JP5387173B2 - Semiconductor device and manufacturing method thereof - Google Patents

Description

  The present invention relates to a semiconductor device and a manufacturing method thereof, and more particularly to a semiconductor device having a MISFET including a gate insulating film of a high dielectric constant film and a manufacturing method thereof.

  The speeding up and integration of LSIs has been advanced by miniaturization of MIS type field effect transistors (hereinafter referred to as MISFETs) based on scaling rules. In other words, each part of the MISFET such as the thickness of the gate insulating film and the gate length is reduced in size in the height direction and the lateral direction at the same time, so that the characteristics of the element can be kept normal and the performance can be improved. Made it possible. At present, MISFET continues to be miniaturized, and a gate insulating film having a film thickness of 1 nm or less in terms of silicon oxide film is required as the next generation MISFET.

  Conventionally, a silicon oxide film has been widely used as a gate insulating film. However, it has been pointed out that when the film thickness is about 3 nm or less in the silicon oxide film, the tunnel leakage current becomes remarkable and the function as the insulating film is not achieved. In addition, it has been pointed out that the dopant impurity added to the gate electrode penetrates the gate insulating film and diffuses into the channel region of the silicon substrate due to the thinning of the gate insulating film, thereby changing the MIS characteristics.

  As a technique to reduce leakage current and prevent dopant impurities from penetrating, the physical film thickness can be increased without increasing the effective oxide film thickness by using a gate dielectric material with a higher dielectric constant than silicon oxide. A method has been proposed. In recent years, hafnium-based high dielectric constant materials mainly composed of hafnium oxide such as HfO, HfON, HfSiO, and HfSiON have attracted attention as high-dielectric constant materials, and MISFETs using these hafnium-based materials have been studied. Yes.

  On the other hand, as a gate electrode material, depletion does not occur due to low resistance, and a work function can be controlled by selecting a material, so that a threshold voltage can be made shallow.

JP 2005-191341 A JP 2006-080409 A JP 2006-237371 A JP 2007-266230 A JP 2008-135760 A JP 2008-537359 A

T. W. Hickmott, "Dipole layers at the metal-SiO2 interface", J. Appl. Phys., Vol. 51, No. 8, 1980, pp. 4269-4281 T. Morooka et al., "Vt variation suppressed Al2O3-capped HfO2 gate dielectrics for low Vt pMISFETs with high-k / metal gate stacks", Extended Abstracts of the 2008 International Conference on Solid State Devices and Materials, pp. 24-25 M. Sato et al., "Physical understanding of the reliability improvement of dual high-k CMOSFETs with the fifth element incorporation into HfSiON gate dielectrics", 2008 Symposium on VLSI Technology Digest of Technical Papers, pp. 66-67

  However, when a gate electrode made of a metal material is formed on a gate insulating film containing a hafnium-based material, the threshold voltage of the MISFET may not be controlled depending on the relationship between the work function of the metal gate material and the work function of the semiconductor substrate. there were.

  An object of the present invention is to provide an easy and shallow threshold voltage in a MISFET in which a metal gate is formed on a gate insulating film mainly composed of hafnium oxide, depending on the relationship between the work function of the metal gate material and the work function of the semiconductor substrate. An object of the present invention is to provide a semiconductor device that can be controlled and a manufacturing method thereof.

  According to one aspect of the embodiment, a step of forming a first insulating film mainly composed of silicon oxide on a semiconductor substrate, and a second insulation mainly composed of hafnium oxide on the first insulating film. Forming a film; performing a heat treatment to deposit silicon on the second insulating film; forming a third insulating film having an oxidizing action on silicon on the silicon; A step of forming a metal film on the third insulating film, a step of patterning the metal film to form a gate electrode including the metal film, a heat treatment, and the step of forming the metal film on the third insulating film. There is provided a method of manufacturing a semiconductor device including a step of oxidizing the silicon by an oxidizing action.

According to another aspect of the embodiment, a step of forming a first insulating film mainly composed of silicon oxide on a semiconductor substrate and a first step mainly composed of hafnium oxide on the first insulating film. forming a second insulating film, a heat treatment is performed on the second insulating film, a step of precipitating silicon, a step of oxidizing the silicon, after the step of oxidizing the silicon and oxide wherein After the step of removing silicon and the step of removing silicon, a step of forming a metal film on the second insulating film, patterning the metal film, and forming a gate electrode including the metal film A method of manufacturing a semiconductor device having a process is provided.

  According to still another aspect of the embodiment, a step of forming a first insulating film mainly composed of silicon oxide on a semiconductor substrate and a process mainly composed of hafnium oxide on the first insulating film. A step of forming a second insulating film; a step of performing heat treatment to deposit silicon on the second insulating film; a step of removing the silicon; and a metal film on the second insulating film. There is provided a method for manufacturing a semiconductor device, which includes a step of forming a gate electrode, and a step of patterning the metal film to form a gate electrode including the metal film.

  According to still another aspect of the embodiment, a step of forming a first insulating film mainly composed of silicon oxide on a semiconductor substrate and a process mainly composed of hafnium oxide on the first insulating film. A step of forming a second insulating film; and exposing the surface of the second insulating film to an atmosphere containing a dopant impurity capable of imparting a predetermined conductivity type to silicon; and on the second insulating film, Forming a dopant adhesion layer formed by adhering the dopant impurities, forming a metal film on the second insulating film on which the dopant adhesion layer is formed, patterning the metal film, A step of forming a gate electrode of a metal film and a heat treatment are performed to deposit silicon between the second insulating film and the metal film, and the dopant impurity of the dopant adhesion layer is added to the silicon That a method of manufacturing a semiconductor device and a step is provided.

  According to still another aspect of the embodiment, a step of forming a first insulating film mainly composed of silicon oxide on a semiconductor substrate and a process mainly composed of hafnium oxide on the first insulating film. Forming a second insulating film, forming a metal film on the second insulating film, introducing a dopant impurity into the metal film, and patterning the metal film. A step of forming a gate electrode of the metal film and a heat treatment to deposit silicon between the second insulating film and the metal film, and to add the dopant impurity in the metal film into the silicon A method for manufacturing a semiconductor device is provided.

  According to still another aspect of the embodiment, a first insulating film formed on a semiconductor substrate and mainly made of silicon oxide, and formed on the first insulating film and mainly made of hafnium oxide. A second insulating film, a third insulating film formed on the second insulating film, mainly made of silicon oxide, and formed on the third insulating film; Ta, Mo, Mn, Fe, A gate insulating film having a fourth insulating film mainly composed of an oxide of Ni, Ru, Co, Cu, Pt or Zn, and a metal film formed on the gate insulating film and in contact with the fourth insulating film A semiconductor device is provided.

  According to the disclosed semiconductor device and the manufacturing method thereof, even when silicon is deposited between the gate insulating film and the gate electrode by the heat treatment in the MISFET formation process, the silicon can be replaced with the silicon oxide film. As a result, the effect of the threshold voltage control by the work function of the metal gate film can be suppressed from being inhibited by the deposited silicon film, and the threshold voltage can be controlled by the relationship between the work function of the metal gate film and the silicon substrate. .

FIG. 1 is a process cross-sectional view (part 1) illustrating a method for manufacturing a semiconductor device according to a reference example. FIG. 2 is a process cross-sectional view (part 2) illustrating the method for manufacturing the semiconductor device according to the reference example. FIG. 3 is a process cross-sectional view (part 3) illustrating the method for manufacturing the semiconductor device according to the reference example. FIG. 4 is a schematic cross-sectional view showing the structure of the semiconductor device according to the first embodiment. FIG. 5 is a process cross-sectional view (part 1) illustrating the method for manufacturing the semiconductor device according to the first embodiment. FIG. 6 is a process cross-sectional view (part 2) illustrating the method for manufacturing the semiconductor device according to the first embodiment. FIG. 7 is a process cross-sectional view (part 3) illustrating the method for manufacturing the semiconductor device according to the first embodiment. FIG. 8 is a process cross-sectional view (part 4) illustrating the method for manufacturing the semiconductor device according to the first embodiment. FIG. 9 is a process cross-sectional view (part 5) illustrating the method for manufacturing the semiconductor device according to the first embodiment. FIG. 10 is a process cross-sectional view (No. 6) illustrating the method for manufacturing the semiconductor device according to the first embodiment. FIG. 11 is a process cross-sectional view (No. 7) illustrating the method for manufacturing the semiconductor device according to the first embodiment. FIG. 12 is a process cross-sectional view (No. 8) illustrating the method for manufacturing the semiconductor device according to the first embodiment. FIG. 13 is a diagram (No. 1) showing an RBS spectrum of a sample prepared for verifying silicon deposition. FIG. 14 is a diagram (part 2) showing an RBS spectrum of a sample prepared for verifying the deposition of silicon. FIG. 15 is a diagram (No. 3) showing an RBS spectrum of a sample prepared for verifying the deposition of silicon. FIG. 16 is a graph showing the relationship between the gate length of the P-type MISFET and the threshold voltage. FIG. 17 is a graph showing the relationship between the gate length of N-type MISFET and the threshold voltage. FIG. 18 is a graph showing a CV measurement result of a P-type MISFET. FIG. 19 is a schematic cross-sectional view showing the structure of the semiconductor device according to the second embodiment. FIG. 20 is a process cross-sectional view (part 1) illustrating the method for manufacturing the semiconductor device according to the second embodiment. FIG. 21 is a process cross-sectional view (part 2) illustrating the method for manufacturing the semiconductor device according to the second embodiment. FIG. 22 is a schematic cross-sectional view showing the structure of the semiconductor device according to the third embodiment. FIG. 23 is a process cross-sectional view (part 1) illustrating the method for manufacturing the semiconductor device according to the third embodiment. FIG. 24 is a process cross-sectional view (part 2) illustrating the method for manufacturing the semiconductor device according to the third embodiment. FIG. 25 is a schematic cross-sectional view showing the structure of the semiconductor device according to the fourth embodiment. FIG. 26 is a process cross-sectional view (part 1) illustrating the method for manufacturing the semiconductor device according to the fourth embodiment. FIG. 27 is a process cross-sectional view (part 2) illustrating the method for manufacturing the semiconductor device according to the fourth embodiment. FIG. 28 is a schematic sectional view showing the structure of the semiconductor device according to the fifth embodiment. FIG. 29 is a process cross-sectional view (part 1) illustrating the method for manufacturing the semiconductor device according to the fifth embodiment. FIG. 30 is a process cross-sectional view (part 2) illustrating the method for manufacturing the semiconductor device according to the fifth embodiment; FIG. 31 is a schematic cross-sectional view showing the structure of the semiconductor device according to the sixth embodiment. FIG. 32 is a process cross-sectional view (part 1) illustrating the method for manufacturing the semiconductor device according to the sixth embodiment. FIG. 33 is a process cross-sectional view (part 2) illustrating the method for manufacturing the semiconductor device according to the sixth embodiment. FIG. 34 is a schematic sectional view showing the structure of the semiconductor device according to the seventh embodiment. FIG. 35 is a process cross-sectional view (part 1) illustrating the method for manufacturing the semiconductor device according to the seventh embodiment. FIG. 36 is a process cross-sectional view (part 2) illustrating the method for manufacturing the semiconductor device according to the seventh embodiment;

[Reference example]
A method for manufacturing a semiconductor device according to a reference example will be described with reference to FIGS. 1 to 3 are process cross-sectional views illustrating a method of manufacturing a semiconductor device according to this reference example.

  This reference example is an example of a manufacturing method performed by the present inventors in the process of examining a semiconductor device having a gate insulating film including a high dielectric constant film and a gate electrode including a metal film in contact with the gate insulating film. is there.

  First, an element isolation film 12 of a silicon oxide film is formed in the silicon substrate 10 by, eg, STI (Shallow Trench Isolation) method (FIG. 1A).

  Next, a predetermined well (not shown) is formed in the silicon substrate 10 on which the element isolation film 12 has been formed, if necessary, by photolithography and ion implantation.

  Next, a silicon oxide film 14 is formed on the silicon substrate 10 on which the element isolation film 12 has been formed, for example, by a thermal oxidation method (FIG. 1B).

  Next, a hafnium oxide film 16 is formed on the silicon oxide film 14 by, eg, ALD (Atomic Layer Deposition) method (FIG. 1C).

  Next, a titanium nitride (TiN) film 22 is formed on the hafnium oxide film 16 by, for example, a PVD (Physical Vapor Deposition) method. The titanium nitride film 22 is a film that becomes a metal gate film of the MISFET.

  Next, a polysilicon film 24 is formed on the titanium nitride film 22 by, eg, thermal CVD (FIG. 2A).

  Next, the polysilicon film 24, the titanium nitride film 22, the hafnium oxide film 16, and the silicon oxide film 14 are patterned by photolithography and dry etching, and a gate electrode 28 of a laminated film of the titanium nitride film 22 and the polysilicon film 24 is formed. Form.

  Next, ion implantation is performed using the gate electrode 28 as a mask, and impurity diffusion regions 30 serving as extension regions are formed on the surface of the silicon substrate 10 on both sides of the gate electrode 28 (FIG. 2B).

  Next, for example, a silicon nitride film is deposited and etched back on the entire surface by, eg, CVD, and a sidewall insulating film 32 of a silicon nitride film is formed on the side wall portion of the gate electrode 28.

  Next, ion implantation is performed using the gate electrode 28 and the sidewall insulating film 32 as a mask to form impurity diffusion regions 34 on the surface of the silicon substrate 10 on both sides of the gate electrode 28.

  Next, heat treatment is performed in, for example, a nitrogen atmosphere to activate the introduced impurities. By this heat treatment, the impurities forming the impurity diffusion regions 30 and 34 are activated, and the source / drain regions 36 are formed (FIG. 3A).

  According to the above manufacturing method, a semiconductor device having the gate insulating film 40 having a stacked structure of the silicon oxide film 14 and the hafnium oxide film 16 and the gate electrode 38 having a stacked structure of the titanium nitride film 22 and the polysilicon film 24 is obtained. It was inferred that it could be formed (see FIG. 3 (a)).

  However, in the actually manufactured semiconductor device, it is considered that the threshold voltage can be controlled originally by the relationship between the work function of the titanium nitride film 22 and the work function of the silicon substrate 10, but the threshold voltage cannot be controlled theoretically. There was found.

  When the inventors of the present invention have made extensive studies on this, as shown in FIG. 3B, the silicon film 18 is interposed between the hafnium oxide film 16 of the gate insulating film 40 and the titanium nitride film 22 of the gate electrode 28 as shown in FIG. Was found to be formed. It has been clarified for the first time that the threshold voltage of the MISFET cannot be controlled theoretically due to the presence of the silicon film 18.

  The inventors of the present application infer as follows about the reason why the silicon film 18 is formed and the reason why the threshold voltage cannot be controlled theoretically due to the presence of the silicon film 18.

  The hafnium oxide film 16 is a film having many defects, and a large number of oxygen vacancies are generated in the film. Therefore, when high-temperature heat treatment such as activation annealing is performed when forming the source / drain regions 36, oxygen vacancies in the hafnium oxide film 16 take in oxygen in the silicon oxide film 14 and become more stable. Try to be.

  As a result, oxygen in the silicon oxide film 14 diffuses into the hafnium oxide film 16, and the composition of silicon in the silicon oxide film 14 becomes excessive compared to the stoichiometric composition. This excess silicon is deposited at the interface between the hafnium oxide film 16 and the titanium nitride film 22 to form a silicon film 18. In addition to this, the silicon forming the silicon film 18 may be diffused from the polysilicon film 24 side.

  The deposited silicon film 18 is non-doped silicon, and the Fermi level is located in the vicinity of the forbidden band center (mid gap). As a result, when the gate electrode 28 is formed on the silicon film 18, the effect of the threshold voltage control by the work function of the titanium nitride film 22 is hindered, and depending on the relationship between the work function of the silicon film 18 and the work function of the silicon substrate 10. It is considered that the threshold voltage is defined and the threshold voltage of the MISFET becomes deep (absolute value is large).

[First Embodiment]
The semiconductor device and the manufacturing method thereof according to the first embodiment will be described with reference to FIGS.

  FIG. 4 is a schematic cross-sectional view showing the structure of the semiconductor device according to the present embodiment. 5 to 12 are process cross-sectional views illustrating the method for fabricating the semiconductor device according to the present embodiment. FIG. 13 to FIG. 15 are diagrams showing RBS spectra of samples prepared for verifying silicon deposition. 16 and 17 are graphs showing the relationship between the gate length of the MISFET and the threshold voltage. FIG. 18 is a graph showing a CV measurement result of a P-type MISFET.

  First, the structure of the semiconductor device according to the present embodiment will be explained with reference to FIG.

  An element isolation film 12 that defines an active region is embedded in the surface of the silicon substrate 10. On the active region of the silicon substrate 10 defined by the element isolation film 12, a gate insulating film having a stacked structure of a silicon oxide film 14, a hafnium oxide film 16, a silicon oxide film 38, and a TaO (CN) film 20 is formed. 40 is formed. A gate electrode 28 having a laminated structure of the titanium nitride film 22 and the polysilicon film 24 is formed on the gate insulating film 40. A sidewall insulating film 32 is formed on the side wall portion of the gate electrode 28. Source / drain regions 36 are formed in the silicon substrate 10 on both sides of the gate electrode 28.

  As described above, in the semiconductor device according to the present embodiment, the gate insulating film 40 has the laminated structure of the silicon oxide film 14, the hafnium oxide film 16, the silicon oxide film 38, and the TaO (CN) film 20. Yes. A silicon oxide film 38 and a TaO (CN) film 20 are formed between the hafnium oxide film 16 of the gate insulating film 40 and the titanium nitride film 22 of the gate electrode 28. There is no such undoped silicon.

  Therefore, according to the semiconductor device according to the present embodiment, the influence of Fermi level pinning can be suppressed, and the threshold voltage can be controlled by the relationship between the work function of the titanium nitride film 22 and the work function of the silicon substrate 10.

  FIG. 4 is an example of a P-type MISFET. As the metal gate film, it is desirable to appropriately select a metal material having a work function capable of obtaining a desired threshold voltage according to the conductivity type of the MISFET to be formed. As the metal gate material for the P-type MISFET, for example, the above-described TiN can be applied, and as the metal gate material for the N-type MISFET, for example, Ti, TaN, TaSiN, or the like can be applied.

  Next, the method for fabricating the semiconductor device according to the present embodiment will be explained with reference to FIGS.

  First, an element isolation film 12 of a silicon oxide film embedded in a trench having a depth of, for example, 400 nm is formed in the silicon substrate 10 by, eg, STI method (FIG. 5A).

  Next, a predetermined well (not shown) is formed in the silicon substrate 10 on which the element isolation film 12 has been formed, if necessary, by photolithography and ion implantation.

In the N-type MISFET formation region, for example, boron ions (B ⁺ ) are ion-implanted under the conditions of an acceleration energy of 120 keV and a dose of 1.0 × 10 ¹³ cm ⁻² to form a P-type well. For threshold voltage control of the N-type MISFET, for example, boron ions (B ⁺ ) are ion-implanted under conditions of an acceleration energy of 15 keV and a dose of 1.0 × 10 ¹³ cm ⁻² .

In the P-type MISFET formation region, for example, phosphorus ions (P ⁺ ) are ion-implanted under conditions of an acceleration energy of 300 keV and a dose of 1.0 × 10 ¹³ cm ⁻² to form a P-type well. For controlling the threshold voltage of the P-type MISFET, for example, arsenic ions (As ⁺ ) are ion-implanted under conditions of an acceleration energy of 80 keV and a dose of 1.0 × 10 ¹³ cm ⁻² .

Next, a silicon oxide film 14 having a film thickness of 0.3 nm to 1.0 nm, for example, 0.7 nm is formed on the silicon substrate 10 on which the element isolation film 12 is formed by, eg, thermal oxidation (FIG. 5B). ). The thermal oxidation is performed in an oxidizing atmosphere containing an oxygen element such as O ₃ , O ₂ , or an oxynitride gas.

After the silicon oxide film 14 is formed, for example, plasma treatment may be performed in an atmosphere containing N ₂ gas, followed by heat treatment at 750 ° C. to 1100 ° C., so that the silicon oxide film 14 may be a silicon nitride oxide film. In the plasma processing after the silicon oxide film 14 is formed, it is desirable to optimize the N ₂ plasma processing conditions so that the silicon substrate 10 under the silicon oxide film 14 is not damaged.

The silicon oxide film 14 is not particularly limited as long as it is a silicon-based insulating film mainly composed of silicon oxide. Examples of the silicon-based insulating film mainly composed of silicon oxide include a SiO ₂ film and a SiON film.

  Next, a hafnium oxide film 16 having a film thickness of 0.5 nm to 3 nm, for example, 2.1 nm is formed on the silicon oxide film 14 by, eg, ALD (FIG. 5C). The hafnium oxide film 16 may be formed by a thermal CVD (Chemical Vapor Deposition) method, a PVD method, or the like in addition to the ALD method.

  The hafnium oxide film 16 includes any one of zirconium (Zr), titanium (Ti), aluminum (Al), silicon (Si), tantalum (Ta), lanthanum (La), yttrium (Y), magnesium (Mg), etc. One or more elements may be added. The addition amount of these elements can be appropriately set within a range in which the threshold voltage of the MISFET can be controlled.

The hafnium oxide film 16 is not particularly limited as long as it is a hafnium-based insulating film mainly composed of hafnium oxide. Examples of the hafnium-based insulating film mainly composed of hafnium oxide include an HfO ₂ film, an HfSiO film, an HfSiON film, an HfAlO film, and an HfAlON film.

  Next, if necessary, heat treatment at 500 ° C. to 1050 ° C., for example, 850 ° C. is performed for 5 seconds, for example, to adjust the film quality of the hafnium oxide film 16.

After the hafnium oxide film 16 is formed, the hafnium oxide film 16 may be nitrided by performing plasma treatment in an atmosphere containing N ₂ gas and subsequently performing heat treatment at 750 ° C. to 1100 ° C.

  Next, heat treatment is performed in a nitrogen atmosphere at a temperature of 750 ° C. to 1100 ° C., for example, 1050 ° C. for 5 seconds to deposit a silicon film 18 on the hafnium oxide film 16 (FIG. 6A). This heat treatment is the same heat treatment as activation annealing in forming a source / drain region described later.

  By performing a high-temperature heat treatment such as activation annealing when forming the source / drain regions, the oxygen vacancies in the hafnium oxide film 16 take in oxygen in the silicon oxide film 14 and become a more stable state. To do. As a result, oxygen in the silicon oxide film 14 diffuses into the hafnium oxide film 16, and the composition of silicon in the silicon oxide film 14 becomes excessive compared to the stoichiometric composition. The excess silicon is deposited at the interface between the hafnium oxide film 16 and the titanium nitride film 22 to form a silicon film 18.

  By preliminarily performing the heat treatment for depositing the silicon film 18 before the activation annealing for forming the source / drain regions, it is possible to suppress the deposition of silicon during the activation annealing.

  In the present specification, although expressed as “silicon film”, the deposited silicon does not necessarily exist in a complete film shape. For example, silicon may be deposited in an island shape. The “silicon film” in this specification includes a case where silicon is deposited in an island shape.

  FIGS. 13 to 15 are diagrams showing HRBS (High Resolution Rutherford Backscattering Spectrometry) spectra of a sample prepared for verifying the precipitation of silicon. FIG. 13 is an overview of the spectrum, and FIGS. 14 and 15 are an enlarged view of the spectrum near the C, O, and Si peaks and an enlarged view of the spectrum near the Hf peak, respectively. The horizontal axis indicates the energy of the backscattered particles, and the vertical axis indicates the count number of the backscattered particles.

  In each figure, sample A formed a 0.7 nm thick SiON film and a 2.1 nm thick HfO film on a silicon substrate, and was subjected to heat treatment at 1050 ° C. for 5 seconds in a nitrogen atmosphere. It is a sample. Sample B is a sample that was subjected to the same treatment as Sample A, followed by oxidation in an oxygen atmosphere at 400 ° C. for 30 minutes, and further with dilute hydrofluoric acid. Sample C is a sample that has been treated with ammonia overwater after the same treatment as Sample A. The SiON film corresponds to the silicon oxide film 14 of the present embodiment, and the HfO film corresponds to the hafnium oxide film of the present embodiment.

  In the RBS spectrum, the energy on the horizontal axis can correspond to the depth from the sample surface. For example, in the case of silicon, in the spectra of FIGS. 13 to 15, the energy position of 344 to 346 keV represents the sample surface, and the lower energy side represents the inside of the sample. That is, when silicon is present on the sample surface, a silicon spectrum is observed at an energy position of 344 to 346 keV.

  In Sample A, which was heat-treated at 1050 ° C. for 5 seconds after forming the HfO film, a silicon peak is observed in the vicinity of 344 to 346 keV as shown in FIG. This indicates that silicon is deposited on the surface of the sample A.

  On the other hand, in the spectra of Sample B and Sample C, no silicon peak is observed in the vicinity of 344 to 346 keV. This is because in Sample B, the deposited silicon is oxidized and then removed by dilute hydrofluoric acid treatment, and in Sample C, the deposited silicon is removed by ammonia overwater treatment.

  In FIG. 15, the half width of the hafnium spectrum in sample B is narrow because the surface of the HfO film is slightly removed in the process of oxidizing and removing the deposited silicon. This also suggests that the silicon or silicon oxide film deposited on the HfO film has been removed.

  From the above results, it was verified that silicon was deposited on the surface of the HfO film by performing heat treatment after forming the HfO film.

  Next, a film thickness of 0.3 nm to 1 nm, for example 1 nm, is deposited on the deposited silicon film 18 by, for example, ALD, 25.6% tantalum, 36.1% oxygen, 26.7% carbon, nitrogen A TaO (CN) film 20 containing 11.6% is formed (FIG. 6B). Note that the TaO (CN) film 20 is a factor in increasing the effective oxide film thickness (EOT), and thus the film thickness is desirably 1 nm or less. The TaO (CN) film 20 is preferably made of tantalum as a main raw material, containing 10% to 70% oxygen, 10% to 33% carbon, and 5% to 33% nitrogen.

The TaO (CN) film 20 is formed by, for example, ALD, using, for example, PDMAT (Pentadimethylaminotantalum: [(CH ₃ ) ₂ N] ₅ Ta) as a raw material at a deposition temperature of 150 ° C. to 300 ° C., hydrogen, oxygen, ammonia, nitrogen , By using one or more gases of helium and argon, and repeatedly performing a sequence including any one or more of deposition, purge, reaction gas, and plasma reaction under a pressure of 1 Pa to 1000 Pa. be able to.

The film formed on the silicon film 18 is not limited to the TaO (CN) film 20 as long as it is an oxygen-containing film containing an element having an oxidizing action on silicon. An oxygen-containing film containing an element having an oxidizing action on silicon is generally a metal oxide film other than Al ₂ O ₃ , ZrO ₂ , HfO ₂ , and TiO ₂ . For example, oxidation of tantalum, molybdenum (Mo), manganese (Mn), iron (Fe), nickel (Ni), ruthenium (Ru), cobalt (Co), copper (Cu), platinum (Pt), zinc (Zn) Examples include physical films.

  These oxide films desirably contain nitrogen and carbon like the TaO (CN) film 20 described above. This is because nitrogen and carbon contained in the film act to prevent an element having an oxidizing action on silicon from being silicided. This is because if an element having an oxidizing action on silicon is silicided and has a semiconductor or metallic property, the threshold voltage cannot be controlled by a metal gate film to be formed later.

Next, a titanium nitride (TiN) film 22 of, eg, a 10 nm-thickness is formed on the TaO (CN) film 20 by, eg, PVD method (FIG. 6C). The titanium nitride film 22 is formed by sputtering, for example, in a substrate temperature of −30 ° C. to 400 ° C., RF power of 0 to 2000 W, DC power of 0 to 50000 W, N ₂ gas alone or Ar + N ₂ gas atmosphere. To do. The titanium nitride film 22 is not limited to the PVD method, and may be formed by an ALD method, a CVD method, or the like.

The titanium nitride film 22 is a film that becomes a metal gate film. The metal gate layer, for example, Ti, Hf, Al, TiTa , RuTa, TiSi, WN, TiAlN, TiSiN, TaSiN, TaN, NiSi, NiSi 2, W, WSi 2, TiN, CoSi 2, MoSi 2, ZrN, Apply a laminated film of two or more materials selected from WSi, HfN, IrO ₂ , PtRa, Ir, TaCN, Mo, MoN, RuO ₂ , Ru, Pt, Ni ₃ Si, Ni or the like can do.

  The film that becomes the metal gate film may be formed separately in the N-type MISFET formation region and the P-type MISFET formation region. In this case, Ti, TaN, TaSiN, etc. can be applied as the metal gate film for the N-type MISFET. Further, TiN or the like can be applied as the metal gate film for the P-type MISFET.

  In the specification of the present application, the metal gate material may be collectively expressed as “metal”. The “metal” in this case includes not only the metal element itself but also the metal oxide, metal nitride, metal silicide, metal alloy and the like as described above. These exhibit electrically metallic properties.

  Next, a polysilicon film 24 of, eg, a 10 nm to 100 nm film thickness is formed on the titanium nitride film 22 by, eg, thermal CVD. Instead of the polysilicon film 24, an amorphous silicon film may be deposited.

  The polysilicon film 24 is for forming a gate electrode structure called a so-called MIPS (Metal Insert Polycrystalline Silicon) structure. The gate electrode is not necessarily required to have the MIPS structure, and instead of the polysilicon film 24, for example, a TiN film having a thickness of 10 nm and a W film having a thickness of 50 nm may be formed.

  Next, a silicon nitride film 26 of, eg, a 5 nm to 20 nm film thickness is formed on the polysilicon film 24 by, eg, thermal CVD (FIG. 7A). Note that the silicon nitride film 26 is a film used as a hard mask in the patterning step when forming the gate electrode, and is not necessarily formed.

  Next, the silicon nitride film 26, the polysilicon film 24, the titanium nitride film 22, the TaO (CN) film 20, the silicon film 18, the hafnium oxide film 16, and the silicon oxide film 14 are patterned by photolithography and dry etching, and nitrided. A gate electrode 28 of a laminated film of the titanium film 22 and the polysilicon film 24 is formed.

  Next, the silicon nitride film 26 used as a hard mask is removed (FIG. 7B).

  Next, ion implantation is performed using the gate electrode 28 as a mask, and impurity diffusion regions 30 serving as extension regions are formed on the surface of the silicon substrate 10 on both sides of the gate electrode 28.

The impurity diffusion region 30 for the N-type MISFET is formed, for example, by ion-implanting arsenic ions under conditions of an acceleration energy of 2 keV and a dose amount of 2.0 × 10 ¹⁵ cm ⁻² . The impurity diffusion region 30 for the P-type MISFET is formed, for example, by implanting boron ions under the conditions of an acceleration energy of 0.6 keV and a dose of 2.0 × 10 ¹⁵ cm ⁻² .

  Next, a silicon nitride film having a thickness of about 100 nm, for example, 50 nm is deposited on the entire surface by, eg, CVD. This silicon nitride film is a film to be a side wall insulating film formed on the side wall portion of the gate electrode 28. Instead of the silicon nitride film, a silicon oxide film, a boron nitride film, or a combination of these films may be used.

  Next, the silicon nitride film is etched back by dry etching to form a side wall insulating film 32 of the silicon nitride film on the side wall portion of the gate electrode 28 (FIG. 8A).

  Next, ion implantation is performed using the gate electrode 28 and the sidewall insulating film 32 as a mask to form impurity diffusion regions 34 on the surface of the silicon substrate 10 on both sides of the gate electrode 28.

The impurity diffusion region 34 for the N-type MISFET is formed, for example, by ion-implanting arsenic ions under conditions of an acceleration energy of 5 keV and a dose amount of 5.0 × 10 ¹⁵ cm ⁻² . The impurity diffusion region 34 for the P-type MISFET is formed, for example, by implanting boron ions under conditions of an acceleration energy of 2 keV and a dose of 3.0 × 10 ¹⁵ cm ⁻² .

  Next, for example, in nitrogen atmosphere, 950 ° C. to 1050 ° C. is performed for 0 to 3 seconds, for example, 1000 ° C. for 0 second (spike annealing) to activate the introduced impurities.

  By this heat treatment, impurities in the impurity diffusion regions 30 and 34 are activated, and source / drain regions 36 are formed.

In addition, between the silicon film 18 and the TaO (CN) film 20,
TaO _x (CN) + Si _y → TaO _xy CN + Si _y O _y
Oxidation reaction of silicon represented by the following reaction formula occurs. Even when silicon diffuses from the polysilicon film 24 side to the interface between the titanium nitride film 22 and the silicon film 18 during this heat treatment, an oxidation reaction of silicon represented by the above reaction formula occurs. This reaction occurs because oxygen is more stable in bonding with silicon than with tantalum. By this reaction, the silicon film 18 is replaced by the silicon oxide film 36, and the silicon film 18 between the hafnium oxide film 16 and the TaO (CN) film 20 disappears.

  In the semiconductor device manufacturing method according to the present embodiment, since the heat treatment for depositing the silicon film 18 is performed in advance before the activation annealing for forming the source / drain regions 36, the activation annealing is performed. Silicon does not precipitate.

  In this way, the gate insulating film 40 of the laminated film of the silicon oxide film 14, the hafnium oxide film 16, the silicon oxide film 38, and the TaO (CN) film 20 is formed (FIG. 8B).

  Note that, since the structure of the gate electrode 28 and the gate insulating film 40 does not change in the subsequent processes, the description of the stacked structure of the gate electrode 28 and the gate insulating film 40 is omitted in the drawings that describe this process and thereafter.

  Next, a natural oxide film (not shown) formed on the gate electrode 28 and the source / drain region 36 is removed by wet etching using, for example, a hydrofluoric acid aqueous solution.

  Next, a nickel film 42 having a film thickness of 5 nm to 20 nm, for example, 9 nm is formed on the entire surface by, eg, sputtering. The nickel film 42 is a film for forming a silicide film on the gate electrode 28 and the source / drain region 36. The nickel film 42 may be added with at least one element selected from the group consisting of Pt, Ta, W, Re, Y, Yb, Al, La, and Ti. In addition to nickel, other metal materials that are silicided may be used.

  Next, a titanium nitride film 44 having a film thickness of 5 nm to 50 nm, for example, 10 nm is formed on the nickel film 42 by, eg, sputtering (FIG. 9A). The titanium nitride film 44 is a cap film when a silicide film is formed on the gate electrode 28 and the source / drain regions 36. Instead of the titanium nitride film 44, a titanium film having a thickness of about 5 nm to 50 nm may be used.

  Next, a rapid annealing process is performed in a nitrogen atmosphere at, for example, 450 ° C. for 30 seconds to silicide the portions where the nickel film 42 and silicon are in contact (on the polysilicon film 24 and the source / drain regions 36 of the gate electrode 28). Then, a NiSi film 46 is formed (FIG. 9B). Note that as the heat treatment for silicidation, instead of the rapid annealing treatment, furnace annealing or heat treatment that combines furnace annealing and rapid heating treatment may be used.

  Next, for example, a chemical treatment (SPM treatment) is performed using a mixed solution of sulfuric acid and hydrogen peroxide solution (sulfuric acid: hydrogen peroxide solution = 3: 1), and the titanium nitride film 44 serving as a cap film and an unreacted nickel film. 42 is selectively removed (FIG. 9C). Instead of a mixed solution of sulfuric acid and hydrogen peroxide solution, a mixed solution of hydrochloric acid and hydrogen peroxide solution may be used.

  Next, a silicon nitride film 48 of, eg, a 50 nm-thickness is formed on the entire surface by, eg, thermal CVD at a processing temperature of, eg, 400 ° C. (FIG. 10A). The silicon nitride film 48 may be a stress film called a so-called dual stress liner.

  Next, a silicon oxide film 50 of, eg, a 600 nm-thickness is formed on the silicon nitride film 48 by, eg, plasma CVD at a processing temperature of, eg, 400 ° C. (FIG. 10B).

  Next, the surface of the silicon oxide film 50 is polished and planarized by, for example, a CMP (Chemical Mechanical Polishing) method (FIG. 10C).

  Next, contact holes 52 reaching the NiSi film 46 on the gate electrode 28 and contact holes 54 reaching the NiSi film 46 on the source / drain regions 36 are formed in the silicon oxide film 50 and the silicon nitride film 48 by lithography and dry etching. Is formed (FIG. 11A). During this etching, the silicon nitride film 48 functions as an etching stopper, and unexpected over-etching of the gate electrode 28 and the source / drain region 36 can be prevented.

  Next, Ti having a thickness of, for example, 10 nm and TiN having a thickness of, for example, 10 nm are deposited on the entire surface by, eg, CVD, and a base film having a TiN / Ti structure is formed on the silicon oxide film 50 and the inner walls of the contact holes 52 and 54. 56 is formed.

  Next, a W film 58 of, eg, a 300 nm-thickness is formed on the base film 56 by, eg, CVD (FIG. 11B). As a result, the contact holes 52 and 54 in which the base film 56 is formed are filled with the W film 58.

  Next, the W film 58 and the base film 56 on the silicon oxide film 50 are removed by polishing, for example, by a CMP method, and the contact plug 60 formed by the base film 56 and the W film 58 is formed in the contact holes 52 and 54. It forms (FIG.11 (c)).

  Next, a desired number of metal wiring layers, passivation films, and the like are formed on the silicon oxide film 50 in which the contact plugs 60 are embedded as necessary, thereby completing the semiconductor device according to the present embodiment (FIG. 12). . In FIG. 12, an interlayer insulating film 62 in which a Cu or Cu alloy wiring layer 64 is embedded on a silicon oxide film 50, an interlayer insulating film 66 in which a via portion 68 of Cu or Cu alloy is embedded, and an interlayer insulating film An example in which a wiring layer 70 of Al or Al alloy formed on 66 is formed is shown.

  16 and 17 are graphs showing the relationship between the gate length (Lsem) of the MISFET and the threshold voltage (Vth). FIG. 16 shows a case of a P-type MISFET, and FIG. 17 shows a case of an N-type MISFET. The horizontal axis is the gate length measured by the length measurement SEM.

  In each figure, the mark ● represents the case of the MISFET manufactured by the manufacturing method of the above-described embodiment. (2) shows the case of a MISFET manufactured by a method similar to the manufacturing method according to the above-described embodiment except that an AlOx film is used instead of the TaO (CN) film. The asterisk indicates the case of the MISFET manufactured by the same method as the manufacturing method according to the above-described embodiment except that the TaO (CN) film is not formed. The metal gate film of the gate electrode was a titanium nitride film for both the N-type MISFET and the P-type MISFET.

  In the P-type MISFET, as shown in FIG. 16, in the sample using the AlOx film instead of the TaO (CN) film (marked with ■) and the sample not formed with the TaO (CN) film (marked with ♦), the gate length The threshold voltage Vth at the point where Lsem was 120 nm was about −0.45V.

  Further, in the N-type MISFET, as shown in FIG. 17, in the sample using the AlOx film instead of the TaO (CN) film (■ mark) and the sample not forming the TaO (CN) film (♦ mark), The threshold voltage Vth at the point where the gate length Lsem is 120 nm was about 0.4V.

  For these reasons, the sample using the AlOx film instead of the TaO (CN) film (marked with ■) and the sample without the TaO (CN) film formed with the mark (♦) are used as metal gate films for P-type MISFETs. It can be seen that the benefit of the formed titanium nitride film 22 is not obtained. This is presumably because the deposited silicon film remains on the HfO film.

  In the sample using the AlOx film instead of the TaO (CN) film (marked with ■), the difference from the sample without the TaO (CN) film (marked with ◆) is not seen as described above. This is because AlOx does not contain an element having an oxidizing action on silicon.

  On the other hand, in the sample manufactured by the manufacturing method of the present embodiment (● mark), the threshold voltage Vth of the P-type MISFET at the point where the gate length Lsem is 120 nm is about −0.3V. Further, the threshold voltage Vth of the N-type MISFET at the point where the gate length Lsem is 120 nm is about + 0.55V.

  From these facts, it can be seen that the MISFET manufactured by the manufacturing method of the present embodiment has a shallower (lower absolute value) threshold voltage Vth than the P-type MISFET. This indicates that the threshold voltage Vth of the MISFET can be controlled by the titanium nitride film having a work function larger than the mid gap of silicon. The N-type MISFET has a deeper (larger absolute value) threshold voltage Vth because a P-type metal gate material is used. It has been found that the threshold voltage can also be controlled in the N-type MISFET by the same effect as the P-type MISFET.

  FIG. 18 is a graph showing a CV measurement result of a P-type MISFET. The horizontal axis is the gate voltage Vg, and the vertical axis is the capacitance C of the MIS capacitor. In the figure, the ● marks indicate the case of the MISFET manufactured by the manufacturing method of the present embodiment described above. The asterisk indicates the case of the MISFET manufactured by the same method as the manufacturing method according to the above-described embodiment except that the TaO (CN) film is not formed.

  As shown in FIG. 18, in the sample (● mark) manufactured by the manufacturing method of the present embodiment, the capacitance value is reduced as compared to the sample (♦ mark) in which no TaO (CN) film is formed. . This indicates that the TaO (CN) film formed for oxidizing the deposited silicon remains in the gate insulating film 40 as an insulating film.

  However, as is apparent from the results of FIG. 18, if the TaO (CN) film is too thick, the effective oxide film thickness increases, which is not preferable. Therefore, in order to maintain the commercial value of the semiconductor device, the film thickness is 1 nm. The following is desirable.

  As described above, according to the present embodiment, the heat treatment for depositing surplus silicon on the hafnium oxide film by performing the heat treatment is performed before the activation annealing of the source / drain regions. In the activation annealing, silicon can be prevented from being deposited between the gate insulating film and the gate electrode. Further, since the oxygen-containing film containing an element having an oxidizing action on silicon is formed on the deposited silicon film, the deposited silicon film can be replaced with the silicon oxide film by a heat treatment in a later step. As a result, the effect of the threshold voltage control by the work function of the metal gate film can be suppressed from being inhibited by the deposited silicon film, and the threshold voltage can be controlled by the relationship between the work function of the metal gate film and the silicon substrate. .

[Second Embodiment]
The semiconductor device and the manufacturing method thereof according to the second embodiment will be described with reference to FIGS. Components similar to those of the semiconductor device and the manufacturing method thereof according to the first embodiment shown in FIGS. 4 to 12 are denoted by the same reference numerals, and description thereof is omitted or simplified.

  FIG. 19 is a schematic cross-sectional view showing the structure of the semiconductor device according to the present embodiment. 20 and 21 are process cross-sectional views illustrating the method for manufacturing the semiconductor device according to the present embodiment.

  First, the structure of the semiconductor device according to the present embodiment will be explained with reference to FIG.

  As shown in FIG. 19, the semiconductor device according to the present embodiment is the same as that shown in FIG. 4 except that an AlOx film 72 is formed between the hafnium oxide film 16 and the silicon oxide film 28 of the gate insulating film 40. This is the same as the semiconductor device according to the embodiment. That is, in the semiconductor device according to the present embodiment, the gate insulating film 40 has a stacked structure of the silicon oxide film 14, the hafnium oxide film 16, the AlOx film 72, the silicon oxide film 38, and the TaO (CN) film 20. Is formed.

  An AlOx film 72, a silicon oxide film 38, and a TaO (CN) film 20 are formed between the hafnium oxide film 16 of the gate insulating film 40 and the titanium nitride film 22 of the gate electrode 28. There is no non-doped silicon like the silicon film 18 in the example. Therefore, according to the semiconductor device according to the present embodiment, the influence of Fermi level pinning can be suppressed and the threshold voltage can be controlled by the work function of the titanium nitride film 22.

  The AlOx film 72 is a cap film used to form a dipole near the interface between the silicon oxide film 14 and the hafnium oxide film 16 and to control the threshold voltage of the MISFET. As the cap film, AlOx or the like having a film thickness of about 0.3 nm to 1 nm can be applied for the P-type MISFET, and LaOx, YOx, MgO or the like having a film thickness of about 0.3 nm to 1 nm can be applied to the N-type MISFET. By forming a cap film such as the AlOx film 72, the threshold voltage of the MISFET can be made shallower.

  Next, the method for fabricating the semiconductor device according to the present embodiment will be explained with reference to FIGS.

  First, in the same manner as the semiconductor device manufacturing method according to the first embodiment shown in FIGS. 5A to 5C, the element isolation film 12, the silicon oxide film 14, and the hafnium oxide film are formed on the silicon substrate 10. 16 is formed (FIG. 20A).

  Next, an AlOx film 72 having a film thickness of 0.3 nm to 1 nm, for example, 0.5 nm is formed on the hafnium oxide film 16 by, eg, PVD method (FIG. 20B). The AlOx film 72 may be formed by a thermal CVD method, an ALD method, or the like in addition to the PVD method. In the N-type MISFET formation region, LaOx, YOx, MgO or the like having a film thickness of about 0.3 nm to 1 nm may be formed instead of the AlOx film.

  Next, heat treatment at 750 ° C. to 1100 ° C., for example, 1050 ° C. is performed for 5 seconds to diffuse the aluminum in the AlOx film 72 to the interface between the silicon oxide film 14 and the hafnium oxide film 16. Aluminum diffused at the interface between the silicon oxide film 14 and the hafnium oxide film 16 forms a dipole and can be used for threshold voltage control of the MISFET.

  With this heat treatment, the silicon film 18 is deposited on the surface of the AlOx film 72 (FIG. 20C). By performing a high-temperature heat treatment such as activation annealing when forming the source / drain regions, the oxygen vacancies in the hafnium oxide film 16 take in oxygen in the silicon oxide film 14 and become a more stable state. To do. As a result, oxygen in the silicon oxide film 14 diffuses into the hafnium oxide film 16, and the composition of silicon in the silicon oxide film 14 becomes excessive compared to the stoichiometric composition. The excess silicon is deposited at the interface between the hafnium oxide film 16 and the titanium nitride film 22 to form a silicon film 18.

  By preliminarily performing the heat treatment for depositing the silicon film 18 before the activation annealing for forming the source / drain regions, it is possible to suppress the deposition of silicon during the activation annealing.

  Next, a TaO (CN) film 20, a titanium nitride film 22, polysilicon, and the like are formed on the silicon film 18 in the same manner as the semiconductor device manufacturing method according to the first embodiment shown in FIGS. 6B to 7A. A film 24 and a silicon nitride film 26 are formed (FIG. 21A).

  Next, the semiconductor device according to the present embodiment is completed in the same manner as in the method for manufacturing the semiconductor device according to the first embodiment shown in FIGS.

  At this time, in the step shown in FIG. 8B, the silicon film 18 is replaced with the silicon oxide film 36, and the silicon film 18 between the AlOx film 72 and the TaO (CN) film 20 disappears. As a result, a gate insulating film 40 of a stacked film of the silicon oxide film 14, the hafnium oxide film 16, the AlOx film 72, the silicon oxide film 38, and the TaO (CN) film 20 is formed (FIG. 21B).

  As described above, according to the present embodiment, the heat treatment for depositing surplus silicon on the hafnium oxide film by performing the heat treatment is performed before the activation annealing of the source / drain regions. In the activation annealing, silicon can be prevented from being deposited between the gate insulating film and the gate electrode. Further, since the oxygen-containing film containing an element having an oxidizing action on silicon is formed on the deposited silicon film, the deposited silicon film can be replaced with the silicon oxide film by a heat treatment in a later step. As a result, the effect of the threshold voltage control by the work function of the metal gate film can be suppressed from being inhibited by the deposited silicon film, and the threshold voltage can be controlled by the relationship between the work function of the metal gate film and the silicon substrate. .

  Further, by forming a cap film capable of controlling the threshold voltage of the MISFET by forming a dipole in the hafnium film on the hafnium oxide film, the threshold voltage of the MISFET can be made shallower.

[Third Embodiment]
The semiconductor device and the manufacturing method thereof according to the third embodiment will be described with reference to FIGS. The same components as those of the semiconductor device and the manufacturing method thereof according to the first and second embodiments shown in FIGS. 4 to 21 are denoted by the same reference numerals, and description thereof is omitted or simplified.

  FIG. 22 is a schematic cross-sectional view showing the structure of the semiconductor device according to the present embodiment. 23 and 24 are process cross-sectional views illustrating the method for fabricating the semiconductor device according to the present embodiment.

  First, the structure of the semiconductor device according to the present embodiment will be explained with reference to FIG.

  The semiconductor device according to the present embodiment is the same as the second embodiment shown in FIG. 19 except that the TaO (CN) film 20 is not formed between the silicon oxide film 38 and the titanium nitride film 22 as shown in FIG. It is the same as that of the semiconductor device by. That is, in the semiconductor device according to the present embodiment, the gate insulating film 40 is formed by a laminated structure of the silicon oxide film 14, the hafnium oxide film 16, the AlOx film 72, and the silicon oxide film 38.

  An AlOx film 72 and a silicon oxide film 38 are formed between the hafnium oxide film 16 of the gate insulating film 40 and the titanium nitride film 22 of the gate electrode 28, but are not doped like the silicon film 18 in the reference example. No silicon exists. Therefore, according to the semiconductor device according to the present embodiment, the influence of Fermi level pinning can be suppressed and the threshold voltage can be controlled by the work function of the titanium nitride film 22.

  Next, the method for fabricating the semiconductor device according to the present embodiment will be explained with reference to FIGS.

  First, the element isolation film 12, the silicon oxide film 14, the hafnium oxide film 16, and the AlOx film 72 are formed on the silicon substrate 10 in the same manner as in the semiconductor device manufacturing method according to the first and second embodiments. (FIG. 23 (a)).

  Next, heat treatment at 750 ° C. to 1100 ° C., for example, 1050 ° C. is performed for 5 seconds to diffuse the aluminum in the AlOx film 72 to the interface between the silicon oxide film 14 and the hafnium oxide film 16. Aluminum diffused at the interface between the silicon oxide film 14 and the hafnium oxide film 16 forms a dipole and can be used for threshold voltage control of the MISFET.

  With this heat treatment, the silicon film 18 is deposited on the surface of the AlOx film 72 (FIG. 23B). By performing a high-temperature heat treatment such as activation annealing when forming the source / drain regions, the oxygen vacancies in the hafnium oxide film 16 take in oxygen in the silicon oxide film 14 and become a more stable state. To do. As a result, oxygen in the silicon oxide film 14 diffuses into the hafnium oxide film 16, and the composition of silicon in the silicon oxide film 14 becomes excessive compared to the stoichiometric composition. The excess silicon is deposited at the interface between the hafnium oxide film 16 and the titanium nitride film 22 to form a silicon film 18.

  Next, heat treatment is performed in an atmosphere containing oxygen at a temperature of 300 ° C. to 500 ° C., for example, 400 ° C. for 30 minutes to oxidize the silicon film 18 and replace it with the silicon oxide film 38 (FIG. 23C). Here, the reason why the oxidation temperature is set to 300 ° C. or more is that if it is less than 300 ° C., there is insufficient energy for oxidizing silicon. The reason why the oxidation temperature is set to 500 ° C. or lower is that if the oxidation is performed at a temperature higher than 500 ° C., even silicon of the silicon substrate 10 is oxidized, and the thickness of the silicon oxide film 38 increases.

  Next, the titanium nitride film 22, the polysilicon film 24, and the silicon nitride film 26 are formed on the silicon film 18 in the same manner as the semiconductor device manufacturing method according to the first embodiment shown in FIGS. 6C to 7A. (FIG. 24A).

  Next, the semiconductor device according to the present embodiment is completed in the same manner as in the method for manufacturing the semiconductor device according to the first embodiment shown in FIGS.

  At this time, since the heat treatment for precipitating the silicon film 18 is performed in advance in the step shown in FIG. 23B, the silicon film is not precipitated again in the activation annealing step shown in FIG. As a result, the gate insulating film 40 of the laminated film of the silicon oxide film 14, the hafnium oxide film 16, the AlOx film 72, and the silicon oxide film 38 is formed (FIG. 24B).

  As described above, according to the present embodiment, the heat treatment for depositing surplus silicon on the hafnium oxide film by performing the heat treatment is performed before the activation annealing of the source / drain regions. In the activation annealing, silicon can be prevented from being deposited between the gate insulating film and the gate electrode. Moreover, since the deposited silicon film is replaced with a silicon oxide film before the formation of the metal gate film, the effect of the threshold voltage control by the work function of the metal gate film is suppressed from being inhibited by the deposited silicon film, The threshold voltage can be controlled by the relationship between the metal gate film and the work function of the silicon substrate.

[Fourth Embodiment]
The semiconductor device and the manufacturing method thereof according to the fourth embodiment will be described with reference to FIGS. The same components as those of the semiconductor device and the manufacturing method thereof according to the first to third embodiments shown in FIGS. 4 to 24 are denoted by the same reference numerals, and description thereof is omitted or simplified.

  FIG. 25 is a schematic cross-sectional view showing the structure of the semiconductor device according to the present embodiment. 26 and 27 are process cross-sectional views illustrating the method for fabricating the semiconductor device according to the present embodiment.

  First, the structure of the semiconductor device according to the present embodiment will be explained with reference to FIG.

  The semiconductor device according to the present embodiment is the same as the third embodiment shown in FIG. 22 except that the AlOx film 72 and the silicon oxide film 38 are not formed between the hafnium oxide film 16 and the titanium nitride film 22 as shown in FIG. This is the same as the semiconductor device according to the embodiment. That is, in the semiconductor device according to the present embodiment, the gate insulating film 40 is formed by a laminated structure of the silicon oxide film 14 and the hafnium oxide film 16.

  There is no non-doped silicon like the silicon film 18 in the reference example between the hafnium oxide film 16 of the gate insulating film 40 and the titanium nitride film 22 of the gate electrode 28. Therefore, according to the semiconductor device according to the present embodiment, the influence of Fermi level pinning can be suppressed and the threshold voltage can be controlled by the work function of the titanium nitride film 22.

  Next, the method for fabricating the semiconductor device according to the present embodiment will be explained with reference to FIGS.

  First, the element isolation film 12, the silicon oxide film 14, and the hafnium oxide film 16 are formed on the silicon substrate 10 in the same manner as in the semiconductor device manufacturing method according to the first embodiment.

  Next, an AlOx film 72 having a film thickness of 0.3 nm to 5 nm, for example, 0.5 nm is formed on the hafnium oxide film 16 by, for example, the PVD method. In the N-type MISFET formation region, LaOx, YOx, MgO or the like having a film thickness of about 0.3 nm to 1 nm may be formed instead of the AlOx film.

  Next, heat treatment at 750 ° C. to 1100 ° C., for example, 1050 ° C. is performed for 5 seconds to diffuse the aluminum in the AlOx film 72 to the interface between the silicon oxide film 14 and the hafnium oxide film 16. Aluminum diffused at the interface between the silicon oxide film 14 and the hafnium oxide film 16 forms a dipole and can be used for threshold voltage control of the MISFET.

  With this heat treatment, the silicon film 18 is deposited on the surface of the AlOx film 72 (FIG. 26A). By performing a high-temperature heat treatment such as activation annealing when forming the source / drain regions, the oxygen vacancies in the hafnium oxide film 16 take in oxygen in the silicon oxide film 14 and become a more stable state. To do. As a result, oxygen in the silicon oxide film 14 diffuses into the hafnium oxide film 16, and the composition of silicon in the silicon oxide film 14 becomes excessive compared to the stoichiometric composition. The excess silicon is deposited at the interface between the hafnium oxide film 16 and the titanium nitride film 22 to form a silicon film 18.

  Next, heat treatment is performed in an atmosphere containing oxygen at a temperature of 300 ° C. to 500 ° C., for example, 400 ° C. for 30 minutes to oxidize the silicon film 18 and replace it with the silicon oxide film 38 (FIG. 26B).

  Next, the silicon oxide film 38 and the AlOx film 72 are removed by wet etching using, for example, diluted hydrofluoric acid (FIG. 26C). By removing the silicon oxide film 38 and the AlOx film 72, the effective oxide film thickness of the gate insulating film can be reduced.

Etching of the silicon oxide film 38 and the AlOx film 72 can be performed at room temperature using, for example, dilute hydrofluoric acid of HF: H ₂ O = 1: 100 to 1000 as an etchant. Instead of dilute hydrofluoric acid, BOE (Buffered Oxide Etchant) such as NH ₄ F: HF: H ₂ O may be used. In this case, for example, an etching solution of NH ₄ F: HF: H ₂ O = 40: 0.2: 57.4 can be used.

  In the etching of the silicon oxide film 38 and the AlOx film 72, as can be seen from the RBS spectrum of FIG. 15, a part of the underlying hafnium oxide film 16 is also etched. It is desirable to make the concentration as thin as possible. In this etching, since the AlOx film 72 can be removed together with the silicon oxide film 38, an increase in the effective oxide film thickness of the gate insulating film due to the AlOx film 72 can be prevented. Thereby, the AlOx film 72 can be formed thicker than in the case of the first to third embodiments.

  Next, a titanium nitride film 22, a polysilicon film 24, and a silicon nitride film are formed on the hafnium oxide film 16 in the same manner as the semiconductor device manufacturing method according to the first embodiment shown in FIGS. 26 is formed (FIG. 27A).

  Next, the semiconductor device according to the present embodiment is completed in the same manner as in the method for manufacturing the semiconductor device according to the first embodiment shown in FIGS.

  At this time, since the heat treatment for precipitating the silicon film 18 is performed in advance in the step shown in FIG. 26A, the silicon film is not precipitated again in the activation annealing step shown in FIG. As a result, the gate insulating film 40 of the laminated film of the silicon oxide film 14 and the hafnium oxide film 16 is formed (FIG. 27B).

  As described above, according to the present embodiment, the heat treatment for depositing surplus silicon on the hafnium oxide film by performing the heat treatment is performed before the activation annealing of the source / drain regions. In the activation annealing, silicon can be prevented from being deposited between the gate insulating film and the gate electrode. In addition, since the deposited silicon film is replaced with a silicon oxide film before the metal gate film is formed, the effect of threshold voltage control by the work function of the metal gate film is inhibited by the deposited silicon film. The threshold voltage can be controlled by the relationship between the metal gate film and the work function of the silicon substrate.

[Fifth Embodiment]
The semiconductor device and the manufacturing method thereof according to the fifth embodiment will be described with reference to FIGS. The same components as those of the semiconductor device and the manufacturing method thereof according to the first to fourth embodiments shown in FIGS. 4 to 27 are denoted by the same reference numerals, and description thereof will be omitted or simplified.

  FIG. 28 is a schematic cross-sectional view showing the structure of the semiconductor device according to the present embodiment. 29 and 30 are process cross-sectional views illustrating the method for fabricating the semiconductor device according to the present embodiment.

  First, the structure of the semiconductor device according to the present embodiment will be explained with reference to FIG.

  The semiconductor device according to the present embodiment is the same as that shown in FIG. 28 except that the silicon oxide film 38 is not formed between the AlOx film 72 and the titanium nitride film 22, as shown in FIG. It is the same. That is, in the semiconductor device according to the present embodiment, the gate insulating film 40 is formed by a laminated structure of the silicon oxide film 14, the hafnium oxide film 16, and the AlOx film 72.

  There is no non-doped silicon like the silicon film 18 in the reference example between the hafnium oxide film 16 of the gate insulating film 40 and the titanium nitride film 22 of the gate electrode 28. Therefore, according to the semiconductor device according to the present embodiment, the influence of Fermi level pinning can be suppressed and the threshold voltage can be controlled by the work function of the titanium nitride film 22.

  Next, the method for fabricating the semiconductor device according to the present embodiment will be explained with reference to FIGS.

  First, the element isolation film 12, the silicon oxide film 14, and the hafnium oxide film 16 are formed on the silicon substrate 10 in the same manner as in the semiconductor device manufacturing method according to the first embodiment.

  Next, an AlOx film 72 having a film thickness of 0.3 nm to 3 nm, for example, 0.5 nm is formed on the hafnium oxide film 16 by, for example, the PVD method. In the N-type MISFET formation region, LaOx, YOx, MgO or the like having a film thickness of about 0.3 nm to 1 nm may be formed instead of the AlOx film.

  Next, heat treatment at 750 ° C. to 1100 ° C., for example, 1050 ° C. is performed for 5 seconds to diffuse the aluminum in the AlOx film 72 to the interface between the silicon oxide film 14 and the hafnium oxide film 16. Aluminum diffused at the interface between the silicon oxide film 14 and the hafnium oxide film 16 forms a dipole and can be used for threshold voltage control of the MISFET.

  With this heat treatment, the silicon film 18 is deposited on the surface of the AlOx film 72 (FIG. 29A). By performing a high-temperature heat treatment such as activation annealing when forming the source / drain regions, the oxygen vacancies in the hafnium oxide film 16 take in oxygen in the silicon oxide film 14 and become a more stable state. To do. As a result, oxygen in the silicon oxide film 14 diffuses into the hafnium oxide film 16, and the composition of silicon in the silicon oxide film 14 becomes excessive compared to the stoichiometric composition. The excess silicon is deposited at the interface between the hafnium oxide film 16 and the titanium nitride film 22 to form a silicon film 18.

Next, the silicon film 18 deposited on the AlOx film 72 is removed by wet etching using, for example, a mixed liquid of ammonia and hydrogen peroxide (APM: ammonia perwater). (FIG. 29 (b)). Etching of the silicon film 18 can be performed, for example, using ammonia perwater of NH ₄ OH: H ₂ O ₂ = 1: 2: 110 as an etchant at a temperature of 20 ° C. to 80 ° C., for example.

  In addition, since part of the AlOx film 72 is etched in the etching of the silicon film 18, the AlOx film 72 is made slightly thicker than in the first to third embodiments in consideration of the effective oxide film pressure of the gate insulating film. Can be formed.

  Next, the titanium nitride film 22, the polysilicon film 24, and the silicon nitride film 26 are formed on the AlOx film 72 in the same manner as the semiconductor device manufacturing method according to the first embodiment shown in FIGS. 6C to 7A. Is formed (FIG. 30A).

  Next, the semiconductor device according to the present embodiment is completed in the same manner as in the method for manufacturing the semiconductor device according to the first embodiment shown in FIGS.

  At this time, since the heat treatment for precipitating the silicon film 18 is performed in advance in the step shown in FIG. 29A, the silicon film is not precipitated again in the activation annealing step shown in FIG. As a result, a gate insulating film 40 of a laminated film of the silicon oxide film 14, the hafnium oxide film 16, and the AlOx film 72 is formed (FIG. 30B).

  As described above, according to the present embodiment, the heat treatment for depositing surplus silicon on the hafnium oxide film by performing the heat treatment is performed before the activation annealing of the source / drain regions. In the activation annealing, silicon can be prevented from being deposited between the gate insulating film and the gate electrode. Further, since the deposited silicon film is removed before the formation of the metal gate film, the effect of the threshold voltage control by the work function of the metal gate film is suppressed from being inhibited by the deposited silicon film, The threshold voltage can be controlled by the relationship with the work function of the silicon substrate.

[Sixth Embodiment]
A semiconductor device and a manufacturing method thereof according to the sixth embodiment will be described with reference to FIGS. The same components as those of the semiconductor device and the manufacturing method thereof according to the first to fifth embodiments shown in FIGS. 4 to 30 are denoted by the same reference numerals, and description thereof will be omitted or simplified.

  FIG. 31 is a schematic cross-sectional view showing the structure of the semiconductor device according to the present embodiment. 32 and 33 are process cross-sectional views illustrating the method for fabricating the semiconductor device according to the present embodiment.

  First, the structure of the semiconductor device according to the present embodiment will be explained with reference to FIG.

  In the semiconductor device according to the present embodiment, as shown in FIG. 31, a doped silicon film 74 is formed between the AlOx film 72 and the titanium nitride film 22 instead of the silicon oxide film 38. This is the same as the semiconductor device according to the third embodiment shown in FIG. That is, in the semiconductor device according to the present embodiment, the gate insulating film 40 is formed by a laminated structure of the silicon oxide film 14, the hafnium oxide film 16, and the AlOx film 72, and the gate electrode 28 is doped with the doped silicon film 74. , A titanium nitride film 22, and a polysilicon film 24.

  There is no non-doped silicon like the silicon film 18 in the reference example between the hafnium oxide film 16 of the gate insulating film 40 and the titanium nitride film 22 of the gate electrode 28. Instead, it is doped to a predetermined conductivity type. A silicon film 74 is formed. Therefore, the threshold voltage can be lowered as compared with the case where the non-doped silicon film 18 is formed between the hafnium oxide film 16 and the titanium nitride film 22. The conductivity type of the silicon film 74 is P-type for a P-type MISFET and N-type for an N-type MISFET.

  In the present embodiment, the titanium nitride film 22 is a so-called metal gate film, which is used in the first to fifth embodiments, for controlling a threshold voltage using a metal work function. Absent. The titanium nitride film 22 in this embodiment is mainly intended to suppress gate depletion and to suppress dopant sublimation during the formation of the polysilicon film 24. Therefore, it is not necessary to select according to the conductivity type of the MISFET, and the above-described material for the metal gate can be arbitrarily applied.

  Next, the method for fabricating the semiconductor device according to the present embodiment will be explained with reference to FIGS.

  First, the element isolation film 12, the silicon oxide film 14, the hafnium oxide film 16, and the AlOx film 72 are formed on the silicon substrate 10 in the same manner as in the semiconductor device manufacturing method according to the first and second embodiments. (FIG. 32 (a)).

Next, the surface of the AlOx film 72 is exposed to a gas atmosphere containing an impurity dopant that can impart conductivity to silicon, such as boron, arsenic, aluminum, phosphorus, gallium, indium, antimony, and the like. A layer 76 is formed (FIG. 32B). In the case of an N-type MISFET, for example, it is exposed to a gas atmosphere containing any of phosphorus, arsenic, and antimony, and in the case of a P-type MISFET, for example, it is exposed to a gas atmosphere containing any of boron, aluminum, gallium, and indium. As the gas atmosphere, an atmosphere obtained by vaporizing a solid element may be used, or an atmosphere of a hydrogen compound or an organic compound such as BH ₃ , B ₂ H ₆ , AsH ₃ , and PH ₃ may be used.

  In this embodiment, the heat treatment for forming the dipole and depositing the silicon film 18 is not performed after the formation of the AlOx film 72. However, as in the third to fifth embodiments, formation of the dipole and silicon Heat treatment for deposition of the film 18 may be performed. When heat treatment for forming a dipole and depositing the silicon film 18 is performed, a dopant adhesion layer 76 is formed on the deposited silicon film 18 or dopant impurities are added to the deposited silicon film 18.

  Next, on the AlOx film 72 on which the dopant adhesion layer 76 is formed, the titanium nitride film 22, the poly-silicon film 22, and the poly-oxide film 72 are formed in the same manner as in the semiconductor device manufacturing method according to the first embodiment shown in FIGS. A silicon film 24 and a silicon nitride film 26 are formed (FIG. 33A).

  Next, the semiconductor device according to the present embodiment is completed in the same manner as in the method for manufacturing the semiconductor device according to the first embodiment shown in FIGS.

  At this time, in the activation annealing step shown in FIG. 8B, oxygen vacancies in the hafnium oxide film 16 take in oxygen in the silicon oxide film 14 and try to be in a more stable state. As a result, oxygen in the silicon oxide film 14 diffuses into the hafnium oxide film 16, and the composition of silicon in the silicon oxide film 14 becomes excessive compared to the stoichiometric composition. The excess silicon is deposited at the interface between the hafnium oxide film 16 and the titanium nitride film 22 to form a silicon film 18.

  However, a dopant adhesion layer 76 is formed between the AlOx film 72 and the titanium nitride film 22, and dopant impurities are added from the dopant adhesion layer 76 to the silicon film as the silicon film is deposited. As a result, a doped silicon film 74 is formed between the AlOx film 72 and the titanium nitride film 22. Thereby, the gate insulating film 40 of the laminated film of the silicon oxide film 14, the hafnium oxide film 16, and the AlOx film 72, and the gate electrode of the laminated film of the doped silicon film 74, the titanium nitride film 22, and the polysilicon film 24 are obtained. 28 is formed (FIG. 33B).

  As described above, according to the present embodiment, since the dopant adhesion layer is formed before the formation of the metal gate film, even when a silicon film is deposited between the hafnium oxide film and the metal gate film by the subsequent heat treatment. The dopant impurity can be added to the silicon film from the dopant adhesion layer. As a result, the work function of the gate electrode becomes near the silicon midgap and the threshold voltage can be prevented from deepening.

[Seventh Embodiment]
The semiconductor device and the manufacturing method thereof according to the seventh embodiment will be described with reference to FIGS. The same components as those of the semiconductor device and the manufacturing method thereof according to the first to sixth embodiments shown in FIGS. 4 to 33 are denoted by the same reference numerals, and the description thereof is omitted or simplified.

  FIG. 34 is a schematic cross-sectional view showing the structure of the semiconductor device according to the present embodiment. 35 and 36 are process cross-sectional views illustrating the method for fabricating the semiconductor device according to the present embodiment.

  First, the structure of the semiconductor device according to the present embodiment will be explained with reference to FIG.

  In the semiconductor device according to the present embodiment, as shown in FIG. 34, the gate insulating film 40 is formed by a laminated structure of the silicon oxide film 14, the hafnium oxide film 16, and the AlOx film 72, and the gate electrode 28 is doped. This is the same as the semiconductor device according to the sixth embodiment shown in FIG. 31 in that it is formed of a laminated film of the silicon film 74, the titanium nitride film 22, and the polysilicon film 24.

  As in the case of the sixth embodiment, also in the semiconductor device according to the present embodiment, the silicon film 18 in the reference example is provided between the hafnium oxide film 16 of the gate insulating film 40 and the titanium nitride film 22 of the gate electrode 28. There is no such non-doped silicon, and instead, a silicon film 74 doped to a predetermined conductivity type is formed. Therefore, the threshold voltage can be lowered as compared with the case where the non-doped silicon film 18 is formed between the hafnium oxide film 16 and the titanium nitride film 22. The conductivity type of the silicon film 74 is P-type for a P-type MISFET and N-type for an N-type MISFET.

  In the present embodiment, the titanium nitride film 22 is not a film for controlling the threshold voltage using a metal work function, as in the case of the sixth embodiment. Instead of the titanium nitride film 22, another metal gate material may be applied.

  Next, the method for fabricating the semiconductor device according to the present embodiment will be explained with reference to FIGS.

  First, the element isolation film 12, the silicon oxide film 14, the hafnium oxide film 16, and the AlOx film 72 are formed on the silicon substrate 10 in the same manner as in the semiconductor device manufacturing method according to the first and second embodiments. (FIG. 35 (a)).

  Next, a titanium nitride (TiN) film 22 of, eg, a 10 nm-thickness is formed on the AlOx film 72 by, eg, PVD.

  In this embodiment, the heat treatment for forming the dipole and depositing the silicon film 18 is not performed after the formation of the AlOx film 72. However, as in the third to fifth embodiments, formation of the dipole and silicon Heat treatment for deposition of the film 18 may be performed. When heat treatment for forming the dipole and depositing the silicon film 18 is performed, a titanium nitride film 22 is formed on the deposited silicon film 18.

Next, impurities such as boron, arsenic, aluminum, phosphorus, gallium, indium, and antimony are ion-implanted into the titanium nitride film 22 (FIG. 35B). For an N-type MISFET, for example, any one of phosphorus, arsenic, and antimony is ion-implanted. For a P-type MISFET, for example, any one of boron, aluminum, gallium, and indium is ion-implanted. In the case of a P-type MISFET, for example, boron ions are ion-implanted under the conditions of an acceleration energy of 0.1 keV to 5 keV and a dose amount of 1.0 × 10 ^{13 to} 1.0 × 10 ¹⁶ cm ⁻² .

  In addition, for doping impurities into the titanium nitride film 22, plasma doping, cluster doping, or the like may be used instead of ion implantation.

  Next, a polysilicon film 24 and a silicon nitride film 26 are formed on the titanium nitride film 22 in the same manner as in the semiconductor device manufacturing method according to the first embodiment shown in FIG. 7A (FIG. 36A). .

  The addition of impurities into the titanium nitride film 22 may be performed after the polysilicon film 24 is formed or after the silicon nitride film 26 is formed. Even when impurities are added to the titanium nitride film 22 before the polysilicon film 24 is formed, impurities may be further added after the polysilicon film 24 is formed or after the silicon nitride film 26 is formed.

  Next, the semiconductor device according to the present embodiment is completed in the same manner as in the method for manufacturing the semiconductor device according to the first embodiment shown in FIGS.

  At this time, in the activation annealing step shown in FIG. 8B, oxygen in the silicon oxide film 14 diffuses into the hafnium oxide film 16 and is trapped by oxygen vacancies in the hafnium oxide film 16. As a result, silicon in the silicon oxide film 14 becomes excessive, and a silicon film is deposited between the AlOx film 72 and the titanium nitride film 22.

  However, since the dopant impurity is added in the titanium nitride film 22, the dopant impurity in the titanium nitride film 22 is diffused and activated in the deposited silicon film. As a result, a doped silicon film 74 is formed between the AlOx film 72 and the titanium nitride film 22. Thereby, the gate insulating film 40 of the laminated film of the silicon oxide film 14, the hafnium oxide film 16, and the AlOx film 72, and the gate electrode of the laminated film of the doped silicon film 74, the titanium nitride film 22, and the polysilicon film 24 are obtained. 28 is formed (FIG. 36B).

  As described above, according to the present embodiment, since the dopant impurity is added to the metal gate film after the metal gate film is formed, the silicon film is formed between the hafnium oxide film and the metal gate film by the subsequent heat treatment. Even when it is deposited, dopant impurities can be added to the silicon film from the metal gate film. As a result, the work function of the gate electrode becomes near the silicon midgap and the threshold voltage can be prevented from deepening.

[Modified Embodiment]
The present invention is not limited to the above embodiment, and various modifications are possible.

  For example, in the first and second embodiments, the heat treatment for depositing the silicon film 18 is performed before the TaO (CN) film 20 is formed. However, the silicon film 18 is not necessarily formed before the TaO (CN) film 20 is formed. There is no need to deposit. Silicon deposited during the subsequent heat treatment (for example, activation annealing of the source / drain regions) may be oxidized by the TaO (CN) film 20 at that time. This heat treatment may be performed before the patterning of the gate electrode 28 as long as the TaO (CN) film 20 is formed.

  In the second to seventh embodiments, the AlOx film 72 is formed on the hafnium oxide film 16. However, as in the first embodiment, the AlOx film 72 is not necessarily formed in the third to seventh embodiments. There is no need.

  In the first to seventh embodiments, the example of the MISFET having the gate insulating film using the hafnium-based insulating film mainly composed of hafnium oxide as the high dielectric constant film has been described. The dielectric constant film is not limited to hafnium oxide. For example, instead of hafnium oxide, a metal oxide high dielectric constant material such as aluminum oxide, zirconium oxide, titanium oxide, or lanthanum oxide can be used. Although the inventors of the present application have not made a specific examination, even when aluminum oxide, zirconium oxide, titanium oxide, lanthanum oxide, or the like is used, silicon deposition as shown in Reference Example 1 is expected.

  In addition, various conditions such as the constituent materials, film thicknesses, and processing conditions described in the above embodiment are not limited to those described in the above embodiment, and are within a range in which the effects of the above embodiment can be realized. A trader or the like can appropriately select and set as necessary.

  Regarding the above embodiment, the following additional notes are disclosed.

(Appendix 1) A step of forming a first insulating film mainly composed of silicon oxide on a semiconductor substrate;
Forming a second insulating film mainly composed of hafnium oxide on the first insulating film;
Performing a heat treatment to deposit silicon on the second insulating film;
Forming a third insulating film having an oxidizing action on silicon on the silicon;
Forming a metal film on the third insulating film;
Patterning the metal film to form a gate electrode including the metal film;
And a step of oxidizing the silicon by the oxidation action of the third insulating film by performing a heat treatment.

(Additional remark 2) In the manufacturing method of the semiconductor device of Additional remark 1,
After the step of forming the gate electrode, further comprising the step of introducing a dopant impurity into the semiconductor substrate on both sides of the gate electrode to form an impurity diffusion region,
The method of manufacturing a semiconductor device, wherein the step of oxidizing the silicon also serves as a step of forming source / drain regions by activating the dopant impurities introduced into the semiconductor substrate.

(Additional remark 3) In the manufacturing method of the semiconductor device of Additional remark 1 or 2,
The third insulating film is a film mainly composed of an oxide of Ta, Mo, Mn, Fe, Ni, Ru, Co, Cu, Pt, or Zn.

(Additional remark 4) In the manufacturing method of the semiconductor device of Additional remark 3,
The method for manufacturing a semiconductor device, wherein the third insulating film further contains nitrogen or carbon.

(Appendix 5) Forming a first insulating film mainly composed of silicon oxide on a semiconductor substrate;
Forming a second insulating film mainly composed of hafnium oxide on the first insulating film;
Performing a heat treatment to deposit silicon on the second insulating film;
Oxidizing the silicon;
After the step of oxidizing the silicon, forming a metal film on the second insulating film;
And a step of patterning the metal film to form a gate electrode including the metal film.

(Additional remark 6) In the manufacturing method of the semiconductor device of Additional remark 5,
The method of manufacturing a semiconductor device, further comprising a step of removing the oxidized silicon after the step of oxidizing the silicon and before the step of forming the metal film on the second insulating film.

(Appendix 7) A step of forming a first insulating film mainly composed of silicon oxide on a semiconductor substrate;
Forming a second insulating film mainly composed of hafnium oxide on the first insulating film;
Performing a heat treatment to deposit silicon on the second insulating film;
Removing the silicon;
Forming a metal film on the second insulating film;
And a step of patterning the metal film to form a gate electrode including the metal film.

(Supplementary note 8) In the method for manufacturing a semiconductor device according to any one of supplementary notes 1 to 7,
A semiconductor device further comprising a step of forming a fifth insulating film mainly composed of AlOx, LaOx, YOx, or MgOx after the formation of the second insulating film and before the step of depositing the silicon. Manufacturing method.

(Appendix 9) A step of forming a first insulating film mainly composed of silicon oxide on a semiconductor substrate;
Forming a second insulating film mainly composed of hafnium oxide on the first insulating film;
A dopant adhesion layer formed by exposing the surface of the second insulating film to an atmosphere containing a dopant impurity capable of imparting a predetermined conductivity type to silicon, and depositing the dopant impurity on the second insulating film. Forming a step;
Forming a metal film on the second insulating film on which the dopant adhesion layer is formed;
Patterning the metal film to form a gate electrode of the metal film;
And a step of depositing silicon between the second insulating film and the metal film and adding the dopant impurity of the dopant adhesion layer into the silicon. Manufacturing method.

(Appendix 10) A step of forming a first insulating film mainly composed of silicon oxide on a semiconductor substrate;
Forming a second insulating film mainly composed of hafnium oxide on the first insulating film;
Forming a metal film on the second insulating film;
Introducing a dopant impurity into the metal film;
Patterning the metal film to form a gate electrode of the metal film;
And a step of precipitating silicon between the second insulating film and the metal film, and diffusing the dopant impurity in the metal film into the silicon. Manufacturing method.

(Additional remark 11) In the manufacturing method of the semiconductor device of Additional remark 9 or 10,
After the step of forming the gate electrode, further comprising the step of introducing a dopant impurity into the semiconductor substrate on both sides of the gate electrode to form an impurity diffusion region,
The step of forming the silicon to which the dopant impurity is added also serves as a step of activating the dopant impurity introduced into the semiconductor substrate to form source / drain regions.

(Supplementary note 12) In the method for manufacturing a semiconductor device according to any one of supplementary notes 9 to 11,
The method further includes a step of forming a third insulating film mainly composed of AlOx, LaOx, YOx, or MgOx after the step of forming the second insulating film and before the step of forming the metal film. A method for manufacturing a semiconductor device.

(Supplementary note 13) In the method for manufacturing a semiconductor device according to any one of supplementary notes 1 to 12,
In the step of depositing silicon, the first insulating film is surplus by supplying oxygen from the first insulating film to the second insulating film in order to compensate for oxygen vacancies in the second insulating film. A method of manufacturing a semiconductor device, comprising depositing silicon in an insulating film.

(Supplementary Note 14) A first insulating film formed on a semiconductor substrate and mainly composed of silicon oxide;
A second insulating film mainly formed of hafnium oxide formed on the first insulating film;
A third insulating film formed mainly on silicon oxide and formed on the second insulating film;
A gate insulating film formed on the third insulating film and having a fourth insulating film mainly composed of an oxide of Ta, Mo, Mn, Fe, Ni, Ru, Co, Cu, Pt or Zn;
And a gate electrode having a metal film formed on the gate insulating film and in contact with the fourth insulating film.

(Supplementary Note 15) In the semiconductor device according to Supplementary Note 14,
The fourth insulating film further contains nitrogen or carbon. The semiconductor device.

(Supplementary note 16) In the semiconductor device according to supplementary note 14 or 15,
A semiconductor device further comprising a fifth insulating film mainly composed of AlOx, LaOx, YOx, or MgOx between the second insulating film and the third insulating film.

DESCRIPTION OF SYMBOLS 10 ... Silicon substrate 12 ... Element isolation films 14, 38, 50 ... Silicon oxide film 16 ... Hafnium oxide film 18 ... Silicon film 20 ... TaO (CN) film 22, 44 ... Titanium nitride film 24 ... Polysilicon film 26, 42, 48 ... Silicon nitride film 28 ... Gate electrodes 30, 34 ... Impurity diffusion region 32 ... Side wall insulating film 36 ... Source / drain region 40 ... Gate insulating film 42 ... Nickel film 46 ... NiSi film 52, 54 ... Contact hole 56 ... Under Base film 58 ... W film 60 ... Contact plugs 62 and 66 ... Interlayer insulating films 64 and 70 ... Wiring layer 68 ... Via portion 72 ... AlOx film 74 ... Doped silicon film 76 ... Dopant adhesion layer

Claims (9)

Forming a first insulating film mainly composed of silicon oxide on a semiconductor substrate;
Forming a second insulating film mainly composed of hafnium oxide on the first insulating film;
Performing a heat treatment to deposit silicon on the second insulating film;
Forming a third insulating film having an oxidizing action on silicon on the silicon;
Forming a metal film on the third insulating film;
Patterning the metal film to form a gate electrode including the metal film;
And a step of oxidizing the silicon by the oxidation action of the third insulating film by performing a heat treatment. In the manufacturing method of the semiconductor device according to claim 1,
The third insulating film is a film mainly composed of an oxide of Ta, Mo, Mn, Fe, Ni, Ru, Co, Cu, Pt, or Zn. The method of manufacturing a semiconductor device according to claim 2.
The method for manufacturing a semiconductor device, wherein the third insulating film further contains nitrogen or carbon. Forming a first insulating film mainly composed of silicon oxide on a semiconductor substrate;
Forming a second insulating film mainly composed of hafnium oxide on the first insulating film;
Performing a heat treatment to deposit silicon on the second insulating film;
Oxidizing the silicon;
After the step of oxidizing the silicon, removing the oxidized silicon;
After the step of removing the silicon, forming a metal film on the second insulating film;
And a step of patterning the metal film to form a gate electrode including the metal film. Forming a first insulating film mainly composed of silicon oxide on a semiconductor substrate;
Forming a second insulating film mainly composed of hafnium oxide on the first insulating film;
Performing a heat treatment to deposit silicon on the second insulating film;
Removing the silicon;
Forming a metal film on the second insulating film;
And a step of patterning the metal film to form a gate electrode including the metal film. Forming a first insulating film mainly composed of silicon oxide on a semiconductor substrate;
Forming a second insulating film mainly composed of hafnium oxide on the first insulating film;
A dopant adhesion layer formed by exposing the surface of the second insulating film to an atmosphere containing a dopant impurity capable of imparting a predetermined conductivity type to silicon, and depositing the dopant impurity on the second insulating film. Forming a step;
Forming a metal film on the second insulating film on which the dopant adhesion layer is formed;
Patterning the metal film to form a gate electrode of the metal film;
And a step of depositing silicon between the second insulating film and the metal film and adding the dopant impurity of the dopant adhesion layer to the silicon. Production method. Forming a first insulating film mainly composed of silicon oxide on a semiconductor substrate;
Forming a second insulating film mainly composed of hafnium oxide on the first insulating film;
Forming a metal film on the second insulating film;
Introducing a dopant impurity into the metal film;
Patterning the metal film to form a gate electrode of the metal film;
And a step of precipitating silicon between the second insulating film and the metal film, and diffusing the dopant impurity in the metal film into the silicon. Manufacturing method. In the manufacturing method of the semiconductor device according to any one of claims 1 to 7 ,
A method of manufacturing a semiconductor device, further comprising a step of forming a fifth insulating film mainly composed of AlOx, LaOx, YOx, or MgOx after the step of forming the second insulating film. A first insulating film formed on a semiconductor substrate and mainly composed of silicon oxide;
A second insulating film mainly formed of hafnium oxide formed on the first insulating film;
A third insulating film formed mainly on silicon oxide and formed on the second insulating film;
A gate insulating film formed on the third insulating film and having a fourth insulating film mainly composed of an oxide of Ta, Mo, Mn, Fe, Ni, Ru, Co, Cu, Pt or Zn;
And a gate electrode having a metal film formed on the gate insulating film and in contact with the fourth insulating film.

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