TW201310532A - Method for forming gate insulating film, and device for forming gate insulating film - Google Patents

Abstract

A method for forming a gate insulating film, in which a gate insulating film is formed on a semiconductor substrate, comprises: a film formation step of forming a high-dielectric film on the semiconductor substrate using CVD or ALD; a first modification step of applying radial treatment to, and modifying, the formed high-dielectric film at a temperature lower than the film formation temperature; and a second modification step of applying heat treatment to, and causing crystallization in, the high-dielectric film formed in the first modification step.

Description

Method for forming gate insulating film and device for forming gate insulating film

The present invention relates to a method of forming a gate insulating film and a device for forming a gate insulating film.

Recently, in order to improve the performance of a semiconductor circuit by thinning the film thickness of the gate insulating film of the MOSFET, a high dielectric constant film (High-k film) is used as a gate insulating film, but yttrium oxide is also used therein. The material of the material is attracting attention, and the HfSiON film or the HfO ₂ film is put into practical use in a state where the dielectric constant is low (for example, Patent Document 1).

In the film formation method of the HfSiON film or the HfO ₂ film-like ruthenium oxide material film, CVD (Chemical Vapor Deposition) or ALD (Atomic Layered Deposition) is used. . Among these, the film formation temperature of CVD is 500 ° C at a relatively high temperature, whereas the ALD system can form a film at a low temperature of about 300 ° C, and the step coverage is also better with ALD. Therefore, ALD is gradually preferred.

In addition, recently, the dielectric constant of the gate insulating film has been further increased, and in order to improve the film quality and improve the dielectric constant, annealing at a high temperature (above the film forming temperature to about 1000 ° C) is often used (for example, Patent Document 2). . Further, attempts have been made to control the annealing method to form a crystal state of HfO ₂ into Cubic or Tetragonal having a higher dielectric constant to further improve the dielectric constant (for example, Patent Document 3).

Prior technical literature Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2006-128547

Patent Document 2: US Patent Publication No. 2005/0136690A1

Patent Document 3: International Publication No. 2006/025350

However, with the miniaturization of the semiconductor integrated circuit, mass production uses a Gate-Last method of fabricating a MOSFET at the end of the project. In the Gate-Last method, a diffusion process requiring heat treatment at a high temperature is performed in the first half of the process, and when a gate is formed, a part of the metal wiring may be formed. In the case as described above, heat treatment (annealing) at a high temperature as is conventionally performed after forming the gate insulating film to modify the High-k film is difficult to perform, and the annealing temperature and annealing time (heat) The budget (Thermal budget) imposes restrictions. Therefore, it is difficult to obtain a High-k film having a good film quality and a high dielectric constant.

Accordingly, an object of the present invention is to provide a method of forming a gate insulating film of a gate insulating film which can obtain a high dielectric constant with a small thermal budget, and a device for forming a gate insulating film.

According to a first aspect of the present invention, a method of forming a gate insulating film, which is a method of forming a gate insulating film for forming a gate insulating film on a semiconductor substrate, has a film forming process by CVD Or ALD, forming a high dielectric constant film on a semiconductor substrate; the first modification project is to form a high dielectric of the film formed at a temperature lower than the film forming temperature. The coefficient film is subjected to radical treatment for modification; and the second modification process is performed by subjecting the high dielectric constant film formed in the first modification process to heat treatment to be crystallized.

According to a second aspect of the present invention, there is provided a method of forming a gate insulating film which is a method of forming a gate insulating film for forming a gate insulating film on a semiconductor substrate, comprising: a film forming process by CVD Or ALD, forming a high dielectric constant film on a semiconductor substrate; the first modification project is to perform a radical treatment on the formed high dielectric constant film at a temperature lower than the crystallization temperature. The film is obtained in an amorphous state, and the second modification process is performed by performing a rapid temperature rise and fall process on the high dielectric constant film after the first modification process by heat treatment.

According to a third aspect of the present invention, there is provided a method of forming a gate insulating film which is a method of forming a gate insulating film for forming a gate insulating film on a semiconductor substrate, comprising: a film forming process by CVD Or ALD, forming a high-k film on a semiconductor substrate; and modifying the substrate by irradiating the high-k film with microwaves and modifying the high-k film by microwave heating.

According to a fourth aspect of the present invention, there is provided a method of forming a gate insulating film which is a method of forming a gate insulating film for forming a gate insulating film on a semiconductor substrate, comprising: a film forming process by CVD Or ALD, forming a high dielectric constant film on a semiconductor substrate; and modifying the process by modifying the high dielectric constant film by heating the high dielectric constant film with a light emitting diode.

According to a fifth aspect of the present invention, there is provided a device for forming a gate insulating film, which is a device for forming a gate insulating film of a gate insulating film on a semiconductor substrate, comprising: a film forming device by CVD Or ALD, forming a high dielectric constant film on a semiconductor substrate; and the first modification processing device performing a radical treatment on the formed high dielectric constant film at a temperature lower than a film formation temperature The second modification treatment device is configured to perform crystallization by heating the high dielectric constant film after the first modification treatment by the first modification treatment device, and the control unit is configured to The film formation process of the film formation apparatus, the first modification process of the first modification process device, and the second modification process of the second modification process device are performed in this order.

According to a sixth aspect of the present invention, there is provided a device for forming a gate insulating film, comprising: a processing container for accommodating a semiconductor substrate; and a gas supply mechanism for supplying a film forming film into the processing container a film forming gas for an electric coefficient film; a plurality of microwave introducing means having: a waveguide for guiding microwaves, a planar antenna for irradiating microwaves and forming a slot, and a proximity of the planar antenna to integrate impedance a pellet tuner, and introducing microwaves into the processing container; and a microwave irradiation mechanism for irradiating the semiconductor substrate with microwaves, wherein: forming a film of a high dielectric constant film; and using the microwave The first modification process is performed by the microwave plasma generated by the microwave introduced by the introduction mechanism, and the second modification process of performing microwave heating by the microwave irradiation means.

Embodiments of the present invention will be specifically described below with reference to the accompanying drawings.

<basic mechanism>

The relationship between the dielectric constant ε of the dielectric and the density can be grasped by Clausius-Mossotti as shown in the following formula (1).

(4/3). Πnα=(ε-1)/(ε+2).........(1)

Where α is the polarization ratio and n is the density of the dipole.

That is, on the left (4/3). The πnα system is proportional to the density. If ε is taken on the horizontal axis and (4/3) is plotted on the vertical axis. When πnα, the relationship shown in Fig. 1 is formed, and the higher the density of the dielectric, the higher the dielectric constant.

The HfO ₂ film system having a high-k film has a dielectric constant ε of about 12, a film thickness of 3 nm, and an EOT (Equivalent Oxide Thickness: SiO ₂ capacity conversion film thickness) of 1.02 nm. However, as shown in FIG. The dielectric constant ε is increased to about 20, and the EOT is formed to be 0.6 nm at a film thickness of 3 nm. Therefore, the density may be increased by 10%.

Therefore, in the present invention, the density of the High-k film constituting the gate insulating film is increased by the treatment of a small thermal budget, and the dielectric constant of the film is increased as the first basic concept. Further, in order to obtain a high dielectric constant and density, it is necessary to crystallize the film.

<First embodiment>

In the first embodiment, in consideration of the above, the gate insulating film is formed by the method described below. Figure 2 is a diagram for explaining the first embodiment of the present invention. A flow chart of a method of forming a gate insulating film.

First, the surface of the tantalum wafer 1 is cleaned by dilute hydrofluoric acid or the like, and if necessary, pretreatment (formation 1) of forming an interface layer made of SiO ₂ is performed, and then a high-k film is formed ( Project 2). In the case of a High-k film, a film of a tantalum oxide material, typically a hafnium oxide (HfO ₂ ) film or a niobate (HfSiOx) film, can be suitably used.

The film formation system at this time can be performed by CVD or ALD. In particular, it is preferably carried out by ALD which can form a film at a low temperature and has good step coverage.

When a film of HfO ₂ is formed by CVD or ALD, a Hf source gas and an oxidizing agent are used as a film forming gas.

The Hf source may be suitably used as an organometallic compound, and examples thereof include amide-based organic compounds such as TDEAH (tetrakis(diethylamino)phosphonium) and tetrakis(ethylmethylamino acid) ruthenium (TEMAH). An anthracene compound or an alcohol compound such as tetra-t-butoxyfluorene (HTB) is an organic hydrazine compound. As the oxidizing agent, O ₃ gas, H ₂ O gas, O ₂ gas, NO ₂ gas, NO gas, N ₂ O gas or the like can be used. The oxidant can also be plasmad to increase reactivity. Further, it is also possible to use radical oxidation of O ₂ gas and H ₂ gas.

When the HfO ₂ film is formed by CVD, the Hf source is irradiated while the Hf source is heated, and the Hf source is reacted on the germanium wafer or the interface layer thereon to form a film of HfO ₂ . Further, in the case of ALD, the HfO ₂ film is formed by alternately repeatedly adsorbing the Hf source thin layer and then supplying the oxidizing agent.

When a HfSiOx film is formed by CVD or ALD, a Hf source gas, a Si source gas, and an oxidizing agent are used as a film forming gas.

The same as the HfO ₂ film may be used as the Hf source or the oxidizing agent. Examples of the Si source include a guanamine-based organic ruthenium compound such as TDMAS (tetrakis(dimethylamino)decane) or an alcohol compound-based organic ruthenium compound such as TEOS (tetraethoxydecane) or dioxane (Si). ₂ H ₆ ) and other inorganic decane compounds.

When a HfSiOx film is formed by CVD, the HfSiOx film is formed by heating the germanium wafer while supplying the Hf source, the Si source gas, and the oxidant on the germanium wafer or the interface layer thereon. . Further, in the case of ALD, for example, an Hf source film is adsorbed after the Hf source thin layer is adsorbed, and then oxidized, and then the Si source thin layer is adsorbed and then oxidized to form a film of HfSiOx film.

When the HfO ₂ film or the HfSiOx film is formed by the above CVD, a film forming temperature of 350 to 600 ° C, for example, about 500 ° C is used, and when film formation by ALD, 150 to 350 ° C, for example, about 300 ° C is used. Film formation temperature.

As shown above, in the state in which film formation by CVD or ALD is maintained, as shown in Fig. 3 (a), the film contains a large amount of impurities, and the atoms are irregularly arranged in an amorphous state. Therefore, in this state, the density is low and the film quality is also inferior, so that the dielectric constant is low. In particular, in the case of ALD, since the film formation is performed at a low temperature, impurities are likely to remain.

Therefore, in the present embodiment, after the film formation, the first modification treatment (Project 3) is performed by radical treatment at a low temperature. By this radical treatment, as shown in FIG. 3(b), impurities in the film are removed to enhance the film quality, and the density of the film is increased. If the temperature of the radical treatment exceeds the film formation temperature, the effect of increasing the density is lowered, so that the film formation temperature is preferred. the following. In the case of the radical treatment as described above, it is suitable to use ultraviolet-ray-excited radical oxidation treatment and microwave plasma treatment.

The modification process preferably has a small thermal budget, and the High-k film itself and the interface layer are not coated as much as possible to effectively remove impurities in the film. From the viewpoint of the above, the 350 can be suitably used. Ultraviolet-excited radical oxidation treatment below °C. In order to suppress the film formation of the interface layer as much as possible, it is suitable to use a UV-excited radical oxidation treatment at room temperature. Further, the ultraviolet excitation radical oxidation treatment is preferably carried out under an atmosphere containing O ₂ gas, and preferably, the partial pressure of the O ₂ gas is 1.33 Pa or more. The ultraviolet excitation radical oxidation treatment as described above is carried out using an ultraviolet irradiation apparatus shown in Fig. 22 which will be described later.

In addition, the microwave plasma has the advantages of high plasma density and low electron temperature. As the processing gas, an O ₂ gas, a rare gas such as Ar, an N ₂ gas, or the like can be suitably used. Specifically, O ₂ gas, O ₂ gas + rare gas, rare gas, rare gas + N ₂ gas can be used. Among them, when O ₂ gas is used, there is a tendency for the interface layer to be formed. Further, the temperature at the time of microwave plasma treatment is preferably 350 ° C or less. The microwave plasma processing system as described above can be carried out using the microwave plasma processing apparatus shown in Figs. 23 and 24 to be described later.

The impurities can be removed by radical treatment at a low temperature as described above, but since the crystallization is not sufficient, the dielectric constant is not sufficiently increased. Therefore, after the first modification process of the process 3, the second modification process is performed, and the High-k film is crystallized as shown in FIG. 3(c) (Project 4).

The second modification treatment is a heat treatment for supplying energy for crystallization, and must be performed at a thermal budget to the extent that it does not affect the heat of the element. Since the High-k film removes impurities by the first modification process, the film can be crystallized with a small thermal budget in the second modification process.

In the crystallization treatment under the small thermal budget as described above, sharp-wave annealing using an RTP (Rapid Thermal Process) device by lamp heating or the like can be cited. Although the sharp-wave annealing is a high temperature of 600 to 900 ° C, it is performed in a short time of about 0.1 to 1 sec, so that it can be processed under a small thermal budget. Further, it may be a heat treatment at a temperature of 700 ° C or lower using a resistance heating heat treatment. The holding time at this time is preferably 3 minutes or less. At this time, in order to sufficiently perform crystallization, it is preferably 450 ° C or more.

Further, in the second modification process, microwave irradiation treatment (MIT) is also suitable. The MIT system can directly heat the High-k film by internal heating by electromagnetic wave energy, and can be crystallized at a low temperature of 500 ° C or lower. Therefore, it is possible to carry out a modification process with an extremely small thermal budget and little heat diffusion or reoxidation. The microwave irradiation treatment as described above can be carried out using a microwave heating apparatus shown in Fig. 28 which will be described later.

Further, in the second modification treatment, heat treatment by a light-emitting diode (LED) is exemplified. LED heating does not utilize the black body radiation of the heating source, but uses electromagnetic radiation caused by the recombination of electrons and holes, so the thermal budget is small, and the temperature rise and fall is extremely high. In addition, most of GaN or GaAs used as an LED element has a high absorptivity to germanium, but has a low absorptivity to HfO ₂ or HfSiOx, so that the temperature of the HfO ₂ film or the HfSiOx film is not raised. Crystallization. The LED heating system as shown above can be carried out using the LED heating device shown in FIG.

The second modification treatment can also be carried out by UVRF treatment in which ultraviolet irradiation and radical irradiation are used in combination.

In the above process, the film formation process of the project 2, the first modification process of the project 3, and the second modification process of the project 4 may be performed using different processing devices, or the same device may be used for the engineering 2 In the first modification process of the film formation process and the process 3, the first modification process of the work 3 and the second modification process of the work 4 may be performed in the same apparatus, and the works 2 to 4 may be performed in the same apparatus.

Further, in the above process, the first modification process of the process 3 of two or more times may be repeated, or the second modification process of the process 4 of two or more times may be repeated. In addition, after the film formation process of the process 2 and the first modification process of the process 3 are continuously performed, the process 2 and the process 3 of the process 3 may be repeated one more time. In addition, after the 1 modification process of the process 3 and the 2nd modification process of the process 4 are continuously performed, the continuous process of the process 3 and the process 4 of one or more times may be repeated. In addition, after continuous engineering 2~4, the continuous processing of 2~4 of the above engineering may be repeated. When the reverse project 2 and the project 3 are repeated, the reverse project 3 and the project 4 and the reverse project 2 to 4 are preferably performed in the same device and in the same chamber.

In the film formation process of the reverse process 2 and the first modification process of the process 3, it is considered that the first modification process is performed every time a predetermined film thickness is formed, but the first film formation film thickness is increased by adding a plurality of times. When thinning, it is determined that after In the first modification process, the interface oxide film between the thin layer of the High-k film and the germanium wafer is increased, and the EOT is increased.

In order to solve the problem as described above, it is effective to thicken the initial film formation film irrespective of the number of times of overturning, and to thicken it to some extent. Specifically, it is preferable to form the initial film formation film thickness to 1.05 nm or more.

The experimental results indicating the situation are described below.

Here, in the film formation process of the process ₂ , the HfO ₂ film is formed by ALD, and in the first modification process, the microwave plasma treatment (radical treatment) is performed. In the case of the apparatus, the film formation process shown in FIG. 31, which will be described later, and the first modification process are performed in the same chamber.

4 is a view showing a case where the number of cycles of the first modification treatment by the microwave plasma treatment (radical treatment) by 40 sec is performed when a 2.5 nm HfO ₂ film is formed by the ALD film formation process of 31 cycles. A plot of the film thickness of the interfacial layer (SiO ₂ film). As shown in the figure, the film thickness of the interface layer at the time of performing the first modification treatment after the film formation at 31 cycles was 0.16 nm, which was the same film thickness as that in the case where the reforming treatment was not performed, and there was no film formation. When the film thickness (the number of cycles) until the first modification treatment is made thinner (less), the thickness of the interface layer increases, and the film is strongly increased in the vicinity of 0.54 nm in 8 cycles. As can be seen from the figure, the thickness of the boundary film (the film thickness of the interface layer does not increase the film thickness) is 15 cycles, but at 15 cycles (film thickness: 1.25 nm), the thickness of the interface layer is 0.24 nm, and 31 Compared with the cycle, the film is increased. Therefore, in order to prevent film formation in 15 cycles, it is necessary to make the microwave plasma treatment (radical treatment) as the first modification process weaker. The film thickness of the interface layer is determined by X-ray photoelectron spectroscopy (XPS) (the same applies hereinafter).

Therefore, the treatment time of the microwave plasma treatment (radical treatment) performed after 15 cycles of film formation was changed. Fig. 5 is a view showing the relationship between the microwave plasma treatment time after film formation for 15 cycles on the horizontal axis and the thickness of the interface layer on the vertical axis. As shown in the figure, it is understood that when the time for the first modification treatment by the microwave plasma treatment is reduced to 10 sec, the film formation disappears even for 15 cycles.

Next, film formation was performed for 31 cycles by changing the timing and length of the microwave plasma treatment as the first modification process. Fig. 6 is a graph showing the relationship between the number of reforming start cycles and the film thickness of the interface layer at this time. In the figure, the rhombic plot is performed after the film formation to the illustrated cycle, and the microwave plasma treatment as the first modification process is performed for 1 sec, and then the first modification process is performed for 1 sec. The microwave plasma processor, after performing the film formation to the illustrated cycle, performs the microwave plasma treatment as the first modification process for 3 sec, and then performs the film for 1 cycle, that is, 1 sec. The microwave plasma processor of the first modification process. In addition, the plot of × is performed after the film formation is performed until the cycle shown in the figure, and the microwave plasma treatment as the first modification process is performed for 10 sec, and then the film formation of the remaining cycle is performed, and the four-corner plot is formed at 15 cycles. After the film, the microwave plasma treatment as the first modification treatment was performed for 10 sec, and then the remaining 16-cycle film formation process was performed (see FIG. 5). The conditions of the microwave plasma treatment are as follows: chamber pressure: 20 Pa, microwave output of each of the microwave introduction mechanisms: 200 W, gap between the microwave introduction mechanism and the wafer: 80 mm.

As shown in FIG. 6, the period until the start of the first modification process is confirmed. The number was 13 cycles or more and no interfacial layer filming was observed. That is, the film thickness of 13 cycles is the limit film thickness. The 13 cycle system corresponds to a film thickness of 1.05 nm. Therefore, when the film formation process of the process 2 and the first modification process of the process 3 are repeated, the first film formation process is performed with a film thickness of 1.05 nm or more, and the plasma process of the first modification process of 10 sec or less is performed. good. In other words, when the number of times of the film formation treatment and the first modification treatment is 2 or more, the film thickness is not divided into a ratio, and the film thickness of the first film formation treatment is 1.05 nm or more without any reciprocal number. good.

From the above experimental results, it is understood that the preferred upper limit of the film thickness of the first film formation is not derived, but the film thickness of the first film formation is preferably as small as 1.21 nm or less. 1.21 nm corresponds to 15 cycles in the above experiment.

As described above, after the High-k film is formed by CVD or ALD, the film is improved by removing the impurities in the film by the first modification treatment by radical treatment at a temperature lower than the film formation temperature. Moreover, the density of the film can be increased, and the film can be crystallized with a small thermal budget by the subsequent heat treatment, and the dielectric constant of the film is greatly increased. Further, by selecting conditions, filming of the interface layer and the like can be suppressed.

(Basic experiment in the first embodiment)

FIG. 7 is a view showing the concentration of impurities (carbon) in the film thickness direction after the first modification treatment is performed after the HfO ₂ film is formed by ALD. The sample was formed on Si, and the HfO ₂ film treated with in-situ three times at 3.5 nm was formed to have a thickness of 10 nm, and the HfO ₂ film of as depo was formed to have a thickness of 10 nm. As a result, in the case of 450 ° C which is a high temperature treatment, the carbon concentration is high at a film formation temperature of 310 ° C. It is advantageous to derive the temperature of the first modification treatment to perform at a low temperature.

Fig. 8 is a graph showing the relationship between the amount of film formation and the film thickness of the interface layer at the time of various reforming treatments, and an enlarged view of a portion surrounded by a circle is also shown. The ultraviolet irradiation treatment (UV-O) in an oxygen gas atmosphere and the microwave plasma treatment (microwave plasma-O) in an oxygen gas atmosphere are as shown by a thick solid line, and it is confirmed that the temperature rises and the interface layer increases. However, UV-O (■RT std UV, □RT UV time, ▲RT UV press) at room temperature is a condition in which the interface layer hardly increases the film thickness and the film thickness itself does not become thick.

9A is a graph showing the relationship between the oxidation temperature of UV-O and the thickness of the interface layer, and FIG. 9B is a standard condition for setting the thickness of the interface layer in various conditions of UV-O at room temperature to 450 ° C and 0.10 Torr. The comparison of the processing time is compared. As can be seen from the figures, as the temperature of the UV-O decreases, the thickness of the interface layer becomes smaller, and the UV-O at room temperature can be reduced by about 0.2 nm as compared with the standard conditions.

FIG. 10 shows a change in X-ray irradiation in the XPS measurement by the binding energy of 4f of Hf at the time of each treatment, and shows the stability of the film. As can be seen from the figure, in the annealing at 700 ° C, the change in the binding energy of 4f of Hf is small and the stability of the film is high. However, the UV irradiation treatment in the O ₂ gas atmosphere and the microwave plasma treatment are performed. The change in the binding energy of 4f of Hf is large.

11A, 11B, and 11C show the as depo state of the HfO ₂ film having a thickness of 2.5 nm, and the valence band of the HfO ₂ film when the annealing is performed at 900 ° C for 10 minutes and at 90 ° C for 10 minutes. A plot of the X-ray photoelectron spectroscopy (XPS) spectrum in a (valence band). In the figure, the amorphous film when the as depo is confirmed by the spectral change can be crystallized in the same manner as the ordinary high-temperature annealing at 900 ° C for 10 minutes even in the sharp-wave annealing with a small thermal budget.

12A and 12B are diagrams showing the as depo state of the HfO ₂ film having a film thickness of 4.0 nm and the XPS spectrum when the MIT is performed at 600 W for 30 min. From the figure, it was confirmed that crystallization was carried out by performing MIT at 600 W for 30 minutes at a film thickness of 4.0 nm. In addition, FIG. 13 is a view showing an as depo state of an HfO ₂ film having a film thickness of 2.5 nm, and an XPS spectrum when a sharp wave annealing is performed at 600 ° C and a MIT is performed at 2000 W for 30 min. When the film thickness was 2.5 nm, it was confirmed that the output was longer than 2000 W and 30 min, and the conditions were long, and the crystallization was performed in the same manner as in the case of the spike annealing at 600 °C.

(Electrical characteristics in the first embodiment)

Next, the result of measuring the electrical characteristics of the gate insulating film obtained in the first embodiment will be described.

Here, after the interfacial wafer is pretreated to form an interface layer (SiO ₂ film), a film of various thicknesses of HfO ₂ film is formed as a High-k film, and then microwave plasma treatment as shown in FIG. 23 described later is used. The apparatus was subjected to Ar plasma treatment or Ar nitrogen plasma treatment as the first modification treatment under the following conditions, and then subjected to respective temperatures of 530 ° C, 580 ° C, 630 ° C, and 680 ° C by means of an electric resistance heater. The UVRF process of the UVRF module for 1 min is used as the second modification process to form a gate insulating film.

. Ar plasma treatment

Wafer temperature: 250 ° C

Pressure: 20Pa

Microwave power: 2000W

Ar gas flow rate: 2000mL/min (sccm)

Processing time: 5sec

. Ar nitrogen plasma treatment

Wafer temperature: 250 ° C

Pressure: 20Pa

Microwave power: 1500W

N ₂ gas flow rate: 200mL/min (sccm)

Ar gas flow rate: 1000mL/min (sccm)

Processing time: 5sec

The electrical characteristics of the gate insulating film obtained as shown above are shown in Fig. 14. Fig. 14 is a view showing the relationship between the EOT of the film on the horizontal axis and the leakage current (Jg) on the vertical axis. In the figure, the broken line indicates the tendency when the reforming treatment is not performed, the white circle indicates the case where the first modification treatment is performed with Ar plasma, and the black circle indicates the case where the first modification treatment is performed with the Ar nitrogen plasma. Further, the numbers plotted are the temperatures of the second reforming process.

As shown in the figure, it is understood that EOT and leakage current tend to be improved by performing the first modification process and the second modification process. Further, among the above conditions, it was confirmed that after the Ar nitrogen plasma treatment was performed as the first modification treatment, the second modification was performed at 680 ° C, and the EOT and the leakage current were observed. Most reduced.

<Second embodiment>

In the first embodiment described above, a high-density crystallized High-k film is obtained, and a high dielectric constant is obtained. However, for example, in the case of the HfO ₂ film, in the usual crystallization treatment, the crystal is monoclinic (monoclinic crystal), and the dielectric constant is at most about 16. Therefore, in the second embodiment, cubic (cubic crystal) (dielectric constant = 29) and tetragonal (tetragonal crystal) (dielectric constant = 70) having a higher dielectric constant are crystallized to form a high-k film. The electrical coefficient rises.

In the present embodiment, as shown in FIG. 15, the pretreatment (Project 11) is performed in the same manner as the first embodiment of the first embodiment, and the CVD or ALD is used in the same manner as the second project of the first embodiment. The membrane oxide material film, typically HfO ₂ film, HfSiOx film, is used as a High-k film (Engineering 12).

After the film formation, the first modification treatment was carried out by radical treatment at a low temperature, and at this time, the High-k film was in an amorphous state (Project 13). In order to form the High-k film in an amorphous state at the end of the work 13, in the film formation process of the work 12, the film is formed into a film at a low temperature which is almost uncrystallized and becomes amorphous, or in the process 13 At the time of radical treatment at a low temperature, the Ar ion plasma is irradiated onto the High-k film by applying a bias voltage to positively amorphize the film.

The radical treatment for amorphization may be applied to a tantalum substrate in a microwave plasma treatment using a rare gas such as an Ar gas. The Ar ion is irradiated to the film by a frequency bias, thereby being amorphous.

In the state as described above, the second modification process by the rapid temperature rise and fall of 450 ° C or higher is performed (Project 14). According to the second modification treatment, the high temperature phase which is crystallized at the time of heating, that is, the cubic can be brought to room temperature to increase the dielectric constant.

Here, the reason why the High-k film is formed into an amorphous state before the work 14 is because if only a slight monoclonic crystal is crystallized before the work 14, it does not depend on the subsequent processing, and most of them become monoclinic, and The crystallization control is not easy to carry out.

In order to carry out crystallization control, it is preferred to include a component which promotes a phase change in the film. For example, when the High-k film is HfO ₂ , examples of the component that promotes phase change include Si, Zr, Y, Ce, Sr, N, and the like. In the method of containing such a method, a method of laminating a HfOrOx film or an HfSiOx film or the like on a HfO ₂ film, or a method of using a compound containing the components as a film forming material at the time of film formation, or the like may be mentioned. In addition, it is also effective to dope these components in the film. Further, it is also preferred to introduce Ti or Ba as a component for promoting polarization. In the method of containing Ti, a method of laminating HfTiOx or a method of using Ti as a part of a film forming raw material when Ti is formed at the time of film formation can be used.

Among these components, tetragonal having a high dielectric constant can be crystallized, and therefore it is preferable to contain N in the film. In order to contain N in the High-k film, it is preferred to use a method of doping N into the film in addition to Ar ions in addition to Ar ions, and doping N in the film.

(Experimental results in the second embodiment)

After will, spike annealing is performed by the ALD HfO ₂ film 250 to the film formation deg.] C to 310 deg.] C HfO ₂ film deposition at 900 ℃, by in-plane XRD crystallinity grasped. Among them, the HfO ₂ film formed at 250 ° C was amorphous in the as depo state, and the HfO ₂ film formed at 310 ° C was slightly crystallized in the as depo state. The results of the in-plane XRD are shown in Fig. 16. As shown in the figure, it was confirmed that the X-ray diffraction intensity of the cubic or tetragonal portion where the sharp-wave annealing was performed at 250 ° C after the film formation at 310 ° C and the sharp-wave annealing was performed was high.

<Third embodiment>

In the third embodiment, only the above-described microwave irradiation processing (MIT) is performed as the modification processing. In other words, in the first embodiment, MIT is used as the second modification process for crystallization. However, in the present embodiment, the density is increased and crystallized by MIT.

Specifically, as shown in FIG. 17 , the same pretreatment as in the first embodiment (the first step 21) is performed, and then the film formation of the High-k film is performed by CVD or ALD in the same manner as in the second embodiment ( Project 22), followed by a modification process by MIT (Project 23).

Since the MIT system can cause electromagnetic wave energy to act inside the film as described above, it is possible to simultaneously increase the density and crystallization of the film with an extremely small thermal budget. In the microwave frequency at this time, 860 MHz or more can be used, and high-frequency microwave irradiation such as 2.45 GHz or 5.8 GHz can be expected, and a higher modification effect can be expected.

Further, the microwave electric field formed by MIT is not only crystallized into monoclinic, but also has a possibility of acting on a portion of the high-k film which is polarized and controlling crystallinity. Actually, after the HfO ₂ film was formed by ALD, the density of the film was formed to be about 9.8 g/cm ² as a result of MIT treatment, and the theoretical density of the HfO ₂ film of monoclinic was 9.68 g/cm. ² is a higher value. From this, it was estimated that the cube having a higher density (density 10.2 g/cm ² ) was crystallized.

(Electrical characteristics in the third embodiment)

Next, the results of measuring the electrical characteristics of the gate insulating film obtained in the third embodiment will be described.

Here, after the pre-treatment of the germanium wafer to form the interface layer (SiO ₂ film), the HfO ₂ film having a film thickness of 2.5 nm and 3.5 nm is formed as a High-k film, and then, as shown in FIG. 28, which will be described later. The processing device performs a modification process by MIT to form a gate insulating film. The conditions at this time were set to microwave output: 2000 W, processing time: 3 min.

The electrical characteristics of the gate insulating film obtained as shown above are shown in Fig. 18. 18 is a view showing the relationship between the EOT of the film on the horizontal axis and the leakage current (Jg) on the vertical axis. In Fig. 18, for comparison, the as depo who has not undergone the upgrading treatment and the lamp annealing at 700 °C are also plotted as the reformer.

As shown in the figure, after confirming the film formation, the leakage current was greatly improved by performing the modification treatment by MIT.

<Fourth embodiment>

In the fourth embodiment, only the heat treatment by the above-described light-emitting diode (LED) is performed as the reforming process. In other words, in the first embodiment, LED heating is used as the second modification treatment for crystallization. However, in the present embodiment, the LED is heated to increase the density and crystallization.

Specifically, as shown in FIG. 19, the same pretreatment as in the first embodiment (the construction 31) is performed, and thereafter, the film formation of the High-k film is performed by CVD or ALD in the same manner as in the second embodiment. (Project 32), followed by a modification process by LED heating (Project 33).

As described above, the LED heating system is not a black body radiation using a heating source, but uses electromagnetic heating by recombination of electrons and holes, and has high absorption rate to the substrate, so that HfO ₂ can be made. The temperature of the film or HfSiOx film can be modified without a rise in temperature. Since a certain amount of impurities can be removed by the LED, it is possible to increase the density and crystallization by heating only with the LED.

<Processing System for Realizing an Embodiment of the Present Invention>

Next, an example of a system for realizing the method of the present embodiment will be described.

Fig. 20 is a view showing an example of a processing system for realizing the above-described first embodiment. The processing system 100 is a processor that performs the process 2 after performing the pre-processed pre-processed wafer.

As shown in FIG. 20, the processing system 100 includes two film forming apparatuses 1 and 2 for forming a High-k film, and a first modified portion of the High-k film. The first modification processing device 3 and the second modification processing device 4 that performs the second modification process, the film formation devices 1 and 2, and the first and second modification processing devices 3 and 4 are The four sides of the hexagonal wafer transfer chamber 5 are provided correspondingly. Further, load lock chambers 6 and 7 are provided in the other two sides of the wafer transfer chamber 5, respectively. The wafer loading/unloading chamber 8 is disposed on the opposite side of the load lock chambers 6 and 7 from the wafer transfer chamber 5, and is mounted on the opposite side of the wafer loading/unloading chamber 8 from the load lock chambers 6 and 7.埠9, 10, and 11 of three FOUPs (front open general-purpose containers) F that accommodate 矽 wafers (hereinafter simply referred to as wafers) W.

The film forming apparatus 1 and 2, the first and second reforming processing apparatuses 3 and 4, and the load lock chambers 6 and 7 are connected to the respective sides of the wafer transfer chamber 5 through the gate valve G as shown in the figure. By opening the gate valves G and communicating with the wafer transfer chamber 5, the wafer transfer chamber 5 is blocked by closing the gate valves G. Further, a gate valve G is also provided in a portion of the load lock chambers 6 and 7 that is connected to the wafer loading/unloading chamber 8, and the load lock chambers 6 and 7 are connected to the wafer loading/unloading chamber 8 by opening the gate valve G. By closing the wafer, the wafer loading/unloading chamber 8 is blocked.

A wafer transfer device that carries in and out the wafer W to the film forming apparatus 1 and 2, the first and second reforming processing apparatuses 3 and 4, and the load lock chambers 6 and 7 is provided in the wafer transfer chamber 5 12. The wafer transfer device 12 is disposed substantially at the center of the wafer transfer chamber 5, and has two carrier sheets 14a and 14b for holding the wafer W at the tip end of the rotatable and expandable/retractable rotating/expanding portion 13. The carrier sheets 14a, 14b are attached to the rotation/expansion portion 13 in such a manner as to face each other in opposite directions. Wherein, the wafer transfer chamber 5 The system is maintained at a predetermined degree of vacuum.

A HEPA filter (not shown) is provided in a ceiling portion of the wafer loading/unloading chamber 8, and clean air such as organic matter or fine particles is removed by the HEPA filter, and is supplied to the wafer loading/unloading chamber 8 in a downward flow state. The wafer W is carried in and out at a normal atmospheric air atmosphere. Each of the three cymbals 9, 10, and 11 for mounting the FOUP F in the wafer loading/unloading chamber 8 is provided with a shutter (not shown), and the wafers W or vacant are directly mounted on the cymbals 9, 10, and 11 When the FOUP is mounted, the door is disengaged and communicates with the wafer loading/unloading chamber 8 while preventing the intrusion of outside air. Further, an alignment chamber 15 is provided on the side surface of the wafer loading/unloading chamber 8, where the alignment of the wafer W is performed.

In the wafer loading/unloading chamber 8, a wafer transfer device 16 that carries in and out of the wafer W to the FOUP F and loads and transports the wafer W into the load lock chambers 6 and 7 is provided. The wafer transfer device 16 has two multi-joint arms, and can travel on the rails 18 along the arrangement direction of the FOUP F, and the wafers W are placed on the hand 17 at the front end to carry them. In FIG. 20, one of the hand portions 17 is present in the wafer loading/unloading chamber 8 and the other hand is inserted into the FOUP F.

The components of the processing system 100, for example, the film forming apparatus 1, the first and second modification processing apparatuses 3 and 4, the wafer transfer apparatuses 12 and 16, etc. are formed to be connected to the control unit 20 composed of a computer. To control the composition. Further, the control unit 20 is connected to a user interface 21 including a keyboard for inputting a command or the like for an operator management system, a display for visualizing the system operation state, and the like. this Further, the control unit 20 is connected to a storage unit 22 that stores a control program for realizing various processes executed in the system by the control of the control unit 20, or for causing each component to perform processing in accordance with processing conditions. The program also processes the recipe. The processing recipe is a memory medium that is memorized in the storage unit 22. The memory medium can be a hard disk, or can be a removable person such as a CDROM, a DVD, or a flash memory. In addition, the formulation may be appropriately transferred by other means, for example, through a dedicated line.

Then, if necessary, the arbitrary processing recipe is called by the memory unit 22 by the instruction from the user interface 21, and the control unit 20 is executed, whereby the control unit 20 performs the desired operation in the processing system. Processing. Here, the control unit 20 may directly control each component, or may provide an individual controller in each component, and perform control by transmitting the components.

In the processing system 100 as described above, first, the FOUP F in which the preprocessed wafer W is accommodated is loaded.

Then, the wafer transfer device 16 in the clean air gas atmosphere held at atmospheric pressure is loaded into the wafer transfer device 16 in the carry-out chamber 8 to take out one wafer W from the FOUP F and carry it into the alignment chamber 15 to perform wafer processing. The alignment of W. Next, the wafer W is carried into any of the load lock chambers 6 and 7, and after the vacuum is sucked in the load lock, the wafer transfer device 12 in the wafer transfer chamber 5 takes out the load lock. The wafer is loaded into the film forming apparatus 1 or 2, and the film forming process of the process 2 is performed. The wafer W after the film formation by the High-k film is taken out by the wafer transfer device 12, and then transferred to the first modification processing device 3 to perform the first modification process of the process 3. Thereafter, the first modification processing device 3 is taken out by the wafer transfer device 12 The wafer W is inserted into the second modification processing device 4 to perform the second modification process of the process 4. After that, the wafer W after the film formation is carried into the load lock chambers 6 and 7 by the wafer transfer device 12, and the wafers are transferred to the wafers in the wafer loading/unloading chamber 8 after being restored to atmospheric pressure. The device 16 takes out the wafer W in the load lock chamber and is housed in any of the FOUP F. The operation shown above is performed on the wafer W of one batch, and one set of processing is completed. By the treatment as described above, the film formation process, the first modification process, and the second modification process can be continuously performed without breaking the vacuum, and a high-density and crystallized good gate insulating film can be formed.

<film forming apparatus>

Next, the film forming apparatus 1 (2) of the second embodiment will be described.

Fig. 21 is a cross-sectional view showing an example of the film forming apparatus 1. The film forming apparatus 1 has a substantially cylindrical chamber 31 that is airtight, and is disposed in a state in which it is supported by a cylindrical support member 33 provided at a lower central portion thereof. The susceptor 32 of the wafer W as the object to be processed. The susceptor 32 is made of a ceramic such as AIN. Further, a heater 35 is buried in the susceptor 32, and a heater power source 36 is connected to the heater 35. On the other hand, a thermocouple 37 is provided on the top of the susceptor 32, and the signal of the thermocouple 37 is transmitted to the controller 38. Next, the controller 38 transmits an instruction to the heater power source 36 in accordance with the signal of the thermocouple 37, and controls the heating of the heater 35 to control the wafer W to a predetermined temperature.

Among them, a quartz lining 39 for preventing accumulation of deposits is provided on the inner wall of the chamber 31 and the outer periphery of the susceptor 32 and the support member 33. In quartz A flushing gas (shield gas) is passed between the lining 39 and the wall portion of the chamber 31, thereby preventing deposits from accumulating on the wall portion to prevent contamination. Further, the quartz lining 39 can be removed to perform maintenance in the chamber 31 efficiently.

A circular hole 31b is formed in the sky wall 31a of the chamber 31, and is thereby embedded in the shower head 40 which protrudes toward the inside of the chamber 31. The shower head 40 is for discharging the film forming gas into the chamber 31, and a first introduction path 41 into which the material gas is introduced and a second introduction path 42 into which the oxidizing agent is introduced are connected to the upper portion. Spaces 43, 44 are provided in the upper and lower sections of the shower head 40. The first introduction path 41 is connected to the upper space 43, and the first gas discharge path 45 extends from the space 43 to the bottom surface of the shower head 40. The second introduction path 42 is connected to the lower space 44, and the second gas discharge path 46 extends from the space 44 to the bottom surface of the shower head 40. That is, the shower head 40 is formed as a post-mixed type in which the metal material gas and the oxidizing agent are not mixed and uniformly diffused in the spaces 43, 44 and independently discharged from the discharge paths 45 and 46.

Among them, the susceptor 32 can be raised and lowered by an elevating mechanism (not shown) to adjust the process gap so that the space exposed to the material gas is minimized.

An exhaust chamber 51 that protrudes downward is provided on the bottom wall of the chamber 31. An exhaust pipe 52 is connected to the side surface of the exhaust chamber 51, and an exhaust device 53 is connected to the exhaust pipe 52. The exhaust device 53 is then actuated, whereby the pressure in the chamber 31 can be reduced to a predetermined degree of vacuum.

The sidewall of the chamber 31 is provided for: in the wafer transfer chamber 5 The loading/unloading port 54 for loading and unloading the wafer W; and the gate valve G for opening and closing the loading/unloading port 54.

In the case of CVD, the raw material gas and the oxidizing agent can be supplied to the shower head 40 through the first introduction path 41 and the oxidant through the second introduction path 42 as in the case of CVD. In the case of ALD, it is alternately supplied. The raw material gas system is supplied with a liquid raw material by, for example, a raw material container, and is vaporized by a gasifier to be supplied.

In the film forming apparatus configured as described above, first, after the wafer W is carried into the chamber 31, it is exhausted to form a predetermined vacuum state, and the wafer W is heated by the heater 35. Heat to a predetermined temperature.

In this case, in the case of CVD, the first introduction path 41 and the second introduction path 42 are transmitted through the shower head 40, and the source gas and the oxidant are introduced into the chamber 31. These are alternately introduced into the chamber 31.

Thereby, the raw material gas reacts with the oxidant on the heated wafer W, and a predetermined High-k film is formed on the wafer W.

<First Example of First Modification Processing Apparatus>

Next, a first example of the first modification processing device will be described.

The first example is an example of an ultraviolet irradiation device. Fig. 22 is a cross-sectional view showing a first example of the first modification processing device. In this example, the first modification processing device 3-1 has a substantially cylindrical chamber 61 configured to be airtight, and is rotatably provided in the chamber 61 to rotatably support the wafer. Support member 62 of W. The rotation shaft 63 of the support member 62 extends downward, borrowing Rotation is performed by the rotary drive mechanism 64 outside the chamber 61.

An exhaust path 65 is provided in an annular shape on the outer circumference of the chamber 61, and the chamber 61 and the exhaust path 65 are connected to each other through the exhaust hole 66. Next, an exhaust mechanism (not shown) such as a vacuum pump is connected to at least one portion of the exhaust passage 65, and the inside of the chamber 61 is exhausted.

An ultraviolet lamp 67 that emits ultraviolet rays is provided on the wall of the chamber 61, and the wafer W in the chamber 61 is irradiated with ultraviolet rays. Further, a gas introduction pipe 68 is inserted into the ceiling of the chamber 61, a gas supply pipe 69 is connected to the gas introduction pipe 68, and the gas supply pipe 69 and the gas introduction pipe 68 are passed through, and the O ₂ gas is introduced into the chamber 61. .

A lamp chamber 70 is provided at the bottom of the chamber 61, and a light-transmitting plate 71 made of a transparent material such as quartz is provided on the upper surface of the lamp chamber 70. A plurality of heating lamps 72 are provided in the lamp chamber to heat the wafer W. The bellows 73 is provided between the bottom surface of the lamp chamber 70 and the rotation drive mechanism 64 so as to surround the rotation shaft 63.

In the first modification processing apparatus 3-1 configured as described above, first, after the wafer W is loaded into the chamber 61, the exhaust gas is exhausted to a predetermined vacuum state, and the rotary drive mechanism 64 is driven. The wafer W is rotated by the support member 62, and the wafer W is heated to a predetermined temperature by the lamp 72 of the lamp chamber 70 as needed. If it is treated at room temperature, the lamp 72 is not used.

In this state, O ₂ gas is introduced into the chamber 61, and the ultraviolet lamp 67 is irradiated, whereby the High-k film on the wafer W is subjected to ultraviolet excitation radical oxidation treatment as the first modification treatment. Thereby, impurities of the High-k film are removed, and the film is densified.

<Second example of the first modification processing device>

Next, a second example of the first modification processing device will be described. The second example is an example of a microwave plasma processing apparatus, and is configured as a microwave plasma processing apparatus of a RLSA (Radial Line Slot Antenna) microwave plasma type. Fig. 23 is a cross-sectional view showing a second example of the first modification processing device. In this example, the first reforming treatment device 3-2 includes a substantially cylindrical chamber 81, a susceptor 82 provided therein, and a gas introduction of a process gas introduced into a side wall of the chamber 81. a portion 83 that faces the upper portion of the chamber 81, a planar antenna 84 in which a plurality of microwave transmission holes 84a are formed, a microwave generating portion 85 that generates microwaves, and a microwave generating portion 85 that leads to a planar antenna Microwave transfer mechanism 86 of 84.

A microwave transmitting plate 91 made of a dielectric material is provided below the planar antenna 84, and a shield member 92 is provided on the planar antenna 84. The shield member 92 is formed in a water-cooled configuration. Among them, a late wave material made of a dielectric material may be provided on the upper surface of the planar antenna 84.

The microwave transmission mechanism 86 includes a waveguide 101 extending in the horizontal direction by the microwave generating unit 85, and a coaxial waveguide 102 composed of the inner conductor 103 and the outer conductor 104 extending upward from the planar antenna 84. And a mode conversion mechanism 105 provided between the waveguide 101 and the coaxial waveguide 102. Wherein, reference numeral 93 is an exhaust pipe.

A high frequency power source 106 for ion introduction is connected to the susceptor 82, Ions can be introduced into the High-k film to form the film into an amorphous state.

The first modification processing device 3-2 configured as described above transmits the microwave generated by the microwave generating unit 85 to the planar antenna 84 in a predetermined pattern through the microwave transmission mechanism 86, and passes through the microwave transmission hole of the planar antenna 84. 84a and the microwave transmitting plate 91 are uniformly supplied into the chamber 81, and the processing gas supplied from the gas introduction portion 83 is plasma-formed by the microwave to be on the wafer W by the radical in the plasma. The High-k film was subjected to a first modification treatment (microwave plasma treatment). As the processing gas, O ₂ gas, O ₂ gas + rare gas, rare gas, rare gas + N ₂ gas can be used.

<The third example of the first modification processing device>

Next, a third example of the first modification processing device will be described.

The third example is an example of a microwave plasma apparatus using a plurality of small microwave irradiation mechanisms. Fig. 24 is a cross-sectional view showing a third example of the first modification processing device. In this example, the first reforming treatment device 3-3 has a substantially cylindrical chamber 111 that is airtight, and is provided in the chamber 111 in a state where the center is supported by the support leg 113. The susceptor 112 on which the wafer W is placed. The susceptor 112 is embedded in the heater 114, and the heater 114 is connected to the heater power source 115. The wafer is controlled by a controller (not shown) according to a temperature signal of a thermocouple (not shown). The temperature of W.

An exhaust path 116 is provided in an annular shape on the outer circumference of the chamber 111, and the chamber 111 and the exhaust path 116 are connected to each other through the exhaust hole 117. Next, an exhaust mechanism such as a vacuum pump is connected to at least one portion of the exhaust path 116 (not As shown in the figure, the chamber 111 is exhausted.

As shown in Fig. 25, the sky wall of the chamber 111 is provided with six microwave introduction mechanisms 118 constituting a microwave plasma source and introducing microwaves for plasma generation into the chamber 111. The microwave introduction mechanism 118 is configured to have a mechanism for introducing the microwave of the second example into a small size, and has a waveguide composed of a cylindrical coaxial cable; a planar antenna provided at the front end thereof; and a waveguide that is movably provided Tube tuner. Since the tuner and the antenna unit are integrally provided, the tuner can be formed as a pellet tuner of a simple structure, and the microwave introduction mechanism 118 can be formed into an extremely compact structure.

Further, the ceiling wall of the chamber 111 is inserted into the gas introduction pipe 119, the gas supply pipe 120 is connected to the gas introduction pipe 119, and the gas supply pipe 120 and the gas introduction pipe 119 are transmitted, and the process gas is introduced into the chamber 111. Inside.

The first modification processing device 3-3 configured as described above firstly carries out the wafer W in the chamber 111, and then exhausts it to form a predetermined vacuum state, and the microwave generating unit (not shown) The generated microwave is amplified by the amplifier and guided to the microwave introduction mechanism 118 through the waveguide, and the microwave is introduced into the chamber 111 by the planar antenna built therein, and the gas is supplied through the gas supply tube 120 and the gas introduction tube 119. A processing gas is introduced into the 111, and the processing gas is plasma-formed by the microwave, and the high-k film on the wafer W is subjected to a first modification treatment (microwave plasma treatment) by the radicals in the plasma. As the processing gas, O ₂ gas, O ₂ gas + rare gas, rare gas, rare gas + N ₂ gas can be used.

The microwave introduction mechanism 118 of this example is a compact structure, and thus is set from The degree is high, the angle can be made variable according to the height position of the wafer W, and the like, and the wafer W can be efficiently irradiated with microwaves.

<First Example of Second Modification Processing Apparatus>

Next, a first example of the second modification processing device will be described.

The first example is constituted by an RTP apparatus which is heated by a lamp, and is subjected to a sharp-wave annealing of the High-k film. Fig. 26 is a cross-sectional view showing a first example of the second modification processing device. In this example, the second reforming treatment device 4-1 has a substantially cylindrical chamber 121 that is airtight, and is rotatably provided in the chamber 121 to rotatably support the crystal. Support member 122 of circle W. The rotation shaft 123 of the support member 122 extends downward, and is rotated by a rotation driving mechanism 124 outside the chamber 121.

An exhaust path 125 is provided in an annular shape on the outer circumference of the chamber 121, and the chamber 121 and the exhaust path 125 are connected to each other through the exhaust hole 126. Next, an exhaust mechanism (not shown) such as a vacuum pump is connected to at least one portion of the exhaust path 125, and the inside of the chamber 121 is exhausted.

The gas introduction pipe 128 is inserted into the ceiling wall of the chamber 121, the gas supply pipe 129 is connected to the gas introduction pipe 128, and the gas supply pipe 129 and the gas introduction pipe 128 are passed through, and the process gas is introduced into the chamber 121. In terms of the processing gas, a rare gas such as an Ar gas or an N ₂ gas can be suitably used.

A lamp chamber 130 is provided at the bottom of the chamber 121, and a light-transmitting plate 131 made of a transparent material such as quartz is disposed on the upper surface of the lamp chamber 130. Set in the lamp room There is a plurality of heating lamps 132 that heat the wafer W. The bellows 133 is provided between the bottom surface of the lamp chamber 130 and the rotation drive mechanism 124 so as to surround the rotation shaft 123.

In the second modification processing apparatus 4-1 configured as described above, first, after the wafer W is carried into the chamber 121, the inside of the wafer W is exhausted to form a predetermined vacuum state, and a chamber is faced. When the processing gas is introduced into the 121, the wafer W is rotated by the rotation driving mechanism 124 through the support member 122, and the wafer W is rapidly heated by the lamp 132 of the lamp chamber 130, and when the temperature is set to a predetermined temperature, The lamp 132 is turned OFF and rapidly cooled. Thereby, the crystallization treatment of the High-k film can be performed with a small thermal budget.

Among them, the wafer W may not necessarily rotate. Further, the lamp chamber 130 may be disposed above the wafer W. At this time, a cooling mechanism can be provided on the back side of the wafer W, and the temperature can be lowered more rapidly.

<Second Example of Second Modification Processing Apparatus>

Next, a second example of the second modification processing device will be described.

The second example is an example of a heating device having a resistance heater. Fig. 27 is a cross-sectional view showing a second example of the second modification processing device. In this example, the second reforming treatment device 4-2 has a substantially cylindrical chamber 141 that is airtight, and is provided in the chamber 141 with the center supported by the support legs 143. The susceptor 142 on which the wafer W is placed. A resistor heater 144 is embedded in the pedestal 142, and a heater power source 145 is connected to the heater 144, and is controlled by a temperature signal of a thermocouple (not shown). A device (not shown) controls the temperature of the wafer W.

An exhaust path 146 is provided in an annular shape on the outer circumference of the chamber 141, and the chamber 141 and the exhaust path 146 are connected to each other through the exhaust hole 147. Next, an exhaust mechanism (not shown) such as a vacuum pump is connected to at least one portion of the exhaust path 146, and the inside of the chamber 141 is exhausted.

The gas introduction pipe 148 is inserted into the ceiling wall of the chamber 141, the gas supply pipe 149 is connected to the gas introduction pipe 148, and the gas supply pipe 149 and the gas introduction pipe 148 are passed through, and the process gas is introduced into the chamber 141. As the processing gas, a rare gas such as an Ar gas or an N ₂ gas can be suitably used.

In the second modification processing apparatus 4-2 configured as described above, first, the wafer W is carried into the chamber 141, and then exhausted therein to be in a predetermined vacuum state, and a chamber 141 is faced. The wafer W is heated by the electric resistance heater 144 while the processing gas is introduced thereinto, and the temperature is maintained for a predetermined time at a predetermined temperature of 700 ° C or lower, and then the electric resistance heater is turned off.

Since the annealing treatment is performed at a relatively low temperature as described above, the crystallization treatment of the High-k film can be performed with a small thermal budget.

<Third Example of Second Modification Processing Apparatus>

Next, a third example of the second modification processing device will be described.

The third example is an example of a microwave heating apparatus using a plurality of microwave irradiation mechanisms. Fig. 28 is a cross-sectional view showing a third example of the second modification processing device. In this example, the second modification processing device 4-3 is configured to be airtight. The cylindrical chamber 151 is provided with a mounting table 152 on which the wafer W is placed in the center of the chamber 151 with the support leg 153 supported.

An exhaust path 155 is formed in an annular shape on the outer circumference of the chamber 151, and the chamber 151 and the exhaust path 155 are connected to each other through the exhaust hole 156. Next, an exhaust mechanism (not shown) such as a vacuum pump is connected to at least one portion of the exhaust path 155, and the inside of the chamber 151 is exhausted.

Six microwave irradiation mechanisms 157 that irradiate microwaves are provided in the sky wall of the chamber 151. The microwave irradiation unit 157 is configured to irradiate microwaves of a predetermined wavelength of 860 MHz or more to microwave the High-k film formed on the wafer W.

Further, the gas wall introduction pipe 158 is inserted into the gas wall of the chamber 151, the gas supply pipe 159 is connected to the gas introduction pipe 158, and the gas is introduced into the chamber 151 through the gas supply pipe 159 and the gas introduction pipe 158. . As the processing gas, a rare gas such as an Ar gas or an N ₂ gas can be suitably used.

The second modification processing apparatus 4-3 configured as described above first passes through the gas supply pipe 159 and after the wafer W is carried into the chamber 151, and is exhausted to form a predetermined vacuum state. The gas introduction pipe 158 introduces a processing gas into the chamber 151, and irradiates the microwave of a predetermined wavelength to the wafer W by the microwave irradiation means 157 at a predetermined output, and the High-k is heated by internal heating by electromagnetic energy. The film is heated directly. Therefore, the High-k film can be crystallized at a low temperature of 400 ° C or lower.

Wherein, the microwave heating device can also be used as the third embodiment. The modification processing device is used.

<Fourth Example of Second Modification Processing Apparatus>

Next, a fourth example of the second modification processing device will be described.

The fourth example is an example of an LED heating device using LEDs. Fig. 29 is a cross-sectional view showing a fourth example of the second modification processing device. In this example, the second reforming treatment device 4-4 has a substantially cylindrical chamber 161 that is airtight, and is provided in the chamber 161 with the center supported by the support leg 163. The mounting table 162 on which the wafer W is placed.

An exhaust path 165 is provided in an annular shape on the outer circumference of the chamber 161, and the chamber 161 and the exhaust path 165 are connected to each other through the exhaust hole 166. Next, an exhaust mechanism (not shown) such as a vacuum pump is connected to at least one portion of the exhaust path 165, and the inside of the chamber 161 is exhausted.

An LED unit 170 is provided at an upper portion of the chamber 161. The LED unit 170 is embedded in the center of the ceiling wall of the chamber 161, and has a cylindrical copper cooling member 171 having a diameter slightly larger than the mounting table 162, and a cooling member 171 opposed to the wafer W. a circular recess 172 provided to correspond to the wafer W; an LED array 175 on which the plurality of LEDs 174 are mounted on the support member 173 formed of the good thermal conductive insulating member in the recess 172; and a cover recess 172 The method is such that the light is transmitted through the light transmitting member 176 from the LED such as quartz. The cooling member 171 is provided with a cooling medium flow path 177 in which the LED 174 can be cooled by flowing through a cooled liquid cooling medium that can be cooled to below 0 ° C, for example, about -50 ° C.

The gas introduction pipe 168 is inserted into the ceiling wall of the chamber 161, the gas supply pipe 169 is connected to the gas introduction pipe 168, and the gas supply pipe 169 and the gas introduction pipe 168 are passed through, and the process gas is introduced into the chamber 161. As the processing gas, a rare gas such as an Ar gas or an N ₂ gas can be suitably used.

The second modification processing apparatus 4-4 configured as described above first passes through the gas supply pipe 169 and after the wafer W is carried into the chamber 161, and is exhausted to form a predetermined vacuum state. The gas introduction pipe 168 introduces a processing gas into the chamber 161, and energizes the LED 174 to perform LED heat treatment. LED heating does not utilize the black body radiation of the heating source, but utilizes the electromagnetic radiation caused by the recombination of electrons and holes, so the thermal budget is small and the cooling rate is extremely high. In addition, most of GaN or GaAs used as an LED element has a high absorptivity to germanium, but has a low absorptivity to HfO ₂ or HfSiOx. Therefore, the temperature of the HfO ₂ film or the HfSiOx film is not increased, and the crystal is crystallized. Chemical.

However, the LED heating device can also be used as the modification processing device of the fourth embodiment.

<Example 1 of a device capable of performing a film formation process and a first modification process in the same chamber>

The above shows an example in which one processing device performs one project. However, from the viewpoint of efficiency of processing or reduction of device cost, in this example, it is shown that the film forming process and the first reforming process can be performed in the same chamber. An example of a device. Figure 30 shows that the film formation process and the first modification can be performed in the same chamber. A cross-sectional view of Example 1 of the device being processed. The processing device 180 has a substantially cylindrical chamber 181 that is airtight, and a support member 182 that rotatably supports the wafer W is rotatably provided in the chamber 181. The rotation shaft 183 of the support member 182 extends downward, and is rotated by a rotation driving mechanism 184 outside the chamber 181. Further, the rotating shaft can be raised and lowered by a lifting mechanism (not shown), whereby the supporting member 182 can be raised and lowered.

An exhaust path 185 is provided in an annular shape on the outer circumference of the chamber 181, and the chamber 181 and the exhaust path 185 are connected to each other through the exhaust hole 186. Next, an exhaust mechanism (not shown) such as a vacuum pump is connected to at least one portion of the exhaust path 185, and the inside of the chamber 181 is exhausted.

An ultraviolet lamp 187 that irradiates ultraviolet rays is provided on the ceiling of the chamber 181, and the wafer W in the chamber 181 is irradiated with ultraviolet rays. Further, a plurality of gas introduction plugs 190 are inserted into the ceiling of the chamber 181, and the first holes 191 and the second holes 192 are vertically inserted into the gas introduction plugs 190. Then, the first gas pipe 193 to which the material gas for film formation is supplied is connected to the first hole 191, and the oxidizing agent used for film formation is connected to the second hole 192, and the first modification process is used. The second gas pipe 194 of the O ₂ gas used. However, when the oxidizing agent is O ₂ gas, only the O ₂ gas may be supplied from the second gas pipe 194.

A lamp chamber 200 is provided at the bottom of the chamber 181, and a light-transmitting plate 201 made of a transparent material such as quartz is provided on the upper surface of the lamp chamber 200. A plurality of heater lamps 202 are provided in the lamp chamber 200 to heat the wafer W. Wherein, between the bottom surface of the lamp chamber 200 and the rotation driving mechanism 184, the rotation axis 183 is enclosed. The manner is provided with a bellows 203.

In the processing apparatus 180 configured as described above, first, the wafer W is carried into the chamber 181 and placed on the support member 182. Then, the process gap is adjusted so that the space exposed to the material gas is minimized by an elevating mechanism (not shown), and then the inside of the chamber 181 is exhausted to form a predetermined vacuum state, and the heat lamp is used. 202 heats the wafer W to a predetermined temperature, and simultaneously or alternately supplies the material gas and the oxidant from the gas introduction plug 190 to form a High-k film such as an HfO ₂ film or an HfSiOx film by CVD or ALD. As the raw material gas and the oxidizing agent, those described above can be used. Further, the raw material gas system is supplied by, for example, pressing a liquid raw material by a raw material container and vaporizing it by a gasifier.

The material gas supplied from the gas introduction plug 190 reacts with the oxidant on the heated wafer W to form a predetermined High-k film on the wafer W.

After the film formation, the supply of the material gas and the oxidant is stopped, and if necessary, the chamber 181 is rinsed, the process gap is adjusted, and the first modification process is performed in the same chamber.

First, the inside of the chamber 181 is formed into a predetermined vacuum state, and the wafer W is rotated by the support member 182 by the rotation driving mechanism 184, and the wafer W is heated by the heating lamp 202 of the lamp chamber 200 as needed. Heat to a predetermined temperature. If it is treated at room temperature, the heater lamp 202 is not used.

In this state, O ₂ gas is introduced into the chamber 181, and the ultraviolet lamp 187 is irradiated, whereby the High-k film on the wafer W is subjected to ultraviolet excitation radical oxidation treatment as the first modification treatment. Thereby, impurities of the High-k film are removed, and the film is densified.

As described above, since the film formation process and the first modification process can be performed in the same chamber, the efficiency of the process can be achieved, and the device cost can be reduced.

<Example 2 of a device capable of performing film formation processing and first modification treatment in the same chamber>

Example 2 of a device capable of performing a film formation process and a first modification process in the same chamber. Fig. 31 is a cross-sectional view showing an example 2 of an apparatus which can perform a film forming process and a first modification process in the same chamber.

In this example, the processing apparatus 210 has a substantially cylindrical chamber 211 that is configured to be airtight, and a wafer W is placed in the chamber 211 with the support leg 213 supported in the center thereof. Base 212. The susceptor 212 is embedded in a heater 214, and a heater power source 215 is connected to the heater 214. The wafer is controlled by a controller (not shown) according to a temperature signal of a thermocouple (not shown). The temperature of W. The base 212 can be raised and lowered by a lifting mechanism (not shown).

An exhaust path 216 is provided in an annular shape on the outer circumference of the chamber 211, and the chamber 211 and the exhaust path 216 are connected to each other through the exhaust hole 217. Next, an exhaust mechanism (not shown) such as a vacuum pump is connected to at least one portion of the exhaust path 216, and the inside of the chamber 211 is exhausted.

In the sky wall system of the chamber 211, six microwave introduction mechanisms 218 are provided in the same manner as in Fig. 24 . The microwave introduction mechanism 218 is configured to be small in a mechanism for introducing the microwave of the second example, and includes a waveguide composed of a cylindrical coaxial cable, a planar antenna provided at the tip end thereof, and a movable guide. Wave tube The tuner of the way.

A gas discharge member 220 that emits a gas in a radial direction is provided inside the ceiling wall of the chamber 211. The gas radiation member 220 is attached to the guide member 223 having a central concave shape, and is discharged toward the wafer W by the gas system radially discharged by the gas radiation member 220. The gas discharge member 220 has a hemispherical shape and is provided with a plurality of holes which are divided into two systems, and the first gas pipe 221 for supplying a material gas for film formation is connected to the hole of the first group, and the second group is connected to the second group. The hole is connected to a second gas pipe 222 for supplying an oxidizing agent and a processing gas used in the first reforming process.

In the processing apparatus 210 configured as described above, the wafer W is first carried into the chamber 211 and placed on the susceptor 212. Then, the process gap is adjusted so that the space exposed to the material gas is minimized by an elevating mechanism (not shown), and then the inside of the chamber 211 is exhausted to form a predetermined vacuum state, and the heater is used. 214: The wafer W is heated to a predetermined temperature, and the source gas and the oxidant are simultaneously or alternately supplied from the gas discharge member 220, and a High-k film such as an HfO ₂ film or an HfSiOx film is formed by CVD or ALD. As the raw material gas and the oxidizing agent, those described above can be used. Further, the raw material gas system is supplied by, for example, pressing a liquid raw material by a raw material container and vaporizing it by a gasifier.

The material gas supplied from the gas radiation member 220 reacts with the oxidant on the heated wafer W to form a predetermined High-k film on the wafer W.

After the film formation, the supply of the material gas and the oxidant is stopped, and the process gap is adjusted after rinsing the chamber 211 as needed, and the first chamber is placed in the same chamber. Modification treatment.

First, the inside of the chamber 211 is exhausted to form a predetermined vacuum state, and the microwave generated in the microwave generating unit (not shown) is amplified by an amplifier and transmitted to the microwave introducing mechanism 218 through the waveguide, and is placed in the space. The built-in planar antenna introduces microwaves into the chamber 211, and the gas discharge member 220 radially introduces the processing gas into the chamber 211, and plasma-processes the gas by the microwave to generate free radicals in the plasma. The first modification process (microwave plasma treatment) is performed on the High-k film on the wafer W. As the processing gas, O ₂ gas, O ₂ gas + rare gas, rare gas, rare gas + N ₂ gas can be used.

Since the microwave introduction mechanism 218 of the present embodiment has a simplified structure, the degree of freedom of installation is high, the angle can be made variable according to the height position of the wafer W, and the like, and the wafer W can be efficiently irradiated with microwaves.

In this example, the film formation process and the first modification process can be performed in the same chamber, so that the processing efficiency can be achieved and the device cost can be reduced.

<Example 3 of a device capable of performing a film formation process and a first modification process in the same chamber>

An example 3 of a device capable of performing a film forming process and a first modification process in the same chamber is shown. Fig. 32 is a cross-sectional view showing an example 3 of a device which can perform a film forming process and a first modification process in the same chamber. In the example 3 and the example 2, the gas introduction method is different, and the other common parts are denoted by the same reference numerals, and the description thereof is omitted.

In this example, the processing device 210' is inserted into the plurality of gas introduction plugs 230 in the wall of the chamber 211, and the first holes 231 and the second holes 232 are vertically inserted into the gas introduction plugs 230. Then, the first gas pipe 233 to which the material gas for film formation is supplied is connected to the first hole 231, and the oxidizing agent used for film formation is connected to the second hole 232, and the first modification process is performed. The second gas pipe 234 of the processing gas to be used.

Also in the apparatus having the above configuration, as in the case of Example 2, the film formation process and the first modification process can be continuously performed in the same chamber 211.

<Example of a device capable of performing a film formation process, a first modification process, and a second modification process in the same chamber>

Example 2 of a device capable of performing a film formation process, a first modification process, and a second modification process in the same chamber. Fig. 33 is a cross-sectional view showing an example 2 of a device which can perform a film forming process, a first modification process, and a second modification process in the same chamber.

In this example, the processing apparatus 240 has a chamber 241 having a substantially cylindrical shape that is airtight, and a wafer W is placed in the chamber 241 while the center thereof is supported by the support leg 243. Base 242. A heater 244 is embedded in the susceptor 242, and a heater power source 245 is connected to the heater 244, and the controller is controlled by a controller (not shown) according to a temperature signal of a thermocouple (not shown). The temperature of the circle W. The base 242 can be raised and lowered by a lifting mechanism (not shown).

An exhaust path 246 is provided in an annular shape on the outer circumference of the chamber 241, and the chamber 241 and the exhaust path 246 are connected to each other through the exhaust hole 247. Then, at At least one portion of the exhaust path 246 is connected to an exhaust mechanism (not shown) such as a vacuum pump, and the inside of the chamber 241 is exhausted.

In the sky wall of the chamber 241, as shown in Fig. 34, three microwave introduction mechanisms 248 and three microwave irradiation mechanisms 249 are alternately arranged in a circumferential direction. The microwave introduction mechanism 248 is configured in the same manner as the microwave introduction mechanism 118 described above, and the microwave irradiation mechanism 249 is configured in exactly the same manner as the microwave irradiation mechanism 157 described above.

A plurality of gas introduction plugs 250 are inserted into the ceiling of the chamber 241, and the first holes 251 and the second holes 252 are vertically penetrated to the gas introduction plug 250. Then, the first gas pipe 253 to which the material gas for film formation is supplied is connected to the first hole 251, and the oxidizing agent used for film formation is connected to the second hole 252, and the first modification process is used. The processing gas used and the second gas pipe 254 of the processing gas used in the second reforming process.

In the processing apparatus 240 configured as described above, first, the wafer W is carried in the chamber 241 and placed on the susceptor 242. Then, the process gap is adjusted so that the space exposed to the material gas is minimized by an elevating mechanism (not shown), and then the inside of the chamber 241 is exhausted to form a predetermined vacuum state, and the heater is used. 244 heats the wafer W to a predetermined temperature, and simultaneously or alternately supplies the material gas and the oxidant from the gas introduction plug 250 to form a High-k film such as an HfO ₂ film or an HfSiOx film by CVD or ALD. As the raw material gas and the oxidizing agent, those described above can be used. Further, the raw material gas system is supplied by, for example, pressing a liquid raw material from a raw material container and vaporizing it by a gasifier.

The raw material gas and oxidant system supplied from the gas introduction plug 250 A predetermined high-k film is formed on the wafer W by reacting on the heated wafer W.

After the film formation, the supply of the material gas and the oxidizing agent is stopped, and if necessary, the chamber 241 is rinsed, the process gap is adjusted, and the first modification process is performed in the same chamber.

First, the inside of the chamber 241 is evacuated to a predetermined vacuum state, and the microwave generated in the microwave generating unit (not shown) is amplified by an amplifier and transmitted to the microwave introducing unit 248 through the waveguide. The planar antenna built in the space introduces the microwave into the chamber 241, and the processing gas is introduced into the chamber 241 by the gas introduction plug 250, and the processing gas is plasmaized by the microwave, by the free radical in the plasma, The High-k film on the wafer W is subjected to a first modification process (microwave plasma treatment). As the processing gas, O ₂ gas, O ₂ gas + rare gas, rare gas, rare gas + N ₂ gas can be used.

After the completion of the first modification process, the output of the microwave introduction mechanism 248 is stopped, and if necessary, the chamber 241 is rinsed, the process gap is adjusted, and the second modification process (microwave irradiation process) is performed in the same chamber.

While introducing the processing gas into the chamber 241 through the gas introduction plug 250, the microwave of a predetermined wavelength is irradiated toward the wafer W by the microwave irradiation means 249 at a predetermined output, and the internal heating by the electromagnetic wave energy is applied to the High. -k film is heated directly. Therefore, the High-k film can be crystallized at a low temperature of 400 ° C or lower.

Since the film formation process, the first modification process, and the second modification process can be performed in the same chamber as described above, the processing efficiency is extremely high and can be greatly increased. Reduce the cost of the device.

However, the present invention can be variously modified and is not limited to the above embodiment. For example, in the above embodiment, an example in which an HfO ₂ film or an HfSiOx film is mainly used as a High-k film is described, but the invention is not limited thereto. Further, regarding the radical treatment applied to the first modification treatment, if the thermal budget is small, it is not limited to the above embodiment. Further, in the above embodiment, a germanium wafer (germanium substrate) is used, but other semiconductor substrates may be used.

Further, it is also within the scope of the invention to appropriately combine the constituent elements of the above-described embodiments or to partially remove the constituent elements of the above-described embodiments without departing from the scope of the invention.

1, 2‧‧‧ film forming treatment device

3, 3-1, 3-2, 3-2, 3-3‧‧‧ first modification processing device

4, 4-1, 4-2, 4-3, 4-4‧‧‧ second modification processing device

5‧‧‧Transport room

6, 7‧‧‧ load lock room

8‧‧‧Wood loading and unloading room

9, 10, 11‧‧‧埠

12.16‧‧‧Transportation agencies

13‧‧‧Rotation/Flexure Department

14a, 14b‧‧‧ carrier sheets

15‧‧‧Alignment chamber

17‧‧‧Hands

18‧‧‧ rails

20‧‧‧Control Department

21‧‧‧User interface

22‧‧‧Memory Department (memory media)

31, 61, 81, 111, 121, 141, 151, 161, 181, 211, 241‧‧ ‧ chamber

31a‧‧‧天壁

31b‧‧‧round hole

32, 82, 112, 142, 212, 242 ‧ ‧ pedestals

33, 62, 122, 173, 182 ‧ ‧ supporting components

35, 114, 144, 214, 244‧‧ heaters

36, 115, 145, 215, 245‧‧‧ heater power supply

37‧‧‧ thermocouple

38‧‧‧ Controller

39‧‧‧Quartz lining

40‧‧‧washing head

41‧‧‧1st introduction road

42‧‧‧2nd introduction road

43, 44‧‧‧ space

45‧‧‧1st gas discharge path

46‧‧‧2nd gas discharge path

51‧‧‧Exhaust chamber

52‧‧‧Exhaust pipe

53‧‧‧Exhaust device

54‧‧‧ moving into and out

63, 123, 183‧‧‧ rotating shaft

64,124,184‧‧‧Rotary drive mechanism

65, 116, 125, 146, 155, 165, 185, 216, 246‧‧ ‧ exhaust path

66, 117, 126, 147, 156, 166, 186, 217, 247‧‧ vents

67, 187‧‧‧ UV light

68, 119, 128, 148, 158, 168‧‧‧ gas introduction tube

69, 120, 129, 149, 159, 169‧‧‧ gas supply pipe

70, 130, 200‧‧ ‧ lamp room

71, 131, 201‧‧‧ Translucent panels

72, 132, 202‧ ‧ heating lamps

73, 133, 203‧‧‧ telescopic bladder

83‧‧‧Gas introduction department

84‧‧‧ planar antenna

84a‧‧‧Microwave through hole

85‧‧‧Microwave Generation Department

86‧‧‧Microwave transmission mechanism

91‧‧‧Microwave transmission plate

92‧‧‧Shielding members

93‧‧‧Exhaust pipe

100‧‧‧Processing system

101‧‧‧guide tube

102‧‧‧ coaxial waveguide

103‧‧‧ Inner conductor

104‧‧‧Outer conductor

105‧‧‧Mode change mechanism

106‧‧‧High frequency power supply

113, 143, 153, 163, 213, 243 ‧ ‧ support feet

118, 218, 248‧‧‧ microwave induction mechanism

152, 162‧‧‧ mounting table

157‧‧‧Microwave Irradiation Mechanism

170‧‧‧LED unit

171‧‧‧Cooling components

172‧‧‧ recess

174‧‧‧LED

175‧‧‧LED array

176‧‧‧Light transmission members

177‧‧‧ Cooling media flow path

180, 210, 210', 240‧‧‧ processing devices

190, 230, 250‧‧‧ gas introduction embolization

191, 231, 251‧‧‧1 hole

192, 232, 252‧‧‧ second hole

193, 221, 233, 253 ‧ ‧ 1st gas piping

194, 222, 234, 254‧‧‧ second gas piping

220‧‧‧ gas release member

223‧‧‧Guide members

249‧‧‧Microwave Irradiation Mechanism

F‧‧‧FOUP (front open general purpose container)

G‧‧‧ gate valve

W‧‧‧Semiconductor Wafer

Figure 1 is a diagram for explaining the basic mechanism of the present invention.

Fig. 2 is a flow chart showing a method of forming an insulating film according to the first embodiment of the present invention.

Fig. 3 is a view showing a state of a film at the time of each of the first embodiment of the present invention.

4 is a graph showing the thickness of the interface layer when the number of cycles of the first modification treatment is changed by the microwave plasma treatment for 40 sec when the HfO ₂ film having a thickness of 2.5 nm is formed by the ALD film formation process of 31 cycles. Figure.

Fig. 5 is a graph showing the relationship between the microwave plasma treatment time and the thickness of the interface layer after 15 cycles of film formation.

Figure 6 shows the timing of processing the microwave plasma as the first modification process. A graph showing the relationship between the number of reforming start cycles and the film thickness of the interface layer at the time of film formation of 31 cycles in which the order and the length were changed.

FIG. 7 is a view showing the concentration of impurities (carbon) in the film thickness direction after the first modification treatment is performed after the HfO ₂ film is formed by ALD.

Fig. 8 is a graph showing the relationship between the amount of film formation and the film thickness of the interface layer at the time of various reforming treatments, and an enlarged view of a portion surrounded by the circle.

Fig. 9A is a graph showing the relationship between the oxidation temperature of UV-O and the thickness of the interface layer.

Fig. 9B is a graph comparing the thickness of the interface layer in various conditions of UV-O at room temperature with the case of treatment under standard conditions of 450 ° C and 0.10 Torr.

Fig. 10 is a graph showing changes in the binding energy of 4f of Hf at the time of each treatment, and showing the stability of the film.

Fig. 11A is a view showing an X-ray photoelectron spectroscopy (XPS) spectrum of an as depo state of an HfO ₂ film having a film thickness of 2.5 nm.

Fig. 11B is a view showing the X-ray photoelectron spectroscopy (XPS) spectrum when the HfO ₂ film having a film thickness of 2.5 nm is subjected to sharp-wave annealing at 900 °C.

Fig. 11C is a view showing an X-ray photoelectron spectroscopy (XPS) spectrum when an HfO ₂ film having a film thickness of 2.5 nm is annealed at 900 ° C for 10 minutes.

Fig. 12A is a view showing an XPS spectrum of an as depo state of an HfO ₂ film having a film thickness of 4.0 nm.

Fig. 12B is a graph showing the XPS spectrum when the MIT of the HfO ₂ film having a film thickness of 4.0 nm was performed at 600 W for 30 min.

Fig. 13 is a view showing an as depo state of an HfO ₂ film having a film thickness of 2.5 nm, a sharp wave annealing at 600 ° C, and an XPS spectrum when MIT is performed at 2000 W for 30 min.

Fig. 14 is a view showing electrical characteristics in the first embodiment.

Fig. 15 is a flow chart showing a method of forming an insulating film according to a second embodiment of the present invention.

FIG. 16 for display system 250 ℃ HfO ₂ film at the film formation, the HfO ₂ film and the film formation at 310 deg.] C, results in FIG. In-plane XRD performed after annealing at 900 ℃ spike of.

Fig. 17 is a flow chart showing a method of forming an insulating film according to a third embodiment of the present invention.

Fig. 18 is a view showing electrical characteristics in the third embodiment.

Fig. 19 is a flow chart showing a method of forming an insulating film according to a fourth embodiment of the present invention.

Fig. 20 is a view showing an example of a processing system for realizing the first embodiment.

Fig. 21 is a cross-sectional view showing an example of a film forming apparatus.

Fig. 22 is a cross-sectional view showing a first example of the first modification processing device.

Fig. 23 is a cross-sectional view showing a second example of the first modification processing device.

Fig. 24 is a cross-sectional view showing a third example of the first modification processing device.

Fig. 25 is a view showing an arrangement state of a microwave introduction mechanism used in a third example of the first modification processing device.

Fig. 26 is a cross-sectional view showing a first example of the second modification processing device.

Fig. 27 is a cross-sectional view showing a second example of the second modification processing device.

Fig. 28 is a cross-sectional view showing a third example of the second modification processing device.

Fig. 29 is a cross-sectional view showing a fourth example of the second modification processing device.

Fig. 30 is a cross-sectional view showing an example 1 of an apparatus which can perform a film forming process and a first modification process in the same chamber.

Fig. 31 is a cross-sectional view showing an example 2 of an apparatus which can perform a film forming process and a first modification process in the same chamber.

Fig. 32 is a cross-sectional view showing an example 3 of a device which can perform a film forming process and a first modification process in the same chamber.

Fig. 33 is a cross-sectional view showing an example of an apparatus which can perform a film forming process, a first modification process, and a second modification process in the same chamber.

Fig. 34 is a view showing an arrangement state of a microwave introducing mechanism and a microwave irradiation mechanism of the apparatus of Fig. 33;

Claims (37)

A method for forming a gate insulating film, which is a method for forming a gate insulating film for forming a gate insulating film on a semiconductor substrate, comprising: a film forming process for forming a film on a semiconductor substrate by CVD or ALD a high dielectric constant film; a first modification project in which a high dielectric constant film formed by the film formation is subjected to radical treatment at a temperature lower than a film formation temperature; and a second modification project, The high dielectric constant film formed in the first modification process is subjected to heat treatment to be crystallized. The method for forming a gate insulating film according to the first aspect of the invention, wherein the high dielectric constant film is a film of an Hf-based oxide material. The method for forming a gate insulating film according to the second aspect of the invention, wherein the high dielectric constant film is a hafnium oxide film or a niobate film. The method for forming a gate insulating film according to the first aspect of the invention, wherein the first modification process is performed by ultraviolet excitation radical oxidation treatment. The method for forming a gate insulating film according to claim 1, wherein the first modification process is performed by microwave plasma treatment. The method for forming a gate insulating film according to the fifth aspect of the invention, wherein the microwave plasma treatment uses an oxygen-containing gas as a processing gas, or a rare gas, or nitrogen, or a mixture of two or more thereof. Mixing gas is carried out. The method for forming a gate insulating film according to claim 5, wherein the microwave plasma processing is performed by using microwaves with slots The microwave is introduced into the processing container by the surface antenna, and the plasma gas is excited by the microwave. The method for forming a gate insulating film according to the fifth aspect of the invention, wherein the microwave plasma processing system comprises: a microwave guiding mechanism for guiding microwaves, irradiating microwaves, and forming The planar antenna of the slot and the pellet tuner provided in proximity to the planar antenna and integrating the impedance are performed by the plurality of microwave introducing mechanisms radiating microwaves and plasma-treating the processing gas. The method for forming a gate insulating film according to claim 1, wherein the second modification process is performed by rapid heating treatment by heating with a lamp. The method of forming a gate insulating film according to the first aspect of the invention, wherein the second modification process is performed by annealing at a temperature of 700 ° C or lower. The method for forming a gate insulating film according to claim 1, wherein the second modification process is performed by heating by microwave irradiation. The method of forming a gate insulating film according to the first aspect of the invention, wherein the second modification process is performed by heating by using a light-emitting diode. The method of forming a gate insulating film according to the first aspect of the invention, wherein the film forming process and the first modification engineering are repeated. Such as the formation of the gate insulating film of claim 13 In the method, the thickness of the high dielectric constant film formed during the initial film formation process is 1.05 nm or more. The method for forming a gate insulating film according to claim 14, wherein the thickness of the high dielectric constant film formed in the first film forming process is 1.21 nm or less. The method for forming a gate insulating film according to claim 13, wherein the film forming process and the first modification engineering are performed in the same chamber. A method for forming a gate insulating film, which is a method for forming a gate insulating film for forming a gate insulating film on a semiconductor substrate, comprising: a film forming process for forming a film on a semiconductor substrate by CVD or ALD a high dielectric constant film; a first modification process in which a high dielectric constant film formed by the film formation is subjected to radical treatment at a temperature lower than a crystallization temperature to be modified, and an amorphous state is obtained. And a second modification process for performing crystallization control by rapidly increasing and lowering the high dielectric constant film after the first modification process by heat treatment. The method for forming a gate insulating film according to claim 17, wherein the film forming process is performed at a temperature at which the formed high dielectric constant film is in an amorphous state. The method for forming a gate insulating film according to the seventeenth aspect of the invention, wherein the first modified engineering system is characterized in that ions are implanted into the high dielectric constant film to be amorphous. The method for forming a gate insulating film according to claim 17, wherein the second modification process is performed at 450 ° C or higher. The method for forming a gate insulating film according to claim 17, wherein the second modification process is performed by heating by microwave irradiation. The method for forming a gate insulating film according to claim 17, wherein the high dielectric constant film is an HfO ₂ film. A method of forming a gate insulating film according to claim 22, wherein at least one of Si, Zr, Y, Ce, Sr, and N is introduced into the HfO ₂ film. A method of forming a gate insulating film according to claim 22, wherein Ti or Ba is introduced into the HfO ₂ film. A method for forming a gate insulating film, which is a method for forming a gate insulating film for forming a gate insulating film on a semiconductor substrate, comprising: a film forming process for forming a film on a semiconductor substrate by CVD or ALD a high dielectric constant film; and a upgrading process, wherein the high dielectric constant film is irradiated with microwaves, and the high dielectric constant film is modified by microwave heating. A method for forming a gate insulating film, which is a method for forming a gate insulating film for forming a gate insulating film on a semiconductor substrate, comprising: a film forming process for forming a film on a semiconductor substrate by CVD or ALD a high dielectric constant film; and a modification process for modifying a high dielectric constant film by heating the high dielectric constant film with a light emitting diode. A device for forming a gate insulating film, which is a device for forming a gate insulating film of a gate insulating film on a semiconductor substrate, comprising: a film forming device which forms a film on a semiconductor substrate by CVD or ALD a high dielectric constant film; the first modified processing device performs a radical treatment on the formed high dielectric constant film at a temperature lower than a film forming temperature; and the second modified processing device The crystallization is performed by performing heat treatment on the high dielectric constant film after the first modification treatment by the first modification processing device, and the control unit is formed by the film formation process of the film formation apparatus. The first modification process of the first modification processing device and the second modification process of the second modification processing device are performed in this order. The device for forming a gate insulating film according to claim 27, wherein the first modifying device includes a processing container that houses the substrate to be processed, and a gas supply mechanism that supplies an oxygen-containing gas to the processing container; An ultraviolet light supply source that supplies ultraviolet rays to the processing container. The device for forming a gate insulating film according to claim 27, wherein the first modification processing device introduces a microwave into a processing container by using a planar antenna having a slot, and excites the plasma by the microwave. Gas. The apparatus for forming a gate insulating film according to claim 27, wherein the first modifying processing device has a plurality of microwave introducing means having a waveguide for guiding microwaves, irradiating microwaves, and forming a groove. The planar antenna of the hole and the proximity of the planar antenna and the impedance integration In the pellet tuner, the plurality of microwave introducing means radiates microwaves to plasma the processing gas to perform the first modification process. The device for forming a gate insulating film according to claim 27, wherein the second modifying device includes a processing container that houses the substrate to be processed, and a heating lamp that rapidly heats the substrate in the processing container. The device for forming a gate insulating film according to claim 27, wherein the second modifying device includes: a processing container that houses the substrate to be processed; a resistance heater that heats the substrate to be processed; and a heating temperature Control the control mechanism below 700 °C. The device for forming a gate insulating film according to claim 27, wherein the second modifying device includes a processing container that houses the substrate to be processed, and a microwave irradiation mechanism that irradiates the semiconductor substrate with microwaves. The device for forming a gate insulating film according to claim 27, wherein the second modifying device includes a processing container that houses the semiconductor substrate, and a plurality of light emitting diodes that heat the semiconductor substrate. The apparatus for forming a gate insulating film according to claim 27, wherein the film forming apparatus, the first modifying processing apparatus, and the second modifying processing apparatus are incorporated in a vacuum to carry the semiconductor A multi-chamber system for a substrate transfer device. The apparatus for forming a gate insulating film according to claim 27, wherein the film forming apparatus and the first processing apparatus are provided in a common processing container. A device for forming a gate insulating film, comprising: a processing container for accommodating a semiconductor substrate; and a gas supply mechanism for supplying a film forming gas for forming a film of a high dielectric constant film into the processing container a plurality of microwave introduction mechanisms having: a waveguide for guiding microwaves, a planar antenna for irradiating microwaves and having slots, and a pellet tuner for abutting the planar antenna and integrating impedance, and a microwave introduced into the processing container; and a microwave irradiation mechanism that irradiates the semiconductor substrate with microwaves, and performs film formation of the high dielectric constant film in the processing container; and is generated by microwaves introduced by the microwave introducing mechanism The first modification process is performed by the microwave plasma; and the second modification process of performing microwave heating by the microwave irradiation means.