KR20110132214A - Hydrophobic conversion processing method and hydrophobic conversion processing apparatus - Google Patents

Abstract

PURPOSE: A hydrophobic treatment method and apparatus are provided to secure stable and high hydrophobic property using hexamethyl disilazane gas as carrier gas of H2O. CONSTITUTION: A reaction accelerator which accelerates the hydrophobic of a substrate is provided to the substrate. The substrate which is carried in the inner side of a treatment basin(30) is heated. The steam vapor of the reaction accelerator is adsorbed on the surface of the substrate. Hydrophobic treatment gas is provided to the surface of the substrate. The reaction of silicon of the hydrophobic treatment gas and oxygen of the surface of the substrate is accelerated by the reaction accelerator.

Description

HYDROPHOBIC CONVERSION PROCESSING METHOD AND HYDROPHOBIC CONVERSION PROCESSING APPARATUS}

The present invention relates to a hydrophobization treatment method and a hydrophobization treatment apparatus for performing a hydrophobization treatment on a substrate.

As one of a series of processes of forming a resist pattern in a manufacturing process such as a semiconductor device or an LCD substrate, there is a hydrophobization treatment for a substrate, for example, a semiconductor wafer W (hereinafter referred to as "wafer"). . This treatment is performed to improve the adhesion between the base film and the resist film before applying the resist liquid to the wafer W. FIG.

Such hydrophobization treatment is carried out by loading the wafer W on a mounting table in the processing container, and supplying a HMDS (hexamethyl disilazane) gas into the processing container while the wafer W is heated. For example, the HMDS gas is obtained by introducing nitrogen (N ₂ ) gas, which is a carrier gas into the storage tank of the HMDS liquid, and vaporizing the HMDS liquid, and the gas is supplied into the processing vessel together with the N ₂ gas. In this way, by supplying the HMDS gas to the wafer W, a thin film is formed on the surface of the wafer W, and the surface of the hydrophilic wafer W is changed to hydrophobic.

By the way, the measurement of a contact angle is known as one of the evaluation methods of hydrophobization treatment. In this method, it is determined that the larger the contact angle is, the larger the hydrophobicity is, and the target contact angle is set also in the hydrophobization treatment in forming a resist pattern. If the target contact angle cannot be obtained on the surface of the wafer W, the adhesion between the base film and the resist film is insufficient and pattern collapse occurs, resulting in a decrease in yield.

In the above-mentioned method, hydrophobization treatment is usually performed by setting the mounting table temperature at 90 ° C. and the processing time at about 30 seconds. If it is carried out under these treatment conditions, a contact angle of about 60 to 70 ° can be secured, but a target contact angle may not be obtained due to factors such as deterioration of the HMDS gas. At this time, if the processing time is extended, the contact time with the HMDS gas on the surface of the wafer W becomes long, so that the hydrophobization treatment proceeds sufficiently and the contact angle can be increased. However, from the viewpoint of improving the throughput of the process, it is not profitable to lengthen the processing time, and it is preferable to improve the hydrophobicity without lengthening the processing time.

By the way, patent document 1 describes the technique of carrying out a hydrophobization process by loading a board | substrate on a heating plate. According to this technique, although hydrophobicity can be improved by adjusting the temperature of a board | substrate, the establishment of the technique which can ensure stable and high hydrophobicity by a simpler method is calculated | required.

Japanese Patent Application Laid-Open No. 2009-194239 (Fig. 12 to Fig. 15, etc.)

SUMMARY OF THE INVENTION The present invention has been made to solve such a problem, and an object of the present invention is to provide a hydrophobization treatment method and a hydrophobization treatment apparatus capable of securing stable and high hydrophobicity.

In the hydrophobization treatment method of the present invention, a hydrophobization treatment gas containing trimethylsilyl groups is supplied to a substrate containing silicon and having a hydroxyl group on the surface thereof in a processing container, and -O (CH ₃ ) ₃ is applied to the surface of the substrate. In the hydrophobization treatment method of generating a hydrophobic group consisting of:

Vaporizing a reaction promoter for promoting hydrophobicity of the substrate and supplying the substrate to the substrate;

Heating the substrate brought into the processing container;

A step of supplying the hydrophobization treatment gas to the surface of the substrate in a state in which vapor of the reaction accelerator is adsorbed on the surface of the heated substrate,

The reaction accelerator promotes the reaction between the silicon of the hydrophobization treatment gas and the oxygen on the substrate surface.

Here, the reaction accelerator may be a material selected from water, ammonia, amines and alcohols. In addition, the process of vaporizing the said reaction promoter and supplying it to a board | substrate is performed at least in the timing of heating up a board | substrate to a preset temperature, and after heating a board | substrate to a preset temperature before heating a board | substrate.

The vapor of the reaction accelerator may be supplied to the processing vessel after being mixed with the hydrophobization treatment gas. Moreover, you may make it evaporate by heating the storage part of the liquid of the reaction accelerator provided in the said processing container. In addition, before carrying a board | substrate into the said processing container, you may make it supply the vapor of the said reaction promoter to the said board | substrate.

In addition, the hydrophobization treatment apparatus of the present invention supplies a hydrophobization treatment gas containing trimethylsilyl group to a substrate containing silicon, which is loaded in a loading section in a processing container, and having a hydroxyl group on the surface thereof, to the surface of the substrate. in the hydrophobic treatment apparatus for creating a group consisting of a small number of -O (CH _{3) 3,}

Heating means provided in the processing container for heating the substrate;

A hydrophobization treatment gas supply path for supplying the hydrophobization treatment gas into the processing container;

A reaction accelerator supplying means for vaporizing and supplying a reaction accelerator for promoting hydrophobicity of the substrate in the processing container,

In the processing container, the hydrophobization treatment gas is supplied to the surface of the substrate in a state where the vapor of the reaction accelerator is adsorbed on the surface of the heated substrate, and the reaction accelerator is used to provide silicon and the substrate of the hydrophobization treatment gas. It is characterized by promoting the reaction of oxygen on the surface.

The reaction promoter may be a material selected from water, ammonia, amines and alcohols. The reaction accelerator supply means may be configured as a reaction accelerator supply path for supplying the vapor of the reaction accelerator into the processing container. At this time,

The reaction accelerator supplying path is also used as the hydrophobization treatment gas supply passage, and the vapor of the reaction accelerator may be mixed with the hydrophobization treatment gas and then supplied to the processing vessel. The reaction accelerator supplying means may include a storage portion of the liquid of the reaction accelerator provided in the processing vessel and a heating portion for heating the storage portion, and may vaporize the reaction accelerator in the processing vessel.

According to the present invention, in a processing vessel, a substrate surface comprising silicon and having a hydroxyl group on the surface thereof and a hydrophobization treatment gas containing trimethylsilyl group are brought into contact with each other to form -O (CH ₃ ) ₃ on the substrate surface. In the hydrophobization process which produces | generates a hydrophobic group, the said hydrophobization process gas is supplied to the surface of the said board | substrate in the state in which the vapor of the reaction promoter is adsorbed to the surface of the heated board | substrate. The reaction accelerator promotes a reaction in which the silicon of the hydrophobization treatment gas and oxygen on the surface of the substrate are bonded to form the hydrophobic group on the surface of the substrate, so that stable and high hydrophobicity can be secured by performing the hydrophobization treatment. .

BRIEF DESCRIPTION OF THE DRAWINGS The process chart explaining the outline of the hydrophobization processing method which concerns on embodiment of this invention.
2 is an explanatory diagram for explaining a hydrophobization treatment when HMDS gas is used as the hydrophobization treatment gas.
Fig. 3 is a characteristic diagram showing activation energy obtained from quantum chemical calculations for the case where HMDS gas is used as the hydrophobization treatment gas.
4 is a configuration diagram showing an embodiment of a hydrophobicization processing system using the hydrophobicization processing apparatus of the present invention.
Fig. 5 is a sectional view and a plan view showing one embodiment of a hydrophobization treatment apparatus of the present invention.
6 is a cross-sectional view showing an example of a vaporization unit installed in the hydrophobic treatment system.
7 is a process chart for explaining the operation of the hydrophobic treatment apparatus.
8 is a flowchart for explaining the hydrophobization treatment method of the present invention.
9 is a configuration diagram illustrating another example of the hydrophobization processing system.
FIG. 10 is a flowchart for explaining a hydrophobic treatment method performed in the hydrophobic treatment system shown in FIG. 9. FIG.
11 is a configuration diagram showing still another example of the hydrophobization processing system.
12 is a configuration diagram showing still another example of the hydrophobicization processing system.
13 is a sectional view and a plan view showing another example of the hydrophobization treatment apparatus of the present invention.
14 is a cross-sectional view showing still another example of the hydrophobization treatment apparatus of the present invention.
FIG. 15 is a flowchart for explaining the operation of the hydrophobization treatment apparatus shown in FIG. 14. FIG.
16 is a cross-sectional view showing still another example of the hydrophobization treatment apparatus of the present invention.
FIG. 17 is a flowchart for explaining the operation of the hydrophobization treatment device shown in FIG. 16; FIG.
18 is a cross-sectional view showing still another example of the hydrophobization treatment apparatus of the present invention.
19 is a block diagram illustrating another example of the supply of water vapor.
20 is an explanatory diagram showing another example of a reaction accelerator.
21 is a cross-sectional view showing a hydrophobization processing apparatus used in the embodiment.
Fig. 22 is a characteristic diagram showing an embodiment performed to confirm the effect of the present invention.
23 is a characteristic diagram showing the result of the said Example.
Fig. 24 is a characteristic diagram showing the result of another embodiment performed to confirm the effect of the present invention.

First, the outline | summary of this invention is demonstrated based on FIG. The present invention is made by contacting a surface of a substrate including silicon (Si) with a hydroxyl group (OH group), for example, a surface of a wafer (W), and a hydrophobization treatment gas containing a trimethylsilyl group to contact the wafer (W). It relates to a hydrophobization treatment for generating a hydrophobic group consisting of -O (CH ₃ ) ₃ on the surface. Then, the reaction accelerator for promoting hydrophobicity of the wafer W is vaporized and supplied to the wafer W, and in the state where the vapor of the reaction accelerator is adsorbed on the heated wafer W surface, the wafer W The hydrophobization treatment gas is supplied to the surface of the wafer to hydrophobize the surface of the wafer (W). Hereinafter, the reaction accelerator of water, hydrophobic treatment gas HMDS gas: for _{(CH 3) 3 SiNHSi (CH} 3) 3, a wafer (W) to be formed on the surface minority group -O (CH _{3) 3,} if for example the Proceed to explanation.

FIG. 1A shows a wafer W carried in a processing container, and the OH group on the surface of the wafer W is caused by moisture in the outside air adsorbed during clean room conveyance. When water vapor and HMDS gas are supplied into this processing container, water vapor is adsorbed on the wafer surface, and this water vapor acts as a reaction accelerator (catalyst), and the hydrophobic reaction shown in Basic Reaction Formula 1 below proceeds.

Scheme 1

SiOH in Scheme 1 is an OH group on the surface of the wafer W, as shown in FIGS. 1A and 1B, and in FIG. 1B, the water vapor supplied into the processing vessel is a wafer W. It shows the adsorption on the surface. By this reaction, as shown in FIG. 1 (c), the wafer (W) surface is created due to the small number ₃ OSi (CH _3), the surface of the wafer (W) is hydrophobic.

In this hydrophobic reaction, for example, as shown in FIG. 2, Si—N bond of HMDS gas is cleaved, and Si, in which the bond with N is broken, is bonded to O of OH bond, and OSi (CH ₃ ), which is a hydrophobic group ₃ is generated. On the other hand, H released from the OH bond is bonded to N of the cleaved Si-N bond to generate (CH ₃ ) ₃ SiNH ₂ .

Here, as to the reason why the hydrophobization reaction is promoted by the presence of water vapor, as shown in FIG. 3, when water vapor (H ₂ O) is present in a transition state, the activation energy of the reaction is lower than when water vapor is not present. It is considered that the hydrophobization reaction is likely to proceed. In addition, the activation energy shown in FIG. 3 is a rough value.

And the mechanism by which activation energy becomes small by presence of water vapor is estimated as follows. That is, the HMDS molecule has a three-dimensional structure, and in order for the HMDS to react with SiOH, the HMDS molecule needs to be at an angle with respect to SiOH. At this time, when water vapor is involved, as shown in FIG. 3, in the transition state, N in the HMDS bonds with SiOH through H ₂ O, and then the hydrogen bond is replaced, and SiOSi (CH ₃ ) is replaced. _{It is} thought that ₃ and (CH ₃ ) ₃ SiNH ₂ are produced. On the other hand, when water vapor is not involved, Si in HMDS and O in SiOH react as shown in FIG. 2.

Therefore, when water vapor is involved, the degree of freedom of the angle of HMDS for reacting with SiOH increases in the transition state, and as a result, the Si of HMDS and O of SiOH tend to react, resulting in lowering the activation energy. It is assumed that.

However, HMDS is known to be hydrolyzed by H ₂ O. However, when H ₂ O is present in the gaseous state as water vapor, hydrolysis hardly occurs while being supplied to the hydrophobic treatment apparatus, and as is apparent from the examples described later, the hydrophobization treatment proceeds rapidly on the wafer W surface. do. On the other hand, when H ₂ O exists in the liquid state, the collision probability between HMDS and H ₂ O increases, and hydrolysis occurs.

From this, when H ₂ O is adsorbed on the wafer W in a liquid state, the hydrolysis reaction proceeds. However, when H ₂ O adsorbed on the wafer W comes into contact with the HMDS gas in a gaseous state, the above-described hydrolysis reaction proceeds. As described above, the catalyst material acts as a catalyst material, and in the presence of SiOH, the OH removing action acts to produce the hydrophobic group described above.

By the way, the hydrophobization treatment is performed by, for example, loading the wafer W on a hot plate heated to 90 ° C. in advance for 30 seconds, and supplying water vapor to the wafer W before heating the wafer W. , At the time of raising the wafer W to a set temperature of 90 ° C. and at least one timing of heating the wafer W to a set temperature.

When water vapor is supplied before heating the wafer W, when the wafer W is heated, water vapor is sufficiently adsorbed, and HMDS gas is supplied to the surface of the wafer W in this state. If water vapor is present, the activation energy is reduced as described above. Thus, even if the temperature of the wafer W is lower than the set temperature, a hydrophobic reaction occurs, and while the temperature of the wafer W is elevated, the hydrophobic reaction sufficiently proceeds. In addition, even when water vapor is supplied while the wafer W is heated to the set temperature, hydrophobization reaction occurs even when the temperature of the wafer W is lower than the set temperature as described above, so that the wafer W is heated thereafter. , The hydrophobic reaction proceeds sufficiently.

In addition, when the steam is supplied after heating the wafer W to the set temperature, since the set temperature is 90 ° C., the vapor adsorbed on the wafer W may volatilize, but since the vapor is continuously supplied, Water vapor is always adsorbed on the wafer W surface. The hydrophobization reaction is accelerated by the adsorbed water vapor. At this time, in the hydrophobic treatment, for example, the reaction rate increases when the wafer W is heated to a set temperature, so that the hydrophobization reaction proceeds faster by supply of steam.

Therefore, the water vapor contributing to promoting the hydrophobic reaction may be supplied such that the HMDS gas and the surface of the wafer W come into contact with each other while the water vapor is adsorbed on the wafer W surface. May be supplied from the outside to the processing vessel, or vapor may be generated by a vaporizer and supplied directly to the processing vessel. In addition, water vapor may be adsorbed to the wafer W before being carried into the processing container, and the wafer W may be carried into the processing container. In addition, steam may be generated inside the processing container.

However, as described above, when H ₂ O is in contact with the HMDS gas in the liquid state, the hydrolysis reaction proceeds, and the HMDS gas is not easily brought into contact with the wafer W by water. For this reason, when supplying HMDS gas and water vapor to a processing container by a common supply path, it is required not to condense water vapor in this supply path.

In addition, in the processing container, even if water vapor is adsorbed on the surface of the wafer W, a part of it will evaporate when the wafer W is heated. Therefore, while the water vapor is adsorbed on the wafer W surface, the HMDS gas supply timing to the processing vessel, the HMDS gas concentration, the water vapor supply timing, or the wafer so that the HMDS gas and the wafer W surface come into contact with each other. The method of temperature rising of (W) is determined. For example, when steam is supplied to the processing container after the wafer W is heated, the hydrophobic reaction can be sufficiently promoted by increasing the HMDS gas concentration.

In addition, about the supply amount of steam, it is recognized by the Example mentioned later that when there is much supply amount of steam, higher hydrophobicity can be ensured. However, if the amount of water vapor supplied increases, there is a risk of condensation in the processing container. Therefore, the supply amount of steam is set so that the processing container is not condensed by processing conditions such as the heating temperature of the wafer W and the processing time. .

Hereinafter, the specific water vapor supply method is demonstrated with reference to drawings. It is a block diagram which shows one Embodiment of the hydrophobicization processing system provided with the hydrophobicization processing apparatus of this invention.

In this invention, as a method of adding water vapor to a processing container,

(1) Example of using N ₂ gas as a carrier gas of water vapor, joining with HMDS gas, and supplying it to a processing vessel.

(2) Example using HMDS gas as carrier gas of water vapor.

Is employed and will be described below by dividing each example. The example shown in Fig. 4 is a case of using the N ₂ gas as a carrier gas of water vapor.

In FIG. 4, the code | symbol 1 is a storage tank which stores HMDS liquid, The downstream side is provided with the HMDS vaporization unit 2 via the supply path 11 provided with the pump P and the color back valve SV. Reference numeral 20 in the drawings denotes a temperature controller of the HMDS vaporization unit 2. The HMDS vaporization unit 2 is connected with a supply source 21 of N ₂ gas via a supply path 22 provided with a valve AV1 upstream thereof, while a valve AV3 and a filter F downstream thereof. ), The processing container of the hydrophobization processing unit (ADH) 3 is connected via the supply path 23 which provided the density | concentration sensor T and the valve AV4 in this order from the upstream. 4, the supply path 24 branching from the supply path 23 may be provided between the concentration sensor T and the hydrophobization processing unit 3. AV7 is a valve provided in the supply passage 24.

In the figure, reference numeral 4 denotes an H ₂ O vaporization unit, the upstream side of which is connected to the supply source 42 of N ₂ gas via a supply passage 41 having a valve AV8, while the downstream side thereof has a switching valve AV9. It is connected to the downstream side of the density sensor T of the said supply path 23 through the supply path 43 provided with the said supply path 43. Further, the supply 43 is connected to a supply source 45 of the N ₂ gas through a supply (44) having a valve (AV10).

In addition, the processing vessel of the hydrophobization processing unit 3 is exhausted through an exhaust passage 51, and the exhaust passage 51 is provided by a supply passage 52 having a valve AV2 and a valve AV5. is connected to the source 5 of the purge gas is N ₂ gas. This supply path 52 is also connected to the said supply path 23. Moreover, the switching valve AV9 is comprised so that it may switch to the exhaust path 53 connected to the exhaust path 51, and may connect. Moreover, the upstream side of the valve AV4 of the supply path 23 mentioned above is connected to the said exhaust path 53 by the exhaust path 54 provided with the valve AV6. Here, in FIG. 4, in the area | region enclosed by a double wire, in order to suppress the condensation of HMDS gas or water vapor, the heating means which consists of a heater is wound up, for example, and temperature is adjusted so that HMDS gas or water vapor does not condensate. It is.

And the detection value of the density sensor T is output to the control part 100 mentioned later, and the control part 100 of the pump P and the HMDS vaporization unit 2 is based on the detection value of the density sensor T. It is configured to output a control signal to the temperature controller 20. For example, when the detected value of the concentration sensor T is lower than the set value, control is performed to increase the flow rate of the HMDS liquid by the pump P or to raise the temperature of the HMDS vaporization unit 2. All.

Subsequently, an embodiment of the hydrophobicization processing unit 3 which is the hydrophobicization processing apparatus of the present invention will be described with reference to FIG. 5. In the figure, reference numeral 30 denotes a processing container, one end side of which is open as the conveyance port 31 of the wafer W, and is configured to be opened and closed by the shutter 32. Although FIG. 5 shows the state in which the shutter 32 is closed, in this example, even when the shutter 32 is closed, it is comprised so that the clearance gap for introduction of outside air may open slightly.

Inside the processing container 30, a hot plate 33 constituting the mounting portion of the wafer W is provided so as to be supported by the support block 34 around it. This hot plate 33 is provided with the heating part which consists of a heater which is not shown in figure, for example, and is corresponded to the heating means which heats the board | substrate of this invention. In addition, the hot plate 33 is provided with a lift pin mechanism 35 for use in transferring the wafer W between the external conveying means and the hot plate 33. Moreover, in order to prevent the condensation of water vapor, the heating means 36 which consists of a heater is built in the ceiling part of the processing container 30, for example.

In the ceiling part of the said processing container 30, the gas discharge part 37 is provided in the vicinity of the said conveyance port 31. As shown in FIG. This gas discharge part 37 is formed so that the diameter of the wafer W may be covered, for example along the width direction (Y direction in FIG. 5 (b)) of the conveyance port 31. As shown in FIG. In the figure, reference numeral 37a is a gas supply part connected to the gas discharge part 37, and one end side of the above-described supply path 23 (also supply path 24) is connected to the gas supply part 37a.

In this example, vapor and hydrophobization treatment gas of the reaction accelerator are supplied into the processing vessel 30 through the supply passage 23 (also the supply passage 24). Therefore, the said supply path 23 is corresponded to the hydrophobization process gas supply path which supplies the hydrophobization process gas into the process container 30. In addition, in this example, as a reaction accelerator supplying means for vaporizing and supplying a reaction accelerator in the processing vessel 30, a reaction accelerator supply path for supplying the vapor of the reaction accelerator is provided in the processing vessel 30. The furnace is configured as a supply passage 23 common to the hydrophobization treatment gas supply passage.

A suction exhaust port 38 is formed in the ceiling of the processing container 30 so as to face the gas discharge portion 37 with the wafer W loaded on the hot plate 33 interposed therebetween. This suction exhaust port 38 is provided so as to cover the diameter of the wafer W, for example, along the width direction of the conveyance port 31. In the figure, reference numeral 38a denotes an exhaust portion connected to the suction exhaust port 38, and the exhaust passage 51 described above is connected to the exhaust portion 38a. These gas discharge parts 37 and suction exhaust ports 38 may be formed in a slit shape, or small holes may be arranged at regular intervals. In this example, exhaust means for exhausting the inside of the processing container 30 is configured by the suction exhaust port 38, the exhaust part 38a, and the exhaust path 51.

Subsequently, the HMDS vaporization unit 2 and the H ₂ O vaporization unit 4 will be briefly described with reference to FIG. 6. Since these are configured in the same manner, the H ₂ O vaporization unit 4 will be described as an example. As a H ₂ O vaporization method, water is stored to inlet or bubble a carrier gas to vaporize, or a method of raising the temperature to evaporate at a constant pressure, and heating the water in advance to lower the pressure at one time to vaporize it. Various methods, such as a method, the method of mixing water and the heated carrier gas in the gas-liquid mixing part in front of an outlet, and passing through an outlet and depressurizing and vaporizing, can be used.

In addition, the method shown in FIG. 6 is used as a method of controlling the amount of vaporization. For example, in the example shown to FIG. 6A, water is stored in the processing container 400, and control of vaporization amount is adjusted by adjusting heating temperature. For example, in the hydrophobization processing system of FIG. The HMDS vaporization unit 2 and the H ₂ O vaporization unit 4 of this system are employed. In this example, a predetermined amount of water is fed through a supply path 411 into the processing container 400 by a pump (not shown), and the heating means 420 is formed by a heater provided around the processing container 400. It vaporizes by heating. Carrier gas, N ₂ gas in this example, is always introduced into the processing container 400 through the supply path 41, and vaporized water vapor is supplied to the processing container 400 through the supply path 43 together with the N ₂ gas. It flows out of. In the figure, reference numeral 412 denotes a discharge path discharged when excess water is supplied into the processing container 61.

Moreover, also in the HMDS vaporization unit 2, it is comprised similarly, the HMDS liquid of a predetermined amount is conveyed by the pump P via the supply path 11 in the process container 400, and the periphery of the process container 400 is carried out. It is comprised so that it may vaporize by heating by the heating means 420 which consists of a heater provided in the inside. In addition, N ₂ gas, which is a carrier gas, is constantly introduced into the processing container 400 through the supply path 22, and the HMDS gas vaporized in the processing container 400 is supplied through the supply path 23 together with the N ₂ gas. It flows out from the processing container 400. At this time, temperature control of the heating means 420 is performed by the temperature controller 20.

In the example shown in FIG. 6B, water is dropped into the processing container 400, and the amount of H ₂ O vaporization is controlled by adjusting the amount of dropping. In this example, water of the flow rate controlled by the mass flow controller or the pump is dripped in the processing container 400, and it vaporizes by heating by the heating means 420 provided around the processing container 400, The amount of H ₂ O vaporization is controlled from the heating temperature of the processing vessel 400 and the dropping amount of water. Carrier gas, N ₂ gas in this example, is constantly introduced into the processing vessel 400 through the supply passage 41, and vaporized water vapor is supplied from the processing vessel 400 through the supply passage 43 together with the N ₂ gas. Going out In the processing container 400, a fin structure for promoting vaporization may be provided.

As the processing container 400 shown to Fig.6 (a), (b), it is preferable to use materials with high thermal conductivity, such as copper (Cu) and aluminum (Al). In addition, when HMDS gas is used as a carrier gas of water vapor, in addition to hydrophobic treatment, HMDS gas remains in the processing container 400 so that hydrolysis proceeds and ammonia (NH ₃ ) that inhibits hydrophobic generation does not occur. It is preferable to introduce N ₂ gas into the H ₂ O vaporization unit 4 at all times. In addition, the heating means for heating the processing container 400 may be a heating plate provided under the processing container 400.

In the structure of FIG. 6C, water is stored in the processing container 400, and the H ₂ O vaporization amount is controlled by the pressure reduction control. In this example, the predetermined amount of water is fed into the processing container 400 by a pump (not shown) via the supply path 411, and the processing container is provided by the heating means 420 provided around the processing container 400. Heat 400. On the other hand, the processing vessel 400 is provided with a flow path 431 for flowing out vaporized water vapor, and the flow path 431 through the ejector part 430, supply paths 41 and 43 of the N ₂ gas, which is a carrier gas. ) Is connected. And by the ejector effect which the ejector part 430 generate | occur | produces by the flow of this carrier gas, the inside of the processing container 400 is depressurized through the flow path 431, and it combines with the heating by the heating means 420, and water Vaporize. The vaporized water vapor is sucked from the flow path 431 by the ejector effect of the flow of the carrier gas, and flows out from the supply path 43 together with the carrier gas. In this method, even when HMDS gas is used as a carrier gas of water vapor, there is an advantage that HMDS gas is difficult to invade into the processing container 400. In addition, the heating means for heating the processing container 400 may be a heating plate provided under the processing container 400.

In the vaporization of HMDS, a vaporization filter may be used to control the vaporization amount by controlling the temperature of the vaporization filter and controlling the HMDS liquid supply amount.

The hydrophobicization processing system is configured to be controlled by the control unit 100. This control part 100 consists of a computer, for example, and is provided with the program, a memory, and a CPU. In the program, a command (each step) is issued to send a control signal from the control part 100 to each part of the hydrophobicization processing system and advance the predetermined hydrophobicization process. This program is stored in a storage unit such as a computer storage medium, for example, a flexible disk, a compact disk, a hard disk, or an MO (magnet) disk, and is installed in the control unit 100.

Subsequently, the hydrophobic treatment method of the present invention performed by the hydrophobic treatment apparatus described above will be described with reference to FIGS. 7 and 8. First, temperature control of the HMDS vaporization unit 2 and the H ₂ O vaporization unit 4 is started (step S1). Subsequently, the pump P is operated to supply a predetermined amount of HMDS liquid from the HMDS liquid storage tank to the HMDS vaporization unit 2 (step S2). Subsequently, in the H ₂ O vaporization unit 4, the amount of vaporization of the H ₂ O is controlled as described above (step S3).

Subsequently, the valves AV1, AV3, AV4, AV8 and AV9 are opened. Thereby, the HMDS gas generated in the HMDS vaporization unit _{2 using} the N ₂ gas from the N ₂ source 21 as the carrier gas is supplied to the hydrophobization processing unit 3 via the supply passage 23, and N ₂ Water vapor generated in the H ₂ O vaporization unit 4 using the N ₂ gas from the source 42 as the carrier gas is supplied to the hydrophobization processing unit 3 through the supply paths 43 and 23 (step S4, FIG. 7). (A)]. That is, the HMDS gas and the water vapor are joined in the supply path 23 and supplied to the hydrophobization processing unit 3 by the N ₂ gas which is the carrier gas. At this time, the concentration of the HMDS gas is measured by the concentration sensor T at a predetermined timing at all times, and the temperature controller 20 of the pump P or the HMDS vaporization unit 2 controls the feedback based on the detected value. HMDS gas concentration is controlled so that the concentration of water vapor in the HMDS gas becomes a desired concentration.

In addition, as shown in FIG. 7A, the processing container 30 is closed by the shutter 32 and is exhausted at an exhaust amount of, for example, about 5 to 15 L / min. At this time, even when the shutter 32 is closed as described above, since the gap for introducing the outside air is formed, the outside air enters into the processing container 30, whereby moisture contained in the outside air enters the processing container 30. Is introduced. In order to stabilize the water vapor concentration, the valves AV1, AV3, AV6, AV8 and AV9 are opened before the hydrophobization treatment is started to supply the HMDS gas and the water vapor to the supply passage 23 and the exhaust passages 54 and 53. You may exhaust through.

Subsequently, the shutter 32 is opened, and the wafer W is loaded into the processing container 30 through the transfer port 31 by an external transfer mechanism (not shown) (step S5, FIG. 7B). ]. Then, the wafer W is transferred onto the hot plate 33 using the push pin mechanism 35, and the shutter 32 is closed. At this time, since HMDS gas and water vapor are supplied into the processing container 30 in advance, the wafer W is carried into the processing container 30 while the HMDS gas and water vapor are adsorbed on the surface thereof, and is heated to 90 ° C. in advance. Will be delivered on (33).

Subsequently, as shown in FIG. 7C, the hydrophobization process is performed (step S6). In this hydrophobic treatment, the wafer W is heated by the hot plate 33 while supplying HMDS gas and water vapor from the gas discharge part 37 into the processing container 30, while the inside of the processing chamber 30 is 5 to 15 L /. Exhaust is performed in an exhaust state of about min. In this manner, after the wafer W is loaded on the hot plate 33, hydrophobization treatment is performed for about 15 to 30 seconds. Here, in the processing container 30, since the gas discharge part 37 and the suction exhaust port 38 are formed to face each other with the wafer W interposed therebetween, one direction from the conveyance port 31 side to the suction exhaust port 38 side. An air stream flowing to it is formed.

Subsequently, as shown in Fig. 7D, the valves AV1, AV3, AV4, AV8, AV9 are closed and the valves AV2, AV4, AV10 (or valves AV2, AV7, AV10) are closed. at the same time opening to the supply of N ₂ gas through the {52, 23 - or supply (52, 24)} as supplied from the purge N ₂ gas supply source (5) into the processing vessel (30), N ₂ gas The N ₂ gas is supplied from the source 45 through supply paths 44 and 23 (or supply paths 44 and 24). In this manner, the N ₂ purge in the processing container 30 is started (step S7), and the shutter 32 is opened to take out the wafer W (step S8).

After the carrying out of the wafer W is completed, the shutter 32 is closed to continuously supply the purge N ₂ gas into the processing container 30 to perform a substitution process (FIG. 7E, step S9). When performing this substitution process, you may exhaust the inside of the processing container 30 in the high exhaust state of about 30-100 L / min, for example. After the inside of the processing container 30 is replaced by the N ₂ gas, the valves {AV2, AV4, AV10 (or the valves AV2, AV7, AV10)] are closed, and the valves AV1, AV3, AV5 are opened. Thus, the N ₂ gas is passed through the supply passages 22, 23, and 52 and the exhaust passage 51, and residual HMDS remaining in these supply passages is discharged (step S10). In addition, except during the processing, the valve AV8 is opened to supply the N ₂ gas to the hydrophobization processing unit 3 through the H ₂ O vaporization unit 4 and the supply paths 43 and 23, and the exhaust path ( 51).

In such a hydrophobic treatment method, since water vapor is supplied to the processing container 30 together with HMDS gas, as described above, steam acts as a reaction accelerator (catalyst) to promote the hydrophobic treatment. For this reason, by the simple method of supplying water vapor, a contact angle of 65 ° or more can always be obtained even under treatment conditions in which the hot plate temperature is 90 ° C. and the hydrophobization treatment time is 30 seconds. By performing this hydrophobization treatment, high hydrophobicity is achieved. It can be secured.

In addition, since N ₂ gas is used as a carrier gas and HMDS gas and water vapor are combined in front of the processing vessel 30 and then supplied to the processing vessel 30, water vapor condenses in the piping, where the HMDS gas flows through. Thus, there is no fear that the HMDS gas will be hydrolyzed, and steam and HMDS gas can be introduced into the processing container 30 in a stable state.

In addition, HMDS gas is supplied to the processing container 30 before the wafer W is brought into the processing container 30, and before the wafer W is transferred to the hot plate 33, the inside of the processing container 30 is HMDS. It can be set to a gas atmosphere. Therefore, even when the wafer W is brought into the processing container 30, the HMDS gas is in contact with the surface of the wafer W, so that the reaction with the HMDS gas is surely started while moisture is adsorbed on the surface of the wafer W. You can. Thereby, the water adsorbed on the surface of the wafer W can be fully contributed to the hydrophobic reaction.

In addition, since the inside of the processing container 30 is in the HMDS gas atmosphere, the entire surface of the wafer W is in contact with the HMDS gas at the start of heating the wafer W. For this reason, before water vapor adsorb | sucked to the wafer W is volatilized by the heating of the wafer W, hydrophobization process is performed on the whole surface of the wafer W, and hydrophobization process can be performed reliably in presence of reaction promoter. .

In addition, even after the wafer W is brought into the processing container 30, since HMDS gas and water vapor are continuously introduced into the processing container 30, water vapor is always supplied to the surface of the wafer W, and the wafer W is supplied. It can react with HMDS gas while water is adsorbed on the surface.

In addition, the outside air containing the moisture of about 40% RH of humidity at room temperature can be introduced into the processing container 30 from the outside air introduction gap of the shutter 32 at the room temperature. Since the moisture in the outside air is heated inside the processing container 30, the water vapor is adsorbed onto the wafer W because of the introduction of the outside air, so that the water vapor can be supplied to the wafer W surface.

In addition, in the above-mentioned example, although water vapor is continuously supplied into the processing container 30 before carrying in the wafer W until the hydrophobization process is complete after carrying in the wafer W, the water vapor is the wafer W May be supplied only to the processing container 30 before carrying it into the processing container 30, or may be supplied only while the wafer W is carried into the processing container 30. Here, while the wafer W is carried into the processing container 30, one end side of the wafer W enters the processing container 30 and transfer of the wafer W to the hot plate 33 is performed. We say while to end. In addition, after carrying the wafer W into the processing container 30, you may make it supply steam only during the temperature which raises the wafer W to a predetermined temperature, for example, 90 degreeC. In addition, the wafer W may be carried into the processing container 30 to supply steam only after the wafer W is heated to a set temperature. In addition, any of these timings may be combined to supply water vapor into the processing container 30.

As described above, the HMDS gas may pressurize the HMDS tank 6 supplied with the HMDS liquid therein to vaporize the HMDS liquid, as shown in FIG. 9. In this example, in the configuration of FIG. 4 described above, an HMDS tank 6 is provided instead of the HMDS vaporization unit 2. The HMDS tank 6 is connected to a storage tank 1 for storing HMDS liquid through a supply passage 61 provided with a valve AV11, and a pressurized N ₂ gas supply 62 is provided with a valve AV12. It is connected via the supply path 63 provided with. The HMDS gas generated by pressurization of the N ₂ gas is configured to be sent to the hydrophobic treatment unit 3 through the supply path 64 and the supply path 23 provided with the valve AV13. The supply path 64 is provided with a filter F and a concentration sensor T downstream of the valve AV13. In addition, the purge N ₂ gas source 5 is connected between the valve AV13 in the supply path 64 and the filter F by the supply path 52 provided with the valve AV5. In addition, since the structure of the downstream side of density | concentration sensor T is the same as that of the downstream side of density | concentration sensor T in FIG. 4, description is abbreviate | omitted.

In FIG. 9, the area | region enclosed by the double wire | line is temperature-controlled by the heating means which consists of a heater, for example, in order to suppress condensation of HMDS gas or water vapor | steam, and HMDS gas or water vapor | steam is not condensed. In addition, the detection value of the concentration sensor T is output to the control part 100, and the control part 100 transmits a control signal to the temperature controller 60 of the HMDS tank 6 based on the detection value of the concentration sensor T. Is configured to output For example, when the detection value of the concentration sensor T is low, control is performed to raise the HMDS concentration by raising the heating temperature of the HMDS tank 6.

In this hydrophobic treatment system, as shown in FIG. 10, first, the valve AV11 is opened, and a predetermined amount of HMDS liquid is supplied from the storage tank 1 to the HMDS tank 6 (step S11). Then, the temperature control of the HMDS tank 6 is started (step S12). At this time, the valves AV13 and AV6 are opened to exhaust excess HMDS gas through the supply path 64 and the exhaust paths 54, 53, and 51. Subsequently, in the H ₂ O vaporization unit 4, the amount of vaporization of the H ₂ O is controlled as described above (step S13).

Subsequently, with the valves AV13 and AV6 open, the valves AV12, AV13, AV4 and AV8 are opened to switch the valve AV9 to the supply path 43. Thereby, the HMDS gas generated in the HMDS tank 6 using the N ₂ gas from the N ₂ source 62 as the carrier gas is supplied to the hydrophobicization processing unit 3 via the supply paths 64 and 23, and the N Water vapor generated in the H ₂ O vaporization unit 4 using the N ₂ gas from the _binary source 42 as the carrier gas is supplied to the hydrophobicization processing unit 3 through the supply paths 43 and 23 (step S14). At this time, the concentration of the HMDS gas is measured by the concentration sensor T at a predetermined timing at all times, and based on the detected value, the temperature controller of the HMDS tank 6 so that the water vapor concentration in the HMDS gas becomes a predetermined concentration. 60) is feedback controlled.

Subsequently, the wafer W is carried into the processing container 30 through the transfer port 31 (step S15). Then, the wafer W is transferred onto the hot plate 33 using the push pin mechanism 35 to close the shutter 32 and at the same time, the HMDS gas from the gas discharge part 37 in the processing container 30. And while supplying steam and exhausting the inside of the processing container 30, hydrophobization process is performed (step S16). In addition, in order to stabilize the H ₂ O concentration, the valves AV12, AV13, AV6, AV8 are opened before the start of the hydrophobization treatment, and the valve VAV9 is switched to the discharge passage 54 side, whereby HMDS gas and water vapor are vaporized. The gas may be exhausted through the supply paths 64 and 23 and the exhaust paths 54 and 53.

Thereafter, the valves AV12, AV13, AV4, AV8, AV9 are closed, and the valves AV4, AV5, AV10 (or valves AV5, AV7, AV10) are opened to purge the process vessel 30. N ₂ is supplied into the gas source 5 and the N ₂ gas source 52 to the supply from the {52, 41, 23 - or supply (52, 41, 24)} of the processing vessel 30 through. Then, the N ₂ purge in the processing container 30 is started (step S17), and the shutter 32 is opened to take out the wafer W (step S18).

In this manner, after the completion of the carrying out of the wafer W, the shutter 32 is closed, and the purge N ₂ gas is continuously supplied into the processing container 30 to perform the substitution process (step S19). In addition, except during processing, the valve AV8 is opened, the valve AV9 is switched to the supply path 43 side, and the H ₂ O vaporization unit 4 and the supply path 43 are always supplied from the N ₂ gas source 42. , 23 may be supplied to the hydrophobic treatment unit 3, and may be discharged through the exhaust passage 51.

Also in this configuration, by using the N ₂ gas as a carrier gas of water vapor, and supplied to the HMDS gas and then mixed with the process vessel 30. The For this reason, like the above-mentioned embodiment, the HMDS gas and the wafer W can be brought into contact with each other in the presence of water vapor, and the water vapor promotes the hydrophobization reaction. Therefore, in the said hydrophobization process, the target contact angle can be obtained and can ensure stable and high hydrophobicity.

Subsequently, an example of using the HMDS gas as the carrier gas of H ₂ O will be described with reference to FIGS. 11 and 12. In addition, since the structure of FIG. 11 performs vaporization of HMDS using the HMDS vaporization unit 2, the structure of the upstream of concentration sensor T is the same as that of FIG. 4, and abbreviate | omits description.

In this example, the downstream side of the concentration sensor T is connected to the H ₂ O vaporization unit 4 via the supply passage 65. The downstream side of the H ₂ O vaporization unit 4 is connected to the processing vessel 30 of the hydrophobization processing unit ADH 3 via a supply path 66 provided with a valve AV24, and at the same time, the valve ( It is connected to the exhaust path 51 via the discharge path 67 provided with AV26.

In this case, it is preferable to provide the H ₂ O vaporization unit 4 in the immediate vicinity of the hydrophobization treatment unit 3 so that the influence of the hydrolysis of the HMDS gas does not occur. Moreover, as shown by the dotted line in FIG. 11, between the density | concentration sensor T and the hydrophobicization processing unit 3, the supply path 68 provided with the valve AV27 which branches off from the supply path 65 is provided. You may also In addition, in FIG. 11, the area | region enclosed by the double line containing the supply path which connects the HMDS vaporization unit 4 and the hydrophobization processing unit 3 is a heater, for example, in order to suppress condensation of HMDS gas or water vapor. The heating means made up is wound up and temperature-controlled by the temperature which does not condensate HMDS gas or water vapor | steam. The detection value of the concentration sensor T is output to the control unit 100, and the control unit 100 controls the temperature controller of the pump P and the HMDS vaporization unit 2 based on the detection value of the concentration sensor T. It is configured to output a control signal to 20.

In such a hydrophobization treatment system, first, temperature control of the HMDS vaporization unit 2 and the H ₂ O vaporization unit 4 is started. Subsequently, the pump P is operated to supply a predetermined amount of HMDS liquid from the HMDS liquid storage tank 1 to the HMDS vaporization unit 2, and subsequently in the H ₂ O vaporization unit 4, as described above. Similarly, the amount of vaporization of H ₂ O is controlled.

Subsequently, the valves AV1, AV3, and AV24 are opened. Thereby, HMDS gas generated in the HMDS vaporization unit 2 using N ₂ gas from the N ₂ source 21 as a carrier gas is hydrophobized through the supply paths 23 and 65 and the H ₂ O vaporization unit 4. It is supplied to the processing unit 3. At this time, water vapor generated in the H ₂ O vaporization unit 4 is supplied to the hydrophobization processing unit 3 using the HMDS gas as the carrier gas. At this time, the concentration of the HMDS gas is measured by the concentration sensor T at a predetermined timing at all times, and the temperature controller 20 of the pump P or the HMDS vaporization unit 3 controls feedback based on the detected value. Thus, the concentration of the HMDS gas is controlled to fall within a predetermined range. In addition, in order to stabilize the H ₂ O concentration, the valves AV1, AV3, AV26 may be opened prior to the start of the hydrophobic treatment to exhaust the HMDS gas and the water vapor through the discharge path 67.

Subsequently, the shutter 32 is opened, the wafer W is loaded into the processing container 30 through an inlet by an external transport mechanism (not shown), and the wafer W is transferred onto the hot plate 33. The predetermined hydrophobicization process is performed. Subsequently, the valves AV1, AV3, AV24 are closed, and the valves AV2, AV24 (or valves AV2, AV27) are opened to supply the purge N ₂ gas source 5 into the processing vessel 30. The N ₂ gas is introduced through the furnaces 52, 65, 66 (or the supply passages 52, 65, 68) (step S7). After the shutter 32 is opened, and the wafer W is taken out, the shutter 32 is closed to continuously supply the purge N ₂ gas into the processing container 30 to perform a substitution process.

In this way, after the inside of the processing container 30 is replaced with the N ₂ gas, the valves {AV2, AV24 {or the valves AV2, AV27)} are closed, and the valves AV1, AV3, AV5 are opened and supplied. The N ₂ gas is supplied from the N ₂ gas source 21 into the furnace 23, and HMDS remaining in these supply paths 23 is discharged through the exhaust path 51. In addition, during the processing, the valves AV2 and A26 may be opened to always discharge the N ₂ gas through the H ₂ O vaporization unit 4, the supply path 23, and the discharge paths 67 and 51. In this way, the remaining of the HMDS gas into the H ₂ O vaporization unit 4 is prevented.

In such a hydrophobic treatment system, the HMDS gas is supplied to the processing vessel 30 using H ₂ O as a carrier gas. Thus, as in the above-described embodiment, the HMDS gas and the wafer W are present in the state where water vapor is present. Can be contacted. Therefore, since the hydrophobic reaction is promoted by this steam, the target contact angle can be obtained by the hydrophobic treatment, thereby ensuring stable and high hydrophobicity.

As described above, even when HMDS gas is used as a carrier gas of water vapor, an HMDS tank 6 may be provided instead of the HMDS vaporization unit 2 as shown in FIG. 12. In the example shown in FIG. 12, the upstream side of the density sensor T is comprised similarly to the example shown in FIG. 9, and the downstream side of the density sensor T is comprised similarly to the example shown in FIG.

In such a hydrophobic treatment system, first, the valve AV11 is opened to supply a predetermined amount of HMDS liquid from the storage tank 1 to the HMDS tank 6, and then the temperature control of the HMDS tank 6 is started. At this time, the valves AV13 and AV26 are opened to exhaust excess HMDS gas through the supply paths 64 and 65 and the discharge path 67. Subsequently, in the H ₂ O vaporization unit 4, the amount of vaporization of H ₂ O is controlled as described above.

Subsequently, the valves AV12, AV13, and AV24 are opened to supply the HMDS gas generated in the HMDS tank 6 by the supply of the N ₂ gas from the N ₂ circle 62 to the supply paths 64 and 65, and H _2. The hydrophobization processing unit 3 is supplied via the O vaporization unit 4. That is, water vapor is supplied to the hydrophobization processing unit 3 using HMDS gas as a carrier gas. At this time, the concentration of the HMDS gas is measured by the concentration sensor T at a predetermined timing at all times, and based on this detected value, the temperature controller 60 of the HMDS tank 6 to enter the predetermined range. Is feedback controlled.

Subsequently, the wafer W is carried into the processing container 30 through the transfer port 31 and transferred onto the hot plate 33 to close the shutter 32. And while supplying HMDS gas and water vapor from the gas discharge part 37 into the processing container 30, while performing the hydrophobization process while exhausting the inside of the processing container 30. In addition, in order to stabilize the H ₂ O concentration, the valves AV12, AV13, and AV26 are opened prior to the start of the hydrophobic treatment to exhaust HMDS gas and water vapor through the supply passages 68 and 65 and the discharge passage 67. You may do so.

Thereafter, the valves AV12, AV13, and AV24 are closed, and the valves AV24 and AV5 (or valves AV5 and AV27) are opened to purge the N ₂ gas source 5 into the processing vessel 30. N ₂ gas is supplied into the processing container 30. Then, the N ₂ purge in the processing container 30 is started and the wafer W is carried out. In this way, after exit out of the wafer (W), by continuously supplying a N ₂ gas into the processing container 30, a replacement process is carried out. In addition, the valves AV5 and AV26 may be opened outside the processing to discharge the N ₂ gas through the H ₂ O vaporization unit 4 and the discharge paths 67 and 51.

Thus even in this configuration, because the supplying HMDS gas to the processing vessel 30 by using as a carrier gas of H ₂ O, as in the above-described embodiment, contact the HMDS gas and the wafer (W) in a state in which water vapor is present You can. Therefore, since the hydrophobization reaction is promoted by this water vapor, the desired contact angle can be obtained by the hydrophobization treatment, thereby ensuring stable and high hydrophobicity.

In addition, steam may be generated inside the processing vessel 30 of the hydrophobization processing unit 3. Specifically, with reference to FIG. 13, the hydrophobization processing unit 3 shown in FIG. 13 includes an H ₂ O storage part 300 that forms a reservoir of the liquid of the reaction accelerator in the hydrophobization processing unit 3 shown in FIG. 5. ) Is installed. For example, the H ₂ O storage part 300 is provided in the vicinity of the hot plate 33 and, for example, as shown in FIG. 13B, the support block 34 on the transport port 31 side is provided. In the vicinity of the hot plate 33 on the surface, it is comprised as a groove part along the arc of the hot plate 33. Therefore, the H ₂ O reservoir 300 is provided on the side opposite to the suction exhaust port 38 through the wafer W on the hot plate 33.

In addition, the support block 34 is provided with a flow path 301 for supplying water, which is a liquid of a reaction accelerator, to the H ₂ O reservoir 300, and the other end side of the flow path 301 is connected to the pump P1. It is connected to the water reservoir 302 through. In this manner, water is always supplied to the H ₂ O reservoir 300. The support block 34 on to heat, the art H ₂ O reservoir 300, the vicinity of the H ₂ O storage unit 300 in, for example, a heating unit 303 composed of a heater is installed.

In such a configuration, the H ₂ O storage part 300 is vaporized by heat from the heating part 303 and the hot plate 33. Therefore, the hot plate 33 also has a function as a heating unit for heating the H ₂ O storage unit 300. At this time, since the H ₂ O storage part 300 is provided on the conveyance port 31 side, and is installed on the opposite side to the suction exhaust port 38 through the hot plate 33, vaporized water vapor is formed on the wafer W surface side. Aeration is exhausted. Therefore, water vapor can be reliably adsorbed on the wafer W surface.

Thus, when employ | adopting the structure which vaporizes water in the processing container 30, it is not necessary to supply water vapor | steam into the processing container 30 from the outside, and in the supply of water vapor from the outside and in the processing container 30, The generation of water vapor may be combined.

Subsequently, another example of the hydrophobization processing unit 3 will be described with reference to FIG. 14. The hydrophobization processing unit 3 of this example is configured to supply HMDS gas and water vapor from the shower head in the processing container 310. In this example, the processing container 310 is divided into the lower container 311 and the upper container 312 up and down, for example, the upper container 312 is provided so that the lower container 311 can be elevated. .

In addition, a plurality of gas supply holes 314 are formed in the top plate 313 of the upper container 312, and a processing gas supply part 315 is connected to the gas supply hole 314, and this processing gas supply part 315 is provided. ) Is connected to a supply path of HMDS gas and water vapor, which is constituted by a supply path 23 in FIG. 4. In this way, the shower head which supplies HMDS gas and water vapor in a shower shape is comprised above the hotplate 33 in the process container 310. As shown in FIG. In this example, the supply passage 23 and the processing gas supply unit 315 constitute a hydrophobization treatment supply passage and a reaction accelerator supply passage.

In addition, a supply path 316 of N ₂ gas, which is a purge gas, is connected to the top plate 313, for example. Further, Figs. 4, 9, in Fig. 11, Fig. 12, N ₂ purge gas, but configured to be supplied to the hydrophobic treatment unit to the same supply and the HMDS gas, in the case of using the art embodiment of a hydrophobic treatment unit, a fuzzy A dedicated supply passage for supplying the N ₂ purge gas to the hydrophobic treatment unit from the N ₂ gas source is provided. In addition, in order to suppress condensation of HMDS gas or water vapor, the ceiling plate 313 is provided with the heating means 36 which consists of a heater.

In addition, an intermediate plate 320 having a plurality of gas supply holes 321 is provided below the ceiling plate 313. For example, the gas supply holes 321 may include a gas supply hole formed in the ceiling plate 313. It is formed in the position shifted from the lower side of the gas supply hole 314 so that it may not interfere with 314. As shown in FIG. The intermediate plate 320 is configured to be movable up and down between a processing position above the wafer W on the hot plate 33 and an upper side of the processing position, and directly below the top plate 313. . The processing position is a position at the time of supplying the HMDS gas or the like into the processing container 310, and is a position shown in FIG. 14. Also referred to as the purge position is a position to supply the N ₂ purge gas into the processing container 300. In this example, when the intermediate plate 320 is in the processing position, the periphery thereof is supported by the protrusion 318 provided on the side wall 317 so as to be pushed up to the purge position by the lifting pin mechanism 322. Consists of.

Moreover, the processing container 310 is comprised so that it may exhaust from the exhaust part 330 provided in the ceiling part through the exhaust path 331 formed in the side wall part 317, This exhaust part 330 is a thing of FIG. It is connected to the exhaust path 51. Thereby, the gas supplied from the shower head in the process container 310 is comprised so that it may exhaust from the outer edge part of the process container 310. The rest of the configuration is similar to that of the hydrophobicization processing unit 3 shown in FIG. 5 described above.

In this hydrophobization processing unit 3, first, as shown in FIG. 15A, the upper container 312 is raised to form an opening for loading the wafer W between the lower container 311. Wafer W is carried into the processing container 310. At this time, the inside of the processing container 310 may be exhausted in the high exhaust state. Subsequently, as shown in FIG. 15B, the upper container 312 is lowered, the processing container 310 is sealed, and the supply of the HMDS gas and water vapor is started, and the processing container 310 is opened. The wafer is evacuated, mounted on the hot plate 33 by the lift pins 35, and subjected to hydrophobic treatment. At this time, the HMDS gas and water vapor are supplied into the processing container 310 in a shower shape through the processing gas supply part 315 and the gas supply hole 314 formed in the ceiling plate 313, and through the exhaust path 318 installed on the outer circumference. Exhausted.

And as shown in FIG.15 (c), after completion | finish of hydrophobization process, the intermediate plate 320 is raised from the lifting pin mechanism 322 to the purge position, and a substitution process is started. As a result, the N ₂ gas flows from the central portion of the processing container 310 toward the exhaust passage 318 provided at the outer peripheral portion. In this way, after replacing the inside of the processing container 310 with N ₂ gas, as shown in FIG. 15D, the intermediate plate 320 is lowered to the processing position, and the upper container 312 is lowered. It raises and the wafer W is carried out. At the time of this substitution process or when the upper container 312 is raised, the inside of the processing container 310 may be exhausted in the high exhaust state.

In such a structure, since HMDS gas and water vapor are supplied from the shower head, HMDS gas and water vapor can be supplied quickly and uniformly to the whole surface of the wafer W. As shown in FIG. In other words, the supply amount can be aligned while the supply time difference of the HMDS gas or the like is eliminated between the central portion and the outer peripheral portion of the wafer W. Thereby, before the temperature of the wafer W rises and all the water vapor adsorbed on the wafer W is vaporized, the HMDS gas can be uniformly supplied to the entire surface of the wafer W, thereby advancing the hydrophobization process quickly. You can.

Further, when N ₂ substitution process, the intermediate plate 320 is raised, is in supplying the N ₂ gas from a central portion of the processing vessel 310 and, since the exhaust from the outer periphery, the flow of N ₂ gas one-way flow, N Compared with the case where ₂ gases are supplied in the shower shape, the substitution process can be advanced quickly.

Next, another example of the hydrophobization processing unit 3 will be described with reference to FIG. 16. This example is a structure which supplies HMDS gas and water vapor from the outer periphery of the processing container 330 into the processing container 330, and exhausts it from the center part of the processing container 330. As shown in FIG. In this example, the processing container 330 is divided up and down into the lower container 331 and the upper container 332, for example, the upper container 332 is installed to be elevated relative to the lower container 331 have. The structure of the lower container 331 is the same as that of the hydrophobization processing unit shown in FIG.

The upper container 332 has an exhaust path 333 formed at the center thereof, and a gas chamber 335 is formed at the top plate 334. The gas supply hole 336 is formed in the outer peripheral part of the lower surface of this gas chamber 335, and the supply path 23 of HMDS gas and water vapor is connected to the said gas chamber 335. As shown in FIG. In this example, the supply passage 23 constitutes a hydrophobization treatment supply passage and a reaction accelerator supply passage. The ceiling plate 334 is provided with a heating means 36 made of a heater so as not to condense HMDS gas or water vapor. The rest of the configuration is similar to that of the hydrophobization processing unit 3 shown in FIG.

In the hydrophobization processing unit 3, first, as shown in FIG. 17A, the upper container 332 is raised to form an opening for loading wafers between the lower container 331 and the wafer ( W) is brought into the processing vessel 330. At this time, the inside of the processing container 330 may be switched to the high exhaust state. Subsequently, as shown in FIG. 17B, the upper container 332 is lowered to form the processing container 330, and the supply of the HMDS gas and water vapor is started, and the wafer is transferred to the hot plate 33. It is loaded and hydrophobization processing is performed. At this time, the HMDS gas and water vapor are supplied from the supply passage 24 into the processing vessel 330 through the gas chamber 335. At this time, since the HMDS gas and the water vapor are supplied from the outer circumferential portion of the processing container 330 and are exhausted from the central portion of the processing container 330, a gas flow from the outside to the inside is formed in the processing container 330.

In this way, as shown in Fig. 17 (c), after the hydrophobic treatment was completed, the supplied into the processing vessel 330 through the gas chamber 335 with N ₂ gas for purging from the supply path 24, the substitution processing Initiate. After completion of the substitution process, as shown in FIG. 17D, the upper container 332 is raised to carry out the wafer W. As shown in FIG. At the time of this substitution process and the carrying out of the wafer W, the inside of the processing container 330 may be switched to the high exhaust state. In addition, when the upper container 332 is in contact with the lower container 331, a gap for introducing a small amount of outside air is formed between the two, and water having a humidity of about 40% RH in the processing container 330 is formed from the gap. You may make it introduce the external air containing these.

In such a structure, since HMDS gas etc. are supplied from the outer peripheral part of the processing container 330, and it is exhausted from the center part, the leakage of the atmosphere to the exterior of the processing container 330 can be expected.

Further preferably, the hydrophobic treatment in the unit, so as to install the H ₂ O storage portion 340 as shown in Fig. The H ₂ O reservoir 340 of this example is provided in the vicinity of the hot plate 33 in the support block 34, for example, along the periphery of the hot plate 33. Support block 34, the heating section 342 to heat the flow passage 341, and, the flow path 341 and the H ₂ O reservoir section 340 for supplying water in a H ₂ O reservoir 340 It is provided, and the said flow path 341 is comprised so that water may be supplied from the water tank 343 by the pump P2.

In such a configuration, first, after the previous process is finished, a certain amount of water is supplied to the H ₂ O reservoir 340 by the pump P2 before starting the next process. The upper container 332 is raised to carry the wafer W into the processing container 330. At this time, the water of the H ₂ O reservoir 340 is heated and vaporized by the heating means 342 and the hot plate 33 to generate water vapor. Subsequently, the wafer W is loaded on the hot plate 33 to lower the upper container 332. Thereafter, the supply of the HMDS gas into the processing vessel 30 through the supply passage 24 is started to perform the hydrophobization treatment.

After completion of the hydrophobization treatment, the supply of the HMDS gas is stopped, the N ₂ gas is supplied through the supply passage 24, and the atmosphere in the processing container 330 is replaced with the N ₂ gas atmosphere. After completion of the substitution process, the upper container 332 is lifted up and the wafer W is carried out. In this manner, after the processing is completed for one wafer W, water is supplied to the H ₂ O storage 340. In such a process, the upper container 332 may be raised or switched to the high exhaust state during the substitution process. In addition, in conjunction with the generation of water vapor inside the processing container 332, water vapor may be supplied from the outside of the processing container 332 together with the HMDS gas.

Moreover, before carrying in the wafer W into the processing container 3 of the hydrophobization processing unit 3, you may make it perform the process of vaporizing a reaction promoter and supplying it to a board | substrate by supplying water vapor to the said wafer W. . In the example shown in Figure 19, by loading the wafer (W) on an external conveyance mechanism 7, for example, transport from the H ₂ O gasification unit 4 is installed in the vicinity of the hydrophobic treatment unit (3) Organization ( It is comprised so that water vapor may be supplied to the wafer W on 7). The wafer W supplied with water vapor from the H ₂ O vaporization unit 4 is transferred to the hydrophobization processing unit 3 by the transfer mechanism 7. Further, water vapor is supplied from the H ₂ O vaporization unit 4 to the wafer W on the mounting table provided in the vicinity of the hydrophobization processing unit 3, after which the wafer W is transferred to the hydrophobization processing unit 3. You may make it convey. As described above, in the configuration in which water vapor is supplied to the wafer W before the wafer W is loaded into the hydrophobization processing unit 3, the wafer W is loaded into the hydrophobization processing unit 3, thereby providing an HMDS gas. It is necessary that water vapor does not condense on the wafer W surface until is supplied.

In the above, when heating the wafer W, it is preferable to rapidly raise the wafer W to a temperature suitable for the hydrophobization treatment before the initial adsorption moisture volatilizes and disappears from the surface of the wafer W. Here, initial adsorption moisture is moisture adsorb | sucked to the wafer W before carrying in to a process container. For this reason, when the gap between the wafer W and the hot plate increases, the temperature increase rate of the wafer W decreases, so that the contact bake for heating the wafer W in contact with the hot plate or the gap between the wafer W and the hot plate is 0.03. It is preferable to employ a proximity gap bake system of about mm to 0.05 mm.

In the present invention, as a reaction accelerator for promoting hydrophobization of the wafer W, those having hydrogen bonds such as ammonia (NH ₃ ), amines and alcohols can be used in addition to water. At this time, in the case of using a gas at room temperature and normal pressure as a reaction accelerator, the concentration-controlled gas is treated in the hydrophobization treatment unit 3 using, for example, a permeation tube method for liquefying at high pressure and encapsulating the tube. It is preferable to supply in the container 30.

Hereinafter, the case where NH ₃ is interposed in the hydrophobic reaction will be described with reference to the drawings. In this case, when NH ₃ is interposed in a transition state, as shown in FIG. 20A, it is inferred that the activation energy of the reaction is lowered than when NH ₃ is not interposed. In the case where NH ₃ is involved, in the transition state, N in the HMDS bonds with SiOH through NH ₃ , and then the hydrogen bond is replaced, thereby producing SiOSi (CH ₃ ) ₃ and (CH ₃ ) ₃ SiNH ₂ . I think. For this reason, in the transition state, the degree of freedom of the angle of the three-dimensional structure of HMDS becomes large, As a result, Si and H of SiOH of HMDS become easy to react, and it is guessed that activation energy falls. As described above, when having hydrogen bonds such as H ₂ O, NH ₃ , amines, alcohols, or the like is involved, replacement of hydrogen bonds in the transition state occurs as described above, and the activation energy of the reaction is lowered. It is considered to act as a catalyst for promoting the reaction of the hydrophobization reaction.

As hydrophobization treatment gas other than HMDS gas, for example, a silylating agent having a silyl alkyl group such as TMSDMA (Trimethylsilyldimethylamine), TMSDEA (N-Trimethylsilyldiethylamine), or BSA [N, O-bis (trimethylsilyl) acetamide] can be used. . Since these silylating agents also cause surface reactions in the same reaction mechanism as HMDS, it is thought that these also promote the hydrophobization reaction by adding a reaction accelerator having a hydrogen bond, such as water, like HMDS.

When TMSDMA is used as the hydrophobization treatment gas, the hydrophobization reaction proceeds according to the basic reaction formula shown in Scheme 2 below to generate OSi (CH ₃ ) _{3 as a} hydrophobic group.

Scheme 2

Further, in the case of using a process gas TMSDEA hydrophobic, depending on the basic reaction scheme shown in Scheme 3, the hydrophobic reaction is in progress, a small number of group OSi (CH _{3) 3} is generated.

Scheme 3

Further, in the case of using BSA as a hydrophobic treatment gas, according to the basic scheme shown in Scheme 4, the hydrophobic reaction is in progress, a small number of group OSi (CH _{3) 3} is generated.

Scheme 4

[Example]

Below, the Example performed in order to confirm the contribution of the water | hydrophobization treatment reaction is demonstrated.

(First embodiment)

The wafer W in which the initial adsorption moisture exists is carried into the processing container of a hydrophobization processing unit, the wafer W is loaded on the heated hotplate, HMDS gas is introduced while the wafer W is heated, and hydrophobization treatment is carried out. After the treatment, the contact angle was measured by the curve fitting method. Here, as shown in FIG. 21, the hydrophobization processing unit introduce | transduces HMDS gas from the center of the processing container 71, and set it as the structure which exhausts from the outer periphery of the processing container 71. FIG. In addition, the temperature of the hot plate 72 at the time of loading the wafer W was set to 90 degreeC, and the hydrophobization process was performed for 30 second after loading on the hot plate 72. FIG. The temperature change and the processing state of the wafer W at this time are shown in Fig. 22A.

(2nd Example)

Carry a wafer (W) in the initial adsorbed water present in the processing vessel 71 of the hydrophobic treatment unit, and heating the wafer (W) while supplying N ₂ gas in the art the process container 71 by the baking treatment at 120 ℃ 1 minute was performed and the initial supply moisture on the wafer W was removed. Thereafter, HMDS gas was introduced to carry out hydrophobization treatment for 30 seconds, and the contact angle was measured after the treatment. The temperature change and the processing state of the wafer W at this time are shown in Fig. 22B.

(Third Embodiment)

Carry a wafer (W) in the initial adsorbed water present in the processing vessel 71 of the hydrophobic treatment unit, and heating the wafer (W) while supplying N ₂ gas in the art the process container 71 by the baking treatment at 120 ℃ 1 minute was performed and the initial supply moisture on the wafer W was removed. Thereafter, the wafer W was once taken out from the processing container 71 and exposed for about 30 minutes in an atmosphere of 40% RH humidity. Subsequently, the wafer W was brought into the processing container 71 again, HMDS gas was introduced while the wafer W was heated, hydrophobization treatment was performed for 30 seconds, and the contact angle was measured after the treatment. The temperature change and the processing state of the wafer W at this time are shown in Fig. 22C.

(Example 4)

The wafer W in which the initial adsorption moisture exists is carried into the processing container 71 of the hydrophobization processing unit, and while baking the wafer W, N ₂ gas is supplied to the processing container 71 to perform baking for 1 minute. The initial supply moisture on the wafer W was removed. Thereafter, water vapor at a dew point of 22 ° C was introduced together with the HMDS gas to carry out hydrophobization treatment for 30 seconds, and the contact angle was measured after the treatment. The temperature change and the processing state of the wafer W at this time are shown in Fig. 22D.

(result)

23 shows the contact angles of the first to fourth embodiments. As a result, as in the second embodiment, when the baking treatment by N ₂ purge is performed before the hydrophobization treatment, and the hydrophobization treatment is performed again after removing the water adsorbed on the surface, the baking treatment is not performed (first embodiment). In comparison, the contact angle was greatly reduced.

Moreover, when the hydrophobization process is performed after leaving the wafer W in the atmosphere of 40% RH after baking process (3rd Example), or when water is added at the time of the hydrophobization process after baking process (4th Example) ), The contact angle was restored to a state close to the first embodiment.

From this, it was confirmed that the contact angle is increased by performing the hydrophobization treatment in the state where water is present on the wafer W. As shown in FIG. In addition, even when the initial adsorption water is removed, it is understood that it is important to perform the hydrophobization treatment in the state where water vapor is adsorbed on the surface of the wafer W, such as supply of water vapor.

(Fifth Embodiment)

Using the hydrophobization treatment system shown in FIG. 12 described above, the HMDS gas is used as a carrier gas of steam while the hot plate 33 temperature of the hydrophobization treatment unit 3 is 90 deg. C and the hydrophobization treatment time is 30 seconds. The gas was supplied at a flow rate of 2.5 L / min, hydrophobization treatment was performed in accordance with the above-described process, and the contact angle was measured after the treatment. At this time, the H ₂ O vaporization unit 4 is similarly hydrophobicized in the case of not supplying water vapor and in the case of changing the water temperature of the H ₂ O vaporization unit 4 by using the structure of FIG. 6A. The contact angle was measured for each case. This result is shown in FIG.

It is understood from FIG. 24 that, in the case of supplying steam, the contact angle becomes larger as compared with the case of not supplying steam, and the higher the water temperature of the H ₂ O vaporization unit 4 becomes, the larger the contact angle becomes. It is recognized that the higher the water temperature of the H ₂ O vaporization unit 4 is, the larger the amount of vaporization becomes and the supply amount of water vapor increases, so that the contact angle increases as the supply amount of water vapor increases.

In the above, in the hydrophobization treatment apparatus of the present invention, the hydrophobization treatment gas supply passage and the reaction accelerator supply passage may be provided separately. In addition, when the hydrophobization process gas supply path and the reaction accelerator supply path are common, the hydrophobization process gas and the vapor of the reaction accelerator may be supplied at independent timings, regardless of the separate cases. For example, water vapor may be first supplied into the processing vessel, and then hydrophobized processing gas may be supplied. In addition, the structure of a hydrophobization processing unit is not limited to the above-mentioned embodiment, Moreover, the means which vaporizes a reaction accelerator and the means which vaporizes and supplies the vaporized reaction promoter to the wafer W are also limited to the above-mentioned embodiment. It doesn't work.

As described above, the hydrophobic treatment of the present invention can be applied to hydrophobic treatment of substrates such as glass substrates for flat panel displays (FPD) other than the semiconductor wafer (W).

W: Wafer
2: HMDS vaporization unit
3: hydrophobization processing unit
30 processing container
33: hotplate
303: H ₂ O reservoir
4: H ₂ O vaporization unit

Claims (11)

In a processing container, comprising a hydrophobic silicon, and generating a substrate having hydroxyl groups on the surface, and trimethyl silyl supplying a hydrophobic treatment comprising a gas, the surface of the substrate made of a small number of groups -O (CH _{3) 3} In the processing method,
Vaporizing a reaction promoter for promoting hydrophobicity of the substrate and supplying the substrate to the substrate;
Heating the substrate brought into the processing container;
A step of supplying the hydrophobization treatment gas to the surface of the substrate in a state in which vapor of the reaction accelerator is adsorbed on the surface of the heated substrate,
The hydrophobization treatment method characterized by promoting the reaction of the silicon of a hydrophobization process gas and oxygen of the surface of a board | substrate with the said reaction promoter. The method of claim 1, wherein the reaction promoter is a material selected from water, ammonia, amines, and alcohols. The process of claim 1 or 2, wherein the step of vaporizing and supplying the reaction accelerator to the substrate comprises at least one of heating the substrate to a set temperature and heating the substrate to a set temperature before heating the substrate. A hydrophobization processing method, characterized in that the timing is carried out. The hydrophobization treatment method according to claim 1 or 2, wherein the vapor of the reaction promoter is supplied to the treatment vessel after being mixed with the hydrophobization treatment gas. The hydrophobization treatment method according to claim 1 or 2, wherein the reaction accelerator is vaporized by heating a storage portion of a liquid of the reaction accelerator provided in the processing container. The hydrophobic treatment method according to claim 1 or 2, wherein the vapor of the reaction accelerator is supplied to the substrate before the substrate is loaded into the processing container. Comprising a silicon loaded into the loading portion in the processing container, on a substrate having a hydroxyl group at the surface, by supplying a hydrophobic treatment gas comprising a trimethylsilyl, a surface of the substrate made of a -O (CH _{3) 3} In the hydrophobization processing apparatus which produces | generates a hydrophobic group,
Heating means provided in the processing container for heating the substrate;
A hydrophobization treatment gas supply path for supplying the hydrophobization treatment gas into the processing container;
A reaction accelerator supplying means for vaporizing and supplying a reaction accelerator for promoting hydrophobicity of the substrate in the processing container,
In the processing container, the hydrophobization treatment gas is supplied to the surface of the substrate in a state where the vapor of the reaction accelerator is adsorbed on the surface of the heated substrate, and the reaction accelerator is used to provide silicon and the substrate of the hydrophobization treatment gas. A hydrophobic treatment apparatus characterized by promoting the reaction of oxygen on the surface. The hydrophobic treatment apparatus according to claim 7, wherein the reaction promoter is a substance selected from water, ammonia, amine and alcohol. The hydrophobic treatment apparatus according to claim 7 or 8, wherein the reaction accelerator supplying means is a reaction accelerator supplying passage for supplying steam of the reaction accelerator into the processing vessel. The hydrophobization treatment apparatus according to claim 9, wherein the reaction accelerator supply passage is also used as a hydrophobization treatment gas supply passage, and the vapor of the reaction accelerator is supplied to the treatment vessel after being mixed with the hydrophobization treatment gas. 9. The reaction accelerator supplying means according to claim 7 or 8, wherein the reaction accelerator supplying means comprises a storage portion of the liquid of the reaction accelerator provided in the processing vessel and a heating portion for heating the storage portion, and vaporizing the reaction accelerator in the processing vessel. A hydrophobic treatment apparatus characterized by the above-mentioned.

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