KR20070016071A - Method and apparatus for forming silicon-containing insulating film - Google Patents

Abstract

A substrate to be processed in a processing region capable of selectively supplying a first processing gas containing a silane-based gas, a second processing gas including a gas selected from the group consisting of a nitridation gas, an oxynitride gas, and an oxidizing gas, and a purge gas A silicon-containing insulating film is formed by CVD on it. This film forming method alternately includes first to fourth steps. In the first, second, third and fourth processes, the first processing gas, the purge gas, the second processing gas and the purge gas are supplied, respectively, and the supply of the remaining two gases is stopped. Throughout the first to fourth processes, the inside of the processing region is continuously evacuated through an exhaust passage in which an opening degree adjustment valve is arranged. The opening degree of the valve in a 1st process is set to 5 to 95% of the opening degree of the valve in a 2nd and 4th process.

Wafer boat, lifting mechanism, gas dispersion nozzle, gas excitation part, exhaust port, valve port

Description

METHOD AND APPARATUS FOR FORMING SILICON-CONTAINING INSULATING FILM}

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

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

Fig. 3 is a longitudinal sectional view showing a valve unit (opening degree adjustment valve) used in the exhaust system of the apparatus shown in Fig. 1;

4 is a cross-sectional view of the valve unit shown in FIG.

Fig. 5 is a timing chart showing the degree of opening of the gas supply and the exhaust passage in the film forming method according to the first embodiment of the present invention.

FIG. 6 is a graph showing generation of particles in a processing container obtained by the film forming process of the first example PE1 and the first comparative example CE1 in Experiment 1. FIG.

Fig. 7 is a timing chart showing the degree of opening of the gas supply and the exhaust passage in the film forming method according to the second embodiment of the present invention.

Fig. 8 is a timing chart showing the degree of opening of the gas supply and the exhaust passage in the film forming method according to the third embodiment of the present invention.

Fig. 9 is a graph showing the DCS pressure dependency of the wet etching rate of the film obtained by the film forming process of Example 2 in Experiment 2.

Fig. 10 is a diagram showing a vacuum exhaust system of the film forming apparatus (vertical CVD apparatus) according to the fourth embodiment of the present invention.

Fig. 11 is a timing chart showing the opening degree of the exhaust passage in the film forming method according to the fourth embodiment.

Fig. 12 is a diagram showing first, third and fourth processing gas supply systems of the film forming apparatus (vertical CVD apparatus) according to the fifth embodiment of the present invention.

Fig. 13 is a block diagram showing an outline of the configuration of the main control section.

14 is a schematic configuration diagram showing a conventional vertical film forming apparatus disclosed in Patent Document 2. FIG.

Fig. 15 is a timing chart showing the degree of opening of the gas supply and the exhaust passage in the film forming method disclosed in Patent Literature 2;

<Explanation of symbols for the main parts of the drawings>

2: film forming apparatus

12: wafer boat

25 lifting mechanism

36: gas dispersion nozzle

48: subject fisherman

50 gas excitation

52: exhaust port

70: heater

84: exhaust passage

86: valve unit

90: valve housing

92 valve valve

94: valve seat

98: valve driving unit

100: actuator

[Document 1] Japanese Unexamined Patent Publication No. 2002-60947

[Document 2] Japanese Unexamined Patent Publication No. 2004-281853

TECHNICAL FIELD This invention relates to the film-forming method and apparatus which form a silicon containing insulating film on a to-be-processed substrate, such as a semiconductor wafer, for example in a system for semiconductor processing. Herein, semiconductor processing is performed by forming a semiconductor layer, an insulating layer, a conductive layer, or the like in a predetermined pattern on a substrate to be processed, such as a wafer, a glass substrate for a liquid crystal display (LCD), or a glass panel display (FPD). And various processes performed to manufacture a structure including a semiconductor device, a wiring connected to the semiconductor device, an electrode, or the like on the substrate to be processed.

In the manufacture of a semiconductor device constituting a semiconductor integrated circuit, various processes such as film formation, etching, oxidation, diffusion, modification, annealing, and removal of a natural oxide film are performed on a substrate to be processed, for example, a semiconductor wafer. Japanese Laid-Open Patent Publication No. 2002-60947 (Special Document 1) discloses a semiconductor processing method of this kind in a vertical (so-called batch) heat treatment apparatus. In this method, a semiconductor wafer is first moved from a wafer cassette onto a vertical wafer boat and supported in multiple stages. For example, 25 wafers can be accommodated in the wafer cassette, and 30 to 150 wafers can be loaded in the wafer boat. Next, the wafer boat is loaded from below into the processing vessel and the processing vessel is hermetically closed. Next, predetermined heat treatment is performed in a state where various processing conditions such as the flow rate of the processing gas, the processing pressure, and the processing temperature are controlled.

Conventionally, a silicon oxide film (SiO ₂ film) has been mainly used as an insulating film of a semiconductor device. However, in recent years, with the demand for higher integration and finer semiconductor integrated circuits, silicon nitride films (Si ₃ N ₄ films) have been used in place of silicon oxide films depending on the use. For example, the silicon nitride film is disposed as an oxidation resistant film, a diffusion barrier film of impurities, and a sidewall film of a gate electrode structure. Since the silicon nitride film has a low diffusion coefficient of impurities and a high oxidation barrier property, it is very suitable as the insulating film as described above.

In recent years, with the demand for further high integration and high miniaturization of semiconductor integrated circuits, it is required to reduce the thermal history in the manufacturing process of semiconductor devices and to improve the characteristics of the devices. Also in the vertical processing apparatus, improvement of the semiconductor processing method based on such a request is calculated | required. For example, also in the CVD process, a method is formed in which a layer having an atomic or molecular level thickness is repeatedly formed one by one or several layers while supplying source gas or the like intermittently (for example, Japanese Patent Laid-Open No. 2004-281853). Publication (Patent Document 2)]. Such a film formation method is generally referred to as ALD (Atomic layer Deposition), whereby the target processing can be performed without exposing the wafer to such high temperature. In addition, since film deposition by ALD has good step coverage, it is suitable for filling recesses, for example, inter-gate gaps, in the semiconductor device, which are narrowed with the miniaturization of the device.

An object of the present invention is to provide a film forming method and apparatus for forming a silicon-containing insulating film capable of suppressing generation of particles without lowering the throughput of the treatment.

A first point of the present invention is to selectively supply a first processing gas containing a silane-based gas, a second processing gas including a gas selected from the group consisting of nitriding gas, oxynitride gas and oxidizing gas, and a purge gas A method of forming a silicon-containing insulating film by forming a silicon-containing insulating film on the substrate to be processed by CVD in a possible processing region,

A first step of supplying the first processing gas to the processing region, and stopping supply of the second processing gas and purge gas to the processing region;

A second step of supplying the purge gas to the processing region and stopping supply of the first and second processing gases to the processing region;

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

A fourth step of alternately providing the purge gas to the processing region and stopping the supply of the first and second processing gases to the processing region;

Throughout the first step to the fourth step, the inside of the processing region is continuously evacuated through an exhaust passage in which an opening degree adjustment valve is arranged, and the opening degree of the valve in the first step is determined by the second step. And 5 to 95% of the opening degree of the valve in the fourth step.

A second viewpoint of the present invention is a film forming apparatus of a silicon-containing insulating film,

A processing container having a processing area for storing a substrate to be processed;

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

A heater for heating the substrate to be processed in the processing region;

An exhaust system for exhausting the inside of the processing region through an exhaust passage in which an opening degree adjustment valve is disposed;

A first processing gas supply system for supplying a first processing gas containing a silane-based gas to the processing region;

A second processing gas supply system for supplying a second processing gas containing a gas selected from the group consisting of nitriding gas, oxynitride gas and oxidizing gas to the processing region;

A purge gas supply system for supplying a purge gas to the processing region;

A control unit for controlling the operation of the apparatus,

The control unit, in order to form a silicon-containing insulating film on the substrate to be processed by CVD,

A first step of supplying the first processing gas to the processing region, and stopping supply of the second processing gas and purge gas to the processing region;

A second step of supplying the purge gas to the processing region and stopping supply of the first and second processing gases to the processing region;

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

While supplying the purge gas to the processing region, a fourth step of stopping supply of the first and second processing gases to the processing region is performed alternately,

In the first to fourth steps, the inside of the processing region is continuously evacuated through the exhaust passage, and the opening degree of the valve in the first step is determined in the second and fourth steps. Is set to 5 to 95% of the valve opening degree.

A third viewpoint of the present invention is a computer readable medium containing program instructions for executing on a processor,

The program instruction, when executed by a processor, includes a first processing gas containing a silane-based gas, a second processing gas including a gas selected from the group consisting of a nitriding gas, an oxynitride gas, and an oxidizing gas, and a purge gas. In a film forming apparatus for forming a silicon-containing insulating film by CVD on a substrate to be processed in a processing region that can be selectively supplied,

A first step of supplying the first processing gas to the processing region, and stopping supply of the second processing gas and purge gas to the processing region;

A second step of supplying the purge gas to the processing region and stopping supply of the first and second processing gases to the processing region;

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

A fourth step of alternately providing the purge gas to the processing region and stopping the supply of the first and second processing gases to the processing region;

Throughout the first step to the fourth step, the inside of the processing region is continuously evacuated through an exhaust passage in which an opening degree adjustment valve is arranged, and the opening degree of the valve in the first step is determined by the second step. And a film forming process for setting the valve to 5 to 95% of the opening degree of the valve in the fourth step.

Additional objects and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention can be realized and attained, in particular, by the tools and combinations indicated below.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate the preferred embodiments of the present invention and together with the foregoing general description and the detailed description of the preferred embodiments described below, serve to explain the principles of the invention.

MEANS TO SOLVE THE PROBLEM The present inventors studied the problem which arises in the film-forming apparatus for the conventional semiconductor processing disclosed by patent document 2 in the development process of this invention. As a result, the present inventors obtained the knowledge as described below.

It is a schematic block diagram which shows the conventional vertical type film-forming apparatus disclosed by patent document 2. FIG. FIG. 15 is a timing chart showing the degree of opening of the gas supply and the exhaust passage in the film forming method disclosed in Patent Document 2. FIG.

As shown in Fig. 14, a plurality of semiconductor wafers W supported in multiple stages on the wafer boat 304 are accommodated in the processing vessel 302 of this apparatus. The processing vessel 302 is connected to a supply system of dichlorosilane (DCS: SiH ₂ Cl ₂ ) gas, which is a silane gas, and ammonia (NH ₃ ) gas, which is a nitride gas. In addition, an exhaust system 306 in which an exhaust valve 308 and a vacuum pump 310 are sequentially provided is connected to the processing container 302. At the time of processing, as shown in Fig. 15, DCS gas and ammonia gas are intermittently supplied in the processing container 302 with a purge period. At this time, since the DCS gas has a low vapor pressure, the exhaust valve 308 is completely closed when the DCS gas is supplied. This increases the pressure in the processing vessel 302 to help adsorption of DCS gas onto the wafer surface (increases the amount of adsorption).

However, in the above method, the pressure in the container 302 becomes equilibrium for a moment when the exhaust valve 308 is completely closed. For this reason, the microparticles | fine-particles of reaction byproducts, such as ammonium chloride, etc. which adhered to the inner wall of an exhaust system, etc. may peel and fall back and may flow. Such fine particles may adhere to the wafer surface or the like and become a nucleus for particle generation.

As the exhaust valve 308, a so-called combination valve having both functions of an on-off valve and a pressure regulating valve can be used. In this case, the reaction byproducts are deposited on the sealing member such as the O-ring disposed in the combination valve when the exhaust valve 308 is completely closed. As a result, the deposit may hinder the sealability of the sealing member and cause internal leakage. As a countermeasure to this problem, the sealing member can be heated above the sublimation temperature of the reaction byproduct to prevent adhesion of the reaction byproduct. However, in this countermeasure, it is necessary to heat-resistant the exhaust valve 308, which makes the valve structure complicated and not practical.

EMBODIMENT OF THE INVENTION Below, embodiment of this invention comprised based on such knowledge is demonstrated with reference to drawings. In addition, in the following description, the same code | symbol is attached | subjected about the component which has substantially the same function and structure, and duplication description is performed only when necessary.

1 is a cross-sectional view showing a film forming apparatus (vertical CVD apparatus) according to an embodiment of the present invention. 2 is a cross-sectional plan view showing a part of the apparatus shown in FIG. The film forming apparatus 2 includes a first processing gas containing a dichlorosilane (DCS) gas, which is a silane-based gas, a second processing gas containing an ammonia (NH ₃ ) gas, which is a nitriding gas, and an inert gas such as an N ₂ gas. A processing region capable of selectively supplying a purge gas made of gas is provided. The film forming apparatus 2 is configured to form a silicon nitride film by CVD on the substrate to be processed in such a processing region. In addition, as described later, a third processing gas containing BCl ₃ gas, which is a boron-containing gas, and / or a fourth processing gas containing C ₂ H ₄ gas (ethylene gas), which is a hydrocarbon gas, is selectively supplied to the processing region. It can be configured as possible.

The film forming apparatus 2 has a cylindrical-shaped processing container 4 having a ceiling having an open lower end portion defining therein a processing region 5 for storing and processing a plurality of semiconductor wafers (to-be-processed substrates) superimposed at intervals. Has The whole of the processing container 4 is formed of, for example, quartz. The ceiling plate 6 made of quartz is arranged and sealed on the ceiling in the processing container 4. A manifold 8 formed in a cylindrical shape is connected to the lower end opening of the processing container 4 via a sealing member 10 such as an O-ring. Moreover, the whole manifold 8 can also be comprised by the cylindrical processing container made from a cylindrical shape, without providing separately.

The manifold 8 is made of stainless steel, for example, and supports the lower end of the processing vessel 4. The wafer boat 12 made of quartz is lifted and lowered through the lower end opening of the manifold 8, thereby loading / unloading the wafer boat 12 with respect to the processing container 4. In the wafer boat 12, a plurality of semiconductor wafers W are stacked in multiple stages as a substrate to be processed. For example, in the case of this embodiment, the support column 12A of the wafer boat 12 can support the wafer W which is 300 mm in diameter about 50-100 sheets, for example in multiple steps at substantially equal pitch. Become.

The wafer boat 12 is mounted on the table 16 via a quartz insulator 14. The table 16 is supported on the rotating shaft 20 passing through the lid 18 made of, for example, stainless steel to open and close the lower end opening of the manifold 8.

For example, a magnetic fluid sealing portion 22 is interposed in the penetrating portion of the rotary shaft 20 to rotatably support the rotary shaft 20 while hermetically sealing it. The sealing member 24 which consists of O-rings etc. is interposed in the peripheral part of the lid | cover body 18, and the lower end part of the manifold 8, for example, and maintains the sealing property in a container.

The rotary shaft 20 is provided at the tip of the arm 26 supported by the lifting mechanism 25 such as a boat elevator, for example. By the elevating mechanism 25, the wafer boat 12, the lid 18, and the like are raised and lowered integrally. In addition, the table 16 may be fixed to the cover body 18 side to process the wafer W without rotating the wafer boat 12.

The gas supply part for supplying predetermined process gas to the process area | region 5 in the process container 4 is connected to the side part of the manifold 8. The gas supply unit includes a second process gas supply system 28, a first process gas supply system 30, and a purge gas supply system 32. The first processing gas supply system 30 supplies a first processing gas containing a DCS (dichlorosilane) gas as the silane-based gas. The second processing gas supply system 28 supplies a second processing gas containing ammonia (NH ₃ ) gas as the nitriding gas. The purge gas supply system 32 supplies an inert gas, for example N ₂ gas, as the purge gas. Although an appropriate amount of carrier gas is mixed with the first processing gas and the second processing gas as necessary, the following description does not refer to the carrier gas for ease of explanation.

Specifically, the second process gas supply system 28, the first process gas supply system 30, and the purge gas supply system 32 penetrate inwardly through the side wall of the manifold 8 and extend upwardly. Gas dispersion nozzles 34, 36, and 38 each consisting of a quartz tube. Each gas dispersion nozzle 34, 36, 38 is provided with a plurality of gas injection holes 34A, 36A, 38A along its longitudinal direction (up and down direction) and over the entire wafer W on the wafer boat 12. It is formed at intervals of. The gas injection holes 34A, 36A, 38A comprise a second process gas (NH ₃ gas) approximately uniformly in the horizontal direction to form a gas stream parallel to the plurality of wafers W on the wafer boat 12. ), A first processing gas (including a DCS) and a purge gas (N ₂ ) are respectively supplied.

The nozzles 34, 36, 38 are connected to gas sources 28S, 30S, 32S of NH ₃ gas, DCS gas and N ₂ gas, respectively, via gas supply lines (gas passages) 42, 44, 46. On the gas supply lines 42, 44, 46, on-off valves 42A, 44A, 46A and flow controllers 42B, 44B, 46B such as mass flow controllers are arranged. As a result, the NH ₃ gas, the DCS gas, and the N ₂ gas can be supplied while controlling the flow rate.

The gas excitation part 50 is arrange | positioned along the height direction in a part of the side wall of the processing container 4. On the opposite side of the processing vessel 4 facing the gas excitation section 50, an elongated exhaust port 52 formed by shaving the side wall of the processing vessel 4 in the vertical direction, for example, to evacuate the internal atmosphere. Is placed.

Specifically, the gas excitation section 50 has a vertically long and narrow opening 54 formed by shaving the sidewall of the processing container 4 in a predetermined width along the vertical direction. The opening 54 is covered by a quartz cover 56 hermetically welded to the outer wall of the processing container 4. The cover 56 has a cross-sectional recessed shape so as to protrude out of the processing container 4 and has a long and thin shape vertically.

By this structure, the gas excitation part 50 which protrudes from the side wall of the processing container 4 and is open to the processing container 4 is formed. That is, the internal space of the gas excitation part 50 communicates with the processing region 5 in the processing container 4. The opening 54 is formed long enough in the vertical direction to cover all the wafers W held in the wafer boat 12 in the height direction.

A pair of elongated electrodes 58 are disposed on the outer surfaces of both side walls of the cover 56 so as to face each other along the longitudinal direction (up and down direction). The high frequency power supply 60 for plasma generation is connected to the electrode 58 via the power supply line 62. By applying a high frequency voltage of, for example, 13.56 MHz to the electrode 58, a high frequency electric field for exciting plasma is formed between the pair of electrodes 58. The frequency of the high frequency voltage is not limited to 13.56 MHz, but other frequencies, for example, 400 kHz or the like may be used.

The gas dispersion nozzle 34 of the second processing gas is bent radially outward of the processing container 4 at a position lower than the wafer W at the lowest level on the wafer boat 12. Thereafter, the gas dispersion nozzle 34 stands vertically at the innermost position (part spaced farthest from the center of the processing container 4) in the gas excitation section 50. As also shown in Fig. 2, the gas dispersion nozzle 34 is positioned between the pair of opposing electrodes 58 (the position where the high frequency electric field is strongest), that is, the plasma generating region PS in which the main plasma is actually generated. It is installed at a position spaced outward. The second processing gas containing NH ₃ gas injected from the gas injection hole 34A of the gas dispersion nozzle 34 is injected toward the plasma generating region PS, where it is excited (decomposed or activated), and in that state It is supplied to the wafer W on the wafer boat 12.

An outer protective cover 64 made of, for example, quartz is provided outside the cover 56 to cover it. A cooling mechanism (not shown) made of a refrigerant passage is disposed at an inner side of the insulating protective cover 64 and facing the electrode 58. The electrode 58 is cooled by flowing, for example, cooled nitrogen gas as a refrigerant in the refrigerant passage. In addition, a shield (not shown) is disposed outside the insulation protective cover 64 to cover the cover to prevent leakage of high frequency.

The gas dispersion nozzles 36 and 38 of the first processing gas and the purge gas are disposed near the outer side of the opening 54 of the gas excitation unit 50, that is, on both sides of the outer side of the opening 54 (in the processing container 4). It is arranged to stand vertically to face each other. Gas jet nozzles (36, 38) the purge gas toward the center of the processing vessel (4) than the gas-injection holes (36A, 38A) made of a first processing gas and the N ₂ gas containing DCS gas is respectively spray formed .

On the other hand, an exhaust port cover member 66 formed so as to cover the gas excitation section 50 and formed into a cross-section inverted c-shape made of quartz is provided by welding. The exhaust cover member 66 extends upward along the sidewall of the processing container 4, and a gas outlet 68 is formed above the processing container 4. The gas outlet 68 is connected to a vacuum exhaust system GE in which a vacuum pump or the like is disposed.

The heater 70 which heats the atmosphere in the process container 4 and the wafer W is arrange | positioned so that the process container 4 may be surrounded. In the vicinity of the exhaust port 52 in the processing container 4, a thermocouple (not shown) for controlling the heater 70 is disposed.

The vacuum exhaust system GE has an exhaust passage 84 connected to the gas outlet 68, and releases the valve unit (valve for adjusting the opening degree) 86, the vacuum pump 88, and unnecessary substances in order from the upstream side thereof. Unit 89 is disposed. The valve unit 86 consists of a so-called combination valve and has both functions of an on-off valve and a pressure regulating valve. That is, the valve unit 86 has the function of a valve that can arbitrarily set the valve opening degree, including full open and full close. 3 and 4 are longitudinal and cross sectional views showing the valve unit 86.

3 and 4, the valve unit 86 has a cylindrical valve housing 90 provided in the middle of the exhaust passage 84. As shown in FIG. Inside the valve housing 90, a valve seat 94 having a valve opening 92 is disposed. The valve drive part 98 is arrange | positioned at the upstream side of the valve seat 94, and the rod 102 extends from the actuator 100 toward downstream. At the distal end of the rod 102, a valve member 104 is provided which seats on the valve seat 94 and closes the valve port 92. Between the valve member 104 and the valve drive 98 an expandable bellows 103 surrounding the rod 102 is disposed to protect the actuator 100. In the valve member 104, a sealing member 106 made of, for example, an O-ring or the like is disposed so as to completely close the valve mechanism 92. In the circumference | surroundings of the valve drive part 98, the some communication path 96 for making exhaust flow is arrange | positioned annularly.

The valve unit 86 can be set to any valve opening degree including a fully closed state and a fully open state by reciprocating the valve member 104. The valve member 104 may be heated to a predetermined temperature, for example 150 ° C., to prevent the attachment of the reaction byproduct. The configuration of the valve unit 86 is merely an example and is not limited to this configuration.

The film forming apparatus 2 further includes a main controller 48 made of a computer or the like for controlling the operation of the entire apparatus. The main control unit 48 performs the film forming process described later according to the processing recipe of the film forming process stored in advance in the storage unit accompanying this, for example, the film thickness and composition of the film to be formed. In this storage section, the relationship between the processing gas flow rate and the thickness and composition of the film is stored in advance as control data. Therefore, the main control part 48 includes the elevating mechanism 25, the gas supply systems 28, 30, and 32, and the exhaust system GE (the valve unit 86) based on these stored process recipes or control data. Box, the gas excitation unit 50, the heater 70 and the like can be controlled.

Next, a film formation method (so-called ALD (Atomic Layer Deposition) film formation) performed using the apparatus shown in FIG. 1 will be described. In this film forming method, the first processing gas containing dichlorosilane (DCS) gas, which is a silane-based gas, and the ammonia (NH ₃ ) gas, which is a nitride gas, are disposed in the processing region 5 containing the wafer W. A second processing gas that is included is selectively supplied, and a silicon nitride film is formed on the wafer W by CVD.

First, the wafer boat 12 of normal temperature holding the plurality of sheets, for example, 50 to 100 300 mm wafers W is loaded into the processing container 4 set at a predetermined temperature. Next, the inside of the processing container 8 is evacuated and maintained at a predetermined processing pressure, and the wafer temperature is raised to stand by until it is stabilized at the film forming processing temperature. Next, the flow rate is controlled intermittently from the gas dispersion nozzles 36, 34, 38 while respectively controlling the flow rate of the first process gas containing the DCS gas and the second process gas containing the NH ₃ gas and the N ₂ gas. do.

Specifically, the first processing gas containing the DCS gas is supplied from the gas injection hole 36A of the gas dispersion nozzle 36 to form a gas flow parallel to the plurality of wafers W on the wafer boat 12. do. During this time, molecules of DCS gas or molecules or atoms of decomposition products generated by the decomposition thereof are adsorbed on the wafer.

On the other hand, the second processing gas containing the NH ₃ gas is supplied from the gas injection hole 34A of the gas dispersion nozzle 34 to form a gas flow parallel to the plurality of wafers W on the wafer boat 12. . The second processing gas is selectively excited when passing through the plasma generating region PS between the pair of electrodes 58, thereby partially converting the plasma. At this time, for example, _{N *, NH *, NH 2} *, NH 3 * radicals, such as (activated species) is generated (symbol "*" denotes that the radical). These radicals flow out from the opening 54 of the gas excitation section 50 toward the center of the processing container 4, and are supplied in a laminar flow state between the wafers W.

The radical reacts with molecules of the DCS gas attached to the surface of the wafer W, thereby forming a silicon nitride film on the wafer W. As shown in FIG. On the contrary, the same reaction occurs even when the DCS gas flows in a place where radicals are attached to the surface of the wafer W, and a silicon nitride film is formed on the wafer W. FIG.

Further, a purge gas made of N ₂ gas is supplied into the processing region 5 immediately after the process of supplying the first process gas containing the DCS gas and immediately after the process of supplying the second process gas containing the NH ₃ gas. The purge gas is supplied from the gas injection hole 38A of the gas dispersion nozzle 38 to form a gas flow parallel to the plurality of wafers W on the wafer boat 12. The purge gas flow removes the DCS gas and its decomposed components, or the NH ₃ gas and its decomposed components remaining in the processing region 5.

During the above-described film forming process, the processing region 5 is continuously evacuated by the vacuum exhaust system GE via the exhaust passage 84. Here, 5 to 95% of the opening degree in the process of controlling the opening degree of the valve unit 86 of the exhaust passage 84, and supplying the purge gas to the opening degree in the process of supplying a 1st process gas. Set to.

<First Embodiment>

Fig. 5 is a timing chart showing the degree of opening of the gas supply and the exhaust passage in the film forming method according to the first embodiment of the present invention. As shown in Fig. 5, in the film forming method according to this embodiment, the first to fourth steps (T1 to T4) are alternately repeated. That is, the silicon nitride film of the final thickness is obtained by repeating the cycle which consists of 1st-4th process (T1-T4) many times, and laminating | stacking the thin film of the silicon nitride film formed for every cycle.

Specifically, in the first step T1, the first processing gas (denoted as DCS in FIG. 5) is supplied to the processing region 5, while the second processing gas (FIG. 5) is supplied to the processing region 5. In FIG. 5, supply of NH ₃ ) and purge gas (in FIG. 5, N ₂ ) are stopped. In the second step T2, the purge gas is supplied to the processing region 5, and the supply of the first and second processing gases to the processing region 5 is stopped. In the third step T3, the second processing gas is supplied to the processing region 5, and the supply of the first processing gas and the purge gas to the processing region 5 is stopped. In addition, in the third process T3, the RF power supply 60 is turned on from the middle to make the second process gas plasma in the gas excitation unit 50, so that the second process gas is supplied between the sub processes T3b. It supplies to the process area | region 5 in an excited state. In the fourth step T4, the purge gas is supplied to the processing region 5, and the supply of the first and second processing gases to the processing region 5 is stopped.

Throughout the first to fourth processes, the treatment region 5 is continuously evacuated by the vacuum exhaust system GE via the exhaust passage 84. In the second and fourth processes T2 and T4, the opening degree of the valve unit 86 of the exhaust passage 84 is set to 100% (completely open). Thereby, the reactive gas remaining in the process region 5 can be quickly excluded by the purge gas. In addition, also in 3rd process T3, the opening degree of the valve unit 86 of the exhaust path 84 is set to 100% (full opening). Thereby, radicals derived from NH ₃ can be actively supplied onto the wafer W, and the reaction with molecules and the like of the DCS gas adsorbed onto the wafer W can be promoted (improved film formation rate).

In addition, in 1st process T1, the opening degree of the valve unit 86 is set to 5 to 20%. This valve opening degree is set in consideration of the balance between the promotion of the adsorption of DCS to the wafer W and the reduction of the number of particles present in the processing region 5. That is, especially in the case of DCS gas, since its vapor pressure is low, adsorption to the wafer surface is not good. In order to assist the adsorption of such gas onto the wafer surface (increasing the amount of adsorption), it is preferable to increase the pressure of the processing region 5 in the first step. Therefore, decreasing the opening degree of the valve unit 86 is an important factor for determining to improve the film formation rate and increase the throughput of the treatment. In this respect, the smaller the valve opening degree in the first step is, the better.

On the other hand, in the first step T1, when the opening degree of the valve unit 86 is set to 0% (completely closed), various problems related to particles occur as described above. For this reason, the opening degree of the valve unit 86 is set to the above-mentioned value, and even in the 1st process T1, the gas stream which flows into an exhaust system in the process area | region 5 is always formed. As a result, even if deposits or the like peel off from the inner wall of the exhaust system due to a change in pressure, for example, this does not flow backward and adheres to the surface of the wafer W or the like. In addition, since the valve opening degree is not 0% (completely closed), reaction by-products such as ammonium chloride do not adhere to the sealing member 106 of the valve unit 86. Therefore, it is possible to prevent the internal leakage due to deposits on the valve unit 86. From these viewpoints, the larger the valve opening degree in a 1st process becomes more preferable.

From the viewpoint as described above, in the first embodiment, the opening degree of the valve unit 86 balances the promotion of the adsorption of DCS to the wafer W and the reduction of the number of particles present in the processing region 5. It is used as a parameter to control. Specifically, in the first embodiment, as described above, the valve opening degree Vd1 in the first step is set to 5 to 20% of the valve opening degree in the second and fourth steps. If the valve opening degree Vd1 is smaller than 5%, the exhaust effect of the particles or the substance serving as the nucleus of the particle generation becomes insufficient. If it is larger than 20%, the adsorption efficiency of the first processing gas to the wafer surface is less than the allowable range.

In the first step T1, since the opening degree of the valve unit 86 becomes small, the pressure in the processing region 5 is reduced from the lowest value (indicated as Low in FIG. 5) to the highest value in FIG. 5. It is gradually raised to (High). However, this pressure gradually returns from the highest value to the lowest value by setting the opening degree of the valve unit 86 at 100% in the second step T2.

In FIG. 5, the first process T1 is about 1 to 120 seconds, for example about 5 seconds, and the second process T2 is about 1 to 30 seconds, for example about 5 seconds, and the third process (T3). ) Is about 1 to 120 seconds, for example about 10 seconds, sub-process T3b is 1 to 120 seconds, for example about 8 seconds, and fourth process (T4) is 1 to 30 seconds, for example about It is set to 5 seconds. In addition, the film thickness normally formed by 1 cycle of 1st-4th process (T1-T4) is about 0.05-0.11 nm. Therefore, if the target film thickness is 70 nm, for example, this cycle is repeated about 600 times. However, these time and thickness are only shown as an example and are not limited to this numerical value.

In the third process T3, the RF power supply 60 is turned on after the predetermined time Δt has elapsed to convert the second processing gas into plasma in the gas excitation unit 50, thereby reducing the amount of time between the sub-processes T3b. 2 The processing gas is supplied to the processing region 5 in the excited state. This predetermined time Δt is a time until the flow rate of the NH ₃ gas is stabilized, for example, about 1 second. However, the second processing gas may be converted into plasma in the gas excitation unit 50 over the entire period of the supply period of the second processing gas. In this way, after the flow rate of the second processing gas is stabilized, the RF power is turned on to generate the plasma, whereby the concentration uniformity of the active species in the interplanar direction (height direction) of the wafer W can be improved.

The processing conditions of the film forming process are as follows. The flow rate of the DCS gas is in the range of 50 to 2000 sccm, for example 1000 sccm (1 slm). The flow rate of NH ₃ gas is in the range of 100 to 5000 sccm, for example 3000 sccm. The flow rate of the N ₂ gas is in the range of 300 to 5000 sccm, for example 3000 sccm. The treatment temperature is lower than that of the normal CVD treatment, specifically, in the range of 250 to 700 ° C, and preferably in the range of 350 to 600 ° C. If the treatment temperature is lower than 250 ° C., no reaction occurs and almost no film is deposited. If the processing temperature is higher than 700 DEG C, a deposited film by CVD with poor film quality is formed, and thermal damage is caused to a metal film or the like already formed.

The processing pressure has a minimum value (indicated by a low in Fig. 5) in the range of 0 to 5 Torr, preferably in the range of 0 to 1 Torr. In addition, the highest value (represented by a gora in Fig. 5) is in the range of 0.1 to 10 Torr, preferably in the range of 0.1 to 5 Torr. 1 Torr = 133.3 kPa. For example, the processing pressure is 1 Torr in the first step (adsorption step) T1 and 0.3 Torr in the third step (nitriding step using plasma) T3. When the processing pressure is less than 0.1 Torr, the film formation rate is below the practical level. If the processing pressure is larger than 10 Torr, plasma will not be generated sufficiently.

Experiment 1

The silicon nitride film was formed using the apparatus shown in FIG. 1, and the generation | occurrence | production of the particle at that time was evaluated. As a first example, a film formation process was performed according to the timing chart of the first embodiment shown in FIG. The criteria of the processing conditions of the film forming process in the first example are as described in the description of the first embodiment. In addition, as a 1st comparative example, the film-forming process was performed on the conditions similar to 1st Example except having made valve opening degree of the exhaust system into 0% in the 1st process. In the first example and the first comparative example, each time the film forming process was performed, the number of particles on the wafer at that time was counted.

FIG. 6 is a graph showing the generation of particles in the processing container obtained by the film forming process of the first example PE1 and the first comparative example CE1 in Experiment 1. FIG. In Fig. 6, the left side shows data of the first embodiment PE1, and the right side shows data of the first comparative example CE1. The horizontal axis represents the number of wafer processes (runs). The left vertical axis represents the number of particles. The right vertical axis represents the integrated film thickness (占 퐉) formed on the wafer. In the graphs, the curves X1 and X2 each show an integrated film thickness, and the vertical bars indicate the number of particles.

As shown in Fig. 6, in the first comparative example CE1, a large amount of particles were suddenly generated at a high frequency regardless of the number of runs, which was not preferable. On the other hand, in the case of the first example PE1, the number of particles generated for the first comparative example was much smaller, and more stable with a low number of particles. Therefore, according to the film-forming method which concerns on 1st Embodiment, it was confirmed that a favorable result is obtained without generating a large amount of particles unexpectedly.

<2nd embodiment>

Fig. 7 is a timing chart showing the degree of opening of the gas supply and the exhaust passage in the film forming method according to the second embodiment of the present invention. In the timing chart shown in Fig. 5, the opening degree of the valve unit 86 of the exhaust passage 84 is set to 100% (fully open) in the third step T3 for supplying the NH ₃ gas. In contrast, in the timing chart shown in Fig. 7, in the third step T3 of supplying the NH ₃ gas, the opening degree of the valve unit 86 of the exhaust passage 84 is slightly smaller than 100% (full opening). Is set. As a result, according to the processing control the pressure of the processing zone (5), increase the density of radicals derived from the NH ₃ can also be optimized.

Third Embodiment

8 is a timing chart showing the degree of opening of the gas supply and the exhaust passage in the film forming method according to the third embodiment of the present invention. In the third embodiment, the opening degree of the valve unit 86 is used as a parameter for controlling one or both of the stress generated in the silicon nitride film formed by the film forming process and the potential etching rate of the silicon nitride film. Specifically, in the third embodiment, the valve opening degree Vd1 in the first step is set to 80 to 95% of the valve opening degree in the second and fourth steps. Therefore, in the first step, the pressure in the processing region 5 is controlled so as not to rise slightly, thereby making it possible to improve the stress, etching rate and the like of the silicon nitride film.

Experiment 2

The silicon nitride film was formed using the apparatus shown in FIG. 1, and the etching rate was evaluated. As a second example, a silicon nitride film was formed by performing a film forming process in accordance with the timing chart of the third embodiment shown in Fig. 8, and wet etching of this film was performed. The criteria of the processing conditions of the film forming process in the second example are as described in the description of the first embodiment. Specifically, the RF power was set at 250 watts (at the time of supply of NH ₃ ) and the film formation temperature was set at 400 ° C. As the pressure (reach pressure value) of the processing region 5 in the first step T1 for supplying the DCS gas, three different values of 1.2 Torr, 3.5 Torr, and 5.2 Torr were used. In addition, as the wet etching, the wafer on which the silicon nitride film was formed was immersed in 0.1% DHF (dilution HF) for 60 seconds.

9 is a graph showing the DCS pressure dependency of the wet etching rate of the film obtained by the film forming process of Example 2 in Experiment 2. FIG. In Fig. 9, the horizontal axis represents the processing pressure Torr at the time of DCS supply. The vertical axis represents the etching rate of the film by wet etching. As shown in Fig. 9, it was confirmed that the etching rate can be controlled over the range of 3.4 to 3.8 nm / minute by changing the pressure in the first step within the range of 1.2 to 5.2 Torr.

<4th embodiment>

Fig. 10 is a diagram showing a vacuum exhaust system of the film forming apparatus (vertical CVD apparatus) according to the fourth embodiment of the present invention. In the apparatus shown in FIG. 1, the vacuum exhaust system GE has only one system exhaust passage 84. In this case, for example, ammonium chloride is formed as a reaction by-product in the vacuum exhaust system GE, and there is a concern that the inside of the exhaust system is blocked. In contrast, in the vacuum exhaust system GEX of the fourth embodiment, as shown in Fig. 10, the first processing gas including DCS and the second processing gas including NH ₃ are respectively separated from the first exhaust system and the second exhaust system. Exhausted.

Specifically, the exhaust passage 84A of the first exhaust system and the exhaust passage 84B of the second exhaust system are arranged in parallel. In each of the exhaust passages 84A and 84B, valve units (opening-adjustment valves) 86A and 86B having the same structure as those of the vacuum exhaust system GE described above, vacuum pumps 88A and 88B and harmful units 89A, 89B) are interposed sequentially. The first processing gas DCS and the gas supplied at the same time are mainly discharged from the first exhaust passage 84A. The second processing gas NH ₃ and the gas supplied at the same time are mainly discharged from the second exhaust passage 84B.

The total valve opening degree of the two valve units 86A and 86B provided in both the exhaust passages 84A and 84B is equivalently controlled as one valve opening degree. That is, the main control part 48 controls so that the total valve opening degree of both valve unit 86A, 86B may correspond with the valve opening degree of the valve unit 86 mentioned above, and is shown in FIG. 5, FIG. Perform the film forming method.

11 is a timing chart showing the degree of opening of the exhaust passage in the film forming method according to the fourth embodiment. Here, the valve operation | movement equivalent to the operation | movement of the valve unit 86 in the case of 1st Embodiment shown in FIG. 5 is shown. Therefore, other aspects, such as the supply mode of the gas which are not shown in FIG. 11, are the same as that shown in FIG. That is, the valve unit 86A for the first process gas controls the valve opening degree to repeat the state of Vd1 and the fully closed state, and the second process gas valve unit 86B to repeat the fully open state and the fully closed state. do.

Specifically, in the first step T1, the valve opening degree of the valve unit 86A is in the state of Vd1 to flow the first processing gas, and the other valve unit 86B has a 0% (completely closed) state. do. In the third process T3, the valve unit 86A is in a 0% (fully closed) state, and the valve unit 86B is in a 100% (fully open) state to allow the second processing gas to flow. As a result, the first processing gas and the second processing gas pass through different exhaust passages 84A and 84B. Since both gases are not mixed in the exhaust system, no reaction by-products are generated, and the inside of the vacuum exhaust system GEX is not blocked.

<Fifth Embodiment>

Fig. 12 is a diagram showing first, third and fourth processing gas supply systems of the film forming apparatus (the vertical CVD apparatus) according to the fifth embodiment of the present invention. In the fifth embodiment, the doping gas is supplied to the processing region 5 together with the first processing gas containing the DCS in the first step T1. The doping gas includes one or both of a third processing gas containing boron containing gas (here, BCl ₃ gas) and a fourth processing gas containing ethylene (C ₂ H ₄ gas) gas. Here, the case where both of 3rd and 4th process gas are used is illustrated. In this case, the formed thin film is an insulating film made of boron doped silicon carbon nitride (SiBCN) containing boron and carbon.

As shown in Fig. 12, the first, third and fourth process gas supply systems 130, 132, and 134 are connected to a common mixed gas supply system 135. The mixed gas supply system 135 has a gas mixing tank 142 for mixing the first, third and fourth processing gases. The gas mixing tank 142 is set to a size, for example, about 4 liters, which temporarily mixes the gases uniformly and at the same time collects a sufficient amount of the mixed gas (changes according to the gas flow rate). The gas mixing tank 142 is connected to the gas dispersion nozzle 36 (refer FIG. 1) which consists of a quartz tube via the mixed gas supply line 144 in which the opening-closing valve 144A is arrange | positioned.

The gas mixing tank 142 passes through the gas supply lines (gas passages) 150, 152, and 154 of the first, third and fourth process gas supply systems 130, 132, and 134, and the DCS gas, the BCl ₃ gas, and the like. It is respectively connected to the gas source (130S, 132S, 134S) of the C ₂ H ₄ gas. On the gas supply lines 150, 152 and 154, on-off valves 150A, 152A and 154A and flow controllers 150B, 152B and 154B such as mass flow controllers are arranged. As a result, the DCS gas, the BCl ₃ gas, and the C ₂ H ₄ gas can be supplied while controlling the flow rate.

As an aspect of formation and supply of a mixed gas, the following two aspects are typical. In the first aspect, the first, third and fourth processing gases are continuously supplied from the first, third and fourth processing gas supply systems 130, 132, and 134 to the gas mixing tank 142 while the gas is supplied. The mixed gas is supplied in a pulse shape from the mixing tank 142 to the processing region 5 (see FIG. 1). In a second aspect, the first, third and fourth processing gases are pulsed in a first phase from the first, third and fourth processing gas supply systems 130, 132, 134 to the gas mixing tank 142. While supplying together, the mixed gas is supplied from the gas mixing tank 142 to the processing region 5 in a second phase opposite to the first phase.

To realize this, opening / closing valves 150A, 152A and 154A of the first, third and fourth process gas supply systems 130, 132 and 134 and opening and closing valves 144A of the mixed gas supply system 135 are opened and closed. Is operated as follows based on the instruction from the main control unit 48. In the case of the first aspect, the opening / closing valves 150A, 152A, and 154A are all kept open over a plurality of cycles from the start of the film forming process to completion, while the opening / closing valve 144A is opened and closed in a pulse shape. In the case of the second aspect, the opening / closing valves 150A, 152A, and 154A are opened and closed in a pulse shape over a plurality of cycles from the start of the film forming process to completion, while the opening / closing valve 144A is pulsed in the reverse phase. It is opened and closed.

<Matters and Modifications Common to First to Fifth Embodiments>

The method according to the first to fifth embodiments is executed under the control of the main control unit 48 based on the processing program as described above. 13 is a block diagram showing an outline of the configuration of the main controller 48. As shown in FIG. The main control unit 48 has a CPU 210, to which a storage unit 212, an input unit 214, an output unit 216, and the like are connected. The storage unit 212 stores a processing program and a processing recipe. The input unit 214 includes an input device for communicating with a user, for example, a keyboard or pointing device, a drive of a storage medium, and the like. The output unit 216 outputs a control signal for controlling each device of the processing apparatus. 13 also shows a storage medium 218 that can be attached to or detached from a computer.

The method according to the embodiment described above is a program command for executing on a processor, and can be applied to various semiconductor processing apparatuses by writing to a computer-readable storage medium. Alternatively, this kind of program instruction can be transmitted to a variety of semiconductor processing apparatuses by the communication medium. The storage medium is, for example, a magnetic disk (a flexible disk, a hard disk (for example, a hard disk included in the storage unit 212), etc.), an optical disk (CD, DVD, etc.), a magnetic optical disk (MO, etc.), a semiconductor memory. And so on. The computer which controls the operation of the semiconductor processing apparatus executes the above-described method by reading a program command stored in the storage medium and executing it on a processor.

In 1st-5th embodiment, DCS gas is illustrated as a silane type gas in a 1st process gas. In this regard, as the silane-based gas, dichlorosilane (DCS), hexadichlorodisilane (HCD), monosilane (SiH ₄ ), disilane (Si ₂ H ₆ ), hexamethyldisilazane (HMDS), tetrachloro One or more gases selected from the group consisting of silane (TCS), disyrylamine (DSA), trisyrylamine (TSA), and biscial butylaminosilane (BTBAS) can be used.

In the first to fifth embodiments, ammonia (NH ₃ ) gas and nitrogen (N ₂ ) gas can be used as the nitride gas in the second processing gas. In addition, when the present invention is applied to the formation of a silicon oxynitride film, an oxynitride gas such as dinitrogen monoxide (N ₂ O) or nitrogen monoxide (NO) may be used instead of the nitriding gas. In addition, when the present invention is applied to the formation of a silicon oxide film, an oxidizing gas such as oxygen (O ₂ ) or ozone (O ₃ ) can be used instead of the nitride gas.

In the fifth embodiment, the BCl ₃ gas is exemplified as the boron containing gas for doping boron. In this regard, the boron-containing gas may include one or more gases selected from the group consisting of BCl ₃ , B ₂ H ₆ , BF ₃ , and B (CH ₃ ) ₃ .

In 1st-5th embodiment, it has the structure which integrated the excitation part 50 which forms a plasma as the film-forming apparatus 2 in the processing container 4 integrally. Instead, the excitation section 50 is provided as a separate member from the processing container 4, and NH ₃ gas is previously excited outside the processing container 4 (so-called remote plasma), and the excitation NH ₃ gas is processed into the processing container 4. You may supply to the inside. The substrate to be processed is not limited to a semiconductor wafer, but may be other substrates such as an LCD substrate and a glass substrate.

Additional advantages and modifications will readily occur to those skilled in the art. Thus, the invention is not to be limited to the specific details and representative embodiments shown and described herein, in its broadest sense. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.

According to the present invention, it is possible to provide a film forming method and apparatus for forming a silicon-containing insulating film capable of suppressing the generation of particles without lowering the throughput of the treatment.

Claims (20)

A substrate to be processed in a processing region capable of selectively supplying a first processing gas containing a silane-based gas, a second processing gas including a gas selected from the group consisting of a nitridation gas, an oxynitride gas, and an oxidizing gas, and a purge gas A method of forming a silicon-containing insulating film for forming a silicon-containing insulating film by CVD on it, A first step of supplying the first processing gas to the processing region, and stopping supply of the second processing gas and purge gas to the processing region; A second step of supplying the purge gas to the processing region and stopping supply of the first and second processing gases to the processing region; A third step of supplying the second processing gas to the processing region while stopping supply of the first processing gas and the purge gas to the processing region; A fourth step of alternately providing the purge gas to the processing region and stopping the supply of the first and second processing gases to the processing region; Throughout the first step to the fourth step, the inside of the processing region is continuously evacuated through an exhaust passage in which an opening degree adjustment valve is arranged, and the opening degree of the valve in the first step is determined by the second step. And the film-forming method of the silicon containing insulating film set to 5 to 95% of the opening degree of the said valve in a 4th process. The method for forming a silicon-containing insulating film according to claim 1, wherein the third step has an excitation period for supplying the second processing gas to the processing region in an excited state by an excitation mechanism. The method of claim 1, wherein the first process is set to supply a doping gas to the processing region together with the first processing gas. 4. The method for forming a silicon-containing insulating film according to claim 3, wherein the first processing gas and the doping gas are supplied to the processing region after mixing in a gas mixing tank disposed outside the processing region. The method of claim 1, wherein the first processing gas is dichlorosilane, hexachlorodisilane, monosilane, disilane, hexamethyldisilazane, tetrachlorosilane, disyrylamine, trisilylamine, bisbutylbutylaminosilane A film-forming method of a silicon-containing insulating film containing at least one gas selected from the group consisting of. The method of claim 1, wherein the second processing gas comprises at least one gas selected from the group consisting of ammonia, nitrogen, dinitrogen monoxide, nitrogen monoxide, oxygen, and ozone. The method of claim 1, wherein the purge gas is nitrogen gas. 4. The method of claim 3, wherein the doping gas comprises a third process gas comprising ethylene gas and a third process gas containing a boron-containing gas selected from the group consisting of BCl ₃ , B ₂ H ₆ , BF ₃ , B (CH ₃ ) ₃ . 4 The film-forming method of the silicon containing insulating film containing one or both of process gas. 2. The excitation mechanism according to claim 1, wherein the excitation mechanism has a plasma generating region disposed between the supply port of the second processing gas and the substrate in a space communicating with the processing region, and the second processing gas is the plasma generating region. A film forming method of a silicon-containing insulating film excited when passing through. 10. The method of claim 9, wherein the first processing gas and the purge gas are supplied to the processing region between the plasma generation region and the substrate. 2. The silicon according to claim 1, wherein a plurality of substrates to be processed are stacked in a vertically spaced state in the processing region, and the plurality of substrates are heated by a heater disposed around the processing region. The film formation method of a containing insulating film. 12. The plurality of substrates of claim 11, wherein each of the first and second processing gases and the purge gas is arranged in a vertical direction across the plurality of substrates to form a gas flow parallel to the plurality of substrates to be processed. The film-forming method of the silicon containing insulating film supplied from the gas injection hole of the same. The exhaust gas passage of claim 1, wherein the exhaust passage has first and second exhaust passages for exclusively exhausting the first and second processing gases, respectively, and the valve is disposed in the first and second exhaust passages, respectively. A method for forming a silicon-containing insulating film, comprising first and second valves for adjusting the opening degree, and wherein the overall opening degree of the first and second valves is equally controlled as the opening degree of one valve. The degree of opening of the valve in the first step according to claim 1, wherein a balance between promotion of adsorption of the silane-based gas on the substrate to be treated and reduction of the number of particles present in the processing region is controlled. The film-forming method of the silicon containing insulation film which sets to 20 to 20% of the opening degree of the said valve in the said 2nd and 4th process. The opening degree of the said valve in the said 1st process is controlled so that the one or both of the stress which arises in the said silicon containing insulating film, and the potential etching rate which the said silicon containing insulating film has can be controlled. The film-forming method of the silicon containing insulating film set to 80 to 95% of the opening degree of the said valve in a process. The film-forming method of the silicon containing insulating film of Claim 1 which sets the opening degree of the said valve in a said 3rd process larger than the opening degree of the said valve in a said 1st process. The film-forming method of the silicon containing insulating film of Claim 16 which sets the opening degree of the said valve in a said 3rd process to below the opening degree of the said valve in a said 2nd and 4th process. It is a film-forming apparatus of a silicon containing insulating film, A processing container having a processing area for storing a substrate to be processed; A support member for supporting the substrate to be processed in the processing region; A heater for heating the substrate to be processed in the processing region; An exhaust system for exhausting the inside of the processing region through an exhaust passage in which an opening degree adjustment valve is disposed; A first processing gas supply system for supplying a first processing gas containing a silane-based gas to the processing region; A second processing gas supply system for supplying a second processing gas containing a gas selected from the group consisting of nitriding gas, oxynitride gas and oxidizing gas to the processing region; A purge gas supply system for supplying a purge gas to the processing region; A control unit for controlling the operation of the apparatus, The control unit, in order to form a silicon-containing insulating film on the substrate to be processed by CVD, A first step of supplying the first processing gas to the processing region, and stopping supply of the second processing gas and purge gas to the processing region; A second step of supplying the purge gas to the processing region and stopping supply of the first and second processing gases to the processing region; A third step of supplying the second processing gas to the processing region while stopping supply of the first processing gas and the purge gas to the processing region; While supplying the purge gas to the processing region, a fourth step of stopping supply of the first and second processing gases to the processing region is performed alternately, In the first to fourth steps, the inside of the processing region is continuously evacuated through the exhaust passage, and the opening degree of the valve in the first step is determined in the second and fourth steps. The film-forming apparatus of the silicon containing insulating film set to 5 to 95% of the opening degree of the said valve of the said. 19. The substrate according to claim 18, wherein a plurality of substrates to be processed are stacked in the processing region in a stacked state at intervals up and down, and the plurality of substrates are heated by the heater disposed around the processing region. And each of the first and second processing gases and the purge gas are arranged in a vertical direction across the plurality of substrates to form a gas flow parallel to the plurality of substrates to be processed. A film forming apparatus for a silicon-containing insulating film, which is supplied from a film. A computer readable medium containing program instructions for executing on a processor, The program instruction, when executed by a processor, includes a first processing gas containing a silane-based gas, a second processing gas including a gas selected from the group consisting of a nitriding gas, an oxynitride gas, and an oxidizing gas, and a purge gas. In a film forming apparatus for forming a silicon-containing insulating film by CVD on a substrate to be processed in a processing region that can be selectively supplied, A first step of supplying the first processing gas to the processing region, and stopping supply of the second processing gas and purge gas to the processing region; A second step of supplying the purge gas to the processing region and stopping supply of the first and second processing gases to the processing region; A third step of supplying the second processing gas to the processing region while stopping supply of the first processing gas and the purge gas to the processing region; A fourth step of alternately providing the purge gas to the processing region and stopping the supply of the first and second processing gases to the processing region; Throughout the first step to the fourth step, the inside of the processing region is continuously evacuated through an exhaust passage in which an opening degree adjustment valve is arranged, and the opening degree of the valve in the first step is determined by the second step. And a film-forming process for setting the film to 5 to 95% of the opening degree of the valve in the fourth step.

Images