CN1716538A - Film-forming method and film-forming apparatus - Google Patents

Abstract

The present invention relates to a film formation method for semiconductor processing, in which a first process gas for film formation and a second process gas that reacts with the first process gas are supplied into a process chamber that accommodates a target substrate, and a thin film is formed on the target substrate by CVD. The film forming method alternately includes first to fourth steps. In the first step, first and second process gases are supplied to the process field. In the second step, the supply of the first and second process gases to the process field is stopped. In the third step, the supply of the first process gas to the process field is stopped while the supply of the second process gas to the process field is performed. In the fourth step, the supply of the first and second process gases to the process field is stopped.

Description

Film-forming method and film-forming apparatus

technical field

The present invention relates to a film forming apparatus and method for semiconductor processing for forming a thin film on a substrate to be processed such as a semiconductor wafer. Here, the so-called semiconductor processing refers to forming a semiconductor layer in a predetermined pattern on a substrate to be processed such as a wafer or a glass substrate for LCD (Liquid Crystal Display) or FPD (Flat Panel Display), Insulation layer, conductive layer, etc. Various processes are performed to manufacture structures including semiconductor devices or wiring, electrodes, etc. connected to semiconductor devices on the substrate to be processed.

Background technique

When manufacturing a semiconductor device constituting a semiconductor integrated circuit, various processes such as film formation, oxidation, diffusion, modification, annealing, and etching are performed on a substrate to be processed, such as a semiconductor wafer. Japanese Unexamined Patent Publication No. 2004-6801 discloses a method of performing these semiconductor treatments in a vertical (so-called batch) heat treatment apparatus. In this method, a semiconductor wafer is first transferred from a wafer cassette to a vertical wafer holder and supported in a multi-stage formation. In the wafer cassette, for example, 25 wafers can be accommodated, and 30 to 150 wafers can be loaded on the wafer holder. Then, the wafer holder is turned into the processing container from below, and at the same time, the processing container is hermetically sealed. Then, predetermined heat treatment is performed while controlling various processing conditions such as the flow rate of the processing gas, the processing pressure, and the processing temperature.

In recent years, along with the demand for higher integration and miniaturization of semiconductor integrated circuits, it is desired to reduce the thermal hysteresis in the manufacturing process of semiconductor devices and improve the characteristics of the devices. In a vertical processing apparatus, it is desired to improve the method of semiconductor processing according to certain requirements. For example, in the CVD (Chemical Vapor Deposition) method of film formation, there is a method of repeatedly forming one or more layers of atomic or molecular level thickness layers while intermittently supplying raw material gases. (For example, JP-A-6-45256 and JP-A-11-87341). Such a film-forming method is generally called ALD (Atomic layer Deposition atomic layer deposition) method, thereby, even if the wafer is not exposed to such a high temperature, it can be processed for the purpose.

Fig. 13 is a diagram showing the gas supply and RF application in the conventional film formation method in the case of forming a silicon nitride film (SiN) using dichlorosilane (DCS) as a silane-based gas and _NH3 as a nitride gas. Morphological timing diagram. As shown in FIG. 13, DCS and NH ₃ gases were intermittently alternately supplied in the processing container with a purge period interposed therebetween. RF (high frequency) is applied when NH ₃ gas is supplied to promote the nitriding reaction that generates plasma in the processing container. That is, DCS is first supplied into the processing container, whereby one or several layers of DCS are adsorbed on the wafer surface at the molecular level. The remaining DCS is discharged during cleaning. Then, plasma is generated by supplying NH ₃ , and a silicon nitride film is formed by nitriding at a low temperature. By repeating a series of such steps, a film having a predetermined thickness is completed.

In the above-mentioned film forming method, not only a relatively good step-like coverage is obtained, but also compared with the film forming method of high temperature CVD, due to the low temperature, the Si-H bond in the film can be reduced, and the characteristics of the film quality can be improved. . However, in such a conventional film forming method, although the reaction is accelerated by the plasma, the film forming rate is relatively low, and the productivity is also low.

Contents of the invention

An object of the present invention is to provide a film forming method and a film forming apparatus capable of greatly increasing the film forming rate while maintaining the high quality of the film.

A first aspect of the present invention is a film forming method for semiconductor processing, in which a first processing gas for film formation and a first processing gas that reacts with the first processing gas are supplied in a processing region that accommodates a substrate to be processed. Two process gases, the method for forming a thin film on the above-mentioned substrate to be processed by CVD, is characterized in that it includes the following intersecting steps:

a first step of supplying the first and second processing gases to the processing region,

a second step of stopping the supply of the first and second processing gases to the processing region,

a third step of stopping supply of the first processing gas to the processing region while supplying the second processing gas to the processing region;

A fourth step of stopping the supply of the first and second processing gases to the processing region.

A second aspect of the present invention is a film-forming method for semiconductor processing. The film-forming method includes supplying a first processing gas for film formation, a first processing gas that reacts with the first processing gas, into a processing region that accommodates a substrate to be processed. The second processing gas and the third processing gas different from any one of the first and second processing gases, the method for forming a thin film on the above-mentioned substrate to be processed by CVD, is characterized in that it includes the following intersecting steps:

While supplying the above-mentioned first and third processing gases to the above-mentioned processing area, the first process of stopping the supply of the above-mentioned second processing gas to the above-mentioned processing area, the above-mentioned first process includes: The period during which the state is supplied to the above processing area,

a second step of stopping the supply of the first to third processing gases to the processing region,

a third step of stopping supply of the first and third processing gases to the processing region while supplying the second processing gas to the processing region;

A fourth step of stopping the supply of the first to third processing gases to the processing region.

A third aspect of the present invention is a film-forming device for semiconductor processing, characterized in that it includes:

a processing container having a processing area for receiving a substrate to be processed,

A support member supporting the substrate to be processed in the processing region,

a heater for heating the above-mentioned substrate to be processed in the above-mentioned processing area,

Exhaust system for the discharge of gas in the above-mentioned treatment area,

a first processing gas supply system for supplying a first processing gas for film formation to the processing region,

a second processing gas supply system that supplies a second processing gas that reacts with the first processing gas to the processing region,

an excitation mechanism that selectively excites the second processing gas supplied to the processing region,

The control part that controls the operation of the above-mentioned devices.

A fourth aspect of the present invention is a computer-readable medium comprising program instructions executed in a processor, characterized in that,

Film formation for semiconductor processing that supplies a first processing gas for film formation and a second processing gas that reacts with the first processing gas into a processing area that accommodates the substrate to be processed, and forms a thin film on the substrate to be processed by CVD. In the device, when the above-mentioned program instructions are executed by the processor, the following steps are interactively implemented,

a first step of supplying the first and second processing gases to the processing region,

a second step of stopping the supply of the first and second processing gases to the processing region,

A third step of stopping supply of the first processing gas to the processing area while supplying the second processing gas to the processing area,

A fourth step of stopping the supply of the first and second processing gases to the processing region.

A fifth aspect of the present invention is a computer-readable medium containing program instructions for execution on a processor, characterized in that,

A first processing gas for film formation, a second processing gas that reacts with the first processing gas, and a third processing gas that is different from any of the first and second processing gases are supplied to the processing area that accommodates the substrate to be processed. In the film-forming device for semiconductor processing that forms a thin film on the above-mentioned substrate to be processed by processing gas by CVD, when the above-mentioned program instructions are executed by the processor, the following steps are alternately implemented,

While supplying the above-mentioned first and third processing gases to the above-mentioned processing area, the first process of stopping the supply of the above-mentioned second processing gas to the above-mentioned processing area, the above-mentioned first process has the step of exciting the above-mentioned third processing gas by an excitation mechanism The period during which the state is supplied to the above processing area,

a second step of stopping the supply of the first to third processing gases to the processing region,

A third step of stopping supply of the first and third processing gases to the processing region while supplying the second processing gas to the processing region,

A fourth step of stopping the supply of the first to third processing gases to the processing region.

In the first to fifth aspects, the first processing gas includes a silane-based gas, the second processing gas includes a nitriding gas or a nitrogen oxide gas, and the third processing gas includes a gas selected from nitrogen, a rare gas, and a nitrogen oxide gas. gas. For example, the above-mentioned first processing gas includes dichlorosilane (DCS), hexachlorodisilane (HCD), monosilane (SiH ₄ ), disilane (Si ₂ H ₆ ), hexamethyldisilazane (HMDS) , tetrachlorosilane (TCS), disilylamine (DSA), trisilylamine (TSA), and bis-tert-butylaminosilane (BTBAS). The second processing gas includes, for example, one or more gases selected from ammonia [NH ₃ ], nitrogen [N ₂ ], nitrous oxide [N ₂ O], and nitrogen monoxide [NO].

Other objects and advantages of the present invention will be stated in the following description, and some of them will be understood in detail from the description or through the practice of the present invention. The objects and advantages of the present invention can be realized and obtained by means of the ways and combinations particularly pointed out hereinafter.

Description of drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate preferred embodiments of the invention and, together with the general description given above and the detailed description of the preferred embodiment given below, serve to explain the principles of the invention .

FIG. 1 is a cross-sectional view showing a film formation apparatus (vertical CVD apparatus) according to a first embodiment of the present invention.

FIG. 2 is a cross-sectional plan view showing a portion of the apparatus shown in FIG. 1. FIG.

3 is a timing chart showing gas supply and RF application states in the film forming method of the first embodiment.

4 is a graph showing film thickness data of a silicon nitride film obtained in Experiment 1 of the first embodiment.

FIG. 5 is a graph showing the silicon nitride film formation rate obtained in Experiment 1. FIG.

FIG. 6 is a graph showing the in-plane uniformity of the silicon nitride film thickness obtained in Experiment 1. FIG.

FIG. 7 is a schematic diagram showing the results of infrared diffraction of the silicon nitride film obtained in Experiment 1. FIG.

8 is a timing chart showing gas supply and RF application in a film forming method according to a modified example of the first embodiment.

9 is a cross-sectional view showing a film formation apparatus (vertical CVD apparatus) according to a second embodiment of the present invention.

10 is a timing chart showing gas supply and RF application in the film forming method of the second embodiment.

11A is a graph showing the silicon nitride film formation rate obtained in Experiment 3 of the second embodiment.

FIG. 11B is a graph showing the rate of improvement in the silicon nitride film formation rate obtained in Experiment 3. FIG.

Fig. 12 is a block diagram showing an outline of the configuration of the main control section.

FIG. 13 is a timing chart showing gas supply and RF application in a conventional film forming method.

Detailed ways

Embodiments of the present invention will be described below with reference to the drawings. In the following description, the same symbols are used for structural elements having substantially the same function and structure, and descriptions are repeated only when necessary.

<First Embodiment>

FIG. 1 is a cross-sectional view showing a film formation apparatus (vertical CVD apparatus) according to a first embodiment of the present invention. FIG. 2 is a cross-sectional plan view showing a portion of the apparatus shown in FIG. 1. FIG. This film forming apparatus 2 is supplied with a source gas (first process gas) containing dichlorosilane (DCS) as a silane-based gas and a support gas (second process gas) containing ammonia (NH ₃ ) as a nitriding gas. , It is formed by depositing a silicon nitride film (SiN).

The film-forming device 2 has a cylindrical processing container 4, which defines a processing area 5 for accommodating a plurality of semiconductor wafers (substrates to be processed) stacked at a certain interval for processing. The processing container 4 has a Open and topped. The entire processing vessel 4 is made of, for example, quartz. On the top of the processing container 4, a top plate 6 made of quartz is arranged to seal the top. A cylindrical manifold 8 is connected to the opening at the lower end of the processing container 4 through a sealing member 10 such as an O-ring.

The manifold 8 is made of, for example, stainless steel, and is supported at the lower end of the processing vessel 4 . Through the opening of the lower end of the manifold 8 , the wafer holder 12 made of quartz is raised and lowered, thereby loading/unloading the wafer holder 12 into the processing container 4 . A plurality of semiconductor wafers W serving as substrates to be processed are placed in multiple stages on the wafer holder 12 . For example, in this embodiment, for example, about 50 to 100 wafers W with a diameter of 300 mm can be supported on the pillars 12A of the wafer holder 12 in multiple stages at approximately equal pitches.

The wafer holder 12 is placed on a workbench 16 by means of an insulated cylinder 14 made of quartz. The table 16 is supported on a rotating shaft 20 , and the rotating shaft passes through a cover 18 made of stainless steel, for example, at the lower end of the opening and closing manifold 8 .

The penetrating portion of the rotary shaft 20 is provided with, for example, a magnetic fluid seal 22 to support the rotary shaft 20 to be rotatable while maintaining airtightness. Around the cap 18 and at the lower end of the manifold 8, a sealing member 24 formed of, for example, an O-ring or the like is provided to maintain the airtightness in the container.

The rotating shaft 20 is mounted on the front end of an articulated arm 26 supporting a lifting mechanism 25 such as a stand lift. The wafer holder 12 is raised and lowered together with the cover 18 and the like by the raising and lowering mechanism 25 . In addition, the stage 16 is also fixedly provided on the cover 18 side, and the wafer W can be processed without rotating the wafer holder 12 .

A gas supply portion for supplying a predetermined processing gas to the processing region 5 in the processing chamber 4 is connected to a side surface of the manifold 8 . The gas supply section includes an assist gas supply system (second process gas supply system) 28 , a source gas supply system (first process gas supply system) 30 , and a purge gas supply system 32 . The source gas supply system 30 supplies, for example, a silane-based gas DCS (dichlorosilane) as a film-forming source gas. The supporting gas supply system 28 supplies, for example, ammonia gas (NH ₃ ) as a supporting gas (second processing gas) that reacts with the source gas while selectively forming a plasma. The purge gas supply system 32 supplies an inert gas such as nitrogen N ₂ as a purge gas. In the source gas and supporting gas (first and second process gases), an appropriate amount of carrier gas may be mixed as necessary, but will not be mentioned below for simplification of description.

Specifically, the raw gas supply system 30 has two gas dispersing nozzles 36, which are made of quartz tubes and extend inwardly through the sidewall of the manifold 8 and turn upwards (refer to FIG. 2 ). In each gas distribution nozzle 36 , a plurality of gas injection holes 36A are formed at regular intervals along the longitudinal direction (vertical direction) of all the wafers W on the wafer holder 12 . Each gas injection hole 36A forms an air flow parallel to the plurality of wafers W on the wafer holder 12, and supplies the source gas substantially uniformly in the horizontal direction. It is also possible to arrange only one gas dispersing nozzle 36 instead of two.

The support gas supply system 28 also has two gas dispersion nozzles 34, which are also made of quartz tubes, and extend inwardly through the side wall of the manifold 8 and turn upwards. In the gas distribution nozzle 34 , a plurality of gas injection holes 34A are formed at regular intervals along the longitudinal direction (vertical direction) of all the wafers W on the wafer holder 12 . Each gas injection hole 34A forms an air flow parallel to the plurality of wafers W on the wafer holder 12, and supplies the supporting gas substantially uniformly in the horizontal direction. The purge gas supply system 32 has gas nozzles 38 provided through the side walls of the manifold 8 .

The nozzles 34 , 36 , 38 are connected to NH ₃ gas, DCS gas, and N ₂ gas sources 41 , 43 , 45 through gas supply lines (gas passages) 42 , 44 , 46 , respectively. On-off valves 42A, 44A, 46A and flow controllers 42B, 44B, 46B such as mass flow controllers are disposed on the gas supply lines 42 , 44 , 46 . Thereby, NH ₃ gas, DCS gas, and N ₂ gas can be supplied while controlling these gases separately.

On a part of the side wall of the processing container 4, a gas exciting part 50 is arranged along the height direction thereof. On the other side of the processing container 4 opposite to the gas excitation part 50, an elongated exhaust port 52 is arranged to discharge the internal ambient gas to form a vacuum, for example, by cutting the side wall of the processing container 4 in the vertical direction. A part is formed.

Specifically, the gas exciting portion 50 has a vertically elongated opening 54 formed by cutting the side wall of the processing container 4 with a constant width along the vertical direction. The opening 54 is covered with a cover 56 made of quartz, which is welded to the outer wall of the processing container 4 to be airtight. The cover 56 has a concave cross section, protrudes to the outside of the processing container 4, and has a vertically elongated shape.

With such a structure, the gas excitation part 50 protrudes from the side wall of the processing container 4 and opens to the inside of the processing container 4 on one side. That is, the inner space of the gas excitation part 50 communicates with the processing region 5 inside the processing container 4 . The opening 54 is formed to have a sufficient length in the vertical direction so that it can cover all the wafers held on the wafer holder 12 in the height direction.

On the outer surfaces of both side walls of the cover 56, a pair of elongated electrodes 58 are arranged to face each other along its longitudinal direction (vertical direction). A high-frequency power source 60 for generating plasma is connected to the electrode 58 through a power supply line. By applying a high-frequency voltage of, for example, 13.56 MHz to the electrodes 58 , a high-frequency electric field for exciting plasma is formed between the pair of electrodes 58 . In addition, the frequency of the high-frequency voltage is not limited to 13.56 MHz, and other frequencies such as 400 kHz may also be used.

The gas distribution nozzle 34 is located at a lower position than the lowermost wafer on the wafer holder 12 , and is curved outward in the radial direction of the processing chamber 4 . Then, the gas dispersion nozzle 34 is erected vertically at the deepest position in the gas exciting part 50 (the part farthest from the center of the processing chamber 4 ). As shown in FIG. 2, the gas dispersing nozzle 34 is provided in a region sandwiched by a pair of opposing electrodes 58 (the position where the high-frequency electric field is the strongest), that is, in a plasma generation region where plasma is actually mainly generated. PS outward position. The second process gas containing _NH gas ejected from the gas injection holes 34A of the gas dispersion nozzle 34 is injected toward the plasma generation region PS, where it is excited (decomposed or activated), and is supplied to the wafer holder in this state. 12 on wafer W.

On the outer side of the cover 56 , an insulating protective case 64 made of, for example, quartz is installed to cover the cover 56 . In a portion facing the electrode 58 as the inner side of the insulating sheath 64, a cooling mechanism (not shown) constituted by a refrigerant passage is arranged. Cooled nitrogen gas, for example, flows through the refrigerant channel to cool the electrode 58 . In addition, a shield (not shown) is provided on the outer side of the insulating sheath 64 to cover it and prevent high-frequency leakage.

Near the outside of the opening 54 of the gas exciting part 50 , that is, on both sides of the outside of the opening 54 (inside the processing chamber 4 ), two gas dispersing nozzles 36 are arranged upright. The source gas containing DCS gas is sprayed toward the center of the processing chamber 4 from each gas nozzle 36A formed on the gas distribution nozzle 36 .

In addition, an exhaust cover member 66 made of quartz and having a U-shaped cross section is attached to the exhaust port 52 facing the gas excitation part 50 by welding to cover the exhaust port. The exhaust cover member 66 extends upward along the side wall of the processing container 4 to form a gas outlet 68 above the processing container 4 . A vacuum exhaust system GE equipped with a vacuum pump and the like is connected to the gas outlet 68 .

To surround the processing container 4, a heater 70 for heating the ambient gas and the wafer W in the processing container 4 is provided. A thermocouple (not shown) for controlling the heater 70 is provided near the exhaust port 70 in the processing container 4 .

Furthermore, the film forming apparatus 2 includes a main control unit 48 composed of a computer or the like for controlling the operation of the entire apparatus. The main control section 48 performs the film formation process described below based on the processing parameters of the film formation process, such as the thickness or composition of the film to be formed, stored in advance in its attached memory section. The relationship between the flow rate of the process gas and the thickness and composition of the film is stored in this storage section as pre-stored control data. Therefore, the main control part 48 can control the lifting mechanism 25, the gas supply systems 28, 30, 32, the exhaust system GE, the gas excitation part 50, the heater 70, etc. based on these stored processing parameters or control data.

Next, a method of film formation (so-called ALD film formation) using the apparatus shown in FIG. 1 will be described. Briefly, in this film forming method, source gas (first process gas for film formation) and supporting gas (second process gas reacting with the first process gas) are supplied into process region 5 containing wafer W, and CVD forms a thin film on the wafer W.

First, a wafer holder 12 holding a plurality of, for example, 50 to 100 wafers W with a size of 300 mm at normal temperature is loaded into the processing container 4 set at a predetermined temperature. Then, while the inside of the processing container 8 is evacuated and maintained at a predetermined processing pressure, the temperature of the wafer is raised until it stabilizes at the processing temperature for film formation.

Next, the source gas containing DCS gas and the supporting gas containing NH ₃ gas are intermittently supplied from the gas distribution nozzles 36 and 34 while controlling the respective flow rates. Specifically, the source gas is supplied from the gas injection holes 36A of the gas distribution nozzle 36 so that parallel gas flows are formed with respect to the plurality of wafers W on the wafer holder 12 . In addition, the assist gas is supplied from the gas injection holes 36A of the gas distribution nozzle 34 so that parallel gas flows are formed with respect to the plurality of wafers W on the wafer holder 12 . The two gases react on the wafer W, whereby a silicon nitride film is formed on the wafer W.

When the assist gas supplied from the gas injection holes 36A of the gas distribution nozzle 34 passes through the plasma generation region PS between the pair of electrodes 58 , a part thereof is selectively plasma-formed. At this time, free radicals (active seeds) such as N ^* , NH ^* , NH ₂ ^* , NH ₃ ^* , etc. are generated (the symbol * indicates a free radical). These radicals flow from the opening 54 of the gas excitation part 50 to the center of the processing chamber 4, and are supplied between the wafers W in a laminar flow state.

The aforementioned radicals react with DCS gas molecules adsorbed on the surface of the wafer W, whereby a silicon nitride film is formed on the wafer W. On the other hand, the same reaction takes place at the site where radicals are adsorbed on the surface of the wafer W, and a silicon nitride film is formed on the wafer W when the DCS gas flows.

3 is a timing chart showing gas supply and RF application states in the film forming method of the first embodiment. As shown in FIG. 3 , in the film forming method of this embodiment, first to fourth periods (first to fourth processes) T1 to T4 are alternately repeated. That is, the cycle consisting of the first to fourth periods T1 to T4 is repeated a plurality of times, and the silicon nitride film formed in each cycle is laminated with thin films to obtain a silicon nitride film having a final thickness.

Specifically, in the first period (first step) T1, a source gas (shown as DCS in FIG. 3 ) and a support gas (shown as NH ₃ in FIG. 3 ) are supplied to the processing region 5 . In the second period (second step) T2, the supply of the source gas and the assist gas to the processing region 5 is stopped. In the third period (third step) T3 , supply of the source gas to the processing area 5 is stopped while supplying the supporting gas to the processing area 5 . In addition, in the third period T3 , by turning on the RF power supply 60 , the assisting gas in the gas excitation part 50 is plasma-formed, thereby supplying the assisting gas in an excited state to the processing region 5 . In the fourth period (fourth step) T4, the supply of the source gas and the assist gas to the processing region 5 is stopped.

The second and fourth periods T2 and T4 are used during the purge period to remove residual gas in the processing container 4 . The so-called cleaning here refers to evacuating the inside of the processing container 4 while flowing an inert gas such as _N gas, or stopping the supply of all gases, and evacuating the inside of the processing container 4 to remove the inside of the processing container 4. of residual gas. Furthermore, during the first and third periods T1 and T3, when the source gas and the assist gas are supplied, the evacuation of the processing chamber 4 may be stopped. However, when the processing chamber 4 is evacuated while supplying the source gas and the supporting gas, the processing chamber 4 can be continuously evacuated throughout the first to fourth periods T1 to T4.

In Fig. 3, the first period T1 is set to about 1-20 seconds, such as about 10 seconds, the second period T2 is set to about 1-20 seconds, such as about 10 seconds, and the third period T3 is set to about 1 second. ~30 seconds, for example, about 10 seconds, and the fourth period T4 is set to be about 1 to 20 seconds, for example, about 10 seconds. However, these times are merely examples, and are not limited to these numerical values.

As described above, the purge periods T2 and T4 are interleaved between the period T1 in which the supporting gas containing NH ₃ gas and the source gas containing DCS are supplied together, and the period T3 in which the supporting gas containing NH ₃ gas is supplied alone. Thereby, while maintaining the high quality of the formed silicon nitride film, the film formation rate can be greatly increased. We think that there are the following reasons. That is, when the source gas and the supporting gas are supplied together during the first period T1, a part of the DCS molecules adsorbed on the wafer surface is incompletely nitrided by the simultaneously supplied NH ₃ gas. Therefore, in the first period T1, when the adsorption amount is not saturated, the adsorption of DCS gas molecules continues, and as a result, the adsorption amount of DCS gas is higher than that in the conventional method (flowing raw material gas alone). Then, in the third period T3, the incompletely reacted portion is fully reacted by NH ₃ gas excited by plasma so that a silicon nitride film is formed at a high film formation rate.

The film-forming treatment described above was performed under the following treatment conditions. The flow rate of the DCS gas is in the range of 100 to 3000 sccm, for example, 1000 sccm (1 slm). The flow rate of NH ₃ gas is in the range of 100-5000 sccm, for example, 1000 sccm. The treatment temperature is lower than the usual CVD treatment, specifically 180-600°C (exclusive), for example, 550°C. When the treatment temperature is lower than 180°C, the reaction cannot occur and there is almost no film accumulation. However, when the processing temperature is higher than 600°C, a deposited film with poorer quality than CVD will be formed.

The processing pressure ranges from 27Pa (0.2Torr) to 1330Pa (10Torr), for example, 1Torr in the first period (adsorption process) T1, and 0.3Torr in the third period (plasma nitridation process) T3. When the processing pressure is less than 27Pa, the film forming speed is lower than the practical level. In the case where the processing pressure is greater than 1330 Pa, the plasma cannot be sufficiently excited.

In the first period (adsorption step) T1, the flow ratio [DCS/NH ₃ ] of gas DCS and NH ₃ is set within a range of about 1/10 to 10. When the flow ratio of gas NH ₃ is too small, the effect of simultaneously supplying NH ₃ gas will not be produced. And when the flow ratio of _NH3 is too much, no film-forming bulk will be produced.

<Experiment 1>

In Experiment 1, silicon nitride films formed by the film formation method of the first embodiment using the timing chart shown in FIG. 3 and the conventional film formation method (ALD method) according to the timing chart shown in FIG. 13 were evaluated. In the two examples PE1 and PE2 of the first embodiment, the supplied amounts of NH ₃ were taken to be 500 sccm (0.5 slm) and 1000 sccm (1 slm), respectively. In Comparative Example CE1 of the conventional film formation method, the supply amount of NH ₃ was set to 1000 sccm (1 slm). The number of cycles of film formation was 160 in total.

FIG. 4 is a graph showing film thickness data of a silicon nitride film obtained in Experiment 1. FIG. FIG. 5 is a graph showing the silicon nitride film formation rate obtained in Experiment 1. FIG. FIG. 6 is a graph showing the in-plane uniformity of the film thickness of the silicon nitride film obtained in Experiment 1. FIG. FIG. 7 is a graph showing the results of infrared diffraction of a silicon nitride film obtained in Experiment 1. FIG. "TOP", "CTR" and "BTM" in FIGS. 4 to 7 denote the positions of the semiconductor wafers located at the top, center and bottom of the wafer holder, respectively.

Regarding the film thickness TH (nm) of the silicon nitride film shown in FIG. 4, in Comparative Example CE1, TH is about 15 nm regardless of the position of the wafer. In both embodiments PE1 and PE2, TH is around 20nm regardless of the position of the wafer. That is, it was confirmed that both Examples PE1 and PE2 can deposit a silicon nitride film having an equal thickness as compared with Comparative Example CE1.

Regarding the film formation rate Rth per cycle (nm/cycle) shown in FIG. 5 , in Comparative Example CE1, Rth was about 0.1 nm. In the two examples PE1 and PE2, Rth is about 0.12-0.13 nm. That is, it can be confirmed that the film formation speed is increased in both Examples PE1 and PE2 compared with Comparative Example CE1.

Regarding the uniformity PTuni (±%) of the film thickness shown in FIG. About 3.0 to 4.0%. That is, it was confirmed that the in-plane uniformity of the film thickness can be improved in both Examples PE1 and PE2 compared with Comparative Example CE1.

Regarding the infrared intensity LD (a.u) obtained from the infrared diffraction of the film shown in Fig. 7, in Comparative Example CE11, at the position of wavenumber 2200, the "Si-H bond" is displayed on the LD. of peak P1. As Comparative Example CE11, a silicon nitride film formed by LP (low pressure)-CVD using hexachlorodisilane (HCD) as a process gas was used. On the other hand, in Example PE1, the LD was substantially flat as a whole. That is, it was confirmed that the film quality of the film formed in Example PE1 was better than that in Comparative Example CE11.

According to the timing chart of FIG. 3 , RF is not applied during T1 when the supporting gas containing NH ₃ gas and the source gas containing DCS gas are supplied together, and RF is applied during T3 when the supporting gas containing NH ₃ gas is supplied alone. This timing diagram can be replaced by the applied RF state shown in FIG. 8 . FIG. 8 is a film forming method in a modified example of the first embodiment, showing timing charts of gas supply and RF application.

According to the timing chart of FIG. 8 , RF is applied to excite during the period T1 during which the supporting gas containing NH ₃ gas and the source gas containing DCS gas are supplied together and the period T3 during which the supporting gas containing NH ₃ gas is separately supplied. support gas. In this case, during the first period T1, the supporting gas is excited when the source gas flows, and DCS and NH ₃ radicals are adsorbed on the semiconductor wafer W. Then, in the third period T3, the incompletely reacted portion is completely reacted by NH ₃ gas excited by plasma, and a silicon nitride film is formed at a high film forming rate.

<Experiment 2>

_N2 gas can be used instead of _NH3 gas as the nitriding gas. In the method according to FIG. 3 , the film formation experiment 2 of the silicon nitride film was performed using N ₂ gas instead of NH ₃ gas. As a result, the film formation rate was 0.1 nm/cycle. In addition, in the method of FIG. 8 , the silicon nitride film was formed using N ₂ gas instead of NH ₃ gas, and the film formation rate was 0.5 nm/cycle. Therefore, it was confirmed that by the method of FIG. 8 , when N ₂ gas is used instead of NH ₃ gas as the nitriding gas, the film formation rate can be greatly increased.

<Second Embodiment>

9 is a cross-sectional view showing a film formation apparatus (vertical CVD apparatus) according to a second embodiment of the present invention. The film forming apparatus 2X of the second embodiment includes an assist gas supply system (second process gas supply system) 28 , a source gas supply system (first process gas supply system) 30 , and a purge gas supply system 32 , and an assist gas supply system (third process gas supply system) 84 . The assist gas supply system 84 supplies assist gas that is different from both the source gas and the assist gas. Specifically, the assist gas contains a gas selected from nitrogen gas, rare gas, and nitrogen oxide gas, and in this embodiment, is composed of, for example, N ₂ or Ar gas. The film forming apparatus 2X shown in FIG. 9 has substantially the same structure as the film forming apparatus 2 shown in FIG. 1 with respect to parts other than those related to the assist gas supply system 84 .

The assist gas supply system 84 has the same gas distribution nozzle 34 as the assist gas supply system 28 , and therefore shares the gas injection holes 34A formed in the gas distribution nozzle 34 . To this end, the nozzle 34 is connected to a gas source 85 of N ₂ or Ar gas via a gas supply line (gas channel) 86 of an auxiliary gas supply system 84 . On the gas supply line 86 are provided an on-off valve 86A and a flow controller 86B such as a mass flow controller. This makes it possible to supply gas while controlling the flow rate of _N2 or Ar gas. As described above, nitrogen oxide gas may be used as the auxiliary gas instead of nitrogen gas or inert gas such as rare gas.

As described above, the gas dispersion nozzle 34 is made of a quartz tube, and extends inwardly through the side wall of the manifold 8 and bends upward. In the gas distribution nozzle 34 , a plurality of gas injection holes 34A are formed at predetermined intervals along its length (vertical direction) so as to face all the wafers W on the wafer holder 12 . Each gas injection hole 34A forms a parallel gas flow toward a plurality of wafers W on the wafer holder 12, and supplies support gas or assist gas substantially uniformly in the horizontal direction. The assist gas supply system 84 may not share the gas distribution nozzle 34 with the assist gas supply system 28 , and may be provided with a gas distribution nozzle for assist gas at the same time as the gas distribution nozzle 34 .

Next, a film formation method (so-called ALD film formation) performed using the apparatus shown in FIG. 9 will be described. Roughly speaking, in this film forming method, a source gas (first process gas for film formation) and an assisting gas (second process gas reacting with the first process gas) are supplied into the process region 5 in which the wafer W is accommodated, and as described above, The assist gas (third process gas) forms a thin film on the wafer W by CVD.

First, the wafer holder 12 holding a plurality of, for example, 50 to 100 wafers W with a size of 300 mm at room temperature is transported into the processing container 4 set at a predetermined temperature. Then, while evacuating the inside of the processing chamber 8 to maintain a predetermined processing pressure, the temperature of the wafer is raised until it stabilizes at the processing temperature for film formation.

Next, the source gas containing DCS, the auxiliary gas containing NH ₃ , and the auxiliary gas are intermittently supplied from the gas distribution nozzles 36 and 34 while controlling the flow rates, respectively. Specifically, the source gas is supplied from the gas injection holes 36A of the gas distribution nozzle 36 so as to form parallel gas flows against the plurality of wafers W on the wafer holder 12 . In addition, from the gas injection holes 36A of the gas distribution nozzle 34 , the supporting gas and the assisting gas are supplied so as to form parallel gas flows against the plurality of wafers W on the wafer holder 12 . The DCS gas and the NH ₃ gas react on the wafer W, whereby a silicon nitride film is formed on the wafer W.

FIG. 10 is a timing chart showing gas supply and RF application in the film forming method of the second embodiment. As shown in FIG. 10 , in the film forming method of this embodiment, the first to fourth periods (first to fourth processes) T11 to T14 are alternately repeated. That is, the cycle consisting of the first to fourth periods T11 to T14 is repeated a plurality of times, and the silicon nitride film of the final thickness is obtained by laminating thin films of the silicon nitride film formed in each cycle.

Specifically, in the first period (first process) T11, on the one hand, a source gas (shown as DCS in FIG. 10 ) and an auxiliary gas (shown as _N2 or Ar in FIG. 10 ) are supplied to the processing region 5, Simultaneously, the supply of the supporting gas (shown as NH ₃ in FIG. 10 ) to the processing region 5 is stopped. In the first period T11 , the RF power supply 60 is turned on, the assist gas is plasma-formed by the gas excitation unit 50 , and the assist gas in an excited state is supplied to the processing region 5 . In the second period (second step) T12, supply of the raw material gas, the auxiliary gas, and the auxiliary gas to the processing region 5 is simultaneously stopped. In the third period (third step) T13 , supply of the source gas and the assist gas to the processing region 5 is stopped while the assist gas is being supplied to the processing region 5 . On the other hand, in the third period T13, the RF power supply 60 is turned on from the middle, and the supporting gas is plasma-formed by the gas excitation part 50, thereby supplying the supporting gas in an excited state to the processing region 5 only in the sub-period T13b. . In the fourth period (fourth step) T14, the supply of the raw material gas, the auxiliary gas, and the auxiliary gas to the processing region 5 is stopped.

The second and fourth periods T12 and T14 are used as purge periods to discharge residual gas in the processing container 4 . The so-called cleaning here refers to vacuum exhausting the inside of the processing container 4 while flowing an inert gas such as _N2 gas, or completely stopping the supply of various gases, and vacuum exhausting the inside of the processing container 4 to remove the processing container 4. residual gas in. During the first and third periods T11 and T13, the evacuation of the processing chamber 4 may be stopped while supplying the source gas, the auxiliary gas, and the auxiliary gas. However, when the process container 4 is evacuated while supplying the source gas, assist gas, and assist gas, the process container 4 may be continuously evacuated throughout the first to fourth periods T11 to T14.

In Fig. 10, the first period T11 is set to about 1 to 20 seconds, for example about 10 seconds, the second period T12 is set to about 1 to 20 seconds, for example about 10 seconds, and the third period T13 is set to about 1 to 30 seconds , for example about 20 seconds, the sub-period T13b is set at about 1-25 seconds, for example about 15 seconds, and the fourth period T14 is set at about 1-20 seconds, for example about 10 seconds. However, these times are merely examples and are not limited to these numerical values.

As described above, by adding and exciting the auxiliary gas, the decomposition of the raw material gas supplied at the same time is promoted by the active seeds of the auxiliary gas. As a result, the film formation rate of the silicon nitride film can be increased. At this time, especially when _N2 gas is used as an auxiliary gas, not only the decomposition of the raw material gas can be promoted, but also the active seeds of nitrogen and the active seeds of silicon can be directly combined to form SiN directly. As a result, the film formation rate of the silicon nitride film can be further increased.

In the second embodiment, the processing temperature and processing pressure, and the flow rates of various gases such as DCS gas and NH ₃ gas are the same as those in the first embodiment. The flow rate of the auxiliary gas is set to be lower than the flow rate of DCS gas as the source gas, for example, about 1/10 of the flow rate of DCS gas.

In the third period T13, after the predetermined time Δt has elapsed, the RF power supply 60 is turned on, and the assisting gas at the gas excitation part 50 is plasmaized, thereby supplying gas in an excited state to the processing region 5 only in the sub-period T13b. support gas. This so-called predetermined time Δt is the time until the NH ₃ gas flow is stabilized, for example, about 5 seconds. However, as in the first embodiment, the assisting gas may be plasma-formed in the gas excitation part 50 throughout the supply of the assisting gas. Turning on the RF power supply to generate plasma after the flow rate of the supporting gas is stabilized in this way can improve the uniformity of the active seed concentration between the two surfaces of the wafer W (in the height direction).

<Experiment 3>

Evaluation Experiment 3 was performed to form a silicon nitride film using the film forming method of the second embodiment according to the timing chart shown in FIG. 10 and the conventional film forming method (ALD) according to the timing chart shown in FIG. 13 . In the two examples PE11 and PE12 of the second embodiment, N ₂ gas and Ar gas are used as auxiliary gases, respectively. Comparative Example CE1 of the conventional film formation method does not use an assist gas, and follows the timing chart shown in FIG. 13 (substantially the same as Comparative Example CE1 of Experiment 1). The number of cycles of film formation was 160 in total.

FIG. 11A is a graph showing the film formation rate of the silicon nitride film obtained in Experiment 3. FIG. FIG. 11B is a graph showing the rate of improvement in the silicon nitride film formation rate obtained in Experiment 3. FIG. Furthermore, "TOP", "CTR" and "BTM" in FIG. 11A and FIG. 11B indicate the top, center and bottom positions of the semiconductor wafer in the wafer holder, respectively.

Regarding the film formation rate Rth (nm/cycle) corresponding to one cycle shown in FIG. 11A , in Comparative Example CE1, Rth was about 0.1 nm regardless of the position of the wafer. In Example PE11 using N ₂ gas as an assist gas, Rth is about 0.45 to 0.55 nm. In Example PE12 using Ar gas as an assist gas, Rth was about 0.25 to 0.4 nm.

Regarding the film formation rate improvement rate IRth (%) shown in FIG. 11B , in Example PE11 using N ₂ gas as an assist gas, IRth was about 150 to 300%. In Example PE12 using Ar gas as an assist gas, IRth was about 300 to 500%.

That is, compared with Comparative Example CE1, it was confirmed that both Examples PE11 and PE12 can increase the film formation rate. In addition, the film-forming rate of Example PE11 was also higher than that of Example PE12, and it is considered that the reason is as follows. That is, as mentioned above, the active seeds of _N2 gas not only promote the decomposition of the raw material gas, but also can directly react with the excited silicon to form silicon nitride.

<Common Items and Variation Examples with First and Second Embodiments>

The methods of the first and second embodiments are carried out under the control of the main control section 48 based on the processing program as described above. FIG. 12 is a schematic block diagram showing the configuration of the main control section 48 . The main control unit 48 has a CPU 210, and a storage unit 212, an input unit 214, an output unit 216, and the like are connected thereto. In the storage section 212, processing programs and method parameters are stored. The input part 214 includes an input device for interacting with a user, such as a keyboard or a pointing device, and a drive for a storage medium. The output section 216 outputs control signals for controlling each device of the processing device. Figure 12 also shows a storage medium 218 that can be taken offline.

The methods of the above-described embodiments can be applied to various semiconductor processing devices by writing them on a computer-readable storage medium as program instructions to be executed on a processor. Alternatively, such program instructions can be applied to various semiconductor processing devices transmitted via a communication medium. This storage medium is, for example, a magnetic disk (floppy disk, hard disk (one example is the hard disk in the storage section 212), etc.), an optical disk (CD, DVD, etc.), a magneto-optical disk (MO, etc.), a semiconductor memory, and the like. The computer that controls the operation of the semiconductor processing device implements the above method by reading program instructions stored in the storage medium and executing them on the processor.

In the first and second embodiments, DCS gas is used as the silane-based gas of the source gas. However, it is not limited thereto. As the raw material gas, a gas selected from dichlorosilane (DCS), hexachlorodisilane (HCD), monosilane [SiH ₄ ], disilane [Si ₂ H ₆ ], hexamethyldisilane, One or more gases of aminopropane (HMDS), tetrachlorosilane (TCS), disilylamine (DSA), trisilylamine (TSA) and bis-tert-butylaminosilane (BTBAS).

In addition, in the first and second embodiments, nitrogen oxide gases such as nitrous oxide [N ₂ O] and nitrogen oxide [NO] may be used as supporting gas instead of nitriding gases such as NH ₃ gas and N ₂ gas. It is also possible to use an oxidizing gas instead of a nitriding gas as a supporting gas.

In addition, in the second embodiment, a rare gas is used as an auxiliary gas, but it is not limited to Ar gas, and He, Ne, Kr, Xe, etc. can be used. Nitrogen oxides such as dinitrogen oxide [N ₂ O], nitrogen oxide [NO], and nitrogen dioxide [NO ₂ ] can also be used as an auxiliary gas.

In the first and second embodiments described above, as the film forming apparatus 2, there is a combined structure in which the excitation portion 50 for forming plasma and the processing container 4 are integrated. Alternatively, the excitation unit 50 and the processing container 4 may be provided separately, NH ₃ gas may be previously excited outside the processing container 4 (so-called remote plasma), and the excited NH ₃ gas may be supplied into the processing container 4 . The substrate to be processed is not limited to a semiconductor wafer, and may be other substrates such as LCD substrates and glass substrates.

Additional advantages and modifications will readily appear to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and representative embodiments shown and described herein. Various changes may be made without departing from the spirit and scope of the general inventive concept as defined in the claims and their equivalents.

Claims (30)

1. film build method that semiconductor processes is used, this film build method be supply with in the processing region that holds processed substrate that film forming uses first handle gas and with described first handle second of gas reaction and handle gas, by CVD film forming method on described processed substrate, it is characterized in that: this method comprises following intersection operation:

Supply with first operation of the described first and second processing gases to described processing region;

Stop to supply with second operation of the described first and second processing gases to described processing region;

Supplying with the described second processing gas to described processing region when, stop to supply with the 3rd operation of the described first processing gas to described processing region; With

Stop to supply with the 4th operation of the first and second processing gases to described processing region.

2. the method described in claim 1 is characterized in that: described the 3rd operation comprise by excitation mechanism make described second handle gas with excited state supply with described processing region during.

3. the method described in claim 2 is characterized in that: described first operation do not comprise by described excitation mechanism excite described second handle gas during.

4. the method described in claim 2 is characterized in that: described first operation be included in by described excitation mechanism make described second handle gas with excited state supply with described processing region during.

5. the method described in claim 2, it is characterized in that: described excitation mechanism is included in the space that is communicated with described processing region, be configured in described second and handle the supply port of gas and the plasma generation area between the described substrate, described second handles gas is excited by described plasma generation area the time.

6. the method described in claim 5 is characterized in that: described first handles gas supplies with described processing region between described plasma generation area and described substrate.

7. the method described in claim 1 is characterized in that: the described second and the 4th operation comprise respectively to described processing region supply with purge gas during.

8. the method described in claim 1 is characterized in that: in the operation that forms described film, continue the exhaust in the described processing region.

9. the method described in claim 1 is characterized in that: described first handles gas contains silane-based gas, and described second handles gas contains nitriding gas or nitrogen oxidizing gas.

10. the method described in claim 9, it is characterized in that: described first handles gas contains more than one the gas that is selected from dichlorosilane, hexachloro-silane, single silane, disilane, hexamethyldisilazane, tetrachloro silicane, disilazane, nitrilotrisilane, dual-tert-butyl amino silane, and described second handles gas contains and be selected from ammonia, nitrogen, nitrous oxide, nitric oxide production more than one gas.

11. semiconductor processes film build method, this film build method be supply with in the processing region that holds processed substrate that film forming uses first handle gas, with described first handle second of gas reaction handle gas and with first and second the 3rd any all different processing gases of handling in the gases, by CVD film forming method on described processed substrate, it is characterized in that: this method comprises following intersection operation:

Supplying with the described first and the 3rd processing gas to described processing region when, stop to supply with first operation of the described second processing gas to described processing region, described first operation has by excitation mechanism, make the described the 3rd handle gas with excited state supply with described processing region during;

Stop to supply with second operation of described first to the 3rd processing gas to described processing region;

Supplying with the described second processing gas to described processing region when, stop to supply with the 3rd operation of the described first and the 3rd processing gas to described processing region; With

Stop to supply with the 4th operation of first to the 3rd processing gas to described processing region.

12. the method described in claim 11, it is characterized in that: described excitation mechanism have with space that described processing region is communicated with in, be configured in the described the 3rd and handle the supply port of gas and the plasma generation area between the described substrate, the described the 3rd handles gas is excited by described plasma generation area the time.

13. the method described in claim 12 is characterized in that: described first handles gas supplies with described processing region between described plasma generation area and described substrate.

14. the method described in claim 11 is characterized in that: described the 3rd operation has under the state that is excited the described second processing gas by described excitation mechanism supplies with the duration of exciting of described processing region with it.

15. the method described in claim 14 is characterized in that: described the 3rd operation had and does not make described second to handle gas under the state that described excitation mechanism is excited before described duration of exciting, with its supply with described processing region during.

16. the method described in claim 14 is characterized in that: described second handles gas and the described the 3rd handles the total supply port of gas.

17. the method described in claim 11 is characterized in that: the described second and the 4th operation has respectively during described processing region supply purge gas.

18. the method described in claim 11 is characterized in that; In the operation that forms described film, continue the exhaust in the described processing region.

19. the method described in claim 11, it is characterized in that: described first handles gas contains silane-based gas, described second handles gas contains nitriding gas or nitrogen oxidizing gas, and the described the 3rd handles gas contains the gas that is selected from nitrogen, rare gas, the nitrogen oxide.

20. the method described in claim 19, it is characterized in that: described first handles gas contains more than one the gas that is selected from dichlorosilane, hexachloro-silane, single silane, disilane, hexamethyldisilazane, tetrachloro silicane, disilazane, nitrilotrisilane, dual-tert-butyl amino silane, and described second handles gas contains and be selected from ammonia, nitrogen, nitrous oxide, nitric oxide production more than one gas.

21. the film formation device that semiconductor processes is used is characterized in that: have:

Container handling with the processing region that holds processed substrate,

In described processing region, support the holding components of described processed substrate,

Heat the heater of the described processed substrate in the described processing region,

Discharge the gas extraction system of gas in the described processing region,

Supply with first treating-gas supply system of film forming to described processing region with the first processing gas,

Supply with second treating-gas supply system of handling gas with second of the described first processing gas reaction to described processing region,

Described second of the described processing region supply of subtend handle the excitation mechanism that gas excites selectively,

Control the control section of described device action.

22. the device described in claim 21, it is characterized in that: described excitation mechanism have with space that described processing region links to each other in, be configured in described second and handle the supply port of gas and the plasma generation area between the described substrate, described second handles gas is excited by described plasma generation area the time.

23. the device described in claim 22 is characterized in that: described plasma generation area has by being attached to electrode and the high frequency electric source in the described container handling, handles the high-frequency electric field that forms between gas supply port and the described substrate described second.

24. the device described in claim 21, it is characterized in that: the structure of described processing region makes that the processed substrate of described multi-disc is set at the described heater heats around the described processing region can hold the processed substrate of multi-disc last having at interval under the stacked state.

25. the device described in claim 21, it is characterized in that: described first and second handle gas, be supplied to from a plurality of first gas jetting holes and a plurality of second gas jetting hole of arranging facing to the above-below direction of described a plurality of processed substrates respectively, form parallel gas flow with respect to described a plurality of processed substrates.

26. the device described in claim 21 is characterized in that:

In order to form film by CVD on described processed substrate, described control section intersects implements following operation:

Supply with first operation of the described first and second processing gases to described processing region;

Stop to supply with second operation of the described first and second processing gases to described processing region;

Supplying with the described second processing gas to described processing region when, stop to supply with the 3rd operation of the described first processing gas to described processing region; With

Stop to supply with the 4th operation of the described first and second processing gases to described processing region.

27. the device described in claim 21, it is characterized in that: also have the 3rd treating-gas supply system from the 3rd any all different processing gas of gases to described processing region supply and first and second that handle, the described the 3rd handles gas and described second handles the total supply port of gas, and is excited by described excitation mechanism selectively.

28. the device described in claim 27 is characterized in that:

In order to form film by CVD on described processed substrate, described control section intersects implements following operation:

Supplying with the described first and the 3rd processing gas to described processing region when, stop to supply with first operation of the described second processing gas to described processing region, described first operation has by excitation mechanism, make the described the 3rd handle gas with excited state supply with described processing region during;

Stop to supply with second operation of described first to the 3rd processing gas to described processing region;

Supplying with the described second processing gas to described processing region when, stop to supply with the 3rd operation of the first and the 3rd processing gas to described processing region; With

Stop to supply with the 4th operation of described first to the 3rd processing gas to described processing region.

29. a medium that comprises the embodied on computer readable of the program command that is used for moving on processor is characterized in that:

Supply with in the processing region that holds processed substrate that film forming uses first handle gas and with described first handle second of gas reaction and handle gas, in the CVD film formation device that film forming semiconductor processes is used on described processed substrate, described program command is when being moved by processor, alternatively implement following operation

Supply with first operation of the described first and second processing gases to described processing region;

Stop to supply with second operation of the described first and second processing gases to described processing region;

Supplying with the described second processing gas to described processing region when, stop to supply with the 3rd operation of the first processing gas to described processing region; With

Stop to supply with the 4th operation of the described first and second processing gases to described processing region.

30. a medium that comprises the embodied on computer readable of the program command that is used for moving on processor is characterized in that:

Supply with in the processing region that holds processed substrate that film forming uses first handle gas, with described first handle second of gas reaction handle gas and with first and second any all different the 3rd processing gases of handling in the gases, in the CVD film formation device that film forming semiconductor processes is used on described processed substrate, described program command is when being moved by processor, alternatively implement following operation

Supplying with the described first and the 3rd processing gas to described processing region when, stop to supply with first operation of the described second processing gas to described processing region, described first operation has by excitation mechanism, make the described the 3rd handle gas with excited state supply with described processing region during;

Stop to supply with second operation of described first to the 3rd processing gas to described processing region;

Supplying with the described second processing gas to described processing region when, stop to supply with the 3rd operation of the first and the 3rd processing gas to described processing region; With

Stop to supply with the 4th operation of described first to the 3rd processing gas to described processing region.

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