JP2002100621A - Apparatus and method for forming film, substrate on which film is formed by using the same and liquid crystal apparatus using the substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve a shape of a membrane interface at a contact hole. SOLUTION: Just before starting to form a film, an opening of a dispersion head 152 is closed by a dispersion head cover (D/H cover) 150. When closed, a gas is not supplied to a substrate 149. A TBS gas flows into the dispersion head 152 in the closed state and replaces. When preliminary replacement completes, the D/H cover 150 moves and the substrate 149 sucked by a heater 151 is disposed on the opening. Forming of the film is started when the gas is supplied to the substrate 149. At this time the dispersion head 152 is filled with the TEB gas so that the change of a etching ratio of a membrane interface is suppressed and the shape of the membrane interface is improved when forming of the film is started.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film forming apparatus and a film forming method for improving a shape of a contact hole for electrically connecting two conductive layers disposed via an insulating film, and a film formed by the method. And a liquid crystal device using the substrate.

[0002]

2. Description of the Related Art As shown in FIG. 14, a liquid crystal device 200 using an electrode substrate is constituted, for example, by sandwiching a liquid crystal layer 50 between a counter substrate 20 and an array substrate 10 as an electrode substrate. The opposing substrate 20 includes an opposing electrode 21 on a substrate 70.
Are arranged and configured. On the other hand, the array substrate 10 is configured by arranging a plurality of scanning lines 3a and a plurality of data lines 6a that intersect each other, a switching element 30 and a pixel electrode 9a at each intersection on a substrate 60. Specifically, in the array substrate 10, a semiconductor layer 1a constituting the switching element 30 is formed on a substrate 60, and a gate insulating film 2 is formed so as to cover the semiconductor layer 1a. A scanning line 3 a is formed on the gate insulating film 2, and an interlayer insulating film 4 is formed so as to cover the gate insulating film 2. Interlayer insulating film 4
A data line 6a electrically connected to the semiconductor layer 1a via a contact hole 5 formed in the gate insulating film 2 and the interlayer insulating film 4 is formed thereon, and an insulating film 207 is formed so as to cover the data line 6a. Is formed. On the insulating film 207, an IT electrically connected to the semiconductor layer 1a via a contact hole 8 formed in the gate insulating film 2, the interlayer insulating film 4, and the insulating film 207 by wet etching or the like.
A pixel electrode 9a made of O (Indium Tin Oxide) is formed.

As the above-mentioned insulating film 207, for example, FIG.
As shown in FIG. 5, a stack of three insulating films, a first insulating film 207a, a second insulating film 207b, and a third insulating film 207c can be used. FIG. 15 is a partially enlarged view of the vicinity of the contact hole 8 in FIG. These three insulating films 207a, 207b, and 207c have different impurities. Lowermost first insulating film 207
a is a silicon oxide film (BPSG film) to which B (boron) and P (phosphorus) are added, and the second insulating film 207b of the intermediate layer is B
, And the uppermost third insulating film 207c is a silicon oxide film (NSG film) to which impurities such as B and P are not added.

As the insulating film 207 formed so as to cover the data line 6a, a BPSG film 207a is adopted because the step difference burying property by the contact hole 8 is good. However, if the data line 6a is formed of aluminum or the like, sufficient heat treatment cannot be performed when forming the BPSG film 207a. Therefore, the BSG film 207b which reacts with moisture and has good hygroscopicity is changed to the BPSG film 207a.
Form on top. Further, an NSG film 207c is formed in order to sufficiently remove moisture in consideration of a subsequent photo process.

[0005] The laminated insulating film 207 is formed continuously in the same CVD apparatus, and the film formation is performed by starting and stopping the supply of the impurity gas together with the supply of the source gas in the apparatus. FIG. 16 shows a supply state of the source gas, the impurity gas, and the N ₂ gas supplied into the apparatus when the insulating film 207 is formed. In FIG. 16, the vertical axis represents the gas flow supplied into the apparatus, and the horizontal axis represents time. In FIG. 16, line 244 is O ₃ gas, line 245 is N ₂ gas, line 24
6 is a TEOS (tetraethylorthosilicate) gas as a source gas, and a line 247 is a TMO as an impurity gas.
P (PO (OCH ₃ ) ₃ ) (trimethyl phosphate)
Gas, line 248 is TEB (B (OC
₂ H ₅ ) ₃ ) (triethyl borate) gas. As shown in FIG.
G film (first insulating film 207a), BSG film (second insulating film 2)
07b), when the NSG film (the third insulating film 207c) is continuously formed, the supply of the O ₃ gas and the TEOS gas is continuously performed. On the other hand, the supply of the impurity gas is such that the TEB gas and the TMOP gas are always supplied at a constant flow rate when the BPSG film is formed. During the formation of the BSG film, the supply of the TMOP gas is stopped, and the supply of the TEB gas is continuously performed. When the NSG film is formed, the supply of the TEB gas is stopped.

[0006]

When the contact hole 8 for electrically connecting the semiconductor layer 1a and the pixel electrode 9a is formed by a dry etching method, the dry etching method is anisotropic etching. A contact hole 8 having a side surface substantially perpendicular to the substrate is formed.
Therefore, an ITO film is hardly formed on the side surface of the contact hole 8, and a connection failure between the semiconductor layer 1a and the pixel electrode 9a has occurred.

On the other hand, when the contact hole 8 is formed by the wet etching method, the contact hole has a tapered shape in which the opening is widened from the substrate toward the surface of the insulating film because the wet etching method is isotropic etching. Therefore, an ITO film is easily formed on the side surface of the contact hole, and the connection between the semiconductor layer and the pixel electrode is improved.

However, when a laminated film formed by laminating a plurality of films having different contained impurities is used as the insulating film 207 as described above, the etching ratio of each film is different, and the film adjacent to the contact hole 8 is formed. As shown in FIG. 15, the interlayer insulating film 4, the first insulating film 207a, the second insulating film 207b, and the third insulating film 2 are provided near the interface where they contact each other.
A V-shaped cut 18 is formed at each interface of 07c.
For this reason, the step of the ITO film occurs near the cut 18, and a connection failure between the semiconductor layer 1 a and the pixel electrode 9 a occurs. In particular, a large cut occurs at the interface between the NSG film and the BPSG film.

The present invention has been made in view of the above problems, and has been made in consideration of a stacked film in which a plurality of insulating films having different impurities are stacked, an insulating film containing impurities and an insulating film containing no impurities. When a contact hole is formed in a laminated film in which a film is laminated, an insulating film which does not have a connection failure between a semiconductor layer and a pixel electrode and in which a well-shaped contact hole is easily formed can be formed. Membrane equipment,
An object of the present invention is to provide a film forming method, a substrate formed by the method, and a liquid crystal device using the substrate.

[0010]

According to a film forming method of the present invention, at least a TEB source among a plurality of film forming gases is supplied to a gas supply portion to a substrate immediately before film formation by ozone TEOS normal pressure CVD. A preliminary replacement procedure for replacing the gas in the gas supply unit in a state where the gas is not in contact with the substrate, and after the completion of the preliminary replacement, supplying a gas from the gas supply unit to the substrate to form a film. And a film forming procedure to be started.

According to such a configuration, in the preliminary replacement procedure, a TEB source having a sufficient concentration fills the gas supply section. The substrate is not in contact with the gas during this pre-replacement procedure. When the film forming procedure is started, the gas in the gas supply unit is supplied to the substrate, and the film is formed. At the start of film formation, a sufficient concentration of TEB gas is used for film formation, so that a change in the etching ratio at the film interface of the contact hole can be suppressed.

In one aspect of the film forming method of the present invention, the preliminary replacement step includes performing a replacement by flowing a gas into a dispersion head of the gas supply unit that directly supplies a gas to the substrate. Features.

According to such a configuration, at the start of film formation, a sufficient concentration of TEB gas can be supplied to the substrate, and a change in the etching ratio at the film interface can be suppressed.

In one aspect of the film forming method of the present invention, the preliminary replacement step includes flowing a gas in a supply pipe to a dispersion head of the gas supply unit that supplies a gas directly to the substrate. The replacement is performed.

According to such a configuration, at the start of film formation, a sufficient concentration of TEB gas can be easily supplied to the substrate, and a change in the etching ratio at the film interface can be suppressed.

The preliminary replacement step is characterized in that the gas is prevented from coming into contact with the substrate by a cover that closes an opening of the gas supply unit.

According to such a configuration, since the opening of the gas supply section is closed by the cover, the concentration of the TEB gas can be made sufficiently high.

Further, as the preliminary replacement procedure, a method of preventing a gas from contacting the substrate by disposing a quartz glass shutter between the opening of the gas supply unit and the substrate is adopted. You can also.

According to such a configuration, the shutter is heated at the time of the preliminary replacement, and the change in the etching rate at the film interface at the start of the film formation can be suppressed.

The shutter is formed of quartz glass.

According to such a configuration, the shutter can be sufficiently heated in the preliminary replacement procedure.

The preliminary replacement procedure is performed for a time of one second or more.

According to such a configuration, the concentration of the TEB gas can be sufficiently increased by the preliminary replacement.

A film forming apparatus according to the present invention includes a dispersion head for supplying a film forming gas to a substrate, a cover for closing a gas supply port of the dispersion head with respect to the substrate, and the cover In a state where the gas supply port is closed, at least a TEB source is supplied to the dispersion head from among a plurality of film forming gases for enabling film formation by ozone TEOS normal pressure CVD, and a supply for pre-replacement of the gas is performed. Means, and substrate support means for moving the cover in accordance with the movement of the cover after the completion of the preliminary replacement and disposing the substrate at a gas supply port of the dispersion head.

According to such a configuration, the cover closes the gas supply port of the dispersion head immediately before the film formation, and in this state, the supply means is connected to the ozone TEOS normal pressure CV.
At least a TEB source among a plurality of film forming gases for enabling film formation by D is supplied to the dispersion head. By this preliminary replacement, the concentration of the TEB gas becomes sufficiently high. When the preliminary replacement is completed, the substrate supporting means arranges the substrate in the gas supply port according to the movement of the cover, and starts film formation. Since the dispersion head is filled with the TEB gas at the start of film formation, a change in the etching ratio at the film interface at the start of film formation can be suppressed.

The substrate supporting means has a heater function for heating the substrate.

According to such a configuration, since the substrate is heated, a change in the etching rate at the film interface at the start of film formation can be suppressed.

According to the present invention, there is provided a film forming apparatus comprising: a dispersion head for supplying a film forming gas to a substrate; substrate support means for arranging the substrate at a gas supply port of the dispersion head; A plurality of components for enabling film formation by ozone TEOS normal pressure CVD in a state where the gas supply port is closed by the shutter; Supply means for supplying at least a TEB source of the film gas to the dispersion head to perform preliminary replacement of the gas, and after completion of the preliminary replacement, removing the shutter to enable film formation. I do.

According to such a configuration, immediately before film formation, the gas supply port of the dispersion head is closed by the shutter. In this state, the supply means flows at least a TEB source among a plurality of film forming gases for enabling film formation by ozone TEOS normal pressure CVD to the dispersion head. When the preliminary replacement is completed, the shutter is released and the film formation is started. The shutter is heated at the time of the preliminary replacement, and the change in the etching ratio at the film interface at the start of the film formation can be suppressed.

The shutter is formed of quartz glass.

According to such a configuration, the shutter can be sufficiently heated in the preliminary replacement procedure.

According to the present invention, there is provided a film forming apparatus comprising: a dispersion head for supplying a film forming gas to a substrate; a supply pipe for supplying a gas to the dispersion head; Support means and ozone TEOS atmospheric pressure CVD disposed at gas supply port
Immediately before film formation by T
Supply means for supplying an EB source to the supply pipe to perform preliminary replacement of gas, and after completion of the preliminary replacement, supplying a gas to the dispersion head via the supply pipe to enable film formation. It is characterized by having.

According to such a configuration, at the time of preliminary replacement,
The concentration of TEB gas in the supply line becomes sufficiently high. Accordingly, the concentration of the TEB gas in the dispersion head becomes relatively high at the start of the film formation, and the change in the etching ratio at the film interface can be suppressed.

A substrate according to the present invention is characterized by being formed by the above-described film forming method.

According to such a configuration, a change in the etching ratio at the film interface is suppressed, and the shape of the contact hole is improved.

A liquid crystal device according to the present invention is characterized by using a substrate formed by the above-described film forming method.

According to such a configuration, a device free from a connection failure between the semiconductor layer and the pixel electrode can be obtained.

[0038]

Embodiments of the present invention will be described below in detail with reference to the drawings. FIG. 1 shows the first embodiment of the present invention.
It is a schematic diagram which shows the film-forming apparatus which concerns on embodiment. FIG.
FIG. 2 is an explanatory diagram showing a CVD apparatus to which the first embodiment is applied. FIG. 3 shows various elements in a plurality of pixels formed in a matrix forming an image forming area of the liquid crystal device;
It is an equivalent circuit diagram of wiring etc. FIG. 4 is a sectional view showing the liquid crystal device in detail.

First, the structure of the liquid crystal device will be described with reference to FIGS.

In FIG. 1, the liquid crystal device comprises a display area and a peripheral drive circuit area for controlling the display area.

The display area includes the capacitor lines 3b arranged in parallel.
And a scanning line 3a, a data line 6a arranged to intersect with the scanning line 3a, a pixel electrode 9a arranged in a matrix at each intersection of the scanning line 3a and the data line 6a, and a pixel electrode 9a. And a thin film transistor (hereinafter, referred to as TFT) 30 as a switching element for controlling. The TFT 3 is connected to the data line 6a to which the image signal is supplied.
The source region of the semiconductor layer 0 is electrically connected, and the gate electrode of the TFT 30 is electrically connected to the scanning line 3a to which a scanning signal is supplied. The pixel electrode 9a is a TFT3
, Sn, which is electrically connected to the drain region of the semiconductor layer of No. 0 and is switched for a predetermined period of time by the TFT 30 as a switching element, the image signals S1, S2,... Is written at the timing of. Image signals S1, S2,..., Sn of a predetermined level written in the liquid crystal via the pixel electrodes 9a
Is held for a certain period of time between a counter electrode (described later) formed on a counter substrate described later. Also, the capacitance line 3b
Is provided to prevent the image signal held in the liquid crystal from leaking.

On the other hand, the peripheral drive circuit area includes a scan line drive circuit 104, a data line drive circuit 101, a sampling circuit 301, and a precharge circuit 201. The scanning line driving circuit 104 supplies the scanning signals G1, G2,... To the scanning line 3a at a predetermined timing based on the power supplied from the external control circuit, the reference clock CLY, its inverted clock, and the like.
Gm is applied in a pulsed manner in a line-sequential manner. The data line driving circuit 101 adjusts the timing at which the scanning line driving circuit 104 applies the scanning signals G1, G2,..., Gm based on the power supplied from the external control circuit, the reference clock CLX, its inverted clock, and the like. , Xn from the shift register as a sampling circuit drive signal for each data line 6a are supplied to the sampling circuit 301 at a predetermined timing via the sampling circuit drive signal line 306. The precharge circuit 201 includes, for example, a TFT 202 as a switching element and connects the TFT 202 to each data line 6a.
The precharge signal line 204 is provided for each TFT2.
The precharge circuit drive signal line 206 is connected to the gate electrode of the TFT 202. In operation, power of a predetermined voltage required for writing the precharge signal NRS is supplied from an external power supply via the precharge signal line 204, and the power is supplied via the precharge circuit drive signal line 206.
Image signals S1, S2,..., Sn for each data line 6a
Precharge signal NRS at a timing preceding the supply of
The precharge circuit drive signal NRG is supplied from the external control circuit so as to write. Precharge circuit 201
Are preferably image signals S1, S2,
, A precharge signal NRS (image auxiliary signal) corresponding to Sn is supplied. The sampling circuit 301 is a TFT
302 is provided for each data line 6a.
04 is connected to the source electrode of the TFT 302, and the sampling circuit drive signal line 306 is connected to the gate electrode of the TFT 302. When the image signals S1, S2,..., Sn are input via the image signal line 304, they are sampled. That is, the transfer signals X1, X as sampling circuit drive signals from the data line drive circuit 101 via the sampling circuit drive signal line 306.
, Xn are input, the image signals S1, S2,..., Sn from the respective image signal lines 304 are sequentially applied to the data lines 6a.

As shown in FIG. 4, the liquid crystal device 200 has a structure in which a liquid crystal 50 is interposed between a counter substrate 20 and an array substrate 10. The opposing substrate 20 and the array substrate 10 are adhered along a peripheral portion of the substrate with a rectangular sealing material except for a portion serving as a liquid crystal injection port, and the liquid crystal injection port is sealed with a sealing material.

In FIG. 4, the array substrate 10 is
A plurality of transparent pixel electrodes 9a are provided in a matrix on 0, and data lines 6a extending in one vertical direction and extending in one horizontal direction are respectively provided along vertical and horizontal boundaries of the pixel electrodes 9a. Scanning line 3a is provided. Pixel electrode 9a
Are provided at each intersection between the scanning line 3a and the data line 6a, and each pixel electrode 9a is provided with a TFT disposed at each intersection.
30 and is electrically connected. The TFT 30 has a semiconductor layer 1a, a gate insulating film 2 covering the semiconductor layer 1a, and a gate electrode forming a part of the scanning line 3a. The semiconductor layer 1a has a channel region 1 corresponding to the gate electrode 3a.
a ′, a low-concentration source region 1b and a low-concentration drain region 1c disposed so as to sandwich the channel region 1a ′,
It has an LDD structure composed of a high-concentration source region 1d and a high-concentration drain region 1e arranged so as to sandwich them, and further has a capacitor electrode 1f.

The high-concentration source region 1 d is
It is electrically connected to a data line 6a via a contact hole 5 formed in an interlayer insulating film 4 and a gate insulating film 2 disposed thereon.

On the interlayer insulating film 4, a three-layer insulating film, a first insulating film 7a, a second insulating film 7b, and a third insulating film 7c formed by the apparatus shown in FIGS. Laminated film 7
Is arranged. These three insulating films 7a, 7b, 7c
Have different impurities. The lowermost first insulating film 7a is made of BPSG (B, P
(Silicon oxide film containing a). The second insulating film 7b of the intermediate layer is made of a BSG (silicon oxide film containing B) film. BSG film is highly hygroscopic and has a high moisture content.
Since the water content of the PSG film is absorbed, the BSG film is formed, so that deterioration of the switching element due to water diffusion can be prevented. The uppermost third insulating film 7c is made of NSG
(Silicon oxide film containing no impurities such as B and P) is formed. By forming the NSG film, the adhesion of the resist can be improved.

The high-concentration drain region 1e is electrically connected to the pixel electrode 9a via a contact hole 8 formed in the gate insulating film 2, the interlayer insulating film 4, and the laminated film 7. The contact hole 8 has a tapered shape in which an opening widens from the substrate toward the surface of the laminated film 7. The capacitance line 3b is linearly arranged substantially in parallel with the scanning line 3a, forms a storage electrode and a storage capacitor 1f via the gate insulating film 2, and further forms a pixel electrode via the interlayer insulating film 4 and the laminated film 7. 9a and a storage capacitor. Further, the laminated film 7
An alignment film 16 formed by aligning a polyimide film is disposed on the pixel electrode 9a so as to cover the pixel electrode 9a.

In the present embodiment, as will be described later, since the insulating films 7a, 7b and 7c are formed using the apparatus shown in FIG. 1, a V-shaped portion is formed near the interface between the insulating films 7a, 7b and 7c. No cut has occurred. Therefore, IT
There is no disconnection of the O film, and there is no connection failure between the pixel electrode 9a and the semiconductor layer 1a. Therefore, a defective lighting of the pixel electrode due to a defective connection between the pixel electrode and the semiconductor layer does not occur, and a high-quality liquid crystal device can be obtained.

On the other hand, in the opposing substrate 20, a matrix light-shielding film 23 substantially corresponding to the scanning lines 3a and the data lines 6a is formed on the substrate 70, and the opposing electrode 21 is arranged so as to cover the light-shielding film 23. Further, an alignment film 15 is provided.

Next, referring to FIG. 2, insulating films 7a, 7b,
A CVD apparatus for forming 7c will be described. Here, a normal pressure CVD apparatus is used. CV for forming the laminated film 7
As shown in FIG. 2, the D apparatus 100 transmits the film forming gas to the substrate 1.
The substrate 149 is sucked and held by the dispersion head 152 which is a part of a gas supply unit to be supplied to the substrate 49,
A heater 151 for heating the substrate 149 to, for example, 400 ° C.
And a film forming gas supply pipe 153 that supplies a film forming gas to the dispersion head 152.

As a film forming gas, a source gas, an impurity gas, and a nitrogen (hereinafter, N ₂ ) gas are used. As source gas, TEOS gas and O ₃ gas are used,
The TEOS gas supply tube 156 and the O ₃ gas supply tube 154 supply the film formation gas supply tube 153, respectively. As impurity gases, TEB (B (OC ₂ H ₅ ) ₃ ) (triethyl borate) gas and TMOP (PO (OCH ₃ ) ₃ )
(Trimethyl phosphate) gas, and a TEB gas supply pipe 157 and a TMOP gas supply pipe 15
8 is supplied to the film forming gas supply pipe 153. The nitrogen gas is supplied to the film forming gas supply pipe 153 by the nitrogen gas supply pipe 155.
Supplied to

The above-mentioned TEOS gas is supplied to a nitrogen gas supply pipe 126 to TEOS 136 which is a liquid source contained in a container.
From by flowing N ₂ gas, and increasing the inner pressure of the vapor phase in the TEOS136. In addition, TEOS solution is 60 ° C.
The TEOS gas is generated from the liquid phase to the gas phase at a constant vapor pressure. TE according to N ₂ gas flow rate
The OS gas is supplied to the deposition gas supply pipe 153 via the TEOS gas supply pipe 156. In the nitrogen gas supply pipe 126, a mass flow controller 116 as a flow rate control means is disposed between a nitrogen gas source (not shown) and a container containing the TEOS 136, and the mass flow controller 116 supplies the liquid to a liquid source. and controlling the flow rate of N2 gas, and controls the flow rate of TEOS gas in accordance with the flow rate of N ₂ gas supplied to the liquid source.

TMOP gas is supplied from a nitrogen gas supply pipe 126 to TMOP 137 which is a liquid source contained in a container.
By flowing _two gases, the internal pressure of the gas phase in the TMOP 137 is increased. In addition, the TMOP liquid is kept at a constant temperature of 60 ° C.
P gas is generated. The TMOP gas is supplied to the deposition gas supply pipe 153 via the TMOP gas supply pipe 157.
The nitrogen gas supply pipe 127 has a nitrogen gas source (not shown) and T
A mass flow controller 117 as a flow control means is disposed between the MOP gas 137 and a container containing the MOP gas 137. The mass flow controller 117 controls the flow rate of the N ₂ gas supplied to the liquid source, and The flow rate of the TMOP gas is controlled according to the flow rate of the supplied N ₂ gas.

As for the TEB gas, the internal pressure of the gas phase in the TEB 138 is increased by flowing N ₂ gas from the nitrogen gas supply pipe 128 to the TEB 138 which is a liquid source contained in the container. The TEB liquid is kept at a constant temperature of 60 ° C., and a TEB gas is generated from a liquid phase to a gaseous phase at a constant vapor pressure. The TEB gas is supplied to the film forming gas supply pipe 153 via the TEB gas supply pipe 158. Nitrogen gas supply pipe 1
At 28, a mass flow controller 118 as a flow control means is disposed between a nitrogen gas source (not shown) and a container containing the TEB 138, and the N ₂ gas supplied to the liquid source by the mass flow controller 118 is disposed. The flow rate is controlled, and the flow rate of the TEB gas is controlled according to the flow rate of the N ₂ gas supplied to the liquid source.

In this embodiment, the mass flow controller 118 controls the BPS even when a dispersion head cover 150 described later is closed immediately before the start of film formation.
The G film forming source (Si, P, B, O ₃ ) is supplied to the dispersion head 152.

In FIG. 1, the dispersion head 1
52, an upper surface is opened, and the substrate 14
9 can be arranged. The dispersion head 152 uniformly distributes the reaction gas of various gases supplied from the film forming gas supply pipe 153 from the opening to the substrate 1.
49 to form a film on the substrate 149. Heater 15
1 is such that the substrate 149 can be adsorbed on the bottom surface, and the substrate 149 can be disposed on the opening of the dispersion head 152 so as to substantially close the opening while adsorbing the substrate 149 on the bottom surface. Has become. The dispersion head 152 is also provided with an exhaust port 159 for exhausting gas.

In the present embodiment, a dispersion head cover (hereinafter referred to as D / H) is disposed above the opening of the dispersion head 152 in conjunction with the heater 151.
150). The D / H cover 150 includes a heater 151 and a dispersion head 15.
When the heater is not located on the opening 2 and is located on the opening and closes the opening, the heater is turned on by the dispersion head 152.
Is moved from above the opening by moving over the opening.

Next, a method of manufacturing the above-described array substrate of the liquid crystal device will be described with reference to FIGS. 5 to 8 are diagrams for explaining the manufacturing process of the array substrate, and are process diagrams showing each layer on the array substrate side in each process corresponding to FIG. FIG. 9 is an explanatory diagram for explaining a change over time in the flow rate of each film forming gas such as a source gas and an impurity gas of the CVD apparatus according to the first embodiment.
FIG. 10 is a flowchart for explaining a film forming process according to the first embodiment.

First, a quartz substrate, a substrate such as hard glass,
For example, a quartz substrate 60 is prepared. Here, preferably N
₂ Inert gas atmosphere such as (nitrogen) and about 900-130
Annealing is performed at a high temperature of 0 ° C., and pre-processing is performed so that distortion generated in the quartz substrate 10 in a high-temperature process performed later is reduced. That is, the quartz substrate 6 is preliminarily adjusted to the highest temperature at the highest temperature in the manufacturing process.
0 is heat-treated at the same temperature or higher.

Next, as shown in FIG. 5A, the entire surface of the quartz substrate 60 treated as described above is
In a relatively low-temperature environment of 0 ° C., preferably about 500 ° C., amorphous CVD is performed by low-pressure CVD (for example, CVD at a pressure of about 20 to 40 Pa) using monosilane gas, disilane gas, or the like at a flow rate of about 400 to 600 cc / min (second). A silicon film is formed. Then, in a nitrogen atmosphere, about 600
The polysilicon film 1 is subjected to an annealing treatment at about 700 ° C. for about 1 to 10 hours, preferably 4 to 6 hours.
To a thickness of about 50-200 nm, preferably about 100 nm
The solid phase is grown to a thickness of

At this time, when an n-channel type TFT 30 is formed as the TFT 30, a dopant of a group V element such as Sb (antimony), As (grinding element), or P (phosphorus) is slightly added to the channel region. It may be doped by ion implantation or the like. When the TFT 30 is a p-channel type, a dopant of a group III element such as B (boron), Ga (gallium), or In (indium) may be slightly doped by ion implantation or the like. The polysilicon film 1 may be directly formed by a low pressure CVD method or the like without passing through the amorphous silicon film. Alternatively, the polysilicon film 1 may be formed by implanting silicon ions into a polysilicon film deposited by a low-pressure CVD method or the like to make the polysilicon film once amorphous (amorphized), and then recrystallize by annealing or the like.

Next, as shown in FIG. 5B, a semiconductor layer 1a made of polysilicon having a predetermined pattern is formed by a photolithography process, an etching process and the like. Part of the semiconductor layer 1a functions as an electrode for a storage capacitor.

Next, as shown in FIG.
a at a temperature of about 900-1300 ° C., preferably about 100
By performing thermal oxidation at a temperature of 0 ° C., a gate insulating film 2 made of a thermally oxidized silicon film having a relatively small thickness of about 30 nm is formed. Here, after the thermal silicon oxide film is formed, a high-temperature silicon oxide film (H
A gate insulating film 2 having a multilayer structure may be formed by depositing a relatively thin thickness of about 50 nm or a silicon nitride film.

Next, as shown in FIG.
After depositing a polysilicon film 3 by a method such as phosphorus (P)
Is thermally diffused to make the polysilicon film 3 conductive. Or P
A doped silicon film in which ions are introduced simultaneously with the formation of the polysilicon film 3 may be used.

Next, as shown in FIG. 5E, the capacitor line 3a and the scanning line 3a having a predetermined pattern are formed by a photolithography process using a resist mask, an etching process and the like.
b is formed. The layer thickness of the capacitance line 3b and the scanning line 3a is, for example, about 350 nm.

Next, as shown in FIG.
Is an n-channel TFT having an LDD structure,
First, in order to form a low-concentration source region 1b and a low-concentration drain region 1c in the semiconductor layer 1, a dopant 59 of a group V element such as P is reduced using the gate electrode 3a forming a part of the scanning line 3a as a diffusion mask. Doping with a concentration (for example, P ions at a dose of 1 to 3 × 10 ¹³ / cm ² ).
Thereby, the semiconductor layer 1a under the gate electrode 3a becomes the channel region 1a '. By doping this impurity, the capacitance line 3
b and the scanning line 3a are also reduced in resistance.

Subsequently, as shown in FIG.
30 and the high-concentration source region 1b and the high-concentration drain
In order to form the gate region 1c, the width is wider than the gate electrode 3a.
The resist layer 62 is formed on the gate electrode 3a with a wide mask.
After the formation, a dopant 61 of a group V element such as P
At a high concentration (for example, 1 to 3 × 10^Fifteen/ Cm ^Two
), And the TFT 30 having the LDD structure is doped.
obtain. When the TFT 30 is of a p-channel type,
A low-concentration source region 1b and a low-concentration drain
Region 1c, high-concentration source region 1d and high-concentration drain
In order to form the dopant region 1e, a group III element such as B
Dope using a punt. In addition, for example, low concentration
It is also possible to use a TFT with an offset structure without performing
P ions and B ions using the gate electrode 3a as a mask.
Self-aligned type by ion implantation technology using
It may be a TFT.

The resistance of the capacitance line 3b and the scanning line 3a is further reduced by the impurity doping.

Next, as shown in FIG. 6C, the scanning lines 3a
And TEOS as a film forming gas at a film forming temperature of 680 ° C. by using a low pressure CVD method so as to cover the capacitance line 3b.
An interlayer insulating film 4 made of a 00 nm thick NSG film is formed.

Next, as shown in FIG. 6D, a resist pattern film 71 from which the resist corresponding to the contact hole 5 has been removed is formed on the interlayer insulating film 4. Thereafter, using this resist pattern film 71 as a mask, CF
By performing a dry etching method using ₄ as an etching gas, the portion of the interlayer insulating film 4 and the gate insulating film 2 are etched, and a contact hole 5 is formed. Note that the contact hole 5 may be formed by using a wet etching method instead of the dry etching method. After forming the contact holes 5, the resist pattern film 71 is removed.

Next, as shown in FIG. 7A, a low-resistance metal such as Al (aluminum) or a metal silicide containing Al is applied on the interlayer insulating film 4 by sputtering or the like to form a conductive film. As No. 6, it is deposited to a thickness of about 300 nm.
Further, as shown in FIG. 7B, the conductive film 6 is patterned through a photolithography step, an etching step, and the like to form a data line 6a.

Next, as shown in FIG.
Insulating film 7a made of BSG, second insulating film 7 made of BSG
(b) A laminated film 7 is formed by laminating a third insulating film 7c made of NSG. As described above, the method shown in FIGS. 9 and 10 using the apparatus shown in FIGS. 1 and 2 is employed for forming the laminated film 7.

The chemical reaction between O ₃ and TEOS in normal pressure CVD is represented by the following equations (1) to (3). The final product is SiO ₂ and the by-products are ethanol, moisture, CO ₂ .

The above equation (1) indicates that TEOS and O ₃ are about 4
The reaction proceeds at 00 ° C., and indicates that CO ₂ and H ₂ O are generated as by-products. Equation (2) indicates that TEOS and H ₂ O react to generate silanol (Si (OH) ₄ ) and methanol in a reaction that proceeds even at room temperature. Equation (3) shows that silanol self-dissociates and S
This shows a process of generating iO ₂ and H ₂ O.

The above equation (2) shows that methanol increases with time. Considering the chemical equilibrium, it can be seen that the H ₂ O partial pressure increases to suppress the reaction. Therefore, finally, the dispersion head 15
In 2, methanol and H ₂ O will increase.

As described above, when the TEB gas is supplied into the dispersion head 152 in which H ₂ O is increased, a reaction represented by the following equation (4) may occur. B (OC ₂ H ₅ ) ₃ + H ₂ O → B ₂ O ₃ + 4C ₂ H ₅ OH (4) In the above formula (4), the Gibbs standard formation energy of B ₂ O ₃ is −1193.7 kJ / mol. , Very low.
Therefore, in the dispersion head 152, B ₂
It is considered that O ₃ is extremely easily generated and the TEB gas reacts with much of the residual H ₂ O.

That is, the H ₂ O increased with time in the dispersion head 152 by the reaction of the above formula (2).
Reacts abruptly with the TEB gas in the initial stage of film formation, and the amount of B source in the initial stage of film formation decreases, particularly at the interface. For this reason, it is considered that a V-shaped cut occurs.

Therefore, in the present embodiment, at the start of film formation, the film formation is started after the dispersion head 152 is filled with a sufficient TEB gas. This prevents the occurrence of a V-shaped cut in the vicinity of the interface.

That is, at the start of the process of forming the laminated film 7, the D / H cover 150 is closed as shown in FIG. FIG. 1 shows this state. The substrate 149 such as an array substrate is adsorbed by the heater 151, but is not disposed on the opening of the dispersion head 152, and the opening is closed by the D / H cover 150 ( Step S1). Therefore, the substrate 149 does not come into contact with the deposition gas.

Next, in this state, preliminary replacement for film formation is started in step S2. FIG. 9 shows a supply state of the source gas, the impurity gas, and the N ₂ gas supplied into the dispersion head 152. In FIG. 9, the vertical axis indicates the flow rate of gas supplied into the apparatus, and the horizontal axis indicates time. In FIG. 9, a line 144 represents an O ₃ gas supply pipe 15.
4 shows a change in the supply amount of O ₃ gas as a source gas supplied from FIG. A line 145 indicates a change in the supply amount of the N ₂ gas supplied from the nitrogen gas supply pipe 155. Also,
A line 146 indicates a change in the supply amount of the TEOS gas as the source gas supplied from the TEOS gas supply pipe 156. A line 147 indicates a change in the supply amount of the TMOP gas as the impurity gas supplied from the TMOP gas supply pipe 157. A line 148 indicates a supply state of the TEB gas as the impurity gas supplied from the TEB gas supply pipe 158 into the apparatus.

Before forming the BPSG film (first insulating film 7a), N ₂ gas, O ₃ gas, TEOS gas, TMOP gas and TEB gas are supplied into the dispersion head 152 as a film forming gas, Substitution is performed (step S3).

As shown in FIG. 9, N ₂ gas is supplied into the dispersion head 152 at a flow rate of 181 / min, and O ₃ gas is supplied at a flow rate of 7.51 / min. The flow rate of the TEOS gas is 2.51 / min, which is the flow rate of the gas flowing from the TEOS gas supply pipe 156. The flow rate of the TMOP gas is 1.21 / min, which is the flow rate of the gas flowing from the TMOP gas supply pipe 157. The flow rate of the TEB gas was 0.551 / min.
It is the flow rate of the gas flowing from 58. At the time of the preliminary replacement, only the TEB gas may be supplied into the dispersion head 152.

The pre-replacement time is 1 second or more, for example, about 5 seconds.
Set to seconds. After 5 seconds, the D / H cover 15
0 is slid to dispose the substrate 149 on the opening of the dispersion head 152 (step S4).

The heater 151 is mounted on the substrate 14
9 to about 400 ° C. In this state, the substrate 1
49 is the dispersion head 15 after the preliminary replacement is completed.
The film formation gas is supplied to the substrate 149 for about 190 seconds. Thus, a BPSG film (first insulating film 7a) having a thickness of about 600 nm is formed on the substrate 149.

Next, at the time of forming the BSG film (second insulating film 7b), N ₂ gas, O ₃ gas, TEOS gas and TEB gas are supplied onto the substrate 149. N ₂ gas, O ₃ gas, TE
The OS gas and the TEB gas are BPSG films (first insulating film 7).
After the formation of a), the supply is continued without changing the flow rate. Then, after a lapse of 15 seconds from the start of the formation of the BSG film, the supply of the TEB gas is stopped. This gives 6
The second insulating film 7b having a thickness of 0 nm can be formed.

Next, when forming the NSG film (third insulating film 7c), N ₂ gas, O ₃ gas and TEOS gas are supplied onto the substrate. The N ₂ gas and the O ₃ gas are the BSG film (the second insulating film 7).
After the formation of b), the supply is continued without changing the flow rate. After 5 seconds from the start of the NSG film formation, the TEOS gas is reduced so that its flow rate becomes 1.01 / min, and the film is opened for 210 seconds while maintaining the supply amount. Note that T
The flow rate of the N ₂ gas supplied from the nitrogen gas supply pipe 128 used for the liquid source when supplying the EB gas is 0.55
1 / min. Thus, the third insulating film 7c having a thickness of 80 nm can be formed. Thus, the laminated film 7 is formed.

Here, since the previously formed data line contains Al, the process temperature after the formation of the data line is, for example, 450 ° C. or less in order to prevent a change in the shape of the data line due to thermal expansion or the like due to heat treatment. Since it is desirable to perform the process, the film is formed under a low temperature condition. In this embodiment mode, a film can be formed at a low temperature because the film formation gas includes the TEOS gas and the O ₃ gas.

Since the laminated film 7 is formed after filling the dispersion head 152 with TEB gas immediately before the start of the film formation, when the contact hole 8 is formed by the wet etching method, as shown in FIG. As shown, a V-shaped cut does not occur near the interface between different insulating films. Therefore, even when the ITO film described later is formed, no disconnection of the ITO film occurs, and no connection failure occurs between the pixel electrode 9a and the semiconductor layer 1a.

After the formation of the laminated film 7, a resist pattern film 72 from which the resist corresponding to the contact hole 8 has been removed is formed on the laminated film 7, as shown in FIG. Then, after performing dry etching using the resist pattern film 72 as a mask, a wet etching method using buffered hydrofluoric acid as an etchant is performed to remove the laminated film 7 by etching, thereby forming the contact holes 8.
To form The contact hole 8 may be formed by performing wet etching after dry etching. After forming the contact holes 8, the resist pattern film 72 is removed.

Next, as shown in FIG. 7B, a transparent conductive thin film 9 such as an ITO film is deposited on the laminated film 7 by sputtering or the like to a thickness of about 50 to 200 nm. As shown in FIG. 7C, the pixel electrode 9a is formed by a photolithography process, an etching process, and the like. As described above, since the contact hole 8 has no cut or the like at the interface between the interlayer insulating film 4 and the laminated film 7,
A TO film is efficiently formed on the side surface of the contact hole 8. As a result, a connection failure between the semiconductor layer 1a and the pixel electrode 9a does not occur, and a high-quality array substrate can be obtained.

Subsequently, after applying a coating liquid for a polyimide-based alignment film on the pixel electrode 9a, a rubbing treatment is performed so as to have a predetermined pretilt angle and in a predetermined direction. 4) is formed to form an array substrate.

On the other hand, as for the counter substrate 20 shown in FIG. 4, a glass substrate 70 and the like are first prepared, and the light shielding film 23 is
For example, it is formed through a photolithography process and an etching process after sputtering metal chromium. Thereafter, the counter electrode 21 is formed by depositing an ITO film to a thickness of about 50 to 200 nm on the entire surface of the substrate 70 by a sputtering process or the like. Further, after applying a coating liquid for a polyimide-based alignment film on the entire surface of the counter electrode 21, a rubbing process or the like is performed so as to have a predetermined pretilt angle and a predetermined direction, thereby forming the alignment film 15.

Finally, the T on which each layer is formed as described above
The FT array substrate 10 and the counter substrate 20 are bonded together with a sealing material so that the alignment films 16 and 15 face each other.
In the space between the two substrates, for example, a liquid crystal obtained by mixing a plurality of types of nematic liquid crystals is sucked, and a liquid crystal 50 having a predetermined layer thickness is drawn.
Is formed, and the liquid crystal device 200 is manufactured.

As described above, in the present embodiment, at the time of forming the laminated film 7, the preliminary replacement is performed for a predetermined time immediately before the film formation, and the TEB gas is supplied to the dispersion head 152.
After sufficiently filling the inside, the substrate 149 is arranged on the opening of the dispersion head 152 to form a film, and a sufficient concentration of TEB gas can be supplied from the start of the film formation. As a result, the occurrence of a V-shaped cut near the interface can be prevented. Accordingly, a contact hole is formed in a stacked film in which a plurality of insulating films having different impurities are stacked or a stacked film in which an insulating film containing impurities and an insulating film not containing impurities are stacked. In this case, a contact hole having a good shape without a connection failure between the semiconductor layer and the pixel electrode can be formed.

The source gas and the impurity gas are not limited to those in the above embodiment.

By the way, in the first embodiment,
Before the substrate 149 is placed in the opening of the dispersion head 152, the TEB gas is replaced for a predetermined time so that the TEB gas is removed before the film formation.
It is designed to fill inside. Before the film formation, the TEB gas may be filled in the dispersion head 152 at a sufficient concentration. Therefore, it is not always necessary to close the opening of the dispersion head 152 with the D / H cover 150, and a certain effect can be obtained even if the preliminary replacement is performed in the opened state.

FIG. 12 is a schematic diagram showing a second embodiment of the present invention.

The present embodiment differs from the first embodiment in that the D / H cover 150 is omitted and a quartz glass 160 that can be inserted and removed is provided between the substrate 149 and the opening of the dispersion head 152. different.

In the present embodiment, at the time of preliminary replacement, quartz glass 160 is inserted between substrate 149 and the opening of dispersion head 152, and quartz glass
The opening is closed by 60. At the end of the preliminary replacement, the quartz glass 160 is removed and the substrate 149 is removed.
Is exposed to the opening, and a deposition gas is supplied from the dispersion head 152 to the substrate 149.

Also in the embodiment having such a structure, at the time of film formation, a sufficient concentration of TEB gas is supplied to the substrate 149.
Can be supplied to

Thus, also in the present embodiment, the first
The same effect as that of the embodiment can be obtained.

FIG. 13 is a schematic view showing a gas supply pipe employed in the third embodiment of the present invention.

In this embodiment, a dispersion head (D / H) 170 is employed. The dispersion head 170 may have the same configuration as the dispersion head 152 of FIG. 1 including the D / H cover 150, or may not include the D / H cover.
In the present embodiment, the dispersion head 17
A gas supply line 171 to zero is provided with a valve 172 and a pre-replacement supply line 173. A valve 174 is attached to the preliminary replacement supply line 173.

In the embodiment configured as described above, at the time of preliminary replacement, the valve 172 is closed and the valve 17 is closed.
4 is opened. Thus, the film forming gas (TEB) is supplied through the gas supply line 171 and the preliminary replacement supply line 173.
Gas) flows and the gas supply line 171 to the valve 172
Is filled with the deposition gas. When the preliminary replacement is completed, the valve 174 is closed and the valve 172 is opened. Thus, the film forming gas is supplied to the dispersion head 170 via the gas supply pipe 171. Thus, also in the present embodiment, it is possible to supply a relatively sufficient concentration of TEB gas to the substrate at the start of film formation.

In the present embodiment, the inside of the dispersion head 170 cannot be replaced, but the gas supply pipe 171 can be replaced. Even in this case, a certain effect can be obtained.

In the above embodiment, an array substrate of a liquid crystal device has been described as an example. However, the present invention can be applied to a semiconductor substrate, and an insulating film containing different impurities is laminated on the substrate. A stacked film or a stacked film including an insulating film containing no impurity and an insulating film containing an impurity is formed, and two conductive layers are arranged via the stacked film, and the two conductive layers are stacked. The present invention can be applied to an electrode substrate having a structure electrically connected through a contact hole formed in a film. That is, when forming a laminated film as a continuous film, by increasing the TEB gas concentration in the dispersion head immediately before film formation, a different insulating film can be formed when a contact hole is formed in the laminated film by wet etching. The occurrence of a V-shaped cut near the interface between them can be prevented. Therefore, it is possible to prevent the occurrence of a connection failure between the two conductive layers.

[0107]

As described above, according to the present invention, a laminated film in which a plurality of insulating films having different impurities are laminated,
When a contact hole is formed in a stacked film in which an insulating film containing impurities and an insulating film containing no impurities are stacked, no defective connection between the semiconductor layer and the pixel electrode can be obtained. This has an effect that an insulating film in which a contact hole is easily formed can be formed.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a film forming apparatus according to a first embodiment of the present invention.

FIG. 2 is an explanatory view showing a CVD apparatus to which the first embodiment is applied.

FIG. 3 is an equivalent circuit diagram of various elements, wiring, and the like in a plurality of pixels formed in a matrix forming an image forming region of the liquid crystal device.

FIG. 4 is a cross-sectional view illustrating a liquid crystal device in detail.

5 is a diagram for explaining a manufacturing process of the array substrate, and is a process diagram showing each layer on the array substrate side in each process corresponding to FIG.

6 is a diagram for explaining a manufacturing process of the array substrate, and is a process diagram showing each layer on the array substrate side in each process corresponding to FIG.

FIG. 7 is a diagram for explaining a manufacturing process of the array substrate, and is a process diagram showing each layer on the array substrate side in each process corresponding to FIG. 4;

8 is a diagram for explaining a manufacturing process of the array substrate, and is a process diagram showing each layer on the array substrate side in each process corresponding to FIG.

FIG. 9 is an explanatory diagram for explaining a change over time of a flow rate of each film forming gas such as a source gas and an impurity gas of the CVD apparatus in the first embodiment.

FIG. 10 is a flowchart illustrating a film forming process according to the first embodiment.

FIG. 11 is a schematic view showing the vicinity of a contact hole formed in the first embodiment.

FIG. 12 is a schematic view showing a second embodiment of the present invention.

FIG. 13 is a schematic diagram showing a gas supply pipe employed in a third embodiment of the present invention.

FIG. 14 is a cross-sectional view illustrating a liquid crystal device using a substrate manufactured by a conventional film forming method.

FIG. 15 is a schematic diagram for explaining a problem of the conventional example.

FIG. 16 is an explanatory diagram for explaining a conventional film forming method.

[Explanation of symbols]

 149: substrate 150: dispersion head cover 151: heater 152: dispersion head 153: film forming gas supply pipe

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/316 G02F 1/136 500 5F058 21/768 H01L 21/90 K 5G435 (72) Inventor Hidekazu Kato Nagano 3-5-5 Yamato, Suwa-shi, Japan Seiko Epson Corporation (72) Inventor Kyoji Momoi 3-53-5 Yamato, Suwa-shi, Nagano F-term in Seiko Epson Corporation 2H092 JA24 JA34 JA46 JA46 JB56 KA04 KA05 KB22 KB24 KB25 MA05 MA19 MA27 NA11 NA16 PA01 PA02 PA06 4K030 AA06 AA09 AA14 AA18 AA20 BA29 BA30 BB03 BB12 CA05 CA06 DA02 DA06 EA03 EA05 HA02 JA09 JA11 KA12 KA23 KA46 LA18 4M104 AA01 ABA10 BB02 DD19 BB02 DD19 DD37 DD63 EE02 EE12 EE15 GG09 GG10 GG14 GG20 HH15 5F033 GG04 HH04 HH08 HH09 HH17 HH38 JJ01 JJ08 J J09 JJ38 LL04 NN32 PP15 QQ08 QQ09 QQ10 QQ11 QQ19 QQ22 QQ37 QQ58 QQ59 QQ65 RR04 RR13 RR15 RR22 SS04 SS11 SS12 SS13 SS21 TT02 VV15 XX02 5F045 AB32 AC07 AC19 BB04 CA15 DC52 DC57 EE0218 BF25 BF29 BF33 BH13 BJ05 5G435 AA17 BB12 CC09 HH14 KK05 KK10

Claims (14)

[Claims] 1. Immediately before film formation by ozone TEOS normal pressure CVD, at least a TEB source of a plurality of film formation gases is caused to flow to a gas supply unit to a substrate, and the gas is not contacted with the substrate. A preliminary replacement procedure for replacing the gas in the supply unit, and a film formation procedure for starting the film formation by supplying the gas from the gas supply unit to the substrate after the completion of the preliminary replacement. Film forming method. 2. The pre-replacement step according to claim 1, wherein in the pre-replacement step, the replacement is performed by flowing a gas into a dispersion head of the gas supply unit that supplies the gas directly to the substrate. Membrane method. 3. The pre-replacement step, wherein the replacement is performed by flowing a gas into a supply pipe of a supply head for supplying a gas directly to the substrate in the gas supply unit. 2. The film forming method according to 1. 4. The film forming method according to claim 1, wherein in the preliminary replacement step, the gas is prevented from coming into contact with the substrate by a cover that closes an opening of the gas supply unit. 5. The pre-replacement step, wherein a gas is prevented from contacting the substrate by arranging a shutter between an opening of the gas supply unit and the substrate. 2. The film forming method according to 1. 6. The method according to claim 1, wherein the shutter is formed of quartz glass. 7. The film forming method according to claim 1, wherein the preliminary replacement procedure is performed for a time of one second or more. 8. A dispersion head for supplying a deposition gas to a substrate, a cover for closing a gas supply port of the dispersion head for the substrate, and the gas supply port is closed by the cover. A supply means for supplying at least a TEB source to the dispersion head from among a plurality of film forming gases for enabling film formation by ozone TEOS normal pressure CVD in the state and performing preliminary replacement of the gas; And a substrate supporting means for moving the substrate in accordance with the movement of the cover and disposing the substrate at a gas supply port of the dispersion head. 9. The film forming apparatus according to claim 8, wherein the substrate supporting means has a heater function for heating the substrate. 10. A dispersion head for supplying a deposition gas to a substrate, substrate support means for arranging the substrate at a gas supply port of the dispersion head, and a gas supply port of the substrate and the dispersion head. A shutter that can be inserted and withdrawn between the shutter, and at least a TEB source among a plurality of film forming gases for enabling film formation by ozone TEOS normal pressure CVD in a state where the gas supply port is closed by the shutter. And a supply means for supplying a gas to the dispersion head to perform preliminary replacement of gas, and after completion of the preliminary replacement, removing the shutter to enable film formation. 11. The film forming apparatus according to claim 10, wherein the shutter is formed of quartz glass. 12. A dispersion head for supplying a film formation gas to a substrate, a supply pipe for supplying a gas to the dispersion head, and the substrate disposed at a gas supply port of the dispersion head. Immediately before film formation by ozone TEOS normal pressure CVD, at least TEB of a plurality of film formation gases is used.
A supply means for supplying a source to the supply pipe to perform a preliminary replacement of gas, and after the completion of the preliminary replacement, supplying a gas to the dispersion head via the supply pipe to enable film formation. A film forming apparatus, comprising: 13. A substrate formed by the film forming method according to claim 1. Description: 14. A liquid crystal device using the substrate according to claim 13.