JP2003105526A - Method of depositing silicon compound film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of depositing a film of a silicon compound, by which a high quality deposited film of the silicon compound can be obtained with a high throughput and especially, the film of the silicon compound having a good gas barrier performance is formed. SOLUTION: A vapor deposition material containing a silicon oxide as a main component is arranged at a vapor deposition material arrangement section provided at a film deposition chamber, and a substrate is placed at a place opposed to the vapor deposition material arrangement section (arranging process). Then, a silicon compound layer is formed by supplying plasma beams toward the vapor deposition material arrangement section so as to vaporize a vapor deposition substance from the vapor deposition material, at the same time, introducing a reaction gas into the film deposition chamber, and sticking the vapor deposition substance onto the surface of the substrate (sticking process). Thereafter, the substrate on which the silicon compound layer is formed is removed from the film deposition chamber and cooled (cooling process). The silicon compound film is formed on the surface of the substrate by repeating the sticking process and the cooling process at least two times.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for forming a silicon compound film on a surface of a substrate, and more particularly to a method for forming a silicon compound film using a plasma beam.

[0002]

2. Description of the Related Art A silicon oxynitride film (SiOxNy film) is
Since it has a high gas barrier property for preventing permeation of water vapor and oxygen and further high transparency, it is expected to be widely used in the future as a barrier film for plastic displays.

As a method for forming such a silicon oxynitride film, there is a method using, for example, a reactive sputtering method. In this reactive sputtering method, argon for sputtering is incident on a target made of silicon nitride in an atmosphere of argon and oxygen, and sputtered particles of silicon nitride or the like emitted from the target are turned into plasma at a high frequency. By depositing the sputtered particles activated in this way on the substrate and causing an oxidation reaction, a silicon oxynitride film is formed on the substrate.

[0004]

However, in the above reactive sputtering method, when an insulating material such as silicon nitride is used as a target, the amount of energy input to the target is limited. Therefore, in the method for forming a silicon oxynitride film using the reactive sputtering method, the film formation rate is limited and it is difficult to improve throughput.

Further, the reactive sputtering method generally has a low efficiency of converting sputtered particles into plasma, and therefore the reactivity of sputtered particles is low. Therefore, in order to increase the reactivity of sputtered particles, it is necessary to perform treatment under high temperature conditions. There is. Therefore, the reactive sputtering method is not suitable as a technique for forming a high-quality film on the surface of a material having relatively low heat resistance such as an organic EL element material.

[0006] Therefore, the applicant of the present invention, at a high film formation rate,
As a film-forming technique capable of forming a high-quality film even at a low temperature, a vapor deposition material made of silicon oxide is evaporated by using a plasma beam in a reaction gas atmosphere containing nitrogen and oxygen as necessary, and a substrate is formed. A film forming method for forming a silicon oxynitride film by adhering to a substrate is being studied.

The present invention was made in order to further improve the film forming technique under study by the present applicant, and it is possible to obtain a high quality film with high throughput.
An object of the present invention is to provide a method for forming a silicon compound film having a further improved gas barrier property.

[0008]

According to the method for forming a silicon compound film of the present invention, a vapor deposition material containing silicon oxide as a main component is placed in a vapor deposition material placement portion provided in a deposition chamber, and An arranging step of arranging the substrate at a position facing the vapor deposition material arranging section, supplying a plasma beam toward the vapor deposition material arranging section to evaporate a vapor deposition substance from the vapor deposition material, and a reaction gas into the film forming chamber. There is a deposition step of introducing and depositing the vapor deposition material on the surface of the substrate to form a silicon compound layer, and a cooling step of evacuating the substrate on which the silicon compound layer is formed from the deposition chamber to cool it. The depositing step and the cooling step are repeated at least twice to form a silicon compound film on the surface of the substrate.

As a result, it is possible to obtain a substrate on which a silicon compound film, which has transparency and is particularly excellent in gas barrier properties, is formed with high throughput.

In this case, it is more preferable that the reactive gas is at least one of nitrogen and oxygen because the degree of freedom in controlling the film composition of the silicon compound film is increased.

Further, in this case, it is more preferable to change the composition ratio of the nitrogen and the oxygen constituting the reaction gas from the composition ratio in the previous adhesion process in the adhesion process subsequent to the cooling process.

Further, in the method of forming a silicon compound film according to the present invention, the vapor deposition material having silicon oxide as a main component is placed in the vapor deposition material placement portion provided in the deposition chamber, and the vapor deposition material placement portion is placed. An arrangement step of arranging the substrate at a position facing
A plasma beam is supplied toward the vapor deposition material placement portion to vaporize the vapor deposition substance from the vapor deposition material, and a gas containing nitrogen and oxygen is introduced as a reaction gas into the film forming chamber,
A film forming step of forming the silicon oxynitride film by adhering the vapor deposition material to the surface of the substrate, and in the film forming step of the film forming step, the composition ratio of the nitrogen and the oxygen of the reaction gas is changed. It is characterized by changing at least once.

As a result, the effects of the invention described above can be obtained without specially providing a cooling step, and the film forming apparatus and the film forming operation are simplified, which is preferable.

In this case, it is more preferable to sequentially change the composition ratio of the nitrogen and the oxygen of the reaction gas in the film forming process of the film forming step.

BEST MODE FOR CARRYING OUT THE INVENTION A preferred embodiment of the method for forming a silicon compound film according to the present invention (hereinafter referred to as an example of the present embodiment) will be described below with reference to the drawings.

First, a film forming apparatus suitable for carrying out the method for forming a silicon compound film according to the present embodiment (hereinafter, simply referred to as a film forming method) will be described with reference to FIGS. 1 and 2. To do.

The film forming apparatus includes a vacuum chamber 10 which is a film forming chamber.
A plasma gun 30 which is a plasma source for supplying the plasma beam PB into the vacuum container 10, an anode member 50 which is arranged at the bottom of the vacuum container 10 and receives the plasma beam PB, and a substrate which is a target for film formation. The substrate holding member WH that holds W is provided in the carrying path 61 above the anode member 50.

The plasma gun 30 is disclosed in JP-A-9-1942.
The pressure gradient type plasma gun disclosed in Japanese Patent No. 32, 32, etc., and its main body portion is attached to a cylindrical portion 12 provided on the side wall of the vacuum container 10. This body part is the cathode 3
The glass tube 32 has one end closed by 1. Inside the glass tube 32, a cylinder 33 made of molybdenum is fixed to the cathode 31 and is arranged concentrically with the glass tube 32. Inside the cylinder 33, a disk made of lanthanum hexaboride (LaB ₆ ). 34 and pipe 35 made of tantalum
And are built in. First and second intermediate electrodes 41, 42 are coaxially arranged in series between the end of the glass tube 32 opposite to the cathode 31 and the end of the tubular portion 12 provided in the vacuum container 10. Has been done. An annular permanent magnet 44 for focusing the plasma beam PB is incorporated in the first intermediate electrode 41, while an electromagnet coil 45 for focusing the plasma beam PB is also provided in the second intermediate electrode 42. It is built in. Further, around the cylindrical portion 12, a steering coil 47 that guides the plasma beam PB generated in the cathode 31 and drawn to the first and second intermediate electrodes 41 and 42 into the vacuum container 10 is provided. .

The operation of the plasma gun 30 is controlled by a gun driving device (not shown). Thereby, the cathode 31
It is possible to turn on / off the power supply to or to adjust the supply voltage and the like. Furthermore, the first and second intermediate electrodes 41,
42, electromagnet coil 45 and steering coil 47
The power supply to can be adjusted. As a result, the intensity and distribution of the plasma beam PB supplied into the vacuum chamber 10 can be controlled.

The pipe 35 disposed on the innermost side of the plasma gun 30 supplies a carrier gas, which is a source of the plasma beam PB and is made of an inert gas such as argon (Ar), to the plasma gun 30 and thus to the vacuum container 10. Flow meter 93 and flow control valve 94
It is connected to the inert gas source 90 via.

The anode member 50 arranged at the bottom of the vacuum chamber 10 comprises a hearth 51 which is a main anode for guiding the plasma beam PB downward, and an annular auxiliary anode 52 which is arranged around the hearth 51.

The hearth 51 is made of a conductive material and is supported by the vacuum container 10 which is grounded via an insulator (not shown). The hearth 51 is controlled to an appropriate positive potential by the anode power supply device 80, and attracts the plasma beam PB emitted from the plasma gun 30 downward.

The hearth 51 is a vapor deposition material arranging portion, has a through hole TH in the central portion where the plasma beam PB is incident, and a columnar or rod-shaped material rod 53 which is a vapor deposition material is loaded in the through hole TH. The material rod 53 is SiO
Alternatively, the tablet is formed by molding SiO ₂ into a predetermined shape. The material rod 53 is heated by the current of the plasma beam PB and sublimes to generate a vapor deposition substance. The material supply device 58 provided in the lower portion of the vacuum container 10 includes the material rod 5
3 has a structure of successively loading the through holes TH of the hearth 51 and gradually raising the loaded material rod 53. Even if the upper end of the material rod 53 evaporates and is consumed, the upper end of the hearth is reduced. It is possible to always project a certain amount from the through hole TH of 51.

The auxiliary anode 52 is composed of an annular container which is arranged concentrically with the hearth 51 and around the hearth 51. An annular permanent magnet 55 made of ferrite or the like and a coil 56 concentrically stacked with the permanent magnet 55 are housed in the annular container. These permanent magnets 5
5 and the coil 56 are magnetic field control members, and the hearth 5
A cusp-shaped magnetic field is formed immediately above 1. Thereby, the direction of the plasma beam PB incident on the hearth 51 can be corrected.

The coil 56 of the auxiliary anode 52 constitutes an electromagnet and is supplied with electric power from the anode power supply device 80 to generate a permanent magnet 55.
An additional magnetic field is formed so as to have the same direction as the central magnetic field generated by That is, by changing the current supplied to the coil 56, the direction of the plasma beam PB incident on the hearth 51 can be finely adjusted.

The container for the auxiliary anode 52 is also made of a conductive material like the hearth 51. The auxiliary anode 52 is attached to the hearth 51 via an insulator (not shown). By changing the voltage applied from the anode power supply device 80 to the auxiliary anode 52, the electric field above the hearth 51 can be supplementarily controlled. That is, the potential of the auxiliary anode 52 is set to the hearth 5
1 is the same as the plasma beam PB, the auxiliary anode 52
Plasma beam PB to Haas 51
Supply will be reduced. On the other hand, when the potential of the auxiliary anode 52 is lowered to the same level as that of the vacuum container 10, the plasma beam PB is attracted to the hearth 51 and the material rod 53 is heated.

A transfer path 61 is provided which communicates with the upper space of the vacuum container 10 and extends in the horizontal direction. The transport mechanism 60 functions as a substrate holding unit, is arranged at equal intervals in the transport path 61, and has a large number of rollers 62 that stably support the edge portion of the substrate holding member WH at a plurality of locations, and the rollers 62 at an appropriate speed. And a drive device for moving the substrate holding member WH in the horizontal direction at a constant speed. A plurality of substrates W are held on the substrate holding member WH.

When the substrate holding member WH is located above the vacuum chamber 10, that is, above the film forming chamber, in other words, above the hearth 51 (film forming zone) A1, the vapor deposition material evaporated from the material rod 53 is the substrate W. And the film forming operation is performed. On the other hand, in a state where the substrate holding member WH moves to one of the regions (cooling zones) A2 and A3 at both ends of the transport path 61 and is retracted from the film forming chamber, the film forming operation is stopped and the substrate holding member WH is placed in a cooling atmosphere. By doing so, the cooling operation of the substrate W is performed.

The oxygen gas supply device 71 and the nitrogen gas supply device 72 respectively supply (introduce) an appropriate amount of oxygen (O ₂ ) gas and nitrogen (N ₂ ) gas to the vacuum container 10 as an atmospheric gas at an appropriate timing. ) Is a gas supply means. The supply lines from the oxygen gas source 71a containing the oxygen gas and the nitrogen gas source 72a containing the nitrogen gas are connected to the vacuum container 10 via flow rate adjusting valves 71b and 72b and flow meters 71c and 72c, respectively.

The hearth gas supply device 73 is for supplying an inert gas such as argon to the hearth 51 at an appropriate timing and in an appropriate amount. The inert gas branched from the inert gas source 90 passes through the hearth 51 via the flow rate control valve 73b and the flow meter 73c of the hearth gas supply device 73.
It is guided to a gas introduction port (not shown) provided in the above and is discharged around the material rod 53.

The exhaust device 76 appropriately exhausts the gas in the vacuum container 10 via the vacuum gate 76a by the exhaust pump 76b.

The vacuum pressure measuring device 77 can measure the partial pressure of oxygen gas, nitrogen gas, etc. in the vacuum container 10, and the measurement result is monitored by the atmosphere control device 78.

The atmosphere control device 78 controls the supply amount of oxygen gas, nitrogen gas and argon gas into the vacuum container 10 through the oxygen gas supply device 71, the nitrogen gas supply device 72, the hearth gas supply device 73 and the like. Each can be adjusted. Further, the atmosphere control device 78, based on the measurement result of the vacuum pressure measuring device 77, the oxygen gas supply device 71,
By controlling the operations of the nitrogen gas supply device 72, the hearth gas supply device 73, the exhaust device 76, and the like, the partial pressures of the oxygen gas, the nitrogen gas, and the argon gas in the vacuum container 10 can be controlled to the target values.

Here, the structure of the hearth 51 is shown in FIG.
Further description will be made with reference to.

The hearth 51 includes a first base member 51a having a cooling cavity CA and a first base member 51a.
A second cylindrical base member 51b fixed on the upper side,
And a cone-shaped guide member 51c fixed on the base member 51b. These first base member 51a, second
The base member 51b and the guide member 51c are fixed such that the centers of the openings THa, THb, and THc provided in the base member 51b and the guide member 51c are aligned with each other, and the through holes TH are formed by the openings THa, THb, and THc.

The first base member 51a and the second base member 51b are both made of a copper material, have high thermal conductivity and conductivity, and are appropriately cooled by the cooling water supplied to the cavity CA.

The guide member 51c is made of a carbon material, has high conductivity and heat resistance, and has a plasma beam PB.
Attract. The guide member 51c may be made of a refractory metal.

The first base member 51a and the second base member 51b are provided with a gas introduction pipe 51f to which a pipe extending from the hearth gas supply device 73 is connected, and the tip of the gas introduction pipe 51f has a through hole TH. Is in communication with. Therefore, the argon gas supplied from the inert gas source 90 is discharged to the side surface of the material rod 53 via the gas introduction pipe 51f. As a result, the density of the argon gas above the guide member 51c increases, and the plasma beam PB
Are attracted to the guide member 51c. That is, even if the material rod 53 is a material having low conductivity such as SiO, plasma can be efficiently supplied to the material rod 53, and the efficiency of film formation can be improved.

A method for forming a silicon compound film according to the first to third examples of the present embodiment using the film forming apparatus described above will be described below. (Arrangement Step) First, the material rod 53 is attached to the through hole TH (vapor deposition material arrangement portion) of the hearth 51 arranged in the lower portion of the vacuum container (film formation chamber) 10. The vapor deposition material forming the material rod 53 contains silicon oxide such as silicon monoxide (SiO) or silicon dioxide (SiO ₂ ) as a main component. If the vapor deposition material further contains cerium, calcium, or the like, the film can be densified. On the other hand, the substrate W is held by the substrate holding members WH arranged on the transport path 61 provided at the opposite position above the hearth 51. The substrate W is, for example, a plastic film having a thickness of 0.1 mm. A glass substrate may be used as the substrate W. (Adhesion Step (Film Forming Step)) Next, when the silicon compound is adhered and formed (film formation) on the substrate W, the vacuum container 10 is previously prepared.
Atmosphere gas (reaction gas) such as nitrogen gas is introduced into. In this case, only the nitrogen gas is introduced in the film forming method according to the first example of the present embodiment, and the oxygen gas is further introduced together with the nitrogen gas in the film forming method according to the second example of the present embodiment.

On the other hand, an electric discharge is generated between the cathode 31 of the plasma gun 30 and the hearth 51 to generate a plasma beam PB. The plasma beam PB reaches the hearth 51 under the guidance of the magnetic field determined by the steering coil 47 and the permanent magnet 55 in the auxiliary anode 52. At this time, since the argon gas is supplied around the material rod 53, the plasma beam PB is easily supplied to the hearth 5.
Attracted to 1.

The material rod 53 exposed to the plasma is gradually heated. When the material rod 53 is sufficiently heated, the material rod 53 is sublimated, and vapor deposition substances such as silicon monoxide, silicon dioxide, or silicon are evaporated (emitted).

The vapor deposition material is ionized by the plasma beam PB and becomes highly active and adheres (incidents) to the substrate W. Silicon monoxide, silicon dioxide, or silicon deposited on the substrate W reacts with nitrogen gas or oxygen gas in the atmospheric gas to form a silicon oxynitride layer (SiOxNy layer) which is a silicon compound layer on the substrate W. It

In the attaching step described above, normally,
By continuing this silicon oxynitride layer forming process for a predetermined time, the thickness of the silicon oxynitride layer is increased, and finally a silicon oxynitride film (SiOxNy film) is formed. (Adhesion Step / Cooling Step) On the other hand, in the film forming method according to the first and second examples of the present embodiment, the substrate W on which the silicon compound layer is formed is removed from the region above the vacuum container 10 together with the adhesion step. The film forming zone A1 (see FIG. 1) is further provided with a cooling step of evacuating to a region (cooling zone) A2 or A3 at both ends of the transport path 61 and cooling. Then, a silicon compound film is formed by repeating the attaching step and the cooling step.

As the attaching step, the substrate W is formed in the area A1.
A silicon compound layer is formed on. Then, as a cooling process,
The substrate holding member WH that holds the substrate W is moved and placed in the area A2 or A3 for a predetermined time, so that the substrate W
Is allowed to cool. At this time, if necessary, an appropriate cooling gas may be introduced into the region A2 or A3 to positively cool in a short time.

Then, in the first example of the present embodiment, the attaching step and the cooling step are repeated at least twice. In this case, although it depends on the number of repetitions, the attachment time in the attachment step is preferably about 5 to 60 s, and the cooling time in the cooling step is preferably about 5 to 120 s.

Further, in the second example of the present embodiment, in the adhering step subsequent to the cooling step, the composition ratios of nitrogen gas and oxygen gas constituting the atmospheric gas are changed from the composition ratios in the previous adhering step. That is, the composition of the atmosphere gas for the next deposition step is switched in the time zone of the cooling step after the previous deposition step is completed, and after the cooling step is completed, in the next deposition step, The adhesion treatment is performed under an atmosphere gas having a composition different from that of the adhesion process. In this case, the operation for changing the composition of the atmosphere gas is 1 to 10
It can be performed within a time of about s. When the deposition process and the cooling process are repeated many times, the composition of the atmosphere gas may be switched only in any deposition process, or may be performed in all deposition processes. The range of change in the composition of the atmosphere gas is, for example, for an argon gas amount of 1, an oxygen gas amount and a nitrogen gas amount of 0 to 5 (argon: oxygen: nitrogen = 1: 0 to 0).
5: 5 to 0 (volume ratio)).

The film forming pressure (adhesion pressure) at this time
Is preferably 0.05 to 0.5 Pa, and is the same in the following examples.

Through the above steps, the first embodiment of the present embodiment
And the silicon compound film is formed on the substrate by the film forming method according to the second example. The silicon compound film formed at this time is
It is a silicon compound film containing silicon oxynitride or silicon oxide as a main component, or a silicon compound film in which these components are combined, depending on the conditions of the reaction gas.

Next, a film forming method according to the third example of the present embodiment will be described.

In the film forming method according to the third example of the present embodiment, unlike the first and second examples of the present embodiment,
The film forming step (adhesion step) does not have the above cooling step.

However, in the third example of the present embodiment, in the film forming process of the film forming step, a mixed gas of nitrogen gas and oxygen gas is used as an atmosphere gas, and the composition ratio of nitrogen gas and oxygen gas is set. Change at least once. In this case, the composition ratio may be drastically changed only once, or the composition ratio may be gradually and continuously changed over the entire film forming process. The conditions for changing the composition ratio can be based on the conditions of the first and second examples described above. In this case, the supply of either the nitrogen gas or the oxygen gas may be temporarily interrupted, and only the other gas may be introduced.

As described above, the silicon dioxide silicon oxide film as the silicon compound film is formed on the substrate by the film forming method according to the third example of the present embodiment.

The method of forming a silicon compound film according to the first to third examples of the present embodiment described above does not have some commonality in the processing method itself in each processing step.

However, instead of continuously increasing the thickness of the silicon compound layer having substantially the same structure under a predetermined film forming condition for a predetermined time, the film forming condition is substantially changed during the film forming process. In all respects, all examples are common.

Each of the obtained silicon compound films has a high gas barrier property.

That is, the first example of the present embodiment has a cooling step between a plurality of deposition steps, so that, for example, even if the atmospheric gas conditions of a plurality of deposition steps are the same. , The silicon compound layer generated in the present adhesion process is not formed continuously on the silicon compound layer generated in the previous adhesion process in terms of crystal structure, but so to speak, two silicon compound layers are laminated. It is thought that it is in the form. At this time, for example, even if each of the two silicon compound layers has a defect structure which causes the gas barrier property to be impaired, the continuity of the defect structure is interrupted between the two silicon compound layers to form the defect structure. It is considered that the gas barrier property of the obtained silicon compound layer film is improved.

Similarly, in the second example of the present embodiment, the crystal structure of each silicon compound layer is changed by changing the atmospheric gas conditions in a plurality of deposition steps, and the second example of the present embodiment It is considered that the effect of Example 1 is more prominent, and in Example 3 of the present embodiment, the atmospheric gas conditions in a plurality of deposition steps are made different even without the cooling step. It is considered that the above-mentioned effects can be obtained.

[0057]

EXAMPLES The present invention will be further described with reference to examples.
The present invention is not limited to the embodiments described below. (Example 1) As a substrate, a plastic film having a thickness of 0.1 mm was used. Silicon monoxide was used as the vapor deposition material forming the material rod. The film forming condition is a discharge current of 120.
A, the film forming pressure was 0.1 Pa, and the atmospheric gas conditions were argon: oxygen: nitrogen = 1: 0: 5.

Under the above conditions, while the substrate was being transported, the deposition operation in the film forming zone was carried out for 10 s, the cooling operation in the cooling zone was carried out for 30 s, and the cycle of the deposition operation and the cooling operation was repeated four times. The thickness of the silicon oxynitride film formed on the surface of the substrate was 100 nm.

The obtained silicon oxynitride film of Example 1 had a water vapor permeability of 0.23 g / m ² day. For comparison, the water vapor transmission rate measured for the silicon oxynitride film obtained by carrying out one film formation operation for 40 s under constant film formation conditions without adding a cooling operation was 0.66 g / m ² day. there were. (Example 2) As a substrate, a plastic film having a thickness of 0.1 mm was used. Silicon monoxide was used as the vapor deposition material forming the material rod. The film forming condition is a discharge current of 120.
A, the film forming pressure was 0.1 Pa, and the atmosphere gas conditions were such that switching between argon: oxygen: nitrogen = 1: 0: 5 and argon: oxygen: nitrogen = 1: 5: 0 was performed in each deposition step.

Under the above conditions, while the substrate was being transported, the deposition operation in the film forming zone was carried out for 10 s, the cooling operation in the cooling zone was carried out for 30 s, and the cycle of the deposition operation and the cooling operation was repeated four times. At this time, the switching operation of the atmospheric gas conditions described above was performed during the cooling step, which is the interval from the previous attaching step to the next attaching step. The thickness of the silicon compound film containing silicon oxynitride as a main component formed on the substrate surface was 100 nm.

The obtained silicon compound film of Example 2 had a water vapor transmission rate of 0.22 g / m ² day.

[0062]

According to the method for depositing a silicon compound film of the present invention, the vapor deposition material mainly containing silicon oxide is placed in the vapor deposition material placement portion provided in the deposition chamber, and the vapor deposition material placement is performed. An arranging step of arranging the substrate at a position facing the section,
A plasma beam is supplied toward the vapor deposition material placement portion to vaporize the vapor deposition material from the vapor deposition material, and a reaction gas is introduced into the film forming chamber to deposit the vapor deposition material on the surface of the substrate to form a silicon compound layer. And a cooling step in which the substrate on which the silicon compound layer is formed is withdrawn from the film forming chamber and cooled. The adhesion step and the cooling step are repeated at least twice to form a silicon compound film on the surface of the substrate. To film
It is possible to obtain a substrate on which a silicon compound film having transparency and particularly excellent gas barrier properties is formed with high throughput.

Further, according to the method for forming a silicon compound film of the present invention, the reaction gas is at least one of nitrogen and oxygen, and the reaction gas is used in the deposition step subsequent to the cooling step. Since the composition ratio of constituent nitrogen and oxygen is changed from the composition ratio in the previous deposition step, the degree of freedom in controlling the film composition of the silicon compound film increases.

Further, according to the method for forming a silicon compound film of the present invention, the vapor deposition material mainly containing silicon oxide is placed in the vapor deposition material placement portion provided in the deposition chamber, and the vapor deposition material placement is performed. And a film forming chamber in which a plasma beam is supplied toward the vapor deposition material placement portion to vaporize the vapor deposition substance from the vapor deposition material and a gas containing nitrogen and oxygen is used as a reaction gas. And a vapor deposition material is attached to the surface of the substrate to form a silicon oxynitride film.
Since the composition ratios of nitrogen and oxygen of the reaction gas are changed at least once, the effects of the above invention can be obtained without specially providing a cooling step, and the film forming apparatus and the film forming operation are simplified.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of an ion plating apparatus used in a method for forming a silicon compound film according to this embodiment.

2 is a schematic sectional view of a hearth of the ion plating apparatus of FIG.

[Explanation of symbols]

10 vacuum container 30 plasma gun 50 Anode member 51 Hearth 53 Material Rod 60 transport mechanism 61 Transport path 71 Oxygen gas supply device 73 Nitrogen gas supply device 78 Atmosphere control device

Claims (5)

[Claims] 1. A vapor deposition material containing silicon oxide as a main component is placed in a vapor deposition material placement portion provided in a film forming chamber, and
An arranging step of arranging the substrate at a position facing the vapor deposition material arranging section, supplying a plasma beam toward the vapor deposition material arranging section to evaporate a vapor deposition substance from the vapor deposition material, and a reaction gas into the film forming chamber. And depositing the vapor deposition material on the surface of the substrate to form a silicon compound layer, and a cooling step of evacuating the substrate on which the silicon compound layer is formed and cooling the substrate. A method for forming a silicon compound film, which comprises forming the silicon compound film on the surface of the substrate by repeating the attaching step and the cooling step at least twice or more. 2. The method for forming a silicon compound film according to claim 1, wherein the reaction gas is at least one of nitrogen and oxygen. 3. In the adhesion step subsequent to the cooling step,
3. The method for forming a silicon compound film according to claim 2, wherein the composition ratio of the nitrogen and the oxygen forming the reaction gas is changed from the composition ratio in the previous deposition step. 4. A vapor deposition material containing silicon oxide as a main component is placed in a vapor deposition material placement portion provided in a film forming chamber, and
An arranging step of arranging the substrate at a position facing the vapor deposition material arranging section, and supplying a plasma beam toward the vapor deposition material arranging section to evaporate the vapor deposition substance from the vapor deposition material and to generate a gas containing nitrogen and oxygen. Introduced into the film forming chamber as a reaction gas,
A film forming step of forming the silicon oxynitride film by adhering the vapor deposition material to the surface of the substrate, wherein in the film forming step of the film forming step, the composition ratio of the nitrogen and the oxygen of the reaction gas is adjusted. A method for forming a silicon compound film, which comprises changing at least once. 5. A vapor deposition material containing silicon oxide as a main component is placed in a vapor deposition material placement portion provided in a film forming chamber,
An arranging step of arranging the substrate at a position facing the vapor deposition material arranging section, and supplying a plasma beam toward the vapor deposition material arranging section to evaporate the vapor deposition substance from the vapor deposition material and to generate a gas containing nitrogen and oxygen. Introduced into the film forming chamber as a reaction gas,
A film forming step of forming the silicon oxynitride film by adhering the vapor deposition material to the surface of the substrate, wherein in the film forming step of the film forming step, the composition ratio of the nitrogen and the oxygen of the reaction gas is adjusted. A method for forming a silicon compound film, which comprises sequentially changing the film thickness.