Manufacturing method for semiconductor device, and substrate processing apparatus

The present invention relates to a method for manufacturing a semiconductor device for forming a thin film on a substrate, and a substrate processing device.

One of the semiconductor manufacturing processes is a CVD (Chemical Vapor Deposition) process in which a predetermined film formation process is performed on the surface of a substrate (a substrate to be processed in which a fine electric circuit pattern based on a silicon wafer or glass is formed). is there. This is a pattern of a fine electric circuit provided on a substrate by loading a substrate in an airtight reaction chamber, heating the substrate by a heating means provided in the chamber, causing a chemical reaction while introducing a raw material gas onto the substrate. A thin film is uniformly formed on the top. In such a reaction chamber, the thin film is also formed on structures other than the substrate. In the CVD apparatus shown in FIG. 10, a shower head 6 and a susceptor 2 are provided in the reaction chamber 1, and the substrate 4 is placed on the susceptor 2. The raw material gas is introduced into the reaction chamber 1 through the raw material supply pipe 5 connected to the shower head 6, and is supplied onto the substrate 4 through a large number of holes 8 provided in the shower head 6. The gas supplied on the substrate 4 is exhaust-treated through the exhaust pipe 7. The substrate 4 is heated by a heater 3 provided below the susceptor 2.

As such a CVD device, amorphous HfO using an organic chemical material as a film forming raw material₂There is a CVD device that uses the MOCVD (Metal Organic Chemical Vapor Deposition) method that can form films and amorphous Hf silicate films. To.

As a film forming raw material, Hf [OC (CH)₃)₃]₄(Hereafter, Hf- (OtBu)₄(Abbreviated as), Hf [OC (CH)₃)₂CH₂OCH₃]₄(Hereafter, Hf- (MMP)₄(Abbreviated as), however, MMP: 1 methoxy-2-methyl-2-propoxy Hf [O-Si- (CH)₃)]₄(Hf-(OSi)₄(Abbreviated as) is used.

Among them, for example, Hf- (OtBu)₄, Hf- (MMP)₄Many organic materials are in the liquid phase at normal temperature and pressure. Therefore, for example, Hf- (MMP)₄Is used by heating and converting it into gas by vapor pressure.

By the way, the thin film deposited by using the MOCVD method as described above has a problem that it is difficult to obtain the flatness of the film surface. In particular, the above problem becomes remarkable in the MOCVD method in which the deposition rate of the thin film is determined by the surface reaction rate-determining. It is known that the surface reaction rate-determining causes a time delay in starting the thin film deposition on the substrate surface. This time is called the incubation time. During this incubation time, there is a nucleation process in which island-like deposition occurs on the substrate, and it is thought that irregularities are formed during this nucleation process and the flatness of the thin film is lost.

FIG. 7 shows the concept of the unevenness of the thin film 31 formed on the substrate 4. It is presumed that the convex portion 33 of the thin film surface 32 is formed during the nucleation process. The difference between the maximum value of the convex portion 33 and the minimum value of the concave portion 34 indicates the difference H of the height of the unevenness, and this difference H is called flatness. It is said that it is excellent.

Figure 8 shows a conceptual diagram of nuclear development (island formation) that is presumed to occur during the incubation time. The substrate for film formation is a thin SiO on the surface of the silicon substrate 4 or the silicon substrate 4.₂Thin Si on the surface of the silicon substrate 4 with a film attached₃N₄It has a film .. A nucleus 35 is formed on the surface of the substrate or the surface of the base film 30. This nucleus 35 grows into a thin film. At this time, the film is likely to be attached to the nucleus 35, but it is difficult to attach the film to the substrate surface or the base film surface 30 on which the nucleus 35 is not formed. Therefore, as shown in FIG. 7, it is difficult to obtain the flatness of the thin film surface 32 of the thin film deposited by the MOCVD method.

The flatness of the thin film surface 32 becomes a factor that lowers the reliability of the semiconductor device product, which is the final product, and has become a big problem as the device size is reduced.

Conventionally, the following have been published as publicly known examples of film formation technology using CVD.

(1) Japanese Patent Application Laid-Open No. 9-82696 (Public Example 1) In Known Example 1, oxygen radicals and organic silane gas (TEOS) are simultaneously supplied at a low temperature (-50 to + 50 ° C) and oxidized by a condensed CVD method. A cohesive film forming step (first step) for forming a cohesive film of a silicon film, and then the substrate is set to a high temperature (400 to 600 ° C) with oxygen radicals flowing, and the agglomerated film is heat-treated in an oxygen radical atmosphere. This is a method of forming a silicon oxide film having a desired film thickness by repeating the modification step (second step) of modifying (removing impurities such as C and H) a plurality of times in the same reaction chamber. Impurities such as C and H can be uniformly removed by forming a film thinner than the finally formed film in the first step and modifying the aggregated film in the second step.

(2) Japanese Unexamined Patent Publication No. 2001-68485 (Public Example 2) Known Example 2 is a Zn beam and an oxygen radical beam on a sapphire substrate at a temperature (200 to 600 ° C) lower than the growth temperature of single crystal ZnO. In the process of growing the low-temperature growth ZnO layer (first step) by simultaneously irradiating with, and at a temperature higher than the growth temperature of the low-temperature growth ZnO (600 to 800 ° C), low-temperature growth while irradiating an oxygen radical beam. A step of heat-treating (flattening) the ZnO layer (second step) and simultaneous irradiation of a Zn beam and an oxygen radical beam at 600 to 800 ° C are performed to form a high-temperature-growth single-crystal ZnO layer on the low-temperature-growth ZnO layer. It is a method having a step of growing (third step). The low-temperature growth layer grown in the first step is flattened in the second step, and the high-temperature growth single crystal layer is grown in the third step to improve the crystallinity.

(3) Japanese Patent Application Laid-Open No. 6-45322 (Public Example 3) In Known Example 3, the natural oxide film on the surface of the poly-Si film is removed by hydrogen annealing, and then the substrate is heated without exposing the substrate to the atmosphere. Transport to phase growth furnace. After transport, SiH at low temperature (700 ° C) on a poly-Si membrane₂Cl₂Gas and NH₃Gas is supplied simultaneously to form a first SiN film with a first film thickness (5 angstroms) (first step), then the temperature is raised (700 800 ° C), and SiH₂Cl₂Gas and NH₃Manufacture of a SiN film by supplying gas at the same time to form a second SiN film having a second film thickness (100 angstroms) thicker than the first film thickness (second step) on the first SiN film. The method. By growing at a low temperature in the first step, the surface density of the growth nuclei becomes high and a film having excellent flatness can be obtained, and in the second step, a SiN film having a desired film thickness can be formed.<patcit num="1"><text>Japanese Unexamined Patent Publication No. 9-82696 (pages 2-9, Fig. 1)</text></patcit><patcit num="2"><text>Japanese Unexamined Patent Publication No. 2001-68485 (Pages 2-4, Fig. 1)</text></patcit><patcit num="3"><text>Japanese Unexamined Patent Publication No. 6-45322 (Pages 2-4, Fig. 1)</text></patcit>

<p> However, the above-mentioned known examples have the following problems. (1) In Known Examples 1 and 2, the raw material gas and radicals are simultaneously supplied in the first step (low temperature treatment). However, since oxygen radicals are highly reactive, particles are generated when the raw material gas and oxygen radicals are supplied at the same time. (2) As in Known Examples 1 to 3, a film formation including a high temperature second step is followed by a low temperature first step. In the method, the throughput (productivity) is lowered because the substrate needs to be heated after the first step of low temperature. In Known Examples 1 and 3, both the first layer and the second layer (hereinafter) are formed by the CVD method, and in Known Examples 2, both the first layer and the second layer are formed by the MBE method. are doing.</p><p> An object of the present invention is to provide a method for manufacturing a semiconductor device and a substrate processing device capable of improving the flatness of a thin film without generating particles. Another object of the present invention is to provide a method for manufacturing a semiconductor device capable of improving the flatness of a thin film without lowering the productivity.</p>

<p> The first invention is a method in which a raw material gas is adhered to a substrate in a state where the substrate temperature is lower than the film formation temperature by the thermal CVD method, and then a reactant different from the raw material gas is supplied onto the substrate. The first thin film layer forming step of forming the thin film layer 1 and the second thin film layer being formed on the first thin film layer by the thermal CVD method using the raw material gas after raising the substrate temperature to the film formation temperature. It has two thin film layer forming steps, and the first thin film layer forming step and the second thin film layer forming step are performed in the same reaction chamber, and the first thin film layer forming step is for forming a second thin film layer. This is a method for manufacturing a semiconductor device, which is performed before supplying the raw material gas to the film, and during the process of raising the substrate temperature to raise the substrate temperature to the thin film temperature. In the first thin film layer forming step, since the raw material gas is adhered to the substrate in a state where the substrate temperature is lower than the film formation temperature by the thermal CVD method, the raw material gas can be adhered to the substrate without reacting. After that, a film formation reaction in which a film is forcibly formed occurs by supplying a reactant different from the raw material gas, so that an incubation time does not occur and the nuclear generation process can be omitted. Therefore, the first thin film layer having excellent flatness can be formed. Further, in the second thin film layer forming step, since the second thin film layer is formed on the first thin film layer having excellent flatness, a thin film with improved flatness can be formed. Moreover, since the second thin film layer is formed by the thermal CVD method, better film quality can be obtained as compared with the case of forming by the ALD method. Further, the first thin film layer may be formed in a state where the temperature is set and maintained lower than the film formation temperature, but the first thin film layer is formed during the temperature rise to the film formation temperature without lowering the productivity. The flatness of the thin film layer and thus the second thin film layer can be improved.</p><p> The second invention is the manufacture of a semiconductor device according to the first invention, wherein in the first thin film layer forming step, supply of a raw material gas to a substrate and supply of a reactant are repeated a plurality of times. The method. By repeating the supply of the raw material gas and the supply of the reactant multiple times, even if a part where the film is not formed occurs when the raw material gas and the reactant are supplied only once. The part can be filled and the flatness can be further improved.</p><p> According to the third invention, in the first invention, in the first thin film layer forming step, a non-reactive gas is supplied between the supply of the raw material gas on the substrate and the supply of the reactant. This is a characteristic method for manufacturing a semiconductor device. When a non-reactive gas is supplied between the supply of the raw material gas and the supply of the reactant, the amount of the raw material gas adsorbed on the substrate becomes uniform. Further, since the raw material gas and the reactant can be prevented from being present in the atmosphere at the same time, the generation of particles can be prevented.</p><p> A fourth invention is a method for manufacturing a semiconductor device according to the first invention, wherein the substrate temperature in the first thin film layer forming step is within the range of 200 ° C. or higher and 390 ° C. or lower. is there. Since the first thin film layer is formed when the substrate temperature is 390 ° C or lower, the film formation rate does not occur even when the raw material gas is passed, and the raw material gas can be adhered to the substrate without reaction. On the other hand, since the first thin film layer is formed when the substrate temperature is 200 ° C. or higher, a film having good adhesion to the substrate can be formed.</p><p> A fifth invention is a method for manufacturing a semiconductor device according to the first invention, wherein the raw material gas is an organic raw material gas. In particular, organic raw material gas that makes it difficult to obtain flatness on the film surface When used, the flatness can be improved, so that the merit of the present invention is great.</p><p> A sixth invention is a method for manufacturing a semiconductor device according to the first invention, wherein the raw material gas is a gas obtained by vaporizing a raw material containing Hf, and the thin film formed is a film containing Hf. .. Here, specifically, the film containing Hf is HfO.₂, HfON, etc. HfO_xN_Y, HfSiO, etc. HfSiO_x, HfSiON, HfAlO, etc. Hf-Al-O_x, Or HfAlON and the like.</p><p> According to the seventh invention, in the first invention, the raw material gas is Hf [OC (CH).₃)₂CH₂OCH₃]₄It is a gas obtained by vaporizing, and the thin film to be formed is a film containing Hf, which is a method for manufacturing a semiconductor device.</p><p> An eighth invention is a method for manufacturing a semiconductor device according to the first invention, wherein the reactant contains an oxygen atom. The reactants contain oxygen atoms, but in the first thin film layer forming step, the substrate is directly fed by the reactants by adhering the raw material gas onto the substrate and then supplying the reactants onto the substrate. There is no concern that it will be oxidized.</p><p> A ninth aspect of the present invention is the method for manufacturing a semiconductor device according to the first aspect, wherein the reactant contains a gas obtained by activating a gas containing an oxygen atom with plasma. In one example, oxygen radicals can be used as the reactants. The case where the oxygen radical is supplied onto the substrate is not limited to the case where the oxygen-containing gas is activated outside the reaction chamber to generate the oxygen radical and then supplied onto the substrate, and the oxygen-containing gas is not activated. It also includes a case where oxygen radicals generated by heat or the like in the reaction chamber are supplied onto the substrate after being supplied to the reaction chamber.</p><p> A tenth invention is a method for manufacturing a semiconductor device, characterized in that, in the first invention, the raw material gas and the reactant are supplied from the same supply port. By supplying the raw material gas and the reactant from the same supply port, the foreign matter adhering to the inside of the supply port can be coated with the same film as the film formed on the substrate by this method. This makes it possible to prevent the foreign matter from reaching the substrate together with the flow of the raw material gas or the reactant. In particular, when the raw material gas or the reactant is supplied onto the substrate in a downflow, it is possible to reliably prevent the foreign matter from falling onto the substrate during the treatment. Further, when the reaction chamber is cleaned with the cleaning gas, it is possible to obtain the effect that foreign substances such as by-products adsorbed inside the supply port and the cleaning gas can be reliably removed without leaving.</p><p> In the eleventh invention, in the first invention, when the raw material gas and the reactant are supplied from separate supply ports and the raw material gas is supplied to the substrate from the supply port for the raw material gas, the raw material gas is used for the reactant. When the non-reactive gas is supplied to the supply port of the above and the reactant is supplied to the substrate from the supply port for the reactant, the non-reactive gas is supplied to the supply port for the raw material gas. It is a manufacturing method of. Since the raw material gas and the reactant are supplied from separate supply ports, the formation of a cumulative film formed inside the supply port can be suppressed. Further, when one of the raw material gas and the reactant is supplied, if the non-reactive gas is supplied from the other supply port, it is possible to prevent the two from coming into contact with each other at each supply port. Cumulative film formation inside the gas can be further suppressed.</p><p> According to the twelfth invention, in the first invention, when the raw material gas is supplied to the substrate, the reactant is exhausted so as to bypass the reaction chamber without stopping, and when the reactant is supplied to the substrate, the reactant is exhausted. This is a method for manufacturing a semiconductor device, characterized in that the raw material gas is exhausted so as to bypass the reaction chamber without stopping. If the flow of the reaction product and the raw material gas is not stopped and the reaction chamber is bypassed, the raw material gas or the raw material gas can be immediately supplied onto the substrate simply by switching the flow. Therefore, the throughput can be improved.</p><p> According to the thirteenth invention, in the first invention, in the second thin film layer forming step, a step of forming a thin film by a thermal CVD method and a step of supplying a reactant to the formed thin film are repeated a plurality of times. This is a method for manufacturing a semiconductor device. After forming a thin film by the thermal CVD method, by supplying a reactant to the thin film, it is possible to perform treatments such as removing impurities mixed in the thin film each time. Therefore, by repeating these steps, the effectiveness of impurity removal and the like can be improved and a high-quality film can be formed as compared with the case where a normal CVD method is simply performed.</p><p> A fourteenth invention is a method for manufacturing a semiconductor device, characterized in that, in the first invention, the first thin film layer forming step and / and the second thin film layer forming step are performed while rotating a substrate. By performing the first thin film layer forming step and / and the second thin film layer forming step while rotating the substrate, the flatness of the formed film can be improved.</p><p> A fifteenth invention is a method for manufacturing a semiconductor device according to the first invention, which comprises a step of supplying hydrogen radicals on a substrate before the first thin film layer forming step. By supplying hydrogen radicals onto the substrate before the formation of the first thin film layer, the surface of the substrate is cleaned and hydrogen terminated. As a result, the bonding force between the substrate and the first thin film layer is enhanced, and the adhesion is improved.</p><p> A sixth aspect of the present invention is to attach a raw material gas onto the substrate in a state where the substrate temperature is lower than the film formation temperature by the thermal CVD method, and then supply a reactant different from the raw material gas onto the substrate. The first thin film layer forming step of forming the thin film layer 1 and the formation of the second thin film layer for forming the second thin film layer on the first thin film layer using the raw material gas after raising the substrate temperature to the film formation temperature. The second thin film layer forming step is a semiconductor characterized by repeating a step of forming a thin film by a thermal CVD method and a step of supplying a reactant to the formed thin film a plurality of times. It is a manufacturing method of the device. In the first thin film layer forming step, the raw material gas can be adhered to the substrate in an unreacted state when the substrate temperature is lower than the film formation temperature. After that, a film formation reaction in which a film is forcibly formed occurs by supplying a reactant different from the raw material gas, so that an incubation time does not occur and the nuclear generation process can be omitted. Therefore, the first thin film layer having excellent flatness can be formed. Further, in the second thin film layer forming step, since the second thin film layer is formed on the first thin film layer having excellent flatness, a thin film with improved flatness can be formed. Further, in the second thin film layer forming step, after forming a thin film by the thermal CVD method, by supplying a reactant to the thin film, impurities mixed in the thin film (for example, C, H etc.) can be removed. Therefore, by repeating these steps, the effectiveness of impurity removal and the like can be improved and a high-quality film can be formed as compared with the case where a normal CVD method is simply performed.</p><p> A seventeenth invention is a method for manufacturing a semiconductor device according to a sixteenth invention, wherein in the first thin film layer forming step, supply of a raw material gas to a substrate and supply of a reactant are repeated a plurality of times. is there. By repeating the supply of the raw material gas and the supply of the reactant multiple times, even if a part where the film is not formed occurs when the raw material gas and the reactant are supplied only once. The part can be filled and the flatness can be further improved.</p><p> In the eighteenth invention, a reaction product obtained by adhering a raw material gas onto a substrate in a state where the substrate temperature is lower than the film formation temperature by the thermal CVD method and then activating the gas containing oxygen atoms with plasma is used as the substrate. The first thin film layer forming step of forming the first thin film layer by supplying it upward, and after raising the substrate temperature to the film formation temperature, the first thin film layer is placed on the first thin film layer by a thermal CVD method using a raw material gas. It is a method for manufacturing a semiconductor device, which comprises a second thin film layer forming step for forming two thin film layers. In the first thin film layer forming step, the raw material gas can be adhered to the substrate in an unreacted state when the substrate temperature is lower than the film formation temperature. After that, a membrane is forcibly formed by supplying a reactant. Since the film formation reaction occurs, the incubation time does not occur and the nuclear development process can be omitted. Therefore, the first thin film layer having excellent flatness can be formed. Further, in the second thin film layer forming step, since the second thin film layer is formed on the first thin film layer having excellent flatness, a thin film with improved flatness can be formed. Moreover, since the second thin film layer is formed by the thermal CVD method, better film quality can be obtained as compared with the case of forming by the ALD method. Further, the reactant is obtained by activating a gas containing an oxygen atom by plasma, and this can be achieved by adhering the raw material gas on the substrate and then supplying the reactant on the substrate in this order. There is no concern that the substrate will be directly oxidized by the reactants.</p><p> The nineteenth invention comprises a step of adhering a raw material gas onto a substrate and a step of forming a film by supplying a reaction product obtained by activating a gas containing oxygen atoms with plasma to the substrate. This is a method for manufacturing a semiconductor device, which is characterized by repeating the process a plurality of times in order. Since the film formation reaction in which a film is forcibly formed occurs by supplying the reactant after adhering the raw material gas on the substrate, the incubation time does not occur and the nucleation process can be omitted. Therefore, a film having excellent flatness can be formed. The reactant is obtained by activating a gas containing oxygen atoms with plasma, and the reaction is carried out by adhering the raw material gas onto the substrate and then supplying the reactant onto the substrate. There is no concern that the substrate will be directly oxidized by the substance. Therefore, even when each of the above steps is repeated a plurality of times, the effect of suppressing the formation of a film having a low dielectric constant can be obtained.</p><p> The twentieth invention comprises a processing chamber for processing a substrate, a heater for heating the substrate in the processing chamber, a raw material gas supply system for supplying a raw material gas, and a reactant supply system for supplying a reactant different from the raw material gas. After supplying the exhaust port for exhausting the processing chamber and the raw material gas so as to adhere to the substrate during the temperature rise of the substrate in a state where the substrate temperature is lower than the film formation temperature by the thermal CVD method, the reactant is supplied onto the substrate. The substrate processing apparatus is characterized by having a control means for controlling the supply of the raw material gas onto the substrate after raising the substrate temperature to the film formation temperature.</p><p> In the 21st invention, in a state where the substrate temperature is lower than the film formation temperature, the raw material gas is supplied onto the substrate and adhered in an unreacted state, and then oxygen radicals are supplied onto the substrate to supply the first thin film. A first thin film layer forming step of forming a layer, and after raising the substrate temperature to the film formation temperature, a raw material gas is supplied onto the substrate to form a second thin film layer on the first thin film layer by a thermal CVD method. It is a method for manufacturing a semiconductor device, which comprises a second thin film layer forming step.</p><p> In the 22nd invention, in the 21st invention, the formation of the first thin film layer raises the substrate temperature to the film formation temperature before supplying the raw material gas to form the second thin film layer. It is a method of manufacturing a semiconductor device, which is characterized in that it is carried out inside.</p><p> The 23rd invention is a method for manufacturing a semiconductor device according to the 21st or 22nd invention, wherein in the first thin film layer forming step, the supply of the raw material gas and the supply of oxygen radicals on the substrate are repeated a plurality of times. Is.</p><p> A twelfth invention is characterized in that, in the 21st to 23rd inventions, in the first thin film layer forming step, a non-reactive gas is supplied between the supply of the raw material gas and the supply of the oxygen radical on the substrate. This is a method for manufacturing a semiconductor device.</p><p> The 25th invention includes a reaction chamber for processing a substrate, a heater for heating a substrate in the reaction chamber, a raw material gas supply port for supplying a raw material gas into the reaction chamber, and a radical supply port for supplying an oxygen radical into the reaction chamber. , The substrate is heated by a heater, and the raw material gas is supplied so as to adhere to the substrate in the reaction chamber in an unreacted state when the substrate temperature is lower than the film formation temperature, and then oxygen radicals are reacted. Controlled to form the first thin film layer by supplying it on the substrate in the room, then raising the substrate temperature to the film formation temperature, and then supplying the raw material gas on the substrate in the reaction chamber to form the second thin film layer. It is a substrate processing apparatus characterized by having a control means for the operation.</p><p> By having a control means for controlling the supply of oxygen radicals on the substrate after adhering the raw material gas to the substrate in an unreacted state, then raising the temperature to the film formation temperature, and then supplying the raw material gas on the substrate. The method for manufacturing a semiconductor device according to the 21st invention can be easily carried out. Further, if a control means for controlling the supply of oxygen radicals to the substrate after supplying the raw material gas so as to adhere unreacted to the substrate in the reaction chamber during the temperature rise of the substrate is provided, the 22nd The method for manufacturing a semiconductor device according to the present invention can be easily carried out. Further, if a control means for controlling the supply of the raw material gas and the supply of the oxygen radical to be repeated a plurality of times is provided, the method for manufacturing the semiconductor device of the 23rd invention can be easily implemented. Further, if a non-reactive gas supply means for supplying the non-reactive gas and a control means for controlling the supply of the non-reactive gas between the supply of the raw material gas and the supply of the oxygen radical are provided, the 24th The method for manufacturing a semiconductor device according to the present invention can be easily carried out.</p><p> A twenty-sixth invention is a method for manufacturing a semiconductor device or a substrate processing device, characterized in that hydrogen radicals are supplied onto a substrate before the formation of the first thin film layer in the 21st to 25th inventions. ..</p><p> The 27th invention is a method for manufacturing a semiconductor device or a substrate processing device, characterized in that the raw material gas is an organic raw material gas in the 21st to 25th inventions.</p><p> In the 28th invention, in the 21st to 25th inventions, the raw material gas is Hf [OC (CH).₃)₂CH₂OCH₃]₄Is a vaporized gas, and the thin film formed is HfO.₂A method for manufacturing a semiconductor device or a substrate processing device, which is characterized by being a film. When forming a film by the CVD method using an organic raw material, oxygen-containing gas is usually supplied together, but Hf [OC (CH)₃)₂CH₂OCH₃]₄When using, the amount of specific elements (impurities) such as C and H mixed can be reduced by not supplying the oxygen-containing gas together.</p><p> The 29th invention is a method for manufacturing a semiconductor device or a substrate processing device according to the 28th invention, wherein the substrate temperature in the process of forming the first thin film layer is 200 ° C. or higher and 390 ° C. or lower. ..</p><p> The thirtieth invention is characterized in that, in the twenty-first to twenty-fifth inventions, the formation of the second thin film layer includes a film forming step of forming the thin film and a step of supplying oxygen radicals to the formed thin film. It is a manufacturing method of a semiconductor device or a substrate processing device. In addition to the film forming step of forming the thin film layer, there is a step of supplying oxygen radicals to the thin film, and the specific elements (impurities such as C and H) are removed by this step. 2 Specific elements such as impurities such as C and H in the film formed in the process of forming the thin film layer can be effectively removed.</p><p> A thirty-first invention, in the twenty-first to twenty-fifth inventions, comprises a step of forming a second thin film layer and a step of supplying an oxygen radical to the formed thin film. A method for manufacturing a semiconductor device or a substrate processing device, which comprises forming a thin film layer having a desired film thickness by repeating these steps a plurality of times. In the process of forming the second thin film layer, the film forming step and the step of supplying oxygen radicals are repeated a plurality of times, so that the thin film layer having a predetermined film thickness can be formed and the film formed in the process of forming the second thin film layer. The amount of specific elements (impurities such as C and H) removed can be increased.</p><p> In the 32nd invention, in the 21st to 25th inventions, at least the process of forming the first thin film layer is performed while rotating the substrate, which is a method for manufacturing a semiconductor device or a substrate treatment. It is a device. If at least the process of forming the first thin film layer is performed while rotating the substrate, the substrate can be uniformly processed over the plane, so that the flatness of the first thin film layer and further, the second thin film layer formed on the first thin film layer can be treated uniformly. Flatness is improved.</p><p> The 33rd invention is a method for manufacturing a semiconductor device, which is characterized in that, in the 21st to 25th inventions, both the first thin film layer forming step and the second thin film layer forming step are performed while rotating the substrate. It is a substrate processing device.</p><p> A thirty-fourth invention is a method for manufacturing a semiconductor device or a substrate processing device according to the twenty-first to twenty-fifth inventions, wherein the raw material gas and the oxygen radical are supplied from separate supply ports.</p><p> The 35th invention is the 24th invention, in which the non-reactive gas is supplied from the oxygen radical supply port when the raw material gas is supplied on the substrate, and the raw material gas is supplied when the oxygen radical is supplied on the substrate. A method for manufacturing a semiconductor device or a substrate processing device, which comprises supplying a non-reactive gas from a supply port of the above.</p><p> According to the thirty-sixth invention, in the twenty-fourth invention, when the raw material gas is supplied to the substrate, the oxygen radicals are not stopped but flowed so as to bypass the reaction chamber, and when the oxygen radicals are supplied to the substrate, the raw materials A method for manufacturing a semiconductor device or a substrate processing device, wherein the gas is allowed to flow so as to bypass the reaction chamber without being stopped.</p>

<p> According to the present invention, the flatness of the thin film can be improved without generating particles. Further, according to the present invention, the flatness of the thin film can be improved without lowering the productivity.</p>

Embodiments of the present invention will be described below. In this embodiment, HfO in an amorphous state is obtained by the MOCVD method.₂Membrane (hereinafter simply HfO₂The case of forming a film) will be described.

[First Embodiment] FIG. 9 is a schematic view showing an example of a single-wafer CVD apparatus which is a substrate processing apparatus according to the embodiment. A radical generation unit 11, a substrate rotation unit 12, an inert gas supply unit 10, and a bypass tube 14 are mainly added to the conventional reaction chamber 1 (FIG. 10).

As shown in the figure, a hollow heater unit 18 whose upper opening is covered with a susceptor 2 is provided in the reaction chamber 1. A heater 3 is provided inside the heater unit 18, and the heater 3 heats the substrate 4 mounted on the susceptor 2 to a predetermined temperature. The substrate 4 mounted on the susceptor 2 is, for example, a semiconductor silicon wafer, a glass substrate, or the like.

A substrate rotating unit 12 is provided outside the reaction chamber 1, and the substrate rotating unit 12 can rotate the heater unit 18 in the reaction chamber 1 to rotate the substrate 4 on the susceptor 2. The substrate 4 is rotated by the raw material gas introduced from the film-forming raw material supply unit 9 described later, the inert gas introduced from the inert gas supply unit 10, and the radicals introduced from the radical generation unit 11 on the surface of the substrate 4. This is to ensure that the inside is evenly distributed. As a result, in the first thin film layer forming step described later, the raw material gas can be uniformly adhered to the in-plane of the substrate 4 without reacting, and the raw material gas uniformly adhering to the in-plane of the substrate 4 can be adhered to. Oxygen radicals, which are reactants different from the raw material gas, can be uniformly supplied, and a uniform reaction can be generated over the plane of the substrate 4. Therefore, a uniform first thin film layer is provided over the substrate surface. Can be formed. Further, in the second thin film layer forming step described later, the second thin film layer can be uniformly formed over the substrate surface, and impurities such as C and H, which are specific elements in the formed film, can be uniformly formed in the substrate surface. Can be removed quickly and evenly.

Further, a shower head 6 having a large number of holes 8 is provided above the susceptor 2 in the reaction chamber 1. The shower head 6 is divided into a film-forming shower head portion 6a and a radical shower head portion 6b by a partition plate 15, and gas can be separately ejected in a shower shape from the divided shower head portions 6a and 6b. There is.

A film-forming raw material supply unit 9 for supplying the raw material gas and an inert gas supply unit 10 for supplying the inert gas as the non-reactive gas are provided outside the reaction chamber 1. The film-forming raw material supply unit 9 includes a liquid raw material supply unit 91 that supplies an organic liquid raw material such as MO (Metal Organic) as a film-forming raw material, and a liquid flow rate as a flow control means for controlling the liquid supply amount of the film-forming raw material. It has a control device 92 and a vaporizer 93 that vaporizes the film-forming raw material. Hf- (MMP) as a film forming raw material₄Use organic materials such as. The inert gas supply unit 10 includes an inert gas supply source 101 that supplies an inert gas as an inert gas, and a mass flow controller 102 as a flow control means that controls the supply amount of the inert gas. Ar, He, N as inert gases₂Etc. are used. The raw material gas supply pipe 5b provided in the film-forming raw material supply unit 9 and the inert gas supply pipe 5a provided in the inert gas supply unit 10 are integrated and connected to the film-forming shower head portion 6a. It communicates with the raw material supply pipe 5. The raw material gas supply system of the present invention includes a film-forming raw material supply unit 9, a raw material gas supply pipe 5b, a raw material supply pipe, a valve, and the like.

The raw material supply pipe 5 is HfO on the substrate 4.₂In the first thin film layer forming step and the second thin film layer forming step of forming a film, a mixed gas of a raw material gas and an inert gas is supplied to the film forming shower head portion 6a of the shower head 6. Valves 21 and 20 are provided in the raw material gas supply pipe 5b and the inert gas supply pipe 5a, respectively, and the supply of the mixed gas of the raw material gas and the inert gas is controlled by opening and closing these valves 21 and 20, respectively. Is possible.

Further, a radical generation unit 11 for generating radicals is provided outside the reaction chamber 1. The radical generation unit 11 is composed of, for example, a remote plasma unit. On the upstream side of the radical generation unit 11, the argon supply unit 50, which supplies argon (Ar) via the gas supply pipe 40, and oxygen (O).₂) Supply oxygen supply unit 60, and chlorine fluoride (ClF)₃) Supply ClF₃The supply unit 70 is connected. These units 50, 60, 70 include gas supply sources 51,61,71, mass flow controllers 52,62,72 as flow rate control means for controlling the supply amount of the gas, and gas supply pipes 40 for the gas. It has valves 53, 63, 73 that turn on / off the flow to. The control device 25 controls the opening and closing of each of the valves 53, 63, 73 to form argon (Ar), which is a gas for plasma generation, during film formation in the first thin film layer forming step and in the second thin film layer forming step. Oxygen used for removing impurities in₂, And ClF used in the cleaning process to remove the cumulative film formed on structures other than the substrate.₃Can be selectively supplied to the radical generation unit 11. The gas supplied from these gas supply units 50, 60, 70 is activated by, for example, plasma in the radical generation unit 11, and a radical as a reactant is generated.

A radical supply pipe 13 connected to the radical shower head portion 6b is provided on the downstream side of the radical generation unit 11, and the shower head 6 is provided in the first thin film layer forming step, the second thin film layer forming step, or the cleaning step. An oxygen radical or a chlorine fluorinated radical as a reaction product is supplied to the radical shower head portion 6b. Further, the radical supply pipe 13 is provided with a valve 24, and the radical supply is controlled by opening and closing the valve 24. It is possible. The reactant supply system of the present invention includes an argon supply unit 50, an oxygen supply unit 60, a gas supply pipe 40, a radical generation unit 11, a radical supply pipe 13, a valve 24, and the like.

The radical generation unit 11 supplies the radicals generated in the first thin film layer forming step, the second thin film layer forming step, and the cleaning step into the reaction chamber 1. The radical as a reactant used in the first thin film layer forming step and the second thin film layer forming step is Hf- (MMP) as a raw material.₄When an organic material such as is used, for example, an oxygen radical is preferable. This is because in the first thin film layer forming step, a film forming reaction is used in which a film is forcibly formed by supplying oxygen radicals on the substrate 4 to which the raw material gas is adhered without reacting. .. In addition, in the second thin film layer forming step, HfO₂This is because the impurity removal treatment such as C and H can be efficiently carried out immediately after the film formation. In addition, the radical used in the cleaning process for removing the cumulative film formed on structures other than the substrate is ClF.₃Radicals are good.

The film-forming shower head portion 6a and the radical shower head portion 6b including the raw material supply pipe 5 and the radical supply pipe 13 provided in the reaction chamber 1 supply the raw material gas to the substrate 4 and the radicals to be supplied to the substrate 4, respectively. Separate supply ports are configured to supply. The one including the film-forming shower head portion 6a is the raw material gas supply port, and the one including the radical shower head portion 6b is the radical supply port. However, in one modification of the present invention, the partition plate 15 may be omitted. In that case, Hf- (MMP)₄The raw material gas such as, and the reactant such as oxygen radicals are supplied from the same supply port. The supply port in this case refers to the one including the entire shower head 6. That is, in this case, the same shower head 6 shares the raw material gas supply port and the radical supply port. As a result, the configuration of the apparatus can be simplified by omitting the partition plate 15, and the raw material gas and the reactants are respectively ejected from all the holes 8 in the entire shower head 6, so that these can be ejected from the substrate 4. It can be supplied more uniformly in the plane.

The reaction chamber 1 is provided with an exhaust port 7a for exhausting the reaction chamber, and the exhaust port 7a is connected to an exhaust pipe 7 communicating with an abatement device (not shown). A raw material recovery trap 16 for recovering the gas raw material is installed in the exhaust pipe 7. The raw material recovery trap 16 is commonly used in the first thin film layer forming step, the second thin film layer forming step, and the cleaning step. The exhaust system is composed of the exhaust port 7a and the exhaust pipe 7.

Further, the raw material gas supply pipe 5b and the radical supply pipe 13 have a raw material gas bypass pipe 14a and a radical bypass pipe 14b (these are simply referred to as bypass pipes 14) connected to the raw material recovery trap 16 provided in the exhaust pipe 7. Each is provided. Valves 22 and 23 are provided in the raw material gas bypass pipe 14a and the radical bypass pipe 14b, respectively. As a result, when the raw material gas is supplied onto the substrate 4 in the reaction chamber 1, it is exhausted via the radical bypass pipe 14b and the raw material recovery trap 16 so as to bypass the reaction chamber 1 without stopping the supply of radicals. deep. Further, when supplying radicals onto the substrate 4 in the reaction chamber 1, the radicals are exhausted through the raw material gas bypass pipe 14a and the raw material recovery trap 16 so as to bypass the reaction chamber 1 without stopping the supply of the raw material gas. deep. That is, at least during the substrate processing, the supply of the raw material gas from the film-forming raw material supply unit 9 and the supply of the radicals from the radical generation unit 11 are not stopped, and both of them are always flowing.

A control device 25 for controlling the opening and closing of the valves 20 to 24 is provided. The control device 25 heats the substrate 4 to raise the substrate temperature to the film formation temperature at a predetermined speed, and controls the heater so as to maintain the film formation temperature after the temperature rise. Further, in the first thin film layer forming step, the raw material gas is not reacted on the substrate 4 from the film forming shower head portion 6a in a state where the substrate temperature is lower than the film forming temperature (for example, during the film forming temperature). After supplying so that it adheres as it is, radical shower -Control to supply oxygen radicals from the head portion 6b onto the substrate 4. Then, the supply of the raw material gas and the supply of the oxygen radical to the substrate 4 are controlled to be repeated a plurality of times. Further, in the second thin film forming step, after the substrate temperature is raised to the film forming temperature, the raw material gas is supplied from the film forming shower head portion 6a onto the substrate 4 to form a film, and then the film is formed. It is controlled to supply oxygen radicals to the film. Then, the supply of the raw material gas to the substrate 4 and the supply of the oxygen radicals are controlled to be repeated a plurality of times. During this period, the inside of the reaction chamber 1 is always controlled to be exhausted from the exhaust port 7a. In addition, the inert gas (Ar, He, N) between the supply of the raw material gas and the supply of the oxygen radical₂Etc.) to supply.

Next, using the substrate processing apparatus having the configuration shown in FIG. 9 described above, the incubation time is suppressed by using a process different from the conventional one, and HfO₂The procedure for forming a film is shown.

FIG. 1 shows the process flow of the first embodiment. Before loading the substrate 4 into the reaction chamber 1, only the valve 20 was opened, and the N, which is an inert gas, was opened.₂Only gas is allowed to flow 1 to 5 SLM in the reaction chamber 1. After that, the substrate 4 is inserted into the reaction chamber 1 and placed on the susceptor 2, and while the substrate 4 is rotated by the substrate rotation unit 12, power is supplied to the heater 3 to set the temperature of the substrate 4 as the film formation temperature. Start heating the substrate for uniform heating to 350-500 ° C (step 201). The film formation temperature varies depending on the reactivity of the organic material used, but for example, Hf- (MMP).₄When using, the range of 390 to 440 ° C is preferable. Further, when the substrate 4 is present in the reaction chamber 1 at least when the substrate 4 is transported or when the substrate is heated (including heating of the substrate and heating during film formation), a valve provided in the inert gas supply pipe 5a is provided. Open 20 and Ar, He, N₂By constantly flowing an inert gas such as, particles and metal contaminants can be prevented from adhering to the substrate 4. Further, the inert gas is always allowed to flow even when the substrate 4 does not exist in the reaction chamber 1, such as before the substrate 4 is carried into the reaction chamber 1 or after the substrate 4 is carried out from the reaction chamber 1. This is even more preferable.

In the conventional method, the inert gas (N) is used during the temperature rise of the substrate.₂Etc.) were simply supplied on the board 4. However, in the present embodiment, the first thin film layer forming step A is started in a state where the substrate temperature is started and the substrate temperature is lower than the film formation temperature by the thermal CVD method. That is, in the first thin film layer forming step A, first, in the film forming raw material supply step 202, the organic liquid raw material supplied from the liquid raw material supply unit 91 is flow-controlled by the liquid flow rate control device 92 and supplied to the vaporizer 93. Vaporize. Then, while the temperature of the substrate is being raised, the valve 21 is opened, and Hf- (MMP) as an organic liquid raw material is released from the film forming raw material supply unit 9.₄The raw material gas vaporized from the above is supplied onto the substrate 4 in a predetermined amount, for example, 0.1 g / min for about 10 seconds. The raw material gas is guided to the film-forming shower head portion 6a and is supplied in a shower shape onto the substrate 4 on the susceptor 2 via a large number of holes 8. After that, the valve 21 is closed, the valve 22 is opened, and the raw material gas is exhausted from the bypass pipe 14a to stop the supply of the raw material gas onto the substrate 4. As a result, the supply of the film-forming raw material for adhering the raw material gas on the substrate 4 is completed (step 202). In this step, since the substrate temperature is low, the raw material gas adhering to the substrate 4 does not cause a decomposition reaction. Further, after about 10 seconds, the valve 21 provided in the raw material gas supply pipe 5b is closed, the valve 22 provided in the raw material gas bypass pipe 14a is opened, and the raw material gas supplied from the film forming raw material supply unit 9 is reacted. Since the gas is exhausted through the raw material gas bypass pipe 14a so as to bypass the chamber 1, the supply of the raw material gas is not stopped.

During the supply of the film-forming raw material and the next RPO (remote plasma oxidation) treatment, the valve 20 provided in the inert gas supply pipe 5a is left open, and N₂Always allow the inert gas such as, etc. to flow.

After the film forming raw material supply step 202, the RPO treatment (step 203) is performed. Here, RPO (remote plasma oxidation) treatment refers to oxygen-containing gas (O).₂, N₂It is a remote plasma oxidation treatment that oxidizes a membrane in an oxygen radical atmosphere as a reactant generated by activating O, NO, etc.) with plasma. In the RPO process, the valve 53 of the Ar gas supply unit 50 is opened in advance, and the Ar gas supplied from the Ar gas supply source 50 is flow-controlled by the mass flow controller 52 and supplied to the radical generation unit 11 to generate Ar plasma. After generating Ar plasma, O₂Open valve 63 of gas supply unit 60, O₂Gas source 61 O supplied from the source₂The gas is supplied to the radical generation unit 11 that generates Ar plasma by controlling the flow rate with the mass flow controller 63, and O₂To activate. As a result, oxygen radicals are generated. Then, the valve 24 is opened, and oxygen radicals as a reaction product generated by activating oxygen with plasma by the radical generation unit 11 are transmitted through the radical shower head portion 6b separated from the film-forming shower head portion 6a. Shower-like supply on substrate 4 for about 15 seconds. After that, the valve 24 is closed and the valve 23 is opened, and oxygen radicals are exhausted from the bypass pipe 14b so as to bypass the reaction chamber 1. As a result, the supply of oxygen radicals on the substrate 4 is stopped. When oxygen radicals are supplied to the unreacted raw material gas adhering to the substrate 4, a film formation reaction of forcibly forming a film occurs, and the first thin film layer is formed on the substrate 4. HfO₂Membranes are deposited by a few to tens of angstroms (step 203). After about 15 seconds, the valve 24 provided in the radical supply pipe 13 is closed, the valve 23 provided in the radical bypass pipe 14b is opened, and the oxygen radical supplied from the radical generation unit 11 bypasses the reaction chamber 1. As a result, the radical bypass pipe 14b is used for exhausting, so that the supply of oxygen radicals from the radical generation unit 11 is not stopped.

Conventionally, the thin film was not deposited during the temperature rise of the substrate, but in the present embodiment, the thin film of the first layer is deposited during the temperature rise of the substrate. HfO which is the first layer₂The film is formed. As a result, when the raw material gas is supplied onto the substrate 4 after the temperature rise of the substrate is completed, the HfO of the first layer is obtained.₂HfO of the second layer with the film as the base₂Since a film is formed, the incubation time that has been generated by the conventional method does not occur, the nuclear development process can be omitted, and as a result, a thin film having excellent flatness can be formed. Be done.

After the RPO treatment in step 203, wait until the substrate 4 rises to a predetermined film formation temperature of 390 to 440 ° C. The heating time is usually 1 minute to 2 minutes and 30 seconds. During this period, if there is time to spare, it is preferable to repeat the cycle of the film forming raw material supply step 202 and the RPO treatment step 203 a plurality of times because the flatness is effective. Further, N between the film forming raw material supply step 202 and the RPO processing step 203.₂It is advisable to provide an interval gas supply step for supplying the inert gas such as.

After the first thin film layer forming step, the substrate temperature reaches the film forming temperature by a predetermined thermal CVD method, and then the second thin film layer forming step B is started. First, in the film forming process in step 205, the valve 22 is closed, the valve 21 is opened, and the film forming raw material supply unit 9 is subjected to Hf- (MMP).₄The raw material gas vaporized from the above is supplied to the substrate 4 in the reaction chamber 1. During the supply of this raw material gas and during the next RPO treatment (step 206), the valve 20 is left open and the inert gas (N) is released from the inert gas supply unit 10.₂If the raw material gas is always flowed, the raw material gas is diluted with the inert gas and stirred, which is good. The raw material gas supplied from the raw material gas supply pipe 5b and the inert gas supplied from the inert gas supply pipe 5a are mixed in the raw material supply pipe 5 and guided to the film forming shower head portion 6a as a mixed gas. It is supplied in a shower shape onto the substrate 4 on the susceptor 2 via a large number of holes 8. By supplying the mixed gas for a predetermined time, HfO, which is a second thin film layer having a predetermined film thickness, is placed on the first thin film layer by a thermal CVD method.₂A membrane is formed (step 205). After the predetermined time, the valve 21 is closed and the valve 22 is opened to stop the supply of the raw material gas onto the substrate 4 and exhaust the raw material gas through the raw material gas bypass pipe 14a (note that the raw material gas is exhausted onto the substrate 4). The supply of raw material gas is stopped, but the raw material gas from the film-forming raw material supply unit 9 Supply does not stop. ).

After the film formation process in step 205, the RPO process (step 206) as a modification process for modifying the film is started. After closing the valve 21, the valve 24 is opened and oxygen radicals as a reactant obtained by activating oxygen with plasma by the radical generation unit 11 are supplied onto the substrate 4 for a desired time, and a specific element mixed in the membrane is supplied. The RPO process is completed by removing impurities such as -OH and -CH. Similar to the first thin film layer forming step A, in the second thin film layer forming step B, the substrate 4 is kept at a predetermined temperature (the same temperature as the film forming temperature) by the heater 3 while rotating, so that C and H Impurities such as can be removed quickly and uniformly. After the desired time, the valve 24 is closed and the valve 23 is opened to stop the supply of oxygen radicals onto the substrate 4 and exhaust the oxygen radicals through the radical bypass tube 14b (note that oxygen on the substrate 4). The supply of radicals is stopped, but the supply of oxygen radicals from the radical generation unit 11 is not stopped.)

Again, repeating the cycle of the film forming process step 205 and the RPO process step 206 a plurality of times is good because the effect of removing impurities is improved. The film thickness of the second thin film layer at this time is, for example, about 50 angstroms in total. The processed substrate is carried out of the apparatus (step 207).

As described above, in the present embodiment, unlike the conventional example in which gas and radicals are simultaneously supplied in the first thin film layer forming step of the low temperature treatment, the raw material gas and oxygen radicals are not supplied at the same time. One type is supplied, or one type is alternately supplied multiple times. The reason for this is that the raw material gas is adhered to the substrate in an unreacted state at a temperature lower than the film formation temperature by the thermal CVD method, and then the film is forcibly formed by supplying oxygen radicals as a reactant. This is because the film formation reaction of forming is used. It is also to prevent the generation of particles by simultaneously supplying the highly reactive oxygen radical and the raw material gas. The supply of oxygen radicals in the first thin film layer forming step has the effect of forcibly causing a film formation reaction and preventing impurities from being incorporated into the film as much as possible.

The preferable temperature range in the first thin film layer forming step A of the embodiment is as follows. If the substrate temperature is too high in the first thin film layer forming step A, the raw material gas is decomposed and formed on the substrate, and the raw material gas cannot be adhered to the substrate in an unreacted state. Therefore, it is considered necessary to set the substrate temperature to at least 390 ° C or less so that the film formation rate by the thermal CVD method does not occur. On the contrary, if the substrate temperature is too low, the adhesion between the thin film and the substrate deteriorates and the substrate is easily peeled off. Therefore, it is considered that a temperature of at least 200 ° C or higher is necessary. From the above, it is considered that the substrate temperature in the first thin film layer forming step is preferably 200 ° C or higher and 390 ° C or lower. The conditions such as the pressure range may be the same as those in the second thin film layer forming step B below.

Further, a preferable condition in the film forming step in the second thin film layer forming step B is Hf- (MMP) as a raw material.₄When using, the treatment temperature is 390 to 440 ° C and the pressure is about 100 Pa or less as described above. The preferred conditions for the RPO treatment step after the film formation step are a treatment temperature of 390 to 440 ° C, a pressure range of about 100 to 1000 Pa, and O for radical generation.₂The flow rate is 100 sccm, and the flow rate of the inert gas Ar is 1 slm. The film forming step and the RPO step are preferably performed at substantially the same temperature (preferably, the set temperature of the heater is not changed and is constant). This is because by not causing temperature fluctuations in the reaction chamber, particles due to thermal expansion of peripheral members such as shower plates and susceptors are less likely to be generated, and metal ejection from metal parts (metal contamination) can be suppressed. Is.

To compare with the process flow of the first embodiment, FIG. 2 shows the process flow of the conventional example. The figure is shown. In the conventional example, the inert gas (N) is simply used while the substrate is being heated.₂Etc.) was only supplied to the substrate (step 204), but in the present embodiment, the raw material gas is further flowed while the substrate is heated, and then radicals as a reactant are flowed to form the first thin film layer. (Steps 202, 203). Therefore, in the present embodiment, the newly added step of forming the insulating layer to be the first thin film layer utilizes the substrate temperature rise time of the conventional process, so that the flatness of the CVD thin film is not lowered. Can be improved.

Further, since the second thin film layer is formed by adopting the thermal CVD method, the film quality is good unlike the film formed by the ALD method. That is, ALD (Atomic Layer Deposition) has a low processing temperature and pressure, and forms a film one atomic layer at a time. However, since the film is formed at a low temperature from the beginning to the end, the amount of impurities incorporated into the film is large and the film quality is poor. bad. On the other hand, in the present embodiment, the first thin film layer forming step A is performed at a temperature lower than the film forming temperature by the thermal CVD method (several to several tens of angstroms / cycle), but the second thin film layer forming step B is ALD. Since a thin film (about 10 to 15 angstroms) is formed multiple times using a thermal CVD reaction with a higher processing temperature and pressure than ALD, a film with finer density and better film quality than ALD can be obtained.

Further, by the RPO treatment (step 206) performed as a modification treatment after the film formation treatment (step 205), impurities such as hydrogen (H) and carbon (C) in the film can be effectively removed and the concentration thereof can be reduced. Therefore, the electrical characteristics can be improved. In addition, the departure of hydrogen (H) suppresses the movement of Hf atoms, prevents crystallization, and improves electrical characteristics. It can also promote the oxidation of the membrane and repair oxygen defects in the membrane. In addition, the release gas from the cumulative membrane deposited on the reaction chamber wall, the susceptor, and other parts other than the substrate can be quickly reduced, and the film thickness can be controlled with high reproducibility.

In the embodiment, the RPO treatment is performed as the reforming treatment in step 206, but the present invention is not limited to this. As an alternative to RPO processing ((1) below), for example, there are the following ((2) to (8) below). (1) For inert gas such as Ar, O₂RPO processing performed by mixing (2) For inert gas such as Ar, N₂RPN (Remote Plasma Nitridation) processing performed by mixing (3) For inert gas such as Ar, N₂And H₂RPNH (Remote Plasma Nitridation Hydrogenation) treatment performed by mixing with (4) For inert gas such as Ar, H₂RPH (Remote Plasma Hydrogenation) processing performed by mixing with (5) For inert gas such as Ar, H₂RPOH (Remote Plasma Oxidation Hydrogenation) treatment performed by mixing with O (6) For inert gases such as Ar, O2 and H₂RPOH treatment performed by mixing (7) For inert gas such as Ar, N₂RPON (Remote Plasma Oxidation Nitridation) processing performed by mixing with O (8) For inert gas such as Ar, N₂And O₂RPON processing performed by mixing and

Further, in the second thin film layer forming step B, by repeating the cycle of the film forming process step 205 and the RPO process step 206 a plurality of times, the efficiency of removing impurities in the film can be improved as described above. In addition, the film can be maintained in an amorphous state, and as a result, the leakage current can be reduced. In addition, the flatness of the film surface can be improved, and the film thickness uniformity can be improved. In addition, the film can be densified (maximizing the defect repair effect), and the deposition rate can be precisely controlled. Furthermore, the undesired interface layer formed at the interface between the film-forming base and the film to be deposited can be thinned.

Further, the cycle of the film forming process step 205 and the RPO process step 206 is repeated a plurality of times. In this case, the film thickness per cycle is preferably 0.5 Å to 30 Å (1/6 to 10 atomic layers). In particular, HfO such as CH and OH in about 7 cycles₂The effect of reducing the amount of impurities in the film becomes extremely large, and even if the number of cycles is increased further, the effect of reducing the amount of impurities is slightly improved, but there is not much change, so the film thickness per cycle is about 15 Å (5). Atomic layer) is considered to be more preferable. If 30 Å or more is deposited in one cycle, impurities in the film will increase and will crystallize immediately, resulting in a polycrystalline state. Since there are no gaps in the polycrystalline state, it is difficult to remove C, H, etc. However, if the film thickness formed by one cycle is thinner than 30 Å, it becomes difficult to form a crystallized structure, and the thin film can be maintained in an amorphous state even if there are impurities. Since the amorphous state has many gaps (squashed state), impurities such as C and H in the film are removed by depositing the thin film while maintaining the amorphous state and performing RPO treatment before the thin film crystallizes. It becomes easier to do. That is, the film thickness obtained by a plurality of cycle treatments with the film thickness per cycle being about 0.5 Å to 30 Å is in a state of being difficult to crystallize. The amorphous state has the advantage that the leak current is less likely to flow than the polycrystalline state.

FIG. 3 shows a timing chart in which the first thin film layer forming step [raw material gas supply oxygen radical supply] is repeated for n cycles during the temperature rise in the process of the first embodiment described above. (a) shows the substrate temperature rise characteristic, the horizontal axis shows time, and the vertical axis shows temperature. (b) is Hf- (MMP)₄The raw material gas supply timing and (c) indicate the oxygen radical supply timing, the horizontal axis indicates time, and the vertical axis indicates the supply amount (arbitrary unit). In this embodiment, Hf- (MMP) is used until the substrate temperature rises to 390 ° C.₄After flowing the gas for 10 seconds, the inert gas N is used as an interval gas supply step.₂For 5 seconds, then oxygen radical O₂For 15 seconds, then as an interval gas supply step, the inert gas N₂Is repeated n times in a cycle of flowing for 5 seconds. When the substrate temperature reaches the film formation temperature of 440 ° C, the second thin film layer forming step [raw material gas supply oxygen radical supply] is repeated for m cycles. In the second thin film layer forming step as well, it is preferable to perform an interval gas supply step between the supply of the raw material gas and the supply of the oxygen radical as in the first thin film layer forming step. In addition, the inert gas N is used throughout the entire process.₂Since the gas continues to flow, if both the supply of the raw material gas to the reaction chamber and the supply of oxygen radicals are stopped, the N₂Only flows, and the interval gas supply step is automatically performed.

FIG. 5 is a diagram showing the flatness of the thin film formed in the first thin film layer forming step by the embodiment process. The horizontal axis shows the number of cycles during the temperature rise of the substrate, and the vertical axis shows the flatness (arbitrary unit). The conventional process corresponds to the case where the number of cycles is zero. According to this, it can be seen that the flatness of the thin film is improved as the number of cycles during the temperature rise of the substrate increases, although the number of cycles almost reaches a plateau when the number of cycles is 2 or more. Therefore, the reliability of the semiconductor device, which is the final product, can be improved, and the device size can be effectively reduced.

By the way, the reason why the supply of the raw material gas and the supply of the oxygen radical are repeated a plurality of times in the first thin film layer forming step A is as follows. As shown in FIG. 6, when the raw material gas is supplied to the substrate 4 and the oxygen radicals are supplied only once, there may be a part where the film is not formed. In that case, by repeating the supply of the raw material gas the supply of oxygen radicals a plurality of times, the portion where the film was not formed can be repaired and filled, and a flat first thin film layer can be formed. Therefore, even in the MOCVD method in which the deposition rate of the thin film is determined by the surface reaction rate-determining, the incubation time can be shortened and the film surface of the deposited thin film can be made flat.

Further, in the first thin film layer forming step and / and the second thin film layer forming step, the non-reactive gas is supplied between the supply of the raw material gas and the supply of oxygen radicals (interval gas supply process), and then For the reason. Non-reactive gas (N) after supply of raw material gas and before supply of oxygen radicals₂, Ar, He, etc.), the amount of the raw material gas adsorbed on the substrate becomes uniform due to the supply of the inert gas. Further, the raw material gas in the atmosphere in the reaction chamber when the oxygen radical is supplied after the raw material gas is supplied can be removed, and the raw material gas and the oxygen radical can be prevented from coexisting in the reaction chamber at the same time. Occurrence can be prevented. Further, even when the supply of the raw material gas and the supply of the oxygen radical are repeated a plurality of times alternately, if the non-reactive gas is supplied between the supply of the raw material gas and the supply of the oxygen radical, the raw material gas can be supplied. The amount of adsorption becomes uniform, the raw material gas in the atmosphere when the oxygen radicals are supplied after the raw material gas is supplied can be removed, and the oxygen radicals in the atmosphere when the raw material gas is supplied after the supply of the oxygen radicals can be removed. It is possible to prevent the raw material gas and the oxygen radical from being present in the room at the same time. As a result, the generation of particles can be prevented.

The reason why the shower head 6 is divided into the film-forming shower head portion 6a and the radical shower head portion 6b is as follows. When the raw material adsorbed inside the shower head 6 reacts with oxygen radicals, a cumulative film is also formed inside the shower head 6. By partitioning the shower head 6 to which the raw material gas and the oxygen radicals are supplied, it is possible to effectively prevent the raw material and the oxygen radicals from reacting with each other and suppress the formation of a cumulative film.

In addition to partitioning the shower head 6, when the raw material gas is further flowed to the substrate 4, the inert gas is flowed from the inert gas supply unit (not shown) to the radical shower head portion 6b, and the oxygen radical is flowed to the substrate 4. In this case, it is preferable to flow the inert gas from the inert gas supply unit 10 to the film-forming shower head portion 6a. It is preferable that the inert gas supply unit that supplies the inert gas to the radical shower head portion 6b and the inert gas supply unit that supplies the inert gas to the film-forming shower head portion 6a are shared. In this way, if the inert gas is allowed to flow through the shower head portions 6b and 6a on the unused side in the step of supplying the raw material gas and the step of supplying the oxygen radical, respectively, the inert gas can be more effectively introduced into the shower head 6. Cumulative film formation can be suppressed.

As described above, for example, by omitting the partition plate 15, Hf- (MMP)₄And other raw material gases and reactants such as oxygen radicals can be supplied from the same supply port. In that case, HfO removes foreign matter (particle source) adhering to the inside of the supply port, that is, the shower head 6.₂It can be coated with a film. This results in Hf- (MMP)₄It is possible to prevent the foreign matter from reaching the substrate 4 together with the flow of the raw material gas such as or the reaction product such as oxygen radicals. In particular, in the apparatus shown in FIG. 9, since the raw material gas and the reactant are supplied onto the substrate 4 in a downflow, it is possible to reliably prevent the foreign matter from falling onto the substrate 4 during the processing. Also, the reaction chamber 1 is cleaned with a cleaning gas (for example, ClF).₃When cleaning with a gas containing Cl, etc.), foreign substances such as by-products adsorbed inside the reaction chamber 1 and the inside of the shower head 6 and the cleaning gas can be reliably removed without leaving a residue. Further, the film coated inside the shower head is exposed to the reactant after coating, whereby the amount of impurities such as C and H contained in the coating film inside the shower head can be significantly reduced.

In the cleaning step of removing the cumulative film formed on the structure other than the substrate, the valve 53 of the Ar gas supply unit 50 is opened in advance, and the flow rate of the Ar gas supplied from the Ar gas supply source 50 is controlled by the mass flow controller 52. Is supplied to the radical generation unit 11 to generate Ar plasma. After generating Ar plasma, ClF₃Open valve 73 of gas supply unit 70, ClF₃ClF supplied from 71 gas sources₃The gas is supplied to the radical generation unit 11 that generates Ar plasma by controlling the flow rate with the mass flow controller 73, and ClF₃To activate. This will result in ClF₃Radicals are generated. Then, the valve 24 is opened, and ClF is performed by the radical generation unit 11.₃ClF generated by activating with plasma₃Radicals are showered into the reaction chamber 1 via the shower head 6. Supply to.

Further, the reason why the oxygen radicals and the raw material gas used in the next step are exhausted from the bypass pipe 14 without stopping during the supply of the raw material gas and the oxygen radicals to the reaction chamber is as follows. In order to supply the raw material gas and oxygen radicals, it is necessary to prepare for vaporization of the liquid raw material in the vaporizer 93, stabilization of the vaporized raw material gas, generation and stabilization of oxygen radicals in the radical generation unit 11, and the like. It takes time to start. Therefore, during the treatment, the supply of the raw material gas and the oxygen radical is always continued without being stopped, and when not in use, the gas is exhausted from the bypass pipe 14. As a result, the supply of the raw material gas and oxygen radicals to the reaction chamber can be started immediately by simply switching the valves 21 to 24 at the time of use, and the throughput can be improved.

In addition, while the substrate processing apparatus is in operation, the reaction chamber 1 is always filled with an inert gas (N).₂, Ar, He, etc.) should be supplied. Specifically, the valve 20 is opened before the substrate is conveyed so that the inert gas is constantly supplied from the inert gas supply unit 10 into the reaction chamber 1. Inert gas is always flowed during substrate transfer, substrate temperature rise, heating after substrate temperature rise, as well as raw material gas supply and oxygen radical supply. As a result, the reaction chamber can be constantly purged with an inert gas, and particles and metal pollutants can adhere to the substrate, and the raw material gas adhering to the exhaust port 7a and the exhaust pipe 7 can be back-diffused into the reaction chamber. Further, it is possible to prevent back diffusion of oil from a vacuum pump (not shown) into the reaction chamber.

Further, in the embodiment, as described above, the inert gas continues to flow even when the raw material gas is supplied or the oxygen radical is supplied. As a result, the raw material gas and oxygen radicals can be agitated in the reaction chamber 1. Further, since the inert gas is constantly flowing, if the supply of the raw material gas and the oxygen radical to the reaction chamber 1 is stopped, the state in which the inert gas is automatically supplied to the substrate 4, that is, N.₂It can be in a purged state. Therefore, there is also an advantage that the above-mentioned interval gas supply process can be easily executed.

Further, in the first thin film layer forming step, a material containing an oxygen atom is used as the reactant, and the raw material is supplied (step 202) and the reactant is supplied (step 203) in this order for the following reason. according to. That is, the reactant containing oxygen atoms (here, the oxygen radical generated by activating oxygen gas with plasma) also functions as an oxidant, but if the treatment proceeds in the order of oxidant adhesion raw material supply. Assuming that the oxidizing agent directly adheres to the underlying substrate, the oxidation reaction gradually proceeds on the surface of the substrate. As a result, SiO as an interface layer₂There arises a problem that a layer having a low dielectric constant such as is easily formed. The oxidation reaction tends to increase as the substrate temperature rises. Therefore, as in the present invention, Hf- (MMP)₄By performing RPO treatment (step 203) after adhering to the substrate (step 202), oxygen radicals and Ar radicals are supplied to the substrate surface by this PRO treatment, and Hf- (MMP).₄When decomposing and oxidizing, the substrate surface is Hf- (MMP).₄Since it is covered with, a direct oxidation reaction to the substrate (for example, Si) is less likely to occur. Moreover, Hf- (MMP) during temperature rise, that is, when the substrate temperature is 300 ° C or less.₄However, the oxidation reaction on the surface of the substrate does not easily proceed. This is Hf- (MMP)₄This is because the oxidizing agent (oxygen species) required to oxidize the substrate does not exist at the time of adhering. The interface layer is SiO₂It tends to be Hf silicate with a slightly higher permittivity than. Therefore, according to the present invention, the effect of reducing the EOT (effective film thickness) of the low dielectric constant film can be obtained as compared with the case where the treatment is carried out in the order of oxidant adhesion raw material supply as described above.

The mechanism of self-decomposition, semi-self-decomposition, and adsorption of the film-forming raw material in the first thin film layer forming step and the second thin film layer forming step in the process of the present embodiment is as follows. If the substrate temperature is lower than the predetermined critical temperature, the adsorption reaction of the film-forming raw material becomes the main. If the substrate temperature is higher than that, the autolysis reaction of the film-forming raw material becomes the main. As in the present embodiment, Hf- (MMP) is used as a film forming raw material.₄When is used, the critical temperature is considered to be around 300 ° C. That is, in the first thin film layer forming step A performed during the temperature rise of the substrate, when the film-forming raw material is supplied to the substrate 4 which has not yet reached 300 ° C in step 202, the adsorption reaction of the film-forming raw material mainly occurs. On the other hand, in the second thin film layer forming step B performed after the substrate temperature has risen to 390 to 440 ° C, when the film-forming raw material is supplied to the substrate 4 in step 205, the self-decomposition reaction of the film-forming raw material is the main. Happens to. Hf- (MMP)₄The reaction formula in the case of adsorbing and then oxidizing is as follows. Hf [OC (CH)₃)₂CH₂OCH₃]₄+ 24O₂ HfO₂+ 16CO₂+ 22H₂O Also, Hf- (MMP)₄The reaction formula of the autolysis reaction of is as follows. Hf [OC (CH)₃)₂CH₂OCH₃]₄ Hf (OH)₄+ 4C (CH)₃) 2CH₂OCH₂ Hf (OH)₄ HfO₂+ 2H₂O However, the adsorption reaction of the film-forming raw material is not completely eliminated in any temperature range, and the autolysis reaction and the adsorption reaction of the film-forming raw material overlap in all the CVD reactions (semi-self-decomposition reaction). That is, even in the second thin film layer forming step of the present embodiment, although the autolysis reaction of the film-forming raw material is the main component, the autolysis reaction and the adsorption reaction overlap each other. The inventors have obtained experimental results that impurities can be reduced by focusing on the autolysis reaction.

[Second Embodiment] In the process timing of FIG. 3 according to the first embodiment described above, the first thin film layer was formed during the temperature rise, but it was not during the temperature rise and was predetermined. The first thin film layer may be formed while maintaining a low temperature (200 ° C or more and 390 ° C or less). FIG. 4 shows a timing chart of the second embodiment process in which the first thin film layer forming step [raw material gas supply oxygen radical supply] is repeated for n cycles while maintaining such a low temperature. (a) shows the substrate temperature rise characteristic, the horizontal axis shows time, and the vertical axis shows temperature. (b) is Hf- (MMP)₄The raw material gas supply timing and (c) indicate the oxygen radical supply timing, the horizontal axis indicates time, and the vertical axis indicates the supply amount (arbitrary unit).

In the second embodiment, instead of raising the temperature of the substrate at once to the film formation temperature of 440 ° C, the temperature rise is temporarily stopped in the middle of the temperature rise to maintain the temperature at that time, and then to the film formation temperature. We adopt a process of raising the temperature, which is a two-step process of set temperature. The first set temperature is the first thin film layer formation temperature of 200 to 390 ° C, and the second set temperature is the film formation temperature of 440 ° C. Hf- (MMP) while maintaining the first set temperature₄After flowing the gas for 10 seconds, the inert gas N is used as an interval gas supply step.₂For 5 seconds, then oxygen radical O as a reactant₂Is allowed to flow for 15 seconds, and then the inert gas N is used as an interval gas supply step.₂Repeat n times for 5 seconds. After that, the temperature of the substrate is raised again, and when the substrate temperature reaches the film formation temperature of 440 ° C, the second thin film layer forming step [raw material gas supply oxygen radical supply] is repeated for m cycles. In the second thin film layer forming step as well, it is preferable to perform an interval gas supply step between the supply of the raw material gas and the supply of the oxygen radical as a reactant as in the first thin film layer forming step. Inert gas N throughout the entire process₂Since the gas continues to flow, if both the supply of the raw material gas to the reaction chamber and the supply of oxygen radicals are stopped, the N₂Only flows, and the interval gas supply step is automatically performed.

In the case of this second embodiment, the productivity is inferior to that of the first embodiment by the amount of the first step, but even so, by increasing the temperature rise rate, the first thin film layer formation temperature ( The total time of the temperature rise time from 200 to 390 ° C), the first thin film layer formation time, and the temperature rise time to the second thin film layer formation temperature (440 ° C) is used as the substrate temperature rise time of the conventional process. Get closer For example, the flatness of the CVD thin film can be improved without significantly reducing the productivity.

Further, in the embodiment, since the first thin film layer is formed in a state where the substrate temperature is lower than the film formation temperature by the thermal CVD method, the bonding force between the substrate 4 and the film may be weakened and the adhesion may be deteriorated. In such a case, hydrogen (H) is passed through the gas supply pipe 40 on the upstream side of the radical generation unit 11.₂) A hydrogen supply unit for supplying gas is provided, and immediately after loading the substrate, hydrogen (H) is generated by the radical generation unit 11.₂) It is advisable to supply the hydrogen radicals generated by activating the gas with plasma onto the substrate 4 (RPH (Remote Plasma Hydrogenation) treatment). The surface is cleaned by hydrogen radicals, pollutants are eliminated, the surface of the substrate is terminated with hydrogen, and the adhesion to the next deposited film is improved. Therefore, after loading the substrate, hydrogen radicals are supplied to the substrate to perform surface treatment on the substrate, and then the film-forming raw material is supplied (step 202) and RPO treatment (step 203) is performed to bond the film and the substrate 4. The binding force is increased and the adhesion can be improved. It is considered that the improvement in adhesion is due to the fact that when hydrogen intervenes when the film and the substrate 4 are bonded at the atomic level, the bonding is likely to occur even in a state where the energy is relatively low, that is, when the substrate temperature is low.

[Third Embodiment] FIG. 11 shows a process flow according to the third embodiment. As shown in the figure, in the present embodiment, the step of adhering the raw material gas onto the substrate from the loading of the substrate into the reaction chamber (step 201) to the removal of the substrate from the reaction chamber (step 207). (Step 202) and a film (HfO) by supplying a reactant obtained by activating a gas containing oxygen atoms with plasma onto a substrate.₂The film formation is performed by repeating the step (step 203) of forming the film) a plurality of times in this order. That is, in the present embodiment, the film is formed by repeating the [film formation raw material supply (step 202) RPO treatment (step 203)] for n cycles from the beginning to the end without performing the second thin film layer forming step. .. Here, by performing the film forming raw material supply (step 202) and the RPO treatment (step 203) in this order, the effect that the EOT (effective film thickness) of the low dielectric constant film can be thinned can be obtained as described above. ..

In this case, it is preferable to perform purging with an inert gas (non-reactive gas) between the film-forming raw material supply (step 202) and the RPO treatment (step 203). Further, it is preferable to perform purging with an inert gas between the RPO treatment (step 203) and the supply of the film-forming raw material in the next cycle (step 202). By doing so, the amount of the raw material gas adsorbed on the substrate becomes uniform, and the raw material gas and the reactant can be prevented from coexisting in the atmosphere of the reaction chamber at the same time, so that the generation of particles can be prevented. ..

As an example, the substrate temperature is set to 250 to 300 ° C, the pressure in the reaction chamber is set to 50 to 300 Pa, and Hf- (MMP).₄Set the flow rate to 0.01 to 0.2 g / min, set [Film formation raw material supply (step 202) Inactive gas purge RPM treatment (step 203) Inactive gas purge] as one cycle, and repeat this for 80 cycles to HfO.₂A film was formed. Here, the time of one cycle is set to 40 seconds. The breakdown of 40 seconds is the raw material supply time to the substrate (step 202): 10 seconds, the inert gas purge time: 5 seconds, the RPO processing time (step 203): 20 seconds, and the inert gas purge time: 5 seconds. As a result, HfO formed per cycle₂The film thickness was about 0.6 Å / cycle, and when this was carried out for 80 cycles, the total film thickness was about 5 nm. Also, the HfO formed in this process₂The interface layer (low dielectric constant layer) of the film is in the Hf silicate state, and its thickness is estimated to be about 0.6 nm. This estimated value can be easily estimated from the electrical characteristics. In this case as well, HfO is performed in a state where the substrate temperature is lower than the film formation temperature by the thermal CVD method.₂Substrate 4 and HfO to form a film₂In some cases, the bonding force with the film is weakened and the adhesion is deteriorated. In this case as well, after loading the substrate, [supply of film-forming raw material (step 202) inert gas purge RPO treatment (step 203) inert gas purge ] Is preferably performed before the RPH treatment.

In each of the above-described embodiments, oxygen O is used to generate oxygen radicals.₂Was used, but O₂Besides N₂O, NO, O₃Oxygen-containing gas such as can be used. N₂O for O and NO₂In the same manner as above, it is activated by the radical generation unit 11 to generate oxygen radicals, which are then supplied to the reaction chamber 1. But N₂O and O₃May be supplied to the reaction chamber 1 as it is without being activated. This is because, although the oxygen radicals are supplied without being activated, oxygen radicals are generated by heat in the reaction chamber 1 after the supply, so that the oxygen radicals are substantially supplied to the substrate. Therefore, when the oxygen radical of the present invention is supplied onto the substrate, N₂O, O₃Is also included in the case of supplying as it is without activating.

Further, in the above-described embodiment, HfO in an amorphous state₂Although the case of forming a film has been described, the present invention can be widely applied to the case of forming a film containing Hf such as an amorphous Hf silicate film. Furthermore, the present invention is HfO.₂Not limited to membranes containing Hf such as membranes, Ta₂O₅Membrane and ZrO₂It can also be applied to the formation of other metal oxide films such as membranes. Examples of the film other than the film containing Hf and which can be formed by applying the present invention include the following films (1) to (8). (1) PET (Ta (OC)₂H₅)₅) TaO film (tantalum oxide film) (2) Zr- (MMP)₄ZrO film (zirconium oxide film) (3) Al- (MMP)₃AlO film (aluminum oxide film) (4) Zr- (MMP)₄And Si- (MMP)₄ZrSiO film (oxidized Zr silicate film) and ZrSiON film (acid nitriding Zr silicate film) (5) Zr- (MMP)₄And Al- (MMP)₃ZrAlO film and ZrAlON film using (6) Ti- (MMP)₄TiO film (titanium oxide film) (7) Ti- (MMP)₄And Si- (MMP)₄TiSiO and TiSiON films (8) Ti- (MMP)₄And Al- (MMP)₃TiAlO, TiAlON film using

Further, the base film for film formation is not limited to the silicon substrate, and the surface of the silicon substrate is thinly SiO.₂Thin Si on the surface of a silicon substrate or one with a film attached₃N₄It may be the one with a film attached.

<figref num="1">It is a process flow diagram by 1st Embodiment.</figref><figref num="2">It is a flow diagram of a process by a conventional example.</figref><figref num="3">It is a figure which shows the relationship between the substrate temperature and a gas cycle by 1st Embodiment.</figref><figref num="4">It is a figure which shows the relationship between the substrate temperature and a gas cycle by 2nd Embodiment.</figref><figref num="5">It is a figure which shows the relationship between the number of cycles, and the flatness during heating and heating of a substrate according to an embodiment.</figref><figref num="6">It is explanatory drawing of the 1st thin film layer formation process by embodiment.</figref><figref num="7">It is a conceptual explanatory view of the flatness of a thin film formed on a general substrate.</figref><figref num="8">It is a conceptual explanatory diagram of a general nuclear development process.</figref><figref num="9">It is a schematic explanatory view of the reaction chamber by embodiment.</figref><figref num="10">It is a conceptual explanatory view of the CVD reaction chamber of a conventional example.</figref><figref num="11">It is a process flow diagram by the 3rd Embodiment.</figref>

Code description

1 Reaction chamber 3 heater 4 board 5 Raw material supply pipe 6 Shower head (supply port) 6a Film-forming shower head (raw material gas supply port) 6b Radical shower head (radical supply port) 7a Exhaust port 9 Film formation raw material supply unit 10 Inert gas supply unit 11 Radical generation unit 25 Control device (control means) 20 ~ 24 valves