become, and has the inhomogeneity situation that can not get desired plasma.In addition, the efficient of microwave is also insufficient.
Summary of the invention
The object of the present invention is to provide a kind of microwave plasma processing apparatus, it is radiated microwaves equably, can form the high plasma of uniformity, and, can import microwave power efficiently.
According to first viewpoint of the present invention, a kind of microwave plasma processing apparatus is provided, form the plasma of handling gas by microwave, and on handled object, implement plasma treatment by this plasma, have: the chamber that contains handled object; The mounting table of mounting handled object in described chamber; The microwave that produces microwave produces the source; The waveguide pipe that will guide to described chamber by the microwave that microwave generation source produces; With the microwave that is imported into described waveguide pipe to flat plane antenna described chamber radiation, that constitute by conductor; Constitute the roof of described chamber, and make microwave penetrating plate microwave penetrating, that constitute by dielectric in the microwave radiation hole by described flat plane antenna; In described chamber, supply with the processing gas supply part of handling gas, described flat plane antenna has a plurality of microwave radiation hole long on the direction, its surface is under the situation of zone line that concentric shape ground is divided into middle section, outer regions, middle section and outer regions, towards different described microwave radiation hole to a plurality of at described middle section and described outer regions assortment with concentric circles, do not form the microwave radiation hole on described zone line, described microwave penetrating plate is formed with recess on its microwave radiation face.
In described first viewpoint, described recess be preferably formed in by mounting on the corresponding part of the handled object on the described mounting table.In addition, described microwave penetrating plate preferably is the cross section arcuation.And preferably corresponding with the described recess of described microwave penetrating plate part is smooth.
According to second viewpoint of the present invention, a kind of microwave plasma processing apparatus is provided, form the plasma of handling gas by microwave, and on handled object, implement plasma treatment by this plasma, have: the chamber that contains handled object; The mounting table of mounting handled object in described chamber; The microwave that produces microwave produces the source; The waveguide pipe that will guide to described chamber by the microwave that microwave generation source produces; With the microwave that is imported into described waveguide pipe to flat plane antenna described chamber radiation, that constitute by conductor; Constitute the roof of described chamber, and make microwave penetrating plate microwave penetrating, that constitute by dielectric in the microwave radiation hole by described flat plane antenna; In described chamber, supply with the processing gas supply part of handling gas, described flat plane antenna has a plurality of microwave radiation hole long on the direction, its surface is under the situation of zone line that concentric shape ground is divided into middle section, outer regions, middle section and outer regions, towards different described microwave radiation hole to a plurality of at described middle section and described outer regions assortment with concentric circles, do not form the microwave radiation hole on described zone line, described microwave penetrating plate forms concavo-convex on its microwave radiation face.
In described second viewpoint, the microwave radiation face of described microwave penetrating plate alternately forms protuberance and recess with concentric shape.
In described first and second viewpoint, described paired microwave radiation hole is preferably formed to a termination of its length direction near, and the other end expands to be opened.Under this situation, preferably constitute described microwave radiation hole each right microwave radiation hole length direction each other angulation be 80～100 °.In addition, it is shorter than the length of the length direction in the microwave penetrating hole that is formed on described outer regions to be preferably formed in the length of length direction in microwave penetrating hole of described middle section.And the microwave radiation face of described microwave penetrating plate can constitute at its circumference has outstanding protuberance in the form of a ring downwards.
According to the present invention, the flat plane antenna of radiated microwaves is constructed as follows: make its surperficial doubting be divided into middle section with concentric shape, under the situation of the zone line of outer regions and middle section and outer regions, towards mutually different microwave radiation hole to a plurality of at described middle section and described outer regions assortment with concentric circles, do not form the microwave radiation hole at described zone line, and, the microwave radiation face of microwave penetrating plate is constituted to be formed with recess or to form concavo-convex, therefore, in the microwave penetrating plate, microwave is propagated to periphery from central division, and see through the microwave penetrating plate from the microwave radiation hole, when microwave is radiated in chamber, make standing wave and reflected wave few, thereby can effectively and evenly radiate, can form the high plasma of uniformity.
Description of drawings
Fig. 1 is the summary cutaway view of the related microwave plasma processing apparatus of expression an embodiment of the invention.
Fig. 2 is the figure of the structure of the expression flat plane antenna that uses microwave plasma processing apparatus shown in Figure 1.
Fig. 3 A is other the cutaway view of structure example that expression is formed on recess on the microwave penetrating plate.
Fig. 3 B is other the cutaway view of structure example that expression is formed on recess on the microwave penetrating plate.
Fig. 3 C is other the cutaway view of structure example that expression is formed on recess on the microwave penetrating plate.
Fig. 3 D is other the cutaway view of structure example that expression is formed on recess on the microwave penetrating plate.
Fig. 3 E is other the cutaway view of structure example that expression is formed on recess on the microwave penetrating plate.
Fig. 4 is the figure of part of the gas supply system of the related microwave plasma processing apparatus of expression other execution mode of the present invention.
Fig. 5 A is the figure of position that the electric-field intensity distribution of Fig. 6 A is obtained in expression.
Fig. 5 B is the figure of position that the electric-field intensity distribution of Fig. 6 B is obtained in expression.
Fig. 6 A is the figure of the electric-field intensity distribution of the arch lower surface of expression when using the microwave penetrating plate of cross section arcuation (arch).
Fig. 6 B is the figure of the electric-field intensity distribution of its lower surface under the situation of the expression microwave penetrating plate that uses even shape.
Fig. 7 A is the figure of position that the electric-field intensity distribution of Fig. 8 A is obtained in expression.
Fig. 7 B is the figure of position that the electric-field intensity distribution of Fig. 8 B is obtained in expression.
Fig. 8 A is from microwave penetrating plate above the down figure of the electric-field intensity distribution of the part of 30mm position of expression when using the microwave penetrating plate of cross section arcuation.
Fig. 8 B is from microwave penetrating plate above the down figure of the electric-field intensity distribution of the part of 30mm position of expression when using the microwave penetrating plate of even shape.
Fig. 9 is the figure of expression as the electron density distribution of the oxidation plasma in each microwave power under the situation of microwave penetrating plate use even shape parts.
Figure 10 is the figure of expression as the electron density distribution of the oxidation plasma in each microwave power under the situation of microwave penetrating plate use cross section arcuation parts.
Figure 11 is the figure of expression as the electron density distribution of the nitridation plasma in each microwave power under the situation of microwave penetrating plate use even shape parts.
Figure 12 is the figure of expression as the electron density distribution of the nitridation plasma in each microwave power under the situation of microwave penetrating plate use cross section arcuation parts.
Figure 13 is the partial sectional view of the microwave plasma processing apparatus of expression other execution mode of the present invention.
Figure 14 is the upward view of the microwave penetrating plate of Figure 13.
Figure 15 is the partial sectional view of the microwave plasma processing apparatus of expression other execution mode of the present invention.
Embodiment
Below, the limit is with reference to accompanying drawing, and the limit describes embodiments of the present invention.
Fig. 1 is a cutaway view of schematically representing the microwave plasma processing apparatus of an embodiment of the invention.This plasma processing unit is by having the flat plane antenna of many slits, especially by RLSA (Radial Line Slot Antenna; Radial transmission line slit (slit) antenna) import microwave and produce plasma in process chamber, thus, formation can produce the RLSA microwave plasma processing apparatus of the microwave plasma of high density and low electron temperature.
This plasma processing unit 100 constitutes air-tightness, has the chamber 1 roughly cylindraceous of ground connection.Substantial middle portion at the diapire 1a of chamber 1 is formed with circular peristome 10, is formed with the exhaust chamber 11 that is communicated with and gives prominence to this peristome 10 on diapire 1a downwards.
Be provided with pedestal (mounting table) 2 in chamber 1, this pedestal 2 is made of potteries such as AlN, is used for horizontal supporting as the semiconductor wafer of processed substrate (below, note is made " wafer ") W.This pedestal 2 is supported by support unit 3, and this support unit 3 is cylindric for what extend upward from the bottom center of exhaust chamber 11, and is made of potteries such as AlN.Be provided with the guided rings 4 that is used to guide wafer W in the outer edge of pedestal 2.In addition, be embedded with the heater 5 of resistance heating type in pedestal 2, this heater 5 is by being powered from heater power source 6 and pedestal 2 is heated, thereby by this heat, the wafer W as handled object heated.At this moment, for example treatment temperature can be controlled in the scope of room temperature to 800 ℃.In addition, at the liner cylindraceous 7 that constitutes by the less highly purified quartz of impurity that is provided with in interior week of chamber 1.Prevent the pollution of metal etc. by this liner 7, and can form clean environment.In addition, for to carrying out even exhaust in the chamber 1, be provided with the shield 8 of ring-type at the outer circumferential side of pedestal 2, this shield 8 is made of the less highly purified quartz of impurity, has a plurality of steam vent 8a, and this shield 8 is by a plurality of pillars 9 supportings.
On pedestal 2, be used for supporting wafer W and the wafer supporting pin (not shown) of its lifting can be provided with respect to surface outstanding (stretching out), the retraction of pedestal 2 (returning).
The gas that the sidewall of chamber 1 is provided with in the form of a ring imports parts 15, has been formed uniformly gas radiation hole.On these gas importing parts 15, be connected with gas supply part 16.Gas imports parts can be configured to shower shape (spray shape, showerhead).This gas supply part 16 has for example Ar gas supply source 17, O
2 Gas supply source 18, H
2 Gas supply source 19, these gases arrive gas via gas line 20 respectively and import parts 15, and the gas radiation hole that imports parts 15 from gas imports in the chamber 1 equably.On each gas line 20, be provided with mass flow controller 21 with and the open and close valve 22 of front and back.In addition,,, for example gases such as Kr, He, Ne, Xe can also be used, in addition, rare gas can also be do not comprised as described later as other rare gas except Ar gas.
Be connected with blast pipe 23 in the side of described exhaust chamber 11, on this blast pipe 23, be connected with the exhaust apparatus 24 that comprises high speed vacuum pump.And, moving by making this exhaust apparatus 24, the gas in the chamber 1 is discharged in the 11a of the space of exhaust chamber 11 equably, and carries out exhaust via blast pipe 23.Thus, can make reduce pressure at high speed in the chamber 1 specified vacuum degree, for example 0.133Pa.
Sidewall at chamber 1 is provided with: and the carrying room (not shown) adjacent with plasma processing apparatus 100 between be used to carry out that moving into of wafer W take out of moves into and take out of mouthfuls 25; With being moved into, this takes out of mouthful 25 gate valves that open and close 26.
The top of chamber 1 becomes peristome, and at the cap (lid) 27 that is provided with ring-type on this peristome in chamber 1 in the mode of giving prominence to along circumference, its ledge becomes support 27a.By dielectric, for example quartz or Al
2O
3, pottery such as AlN constitutes, and the microwave penetrating plate 28 of microwave penetrating of the round partial wave of microwave radiation hole 32 (slit) radiation from flat plane antenna 31 described later is arranged on this support 27 airtightly via seal member 29.Thus, be retained in the chamber 1 airtight.This microwave penetrating plate 28 of microwave penetrating radiates in chamber 1, generates an electromagnetic field in chamber 1.This microwave penetrating plate 28 is formed with recess 28a at the central portion of the microwave radiation face of its lower surface.And recess 28a is shaped as the cross section arcuation, and the diameter of recess 28a is bigger than the diameter of wafer W, and the part corresponding with wafer W of recess 28a is even shape.The thickness of the microwave penetrating plate 28 of the part corresponding with recess 28a of this moment is preferably 1/4 * λ g (λ g: the wavelength in pipe of microwave).Be under the situation of 2.45GHz for example, be preferably 10～30mm (1/10 * λ g～1/4 * λ g) at microwave.In addition, the height of recess 28 is preferably 15～25mm (1/8 * λ g～1/5 * λ g).
Above microwave penetrating plate 28, the mode with relative with pedestal 2 is provided with discoideus flat plane antenna 31.These flat plane antenna 31 fastenings are in the sidewall upper of chamber 1.Flat plane antenna 31 has the diameter bigger slightly than microwave penetrating plate 28, be to be the conductive material of 0.1～several mm (for example 1mm) by thickness, for example the surface is by the plectane of silver-plated or gold-plated copper or aluminium or Ni formation, and a plurality of microwave radiation hole 32 (slit) forms with the pattern of regulation with connecting.
Specifically, as shown in Figure 2, microwave radiation hole 32 has long in one direction shape, and is paired towards two different microwave radiation holes 32, microwave radiation hole 32 radiated the microwave of round partial wave from this.And, be divided into concentric shape at face under the situation of zone line 31b of middle section 31a, outer regions 31c and middle section and outer regions flat plane antenna 31, such microwave radiation hole 32 a plurality of to having with the concentric circles assortment in middle section 31a and outer regions 31c do not form microwave radiation hole 32 at zone line 31b.Distance at the center of the central point in the microwave radiation hole 32 of the inboard that makes middle section 31a and flat plane antenna 31 is 1 o'clock, and the distance at the central point in the microwave radiation hole 32 of the inboard of preferred exterior lateral area and the center of flat plane antenna 31 is 2～4, most preferably is 2.58.
The end that paired microwave radiation hole 32 forms its length direction is close, and the other end expands opens (opening), and in Fig. 2, length direction angulation each other is about 90 °.This angle is preferably 80～100 °, more preferably 85～95 °.In addition, microwave radiation hole 32 in Fig. 2 with respect to having angle near 45 ° from the center of flat plane antenna 31 by the line at its length direction center.Preferred 40～50 ° of this angle.And the length of length direction in microwave radiation hole 32 that is formed on middle section 31a is shorter than the length of the length direction in the microwave radiation hole 32 that is formed on outer regions 31c.In addition, the microwave radiation hole 32 of outer regions 31c and middle section 31a to all uniformly-spaced to form.In this embodiment, microwave radiation hole 32 to being provided with 24 at outer regions 31c, be provided with 6 at middle section 31a.But, these numbers are not particularly limited, and can characteristic as requested determine.
About the recess 28a of described microwave penetrating plate 28 and the position relation in microwave radiation hole 32, preferred recess 28a relates to mutually with at least a portion in the microwave penetrating hole 32 of the inboard of the centering in the microwave radiation hole 32 that is formed on outer regions 31c.Thus, can improve electric field strength in the lower surface of the part corresponding with the recess 28a of microwave penetrating plate 28.
At the upper surface of this flat plane antenna 31, be provided with the slow wave spare (slow wave structure, slow wave structure) 33 that constitutes by for example resins such as quartz, polytetrafluoroethylene, polyimides with dielectric constant bigger than vacuum.This slow wave spare 33 because the wavelength of microwave is elongated in a vacuum, therefore, has wavelength that shortens microwave and the function of adjusting plasma.In addition, between flat plane antenna 31 and the microwave penetrating plate 28, in addition, difference is bonding between slow wave spare 33 and the flat plane antenna 31 disposes (connecting airtight), but also can dispose discretely.The configuration of the slit 32 by flat plane antenna 31 and slow wave spare 33 can the inhibitory reflex ripples, can improve microwave and import efficient.
At the upper surface of chamber 1, be provided with the cap assembly with waveguide pipe function 34 that for example constitutes by metal materials such as aluminium or stainless steel, copper in the mode that covers these flat plane antennas 31 and slow wave spare 33.The upper surface of chamber 1 and cap assembly 34 are sealed by seal member 35.Be formed with cooling water stream 34a on cap assembly 34, the cooling water that circulates in this cooling water stream 34a thus, cools off cap assembly 34, slow wave spare 33, flat plane antenna 31, microwave penetrating plate 28.Thus, can prevent that microwave penetrating plate 28, flat plane antenna 32, slow wave spare 33, cap assembly 34 from causing distortion and damaged because of plasma is heated.In addition, cap assembly 34 ground connection.
Central authorities at the upper wall of cap assembly 34 are formed with peristome 36, are connected with waveguide pipe 37 on this peristome.In the end of this waveguide pipe 37, be connected with microwave generating apparatus 39 via matching circuit 38.Thus, the microwave of for example frequency 2.45GHz that is produced by microwave generating apparatus 39 phoresys to described flat plane antenna 31 via waveguide pipe 37.In addition, as the frequency of microwave, can use 8.35GHz, 1.98GHz etc.
Waveguide pipe 37 comprises the coaxial waveguide pipe 37a of the cross section circle of extending upward from the peristome 36 of described cap assembly 34; With the rectangular wave guide 37b that extends in the horizontal direction that is connected via mode converter 40 in the upper end of this coaxial waveguide pipe 37a.Mode converter 40 between rectangular wave guide 37b and the coaxial waveguide pipe 37a has and will be transformed into the function of TEM pattern with the microwave of TE mode propagation in rectangular wave guide 37b.Be extended with metal inner wires 41 such as stainless steel (SUS), copper, aluminium at the center of coaxial waveguide pipe 37a, the bottom of this inner wire 41 is inserted among the hole 31d at the center that is formed on flat plane antenna 31, and is connected fixing by screw thread from opposition side.Thus, microwave is evenly propagated to the flat waveguide pipe that is formed by flat plane antenna 31 and cap assembly 34 effectively via the inner wire 41 of coaxial waveguide pipe 37a, and sees through microwave penetrating plate 28 radiation in chamber 1 equably from the microwave penetrating hole 32 of flat plane antenna 31.
Each component part of microwave plasma processing apparatus 100 is connected on the have microprocessor process controller 50 of (computer) and Be Controlled.In process controller 50, be connected with user interface 51 and storage part 52, wherein, the keyboard of user interface 51 input operation of instructing for article on plasma body processing unit 100 manages etc. and display that the operational situation of plasma processing apparatus 100 shows visually etc. is constituted by the operator; Storage part 52 stores scheme (recipe), and this scheme promptly is used for being used for carrying out the program of handling in each component part of plasma processing apparatus 100 by the control program of the various processing of plasma processing apparatus 100 execution and according to treatment conditions by the control realization of process controller 50.Scheme is stored in the storage medium in the storage part 52.Storage medium can be hard disk or semiconductor memory, also can be memory movably such as CDROM, DVD, flash memory.In addition, can also for example scheme suitably be transmitted from other device via special circuit.
And, as required, by from indication of user interface 51 etc., scheme accesses and makes it to carry out process controller 50 from storage part 52 arbitrarily, thus, under the control of process controller 50, can in plasma processing apparatus 100, carry out desirable processing.
Below, the action of carrying out the plasma oxidation processing according to the plasma processing apparatus 100 that constitutes is like this described.
At first, the valve 26 that opens the sluices is taken out of mouthful 25 wafer W that should carry out oxidation processes and is moved in the chamber 1 from moving into, and is positioned on the pedestal 2.
Then, from the Ar gas supply source 17 and the O of gas supply system 16
2 Gas supply source 18 imports Ar gas and O with the flow of regulation and via gas importing parts 15 in chamber 1
2Gas maintains predetermined process pressure.Processing pressure in the chamber 1 for example is the scope of 6.7～677Pa.In addition, the ratio (flow-rate ratio is a volume ratio) of the oxygen in the processing gas is 0.1～100%.Handle the flow of gas, for example, Ar gas: 0～5000mL/min, O
2Gas: 1～1000mL/min.
In addition, except from Ar gas supply source 17 and O
2The Ar gas and the O of gas supply source 18
2Beyond the gas, can also be with requirement ratio from H
2 Gas supply source 19 imports H
2Gas.By supplying with H
2Gas can improve the oxidation ratio in the plasma oxidation processing.This be because, by supplying with H
2Gas generates the OH free radical, and it helps to improve the oxidation ratio.Under this situation, H
2Ratio be preferably 0.1～10% with respect to the amount of handling gas integral body.H
2The flow of gas is preferably 1～500mL/min (sccm).
In addition, treatment temperature can be 200～800 ℃ scope, preferred 400～600 ℃.
Next, will be from the microwave of microwave generating apparatus 39 via matching circuit 38 guiding waveguide pipe 37.Microwave is fed into flat plane antenna 31 by rectangular wave guide 37b, mode converter 40 and coaxial waveguide pipe 37a successively.Microwave phoresys with the TE pattern in rectangular wave guide 37b, the microwave of this TE pattern is transformed into the TEM pattern by mode converter 40, and in coaxial waveguide pipe 37a, phoresy to the flat waveguide pipe that constitutes by flat plane antenna 31 and cap assembly 34, thereby from the microwave radiation hole 32 of flat plane antenna 31 to being radiated as the circle partial wave, and the superjacent air space that sees through the wafer W of microwave penetrating plate 28 to chamber 1 in radiates.At this moment, the power of microwave generating apparatus 39 is preferably 0.5～5kW (0.2～2.5W/cm
2).
In chamber 1, form electromagnetic field, Ar gas, O by the microwave that in chamber 1, radiates via microwave penetrating plate 28 from flat plane antenna plate 31
2Gas etc. are by plasmaization, by this plasma the silicon face of wafer W are carried out oxidation.This microwave plasma by microwave radiation hole 32 radiated microwaves from the majority of flat plane antenna plate 31, becomes roughly 1 * 10
10～5 * 10
12/ cm
3Or above highdensity plasma, its electron temperature is reduced to about 0.5～2eV, is being reduced to below the 1.1eV near the wafer.That is, owing to be the plasma of low electron temperature, therefore,, has the advantage that can form high-quality silicon oxide layer because of the ion in the plasma etc. causes the damage of oxide-film to reduce.
But, microwave is propagated to periphery in flat plane antenna 31 from central division, in this process, the microwave of circle partial wave sees through the microwave penetrating plate 38 that is made of dielectric from a plurality of slits 32 and radiates in chamber 1, but, when seeing through the microwave penetrating plate 28 that constitutes by dielectric, because the influence of generation reflected wave etc., microwave can not be imported in the chamber equably, for example central portion partly becomes more high than the electric field strength of periphery, and the electric field strength of dielectric inside becomes inhomogeneous, therefore, generation can not obtain the inhomogeneity situation of desired plasma, not necessarily can carry out uniform plasma treatment.Therefore, the film thickness uniformity of oxide-film becomes 5% front and back.
Therefore, in the present embodiment, as flat plane antenna 31, as shown in Figure 2, under the situation of the zone line 31b that concentric shape ground, the surface of flat plane antenna 31 is divided into middle section 31a, outer regions 31c and these middle sections and outer regions, the microwave radiation hole 32 of the microwave of radiation circle partial wave have a plurality ofly in middle section 31a and outer regions 31c, being the concentric circles assortment, do not form microwave radiation hole 32 at zone line 31b.Thus, microwave is propagated to periphery from the central part of microwave penetrating plate 28, in 32 whens radiation from the microwave radiation hole, can radiate equably.In addition, owing on the microwave radiation face of microwave penetrating plate 28, be formed with recess 28a, therefore, the thickness attenuation of the central portion of microwave penetrating plate 28, generation that can the inhibitory reflex ripple and radiated microwaves effectively, and, can will radiate under its inhomogeneity state keeping from the uniform microwave of the slit 32 of flat plane antenna 31.Therefore, increase microwave penetrating plate 28 the microwave radiation face electric field strength and it is become evenly, can improve the inner evenness of plasma intensity.Especially, under the situation of present embodiment, recess 28a is shaped as the cross section arcuation, the diameter of recess 28a is bigger than the diameter of wafer W, and the part corresponding with the wafer W of recess 28a becomes even shape, so, on the part corresponding, be formed uniformly electric field with wafer W, and, also supplied with electric field from the side of wafer W.Therefore, the uniformity of the electric field strength in the wafer W face is higher.
In addition, the termination to the length direction that forms its each microwave radiation hole 32 that is formed on microwave radiation hole 32 on the flat plane antenna 31 is near, and the other end expands and opens, and therefore, can access the microwave power effect of importing to chamber 1 in efficiently and equably.In addition, make these length directions each other angulation be 80～100 °, be preferably 85～95 °, for example by forming about 90 °, can further improve the power efficiency and the uniformity that import the microwave in the chamber 1.In addition, the power efficiency and the uniformity that are imported into the microwave in the chamber 1 thus, similarly, can further be improved with respect to the angle of the line one-tenth that passes through its length direction center from the center of flat plane antenna 31 near 45 ° in microwave radiation hole 32.And, the length of length direction that is formed on the microwave radiation hole 32 of middle section 31a forms shortlyer than the length of the length direction in the microwave radiation hole 32 that is formed on outer regions 31c, thus, similarly can further improve the power efficiency and the uniformity of microwave.
In addition, in said embodiment, the recess 28a of microwave penetrating plate 28 is the cross section arcuation, but be not limited thereto, can adopt the such such different shapes such as dome-type recess 28f of the recess 28e with cut-out (step) shape, Fig. 3 E of recess 28d, Fig. 3 D of the such cross section rectangle of the such cross section of recess 28b, Fig. 3 B of the such cross section chevron of Fig. 3 A trapezoidal recess 28c, Fig. 3 C.But, microwave penetrating plate 28 effects as shown in Figure 1 are best.
Below, other execution mode of the present invention is described.
In execution mode before, the microwave plasma processing apparatus that carries out oxidation processes is illustrated, but, in the present embodiment, replace oxidation processes and carry out nitrogen treatment.Fig. 4 is the figure of part of gas supply system of the microwave plasma processing apparatus of expression present embodiment, as shown in Figure 4, in the present embodiment, replaces gas supply system 16, use to have Ar gas supply source 17 ', N
2Gas supply source 18 ' gas supply system 16 ', with Ar gas and N
2When gas is supplied with in chamber 1, thereby the microwave plasma that similarly forms nitrogen carries out nitrogen treatment, and structure in addition is identical with Fig. 1.As the condition of nitrogen treatment of this moment, for example, the pressure that can list temperature and be in 300～800 ℃, chamber 1 is that 1.3～133Pa, Ar gas flow are 0～5000mL/min, N
2Gas flow is 1～1000mL/min.
Below, analog result is described.Here, show the analog result of microwave plasma processing apparatus, wherein, in microwave plasma processing apparatus, as flat plane antenna, use flat plane antenna shown in Figure 2, use the microwave penetrating plate of the cross section arcuation of even shape and Fig. 1 as the microwave penetrating plate.The condition of this moment is as follows.In addition, simulation is carried out under the following conditions: plasma electron density is 5～9 * 10 near the lower surface of microwave penetrating plate
10/ cm
3, from the upper surface of microwave penetrating plate down the plasma electron density of the position of 66.5mm be 1 * 10
12/ cm
3
Boundary condition: complete conductor
Microwave frequency: 2.45G
Input power: 2000W
Microwave penetrating plate: SiO
2
Dielectric constant: SiO
2=4.2, air=1.0
Cavity indoor pressure: 13.3Pa (100mTorr)
Temperature: 500 ℃
At first, under this condition, supply with microwave and, the lower surface electric field strength of the microwave penetrating plate of this moment is simulated from microwave penetrating plate radiated microwaves.
Under the situation of the microwave penetrating plate of the cross section arcuation that uses Fig. 1, shown in Fig. 5 A, obtain by electric-field intensity distribution along the face shown in the L1 line of the lower surface of the arch of microwave penetrating plate, under the situation of the microwave penetrating plate that uses even shape, shown in Fig. 5 B, obtain the electric-field intensity distribution of the lower surface (L2 line) of microwave penetrating plate.Its result is represented in Fig. 6 A, Fig. 6 B respectively.Under the situation of microwave penetrating plate that is the cross section arcuation, as shown in Figure 6A, with higher and even as the electric field strength in the wafer W corresponding concave part of the lower surface of microwave radiation face, and in contrast to this, under the situation of microwave penetrating plate that is even shape, shown in Fig. 6 B, as the lower surface of microwave radiation face, the electric field strength of integral part that comprises the part corresponding with wafer is lower and inhomogeneous.
Secondly, the electric field strength of the short transverse of simulated microwave transmitting plate.
Under the situation of the microwave penetrating plate of the cross section arcuation that uses Fig. 1, shown in Fig. 7 A, obtain from the upper surface of the microwave penetrating plate electric-field intensity distribution of the part of 30mm position down, under the situation of the microwave penetrating plate that uses even shape, shown in Fig. 7 B, obtain from the upper surface of the microwave penetrating plate electric-field intensity distribution of the part of 30mm position down.And its result is illustrated respectively among Fig. 8 A, Fig. 8 B.Under the situation of microwave penetrating plate that is the cross section arcuation, shown in Fig. 8 A, generally electric field strength is higher and uniformity is also high, but, under the situation of microwave penetrating plate that is even shape, shown in Fig. 8 B, the part spot that electric field strength is high exists assortedly, and electric field strength and uniformity are all lower.This is owing to during as the inside of dielectric microwave penetrating plate, have the part that produces reflected wave in microwave penetrating.
Below, obtain power-balance from analog result.Its result is that under the situation of the microwave penetrating plate that uses the cross section arcuation, in the power of whole 2000W, the power that enters chamber is 1344W, is 1301W by the plasma power absorbed, is reflected into 656W.On the other hand, under the situation of the microwave penetrating plate that uses even shape, in the power of whole 2000W, enter the 234W that is of chamber, be 216W, be reflected into 1766W by what plasma absorbed.From its result as can be known, under situation of the present invention, can supply with microwave effectively by the utmost point.
Below, reality is formed plasma, the knot that carries out oxidation processes describes.
Here, use parts shown in Figure 2 as flat plane antenna, use the parts of cross section even shape and Fig. 1 arcuation as the microwave penetrating plate, by using the microwave plasma processing apparatus of above-mentioned parts respectively, the at first actual distribution that forms oxidation plasma and obtain the electron density in the plasma.As condition, to make cavity indoor pressure be 133Pa (1Torr), make the Ar gas flow is 1500mL/min (sccm), make O
2Gas flow is 150mL/min (sccm), makes microwave power be changed to 2000W, 3000W, 4000W.The electron density distribution of this moment is illustrated among Fig. 9 and Figure 10.As shown in these figures as can be known, than the microwave penetrating plate that uses even shape, the uniformity of the electron density under the situation of the microwave penetrating plate of use cross section arcuation in the plasma is higher.
Below, by same device, the actual oxidation processes of carrying out.As condition, to make cavity indoor pressure be 266Pa (2Torr), make the Ar gas flow is 2000mL/min (sccm), make O
2Gas flow is 200mL/min (sccm), make microwave power be transformed to 2000W, 3000W, 4000W, make base-plate temp and be 400 ℃ and carry out the oxidation processes of 30sec, obtains film thickness distribution in the face of oxide-film.
Under the situation of the microwave penetrating plate that uses even shape, average film thickness is 1.22nm under the situation of 2000W, standard deviation is 3.39%, average film thickness is 1.34nm under the situation of 3000W, standard deviation is 2.27%, with respect to this, under the situation of the microwave penetrating plate of the Fig. 1 that uses the cross section arcuation, average film thickness is 1.16nm under the situation of 2000W, standard deviation is 0.90%, and average film thickness is 1.26% under the situation of 3000W, and standard deviation is 1.02%, the combination of the antenna by Fig. 2 and the microwave penetrating plate of cross section arcuation can confirm that the film thickness distribution of the oxide-film in the wafer face becomes less.
Secondly, reality is formed plasma, and the result who carries out nitrogen treatment describes.
Here similarly, adopt as flat plane antenna and use parts shown in Figure 2 and use the microwave plasma processing apparatus of the parts of cross section even shape and Fig. 1 arcuation as the microwave penetrating plate.At first, the actual distribution that forms nitridation plasma and obtain the electron density in the plasma.As condition, to make cavity indoor pressure be 6.7Pa (50mTorr), make the Ar gas flow is 1000mL/min (sccm), make N
2Gas flow is 40mL/min (sccm), makes microwave power be changed to 600W, 800W, 1000W, 1500W, 2000W.The electron density distribution of this moment is illustrated among Figure 11 and Figure 12.As shown in these figures, owing to be under low-pressure state, to carry out plasma under the situation of nitridation plasma to generate, therefore, distribute with different under situation as the oxidation plasma of higher pressure, but, still can confirm, when being the microwave penetrating plate of even shape, plasma electron density distributes and has the uneven tendency that becomes, and the uniformity of the electron density under the situation of the microwave penetrating plate that uses the cross section arcuation in the plasma is higher.
Below, by same device, the actual nitrogen treatment that carries out.Condition is identical with described condition, and to make cavity indoor pressure be 6.7Pa (50mTorr), make the Ar gas flow is 1000mL/min (sccm), make N
2Gas flow is 40mL/min (sccm), and making microwave power be changed to 600W, 800W, 1000W, 1500W, 2000W, making base-plate temp is 250 ℃, carries out the nitrogen treatment of 30sec, obtains the interior film thickness distribution of face of nitride film.
Under the situation of the microwave penetrating plate that uses even shape, when 800W, the thickness of nitride film becomes the most even, and average film thickness is 1.74nm, and standard deviation is 1.25%, in contrast to this, under the situation of the microwave penetrating plate of the Fig. 1 that uses the cross section arcuation, when 1500W, the thickness of nitride film becomes the most even, average film thickness is 2.02nm, and standard deviation is 0.62%.Hence one can see that, the combination of the antenna by Fig. 2 and the microwave penetrating plate of cross section arcuation, and the film thickness distribution of the nitride film in the wafer face diminishes.
Below, other execution mode of the present invention is described.
Figure 13 is the partial sectional view of the microwave plasma processing apparatus of expression other execution mode of the present invention.As shown in figure 13,,, use the microwave penetrating face of its lower surface to form concavo-convex parts here as microwave penetrating plate 28.Particularly, shown in the upward view of Figure 14, protuberance 28g and recess 28h alternately form concentric circles.
By such structure, can effectively prevent from the face of microwave penetrating plate 28, to form standing wave on the direction, even by so concavo-convex microwave penetrating plate 28, also can improve the uniformity of the microwave of radiation, and radiated microwaves efficiently.
In addition, the assortment of protuberance and recess not necessarily is defined in concentric circles, can also be suitable for other various assortments.
Below, other embodiment of the present invention is described.
Figure 15 is the partial sectional view of the microwave plasma processing apparatus of expression other execution mode of the present invention.As shown in figure 15, here, as microwave penetrating plate 28, use its outboard end be formed with from microwave radiation towards below the parts of protuberance 28i of outstanding ring-type.
By such structure, can further stop the plasma of generation chamber 1 in spread laterally by protuberance 28i, can effectively prevent the damage of support 27 parts such as grade and paradoxical discharge etc.
In addition, the invention is not restricted to described execution mode, can carry out various distortion.For example, in said embodiment, the situation that the present invention is applicable to oxidation processes and nitrogen treatment is represented, still, be not limited thereto, the present invention can also be applicable to other surface.In addition, be not limited to such surface treatment, also be applicable in other the plasma treatment such as etching, resist ashing and CVD.In addition, in said embodiment,, be illustrated as example, but be not limited thereto, can also be applicable to other handled object such as flat panel display (FPD) substrate certainly with the situation of using semiconductor wafer as handled object.
Claims (14)
1. a microwave plasma processing apparatus forms the plasma of handling gas by microwave, by this plasma handled object is implemented plasma treatment, it is characterized in that, comprising:
Contain the chamber of handled object;
The mounting table of mounting handled object in described chamber;
The microwave that produces microwave produces the source;
The microwave that will be produced by microwave generation source is to the waveguide pipe of described chamber channeling conduct;
The flat plane antenna that the microwave that is directed to described waveguide pipe is radiated to described chamber, constitute by conductor;
Constitute the roof of described chamber, make microwave penetrating plate microwave penetrating, that constitute by dielectric in the microwave radiation hole by described flat plane antenna; With
In described chamber, supply with the processing gas supply part of handling gas,
Described flat plane antenna has a plurality of microwave radiation hole long on the direction, be under the situation of zone line that concentric shape ground is divided into middle section, outer regions and middle section and outer regions on the surface that makes described flat plane antenna, towards different described microwave radiation hole to having a plurality of at described middle section and described outer regions assortment with concentric circles, do not form the microwave radiation hole at described zone line
Described microwave penetrating plate is formed with recess on its microwave radiation face.
2. microwave plasma processing apparatus as claimed in claim 1 is characterized in that:
Described paired microwave radiation hole shape becomes, and a termination of its length direction is near, and the other end expands to be opened.
3. microwave plasma processing apparatus as claimed in claim 2 is characterized in that:
Constitute described microwave radiation hole each right microwave radiation hole length direction each other angulation be 80～100 °.
4. microwave plasma processing apparatus as claimed in claim 1 is characterized in that:
The length of length direction in microwave penetrating hole that is formed on described middle section is shorter than the length of the length direction that is formed on the microwave penetrating hole on the described outer regions.
5. microwave plasma processing apparatus as claimed in claim 1 is characterized in that:
Described recess is formed on and the corresponding part of the handled object of mounting on described mounting table.
6. microwave plasma processing apparatus as claimed in claim 5 is characterized in that:
Described microwave penetrating plate is the cross section arcuation.
7. microwave plasma processing apparatus as claimed in claim 6 is characterized in that:
The part corresponding with the described recess of described microwave penetrating plate is smooth.
8. microwave plasma processing apparatus as claimed in claim 1 is characterized in that:
The microwave radiation face of described microwave penetrating plate has outstanding protuberance in the form of a ring downwards at its circumference.
9. microwave plasma processing apparatus, this microwave plasma processing apparatus forms the plasma of handling gas by microwave, by this plasma handled object is implemented plasma treatment, it is characterized in that, comprising:
Contain the chamber of handled object;
The mounting table of mounting handled object in described chamber;
The microwave that produces microwave produces the source;
The microwave that will be produced by microwave generation source is to the waveguide pipe of described chamber channeling conduct;
With the microwave that is directed to described waveguide pipe to flat plane antenna described chamber radiation, that constitute by conductor;
Constitute the roof of described chamber, make microwave penetrating plate microwave penetrating, that constitute by dielectric in the microwave radiation hole by described flat plane antenna; With
In described chamber, supply with the processing gas supply part of handling gas,
Described flat plane antenna has a plurality of microwave radiation hole long on the direction, be under the situation of zone line that concentric shape ground is divided into middle section, outer regions and middle section and outer regions on the surface that makes described flat plane antenna, towards different described microwave radiation hole to having a plurality of at described middle section and described outer regions assortment with concentric circles, do not form the microwave radiation hole at described zone line
Described microwave penetrating plate forms concavo-convex on its microwave radiation face.
10. microwave plasma processing apparatus as claimed in claim 9 is characterized in that:
Described paired microwave radiation hole shape becomes, and a termination of its length direction is near, and the other end expands to be opened.
11. microwave plasma processing apparatus as claimed in claim 10 is characterized in that:
Constitute described microwave radiation hole each right microwave radiation hole length direction each other angulation be 90 °.
12. microwave plasma processing apparatus as claimed in claim 9 is characterized in that:
The length of length direction in microwave penetrating hole that is formed on described middle section is shorter than the length of the length direction in the microwave penetrating hole that is formed on described outer regions.
13. microwave plasma processing apparatus as claimed in claim 9 is characterized in that:
The microwave radiation face of described microwave penetrating plate alternately forms protuberance and recess with concentric shape.
14. microwave plasma processing apparatus as claimed in claim 9 is characterized in that:
The microwave radiation face of described microwave penetrating plate has outstanding protuberance in the form of a ring downwards at its circumference.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008021346 | 2008-01-31 | ||
| JP2008-021346 | 2008-01-31 | ||
| PCT/JP2009/051563 WO2009096515A1 (en) | 2008-01-31 | 2009-01-30 | Microwave plasma processing device |
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| Publication Number | Publication Date |
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| CN102090153A true CN102090153A (en) | 2011-06-08 |
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| CN2009801039491A Pending CN102090153A (en) | 2008-01-31 | 2009-01-30 | Microwave plasma processing device |
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|---|---|
| US (1) | US20100307685A1 (en) |
| JP (1) | JP5422396B2 (en) |
| KR (1) | KR20100106602A (en) |
| CN (1) | CN102090153A (en) |
| WO (1) | WO2009096515A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109477213A (en) * | 2016-07-28 | 2019-03-15 | 尼奥科特股份公司 | It prepares the method for the annular membrane of synthetic material and implements the device of this method |
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| JP2012109080A (en) * | 2010-11-16 | 2012-06-07 | Tokyo Electron Ltd | Plasma processing apparatus and plasma processing method |
| JP2014112644A (en) * | 2012-11-06 | 2014-06-19 | Tokyo Electron Ltd | Plasma processing apparatus and plasma processing method |
| JP6134274B2 (en) * | 2014-02-17 | 2017-05-24 | 株式会社東芝 | Semiconductor manufacturing apparatus and semiconductor device manufacturing method |
| JP2016086099A (en) * | 2014-10-27 | 2016-05-19 | 東京エレクトロン株式会社 | Plasma processing apparatus |
| WO2020188744A1 (en) * | 2019-03-19 | 2020-09-24 | 株式会社Ｋｏｋｕｓａｉ Ｅｌｅｃｔｒｉｃ | Method for manufacturing semiconductor device, substrate processing device, and program |
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- 2009-01-30 JP JP2009551593A patent/JP5422396B2/en not_active Expired - Fee Related
- 2009-01-30 US US12/865,519 patent/US20100307685A1/en not_active Abandoned
- 2009-01-30 KR KR1020107018924A patent/KR20100106602A/en not_active Application Discontinuation
- 2009-01-30 CN CN2009801039491A patent/CN102090153A/en active Pending
- 2009-01-30 WO PCT/JP2009/051563 patent/WO2009096515A1/en active Application Filing
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2009096515A1 (en) | 2009-08-06 |
| KR20100106602A (en) | 2010-10-01 |
| JP5422396B2 (en) | 2014-02-19 |
| JPWO2009096515A1 (en) | 2011-05-26 |
| US20100307685A1 (en) | 2010-12-09 |
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Application publication date: 20110608 |