WO2006132262A1 - プラズマ窒化処理方法、半導体装置の製造方法およびプラズマ処理装置 - Google Patents
プラズマ窒化処理方法、半導体装置の製造方法およびプラズマ処理装置 Download PDFInfo
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- WO2006132262A1 WO2006132262A1 PCT/JP2006/311397 JP2006311397W WO2006132262A1 WO 2006132262 A1 WO2006132262 A1 WO 2006132262A1 JP 2006311397 W JP2006311397 W JP 2006311397W WO 2006132262 A1 WO2006132262 A1 WO 2006132262A1
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- plasma
- silicon
- nitriding
- silicon nitride
- nitride film
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
- H01L21/02252—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by plasma treatment, e.g. plasma oxidation of the substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/0217—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
- H01L21/02247—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by nitridation, e.g. nitridation of the substrate
-
- 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
- H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
- H01L21/02312—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment treatment by exposure to a gas or vapour
- H01L21/02315—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment treatment by exposure to a gas or vapour treatment by exposure to a plasma
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
- H01L21/28158—Making the insulator
- H01L21/28167—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation
- H01L21/28202—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation in a nitrogen-containing ambient, e.g. nitride deposition, growth, oxynitridation, NH3 nitridation, N2O oxidation, thermal nitridation, RTN, plasma nitridation, RPN
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/318—Inorganic layers composed of nitrides
- H01L21/3185—Inorganic layers composed of nitrides of siliconnitrides
Definitions
- Plasma nitriding method, semiconductor device manufacturing method, and plasma processing apparatus Plasma nitriding method, semiconductor device manufacturing method, and plasma processing apparatus
- the present invention uses a plasma to treat a surface of an object to be processed such as a polycrystalline silicon layer or an amorphous silicon layer in silicon of a semiconductor substrate or a flat panel display substrate, and nitrides silicon to form silicon.
- the present invention relates to a plasma nitriding method for forming a nitride film, a method for manufacturing a semiconductor device, and a plasma processing apparatus.
- a silicon nitride film is formed as a gate insulating film of a transistor.
- a method of forming a silicon nitride film in addition to a method of depositing a silicon nitride film by CVD (Chemical Vapor Deposition), for example, in JP-A-2001-274148, nitrogen is applied to a silicon oxide film by plasma treatment.
- CVD Chemical Vapor Deposition
- a method of forming a silicon oxynitride film by introducing it has been proposed.
- the thickness of the gate insulating film has been increasing. For example, it is required to form a gate insulating film as thin as several nm. In gate insulating films that progress in such thin films, it is important to keep leakage current low and maintain high reliability.
- a silicon oxynitride film SiON
- high-k high dielectric constant
- a silicon nitride film having a higher dielectric constant (7.5) and lower interface state density than a silicon oxide film can be obtained.
- a gate insulating film is formed by directly nitriding silicon by a conventional plasma processing method, if the plasma nitriding process is performed under a temperature condition of room temperature to 400 ° C or less, as shown below, a good result is obtained. It is difficult to obtain insulating film characteristics, which causes a problem.
- a gate insulating film is formed by low-temperature plasma processing, and then processing at a high temperature exceeding 500 ° C. (for example, film formation of a polysilicon electrode) is performed. There is a problem that the insulating film characteristics of the gate insulating film fluctuate due to the heat applied during the process.
- An object of the present invention is to provide a method capable of directly nitriding silicon using plasma to form a high-quality thin silicon nitride film.
- a first aspect of the present invention is to perform a nitriding process by causing a plasma of a nitrogen-containing gas to act on silicon on the surface of an object to be processed in a processing container of a plasma processing apparatus, A plasma nitriding method for forming a silicon nitride film,
- the plasma is a microwave-excited high density plasma
- nitriding temperature is 500 ° C or higher.
- the microwave-excited high-density plasma is preferably formed by introducing microwaves into the processing vessel with a planar antenna having a plurality of slots.
- the nitriding treatment temperature is 600 ° C. or higher and 800 ° C. or lower.
- the processing pressure of the nitriding treatment is preferably 6.7 Pa or more. The processing pressure is more preferably 20 Pa or more.
- the film thickness force of the silicon nitride film is preferably 0.5 nm to 3 nm.
- the silicon nitride film is preferably a gate insulating film.
- the silicon is preferably single crystal silicon, polycrystalline silicon, or amorphous silicon.
- the silicon is preferably single crystal silicon having a substantially (110) surface.
- the plasma nitriding method forms the silicon nitride film when forming a composite material having a dielectric constant higher than that of the silicon nitride film and a high dielectric constant material and the silicon nitride film. May be.
- a second aspect of the present invention is to perform a nitriding process by applying a plasma of a nitrogen-containing gas to silicon on the surface of an object to be processed in a processing container of a plasma processing apparatus, and a gate containing silicon nitride. Including a step of forming an insulating film,
- the plasma is a microwave-excited high density plasma
- nitriding temperature 500 ° C. or higher.
- the second aspect may further include a step of performing a heat treatment at a temperature of 500 ° C or higher after the formation of the gate insulating film.
- a third aspect of the present invention is that a microwave-excited high-density plasma of a nitrogen-containing gas acts on silicon on an object to be processed in a processing container of a plasma processing apparatus when operating on a computer.
- a control program for controlling the plasma processing apparatus so that a plasma nitriding method for forming a silicon nitride film by performing nitriding at a processing temperature of 500 ° C. or higher is performed.
- a fourth aspect of the present invention is a computer-readable storage medium storing a control program that operates on a computer
- the control program performs nitriding treatment at a processing temperature of 500 ° C. or more by causing microwave-excited high-density plasma of nitrogen-containing gas to act on silicon on the object to be processed in the processing container of the plasma processing apparatus at the time of execution.
- a computer-readable storage medium is provided for controlling the plasma processing apparatus such that a plasma nitriding method for forming a silicon nitride film is performed.
- a processing container capable of being evacuated and provided with a support base on which an object to be processed is placed;
- a plasma processing apparatus comprising: a control unit that performs control so as to be performed.
- a high-quality, thin silicon with less damage and defects can be obtained by performing plasma nitriding at a high temperature of 500 ° C or higher using microwave-excited high-density plasma.
- a nitride film can be formed.
- the silicon nitride film obtained by the method of the present invention has a quantitative variation in the intermediate nitriding state (subnitride) at the Si N ZSi interface even if it is processed at a high temperature such as annealing after film formation with high heat resistance. Less interface
- the method of the present invention capable of forming a stable nitride film in this manner is, for example, about 0.5 to 3 nm (preferably about 0.5 to 3 nm) after the 65 nm process node in the process of manufacturing a semiconductor device that is increasingly miniaturized. It can be advantageously used for the purpose of forming a thin gate insulating film of 2 nm).
- FIG. 1 is a schematic sectional view showing an example of a plasma processing apparatus that can be used in the present invention.
- FIG. 2 is a drawing for explaining a planar antenna member.
- FIG. 3A is a diagram illustrating a state in which an element isolation layer is formed in a transistor manufacturing process.
- FIG. 3B is a diagram for explaining a state where plasma nitriding is performed in the process of manufacturing a transistor.
- FIG. 3C is a diagram illustrating a state in which a transistor is formed.
- FIG. 5 A drawing showing the CV curve of an MIS capacitor using a silicon nitride film deposited at 400 ° C.
- FIG. 6 is a drawing showing the Si 2p spectrum of a silicon nitride film formed at 600 ° C.
- FIG. 7 shows a Si 2p spectrum of a silicon nitride film formed at 400 ° C.
- FIG. 8 is a graph plotting the rate of change of N concentration in the film by film thickness.
- FIG. 9 is a graph plotting the half-width of the Nls spectrum of a silicon nitride film by thickness.
- FIG. 10 is a graph showing the relationship between the half width of the Nls spectrum of a silicon nitride film and the film formation conditions.
- FIG. 11 is a graph showing the film formation temperature and the refractive index of the silicon nitride film before and after annealing.
- FIG. 12A is a graph showing the V—I characteristics of the evaluation MISFET.
- FIG. 12B is a graph showing the V—I characteristics of the evaluation MISFET.
- FIG. 13 is a graph showing the V–I characteristics of the evaluation MISFET.
- FIG. 14 is a graph comparing the lZf noise characteristics of the evaluation MOSFET and the evaluation MISFET.
- FIG. 15B The silicon nitride film formed on the Si (110) surface is processed by XPS analysis of Si 2p.
- FIG. 16 is a schematic diagram for explaining the difference in stress (film stress) between the silicon nitride film formed on the Si (110) surface and the silicon nitride film formed on the Si (100) surface.
- FIG. 17 Comparison of gate current characteristics by OT for an evaluation transistor using a silicon nitride film or a silicon oxide film.
- FIG. 18A This is a graph showing the CV measurement results of a silicon nitride film with an EOT of 1.7 nm by the LC resonance method.
- FIG. 18B This is a graph showing the CV measurement results of the silicon nitride film with an EOT of 1.2 nm by the LC resonance method.
- FIG. 1 is a cross-sectional view schematically showing an example of a plasma processing apparatus that can be suitably used in the present invention.
- the plasma processing apparatus 100 has a high density and high density by generating plasma by introducing microwaves into a processing chamber using a planar antenna having a plurality of slots, particularly RLSA (Radial Line Slot Antenna). My low electron temperature It is configured as an RLSA microwave plasma processing device that can generate chromowave-excited plasma.
- This plasma processing apparatus 100 is capable of processing with plasma having a plasma density of 1 ⁇ 10 1 C) to 5 ⁇ 10 12 Zcm 3 and an electron temperature of 0.7 to 2 eV, for example. Accordingly, the plasma processing apparatus 100 can be suitably used for the purpose of forming a gate insulating film in the manufacturing process of various semiconductor devices such as MOS transistors and MOSFETs (field effect transistors).
- the plasma processing apparatus 100 includes a substantially cylindrical chamber 11 that is airtight and grounded.
- a circular opening 10 is formed at a substantially central portion of the bottom wall la of the chamber 11. Further, an exhaust chamber 11 that communicates with the opening 10 and protrudes downward is provided.
- a mounting table 2 made of ceramics such as A1N for horizontally supporting a silicon wafer (hereinafter simply referred to as “wafer”) W as a substrate to be processed.
- the mounting table 2 is supported by a support member 3 having a ceramic force such as a cylindrical A1N extending upward from the bottom center force of the exhaust chamber 11.
- a guide ring 4 for guiding the wafer W is provided on the outer edge of the mounting table 2.
- a resistance heating type heater 5 is embedded in the mounting table 2, and the heater 5 is heated by the heater power supply 5 a to heat the mounting table 2, and the heat is a substrate to be processed. Heat wafer W.
- the mounting table 2 is provided with a thermocouple 6 so that the heating temperature of the wafer W can be controlled in a range from room temperature to 900 ° C., for example.
- wafer support pins (not shown) for supporting the wafer W to be moved up and down are provided so as to protrude and retract with respect to the surface of the mounting table 2.
- a cylindrical liner 7 having a quartz force is provided on the inner periphery of the chamber 11 to prevent metal contamination due to the material constituting the chamber. Further, in order to uniformly exhaust the inside of the chamber 11 on the outer peripheral side of the mounting table 2, a noble plate 8 having a large number of exhaust holes 8a is provided in an annular shape, and this baffle plate 8 is supported by a plurality of support columns 9. ing.
- An annular gas introduction member 15 is provided on the side wall of the chamber 11.
- a gas supply system 16 is connected to the gas introduction member 15.
- the gas introduction member may be arranged in a nozzle shape or a shower shape.
- the gas supply system 16 includes, for example, a rare gas supply source 17 and a nitrogen-containing source.
- a gas supply source 18 is provided, and a rare gas and a nitrogen-containing gas reach the gas introduction member 15 through the gas lines 20 and are introduced into the chamber 11 from the gas introduction member 15.
- Each of the gas lines 20 is provided with a mass flow controller 21 and front and rear opening / closing valves 22.
- Examples of the nitrogen-containing gas include N gas, NH gas, a mixed gas of N and H, and hydra.
- Gin etc. can be used.
- the rare gas for example, Ar gas, Kr gas, Xe gas, He gas or the like can be used.
- An exhaust pipe 23 is connected to a side surface of the exhaust chamber 11, and an exhaust device 24 including a high-speed vacuum pump is connected to the exhaust pipe 23.
- an exhaust device 24 including a high-speed vacuum pump is connected to the exhaust pipe 23.
- the exhaust device 24 is uniformly discharged into the space 1 la of the exhaust chamber 11 through the gas force baffle plate 8 in the chamber 11 and exhausted through the exhaust pipe 23.
- the inside of the chamber 11 can be depressurized at a high speed to a predetermined degree of vacuum, for example, 0.133 Pa.
- a loading / unloading port 25 for loading / unloading the wafer W to / from a transfer chamber (not shown) adjacent to the plasma processing apparatus 100, and the loading / unloading port 25 are opened and closed.
- a gate valve 26 is provided!
- the upper portion of the chamber 11 has an opening, and an annular upper plate 27 is joined to the opening by force.
- the lower part of the inner periphery of the upper plate 27 protrudes toward the inner space of the chamber and forms an annular support part 27a.
- a dielectric material such as quartz, Al 2 O, or A1N ceramics is used to transmit microwaves.
- the overplate 28 is provided in an airtight manner via the seal member 29. Therefore, the inside of the chamber 1 is kept airtight.
- a disc-shaped planar antenna member 31 is provided above the transmission plate 28 so as to face the mounting table 2.
- the planar antenna member 31 is locked to the upper end of the side wall of the chamber 11.
- the planar antenna member 31 is constituted by, for example, a copper plate or a aluminum plate cover whose surface is plated with gold or silver.
- the planar antenna member 31 is formed with a plurality of slot-like microwave radiation holes 32 that radiate microwaves in a predetermined pattern.
- the microwave radiation hole 32 has a long groove shape, for example, as shown in FIG.
- the microwave radiation holes 32 are arranged in a “T” shape, and the plurality of microwave radiation holes 32 are arranged concentrically.
- the length and arrangement interval of the microwave radiation holes 32 are determined in accordance with the wavelength ( ⁇ g) of the microwave mouth wave.
- the distance between the microwave radiation holes 32 is ⁇ g Z2 or g.
- the In FIG. 2, the interval between adjacent microwave radiation holes 32 formed concentrically is indicated by Ar.
- the microwave radiation hole 32 may have another shape such as a circular shape or an arc shape.
- the arrangement form of the microwave radiation holes 32 is not particularly limited, and may be arranged in a concentric shape, for example, in a spiral shape or a radial shape.
- a slow wave material 33 having a dielectric constant larger than that of a vacuum is provided on the upper surface of the planar antenna member 31.
- the slow wave material 33 has a function of adjusting the plasma by shortening the wavelength of the microwave because the wavelength of the microwave becomes longer in vacuum.
- the planar antenna member 31 and the transmission plate 28, and the slow wave member 33 and the planar antenna member 31 may be in close contact with each other or separated from each other.
- a shield lid 34 made of a metal material such as aluminum or stainless steel is provided on the upper surface of the chamber 11 so as to cover the planar antenna member 31 and the slow wave material 33.
- the upper surface of the chamber 11 and the shield cover 34 are sealed by a seal member 35.
- a cooling water flow path 34a is formed in the shield lid 34, and cooling water is allowed to flow therethrough to cool the shield lid 34, the slow wave material 33, the planar antenna member 31, and the transmission plate 28. It has become.
- the shield lid 34 is grounded.
- An opening 36 is formed at the center of the upper wall of the shield lid 34, and a waveguide 37 is connected to the opening.
- a microwave generator 39 for generating microwaves is connected to the end of the waveguide 37 via a matching circuit 38. Thereby, for example, a microwave having a frequency of 2.45 GHz generated by the microwave generator 39 is propagated to the planar antenna member 31 through the waveguide 37.
- the microwave frequency 8.35 GHz, 1.98 GHz, or the like can be used.
- the waveguide 37 includes a coaxial waveguide 37a having a circular cross section extending upward from the opening 36 of the shield lid 34, and a mode converter 40 at the upper end of the coaxial waveguide 37a. And a rectangular waveguide 37b extending in the horizontal direction. Coaxial with rectangular waveguide 37b The mode conversion 40 between the wave tube 37a and the wave guide 37a has a function of converting the microphone mouth wave propagating in the TE mode in the rectangular waveguide 37b into the TEM mode.
- An inner conductor 41 extends in the center of the coaxial waveguide 37a, and the inner conductor 41 is connected and fixed to the center of the planar antenna member 31 at the lower end thereof. Thereby, the microwave is efficiently and uniformly propagated radially and uniformly to the planar antenna member 31 through the inner conductor 41 of the coaxial waveguide 37a.
- Each component of the plasma processing apparatus 100 is connected to and controlled by a process controller 50 having a CPU.
- the process controller 50 includes a keyboard that allows the process manager to input commands to manage the plasma processing apparatus 100, a display that displays and displays the operating status of the plasma processing apparatus 100, and the like.
- One interface 51 is connected!
- the process controller 50 stores a control program (software) for realizing various processes executed by the plasma processing apparatus 100 under the control of the process controller 50, and recipes in which processing condition data is recorded.
- the stored storage unit 52 is connected.
- recipes such as the control program and processing condition data may be stored in a computer-readable storage medium such as a CD-ROM, a hard disk, a flexible disk, or a flash memory. For example, it is possible to transmit the data from time to time through a dedicated line and use it online.
- the silicon nitride film can be formed by directly nitriding silicon (polycrystalline silicon or single crystal silicon) on the wafer W.
- directly nitriding silicon polycrystalline silicon or single crystal silicon
- the gate valve 26 is opened, and a wafer W having a silicon surface is loaded into the chamber 11 from the loading / unloading port 25 and mounted on the mounting table 2. Then, for example, Ar gas or N gas is supplied from the rare gas supply source 17 and the nitrogen-containing gas supply source 18 of the gas supply system 16 to a predetermined flow rate.
- the gas is introduced into the chamber 11 through the gas introduction member 15.
- the flow rate of rare gas such as Ar or Xe is 250 to 2000 mLZmin (sccm)
- the inside of the channel is adjusted to a processing pressure of 6.7 to 1333 Pa (50 mTon: to lOTorr), preferably 20 to 400 Pa (l 50 mTorr to 3 Torr). Further, the temperature of the wafer W is heated to 500 to 900 ° C., preferably 600 to 900 ° C., more preferably about 600 to 800 ° C. At this time, if the processing temperature is less than 500 ° C., it becomes difficult to form a dense and high-quality silicon nitride film, as shown in examples described later. On the other hand, even if nitriding is performed at a processing temperature exceeding 900 ° C, the effect of improving the film quality cannot be expected.
- the microwave from the microwave generator 39 is guided to the waveguide 37 through the matching circuit 38, and sequentially passes through the rectangular waveguide 37b, the mode converter 40, and the coaxial waveguide 37a. And supplied to the planar antenna member 31 via the inner conductor 41. Then, the microwave is radiated from the microwave radiation hole 32 of the planar antenna member 31 to the space above the wafer W in the chamber 11 through the transmission plate 28. The microwave propagates in the rectangular waveguide 37b in the TE mode, and the TE mode microwave is converted to the TEM mode by the mode change ⁇ 40, and the inside of the coaxial waveguide 37a becomes the planar antenna member 31. It is propagated towards.
- the microphone mouth wave power at this time can be set to 1000 to 5000 W, for example.
- the microwave plasma has a high density of about 1 X 10 1 (> ⁇ 5 X 10 12 Zcm 3 and near the wafer W, because microwaves are also radiated by a number of microwave radiation holes 32 of the planar antenna member 31. In the vicinity, the plasma becomes a low electron temperature plasma of about 1.5 eV or less, and the microwave-excited plasma formed in this way has little plasma damage caused by ions, etc.
- the active species in the plasma mainly Radicals (eg N * for N gas, NH gas field
- N * is directly introduced into the silicon by the action of NH *), and a Si N film is uniformly formed on the silicon surface.
- plasma nitriding treatment is used to form a silicon nitride film by directly nitriding silicon (polycrystalline silicon, amorphous silicon, or single crystal silicon) with plasma using the plasma processing apparatus 100.
- the processing temperature (wafer W temperature) is set to 500 ° C or higher, preferably 600 ° C or higher. Because of this, after that, for example at temperatures above 500 ° C Even when the heating process is performed, the intermediate nitridation state at the interface between Si N and Si (
- Si N film silicon nitride film that has a stable Si—N bond and can maintain a stable nitrogen concentration.
- a high-quality silicon nitride film can be formed on the surface of single crystal silicon or polycrystalline silicon. Therefore, the plasma nitriding method of the present invention can be used when a silicon nitride film is formed as a gate insulating film, for example, in the manufacture of various semiconductor devices such as transistors.
- the preferred embodiment is particularly useful for forming a thin film in a next-generation device, for example, a gate insulating film having a thickness of 3 nm or less, preferably 0.5 to 2 nm.
- 3A to 3C are diagrams illustrating an example in which the plasma nitriding method of the present invention is applied in the process of manufacturing a transistor.
- a well (not shown) is formed on a P-type or N-type Si substrate 101, and an element isolation layer 102 is further formed by, for example, the LOCOS method.
- the element isolation layer 102 may be formed by STI (Shallow Trench Isolation).
- a gate insulating film 103 (SiN film) is formed on the surface of the Si substrate 101 by performing a plasma nitriding process with the above-described contents.
- This gate insulating film 103 SiN film
- the film thickness can be set to a force that varies depending on the target device, for example, about 0.5 to 3 nm, preferably about 0.5 to 2 nm.
- a post-nitridation annealing process in which heat treatment is performed at a temperature of, for example, 800 ° C. to 1100 ° C. for about 10 to 60 minutes in an inert gas atmosphere may be performed.
- a polysilicon layer 104 is formed on the formed gate insulating film 103 by CVD under a temperature condition exceeding 400 ° C., for example, and then etched by a photolithography technique to form a gate electrode.
- the gate electrode structure is not limited to a single layer of the polysilicon layer 104, and for example, tungsten, molybdenum, tantalum, titanium, cobalt, nickel, their silicides, A laminated structure including a ride, an alloy or the like can also be used.
- ion implantation and activation treatment are performed to form a source / drain (not shown), and a sidewall 105 made of an insulating film is formed, as shown in FIG. 3C.
- MOS transistor 200 Can be manufactured.
- the Si (100) surface was directly nitrided to form a silicon nitride film having an optical thickness of 1.5 nm.
- the theoretical pressure was 6.7 Pa (50 mTorr).
- the processing temperature was a wafer temperature of 400 ° C or 600 ° C, the microwave frequency was 2.45 GHz, and the microwave power was 5 W / cm 2 .
- annealing was further performed at 600 ° C for 30 minutes in an N atmosphere.
- Si 2p spectrum of the obtained silicon nitride film was analyzed with high sensitivity and high resolution by A1 ⁇ ⁇ -ray excitation.
- Si 2p spectrum uses the Tougard method from the Si 2p photoelectron spectrum.
- the intermediate nitriding state does not follow the suboxide defined by Hollinger et al. [G. Hollinger et al., Appl. Phys. Lett. 44 (1984) 93.] It is assumed that only Si 1+ , Si 2+ , and Si 3+ also have force.
- Table 1 shows the binding energy, half width, and amount (ML) of the intermediate nitriding state (Sf +) when the film was formed at 600 ° C.
- each intermediate nitrided state after obtaining the spectral intensity (NSi n + ) of each intermediate nitrided state after spin separation, the spectral intensity of each intermediate nitrided state normalized to the spectral intensity (NS) of the Si substrate is obtained.
- the total amount of subnitride is 1.29ML, and at the Si N ZSi interface,
- an MIS capacitor using a silicon nitride film formed under the above conditions as a gate insulating film was prepared.
- the C–V curve was measured for this MIS capacitor, and the electrical characteristics of the gate insulating film were evaluated.
- the capacitor was produced according to the following procedure.
- a field oxide film was formed by wet oxidation (1100 ° C.) for element isolation.
- Organic contamination is removed by washing with ozone-dissolved ultrapure water. Can also remove some metal contamination.
- megasonic irradiation is performed to remove fine particles, metals, and oxides.
- FPM cleaning is performed to remove acid and promote hydrogen termination.
- the microroughness (Ra) of the silicon surface is about 0.08 nm.
- a silicon nitride film was formed under the above conditions using the plasma processing apparatus 100, and subsequently an A1 electrode was formed as a gate electrode by vapor deposition, and patterned to obtain a MIS Canon.
- Fig. 4 shows the CV curve for the sample deposited at 600 ° C when annealing was performed under the above conditions and when the force was not applied.
- Figure 5 shows the C–V curves for the sample deposited at 400 ° C when annealing was performed in the same way and when the force was applied.
- the vertical axes in FIGS. 4 and 5 are obtained by dividing the measured electric capacity by the maximum value and standardizing it.
- FIG. 6 and FIG. 7 show Si 2p spectra measured by the above method.
- Figure 6 shows 60
- spectra (escape angle 52 °) when the film was formed at 0 ° C. (nitriding treatment) and when annealed at 600 ° C. after the film formation are shown together.
- Fig. 7 shows both spectra (escape angle 52 °) when the film was formed at 400 ° C and when annealed at 600 ° C after the film formation.
- a silicon substrate is directly nitrided to form a silicon nitride film, and the N concentration in the film is measured by X-ray photoelectron spectroscopy (XPS analysis). It was measured.
- Figure 8 plots the rate of change in N concentration ( ⁇ N) for each film thickness from 3 to 24 hours after plasma nitriding.
- ArZN gas is flowed as the treatment gas
- the wafer temperature was 400 ° C or 800 ° C.
- the pressure was 6.7 Pa or 266.6 Pa (50 mTorr or 2000 mTorr)
- the power supplied to the plasma was 1.5 kW
- the treatment time was 10 to 60 seconds.
- the wafer W used was cleaned with a 1% dilute hydrofluoric acid (DHF) solution.
- DHF dilute hydrofluoric acid
- the Nis spectrum of the formed silicon nitride film was measured by X-ray photoelectron spectroscopy (XPS analysis), and the half width was obtained.
- XPS analysis X-ray photoelectron spectroscopy
- a silicon nitride film was formed by directly nitriding the Si substrate using the plasma processing apparatus 100 based on the following film forming conditions 1 to 3. Thereafter, each silicon nitride film was heated in the following oxidizing atmosphere. For each silicon nitride film, the peak of the Nls spectrum was measured by X-ray photoelectron spectroscopy (XPS analysis), and the half width was obtained. The results are shown in FIG.
- ArZN gas 1000Z200mLZmin (sccm)
- Wafer temperature 400 ° C
- ArZN gas 1000Z200mLZmin (sccm)
- Wafer temperature 800 ° C
- ArZN gas 1000Z200mLZmin (sccm)
- Wafer temperature 800 ° C
- the pressure is 9999.8 Pa (75 Torr) and the O flow rate is 2LZmi.
- Heat treatment was performed for 15 seconds in a high-temperature oxidizing atmosphere at n (slm) and a heating temperature of 1000 ° C.
- the half-value width of the peak of the Nls spectrum is higher than the low temperature nitridation treatment at 400 ° C at 12 Pa (deposition condition 1) (high temperature nitridation at 800 ° C at 12 Pa (deposition) Condition 2) is smaller and further reduced by high-temperature nitridation at 800 ° C (film formation condition 3) at a pressure of 200 Pa.
- FIG. 11 shows the refractive index fluctuation before and after annealing of the silicon nitride film formed at 250 ° C., 400 ° C., and 600 ° C. using the plasma processing apparatus 100 of FIG.
- Xe and NH are used as the processing gas
- the flow ratio XeZNH 1000/1 OOmL / min (s
- the pressure was 6.7 Pa (50 mTorr)
- the microwave power was 700 W.
- the silicon nitride film deposited at each temperature is annealed at 600 ° C in N atmosphere for 30 minutes.
- FIG. 11 shows that a high-density silicon nitride film having a high refractive index can be obtained by increasing the film formation temperature.
- the refractive index variation was small in the sample formed at 600 ° C. Compared to this, it was inferred that the samples deposited at 250 ° C and 400 ° C could form a dense silicon nitride film before annealing, where the refractive index fluctuation range was large.
- the plasma nitriding treatment is performed by nitriding at a high temperature of 500 ° C. or higher, thereby producing a dense, thin film that is less prone to oxidation and less susceptible to oxidation. It was shown that a stable nitride film with little variation in characteristics was formed.
- a silicon nitride film was formed on a silicon substrate under the following nitriding conditions, an evaluation MISFET using this as a gate insulating film was fabricated, and its electrical characteristics were measured.
- This evaluation MISFET has a gate structure in which a silicon nitride film as a gate insulating film is formed on a silicon substrate and a polysilicon electrode is formed on the silicon nitride film.
- the gate width (W) is 20 ⁇ m and the gate length is 0.8 ⁇ m.
- the Si (100) plane and the Si (llO) plane were directly nitrided to form silicon nitride films, respectively.
- the processing pressure was 20 Pa (150 mTorr).
- the processing temperature was a wafer temperature of 600 ° C, the microwave frequency was 2.45 GHz, and the microwave power was 5 WZcm 2 .
- EOT SiO equivalent film thickness; Equivalent
- Oxide Thickness was 2.06 nm for the silicon nitride film on the Si (100) plane and 1.70 nm for the silicon nitride film on the Si (lO) plane.
- FIGS. 12A and 12B show an evaluation MISFET (referred to as “MISFET—100”) using a silicon nitride film on the Si (100) surface as a gate insulating film and a silicon nitride film on the Si (110) surface.
- MISFET—100 evaluation MISFET
- MISFET-110 gate drain of evaluation MISFET
- the drain voltage (V) is 0.05 V and
- MISFET-110 has less drain current (I) and less leakage current than MISFET-100. Also, Figure 12B shows V-
- V-I characteristics when V is 0.4V, 0.6V, 0.8V and 1.OV are shown.
- the MISFET-110 has a larger drain current (I) than MISFET-100.
- MISFET-110 has better electrical characteristics than MISFET-100.
- Figure 13 shows the V-I characteristics when the drain current (I) is specified by the thickness of the insulating film.
- MISFET-110 has a large drain current (I) on the high voltage side.
- Figure 14 compares the lZf noise characteristics of an evaluation MOS FET (referred to as “MOSFET-100”) using a silicon oxide film on the Si (100) surface as the gate insulating film and MISFET-110. Results are shown. In general, silicon nitride film has more defects in the film than silicon oxide film and is known to be inferior in noise characteristics. From Fig. 14, MISFET-110 has lZf noise compared to MOSFE T-100. Is about one-tenth, indicating good noise characteristics.
- MOSFET-100 evaluation MOS FET
- Figure 15A shows the XPS analysis of Si 2p on a silicon nitride film formed on a Si (100) surface.
- Figure 15B shows the Si 2p of the silicon nitride film formed on the Si (l lO) surface.
- Si ° +, Si 1+ , Si 2+ , Si 3+ and si 4+ all indicate Si subnitrides .
- the total amount of Si 1+ , Si 2+ and Si 3+ is 1.293 monolayer (ML) for silicon nitride film formed on Si (100) surface, while Si (110)
- the silicon nitride film formed on the surface was as small as 0.781 monolayer (ML). Therefore, by performing the plasma nitriding process on the Si (110) surface under the above conditions, it is possible to form a silicon nitride film with a smaller amount of subnitride than when a silicon nitride film is formed on the Si (100) surface. found.
- FIG. 16 is a schematic diagram for explaining the difference in stress (film stress) between the silicon nitride film formed on the Si (l lO) plane and the silicon nitride film formed on the Si (100) plane. . Since the silicon nitride film formed on the Si (100) surface has high compressive stress, the surface density of Si is high. On the other hand, the silicon nitride film formed on the Si (110) plane has a relatively low compressive stress compared to the silicon nitride film formed on the Si (100) plane. The surface density of the film is low, and the value is about 9.6 ⁇ 10 14 [atoms / cm 2 ]. This difference in areal density is thought to affect the difference in the amount of subnitride shown in FIGS.
- the difference in surface density between the silicon nitride film formed on the Si (110) surface and the silicon nitride film formed on the Si (100) surface is due to the excellent electrical characteristics described above in MISFET-110. It is thought that
- a silicon nitride film is formed by performing plasma nitriding on the substantial (110) surface of Si rather than the Si (100) surface of silicon. It is preferable.
- substantially (110) plane of Si means that it includes not only the (110) plane but also a slight inclination from the (110) plane, and also includes the (551) plane.
- FIG. 17 compares the gate current characteristics by EOT for an evaluation transistor using a silicon nitride film formed by the method of the present invention and an evaluation transistor using a silicon oxide film. The results are shown.
- FIG. 18A and 18B show the results of CV measurement by the LC resonance method for an evaluation transistor using a silicon nitride film formed by the method of the present invention.
- Fig. 18A shows the result when EOT is 1.7 nm
- Fig. 18B shows the result when EOT is 1.2 nm. From the above results, it was confirmed that the silicon nitride film formed by the method of the present invention exhibits excellent gate current characteristics.
- the apparatus of the present invention can be similarly implemented as long as it is an apparatus capable of generating high-frequency microwave-excited high-density plasma, taking the RLSA plasma processing apparatus 100 as an example.
- the plasma nitriding method of the present invention is not limited to the case of directly nitriding silicon to form a gate insulating film.
- the silicon oxynitride film for example, heat generated by WVG (Water Vapor Generation) Oxidized SiO film, plasma oxidized SiO film, etc.
- k materials eg HfO, RuO, ReO, ZrO, AlO, HfSiO, ZrSiO, and this
- the nitriding treatment is performed according to the plasma of the present invention. It can also be performed by a nitriding method.
- It can also be used for nitriding tunnel oxide films in flash memory and for forming ONO films between floating gates and control gates.
- the present invention can also be applied when the object to be processed is a polycrystalline silicon layer provided on a flat panel display (FPD) substrate typified by a liquid crystal display (LCD).
- FPD flat panel display
- LCD liquid crystal display
- plasma is applied to a polycrystalline silicon layer or an amorphous silicon layer provided on an FPD substrate such as a glass substrate via an insulator layer or an electrode layer by the above method.
- a gate insulating film including a silicon nitride film can be formed.
- the present invention can also be applied when the object to be processed is a compound semiconductor or the like.
- the present invention can be suitably used in the manufacturing process of various semiconductor devices including a step of forming a silicon nitride film by nitriding silicon.
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CN2006800202810A CN101194345B (zh) | 2005-06-08 | 2006-06-07 | 等离子体氮化处理方法和处理装置、半导体装置制造方法 |
US11/917,013 US7968470B2 (en) | 2005-06-08 | 2006-06-07 | Plasma nitriding method, method for manufacturing semiconductor device and plasma processing apparatus |
EP06757104A EP1898456A4 (en) | 2005-06-08 | 2006-06-07 | PLASMA NITRURATION METHOD, SEMICONDUCTOR DEVICE MANUFACTURING METHOD, AND PLASMA PROCESSING APPARATUS |
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- 2006-06-07 WO PCT/JP2006/311397 patent/WO2006132262A1/ja active Application Filing
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Also Published As
Publication number | Publication date |
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CN101194345B (zh) | 2010-05-19 |
TW200739725A (en) | 2007-10-16 |
US20090104787A1 (en) | 2009-04-23 |
JPWO2006132262A1 (ja) | 2009-01-08 |
JP2013225682A (ja) | 2013-10-31 |
TW201403712A (zh) | 2014-01-16 |
KR100942106B1 (ko) | 2010-02-12 |
EP1898456A1 (en) | 2008-03-12 |
KR20080009740A (ko) | 2008-01-29 |
US7968470B2 (en) | 2011-06-28 |
JP5339327B2 (ja) | 2013-11-13 |
CN101194345A (zh) | 2008-06-04 |
EP1898456A4 (en) | 2009-11-18 |
TWI456653B (zh) | 2014-10-11 |
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