US20030232513A1 - Plasma method and apparatus for processing a substrate - Google Patents
Plasma method and apparatus for processing a substrate Download PDFInfo
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- US20030232513A1 US20030232513A1 US10/170,925 US17092502A US2003232513A1 US 20030232513 A1 US20030232513 A1 US 20030232513A1 US 17092502 A US17092502 A US 17092502A US 2003232513 A1 US2003232513 A1 US 2003232513A1
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- 239000000758 substrate Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000012545 processing Methods 0.000 title claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 20
- 150000002500 ions Chemical class 0.000 claims description 19
- 235000012239 silicon dioxide Nutrition 0.000 claims description 15
- 238000012546 transfer Methods 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- -1 nitrogen ions Chemical class 0.000 claims description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 2
- 210000002381 plasma Anatomy 0.000 description 55
- 238000010348 incorporation Methods 0.000 description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 230000008878 coupling Effects 0.000 description 8
- 238000010168 coupling process Methods 0.000 description 8
- 238000005859 coupling reaction Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 230000007246 mechanism Effects 0.000 description 6
- 239000000523 sample Substances 0.000 description 5
- 239000003574 free electron Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—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
- 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
- H01J37/32082—Radio frequency generated discharge
- H01J37/321—Radio frequency generated discharge the radio frequency energy being inductively coupled to the 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
- H01L21/02104—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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/314—Inorganic layers
- H01L21/3143—Inorganic layers composed of alternated layers or of mixtures of nitrides and oxides or of oxinitrides, e.g. formation of oxinitride by oxidation of nitride layers
- H01L21/3144—Inorganic layers composed of alternated layers or of mixtures of nitrides and oxides or of oxinitrides, e.g. formation of oxinitride by oxidation of nitride layers on silicon
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/314—Inorganic layers
- H01L21/318—Inorganic layers composed of nitrides
- H01L21/3185—Inorganic layers composed of nitrides of siliconnitrides
Definitions
- This invention relates to a plasma reactor and a method of processing a substrate by creating a plasma.
- the manufacture of integrated circuits involves the manufacture of field effect transistors in and on silicon or other semiconductor substrates.
- the manufacture of a field effect transistor includes the formation of a gate dielectric layer.
- the dielectric layer is typically grown by exposing silicon of the substrate to oxygen, thereby forming silicon dioxide gate dielectric layers.
- Nitrogen is often incorporated by creating a plasma of nitrogen ions within a chamber and implanting the nitrogen ions into the gate dielectric layer.
- the plasma is typically created utilizing a radio frequency (RF) source, with either an electrode plate (capacitative coupling) or a coil (inductive coupling).
- RF radio frequency
- the RF source creates an RF field within a gas in the chamber, and this coupling creates the plasma.
- a method is provided of processing a substrate, including locating the substrate in a processing chamber, creating a nitrogen plasma in the chamber, the plasma having an ion density of at least 10 10 cm ⁇ 3 , and a potential of less than 20 V, and exposing a layer on the substrate to the plasma to incorporate nitrogen from the plasma into the layer.
- a method of processing a substrate wherein the substrate is located in a plasma processing chamber, a nitrogen-containing gas flows into the chamber, an RF current is provided through a coil to generate an RF field in the chamber, the RF field creating a nitrogen-containing RF plasma out of the gas, the RF current being pulsed, and incorporating nitrogen ions and excited neutrals from the plasma into a gate dielectric layer formed on the substrate.
- a plasma reactor including a chamber having an opening to transfer a substrate into an internal volume of the chamber, a substrate holder in the chamber for holding the substrate, an RF coil externally and adjacent to a wall of the chamber, and a grounded electrode plate between the wall and the RF coil.
- FIG. 1 is a perspective view of a plasma reactor according to an embodiment of the invention.
- FIG. 2 is a cross-sectional side view of upper components of the plasma reactor
- FIG. 3 is a cross-sectional side view illustrating nitrogen ion incorporation into a silicon dioxide gate dielectric layer
- FIG. 4 is a graph illustrating plasma potential as a function of pressure for various RF source powers and electrode plate configuration as measured with a Langmuir probe;
- FIG. 5 is a graph illustrating the floating voltages as a function of pressure for the electrode plate configuration as measured with a Langmuir probe
- FIG. 6 is a graph illustrating electron density as a function of pressure for the electrode plate configuration as measured with a Langmuir probe
- FIG. 7 is a graph illustrating ion density as a function of pressure for the electrode plate configuration as measured with a Langmuir probe
- FIG. 8 is a graph illustrating electron temperature as a function of pressure for the electrode plate configuration as measured with a Langmuir probe
- FIG. 9 is a bottom view of laminate, including an electrode plate, according to an embodiment of the invention.
- FIG. 10 is a cross-sectional side view illustrating the laminate in an installed position
- FIG. 11 is a graph illustrating pulsing of RF power to an RF coil with a 30% duty cycle
- FIG. 12 is a graph similar to FIG. 11 at a 50% duty cycle
- FIG. 13 is a graph illustrating thickness change before and after nitrogen plasma treatment with pulsed RF power, and provides a measure of incorporated nitrogen;
- FIG. 14 is a graph illustrating thickness change for different samples processed at different continuous RF power settings
- FIG. 15 is a graph illustrating thickness change as a function of RF source peak power for two pulsing frequencies
- FIG. 16 is a graph illustrating thickness change as a function of duty cycles for two pulsing frequencies
- FIG. 17 is a graph illustrating optical emissions spectra for 500 W peak power at various pulsing frequencies and duty cycles.
- FIG. 18 illustrates optical emission spectra for a 50% duty cycle at various pulsing frequencies and peak powers.
- FIGS. 1 and 2 illustrate a plasma reactor 10 , according to an embodiment of the invention, including a chamber 12 , a substrate holder 14 , an RF coil 16 , and an electrode plate 18 .
- the electrode plate 18 is connected through a body of the chamber 12 to ground 20 .
- grounding the electrode plate 18 a capacitive coupling between the RF coil 16 and a plasma 22 in an internal volume 24 of the chamber 12 is eliminated.
- the elimination of the capacitive couple reduces the potential of the plasma 22 without dramatically altering other properties of the plasma 22 , such as ion density and electron density.
- the inductive coupling from the RF coil 16 is not eliminated, and this coupling creates and maintains the plasma 22 .
- the plasma reactor 10 further includes a lower transfer chamber 26 and a transfer mechanism 28 .
- the chamber 12 is positioned on top of the transfer chamber 26 .
- An internal volume 30 of the transfer chamber 26 is placed in communication with the internal volume 24 of the chamber 12 through a circular opening 32 in a base of the chamber 12 .
- the substrate holder 14 is secured on top of the transfer mechanism 28 , and the transfer mechanism 28 can be used to elevate or lower the substrate holder 14 .
- the transfer mechanism 28 is operated so that the substrate holder 14 is lowered into the internal volume 30 of the transfer chamber 26 .
- a wafer substrate, positioned on a blade attached to a robot arm, is then transferred through a slit-valve opening in a wall of the transfer chamber 26 into the internal volume 30 .
- the transfer mechanism 28 is then operated to elevate the substrate holder 14 so that the substrate holder 14 contacts a lower surface of the wafer substrate and elevates the wafer substrate off the blade.
- the blade is then removed from the transfer chamber 26 , whereafter the transfer mechanism 28 is again operated to elevate the substrate holder 14 into the opening 32 .
- the wafer substrate, located on the substrate holder 14 then has an upper surface which is exposed to the internal volume 24 of the chamber 12 .
- the chamber 12 includes primarily a conductive body 36 and a dielectric dielectric quartz upper wall 38 .
- the conductive body 36 forms a lower portion of the chamber 12
- the upper wall 38 forms an upper portion of the chamber 12 .
- the conductive body 36 and the upper wall 38 jointly define the internal volume 24 .
- gas nozzle ports 40 are formed through the conductive body 36 into the internal volume 24 .
- the gas nozzle ports 40 are positioned at 90° intervals around the substrate holder 14 .
- the conductive body 36 also defines a vacuum pumping channel 42 on one side thereof.
- the gas nozzle ports 40 are connected through valves to a gas manifold, and the vacuum pumping channel 42 is connected to a pump. When the pump is operated, gases are extracted from the internal volume 24 through the vacuum pumping channel 42 to reduce a pressure within the internal volume 24 .
- the valves can be operated to allow gases from the manifold through the valves and the gas nozzle ports 40 into the internal volume 24 .
- the upper wall 38 has a dome shape
- the electrode plate 18 has a dome shape that conforms to an outer surface of the upper wall 38 .
- the electrode plate 18 is in fact located directly on the upper wall 38 .
- the electrode plate 18 defines a circular opening 44 over a center of the upper wall 38 .
- the upper wall 38 and the electrode plate 18 are symmetrical around a vertical axis 46 .
- the coil 16 spirals around the vertical axis 46 and the opening 44 .
- the coil 16 is positioned on and conforms to the dome shape of the electrode plate 18 .
- One end of the coil 16 is connected to an RF source 50 , and an opposing end of the coil 16 is connected to ground 52 .
- An epitaxial silicon layer 54 is formed on an upper surface of a wafer substrate before the wafer substrate is inserted into the plasma reactor 10 positioned on an upper surface of the substrate holder 14 .
- a thin silicon dioxide layer 58 is grown on the silicon layer 54 , also before the wafer substrate is inserted into the plasma reactor 10 .
- the silicon dioxide layer 58 is on the order of a few angstroms (e.g., 40 ⁇ ) thick, and is later used as a gate dielectric layer in a finally manufactured transistor.
- the purpose of inserting the wafer substrate into the plasma reactor 10 is to incorporate nitrogen (N) into the silicon dioxide layer 58 for purposes of modifying or improving its dielectric properties.
- the plasma 22 of nitrogen ions (N 2 + ) is created within the internal volume 24 .
- the nitrogen ions have energies defined by the properties of the plasma which leads to their being incorporated into the silicon dioxide layer 58 .
- the plasma is created by first reducing the pressure within the internal volume 24 to a predetermined level.
- a nitrogen-containing gas is then introduced into the internal volume 24 .
- the nitrogen-containing gas may, for example, be pure nitrogen (N 2 ), a mixture of nitrogen and helium gases (N 2 /He), a mixture of nitrogen and neon gases (N 2 /Ne), or a mixture of nitrogen and argon gases (N 2 /Ar).
- N 2 pure nitrogen
- N 2 /He a mixture of nitrogen and helium gases
- N 2 /Ne mixture of nitrogen and neon gases
- N 2 /Ar mixture of nitrogen and argon gases
- the RF source 50 is then operated to provide RF current to the coil 16 at a frequency of 13.56 MHz.
- the RF coil 16 generates an RF field which is spread by the electrode plate 18 across the upper wall 38 .
- the circular opening 44 permits the RF field to enter through the upper wall 38 into the internal volume 24 .
- the RF field then couples with the nitrogen gas in the internal volume 24 .
- the RF field initially excites a small number of free electrons.
- the free electrons then collide with other atoms to release more electrons from these atoms.
- the process is continued until a steady-state condition is achieved, where the plasma 22 has a steady amount of free electrons and free ions, a steady electron temperature, and a constant voltage relative to ground.
- a “reservoir” of ions is so created within the internal volume 24 , and the voltage potential of the plasma 22 assists in incorporating ions from this reservoir into the silicon dioxide layer 58 .
- the potential of the substrate and the substrate holder 14 floats freely during the entire process, but there is a difference in the voltage of the plasma 22 and that of the substrate holder 14 , the difference driving the incorporation of the ions.
- the RF coil 16 couples capacitively to the plasma 22 .
- Such a capacitive couple between the RF coil 16 and the plasma 22 increases the voltage of the plasma 22 .
- the capacitive coupling is substantially reduced, and the voltage of the plasma 22 is reduced.
- the plasma potential and the electron temperature are reduced, but ion density remains relatively high.
- plasma potential is preferably less than 10 V.
- Electron temperatures are preferably near or less than 2 eV. Ion density is preferably at least 10 10 cm ⁇ 3 .
- FIG. 4 illustrates experimental results utilizing no electrode plate, a regular ungrounded electrode plate, and a grounded electrode plate, respectively.
- experimental results were obtained when applying 300 W, 500 W, and 900 W of power to the RF coil 16 . Larger blocks or triangles indicate larger power magnitudes.
- the plasma voltage (Vp) is the smallest for a grounded electrode plate, higher for an ungrounded electrode plate, and even higher when there is no electrode plate.
- effective RF power supplied to the RF coil 16 may be between 160 and 3000 W. Potentials below 10 V are not achievable without the grounded electrode plate.
- the potentials do not substantially increase with an increase in power provided to the RF coil. Even very large power magnitudes above 1000 W (e.g., 1400 W), crease plasma voltages below 20 V at pressures above 5 milliTorr (mT), and plasma voltages below 10 V at pressures above 40 mT.
- FIG. 5 illustrates the floating voltage of the plasma for the condition of FIG. 4.
- the potential at which the wafer resides is at or near Vf.
- the substrate voltage (Vs) is the smallest for a grounded electrode plate, higher for an ungrounded electrode plate, and even higher when there is no electrode plate.
- FIGS. 6 and 7 illustrate electron density and ion density, respectively.
- the electron density or the ion density
- ion densities above 50 ⁇ 10 9 are achievable when RF power above 1000 W is provided to the RF coil.
- FIG. 8 illustrates electron temperature. It can be seen that at lower pressures there is relatively little difference in electron temperatures when using a grounded, ungrounded, or no electrode plate. However, at higher pressures, typically above 40 mT, it can be seen that electron temperature is much higher where an ungrounded electrode plate is used, or when no electrode plate is used, than when a grounded electrode plate is used.
- the electrode plate 18 is laminated between two dielectric sheets 60 and 62 .
- the electrode plate 18 and the dielectric sheets 60 and 62 are formed in strips 64 that, when folded toward one another, collectively define a dome shape.
- the dielectric sheet 60 is positioned at the top between the electrode plate 18 and the RF coil 16 .
- the dielectric sheet 62 is located between the electrode plate 18 and the upper wall 38 . Ends of the electrode plate are not covered by the dielectric sheet 62 , to leave exposed lands 66 .
- the exposed lands 66 contact a conductive portion of the conductive body 36 , to ground the electrode plate 18 to the conductive body 36 .
- the lands 66 are disposed on a perimeter of the electrode plate 18 , so that the electrode plate 18 is peripherally grounded. Peripheral grounding of the electrode plate 18 ensures that the entire electrode plate 18 is as close to zero volts as possible.
- the plasma voltage can also be reduced by pulsing the RF power provided to the RF coil 16 .
- the electrode plate 18 was not grounded, although it should be understood that the electrode plate 18 may be grounded in addition to pulsing of the RF power provided to the RF coil 16 .
- RF power having a frequency of 13.56 MHz and a predetermined peak power is provided to the RF coil 16 .
- the RF power may be automatically switched on and off, i.e., “pulsed.”
- the RF power is automatically pulsed at a frequency of 10 kHz.
- the RF power may be pulsed at frequencies between 1 kHz and 100 kHz.
- the composition of the nitrogen plasma is continuously varied by varying the RF current between high and low states.
- the duty cycle i.e., the total amount of time that the RF power is on, is 30%, and in FIG. 12, the duty cycle is 50%.
- the RF source 50 is pulsing-enabled, and both the pulsing frequency and duty cycle are manually adjustable.
- the effective delivered power is the peak power times the duty cycle.
- the duty cycle may be between 10% and 90%.
- the amplitude of the RF power is continually altered between 0% and 100%, but in another example, the amplitude may, for example, be altered between 10% and 100%.
- One way to measure incorporation of nitrogen is by measuring the thickness change (“optical delta”) before and after a nitrogen plasma treatment. A larger thickness change indicates more nitrogen incorporation. As shown in FIG. 13, the amount of incorporated nitrogen using continuous power can also be achieved using pulsed power, with the amount of incorporated nitrogen scaling approximately with the effective delivered power. The change in optical thickness is relatively insensitive to pulsing frequency.
- FIG. 14 illustrates optical delta for samples prepared with continuous RF source power; the saturation in incorporated nitrogen with power is observed for both pulsed and continuous power.
- FIGS. 15 and 16 show the same data as in FIG. 13, plotted against source power and duty cycle, showing the same trends as FIG. 13.
- FIGS. 17 and 18 optical emission spectra are captured with an optical emission spectrometer. As one increases the duty cycle at fixed-peak RF power (500 W), the spectra approach the 500 W continuous power spectra (top line), as can be seen in FIG. 17. Pulsing frequency has a small effect on the observed intensity. FIG. 18 shows that the pulsed RF emission level can be restored to the continuous-power emission level (top line) by increasing peak RF power. Again, the emission is relatively insensitive to pulsing frequency.
- FIGS. 13 to 16 indicate that on-wafer nitrogen incorporation similar to the incorporation of continuous RF power is possible with pulsed-RF plasmas.
- FIGS. 17 and 18 indicate that plasmas of similar ion density to continuous-RF power plasmas can be achieved with pulsed-RF power.
- These data coupled with the effect of pulsed-RF power to reduce the electron temperature and plasma potential relative to continuous power, indicate that the pulsing of RF power provides a method for incorporation of nitrogen into gate dielectric oxides at lower energy levels. While incorporating the same amount of nitrogen in the oxide, nitrogen ions in the pulsed plasmas are accelerated into the wafer less than ions in the continuous-power plasmas because of the lower plasma potentials of the pulsed plasmas. Because of this reduced acceleration, the nitrogen will not penetrate as far into the oxide and the underlying silicon.
Abstract
According to one aspect of the invention, a method is provided of processing a substrate, including locating the substrate in a processing chamber, creating a nitrogen plasma in the chamber, the plasma having an ion density of at least 1010 cm−3, and a potential of less than 20 V, and exposing a layer on the substrate to the plasma to incorporate nitrogen of the plasma into the layer.
Description
- 1). Field of the Invention
- This invention relates to a plasma reactor and a method of processing a substrate by creating a plasma.
- 2). Discussion of Related Art
- The manufacture of integrated circuits involves the manufacture of field effect transistors in and on silicon or other semiconductor substrates. The manufacture of a field effect transistor includes the formation of a gate dielectric layer. The dielectric layer is typically grown by exposing silicon of the substrate to oxygen, thereby forming silicon dioxide gate dielectric layers.
- As logic devices have become smaller, it has become advantageous to include nitrogen into the silicon dioxide gate dielectric layers. Nitrogen is often incorporated by creating a plasma of nitrogen ions within a chamber and implanting the nitrogen ions into the gate dielectric layer. The plasma is typically created utilizing a radio frequency (RF) source, with either an electrode plate (capacitative coupling) or a coil (inductive coupling). The RF source creates an RF field within a gas in the chamber, and this coupling creates the plasma.
- Independent of the type of RF source (plate or coil), there can be significant capacitative coupling from the source to the plasma, which creates a relatively large plasma potential, on the order of tens of volts. Such a large plasma potential may cause excessive bombardment of the silicon dioxide layer with nitrogen ions, which can cause damage to the silicon dioxide layer and even incorporation of nitrogen into the underlying silicon. Damage to the silicon dioxide layer or incorporation of nitrogen into the underlying silicon diminishes the advantages of nitrogen incorporation.
- According to one aspect of the invention, a method is provided of processing a substrate, including locating the substrate in a processing chamber, creating a nitrogen plasma in the chamber, the plasma having an ion density of at least 1010 cm−3, and a potential of less than 20 V, and exposing a layer on the substrate to the plasma to incorporate nitrogen from the plasma into the layer.
- According to another aspect of the invention, a method of processing a substrate is provided, wherein the substrate is located in a plasma processing chamber, a nitrogen-containing gas flows into the chamber, an RF current is provided through a coil to generate an RF field in the chamber, the RF field creating a nitrogen-containing RF plasma out of the gas, the RF current being pulsed, and incorporating nitrogen ions and excited neutrals from the plasma into a gate dielectric layer formed on the substrate.
- According to a further aspect of the invention, a plasma reactor is provided, including a chamber having an opening to transfer a substrate into an internal volume of the chamber, a substrate holder in the chamber for holding the substrate, an RF coil externally and adjacent to a wall of the chamber, and a grounded electrode plate between the wall and the RF coil.
- The invention is further described by way of examples with reference to the accompanying drawings, wherein:
- FIG. 1 is a perspective view of a plasma reactor according to an embodiment of the invention;
- FIG. 2 is a cross-sectional side view of upper components of the plasma reactor;
- FIG. 3 is a cross-sectional side view illustrating nitrogen ion incorporation into a silicon dioxide gate dielectric layer;
- FIG. 4 is a graph illustrating plasma potential as a function of pressure for various RF source powers and electrode plate configuration as measured with a Langmuir probe;
- FIG. 5 is a graph illustrating the floating voltages as a function of pressure for the electrode plate configuration as measured with a Langmuir probe;
- FIG. 6 is a graph illustrating electron density as a function of pressure for the electrode plate configuration as measured with a Langmuir probe;
- FIG. 7 is a graph illustrating ion density as a function of pressure for the electrode plate configuration as measured with a Langmuir probe;
- FIG. 8 is a graph illustrating electron temperature as a function of pressure for the electrode plate configuration as measured with a Langmuir probe;
- FIG. 9 is a bottom view of laminate, including an electrode plate, according to an embodiment of the invention.
- FIG. 10 is a cross-sectional side view illustrating the laminate in an installed position;
- FIG. 11 is a graph illustrating pulsing of RF power to an RF coil with a 30% duty cycle;
- FIG. 12 is a graph similar to FIG. 11 at a 50% duty cycle;
- FIG. 13 is a graph illustrating thickness change before and after nitrogen plasma treatment with pulsed RF power, and provides a measure of incorporated nitrogen;
- FIG. 14 is a graph illustrating thickness change for different samples processed at different continuous RF power settings;
- FIG. 15 is a graph illustrating thickness change as a function of RF source peak power for two pulsing frequencies;
- FIG. 16 is a graph illustrating thickness change as a function of duty cycles for two pulsing frequencies;
- FIG. 17 is a graph illustrating optical emissions spectra for 500 W peak power at various pulsing frequencies and duty cycles; and
- FIG. 18 illustrates optical emission spectra for a 50% duty cycle at various pulsing frequencies and peak powers.
- FIGS. 1 and 2 illustrate a
plasma reactor 10, according to an embodiment of the invention, including achamber 12, asubstrate holder 14, anRF coil 16, and anelectrode plate 18. Theelectrode plate 18 is connected through a body of thechamber 12 toground 20. By grounding theelectrode plate 18, a capacitive coupling between theRF coil 16 and aplasma 22 in aninternal volume 24 of thechamber 12 is eliminated. The elimination of the capacitive couple reduces the potential of theplasma 22 without dramatically altering other properties of theplasma 22, such as ion density and electron density. The inductive coupling from theRF coil 16 is not eliminated, and this coupling creates and maintains theplasma 22. - Referring specifically to FIG. 1, the
plasma reactor 10 further includes alower transfer chamber 26 and atransfer mechanism 28. Thechamber 12 is positioned on top of thetransfer chamber 26. Aninternal volume 30 of thetransfer chamber 26 is placed in communication with theinternal volume 24 of thechamber 12 through acircular opening 32 in a base of thechamber 12. Thesubstrate holder 14 is secured on top of thetransfer mechanism 28, and thetransfer mechanism 28 can be used to elevate or lower thesubstrate holder 14. - In use, the
transfer mechanism 28 is operated so that thesubstrate holder 14 is lowered into theinternal volume 30 of thetransfer chamber 26. A wafer substrate, positioned on a blade attached to a robot arm, is then transferred through a slit-valve opening in a wall of thetransfer chamber 26 into theinternal volume 30. Thetransfer mechanism 28 is then operated to elevate thesubstrate holder 14 so that the substrate holder 14 contacts a lower surface of the wafer substrate and elevates the wafer substrate off the blade. The blade is then removed from thetransfer chamber 26, whereafter thetransfer mechanism 28 is again operated to elevate thesubstrate holder 14 into theopening 32. The wafer substrate, located on thesubstrate holder 14, then has an upper surface which is exposed to theinternal volume 24 of thechamber 12. - The
chamber 12 includes primarily aconductive body 36 and a dielectric dielectric quartzupper wall 38. Theconductive body 36 forms a lower portion of thechamber 12, and theupper wall 38 forms an upper portion of thechamber 12. Theconductive body 36 and theupper wall 38 jointly define theinternal volume 24. - Four
gas nozzle ports 40 are formed through theconductive body 36 into theinternal volume 24. Thegas nozzle ports 40 are positioned at 90° intervals around thesubstrate holder 14. Theconductive body 36 also defines avacuum pumping channel 42 on one side thereof. Thegas nozzle ports 40 are connected through valves to a gas manifold, and thevacuum pumping channel 42 is connected to a pump. When the pump is operated, gases are extracted from theinternal volume 24 through thevacuum pumping channel 42 to reduce a pressure within theinternal volume 24. The valves can be operated to allow gases from the manifold through the valves and thegas nozzle ports 40 into theinternal volume 24. - Referring more specifically to FIG. 2, the
upper wall 38 has a dome shape, and theelectrode plate 18 has a dome shape that conforms to an outer surface of theupper wall 38. Theelectrode plate 18 is in fact located directly on theupper wall 38. Theelectrode plate 18 defines acircular opening 44 over a center of theupper wall 38. Theupper wall 38 and theelectrode plate 18 are symmetrical around avertical axis 46. - The
coil 16 spirals around thevertical axis 46 and theopening 44. Thecoil 16 is positioned on and conforms to the dome shape of theelectrode plate 18. One end of thecoil 16 is connected to anRF source 50, and an opposing end of thecoil 16 is connected to ground 52. - Reference is now made to FIGS. 2 and 3 in combination. An
epitaxial silicon layer 54 is formed on an upper surface of a wafer substrate before the wafer substrate is inserted into theplasma reactor 10 positioned on an upper surface of thesubstrate holder 14. A thinsilicon dioxide layer 58 is grown on thesilicon layer 54, also before the wafer substrate is inserted into theplasma reactor 10. Thesilicon dioxide layer 58 is on the order of a few angstroms (e.g., 40 Å) thick, and is later used as a gate dielectric layer in a finally manufactured transistor. The purpose of inserting the wafer substrate into theplasma reactor 10 is to incorporate nitrogen (N) into thesilicon dioxide layer 58 for purposes of modifying or improving its dielectric properties. Theplasma 22 of nitrogen ions (N2 +) is created within theinternal volume 24. The nitrogen ions have energies defined by the properties of the plasma which leads to their being incorporated into thesilicon dioxide layer 58. - The plasma is created by first reducing the pressure within the
internal volume 24 to a predetermined level. A nitrogen-containing gas is then introduced into theinternal volume 24. The nitrogen-containing gas may, for example, be pure nitrogen (N2), a mixture of nitrogen and helium gases (N2/He), a mixture of nitrogen and neon gases (N2/Ne), or a mixture of nitrogen and argon gases (N2/Ar). For purposes of further discussion, examples are given where the gas is pure nitrogen gas. - The
RF source 50 is then operated to provide RF current to thecoil 16 at a frequency of 13.56 MHz. TheRF coil 16 generates an RF field which is spread by theelectrode plate 18 across theupper wall 38. Thecircular opening 44 permits the RF field to enter through theupper wall 38 into theinternal volume 24. The RF field then couples with the nitrogen gas in theinternal volume 24. The RF field initially excites a small number of free electrons. The free electrons then collide with other atoms to release more electrons from these atoms. The process is continued until a steady-state condition is achieved, where theplasma 22 has a steady amount of free electrons and free ions, a steady electron temperature, and a constant voltage relative to ground. A “reservoir” of ions is so created within theinternal volume 24, and the voltage potential of theplasma 22 assists in incorporating ions from this reservoir into thesilicon dioxide layer 58. The potential of the substrate and thesubstrate holder 14 floats freely during the entire process, but there is a difference in the voltage of theplasma 22 and that of thesubstrate holder 14, the difference driving the incorporation of the ions. - Without grounding the
electrode plate 18, theRF coil 16 couples capacitively to theplasma 22. Such a capacitive couple between theRF coil 16 and theplasma 22 increases the voltage of theplasma 22. Conversely, by grounding theelectrode plate 18, the capacitive coupling is substantially reduced, and the voltage of theplasma 22 is reduced. The plasma potential and the electron temperature are reduced, but ion density remains relatively high. To prevent excessive incorporation of nitrogen through the SiO2 and into the silicon substrate, plasma potential is preferably less than 10 V. Electron temperatures are preferably near or less than 2 eV. Ion density is preferably at least 1010 cm−3. - FIG. 4 illustrates experimental results utilizing no electrode plate, a regular ungrounded electrode plate, and a grounded electrode plate, respectively. In each case, experimental results were obtained when applying 300 W, 500 W, and 900 W of power to the
RF coil 16. Larger blocks or triangles indicate larger power magnitudes. At a given power provided to theRF coil 16, the plasma voltage (Vp) is the smallest for a grounded electrode plate, higher for an ungrounded electrode plate, and even higher when there is no electrode plate. In other examples, effective RF power supplied to theRF coil 16 may be between 160 and 3000 W. Potentials below 10 V are not achievable without the grounded electrode plate. What should also be noted is that the potentials do not substantially increase with an increase in power provided to the RF coil. Even very large power magnitudes above 1000 W (e.g., 1400 W), crease plasma voltages below 20 V at pressures above 5 milliTorr (mT), and plasma voltages below 10 V at pressures above 40 mT. - FIG. 5 illustrates the floating voltage of the plasma for the condition of FIG. 4. The potential at which the wafer resides is at or near Vf. Again, it can be seen that the substrate voltage (Vs) is the smallest for a grounded electrode plate, higher for an ungrounded electrode plate, and even higher when there is no electrode plate.
- FIGS. 6 and 7 illustrate electron density and ion density, respectively. For a given magnitude of power applied to the
RF coil 16, there is very little difference between the electron density (or the ion density), when using a grounded electrode plate and when using an ungrounded electrode plate. Although not slow, ion densities above 50×109 are achievable when RF power above 1000 W is provided to the RF coil. - FIG. 8 illustrates electron temperature. It can be seen that at lower pressures there is relatively little difference in electron temperatures when using a grounded, ungrounded, or no electrode plate. However, at higher pressures, typically above 40 mT, it can be seen that electron temperature is much higher where an ungrounded electrode plate is used, or when no electrode plate is used, than when a grounded electrode plate is used.
- Referring to FIGS. 9 and 10, the
electrode plate 18 is laminated between twodielectric sheets electrode plate 18 and thedielectric sheets strips 64 that, when folded toward one another, collectively define a dome shape. Thedielectric sheet 60 is positioned at the top between theelectrode plate 18 and theRF coil 16. Thedielectric sheet 62 is located between theelectrode plate 18 and theupper wall 38. Ends of the electrode plate are not covered by thedielectric sheet 62, to leave exposed lands 66. The exposed lands 66 contact a conductive portion of theconductive body 36, to ground theelectrode plate 18 to theconductive body 36. Thelands 66 are disposed on a perimeter of theelectrode plate 18, so that theelectrode plate 18 is peripherally grounded. Peripheral grounding of theelectrode plate 18 ensures that theentire electrode plate 18 is as close to zero volts as possible. - The plasma voltage can also be reduced by pulsing the RF power provided to the
RF coil 16. In the examples that are now provided, theelectrode plate 18 was not grounded, although it should be understood that theelectrode plate 18 may be grounded in addition to pulsing of the RF power provided to theRF coil 16. - As illustrated in FIGS. 11 and 12, RF power having a frequency of 13.56 MHz and a predetermined peak power is provided to the
RF coil 16. The RF power may be automatically switched on and off, i.e., “pulsed.” In the examples that are provided, the RF power is automatically pulsed at a frequency of 10 kHz. In other examples, the RF power may be pulsed at frequencies between 1 kHz and 100 kHz. The composition of the nitrogen plasma is continuously varied by varying the RF current between high and low states. In FIG. 11, the duty cycle, i.e., the total amount of time that the RF power is on, is 30%, and in FIG. 12, the duty cycle is 50%. TheRF source 50 is pulsing-enabled, and both the pulsing frequency and duty cycle are manually adjustable. The effective delivered power is the peak power times the duty cycle. In other examples, the duty cycle may be between 10% and 90%. In the given example, the amplitude of the RF power is continually altered between 0% and 100%, but in another example, the amplitude may, for example, be altered between 10% and 100%. - One way to measure incorporation of nitrogen is by measuring the thickness change (“optical delta”) before and after a nitrogen plasma treatment. A larger thickness change indicates more nitrogen incorporation. As shown in FIG. 13, the amount of incorporated nitrogen using continuous power can also be achieved using pulsed power, with the amount of incorporated nitrogen scaling approximately with the effective delivered power. The change in optical thickness is relatively insensitive to pulsing frequency.
- FIG. 14 illustrates optical delta for samples prepared with continuous RF source power; the saturation in incorporated nitrogen with power is observed for both pulsed and continuous power.
- FIGS. 15 and 16 show the same data as in FIG. 13, plotted against source power and duty cycle, showing the same trends as FIG. 13.
- In FIGS. 17 and 18, optical emission spectra are captured with an optical emission spectrometer. As one increases the duty cycle at fixed-peak RF power (500 W), the spectra approach the 500 W continuous power spectra (top line), as can be seen in FIG. 17. Pulsing frequency has a small effect on the observed intensity. FIG. 18 shows that the pulsed RF emission level can be restored to the continuous-power emission level (top line) by increasing peak RF power. Again, the emission is relatively insensitive to pulsing frequency.
- FIGS.13 to 16 indicate that on-wafer nitrogen incorporation similar to the incorporation of continuous RF power is possible with pulsed-RF plasmas. FIGS. 17 and 18 indicate that plasmas of similar ion density to continuous-RF power plasmas can be achieved with pulsed-RF power. These data, coupled with the effect of pulsed-RF power to reduce the electron temperature and plasma potential relative to continuous power, indicate that the pulsing of RF power provides a method for incorporation of nitrogen into gate dielectric oxides at lower energy levels. While incorporating the same amount of nitrogen in the oxide, nitrogen ions in the pulsed plasmas are accelerated into the wafer less than ions in the continuous-power plasmas because of the lower plasma potentials of the pulsed plasmas. Because of this reduced acceleration, the nitrogen will not penetrate as far into the oxide and the underlying silicon.
- The simulation of ion implantation into silicon, specifically into Si(100), at various ion energies (10 eV to 30 eV), through a thin oxide layer shows less penetration for lower energy, as can be readily expected. Achieving nitrogen incorporation in such a low-energy fashion with the pulsed-nitrogen plasmas may provide for an improved dielectric that will lead directly to improvements in transistor performance.
- It should be noted that although nitrogen incorporation into a thin gate silicon dioxide has been described, the described processes may have applications for nitrogen incorporation in other gate dielectric materials.
- While certain exemplary embodiments have been described and shown in the accompanying drawings, it is to be understood that such embodiments are merely illustrative and not restrictive of the current invention, and that this invention is not restricted to the specific constructions and arrangements shown and described since modifications may occur to those ordinarily skilled in the art.
Claims (29)
1. A method of processing a substrate, comprising:
creating a nitrogen-containing plasma in the chamber, the plasma having an ion density of at least 1010 cm−3 and a plasma potential of less than 20 V; and
exposing a layer on the substrate to the plasma to incorporate nitrogen of the plasma into the layer on the substrate.
2. The method of claim 1 , wherein the plasma has an electron temperature of less than 2 eV.
3. The method of claim 1 , wherein the layer is silicon dioxide.
4. The method of claim 1 , wherein RF current is provided to a coil located externally adjacent to a dielectric wall of the chamber, the coil creating an RF field in the chamber, the RF field creating the plasma.
5. The method of claim 4 , wherein an electrode is positioned between the coil and the dielectric wall, the electrode being grounded.
6. The method of claim 5 , wherein the electrode reduces the plasma potential to less than 10 V.
7. The method of claim 6 , wherein the wall is dome-shaped, the coil spirals around an axis through the wall, and the electrode has an opening therein.
8. The method of claim 7 , wherein the opening is within the perimeter described by the coil.
9. The method of claim 4 , wherein the amplitude of the RF current is varied between high and low states.
10. The method of claim 9 , wherein effective RF power applied to the coil is between 100 and 3000 W.
11. The method of claim 10 , wherein a pressure in the chamber is at least 5 mT, RF power is at least 1000 W, and ion density is at least 5×1010 cm−3.
12. The method of claim 11 , wherein the pressure is at least 40 mT and the plasma voltage is less than 10 V.
13. The method of claim 9 , wherein the RF current is pulsed at a duty cycle of between 10 and 90%.
14. The method of claim 9 , wherein the RF current is pulsed at a frequency between 1 kHz and 100 kHz.
15. A method of processing a substrate, comprising:
locating the substrate in a plasma-processing chamber;
flowing a nitrogen-containing gas into the chamber;
providing RF current to a coil to generate an RF field in the chamber, the RF field creating a nitrogen-containing RF plasma out of the gas, the amplitude of the RF current being varied between high and low states; and
incorporating nitrogen from the plasma into a layer formed on the substrate.
16. The method of claim 15 , wherein the composition of the nitrogen-containing plasma is varied by pulsing of the RF current.
17. A method of processing a substrate, comprising:
locating the substrate in a plasma-processing chamber;
flowing a gas into the chamber;
providing RF current to a coil located externally adjacent to a dielectric wall of the chamber, an electrode plate being located between the coil and the dielectric wall and being at a voltage below 20 V, the RF field creating an RF plasma out of the gas; and
incorporating nitrogen ions of the plasma into a layer on the substrate.
18. The method of claim 17 , wherein the electrode plate is grounded.
19. The method of claim 17 , wherein the ions are nitrogen ions.
20. The method of claim 17 , wherein a pressure in the chamber is at least 5 mT, RF power applied to the coil is at least 1000 W, a potential of the plasma is less than 20 V, and ion density is at least 5×1010 cm−3.
21. The method of claim 20 , wherein the pressure is at least 40 mT, and the potential of the plasma is less than 10 V.
22. A plasma reactor, comprising:
a chamber, having an opening to transfer a substrate into an internal volume of the chamber;
a substrate holder in the chamber for holding the substrate;
an RF coil externally and adjacent to a nonconductive wall of the chamber; and
an electrode plate between the wall and the RF coil, the electrode plate being at a voltage below 20 V when RF current is provided to the RF coil.
23. The plasma reactor of claim 22 , wherein the electrode plate is grounded.
24. The plasma reactor of claim 23 , wherein the electrode plate is grounded through the chamber.
25. The plasma reactor of claim 24 , wherein the wall is made of quartz.
26. The plasma reactor of claim 23 , wherein the electrode plate is peripherally grounded.
27. The plasma reactor of claim 26 , wherein the wall has a dome shape and the electrode plate has a dome shape positioned over the dome shape of the wall.
28. The plasma reactor of claim 27 , wherein the electrode plate has a plurality of fingers, each contacting a conductive portion of the chamber.
29. A plasma reactor, comprising:
a chamber, having an opening to transfer a substrate into an internal volume of the chamber;
a substrate holder in the chamber for holding the substrate;
an RF coil externally and adjacent to a nonconductive wall of the chamber; and
an RF source connected to the RF coil, the RF source being capable of automatically varying an amplitude of RF current provided to the RF coil.
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US10/170,925 US6660659B1 (en) | 2002-06-12 | 2002-06-12 | Plasma method and apparatus for processing a substrate |
CNB038130793A CN100533651C (en) | 2002-06-12 | 2003-06-12 | Plasma apparatus and method for processing a substrate |
PCT/US2003/018784 WO2003107382A2 (en) | 2002-06-12 | 2003-06-12 | Plasma method and apparatus for processing a substrate |
JP2004514108A JP2005530341A (en) | 2002-06-12 | 2003-06-12 | Plasma method and apparatus for processing a substrate |
KR1020047018470A KR101044366B1 (en) | 2002-06-12 | 2003-06-12 | Plasma method and apparatus for processing a substrate |
US10/461,083 US6831021B2 (en) | 2002-06-12 | 2003-06-12 | Plasma method and apparatus for processing a substrate |
EP03737087A EP1512165A2 (en) | 2002-06-12 | 2003-06-12 | Plasma apparatus and method for processing a substrate |
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