US20030168706A1 - Semiconductor device and method for fabricating same - Google Patents

Semiconductor device and method for fabricating same Download PDF

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US20030168706A1
US20030168706A1 US10/127,571 US12757102A US2003168706A1 US 20030168706 A1 US20030168706 A1 US 20030168706A1 US 12757102 A US12757102 A US 12757102A US 2003168706 A1 US2003168706 A1 US 2003168706A1
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silicon substrate
layer
semiconductor device
nitrogen atoms
silicon
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US10/127,571
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Nobutoshi Aoki
Koichi Kato
Katsuyuki Sekine
Ichiro Mizushima
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Toshiba Corp
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Toshiba Corp
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Assigned to KABUSHIKI KAISHA TOSHIBA reassignment KABUSHIKI KAISHA TOSHIBA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AOKI, NOBUTOSHI, KATO, KOICHI, MIZUSHIMA, ICHIRO, SEKINE, KATSUYUKI
Publication of US20030168706A1 publication Critical patent/US20030168706A1/en
Priority to US11/020,271 priority Critical patent/US7160818B2/en
Priority to US11/250,439 priority patent/US7358198B2/en
Abandoned legal-status Critical Current

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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
    • H01L21/04—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
    • H01L21/28—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
    • H01L21/28185—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation with a treatment, e.g. annealing, after the formation of the gate insulator and before the formation of the definitive gate conductor
    • 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
    • H01L21/28—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
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
    • H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
    • H01L29/51—Insulating materials associated therewith
    • H01L29/511—Insulating materials associated therewith with a compositional variation, e.g. multilayer structures
    • H01L29/513—Insulating materials associated therewith with a compositional variation, e.g. multilayer structures the variation being perpendicular to the channel plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
    • H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
    • H01L29/51—Insulating materials associated therewith
    • H01L29/518—Insulating materials associated therewith the insulating material containing nitrogen, e.g. nitride, oxynitride, nitrogen-doped material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates generally to a semiconductor device having an insulating film, and a method for fabricating the same.
  • a typical semiconductor oxide film has a very great part as an insulating film in various semiconductor devices, the qualities and forming methods thereof have been variously studied.
  • a so-called thermal oxidation process for exposing the surface of a semiconductor to oxygen molecular gas in the atmosphere at high temperatures has been widely used.
  • the thickness of the thermal oxide film is decreasing.
  • the current tunneling through the oxide film rapidly increases to cause a phenomenon that impurities pass through the oxide film to diffuse. For that reason, it is being difficult to improve the performance of elements due to the scale down.
  • Japanese Patent Laid-Open No. 2001-203198 discloses a method for forming an oxynitride film.
  • the surface of a silicon substrate terminates with hydrogen, and hydrogen atoms are removed by heat treatment.
  • nitrogen atoms and oxygen atoms are absorbed onto unbonded bonds in a heating atmosphere of NO gas or NO+O 2 to form a monoatomic oxynitride layer.
  • it is oxidized in the atmosphere to form an oxynitride film having an oxide layer on the side of the silicon substrate and an oxynitride layer on the side of the surface.
  • most of nitrogen atoms in the oxynitride film formed by this method are in a two-coordinate bond state, so that it is difficult to reduce the energy level due to nitrogen atoms in the band gap of the oxynitride film.
  • a semiconductor device comprises a silicon oxynitride film having an oxynitride layer which is formed on at least the surface of a silicon substrate and in which nitrogen atoms are in a three-coordinate bond state, and a silicon oxide layer which is formed between the oxynitride layer and the silicon substrate.
  • a method for fabricating a semiconductor device comprises: forming a layer in which nitrogen atoms are arranged on at least the surface of a silicon substrate; causing the nitrogen atoms in the layer to be in a three-coordinate bond state with silicon atoms existing on the surface of the silicon substrate; and forming a silicon oxide layer between the silicon substrate and the layer while holding the bonding state of the nitrogen atoms of three-coordinate bonds in the layer with the silicon atoms.
  • FIG. 1 is a flow chart showing fabricating steps of a method for fabricating a semiconductor device according to the first embodiment of the present invention
  • FIG. 2 is a block diagram showing the construction of an oxynitride film forming apparatus for use in the fabricating steps in the first embodiment
  • FIG. 3 is a sectional view when an oxynitride layer is formed in the first layer on the surface in the middle of the fabricating steps in the first embodiment
  • FIG. 4 is a sectional view when an oxynitride layer is formed in the first layer on the surface and an oxide layer is formed in the second layer from the surface in the middle of the fabricating steps in the first embodiment;
  • FIG. 5 is a sectional view showing the construction of a MOSFET formed by a fabricating method according to the second embodiment of the present invention.
  • FIG. 6 is a graph showing the relationship between fixed charges and the mobility of electrons on the interface between a silicon substrate and a silicon oxynitride film
  • FIG. 7 is a sectional view when nitrogen atoms are in a three-coordinate bond state on the surface of a silicon substrate in the middle of the fabricating steps in the third embodiment;
  • FIG. 8 is a sectional view of a semiconductor device fabricated by a fabricating method according to the third embodiment of the present invention.
  • FIG. 9 is a sectional view showing the fabricating steps of the fourth embodiment of a fabricating method according to the present invention.
  • FIG. 10 is a sectional view of a semiconductor device after a first nitriding and annealing step is carried out.
  • FIG. 11 is a sectional view of a semiconductor device after a second nitriding and annealing step is carried out.
  • the semiconductor device fabricating method in this first embodiment is a method for fabricating a semiconductor device having an oxynitride film, and the steps of fabricating an oxynitride film are shown in FIG. 1.
  • the fabrication of the oxynitride film in this first embodiment is carried out by using an oxynitride film forming apparatus shown in FIG. 2.
  • the oxynitride film forming apparatus shown in FIG. 2 will be described below.
  • this oxynitride film forming apparatus has a chamber 4 having a heating furnace 3 for housing therein a movable susceptor 2 for supporting thereon a plurality of semiconductor substrates 1 .
  • an NO gas source 5 a nitrogen gas source 6 and an oxygen gas source 7 are connected as atmospheric gas sources.
  • the chamber 4 is provided with a gas inlet 8 for feeding NO gas, nitrogen gas and oxygen gas into the chamber 4 from these gas sources, and a gas outlet 9 for discharging gases.
  • valves 10 , 11 and 12 are mounted, respectively, for enabling the control of the partial pressures of gases.
  • a heater 13 is provided around the chamber 4 to be controlled by a temperature control unit (not shown).
  • FIGS. 1 and 2 the first embodiment of a fabricating method according to the present invention will be described below.
  • a silicon substrate 1 having (100) plane as a principal plane is treated with diluted hydrofluoric acid, so that the surface of the silicon substrate terminates with hydrogen.
  • the silicon substrate terminating with hydrogen is mounted on the susceptor 2 , and the valves 10 , 11 and 12 are open and closed at room temperatures so that the atmosphere in the chamber 4 is only nitrogen gas.
  • the heater 13 provided around the chamber 4 is controlled to raise the temperature of the silicon substrate 1 to 600° C. to completely remove hydrogen from the silicon substrate 1 (see step S 2 in FIG. 1).
  • step S 4 the valves 10 , 11 and 12 are open and closed again so that the atmosphere in the chamber 4 is only nitrogen gas, and the heater 13 is controlled to raise the temperature of the silicon substrate 1 to 900° C. to hold it for one minute.
  • nitrogen atoms in a first layer 15 of the silicon substrate 1 are substantially in a three-coordinate bond state to form a stable structure.
  • the temperature range for providing a three-coordinate bond state is preferably in the range of from 600° C. to 950° C.
  • valves 10 , 11 and 12 are open and closed so that the partial pressure of oxygen in the atmosphere in the chamber 4 is raised to the same level as that in the atmosphere, and the temperature of the silicon substrate 1 is raised to 800° C. to be held for ten minutes.
  • an oxynitride layer is formed in the first layer 15 on the surface of the silicon substrate 1
  • an oxide layer 16 is formed in the second and subsequent layers below the first layer 15 . That is, nitrogen atoms in the first layer 15 on the surface of the silicon substrate 1 are maintained in a three-coordinate bond state to form an oxynitride film on the surface of the silicon substrate and to form the oxide layer 16 in the second and subsequent layers.
  • the energy levels in the band gap are greatly reduced.
  • the oxynitride film is formed on the surface of the silicon substrate 1 , it is preferably formed on the uppermost surface, i.e., the first layer.
  • the oxynitride film having the three-coordinate-bonded nitrogen is formed, and the second and substrate layers from the surface are complete oxide layers. Therefore, it is possible to obtain an oxynitride film wherein the interface structure is a flat structure at an atomic level, and it is possible to obtain a silicon oxynitride film (insulating film) wherein the energy level due to nitrogen atoms in the band gap is reduced.
  • nitrogen molecular radicals may be substituted for nitrogen gas.
  • a gas of a kind which does not react with the semiconductor e.g., an inert gas such as argon gas, may be used.
  • an inert gas such as argon gas
  • a semiconductor other than a silicon substrate a semiconductor causing an oxidation reaction may be used.
  • the fabricating method in this second embodiment uses the fabricating method in the first embodiment to form a gate oxide film of a MOSFET.
  • a field oxide film 18 is formed on a silicon substrate 1 .
  • a gate oxynitride film 19 is formed on the surface of an element region isolated by the field oxide film 18 .
  • the gate oxynitride film 19 having a thickness of 20 ⁇ is formed by the oxynitride film forming method described in the first embodiment.
  • a gate electrode material is deposited thereon to be patterned to form a gate electrode 20 .
  • the gate electrode 20 is used as a mask to form a source region 21 a and a drain region 21 b by ion implantation to obtain a MOSFET.
  • the gate oxynitride film 19 thus formed has a very uniform interface. As a result, the obtained MOSFET has a small variation in threshold voltage, no deterioration of mobility, and stable characteristics.
  • nitrogen atoms in the oxynitride films formed by the above described fabricating methods in the first and second embodiments substantially have the three-coordinate bonds.
  • the allowable contents of nitrogen atoms of coordinate bonds different from the three-coordinate bonds will be described below. If all of nitrogen atoms have the three-coordinate bonds, the fixed charge is zero, whereas if there are nitrogen atoms of coordinate bonds different from the three-coordinate bonds, the fixed charge occurs. Therefore, the amount of nitrogen atoms of coordinate bonds different from the three-coordinate bonds can be defined by the amount of fixed charges since it is in proportion to the amount of fixed charges.
  • the characteristic graph shown in FIG. 6 is obtained.
  • the mobility of electrons rapidly deteriorates if the amount of fixed charges exceeds 1.0 ⁇ 10 11 (cm ⁇ 2 ) to 2.0 ⁇ 10 11 (cm ⁇ 2 ). Therefore, in order to prevent the deterioration of the performance of the element, the amount of fixed charges is preferably 2.0 ⁇ 10 11 (cm ⁇ 2 ) or less.
  • the amount of fixed charges is the value on the interface between the silicon oxynitride film and the silicon substrate. However, it has been understood that the amount of fixed charges hardly varies in a range of 10 ⁇ from the above described interface in a direction perpendicular to the silicon oxynitride film.
  • FIGS. 7 and 8 a method for fabricating a semiconductor device according to the third embodiment of the present invention will be described below.
  • nitrogen atoms are arranged on the surface of a silicon substrate prior to the above described usual oxidation.
  • nitrogen atoms on the surface of the silicon substrate are introduced by plasma nitriding, and thereafter, a high-temperature heating process is carried out.
  • FIG. 7 schematically show nitrogen atoms and silicon atoms on the surface of the silicon substrate 1 after the high-temperature heating process. As can be seen from FIG. 7, nitrogen atoms on the surface of the silicon substrate 1 are in the three-coordinate bond state with adjacent silicon atoms.
  • an oxidation process is carried out under a reduced pressure to oxidize the silicon substrate 1 .
  • Oxidizing conditions can be optionally set.
  • an oxide film having a thickness of 1 nm was formed at an oxygen partial pressure of 40 Torr at a temperature of 700° C.
  • FIG. 8 schematically shows the bonding state of oxygen atoms, nitrogen atoms and silicon atoms on the surface of the silicon substrate 1 and in the oxide film after oxidation. As can be seen from FIG.
  • the fabricating process in this fourth embodiment is a method for fabricating a MOSFET, and forms a gate insulating film using the fabricating method in the third embodiment.
  • nitrogen atoms are arranged on part of the surface of the silicon substrate 1 to form a region 30 , in which nitrogen atoms are in the three-coordinate bond state with silicon atoms, by a high-temperature heat treatment.
  • nitrogen atoms are introduced into the silicon substrate 1 at a low energy (10 eV) with plasma so that the density of nitrogen is 5.0 ⁇ 10 14 cm ⁇ 2 .
  • annealing was carried out at 950° C. for thirty minutes.
  • a method for introducing nitrogen atoms onto the surface of the silicon substrate 1 may use a nitrogen atom containing gas, or use a gas having a reducing action to cause nitrogen atoms to remain on the surface of the silicon substrate after an oxygen containing gas, such as NO gas, is used for introducing nitrogen.
  • an oxygen containing gas such as NO gas
  • the heat treatment was carried out at 950° C. for thirty minutes as a step of causing the three-coordinate bond state.
  • temperature and time can be optionally set.
  • the surface of the silicon substrate 1 is oxidized to form an insulating film (oxynitride film) 32 on the surface of the silicon substrate 1 .
  • the oxide film having a thickness of 1 nm was formed at 700° C. at an oxygen partial pressure of 40 Torr.
  • the oxidation atmosphere, time and the partial pressure of gas can be optionally set, and the radical oxidation or the like can be used.
  • a polysilicon film 34 is deposited on the insulating film 32 .
  • the lithography technique or the like is used for forming a photoresist pattern 36 on the polysilicon film 34 , and the photoresist pattern 36 is used as a mask for patterning the polysilicon film 34 to form a gate electrode 34 a (see FIG. 9( d )).
  • the photoresist pattern 36 and the gate electrode 34 a are used as a mask for implanting impurity ions to form a source region 38 a and a drain region 38 b.
  • nitrogen atoms are form stable three-coordinate bonds with silicon atoms, so that a high quality gate insulating film having a small amount of energy levels in the gap is formed.
  • a uniform and stable MOSFET wherein the variation in threshold voltage is small and the mobility does not deteriorate.
  • nitrogen atoms in the insulating film are substantially in the three-coordinate bond state. Similar to the first and second embodiments, the allowable contents of nitrogen atoms of coordinate bonds different from the three-coordinate bonds in the insulating film are defined by the amount of fixed charges, and the amount of fixed charges is preferably 2.0 ⁇ 10 11 (cm ⁇ 2 ) or less in order to prevent the deterioration of the performance of the element.
  • the step of nitriding the surface of the silicon substrate 1 to provide the three-coordinate bond state by annealing is carried out only one time.
  • a step of nitriding the surface of the silicon substrate 1 to provide the three-coordinate bond state by annealing as shown in FIG. 10 is carried out one time and before the silicon oxide film is formed, a step of nitriding the surface of the silicon substrate 1 to carry out annealing as shown in FIG. 11 may be repeated at least one time.

Abstract

An aspect of the present invention includes; a silicon oxynitride film having an oxynitride layer which is formed on at least the surface of a silicon substrate and in which nitrogen atoms are in a three-coordinate bond state, and a silicon oxide layer which is formed between said oxynitride layer and said silicon substrate.

Description

    CROSS-REFERENCE TO RELATED APPLICATION
  • This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 2002-63117, filed on Mar. 8, 2002; the entire contents of which are incorporated herein by reference. [0001]
    • BACKGROUND OF THE INVENTION
  • 1. Technical Field of The Invention [0002]
  • The present invention relates generally to a semiconductor device having an insulating film, and a method for fabricating the same. [0003]
  • 2. Description of Related Art [0004]
  • Since a typical semiconductor oxide film has a very great part as an insulating film in various semiconductor devices, the qualities and forming methods thereof have been variously studied. As a method for forming a semiconductor oxide film, a so-called thermal oxidation process for exposing the surface of a semiconductor to oxygen molecular gas in the atmosphere at high temperatures has been widely used. With the scale down of elements, it is considered that the thickness of the thermal oxide film is decreasing. However, if the thickness of the oxide film is 2 nm or less, the current tunneling through the oxide film rapidly increases to cause a phenomenon that impurities pass through the oxide film to diffuse. For that reason, it is being difficult to improve the performance of elements due to the scale down. [0005]
  • Therefore, there is considered a method for mixing nitrogen in an oxide film to form an oxynitride film. If nitrogen atoms are introduced into an oxide film, the dielectric constant of the oxynitride film increases, so that the thickness of an oxynitride film having the same capacitance as that of an oxide film can be larger. In addition, since the diffusion of impurities, such as boron, can be suppressed, it has been possible to effectively form a thinner high-performance insulating film by the conversion to an oxide film. [0006]
  • However, if nitrogen atoms are introduced into an oxide film, energy levels due to nitrogen atoms are formed in a band gap in the insulating film although the effective thickness can be decreased. For that reason, if an oxide film into which nitrogen atoms are introduced is used as, e.g., a gate insulating film for a MOS transistor, current drivability decreases due to a degradation of carrier mobility. In order to prevent this, there is considered a method for preventing the scattering of electrons by localizing introduced nitrogen atoms in the vicinity of the surface of the gate insulating film so as to be spaced from the interface between the semiconductor layer and the gate insulating film. However, it is difficult for this method to completely control the doping amount and to reduce the energy level due to nitrogen atoms. [0007]
  • Japanese Patent Laid-Open No. 2001-203198 discloses a method for forming an oxynitride film. In this method, the surface of a silicon substrate terminates with hydrogen, and hydrogen atoms are removed by heat treatment. Thereafter, nitrogen atoms and oxygen atoms are absorbed onto unbonded bonds in a heating atmosphere of NO gas or NO+O[0008] 2 to form a monoatomic oxynitride layer. Thereafter, it is oxidized in the atmosphere to form an oxynitride film having an oxide layer on the side of the silicon substrate and an oxynitride layer on the side of the surface. However, most of nitrogen atoms in the oxynitride film formed by this method are in a two-coordinate bond state, so that it is difficult to reduce the energy level due to nitrogen atoms in the band gap of the oxynitride film.
    • SUMMARY OF THE INVENTION
  • A semiconductor device according to a first aspect of the present invention comprises a silicon oxynitride film having an oxynitride layer which is formed on at least the surface of a silicon substrate and in which nitrogen atoms are in a three-coordinate bond state, and a silicon oxide layer which is formed between the oxynitride layer and the silicon substrate. [0009]
  • A method for fabricating a semiconductor device according to a second aspect of the present invention comprises: forming a layer in which nitrogen atoms are arranged on at least the surface of a silicon substrate; causing the nitrogen atoms in the layer to be in a three-coordinate bond state with silicon atoms existing on the surface of the silicon substrate; and forming a silicon oxide layer between the silicon substrate and the layer while holding the bonding state of the nitrogen atoms of three-coordinate bonds in the layer with the silicon atoms.[0010]
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is a flow chart showing fabricating steps of a method for fabricating a semiconductor device according to the first embodiment of the present invention; [0011]
  • FIG. 2 is a block diagram showing the construction of an oxynitride film forming apparatus for use in the fabricating steps in the first embodiment; [0012]
  • FIG. 3 is a sectional view when an oxynitride layer is formed in the first layer on the surface in the middle of the fabricating steps in the first embodiment; [0013]
  • FIG. 4 is a sectional view when an oxynitride layer is formed in the first layer on the surface and an oxide layer is formed in the second layer from the surface in the middle of the fabricating steps in the first embodiment; [0014]
  • FIG. 5 is a sectional view showing the construction of a MOSFET formed by a fabricating method according to the second embodiment of the present invention; [0015]
  • FIG. 6 is a graph showing the relationship between fixed charges and the mobility of electrons on the interface between a silicon substrate and a silicon oxynitride film; [0016]
  • FIG. 7 is a sectional view when nitrogen atoms are in a three-coordinate bond state on the surface of a silicon substrate in the middle of the fabricating steps in the third embodiment; [0017]
  • FIG. 8 is a sectional view of a semiconductor device fabricated by a fabricating method according to the third embodiment of the present invention; [0018]
  • FIG. 9 is a sectional view showing the fabricating steps of the fourth embodiment of a fabricating method according to the present invention; [0019]
  • FIG. 10 is a sectional view of a semiconductor device after a first nitriding and annealing step is carried out; and [0020]
  • FIG. 11 is a sectional view of a semiconductor device after a second nitriding and annealing step is carried out.[0021]
    • DESCRIPTION OF THE EMBODIMENTS
  • Referring now to the accompanying drawings, the embodiments of the present invention will be described below. [0022]
  • (First Embodiment) [0023]
  • Referring to FIGS. 1 through 4, a method for fabricating a semiconductor device according to the first embodiment of the present invention will be described below. The semiconductor device fabricating method in this first embodiment is a method for fabricating a semiconductor device having an oxynitride film, and the steps of fabricating an oxynitride film are shown in FIG. 1. The fabrication of the oxynitride film in this first embodiment is carried out by using an oxynitride film forming apparatus shown in FIG. 2. Before describing the fabricating method in the first embodiment, the oxynitride film forming apparatus shown in FIG. 2 will be described below. [0024]
  • As shown in FIG. 2, this oxynitride film forming apparatus has a chamber [0025] 4 having a heating furnace 3 for housing therein a movable susceptor 2 for supporting thereon a plurality of semiconductor substrates 1. To this chamber 4, an NO gas source 5, a nitrogen gas source 6 and an oxygen gas source 7 are connected as atmospheric gas sources. The chamber 4 is provided with a gas inlet 8 for feeding NO gas, nitrogen gas and oxygen gas into the chamber 4 from these gas sources, and a gas outlet 9 for discharging gases. On the NO gas source 5, nitrogen gas source 6 and oxygen gas source7, valves 10, 11 and 12 are mounted, respectively, for enabling the control of the partial pressures of gases. A heater 13 is provided around the chamber 4 to be controlled by a temperature control unit (not shown).
  • Referring to FIGS. 1 and 2, the first embodiment of a fabricating method according to the present invention will be described below. [0026]
  • First, as shown at step S[0027] 1 in FIG. 1, a silicon substrate 1 having (100) plane as a principal plane is treated with diluted hydrofluoric acid, so that the surface of the silicon substrate terminates with hydrogen. Then, as shown at step S2 in FIG. 1, the silicon substrate terminating with hydrogen is mounted on the susceptor 2, and the valves 10, 11 and 12 are open and closed at room temperatures so that the atmosphere in the chamber 4 is only nitrogen gas. Subsequently, the heater 13 provided around the chamber 4 is controlled to raise the temperature of the silicon substrate 1 to 600° C. to completely remove hydrogen from the silicon substrate 1 (see step S2 in FIG. 1).
  • Thereafter, as shown at step S[0028] 3, the heater 13 is controlled to lower the temperature of the silicon substrate 1 to 200° C. Moreover, the valve 10 is open and closed to mix NO gas at a partial pressure of 10−6 Torr (=10−6×133.322 Pa) to hold it for one minute. Thus, an oxide film containing nitrogen atoms (an oxynitride film) is formed on the first layer of the silicon substrate 1.
  • Then, as shown at step S[0029] 4, the valves 10, 11 and 12 are open and closed again so that the atmosphere in the chamber 4 is only nitrogen gas, and the heater 13 is controlled to raise the temperature of the silicon substrate 1 to 900° C. to hold it for one minute. Thus, as shown in FIG. 3, nitrogen atoms in a first layer 15 of the silicon substrate 1 are substantially in a three-coordinate bond state to form a stable structure. Furthermore, the temperature range for providing a three-coordinate bond state is preferably in the range of from 600° C. to 950° C.
  • Subsequently, the [0030] valves 10, 11 and 12 are open and closed so that the partial pressure of oxygen in the atmosphere in the chamber 4 is raised to the same level as that in the atmosphere, and the temperature of the silicon substrate 1 is raised to 800° C. to be held for ten minutes. Thus, as shown in FIG. 4, an oxynitride layer is formed in the first layer 15 on the surface of the silicon substrate 1, and an oxide layer 16 is formed in the second and subsequent layers below the first layer 15. That is, nitrogen atoms in the first layer 15 on the surface of the silicon substrate 1 are maintained in a three-coordinate bond state to form an oxynitride film on the surface of the silicon substrate and to form the oxide layer 16 in the second and subsequent layers. Thereafter, a silicon oxynitride film which has the first layer to be an oxynitride layer and the second layer 16 and subsequent layers to be oxide layers and which has an interface structure being a flat structure at an atomic level and a thickness of 20 Å (=2 nm) is formed. Thus, the energy levels in the band gap are greatly reduced. Furthermore, although the oxynitride film is formed on the surface of the silicon substrate 1, it is preferably formed on the uppermost surface, i.e., the first layer.
  • As described above, according to the fabricating method in this embodiment, the oxynitride film having the three-coordinate-bonded nitrogen is formed, and the second and substrate layers from the surface are complete oxide layers. Therefore, it is possible to obtain an oxynitride film wherein the interface structure is a flat structure at an atomic level, and it is possible to obtain a silicon oxynitride film (insulating film) wherein the energy level due to nitrogen atoms in the band gap is reduced. [0031]
  • Furthermore, nitrogen molecular radicals may be substituted for nitrogen gas. [0032]
  • While it has been exposed to an atmosphere of oxygen at 800° C. for ten minutes in this embodiment, various temperatures and times may be combined if the oxynitride film having the three-coordinate-bonded nitrogen in the first layer of the [0033] silicon substrate 1 is formed, and materials other than oxygen may be used if an oxidization reaction occurs.
  • While hydrogen on the surface of the [0034] silicon substrate 1 is removed at the heating step before the oxidizing step, the removal of hydrogen may be carried out at a step other than the heating step.
  • In the place of nitrogen gas, a gas of a kind which does not react with the semiconductor, e.g., an inert gas such as argon gas, may be used. As a semiconductor other than a silicon substrate, a semiconductor causing an oxidation reaction may be used. [0035]
  • (Second Embodiment) [0036]
  • Referring to FIG. 5, a method for fabricating a semiconductor device according to the second embodiment of the present invention will be described below. The fabricating method in this second embodiment uses the fabricating method in the first embodiment to form a gate oxide film of a MOSFET. First, as shown in FIG. 5, a [0037] field oxide film 18 is formed on a silicon substrate 1. On the surface of an element region isolated by the field oxide film 18, a gate oxynitride film 19 is formed. In this case, the gate oxynitride film 19 having a thickness of 20 Å is formed by the oxynitride film forming method described in the first embodiment. Thereafter, a gate electrode material is deposited thereon to be patterned to form a gate electrode 20. Subsequently, the gate electrode 20 is used as a mask to form a source region 21 a and a drain region 21 b by ion implantation to obtain a MOSFET.
  • The [0038] gate oxynitride film 19 thus formed has a very uniform interface. As a result, the obtained MOSFET has a small variation in threshold voltage, no deterioration of mobility, and stable characteristics.
  • Furthermore, in the oxynitride films formed by the above described fabricating methods in the first and second embodiments, nitrogen atoms in the oxynitride films substantially have the three-coordinate bonds. The allowable contents of nitrogen atoms of coordinate bonds different from the three-coordinate bonds will be described below. If all of nitrogen atoms have the three-coordinate bonds, the fixed charge is zero, whereas if there are nitrogen atoms of coordinate bonds different from the three-coordinate bonds, the fixed charge occurs. Therefore, the amount of nitrogen atoms of coordinate bonds different from the three-coordinate bonds can be defined by the amount of fixed charges since it is in proportion to the amount of fixed charges. If the relationship between the amount of fixed charges and the mobility of electrons on the interface between the silicon oxynitride film produced in the above described embodiment and the silicon substrate is simulated, the characteristic graph shown in FIG. 6 is obtained. As can be seen from this characteristic graph, the mobility of electrons rapidly deteriorates if the amount of fixed charges exceeds 1.0×10[0039] 11 (cm−2) to 2.0×1011 (cm−2). Therefore, in order to prevent the deterioration of the performance of the element, the amount of fixed charges is preferably 2.0×1011 (cm−2) or less. Furthermore, in the above descriptions, the amount of fixed charges is the value on the interface between the silicon oxynitride film and the silicon substrate. However, it has been understood that the amount of fixed charges hardly varies in a range of 10 Å from the above described interface in a direction perpendicular to the silicon oxynitride film.
  • (Third Embodiment) [0040]
  • Referring to FIGS. 7 and 8, a method for fabricating a semiconductor device according to the third embodiment of the present invention will be described below. [0041]
  • In the above described first and second embodiments, the method for forming the oxynitride film using NO gas has been described. In the following embodiments, a method for forming an oxide film after arranging nitrogen atoms on the surface of a silicon substrate will be described below. [0042]
  • In the fabricating method in this embodiment, nitrogen atoms are arranged on the surface of a silicon substrate prior to the above described usual oxidation. For example, nitrogen atoms on the surface of the silicon substrate are introduced by plasma nitriding, and thereafter, a high-temperature heating process is carried out. FIG. 7 schematically show nitrogen atoms and silicon atoms on the surface of the [0043] silicon substrate 1 after the high-temperature heating process. As can be seen from FIG. 7, nitrogen atoms on the surface of the silicon substrate 1 are in the three-coordinate bond state with adjacent silicon atoms.
  • Subsequently, an oxidation process is carried out under a reduced pressure to oxidize the [0044] silicon substrate 1. Oxidizing conditions can be optionally set. In this embodiment, an oxide film having a thickness of 1 nm was formed at an oxygen partial pressure of 40 Torr at a temperature of 700° C. FIG. 8 schematically shows the bonding state of oxygen atoms, nitrogen atoms and silicon atoms on the surface of the silicon substrate 1 and in the oxide film after oxidation. As can be seen from FIG. 8, since nitrogen atoms are in the three-coordinate bond state with silicon atoms, the configuration of nitrogen atoms is energetically stable, and the change of state is not carried out even in the oxidation reaction, i.e., the three-coordinate bond state is held, so that nitrogen atoms exist on the surface of the oxide film. Moreover, since nitrogen atoms form stable three-coordinate bonds with silicon atoms, a high quality of insulating film having a small amount of energy levels in the gap is formed similar to the first embodiment.
  • (Fourth Embodiment) [0045]
  • Referring to FIG. 9, a method for fabricating a semiconductor device according to the fourth embodiment of the present invention will be described below. The fabricating process in this fourth embodiment is a method for fabricating a MOSFET, and forms a gate insulating film using the fabricating method in the third embodiment. [0046]
  • First, as shown in FIG. 9([0047] a), nitrogen atoms are arranged on part of the surface of the silicon substrate 1 to form a region 30, in which nitrogen atoms are in the three-coordinate bond state with silicon atoms, by a high-temperature heat treatment. In this embodiment, nitrogen atoms are introduced into the silicon substrate 1 at a low energy (10 eV) with plasma so that the density of nitrogen is 5.0×1014 cm−2. In addition, in order for nitrogen to be in the three-coordinate bond state, annealing was carried out at 950° C. for thirty minutes. Furthermore, a method for introducing nitrogen atoms onto the surface of the silicon substrate 1 may use a nitrogen atom containing gas, or use a gas having a reducing action to cause nitrogen atoms to remain on the surface of the silicon substrate after an oxygen containing gas, such as NO gas, is used for introducing nitrogen. In this embodiment, the heat treatment was carried out at 950° C. for thirty minutes as a step of causing the three-coordinate bond state. However, temperature and time can be optionally set.
  • Then, as shown in FIG. 9([0048] b), the surface of the silicon substrate 1 is oxidized to form an insulating film (oxynitride film) 32 on the surface of the silicon substrate 1. In this embodiment, the oxide film having a thickness of 1 nm was formed at 700° C. at an oxygen partial pressure of 40 Torr. However, the oxidation atmosphere, time and the partial pressure of gas can be optionally set, and the radical oxidation or the like can be used.
  • Then, as shown in FIG. 9([0049] c), a polysilicon film 34 is deposited on the insulating film 32. Subsequently, as shown in FIG. 9(d), the lithography technique or the like is used for forming a photoresist pattern 36 on the polysilicon film 34, and the photoresist pattern 36 is used as a mask for patterning the polysilicon film 34 to form a gate electrode 34 a (see FIG. 9(d)).
  • Then, as shown in FIG. 9([0050] e), the photoresist pattern 36 and the gate electrode 34 a are used as a mask for implanting impurity ions to form a source region 38 a and a drain region 38 b.
  • Then, as shown in FIG. 9([0051] f), after the photoresist pattern 36 is removed, annealing is carried out for activation. Thereafter, the formation of an insulating film between wiring portions and the formation of wiring portions are carried out by a usual method to complete a semiconductor device.
  • As described above, also in this fourth embodiment similar to the third embodiment, nitrogen atoms are form stable three-coordinate bonds with silicon atoms, so that a high quality gate insulating film having a small amount of energy levels in the gap is formed. Thus, it is possible to form a uniform and stable MOSFET wherein the variation in threshold voltage is small and the mobility does not deteriorate. [0052]
  • Furthermore, in the above described third and fourth embodiments, nitrogen atoms in the insulating film are substantially in the three-coordinate bond state. Similar to the first and second embodiments, the allowable contents of nitrogen atoms of coordinate bonds different from the three-coordinate bonds in the insulating film are defined by the amount of fixed charges, and the amount of fixed charges is preferably 2.0×10[0053] 11 (cm−2) or less in order to prevent the deterioration of the performance of the element.
  • In the above described first through fourth embodiments, the step of nitriding the surface of the [0054] silicon substrate 1 to provide the three-coordinate bond state by annealing is carried out only one time. However, after a step of nitriding the surface of the silicon substrate 1 to provide the three-coordinate bond state by annealing as shown in FIG. 10 is carried out one time and before the silicon oxide film is formed, a step of nitriding the surface of the silicon substrate 1 to carry out annealing as shown in FIG. 11 may be repeated at least one time.
  • By repeating the step of nitriding the surface of the [0055] silicon substrate 1 to provide the three-coordinate bond state by annealing, it is possible to enhance the density of nitrogen atoms in the three-coordinate bond state on the surface of the silicon substrate 1, so that it is possible to obtain an insulating film wherein energy levels in the band gap are reduced.
  • As described above, according to the present invention, it is possible to obtain an insulating film wherein the energy levels in the band gap are reduced. [0056]
  • Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and representative embodiments shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concepts as defined by the appended claims and their equivalents. [0057]

Claims (14)

What is claimed is:
1. A semiconductor device comprising a silicon oxynitride film having an oxynitride layer which is formed on at least the surface of a silicon substrate and in which nitrogen atoms are in a three-coordinate bond state, and a silicon oxide layer which is formed between said oxynitride layer and said silicon substrate.
2. The semiconductor device a set forth in claim 1, wherein the amount of fixed charges of said silicon oxynitride film is 2.0×1011 cm−2 or less.
3. The semiconductor device as set forth in claim 1, wherein said oxynitride layer is a monoatomic layer.
4. The semiconductor device as set forth in claim 1, wherein said oxynitride layer is formed on the uppermost surface of said silicon substrate.
5. The semiconductor device as set forth in claim 1, wherein said silicon oxynitride film is a gate insulating film of a field effect transistor.
6. A method for fabricating a semiconductor device comprising:
forming a layer in which nitrogen atoms are arranged on at least the surface of a silicon substrate;
causing said nitrogen atoms in said layer to be in a three-coordinate bond state with silicon atoms existing on the surface of said silicon substrate; and
forming a silicon oxide layer between said silicon substrate and said layer while holding the bonding state of said nitrogen atoms of three-coordinate bonds in said layer with said silicon atoms.
7. The method for fabricating a semiconductor device as set forth in claim 6, wherein said forming of the layer in which the nitrogen atoms are arranged on the silicon substrate is carried out by allowing said silicon substrate to react with a nitrogen containing gas.
8. The method for fabricating a semiconductor device as set forth in claim 7, wherein said nitrogen containing gas consists of nitrogen atoms or nitrogen molecular radicals.
9. The method for fabricating a semiconductor device as set forth in claim 6, wherein said layer in which the nitrogen atoms are arranged on the silicon substrate is a monoatomic layer.
10. The method for fabricating a semiconductor device as set forth in claim 6, wherein said oxynitride layer is formed on the uppermost surface of said silicon substrate.
11. The method for fabricating a semiconductor device as set forth in claim 6, wherein said causing the nitrogen atoms is carried out by carrying out a heat treatment at a temperature of 600° C. to 950° C.
12. The method for fabricating a semiconductor device as set forth in claim 6, wherein said forming of the layer in which the nitrogen atoms are arranged on at least the surface of the silicon substrate, and said causing step are repeated a plurality of times before forming a silicon oxide layer between said silicon substrate and said layer.
13. The method for fabricating a semiconductor device as set forth in claim 6, which further comprises:
forming a gate electrode on said silicon substrate after forming said silicon oxide layer; and
using said gate electrode as a mask to inject impurities into said silicon substrate to form source and drain regions.
14. The method for fabricating a semiconductor device as set forth in claim 6, which further comprises terminating the surface of said silicon substrate with hydrogen before forming said layer in which the nitrogen atoms are arranged on at least the surface of the silicon substrate, and thereafter, raising the temperature of said silicon substrate to completely remove hydrogen.
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