JP2000243745A - Substrate preparing apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate preparing apparatus capable of shortening a time required for the reaction of a film formed on a substrate on a treatment agent. SOLUTION: Methoxytriacetoxysilane(MTAS) is delivered from a treatment agent supply nozzle 22. A reaction accelerating liquid (a mixture liquid of IPA, water, and a base (TMAH)) is delivered from an acceleration agent supply nozzle 32. Both the agents are simultaneously delivered to a substrate W forming a SOG(spin-on-glass) film 1, so that in a state in which the MTAS and reaction acceleration liquid are mixed with each other, they are supplied to the SOG film 1. If the MTAS as ester is mixed with the reaction acceleration agent, the MTAS is hydrolyzed with the TMAH and water, and MTHS is formed. The hydrophile MTHS interacts quickly with the hydrophilic SOG film 1. That is, the time for requiring a reaction of the MTAS on the SOG film 1 with the reaction acceleration agent can be shortened.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor substrate, a glass substrate for a liquid crystal display, a glass substrate for a photomask, a substrate for an optical disk, etc. (hereinafter simply referred to as "substrate"). The present invention relates to a substrate processing apparatus for forming a film, and supplying a processing liquid to the film to cause a reaction between the film and the processing liquid to perform a terminal treatment of the film.

[0002]

2. Description of the Related Art Conventionally, SOG (Spin-on-Glass) coating has been performed on a substrate for the purpose of interlayer insulation and flattening. SOG coating has been performed by applying a SOG solution to a rotating substrate by a rotary coating apparatus. Then, by performing a heat treatment on the substrate after the coating treatment in a heat treatment unit (such as a hot plate), the SO
A G film was formed.

FIG. 2 shows an SOG film 1 formed on a substrate W.
It is a conceptual diagram explaining the situation of. Since the main purpose of forming the SOG film 1 on the substrate W is interlayer insulation, the SOG film 1
The higher the insulation, the better. However, as shown in the figure, since a large number of hydroxyl groups (OH groups) are present at the molecular ends of the SOG film 1 formed on the substrate W, the SOG film 1 exhibits hydrophilicity due to the hydroxyl groups. . Therefore,
The SOG film 1 absorbs moisture in the air, and as a result, the SOG film 1
Has a high dielectric constant, resulting in a decrease in film quality, that is, a decrease in insulation. Further, when the SOG film 1 absorbs moisture, gas is generated in the SOG film 1 at the time of subsequent baking, which may cause a crack in the SOG film 1 to cause film destruction.

For this reason, conventionally, the formed S
Hexamethyldisilazane (hereinafter referred to as “HM”) is formed on the OG film 1.
DS "). Formula 1 is a structural formula of HMDS. FIG. 3 shows that the HMDS is supplied to the S
FIG. 3 is a conceptual diagram illustrating a state of the OG film 1.

[0005]

Embedded image

When HMDS is supplied on the SOG film 1,
Hydroxyl group present at the molecular end of SOG film 1 and HMDS
Reacts with each other to treat the hydroxyl group, so that a state as shown in FIG. 3 is obtained. In such a case, the polarity at the molecular terminal portion of the SOG film 1 becomes weak, so that hydrophobicity is developed. Therefore, the problem associated with the moisture absorption of the SOG film 1 as described above is solved.

[0007]

However, as is apparent from FIG. 3, when the terminal treatment of the SOG film 1 is performed by HMDS, one molecule of HM corresponds to one hydroxyl group.
Since the DS reacts, the bonding between the terminal portions after the terminal treatment is weak, and the hydrophobicity of the SOG film 1 can be obtained, but the necessary film strength cannot be obtained.

In order to solve this problem, there is a technique for supplying methoxytriacetoxysilane (hereinafter, referred to as “MTAS”) instead of HMDS. Formula 2 is a structural formula of MTAS. FIG. 4 also shows that the MTAS is supplied to the SO
FIG. 3 is a conceptual diagram illustrating a state of a G film 1.

[0009]

Embedded image

When MTAS is supplied on the SOG film 1,
Hydroxyl group existing at the molecular end of SOG film 1 and MTAS
Are reacted with each other to generate acetic acid, and a state as shown in FIG. 4 is obtained. In the state shown in FIG. 4, the polarity at the molecular terminal portion of the SOG film 1 becomes weak as in the case of FIG. 3, and thus the SOG film 1 becomes hydrophobic. FIG.
As shown in the figure, one molecule of MTAS is used for three hydroxyl groups.
Reacts, so that the terminal portion after the terminal treatment forms a steric bond to improve the strength, and thus the SOG film 1
Is also improved. That is, if MTAS is used, it is possible to achieve both hydrophobicity of the SOG film 1 and increase in strength.

However, since MTAS itself is hydrophobic, a reaction with the hydrophilic SOG film 1 having a hydroxyl group terminal hardly occurs, and there has been a problem that the terminal treatment requires a long time.

The present invention has been made in view of the above problems, and has as its object to provide a substrate processing apparatus capable of shortening the time required for a reaction between a film formed on a substrate and a processing liquid.

[0013]

In order to solve the above-mentioned problems, a first aspect of the present invention is to form a predetermined film on a main surface of a substrate and supply a processing solution to the film to form the film and the processing solution. A substrate processing apparatus for processing the film by reacting with a liquid, wherein the reaction promoting liquid for promoting the reaction and the processing liquid are mixed and supplied onto the film.

According to a second aspect of the present invention, in the substrate processing apparatus according to the first aspect of the present invention, the film includes an SOG film, the processing liquid includes an ester, and the reaction accelerating liquid is mixed with the ester. In addition to being miscible, the ester is hydrolyzed in the reaction promoting liquid.

According to a third aspect of the present invention, in the substrate processing apparatus according to the second aspect of the present invention, the processing solution is methoxytriacetoxysilane, and the reaction promoting solution contains isopropyl alcohol, water and a predetermined base. Not.

[0016]

Embodiments of the present invention will be described below in detail with reference to the drawings.

FIG. 1 is a view showing an example of a substrate processing apparatus according to the present invention. This substrate processing apparatus is an apparatus that performs post-processing of the SOG film 1 formed on the main surface of the substrate W, that is, terminal processing of a hydroxyl group.

The substrate W on which the SOG film 1 is formed is held in a horizontal position by the turntable 10. The turntable 10 is rotatable by a motor (not shown). Two types of liquids can be supplied to the substrate W held by the turntable 10. That is, MTAS, which is a processing liquid for performing terminal treatment, can be supplied from the processing liquid supply nozzle 22, and a reaction promoting liquid for promoting the reaction between MTAS and the hydroxyl group of the SOG film 1 is supplied from the promoting liquid supply nozzle 32. be able to.

The MTAS is sent from a processing liquid supply source 20 to a processing liquid supply nozzle 22 via a processing liquid supply control unit 21.
The liquid is discharged from the processing liquid supply nozzle 22 onto the substrate W, more precisely, onto the SOG film 1 formed on the substrate W. The processing liquid supply control unit 21 includes a valve and a mass flow controller, and controls whether MTAS is supplied and the amount of MTAS supplied.

On the other hand, the reaction accelerating liquid is sent from the accelerating liquid supply source 30 to the accelerating liquid supply nozzle 32 via the accelerating liquid supply control unit 31, and is transferred from the accelerating liquid supply nozzle 32 onto the SOG film 1 formed on the substrate W. Discharged. The promotion liquid supply control unit 31 is also configured by a valve and a mass flow controller,
The presence or absence of the reaction promoting liquid and the supply amount are controlled.

The reaction accelerating liquid in this embodiment is isopropyl alcohol (hereinafter referred to as “IPA”), water and tetramethylammonium hydroxide (hereinafter “TMA”).
H ") at a volume ratio of 100: 10: 1. In the present embodiment, the MTA
S and the reaction promoting liquid are simultaneously discharged onto the substrate W. By simultaneously discharging the MTAS and the reaction promoting liquid onto the substrate W, the two liquids are immediately mixed and can be supplied onto the SOG film 1 in a mixed state.

When the MTAS and the reaction promoting liquid are mixed and supplied onto the SOG film 1, the following reaction occurs. First, IPA is an alcohol having 3 carbon atoms,
A hydrophobic liquid having a higher molecular weight than ethanol or the like can be dissolved in IPA. Therefore, when MTAS and the reaction promoting liquid are mixed, the separation of the hydrophobic MTAS and the reaction promoting liquid is prevented by the presence of IPA,
Both liquids are in a mixed state. In other words, IPA is M
It has a role of mixing the TAS with the reaction promoting liquid.

Then, in a state where MTAS and the reaction promoting liquid are mixed, MMA is added with alkali as TMAH.
The hydrolysis reaction of TAS proceeds. That is, TMAH
As a result, water acts on MTAS, and a reaction for producing methoxytrihydroxysilane (MTHS) and acetic acid proceeds. In other words, TMAH and water in the reaction promoting solution have a role of hydrolyzing MTAS.

The MTHS thus produced has the following structural formula.

[0025]

Embedded image

This MTHS and SO having a hydroxyl terminal are used.
When the G film 1 reacts, the state shown in FIG. 4 is obtained. Here, MTHS is an alcohol having three hydrophilic hydroxyl groups, and MTHS itself shows hydrophilicity. Therefore, MT
The reaction speed between HS and the hydrophilic SOG film 1 is high, and the state shown in FIG. 4 can be reached over the entire SOG film 1 in a short time. As described above, the molecular terminals shown in FIG. 4 have both hydrophobicity and high strength.

As described above, in the substrate processing apparatus of the present embodiment, the MTAS and the reaction promoting liquid are supplied onto the SOG film 1 in a mixed state, so that the MTAS and the SOA are mixed.
The time required for the reaction with the G film 1 can be shortened. This can be further expanded as follows.

As described above, if MTAS is used,
Although it is possible to achieve both the hydrophobicity of the SOG film 1 and the increase in strength, the problem is that the MTAS itself is hydrophobic, so that the reaction with the hydrophilic SOG film 1 having a hydroxyl terminal is unlikely to occur. there were. MTAS exhibits hydrophobicity due to its ester having a methyl group at the end.

Therefore, the MTAS, which is an ester, is hydrolyzed once with water and a base to form hydrophilic MTHS, so that the reaction with the hydrophilic SOG film 1 is easily caused. For this purpose, TMAH and water are included in the reaction promoting liquid. In addition, IPA in the reaction promoting solution is used for mixing MTAS and the reaction promoting solution to perform hydrolysis efficiently.

If the reaction with the SOG film 1 easily occurs, the time required for the reaction can be shortened, and the terminal treatment of the hydroxyl group can be performed quickly. That is, the reaction accelerating liquid promotes the reaction between the MTAS, which is an ester, and the SOG film 1.

Although the embodiment of the present invention has been described above, the present invention is not limited to the above-described example.
For example, in the above embodiment, TMAH was included as a base in the reaction accelerating solution. However, the present invention is not limited to this, and another base such as ammonia or amines may be included.

In place of IPA in the reaction accelerating solution, M
Other admixtures that can mix the TAS and the reaction accelerating liquid may be used.

Further, in the above embodiment, the volume ratio of the reaction promoting solution is set to IPA: water: TMAH = 100: 10:
Although it is set to 1, it is not limited to this and may be another ratio.

In other words, the reaction promoting liquid may be any liquid that can mix MTAS and hydrolyze MTAS.

In the above embodiment, the MTAS
And the reaction promoting liquid were simultaneously discharged onto the SOG film 1. However, the present invention is not limited to this. The MTAS and the reaction promoting liquid are mixed in advance in another tank, and then the mixed liquid is discharged. You may. Alternatively, only the MTAS may be first discharged onto the SOG film 1 and the liquid may be added thereto, and then the reaction promoting liquid may be discharged to mix the two liquids. Alternatively, only the reaction promoting liquid may be discharged. After the liquid is filled, MTAS may be discharged to mix the two liquids. In other words, it is only necessary that the MTAS and the reaction accelerating liquid can be supplied onto the SOG film 1 in a mixed state, regardless of the discharge mode of the two liquids.

Further, the substrate processing apparatus according to the present invention can
The apparatus is not limited to the apparatus that causes the MTAS to react with the G film 1, but may be an apparatus that performs terminal treatment of the SOG film 1 by reacting another ester. In this case, as the reaction promoting liquid, a liquid that is miscible with the ester and that can hydrolyze the ester may be prepared according to the ester used.

Further, in the substrate processing apparatus according to the present invention,
The apparatus is not limited to an apparatus that performs terminal processing of the OG film 1, but performs processing of the film by supplying a processing liquid to another film (for example, a photoresist film) formed on the main surface of the substrate. An apparatus may be used in which the reaction between the film and the processing liquid is promoted by supplying the reaction promoting liquid and the processing liquid in a mixed state onto the film.

[0038]

As described above, according to the first aspect of the present invention, since the reaction accelerating solution for accelerating the reaction and the processing solution are supplied onto the film in a mixed state, the reaction accelerating solution is formed on the substrate. The time required for the reaction between the treated film and the treatment liquid can be shortened.

According to the second aspect of the present invention, since the reaction accelerating liquid is miscible with the ester and hydrolyzes the ester, the substance produced by the ester hydrolysis reacts quickly with the SOG film. The effect of the invention of claim 1 can be easily obtained.

According to the third aspect of the present invention, since the reaction promoting solution contains isopropyl alcohol, water and a predetermined base, methoxytriacetoxysilane is hydrolyzed by water and the base to form methoxytrihydroxysilane. And the methoxytrihydroxysilane is SOG
By reacting quickly with the film, the effect of the invention of claim 1 can be easily obtained. In addition, it is possible to make the SOG film hydrophobic and increase strength at the same time.

[Brief description of the drawings]

FIG. 1 is a diagram illustrating an example of a substrate processing apparatus according to the present invention.

FIG. 2 is a conceptual diagram illustrating a state of an SOG film formed on a substrate.

FIG. 3 is a conceptual diagram illustrating the state of the SOG film of FIG. 2 supplied with HMDS.

FIG. 4 is a conceptual diagram illustrating a state of the SOG film of FIG. 2 supplied with MTAS.

[Explanation of symbols]

 1 SOG film 22 Processing liquid supply nozzle 32 Acceleration liquid supply nozzle W Substrate

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/316 H01L 21/30 563 F term (Reference) 2H025 AA13 AA14 AB14 AB16 AB20 DA19 DA35 DA40 EA01 EA04 2H096 AA25 AA28 CA02 5F045 EB19 EM10 HA11 5F046 HA07 5F058 AD05 AF04 AG10 AH01

Claims (3)

[Claims] 1. A substrate processing apparatus for forming a predetermined film on a main surface of a substrate and supplying a processing liquid to the film to cause a reaction between the film and the processing liquid to process the film. A substrate processing apparatus, wherein a reaction accelerating liquid for accelerating the reaction and the treatment liquid are supplied to the film in a mixed state. 2. The substrate processing apparatus according to claim 1, wherein the film includes an SOG film, the processing liquid includes an ester, and the reaction accelerating liquid is miscible with the ester and forms the ester. A substrate processing apparatus that performs hydrolysis. 3. The substrate processing apparatus according to claim 2, wherein the processing liquid is methoxytriacetoxysilane, and the reaction accelerating liquid contains isopropyl alcohol, water, and a predetermined base. apparatus.